CN103709123B - 1, 4-dimethyl-1-alkyl piperazine ionic liquid as well as preparation method and applications thereof - Google Patents
1, 4-dimethyl-1-alkyl piperazine ionic liquid as well as preparation method and applications thereof Download PDFInfo
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- CN103709123B CN103709123B CN201310753948.XA CN201310753948A CN103709123B CN 103709123 B CN103709123 B CN 103709123B CN 201310753948 A CN201310753948 A CN 201310753948A CN 103709123 B CN103709123 B CN 103709123B
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- nitrae
- alkylpiperazine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/037—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements with quaternary ring nitrogen atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1493—Selection of liquid materials for use as absorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/292—Liquid sorbents
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/023—Preparation; Separation; Stabilisation; Use of additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/20—Organic absorbents
- B01D2252/204—Amines
- B01D2252/20436—Cyclic amines
- B01D2252/20447—Cyclic amines containing a piperazine-ring
Abstract
The invention discloses a 1, 4-dimethyl-1-alkyl piperazine ionic liquid. The chemical structural general formula of the 1, 4-dimethyl-1-alkyl piperazine ionic liquid is as shown in the specification, wherein the R is straight-chain alkyl of C1-C10; the negative ion Y<-> is Cl-, Br<->, I<->, C4F9SO3<->, C4H9OSO3<->, C6H13OSO3<->, C8H17OSO3<->, (CF3SO2)2N<->, (CF3SO2)3C<->, (C2F5SO2)2N<-> or (C2F5SO2)3C<->. The invention further discloses a preparation method of the 1, 4-dimethyl-1-alkyl piperazine ionic liquid. The preparation method is simple in process and short in preparation cycle and has the advantages that the product yield reaches above 70%, and the product purity can reach above 96%. The invention further discloses the application of the 1, 4-dimethyl-1-alkyl piperazine ionic liquid serving as a gas chromatography stationary phase and the application of the 1, 4-dimethyl-1-alkyl piperazine ionic liquid in sulfur dioxide gas absorption.
Description
Technical field
The present invention relates to organic synthesis field, be specifically related to a kind of Isosorbide-5-Nitrae-dimethyl-1-alkylpiperazine ionic liquid, preparation method and application thereof.
Background technology
Ionic liquid is generally made up of organic cation and inorganic or organic anion, is the salt be in a liquid state under room temperature or near room temperature temperature.Ionic liquid has the features such as low-steam pressure, thermostability and chemical stability are good, adjustability is strong, can as a kind of excellent green solvent and catalyzer, is widely used in catalyzing and synthesizing, isolation technique, electrochemistry, field of petrochemical industry.Ionic liquid is expected to replace the conventional organic solvents volatile, toxicity is high, inflammable and explosive, is thus subject to the extensive concern of domestic and international academia and industry member.
The ionic liquid of extensive investigation and application at present, mainly using imidazoles, pyridine as positively charged ion, quaternary ammonium salt is relative less with quaternary phosphine salt ionic liquid report, especially piperazines ionic liquid.U.S. Energy Fuels magazine the 26th phase in 2012 2154th ~ 2160 pages reports N methyl piperazine ionic liquid for extracting Arene removal in fuel, achieve better effects, but wherein most of ionic liquid fusing point is higher.
Publication number is that the Chinese patent literature of CN102952097A discloses a kind of two centre piperazine ionic liquid, has following structural formula:
Wherein Y-is selected from BF
4 -, PF
6 -, (CF
3sO
2)
2n
-, (FSO
2)
2n
-and CF
3sO
3 -in one.This invention also provides a kind of preparation method of above-mentioned pair of centre piperazine ionic liquid, and points out its application at electrolytic solution.The preparation cycle of this preparation method is oversize, and does not relate to the purity of product.
Summary of the invention
The invention provides a kind of novel Isosorbide-5-Nitrae-dimethyl-1-alkylpiperazine ionic liquid, and provide the preparation method of described piperazines ionic liquid, technique is simple, the cycle is short and productive rate is higher.The deep desulfuration and the sulfur dioxide gas that the Isosorbide-5-Nitrae prepared-dimethyl-1-alkylpiperazine ionic liquid are used for oil product absorb, and all have higher efficiency.
