CN106008586A - POSS-containing high temperature-resistant solid ionic liquid and preparation method thereof - Google Patents
POSS-containing high temperature-resistant solid ionic liquid and preparation method thereof Download PDFInfo
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000007787 solid Substances 0.000 title claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- -1 aminopropyl Chemical group 0.000 claims abstract description 19
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229940014800 succinic anhydride Drugs 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 89
- 239000002904 solvent Substances 0.000 claims description 64
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 239000000047 product Substances 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 24
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 20
- 239000012043 crude product Substances 0.000 claims description 19
- 238000001704 evaporation Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 239000000376 reactant Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000006228 supernatant Substances 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 230000006837 decompression Effects 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical class CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims description 4
- WGVGZVWOOMIJRK-UHFFFAOYSA-N 1-hexyl-3-methyl-2h-imidazole Chemical class CCCCCCN1CN(C)C=C1 WGVGZVWOOMIJRK-UHFFFAOYSA-N 0.000 claims description 4
- JFYZBXKLRPWSGV-UHFFFAOYSA-N 1-methyl-3-propyl-2h-imidazole Chemical class CCCN1CN(C)C=C1 JFYZBXKLRPWSGV-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- HDXFBBSZRMZTFF-UHFFFAOYSA-N 1-methyl-3-pentyl-2h-imidazole Chemical class CCCCCN1CN(C)C=C1 HDXFBBSZRMZTFF-UHFFFAOYSA-N 0.000 claims description 3
- QLWOUBCORTYSPP-UHFFFAOYSA-N 1h-imidazol-1-ium;hydroxide Chemical compound O.C1=CNC=N1 QLWOUBCORTYSPP-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000011829 room temperature ionic liquid solvent Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 238000002844 melting Methods 0.000 abstract description 6
- 230000008018 melting Effects 0.000 abstract description 6
- 239000007784 solid electrolyte Substances 0.000 abstract description 6
- 230000035484 reaction time Effects 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 2
- YEFAQKYPIMQVAV-UHFFFAOYSA-N CCCN1C=CN(C)C1.O Chemical compound CCCN1C=CN(C)C1.O YEFAQKYPIMQVAV-UHFFFAOYSA-N 0.000 description 9
- SQPFPKSOPRMSDP-UHFFFAOYSA-N C(CCC)N1CN(C=C1)C.O Chemical compound C(CCC)N1CN(C=C1)C.O SQPFPKSOPRMSDP-UHFFFAOYSA-N 0.000 description 7
- BFUNCCGFXJRQPV-UHFFFAOYSA-N CCCCCCN1C=CN(C)C1.O Chemical compound CCCCCCN1C=CN(C)C1.O BFUNCCGFXJRQPV-UHFFFAOYSA-N 0.000 description 7
- 229960001701 chloroform Drugs 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- IYBQNYKGZGGEKT-UHFFFAOYSA-N 1-methyl-3-pentyl-1,2-dihydroimidazol-1-ium;bromide Chemical compound [Br-].CCCCCN1C[NH+](C)C=C1 IYBQNYKGZGGEKT-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
-
- 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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses a POSS-containing high temperature-resistant solid ionic liquid which is prepared by a reaction of carboxyl heptaisobutyl POSS and 1-Cn-3-methylimidazole hydroxide, wherein the carboxyl heptaisobutyl POSS is prepared from aminopropyl heptaisobutyl POSS and succinic anhydride, and the 1-Cn-3-methylimidazole hydroxide is prepared from brominated 1-Cn-3-methylimidazole through the exchange of strongly basic anion exchange resin. A preparation method of the ionic liquid, disclosed by the invention has the advantages of high yield, high purity, good stability, compact process, low cost, short reaction time and capability of realizing large-scale industrial production. The ionic liquid disclosed by the invention is a series of POSS-based high temperature-resistant solid ionic liquid with a melting point ranging from 160 DEG C to 180 DEG C, and can be used for the field of solid electrolyte.
