CN102531991A - Novel multi-amino functionalized ionic liquid and preparation method thereof - Google Patents

Novel multi-amino functionalized ionic liquid and preparation method thereof Download PDF

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CN102531991A
CN102531991A CN2011104377893A CN201110437789A CN102531991A CN 102531991 A CN102531991 A CN 102531991A CN 2011104377893 A CN2011104377893 A CN 2011104377893A CN 201110437789 A CN201110437789 A CN 201110437789A CN 102531991 A CN102531991 A CN 102531991A
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ionic liquid
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张锁江
张金芝
曾少娟
贾彩
董海峰
张香平
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Institute of Process Engineering of CAS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

The invention relates to novel multi-amino functionalized ionic liquid and a general preparation method thereof, and belongs to the fields of functional materials and preparation. The preparation method comprises the following steps: allowing halogenated aliphatic amine with protective groups to react with organic amine such as imidazole, pyrrole, indole, carbazole, pyrazole, 1,2,4-1-H-triazole, 1-H-tetrazole, purine, piperidine, imidazoline, piperazine, primary aliphatic amine, and secondary aliphatic amine in an aprotic solvent, performing protective group removal of the product to obtain amino functionalized liquid with anions being halogen ions, then performing an anion displacement reaction to displace the halogen anions into other anions; the amino functionalized ionic liquid obtained in the invention is insoluble in non-polar solvents, is simple in separation, and can be used repeatedly; the amino functionalized ionic liquid is applicable to the absorption and separation of acidic gas such as carbon dioxide, sulfur dioxide, hydrogen chloride, hydrogen sulfide, and the like.

Description

One type of novel polyamino functionalized ion liquid and preparation method thereof
Technical field:
The present invention relates generally to polyamino functionalized ion liquid and a kind of general preparation method, the absorption that is mainly used in sour gas such as carbonic acid gas, sulfurous gas, hydrogenchloride, hydrogen sulfide with separate.
Background technology:
Since two thousand; The synthetic interest that begins to cause people of functionalized ion liquid; Introduce functional group through the cationic side chain of dialkylimidazolium, thereby give certain special property of ionic liquid, purposes or function, make it become a kind of " task specificity ionic liquid ".The functionalized ion liquid widespread use with separate, field such as catalysis, acid gas absorption.2002, the Bates reported first contain mono amino functionalized ion liquid absorb CO 2Ability near 0.5 equivalent, other has the two amino functional ionic liquids of report, absorbed dose reaches 0.9 equivalent; Ionic liquid steam forces down simultaneously, is difficult to volatilization, is expected to reduce the energy consumption in the industrial desorption process.Therefore, ionic liquid, particularly amino functional ionic liquid are a kind of potential and good CO 2Absorption agent is expected to substitute alcamines reagent, the CO that be used for setting up capture, separates or transform normal pressure stack gas 2, reduce the carbon emission that causes because of the fossil oil use.And among the present invention, the ion liquid synthetic and applied research that contains two amino on the positively charged ion at least also was not in the news up to now.
Summary of the invention:
The objective of the invention is to obtain the polyamino functionalized ion liquid and establish its preparation method.
The amino functional ionic liquid that the present invention is prepared, its general formula are A +B -, A wherein +Be one of structural formula as follows:
Figure BDA0000124178950000011
Glyoxaline cation pyrroles positively charged ion indoles positively charged ion carbazole positively charged ion pyrazoles positively charged ion
Figure BDA0000124178950000012
1,2,4-1H-triazole positively charged ion 1H-tetrazole positively charged ion purine positively charged ion piperidines positively charged ion tetrahydroglyoxaline positively charged ion
Figure BDA0000124178950000013
Piperazine positively charged ion season dizzy positively charged ion 1. season dizzy positively charged ion 2.
R in the formula 1, R 2, R 3, R 4Be C nH 2n+1, n≤14 wherein;
M 1, M 2, M 3, M 4Be the group shown in the formula (I).
H 2N——R 5—— (I)
Or the group (II).
Figure BDA0000124178950000021
R wherein 5, R 6For being C nH 2n, 1≤n≤14 wherein.
