CN106881152A - A kind of heteropoly acid ionic liquid and preparation method thereof - Google Patents
A kind of heteropoly acid ionic liquid and preparation method thereof Download PDFInfo
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- CN106881152A CN106881152A CN201710030442.4A CN201710030442A CN106881152A CN 106881152 A CN106881152 A CN 106881152A CN 201710030442 A CN201710030442 A CN 201710030442A CN 106881152 A CN106881152 A CN 106881152A
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/888—Tungsten
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0287—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre
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Abstract
The invention discloses a kind of heteropoly acid ionic liquid and preparation method thereof, comprise the following steps：1) the N- alkyl imidazoles and butane sultone for weighing equimolar amounts react 24~48h under the conditions of 40-60 DEG C；Vacuum drying, obtains white solid inner salt；2) heteropoly acid and metal carbonate of equimolar amounts are weighed；Metal carbonate is added drop-wise in heteropoly acid solution, 40-60 DEG C of 24~48h of stirring reaction；After removal aqueous solvent, vacuum drying obtains heteropolyacid metal salt.3) heteropolyacid metal salt for weighing equimolar amounts is dropwise added dropwise in white solid inner salt, stirs 12~48h, and after removing aqueous solvent after reaction, vacuum drying obtains heteropoly acid ionic liquid.Ionic liquid of the invention contains sulfonic acid group, metal ion and heteropoly acid radical ion simultaneously, and various research fields can be used for as high activated catalyst with stronger acid and oxidation-reduction quality.
Description
Technical field
The present invention relates to a kind of ionic liquid, and in particular to a kind of heteropoly acid ionic liquid and preparation method thereof；Belong to new
Catalyst and new catalytic material field.
Background technology
Since nineteen fifty-one, it is found that after first ionic liquid at room temperature starts, ionic liquid is due to the physico of uniqueness
Learn property widely to be paid close attention to, its species is continuously developed with application.In recent years, even more as in biomass transformation process
Green solvent and catalyst are widely studied.
Ionic liquid be only be made up of ion and under low temperature (usually less than 373K) for liquid a class material.It is conventional by
Small volume it is higher from molecular fuse salt fusing point, for example, the fusing point of NaCl is about in 1073K.If a kind of salt be by
One or two ion volumes are larger, and diffusion and distribution of charges are asymmetric, and the interaction between ion weakens, and causes to melt
Point is significantly reduced, or even is liquid under normal temperature.Ionic liquid is typically made up of organic cation and inorganic anion, and according to sun
Ion different demarcation is imidazoles, pyridines, pyrrolin class ionic liquid etc., and anion mainly has Cl‐、Br‐、I‐、BF4 ‐、
CH3COO‐、NO3 ‐、HSO4 ‐Deng.Dissolubility according to ionic liquid in water can be divided into hydrophilic ionic-liquid and Hydrophobic Ionic
Liquid.For example, BmimCl, BmimAc, BmimBF4There is hydrophily etc. most ionic liquid, BmimPF6、BPyPF6Etc. for
Hydrophobic ionic liquid.Additionally, the acid-base property according to ionic liquid aqueous solution is further divided into acidic ion liquid, alkali ion
Liquid and neutral ion liquid, wherein acidic ion liquid again include Lewis acidic ion liquids andAcid ion
Liquid.
Because ionic liquid has very strong designability, by changing the various combination of zwitterion, can obtain not
Isostructural ionic liquid.The synthetic method of ionic liquid mainly includes：Direct synthesis technique and two-step synthesis method.
1) direct synthesis technique.With Souza etc. using alkyl imidazole and trifluoromethayl sulfonic acid ester, trifluoroacetic acid second
Ester etc. reacts one-step synthesis method ionic liquid, and with yield higher, but used cost of material is costly.
