CN102898279B - Preparation method for solid metal alkoxide - Google Patents
Preparation method for solid metal alkoxide Download PDFInfo
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- CN102898279B CN102898279B CN201210398632.9A CN201210398632A CN102898279B CN 102898279 B CN102898279 B CN 102898279B CN 201210398632 A CN201210398632 A CN 201210398632A CN 102898279 B CN102898279 B CN 102898279B
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Abstract
The invention relates to a preparation method for solid metal alkoxide, which belongs to the technical field of metal alkoxide preparation. Metal fuel and inorganic salt are mixed to obtain mixture; the obtained mixture is subjected to grinding and compounding in a ball mill to obtain high-activity alcohol reaction metal material; alcohol solvent is added into the obtained high-activity alcohol reaction metal material; at the constant temperature or under the heating condition, the high-activity alcohol reaction metal material reacts with the alcohol solvent; and after reaction is finished, distilling and vacuum drying are carried out to obtain the solid metal alkoxide. According to the preparation method disclosed by the invention, the high-activity alcohol reaction metal material can be prepared with a high-energy ball mill method. The active material can quickly react with the alcohol to generate the metal alkoxide. The method disclosed by the invention has the advantages of high efficiency and simple technology, and the obtained metal alkoxide has a high purity.
Description
Technical field
The present invention relates to a kind of preparation method of solid metal alkoxide, belong to metal alkoxide preparing technical field.
Background technology
Metal alkoxide, is called again metal alkoxide compound or metal acid esters, is described as the metal-organic part of blank broad sense of having filled up between organic chemistry and inorganic chemistry by people.
Metal alkoxide is to react and a series of general formulas of making are the compound of M (OR) n with metal or metal inorganic salt and alcohols, wherein M is that valency is the metal of n, R is alkyl, be respectively the alkyl such as first, second, third, fourth according to the difference of the alcohols of participating in reaction, metal alkoxide especially easily and the nucleophilic reagent such as alcohols, oxy-compound, water react, it is easy of distillation to have, recrystallization technology purification, dissolve in ordinary organic solvents, the characteristics such as facile hydrolysis.
Metal alkoxide is as the important compound of a class, application at aspects such as inorganic synthetic, organic synthesis, directional catalyzing polymerization, function ceramics and nano-functional materials has caused people's extensive concern, especially in recent years along with the widespread use of sol-gel technique, and the continuous growth to high pure and ultra-fine rare earth oxide demand of high-performance ceramic, electronics and magneticsubstance, the research of metal alkoxide and application are subject to people's pay attention to day by day.
The method of synthetic metal alkoxide has direct reaction method and indirect method.Direct reaction method is exactly that metal and alcohol direct reaction generate metal alkoxide, and direct reaction method technique is simple, and cost is low, and product purity is higher, is easier to realize suitability for industrialized production.But very strong element and the alcohol of metallicity such as basic metal, alkaline-earth metal and lanthanon just can generate corresponding metal alkoxide with alcohol generation vigorous reaction (generally need to carry out under protective atmosphere); The slightly weak metal of metallicity needs to have I as Be, Mg, A1, Y and some rare earth element
2, HgCl
2could react with alcohol Deng making catalyzer.
Summary of the invention
The present invention seeks to for metal and alcohol direct reaction difficulty and need to use the feature of toxic catalyzer, providing and in a kind of reaction process, do not need to add I
2, HgCl
2etc. poisonous catalyzer, and can rapidly and efficiently react the method for preparing metal alkoxide.
The object of the invention is to be achieved through the following technical solutions.
