CN102205946A - Liquid phase synthesis method of non-alkali-metal type metal hydroboron - Google Patents
Liquid phase synthesis method of non-alkali-metal type metal hydroboron Download PDFInfo
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- CN102205946A CN102205946A CN 201110111845 CN201110111845A CN102205946A CN 102205946 A CN102205946 A CN 102205946A CN 201110111845 CN201110111845 CN 201110111845 CN 201110111845 A CN201110111845 A CN 201110111845A CN 102205946 A CN102205946 A CN 102205946A
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- borohydride
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Abstract
The invention relates to preparation of a hydroboron, in particular to a liquid phase synthesis method of a non-alkali-metal type metal hydroboron. The liquid phase synthesis method comprises the following steps of: 1, mixing reaction initiators particularly referring to an alkali-metal hydroboron and a metal halide with an organic solvent to obtain a mixture, ball-milling the mixture and performing mechanochemical reaction; 2, filtering or centrifuging ball-milling products to obtain a solution of a synthesized non-alkali-metal type metal hydroboron and an adduct of the non-alkali-metal type metal hydroboron; and 3, removing the solvent and solvent ligands to obtain the non-alkali-metal type metal hydroboron. The method has the advantages of simple production equipment, less operation steps, easiness in controlling the reaction process, safe and reliable reaction conditions, low price for raw materials, low production cost, high yield and purity as well as stable property of the product and the like.
Description
Technical field
The present invention relates to the preparation of hydroborate, relate in particular to a kind of liquid-phase synthesis process of low-cost high yield of non-basic metal metalloid hydroborate.
Background technology
Metal borohydride is a kind of broad-spectrum functional materials.Because its selective reduction ability is strong, be applied to the reduction of aldehyde, ketone, carboxylic acid and derivative thereof, acid amides, imines, nitrile, epoxy compounds, eneyne etc. at industrial circle.In energy and material and technical field thereof, hydroboration calcium and magnesium borohydride have been subjected to domestic and international investigator's extensive attention because its high quality hydrogen-storage amount and volume hydrogen-storage amount are a kind of solid-state hydrogen storage material that has development potentiality.At biomedical sector, because BH
4Have direct oxidation resistant effect, can directly remove reactive oxygen species,, endothelium is played protective effect, and the health of endothelial function is to avoid the important assurance of diseases such as diabetes as superoxide anion, peroxidation nitroso-group etc.Metal borohydride also is expected to be used for preparation and cures scarce BH
4The related drugs of disease.Along with the demand of different field to metal borohydride constantly increases, and to its functionalization, improving constantly of becoming more meticulous and require, low-cost, high-level efficiency prepares the high purity metal hydroborate and has great importance.
At present, except that alkali metal borohydrides such as sodium borohydride and POTASSIUM BOROHYDRIDE, the price of hydroboration calcium and magnesium borohydride is very expensive in the metal borohydride, and is mainly controlled by minority offshore company.For metal borohydrides such as hydroboration strontium, hydroboration barium, zinc borohydrides, reagent company does not see that substantially its product is arranged both at home and abroad, and rarely has the report of its preparation method yet.There is report that Zn (BH is arranged
4)
2.2NH
3Synthetic, but do not see that synthetic Zn (BH is arranged
4)
2The report of method.For hydroboration calcium and magnesium borohydride, currently reported synthetic method mainly contains liquid phase method and solid phase method two classes.
In liquid phase method, with a kind of method that metal hydride and the liquid wet chemical method that refluxes of triethylamine borine are preparation hydroboration calcium and magnesium borohydride, its reaction equation that relates to is:
Wherein, M=Ca, Mg.But this kind procedure is extremely loaded down with trivial details, relate to the long-time backflow under differing temps of metal hydride and triethylamine borine, and with repeatedly washing and the drying of organic solvent n-hexane to the backflow product, wherein employed triethylamine borine is poisonous and cost an arm and a leg, not only threatening operator's safety, also increase production cost, restricted the application in practice of this method.
The liquid phase method of another kind of synthetic hydroboration calcium and magnesium borohydride is to be undertaken by the replacement(metathesis)reaction of metal halide and alkali metal borohydride, and corresponding reaction equation is:
Wherein M=Ca, Mg.It is earlier with reactant ball milling under the solid phase condition, transfer to then in the Glass Containers that corresponding organic solvent is housed and stir for a long time, with wherein metal borohydride of leaching, gained stirs product again by filtering or centrifugal, and processing such as desolvate obtains metal borohydride.This method relates to the repeatedly transfer of reactant, and stirs for a long time the stopping property of glass system is had relatively high expectations.