2) two-step synthesis method.First, there is alkylated reaction in alkyl chloride and alkyl imidazole etc., obtain the halogen of target cationic
Compound.Because the reaction is nucleophilic substitution, belong to high exothermic heat process, therefore, it is miscellaneous in order to avoid being produced in building-up process
Matter with inert atmosphere and lower temperature conditions drying, it is necessary to carry out.By the purification process such as extraction, dry, recrystallization
Afterwards, halide ion is displaced with the slaine containing desired anion, ammonium salt or conjugate acid, then by purification step.Example
Such as, hydrophilic ionic-liquid extracts ionic liquid after reaction generally using water as reaction medium using dichloromethane, removes molten
Agent, after vacuum drying, obtains object ion liquid.
Compared with conventional melt salt and conventional organic solvent, ionic liquid has：(1) liquid state range is wide；(2) saturated vapor
Force down；(3) structure designability；(4) solvability is strong；(5) chemically and thermally stability the features such as.
Functionalized ion liquid (task specific ionic liquids) refers to synthesize for special application
, the ionic liquid of one or more functional groups is introduced in zwitterion.At present, study more is in the side of cation
Such as-OH ,-SH ,-NH are introduced on chain2、‐SO3The functional groups such as H, including acid ion alkali ion liquid, chiral ionic liquid, heteropoly acid ion
Liquid, chelate ionic liquid etc., are widely used in urging for the reactions such as hydroformylation, asymmetric hydrogenation, the coupling of carbon carbon, oxidation
Agent and organic synthesis solvent, extractant etc., with raising reaction selectivity, conversion ratio, easily good stability, the spy such as recovery
Point.But, the feature of current functionalized ion liquid is relatively simple, and solubility under room temperature environment is larger, catalyst
There is larger mechanical loss during recovery.Therefore, design it is a kind of have it is multi-functional, and can be under the solvable room temperature environment of high temperature
Temperature control multifunctional ion liquid in reaction system from separation is very significant.
The content of the invention
In order to solve the shortcoming and defect part of prior art, primary and foremost purpose of the invention is to provide a kind of new many
Functional ion liquid, realize in ionic liquid comprising various active position reached in specific course of reaction Efficient Conversion effect and
Reach the purpose of the mechanical loss for reducing catalyst recovery process.
The object of the invention is achieved through the following technical solutions：
A kind of preparation method of heteropoly acid ionic liquid, comprises the following steps：
(1) the N- alkyl imidazoles and butane sultone for weighing equimolar amounts react 24~48h under the conditions of 40-60 DEG C；Instead
Should after washed with ether, be vacuum dried, obtain white solid inner salt N- alkyl -3- fourth sulfonic group imidazoles；The N- alkyl imidazoles
Carbon chain lengths be 1~6 carbon atom；
(2) heteropoly acid and metal carbonate of equimolar amounts are weighed；Metal carbonate is added drop-wise in heteropoly acid solution,
40-60 DEG C of 24~48h of stirring reaction；After removing aqueous solvent after reaction, vacuum drying obtains heteropolyacid metal salt；It is described miscellaneous many
Acid is phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid, silicomolybdic acid or molybdovanaphosphoric acid；The metal carbonate is basic copper carbonate, basic carbonate
Nickel, basic zinc carbonate, manganese carbonate, cobalt carbonate or sodium carbonate；
(3) heteropolyacid metal salt for weighing equimolar amounts is dropwise added dropwise in white solid inner salt, stirs 12~48h, instead
Should after remove aqueous solvent after, vacuum drying, obtain heteropoly acid ionic liquid.
Further to realize the object of the invention, it is preferable that step (1) the vacuum drying temperature is 40~70 DEG C.
Preferably, step (2) preferably, vacuum drying temperature be 60~80 DEG C, the vacuum drying time be 12~
48h。
Preferably, step (3) the vacuum drying temperature is 60~80 DEG C, and the vacuum drying time is 12~48h.
Preferably, the metal carbonate is in dissolving in and add after water heteropoly acid.
Preferably, the water is deionized water, and in terms of every 10mmol heteropoly acids, the consumption of deionized water is 10~50mL.
