CN101735138A - Method for preparing dissipated metal rhenium ionic liquid - Google Patents
Method for preparing dissipated metal rhenium ionic liquid Download PDFInfo
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- CN101735138A CN101735138A CN200910220619A CN200910220619A CN101735138A CN 101735138 A CN101735138 A CN 101735138A CN 200910220619 A CN200910220619 A CN 200910220619A CN 200910220619 A CN200910220619 A CN 200910220619A CN 101735138 A CN101735138 A CN 101735138A
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Abstract
The invention relates to a method for preparing dissipated metal rhenium ionic liquid. The adopted technical scheme is as follows: the preparation method comprises the following steps: taking a certain amount of alkyl bromide pyridine compound, adding 2-4 times of deionized water for dissolution, adding into OH type anion exchange resin for carrying out ion exchange, and collecting effluent solution which is hydroxyalkyl pyridine; adding the hydroxyalkyl pyridine into ammonium perrhenate water solution, leading the molar ratio of the hydroxyalkyl pyridine to the ammonium perrhenate to be 1:1-1:2, stirring for 3-5 hours at the temperature of 70-90 DEG C, carrying out vacuum distillation for removing water, cooling, then adding mixed solution of anhydrous methanol and acetonitrile, sealing, churning, placing at the temperature of minus 30-minus 40 DEG C for 10-15 hours, carrying out the vacuum distillation, removing the methanol and the acetonitrile and carrying out vacuum drying. The ionic liquid has high yield and is stable to air and water.
Description
Technical field
The invention belongs to the field of chemical synthesis, relate in particular to a kind of preparing dissipated metal rhenium ionic liquid.
Background technology
In recent years, active day by day to ion liquid research, western countries government all drops into the ion liquid research of a large amount of financial supports with relevant enterprise.Simultaneously, ionic liquid also expands to fields such as functional materials, electric light and photoelectric material, storage of solar energy, life science rapidly from Green Chemistry chemical industry and catalytic field.Britain Sedden in 2000 professor and U.S. Rogers teach and have held the ionic liquid specialists meeting at the Crete of Greece.After this, height is stepped on meeting, American Chemical Society's annual meeting, the North Atlantic Treaty Organization, international Green Chemistry meeting etc. and has all been held symposial specially with regard to ionic liquid, generally believes that ion liquid medium and functional materials are containing great potential in the demand side that satisfies social sustainable development and scientific and technical self-growth.European Commission has formulated development planning in ion liquid 3 years, estimates to set up in the period of 1999-2002 three ion liquid pilot plants.The Japan in Asia, Korea S and famous in the world chemical transnational company also spare no high price to support ion liquid research work.Held the academic conference of first ionic liquid in Austrian Salzburg in 2005, and made ionic liquid occupy the one seat of oneself in the scientific research field.At present, the large-scale industrial application in first ionic liquid field is accomplished in German BASF AG in 2002-2003 in the world.In Britain and France, relate to ion liquid multinomial technology and begun to enter the industrial application stage.And a plurality of research institutions of the U.S. are all carrying out ionic liquid research; The research of Japan in this field also has the gesture of catching up from behind.People recognize that gradually ionic liquid has been not only the green substitute of conventional solvent, and it also has more wide development space.At new function material, environmental science, analysis science, electric light and photoelectric material, life science, fields such as storage of solar energy, ionic liquid has all begun to show up prominently, and demonstrates huge development potentiality.
Rhenium is a metal of finding in the rare and scatter element the latest, because rhenium and compound thereof be at chemical industry, and the military project material, catalyzer, the widespread use of aspects such as refractory metal has caused people's very big attention.Exist 5 electronics of unsaturated 4d layer in the rhenium atom structure and be easy to and discharge, and 2 electronics of 6s layer easily participate in reaction formation covalent linkage, add characteristics such as its lattice parameter is bigger, make rhenium and compound thereof have excellent catalytic activity, and in many industrial production such as petrochemical industry, obtained successful application.Mahdi M.Abu-Omar in 2000 etc. for methyl rhenium trioxide at ionic liquid ([Emim] BF
4) in catalytic epoxidation carried out experimental study, the result shows: in such individual system, some conversion of olefines rates and epoxidation productive rate are all more than 95%.Now the ionic liquid of synthetic dissipated metal gallium, indium exists air and the unsettled defective of moisture, has greatly limited its application in each field of chemical industry.Rhenium has highly selective as catalyzer, high yield, and the characteristics that consumption is few, and also reaction end back is recyclable, and cycling and reutilization has reduced environmental pollution.If the dissipated metal rhenium ionic liquid of energy synthesizing new both can overcome the weakness of ionic liquid to air and water sensitive, can realize the special catalytic performance of dissipated metal again, will produce huge economy and social benefit.
