CN105924465A - POSS-base high-temperature-resisting room temperature ionic liquid and preparation method thereof - Google Patents
POSS-base high-temperature-resisting room temperature ionic liquid and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 55
- 239000011829 room temperature ionic liquid solvent Substances 0.000 title abstract 4
- 239000002608 ionic liquid Substances 0.000 claims abstract description 69
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 5
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 85
- 239000002904 solvent Substances 0.000 claims description 58
- 238000006243 chemical reaction Methods 0.000 claims description 44
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 25
- 239000000047 product Substances 0.000 claims description 22
- 239000012043 crude product Substances 0.000 claims description 18
- 230000006837 decompression Effects 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 17
- 230000031709 bromination Effects 0.000 claims description 16
- 238000005893 bromination reaction Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 14
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 14
- 229940014800 succinic anhydride Drugs 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000006228 supernatant Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- 239000000376 reactant Substances 0.000 claims description 11
- -1 aminopropyl Chemical group 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 150000002460 imidazoles Chemical class 0.000 claims description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- KYCQOKLOSUBEJK-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCCCN1C=C[N+](C)=C1 KYCQOKLOSUBEJK-UHFFFAOYSA-M 0.000 claims description 4
- WGVGZVWOOMIJRK-UHFFFAOYSA-N 1-hexyl-3-methyl-2h-imidazole Chemical compound CCCCCCN1CN(C)C=C1 WGVGZVWOOMIJRK-UHFFFAOYSA-N 0.000 claims description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- QLWOUBCORTYSPP-UHFFFAOYSA-N 1h-imidazol-1-ium;hydroxide Chemical class O.C1=CNC=N1 QLWOUBCORTYSPP-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 2
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 230000009477 glass transition Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 abstract 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 abstract 1
- 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
- 239000007788 liquid Substances 0.000 description 6
- 238000005349 anion exchange Methods 0.000 description 5
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000004017 vitrification Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 210000000270 basal cell Anatomy 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001757 thermogravimetry curve 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses POSS-base room temperature ionic liquid which can be used at the high temperature. The POSS-base room temperature ionic liquid is prepared by reacting carboxyl(7)octyl POSS and hydroxide 1-Cn-3-methylimidazole, wherein carboxyl(7)octyl POSS is prepared from aminopropyl(7)octyl POSS and butanedioic anhydride, and hydroxide 1-Cn-3-methylimidazole is obtained by exchanging bromination1-Cn-3 methylimidazole through strong-basic anion exchange resin. The preparation method for the ionic liquid containing POSS has the advantages that the yield and purity are high, stability is good, the process is compact, cost is low, the reaction time is short, and large-scale industrial production can be achieved. The method can be used for preparing a series of POSS-base high-temperature-resisting ionic liquid, the glass transition temperature is lower than -15 DEG C, due to very good electrical conductivity, the POSS-base room temperature ionic liquid can be used for electrolyte, and the using temperature range of batteries is expanded.
Description
Technical field
The present invention relates to a kind of ionic liquid and preparation method thereof, particularly relate to ionic liquid modified for a kind of POSS and
Its preparation method, is applied to the material modified technical field of POSS.
Background technology
The salt that ionic liquid is made up of negative ions, is liquid under usual room temperature.Ionic liquid has extremely low steam
Pressure, good ionic conductivity, wider electrochemical window and dissolubility good to Organic substance and high molecular polymer, therefore
It is used for organic synthesis, electrochemistry and conductive material.But the usual thermally-stabilised difference of current ionic liquid, at about 150 DEG C just
Can start to decompose, be unfavorable for the extensive application of ionic liquid.POSS contains the cagelike structure of-Si-O-Si-composition, has very well
Heat stability.But its heat-resisting quantity, low temperature rheology and kinetics performance are the most preferable, the most preferably play
The combination property of POSS, opens up its application, becomes technical problem urgently to be resolved hurrily.
Summary of the invention
In order to solve prior art problem, it is an object of the invention to the deficiency overcoming prior art to exist, it is provided that a kind of
Ionic liquid at room temperature of POSS based high-temp-resistant and preparation method thereof, utilizes the cage modle rigid structure of POSS to have good thermally-stabilised
Property feature, by POSS is incorporated in the anion of ionic liquid, final synthesis one can below 220 DEG C under high temperature just
The ionic liquid often used.The present invention, by the POSS of heat resistant structure is introduced anionic group, synthesizes a series of vitrification temperature
The degree resistant to elevated temperatures ionic liquid at room temperature less than-15 DEG C, and find that decomposing does not occurs in product at 270 DEG C by TGA test,
Can be used for electrolyte, improve the use temperature range of battery.