Preferably, step (2) and step (3) the removal aqueous solvent are removed with Rotary Evaporators.
Preferably, the N- alkyl imidazoles are methylimidazole, ethyl imidazol(e) or propyl imidazole.
A kind of heteropoly acid ionic liquid, is obtained by above-mentioned preparation method；The ionic liquid has the miaow containing alkyl chain
Cation of the azole with sulfonic acid group；And metal ion and heteropoly acid root are anion ion liquid.
Relative to prior art, the invention has the advantages that：
1) present invention has synthesized the multi-functional heteropoly acid ionic liquid of a series of new.The synthetic method for being used is using green
Solvent-water, has the advantages that simple to operate, yield is high, easy purification.
2) the heteropoly acid ionic liquid obtained by the present invention contains sulfonic group cation, transition metal ions, heteropoly acid root
Ion, with acid and stronger oxidation-reduction quality, can turn into the catalyst of high activity, and at ambient temperature can it is spontaneous from
Reaction system can reach the purpose of the mechanical loss being reduced as far as in catalyst recovery process from precipitation.
Brief description of the drawings
Fig. 1 is the nuclear magnetic resonance figures of the intermediate ion liquid 1- methyl -4- fourth sulfonic acid phosphotungstic acid copper ion liquid of embodiment 1.
Fig. 2 is the FTIR spectrum of the intermediate ion liquid 1- methyl -4- fourth sulfonic acid phosphotungstic acid copper ion liquid of embodiment 1
Figure.
Fig. 3 is the thermal analysis curue of the intermediate ion liquid 1- methyl -4- fourth sulfonic acid phosphotungstic acid copper ion liquid of embodiment 1.
Specific embodiment
To more fully understand the present invention, the invention will be further described with reference to the accompanying drawings and examples, but this hair
Bright implementation method not limited to this.
Embodiment 1
Ionic liquid 1- methyl -4- fourth sulfonic acid phosphotungstic acid copper ion liquid (BSmimCuPW12O40) preparation：
(1) methylimidazole and butane sultone for weighing equimolar amounts react 24h under the conditions of 50 DEG C；Ether is used after reaction
Washing, is vacuum dried at 60 DEG C, obtains white solid inner salt 1- methyl -3- fourth sulfonic group imidazoles；
(2) equimolar amounts basic copper carbonate and phosphotungstic acid H are weighed3PW12O40Solution；Basic copper carbonate is scattered in the aqueous solution
In, and it is added dropwise to phosphotungstic acid H3PW12O40In solution, after continuing to stir 24h, aqueous solvent, 60 DEG C are removed with Rotary Evaporators
Lower vacuum drying, obtains phosphotungstic acid copper CuHPW12O40。
(3) by phosphotungstic acid copper CuHPW12O40The aqueous solution is added drop-wise to the white inner salt 1- methyl -3- of equimolar amounts while stirring
In fourth sulfonic group imidazoles, 50 DEG C of reaction 48h remove aqueous solvent after reaction with Rotary Evaporators, are vacuum dried at 60 DEG C, obtain final product
Ionic liquid 1- methyl -4- fourth sulfonic acid phosphotungstic acid copper ion liquid Bs SmimCuPW12O40。
Gained ionic liquid is respectively adopted nuclear magnetic resonance, FTIR spectrum etc. and determines its structure, and correlated results is shown in attached
Fig. 1 and 2, the characterization result of nuclear magnetic resonance is as follows：Chemical shift ppm 8.71 (s, 1H), 7.59-7.54 (m, 2H), 4.37 (m,
2H),4.07(s,3H),3.05(m,2H),2.14(m,2H),1.84(m,2H)；The characterization result of FTIR spectrum is as follows：
Wave number (cm‐1)3562,3490,3153,2938,1971,1606,1448,1169,1076,976,890,789,596,518.Core
Magnetic resonance illustrates that the ionic liquid has the cationic structural of object ion liquid with the signal peak of FTIR spectrum, and pure
Degree is higher；Its heat endurance (accompanying drawing 3) is determined using thermal analyzer, the as shown by data ionic liquid is with preferably thermally-stabilised
Property, all without decomposition in environment of the temperature less than 573K；Using its organic element content of determination of elemental analysis, using plasma
Body atomic emission spectrum determines its metal element content.Correlated results is as shown in table 1.Synthesized ionic liquid is in room temperature condition
Solubility under (293K) in ethanol is only 2.3%, and the ionic liquid for being heated to the synthesis after 353K can just be completely dissolved.Cause
This, synthesized ionic liquid had both had the characteristic of general ionic liquid, and the oxidisability with heteropoly acid, and can be complete under high temperature
CL from precipitation, therefore can have broad application prospects on homogeneous acidity catalytic oxidation at room temperature.
