CN103694267B - The purification process of the two tetraethyl ammoniums of a kind of decahydro ten boric acid - Google Patents
The purification process of the two tetraethyl ammoniums of a kind of decahydro ten boric acid Download PDFInfo
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Abstract
The purification process that the invention discloses the two tetraethyl ammoniums of a kind of decahydro ten boric acid, the method is: the mixture that (1) obtains pyrolytic reaction is hydrolyzed by a certain amount of deionized water, under room temperature, filters, evaporate to dryness filtrate obtains hydrolysis prods; (2) by a certain amount of recrystallizing methanol of hydrolysis prods of step (1) gained, cooled and filtered, filter cake is through a small amount of methanol wash, and product must be recrystallized after being dried; (3), by a certain amount of deionized water dissolving of recrystallization product of step (2) gained, adopt at a certain temperature charcoal absorption purifying to obtain the two tetraethyl ammonium products of decahydro ten boric acid that purity is greater than 99.9%.
Description
Technical field
The present invention relates to the purification process of the two tetraethyl ammoniums of a kind of decahydro ten boric acid.
Background technology
Polyhedral boranes have armaticity, heat resistance and excellent chemistry owing to having the delocalization of boron cage electronicsStability, is applied to multiple fields such as high-energy fuel, functional material, biological medicine and catalyst. Conventional polyhedron hydroborationCompound is mainly divided into borine, carborane and ionic compound thereof etc. The two tetraethyl ammoniums of decahydro ten boric acid are a kind of important borinesAnionic compound, not only can be used as solid propellant combustion rate conditioning agent or high-energy fuel, also can be used as other polyhedron hydroborationsCompound is as carborane or the boratory synthetic precursor of decahydro ten.
The main synthetic method of the two tetraethyl ammoniums of decahydro ten boric acid is that tetrahydrochysene tetraethylammonium borate is the pyrolytic reaction method of raw material, the partyIn the product component of method gained, containing multiple borine anionic compound, separation and purification difficulty is larger. As in patent US4391993 withTetrahydrochysene tetraethylammonium borate compound, in triethylamine borine, carries out the two tetrems of synthetic decahydro ten boric acid of pyrolytic reaction at 186 DEG CBase ammonium, contains other multiple borine ionic impurity, as B in product6H6 -2，B9H9 -2，B11H14 -1，B12H12 -2Deng, but this is specialPurification process and the purity of the two tetraethyl ammoniums of unexposed principal product decahydro ten boric acid in the post-processing operation of profit.
Summary of the invention
The defect or the deficiency that exist for above-mentioned prior art, the invention provides that a kind of purification step is less, solvent load is less,And the purification process of the two tetraethyl ammoniums of decahydro ten boric acid that product purity is high.
The purification process of the two tetraethyl ammoniums of a kind of decahydro ten boric acid provided by the invention, comprises the following steps:
A purification process for the two tetraethyl ammoniums of decahydro ten boric acid, is characterized in that: the method method comprises the steps:
(1) by two the decahydro obtaining through pyrolytic reaction ten boric acid certain proportion deionized water and stirring hydrolysis for tetraethyl ammonium crude product,At 5～100 DEG C of temperature, reaction 0.5～8h, filters under room temperature, by the concentrated filtrate hydrolysis prods that obtains; Wherein decahydro ten boric acid are twoThe mass ratio of tetraethyl ammonium crude product and deionized water is 1:5～1:10; Impurity B in this step6H6 -2，B9H9 -2，B11H14 -1Being hydrolyzed to react with water generates boric acid, and containing B12H12 -2Impurity because solubility in water is much smaller than principal product decahydro ten boronThe two tetraethyl ammoniums of acid, are therefore isolated by filtration.