Creating purpose for reaching foregoing invention, the present invention uses following technical proposals:
A kind of ionic liquid at room temperature of POSS based high-temp-resistant, its general structure is:
Wherein,N=2～5.
The preparation method of the ionic liquid at room temperature of a kind of POSS based high-temp-resistant, is modified POSS, utilizes carboxyl POSS
With hydroxide imidazoles, it is synthesized by acid-base neutralization, the synthesis of the preparation method of the ionic liquid at room temperature of POSS based high-temp-resistant
Route is:
Wherein,N=2～5.
As currently preferred technical scheme, the concrete step of the preparation method of the ionic liquid at room temperature of POSS based high-temp-resistant
Rapid as follows:
(1) preparation of compound b:
Using compound a as raw material, using the 1-Cm-3-Methylimidazole. of bromination as compound a, wherein m=2,3,4 or 5,
The chemical formula of the most described compound a is:WhereinN=2～5, by compound a
Add the strong-base anion-exchange resin post that deionized water moistened, prepare compound b aqueous solution, the compound b water that will obtain
Solution removes deionized water therein by vacuum lyophilization, the 1-Cm-3-methyl miaow that compound b is hydroxide of gained
Azoles, its chemical formula is:Compound a preferably employs the 1-Cn-3-Methylimidazole. of bromination, be m=2,3,
4,5 time bromination 1-propyl group-3-Methylimidazole., 1-butyl-3-methylimidazolium bromide, bromination 1-amyl group-3-Methylimidazole. or bromine
Change 1-hexyl-3-Methylimidazole.；
(2) preparation of compound d:
Using aminopropyl seven octyl group POSS as compound c, compound c chemical formula it is:
, whereinCompound c and succinic anhydride is used to make
For raw material, be 1:(1～1.5 according to the molar ratio of compound c: succinic anhydride) ratio respectively take raw material, then by weighed amount
Compound c, succinic anhydride be dissolved in the first solvent respectively, respectively obtain the first solvent dissolved with succinic anhydride and dissolved with compound
First solvent of c, pours into the first solvent dissolved with succinic anhydride in flask, and makes to pour into dissolved with first solvent of compound c
Constant pressure funnel；Under the conditions of being stirred at room temperature, the solution in constant pressure funnel is added dropwise in the solution in flask,
Form the first reaction system solution, after being added dropwise to complete, take off constant pressure funnel, change condensing tube into, reaction bulb is placed in 80 DEG C
Under oil bath pan in, be stirred at reflux 1-15h, make the first reaction system solution generation chemical reaction, stopped reaction, from product system
In, steam the first solvent by decompression, obtain compound d crude product；The second solvent is added again, so in compound d crude product
Rear being centrifuged obtains clear liquor, clear liquor decompression is steamed the second solvent, obtains compound d, the most under vacuum, at 60 DEG C
Under be dried 24h, obtain compound d pure products, the compound d of gained is carboxylated seven octyl groups POSS, and its chemical formula is:
First solvent preferably employs oxolane, different
Any one solvent or the most several mixed solvents in propanol and methanol；Second solvent preferably employs in hexamethylene and petroleum ether
Any one solvent or the two mixed solvent；
(3) preparation of compound e:
The compound b that will prepare in described step (1) and the compound d prepared in described step (2) is as reaction
Thing, according to compound b: the molar ratio of compound d is (1～1.5): the ratio of 1 weighs reactant respectively, then by weighed amount
Compound b be dissolved in the 3rd solvent, weighed compound d is dissolved in the 4th solvent, then by dissolved with the of compound b
Three solvents and the 4th solvent dissolved with compound d join in flask in the lump, form the second reaction system solution, at room temperature stir
Mix 2-15h, make the second reaction system solution generation chemical reaction, after reaction terminates, from product system, steamed by decompression molten
Agent, obtains compound e crude product；Then in compound e crude product, add the 5th solvent, then by dissolved with the of compound e
Five solvents are centrifuged, and obtain the supernatant, supernatant decompression is boiled off solvent, finally gives compound e pure products, gained
Compound e be POSS base ionic liquid, its chemical formula is:
3rd solvent preferably employs any one solvent or the most several mixed solvents in methanol, water and chloroform；
4th solvent preferably employs any one solvent or the most several mixing in oxolane, chloroform, chloropropane and toluene
Solvent；Second solvent preferably employs any one solvent or the two mixed solvent in hexamethylene and petroleum ether.