The ionic liquid 1- methyl -4- fourth sulfonic acid phosphotungstic acid copper ion liquid Bs SmimCuPW of table 112O40Essential element composition
Embodiment 2
Ionic liquid 1- methyl -4- fourth sulfonic acid phosphotungstic acid manganese ion liquid Bs SmimMnPW12O40Preparation：
(1) methylimidazole and butane sultone for weighing equimolar amounts react 24h under the conditions of 50 DEG C；Ether is used after reaction
Washing, is vacuum dried at 60 DEG C, obtains white solid inner salt 1- methyl -3- fourth sulfonic group imidazoles；
(2) weigh equimolar amounts manganese carbonate to be scattered in the aqueous solution, and be added dropwise to phosphotungstic acid H3PW12O40In solution,
After continuing to stir 24h, aqueous solvent is removed with Rotary Evaporators, be vacuum dried at 60 DEG C, obtain phosphotungstic acid manganese MnHPW12O40。
(3) by phosphotungstic acid manganese MnHPW12O40The aqueous solution is added drop-wise to the white inner salt 1- methyl -3- of equimolar amounts while stirring
In fourth sulfonic group imidazoles, 60 DEG C of reaction 48h remove aqueous solvent after reaction with Rotary Evaporators, are vacuum dried at 60 DEG C, obtain final product
Ionic liquid 1- methyl -4- fourth sulfonic acid phosphotungstic acid manganese ion liquid Bs SmimMnPW12O40.Synthesized ionic liquid is in room temperature bar
Solubility under part (293K) in ethanol is only 1.2%, and the ionic liquid for being heated to the synthesis after 333K can just be completely dissolved.
Embodiment 3
Ionic liquid 1- methyl -4- fourth sulfonic acid phosphotungstic acid cobalt ions liquid Bs SmimCoPW12O40Preparation：
(1) methylimidazole and butane sultone for weighing equimolar amounts react 24h under the conditions of 50 DEG C；Ether is used after reaction
Washing, is vacuum dried at 60 DEG C, obtains white solid inner salt 1- methyl -3- fourth sulfonic group imidazoles；
(2) weigh equimolar amounts manganese carbonate to be scattered in the aqueous solution, and be added dropwise to phosphotungstic acid H3PW12O40In solution,
After continuing to stir 24h, aqueous solvent is removed with Rotary Evaporators, be vacuum dried at 60 DEG C, obtain phosphotungstic acid cobalt CoHPW12O40。
(3) by phosphotungstic acid cobalt CoHPW12O40The aqueous solution is added drop-wise to the white inner salt 1- methyl -3- of equimolar amounts while stirring
In fourth sulfonic group imidazoles, 55 DEG C of reaction 48h remove aqueous solvent after reaction with Rotary Evaporators, are vacuum dried at 60 DEG C, obtain final product
Ionic liquid 1- methyl -4- fourth sulfonic acid phosphotungstic acid cobalt ions liquid Bs SmimCoPW12O40.Synthesized ionic liquid is in room temperature bar
Solubility under part (293K) in ethanol is only 2.5%, and the ionic liquid for being heated to the synthesis after 323K can just be completely dissolved.
