CN102516092A - Dicarboxylic hydrogen salt ionic liquid with asymmetric chemical structure and weak acidity, and preparation method thereof - Google Patents
Dicarboxylic hydrogen salt ionic liquid with asymmetric chemical structure and weak acidity, and preparation method thereof Download PDFInfo
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 84
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 71
- 239000001257 hydrogen Substances 0.000 title claims abstract description 60
- 239000000126 substance Substances 0.000 title claims abstract description 33
- -1 hydrogen salt Chemical class 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 15
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 56
- 150000002500 ions Chemical class 0.000 claims description 39
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 31
- 239000002904 solvent Substances 0.000 claims description 29
- 230000002378 acidificating effect Effects 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 17
- 239000011591 potassium Substances 0.000 claims description 17
- 229910052700 potassium Inorganic materials 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 16
- 238000001291 vacuum drying Methods 0.000 claims description 14
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 11
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 10
- 238000005660 chlorination reaction Methods 0.000 claims description 9
- 239000011976 maleic acid Substances 0.000 claims description 8
- 239000001384 succinic acid Substances 0.000 claims description 8
- DECWYWSYTFTUAV-UHFFFAOYSA-N 1-methyl-2-propylimidazole Chemical class CCCC1=NC=CN1C DECWYWSYTFTUAV-UHFFFAOYSA-N 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 claims description 3
- XBMRWQWMMIYMLY-UHFFFAOYSA-N CN(C)C.C(CCC)N Chemical compound CN(C)C.C(CCC)N XBMRWQWMMIYMLY-UHFFFAOYSA-N 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- MPDDDPYHTMZBMG-UHFFFAOYSA-N butyl(triethyl)azanium Chemical compound CCCC[N+](CC)(CC)CC MPDDDPYHTMZBMG-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- UBPYJORUAYZUOF-UHFFFAOYSA-N hexyl(tripropyl)azanium Chemical compound CCCCCC[N+](CCC)(CCC)CCC UBPYJORUAYZUOF-UHFFFAOYSA-N 0.000 claims description 2
- SDZQEZNDOPDYPP-UHFFFAOYSA-N n,n-dimethylmethanamine;propan-1-amine Chemical compound CCCN.CN(C)C SDZQEZNDOPDYPP-UHFFFAOYSA-N 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims 2
- 239000000047 product Substances 0.000 abstract description 29
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000008018 melting Effects 0.000 abstract description 4
- 238000002844 melting Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 150000001768 cations Chemical class 0.000 abstract 2
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 abstract 1
- 150000001450 anions Chemical class 0.000 abstract 1
- 239000006227 byproduct Substances 0.000 abstract 1
- BDRTVPCFKSUHCJ-UHFFFAOYSA-N molecular hydrogen;potassium Chemical compound [K].[H][H] BDRTVPCFKSUHCJ-UHFFFAOYSA-N 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 description 17
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 12
- 238000012512 characterization method Methods 0.000 description 12
- 238000002390 rotary evaporation Methods 0.000 description 12
- 238000001228 spectrum Methods 0.000 description 12
- HGGLDADJQQPKKC-UHFFFAOYSA-N 2-butyl-1-methylimidazole Chemical class CCCCC1=NC=CN1C HGGLDADJQQPKKC-UHFFFAOYSA-N 0.000 description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- 239000001530 fumaric acid Substances 0.000 description 4
- BMDRYIFEJILWIP-UHFFFAOYSA-M butyl(triethyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CC)(CC)CC BMDRYIFEJILWIP-UHFFFAOYSA-M 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 150000002892 organic cations Chemical class 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 229910016467 AlCl 4 Inorganic materials 0.000 description 1
- SUDSVUMZDDHFHW-UHFFFAOYSA-N C[NH+](C)C.[Cl-].C(CC)[NH3+].[Cl-] Chemical compound C[NH+](C)C.[Cl-].C(CC)[NH3+].[Cl-] SUDSVUMZDDHFHW-UHFFFAOYSA-N 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 231100000987 absorbed dose Toxicity 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011831 acidic ionic liquid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- NXBYTCLDSQEGMC-UHFFFAOYSA-M hexyl(tripropyl)azanium;chloride Chemical compound [Cl-].CCCCCC[N+](CCC)(CCC)CCC NXBYTCLDSQEGMC-UHFFFAOYSA-M 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a dicarboxylic hydrogen salt ionic liquid with an asymmetric chemical structure and a weak acidity. The cation of the ionic liquid is a tetraalkyl quaternary ammonium cation with the asymmetric structure or an N,N-dialkylimidazole cation with the asymmetric structure, and the anion is a dicarboxylic hydrogen radical anion. The ionic liquid of the invention, which has a low viscosity and a low melting point, can truly meet industrial application requirements. According to the invention, chlorinated tetraalkyl quaternary ammonium with the asymmetric structure or chlorinated N,N-dialkylimidazole with the asymmetric structure and potassium hydrogen dicarboxylate are adopted as raw materials, the target ionic liquid is obtained through one-step synthesis by adopting a microwave process, and the ionic liquid which has the advantages of simple preparation process, high product yield and purity, no byproduct, and low synthetic cost is very suitable for the industrialized production. The dicarboxylic hydrogen salt ionic liquid with the asymmetric chemical structure and the weak acidity of the invention can be used to rapidly and efficiently absorb SO2. The invention discloses a preparation method of the ionic liquid.