Description
Technical Field
The invention relates to an ionic liquid and a preparation method thereof, in particular to a POSS modified ionic liquid and a preparation method thereof, which are applied to the technical field of POSS modified materials.
Background
The ionic liquid is an ionic compound consisting of positive and negative ions and having a melting point lower than 100 ℃, and is widely used for research of electrolytes due to good ionic conductivity and a wide electrochemical window. As electronic products are developed to be portable and wearable, the electrolyte of batteries and super capacitors also needs to have flexibility, and thus the solid electrolyte formed by doping lithium salt with solid ionic liquid becomes a hot point of research. POSS contains a cage-type structure consisting of-Si-O-Si-, and has good thermal stability. However, the high temperature resistance, low temperature rheology and reaction kinetics performance of the POSS are not ideal, and how to better exert the comprehensive performance of the POSS and develop the application field of the POSS becomes a technical problem to be solved urgently.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to overcome the defects in the prior art and provide a high-temperature-resistant solid ionic liquid containing POSS and a preparation method thereof, POSS with a cage-type structure consisting of-Si-O-Si-is introduced into the ionic liquid, and the rigid cage-type structure has good heat resistance, so that the high-temperature ionic liquid with good thermal stability is synthesized, the melting point is about 170 ℃, and the decomposition does not occur at 250 ℃, therefore, the high-temperature ionic liquid prepared by the invention can be used at 250 ℃ of 170 plus materials, and has a certain application prospect in solid electrolytes.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a high-temperature-resistant solid ionic liquid containing POSS has a structural general formula as follows:
wherein,n＝2～5。
a preparation method of POSS-containing high-temperature-resistant solid ionic liquid is characterized in that POSS is modified, carboxyl POSS and imidazole hydroxide are utilized to be synthesized through acid-base neutralization reaction, and the synthetic route of the preparation method of POSS-containing high-temperature-resistant solid ionic liquid is as follows:
wherein,n＝2～5。
as the preferred technical scheme of the invention, the preparation method of the POSS-containing high-temperature-resistant solid ionic liquid comprises the following specific steps:
(1) preparation of compound b:
using a compound a as a raw material, and using brominated 1-Cn-3-methylimidazole as a compound a, wherein n is 2, 3, 4 or 5, namely the chemical formula of the compound a is as follows:whereinAdding the compound a into a strongly basic anion exchange resin column which is wetted by deionized water to prepare a compound b aqueous solution, and removing the deionized water from the obtained compound b aqueous solution through vacuum freeze drying, wherein the obtained compound b is 1-Cn-3-methylimidazole through hydrogen oxidation, and the chemical formula of the compound b is as follows:the compound a is preferably brominated 1-Cn-3-methylimidazole, namely brominated 1-propyl-3-methylimidazole, brominated 1-butyl-3-methylimidazole, brominated 1-pentyl-3-methylimidazole or brominated 1-hexyl-3-methylimidazole when n is 2, 3, 4 or 5;
(2) preparation of compound d:
aminopropyl heptaisobutyl POSS is used as a compound c, and the chemical formula of the compound c is as follows:whereinTaking a compound c and succinic anhydride as raw materials, respectively taking the raw materials according to the molar ratio of the compound c to the succinic anhydride of 1 (1-1.5), respectively dissolving the weighed compound c and succinic anhydride in a first solvent to respectively obtain the first solvent in which the succinic anhydride is dissolved and the first solvent in which the compound c is dissolved, pouring the first solvent in which the succinic anhydride is dissolved into a flask, and pouring the first solvent in which the compound c is dissolved into a constant-pressure dropping funnel; in thatUnder the condition of stirring at room temperature, dropwise adding the solution in a constant-pressure dropping funnel into the solution in the flask to form a first reaction system solution, after dropwise adding is completed, taking down the constant-pressure dropping funnel, replacing the constant-pressure dropping funnel with a condenser pipe, placing a reaction bottle in an oil bath kettle at the temperature of 80 ℃, stirring and refluxing for 1-15 hours to enable the first reaction system solution to perform chemical reaction, stopping the reaction, and evaporating a first solvent from a product system through decompression to obtain a crude product of a compound d; and adding a second solvent into the crude product of the compound d, centrifuging to obtain a clear liquid, evaporating the clear liquid under reduced pressure to remove the second solvent to obtain a compound d, and drying at 60 ℃ for 24 hours under vacuum conditions to obtain a pure product of the compound d, wherein the obtained compound d is carboxylated heptaisobutyl POSS and has the chemical formula:
the first solvent is preferably any one solvent or a mixture of any several solvents of tetrahydrofuran, isopropanol and toluene; the second solvent is preferably any one solvent or a mixed solvent of cyclohexane and petroleum ether;
(3) preparation of compound e:
taking the compound b prepared in the step (1) and the compound d prepared in the step (2) as reactants, respectively weighing the reactants according to the molar ratio of the compound b to the compound d being (1-1.5) to 1, dissolving the weighed compound b in a third solvent, dissolving the weighed compound d in a fourth solvent, adding the third solvent in which the compound b is dissolved and the fourth solvent in which the compound d is dissolved into a flask together to form a second reaction system solution, stirring at room temperature for 2-15h to perform a chemical reaction on the second reaction system solution, and after the reaction is finished, evaporating the product system, and reducing the pressure of the solvent to obtain a crude product of the compound e; and then adding a fifth solvent into the crude product of the compound e, centrifuging the crude product of the compound e through the fifth solvent dissolved with the compound e to obtain a supernatant, and evaporating the supernatant under reduced pressure to remove the solvent to finally obtain a pure product of the compound e, wherein the obtained compound e is POSS-based ionic liquid and has the chemical formula:
the third solvent preferably adopts any one solvent or a mixture of any two of methanol, water and chloroform; the fourth solvent preferably adopts any one solvent or a mixture of any several solvents of tetrahydrofuran, trichloromethane, chloropropane and toluene; the second solvent is preferably any one or a mixture of cyclohexane and petroleum ether.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. the POSS-containing solid ionic liquid prepared by the invention has the characteristic of high temperature resistance due to the introduction of POSS, can be used as a substrate of a solid electrolyte, and has the advantages of easy reaction, high yield, high purity, good stability and definite structure;
2. the preparation method has the advantages of easy control of reaction, compact process, short reaction time, high product purity and high yield, and can be used for large-scale production.
Drawings
FIG. 1 shows a POSS-containing high-temperature-resistant solid ionic liquid prepared according to one embodiment of the present invention13C NMR chart.
FIG. 2 is a DSC of a high temperature resistant solid ionic liquid containing POSS prepared in one embodiment of the present invention.
FIG. 3 is a TGA diagram of a high temperature resistant solid ionic liquid containing POSS prepared in accordance with one embodiment of the present invention.
