CN103833676B - Morpholine class ionic liquid and its preparation method and application - Google Patents

Morpholine class ionic liquid and its preparation method and application Download PDF

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CN103833676B
CN103833676B CN201210486682.2A CN201210486682A CN103833676B CN 103833676 B CN103833676 B CN 103833676B CN 201210486682 A CN201210486682 A CN 201210486682A CN 103833676 B CN103833676 B CN 103833676B
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morpholine
ionic liquid
organic solvent
class ionic
alkyl
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CN103833676A (en
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周明杰
刘大喜
袁新生
王要兵
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/13—Energy storage using capacitors

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Abstract

The present invention relates to a kind of morpholine class ionic liquid, its chemical structural formula is as follows: wherein, R to be carbonatoms be 2 ~ 6 alkyl, Y -for (CF 3sO 2) 2n -or (FSO 2) 2n -this morpholine class ionic liquid room temperature or close to the condition of room temperature under be composed entirely of ions, specific conductivity is high, fusing point is low, electrochemical window is wide, non-volatile, non-combustible, Heat stability is good and not nontoxic containing halogen impurities, thus can be applied in the ultracapacitor or field of lithium ion battery that manufacture height ratio capacity.In addition, the invention still further relates to preparation method and the application thereof of this morpholine class ionic liquid.

Description

Morpholine class ionic liquid and its preparation method and application
[technical field]
The present invention relates to a kind of capacitor electrolyte field, particularly relate to a kind of morpholine class ionic liquid and preparation method thereof, also relate to simultaneously a kind of use this morpholine class ionic liquid electrolytic solution and compound method and ultracapacitor.
[background technology]
Ultracapacitor is a kind of novel energy storage component between rechargeable battery and electrical condenser, have that volume is little, capacity is large, charge velocities is fast, have extended cycle life, discharging efficiency is high, operating temperature range is wide, the advantage such as good reliability and contaminant-free maintenance-free, be a kind of novel, efficient, practical energy accumulating device, be thus widely used in the AC-battery power source etc. of military field, device for mobile communication, computer and electromobile.The energy that ultracapacitor stores be proportional to applied voltage square, thus, improve the specific energy that the voltage that applies can increase considerably ultracapacitor.But the ionic liquid adopting two-step approach to prepare inevitably all can introduce halogens, and these halogen impurities ions can cause the stability of ionic liquid to reduce, the shortcoming that fusing point raises and electrochemical window narrows.
[summary of the invention]
Based on this, be necessary morpholine class ionic liquid that a kind of not halogen-containing element is provided and preparation method thereof.
A kind of morpholine class ionic liquid, chemical structural formula is as follows:
Wherein, R to be carbonatoms be 2 ~ 6 alkyl, Y -for (CF 3sO 2) 2n -or (FSO 2) 2n -.
This morpholine class ionic liquid room temperature or close to the condition of room temperature under be composed entirely of ions, specific conductivity is high, fusing point is low, electrochemical window is wide, non-volatile, non-combustible, Heat stability is good and not nontoxic containing halogen impurities, particularly decomposition voltage is high, be difficult under high voltage condition decompose, thus the ultracapacitor or field of lithium ion battery that manufacture height ratio capacity can be applied in.
A preparation method for morpholine class ionic liquid, comprises the steps:
Under inert atmosphere protection, by alkyl morpholine derivative and methylating reagent MY in molar ratio 1:1 ~ 1.2:1 add in organic solvent, the mass ratio of described organic solvent and alkaryl moiety derivative is 0.8:1 ~ 1.4:1, stirring reaction 3 hours ~ 15 hours under temperature is 60 DEG C ~ 80 DEG C conditions, then excessive described alkyl morpholine derivative and described organic solvent is removed, collect colourless liquid, after washing, vacuum-drying obtains morpholine class ionic liquid, wherein, described alkyl morpholine derivative is ethyl morpholine, propylmorpholin, butyl morpholine, amyl group morpholine or hexylmorpholine, described methylating reagent MY is N-methyl-bis-(fluoroform sulphonyl) amine or N-methyl-bis-(fluorine sulphonyl) amine, its chemical structural formula is as follows:
Wherein, R to be carbonatoms be 2 ~ 6 alkyl, Y -for (CF 3sO 2) 2n -or (FSO 2) 2n -.
