CN102167683B - Bivalent cation magnetic ionic liquids and preparation method thereof - Google Patents

Bivalent cation magnetic ionic liquids and preparation method thereof Download PDF

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CN102167683B
CN102167683B CN 201110044356 CN201110044356A CN102167683B CN 102167683 B CN102167683 B CN 102167683B CN 201110044356 CN201110044356 CN 201110044356 CN 201110044356 A CN201110044356 A CN 201110044356A CN 102167683 B CN102167683 B CN 102167683B
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张锁江
李小华
杨富明
周清
吕兴梅
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Institute of Process Engineering of CAS
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Abstract

The invention relates to bivalent cation magnetic ionic liquids and a preparation method thereof, and belongs to the technical fields of novel chemical materials and preparation. N-alkyl imidazole, 1,m-dibromoalkane, 1,m-dicholoroalkane, ferric trichloride, lanthanide metal oxide, potassium rhodanide and aqueous solution of perchloric acid are taken as raw materials to be prepared into the bivalent cation magnetic ionic liquids with different anion structures; and compared with the conventional magnetic ionic liquid, the magnetic ionic liquids have high magnetism, magnetic controllability and higher thermal stability. The invention realizes magnetic designability of the magnetic ionic liquids for the first time, and promotes the application of the magnetic ionic liquids in the fields such as aviation, medicines, biology and the like.

Description

Bivalent cation magnetic ionic liquids and preparation method thereof
Technical field:
The present invention relates to a kind of ionic liquid and preparation method thereof, especially a kind of have divalent cation and contain Fe or contain the preparation method of magnetic ionic liquids and such ionic liquid of Dy anion structure, the magnetic ionic liquids of the type is different from conventional magnetic ionic liquids, have the magnetic adjustability, belong to novel magnetic material and preparing technical field thereof.
Background technology:
Ionic liquid at room temperature is by organic cation and inorganic or organic anion consists of, be the salt of liquid state at room temperature or near room temperature temperature.Because it has the textural property designability, the ionic liquid of increasing functionalization is by a large amount of developing.
Wherein, magnetic ionic liquids is the ionic liquid of the magnetic functionalization of a kind of tool, except the special property with ionic liquid, it produces certain response in magnetic field to external world, and the existence of metal ion makes it have special optics and catalytic performance.2004, Satoshi Hayashi and Hiro-o Hamaguchi found [Bmim] FeCl first 4Ionic liquid has magnetic, and has proposed first the concept of magnetic ionic liquids.But due to shortcomings such as its magnetic are weak, structure is more single, magnetic is uncontrollable, the application and development of magnetic ionic liquids is limited by very large.Subsequently, in order to solve this difficult problem, a large amount of magnetic ionic liquids are produced out.2006, Yoshida etc. prepared the iron content class magnetic ionic liquids of different structure: [C by the carbochain length of change glyoxaline cation and the halogen in the iron content negatively charged ion 2Mim] FeCl 4, [C 6Mim] FeCl 4, [C 6Mim] FeCl 4, [C 2Mim] FeBr 4, [C 6Mim] FeBr 4, [C 8Mim] FeBr 4Deng.2007, Del Sesto etc. prepared quaternary phosphonium salt magnetic ionic liquids.2008, Bert mallick etc. prepared the novel ferromagnetic ionic liquid [C that has 6Mim] 5-x[Dy (SCN) 8-x(H 2O) x], find that it has stronger response in magnetic field to external world, its effective magnetic moment is 2 times of iron content class magnetic ionic liquids.
Bivalent cation magnetic ionic liquids belongs to a kind of of magnetic ionic liquids, and such magnetic ionic liquids has the divalent cation structure, belongs to reported first, and its preparation method is also that the present invention mentions first.Magnetic ionic liquids of the present invention has overcome the shortcoming that conventional magnetic ionic liquids magnetic can not design, by changing the length that connects the carbochain between two imidazole rings or pyridine ring in positively charged ion, the magnetic of bivalent cation magnetic ionic liquids can change a lot thereupon, thereby, realize its magnetic controllability.
Summary of the invention:
Technical problem to be solved by this invention is: bivalent cation magnetic ionic liquids and preparation method thereof.The shortcomings such as existing magnetic ionic liquids exists that structure is single, magnetic is weak and the magnetic adjustability is relatively poor, the present invention has designed a kind of functional magnetic ionic liquid with divalent cation structure, by changing in divalent cation the length of carbochain between two imidazole rings or pyridine ring, the magnetic of magnetic ionic liquids will change a lot, thereby realize the magnetic controllability of magnetic ionic liquids.In addition, the invention provides the preparation method of such magnetic ionic liquids.