Description
Technical field
The present invention relates to one type and have asymmetric chemical structure and weakly acidic di-carboxylic acid hydrogen salt ionic liquid and method for making thereof.
Background technology
Ionic liquid is a kind of green solvent or the reaction medium that new development is in recent years got up, and it is made up of organic cation and organic or inorganic negatively charged ion, in the scope of room temperature or room temperature to 100 ℃, is one type of organic melting salt of liquid state.Ionic liquid has many special propertys such as " zero " vp, lower melting point, high thermal stability and high resolution, is described as a new generation's " green solvent ", has application prospect at numerous areas such as chemicals.At present, found to surpass 2000 kinds with the ionic liquid of bibliographical information, according to the difference of organic cation parent, ionic liquid can be divided into four types substantially: imidazole salt, pyridine salt, quaternary ammonium salt, quaternary phosphine salt.Ion liquid negatively charged ion then is mainly AlCl
4 -, BF
4 -, PF
4 -, CH
3COO
-, CF
3COO
-, CF
3SO
3 -, (CF
3SO
2)
2N
-, H
2PO
4 -, HSO
4 -Deng acid ion, also can be Cl in some cases
-, Br
-, I
-, NO
3 -, ClO
4 -Deng inorganic anion.At present, prepare ion liquid method and mainly be divided into two kinds: single stage method and two-step approach.Single stage method employing tertiary amine and halogenated alkane or ester class or organic acid are raw material, direct addition or neutralization reaction in alcoholic solution or alcohol solution, and a step generates object ion liquid.This kind method technology is simple, production efficiency is high, no coupling product generates, ionic liquid purity is high, but its shortcoming is also comparatively obvious, and is less etc. like synthetic ionic liquid kind.The key step of two-step approach is: the first step generates the quaternary ammonium haloid by tertiary amine and halogenated alkane reaction earlier earlier, and second step was replaced into required target negatively charged ion with halide anion in the quaternary ammonium salt, thereby obtained object ion liquid.The advantage of two-step approach is to prepare " functionalization " ionic liquid with special property, and shortcoming is that complicated process of preparation, production cost are high, productive rate is low.
At present, bibliographical information the has been arranged functionalized ion liquid of some carboxyl groups, these carboxylic groups generally all are grafted on the ion liquid cationic structural.Although the ionic liquid that constitutes thus also is weakly acidic; But character such as ion liquid fusing point of this kind and viscosity are not ideal enough on the one hand; Their building-up process is complicated on the other hand, and reactions step is many, and the isolation and purification process also is not easy; Cause ion liquid production cost also high thus, do not have a practicality.People such as H.Ohno (Chem.Commun., 2007,29,3089-3091; Green Chem., 2007,11 (9); 1155-1157) once with the tetrabutyl season phosphine or choline be that positively charged ion has synthesized several kinds of weakly acidic di-carboxylic acid hydrogen salt ionic liquids; But these ionic liquid fusing points are high, and viscosity is also very big, and various physicochemical property indexs are very undesirable; Greatly limited the ion liquid application of this type, this with such ionic liquid in the design of cationic chemical structure is unreasonable that substantial connection arranged.Generally speaking, lower melting point and low viscous slightly acidic functionalized ion liquid still comparatively lack, and the functionalized ion liquid production cost for preparing weakly acidic carboxyl group is still very high, do not break through the large-scale industry rank yet and produce this bottleneck of ionic liquid.