(2), by step (1) gained hydrolysis prods certain proportion recrystallizing methanol, carry out Separation of Solid and Liquid, filter cake warp after coolingAlcohols solvent washing, obtains the product that is recrystallized after being dried; Wherein the mass ratio of hydrolysis prods and methyl alcohol is 1:10～1:25; At thisIn step reflux course, the two tetraethyl ammoniums of decahydro ten boric acid are dissolved in methyl alcohol, and the two tetraethyl ammoniums of cooling rear decahydro ten boric acid are analysedGo out crystal, and step (1) in hydrolysis generate boric acid react with methyl alcohol generation methyl borate be dissolved in methyl alcohol, thereby and main productThing separates.
(3) the recrystallization product of step (2) gained being carried out to adsorption and purification, to obtain purity be the two tetrems of 99.9% decahydro ten boric acidBase ammonium product; Wherein adsorbent is molecular sieve, active carbon or silica gel; Eluting solvent is that deionized water, methyl alcohol or water-methanol mixSolvent; Adsorption and purification temperature is 10～95 DEG C, wherein, and recrystallization product and deionized water and recrystallization product and adsorbentMass ratio is respectively: recrystallization product: deionized water=1:5～1:20; Recrystallization product: adsorbent (dry weight)=1:1～5:1.In this step, other impurity producing in course of reaction, hydrolysis and recrystallization process is separated by the absorption of adsorbent.
The preferred technical step of the present invention is as follows:
(1) by two the decahydro obtaining through pyrolytic reaction ten boric acid certain proportion deionized water and stirring hydrolysis for tetraethyl ammonium crude product,At 65 DEG C of temperature, reaction 2h, filters under room temperature, by the concentrated filtrate hydrolysis prods that obtains; The wherein two tetraethyl ammoniums of decahydro ten boric acidThe mass ratio of crude product and deionized water is 1:7;
(2), by step (1) gained hydrolysis prods certain proportion recrystallizing methanol, carry out Separation of Solid and Liquid, filter cake warp after coolingMethanol wash, obtains the product that is recrystallized after being dried; Wherein the mass ratio of hydrolysis prods and methyl alcohol is 1:15;
(3) by the recrystallization product of step (2) gained taking deionized water as solvent, active carbon is adsorbent, at 75 DEG C, entersRow adsorption and purification, filters after 0.5h, and concentrated filter obtains purity and be 99.9% the two tetrems of decahydro ten boric acid after gained solid dryingBase ammonium product; Wherein, recrystallization product: deionized water=1:10; Recrystallization product: adsorbent=2:1.
The present invention compared with prior art has following technical advantage:
1) the present invention only needs hydrolysis, recrystallizing methanol and adsorption and purification three steps, and documents need just can obtain purity through four stepsHigh product.
2) consumption of organic solvent of the present invention is less, and only at an organic solvent methyl alcohol of re-crystallization step, and in documents, three steps are dividedDo not use the organic solvents such as acetonitrile, ethanol, methyl alcohol.
3) this purification process adopts adsorption and purification, and product purity is high, reaches 99.9%.
Detailed description of the invention
The synthetic reaction equation of the two tetraethyl ammonium crude products of decahydro ten boric acid is as shown below:
10(C2H5)4NBH4→[(C2H5)4N]2B10H10+8(C2H5)3N+8C2H6+11H2
For example: 500g tetrahydrochysene tetraethylammonium borate and triethylamine borine are joined in reaction bulb, in nitrogen replacement reaction systemAir, under stirring, be heated to 186 DEG C, keep this thermotonus 16h, under nitrogen protection, be cooled to room temperature, filter reaction mixLiquid, fully washs filter cake three times with benzinum, obtains the two tetraethyl ammonium crude products of 150g decahydro ten boric acid after filtration cakes torrefaction.
The purifying of the two tetraethyl ammoniums of embodiment 1 decahydro ten boric acid
(1) two 50g decahydro ten boric acid tetraethyl ammonium crude products and 350g deionized water are joined in 1L reaction bulb, temperature is65 DEG C, stirring reaction 2h, is cooled to room temperature and filters, and by filtrate evaporate to dryness, obtains 40g white solid;
(2) (1) step hydrolysis gained 40g solid and 600mL methyl alcohol are joined in 1L reaction bulb, after backflow 1h, coldBut to room temperature, filter, a small amount of methanol wash of filter cake, obtains white crystal 36g after being dried.