The invention discloses a kind of Isosorbide-5-Nitrae-dimethyl-1-alkylpiperazine ionic liquid, there is following chemical structure of general formula:
Wherein, R is C
1~ C
10straight chained alkyl;
Negatively charged ion Y
-for Cl
-, Br
-, I
-, C
4f
9sO
3 -, C
4h
9oSO
3 -, C
6h
13oSO
3 -, C
8h
17oSO
3 -, (CF
3sO
2)
2n
-, (CF
3sO
2)
3c
-, (C
2f
5sO
2)
2n
-or (C
2f
5sO
2)
3c
-.
The invention also discloses the preparation method of described Isosorbide-5-Nitrae-dimethyl-1-alkylpiperazine ionic liquid.
As negatively charged ion Y
-for Cl
-, Br
-or I
-time, the preparation method of described Isosorbide-5-Nitrae-dimethyl-1-alkylpiperazine ionic liquid is as follows:
Be 1 of 1:1 ~ 1.5 by mol ratio, 4-lupetazin and haloalkane are dissolved in ethyl acetate respectively, again by 1, in 4-lupetazin/ethyl acetate solution instillation haloalkane/ethyl acetate solution, under nitrogen protection, at 20 ~ 80 DEG C, react 12 ~ 48h, after removing solvent, washing, drying, obtain described Isosorbide-5-Nitrae-dimethyl-1-alkylpiperazine ionic liquid;
Be specially:
Be 1 of 1:1 ~ 1.5 by mol ratio; 4-lupetazin and haloalkane are dissolved in ethyl acetate respectively, then by Isosorbide-5-Nitrae-lupetazin/ethyl acetate solution instillation haloalkane/ethyl acetate solution; under nitrogen protection; at 20 ~ 80 DEG C, react 12 ~ 48h, be cooled to room temperature, evaporating solvent; gained solid washs through ethyl acetate; again after drying, described Isosorbide-5-Nitrae-dimethyl-1-alkylpiperazine ionic liquid is obtained.
Alkyl in described haloalkane is selected from C
1~ C
10straight chained alkyl.
As negatively charged ion Y
-for C
4f
9sO
3 -, C
4h
9oSO
3 -, C
6h
13oSO
3 -, C
8h
17oSO
3 -, (CF
3sO
2)
2n
-, (CF
3sO
2)
3c
-, (C
2f
5sO
2)
2n
-or (C
2f
5sO
2)
3c
-time, the preparation method of described Isosorbide-5-Nitrae-dimethyl-1-alkylpiperazine ionic liquid is as follows:
Be M by equimolar Isosorbide-5-Nitrae-dimethyl-1-alkylpiperazine halogenide and general formula
+y
-metal-salt be dissolved in respectively in water, after stirred at ambient temperature 6 ~ 12h, after adding organic solvent stratification, organic phase, through washing, dry, obtains described Isosorbide-5-Nitrae-dimethyl-1-alkylpiperazine ionic liquid;
Be specially:
Be M by equimolar Isosorbide-5-Nitrae-dimethyl-1-alkylpiperazine halogenide and general formula
+y
-metal-salt be dissolved in respectively in water, after stirred at ambient temperature 6 ~ 12h, add methylene dichloride stratification, organic phase washed with water at least 3 times, after drying, obtain described Isosorbide-5-Nitrae-dimethyl-1-alkylpiperazine ionic liquid.
Alkyl in described Isosorbide-5-Nitrae-dimethyl-1-alkylpiperazine halogenide is selected from C
1~ C
10straight chained alkyl;
As preferably, described M
+y
-the M of metal-salt
+be selected from Na
+, K
+or Li
+
The invention also discloses the application of a kind of Isosorbide-5-Nitrae-dimethyl-1-alkylpiperazine ionic liquid in absorbing as GC stationary phase and sulfur dioxide gas.