Embodiment 4
Ionic liquid 1- methyl -4- fourth sulfonic acid phosphotungstic acid nickel ion liquid Bs SmimNiPW12O40Preparation：
(1) methylimidazole and butane sultone for weighing equimolar amounts react 24h under the conditions of 50 DEG C；Ether is used after reaction
Washing, is vacuum dried at 60 DEG C, obtains white solid inner salt 1- methyl -3- fourth sulfonic group imidazoles；
(2) weigh equimolar amounts basic carbonate manganese to be scattered in the aqueous solution, and be added dropwise to phosphotungstic acid H3PW12O40Solution
In, after continuing to stir 24h, aqueous solvent is removed with Rotary Evaporators, it is vacuum dried at 60 DEG C, obtain phosphotungstic acid nickel HPW12O40。
(3) by phosphotungstic acid nickel HPW12O40The aqueous solution is added drop-wise to the white inner salt 1- methyl -3- of equimolar amounts while stirring
In fourth sulfonic group imidazoles, 60 DEG C of reaction 48h remove aqueous solvent after reaction with Rotary Evaporators, are vacuum dried at 60 DEG C, obtain final product
Ionic liquid 1- methyl -4- fourth sulfonic acid phosphotungstic acid nickel ion liquid Bs SmimNiPW12O40.Synthesized ionic liquid is in room temperature bar
Solubility under part (293K) in ethanol is only 2.4%, and the ionic liquid for being heated to the synthesis after 333K can just be completely dissolved.
Embodiment 5
Ionic liquid 1- methyl -4- fourth sulfonic acid sodium phosphotungstate ionic liquids BSmimNa2PW12O40Preparation：
(1) methylimidazole and butane sultone for weighing equimolar amounts react 24h under the conditions of 50 DEG C；Ether is used after reaction
Washing, is vacuum dried at 60 DEG C, obtains white solid inner salt 1- methyl -3- fourth sulfonic group imidazoles；
(2) weigh equimolar amounts sodium carbonate to be scattered in the aqueous solution, and be added dropwise to phosphotungstic acid H3PW12O40In solution,
After continuing to stir 24h, aqueous solvent is removed with Rotary Evaporators, be vacuum dried at 60 DEG C, obtain sodium phosphotungstate Na2HPW12O40。
(3) by sodium phosphotungstate Na2HPW12O40The aqueous solution is added drop-wise to the white inner salt 1- methyl -3- of equimolar amounts while stirring
In fourth sulfonic group imidazoles, 40 DEG C of reaction 48h remove aqueous solvent after reaction with Rotary Evaporators, are vacuum dried at 60 DEG C, obtain final product
Ionic liquid 1- methyl -4- fourth sulfonic acid sodium phosphotungstate ionic liquids BSmimNa2PW12O40.Synthesized ionic liquid is in room temperature bar
Solubility under part (293K) in ethanol is only 3.1%, and the ionic liquid for being heated to the synthesis after 313K can just be completely dissolved.
Embodiment 6
Ionic liquid 1- methyl -4- fourth sulfonic acid phosphotungstic acid zinc ion liquid Bs SmimZnPW12O40Preparation：
(1) methylimidazole and butane sultone for weighing equimolar amounts react 24h under the conditions of 50 DEG C；Ether is used after reaction
Washing, is vacuum dried at 60 DEG C, obtains white solid inner salt 1- methyl -3- fourth sulfonic group imidazoles；
(2) weigh equimolar amounts basic zinc carbonate to be scattered in the aqueous solution, and be added dropwise to phosphotungstic acid H3PW12O40Solution
In, after continuing to stir 24h, aqueous solvent is removed with Rotary Evaporators, it is vacuum dried at 60 DEG C, obtain phosphotungstic acid zinc ZnHPW12O40。
(3) by phosphotungstic acid zinc ZnHPW12O40The aqueous solution is added drop-wise to the white inner salt 1- methyl -3- of equimolar amounts while stirring
In fourth sulfonic group imidazoles, 45 DEG C of reaction 48h remove aqueous solvent after reaction with Rotary Evaporators, are vacuum dried at 60 DEG C, obtain final product
Ionic liquid 1- methyl -4- fourth sulfonic acid phosphotungstic acid zinc ion liquid Bs SmimZnPW12O40.Synthesized ionic liquid is in room temperature bar
Solubility under part (293K) in ethanol is only 1.5%, and the ionic liquid for being heated to the synthesis after 343K can just be completely dissolved.