Summary of the invention
In order to address the above problem, the object of the present invention is to provide a class new, have katalysis and to the stable dissipated metal rhenium ionic liquid of empty G﹠W.
Another object of the present invention provides a kind of method for preparing dissipated metal rhenium ionic liquid.
Among the present invention, the structural formula of dissipated metal rhenium ionic liquid is as follows:
Wherein, R is that carbon atom is 2～6 alkyl.
Preparing dissipated metal rhenium ionic liquid is as follows:
Get a certain amount of bromination alkyl pyridine compounds, add the less water dissolving, join and carry out ion-exchange in the oh type anionite-exchange resin, collect effusive solution, till detecting the chlorine or bromine ion, the hydroxyalkyl pyridine is joined in the ammonium perrhenate aqueous solution, the mol ratio of hydroxyalkyl pyridine and ammonium perrhenate is 1: 1～1: 2, stirs 3～5 hours at 60～80 ℃, and rotary evaporation is removed moisture content, the cooling back adds ethyl acetate and acetonitrile mixing solutions, the sealing vigorous stirring was placed underpressure distillation 10～15 hours in-30～-40 ℃, remove and desolvate vacuum-drying.
At first, carry out anionresin by anionite-exchange resin with bromination alkyl pyridine compound.Usually, anionite-exchange resin is used the salt acid soak earlier, to remove impurity wherein; To neutrality, use the NaOH solution soaking with deionized water rinsing again.Same step triplicate is neutral, standby with resin wash to the pH value with deionized water.The ion-exchange column length is 100cm, internal diameter 6cm.The ion exchange resin that aforementioned processing is good continuously flows into ion exchange column, notes air not being brought into the resin gap.With sodium hydroxide flushing ion exchange resin, flow velocity is 10ml/min, uses AgNO
3-HNO
3Mixing solutions constantly detects, till detecting less than chlorion from the liquid that exchanges out.Resin is neutral with deionized water rinsing to effusive solution, and ion exchange resin finally is converted to the OH type by the Cl type.
Bromination alkyl pyridine compound is joined the above-mentioned ion exchange column of handling well exchange, so that bromide anion is exchanged for hydroxide ion.Batch collect effusive solution, and with AgNO
3-HNO
3Detect, in effusive liquid, white precipitate occurs, detect till the bromide anion.The hydroxyalkyl pyridine dilute solution of collecting is removed most of water at the 323.15K rotary evaporation.The OH of hydroxyalkyl pyridine
-With the NH in the ammonium perrhenate
4 +Generate NH
4OH and discharging makes ionic liquid.
The invention has the beneficial effects as follows: the novel dissipated metal rhenium ionic liquid of synthetic of the present invention, stable to empty G﹠W.In technologies such as petrochemical complex hydrogenation, sulphur removal, the existing catalyzer that adopts is a solid catalyst, directly is discharged into nature, contaminate environment; complex process, and adopt dissipated metal rhenium ionic liquid to make catalyzer, technology is simple; can realize homogeneous catalysis, the catalyzer reusable edible has been protected environment.Adopt hydroxyalkyl pyridine and ammonium perrhenate, make ionic liquid, productive rate can reach more than 99%.And by kelene yl pyridines compounds or bromination alkyl pyridine compounds directly with the perrhenate solution reaction, the generation dissipated metal rhenium ionic liquid, its productive rate only is about 35%.
Description of drawings
Fig. 1 is synthetic 1-propyl group among the embodiment 1-ion liquid nucleus magnetic hydrogen spectrum figure of 3-methyl-imidazoles perrhenate
1HNMR.
Fig. 2 is synthetic 1-propyl group among the embodiment 1-3-methyl-ion liquid Raman spectrogram of imidazoles perrhenate.