The preparation method of a kind of solid metal alkoxide of the present invention, the step of the method comprises:
1) metallic fuel is mixed with catalyzer, obtain mixture;
2) mixture step 1) being obtained grinds compound in ball mill, obtains high reactivity alcohol reacting metal material;
3) by step 2) the high reactivity alcohol reacting metal material that obtains joins in alcoholic solvent, and under normal temperature or heating condition, high reactivity alcohol reacting metal material and alcoholic solvent react, and after reaction finishes, distillation, vacuum-drying, obtain solid metal alkoxide;
Above-mentioned steps 1) in metallic fuel and the total mass of catalyzer be 100%, wherein, the mass content of each several part is:
Metallic fuel 80% ~ 99.8%
Catalyzer 0.02% ~ 20%
Above-mentioned steps 1) in metallic fuel be a kind of or its mixture in magnesium powder, aluminium powder, calcium powder, barium powder, lanthanum powder, cerium powder;
Above-mentioned steps 1) in catalyzer be a kind of or its mixture in Repone K, sodium-chlor, iron(ic) chloride, calcium chloride, magnesium chloride, aluminum chloride, cobalt chloride, nickelous chloride, cupric chloride, zinc chloride, silicon chlorides, titanium chloride, bismuth chloride, silver chloride, zirconium chloride, molybdenum chloride, platinum chloride, Industrial Salt or cobalt, nickel, iron, bismuth, molybdenum or metal different valence state oxide compound;
Above-mentioned steps 2) in the setup parameter of ball mill comprise ratio of grinding media to material, rotational speed of ball-mill, cycle index, Ball-milling Time;
Above-mentioned steps 3) in alcoholic solvent be a kind of or its mixture in methyl alcohol, ethanol, propyl alcohol, Virahol, ethylene glycol;
Above-mentioned steps 3) in the alcoholic solution recycling that distills out.
Beneficial effect
The present invention adopts high-energy ball milling method to prepare highly active alcohol reacting metal material, and this active material can react fast and generate metal alkoxide with alcohol; This invention has overcome direct reaction legal system need to add I for alkoxide
2, HgCl
2etc. the shortcoming of poisonous catalyzer, there is technique simple, active material reaction efficiency is high, can various metals collocation prepare composition metal alkoxide; Method efficiency of the present invention is high, and technique is simple, and the metal alkoxide purity obtaining is high.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
1) 100g magnesium powder, 1g cobalt chloride are mixed, obtain mixture;
2) mixture step 1) being obtained is put into and in ball mill, is ground compoundly together with mill ball, obtains high reactivity alcohol reaction magnesium powder, and ball mill adopts 60 rotational speed of ball-mill circulation technologies, and the ratio of grinding media to material of ball mill is 10:1, and Ball-milling Time is 60min;
3) taking 2g step 2) the high reactivity alcohol that obtains reaction magnesium powder joins in the reactor of 250ml, then in reactor, injects 50ml methyl alcohol, and under room temperature, reaction starts, and after 60min, reaction stops; By distillation under vacuum, excessive methyl alcohol is reclaimed, then vacuum-drying obtains solid methanol magnesium, and vacuum-drying temperature is 50 DEG C.The purity that tests out the magnesium methylate obtaining by titrimetry method is 98.1%.
Embodiment 2
1) 100g magnesium powder, 1g cobalt chloride are mixed, obtain mixture;
2) mixture step 1) being obtained is put into and in ball mill, is ground compoundly together with mill ball, obtains high reactivity alcohol reaction magnesium powder, and ball mill adopts 60 rotational speed of ball-mill circulation technologies, and the ratio of grinding media to material of ball mill is 10:1, and Ball-milling Time is 60min;
3) taking 2g step 2) the high reactivity alcohol that obtains reaction magnesium powder joins in the reactor of 250ml, then in reactor, injects 50ml ethanol, and under room temperature, reaction starts, and after 120min, reaction stops; By distillation under vacuum, excessive ethanol is reclaimed, then vacuum-drying obtains solid magnesium ethoxide, and vacuum-drying temperature is 50 DEG C.The purity that tests out the magnesium methylate obtaining by titrimetry method is 98.9%.
Embodiment 3
1) 100g magnesium powder, 1g cobalt chloride are mixed, obtain mixture;
2) mixture step 1) being obtained is put into and in ball mill, is ground compoundly together with mill ball, obtains high reactivity alcohol reaction magnesium powder, and ball mill adopts 60 rotational speed of ball-mill circulation technologies, and the ratio of grinding media to material of ball mill is 10:1, and Ball-milling Time is 60min;
3) taking 2g step 2) the high reactivity alcohol that obtains reaction magnesium powder joins in the reactor of 250ml, then in reactor, notes 50ml propyl alcohol, and reactor is heated to 70 DEG C, and after 245min, reaction stops; By distillation under vacuum, excessive propyl alcohol is reclaimed, then vacuum-drying obtains solid magnesium propylate, and vacuum-drying temperature is 70 DEG C.The purity that tests out the magnesium propylate obtaining by titrimetry method is 99.3%.