Summary of the invention
The object of the present invention is to provide one type to have asymmetric chemical structure and weakly acidic di-carboxylic acid hydrogen salt ionic liquid and method for making thereof.
Technical scheme of the present invention is following:
One type has asymmetric chemical structure and weakly acidic di-carboxylic acid hydrogen salt ionic liquid; It is a quaternary ammonium di-carboxylic acid hydrogen salt; Its positively charged ion is the tetraalkyl quaternary ammonium cation or the N of unsymmetric structure; N-dialkylimidazolium positively charged ion, negatively charged ion are di-carboxylic acid hydrogen root negatively charged ion, and concrete chemical structural formula is:
In the formula: R
1Be selected from C
1～C
3Straight-chain alkyl, R
2Be selected from C
3～C
6Straight-chain alkyl, R
3Be selected from C
1～C
3The saturated or undersaturated alkylene of straight or branched.
In the above-mentioned ionic liquid, described ionic liquid positively charged ion is preferably positively charged ions such as trimethylammonium butyl ammonium, trimethylammonium propyl ammonium, triethyl butyl ammonium or tripropyl hexyl ammonium, perhaps N, N-methyl-propyl imidazoles or N, positively charged ions such as N-methylbutyl imidazoles.
In the above-mentioned ionic liquid, described di-carboxylic acid root negatively charged ion is preferably the hydrogen root negatively charged ion of propanedioic acid, maleic acid, Succinic Acid or pentanedioic acid etc.
In the above-mentioned ionic liquid, described R
2Be preferably it and compare R
1Many two above carbonatomss, such viscosity of il is 20～1000cP, and preferred viscosity of il is 56～714cP, and physicochemical property have great improvement, can really meet industrial application requirements.
A kind of preparation is described to have asymmetric chemical structure and the ion liquid method of weakly acidic di-carboxylic acid hydrogen salt is: with chlorination tetraalkyl quaternary ammonium or the chlorination N with unsymmetric structure; N-dialkylimidazolium and di-carboxylic acid hydrogen potassium are raw material; Both etc. mole join simultaneously in a small amount of butanols, the butanols consumption is 0.5～3 times of theoretical ionic liquid quality, takes out after 30 seconds in reaction earlier under the microwave of 200～400W to stir; Putting into microwave reaction again takes out after 15 seconds and stirs; One step of back finishes reaction after carrying out 3～5 times continuously, and with the solution filtered while hot, underpressure distillation is filtrated to remove and to reclaim most of solvent butanols; Remaining liq sample vacuum-drying 48h to constant weight, is promptly got and has asymmetric chemical structure and weakly acidic di-carboxylic acid hydrogen salt ionic liquid.The reaction formula of process is:
The present invention is through carrying out the imparity design to the ionic liquid cationic structural; Make it have bigger space free volume; Part has overcome the hydrogen bond action between negatively charged ion, thereby makes the ionic liquid of acquisition have lower fusing point and viscosity, makes this type slightly acidic ionic liquid have more practicality.In addition, chlorination tetraalkyl quaternary ammonium or the chlorination N of the present invention to have unsymmetric structure, N-dialkylimidazolium and di-carboxylic acid hydrogen potassium are raw material, as solvent, under microwave condition, use the synthetic object ion liquid of single stage method with a small amount of butanols.This compound method is simple, product yield and purity height, no coupling product, synthesis cycle are short, and raw material cheaply is easy to get, cost is low, very suitable suitability for industrialized production.
The present invention has asymmetric chemical structure and weakly acidic di-carboxylic acid hydrogen salt ionic liquid can be used for SO
2Fast, efficient absorption.At 40 ℃ of SO with 100kPa
2Divide and depress, ionic liquid of the present invention is to SO
2Absorbed dose can reach 1.5molSO
2More than/mol the salt, even at 40 ℃ of SO with 0.4kPa
2Divide and depress, its absorbed dose also reaches 0.1～0.5molSO
2/ mol salt, and, just can reach absorption equilibrium less than 10min because its viscosity is lower, and many functionalized ion liquids often needed several hours just can reach absorption equilibrium.
