CN105348129A - [A336][BDGA] ionic liquid and preparation method therefor - Google Patents
[A336][BDGA] ionic liquid and preparation method therefor Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/20—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
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- C07C231/00—Preparation of carboxylic acid amides
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- C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
- C07D319/12—1,4-Dioxanes; Hydrogenated 1,4-dioxanes not condensed with other rings
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Abstract
The invention relates to [A336][BDGA] ionic liquid and a preparation method therefor and belongs to the field of synthesis of ionic liquid extractants. The preparation method comprises the following steps: (1) adopting isopropanol, sodium metal and methyl trioctyl ammonium chloride as reactants, dissolving the sodium metal in the isopropanol so as to produce sodium isopropoxide, then, subjecting sodium isopropoxide to reaction with methyl trioctyl ammonium chloride, and carrying out hydrolysis, so as to produce methyl trioctyl ammonium hydroxide; (2) adopting diglycolic acid, acetic anhydride and di-n-butylamine as reactants, firstly, dehydrating diglycolic acid so as to obtain diglycolic anhydride, and then, subjecting diglycolic anhydride to reaction with di-n-butylamine, so as to obtain N,N-di-n-butyl acetamido-oxy acetate; and (3) subjecting the quaternary ammonium hydroxide obtained in the step (1) and N,N-di-n-butyl acetamido-oxy acetate obtained in the step (2) to acid/base neutralization reaction, thereby obtaining the [A336][BDGA] ionic liquid product. The preparation method has the characteristics of short production cycle, low cost, high yield and high purity; and meanwhile, the [A336][BDGA] ionic liquid has a good rare-earth extracting and separating effect, thereby having a good market application prospect.
Description
Technical field
The present invention relates to liquid-phase extraction agent synthesis field, refer to one [A336] [BDGA] ionic liquid and preparation method thereof especially.
Background technology
China is rare earth resources state maximum in the world, and rare earth mineral reserve and output occupy prostatitis, the world.Rare-Earth Element Chemistry character is close, and in mineral, association coexists, but the intrinsic property such as optical, electrical, the magnetic of each rare earth element excellence, catalysis often needs single high-purity rare-earth just can fully demonstrate.Therefore, the separating-purifying of rare earth element becomes the significant process of rare-earth industry.China rare earth worker, according to the feature of rare earth resources, develops a series of Rare Earth Separation purification techniques with originality, has achieved the international status of China rare earth big producing country.But, a large amount of acid, alkali industrial chemicals is used in Rare Earth Separation process, cause producing a large amount of brine waste, problem of environmental pollution is very serious, therefore, in order to improve the utilising efficiency of rare earth resources, exploring a kind of efficient, cheap, clean rare earth extraction novel process and research and how being separated easily and obtaining high-purity single rare earth and seem particularly important.
Industrial is at present use traditional phosphorus extractant to carry out extracting and separating rear earth by solvent-extracted method substantially, but this method needs first by extraction agent saponification, and extraction efficiency is not high yet, and phosphorous waste easily produces detrimentally affect to environment.Nowadays, research of Amido Podands Extractant can carry out coordination with rare earth ion due to the structure of its uniqueness, many investigators are attracted, but the recovery be confined to more than Application Areas high activity liquid waste in nuclear industry and process, the report applying it to the Separation Research of rare earth mineral reserve rare earth elements is still rare.On the other hand, ion liquid abstraction agent has designability due to its structure, has won the favor of many investigators in recent years.Studies in China person tends to quaternary ammonium salt ion [A336]
+combine with conventional traditional phosphorus extractant, acidic extractant, obtain good achievement in research, by [A336]
+the content carrying out studying that combines with novel research of Amido Podands Extractant only has a small amount of report abroad.
Summary of the invention
The present invention is not high in order to solve traditional phosphorus extractant extraction efficiency, environment is had to the problems such as detrimentally affect, proposes one [A336] [BDGA] ion liquid abstraction agent and preparation method thereof for above-mentioned prior art.