Technical scheme of the present invention is:
The invention provides a class bivalent cation magnetic ionic liquids, its structural formula is as follows: positively charged ion is divalence, and structure is:
Figure BDA0000047609100000021
Or Wherein, n=1～5, m=1～10; Negatively charged ion is Ln (SCN) 7 4-Or FeCl 4 -, wherein Ln=La, Nd, Eu, Gd, Dy, Er; Magnetic ionic liquids structure after combination is as follows:
Figure BDA0000047609100000023
The negatively charged ion Ln (SCN) that contains provided by the invention 7 4-The preparation method of bivalent cation magnetic ionic liquids be: (1) lanthanide metal oxide (La 2O 3, Nd 2O 3, Eu 2O, Gd 2O 3, Dy 2O 3, Er 2O 3) mix with the high chloro acid solution, stirring reaction under room temperature, drying dewaters, and obtains corresponding lanthanide series metal perchlorate hydrate (La (ClO 4) 36H 2O, Nd (ClO 4) 36H 2O, Eu (ClO 4) 36H 2O, Gd (ClO 4) 36H 2O, Dy (ClO 4) 36H 2O, Er (ClO 4) 36H 2O); (2) take alkyl imidazole or pyridine as raw material, make the divalent cation bromine salt of corresponding different alkyl chain lengths with 50～80 ℃ of stirring reactions of 1, m-, two bromoalkane; It is acetone that divalent cation bromine salt and potassium sulfocyanate carry out the ion exchange reaction solvent, after reaction 24～36h, filters, steam the acetone solvent in filtrate, add methylene dichloride, centrifugal after freezing 12h, get upper strata liquid vacuum-drying, products therefrom is divalent cation thiocyanate ion liquid.(3) Ln (ClO 4) 36H 2O and KSCN mol ratio are mixed in stirring at room reaction 3h in appropriate ethanolic soln at 1: 3, filter, the divalent cation thiocyanate ion liquid that adds 2 times of molar weights to filtrate, stirring at room reaction 24h, separating-purifying namely gets corresponding bivalent cation magnetic ionic liquids.
The negatively charged ion FeCl that contains provided by the invention 4 -The preparation method of bivalent cation magnetic ionic liquids be:
(1) take alkyl imidazole or pyridine as raw material, dropwise drip 1, m-, two enparas, react under 50～80 ℃ of condition of heating and stirring, reaction 36～48h uses washing with acetone 2～3 times while hot, to remove the complete raw material of unreacted, until washing, solid is white, then revolve to steam and remove acetone solvent; The ionic liquid that will contain trace solvent is put into vacuum drying oven in 70 ℃ of dry 24h.Finally obtaining white solid is the divalent cation villaumite.(2) to being dissolved with FeCl 36H 2The acetone soln of O adds the divalent cation villaumite, stirring at normal temperature 6～15h, stopped reaction; Reaction product is revolved steaming, and the most of acetone in deionizing liquid and a small amount of water get yellow powder; The yellow powder thing is washed 2 times with anhydrous diethyl ether, and the raw material that unreacted is complete is removed fully; Then revolve the most of ether that steams in deionizing liquid; The ionic liquid that will contain micro-ether is put into vacuum drying oven in 70 ℃ of dry 12h.Finally obtain divalent cation titanium tetrachloride salt.
The invention has the beneficial effects as follows:
Bivalent cation magnetic ionic liquids provided by the invention and preparation thereof compared with prior art have following unusual effect:
(1) the present invention is to provide a kind of novel ionic liquid, developed the new variety of ionic liquid.
(2) bivalent cation magnetic ionic liquids has overcome the uncontrollable shortcoming of conventional magnetic ionic liquids magnetic, by changing in positively charged ion the length of the carbochain between two imidazole rings or pyridine ring, can prepare the magnetic ionic liquids with different magnetic sizes.
(3) compare with conventional magnetic ionic liquids, the divalent cation structure of such magnetic ionic liquids has improved its thermostability and chemical stability greatly.