Embodiment
Below further specify the present invention through embodiment
Embodiment 1: trimethylammonium butyl quaternary ammonium bimalonate ionic liquid
In the 250mL reaction flask, add trimethylammonium butyl ammonium chloride 15.12g (0.1mol) respectively; Propanedioic acid hydrogen potassium 14.22g (0.1mol) and solvent butanols 15g; Reaction was earlier taken out and is stirred in 30 seconds under the microwave of 240W, put into the microwave reaction again and took out after 15 seconds and stir, and so repeated back one and went on foot 3 times.Reaction finishes the back filtered while hot, and the rotary evaporation of will filtrating to be removing and to reclaim most of solvent butanols, and 70 ℃ of following vacuum-drying 48 hours obtains product trimethylammonium butyl quaternary ammonium bimalonate ionic liquid, product yield 95%, chlorine ion concentration 620ppm.Its chemical structural formula is:
Characterization result: ultimate analysis theoretical value C:54.77%, H:9.65%, N:6.38%, measured value C:54.75%, H:9.61%, N:6.41%.Nucleus magnetic hydrogen spectrum
1H NMR (DCCl
3, 300MHz) δ=2.27 (s, 9H, CH3), 0.96 (t, 3H, CH3), 1.33-1.39 (m, 4H, CH2), 2.36 (m, 2H, CH2), 3.17 (s, 2H, CH2).DSC scanning does not record its fusing point, and viscosity is 56cP in the time of 40 ℃.
Embodiment 2: trimethylammonium butyl quaternary ammonium disuccinate ionic liquid
In the 250mL reaction flask, add trimethylammonium butyl ammonium chloride 15.12g (0.1mol) respectively; Succinic Acid hydrogen potassium 15.62g (0.1mol) and solvent butanols 30g; Reaction was earlier taken out and is stirred in 30 seconds under the microwave of 240W, put into the microwave reaction again and took out after 15 seconds and stir, and so repeated back one and went on foot 5 times.Reaction finishes the back filtered while hot, and the rotary evaporation of will filtrating to be removing and to reclaim most of solvent butanols, and 70 ℃ of following vacuum-drying 48 hours obtains product trimethylammonium butyl quaternary ammonium disuccinate ionic liquid, product yield 96%, chlorine ion concentration 716ppm.Its chemical structural formula is:
Characterization result: ultimate analysis theoretical value C:56.63%, H:9.94%, N:6.00%, measured value C:56.65%, H:9.91%, N:6.01%.Nucleus magnetic hydrogen spectrum
1H NMR (DCCl
3, 300MHz) δ=2.27 (s, 9H, CH3), 0.96 (t, 3H, CH3), 1.33-1.39 (m, 4H, CH2), 2.36 (m, 2H, CH2), 2.50 (s, 4H, CH2).DSC scanning does not record its fusing point, and viscosity is 527cP in the time of 40 ℃.
Embodiment 3: trimethylammonium butyl quaternary ammonium maleic acid hydrogen salt ionic liquid
In the 250mL reaction flask, add trimethylammonium butyl ammonium chloride 15.12g (0.1mol) respectively; Maleic acid hydrogen potassium or FUMARIC ACID TECH GRADE hydrogen potassium 15.42g (0.1mol) and solvent butanols 20g; Reaction was earlier taken out and is stirred in 30 seconds under the microwave of 240W; Put into microwave reaction again and takes out after 15 seconds and stir, so repeat back one and go on foot 4 times.Reaction finishes the back filtered while hot; To filtrate rotary evaporation to remove and to reclaim most of solvent butanols; 70 ℃ of following vacuum-drying 48 hours; Obtain product trimethylammonium butyl quaternary ammonium maleic acid hydrogen salt ionic liquid or trimethylammonium butyl quaternary ammonium FUMARIC ACID TECH GRADE hydrogen salt ionic liquid, product yield 96%, chlorine ion concentration 680ppm.Its chemical structural formula is:
Characterization result: ultimate analysis theoretical value C:57.12%, H:9.15%, N:6.06%, measured value C:57.11%, H:9.14%, N:6.05%.Nucleus magnetic hydrogen spectrum
1H NMR (DCCl
3, 300MHz) δ=2.27 (s, 9H, CH3), 0.96 (t, 3H, CH3), 1.33-1.39 (m, 4H, CH2), 2.36 (m, 2H, CH2), 6.36 (s, 2H, CH).DSC scanning does not record its fusing point, and viscosity is 87cP in the time of 40 ℃.