The present invention compared with prior art, has and the most obviously highlights substantive distinguishing features and remarkable advantage:
The ionic liquid at room temperature of POSS based high-temp-resistant the most of the present invention, easily, productivity is high in reaction, and purity is high, and stability
Good, include the POSS monomer that structure is clear and definite, organic-dissolvable is good, impart the resistant to elevated temperatures characteristic of ionic liquid, and due to
The side chain that POSS contains is longer, also makes the ionic liquid of synthesis at room temperature have good mobility simultaneously；
The reaction of preparation method the most of the present invention is easily controlled, its process intensification, and the response time is short, and product purity is high, productivity
Height, can be with large-scale production.
Accompanying drawing explanation
Fig. 1 is the ionic liquid at room temperature of the POSS based high-temp-resistant of the embodiment of the present invention one preparation1H NMR schemes.
Fig. 2 is the DSC figure of the ionic liquid at room temperature of the POSS based high-temp-resistant of the embodiment of the present invention one preparation.
Fig. 3 is the TGA figure of the ionic liquid at room temperature of the POSS based high-temp-resistant of the embodiment of the present invention one preparation.
Detailed description of the invention
Details are as follows for the preferred embodiments of the present invention:
Embodiment one:
In the present embodiment, the preparation method of the ionic liquid at room temperature of a kind of POSS based high-temp-resistant, specifically comprise the following steps that
(1) preparation of hydroxide 1-hexyl-3-Methylimidazole.:
With bromination 1-hexyl-3-Methylimidazole. as raw material, with its chemical formula i.e. it is:WhereinN=5, the strong alkalinity anion exchange that bromination 1-hexyl-3-Methylimidazole. addition deionized water was moistened
Resin column, prepares hydroxide 1-hexyl-3-Methylimidazole. aqueous solution, by water-soluble for the hydroxide 1-hexyl-3-Methylimidazole. obtained
Liquid removes deionized water therein by vacuum lyophilization, and the compound of gained is hydroxide 1-hexyl-3-Methylimidazole., its
Chemical formula is:
(2) preparation of carboxylated POSS:
Using aminopropyl seven octyl group POSS, its chemical formula is:WhereinEmploying aminopropyl seven octyl group POSS and succinic anhydride are as raw material, according to aminopropyl seven octyl group POSS: fourth
The molar ratio of dicarboxylic anhydride is 1:(1～1.5) ratio respectively take raw material, then by weighed aminopropyl seven octyl group POSS, fourth
Dicarboxylic anhydride is dissolved in oxolane respectively, respectively obtains the oxolane dissolved with succinic anhydride and dissolved with aminopropyl seven octyl group POSS
Oxolane, pours into the oxolane dissolved with succinic anhydride in flask, and makes the tetrahydrochysene furan dissolved with aminopropyl seven octyl group POSS
Mutter and pour constant pressure funnel into；Under the conditions of being stirred at room temperature, the solution in constant pressure funnel is added dropwise in flask
In solution, form the first reaction system solution, after being added dropwise to complete, take off constant pressure funnel, change condensing tube into, reaction bulb is put
In oil bath pan at 80 DEG C, being stirred at reflux 1-15h, make the first reaction system solution generation chemical reaction, stopped reaction, from product
In objects system, steam oxolane by decompression, obtain compound crude product；Hexamethylene is added again in compound crude product,
It is then centrifuged for obtaining clear liquor, clear liquor decompression is steamed hexamethylene, obtains carboxylated POSS compound, then at vacuum condition
Under, at 60 DEG C, it being dried 24h, obtain carboxylated POSS pure products, be carboxylated seven octyl groups POSS, its chemical formula is:
(3) preparation of POSS base ionic liquid:
Will the hydroxide 1-hexyl-3-Methylimidazole. of preparation and preparation in described step (2) in described step (1)
Carboxylated seven octyl groups POSS are as reactant, according to hydroxide 1-hexyl-3-Methylimidazole.: carboxylated seven octyl groups POSS mole
Ratio is (1～1.5): the ratio of 1 weighs reactant respectively, then by molten for weighed hydroxide 1-hexyl-3-Methylimidazole.