In a preferred embodiment, described organic solvent is chloroform, methylene dichloride or tetracol phenixin.
In a preferred embodiment, step removes excessive described alkyl morpholine derivative and described organic solvent is specially: remove excessive alkyl morpholine derivative and described organic solvent by the mode of underpressure distillation, the condition of described underpressure distillation is temperature is 120 DEG C ~ 200 DEG C, and pressure is 0.1Pa ~ 5Pa.
In a preferred embodiment, described washing step is specially: by the colourless liquid repetitive scrubbing in the solution of ethyl acetate or methyl tertiary butyl ether collected.
Above-mentioned preparation process adopts the large-scale industrial production that single stage method efficiency is high, pollution-free, be conducive to morpholine class ionic liquid.
Meanwhile, there is a need to provide a kind of use above-mentionedly not easily to decompose, the electrolytic solution of the good ionic liquid of stability and compound method thereof and ultracapacitor.
A kind of electrolytic solution, comprises morpholine class ionic liquid and organic solvent,
Wherein, the structural formula of described morpholine class ionic liquid is as follows:
R to be carbonatoms be 2 ~ 6 alkyl, Y -for (CF 3sO 2) 2n -or (FSO 2) 2n -;
The quality of morpholine class ionic liquid and organic solvent is 1:5 ~ 2:1 than scope.
In a preferred embodiment, described organic solvent is at least one in acetonitrile, NSC 11801, Methyl ethyl carbonate, propylene carbonate, gamma-butyrolactone and ethyl propionate.
A compound method for electrolytic solution, comprises the steps:
Under inert atmosphere protection; get at least one in acetonitrile, NSC 11801, Methyl ethyl carbonate, propylene carbonate, gamma-butyrolactone and ethyl propionate as organic solvent; in described organic solvent, morpholine class ionic liquid is added in the ratio of the mass ratio 1:5 ~ 2:1 of organic solvent and morpholine class ionic liquid; be uniformly mixed; obtain described electrolytic solution; wherein, the structural formula of described morpholine class ionic liquid is as follows:
R to be carbonatoms be 2 ~ 6 alkyl, Y -for (CF 3sO 2) 2n -or (FSO 2) 2n -.
Electrolytic conductivity containing morpholine class ionic liquid is high, fusing point is low, Heat stability is good and the decomposition voltage of not halogen-containing impurity, particularly electrolytic solution is high, can be widely used in the preparation field of ultracapacitor, obtains the ultracapacitor of high-energy-density.Meanwhile, its process for preparation is simple, uses cheaper starting materials to be easy to get, can large-scale industrial production.
A kind of ultracapacitor, the electrolytic solution of described ultracapacitor comprises the ionic liquid with following structure:
R to be carbonatoms be 2 ~ 6 alkyl, Y -for (CF 3sO 2) 2n -or (FSO 2) 2n -.
By test, use the above-mentioned ultracapacitor containing morpholine class ionic liquid to have higher charging/discharging voltage, and under high charge-discharge voltage conditions, electrolytic solution is highly stable.
[accompanying drawing explanation]
The schema of Fig. 1 preparation method of morpholine class ionic liquid prepared by the embodiment of the present invention.
[embodiment]
Mainly in conjunction with specific embodiments morpholine class ionic liquid and its preparation method and application is described in further detail below.
The morpholine class ionic liquid of present embodiment, chemical structural formula is as follows:
Wherein, R to be carbonatoms be 2 ~ 6 alkyl, Y -for (CF 3sO 2) 2n -or (FSO 2) 2n -.
This morpholine class ionic liquid room temperature or close to the condition of room temperature under be composed entirely of ions, specific conductivity is high, fusing point is low, electrochemical window is wide, non-volatile, non-combustible, Heat stability is good and not halogen-containing impurity is nontoxic, particularly decomposition voltage is high, be difficult under high voltage condition decompose, thus the ultracapacitor or field of lithium ion battery that manufacture height ratio capacity can be applied in.