For solid phase method, thereby the synthetic technology of report is that initial reactant is mixed back synthetic metal borohydride of insulation certain hour under high temperature and high hydrogen pressure in the world.Wherein the preparation method of hydroboration calcium is mainly based on following reaction equation:
With
Principal reaction equation of magnesium borohydride synthetic is:
Their temperature of reaction is usually above 350 ℃, and required hydrogen pressure needs the hundreds of normal atmosphere usually, and soaking time also reaches tens hours, thereby preparation is dangerous high.In addition, solid phase method has also been introduced by product inevitably, the removal difficulty of by product.Harsh high-temperature high-voltage reaction condition and required special reaction device thereof have increased preparation cost, have limited the mass-producing of this method and have used.
In sum, preparation method's process complexity of existing non-basic metal metalloid hydroborate, security is low, cost is high, has restricted the investigator to further investigation and the exploitation of such hydroborate as aspects such as hydrogen storage material, selective reduction thing and medical uses.Therefore it is significant at hydrogen storage material and the application aspect other for development to invent the method for the non-basic metal metalloid of synthesis of high purity hydroborate of a kind of simple, safety, low cost, high yield.
Summary of the invention
In order to overcome the existing deficiency of non-basic metal metalloid hydroborate on technology of preparing, the purpose of this invention is to provide a kind of liquid-phase synthesis process of non-basic metal metalloid hydroborate, this method has low cost, high-efficiency characteristics.
In order to realize above-mentioned purpose, the present invention has adopted following technical scheme:
A kind of liquid-phase synthesis process of non-basic metal metalloid hydroborate, this method comprises the steps:
1) with alkali metal borohydride and metal halide as initial reactant, start material and corresponding organic solvent are mixed, again this mixture is carried out ball milling, implement the mechanical force and chemical reaction;
2) the ball milling product is filtered or centrifugal treating obtain synthesize non-alkali metal borohydride and adduct solution thereof;
3) handle by the part that desolvates and desolvate, make non-basic metal metalloid hydroborate;
Above-mentioned organic solvent has volatile characteristic, volatilization temperature is lower than the decomposition temperature of the non-basic metal metalloid of institute's synthetic hydroborate, and non-alkali metal borohydride of the dissolving of organic solvent and adduct solution thereof, but do not dissolve alkali metal borohydride, metal halide and reactant resistates.
As preferably, above-mentioned non-alkali metal borohydride is non-basic metal metalloid hydroborates such as hydroboration calcium, magnesium borohydride, hydroboration strontium, hydroboration barium or zinc borohydride.
As preferably, above-mentioned metal halide is calcium chloride, Calcium Bromide, calcium iodide, magnesium chloride, magnesium bromide, magnesium iodide, strontium chloride, strontium bromide, strontium iodide, bariumchloride, barium bromide, barium iodide, zinc chloride, zinc bromide or zinc iodide.
As preferably, above-mentioned alkali metal borohydride is sodium borohydride and POTASSIUM BOROHYDRIDE.
As preferably, above-mentioned metal halide is calcium chloride, Calcium Bromide, calcium iodide, magnesium chloride, magnesium bromide, magnesium iodide, strontium chloride, strontium bromide, strontium iodide, bariumchloride, barium bromide, barium iodide, zinc chloride, zinc bromide or zinc iodide.
As preferably, above-mentioned organic solvent select ether, propyl ether, tetrahydrofuran (THF), isopropyl ether, ethyl-butyl ether, diox, methyl tertiary butyl ether, tetrahydropyrans, 1 for use, 3-diox, 1, one or more in one or more in 3-Er Evil pentane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, the dimethyl-tetrahydrofuran and the methylene dichloride.
As preferably, in the step 1) initial reactant and corresponding organic solvent are mixed, again this mixture is carried out ball milling, ratio of grinding media to material is 10～120:1, and rotational speed of ball-mill is 50～500 rev/mins, and the ball milling time is 1～80 hour.Consumption as preferred again, above-mentioned organic solvent is that every gram reactant adopts 5～100 milliliters.
As preferably, step 2) filtering system vacuumizes or feeds argon gas earlier in, liquid phase ball milling product is transferred in the filtering system filtered again.