Embodiment 7
Ionic liquid 1- methyl -4- fourth sulfonic acid phosphomolybdic acid copper ion liquid Bs SmimCuPMo12O40Preparation：
(1) methylimidazole and butane sultone for weighing equimolar amounts react 24h under the conditions of 50 DEG C；Ether is used after reaction
Washing, is vacuum dried at 60 DEG C, obtains white solid inner salt 1- methyl -3- fourth sulfonic group imidazoles；
(2) weigh equimolar amounts basic copper carbonate to be scattered in the aqueous solution, and be added dropwise to phosphomolybdic acid H3PMo12O40It is molten
In liquid, after continuing to stir 24h, aqueous solvent is removed with Rotary Evaporators, be vacuum dried at 60 DEG C, obtain phosphomolybdic acid copper
CuHPMo12O40。
(3) by phosphomolybdic acid copper CuHPMo12O40The aqueous solution be added drop-wise to while stirring the white inner salt 1- methyl of equimolar amounts-
In 3- fourth sulfonic group imidazoles, 55 DEG C of reaction 48h remove aqueous solvent after reaction with Rotary Evaporators, are vacuum dried at 60 DEG C, i.e.,
Obtain ionic liquid 1- methyl -4- fourth sulfonic acid phosphomolybdic acid copper ion liquid Bs SmimCuPMo12O40.Synthesized ionic liquid is in room
Solubility under warm condition (293K) in ethanol is only 1.9%, and the ionic liquid for being heated to the synthesis after 353K could be completely
Dissolving.
Embodiment 8
Ionic liquid 1- propyl group -4- fourth sulfonic acid silico-tungstic acid copper ion liquid Bs SpimCuSiW12O40Preparation：
(1) propyl imidazole and butane sultone for taking equimolar amounts react 24h under the conditions of 50 DEG C；Washed with ether after reaction
Wash, be vacuum dried at 60 DEG C, obtain white solid inner salt 1- propyl group -3- fourth sulfonic group imidazoles；
(2) weigh equimolar amounts basic copper carbonate to be scattered in the aqueous solution, and be added dropwise to silico-tungstic acid H3SiMo12O40It is molten
In liquid, after continuing to stir 24h, aqueous solvent is removed with Rotary Evaporators, be vacuum dried at 60 DEG C, obtain silico-tungstic acid copper
CuHSiW12O40。
(3) by silico-tungstic acid copper CuHSiW12O40The aqueous solution be added drop-wise to while stirring the white inner salt 1- propyl group of equimolar amounts-
In 3- fourth sulfonic group imidazoles, 65 DEG C of reaction 48h remove aqueous solvent after reaction with Rotary Evaporators, are vacuum dried at 60 DEG C, i.e.,
Obtain ionic liquid 1- propyl group -4- fourth sulfonic acid silico-tungstic acid copper ion liquid Bs SpimCuSiW12O40.Synthesized ionic liquid is in room
Solubility under warm condition (293K) in ethanol is only 1.5%, and the ionic liquid for being heated to the synthesis after 343K could be completely
Dissolving.