A preparation method for above-mentioned morpholine class ionic liquid, preparation flow is as follows:
Wherein MY is N-methyl-bis-(fluoroform sulphonyl) amine or N-methyl-bis-(fluorine sulphonyl) amine; R to be carbonatoms be 2 ~ 6 alkyl, Y -for (CF 3sO 2) 2n -or (FSO 2) 2n -.
Specifically comprise the steps:
Step S1: under inert atmosphere protection; by alkyl morpholine derivative and methylating reagent MY in molar ratio 1: 1 ~ 1.2:1 add in organic solvent; the mass ratio of described organic solvent and alkaryl moiety derivative is 0.8:1 ~ 1.4:1, stirring reaction 3 hours ~ 15 hours under temperature is 60 DEG C ~ 80 DEG C conditions.
Wherein, alkyl morpholine derivative is ethyl morpholine, propylmorpholin, butyl morpholine, amyl group morpholine or hexylmorpholine.
Wherein, methylating reagent MY is N-methyl-bis-(fluoroform sulphonyl) amine or N-methyl-bis-(fluorine sulphonyl) amine.
Step S2: then remove excessive described alkyl morpholine derivative and described organic solvent, collects colourless liquid.
The morpholine derivative of the described alkyl that concrete removing is excessive and the step of described organic solvent are remove the morpholine derivative of excessive alkyl and described organic solvent by the mode of underpressure distillation, the condition of described underpressure distillation is temperature is 120 DEG C ~ 200 DEG C, and pressure is 0.1Pa ~ 5Pa.
Step S3: after washing, it is as follows that vacuum-drying obtains its chemical structural formula of morpholine class ionic liquid:
Wherein, R to be carbonatoms be 2 ~ 6 alkyl, Y -for (CF 3sO 2) 2n -or (FSO 2) 2n -.
Wherein, the mode of washing is for adopting ethyl acetate or methyl tertiary butyl ether 50ml repetitive scrubbing more than 3 times.
The large-scale industrial production that above-mentioned preparation process efficiency is high, pollution-free, be conducive to morpholine class ionic liquid.
Meanwhile, present invention also offers a kind of use above-mentionedly not easily to decompose, the electrolytic solution of the good ionic liquid of stability and compound method thereof and ultracapacitor.
The electrolytic solution of one embodiment comprises morpholine class ionic liquid and organic solvent,
Wherein, the structural formula of morpholine class ionic liquid is as follows:
R to be carbonatoms be 2 ~ 6 alkyl, Y -for (CF 3sO 2) 2n -or (FSO 2) 2n -;
The quality of morpholine class ionic liquid and organic solvent is 1:5 ~ 2:1 than scope.
Organic solvent is preferably at least one in acetonitrile, NSC 11801, Methyl ethyl carbonate, propylene carbonate, gamma-butyrolactone and ethyl propionate, and the mass ratio 1:5 ~ 2:1 of organic solvent and morpholine class ionic liquid.
The process for preparation of this electrolytic solution, comprises the steps:
Under inert atmosphere protection; get at least one in acetonitrile, NSC 11801, Methyl ethyl carbonate, propylene carbonate, gamma-butyrolactone and ethyl propionate as organic solvent; in described organic solvent, morpholine class ionic liquid is added in the ratio of the mass ratio 1:5 ~ 2:1 of organic solvent and morpholine class ionic liquid; be uniformly mixed; obtain described electrolytic solution; wherein, the structural formula of described morpholine class ionic liquid is as follows:
R to be carbonatoms be 2 ~ 6 alkyl, Y -for (CF 3sO 2) 2n -or (FSO 2) 2n -.
Electrolytic conductivity containing morpholine class ionic liquid is high, fusing point is low, Heat stability is good and not high containing the decomposition voltage of halogen impurities, particularly electrolytic solution, can be widely used in the preparation field of ultracapacitor, obtain the ultracapacitor of high-energy-density.Meanwhile, its process for preparation is simple, uses cheaper starting materials to be easy to get, can large-scale industrial production.
