CN107828056A - POSS based quaternary ammonium salt class ionic liquids and preparation method thereof - Google Patents
POSS based quaternary ammonium salt class ionic liquids and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of POSS based quaternary ammonium salts class ionic liquid and preparation method thereof, its general structure is：.The present invention synthesizes a series of temperature of initial decomposition ionic liquid more than 200 DEG C, available for electrolyte, improves the security performance and use temperature range of battery by the way that the POSS of heat resistant structure is introduced into cation group by alkylated reaction.Ionic liquid preparation method provided by the invention has process intensification, has a safety feature, and experimental implementation is simple, and the reaction time is short, and product purity is high, and yield is high, the features such as can mass producing.
Description
Technical field
The present invention relates to a kind of POSS based quaternary ammonium salts class ionic liquid and preparation method thereof.
Background technology
Ionic liquid refers to what is be composed entirely of ions, the salt being in a liquid state at less than 100 DEG C, typically by organic cation and
Inorganic anion forms.Ionic liquid have wider fluid temperature stability range, stronger solvability, relatively low vapour pressure,
The advantages that higher electric conductivity, stronger catalytic activity, wider electrochemical window.These advantages make it in organic synthesis, electricity
Chemistry, conductive material and high polymer material preparation etc. are widely used.
The usual thermostabilization of current ionic liquid is poor, will start to decompose at 150 DEG C or so, greatly limit ionic liquid
Application under the high temperature conditions.POSS contains the cagelike structure of-Si-O-Si- compositions, has good heat endurance.
The content of the invention
An object of the present invention is in view of the shortcomings of the prior art, there is provided what one kind can use under the high temperature conditions
POSS based quaternary ammonium salt class ionic liquids.
The second object of the present invention is the preparation method for providing the example liquid.
POSS cage modle rigid structure has good heat endurance, by the cation that POSS is incorporated into ionic liquid
On group, final a kind of ionic liquid that can be used at relatively high temperatures of synthesis.
To reach above-mentioned reaction purpose, reaction mechanism that the present invention uses for：
According to above-mentioned reaction mechanism, the present invention adopts the following technical scheme that：
A kind of POSS based quaternary ammonium salts ionic liquid, it is characterised in that the ionic liquid has following general structure：
Wherein, Y-For：
A kind of method for preparing above-mentioned POSS based quaternary ammonium salt class ionic liquids, it is characterised in that the specific steps of this method
As follows (wherein )：
A. compound a is pressed：Water soluble carbonate：Iodoethane=1:(3~10):The mixed in molar ratio of (3~10) is dissolved in
In one solvent, back flow reaction 2~5 days；Liquid phase must be clarified by filtering, and removed the first solvent, obtained compound b crude product；To this
The second solvent is added in crude product, liquid phase must be clarified by centrifuging, and the clarification liquid phase is removed into the second solvent, obtains compound b,
Its structural formula is：
The structural formula of described compound a is：
The first described solvent is acetonitrile, tetrahydrochysene furan
Mutter or N or dinethylformamide；The second described solvent is dichloromethane, chloroform or acetone；
B. by compound b obtained by step a：Hexafluorophosphate=1：The mol ratio of (1~4) is by compound b and hexafluorophosphoric acid
Salt is dissolved in the second solvent respectively and the 4th solvent is obtained in two kinds of solution, then two kinds of solution is uniformly mixed, 50~70
8~24h of stirring reaction at DEG C；Crude product c is filtered to obtain, adds the dissolving of the second solvent, liquid phase must be clarified by centrifuging, and will clarify liquid phase