Embodiment 9
Ionic liquid 1- ethyl -4- fourth sulfonic acid molybdovanaphosphoric acid hydrogen copper ion liquid Bs SeimCuHPMo11VO40Preparation：
(1) ethyl imidazol(e) and butane sultone for weighing equimolar amounts react 24h under the conditions of 50 DEG C；Ether is used after reaction
Washing, is vacuum dried at 60 DEG C, obtains white solid inner salt 1- ethyl -3- fourth sulfonic group imidazoles；
(2) weigh equimolar amounts basic copper carbonate to be scattered in the aqueous solution, and be added dropwise to molybdovanaphosphoric acid H4PMo11VO40
In solution, after continuing to stir 24h, aqueous solvent is removed with Rotary Evaporators, be vacuum dried at 60 DEG C, obtain molybdovanaphosphoric acid mantoquita
CuH2PMo11VO40。
(3) by molybdovanaphosphoric acid mantoquita CuH2PMo11VO40The aqueous solution is added drop-wise to the white inner salt 1- of equimolar amounts while stirring
In ethyl -3- fourth sulfonic group imidazoles, 65 DEG C of reaction 48h remove aqueous solvent after reaction with Rotary Evaporators, and vacuum is done at 60 DEG C
It is dry, obtain final product ionic liquid 1- ethyl -4- fourth sulfonic acid molybdovanaphosphoric acid hydrogen copper ion liquid Bs SeimCuHPMo11VO40.It is synthesized from
Sub- liquid is only 1.1% in the solubility under room temperature condition (293K) in ethanol, is heated to the ionic liquid of the synthesis after 353K
Body can just be completely dissolved.
Embodiment 10
Ionic liquid 1- ethyl -4- fourth sulfonic acid molybdovanaphosphoric acid dihydro copper ion liquid Bs SeimCuH2PMo10V2O40Preparation：
(1) ethyl imidazol(e) and butane sultone for weighing equimolar amounts react 24h under the conditions of 50 DEG C；Ether is used after reaction
Washing, is vacuum dried at 60 DEG C, obtains white solid inner salt 1- ethyl -3- fourth sulfonic group imidazoles；
(2) weigh equimolar amounts basic copper carbonate to be scattered in the aqueous solution, and be added dropwise to molybdovanaphosphoric acid
H5PMo10V2O40In solution, after continuing to stir 24h, aqueous solvent is removed with Rotary Evaporators, be vacuum dried at 60 DEG C, obtain phosphorus molybdenum
Vanadic acid mantoquita CuH3PMo10V2O40。
(3) by molybdovanaphosphoric acid mantoquita CuH3PMo10V2O40The aqueous solution is added drop-wise to the white inner salt 1- of equimolar amounts while stirring
In ethyl -3- fourth sulfonic group imidazoles, 65 DEG C of reaction 48h remove aqueous solvent after reaction with Rotary Evaporators, and vacuum is done at 60 DEG C
It is dry, obtain final product ionic liquid 1- ethyl -4- fourth sulfonic acid molybdovanaphosphoric acid dihydro copper ion liquid Bs SeimCuH2PMo10V2O40.It is synthesized
Ionic liquid be only 1.0% in the solubility under room temperature condition (293K) in ethanol, be heated to the synthesis after 358K from
Sub- liquid can just be completely dissolved.
Embodiment 11
The hydrogen copper ion liquid B SeimCuH of ionic liquid 1- ethyl -4- fourth sulfonic acid molybdovanaphosphoric acid three3PMo9V3O40Preparation：
(1) ethyl imidazol(e) and butane sultone for weighing equimolar amounts react 24h under the conditions of 50 DEG C；Ether is used after reaction
Washing, is vacuum dried at 60 DEG C, obtains white solid inner salt 1- ethyl -3- fourth sulfonic group imidazoles；
(2) weigh equimolar amounts basic copper carbonate to be scattered in the aqueous solution, and be added dropwise to molybdovanaphosphoric acid H6PMo9V3O40
In solution, after continuing to stir 24h, aqueous solvent is removed with Rotary Evaporators, be vacuum dried at 60 DEG C, obtain molybdovanaphosphoric acid mantoquita
CuH4PMo10V2O40。
(3) by molybdovanaphosphoric acid mantoquita CuH4PMo10V2O40The aqueous solution is added drop-wise to the white inner salt 1- of equimolar amounts while stirring
In ethyl -3- fourth sulfonic group imidazoles, 65 DEG C of reaction 48h remove aqueous solvent after reaction with Rotary Evaporators, and vacuum is done at 60 DEG C
It is dry, obtain final product the hydrogen copper ion liquid B SeimCuH of ionic liquid 1- ethyl -4- fourth sulfonic acid molybdovanaphosphoric acid three3PMo10V2O40.It is synthesized
Ionic liquid be only 1.3% in the solubility under room temperature condition (293K) in ethanol, be heated to the synthesis after 358K from
Sub- liquid can just be completely dissolved.