Technical scheme provided by the invention is: a kind of [A336] [BDGA] ionic liquid, it is characterized in that, described [A336] [BDGA] ionic liquid is a kind of by methyl trioctylphosphine quaternary ammonium ion and N, the compound of N-di-n-butyl acetamido ethoxyacetic acid root negatively charged ion composition, [A336] [BDGA] ionic liquid structural formula is as follows:
The preparation method of described [A336] [BDGA] ionic liquid, is characterized in that, comprise the steps:
(1): sodium Metal 99.5 silk and isopropanol reaction obtain sodium isopropylate;
(2): the sodium isopropylate that step (1) obtains and methyl tricapryl ammonium chloride react, after hydrolysis, methyl trioctylphosphine ammonium hydroxide is generated;
(3): two sweet acid are dewatered the sweet acid anhydrides of generation two in diacetyl oxide environment;
(4): the two sweet acid anhydrides that step (3) obtains are dissolved in Isosorbide-5-Nitrae-dioxane, react under pyridine existent condition with Di-n-Butyl Amine and generate N, N-di-n-butyl acetamido ethoxyacetic acid;
(5): the methyl trioctylphosphine ammonium hydroxide that step (2) obtains and step (4) N, N-di-n-butyl acetamido ethoxyacetic acid carry out acid-base neutralisation and be obtained by reacting [A336] [BDGA] ionic liquid in methylene dichloride.
Virahol in described step (1), step (2), step (4), Di-n-Butyl Amine, pyridine are all through drying treatment, and step (1), step (2), step (4) experimental system keep water-less environment.
In step (1), the mol ratio of sodium Metal 99.5 and Virahol is 1:(5.50 ~ 6.00), temperature of reaction is 50-60 DEG C.
In step (2), the mol ratio of sodium isopropylate and methyl tricapryl ammonium chloride is 1:(1.00 ~ 1.10).
In step (3), the mol ratio of two sweet acid and diacetyl oxide is 1:(3.50 ~ 4.00), the reaction times is 1 ~ 2 hour, and temperature of reaction is 139 ~ 145 DEG C, and need add 3 ~ 5 phosphoric acid, wherein phosphoric acid is as initiator mass concentration >=85%.
After in described step (3), two sweet anhydride reactions complete, the rotary evaporation that reduces pressure at temperature 70 ~ 80 DEG C removing diacetyl oxide, add the toluene of 3 times of residual solution volumes while hot, ambient temperatare puts 10 ~ 12 hours recrystallizations.
In described step (4), the mol ratio of two sweet acid anhydrides and Di-n-Butyl Amine is 1:(1.00 ~ 1.10), the mol ratio of two sweet acid anhydrides and pyridine is 1:(1.00 ~ 1.10), need to react under ice bath, the reaction times is 2 ~ 3 hours.
After described step (4) has been reacted, the rotary evaporation that reduces pressure at temperature 70 ~ 80 DEG C eliminates organic solvent, and then dropwise add 1:1 hydrochloric acid and separate out to there being a large amount of white crystal, decompress filter also washs, collect white crystal N, N-di-n-butyl kharophen ethoxyacetic acid.
In described step (5), the mol ratio of methyl trioctylphosphine ammonium hydroxide and N, N-di-n-butyl kharophen ethoxyacetic acid is (1.00 ~ 1.10): 1, and temperature of reaction is 40 ~ 45 DEG C, and the reaction times is 10 ~ 12 hours.In the reaction process of step (1) preparation [A336] [BDGA] ionic liquid, because sodium Metal 99.5 runs into water reaction acutely, generate hydrogen and also release a large amount of heat, inflammable and explosive, and deposit in case at alcohol, danger is larger.Therefore, Virahol needs into super-dry process, and experimental system must ensure it is anhydrous system.
In step (1), if quantity of isopropanol is very few, the sodium isopropylate crystal that sodium Metal 99.5 and Virahol can be caused to generate is separated out, and is coated on outside unreacted sodium Metal 99.5, affects reaction process.If the add-on of Virahol is excessive, will cause raw-material waste, experimental result shows, the mol ratio of sodium Metal 99.5 and Virahol is 1:(5.50 ~ 6.00) comparatively suitable.
In step (1), when temperature of reaction is 50 ~ 60 DEG C, be conducive to the dissolving of sodium Metal 99.5, the reaction times can be foreshortened to 2 hours by 5 hours, shorten the production cycle, therefore the temperature of reaction of step (1) is 50 ~ 60 DEG C.
