CN103159701A - Method for synthesizing functionalized ionic liquid containing ester groups - Google Patents
Method for synthesizing functionalized ionic liquid containing ester groups Download PDFInfo
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- CN103159701A CN103159701A CN2013101110447A CN201310111044A CN103159701A CN 103159701 A CN103159701 A CN 103159701A CN 2013101110447 A CN2013101110447 A CN 2013101110447A CN 201310111044 A CN201310111044 A CN 201310111044A CN 103159701 A CN103159701 A CN 103159701A
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- methyl
- phenylpiperidines
- bromination
- methyl acetate
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Abstract
The invention discloses a method for synthesizing functionalized ionic liquid containing ester groups and relates to methods for synthesizing ionic liquid. The method has the advantages that the problem that imidazole ionic liquid is poor in electrochemical stability is solved on one hand and the problem that piperidine ionic liquid which is more researched currently is high in viscosity and low in conductivity is solved on the other hand. The method comprises the following steps of: (1) preparing a crude product of brominated N-methyl-N-methyl piperidine acetate; (2) purifying the crude product of brominated N-methyl-N-methyl piperidine acetate; and (3) preparing the ionic liquid, namely N-methyl-N-methyl piperidine acetate bis(trifluoromethanesulfonyl)imide. The ionic liquid synthesized by the method has the electrochemical window of 5.5 V, the viscosity of 89 cP and the conductivity of 4.1 mS.cm<-1> at room temperature (25 DEG C), has excellent electrochemical performance and is applied to the fields of metal electrodeposition and lithium-ion batteries.
Description
Technical field
The present invention relates to a kind of synthetic method of ionic liquid.
Background technology
Ionic liquid (Ionic liquid) refers to the complete organic liquid material that is comprised of ion at room temperature and close temperature, also referred to as room temperature melting salt (Room temperature molten salts).The positively charged ion that forms ionic liquid is generally organic alkyl imidazole, alkyl pyridine, quaternary amine etc., and negatively charged ion is generally Cl
-, Br
-, BF
4 -, PF
6 -, CF
3SO
3 -, N (CN)
2 -Deng.Ionic liquid at room temperature is compared with ordinary organic solvents, not only most of inorganicss and organism is had good solubility, and simultaneously it also has wider electrochemical window, good electroconductibility, almost there is no vapour pressure, higher advantages such as thermostability.Therefore, ionic liquid attracts widespread attention just day by day as the green solvent of a new generation.At present, ionic liquid has been widely used in every field such as extracting and separating, organic reaction, electrochemistry, catalyzer.
Study early about the ionic liquid of imidazoles, this class ionic liquid has lower viscosity and higher specific conductivity, be 36.3cP as viscosity under 1-methyl-3-ethyl imidazol(e) two (trimethyl fluoride sulfonyl) imines (EMITFSI) room temperature, specific conductivity is 10mScm
-1So glyoxaline ion liquid is obtaining pay close attention to widely and study aspect metal electrodeposition and lithium-ion battery electrolytes, but its relatively poor electrochemical stability has but greatly limited it in the application in lithium ion battery field.At present wide concerned piperidines ionic liquid is compared with glyoxaline ion liquid, possesses good electrochemical stability, but its viscosity is higher, specific conductivity is on the low side, be 117cP as viscosity under N-methyl-N-propyl group piperidines two (trifluoromethyl sulphur) imines (PP13TFSI) room temperature, specific conductivity is 2.1mScm
-1, this is restricting the application of such ionic liquid too.
Functionalized ion liquid is to realize by introduce functional group on the positively charged ion of ionic liquid or negatively charged ion, as introducing amido, ether, itrile group etc.Introducing functional group can give ionic liquid special performance, make functionalized ion liquid have the characteristic that many conventional ion liquid are not had, for example, can reduce by introducing specific functional groups viscosity, raising electrochemical stability and the electroconductibility etc. of ionic liquid.
Summary of the invention
The present invention provides a kind of synthetic method that contains the ester group functionalized ion liquid in order to solve the problem that the glyoxaline ion liquid electrochemical stability is relatively poor, the viscosity of piperidines ionic liquid is higher, specific conductivity is lower.