(3) the white crystal 36g of (2) step recrystallization gained is dissolved in 540g deionized water, adds 18g at 75 DEG CActive carbon, keeps temperature to stir 1h, filters mixed liquor, and filtrate is concentrated, and obtains 32g purity and be after gained solid dryingThe two tetraethyl ammonium products of decahydro ten boric acid of 99.96% (HPLC). Structural Identification data are as follows:
Elementary analysis (C16H30N2B10，％)
Theoretical value: C50.79, H13.23, N7.40;
Measured value: C50.80, H13.22, N7.41.
IR(KBr,cm-1)：3515，3010，2992，2949，2451，1459，1183，1034，1008，893，795。
1HNMR(DMSO,δ/ppm)：-0.1353-0.6117(m,8H)，1.2592-1.2958(m,24H)，3.2480-3.2918(m,16H)，3.0696-3.9135(m,2H)。
Above-mentioned appraising datum confirms that the material obtaining is as stated above the two tetraethyl ammoniums of decahydro ten boric acid really.
The purifying of the two tetraethyl ammoniums of embodiment 2 decahydro ten boric acid
(1) two 60g decahydro ten boric acid tetraethyl ammonium crude products and 300g deionized water are joined in 1L reaction bulb, temperature is 5 DEG C,Stirring reaction 8h, filters under room temperature, by filtrate evaporate to dryness, obtains 48g white solid;
(2) (1) step hydrolysis gained 48g solid and 480mL methyl alcohol are joined in 1L reaction bulb, after backflow 3h, coldBut to room temperature, filter, a small amount of methanol wash of filter cake, obtains white crystal 43g after being dried.
(3) the white crystal 43g of (2) step recrystallization gained is dissolved in 215g deionized water, adds 8.6g at 10 DEG CActive carbon, keeps temperature to stir 0.5h, filters mixed liquor, and filtrate is concentrated, and obtains 38.4g pure after gained solid dryingDegree is the two tetraethyl ammonium products of decahydro ten boric acid of 99.92% high performance liquid chromatography (HPLC).
The purifying of the two tetraethyl ammoniums of embodiment 3 decahydro ten boric acid
(1) two 40g decahydro ten boric acid tetraethyl ammonium crude products and 400g deionized water are joined in 1L reaction bulb, temperature is100 DEG C, stirring reaction 0.5h, is cooled to room temperature, filters, and uses deionized water washing leaching cake, by the water evaporate to dryness in filtrate,29g white solid;
(2) (1) step hydrolysis gained 29g solid and 725mL methyl alcohol are joined in 1L reaction bulb, after backflow 0.5h,Be cooled to room temperature, filter, a small amount of methanol wash of filter cake, obtains white crystal 18g after being dried.
(3) the white crystal 18g of (2) step recrystallization gained is dissolved in 360g deionized water, adds 18g activity at 95 DEG CCharcoal, keeps temperature to stir 0.5h, filters mixed liquor, and filtrate is concentrated, and after gained solid drying, obtaining 13g purity is 99.97%(HPLC) the two tetraethyl ammonium products of decahydro ten boric acid.