Therefore, the present invention has solved the shortcomings such as the less and magnetic of existing magnetic ionic liquids magnetic is uncontrollable to a certain extent, realized the designability of magnetic ionic liquids magnetic, to apply the very large promoter action of magnetic ionic liquids at special dimension such as space flight, biology, medicine etc.
Embodiment
Further narrate the present invention below in conjunction with example.Specific examples does not limit claim of the present invention.
Embodiment 1:
Figure BDA0000047609100000041
Synthetic and characterize:
(1) Dysprosium trioxide 8g (0.0211mol) being dissolved in slowly 20g concentration is in 70% high chloro acid solution, and stirring at room reaction 12h revolves to steam and dewaters, and vacuum-drying 48h namely gets Dy (ClO 4) 36H 2O。
(2) take glycol dibromide 10g (0.0532mol) and 13.1011g Methylimidazole (0.1596mol), be placed in the single port flask, under vigorous stirring, temperature is controlled at 70 ℃, after reaction 24h, has a large amount of white powders to generate, after subcooling, filter, filter cake with 3 * 20ml washing with acetone after, vacuum-drying 24h, namely get the white powder product, [C 2(mim) 2] Br 2With 10g (0.0286mol) [C 2(mim) 2] Br 2Ionic liquid and 11.1042g (0.1143mol) KSCN is placed in the single port flask that 100ml is housed, 80 ℃ of heated and stirred backflow 24h, react complete after, filter, steam the acetone solvent in filtrate, add methylene dichloride, be placed in after the standing 12h of refrigerator centrifugal, get upper strata liquid vacuum-drying, namely get the sorrel thick liquid, be [C 2(mim) 2] [SCN] 2Ionic liquid.
(3) take 1.1747g (2.0650mmol) Dy (ClO 4) 36H 2O and 0.6021g (6.1951mmol) KSCN is dissolved in 20ml ethanol, and stirring at room reaction 5h filters, and will 1.2736g (4.1302mmol) [C be housed filtrate adding 2(mim) 2] [SCN] 2The 20ml ethanolic soln in, stirring at room reaction 24h revolves steaming, removes alcohol solvent, adds methylene dichloride, is placed in after the standing 12h of refrigerator centrifugally, gets upper strata liquid vacuum-drying, namely gets dark red colloid product [C 2(mim) 2] 2[Dy (SCN) 7].
(4) [C 2(mim) 2] 2[Dy (SCN) 7] the Infrared Characterization result: 3104,2064,1633,1574,1448,1167,1086,960,834,745,619,477cm -1Its susceptibility is 29.5 * 10 -6Emu g -1
Embodiment 2:
Synthetic and characterize:
(1) Dysprosium trioxide 8g (0.0211mol) being dissolved in slowly 20g concentration is in 70% high chloro acid solution, and stirring at room reaction 12h revolves to steam and dewaters, and vacuum-drying 48h namely gets Dy (ClO 4) 36H 2O。
(2) take Isosorbide-5-Nitrae-ethylene dibromide 15g (0.0695mol) and 17.1113g Methylimidazole (0.2085mol), be placed in the single port flask, under vigorous stirring, temperature is controlled at 70 ℃, after reaction 24h, has a large amount of white powders to generate, after subcooling, filter, filter cake with 3 * 20ml washing with acetone after, vacuum-drying 24h, namely get the white powder product, [C 4(mim) 2] Br 2With 10g (0.0263mol) [C 4(mim) 2] Br 2Ionic liquid and 10.2292g (0.1052mol) KSCN is placed in the single port flask that 100ml is housed, 80 ℃ of heated and stirred backflow 24h, react complete after, filter, steam the acetone solvent in filtrate, add methylene dichloride, be placed in after the standing 12h of refrigerator centrifugal, get upper strata liquid vacuum-drying, namely get the sorrel thick liquid, be [C 4(mim) 2] [SCN] 2Ionic liquid.
(3) take 0.5689g (1.0000mmol) Dy (ClO 4) 36H 2O and 0.2915g (2.9998mmol) KSCN is dissolved in 20ml ethanol, and stirring at room reaction 5h filters, and will 0.6731g (2.0000mmol) [C be housed filtrate adding 4(mim) 2] [SCN] 2The 20ml ethanolic soln in, stirring at room reaction 24h revolves steaming, removes alcohol solvent, adds methylene dichloride, is placed in after the standing 12h of refrigerator centrifugally, gets upper strata liquid vacuum-drying, namely gets dark red colloid product [C 4(mim) 2] 2[Dy (SCN) 7].