Embodiment 4
1) 100g aluminium powder, 2g sodium-chlor, 3g bismuth meal are mixed, obtain mixture;
2) mixture step 1) being obtained is put into and in ball mill, is ground compoundly together with mill ball, obtains high reactivity alcohol reaction magnesium powder, and ball mill adopts 60 rotational speed of ball-mill circulation technologies, and the ratio of grinding media to material of ball mill is 10:1, and Ball-milling Time is 60min;
3) taking 2g step 2) the high reactivity alcohol that obtains reaction aluminium powder joins in the reactor of 250ml, then in reactor, notes 50ml Virahol, starts reaction after reactor is heated to 75 DEG C, and after 300min, reaction stops; By distillation under vacuum, excessive Virahol is reclaimed, then vacuum-drying obtains solid aluminum isopropylate, and vacuum-drying temperature is 70 DEG C.The purity that tests out the aluminum isopropylate obtaining by titrimetry method is 99%.
Embodiment 5
1) 50g aluminium powder, 50g magnesium powder, 2g cobalt chloride, 1g bismuth meal are mixed, obtain mixture;
2) mixture step 1) being obtained is put into and in ball mill, is ground compoundly together with mill ball, obtains high reactivity alcohol reaction alloy powder, and ball mill adopts 60 rotational speed of ball-mill circulation technologies, and the ratio of grinding media to material of ball mill is 10:1, and Ball-milling Time is 60min;
3) taking 2g step 2) the high reactivity alcohol that obtains reaction alloy powder joins in the reactor of 250ml, then in reactor, notes 100ml ethanol, and under normal temperature, reaction starts, and after 120min, reaction stops; By distillation under vacuum, excessive ethanol is reclaimed, then vacuum-drying obtains solid alcohol magnalium, and vacuum-drying temperature is 70 DEG C.Show that by the method that reaction efficiency calculates and titrimetry combines the purity of the Virahol magnalium of preparation is 98.5%.
Embodiment 6
1) 50g aluminium powder, 50g magnesium powder, 2g cobalt chloride, 1g bismuth meal are mixed, obtain mixture;
2) mixture step 1) being obtained is put into and in ball mill, is ground compoundly together with mill ball, obtains high reactivity alcohol reaction alloy powder, and ball mill adopts 60 rotational speed of ball-mill circulation technologies, and the ratio of grinding media to material of ball mill is 10:1, and Ball-milling Time is 60min;
3) taking 2g step 2) the high reactivity alcohol that obtains reaction alloy powder joins in the reactor of 250ml, then in reactor, notes 100ml propyl alcohol, starts reaction after reactor is heated to 75 DEG C, and after 240min, reaction stops; By distillation under vacuum, excessive propyl alcohol is reclaimed, then vacuum-drying obtains solid propyl alcohol magnalium, and vacuum-drying temperature is 70 DEG C.Show that by the method that reaction efficiency calculates and titrimetry combines the purity of the Virahol magnalium of preparation is 98%.
Claims (4)
1. a preparation method for solid metal alkoxide, is characterized in that the step of the method comprises:
1) metallic fuel and inorganic salt are mixed, obtain mixture;
2) mixture step 1) being obtained grinds compound in ball mill, obtains high reactivity alcohol reacting metal material;
3) in step 2) add alcoholic solvent in the high reactivity alcohol reacting metal material that obtains, under normal temperature or heating condition, high reactivity alcohol reacting metal material and alcoholic solvent react, and after reaction finishes, distillation, vacuum-drying, obtain solid metal alkoxide;
Above-mentioned steps 1) in metallic fuel and the total mass of inorganic salt be 100%, wherein, the mass content of each several part is:
Metallic fuel 80%～99.8%
Inorganic salt 0.02%～20%;
Above-mentioned steps 1) in metallic fuel be a kind of or its mixture in magnesium powder, aluminium powder;
Above-mentioned steps 1) in inorganic salt be a kind of or its mixture in sodium-chlor, cobalt chloride;
Above-mentioned steps 3) in alcoholic solvent be a kind of or its mixture in methyl alcohol, ethanol, propyl alcohol, Virahol, ethylene glycol.
