CN102974282A - Preparation method of oxide sol - Google Patents
Preparation method of oxide sol Download PDFInfo
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- CN102974282A CN102974282A CN201210517642XA CN201210517642A CN102974282A CN 102974282 A CN102974282 A CN 102974282A CN 201210517642X A CN201210517642X A CN 201210517642XA CN 201210517642 A CN201210517642 A CN 201210517642A CN 102974282 A CN102974282 A CN 102974282A
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Abstract
The invention belongs to the technical field of sols-gels and discloses a preparation method of oxide sol. The preparation method comprises the following steps of: (1) dissolving an oxide precursor and PEG (polyethylene glycol) in a solvent to obtain a precursor solution; and (2) adding an epoxy compound in the precursor solution obtained in the step (1), ageing for 2-50hours and then adding dilute nitric acid to obtain the oxide sol. According to the preparation method, either cheap inorganic metal salt or a high-purity organic metal salt solution can be used as the precursor, the PEG is used as a dispersant and the epoxy compound is used as a gel accelerant, and therefore the uniform and stable single sol or composite sol can be obtained by controlling the proportions. The preparation method disclosed by the invention is wide in application, simple in reaction process and capable of rapidly obtaining a large batch of sol. The sol prepared by using the preparation method can be used as a raw material for preparing oxide powder, films, blocks and aerogel and has a wide application prospect in the field of sols-gels.
Description
Technical field
The invention belongs to the sol-gel technique field, be specifically related to a kind of preparation method of oxide sol.
Background technology
Sol-gal process be the preparation material wet chemical method in a kind of than new technology, it is a kind of metallo-organic compound, metal inorganic compound or above-mentioned both mixtures process hydrolytie polycondensation processes, progressively gelation and corresponding post processing, and obtains the oxide of different shape or the brand-new technique of other compounds.
Sol-gel process has following advantage: the chemical uniformity of having promoted the multicomponent mixture system; Course of reaction is easy to control, can realize the accurate control composition of overall process and micro-structural; It is wide to prepare material doped scope, and stoichiometry is accurate, is easy to realize the material property modification; Prepared material component is even, product purity is high.
In sol-gal process, uniform and stable colloidal sol is the basis of follow-up preparation powder, film, fiber or block.For transition metal and III, IV, V main group metal and nonmetalloid, its oxide is to fire the different pottery of types of functionality, the important component of glass etc.Therefore, the process of the colloidal sol of the oxide of these elements or composite oxides preparation has obtained extensive and deep research.Have benefited from these research, some colloidal sol commonly used has begun to enter the stage of commercially producing.But these methods still exist the course of reaction variable many at present, the problems such as technique sensitivity.
At present, the method for preparing colloidal sol mainly contains two classes, the one, adopt the inorganic salts Hydrolyze method to prepare colloid, technology path is to introduce precipitating reagent in preparation process, so that inorganic salts are removed the foreign ion that precipitating reagent etc. brings through cyclic washing again after precipitation under certain pH value, then add acid and carry out peptization, clearly this method technique is loaded down with trivial details; Another kind of is to adopt organic alkoxide hydrolysis preparation colloid, but because organic alkoxide very easily is hydrolyzed, and technology controlling and process is difficult, cost is high, is difficult to carry out large-scale production.
Summary of the invention
The invention provides a kind of preparation method of oxide sol, when adopting this preparation method to prepare oxide sol, technical process is controlled easily, is easy to carry out large-scale production.
A kind of preparation method of oxide sol may further comprise the steps:
(1) oxide precursor and PEG are dissolved in the solvent, obtain precursor solution;
(2) under stirring condition, in the resulting precursor solution of step (1), add epoxide, behind the ageing 2-50h, add again rare nitric acid, obtain described oxide sol;
Described PEG is polyethylene glycol, and molecular weight ranges is 200-2000.