By test, use the above-mentioned ultracapacitor prepared containing morpholine class ionic liquid to have higher charging/discharging voltage, and under high charge-discharge voltage conditions, electrolytic solution is highly stable.
Be below specific embodiment part:
In following examples containing atmosphere of inert gases with nitrogen and argon atmosphere for representative.
Embodiment 1:
In the flask of 500mL, add 101.4g chloroform respectively, (126.7g, 1.1mol) ethyl morpholine, (295g, 1.0mol) N-methyl-bis-(fluoroform sulphonyl) amine, under nitrogen atmosphere, be warming up to 70 DEG C, stirring reaction 10 hours.Leave standstill cooling, it is 150 DEG C in temperature, pressure is carry out underpressure distillation under the condition of 3.0Pa, remove excessive reactant, collect colourless liquid 50ml ethyl acetate repetitive scrubbing three times, be then 80 DEG C in temperature, vacuum tightness is carry out vacuum-drying under 0.01MPa condition, obtain two (fluoroform sulphonyl) inferior amine salt of colourless liquid N-ethyl-N-methylmorpholinium, productive rate 93%.
Its hydrogen modal data is as follows:
1HNMR(CDCl 3,400MHz,ppm):3.84(m,2H),3.73(m,2H),3.62(m,2H),3.38(m,2H),3.32(s,3H),3.29(m,2H),1.26(t,3H).
Under inert atmosphere protection, take out two (fluoroform sulphonyl) inferior amine salt of 10gN-ethyl-N-methylmorpholinium, then add 30g acetonitrile wherein, and be uniformly mixed, thus obtain object ion liquid electrolyte.
Embodiment 2:
In the flask of 500mL, add 129g methylene dichloride respectively, (129.2g, 1.0mol) propylmorpholin, (195g, 1.0mol) N-methyl-bis-(fluorine sulphonyl) amine, under nitrogen atmosphere, be warming up to 60 DEG C, stirring reaction 3 hours.Leave standstill cooling, it is 120 DEG C in temperature, pressure is carry out underpressure distillation under the condition of 0.1Pa, remove excessive reactant, collect colourless liquid 50ml methyl tertiary butyl ether repetitive scrubbing three times, be then 70 DEG C in temperature, vacuum tightness is carry out vacuum-drying under 0.01MPa condition, obtain two (fluorine sulphonyl) inferior amine salt of colourless liquid N-propyl group-N-methylmorpholine, productive rate 91%.
Its hydrogen modal data is as follows:
1HNMR(CDCl 3,400MHz,ppm):3.83(m,2H),3.74(m,2H),3.62(m,2H),3.37(m,2H),3.32(s,3H),3.27(m,2H),1.78(m,2H),0.96(t,3H).
At N 2(or Ar 2) under atmosphere protection, take out two (fluorine sulphonyl) inferior amine salt of 10gN-propyl group-N-methylmorpholine, then add 50g propylene carbonate wherein, and be uniformly mixed, thus obtain object ion liquid electrolyte.
Embodiment 3
In the flask of 500mL, add 189g tetracol phenixin respectively, (171.8g, 1.2mol) butyl morpholine, (195g, 1.0mol) N-methyl-bis-(fluorine sulphonyl) amine, under nitrogen atmosphere, be warming up to 80 DEG C, stirring reaction 15 hours.Leave standstill cooling, it is 200 DEG C in temperature, pressure is carry out underpressure distillation under the condition of 5.0Pa, remove excessive reactant, collect colourless liquid 50ml ethyl acetate repetitive scrubbing three times, be then 90 DEG C in temperature, vacuum tightness is carry out vacuum-drying under 0.01MPa condition, obtain two (fluorine sulphonyl) inferior amine salt of colourless liquid N-butyl-N-methylmorpholine, productive rate 89%.