(4) [C 4(mim) 2] 2[Dy (SCN) 7] the Infrared Characterization result: 3140,3093,2953,2057,2044,1637,1618,1560,1465,1443,1420,1339,1161,1103,849,757,739,665,624,484cm -1Its susceptibility is 45.5 * 10 -6Emu g -1
Embodiment 3:
Figure BDA0000047609100000052
Synthetic and characterize:
(1) Dysprosium trioxide 8g (0.0211mol) being dissolved in slowly 20g concentration is in 70% high chloro acid solution, and stirring at room reaction 12h revolves to steam and dewaters, and vacuum-drying 48h namely gets Dy (ClO 4) 36H 2O。
(2) take 1,6-ethylene dibromide 10g (0.0410mol) and 10.0980g Methylimidazole (0.1230mol), be placed in the single port flask, under vigorous stirring, temperature is controlled at 70 ℃, after reaction 24h, has a large amount of white powders to generate, after subcooling, filter, filter cake with 3 * 20ml washing with acetone after, vacuum-drying 24h, namely get the white powder product, [C 6(mim) 2] Br 2With 10g (0.0245mol) [C 6(mim) 2] Br 2Ionic liquid and 9.5236g (0.0980mol) KSCN is placed in the single port flask that 100ml is housed, 80 ℃ of heated and stirred backflow 24h, react complete after, filter, steam the acetone solvent in filtrate, add methylene dichloride, be placed in after the standing 12h of refrigerator centrifugal, get upper strata liquid vacuum-drying, namely get the sorrel thick liquid, be [C 6(mim) 2] [SCN] 2Ionic liquid.
(3) take 0.5689g (1.0000mmol) Dy (ClO 4) 36H 2O and 0.2915g (3.0000mmol) KSCN is dissolved in 20ml ethanol, and stirring at room reaction 5h filters, and will 0.7291g (2.0000mmol) [C be housed filtrate adding 6(mim) 2] [SCN] 2The 20ml ethanolic soln in, stirring at room reaction 24h revolves steaming, removes alcohol solvent, adds methylene dichloride, is placed in after the standing 12h of refrigerator centrifugally, gets upper strata liquid vacuum-drying, namely gets dark red colloid product [C 6(mim) 2] 2[Dy (SCN) 7].
(4) [C 6(mim) 2] 2[Dy (SCN) 7] the Infrared Characterization result: 3144,2936,2858,2057,1564,1462,1165,1088,828,737,654,620,481cm -1Its susceptibility is 41.4 * 10 -6Emu g -1
Embodiment 4:
Figure BDA0000047609100000061
Synthetic and characterize:
(1) add the N-Methylimidazole 24.6g (0.3mol) of greatly excessive new distillation in the there-necked flask that reflux is housed of 100ml, dropwise drip 1 of new distillation, 2-ethylene dichloride 19.8g (0.2mol) (rate of addition is as far as possible slow), react under 70 ℃ of condition of heating and stirring, reaction beginning mixture becomes muddy gradually, until product becomes light yellow solid fully, react approximately 48h, use while hot washing with acetone 3 times, to remove the complete raw material of unreacted, until washing, solid is white, then use the Rotary Evaporators underpressure distillation, most of acetone in deionizing liquid, the ionic liquid that will contain trace solvent is put into vacuum drying oven in 70 ℃ of dry 24h.Finally obtain white solid 1,1 '-dimethyl-3,3 '-ethylenebis imidazoles chlorion liquid, i.e. [C 2(MIm) 2] Cl 2
(2) will be dissolved with the FeCl of 20.54g (0.076mol) 36H 2The 40ml acetone soln of O is poured in the round-bottomed flask of 100ml, then adds the dried [C of 10g (0.038mol) 2(MIm) 2] Cl 2, stirring at normal temperature 12h is to [C 2(MIm) 2] Cl 2The pressed powder completely dissolve, stopped reaction; With reaction product Rotary Evaporators underpressure distillation, the most of acetone in deionizing liquid and a small amount of water get yellow powder; The yellow powder thing is washed 2 times with anhydrous diethyl ether, and the raw material that unreacted is complete is removed fully; Then use the Rotary Evaporators underpressure distillation, the most of ether in deionizing liquid; The ionic liquid that will contain micro-ether is put into vacuum drying oven in 70 ℃ of dry 12h.Finally obtain yellow powder 1,1 '-dimethyl-3,3 '-ethylenebis imidazoles titanium tetrachloride ionic liquid, i.e. [C 2(MIm) 2] [FeCl 4] 2
(3) [C 2(MIm) 2] [FeCl 4] 2The Infrared Characterization result: 3441,3142,3110,3094,1600,1574,1557,1456,1166,932,744,634,620cm -1Its susceptibility is 44.6 * 10 -6Emu g -1

