CN107828056B - POSS (polyhedral oligomeric silsesquioxane) based quaternary ammonium salt ionic liquid and preparation method thereof - Google Patents

POSS (polyhedral oligomeric silsesquioxane) based quaternary ammonium salt ionic liquid and preparation method thereof Download PDF

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CN107828056B
CN107828056B CN201711179534.5A CN201711179534A CN107828056B CN 107828056 B CN107828056 B CN 107828056B CN 201711179534 A CN201711179534 A CN 201711179534A CN 107828056 B CN107828056 B CN 107828056B
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CN107828056A (en
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施利毅
付继芳
陆琦
徐玉峰
李濛濛
陈立亚
余文琪
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University of Shanghai for Science and Technology
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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Abstract

The invention discloses POSS-based quaternary ammonium salt ionic liquid and a preparation method thereof, wherein the POSS-based quaternary ammonium salt ionic liquid has a structural general formula as follows:
Figure DDA0001478894770000011
according to the invention, POSS with a heat-resistant structure is introduced into a cationic group through alkylation reaction to synthesize a series of ionic liquids with initial decomposition temperature of more than 200 ℃, and the ionic liquids can be used for electrolytes, and improve the safety performance and the use temperature range of batteries. The preparation method of the ionic liquid provided by the invention has the characteristics of compact process, good safety performance, simple experimental operation, short reaction time, high product purity, high yield, large-scale production and the like.