Detailed Description
The preferred embodiments of the invention are detailed below:
the first embodiment is as follows:
in this embodiment, a preparation method of a high-temperature resistant solid ionic liquid containing POSS includes the following specific steps:
(1) preparation of 1-hexyl-3-methylimidazole hydroxide:
brominated 1-hexyl-3-methylimidazole is used as a raw material, and the chemical formula is as follows:whereinAdding brominated 1-hexyl-3-methylimidazole into a strongly basic anion exchange resin column which is wetted by deionized water to prepare 1-hexyl-3-methylimidazole hydroxide aqueous solution, and removing the deionized water from the obtained 1-hexyl-3-methylimidazole hydroxide aqueous solution through vacuum freeze drying to obtain the compound which is 1-hexyl-3-methylimidazole hydroxide and has the chemical formula:
(2) preparation of carboxylated POSS:
aminopropyl heptaisobutyl POSS is adopted, and the chemical formula is as follows:whereinThe preparation method comprises the steps of taking aminopropyl heptaisobutyl POSS and succinic anhydride as raw materials, respectively taking the raw materials according to the molar ratio of the aminopropyl heptaisobutyl POSS to the succinic anhydride of 1 (1-1.5), respectively dissolving the weighed aminopropyl heptaisobutyl POSS and succinic anhydride in tetrahydrofuran to respectively obtain tetrahydrofuran in which the succinic anhydride is dissolved and tetrahydrofuran in which the aminopropyl heptaisobutyl POSS is dissolved, and dissolving the succinic anhydride in the tetrahydrofuran to obtain the tetrahydrofuran in which the succinic anhydride is dissolvedThe anhydride tetrahydrofuran is poured into a flask, and the tetrahydrofuran dissolved with aminopropyl heptaisobutyl POSS is poured into a constant pressure dropping funnel; under the condition of stirring at room temperature, dropwise adding the solution in a constant-pressure dropping funnel into the solution in the flask to form a first reaction system solution, after dropwise adding is completed, taking down the constant-pressure dropping funnel, replacing the constant-pressure dropping funnel with a condenser pipe, placing a reaction bottle in an oil bath kettle at the temperature of 80 ℃, stirring and refluxing for 1-15 hours to enable the first reaction system solution to perform chemical reaction, stopping the reaction, and evaporating tetrahydrofuran from a product system through reduced pressure to obtain a crude compound product; and adding cyclohexane into the crude product of the compound, centrifuging to obtain clear liquid, evaporating the clear liquid under reduced pressure to obtain a carboxylated POSS compound, and drying at 60 ℃ for 24 hours under a vacuum condition to obtain a carboxylated POSS pure product, namely carboxylated heptaisobutyl POSS, wherein the chemical formula of the carboxylated POSS pure product is as follows:
(3) preparing POSS-based ionic liquid:
taking the 1-hexyl-3-methylimidazole hydroxide prepared in the step (1) and the carboxylated heptaisobutyl POSS prepared in the step (2) as reactants, respectively weighing the reactants according to the molar ratio of 1-propyl-3-methylimidazole hydroxide to carboxylated heptaisobutyl POSS being (1-1.5): 1, then dissolving the weighed 1-hexyl-3-methylimidazole hydroxide in methanol, dissolving the weighed carboxylated heptaisobutyl POSS in tetrahydrofuran, then adding the methanol in which the 1-hexyl-3-methylimidazole hydroxide is dissolved and the tetrahydrofuran in which the carboxylated heptaisobutyl POSS is dissolved into a flask together to form a second reaction system solution, stirring for 2-15h at room temperature to perform chemical reaction on the second reaction system solution, after the reaction is finished, evaporating the solvent from the product system through decompression to obtain a POSS-based ionic liquid crude product; adding cyclohexane into the POSS-based ionic liquid crude product, centrifuging the cyclohexane dissolved with the POSS-based ionic liquid to obtain supernatant, and evaporating the supernatant under reduced pressure to remove the solvent to finally obtain a POSS-based ionic liquid pure product, wherein the chemical formula of the POSS-based ionic liquid pure product is as follows:
whereinn＝5。
This example prepared a POSS-based room temperature ionic liquid capable of being used at elevated temperatures from carboxyheptaisobutyl POSS and 1-C hydroxiden-3-methylimidazole, wherein the carboxy heptaisobutyl POSS is prepared from aminopropyl heptaisobutyl POSS and succinic anhydride, 1-C hydroxidenBromination of 1-C with (E) -3-methylimidazolen-3-methylimidazole is obtained by exchange with a strongly basic anion exchange resin. The preparation method of the ionic liquid containing POSS has the advantages of high yield, high purity, good stability, compact process, low cost and short reaction time, and can be used for large-scale industrial production. The cage-type rigid structure of POSS prepared by the embodiment has good thermal stability, and the POSS is introduced to the anion of the ionic liquid to finally synthesize the high-temperature ionic liquid capable of being used at the temperature of 170-250 ℃.