Embodiment 4: trimethylammonium butyl quaternary ammonium biglutarate ionic liquid
In the 250mL reaction flask, add trimethylammonium butyl ammonium chloride 15.12g (0.1mol) respectively; Pentanedioic acid hydrogen potassium 17.02g (0.1mol) and solvent butanols 15g; Reaction was earlier taken out and is stirred in 30 seconds under the microwave of 240W, put into the microwave reaction again and took out after 15 seconds and stir, and so repeated back one and went on foot 4 times.Reaction finishes the back filtered while hot, and the rotary evaporation of will filtrating to be removing and to reclaim most of solvent butanols, and 70 ℃ of following vacuum-drying 48 hours obtains product trimethylammonium butyl quaternary ammonium biglutarate ionic liquid, product yield 98%, chlorine ion concentration 690ppm.Its chemical structural formula is:
Characterization result: ultimate analysis theoretical value C:58.27%, H:10.19%, N:5.66%, measured value C:58.27%, H:10.17%, N:5.69%.Nucleus magnetic hydrogen spectrum
1H NMR (DCCl
3, 300MHz) δ=2.27 (s, 9H, CH3), 0.96 (t, 3H, CH3), 1.33-1.39 (m, 4H, CH2), 2.36 (m, 2H, CH2), 1.89 (m, 2H, CH2), 2.36 (t, 4H, CH2).DSC scanning does not record its fusing point, and viscosity is 606cP in the time of 40 ℃.
Embodiment 5: trimethylammonium propyl group quaternary ammonium disuccinate ionic liquid
In the 250mL reaction flask, add trimethylammonium propyl ammonium chloride 13.72g (0.1mol) respectively; Succinic Acid hydrogen potassium 15.62g (0.1mol) and solvent butanols 30g; Reaction was earlier taken out and is stirred in 30 seconds under the microwave of 240W, put into the microwave reaction again and took out after 15 seconds and stir, and so repeated back one and went on foot 5 times.Reaction finishes the back filtered while hot, and the rotary evaporation of will filtrating to be removing and to reclaim most of solvent butanols, and 70 ℃ of following vacuum-drying 48 hours obtains product trimethylammonium butyl quaternary ammonium disuccinate ionic liquid, product yield 95%, chlorine ion concentration 612ppm.Its chemical structural formula is:
Characterization result: ultimate analysis theoretical value C:54.77%, H:9.64%, N:6.39%, measured value C:54.75%, H:9.61%, N:6.39%.Nucleus magnetic hydrogen spectrum
1H NMR (DCCl
3, 300MHz) δ=2.27 (s, 9H, CH3), 0.90 (t, 3H, CH3), 1.44 (m, 2H, CH2), 2.36 (t, 2H, CH2), 2.71 (s, 4H, CH2).DSC scanning does not record its fusing point, and viscosity is 408cP in the time of 40 ℃.
Embodiment 6: triethyl butyl quaternary ammonium disuccinate ionic liquid
In the 250mL reaction flask, add triethyl butyl ammonium chloride 19.38g (0.1mol) respectively; Succinic Acid hydrogen potassium 15.62g (0.1mol) and solvent butanols 30g; Reaction was earlier taken out and is stirred in 30 seconds under the microwave of 240W, put into the microwave reaction again and took out after 15 seconds and stir, and so repeated back one and went on foot 5 times.Reaction finishes the back filtered while hot, and the rotary evaporation of will filtrating to be removing and to reclaim most of solvent butanols, and 70 ℃ of following vacuum-drying 48 hours obtains product triethyl butyl quaternary ammonium disuccinate ionic liquid, product yield 96%, chlorine ion concentration 530ppm.Its chemical structural formula is:
Characterization result: ultimate analysis theoretical value C:61.06%, H:10.61%, N:5.08%, measured value C:61.03%, H:10.64%, N:5.09%.Nucleus magnetic hydrogen spectrum
1H NMR (DCCl
3, 300MHz) δ=0.92 (t, 3H, CH3), 1.15 (t, 9H, CH3), 1.24-1.38 (m, 2H, CH2), 1.49-1.62 (m, 2H, CH2), 2.23 (s, 4H, CH2), 3.12 (t, 2H, CH2), 3.20-3.28 (q, 6H, CH2).DSC scanning does not record its fusing point, and viscosity is 481cP in the time of 40 ℃.