As preferably, in the step 3) desolvating of institute's synthetic non-basic metal metalloid hydroborate and adduct solution thereof handled employing distillatory method and carry out; As preferred again, above-mentioned Distallation systm vacuumizes or feeds argon gas earlier, the non-basic metal metalloid hydroborate and the adduct solution thereof of gained place Distallation systm to distill again, distillation temperature is higher than the boiling point of used organic solvent, but is lower than the temperature of the decomposition of institute's synthetic metal borohydride and adducts thereof; Preferred temperature is 30～200 ℃.
As preferably, method by heating in the step 3) is carried out the desorption processing to depending on to survive in the solvent part of this metal borohydride when forming non-basic metal metalloid hydroborate, Heating temperature is 70 ℃ of starting temperatures of decomposing hydrogen to non-basic metal metalloid hydroborates; As preferred again, by desorption process is implemented the flowing process that successive vacuumizes processing or rare gas element, quicken removal to the solvent part, efficiently obtain highly purified metal borohydride.
The present invention compares with background technology, and the useful effect that has is:
1, the present invention is based on the synthetic non-basic metal metalloid hydroborate of the method for at normal temperatures and pressures start material directly being carried out ball milling in corresponding organic solvent, wherein initial reactant is more cheap alkali metal borohydride of price and metal halide, and the solvent of employing is C2～C8 ethers and methyl chloride etc.Solvent can dissolve the non-basic metal metalloid of institute's synthetic hydroborate, but does not dissolve initial reactant and other reaction product, thereby can realize that the non-basic metal metalloid of institute's synthetic hydroborate separates with the effective of other ball milling product;
2, preparation method's metal borohydride of the present invention synthetic and its leaching once finished, possibility simple to operate, product pollution is little, equipment simple, reaction process is easy to control and stable, reaction conditions is safe and reliable, production cost is low, product productive rate and purity height;
3, the present invention has avoided first solid phase ball milling in the existing liquid phase method, the stirring in liquid phase when leaching and repeatedly complex operations such as product transfer again;
4, preparation process of the present invention is not used organism such as expensive and deleterious triethylamine borine used in the existing liquid phase method, also avoided adopting repeatedly washing and the drying of organic solvent n-hexane, also avoided the use of the high-temperature high-voltage reaction device of the danger of existing solid phase method used High Temperature High Pressure and complex and expensive the backflow product.
Description of drawings
Fig. 1 is the hydroboration calcium adducts (a) of embodiment 1 acquisition and the FT-IR collection of illustrative plates of hydroboration calcium (b).
Fig. 2 is the x-ray diffractogram of powder spectrum of the hydroboration calcium adducts (a) and the hydroboration calcium (b) of embodiment 2 acquisitions.
The hydroboration calcium that Fig. 3 obtains for embodiment 3 put the hydrogen curve.
Fig. 4 is the FT-IR collection of illustrative plates of the magnesium borohydride of embodiment 4 acquisitions.
Embodiment
Embodiment 1
In the glove box of Ar gas atmosphere, 2:1 takes by weighing sodium borohydride and Calcium Chloride Powder Anhydrous in molar ratio, and the ball grinder of packing into is that solvent joins in the ball grinder with the ratio of 25 milliliters of tetrahydrofuran (THF)s of every gram reactant.To this mixture on planetary ball mill with 200 rev/mins rotating speed ball milling 12 hours.The ball milling after product is filtered, to the filtrate processing of under 40 ℃ temperature, desolvating, all evaporate again, obtain the adducts of hydroboration calcium and solvent up to solvent.Wherein, the filtering system and the system of desolvating all vacuumize in advance.Then gained hydroboration calcium adducts is vacuumized the part that desolvates and handle under 150 ℃ temperature, make hydroboration calcium.The FT-IR of hydroboration calcium adducts and hydroboration calcium detects and has shown that hydroboration calcium adducts is through the processing of heating deallocation body, successfully removal tetrahydrofuran (THF) wherein.2200 –, 2400 cm in the FT-IR collection of illustrative plates
-1With 1000 –, 1400 cm
-1The B-H characteristic infrared absorption peak of the hydroboration calcium in the wave-number range has illustrated the generation of hydroboration calcium.
In the glove box of Ar gas atmosphere, 2:1 takes by weighing sodium borohydride and Calcium Chloride Powder Anhydrous in molar ratio, and the ball grinder of packing into is that solvent joins in the ball grinder with the ratio of 35 milliliters of tetrahydrofuran (THF)s of every gram reactant.To this mixture on planetary ball mill with 300 rev/mins rotating speed ball milling 6 hours.The ball milling product is filtered, and filtrate is desolvated under 50 ℃ temperature again, all evaporates up to solvent, makes the adducts of hydroboration calcium and solvent.Wherein the filtering system and the system of desolvating all vacuumize in advance.Gained hydroboration calcium adducts is vacuumized the part that desolvates handle under 180 ℃ temperature, make hydroboration calcium.Powder x-ray diffraction test analysis to hydroboration calcium adducts and hydroboration calcium shows that hydroboration calcium adducts is handled through the deallocation body, has successfully removed tetrahydrofuran (THF) part wherein and has obtained hydroboration calcium.