B -Be one of following negatively charged ion: Cl -, Br -, I -, BF 4 -, PF 6 -, SO 4 2-, SO 3 2-, NO 3-, PO 4 3-, ClO 4 -, AlCl 4 -, Al 2Cl 7 -, SCN -, SbF 6 -, AsF 6 -, CH 3COO -, CH 3(CH 2) nCOO -, CF 3 -, CF 3COO -, C 3F 7COO -, CH 3SO 4 -, C 2H 6SO 4 -, C 8H 17SO 4 -, CH 3SO 3 -, CF 3SO 3 -, C 4F 9SO 3 -, CF 3(CF 2) nSO 3 -, (CF 3SO 2) 3C -, (C 2F 5SO 2) 2N -, Tf 2N -(CF 3SO 2) 2N -), CH 3CH (OH) COO -, dodecyl sodium sulfonate root, Phenylsulfonic acid root, tosic acid root, alpha-amino group acid group mainly comprise L-Ala root (Ala -), Xie Ansuan root (Val -), leucine root (Leu -), Isoleucine root (Ile -), proline(Pro) root (Pro -), phenylalanine(Phe) root (Phe -), tryptophane root (Trp -), methionine(Met) root (Met -), glycocoll root (Gly -), Ser (Ser -), Threonine root (Thr -), halfcystine root (Cys -), tyrosine root (Tyr -), l-asparagine root (Asn-), Stimulina root (Gl n -), Methionin root (Lys -), l-arginine root (Arg -), Histidine root (His -), aspartate (Asp-), glutamate (Glu -) etc.
The preparation method of polyamino functionalized ion liquid is following:
1) halo aliphatic amide halate suc as formula (III) and triphenylmethyl chloride be with mol ratio be preferably 2: 1 in 10: 1～1: 10～mix at 1: 2; Comprise methylene dichloride, chloroform, tetracol phenixin, ether, THF, dioxane, benzene, toluene, acetonitrile, DMSO 99.8MIN., N at non-proton organic solvent; React in dinethylformamide or the acetone; Temperature is 0 ℃ and arrives solvent boiling point; After reaction finished, distillation removed and desolvates, and obtained halo aliphatic amide through trityl as protecting group suc as formula (IV) through organic solvent washing;
Imidazoles pyrroles indole carbazole pyrazoles 1,2, the 4-1-H-triazole
1-H-tetrazole purine piperidines tetrahydroglyoxaline piperazine one-level fat is dizzy
Figure BDA0000124178950000024
Secondary fat is dizzy
HX·H 2N-R 5-X (III)
Figure BDA0000124178950000031
R wherein 5, R 6Be C nH 2n+1, 1≤n≤14 wherein, X is halogen Cl, Br, I;
2) sodium hydride and organic amine comprise imidazoles, pyrroles, indoles, carbazole, pyrazoles, 1; 2; 4-1-H-triazole, 1-H-tetrazole, purine, piperidines, tetrahydroglyoxaline, piperazine, one-level aliphatic amide, secondary aliphatic amine etc.; With mol ratio be preferably 2: 1 in 10: 1～1: 10～mix at 0.5: 1, comprise methylene dichloride, chloroform, tetracol phenixin, ether, THF, dioxane, benzene, toluene, acetonitrile, DMSO 99.8MIN., N at non-proton organic solvent, room temperature reaction in dinethylformamide or the acetone; Add again through the halo aliphatic amide of trityl as protecting group with mol ratio be preferably 2: 1 in 10: 1～1: 10～0.5: 1; After reaction finished, distillation removed and desolvates, and obtained amino halogen type amino functional ionic liquid through trityl as protecting group through organic solvent washing;
3) will mix through the halogen type amino functional ionic liquid and the excessive Hydrogen chloride of trityl as protecting group; Comprise methylene dichloride, chloroform, tetracol phenixin, ether, THF, dioxane, benzene, toluene, acetonitrile, DMSO 99.8MIN., N at non-protonic solvent; React in dinethylformamide or the acetone, distillation removes to desolvate and obtains halogen type amino functional ionic liquid through washing then;
4) ionic liquid of preparation gained is through further reacting a) or b when B-is non-halide-ions, 3)) or c) can make the ionic liquid of other anionics, the preparation method is following:
A) the ionic liquid preparation method of tetrafluoroborate, acetate is following:
Under the room temperature, equimolar halogen type amino functional ionic liquid and silver tetrafluoroborate (or Silver monoacetate) is water-soluble, mix and react through mechanical stirring, halide-ions is separated out, and behind the reacting liquid filtering, concentrate drying obtains containing required anion ion liquid;
B) it is following to contain the ionic liquid preparation method of hexafluoro-phosphate radical:
Under the room temperature, equimolar halogen type amino functional ionic liquid and sodium tetrafluoroborate (or Potassium Hexafluorophosphate) is water-soluble, mix through mechanical stirring; Leave standstill, layering; With deionized water cleaning product layer repeatedly,, obtain containing required anion ion liquid to remove halide anion;
C) negatively charged ion is that the amino functional preparation method of ionic liquid of a-amino acid is following:
From halogen type amino functional ionic liquid, obtaining negatively charged ion through anionite-exchange resin is OH -Alkali ionic liquid, obtaining 20 kinds with amino acid generation acid-base neutralisation reaction then is anionic amino functional ionic liquid with a-amino acid.
