阅读说明：本技术 利用十氢十硼双四乙基铵盐的副产物制备十二氢十二硼双钠盐的方法 (Method for preparing dodecahydrododecaboron disodium salt by using byproduct of decahydrododecaboron bistetraethylammonium salt ) 是由 汪游清 胡孝伦 蒋德刚 申丽坤 于 2020-06-28 设计创作，主要内容包括：本发明涉及一种利用十氢十硼双四乙基铵盐的副产物制备十二氢十二硼双钠盐的方法,属于无机材料合成工艺技术领域。该利用十氢十硼双四乙基铵盐的副产物制备十二氢十二硼双钠盐的方法,包括以下步骤：将十氢十硼双四乙基铵盐的副产物用溶剂溶解后与氢氧化钠溶液反应,反应结束后除去溶剂得到十二氢十二硼双钠盐粗品,十二氢十二硼双钠盐粗品溶解后加入三乙胺盐酸盐溶液以析出十二氢十二硼三乙胺盐,十二氢十二硼三乙胺盐与醇钠溶液反应,即得。该利用十氢十硼双四乙基铵盐的副产物制备十二氢十二硼双钠盐的方法反应时间短,收率高,效率高,反应过程稳定,操作安全。(The invention relates to a method for preparing dodecahydrododecaboron disodium salt by using a byproduct of decahydrododecaboron bistetraethylammonium salt, belonging to the technical field of inorganic material synthesis processes. The method for preparing dodecahydrododecaboron disodium salt by utilizing the byproduct of decahydrododecaboron bistetraethylammonium salt comprises the following steps: dissolving a byproduct of decahydrododecaboron bistetraethylammonium salt with a solvent, reacting the dissolved byproduct with a sodium hydroxide solution, removing the solvent after the reaction is finished to obtain a dodecahydrododecaboron disodium salt crude product, dissolving the dodecahydrododecaboron disodium salt crude product, adding triethylamine hydrochloride solution to separate dodecahydrododecaboron triethylamine salt out, and reacting the dodecahydrododecaboron triethylamine salt with a sodium alkoxide solution to obtain the dodecahydrododecaboron triethylamine salt. The method for preparing dodecahydrododecaboron disodium salt by utilizing the byproduct of decahydrododecaboron bistetraethylammonium salt has the advantages of short reaction time, high yield, high efficiency, stable reaction process and safe operation.)

1. The method for preparing dodecahydrododecaboron disodium salt by utilizing the byproduct of decahydrododecaboron bistetraethylammonium salt is characterized by comprising the following steps: dissolving a byproduct of decahydrododecaboron bistetraethylammonium salt with a solvent, reacting the dissolved byproduct with sodium hydroxide, removing the solvent after the reaction is finished to obtain a dodecahydrododecaboron disodium salt crude product, dissolving the dodecahydrododecaboron disodium salt crude product, adding triethylamine hydrochloride to separate out dodecahydrododecaboron triethylamine salt, and reacting the dodecaboron dodecahydride triethylamine salt with sodium alcoholate to obtain the dodecahydrododecaboron triethylamine salt.

2. The method for preparing dodecahydrododecaboron disodium salt using the byproduct of decahydrododecaboron bistetraethylammonium salt according to claim 1, wherein the solvent dissolving the byproduct of decahydrododecaboron bistetraethylammonium salt is one of dimethyl sulfoxide, N-methylpyrrolidone, and 2-pyrrolidone.

3. The method for preparing dodecahydrododecaboron disodium salt by using the byproduct of decahydrododecaboron bistetraethylammonium salt according to claim 1, wherein the mass ratio of the byproduct of decahydrododecaboron bistetraethylammonium salt to the solvent is 1 (3-12).

4. The method for preparing dodecahydrododecaboron disodium salt by using the byproduct of decahydrododecaboron bistetraethylammonium salt as claimed in claim 1, wherein the reaction temperature of the dissolved byproduct of decahydrododecaboron bistetraethylammonium salt with sodium hydroxide is 110-140 ℃, and the reaction time is 6-10 h.

5. The method for preparing dodecahydrododecaboron disodium salt by using the byproduct of decahydrododecaboron bistetraethylammonium salt according to claim 1 or 4, wherein the molar ratio of the byproduct of decahydrododecaboron bistetraethylammonium salt to sodium hydroxide is 1 (2-5).

6. The method for preparing dodecahydrododecaboron disodium salt by using the byproduct of decahydrododecaboron bistetraethylammonium salt according to claim 1, wherein when the dodecahydrododecaboron triethylamine salt is reacted with sodium alkoxide, the temperature is first raised to reflux reaction for 0.1-2h, and then the temperature is lowered to end the reflux.

7. The method for preparing dodecahydrododecaboron disodium salt using the byproduct of bis-tetraethylammonium decahydrododecaboron salt according to claim 1, wherein the molar ratio of dodecahydrododecaboron triethylamine salt to sodium alkoxide is 1 (0.95-1.03).

Technical Field

The invention belongs to the technical field of inorganic material synthesis processes, and particularly relates to a method for preparing dodecahydrododecaboron disodium salt by using a byproduct of decahydrododecaboron bistetraethylammonium salt.

Background

Dodecahydrododecaboron disodium salt having stable B₁₂The skeleton has wide application in many fields, such as application as an energy storage material or application as a nontoxic medicine in boron neutron capture treatment.