As preferably, the negatively charged ion Y of described Isosorbide-5-Nitrae-dimethyl-1-alkylpiperazine ionic liquid
-for Y
-for C
4f
9sO
3 -, (CF
3sO
2)
2n
-, (CF
3sO
2)
3c
-, (C
2f
5sO
2)
2n
-or (C
2f
5sO
2)
3c
-, more preferably (CF
3sO
2)
2n
-or (C
2f
5sO
2)
2n
-time, better as GC stationary phase.
As preferably, the negatively charged ion Y of described Isosorbide-5-Nitrae-dimethyl-1-alkylpiperazine ionic liquid
-for C
4h
9oSO
3 -, C
6h
13oSO
3 -, C
8h
17oSO
3 -, (CF
3sO
2)
2n
-, (CF
3sO
2)
3c
-, (C
2f
5sO
2)
2n
-or (C
2f
5sO
2)
3c
-time, better to the assimilated efficiency of sulfur dioxide gas.
Compared with prior art, tool of the present invention has the following advantages:
Preparation technology of the present invention is simple, and preparation cycle is shorter, and productive rate reaches more than 70%, and purity can reach more than 96%, can meet industrial requirement very well; The Isosorbide-5-Nitrae prepared-dimethyl-1-alkylpiperazine ionic liquid good stability, viscosity is low, and dissolving power is strong;
The Isosorbide-5-Nitrae that the present invention prepares-dimethyl-1-alkylpiperazine ionic liquid can reach good separation to general organic compound as GC stationary phase;
During the Isosorbide-5-Nitrae that the present invention prepares-dimethyl-1-alkylpiperazine ionic liquid absorbs for sulfur dioxide gas, the sulfurous gas of every mole of ionic liquid absorption 1.5 moles.
Accompanying drawing explanation
Fig. 1 be embodiment 9 prepare ionic liquid for the preparation of GC stationary phase time, to the separating effect of different compound.
Embodiment
Further illustrate the present invention by embodiment below and more specifically determined by claim, but embodiment not regarded as under any condition scope of the present invention is limited:
Embodiment 1: the preparation of chlorination Isosorbide-5-Nitrae-dimethyl-1-ethyl piperazidine ionic liquid
Dropping funnel is being housed, in the 500mL three-necked flask of reflux condensing tube and nitrogen ball, add 1.3mol1-monochloroethane and 100mL ethyl acetate, 1mol1 is added in dropping funnel, slowly instill in the ethyl acetate solution of 1-monochloroethane after 4-lupetazin and 100mL ethyl acetate, stir and react 48 hours at 80 DEG C, be cooled to room temperature, filter, the white solid ethyl acetate obtained is washed, and obtains chlorination Isosorbide-5-Nitrae-dimethyl-1-ethyl piperazidine ionic liquid after 40 DEG C of vacuum-dryings, purity 99%, productive rate 80%.
Embodiment 2: the preparation of iodate Isosorbide-5-Nitrae-dimethyl-1-propylpiperazine ionic liquid
Dropping funnel is being housed, in the 500mL three-necked flask of reflux condensing tube and nitrogen ball, add 1.2mol1-iodopropane and 100mL ethyl acetate, 1mol1 is added in dropping funnel, slowly instill in the ethyl acetate solution of propyl iodide after 4-lupetazin and 100mL ethyl acetate, stir and react 12 hours at 30 DEG C, be cooled to room temperature, filter, the white solid ethyl acetate obtained is washed, and obtains iodate Isosorbide-5-Nitrae-dimethyl-1-propylpiperazine ionic liquid after 40 DEG C of vacuum-dryings, purity 99%, productive rate 86%.