Example two:
this embodiment is substantially the same as the embodiment, and is characterized in that:
in this embodiment, a preparation method of a high-temperature resistant solid ionic liquid containing POSS includes the following specific steps:
(1) preparation of 1-pentyl-3-methylimidazole hydroxide:
the brominated 1-amyl-3-methylimidazole is used as a raw material, and the chemical formula is as follows:whereinAdding 1-pentyl-3-methylimidazole bromide into a strongly basic anion exchange resin column which is wetted by deionized water to prepare a 1-pentyl-3-methylimidazole hydroxide aqueous solution, and removing the deionized water from the obtained 1-pentyl-3-methylimidazole hydroxide aqueous solution through vacuum freeze drying to obtain the compound 1-pentyl-3-methylimidazole hydroxide, wherein the chemical formula is as follows:
(2) preparation of carboxylated POSS: the step is the same as the first embodiment;
(3) preparing POSS-based ionic liquid:
taking the 1-pentyl-3-methylimidazole hydroxide prepared in the step (1) and the carboxylated heptaisobutyl POSS prepared in the step (2) as reactants, respectively weighing the reactants according to the molar ratio of 1-pentyl-3-methylimidazole hydroxide to carboxylated heptaisobutyl POSS being (1-1.5): 1, dissolving the weighed 1-pentyl-3-methylimidazole hydroxide in methanol, dissolving the weighed carboxylated heptaisobutyl POSS in tetrahydrofuran, adding the methanol in which the 1-pentyl-3-methylimidazole hydroxide is dissolved and the tetrahydrofuran in which the carboxylated heptaisobutyl POSS is dissolved into a flask to form a second reaction system solution, stirring for 2-15h at room temperature to perform chemical reaction on the second reaction system solution, after the reaction is finished, evaporating the solvent from the product system through decompression to obtain a POSS-based ionic liquid crude product; adding cyclohexane into the POSS-based ionic liquid crude product, centrifuging the cyclohexane dissolved with the POSS-based ionic liquid to obtain supernatant, and evaporating the supernatant under reduced pressure to remove the solvent to finally obtain a POSS-based ionic liquid pure product, wherein the chemical formula of the POSS-based ionic liquid pure product is as follows:
whereinn＝4。
Example three:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a preparation method of a high-temperature resistant solid ionic liquid containing POSS includes the following specific steps:
(1) preparation of 1-butyl-3-methylimidazole hydroxide:
the brominated 1-butyl-3-methylimidazole is used as a raw material, and the chemical formula is as follows:whereinAdding brominated 1-butyl-3-methylimidazole into a strongly basic anion exchange resin column which is wetted by deionized water to prepare 1-butyl-3-methylimidazole hydroxide aqueous solution, and removing the deionized water from the obtained 1-butyl-3-methylimidazole hydroxide aqueous solution through vacuum freeze drying to obtain the compound 1-butyl-3-methylimidazole hydroxide, wherein the chemical formula is as follows:
(2) preparation of carboxylated POSS: the step is the same as the first embodiment;
(3) preparing POSS-based ionic liquid:
taking the 1-butyl-3-methylimidazole hydroxide prepared in the step (1) and the carboxylated heptaisobutyl POSS prepared in the step (2) as reactants, respectively weighing the reactants according to the molar ratio of 1-butyl-3-methylimidazole hydroxide to carboxylated heptaisobutyl POSS being (1-1.5): 1, then dissolving the weighed 1-butyl-3-methylimidazole hydroxide in methanol, dissolving the weighed carboxylated heptaisobutyl POSS in tetrahydrofuran, then adding the methanol in which the 1-butyl-3-methylimidazole hydroxide is dissolved and the tetrahydrofuran in which the carboxylated heptaisobutyl POSS is dissolved into a flask together to form a second reaction system solution, stirring for 2-15h at room temperature to perform chemical reaction on the second reaction system solution, after the reaction is finished, evaporating the solvent from the product system through decompression to obtain a POSS-based ionic liquid crude product; adding cyclohexane into the POSS-based ionic liquid crude product, centrifuging the cyclohexane dissolved with the POSS-based ionic liquid to obtain supernatant, and evaporating the supernatant under reduced pressure to remove the solvent to finally obtain a POSS-based ionic liquid pure product, wherein the chemical formula of the POSS-based ionic liquid pure product is as follows:
whereinn＝3。
Example four:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, referring to fig. 1 to 3, a preparation method of a high-temperature resistant solid ionic liquid containing POSS includes the following specific steps:
(1) preparation of 1-propyl-3-methylimidazole hydroxide:
the brominated 1-propyl-3-methylimidazole is used as a raw material, and the chemical formula is as follows:whereinAdding brominated 1-propyl-3-methylimidazole into a strongly basic anion exchange resin column which is wetted by deionized water to prepare 1-propyl-3-methylimidazole hydroxide aqueous solution,removing deionized water from the obtained 1-propyl-3-methylimidazole hydroxide aqueous solution through vacuum freeze drying, wherein the obtained compound is 1-propyl-3-methylimidazole hydroxide and has a chemical formula:
(2) preparation of carboxylated POSS: the step is the same as the first embodiment;
(3) preparing POSS-based ionic liquid:
taking the 1-propyl-3-methylimidazole hydroxide prepared in the step (1) and the carboxylated heptaisobutyl POSS prepared in the step (2) as reactants, respectively weighing the reactants according to the molar ratio of 1-propyl-3-methylimidazole hydroxide to carboxylated heptaisobutyl POSS being (1-1.5): 1, then dissolving the weighed 1-propyl-3-methylimidazole hydroxide in methanol, dissolving the weighed carboxylated heptaisobutyl POSS in tetrahydrofuran, then adding the methanol in which the 1-propyl-3-methylimidazole hydroxide is dissolved and the tetrahydrofuran in which the carboxylated heptaisobutyl POSS is dissolved into a flask together to form a second reaction system solution, stirring for 2-15h at room temperature to perform chemical reaction on the second reaction system solution, after the reaction is finished, evaporating the solvent from the product system through decompression to obtain a POSS-based ionic liquid crude product; adding cyclohexane into the POSS-based ionic liquid crude product, centrifuging the cyclohexane dissolved with the POSS-based ionic liquid to obtain supernatant, and evaporating the supernatant under reduced pressure to remove the solvent to finally obtain a POSS-based ionic liquid pure product, wherein the chemical formula of the POSS-based ionic liquid pure product is as follows:
whereinn＝2。
The ionic liquid containing POSS prepared by the embodiment of the invention has the advantages of easy reaction, high yield, high purity and good stability, contains POSS monomer with definite structure and good organic solubility, and endows the ionic liquid with the characteristic of high temperature resistance. The preparation method of the embodiment of the invention has the advantages of compact process, short reaction time, high product purity and high yield, and can be used for large-scale production.