a kind of synthetic method that contains the ester group functionalized ion liquid of the present invention is to be undertaken by following steps: the 1-methyl piperidine and the methyl bromoacetate that with mol ratio are one, 1: 1 mix, react 10～30min at 9～25 ℃ of temperature, generate the thick product of bromination N-methyl-N-methyl acetate phenylpiperidines, two, get the thick product of the bromination N-methyl of step 1 preparation-N-methyl acetate phenylpiperidines, add dehydrated alcohol, wherein the bromination N-methyl-thick product of N-methyl acetate phenylpiperidines and the mass volume ratio of dehydrated alcohol are 1g: (1～6) mL, then at room temperature stir 25～50min, remove the liquid phase thing and clean solid formation 10～15 times with dehydrated alcohol, be placed in again 80 ℃ of oven dry 12h of vacuum drying oven, the bromination N-methyl after being purified-N-methyl acetate phenylpiperidines, three, bromination N-methyl after purifying-N-methyl acetate phenylpiperidines and two (trimethyl fluoride sulfonyl) imine lithium is dissolved in deionized water, the mol ratio of the bromination N-methyl after wherein purifying-N-methyl acetate phenylpiperidines and two (trimethyl fluoride sulfonyl) imine lithium is 1: 1, the mol ratio of the bromination N-methyl after purification-N-methyl acetate phenylpiperidines and deionized water is 1: (6～20), then at room temperature stir 11～18h, take off a layer oily liquids, be washed till with Silver Nitrate detection upper water solution with deionized water and generate without muddiness, be placed in again 80 ℃ of oven dry 20～25h of vacuum drying oven, obtain ionic liquid N-methyl-N-methyl acetate phenylpiperidines two (trimethyl fluoride sulfonyl) imines, namely complete the synthetic method that contains the ester group functionalized ion liquid.
The ionic liquid electrochemical window that the present invention synthesizes is that 5.5V, viscosity are that 39cP, room temperature (25 ℃) specific conductivity are 4.1 * 10
-3S/cm
-1, have excellent chemical property, have application prospect aspect metal electrodeposition and lithium ion battery.
Description of drawings
The infrared spectrogram of ionic liquid N-methyl that Fig. 1 prepares for test-N-methyl acetate phenylpiperidines two (trimethyl fluoride sulfonyl) imines;
The hydrogen nuclear magnetic resonance spectrogram of ionic liquid N-methyl that Fig. 2 prepares for test-N-methyl acetate phenylpiperidines two (trimethyl fluoride sulfonyl) imines;
The anodic polarization curves of ionic liquid N-methyl that Fig. 3 prepares for test-N-methyl acetate phenylpiperidines two (trimethyl fluoride sulfonyl) imines;
The cathodic polarization curve of ionic liquid N-methyl that Fig. 4 prepares for test-N-methyl acetate phenylpiperidines two (trimethyl fluoride sulfonyl) imines.
Embodiment:
embodiment one: a kind of synthetic method that contains the ester group functionalized ion liquid of present embodiment is to be undertaken by following steps: the 1-methyl piperidine and the methyl bromoacetate that with mol ratio are one, 1: 1 mix, react 10～30min at 9～25 ℃ of temperature, generate the thick product of bromination N-methyl-N-methyl acetate phenylpiperidines, two, get the thick product of the bromination N-methyl of step 1 preparation-N-methyl acetate phenylpiperidines, add dehydrated alcohol, wherein the bromination N-methyl-thick product of N-methyl acetate phenylpiperidines and the mass volume ratio of dehydrated alcohol are 1g: (1～6) mL, then at room temperature stir 25～50min, remove the liquid phase thing and clean solid formation 10～15 times with dehydrated alcohol, be placed in again 80 ℃ of oven dry 12h of vacuum drying oven, the bromination N-methyl after being purified-N-methyl acetate phenylpiperidines, three, bromination N-methyl after purifying-N-methyl acetate phenylpiperidines and two (trimethyl fluoride sulfonyl) imine lithium is dissolved in deionized water, the mol ratio of the bromination N-methyl after wherein purifying-N-methyl acetate phenylpiperidines and two (trimethyl fluoride sulfonyl) imine lithium is 1: 1, the mol ratio of the bromination N-methyl after purification-N-methyl acetate phenylpiperidines and deionized water is 1: (6～20), then at room temperature stir 11～18h, take off a layer oily liquids, be washed till with Silver Nitrate detection upper water solution with deionized water and generate without muddiness, be placed in again 80 ℃ of oven dry 20～25h of vacuum drying oven, obtain ionic liquid N-methyl-N-methyl acetate phenylpiperidines two (trimethyl fluoride sulfonyl) imines, namely complete the synthetic method that contains the ester group functionalized ion liquid.
The chemical equation of present embodiment step 1 is:
The synthetic ionic liquid electrochemical window of present embodiment is that 5.5V, viscosity are that 89cP, room temperature (25 ℃) specific conductivity are 4.1mScm
-1, have excellent chemical property, have application prospect aspect metal electrodeposition and lithium ion battery.