Embodiment 3
In the glove box of Ar gas, 2:1 takes by weighing sodium borohydride and Calcium Chloride Powder Anhydrous in molar ratio, packing in the ball grinder, is that solvent joins in the ball grinder with the ratio of 20 milliliters of tetrahydrofuran (THF)s of every gram reactant, on planetary ball mill with 500 rev/mins rotating speed ball milling 3 hours.The ball milling product is filtered, and filtrate is distilled under 60 ℃ temperature and is desolvated, and obtains the adducts of hydroboration calcium and solvent.The filtering system and the system of desolvating all vacuumize in advance.The gained hydroboration calcium adducts part that desolvates under 200 ℃ temperature is handled, made hydroboration calcium.The productive rate that obtains hydroboration calcium has reached more than 80%.To the hydrogen discharging performance test shows of the hydroboration calcium that makes, the hydrogen discharging temperature scope is about 500 ℃ of 200 –, and during to 500 ℃, hydrogen desorption capacity has reached 8.8 wt.%.Calculate from its hydrogen desorption capacity, the purity of synthetic hydroboration calcium has reached more than 90%.
Embodiment 4
In the glove box of Ar gas atmosphere, 2:1 takes by weighing sodium borohydride and Magnesium Chloride Anhydrous in molar ratio, and the ball grinder of packing into is a solvent with the ratio of 40 milliliters of ether of every gram reactant, on planetary ball mill with 200 rev/mins rotating speed ball milling 24 hours.The ball milling product is filtered, to the filtrate processing of under 50 ℃ temperature, desolvating, all evaporate again, obtain the adducts (different with hydroboration calcium adducts is that the magnesium borohydride adducts is a viscous liquid) of magnesium borohydride and solvent up to solvent.Wherein, the filtering system and the system of desolvating all vacuumize in advance.Then gained magnesium borohydride adducts is vacuumized the part that desolvates and handle under 200 ℃ temperature, make magnesium borohydride.2200 – 2400cm in the FT-IR collection of illustrative plates
-1With 1000 – 1400cm
-1The B-H characteristic infrared absorption peak of the magnesium borohydride in the wave-number range has illustrated the generation of magnesium borohydride, and does not have 3000cm
-1About C-H infrared signature peak, the c h bond that does not have ether in the synthetic magnesium borohydride is described.
Claims (10)
1. the liquid-phase synthesis process of a non-basic metal metalloid hydroborate is characterized in that this method comprises the steps:
1) with alkali metal borohydride and metal halide as initial reactant, start material and corresponding organic solvent are mixed, again this mixture is carried out ball milling, implement the mechanical force and chemical reaction;
2) the ball milling product is filtered or centrifugal treating obtain synthesize non-alkali metal borohydride and adduct solution thereof;
3) handle by the part that desolvates and desolvate, make non-basic metal metalloid hydroborate;
Above-mentioned organic solvent has volatile characteristic, volatilization temperature is lower than the decomposition temperature of the non-basic metal metalloid of institute's synthetic hydroborate, and non-alkali metal borohydride of the dissolving of organic solvent and adduct solution thereof, but do not dissolve alkali metal borohydride, metal halide and reactant resistates.
2. the liquid-phase synthesis process of a kind of non-basic metal metalloid hydroborate according to claim 1 is characterized in that: non-alkali metal borohydride is hydroboration calcium, magnesium borohydride, hydroboration strontium, hydroboration barium or zinc borohydride.
3. the liquid-phase synthesis process of a kind of non-basic metal metalloid hydroborate according to claim 2 is characterized in that: metal halide is calcium chloride, Calcium Bromide, calcium iodide, magnesium chloride, magnesium bromide, magnesium iodide, strontium chloride, strontium bromide, strontium iodide, bariumchloride, barium bromide, barium iodide, zinc chloride, zinc bromide or zinc iodide.
4. the liquid-phase synthesis process of a kind of non-basic metal metalloid hydroborate according to claim 1 is characterized in that: alkali metal borohydride is sodium borohydride or POTASSIUM BOROHYDRIDE.