Experimental test analysis:
according to the embodiment of the invention, the carboxyl POSS and the imidazole hydroxide are subjected to acid-base neutralization reaction to synthesize the high-temperature-resistant room-temperature ionic liquid. In the first embodiment, referring to fig. 1-3, fig. 1 is a nuclear magnetic resonance spectrum of an ionic liquid compound,1HNMR(CDCl3,298K,500MHz):(ppm)＝10.89(s,1H,-NCHN-),7.19(d,2H,-CHCH-),6.01(d,1H,-NH-),4.32(t,2H,-NCH2-),4.12(s,3H,-NCH3),3.27(q,2H,-NHCH2-),2.68(t,2H,-CH2COO-),2.55(t,2H,-CH2CO-),1.92(m,2H,-NCH2CH2-),1.87(m,7H,-CH-),1.63(m,2H,-NHCH2CH2-),1.35(m,6H,-CH2CH2CH2CH3),0.98(d,42H,-CH(CH3)2),0.91(t,3H,-CH3),0.62(d,16H,-SiCH2-) and can deduce the successful synthesis of the POSS-ILs ionic liquid according to the actual peak position and the integral ratio of the hydrogen atom. FIG. 2 is a Differential Scanning Calorimetry (DSC) curve of a compound, from which it can be seen that the melting point of the compound is 166.4 deg.C, indicating that the compound is a solid ionic liquid at room temperature. FIG. 3 is a thermogravimetric analysis of a compound showing that the compound does not decompose at temperatures below 249.7 ℃ indicating that the compound is thermally stable at high temperatures. According to the embodiment of the invention, the POSS with the cage structure consisting of-Si-O-Si-is introduced into the ionic liquid, and the rigid cage structure has good heat resistance, so that the high-temperature ionic liquid with good thermal stability is synthesized, the melting point is about 170 ℃, decomposition does not occur at 250 ℃, and the high-temperature ionic liquid has a certain application prospect in solid electrolytes. The preparation method of the ionic liquid of the above embodiment of the invention hasHas high yield, high purity, good stability, compact process, low cost and short reaction time, and can be used for large-scale industrial production. The ionic liquid prepared by the embodiment of the invention is POSS-based high-temperature-resistant solid ionic liquid with the melting point of 160-180 ℃, and can be used in the field of solid electrolytes.
The embodiments of the present invention have been described with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made according to the purpose of the invention, and any changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention shall be equivalent substitutions, so long as the invention meets the purpose of the present invention, and the technical principle and inventive concept of the POSS-containing high temperature resistant solid ionic liquid and the preparation method thereof shall not depart from the scope of the present invention.
Claims (9)
1. The POSS-containing high-temperature-resistant solid ionic liquid is characterized by having a structural general formula as follows:
wherein,n＝2～5。
2. the preparation method of the POSS-based high-temperature-resistant room-temperature ionic liquid is characterized in that the POSS is modified, carboxyl POSS and imidazole hydroxide are utilized to be synthesized through acid-base neutralization reaction, and the synthetic route of the preparation method of the POSS-containing high-temperature-resistant solid-state ionic liquid is as follows:
wherein,n＝2～5。
3. the preparation method of the POSS-containing high-temperature-resistant solid ionic liquid as claimed in claim 2, wherein the specific steps of synthesis are as follows:
(1) preparation of compound b:
using a compound a as a raw material, and using brominated 1-Cn-3-methylimidazole as a compound a, wherein n is 2, 3, 4 or 5, namely the chemical formula of the compound a is as follows:whereinAdding the compound a into a strongly basic anion exchange resin column which is wetted by deionized water to prepare a compound b aqueous solution, and removing the deionized water from the obtained compound b aqueous solution through vacuum freeze drying, wherein the obtained compound b is 1-Cn-3-methylimidazole through hydrogen oxidation, and the chemical formula of the compound b is as follows:
(2) preparation of compound d:
aminopropyl heptaisobutyl POSS is used as a compound c, and the chemical formula of the compound c is as follows:whereinTaking a compound c and succinic anhydride as raw materials, respectively taking the raw materials according to the molar ratio of the compound c to the succinic anhydride of 1 (1-1.5), respectively dissolving the weighed compound c and succinic anhydride in a first solvent to respectively obtain the first solvent in which the succinic anhydride is dissolved and the first solvent in which the compound c is dissolved, pouring the first solvent in which the succinic anhydride is dissolved into a flask, and pouring the first solvent in which the compound c is dissolved into a constant-pressure dropping funnel; under the condition of stirring at room temperature, dropwise adding the solution in a constant-pressure dropping funnel into the solution in the flask to form a first reaction system solution, after dropwise adding is completed, taking down the constant-pressure dropping funnel, replacing the constant-pressure dropping funnel with a condenser pipe, placing a reaction bottle in an oil bath kettle at the temperature of 80 ℃, stirring and refluxing for 1-15 hours to enable the first reaction system solution to perform chemical reaction, stopping the reaction, and evaporating a first solvent from a product system through reduced pressure to obtain a crude product of a compound d; and adding a second solvent into the crude product of the compound d, centrifuging to obtain a clear liquid, evaporating the clear liquid under reduced pressure to remove the second solvent to obtain a compound d, and drying at 60 ℃ for 24 hours under vacuum conditions to obtain a pure product of the compound d, wherein the obtained compound d is carboxyl heptaisobutyl POSS, and the chemical formula of the compound d is as follows:
(3) preparation of compound e:
taking the compound b prepared in the step (1) and the compound d prepared in the step (2) as reactants, respectively weighing the reactants according to the molar ratio of the compound b to the compound d being (1-1.5): 1, dissolving the weighed compound b in a third solvent, dissolving the weighed compound d in a fourth solvent, adding the third solvent in which the compound b is dissolved and the fourth solvent in which the compound d is dissolved into a flask together to form a second reaction system solution, stirring at room temperature for 2-15h, and carrying out chemical reaction on the second reaction system solutionAfter the reaction is finished, evaporating the solvent from the product system by decompression to obtain a compound e crude product; and then adding a fifth solvent into the crude product of the compound e, centrifuging the crude product of the compound e through the fifth solvent dissolved with the compound e to obtain a supernatant, and evaporating the supernatant under reduced pressure to remove the solvent to finally obtain a pure product of the compound e, wherein the obtained compound e is POSS-based ionic liquid and has the chemical formula:
4. the preparation method of the POSS-containing high temperature resistant solid ionic liquid as claimed in claim 3, wherein in the step (1), the compound a is brominated 1-Cn-3-methylimidazole, that is, brominated 1-propyl-3-methylimidazole, brominated 1-butyl-3-methylimidazole, brominated 1-pentyl-3-methylimidazole or brominated 1-hexyl-3-methylimidazole when n ═ 2, 3, 4 or 5.
5. The method for preparing the POSS-containing high-temperature-resistant solid ionic liquid as claimed in claim 3, wherein the POSS-containing high-temperature-resistant solid ionic liquid is prepared by the following steps: in the step (2), the first solvent is any one solvent or a mixture of any several solvents of tetrahydrofuran, isopropanol and toluene.
6. The method for preparing the POSS-containing high-temperature-resistant solid ionic liquid as claimed in claim 3, wherein the POSS-containing high-temperature-resistant solid ionic liquid is prepared by the following steps: in the step (2), the second solvent is any one solvent or a mixed solvent of cyclohexane and petroleum ether.
7. The method for preparing the POSS-containing high-temperature-resistant solid ionic liquid as claimed in claim 3, wherein the POSS-containing high-temperature-resistant solid ionic liquid is prepared by the following steps: in the step (3), the third solvent is any one solvent or a mixture of any several solvents selected from methanol, water and chloroform.
8. The method for preparing the POSS-containing high-temperature-resistant solid ionic liquid as claimed in claim 3, wherein the POSS-containing high-temperature-resistant solid ionic liquid is prepared by the following steps: in the step (3), the fourth solvent is any one solvent or a mixture of any several solvents of tetrahydrofuran, chloroform, chloropropane and toluene.
9. The method for preparing the POSS-containing high-temperature-resistant solid ionic liquid as claimed in claim 3, wherein the POSS-containing high-temperature-resistant solid ionic liquid is prepared by the following steps: in the step (3), the second solvent is any one solvent or a mixed solvent of cyclohexane and petroleum ether.
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| CN107994256A (en) * | 2017-11-23 | 2018-05-04 | 上海大学 | Polymer dielectric film of the class ionic liquid of based quaternary ammonium salt containing POSS and preparation method thereof |
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