Claims (5)

1. bivalent cation magnetic ionic liquids, is characterized in that, (1) positively charged ion is divalence, and structure is:
Figure FDA00003508665900011
Wherein, n=1～5, m=1～10; (2) negatively charged ion is Ln (SCN) 7 4-Or FeCl 4 -, wherein Ln=La, Nd, Eu, Gd, Dy, Er; Magnetic ionic liquids structure after combination is as follows:
2. the preparation method of bivalent cation magnetic ionic liquids claimed in claim 1, contain Ln (SCN) 7 4-The concrete synthetic route of ionic liquid as follows:
Figure FDA00003508665900013
Figure FDA00003508665900021
Figure FDA00003508665900022
Figure FDA00003508665900023
Contain FeCl 4 -The concrete synthetic route of ionic liquid as follows:
Figure FDA00003508665900024
3. method according to claim 2, is characterized in that, contains Ln (SCN) 7 4-The concrete synthesis step of ionic liquid be: (1) lanthanide metal oxide mixes with the high chloro acid solution, stirring reaction under room temperature, drying dewaters, and obtains corresponding lanthanide series metal perchlorate hydrate; (2) take alkyl imidazole or pyridine as raw material, make the divalent cation bromine salt of corresponding different alkyl chain lengths with 50～80 ℃ of stirring reactions of 1, m-, two bromoalkane; It is acetone that divalent cation bromine salt and potassium sulfocyanate carry out the ion exchange reaction solvent, after reaction 24～36h, filters, steam the acetone solvent in filtrate, add methylene dichloride, centrifugal after freezing 12h, get upper strata liquid vacuum-drying, products therefrom is divalent cation thiocyanate ion liquid; (3) Ln (ClO 4) 36H 2O and KSCN mol ratio 1:3 are mixed in stirring at room reaction 3h in appropriate ethanolic soln, filter, the divalent cation thiocyanate ion liquid that adds 2 times of molar weights to filtrate, stirring at room reaction 24h, separating-purifying namely gets corresponding bivalent cation magnetic ionic liquids.
4. method according to claim 3, is characterized in that, the described Ln (SCN) that contains 7 4-The separating and purifying method of bivalent cation magnetic ionic liquids be: when the magnetic ionic liquids that generates is insoluble to alcohol solvent, filter, filter cake is with washing with alcohol 3 times, and drying namely gets bivalent cation magnetic ionic liquids; When the magnetic ionic liquids that generates is dissolved in ethanol, revolve to steam and remove ethanol, raffinate adds methylene dichloride, and stand at low temperature is centrifugal, and except the sub-cloud residual impurity, upper strata liquid revolves steaming, and drying namely gets magnetic ionic liquids.
5. method according to claim 2, is characterized in that, the described FeCl that contains 4 -The concrete synthesis step of ionic liquid be: (1) is take alkyl imidazole or pyridine as raw material, dropwise drip 1, m-two enparas, react under 50～80 ℃ of condition of heating and stirring, reaction 36～48h uses washing with acetone 2～3 times, while hot to remove the complete raw material of unreacted, be white until solid is washed, then revolve to steam and remove acetone solvent; The ionic liquid that will contain trace solvent is put into vacuum drying oven in 70 ℃ of dry 24h; Finally obtaining white solid is the divalent cation villaumite; (2) to being dissolved with FeCl 36H 2The acetone soln of O adds the divalent cation villaumite, stirring at normal temperature 6～15h, stopped reaction; Reaction product is revolved steaming, and the most of acetone in deionizing liquid and a small amount of water get yellow powder; The yellow powder thing is washed 2 times with anhydrous diethyl ether, and the raw material that unreacted is complete is removed fully; Then revolve the most of ether that steams in deionizing liquid; The ionic liquid that will contain micro-ether is put into vacuum drying oven in 70 ℃ of dry 12h; Finally obtain divalent cation titanium tetrachloride salt.
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