Embodiment
The present invention will be further described below in conjunction with accompanying drawing:
Embodiment 1N-butyl-pyridinium perrhenate ([BPy] [ReO
4]) ionic liquid
The preparation method is as follows:
Get the N-butyl-pyridinium after a certain amount of purification, add 2～4 times deionized water dissolving, join in the OH type anionite-exchange resin and carry out ion-exchange, collect effusive solution, till detecting bromide anion.Hydrochloric acid with concentration known carries out accurate titration, calculates the concentration of the solution of collection.It is joined in the ammonium perrhenate aqueous solution, mol ratio is 1: 1,70 ℃ of heated and stirred are after 4 hours, and rotary evaporation is removed moisture content, and adding excessive volume ratio in cooling back is 1: 9 anhydrous methanol and an acetonitrile solution, the sealing vigorous stirring, in-34 ℃ of placements 12 hours, methyl alcohol and acetonitrile were removed in underpressure distillation, the product that obtains in vacuum drying oven, 80 ℃ of vacuum-drying 48 hours.Products therefrom is N-butyl-pyridinium perrhenate ([BPy] [ReO
4]) ionic liquid, productive rate is 99%.
Embodiment 2N-propyl group pyridine perrhenate ([TPy] [ReO
4]) ionic liquid
The preparation method is as follows:
Get the N-propyl group pyridine after a certain amount of purification, add 2～4 times deionized water dissolving, join in the OH type anionite-exchange resin and carry out ion-exchange, collect effusive solution, till detecting bromide anion.Hydrochloric acid with concentration known carries out accurate titration, calculates the concentration of the solution of collection.It is joined in the ammonium perrhenate aqueous solution, mol ratio is 1: 2,65 ℃ of heated and stirred are after 4 hours, and rotary evaporation is removed moisture content, and adding excessive volume ratio in cooling back is 1: 9 anhydrous methanol and an acetonitrile solution, the sealing vigorous stirring, in-34 ℃ of placements 12 hours, methyl alcohol and acetonitrile were removed in underpressure distillation, the product that obtains in vacuum drying oven, 80 ℃ of vacuum-drying 48 hours.Products therefrom is N-butyl-pyridinium perrhenate ([TPy] [ReO
4]) ionic liquid, productive rate is 99%.
Embodiment 3N-ethylpyridine perrhenate ([EPy] [ReO
4]) ionic liquid
The preparation method is as follows:
Get the N-ethylpyridine after a certain amount of purification, add 2～4 times deionized water dissolving, join in the OH type anionite-exchange resin and carry out ion-exchange, collect effusive solution, till detecting bromide anion.Hydrochloric acid with concentration known carries out accurate titration, calculates the concentration of the solution of collection.It is joined in the ammonium perrhenate aqueous solution, mol ratio is 1: 1.5,60 ℃ of heated and stirred are after 4 hours, and rotary evaporation is removed moisture content, and adding excessive volume ratio in cooling back is 1: 9 anhydrous methanol and an acetonitrile solution, the sealing vigorous stirring, in-30 ℃ of placements 12 hours, methyl alcohol and acetonitrile were removed in underpressure distillation, the product that obtains in vacuum drying oven, 80 ℃ of vacuum-drying 48 hours.Products therefrom is N-butyl-pyridinium perrhenate ([EPy] [ReO
4]) ionic liquid, productive rate is 99%.
Embodiment 4N-pentyl pyridine perrhenate ([PPy] [ReO
4]) ionic liquid
The preparation method is as follows:
Get the N-pentyl pyridine after the purification, add 2～4 times deionized water dissolving, join in the OH type anionite-exchange resin and carry out ion-exchange, collect effusive solution, till detecting chlorion.Hydrochloric acid with concentration known carries out accurate titration, calculates the concentration of the solution of collection.It is joined in the ammonium perrhenate aqueous solution, mol ratio is 1: 1.2,80 ℃ of heated and stirred are after 4 hours, and rotary evaporation is removed moisture content, and adding excessive volume ratio in cooling back is 1: 9 anhydrous methanol and an acetonitrile solution, the sealing vigorous stirring, in-34 ℃ of placements 12 hours, methyl alcohol and acetonitrile were removed in underpressure distillation, the product that obtains in vacuum drying oven, 80 ℃ of vacuum-drying 48 hours.Products therefrom is N-butyl-pyridinium perrhenate ([PPy] [ReO
4]) ionic liquid, productive rate is 99%.
Embodiment 5N-hexyl pyridine perrhenate ([HPy] [ReO
4]) ionic liquid
The preparation method is as follows:
Get the N-hexyl pyridine after a certain amount of purification, add 2～4 times deionized water dissolving, join in the OH type anionite-exchange resin and carry out ion-exchange, collect effusive solution, till detecting bromide anion.Hydrochloric acid with concentration known carries out accurate titration, calculates the concentration of the solution of collection.It is joined in the ammonium perrhenate aqueous solution, mol ratio is 1: 1.5,80 ℃ of heated and stirred are after 4 hours, and rotary evaporation is removed moisture content, and adding excessive volume ratio in cooling back is 1: 9 anhydrous methanol and an acetonitrile solution, the sealing vigorous stirring, in-30 ℃ of placements 12 hours, methyl alcohol and acetonitrile were removed in underpressure distillation, the product that obtains in vacuum drying oven, 80 ℃ of vacuum-drying 48 hours.Products therefrom is N-butyl-pyridinium perrhenate ([HPy] [ReO
4]) ionic liquid, productive rate is 99%.