Embodiment 3: the preparation of iodate Isosorbide-5-Nitrae-dimethyl-1-butyl piperazine ionic liquid
Dropping funnel is being housed, in the 500mL three-necked flask of reflux condensing tube and nitrogen ball, add 1.1mol1-butyl iodide and 100mL ethyl acetate, 1mol1 is added in dropping funnel, slowly instill in the ethyl acetate solution of 1-butyl iodide after 4-lupetazin and 100mL ethyl acetate, stir and react 24 hours at 40 DEG C, be cooled to room temperature, filter, the white solid ethyl acetate obtained is washed, and obtains iodate Isosorbide-5-Nitrae-dimethyl-1-butyl piperazine ionic liquid after 50 DEG C of vacuum-dryings, purity 99%, productive rate 91%.
Embodiment 4: the preparation of bromination Isosorbide-5-Nitrae-dimethyl-1-hexyl piperazine ionic liquid
Dropping funnel is being housed, in the 500mL three-necked flask of reflux condensing tube and nitrogen ball, add 1.2mol1-bromohexane and 100mL ethyl acetate, 1mol1 is added in dropping funnel, slowly instill in the ethyl acetate solution of hexyl bromide 1 bromohexane after 4-lupetazin and 100mL ethyl acetate, stir and react 36 hours at 60 DEG C, be cooled to room temperature, evaporating solvent, the solid with ethyl acetate washing obtained, obtains bromination Isosorbide-5-Nitrae-dimethyl-1-hexyl piperazine ionic liquid after 70 DEG C of vacuum-dryings, purity 98%, productive rate 84%.
Embodiment 5: the preparation of chlorination Isosorbide-5-Nitrae-dimethyl-1-octyl group piperazine ionic liquid
Dropping funnel is being housed, in the 500mL three-necked flask of reflux condensing tube and nitrogen ball, add 1.3mol1-chloro-octane and 100mL ethyl acetate, 1mol1 is added in dropping funnel, slowly instill in the ethyl acetate solution of 1-chloro-octane after 4-lupetazin and 100mL ethyl acetate, stir and react 48 hours at 80 DEG C, be cooled to room temperature, evaporating solvent, the solids washed with water obtained, obtains chlorination Isosorbide-5-Nitrae-dimethyl-1-octyl group piperazine ionic liquid after 70 DEG C of vacuum-dryings, purity 98%, productive rate 86%.
Embodiment 6: the preparation of bromination Isosorbide-5-Nitrae-dimethyl-1-decyl piperazine ionic liquid
Dropping funnel is being housed, in the 500mL three-necked flask of reflux condensing tube and nitrogen ball, add 1.1mol1-bromo-decane and 100mL ethyl acetate, 1mol1 is added in dropping funnel, slowly instill in the ethyl acetate solution of 1-bromo-decane after 4-lupetazin and 100mL ethyl acetate, stir and react 24 hours at 50 DEG C, be cooled to room temperature, evaporating solvent, the solids washed with water obtained, obtains bromination Isosorbide-5-Nitrae-dimethyl-1-decyl piperazine ionic liquid after 60 DEG C of vacuum-dryings, purity 98%, productive rate 81%.
The preparation of embodiment 7:1,4-dimethyl-1-ethyl piperazidine butyl sulphate ionic liquid
In 500mL round-bottomed flask, add the chlorination 1 containing preparation in 0.02mol embodiment 1, the aqueous solution 25mL of 4-dimethyl-1-ethyl piperazidine ionic liquid and the aqueous solution 50mL containing 0.02mol butyl sodium sulfate salt, stir and at room temperature react 10 hours, adding 100mL methylene dichloride, organic phase washed with water removing residual halogens, 1 is obtained after 40 DEG C of vacuum-dryings, 4-dimethyl-1-ethyl piperazidine butyl sulphate ionic liquid, purity 98%, productive rate 91%.
The preparation of embodiment 8:1,4-dimethyl-1-propylpiperazine hexyl sulfate ion liquid
In 500mL round-bottomed flask, add the iodate 1 containing preparation in 0.05mol embodiment 2, the dichloromethane solution 50mL of 4-dimethyl-1-propylpiperazine ionic liquid and the aqueous solution 50mL containing 0.05mol sodium hexy1 sulfate salt, stir and at room temperature react 12 hours, organic phase washed with water repeatedly washs removing residual halogens, obtains Isosorbide-5-Nitrae-dimethyl-1-propylpiperazine hexyl sulfate ion liquid after 40 DEG C of vacuum-dryings, purity 97%, productive rate 86%.