In methanol, weighed carboxylated seven octyl groups POSS are dissolved in oxolane, then will be dissolved with hydroxide 1-hexyl-3-first
The methanol of base imidazoles and the oxolane dissolved with carboxylated seven octyl groups POSS join in flask in the lump, form the second reaction system
Solution, is stirred at room temperature 2-15h, makes the second reaction system solution generation chemical reaction, after reaction terminates, from product system
In, steam solvent by decompression, obtain POSS base ionic liquid crude product；Then add in POSS base ionic liquid crude product
Hexamethylene, then by being centrifuged dissolved with the hexamethylene of POSS base ionic liquid, obtain the supernatant, supernatant decompression is steamed
Removing solvent, finally give POSS base ionic liquid pure products, its chemical formula is:
WhereinN=
5。
The present embodiment is prepared for a kind of POSS basal cell temperature ionic liquid that can use under the high temperature conditions, by carboxyl seven octyl group
POSS and hydroxide 1-CnThe reaction of-3-Methylimidazole. is made, wherein carboxyl seven octyl group POSS be by aminopropyl seven octyl group POSS and
Succinic anhydride is made, hydroxide 1-Cn-3-Methylimidazole. is by bromination 1-Cn-3-Methylimidazole. is by strong alkalinity anion exchange tree
Ester exchange obtains.It is high that the preparation method of the present embodiment ionic liquid containing POSS has productivity, and purity is high, good stability, work
Skill is compact, low cost, and the response time is short, can large-scale commercial production.POSS based high-temp-resistant ionic liquid prepared by the present embodiment
Body, vitrification point is less than-15 DEG C, due to its good electric conductivity, can be used for electrolyte, improves the use temperature model of battery
Enclose.
Embodiment two:
The present embodiment is essentially identical with embodiment, is particular in that:
In the present embodiment, the preparation method of the ionic liquid at room temperature of a kind of POSS based high-temp-resistant, specifically comprise the following steps that
(1) preparation of hydroxide 1-amyl group-3-Methylimidazole.:
With bromination 1-amyl group-3-Methylimidazole. as raw material, with its chemical formula i.e. it is:WhereinN=4, the strong alkalinity anion exchange that bromination 1-amyl group-3-Methylimidazole. addition deionized water was moistened
Resin column, prepares hydroxide 1-amyl group-3-Methylimidazole. aqueous solution, by water-soluble for the hydroxide 1-amyl group-3-Methylimidazole. obtained
Liquid removes deionized water therein by vacuum lyophilization, and the compound of gained is hydroxide 1-amyl group-3-Methylimidazole., its
Chemical formula is:
(2) preparation of carboxylated POSS: this step is identical with embodiment one；
(3) preparation of POSS base ionic liquid:
Will the hydroxide 1-amyl group-3-Methylimidazole. of preparation and preparation in described step (2) in described step (1)
Carboxylated seven octyl groups POSS are as reactant, according to hydroxide 1-amyl group-3-Methylimidazole.: carboxylated seven octyl groups POSS mole
Ratio is (1～1.5): the ratio of 1 weighs reactant respectively, then by molten for weighed hydroxide 1-amyl group-3-Methylimidazole.
In methanol, weighed carboxylated seven octyl groups POSS are dissolved in oxolane, then will be dissolved with hydroxide 1-amyl group-3-first
The methanol of base imidazoles and the oxolane dissolved with carboxylated seven octyl groups POSS join in flask in the lump, form the second reaction system
Solution, is stirred at room temperature 2-15h, makes the second reaction system solution generation chemical reaction, after reaction terminates, from product system
In, steam solvent by decompression, obtain POSS base ionic liquid crude product；Then add in POSS base ionic liquid crude product
Hexamethylene, then by being centrifuged dissolved with the hexamethylene of POSS base ionic liquid, obtain the supernatant, supernatant decompression is steamed
Removing solvent, finally give POSS base ionic liquid pure products, its chemical formula is:
Wherein
N=4.