Its hydrogen modal data is as follows:
1HNMR(CDCl 3,400MHz,ppm):3.82(m,2H),3.74(m,2H),3.63(m,2H),3.37(m,2H),3.32(s,3H),3.26(m,2H),1.75(m,2H),1.34(m,2H),0.97(t,3H).
At N 2(or Ar 2) under atmosphere protection, take out two (fluorine sulphonyl) inferior amine salt of 10gN-butyl-N-methylmorpholine, then add 5g acetonitrile wherein, and be uniformly mixed, thus obtain object ion liquid electrolyte.
Embodiment 4:
In the flask of 500mL, add 198g chloroform respectively, (165.1g, 1.05mol) amyl group morpholine, (295g, 1.0mol) N-methyl-bis-(fluoroform sulphonyl) amine, under nitrogen atmosphere, be warming up to 65 DEG C, stirring reaction 7 hours.Leave standstill cooling, it is 180 DEG C in temperature, pressure is carry out underpressure distillation under the condition of 2.0Pa, remove excessive reactant, collect colourless liquid 50ml methyl tertiary butyl ether repetitive scrubbing three times, be then 100 DEG C in temperature, vacuum tightness is carry out vacuum-drying under 0.01MPa condition, obtain two (fluoroform sulphonyl) inferior amine salt of colourless liquid N-amyl group-N-methylmorpholine, productive rate 85%.
Its hydrogen modal data is as follows:
1HNMR(CDCl 3,400MHz,ppm):3.84(m,2H),3.75(m,2H),3.64(m,2H),3.37(m,2H),3.33(s,3H),3.27(m,2H),1.75(m,2H),1.32(m,4H),0.98(t,3H).
At N 2(or Ar 2) under atmosphere protection, take out two (fluoroform sulphonyl) inferior amine salt of 10gN-amyl group-N-methylmorpholine, then add 10g gamma-butyrolactone wherein, and be uniformly mixed, thus obtain object ion liquid electrolyte.
Embodiment 5:
263.8g tetracol phenixin is added respectively, (188.4g, 1.1mol) hexylmorpholine, (295g in the flask of 500mL, 1.0mol) N-methyl-bis-(fluoroform sulphonyl) amine, under nitrogen atmosphere, be warming up to 75 DEG C, stirring reaction 12 hours.Leave standstill cooling, it is 170 DEG C in temperature, pressure is carry out underpressure distillation under the condition of 0.6Pa, remove excessive reactant, collect colourless liquid 50ml ethyl acetate repetitive scrubbing three times, be then 90 DEG C in temperature, vacuum tightness is carry out vacuum-drying under 0.01MPa condition, obtain two (fluoroform sulphonyl) inferior amine salt of colourless liquid N-hexyl-N-methylmorpholine, productive rate 84%.
Its hydrogen modal data is as follows:
1HNMR(CDCl 3,400MHz,ppm):3.82(m,2H),3.74(m,2H),3.63(m,2H),3.37(m,2H),3.32(s,3H),3.26(m,2H),1.75(m,2H),1.32(m,6H),0.96(t,3H).
At N 2(or Ar 2) under atmosphere protection, take out two (fluoroform sulphonyl) inferior amine salt of 10gN-hexyl-N-methylmorpholine, then add 20g gamma-butyrolactone wherein, and be uniformly mixed, thus obtain object ion liquid electrolyte.
Application Example
Electrolytic solution in application above-described embodiment 1 ~ 5 is assembled into ultracapacitor
(specific surface area is about 1400m to take 9g activated carbon fiber 2/ g), 0.5g acetylene black and 0.4gPVDF, and add 60gNMP, fully stir and make it to become the slurry mixed.Then by its blade coating on the aluminium foil crossed through ethanol purge, under the vacuum of 0.01MPa, 80 DEG C are dried to constant weight, and are pressed into Activated Carbon Fiber Electrodes in 12MPa pressure lower roll, and are cut into electrode disk.In the glove box being full of argon gas, pp barrier film and above-mentioned il electrolyte are placed between two activated carbon electrodes disks, on stamping machine, button electrical condenser is made in sealing.