The second solvent is removed, obtains compound c, i.e., seven poly- POSS tetraalkyls hexafluorophosphates, compound c structural formula is：The 4th described solvent is deionized water；
Or step b is replaced with：By compound b obtained by step a and tetrafluoroborate according to 1：Mole score of (1~3)
It is not dissolved in the 3rd solvent and the 4th solvent and is configured to solution, then two kinds of solution is mixed, then stirring reaction 6 at 45~65 DEG C
~30h；Crude product is filtered to obtain, the crude product is dissolved in the second solvent, liquid phase must be clarified by centrifuging, then remove the second solvent, be obtained
Compound d, i.e., seven poly- POSS tetraalkyls tetrafluoroborates, its structural formula are：
The 3rd described solvent be methanol or
Ethanol；
Or step b is replaced with：Compound b obtained by step a and double trifluoromethanesulfonimide lithiums are pressed 1：(1~4)
Mol ratio is dissolved in the 3rd solvent and is sufficiently mixed, and 6~25h of condensing reflux is stirred at 40~65 DEG C, and liquid phase must be clarified by filtering,
The 3rd solvent is removed, obtains crude product；The crude product is dissolved in the second solvent, liquid phase must be clarified by centrifuging, then remove the second solvent,
Compound e, i.e., the double trifluoromethanesulfonimide salt of seven poly- POSS tetraalkyls are obtained, its structural formula is：
Above-mentioned water soluble carbonate is potassium carbonate or sodium carbonate；Described hexafluorophosphate is Potassium Hexafluorophosphate or hexafluoro
Sodium phosphate；Described tetrafluoroborate is potassium tetrafluoroborate or sodium tetrafluoroborate.
The present invention a kind of resistant to elevated temperatures ionic liquid at room temperature of POSS based quaternary ammonium salts class, temperature of initial decomposition 200 DEG C with
On.The beneficial effects of the invention are as follows：The present invention synthesizes a series of resistance to height by the way that the POSS of heat resistant structure is introduced into cation group
The ionic liquid of temperature, the POSS-TFSI-IL of gained is especially prepared by the different iso-octyl POSS of aminopropyl seven, shown by TGA tests
The ionic liquid just decomposes at 400 DEG C or so, available for electrolyte, improves the security performance and temperature in use model of battery
Enclose.This kind of ionic liquid purity is high, and stability is good, includes the POSS monomers that structure is clear and definite, organic-dissolvable is good, assigns
Ionic liquid at room temperature resistant to elevated temperatures characteristic, expand the application of ionic liquid.Preparation method provided by the invention, its work
Skill is compact, has a safety feature, and experimental implementation is simple, and the reaction time is short, and product purity is high, and yield is high, can mass produce.
Brief description of the drawings
POSS-TFSI-IL (the compound e that Fig. 1 is prepared using the iso-octyl POSS of aminopropyl seven as raw material1) TGA figure.
Fig. 2, i.e. compound performance parameter table.
Embodiment
Below in conjunction with the accompanying drawings with embodiment, the present invention is described in more detail.With the iso-octyl of aminopropyl seven
POSS is that a series of ionic liquids prepared by raw material mark b respectively1, c1, d1, e1, using the iso-octyl POSS of aminopropyl seven as raw material system
A series of standby ionic liquids mark b respectively2, c2, d2, e2。
The inventive method embodiment 1:Compound b1(POSS-I-IL) preparation
Successively raw material is weighed by following molar ratio:The iso-octyl POSS of aminopropyl seven：Potassium carbonate：Iodoethane=1:5:4；
Then alleged content of starting materials is separately added into acetonitrile to be placed in reaction bulb, condensing reflux is stirred at 85 DEG C 3 days；Filter to obtain clarified solution
Phase, decompression steam acetonitrile, obtain the crude product containing POSS-I-IL；Dichloromethane is added into crude product, centrifuges to obtain clarified solution
Phase, clarified solution is mutually depressurized and steams dichloromethane, obtain product POSS-I-IL, be placed in drying 24h in 60 DEG C of vacuum drying chambers,
Yield 60%.