Embodiment three:
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, the preparation method of the ionic liquid at room temperature of a kind of POSS based high-temp-resistant, specifically comprise the following steps that
(1) preparation of hydroxide 1-butyl-3-Methylimidazole.:
With 1-butyl-3-methylimidazolium bromide as raw material, with its chemical formula i.e. it is:WhereinN=3, adds the strong alkalinity anion exchange that deionized water moistened by 1-butyl-3-methylimidazolium bromide
Resin column, prepares hydroxide 1-butyl-3-Methylimidazole. aqueous solution, by water-soluble for the hydroxide 1-butyl-3-Methylimidazole. obtained
Liquid removes deionized water therein by vacuum lyophilization, and the compound of gained is hydroxide 1-butyl-3-Methylimidazole., its
Chemical formula is:
(2) preparation of carboxylated POSS: this step is identical with embodiment one；
(3) preparation of POSS base ionic liquid:
Will the hydroxide 1-butyl-3-Methylimidazole. of preparation and preparation in described step (2) in described step (1)
Carboxylated seven octyl groups POSS are as reactant, according to hydroxide 1-butyl-3-Methylimidazole.: carboxylated seven octyl groups POSS mole
Ratio is (1～1.5): the ratio of 1 weighs reactant respectively, then by molten for weighed hydroxide 1-butyl-3-Methylimidazole.
In methanol, weighed carboxylated seven octyl groups POSS are dissolved in oxolane, then will be dissolved with hydroxide 1-butyl-3-first
The methanol of base imidazoles and the oxolane dissolved with carboxylated seven octyl groups POSS join in flask in the lump, form the second reaction system
Solution, is stirred at room temperature 2-15h, makes the second reaction system solution generation chemical reaction, after reaction terminates, from product system
In, steam solvent by decompression, obtain POSS base ionic liquid crude product；Then add in POSS base ionic liquid crude product
Hexamethylene, then by being centrifuged dissolved with the hexamethylene of POSS base ionic liquid, obtain the supernatant, supernatant decompression is steamed
Removing solvent, finally give POSS base ionic liquid pure products, its chemical formula is:
Wherein
N=3.
Embodiment four:
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, see Fig. 1～3, the preparation method of the ionic liquid at room temperature of a kind of POSS based high-temp-resistant, specifically
Step is as follows:
(1) preparation of hydroxide 1-propyl group-3-Methylimidazole.:
With bromination 1-propyl group-3-Methylimidazole. as raw material, with its chemical formula i.e. it is:WhereinN=2, the strong alkalinity anion exchange that bromination 1-propyl group-3-Methylimidazole. addition deionized water was moistened
Resin column, prepares hydroxide 1-propyl group-3-Methylimidazole. aqueous solution, by water-soluble for the hydroxide 1-propyl group-3-Methylimidazole. obtained
Liquid removes deionized water therein by vacuum lyophilization, and the compound of gained is hydroxide 1-propyl group-3-Methylimidazole., its
Chemical formula is:
(2) preparation of carboxylated POSS: this step is identical with embodiment one；
(3) preparation of POSS base ionic liquid:
Will the hydroxide 1-propyl group-3-Methylimidazole. of preparation and preparation in described step (2) in described step (1)
Carboxylated seven octyl groups POSS are as reactant, according to hydroxide 1-propyl group-3-Methylimidazole.: carboxylated seven octyl groups POSS mole
Ratio is (1～1.5): the ratio of 1 weighs reactant respectively, then by molten for weighed hydroxide 1-propyl group-3-Methylimidazole.
In methanol, weighed carboxylated seven octyl groups POSS are dissolved in oxolane, then will be dissolved with hydroxide 1-propyl group-3-first
The methanol of base imidazoles and the oxolane dissolved with carboxylated seven octyl groups POSS join in flask in the lump, form the second reaction system
Solution, is stirred at room temperature 2-15h, makes the second reaction system solution generation chemical reaction, after reaction terminates, from product system
In, steam solvent by decompression, obtain POSS base ionic liquid crude product；Then add in POSS base ionic liquid crude product
Hexamethylene, then by being centrifuged dissolved with the hexamethylene of POSS base ionic liquid, obtain the supernatant, supernatant decompression is steamed
Removing solvent, finally give POSS base ionic liquid pure products, its chemical formula is:
WhereinN=
2。
The above embodiment of the present invention is prepared for containing POSS ionic liquid, and easily, productivity is high in reaction, and purity is high, and stable
Property is good, includes the POSS monomer that structure is clear and definite, organic-dissolvable is good, imparts the resistant to elevated temperatures characteristic of ionic liquid, and by
The side chain contained in POSS is longer, also makes the ionic liquid of synthesis at room temperature have good mobility simultaneously.In the present invention
Stating embodiment preparation method, its process intensification, the response time is short, and product purity is high, and productivity is high, can be with large-scale production.