The present invention is by using epoxide to replace ammoniacal liquor commonly used as gel promoter, add simultaneously entry and PEG as auxiliary agent, reduced the speed of the hydrolytic-polymeric reaction of described oxide precursor, and then the granular size of the oxide sol that generates of control, improved the stability of described oxide sol by rare nitric acid.Whole reaction temperature and controlled, the simple stirring just can obtain large batch of high-quality colloidal sol under room temperature environment, is easy to carry out large-scale production.
As preferably, described oxide precursor is MCl
n, M (OR)
nAnd MOCl
mIn at least a;
Wherein, M is transition metal, III main group, IV main group or V major element;
Described R is C
1～C
5Alkyl;
N is 1～5 positive integer;
M is 1～3 positive integer, and these oxide precursors in the presence of described epoxide and PEG hydrolytic-polymeric reaction can occur controllably, generates oxide sol.
Described R is ethyl more preferably.
As further preferred, described M is Zn, Cu, Ag, Si, Zr or Sn, and described oxide precursor is ethyl orthosilicate more preferably, at least a in zirconium oxychloride and the stannic chloride.The colloidal sol that these oxide precursor generation hydrolytic-polymeric reactions prepare is applied to the film field and has preferably effect.
The consumption of described PEG more preferably described oxide precursor weight 0.1～2%, described PEG can regulate the speed of the hydrolytic-polymeric reaction of described oxide precursor, consumption is too little, regulating effect is not obvious, consumption is too large, can introduce too much impurity in described oxide sol.
Described solvent is that the alcohols solvent that water and Yi Shui dissolve each other forms, as preferably, described solvent is the mixture of water and ethanol, the volume ratio of described water and ethanol is 1: 1～6, by changing the ratio of water and ethanol, the hydrolytic-polymeric reaction speed that can further regulate described oxide precursor.
As preferably, according to different oxide precursors, described solvent adopts diverse ways to add: when described oxide precursor is selected from MCl
nOr MOCl
mThe time, with the described oxide precursor formation solution that is dissolved in the water first, in this solution, add ethanol again; When described oxide precursor is selected from M (OR)
nThe time, described oxide precursor is dissolved in first forms solution in the ethanol, in this solution, add entry again; In described oxide precursor, both contained and be selected from MCl
nOr MOCl
mCompound, contain again and be selected from M (OR)
nCompound the time, will be selected from MCl
nOr MOCl
mCompound be dissolved in the water, will be selected from M (OR)
nCompound be dissolved in the ethanol, then mix.
Among the present invention, obtain at last the concentration of oxide sol by the addition decision of described oxide precursor, as preferably, the consumption of described oxide precursor is 1～40% of described solvent quality, and the addition of described oxide precursor can access stable oxide sol in this scope.
As preferably, described epoxide is expoxy propane or oxirane, these two kinds of epoxides cheaply are easy to get, and the speed of generation ring-opening reaction is moderate in solution, can stably promote the hydrolytic-polymeric reaction of the described oxide precursor of described promotion.As further preferred, in mole, the consumption of described epoxide is 2～6 times of described oxide precursor.
As preferably, the volume ratio of described rare nitric acid and described precursor solution is 0.5～2: 100.
Compare with prior art, beneficial effect of the present invention is embodied in:
(1) the oxide sol purity for preparing is high, the wide and good stability of its solid content adjustable range;
(2) colloidal sol of preparation can be used as the general precursor sol in each field, can reduce viscosity by reducing the solid content of colloidal sol, preparation types of functionality ceramic membrane; Also can improve viscosity, improve the solid content spinning and prepare fiber; Can obtain nano level powder behind the convection drying; Perhaps adding coupling agent becomes organic/inorganic composite material, also can become base stock of preparation aeroge etc.;
(3) scope of applicable substrate is wide, from the transition metal to III, IV, V main group metal and nonmetalloid etc. all can prepare by the method, and for the oxide composite oxide sol, have fabulous versatility.