Embodiment two: what present embodiment was different from embodiment one is: react 20min in step 1 at 10 ℃ of temperature.Other step and parameter are identical with embodiment one.
Embodiment three: what present embodiment was different from embodiment one or two is that bromination N-methyl in the step 2-thick product of N-methyl acetate phenylpiperidines and the mass volume ratio of dehydrated alcohol are 1: 2.Other step and parameter are identical with embodiment one or two.
Embodiment four: what present embodiment was different from one of embodiment one to three is: at room temperature stir 30min in step 2.Other step and parameter are identical with one of embodiment one to three.
Embodiment five: what present embodiment was different from one of embodiment one to four is: clean solid formation 12 times with dehydrated alcohol in step 2.Other step and parameter are identical with one of embodiment one to four.
Embodiment six: what present embodiment was different from one of embodiment one to five is: the mol ratio of the bromination N-methyl after purifying in step 3-N-methyl acetate phenylpiperidines and deionized water is 1: 8.Other step and parameter are identical with one of embodiment one to five.
Embodiment seven: what present embodiment was different from one of embodiment one to six is: at room temperature stir 12h in step 3.Other step and parameter are identical with one of embodiment one to six.
Embodiment eight: what present embodiment was different from one of embodiment one to seven is: be placed in 80 ℃ of oven dry 24h of vacuum drying oven in step 3.Other step and parameter are identical with one of embodiment one to seven.
By following verification experimental verification beneficial effect of the present invention:
test: a kind of synthetic method that contains the ester group functionalized ion liquid of this test is to be undertaken by following steps: the 1-methyl piperidine and the methyl bromoacetate that with mol ratio are one, 1: 1 mix, react 20min at 10 ℃ of temperature, generate the thick product of bromination N-methyl-N-methyl acetate phenylpiperidines, two, get the thick product of the bromination N-methyl of 8g step 1 preparation-N-methyl acetate phenylpiperidines, add the 16ml dehydrated alcohol, then at room temperature stir 30min, remove the liquid phase thing and clean solid formation 12 times with dehydrated alcohol, be placed in again 80 ℃ of oven dry 12h of vacuum drying oven, the bromination N-methyl after being purified-N-methyl acetate phenylpiperidines, three, bromination N-methyl after purifying-N-methyl acetate phenylpiperidines and two (trimethyl fluoride sulfonyl) imine lithium is dissolved in deionized water, the mol ratio of the bromination N-methyl after wherein purifying-N-methyl acetate phenylpiperidines and two (trimethyl fluoride sulfonyl) imine lithium is 1: 1, the mol ratio of the bromination N-methyl after purification-N-methyl acetate phenylpiperidines and deionized water is 1: 8, then at room temperature stir 12h, take off a layer oily liquids, be washed till with Silver Nitrate detection upper water solution with deionized water and generate without muddiness, be placed in again 80 ℃ of oven dry 14h of vacuum drying oven, obtain ionic liquid N-methyl-N-methyl acetate phenylpiperidines two (trimethyl fluoride sulfonyl) imines, namely complete the synthetic method that contains the ester group functionalized ion liquid.
The infrared spectrogram of ionic liquid N-methyl that Fig. 1 prepares for test-N-methyl acetate phenylpiperidines two (trimethyl fluoride sulfonyl) imines contains ester group in product as seen from Figure 1.The hydrogen nuclear magnetic resonance spectrogram of ionic liquid N-methyl that Fig. 2 prepares for test-N-methyl acetate phenylpiperidines two (trimethyl fluoride sulfonyl) imines, 1H NMR: δ (ppm) 5.01-5.30 (t, 4H) wherein, 4.16-4.28 (m, 3H), (3.76-3.87 t, 4H), 3.53-3.65 (m, 2H) 1.89-1.99 (s, 3H), 1.25-1.38 (m, 2H); The anodic polarization curves of ionic liquid N-methyl that Fig. 3 prepares for test-N-methyl acetate phenylpiperidines two (trimethyl fluoride sulfonyl) imines, the negative electrode utmost point polarization curve of ionic liquid N-methyl that Fig. 4 prepares for test-N-methyl acetate phenylpiperidines two (trimethyl fluoride sulfonyl) imines, the anode dissolution electromotive force of ionic liquid is 6.0V as seen from Figure 3, be 0.5V by the negative electrode decomposition voltage that can find out ionic liquid in Fig. 4, therefore, the electrochemical window of ionic liquid is 5.5V.
Hence one can see that, and the ionic liquid of this test preparation has excellent chemical property, has application prospect aspect metal electrodeposition and lithium ion battery.