Experimental test and analysis:
The above embodiment of the present invention utilizes carboxyl POSS and hydroxide imidazoles to be synthesized by acid-base neutralization to have resistance to height
The ionic liquid at room temperature of temperature, in embodiment one, sees Fig. 1～3, and Fig. 1 is the nuclear magnetic resonance, NMR figure of compound,1HNMR(CDCl3,
298K, 500MHz), δ (ppm)=10.26 (s, 1H ,-NCHN-), 7.37 (s, 2H,-CHCH-),6.07(s,1H,-NH-),
4.30(t,2H,-NCH2-),4.08(s,3H,-NCH3),3.24(q,2H,-NHCH2-),2.65(t,2H,-CH2COO-),2.56
(t,2H,-CH2CO-),1.90(m,2H,-NCH2CH2-),1.62(m,2H,-NHCH2CH2-),1.33(m,6H,-
NCH2CH2CH2CH2CH2-),1.34(m,14H,-CH2CH3),1.15(m,14H,-CH2CH2CH3),1.02(m,42H,-
CH2CH2CH2CH2CH2CH3),0.91(t,24H,-CH3),0.78(m,14H,-SiCH2CH2-),0.60(d,16H,-SiCH2-),
According to hydrogen atom actual go out peak position and integration ratio can release POSS-ILs ionic liquid and successfully synthesize.Fig. 2 is compound
Differential scanning calorimetry (DSC) curve chart, as can be seen from the figure the vitrification point of compound is-25.4 DEG C, shows compound
It is at room temperature the liquid with mobility.Fig. 3 is the thermal gravimetric analysis curve figure of compound, and as can be seen from the figure compound exists
Do not occur within the temperature range of less than 277.4 DEG C decomposing, show that compound at high temperature has good heat stability.In the present invention
State embodiment by the POSS of heat resistant structure is introduced anionic group, synthesize resistance to less than-15 DEG C of a series of vitrification point
The ionic liquid at room temperature of high temperature, and find that decomposing does not occurs in product at 270 DEG C, can be used for electrolyte, carries by TGA test
The use temperature range of high battery.
Above in conjunction with accompanying drawing, the embodiment of the present invention is illustrated, but the invention is not restricted to above-described embodiment, it is also possible to
The purpose of the innovation and creation according to the present invention makes multiple change, under all spirit according to technical solution of the present invention and principle
The change made, modify, substitute, combine or simplify, all should be the substitute mode of equivalence, as long as meeting the goal of the invention of the present invention,
The know-why of the ionic liquid at room temperature without departing from POSS based high-temp-resistant of the present invention and preparation method thereof and inventive concept, all
Belong to protection scope of the present invention.
Claims (9)
1. the ionic liquid at room temperature of a POSS based high-temp-resistant, it is characterised in that its general structure is:
Wherein,
2. the preparation method of the ionic liquid at room temperature of a POSS based high-temp-resistant, it is characterised in that be modified POSS, utilizes
Carboxyl POSS and hydroxide imidazoles, be synthesized by acid-base neutralization, the preparation side of the ionic liquid at room temperature of POSS based high-temp-resistant
The synthetic route of method is:
Wherein,
The preparation method of the ionic liquid at room temperature of POSS based high-temp-resistant the most according to claim 2, it is characterised in that synthesis
Specifically comprise the following steps that
(1) preparation of compound b:
Using compound a as raw material, using the 1-Cm-3-Methylimidazole. of bromination as compound a, wherein m=2,3,4 or 5, i.e. institute
The chemical formula stating compound a is:WhereinN=2～5, adds compound a
The strong-base anion-exchange resin post that deionized water moistened, prepares compound b aqueous solution, the compound b aqueous solution that will obtain
Deionized water therein is removed by vacuum lyophilization, the 1-Cm-3-Methylimidazole. that compound b is hydroxide of gained, its
Chemical formula is:
(2) preparation of compound d:
Using aminopropyl seven octyl group POSS as compound c, compound c chemical formula it is:
WhereinUse compound c and succinic anhydride as former
Material, be 1:(1～1.5 according to the molar ratio of compound c: succinic anhydride) ratio respectively take raw material, then by weighedization
Compound c, succinic anhydride are dissolved in the first solvent respectively, respectively obtain the first solvent dissolved with succinic anhydride and dissolved with compound c's
First solvent, pours into the first solvent dissolved with succinic anhydride in flask, and makes to pour constant voltage into dissolved with first solvent of compound c
Dropping funnel；Under the conditions of being stirred at room temperature, the solution in constant pressure funnel is added dropwise in the solution in flask, is formed
First reaction system solution, after being added dropwise to complete, takes off constant pressure funnel, changes condensing tube into, is placed in by reaction bulb at 80 DEG C