The preparation of two (fluoroform sulphonyl) the inferior amine salt ionic liquid of embodiment 9:1,4-dimethyl-1-butyl piperazine
In 500mL round-bottomed flask, add the iodate 1 containing preparation in 0.2mol embodiment 3, the dichloromethane solution 100mL of 4-dimethyl-1-butyl piperazine ionic liquid and the aqueous solution 150mL containing two (fluoroform sulphonyl) the imines lithium salts of 0.2mol, stir and at room temperature react 8 hours, organic phase washed with water repeatedly washs removing residual halogens, obtains two (fluoroform sulphonyl) the inferior amine salt ionic liquid of Isosorbide-5-Nitrae-dimethyl-1-butyl piperazine after 40 DEG C of vacuum-dryings, purity 99%, productive rate 89%.
The preparation of embodiment 10:1,4-dimethyl-1-butyl piperazine butyl sulphate ionic liquid
In 500mL round-bottomed flask, add the iodate 1 containing preparation in 0.1mol embodiment 3, the dichloromethane solution 100mL of 4-dimethyl-1-butyl piperazine ionic liquid and the aqueous solution 100mL containing 0.1mol butyl sodium sulfate salt, stir and at room temperature react 6 hours, organic phase washed with water removing residual halogens, obtains Isosorbide-5-Nitrae-dimethyl-1-butyl piperazine butyl sodium sulfate salt ionic liquid after 40 DEG C of vacuum-dryings, purity 98%, productive rate 83%.
The preparation of embodiment 11:1,4-dimethyl-1-hexyl piperazine octyl sulfate ionic liquid
In 500mL round-bottomed flask, add the bromination 1 containing preparation in 0.05mol embodiment 4, the dichloromethane solution 50mL of 4-dimethyl-1-hexyl piperazine ionic liquid and the aqueous solution 50mL containing 0.05mol octyl sulfate sodium salt, stir and at room temperature react 12 hours, organic phase washed with water removing residual halogens, obtains Isosorbide-5-Nitrae-dimethyl-1-hexyl piperazine octyl sulfate ionic liquid after 40 DEG C of vacuum-dryings, purity 98%, productive rate 84%.
The preparation of two (fluoroform sulphonyl) the inferior amine salt ionic liquid of embodiment 12:1,4-dimethyl-1-octyl group piperazine
In 500mL round-bottomed flask, add the iodate 1 containing preparation in 0.2mol embodiment 5, the dichloromethane solution 150mL of 4-dimethyl-1-octyl group piperazine ionic liquid and the aqueous solution 150mL containing two (fluoroform sulphonyl) the imines lithium salts of 0.2mol, stir and at room temperature react 6 hours, organic phase washed with water repeatedly washs removing residual halogens, 40 DEG C of vacuum-dryings, obtain 1, two (fluoroform sulphonyl) the inferior amine salt ionic liquid of 4-dimethyl-1-octyl group piperazine, purity 98%, productive rate 87%.
The preparation of embodiment 13:1,4-dimethyl-1-decyl piperazine perfluoro butyl sulfosalt ionic liquid
In 500mL round-bottomed flask, add the bromination 1 containing preparation in 0.02mol embodiment 6, the dichloromethane solution 50mL of 4-dimethyl-1-decyl piperazine ionic liquid and the aqueous solution 200mL containing 0.02mol perfluorobutyl potassium salt, stir and at room temperature react 12 hours, organic phase washed with water removing residual halogens, 40 DEG C of vacuum-dryings, obtain 1,4-dimethyl-1-decyl piperazine perfluoro butyl sulfosalt ionic liquid, purity 97%, productive rate 87%.