Embodiment:
The present invention explains with following instance, but the present invention is not limited to following examples, before and after not breaking away from, under the scope of said aim, changes and implements to be included in the technical scope of the present invention.
Embodiment 1
1,3-two (2-(trityl amino) ethyl)-glyoxal ethyline bromine salt synthetic
A) add 2-bromine ethylamine hydrobromide (76.70g in the there-necked flask of 1000mL; 374mmol), (114.83g 412mmol) and methylene dichloride (760mL), stirs trityl chloride; The 100g triethylamine is mixed with the 40mL methylene dichloride, dropwise splash in the there-necked flask through constant pressure funnel; After triethylamine dropwises, at room temperature continue to stir 10 hours; After reaction finishes; Reaction mixture is used deionized water (400mL), 10% phosphoric acid (400mL), deionized water (400mL), saturated nacl aqueous solution (400mL) extracting and separating respectively; Behind anhydrous magnesium sulfate drying; Concentrate the gained organic phase through methanol solvate gradation washing, it is N-trityl-2-bromine ethamine (86.34g, productive rate 63.03%) that suction filtration obtains white solid.
B) add in the 500mL there-necked flask glyoxal ethyline (2.463g, 30mmol), sodium hydride (0.864g, 36mmol) and with the DMF (N, dinethylformamide) that newly steams (150mL); Stirred 15 minutes, and adding N-trityl-2-bromine ethamine (26.373g, 72mmol), back flow reaction; The thin plate detection reaction adds 4mL methyl alcohol, stirring at room 20 minutes after carrying out fully; Concentrate and remove DMF, the gained solid dissolves with the 200mL acetonitrile, and repeatedly washs with the 200mL saturated aqueous common salt; Concentrate acetonitrile layer, the thick product of gained repeatedly washs with 50mL ETHYLE ACETATE, and suction filtration gained solid is used the 50mL washed with dichloromethane; Getting white solid through suction filtration is 1,3-two (2-(trityl is amino) ethyl)-glyoxal ethyline bromine salt (12.69g, productive rate 57.42%).
Embodiment 2
1,3-two (2-amino-ethyl)-glyoxal ethyline bromine salt synthetic
A) add 2-bromine ethylamine hydrobromide (76.70g in the there-necked flask of 1000mL; 374mmol), (114.83g 412mmol) and methylene dichloride (760mL), stirs trityl chloride; The 100g triethylamine is mixed with the 40mL methylene dichloride, dropwise splash in the there-necked flask through constant pressure funnel; After triethylamine dropwises, at room temperature continue to stir 10 hours; After reaction finishes; Reaction mixture is used deionized water (400mL), 10% phosphoric acid (400mL), deionized water (400mL), saturated nacl aqueous solution (400mL) extracting and separating respectively; Behind anhydrous magnesium sulfate drying; Concentrate the gained organic phase through methanol solvate gradation washing, it is N-trityl-2-bromine ethamine (86.34g, productive rate 63.03%) that suction filtration obtains white solid.
B) add in the 500mL there-necked flask glyoxal ethyline (4.926g, 60mmol), sodium hydride (1.728g, 72mmol) with the DMF (N, dinethylformamide) that newly steams (300mL); Stirred 15 minutes, and adding N-trityl-2-bromine ethamine (52.746g, 144mmol); Back flow reaction, thin plate detection reaction add 4mL methyl alcohol after carrying out fully; Stirring at room 20 minutes concentrates and removes DMF, and the gained solid dissolves with the 500mL acetonitrile; And repeatedly wash with the 500mL saturated aqueous common salt, concentrating acetonitrile layer, the thick product of gained repeatedly washs with 90mL ETHYLE ACETATE; It is 1 that suction filtration gets white solid, 3-two (2-(trityl is amino) ethyl)-glyoxal ethyline bromine salt (29.71g, productive rate 56.0%).