Embodiments of the present invention are simultaneously not restricted to the described embodiments, other any real without departing from spirit of the invention
Matter and the change, modification, replacement made under principle, combine, simplify, should be equivalent substitute mode, being included in the present invention
Protection domain within.
Claims (9)
1. a kind of preparation method of heteropoly acid ionic liquid, it is characterised in that comprise the following steps：
(1) the N- alkyl imidazoles and butane sultone for weighing equimolar amounts react 24~48h under the conditions of 40-60 DEG C；After reaction
Washed with ether, be vacuum dried, obtain white solid inner salt N- alkyl -3- fourth sulfonic group imidazoles；The carbon of the N- alkyl imidazoles
Chain length is 1~6 carbon atom；
(2) heteropoly acid and metal carbonate of equimolar amounts are weighed；Metal carbonate is added drop-wise in heteropoly acid solution, 40-60
DEG C 24~48h of stirring reaction；After removing aqueous solvent after reaction, vacuum drying obtains heteropolyacid metal salt；The heteropoly acid is phosphorus
Wolframic acid, phosphomolybdic acid, silico-tungstic acid, silicomolybdic acid or molybdovanaphosphoric acid；The metal carbonate is basic copper carbonate, basic nickel carbonate, alkali
Formula zinc carbonate, manganese carbonate, cobalt carbonate or sodium carbonate；
(3) heteropolyacid metal salt for weighing equimolar amounts is dropwise added dropwise in white solid inner salt, 12~48h is stirred, after reaction
After removal aqueous solvent, vacuum drying obtains heteropoly acid ionic liquid.
2. the preparation method of heteropoly acid ionic liquid according to claim 1, it is characterised in that true described in step (1)
Empty dry temperature is 40~70 DEG C.
3. the preparation method of heteropoly acid ionic liquid according to claim 1, it is characterised in that true described in step (2)
Empty dry temperature is 60~80 DEG C, and the vacuum drying time is 12~48h.
4. the preparation method of heteropoly acid ionic liquid according to claim 1, it is characterised in that true described in step (3)
Empty dry temperature is 60~80 DEG C, and the vacuum drying time is 12~48h.
5. the preparation method of heteropoly acid ionic liquid according to claim 1, it is characterised in that the metal carbonate is
Dissolving in add after water heteropoly acid.
6. the preparation method of heteropoly acid ionic liquid according to claim 5, it is characterised in that the water is deionization
Water, in terms of every 10mmol heteropoly acids, the consumption of deionized water is 10~50mL.
7. the preparation method of heteropoly acid ionic liquid according to claim 1, it is characterised in that step (2) and step (3)
The removal aqueous solvent is removed with Rotary Evaporators.
8. the preparation method of heteropoly acid ionic liquid according to claim 1, it is characterised in that the N- alkyl imidazoles are
Methylimidazole, ethyl imidazol(e) or propyl imidazole.
9. a kind of heteropoly acid ionic liquid, it is characterised in that its preparation method as described in claim any one of 1-8 is obtained；It is described
Ionic liquid has cation of the imidazoles containing alkyl chain with sulfonic acid group；And metal ion and heteropoly acid root are the moon
The ionic liquid of ion.
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