The specific embodiment
Further specify by the following examples the present invention.(each raw material is commercially available, is chemical pure or analyzes pure grade without specifying)
Embodiment 1: preparation SiO
2Colloidal sol
Take ethyl orthosilicate, deionized water, ethanol, PEG400, expoxy propane as raw material, wherein deionized water and ethanol volume ratio are 1: 6, ethyl orthosilicate is counted 2% of water+total ethanol quality by contained siliconoxide mass, expoxy propane adds 3 times of ethyl orthosilicate moles, and the addition of PEG400 is equivalent to SiO in the colloidal sol
2The 1wt% of quality.Fully stirring adds each material process after about 4 hours successively at ambient temperature, forms water white transparency colloidal sol.Ageing after 5 hours dissolved adhesiveness reach the plated film requirement, enter the viscosity of 0.5% rare nitric acid stable sol by the minim of every 200ml colloidal sol 0.5ml, namely obtain required colloidal sol.The average particle size of the gel of this colloidal sol is 20-40nm, and viscosity is 6-20mPas, and be 1 year stabilization time at normal temperatures, and resulting colloidal sol can be used for preparing SiO
2The film powder.
Embodiment 2: preparation ZrO
2-SiO
2Colloidal sol
Take zirconium oxychloride, ethyl orthosilicate, deionized water, ethanol, PEG1000, expoxy propane as raw material, wherein deionized water and ethanol volume ratio are 1: 5, zirconium oxychloride and ethyl orthosilicate mol ratio are 1: 1, both total amounts add up to 5% of water+total ethanol quality by oxide mass, the expoxy propane addition is about zirconium oxychloride and ethyl orthosilicate mole sum 2 times, and the addition of PEG1000 is equivalent to 0.5% of oxide mass in the colloidal sol.Fully stirring adds ethanol successively at ambient temperature, and ethyl orthosilicate fully mixes, with zirconium oxychloride fully dissolving in deionized water, subsequently two solution are mixed, add again PEG1000, and slowly splash into expoxy propane, the uninterrupted process that stirs forms ZrO after about 4 hours
2-SiO
2Water white transparency colloidal sol.Ageing after 3 hours dissolved adhesiveness reach requirement, enter the viscosity of 0.5% rare nitric acid stable sol by the minim of every 100ml colloidal sol 1ml, finally obtain the ZrO of 5% solid content
2-SiO
2Complex sol.The average particle size of the gel of this colloidal sol is 30-60nm, and viscosity is 6-20mPas, and at normal temperatures, be 6 months stabilization time, and resulting complex sol can be used for preparing transparent wear film and porosu solid etc.
Embodiment 3: preparation ZrO
2-SnO
2Complex sol
Take zirconium oxychloride, stannic chloride, deionized water, ethanol, PEG1000, expoxy propane as raw material, wherein deionized water and ethanol volume ratio are 1: 1, zirconium oxychloride and stannic chloride mol ratio are 1: 1, both total amounts add up to 30% of water+total ethanol quality by oxide mass, the expoxy propane addition is about zirconium oxychloride and ethyl orthosilicate mole sum 4 times, and the addition of PEG1000 is equivalent to the 1wt% of oxide mass in the colloidal sol.Fully stirring adds ethanol successively at ambient temperature, stannic chloride, and PEG1000, deionized water, the abundant stirring until dissolving slowly splashes into expoxy propane again behind the zirconium oxychloride, the uninterrupted process that stirs forms ZrO after about 6 hours
2-SnO
2Water white transparency colloidal sol.After the ageing 15 hours, enter the viscosity of 0.5% rare nitric acid stable sol by the minim of every 100ml colloidal sol 1ml, can obtain the ZrO of 30% solid content
2-SnO
2Complex sol.The average particle size of the gel of this colloidal sol is 10-30nm, and viscosity is 6-20mPas, and be 2 years stabilization time, and resulting complex sol can be used for preparing transparent conductive film and fires stannic acid zircon ceramic etc.