In oil bath pan, it is stirred at reflux 1-15h, makes the first reaction system solution generation chemical reaction, stopped reaction, from product system,
Steam the first solvent by decompression, obtain compound d crude product；In compound d crude product, add the second solvent again, then from
Clear liquor decompression, to clear liquor, is steamed the second solvent by gains in depth of comprehension, obtains compound d, under vacuum, the most dry at 60 DEG C
Dry 24h, obtains compound d pure products, and the compound d of gained is carboxylated seven octyl groups POSS, and its chemical formula is:
(3) preparation of compound e:
The compound b that will prepare in described step (1) and the compound d prepared in described step (2), as reactant, presses
According to compound b: the molar ratio of compound d is (1～1.5): the ratio of 1 weighs reactant respectively, then by weighedization
Compound b is dissolved in the 3rd solvent, is dissolved in the 4th solvent by weighed compound d, then the 3rd molten by dissolved with compound b
Agent and the 4th solvent dissolved with compound d join in flask in the lump, form the second reaction system solution, are stirred at room temperature 2-
15h, makes the second reaction system solution generation chemical reaction, after reaction terminates, from product system, steams solvent by decompression,
Obtain compound e crude product；Then in compound e crude product, add the 5th solvent, then it is molten to pass through the dissolved with compound e the 5th
Agent is centrifuged, and obtains the supernatant, supernatant decompression is boiled off solvent, finally gives compound e pure products, the change of gained
Compound e is POSS base ionic liquid, and its chemical formula is:
The preparation method of the ionic liquid at room temperature of POSS based high-temp-resistant the most according to claim 3, it is characterised in that described
In step (1), compound a is the 1-Cn-3-Methylimidazole. of bromination, is bromination 1-propyl group-3-methyl when m=2,3,4,5
Imidazoles, 1-butyl-3-methylimidazolium bromide, bromination 1-amyl group-3-Methylimidazole. or bromination 1-hexyl-3-Methylimidazole..
The preparation method of the ionic liquid at room temperature of POSS based high-temp-resistant the most according to claim 3, it is characterised in that: described
In step (2), described first solvent uses any one solvent or the most several mixing in oxolane, isopropanol and methanol
Solvent.
The preparation method of the ionic liquid at room temperature of POSS based high-temp-resistant the most according to claim 3, it is characterised in that: described
In step (2), described second solvent uses any one solvent or the two mixed solvent in hexamethylene and petroleum ether.
The preparation method of the ionic liquid at room temperature of POSS based high-temp-resistant the most according to claim 3, it is characterised in that: described
In step (3), described 3rd solvent uses any one solvent or the most several mixing in methanol, water and chloroform molten
Agent.
The preparation method of the ionic liquid at room temperature of POSS based high-temp-resistant the most according to claim 3, it is characterised in that: described
In step (3), described 4th solvent uses any one solvent or any in oxolane, chloroform, chloropropane and toluene
Several mixed solvents.
The preparation method of the ionic liquid at room temperature of POSS based high-temp-resistant the most according to claim 3, it is characterised in that: described
In step (3), described second solvent uses any one solvent or the two mixed solvent in hexamethylene and petroleum ether.
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| CN107828056A (en) * | 2017-11-23 | 2018-03-23 | 上海大学 | POSS based quaternary ammonium salt class ionic liquids and preparation method thereof |
| CN107910588A (en) * | 2017-10-27 | 2018-04-13 | 上海大学 | Solid polymer electrolyte of the base ionic liquids of POSS containing room temperature and preparation method thereof |
| 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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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107910588A (en) * | 2017-10-27 | 2018-04-13 | 上海大学 | Solid polymer electrolyte of the base ionic liquids of POSS containing room temperature and preparation method thereof |
| CN107828056A (en) * | 2017-11-23 | 2018-03-23 | 上海大学 | POSS based quaternary ammonium salt class ionic liquids and preparation method thereof |
| 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 |
| CN109400883B (en) * | 2018-11-29 | 2021-03-30 | 中国科学院兰州化学物理研究所 | Space irradiation resistant POSS-based in-situ ionic liquid and preparation method and application thereof |
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