Embodiment 7: triethyl butyl quaternary ammonium maleic acid hydrogen salt ionic liquid
In the 250mL reaction flask, add triethyl butyl ammonium chloride 19.38g (0.1mol) respectively; Maleic acid hydrogen potassium or FUMARIC ACID TECH GRADE hydrogen potassium 15.42g (0.1mol) and solvent butanols 20g; Reaction was earlier taken out and is stirred in 30 seconds under the microwave of 240W; Put into microwave reaction again and takes out after 15 seconds and stir, so repeat back one and go on foot 4 times.Reaction finishes the back filtered while hot; To filtrate rotary evaporation to remove and to reclaim most of solvent butanols; 70 ℃ of following vacuum-drying 48 hours; Obtain product triethyl butyl quaternary ammonium maleic acid hydrogen salt ionic liquid or triethyl butyl quaternary ammonium FUMARIC ACID TECH GRADE hydrogen salt ionic liquid, product yield 97%, chlorine ion concentration 725ppm.Its chemical structural formula is:
Or
Characterization result: ultimate analysis theoretical value C:61.51%, H:9.95%, N:5.12%, measured value C:61.49%, H:9.93%, N:5.16%.Nucleus magnetic hydrogen spectrum
1HNMR (DCCl
3, 300MHz) δ=0.91 (t, 3H, CH3), 1.15 (t, 9H, CH3), 1.22-1.37 (m, 2H, CH2), 1.48-1.62 (m, 2H, CH2), 3.12 (t, 2H, CH2), 3.17-3.31 (q, 6H, CH2), 6.06 (s, 2H, CH).DSC scanning does not record its fusing point, and viscosity is 82cP in the time of 40 ℃.
Embodiment 8: triethyl butyl quaternary ammonium biglutarate ionic liquid
In the 250mL reaction flask, add triethyl butyl ammonium chloride 19.38g (0.1mol) respectively; Pentanedioic acid hydrogen potassium 17.02g (0.1mol) and solvent butanols 15g; Reaction was earlier taken out and is stirred in 30 seconds under the microwave of 240W, put into the microwave reaction again and took out after 15 seconds and stir, and so repeated back one and went on foot 4 times.Reaction finishes the back filtered while hot, and the rotary evaporation of will filtrating to be removing and to reclaim most of solvent butanols, and 70 ℃ of following vacuum-drying 48 hours obtains product triethyl butyl quaternary ammonium biglutarate ionic liquid, product yield 98%, chlorine ion concentration 570ppm.Its chemical structural formula is:
Characterization result: ultimate analysis theoretical value C:62.25%, H:10.80%, N:4.84%, measured value C:62.23%, H:10.82%, N:4.82%.Nucleus magnetic hydrogen spectrum
1H NMR (DCCl
3, 300MHz) δ=0.92 (t, 3H, CH3), 1.16 (t, 9H, CH3), 1.22-1.36 (m, 2H, CH2), 1.47-1.62 (m, 2H, CH2), 1.88-1.97 (m, 2H, CH2), 2.36-2.39 (t, 4H, CH2), 3.11 (t, 2H, CH2), 3.17-3.32 (q, CH2).DSC scanning does not record its fusing point, and viscosity is 714cP in the time of 40 ℃.
Embodiment 9: tripropyl hexyl quaternary ammonium disuccinate ionic liquid
In the 250mL reaction flask, add tripropyl hexyl ammonium chloride 26.39g (0.1mol) respectively; Succinic Acid hydrogen potassium 15.62g (0.1mol) and solvent butanols 70g; Reaction was earlier taken out and is stirred in 30 seconds under the microwave of 240W, put into the microwave reaction again and took out after 15 seconds and stir, and so repeated back one and went on foot 5 times.Reaction finishes the back filtered while hot, and the rotary evaporation of will filtrating to be removing and to reclaim most of solvent butanols, and 70 ℃ of following vacuum-drying 48 hours obtains product tripropyl hexyl quaternary ammonium disuccinate ionic liquid, product yield 95%, chlorine ion concentration 596ppm.Its chemical structural formula is:
Characterization result: ultimate analysis theoretical value C:66.04%, H:11.38%, N:4.05%, measured value C:66.06%, H:11.34%, N:4.09%.Nucleus magnetic hydrogen spectrum
1H NMR (DCCl
3, 300MHz) δ=0.88 (t, 3H, CH3), 0.90 (t, 9H, CH3), 1.29 (m, 4H, CH2), 1.31 (m, 2H, CH2), 1.36 (m, 2H, CH2), 1.44 (m, 6H, CH2), 2.36 (t, 8H, CH2), 2.71 (s, 4H, CH2).DSC scanning does not record its fusing point, and viscosity is 603cP in the time of 40 ℃.