Claims (2)
1. a purification process for the two tetraethyl ammoniums of decahydro ten boric acid, is characterized in that: the method comprises the steps:
(1) by two the decahydro obtaining through pyrolytic reaction ten boric acid certain proportion deionized water and stirring hydrolysis for tetraethyl ammonium crude product,At 5～100 DEG C of temperature, reaction 0.5～8h, filters under room temperature, by the concentrated filtrate hydrolysis prods that obtains; Wherein decahydro ten boric acid are twoThe mass ratio of tetraethyl ammonium crude product and deionized water is 1:5～1:10;
(2), by step (1) gained hydrolysis prods certain proportion recrystallizing methanol, carry out Separation of Solid and Liquid, filter cake warp after coolingAlcohols solvent washing, obtains the product that is recrystallized after being dried; Wherein the mass ratio of hydrolysis prods and methyl alcohol is 1:10～1:25;
(3) the recrystallization product of step (2) gained being carried out to adsorption and purification, to obtain purity be the two tetrems of 99.9% decahydro ten boric acidBase ammonium product; Wherein adsorbent is molecular sieve, active carbon or silica gel; Eluting solvent is that deionized water, methyl alcohol or water-methanol mixSolvent; Adsorption and purification temperature is 10～95 DEG C, wherein, and recrystallization product and deionized water and recrystallization product and adsorbentMass ratio is respectively: recrystallization product: deionized water=1:5～1:20; Recrystallization product: adsorbent=1:1～5:1.
2. the purification process of the two tetraethyl ammoniums of decahydro ten boric acid according to claim 1, is characterized in that: preferred technology stepRapid as follows:
(1) by two the decahydro obtaining through pyrolytic reaction ten boric acid certain proportion deionized water and stirring hydrolysis for tetraethyl ammonium crude product,At 65 DEG C of temperature, reaction 2h, filters under room temperature, by the concentrated filtrate hydrolysis prods that obtains; The wherein two tetraethyl ammoniums of decahydro ten boric acidThe mass ratio of crude product and deionized water is 1:7;
(2), by step (1) gained hydrolysis prods certain proportion recrystallizing methanol, carry out Separation of Solid and Liquid, filter cake warp after coolingMethanol wash, obtains the product that is recrystallized after being dried; Wherein the mass ratio of hydrolysis prods and methyl alcohol is 1:15;
(3) by the recrystallization product of step (2) gained taking deionized water as solvent, active carbon is adsorbent, at 75 DEG C, entersRow adsorption and purification, filters after 0.5h, and concentrated filter obtains purity and be 99.9% the two tetrems of decahydro ten boric acid after gained solid dryingBase ammonium product; Wherein, the mass ratio of material is respectively: recrystallization product: deionized water=1:10; Recrystallization product: absorptionAgent=2:1.
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Citations (4)
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|---|---|---|---|---|
| US4391993A (en) * | 1982-02-12 | 1983-07-05 | The United States Of America As Represented By The Secretary Of The Army | Thermolysis of tetraalkylammonium borohydrides to bis(tetraalkylammonium) decahydrodecaboranes |
| CN102558206A (en) * | 2011-11-18 | 2012-07-11 | 西安近代化学研究所 | Process for synthetizing n-hexyl carborane |
| CN102827093A (en) * | 2012-08-28 | 2012-12-19 | 西安近代化学研究所 | Di-hydrazino-s-tetrazine decahydro decaborate compound |
| CN103288097A (en) * | 2013-05-13 | 2013-09-11 | 西安近代化学研究所 | Preparation method of caesium decahydrodecaborate |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4391993A (en) * | 1982-02-12 | 1983-07-05 | The United States Of America As Represented By The Secretary Of The Army | Thermolysis of tetraalkylammonium borohydrides to bis(tetraalkylammonium) decahydrodecaboranes |
| CN102558206A (en) * | 2011-11-18 | 2012-07-11 | 西安近代化学研究所 | Process for synthetizing n-hexyl carborane |
| CN102827093A (en) * | 2012-08-28 | 2012-12-19 | 西安近代化学研究所 | Di-hydrazino-s-tetrazine decahydro decaborate compound |
| CN103288097A (en) * | 2013-05-13 | 2013-09-11 | 西安近代化学研究所 | Preparation method of caesium decahydrodecaborate |
Non-Patent Citations (1)
| Title |
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| 十二氢十硼双二乙基硫醚络合物新合成法的研究;王广昌等;《化学学报》;19810630;第39卷(第03期);251-254 * |
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