Description

POSS (polyhedral oligomeric silsesquioxane) based quaternary ammonium salt ionic liquid and preparation method thereof
Technical Field
The invention relates to POSS-based quaternary ammonium salt ionic liquid and a preparation method thereof.
Background
Ionic liquids refer to salts which consist entirely of ions, are liquid at temperatures below 100 ℃, and generally consist of organic cations and inorganic anions. The ionic liquid has the advantages of wide liquid temperature stability range, strong dissolving capacity, low vapor pressure, high conductivity, strong catalytic activity, wide electrochemical window and the like. These advantages make it have wide application in organic synthesis, electrochemistry, conductive material and high molecular material preparation.
The prior ionic liquid has poor thermal stability, and can start to decompose at about 150 ℃, thereby greatly limiting the application of the ionic liquid under the high-temperature condition. POSS contains a cage-type structure consisting of-Si-O-Si-, and has good thermal stability.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a POSS-based quaternary ammonium salt ionic liquid which can be used under high-temperature conditions.
The second object of the present invention is to provide a method for preparing the liquid of this example.
The cage-type rigid structure of POSS has good thermal stability, and POSS is introduced to the cationic group of the ionic liquid to finally synthesize the ionic liquid which can be used at higher temperature.
In order to achieve the purpose of the reaction, the reaction mechanism adopted by the invention is as follows:
Figure BDA0001478894750000021
according to the reaction mechanism, the invention adopts the following technical scheme:
a POSS-based quaternary ammonium salt ionic liquid is characterized by having the following structural general formula:
Figure BDA0001478894750000022
wherein, Y-Comprises the following steps:
Figure BDA0001478894750000023
Figure BDA0001478894750000024
the preparation method of the POSS-based quaternary ammonium salt ionic liquid is characterized by comprising the following specific steps (wherein
Figure BDA0001478894750000025
Figure BDA0001478894750000031
)：
a. According to the formula of compound a: water-soluble carbonate: mixing and dissolving iodoethane (1) (3-10) and (3-10) in a first solvent according to a molar ratio, and performing reflux reaction for 2-5 days; filtering by suction to obtain a clear liquid phase, and removing the first solvent to obtain a crude product of the compound b; adding a second solvent into the crude product, performing centrifugal separation to obtain a clear liquid phase, and removing the second solvent from the clear liquid phase to obtain a compound b, wherein the structural formula of the compound b is as follows:
Figure BDA0001478894750000032
the structural formula of the compound a is as follows:
Figure BDA0001478894750000033
the first solvent is acetonitrile, tetrahydrofuran or N-dimethylformamide; the second solvent is dichloromethane, trichloromethane or acetone;
b. compound b obtained according to step a: hexafluorophosphate salt 1: (1-4) respectively dissolving the compound b and hexafluorophosphate in a second solvent and a fourth solvent according to the molar ratio to obtain two solutions, uniformly stirring and mixing the two solutions, and stirring and reacting for 8-24 hours at 50-70 ℃; and (3) performing suction filtration to obtain a crude product c, adding a second solvent for dissolving, centrifuging to obtain a clear liquid phase, and removing the second solvent from the clear liquid phase to obtain a compound c, namely the hepta-POSS tetraalkyl hexafluorophosphate, wherein the structural formula of the compound c is as follows:
Figure BDA0001478894750000041
the fourth solvent is deionized water;
or replacing the step b with: and c, mixing the compound b obtained in the step a and tetrafluoroborate according to the weight ratio of 1: (1-3) respectively dissolving the two solutions in a third solvent and a fourth solvent according to the molar ratio to prepare solutions, mixing the two solutions, and stirring and reacting for 6-30 hours at 45-65 ℃; and (3) performing suction filtration to obtain a crude product, dissolving the crude product in a second solvent, centrifuging to obtain a clear liquid phase, and removing the second solvent to obtain a compound d, namely hepta-POSS tetraalkyl tetrafluoroborate, wherein the structural formula of the hepta-POSS tetraalkyl tetrafluoroborate is as follows:
Figure BDA0001478894750000042
the third solvent is methanol or ethanol;
or replacing the step b with: b, mixing the compound b obtained in the step a and lithium bis (trifluoromethanesulfonyl) imide according to the weight ratio of 1: dissolving the mixture in the molar ratio of (1-4) in a third solvent, fully mixing, stirring at 40-65 ℃, condensing and refluxing for 6-25 h, performing suction filtration to obtain a clear liquid phase, and removing the third solvent to obtain a crude product; dissolving the crude product in a second solvent, centrifuging to obtain a clear liquid phase, and removing the second solvent to obtain a compound e, namely hepta-POSS tetraalkyl bis (trifluoromethane) sulfonyl imide salt, the structural formula of which is as follows:
Figure BDA0001478894750000051
the water-soluble carbonate is potassium carbonate or sodium carbonate; the hexafluorophosphate is potassium hexafluorophosphate or sodium hexafluorophosphate; the tetrafluoroborate is potassium tetrafluoroborate or sodium tetrafluoroborate.
The POSS-based quaternary ammonium salt high-temperature-resistant room-temperature ionic liquid has the initial decomposition temperature of more than 200 ℃. The invention has the beneficial effects that: according to the invention, POSS with a heat-resistant structure is introduced into a cationic group to synthesize a series of high-temperature-resistant ionic liquids, particularly POSS-TFSI-IL prepared from aminopropyl heptaiso-isooctyl POSS, and TGA tests show that the ionic liquid is decomposed at about 400 ℃, and can be used for electrolytes, and the safety performance and the use temperature range of batteries are improved. The ionic liquid has high purity and good stability, contains POSS monomers with definite structures and good organic solubility, endows the room-temperature ionic liquid with high-temperature resistance, and enlarges the application range of the ionic liquid. The preparation method provided by the invention has the advantages of compact process, good safety performance, simple experimental operation, short reaction time, high product purity and high yield, and can be used for large-scale production.