Embodiment 10:N, N-methyl-propyl imidazoles disuccinate ionic liquid
In the 250mL reaction flask, add chlorination N respectively; N-methyl-propyl imidazoles 16.06g (0.1mol), Succinic Acid hydrogen potassium 15.62g (0.1mol) and solvent butanols 45g, reaction was earlier taken out and is stirred in 30 seconds under the microwave of 240W; Put into microwave reaction again and takes out after 15 seconds and stir, so repeat back one and go on foot 5 times.Reaction finishes the back filtered while hot, and the rotary evaporation of will filtrating to be removing and to reclaim most of solvent butanols, and 70 ℃ of following vacuum-drying 48 hours obtains product N, N-methyl-propyl imidazoles disuccinate ionic liquid, product yield 97%, chlorine ion concentration 590ppm.Its chemical structural formula is:
Characterization result: ultimate analysis theoretical value C:54.53%, H:7.49%, N:11.57%, measured value C:54.51%, H:7.48%, N:11.54%.Nucleus magnetic hydrogen spectrum
1H NMR (DCCl
3, 300MHz) δ=0.90 (t, 3H, CH3), δ=1.70 (m, 2H, CH2), 3.72 (s, 3H, CH3), 4.04 (m, 2H, CH2), 6.76-7.29 (s, 3H, CH), 2.71 (s, 4H, CH2).DSC scanning does not record its fusing point, and viscosity is 328cP in the time of 40 ℃.
Embodiment 11:N, N-methylbutyl imidazoles disuccinate ionic liquid
In the 250mL reaction flask, add chlorination N respectively; N-methylbutyl imidazoles 1746g (0.1mol), Succinic Acid hydrogen potassium 15.62g (0.1mol) and solvent butanols 45g, reaction was earlier taken out and is stirred in 30 seconds under the microwave of 240W; Put into microwave reaction again and takes out after 15 seconds and stir, so repeat back one and go on foot 5 times.Reaction finishes the back filtered while hot, and the rotary evaporation of will filtrating to be removing and to reclaim most of solvent butanols, and 70 ℃ of following vacuum-drying 48 hours obtains product N, N-methylbutyl imidazoles disuccinate ionic liquid, product yield 96%, chlorine ion concentration 623ppm.Its chemical structural formula is:
Characterization result: ultimate analysis theoretical value C:56.23%, H:7.87%, N:10.93%, measured value C:56.25%, H:7.84%, N:10.94%.Nucleus magnetic hydrogen spectrum
1H NMR (DCCl
3, 300MHz) δ=0.96 (t, 3H, CH3), 3.63 (s, 3H, CH3), 1.33 (m, 2H, CH2), 1.77 (m, 2H, CH2), 3.73 (t, 2H, CH2), 6.76-7.29 (s, 3H, CH), 2.63 (s, 4H, CH2).DSC scanning does not record its fusing point, and viscosity is 243cP in the time of 40 ℃.