In step (3), for making two sweet sour fast dewaterings generate two sweet acid anhydrides, need add 3 ~ 5 phosphoric acid, wherein phosphoric acid is as initiator mass concentration >=85%, two sweet acid reflux 1 ~ 2 hour in diacetyl oxide, and therefore temperature of reaction should equal or slightly larger than the boiling point 139 DEG C of diacetyl oxide.In step (3), the add-on of diacetyl oxide is too small, then two sweet acid dispersiveness is in a solvent bad, affect reaction process, if diacetyl oxide add-on is excessive, raw-material waste will be caused, and more time and energy consumption need be expended when steaming desolventizes, experimental result shows, the mol ratio of two sweet acid and diacetyl oxide is 1:(3.50 ~ 4.00).
In step (3), after having reacted, the rotary evaporation that reduces pressure at temperature 70 ~ 80 DEG C removes most of diacetyl oxide, adds the toluene of 3 times of residual solution volumes while hot, ambient temperatare puts 10 ~ 12 hours recrystallizations, toluene is the poor solvent of two sweet acid anhydrides, if toluene add-on is very few, then recrystallization is incomplete, if toluene add-on is much, then can cause the waste of raw material, and toluene itself has toxicity, affect body and mind and Environmental Health.
In step (4), because pyridine can be combined with hydrogen ion in the reaction rapidly, form pyridinium salt, thus promote that the forward of reaction carries out, therefore the present invention selects it as the reaction acid binding agent of step (4).
In step (4), meet water due to two sweet acid anhydrides and be easy to react, thus impact experiment productive rate, therefore Di-n-Butyl Amine, organic solvent and pyridine all have to pass through drying treatment, and experimental system must ensure it is anhydrous system.
In step (4), because two sweet acid anhydrides and Di-n-Butyl Amine react for thermopositive reaction, and when temperature is higher, byproduct of reaction is more, and therefore reaction needed is reacted under ice bath, and the time was advisable with 2 ~ 3 hours.
In step (4), after having reacted, the rotary evaporation that reduces pressure at temperature 70 ~ 80 DEG C eliminates organic solvent, evaporation residue liquid is N, N-di-n-butyl acetamido ethoxyacetic acid pyridinium salt, therefore need to drip in 1:1 hydrochloric acid and pyridinium salt in evaporation residue liquid after completion of the reaction, thus obtain N, N-di-n-butyl acetamido ethoxyacetic acid white crystal.
The beneficial effect of technique scheme of the present invention is as follows:
The reagent environmental protection low toxicity adopted in above-mentioned building-up process, by product is few, and environmental pollution is little; Cost of material is cheap, and production cost is low, good in economic efficiency, and [A336] [BDGA] ionic liquid has a good application prospect; Preparation method is simple and practical, and efficiency is high; Aftertreatment is simple, can realize commercialization scale operation, can meet the requirement that current social improves constantly environmental protection.
Accompanying drawing explanation
Fig. 1 is the preparation process of one of the present invention [A336] [BDGA] ionic liquid preparation method.
Embodiment
For making the technical problem to be solved in the present invention, technical scheme and advantage clearly, be described in detail below in conjunction with accompanying drawing 1 and specific embodiment.
A kind of preparation method of [A336] [BDGA] ionic liquid, preparation process as shown in Figure 1.
Embodiment 1
A kind of preparation method of [A336] [BDGA] ionic liquid, its concrete steps are as follows:
(1): 5.16g sodium Metal 99.5 is cut into filament, drop in 100mL Virahol in batches, at 50 DEG C, be back to sodium Metal 99.5 silk dissolve completely, about 2 hours consuming time.
(2): 90.56g methyl tricapryl ammonium chloride is dissolved in 150mL Virahol, slowly be added drop-wise in the middle gained mixed solution of step (1), stir 4 hours at 50 DEG C, after stopped reaction, with G4 sand core funnel decompress filter, the filtrate of gained is mixed by 1:1 with deionized water, water-bath is vibrated 1 hour, vacuum rotary steam at 80 DEG C, removing isopropyl alcohol and water, vacuum-drying obtains the sticky shape methyl trioctylphosphine ammonium hydroxide liquid of 76.88g yellow after 24 hours, productive rate is 89%.
(3): by sweet for 50.03g bis-acid-soluble in 125mL acetic anhydride, be warming up to 139 DEG C, add 3 phosphoric acid and make initiator, stirring and refluxing 1 hour.After reaction stops, at 70 DEG C, rotary evaporation removes most of diacetyl oxide, obtains about 100mL liquid, adds 300mL toluene, stirs, places 12 hours recrystallizations.Decompress filter, obtain 35.94g colourless to white two sweet anhydride crystals, productive rate is 83%.