Drawings
FIG. 1 POSS-TFSI-IL (Compound e) prepared from aminopropyl heptaisooctyl POSS as a starting material1) TGA profile of (a).
FIG. 2 is a table of performance parameters for compounds.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments. Respectively labeling a series of ionic liquids prepared by taking aminopropyl heptaisooctyl POSS as raw material b1，c1，d1，e1Respectively labeling a series of ionic liquids prepared by taking aminopropyl heptaisooctyl POSS as a raw material b2，c2，d2，e2。
Example 1 of the Process of the invention Compound b1Preparation of (POSS-I-IL)
The raw materials are weighed according to the following mol ratio in turn: potassium carbonate: ethyl iodide is 1:5: 4; then adding the weighed raw materials into acetonitrile respectively, placing the mixture into a reaction bottle, stirring at 85 ℃, condensing and refluxing for 3 days; filtering to obtain a clear liquid phase, and distilling out acetonitrile under reduced pressure to obtain a crude product containing POSS-I-IL; and adding dichloromethane into the crude product, centrifuging to obtain a clear liquid phase, decompressing the clear liquid phase, evaporating dichloromethane to obtain a product POSS-I-IL, and placing the product POSS-I-IL in a vacuum drying oven at 60 ℃ for drying for 24h, wherein the yield is 60%.
Method of the invention example 2 Compound c1(POSS-PF6Preparation of-IL)
Weighing the following raw materials in a molar ratio: compound b1: potassium hexafluorophosphate 1: 3; then the compound b1Respectively dissolving potassium hexafluorophosphate and the potassium hexafluorophosphate in acetone and deionized water, uniformly stirring the two solutions, respectively adding the two solutions into a three-necked bottle, and mechanically stirring for 24 hours at 70 ℃; obtaining the product containing POSS-PF by suction filtration6Dissolving the crude product of IL in chloroform, centrifuging to obtain a clear liquid phase, and distilling the clear liquid phase under reduced pressure to obtain the product POSS-PF6IL, dried in a vacuum oven at 60 ℃ for 24h, 72% yield, m.p. -23.86 ℃.
Example 3 of the Process of the invention Compound d1(POSS-BF4Preparation of-IL)
Weighing the following raw materials in a molar ratio: compound b1Sodium tetrafluoroborate 1: 3; then the compound b1And sodium tetrafluoroborateDissolving in methanol and deionized water respectively, stirring the two solutions uniformly, adding the two solutions into a three-mouth reaction bottle respectively, and mechanically stirring at 55 ℃ for 12 hours; obtaining the product containing POSS-BF by suction filtration4Dissolving the crude product of the IL in dichloromethane, centrifuging to obtain a clear liquid phase, and distilling the clear liquid phase under reduced pressure to obtain a product POSS-BF4IL, dried in a vacuum oven at 60 ℃ for 24h, 75% yield, m.p. -18.92 ℃.
Example 4 of the Process according to the invention Compound e1Preparation of (POSS-TFSI-IL)
Weighing the following raw materials in a molar ratio: compound b1Lithium bistrifluoromethanesulfonylimide 1: 2; then weighing the compound b1Lithium bis (trifluoromethanesulfonylimide) was dissolved in ethanol and mixed well, and the solution was placed in a reaction flask and stirred at 65 ℃ under reflux for 18 h. Filtering to obtain a clear liquid phase, and evaporating ethanol under reduced pressure to obtain a crude product containing POSS-TFSI-IL; and adding trichloromethane into the crude product, centrifuging to obtain a clear liquid phase, evaporating the clear liquid phase under reduced pressure to remove the trichloromethane to obtain a product POSS-TFSI-IL, and drying in a vacuum drying oven at 60 ℃ for 24 hours, wherein the yield is 75 percent, and the melting point is-21.25 ℃.
Example 5 of the Process of the invention Compound b2Preparation of (POSS-I-IL)
The raw materials are sequentially weighed according to the following molar ratio: potassium carbonate: ethyl iodide 1:3: 4; then adding the weighed raw materials into tetrahydrofuran respectively, placing the mixture into a reaction bottle, stirring at 75 ℃, condensing and refluxing for 4 days; filtering to obtain a clear liquid phase, and evaporating tetrahydrofuran under reduced pressure to obtain a crude product containing POSS-I-IL; and adding trichloromethane into the crude product, centrifuging to obtain a clear liquid phase, evaporating the clear liquid phase under reduced pressure to obtain a product POSS-I-IL, and drying in a vacuum drying oven at 60 ℃ for 24h with the yield of 65%.
Example 6 method of the invention Compound e2Preparation of (POSS-TFSI-IL)
Weighing the following raw materials in a molar ratio: compound b2Lithium bistrifluoromethanesulfonylimide 1: 3; then weighing the compound b2Lithium bis (trifluoromethanesulfonylimide) dissolved in methanolAnd mixing well, placing the solution in a reaction bottle, stirring at 75 ℃, condensing and refluxing for 16 h. Filtering to obtain a clear liquid phase, and distilling the methanol under reduced pressure to obtain a crude product containing POSS-TFSI-IL; and adding dichloromethane into the crude product, centrifuging to obtain a clear liquid phase, decompressing the clear liquid phase, evaporating dichloromethane to obtain a product POSS-TFSI-IL, and placing the product POSS-TFSI-IL in a vacuum drying oven at 60 ℃ for drying for 24h, wherein the yield is 73%.
The above description is only for the purpose of illustrating preferred embodiments of the present invention and is not intended to limit the scope of the present invention, so that equivalent structural changes made by using the contents of the present specification and the accompanying drawings are included in the scope of the present invention.