The dodecahydrododecaboron disodium salt can be prepared by various methods, such as: adding sodium borohydride into diethylene glycol dimethyl ether in batches, heating to 100 ℃, reacting for a period of time, cooling to below 30 ℃, dropwise adding boron trifluoride ethyl ether, reacting for a period of time at normal temperature after dropwise adding is completed, heating to 100 ℃, reacting for a period of time under heat preservation, heating to 160 ℃, performing reflux reaction for 2 hours, cooling and supplementing sodium borohydride, continuing reflux reaction, cooling, filtering, evaporating filtrate to dryness to obtain a solid, dissolving the solid with water, and performing salt exchange to obtain a product. The preparation method has the following disadvantages: the 10L reactor generally needs 7 days from feeding to obtaining a finished product, the reaction time is long, the production efficiency is low, the obtained finished product is 20-30g, and the yield is low and is about 20-30%; the reaction temperature is high, hydrogen is released in the reaction process, and the operation risk coefficient is high; after the reaction is finished, the product is in the filtrate and is difficult to filter; the solid obtained after the filtrate is evaporated to dryness is added into water, so that the operation is dangerous, a large amount of heat and hydrogen can be discharged, and the treatment time is long.

Disclosure of Invention

The invention aims to provide a method for preparing dodecahydrododecaboron disodium salt by utilizing a byproduct of decahydrododecaboron bistetraethylammonium salt, which has the advantages of short reaction time, high yield, high efficiency, stable reaction process and safe operation.

In order to achieve the above purpose, the invention adopts the technical scheme that:

the method for preparing dodecahydrododecaboron disodium salt by utilizing the byproduct of decahydrododecaboron bistetraethylammonium salt comprises the following steps: dissolving a byproduct of decahydrododecaboron bistetraethylammonium salt with a solvent, reacting the dissolved byproduct with sodium hydroxide, removing the solvent after the reaction is finished to obtain a dodecahydrododecaboron disodium salt crude product, dissolving the dodecahydrododecaboron disodium salt crude product, adding triethylamine hydrochloride to separate out dodecahydrododecaboron triethylamine salt, and reacting the dodecaboron dodecahydride triethylamine salt with sodium alcoholate to obtain the dodecahydrododecaboron triethylamine salt.

Further, the solvent for dissolving the byproduct of the decahydrodecaborane bistetraethylammonium salt is one of dimethyl sulfoxide, N-methylpyrrolidone and 2-pyrrolidone.

Further, the ratio of the byproduct of the decahydrodecaborobistetraethylammonium salt to the solvent is 1 (3-12). Preferably, the ratio of the byproduct of the decahydrododecaboron bistetraethylammonium salt to the solvent is 1 (6-8).

Further, the reaction temperature of the dissolved by-product of the decahydrodecaborane bistetraethylammonium salt and sodium hydroxide is 110-140 ℃, and the reaction time is 6-10 h.

Further, the molar ratio of the byproduct of the decahydrodecaborobistetraethylammonium salt to the sodium hydroxide is 1 (2-5). Preferably, the molar ratio of the byproduct of the decahydrodecaborobistetraethylammonium salt to the sodium hydroxide is 1 (2-3).

Further, when the dodecahydrododecaboron triethylamine salt reacts with sodium alcoholate, the temperature is firstly raised to reflux reaction for 0.1-2h, and then the temperature is lowered to end the reflux.

Further, the molar ratio of the dodecahydrododecaboron triethylamine salt to the sodium alcoholate is 1 (0.95-1.03).

Further, the sodium alkoxide is sodium methoxide or sodium ethoxide.

And calculating the adding amount of the solvent, the sodium hydroxide and the sodium alkoxide by taking the dodecahydrododecahydrododecaboron bistetraethylammonium salt in the byproducts of the decahydrododecaboron bistetraethylammonium salt, namely calculating the molar mass of the byproducts of the decahydrododecaboron bistetraethylammonium salt, and calculating the molar mass of the byproducts of the decahydrododecaboron bistetraethylammonium salt by the molar mass of the pure dodecahydrododecaboron bistetraethylammonium salt.

The invention has the beneficial effects that:

the method for preparing the dodecahydrododecaboron disodium salt by using the byproduct of the decahydrododecaboron bistetraethylammonium salt has the advantages that the raw material is the byproduct of the decahydrododecaboron bistetraethylammonium salt, no effective utilization way is available at present, the dodecahydrododecaboron bistetraethylammonium salt accounts for about 80%, the dodecahydrododecaboron disodium salt prepared by using the bistetraethylammonium dodecahydrododecaborate belongs to the reutilization of the byproduct, the environment is protected, and the energy is saved.

According to the method for preparing dodecahydrododecaboron disodium salt by utilizing the byproduct of decahydrododecaboron bistetraethylammonium salt, the dodecahydrododecaboron disodium salt crude product contains various impurities such as undedecahydroundecabron disodium salt, decahydrododecaboron disodium salt, nonahydrononaboron disodium salt and the like, and after triethylamine hydrochloride is added, dodecahydrododecaboron triethylamine salt is separated out because of insolubility of water, so that pure dodecahydrododecaboron triethylamine salt is obtained. Because dodecahydrododecaboron triethylamine salt is insoluble in water, sodium alcoholate is selected to react with dodecahydrododecaboron triethylamine salt to obtain dodecahydrododecaboron disodium salt.

The method for preparing dodecahydrododecaboron disodium salt by utilizing the byproduct of decahydrododecaboron bistetraethylammonium salt has the advantages of short reaction time, high yield, stable reaction process, no hydrogen gas emission and safe operation.

Drawings

FIG. 1 shows the preparation of disodium dodecahydrododecaboron salt obtained in example 1¹¹B NMR chart.

Detailed Description

The present invention will be further described with reference to the following embodiments and accompanying drawings.