C) add 1 in the 250mL there-necked flask, (4.23g 6.326mmol) and methyl alcohol (50mL), is cooled to 0 ℃ to 3-two (2-(trityl is amino) ethyl)-glyoxal ethyline bromine salt; In reaction mixture, add 3NHCl (12mL), stirring at room 24 hours concentrates and removes methyl alcohol, and the gained liquid concentrator is dissolved in the 40mL deionized water, respectively with 40mL ether washing three times; Revolve at last and steam, obtain yellow solid 1,3-two (2-amino-ethyl)-glyoxal ethyline bromine salt (1.35g, productive rate 94.5%) except that after anhydrating.
Embodiment 3
1,3-two (2-amino-ethyl)-glyoxal ethyline acetate synthetic
A) add 2-bromine ethylamine hydrobromide (76.70g in the there-necked flask of 1000mL; 374mmol), (114.83g 412mmol) and methylene dichloride (760mL), stirs trityl chloride; The 100g triethylamine is mixed with the 40mL methylene dichloride, dropwise splash in the there-necked flask through constant pressure funnel; After triethylamine dropwises, at room temperature continue to stir 10 hours; After reaction finishes; Reaction mixture is used deionized water (400mL), 10% phosphoric acid (400mL), deionized water (400mL), saturated nacl aqueous solution (400mL) extracting and separating respectively; Behind anhydrous magnesium sulfate drying; Concentrate the gained organic phase through methanol solvate gradation washing, it is N-trityl-2-bromine ethamine (86.34g, productive rate 63.03%) that suction filtration obtains white solid.
B) add in the 500mL there-necked flask glyoxal ethyline (4.926g, 60mmol), sodium hydride (1.728g, 72mmol) and with the DMF (N, dinethylformamide) that newly steams (300mL); Stirred 15 minutes, and adding N-trityl-2-bromine ethamine (52.746g, 144mmol); Back flow reaction, thin plate detection reaction add 4mL methyl alcohol after carrying out fully; Stirring at room 20 minutes concentrates and removes DMF, and the gained solid dissolves with the 500mL acetonitrile; And repeatedly wash with the 500mL saturated aqueous common salt, concentrating acetonitrile layer, the thick product of gained repeatedly washs with 90mL ETHYLE ACETATE; It is 1 that suction filtration gets white solid, 3-two (2-(trityl is amino) ethyl)-glyoxal ethyline bromine salt (29.71g, productive rate 56.0%).
C) add 1 in the 250mL there-necked flask, (4.23g 6.326mmol) and methyl alcohol (50mL), is cooled to 0 ℃ to 3-two (2-(trityl is amino) ethyl)-glyoxal ethyline bromine salt; In reaction mixture, add 3NHCl (12mL),, stirring at room 24 hours concentrates and removes methyl alcohol, and the gained liquid concentrator is dissolved in the 40mL deionized water, respectively with 40mL ether washing three times; Revolve at last and steam, obtain yellow solid 1,3-two (2-amino-ethyl)-glyoxal ethyline bromine salt (1.35g, productive rate 94.5%) except that after anhydrating.
D) add 1 in the 100mL there-necked flask, and 3-two (2-amino-ethyl)-glyoxal ethyline bromine salt (1g, 3.97mmol) and deionized water (20mL); (0.75g 1.98mmol) is dissolved in the deionized water (20mL), and dropwise splashes into to there-necked flask plumbic acetate (containing three crystal water).Dropwise room temperature reaction 24 hours; After reaction finishes, filter, the refrigerator and cooled of will filtrate is hidden and is spent the night, suction filtration, revolve steam except that desolvate product 1,3-two (2-amino-ethyl)-glyoxal ethyline acetate (0.91g, productive rate 98.9%).
Embodiment 4
1,2,3-three (2-amino-ethyl) imidazoles bromine salt synthetic
A) add 2-bromine ethylamine hydrobromide (76.70g in the there-necked flask of 1000mL; 374mmol), (114.83g 412mmol) and methylene dichloride (760mL), stirs trityl chloride; The 100g triethylamine is mixed with the 40mL methylene dichloride, dropwise splash in the there-necked flask through constant pressure funnel; After triethylamine dropwises, at room temperature continue to stir 10 hours; After reaction finishes; Reaction mixture is used deionized water (400mL), 10% phosphoric acid (400mL), deionized water (400mL), saturated nacl aqueous solution (400mL) extracting and separating respectively; Behind anhydrous magnesium sulfate drying; Concentrate the gained organic phase through methanol solvate gradation washing, it is N-trityl-2-bromine ethamine (86.34g, productive rate 63.03%) that suction filtration obtains white solid.