The inventive method embodiment 2:Compound c1(POSS-PF6- IL) preparation
Successively raw material is weighed by following molar ratio：Compound b1：Potassium Hexafluorophosphate=1：3；Then by compound b1With
Potassium Hexafluorophosphate is dissolved in acetone and deionized water respectively, and two kinds of solution stir, and is then added separately to two kinds of solution
In there-necked flask, mechanical agitation 24h at 70 DEG C；POSS-PF must be contained by filtering6- IL crude product, add chloroform dissolving, centrifugation
Liquid phase must be clarified, clarified solution is mutually depressurized and steams chloroform, obtains product POSS-PF6- IL, it is placed in 60 DEG C of vacuum drying chambers
Middle dry 24h, yield 72%, -23.86 DEG C of fusing point.
The inventive method embodiment 3:Compound d1(POSS-BF4- IL) preparation
Successively raw material is weighed by following molar ratio：Compound b1:Sodium tetrafluoroborate=1：3；Then by compound b1With
Sodium tetrafluoroborate is dissolved in methanol and deionized water respectively, and two kinds of solution stir, and is then added separately to two kinds of solution
In three mouthfuls of reaction bulbs, mechanical agitation 12h at 55 DEG C；POSS-BF must be contained by filtering4- IL crude product, dichloromethane dissolving is added,
Liquid phase must be clarified by centrifuging, and clarified solution is mutually depressurized and steams dichloromethane, obtain product POSS-BF4- IL, it is placed in 60 DEG C of vacuum and does
24h, yield 75%, -18.92 DEG C of fusing point are dried in dry case.
The inventive method embodiment 4:Compound e1(POSS-TFSI-IL) preparation
Successively raw material is weighed by following molar ratio：Compound b1:Double trifluoromethanesulfonimide lithium=1：2；Then
By weighed compound b1, double trifluoromethanesulfonimide lithiums be dissolved in ethanol and be sufficiently mixed, solution is placed in reaction bulb,
Condensing reflux 18h is stirred at 65 DEG C.Liquid phase must be clarified by filtering, and decompression steams ethanol, obtains the crude product containing POSS-TFSI-IL；To
Chloroform is added in crude product, liquid phase must be clarified by centrifuging, and clarified solution is mutually depressurized and steams chloroform, obtain product POSS-
TFSI-IL, it is placed in drying 24h, yield 75%, -21.25 DEG C of fusing point in 60 DEG C of vacuum drying chambers.
The inventive method embodiment 5:Compound b2(POSS-I-IL) preparation
Successively raw material is weighed by following molar ratio:The iso-octyl POSS of aminophenyl seven：Potassium carbonate：Iodoethane 1:3:4；
Then alleged content of starting materials is separately added into tetrahydrofuran to be placed in reaction bulb, condensing reflux is stirred at 75 DEG C 4 days；Filter clear
Clear liquid phase, decompression steam tetrahydrofuran, obtain the crude product containing POSS-I-IL；Chloroform is added into crude product, is centrifuged
Liquid phase is clarified, clarified solution is mutually depressurized and steams chloroform, obtains product POSS-I-IL, is placed in doing in 60 DEG C of vacuum drying chambers
Dry 24h, yield 65%.
The inventive method embodiment 6:Compound e2(POSS-TFSI-IL) preparation
Successively raw material is weighed by following molar ratio：Compound b2:Double trifluoromethanesulfonimide lithium=1：3；Then
By weighed compound b2, double trifluoromethanesulfonimide lithiums be dissolved in methanol and be sufficiently mixed, solution is placed in reaction bulb,
Condensing reflux 16h is stirred at 75 DEG C.Liquid phase must be clarified by filtering, and decompression steams methanol, obtains the crude product containing POSS-TFSI-IL；To
Dichloromethane is added in crude product, liquid phase must be clarified by centrifuging, and clarified solution is mutually depressurized and steams dichloromethane, obtain product POSS-
TFSI-IL, it is placed in drying 24h, yield 73% in 60 DEG C of vacuum drying chambers.
The preferable possible embodiments of the present invention are the foregoing is only, and are not used to the scope of the claims of limitation invention, therefore all fortune
The equivalent structure made of description of the invention and accompanying drawing content changes, and is all contained in the clear and definite protection domain of the present invention.