Above content is the further description of the present invention being done in conjunction with concrete preferred embodiment, can not assert these explanations that is confined to of implementation of the present invention.For those skilled in the technology concerned under the present invention, without departing from the inventive concept of the premise, can also make some simple deductions or replacement, all should be considered as protection scope of the present invention.
Claims (9)
1. the preparation method of an oxide sol is characterized in that, may further comprise the steps:
(1) oxide precursor and PEG are dissolved in the solvent, obtain precursor solution;
(2) under stirring condition, in the resulting precursor solution of step (1), add epoxide, behind the ageing 2-50h, add again rare nitric acid, obtain described oxide sol.
2. the preparation method of oxide sol according to claim 1 is characterized in that, described oxide precursor is MCl
n, M (OR)
nAnd MOCl
mIn at least a;
Wherein, M is transition metal, III main group, IV main group or V major element;
Described R is C
1～C
5Alkyl;
N is 1～5 positive integer;
M is 1～3 positive integer.
3. the preparation method of oxide sol according to claim 2 is characterized in that, described M is Zn, Cu, Ag, Si, Zr or Sn.
4. the preparation method of oxide sol according to claim 1 is characterized in that, the consumption of described PEG is 0.1～2% of described oxide precursor weight.
5. the preparation method of oxide sol according to claim 1 is characterized in that, described solvent is the mixture of water and ethanol, and the volume ratio of described water and ethanol is 1: 1～6.
6. the preparation method of oxide sol according to claim 5 is characterized in that, the consumption of described oxide precursor is 1～40% of described solvent quality.
7. the preparation method of oxide sol according to claim 1 is characterized in that, described epoxide is expoxy propane or oxirane.
8. the preparation method of oxide sol according to claim 7 is characterized in that, in mole, the consumption of described epoxide is 2～6 times of described oxide precursor.
9. the preparation method of oxide sol according to claim 1 is characterized in that, the volume ratio of described rare nitric acid and described precursor solution is 0.5～2: 100.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104557785A (en) * | 2014-12-31 | 2015-04-29 | 浙江工业大学 | Method for jointly preparing styrene oxide and benzaldehyde by heterogeneous catalytic epoxidized styrene |
| CN112537936A (en) * | 2020-12-28 | 2021-03-23 | 苏州启创新材料科技有限公司 | Aerogel modified high-strength fireproof mortar material and preparation method thereof |
| CN113512363A (en) * | 2021-05-28 | 2021-10-19 | 海南大学 | Fireproof adhesive and preparation method thereof |
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|---|---|---|---|---|
| CN1868581A (en) * | 2006-06-05 | 2006-11-29 | 同济大学 | Method for preparing TiO2/SiO2 aerogel microsphere |
| CN101961626A (en) * | 2010-09-20 | 2011-02-02 | 浙江大学 | Method for preparing ZrO2 aerogel |
| CN102584010A (en) * | 2012-03-15 | 2012-07-18 | 河南工业大学 | Preparation method of multi-component aerogel |
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2012
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| CN1868581A (en) * | 2006-06-05 | 2006-11-29 | 同济大学 | Method for preparing TiO2/SiO2 aerogel microsphere |
| CN101961626A (en) * | 2010-09-20 | 2011-02-02 | 浙江大学 | Method for preparing ZrO2 aerogel |
| CN102584010A (en) * | 2012-03-15 | 2012-07-18 | 河南工业大学 | Preparation method of multi-component aerogel |
Non-Patent Citations (2)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104557785A (en) * | 2014-12-31 | 2015-04-29 | 浙江工业大学 | Method for jointly preparing styrene oxide and benzaldehyde by heterogeneous catalytic epoxidized styrene |
| CN112537936A (en) * | 2020-12-28 | 2021-03-23 | 苏州启创新材料科技有限公司 | Aerogel modified high-strength fireproof mortar material and preparation method thereof |
| CN113512363A (en) * | 2021-05-28 | 2021-10-19 | 海南大学 | Fireproof adhesive and preparation method thereof |
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Application publication date: 20130320 |