5. according to the liquid-phase synthesis process of the described non-basic metal metalloid hydroborate of any claim of claim 1～4, it is characterized in that: organic solvent select ether, propyl ether, tetrahydrofuran (THF), isopropyl ether, ethyl-butyl ether, diox, methyl tertiary butyl ether, tetrahydropyrans, 1 for use, 3-diox, 1, one or more in one or more in 3-Er Evil pentane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, the dimethyl-tetrahydrofuran and the methylene dichloride.
6. the liquid-phase synthesis process of non-basic metal metalloid hydroborate according to claim 1, it is characterized in that: step 1) is mixed initial reactant and corresponding organic solvent, again this mixture is carried out ball milling, ratio of grinding media to material is 10～120:1, rotational speed of ball-mill is 50～500 rev/mins, and the ball milling time is 1～80 hour.
7. according to the liquid-phase synthesis process of claim 1 or 6 described non-basic metal metalloid hydroborates, it is characterized in that: the consumption of organic solvent is that every gram reactant adopts 5～100 milliliters.
8. the liquid-phase synthesis process of non-basic metal metalloid hydroborate according to claim 1 is characterized in that: step 2) filtering system vacuumizes or feeds argon gas earlier, and liquid phase ball milling product is transferred in the filtering system filtered again.
9. the liquid-phase synthesis process of non-basic metal metalloid hydroborate according to claim 1 is characterized in that: step 3) is handled desolvating of institute's synthetic non-basic metal metalloid hydroborate and adduct solution thereof and is adopted the distillatory method to carry out; As preferably, above-mentioned Distallation systm vacuumizes or feeds argon gas earlier, the non-basic metal metalloid hydroborate and the adduct solution thereof of gained place Distallation systm to distill again, distillation temperature is higher than the boiling point of used organic solvent, but is lower than the temperature of the decomposition of institute's synthetic metal borohydride and adducts thereof; As preferred again, temperature is 30～200 ℃.
10. according to the liquid-phase synthesis process of claim 1 or 9 described non-basic metal metalloid hydroborates, it is characterized in that: step 3) is carried out desorption processing to depending on to survive in the solvent part of this metal borohydride by the method for heating when forming non-basic metal metalloid hydroborate, Heating temperature is 70 ℃ of starting temperatures of decomposing hydrogen to non-basic metal metalloid hydroborates; As preferably, implement the flowing process that successive vacuumizes processing or rare gas element in the above-mentioned desorption process, quicken removal to the solvent part, obtain highly purified metal borohydride.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140295260A1 (en) * | 2011-11-17 | 2014-10-02 | Toyota Jidosha Kabushiki Kaisha | Method for producing sulfide solid electrolyte |
| CN106315512A (en) * | 2016-08-10 | 2017-01-11 | 南通南京大学材料工程技术研究院 | Method for inducing and synthesis gamma-Ca(BH4)2 through mechanical force |
| CN108793069A (en) * | 2018-07-03 | 2018-11-13 | 南通志乐新材料有限公司 | A kind of zinc borohydride system hydrogen storage material |
| CN115072663A (en) * | 2022-07-13 | 2022-09-20 | 山东国邦药业有限公司 | Preparation method of lithium borohydride and zinc borohydride |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3113832A (en) * | 1953-05-19 | 1963-12-10 | Gyogyszeripari Ki | Complex borohydrides and a process for their preparation and use |
-
2011
- 2011-05-03 CN CN 201110111845 patent/CN102205946A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3113832A (en) * | 1953-05-19 | 1963-12-10 | Gyogyszeripari Ki | Complex borohydrides and a process for their preparation and use |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140295260A1 (en) * | 2011-11-17 | 2014-10-02 | Toyota Jidosha Kabushiki Kaisha | Method for producing sulfide solid electrolyte |
| CN106315512A (en) * | 2016-08-10 | 2017-01-11 | 南通南京大学材料工程技术研究院 | Method for inducing and synthesis gamma-Ca(BH4)2 through mechanical force |
| CN108793069A (en) * | 2018-07-03 | 2018-11-13 | 南通志乐新材料有限公司 | A kind of zinc borohydride system hydrogen storage material |
| WO2020006839A1 (en) * | 2018-07-03 | 2020-01-09 | 黄倩 | Zinc borohydride hydrogen storage material |
| CN115072663A (en) * | 2022-07-13 | 2022-09-20 | 山东国邦药业有限公司 | Preparation method of lithium borohydride and zinc borohydride |
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Application publication date: 20111005 |