Claims (3)
1. a kind of POSS based quaternary ammonium salts ionic liquid, it is characterised in that the ionic liquid has following general structure：
Wherein, Y-For：
A kind of 2. method for preparing POSS based quaternary ammonium salts class ionic liquid according to claim 1, it is characterised in that the party
Method comprises the following steps that (wherein)：
A. compound a is pressed：Water soluble carbonate：Iodoethane=1:(3~10):It is molten that the mixed in molar ratio of (3~10) is dissolved in first
In agent, back flow reaction 2~5 days；Liquid phase must be clarified by filtering, and removed the first solvent, obtained compound b crude product；To the thick production
The second solvent is added in thing, liquid phase must be clarified by centrifuging, and the clarification liquid phase is removed into the second solvent, obtains compound b, it is tied
Structure formula is：The structural formula of described compound a is：
The first described solvent is acetonitrile, tetrahydrofuran or N
Or dinethylformamide；The second described solvent is dichloromethane, chloroform or acetone；
B. by compound b obtained by step a：Hexafluorophosphate=1：The mol ratio of (1~4) is by compound b and hexafluorophosphoric acid salinity
The second solvent is not dissolved in and the 4th solvent is obtained in two kinds of solution, then two kinds of solution are uniformly mixed, at 50~70 DEG C
8~24h of stirring reaction；Crude product c is filtered to obtain, adds the dissolving of the second solvent, liquid phase must be clarified by centrifuging, and clarification liquid phase is removed
Second solvent, obtains compound c, i.e., seven poly- POSS tetraalkyls hexafluorophosphates, and compound c structural formula is：The 4th described solvent is deionized water；
Or step b is replaced with：By compound b obtained by step a and tetrafluoroborate according to 1：The mol ratio difference of (1~3) is molten
It is configured to solution in the 3rd solvent and the 4th solvent, then two kinds of solution is mixed, then stirring reaction 6 at 45~65 DEG C~
30h；Crude product is filtered to obtain, the crude product is dissolved in the second solvent, liquid phase must be clarified by centrifuging, then remove the second solvent, must be changed
Compound d, i.e., seven poly- POSS tetraalkyls tetrafluoroborates, its structural formula are：
The 3rd described solvent is methanol or ethanol；
Or step b is replaced with：Compound b obtained by step a and double trifluoromethanesulfonimide lithiums are pressed 1：Mole of (1~4)
Than being dissolved in the 3rd solvent and being sufficiently mixed, 6~25h of condensing reflux is stirred at 40~65 DEG C, liquid phase must be clarified by filtering, and be removed
3rd solvent, obtains crude product；The crude product is dissolved in the second solvent, liquid phase must be clarified by centrifuging, then remove the second solvent, must be changed
Compound e, i.e., the double trifluoromethanesulfonimide salt of seven poly- POSS tetraalkyls, its structural formula are：
。
3. preparation method according to claim 2, it is characterised in that described water soluble carbonate is potassium carbonate or carbonic acid
Sodium；Described hexafluorophosphate is Potassium Hexafluorophosphate or sodium hexafluoro phosphate；Described tetrafluoroborate is potassium tetrafluoroborate or four
Sodium fluoborate.
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Cited By (2)
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| CN109400883A (en) * | 2018-11-29 | 2019-03-01 | 中国科学院兰州化学物理研究所 | A kind of anti-space radiation POSS base position ionic liquid and its preparation method and application |
| CN109553637A (en) * | 2018-11-29 | 2019-04-02 | 中国科学院兰州化学物理研究所 | A kind of anti-space radiation POSS base ionic liquid and its preparation method and application |
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| CN109400883A (en) * | 2018-11-29 | 2019-03-01 | 中国科学院兰州化学物理研究所 | A kind of anti-space radiation POSS base position ionic liquid and its preparation method and application |
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| CN109553637B (en) * | 2018-11-29 | 2021-02-23 | 中国科学院兰州化学物理研究所 | Space irradiation resistant POSS-based ionic liquid and preparation method and application thereof |
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