(4): take the two sweet acid anhydrides that 35.83g step (3) is obtained, be dissolved in 150mL1, in 4-dioxane, 57mL Di-n-Butyl Amine and 28mL pyridine mixed, under ice bath, dropwise instill in reaction system, stir 2 hours.After reaction terminates, remove Isosorbide-5-Nitrae-dioxane under reduced pressure, drip 1:1 hydrochloric acid in resistates at 70 DEG C, adularescent crystal is separated out, and decompress filter, obtains 61.34gN, and N-di-n-butyl acetamido ethoxyacetic acid crystal, productive rate is 81%.
(5): by the N obtained in step (4), N-di-n-butyl acetamido ethoxyacetic acid crystal 46.38g is dissolved in 100mL methylene dichloride, with the methyl trioctylphosphine ammonium hydroxide Homogeneous phase mixing obtained in 76.62g step (2), reflux 12 hours at 40 DEG C.After reaction terminates, add 100mL deionized water wash three times, at 25 DEG C, remove methylene dichloride under reduced pressure, and vacuum-drying 5 hours at 75 DEG C, obtain yellow sticky shape [A336] [BDGA] ionic liquid product 107.78g, productive rate is 93%.
Embodiment 2
A kind of preparation method of [A336] [BDGA] ionic liquid, its concrete steps are as follows:
(1): 5.19g sodium Metal 99.5 is cut into filament, drop in 90mL Virahol in batches, at 60 DEG C, be back to sodium Metal 99.5 silk dissolve completely, about 2 hours consuming time.
(2): 91.05g methyl tricapryl ammonium chloride is dissolved in 150mL Virahol, slowly be added drop-wise in the middle gained mixed solution of step (1), stir 4 hours at 50 DEG C, after stopped reaction, with G4 sand core funnel decompress filter, the filtrate of gained is mixed by 1:1 with deionized water, water-bath is vibrated 1 hour, vacuum rotary steam at 80 DEG C, removing Virahol, vacuum-drying obtains the sticky shape methyl trioctylphosphine ammonium hydroxide liquid of 78.92g yellow after 24 hours, productive rate is 91%.
(3): by sweet for 50.01g bis-acid-soluble in 140mL acetic anhydride, be warming up to 145 DEG C, add 5 phosphoric acid and make initiator, stirring and refluxing 2 hours.After reaction stops, at 80 DEG C, rotary evaporation removes most of diacetyl oxide, obtains about 100mL liquid, adds 300mL toluene, stirs, places 10 hours recrystallizations.Decompress filter, obtain 38.89g colourless to white two sweet anhydride crystals, productive rate is 90%.
(4): take the two sweet acid anhydrides that 38.81g step (3) is obtained, be dissolved in 150mL1, in 4-dioxane, 58mL Di-n-Butyl Amine and 28mL pyridine mixed, under ice bath, dropwise instill in reaction system, stir 3 hours.After reaction terminates, remove Isosorbide-5-Nitrae-dioxane under reduced pressure, drip 1:1 hydrochloric acid in resistates at 80 DEG C, adularescent crystal is separated out, and decompress filter, obtains 64.06gN, and N-di-n-butyl acetamido ethoxyacetic acid crystal, productive rate is 78%.
(5): by the N obtained in step (4), N-di-n-butyl acetamido ethoxyacetic acid crystal 46.44g is dissolved in 100mL methylene dichloride, with the methyl trioctylphosphine ammonium hydroxide Homogeneous phase mixing obtained in 78.65g step (2), reflux 10 hours at 45 DEG C.After reaction terminates, add 100mL deionized water wash three times, at 25 DEG C, remove methylene dichloride under reduced pressure, and vacuum-drying 5 hours at 75 DEG C, obtain yellow sticky shape [A336] [BDGA] ionic liquid product 105.60g, productive rate is 91%.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from principle of the present invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. [A336] [BDGA] ionic liquid, it is characterized in that, described [A336] [BDGA] ionic liquid is a kind of by methyl trioctylphosphine quaternary ammonium ion and N, the compound of N-di-n-butyl acetamido ethoxyacetic acid root negatively charged ion composition, [A336] [BDGA] ionic liquid structural formula is as follows:
2. the preparation method of [A336] [BDGA] ionic liquid according to claim 1, is characterized in that, comprise the steps:
(1): sodium Metal 99.5 silk and isopropanol reaction obtain sodium isopropylate;
(2): the sodium isopropylate that step (1) obtains and methyl tricapryl ammonium chloride react, after hydrolysis, methyl trioctylphosphine ammonium hydroxide is generated;
(3): two sweet acid are dewatered the sweet acid anhydrides of generation two in diacetyl oxide environment;
(4): the two sweet acid anhydrides that step (3) obtains are dissolved in Isosorbide-5-Nitrae-dioxane, react under pyridine existent condition with Di-n-Butyl Amine and generate N, N-di-n-butyl acetamido ethoxyacetic acid;
(5): the methyl trioctylphosphine ammonium hydroxide that step (2) obtains and step (4) N, N-di-n-butyl acetamido ethoxyacetic acid carry out acid-base neutralisation and be obtained by reacting [A336] [BDGA] ionic liquid in methylene dichloride.