Utilize charge-discharge test instrument to carry out constant current charge-discharge test to the ultracapacitor assembled in the present embodiment, in the electrochemical window of 0 ~ 3.0V, record ratio capacitance data with the electric current of 0.25A/g as follows:
Embodiment 1 2 3 4 5
Ratio capacitance (F/g) 115 108 95 100 106
As can be seen from the table, the il electrolyte obtained by the embodiment of the present invention is suitable for the electrolytic solution of ultracapacitor, and has good capacitance characteristic in the electrochemical window of 3.0V.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.

Claims (4)

1. a preparation method for morpholine class ionic liquid, is characterized in that, comprises the steps:
Under inert atmosphere protection, by alkyl morpholine derivative and methylating reagent in molar ratio 1:1 ~ 1.2:1 add in organic solvent, the mass ratio of described organic solvent and alkyl morpholine derivative is 0.8:1 ~ 1.4:1, stirring reaction 3 hours ~ 15 hours under temperature is 60 DEG C ~ 80 DEG C conditions, then excessive described alkyl morpholine derivative and described organic solvent is removed, collect colourless liquid, after washing, vacuum-drying obtains morpholine class ionic liquid, wherein, described organic solvent is chloroform, methylene dichloride or tetracol phenixin, described alkyl morpholine derivative is ethyl morpholine, propylmorpholin, butyl morpholine, amyl group morpholine or hexylmorpholine, described methylating reagent is N-methyl-bis-(fluoroform sulphonyl) amine or N-methyl-bis-(fluorine sulphonyl) amine, its chemical structural formula is as follows:
Wherein, R to be carbonatoms be 2 ~ 6 alkyl, Y -for (CF 3sO 2) 2n -or (FSO 2) 2n -.
2. the preparation method of morpholine class ionic liquid as claimed in claim 1, it is characterized in that, step removes excessive described alkyl morpholine derivative and described organic solvent is specially: remove excessive alkyl morpholine derivative and described organic solvent by the mode of underpressure distillation, the condition of described underpressure distillation is temperature is 120 DEG C ~ 200 DEG C, and pressure is 0.1Pa ~ 5Pa.
3. the preparation method of morpholine class ionic liquid as claimed in claim 1, it is characterized in that, described washing step is specially: by the colourless liquid collected repetitive scrubbing in the solution of ethyl acetate or methyl tertiary butyl ether.
4. a compound method for electrolytic solution, is characterized in that, comprises the steps:
Under inert atmosphere protection; get at least one in acetonitrile, NSC 11801, Methyl ethyl carbonate, propylene carbonate, gamma-butyrolactone and ethyl propionate as organic solvent; in described organic solvent, morpholine class ionic liquid is added in the ratio of the mass ratio 1:5 ~ 2:1 of organic solvent and morpholine class ionic liquid; be uniformly mixed; obtain described electrolytic solution; wherein, the structural formula of described morpholine class ionic liquid is as follows:
R to be carbonatoms be 2 ~ 6 alkyl, Y -for (CF 3sO 2) 2n -or (FSO 2) 2n -, described morpholine class ionic liquid adopts to prepare with the following method: under inert atmosphere protection, by alkyl morpholine derivative and methylating reagent in molar ratio 1:1 ~ 1.2:1 add in organic solvent, the mass ratio of described organic solvent and alkyl morpholine derivative is 0.8:1 ~ 1.4:1, stirring reaction 3 hours ~ 15 hours under temperature is 60 DEG C ~ 80 DEG C conditions, then excessive described alkyl morpholine derivative and described organic solvent is removed, collect colourless liquid, after washing, vacuum-drying obtains morpholine class ionic liquid, wherein, described organic solvent is chloroform, methylene dichloride or tetracol phenixin, described alkyl morpholine derivative is ethyl morpholine, propylmorpholin, butyl morpholine, amyl group morpholine or hexylmorpholine, described methylating reagent is N-methyl-bis-(fluoroform sulphonyl) amine or N-methyl-bis-(fluorine sulphonyl) amine.
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