Two (fluoroform sulphonyl) the inferior amine salt ionic liquid of application examples 1:1,4-dimethyl-1-butyl piperazine is for the preparation of GC stationary phase
Quartz capillary column, at 300 DEG C of baking 1h, soaks 24h with the methanol solution of saturated sodium-chloride.The dichloromethane solution coating of two (fluoroform sulphonyl) inferior amine salt ionic liquid of Isosorbide-5-Nitrae-dimethyl-1-butyl piperazine of embodiment 9 preparation of 40 DEG C of pretreated capillary column.Solvent removed in vacuo.Be warming up to 200 DEG C, nitrogen flow 1mL/min, keep 6h, cooling, obtains the capillary column after ionic liquid process.With the heat-up rate of 5 DEG C/min, good separating effect is reached to 11 kinds of compounds, as shown in Figure 1: in figure, 1-n-decane, 2-n-undecane, 3-n-Octanol, 4-N, dinethylformamide, 5-n-nonyl aldehyde, 6-methyl phenyl ketone, 7-N-N-methyl-2-2-pyrrolidone N-, 8-Ortho-Chloro aniline, 9-methyl undecylate, the positive undecyl alcohol of 10-, 11-methyl dodecanoate.
Application examples 2:1,4-dimethyl-1-ethyl piperazidine butyl sulphate ionic liquid is used for the absorption of sulfur dioxide gas
Get 1 of 6g embodiment 7 preparation, 4-dimethyl-1-ethyl piperazidine butyl sulphate ionic liquid is in the glass test tube of band rubber plug, maintenance system temperature is 20 DEG C, bubbling passes into the nitrogen containing 8% sulfurous gas volume fraction, continue 3 hours, weighed the sulfurous gas quality obtaining ionic liquid absorption by Mettler AL204 analytical balance.Result shows, under this condition, Isosorbide-5-Nitrae-dimethyl-1-ethyl piperazidine butyl sulphate ionic liquid can reach ionic liquid to the absorption of sulfurous gas: the mol ratio of sulfurous gas=1:1.5, the ionic liquid after using can by adding heat extraction SO
2recycle.
Claims (6)
1. a preparation method for Isosorbide-5-Nitrae-dimethyl-1-alkylpiperazine ionic liquid, is characterized in that, described Isosorbide-5-Nitrae-dimethyl-1-alkylpiperazine ionic liquid has following chemical structure of general formula:
Wherein, R is C
1~ C
10straight chained alkyl;
Negatively charged ion Y
-for Cl
-, Br
-, I
-, C
4f
9sO
3 -, C
4h
9oSO
3 -, C
6h
13oSO
3 -, C
8h
17oSO
3 -, (CF
3sO
2)
2n
-, (CF
3sO
2)
3c
-, (C
2f
5sO
2)
2n
-or (C
2f
5sO
2)
3c
-;
As negatively charged ion Y
-for Cl
-, Br
-or I
-time, the preparation method of described Isosorbide-5-Nitrae-dimethyl-1-alkylpiperazine ionic liquid is as follows:
Be 1 of 1:1 ~ 1.5 by mol ratio, 4-lupetazin and haloalkane are dissolved in ethyl acetate respectively, again by 1, in 4-lupetazin/ethyl acetate solution instillation haloalkane/ethyl acetate solution, under nitrogen protection, at 20 ~ 80 DEG C, react 12 ~ 48h, after removing solvent, washing, drying, obtain described Isosorbide-5-Nitrae-dimethyl-1-alkylpiperazine ionic liquid;
Alkyl in described haloalkane is selected from C
1~ C
10straight chained alkyl;
As negatively charged ion Y
-for C
4f
9sO
3 -, C
4h
9oSO
3 -, C
6h
13oSO
3 -, C
8h
17oSO
3 -, (CF
3sO
2)
2n
-, (CF
3sO
2)
3c
-, (C
2f
5sO
2)
2n
-or (C
2f
5sO
2)
3c
-time, the preparation method of described Isosorbide-5-Nitrae-dimethyl-1-alkylpiperazine ionic liquid is as follows:
Be M by equimolar Isosorbide-5-Nitrae-dimethyl-1-alkylpiperazine halogenide and general formula
+y
-metal-salt be dissolved in respectively in water, after stirred at ambient temperature 6 ~ 12h, after adding organic solvent stratification, organic phase, through washing, dry, obtains described Isosorbide-5-Nitrae-dimethyl-1-alkylpiperazine ionic liquid;
Described M
+y
-the M of metal-salt
+be selected from Na
+, K
+or Li
+;
Alkyl in described Isosorbide-5-Nitrae-dimethyl-1-alkylpiperazine halogenide is selected from C
1~ C
10straight chained alkyl.