3. the preparation method of [A336] [BDGA] ionic liquid according to claim 2, it is characterized in that, Virahol in described step (1), step (2), step (4), Di-n-Butyl Amine, pyridine are all through drying treatment, and step (1), step (2), step (4) experimental system keep water-less environment.
4. the preparation method of [A336] [BDGA] ionic liquid according to claim 2, is characterized in that, in step (1), the mol ratio of sodium Metal 99.5 and Virahol is 1:(5.50 ~ 6.00), temperature of reaction is 50-60 DEG C.
5. the preparation method of [A336] [BDGA] ionic liquid according to claim 2, is characterized in that, in step (2), the mol ratio of sodium isopropylate and methyl tricapryl ammonium chloride is 1:(1.00 ~ 1.10).
6. the preparation method of [A336] [BDGA] ionic liquid according to claim 2, it is characterized in that, in step (3), the mol ratio of two sweet acid and diacetyl oxide is 1:(3.50 ~ 4.00), reaction times is 1 ~ 2 hour, temperature of reaction is 139 ~ 145 DEG C, need add 3 ~ 5 phosphoric acid, wherein phosphoric acid is as initiator mass concentration >=85%.
7. the preparation method of [A336] [BDGA] ionic liquid according to claim 2, it is characterized in that, after in described step (3), two sweet anhydride reactions complete, the rotary evaporation that reduces pressure at temperature 70 ~ 80 DEG C removing diacetyl oxide, add the toluene of 3 times of residual solution volumes while hot, ambient temperatare puts 10 ~ 12 hours recrystallizations.
8. the preparation method of [A336] [BDGA] ionic liquid according to claim 2, it is characterized in that, in described step (4), the mol ratio of two sweet acid anhydrides and Di-n-Butyl Amine is 1:(1.00 ~ 1.10), the mol ratio of two sweet acid anhydrides and pyridine is 1:(1.00 ~ 1.10), need to react under ice bath, the reaction times is 2 ~ 3 hours.
9. the preparation method of [A336] [BDGA] ionic liquid according to claim 2, it is characterized in that, after described step (4) has been reacted, the rotary evaporation that reduces pressure at temperature 70 ~ 80 DEG C eliminates organic solvent, then dropwise add 1:1 hydrochloric acid to separate out to there being a large amount of white crystal, decompress filter also washs, and collects white crystal N, N-di-n-butyl kharophen ethoxyacetic acid.
10. the preparation method of [A336] [BDGA] ionic liquid according to claim 2, it is characterized in that, methyl trioctylphosphine ammonium hydroxide and N in described step (5), the mol ratio of N-di-n-butyl kharophen ethoxyacetic acid is (1.00 ~ 1.10): 1, temperature of reaction is 40 ~ 45 DEG C, and the reaction times is 10 ~ 12 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107299234A (en) * | 2017-06-14 | 2017-10-27 | 中国科学院过程工程研究所 | A kind of green method of the recovering rare earth from useless fluorescent material and application thereof |
| CN115504901A (en) * | 2022-09-22 | 2022-12-23 | 厦门稀土材料研究所 | [A336] Method for preparing nuclear grade zirconium and nuclear grade hafnium by extracting and separating [ DGA ] type ionic liquid in acid system |
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| CN115504901A (en) * | 2022-09-22 | 2022-12-23 | 厦门稀土材料研究所 | [A336] Method for preparing nuclear grade zirconium and nuclear grade hafnium by extracting and separating [ DGA ] type ionic liquid in acid system |
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