Claims (8)
1. synthetic method that contains the ester group functionalized ion liquid, the synthetic method that it is characterized in that containing the ester group functionalized ion liquid is to be undertaken by following steps: the 1-methyl piperidine and the methyl bromoacetate that with mol ratio are one, 1: 1 mix, react 10～30min at 9～25 ℃ of temperature, generate the thick product of bromination N-methyl-N-methyl acetate phenylpiperidines, two, get the thick product of the bromination N-methyl of step 1 preparation-N-methyl acetate phenylpiperidines, add dehydrated alcohol, wherein the bromination N-methyl-thick product of N-methyl acetate phenylpiperidines and the mass volume ratio of dehydrated alcohol are 1g: (1～6) mL, then at room temperature stir 25～50min, remove the liquid phase thing and clean solid formation 10～15 times with dehydrated alcohol, be placed in again 80 ℃ of oven dry 12h of vacuum drying oven, the bromination N-methyl after being purified-N-methyl acetate phenylpiperidines, three, bromination N-methyl after purifying-N-methyl acetate phenylpiperidines and two (trimethyl fluoride sulfonyl) imine lithium is dissolved in deionized water, wherein, the mol ratio of the bromination N-methyl after purification-N-methyl acetate phenylpiperidines and two (trimethyl fluoride sulfonyl) imine lithium is 1: 1, the mol ratio of the bromination N-methyl after purification-N-methyl acetate phenylpiperidines and deionized water is 1: (6～20), then at room temperature stir 11～18h, take off a layer oily liquids, be washed till with Silver Nitrate detection upper water solution with deionized water and generate without muddiness, be placed in again 80 ℃ of oven dry 20～25h of vacuum drying oven, obtain ionic liquid N-methyl-N-methyl acetate phenylpiperidines two (trimethyl fluoride sulfonyl) imines, namely complete and contain the synthetic of ester group functionalized ion liquid.
2. a kind of synthetic method that contains the ester group functionalized ion liquid according to claim 1 is characterized in that reacting 20min described in step 1 at 10 ℃ of temperature.
3. a kind of synthetic method that contains the ester group functionalized ion liquid according to claim 1, is characterized in that the bromination N-methyl described in the step 2-thick product of N-methyl acetate phenylpiperidines and the mass volume ratio of dehydrated alcohol are 1: 2.
4. a kind of synthetic method that contains the ester group functionalized ion liquid according to claim 1, is characterized in that the at room temperature stirring 30min described in step 2.
5. a kind of synthetic method that contains the ester group functionalized ion liquid according to claim 1 is characterized in that cleaning solid formation 12 times with dehydrated alcohol described in step 2.
6. a kind of synthetic method that contains the ester group functionalized ion liquid according to claim 1 is characterized in that bromination N-methyl-N-methyl acetate phenylpiperidines after the purification described in step 3 and the mol ratio of deionized water are 1: 8.
7. a kind of synthetic method that contains the ester group functionalized ion liquid according to claim 1, is characterized in that the at room temperature stirring 12h described in step 3.
8. a kind of synthetic method that contains the ester group functionalized ion liquid according to claim 1 is characterized in that being placed in 80 ℃ of oven dry 24h of vacuum drying oven described in step 3.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104393340A (en) * | 2014-10-30 | 2015-03-04 | 哈尔滨工业大学 | Gel polymer electrolyte of ester-group-containing functionalized ionic liquid, preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1640931A (en) * | 2004-01-16 | 2005-07-20 | 中国科学院化学研究所 | Volatileness-free polymer electrolyte composition, its preparation method and use |
| JP2005251510A (en) * | 2004-03-03 | 2005-09-15 | Toshiba Corp | Electrolytic solution and electrochemical device |
| CN1838469A (en) * | 2006-04-20 | 2006-09-27 | 武汉大学 | Lithium-sulphur battery electrolyte and chargeable lithium-sulphur battery thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1640931A (en) * | 2004-01-16 | 2005-07-20 | 中国科学院化学研究所 | Volatileness-free polymer electrolyte composition, its preparation method and use |
| JP2005251510A (en) * | 2004-03-03 | 2005-09-15 | Toshiba Corp | Electrolytic solution and electrochemical device |
| CN1838469A (en) * | 2006-04-20 | 2006-09-27 | 武汉大学 | Lithium-sulphur battery electrolyte and chargeable lithium-sulphur battery thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104393340A (en) * | 2014-10-30 | 2015-03-04 | 哈尔滨工业大学 | Gel polymer electrolyte of ester-group-containing functionalized ionic liquid, preparation method and application thereof |
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Application publication date: 20130619 |