2. Isosorbide-5-Nitrae-dimethyl-1-alkylpiperazine ionic liquid, as the application in GC stationary phase, is characterized in that, described Isosorbide-5-Nitrae-dimethyl-1-alkylpiperazine ionic liquid has following chemical structure of general formula:
Wherein, R is C
1~ C
10straight chained alkyl;
Negatively charged ion Y
-for Cl
-, Br
-, I
-, C
4f
9sO
3 -, C
4h
9oSO
3 -, C
6h
13oSO
3 -, C
8h
17oSO
3 -, (CF
3sO
2)
2n
-, (CF
3sO
2)
3c
-, (C
2f
5sO
2)
2n
-or (C
2f
5sO
2)
3c
-.
3. Isosorbide-5-Nitrae according to claim 2-dimethyl-1-alkylpiperazine ionic liquid, as the application in GC stationary phase, is characterized in that, the Y in described Isosorbide-5-Nitrae-dimethyl-1-alkylpiperazine ionic liquid
-for C
4f
9sO
3 -, (CF
3sO
2)
2n
-, (CF
3sO
2)
3c
-, (C
2f
5sO
2)
2n
-or (C
2f
5sO
2)
3c
-.
4. Isosorbide-5-Nitrae according to claim 3-dimethyl-1-alkylpiperazine ionic liquid, as the application in GC stationary phase, is characterized in that, the Y-in described Isosorbide-5-Nitrae-dimethyl-1-alkylpiperazine ionic liquid is (CF
3sO
2)
2n
-or (C
2f
5sO
2)
2n
-.
5. the application of Isosorbide-5-Nitrae-dimethyl-1-alkylpiperazine ionic liquid in sulfur dioxide gas absorbs, it is characterized in that, described Isosorbide-5-Nitrae-dimethyl-1-alkylpiperazine ionic liquid has following chemical structure of general formula:
Wherein, R is C
1~ C
10straight chained alkyl;
Negatively charged ion Y
-for Cl
-, Br
-, I
-, C
4f
9sO
3 -, C
4h
9oSO
3 -, C
6h
13oSO
3 -, C
8h
17oSO
3 -, (CF
3sO
2)
2n
-, (CF
3sO
2)
3c
-, (C
2f
5sO
2)
2n
-or (C
2f
5sO
2)
3c
-.
6. the application of Isosorbide-5-Nitrae according to claim 5-dimethyl-1-alkylpiperazine ionic liquid in sulfur dioxide gas absorbs, is characterized in that, the Y in described Isosorbide-5-Nitrae-dimethyl-1-alkylpiperazine ionic liquid
-for C
4h
9oSO
3 -, C
6h
13oSO
3 -, C
8h
17oSO
3 -, (CF
3sO
2)
2n
-, (CF
3sO
2)
3c
-, (C
2f
5sO
2)
2n
-or (C
2f
5sO
2)
3c
-.
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| CN104174276B (en) * | 2014-08-18 | 2016-06-29 | 南京信息工程大学 | A kind of compound ionic liquid and synthetic method thereof and application |
| US20200299302A1 (en) * | 2017-11-21 | 2020-09-24 | Nitto Denko Corporation | Basic cyclic amino-ammonium ionic liquids compositions and elements including the same |
| CN108069923B (en) * | 2018-01-17 | 2021-07-23 | 浙江蓝德能源科技发展有限公司 | Piperazine composite ionic liquid, preparation method and application thereof in dissolving aramid 1313 |
| CN111097255A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Special use for CO2Absorption separation functional ionic liquid nonaqueous system |
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