Claims (3)

1. A POSS-based quaternary ammonium salt ionic liquid is characterized by having the following structural general formula:
Figure FDA0002495535600000011
wherein, Y-Comprises the following steps:
Figure FDA0002495535600000012
Figure FDA0002495535600000013
2. the method for preparing the POSS-based quaternary ammonium salt ionic liquid according to claim 1, is characterized by comprising the following specific steps:
a. according to the formula of compound a: water-soluble carbonate: mixing and dissolving iodoethane (1) (3-10) and (3-10) in a first solvent according to a molar ratio, and performing reflux reaction for 2-5 days; filtering by suction to obtain a clear liquid phase, and removing the first solvent to obtain a crude product of the compound b; adding a second solvent into the crude product, performing centrifugal separation to obtain a clear liquid phase, and removing the second solvent from the clear liquid phase to obtain a compound b, wherein the structural formula of the compound b is as follows:
Figure FDA0002495535600000014
the structural formula of the compound a is as follows:
Figure FDA0002495535600000021
the first solvent is acetonitrile, tetrahydrofuran or N, N-dimethylformamide; the second solvent is dichloromethane, trichloromethane or acetone;
b. compound b obtained according to step a: hexafluorophosphate salt 1: (1-4) respectively dissolving the compound b and hexafluorophosphate in a second solvent and a fourth solvent according to the molar ratio to obtain two solutions, uniformly stirring and mixing the two solutions, and stirring and reacting for 8-24 hours at 50-70 ℃; and (3) performing suction filtration to obtain a crude product c, adding a second solvent for dissolution, centrifuging to obtain a clear liquid phase, and removing the second solvent from the clear liquid phase to obtain a compound c, namely the hepta-POSS tetraalkyl hexafluorophosphate, wherein the structural formula of the compound c is as follows:
Figure FDA0002495535600000022
the fourth solvent is deionized water;
or replacing the step b with: and c, mixing the compound b obtained in the step a and tetrafluoroborate according to the weight ratio of 1: (1-3) respectively dissolving the two solutions in a third solvent and a fourth solvent according to the molar ratio to prepare solutions, mixing the two solutions, and stirring and reacting for 6-30 hours at 45-65 ℃; and (3) performing suction filtration to obtain a crude product, dissolving the crude product in a second solvent, centrifuging to obtain a clear liquid phase, and removing the second solvent to obtain a compound d, hepta-POSS tetraalkyl tetrafluoroborate, wherein the structural formula of the hepta-POSS tetraalkyl tetrafluoroborate is as follows:
Figure FDA0002495535600000031
the third solvent is methanol or ethanol;
or replacing the step b with: b, mixing the compound b obtained in the step a and lithium bis (trifluoromethanesulfonyl) imide according to the weight ratio of 1: dissolving the mixture in the molar ratio of (1-4) in a third solvent, fully mixing, stirring at 40-65 ℃, condensing and refluxing for 6-25 h, performing suction filtration to obtain a clear liquid phase, and removing the third solvent to obtain a crude product; dissolving the crude product in a second solvent, centrifuging to obtain a clear liquid phase, and removing the second solvent to obtain a compound e, a hepta-POSS tetraalkyl bis (trifluoromethane) sulfonyl imide salt, wherein the structural formula of the hepta-POSS tetraalkyl bis (trifluoromethane) sulfonyl imide salt is as follows:
Figure FDA0002495535600000032
wherein
Figure FDA0002495535600000033
And the compound b, c or e is the POSS-based quaternary ammonium salt ionic liquid.
3. The process according to claim 2, wherein the water-soluble carbonate is potassium carbonate or sodium carbonate; the hexafluorophosphate is potassium hexafluorophosphate or sodium hexafluorophosphate; the tetrafluoroborate is potassium tetrafluoroborate or sodium tetrafluoroborate.
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