Claims (2)
1. preparing dissipated metal rhenium ionic liquid, it is characterized in that: the preparation method is as follows, the alkyl pyridine compounds, add a certain amount of water dissolution, join and carry out ion-exchange in the oh type anionite-exchange resin, the hydroxyalkyl pyridine that obtains is joined in the ammonium perrhenate aqueous solution, the mol ratio of hydroxyalkyl pyridine and ammonium perrhenate is 1: 1～1: 2, stirs 3～5 hours at 60～80 ℃, and rotary evaporation is removed moisture content, the cooling back adds ethyl acetate and acetonitrile mixing solutions, the sealing vigorous stirring was placed underpressure distillation 10～15 hours in-30～-40 ℃, remove and desolvate vacuum-drying;
At first with bromination alkyl pyridine compound, carry out anionresin by anionite-exchange resin, usually, anionite-exchange resin is used the salt acid soak earlier, to remove impurity wherein; With deionized water rinsing to neutrality, use the NaOH solution soaking again, same step triplicate is neutral with resin wash to the pH value with deionized water, standby, the ion-exchange column length is 100cm, internal diameter 6cm, and the ion exchange resin that aforementioned processing is good continuously flows into ion exchange column, note air not being brought into the resin gap, with sodium hydroxide flushing ion exchange resin, flow velocity is 10ml/min, uses AgNO
3-HNO
3Mixing solutions constantly detects, and till detecting less than chlorion from the liquid that exchanges out, resin is neutral with deionized water rinsing to effusive solution, and ion exchange resin finally is converted to the OH type by the Cl type;
Bromination alkyl pyridine compound is joined the above-mentioned ion exchange column of handling well exchange, so that bromide anion is exchanged for hydroxide ion, batch collect effusive solution, and with AgNO
3-HNO
3Detect, white precipitate occurs in effusive liquid, detect till the bromide anion, the hydroxyalkyl pyridine dilute solution of collection is removed most of water at the 323.15K rotary evaporation, the OH of hydroxyalkyl pyridine
-With the NH in the ammonium perrhenate
4 +Generate NH
4OH and discharging makes ionic liquid.
2. a kind of preparing dissipated metal rhenium ionic liquid according to claim 1, described dissipated metal rhenium ionic is characterized in that its structural formula is as follows:
Wherein, R is that carbon atom is 2～6 alkyl.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516177A (en) * | 2011-11-24 | 2012-06-27 | 南京大学 | Preparation method for high-purity ionic liquid |
| CN103073499A (en) * | 2012-11-30 | 2013-05-01 | 辽宁大学 | Method for preparing rhenium ion liquid by extraction method |
| CN103464200A (en) * | 2013-09-22 | 2013-12-25 | 辽宁石油化工大学 | Supported perrhenate ionic liquid as well as preparation method thereof |
| CN106674117A (en) * | 2016-11-30 | 2017-05-17 | 辽宁大学 | Selenium ionic liquid and preparation method thereof |
-
2009
- 2009-12-09 CN CN200910220619A patent/CN101735138A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516177A (en) * | 2011-11-24 | 2012-06-27 | 南京大学 | Preparation method for high-purity ionic liquid |
| CN103073499A (en) * | 2012-11-30 | 2013-05-01 | 辽宁大学 | Method for preparing rhenium ion liquid by extraction method |
| CN103073499B (en) * | 2012-11-30 | 2015-07-29 | 辽宁大学 | A kind of extraction process prepares the method for rhenium ionic liquid |
| CN103464200A (en) * | 2013-09-22 | 2013-12-25 | 辽宁石油化工大学 | Supported perrhenate ionic liquid as well as preparation method thereof |
| CN103464200B (en) * | 2013-09-22 | 2015-09-02 | 辽宁石油化工大学 | A kind of loading type perrhenate ions liquid and preparation method thereof |
| CN106674117A (en) * | 2016-11-30 | 2017-05-17 | 辽宁大学 | Selenium ionic liquid and preparation method thereof |
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Open date: 20100616 |