2. the preparation method of a kind of solid metal alkoxide according to claim 1, it is characterized in that: in step 1), in metallic fuel and inorganic salt, add catalyzer, while adding catalyzer, taking the total mass of metallic fuel, catalyzer and inorganic salt as 100%, wherein, the mass content of each several part is:
Metallic fuel 80%～99.8%
Catalyzer 0.01%～10%
Inorganic salt 0.01%～10%;
The catalyzer adding is one or the mixture in bismuth metal or bismuth metal different valence state oxide compound.
3. the preparation method of a kind of solid metal alkoxide according to claim 1, is characterized in that: step 2) in the setup parameter of ball mill comprise ratio of grinding media to material, rotational speed of ball-mill, cycle index, Ball-milling Time.
4. the preparation method of a kind of solid metal alkoxide according to claim 1, is characterized in that: the alcoholic solution recycling distilling out in step 3).
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| CN103788337B (en) * | 2014-01-14 | 2015-12-02 | 北京理工大学 | A kind of flame retardant polyurethane rigid foam for external wall outer insulation and preparation method thereof |
| CN103993177B (en) * | 2014-05-29 | 2016-05-04 | 山东大学 | A kind of method and application of preparing high activity Ni-Fe alloy based on ball milling chemical method original position |
| CN106410203B (en) * | 2016-11-11 | 2019-07-12 | 南京理工大学 | A method of using metal alkoxide as precursor preparation spherical shape cobalt acid zinc/carbon composite |
| CN108083986B (en) * | 2016-11-22 | 2020-08-04 | 中国科学院大连化学物理研究所 | Organic-inorganic hybrid material, preparation thereof and application thereof in hydrogen storage |
| CN113637174B (en) * | 2021-07-22 | 2022-09-02 | 湖北工业大学 | Concrete toughness-enhanced chain alkanolamine ferric salt composition and preparation method thereof |
| CN113788497B (en) * | 2021-08-12 | 2022-07-26 | 华南理工大学 | Multiphase molybdenum sulfide composite material and preparation method and application thereof |
Citations (5)
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|---|---|---|---|---|
| EP0026547A1 (en) * | 1979-09-27 | 1981-04-08 | Union Carbide Corporation | Process for the preparation of basic salts of alkaline earth metals |
| US4670573A (en) * | 1984-12-17 | 1987-06-02 | Stauffer Chemical Company | Activated preparation of metal alkoxides |
| CN1062135A (en) * | 1991-12-11 | 1992-06-24 | 浙江省明矾石综合利用研究所 | The manufacture method of aluminium alcoholates |
| CN101024599A (en) * | 2007-04-04 | 2007-08-29 | 施碎呈 | Solid magnesium ethoxide and preparing method |
| CN101243094A (en) * | 2005-08-12 | 2008-08-13 | 株式会社资生堂 | Water-soluble metal alcoholate derivative, process for production of the derivative, and solid gelatinous agent for external application comprising the derivative |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1328460C (en) * | 1988-09-30 | 1994-04-12 | Conrad William Kamienski | Mass treatment of cellulosic materials |
-
2012
- 2012-10-19 CN CN201210398632.9A patent/CN102898279B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0026547A1 (en) * | 1979-09-27 | 1981-04-08 | Union Carbide Corporation | Process for the preparation of basic salts of alkaline earth metals |
| US4670573A (en) * | 1984-12-17 | 1987-06-02 | Stauffer Chemical Company | Activated preparation of metal alkoxides |
| CN1062135A (en) * | 1991-12-11 | 1992-06-24 | 浙江省明矾石综合利用研究所 | The manufacture method of aluminium alcoholates |
| CN101243094A (en) * | 2005-08-12 | 2008-08-13 | 株式会社资生堂 | Water-soluble metal alcoholate derivative, process for production of the derivative, and solid gelatinous agent for external application comprising the derivative |
| CN101024599A (en) * | 2007-04-04 | 2007-08-29 | 施碎呈 | Solid magnesium ethoxide and preparing method |
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