B) add in the 1000mL there-necked flask imidazoles (4.085g, 60mmol), sodium hydride 5.76g, 240mmol) and with the DMF (N, dinethylformamide) that newly steams (500mL); Stirred 15 minutes, and adding N-trityl-2-bromine ethamine (79.119g, 216mmol), back flow reaction; The thin plate detection reaction adds 4mL methyl alcohol after carrying out fully, and stirring at room 20 minutes concentrates and removes DMF; The gained solid dissolves with the 500mL acetonitrile, and repeatedly washs with the 500mL saturated aqueous common salt, concentrates acetonitrile layer, and the thick product of gained repeatedly washs with 90mL ETHYLE ACETATE; It is 1,2 that suction filtration gets white solid, 3-three (2-(trityl is amino) ethyl) imidazoles bromine salt (30.14g, productive rate 54.11%).
C) add 1,2 in the 250mL there-necked flask, 3-three (2-(trityl is amino) ethyl) imidazoles bromine salt (5.872g, 6.326mmol) and methyl alcohol (75mL is cooled to 0 ℃; In reaction mixture, add 3NHCl (18mL), stirring at room 24 hours concentrates and removes methyl alcohol, and the gained liquid concentrator is dissolved in the 60mL deionized water, respectively with 60mL ether washing three times; Revolve at last and steam, obtain solid 1,2,3-three (2-amino-ethyl) imidazoles bromine salt (1.65g, productive rate 93.8%) except that after anhydrating.

Claims (3)

1. the functionalized ion liquid of polyamino, its general structure is A +B -, A wherein +Be one of structural formula as follows:
Figure FDA0000124178940000011
Glyoxaline cation pyrroles positively charged ion indoles positively charged ion carbazole positively charged ion pyrazoles positively charged ion
1,2,4-1H-triazole positively charged ion 1H-tetrazole positively charged ion purine positively charged ion piperidines positively charged ion tetrahydroglyoxaline positively charged ion
Figure FDA0000124178940000013
Piperazine positively charged ion season dizzy positively charged ion 1. season dizzy positively charged ion 2.
R in the formula 1, R 2, R 3, R 4Be C nH 2n+1, n≤14 wherein;
M 1, M 2, M 3, M 4Be the group shown in the formula (I),
H 2N——R 5—— (I)
Or the group (II),
Figure FDA0000124178940000014
R wherein 5, R 6Be C nH 2n, 1≤n≤14 wherein;
B -Be one of following negatively charged ion: Cl -, Br -, I -, BF 4 -, PF 6 -, SO 4 2-, SO 3 2-, NO 3-, PO 4 3-, ClO 4 -, AlCl 4 -, Al 2Cl 7 -, SCN -, SbF 6 -, AsF 6 -, CH 3COO -, CH 3(CH 2) nCOO -, CF 3 -, CF 3COO -, C 3F 7COO -, CH 3SO 4 -, C 2H 6SO 4 -, C 8H 17SO 4 -, CH 3SO 3 -, CF 3SO 3 -, C 4F 9SO 3 -, CF 3(CF 2) nSO 3 -, (CF 3SO 2) 3C -, (C 2F 5SO 2) 2N -, Tf 2N -(CF 3SO 2) 2N -), CH 3CH (OH) COO -, dodecyl sodium sulfonate root, Phenylsulfonic acid root, tosic acid root, alpha-amino group acid group mainly comprise L-Ala root (Ala -), Xie Ansuan root (Val -), leucine root (Leu -), Isoleucine root (Ile -), proline(Pro) root (Pro -), phenylalanine(Phe) root (Phe -), tryptophane root (Trp -), methionine(Met) root (Met -), glycocoll root (Gly -), Ser (Ser -), Threonine root (Thr -), halfcystine root (Cys -), tyrosine root (Tyr -), l-asparagine root (Asn-), Stimulina root (Gln -), Methionin root (Lys -), l-arginine root (Arg -), Histidine root (His -), aspartate (Asp-), glutamate (Glu -) etc.