Embodiment 12:N, N-methylbutyl imidazoles biglutarate ionic liquid
In the 250mL reaction flask, add chlorination N respectively; N-methylbutyl imidazoles 17.46g (0.1mol), pentanedioic acid hydrogen potassium 17.02g (0.1mol) and solvent butanols 35g, reaction was earlier taken out and is stirred in 30 seconds under the microwave of 240W; Put into microwave reaction again and takes out after 15 seconds and stir, so repeat back one and go on foot 5 times.Reaction finishes the back filtered while hot, and the rotary evaporation of will filtrating to be removing and to reclaim most of solvent butanols, and 70 ℃ of following vacuum-drying 48 hours obtains product N, N-methylbutyl imidazoles biglutarate ionic liquid, product yield 97%, chlorine ion concentration 610ppm.Its chemical structural formula is:
Characterization result: ultimate analysis theoretical value C:57.76%, H:8.20%, N:10.36%, measured value C:57.77%, H:8.21%, N:10.34%.Nucleus magnetic hydrogen spectrum
1H NMR (DCCl
3, 300MHz) δ=0.96 (t, 3H, CH3), 3.63 (s, 3H, CH3), 1.33 (m, 2H, CH2), 1.77 (m, 2H, CH2), 3.73 (t, 2H, CH2), 6.76-7.29 (s, 3H, CH), 1.88-1.97 (m, 2H, CH2), 2.36-2.39 (t, 4H, CH2).DSC scanning does not record its fusing point, and viscosity is 394cP in the time of 40 ℃.
Embodiment 13:
Accurately take by weighing triethyl butyl quaternary ammonium disuccinate ionic liquid 10g (product of embodiment 6) and place cuvette (the cuvette volume is 100mL),, in cuvette, feed SO at 40 ℃
2Absorb, internal pressure tended to balance in 10 minutes, showed that ionic liquid absorbs SO
2Reached balance.Through calculating, at SO
2When dividing potential drop is 0.4kPa, SO
2Absorbed dose and ion liquid mol ratio be 0.49, at SO
2When dividing potential drop is 100kPa, SO
2Absorbed dose and ion liquid mol ratio be 1.76.
Claims (6)
1. one type has asymmetric chemical structure and weakly acidic di-carboxylic acid hydrogen salt ionic liquid; It is characterized in that: ionic liquid is a quaternary ammonium di-carboxylic acid hydrogen salt; Its positively charged ion is the tetraalkyl quaternary ammonium cation or the N of unsymmetric structure; N-dialkylimidazolium positively charged ion, negatively charged ion are di-carboxylic acid hydrogen root negatively charged ion, and chemical structural formula is:
In the formula: R
1Be selected from C
1～C
3Straight-chain alkyl, R
2Be selected from C
3～C
6Straight-chain alkyl, R
3Be selected from C
1～C
3The saturated or undersaturated alkylene of straight or branched.
2. one type according to claim 1 has asymmetric chemical structure and weakly acidic di-carboxylic acid hydrogen salt ionic liquid; It is characterized in that: described ionic liquid positively charged ion is trimethylammonium butyl ammonium, trimethylammonium propyl ammonium, triethyl butyl ammonium or tripropyl hexyl ammonium cation; Perhaps N; N-methyl-propyl imidazoles or N, N-methylbutyl glyoxaline cation.
3. one type according to claim 1 has asymmetric chemical structure and weakly acidic di-carboxylic acid hydrogen salt ionic liquid, it is characterized in that: the hydrogen root negatively charged ion that described di-carboxylic acid root negatively charged ion is propanedioic acid, maleic acid, Succinic Acid or pentanedioic acid.
4. one type according to claim 1 has asymmetric chemical structure and weakly acidic di-carboxylic acid hydrogen salt ionic liquid, it is characterized in that: described R
2For it compares R
1Many two above carbonatomss.
5. one kind prepares that claim 1 is described to have asymmetric chemical structure and an ion liquid method of weakly acidic di-carboxylic acid hydrogen salt; It is characterized in that: with chlorination tetraalkyl quaternary ammonium or the chlorination N with unsymmetric structure, N-dialkylimidazolium and di-carboxylic acid hydrogen potassium are raw material, both etc. mole join in the butanols simultaneously; The butanols consumption is 0.5～3 times of theoretical ionic liquid quality; Takes out after 30 seconds in reaction earlier under the microwave of 200～400W and to stir, put into the microwave reaction again and takes out after 15 seconds and stir, one step of back repeat 3～5 times continuously after end react; With the solution filtered while hot; Underpressure distillation filtrating to be to remove and to reclaim most of solvent butanols, and remaining liq sample vacuum-drying 48h to constant weight, is promptly got and has asymmetric chemical structure and weakly acidic di-carboxylic acid hydrogen salt ionic liquid.
6. according to claim 1 have asymmetric chemical structure and a weakly acidic di-carboxylic acid hydrogen salt ionic liquid, it is characterized in that can be used for SO
2Absorption rapidly and efficiently.
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