2. the preparation method of polyamino functionalized ion liquid according to claim 1 is characterized in that comprising the steps:
I) halo aliphatic amide halate is to mix in 10: 1～1: 10 suc as formula (III) and triphenylmethyl chloride with mol ratio; Comprise methylene dichloride, chloroform, tetracol phenixin, ether, THF, dioxane, benzene, toluene, acetonitrile, DMSO 99.8MIN., N at non-proton organic solvent; React in dinethylformamide or the acetone; Temperature is 0 ℃ and arrives solvent boiling point; After reaction finished, distillation removed and desolvates, and obtained halo aliphatic amide through trityl as protecting group suc as formula (IV) through organic solvent washing;
HX·H 2N-R 5-X (III)
Figure FDA0000124178940000021
R wherein 5, R 6Definition is C as claim 1 nH 2n, 1≤n≤14 wherein, X is halogen Cl, Br, I;
Ii) sodium hydride and organic amine such as imidazoles, pyrroles, indoles, carbazole, pyrazoles, 1; 2,4-1-H-triazole, 1-H-tetrazole, purine, piperidines, tetrahydroglyoxaline, piperazine, one-level aliphatic amide, secondary aliphatic amine etc., structural formula is following; Mixed in 10: 1～1: 10 with mol ratio; Comprise methylene dichloride, chloroform, tetracol phenixin, ether, THF, dioxane, benzene, toluene, acetonitrile, DMSO 99.8MIN., N with non-proton organic solvent, dinethylformamide or acetone are made solvent, room temperature reaction; The halo aliphatic amide that adds again through trityl as protecting group is 10: 1～1: 10 with mol ratio; After reaction finished, distillation removed and desolvates, and obtained amino halogen type amino functional ionic liquid through trityl as protecting group through organic solvent washing;
Figure FDA0000124178940000022
Imidazoles pyrroles indole carbazole pyrazoles 1,2, the 4-1-H-triazole
Figure FDA0000124178940000023
1-H-tetrazole purine piperidines tetrahydroglyoxaline piperazine one-level aliphatic amide
Figure FDA0000124178940000024
Secondary aliphatic amine
Iii) halogen type amino functional ionic liquid and the excessive Hydrogen chloride of amino through trityl as protecting group is mixed; Comprise methylene dichloride, chloroform, tetracol phenixin, ether, THF, dioxane, benzene, toluene, acetonitrile, DMSO 99.8MIN., N at non-protonic solvent; React in dinethylformamide or the acetone, distillation removes to desolvate and obtains halogen type amino functional ionic liquid through washing then;
Iv) in iii) the ionic liquid of preparation gained through further reacting a) or b) or c) can make the ionic liquid of other anionics, the preparation method is following:
A) the ionic liquid preparation method of tetrafluoroborate, acetate is following:
Under the room temperature, equimolar halogen type amino functional ionic liquid and silver tetrafluoroborate (or Silver monoacetate) is water-soluble, mix and react through mechanical stirring, halide-ions is separated out, reacting liquid filtering, concentrated, drying obtains containing required anion ion liquid;
B) it is following to contain the ionic liquid preparation method of hexafluoro-phosphate radical:
Under the room temperature, equimolar halogen type amino functional ionic liquid and sodium tetrafluoroborate (or Potassium Hexafluorophosphate) is water-soluble, mix through mechanical stirring; Leave standstill, layering; With deionized water cleaning product layer repeatedly,, obtain containing required anion ion liquid to remove halide anion;
C) negatively charged ion is that the amino functional preparation method of ionic liquid of alpha-amino group acid group is following:
From halogen type amino functional ionic liquid, obtaining negatively charged ion through anionite-exchange resin is OH -Alkali ionic liquid, obtaining 20 kinds with amino acid generation acid-base neutralisation reaction then is anionic amino functional ionic liquid with the alpha-amino group acid group.
The absorption that is applied to sour gas such as carbonic acid gas, sulfurous gas, hydrogenchloride and hydrogen sulfide of the functionalized ion liquid of polyamino as claimed in claim 1 with separate.
CN2011104377893A 2011-12-23 2011-12-23 Novel multi-amino functionalized ionic liquid and preparation method thereof Pending CN102531991A (en)

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CN103159632A (en) * 2013-02-28 2013-06-19 南京大学 Ionic liquid compound with anion containing double Lewis base functional groups, preparation method thereof and application thereof
CN103521036A (en) * 2013-10-10 2014-01-22 浙江大学 Method employing metal chelating type ionic liquid to capture sulfur dioxide
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