CN103819668A - Preparation method of ionic liquid polymer - Google Patents
Preparation method of ionic liquid polymer Download PDFInfo
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- CN103819668A CN103819668A CN201410019878.XA CN201410019878A CN103819668A CN 103819668 A CN103819668 A CN 103819668A CN 201410019878 A CN201410019878 A CN 201410019878A CN 103819668 A CN103819668 A CN 103819668A
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- FXXCPGDTVCNKDF-UHFFFAOYSA-N CCCCC[BrH]C Chemical compound CCCCC[BrH]C FXXCPGDTVCNKDF-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to a preparation method of an ionic liquid polymer. The ionic liquid polymer is prepared from a bifunctional nitrogen-containing compound and dihalogenated hydrocarbon through quaterisation reaction. The method provided by the invention provides a novel method for preparing the ionic liquid polymer for the field, the preparation method is simple and practical, and the reaction is easy to control.
Description
Technical field
The present invention relates to a kind of preparation method of ion liquid polymer, belong to ionic liquid preparation field.
Background technology
Ionic liquid (IL), also referred to as room temperature melting salt, is a kind of novel dissolvent of environmental protection, the material being made up of ion that refers to fusing point below 100 ℃ and be in a liquid state at room temperature or near room temperature.Ionic liquid has following characteristics: wider electrochemical window, and stronger dissolving power, lower vapour pressure, has certain viscosity, stronger catalytic activity.Due to its superior performance, ionic liquid has been widely used in organic synthesis, extracting and separating, electrochemistry, nano material preparation, Clean Fuel Production, environmental science, the every field such as catalytic science.Ionic liquid has very significantly advantage as solvent: non-volatile, stable in properties, is easy to reclaim, strong polarity.These features show that ionic liquid may serve as the substitute of organic solvent (Zhang Xingchen, ionic liquid---from theoretical basis to progress, Beijing: Chemical Industry Press, 2008,6:1-12) completely.
Up to now, ionic liquid is widely used.Lithium-ion secondary cell is the green energy resource that 20th century, the nineties, new development was got up.The organic electrolyte of its use is inflammable, explosive, therefore has serious potential safety hazard.And ionic liquid has advantages of that steam forces down, nothing is flammable, thermal capacity is large just, therefore, consider use neutral ion liquid 1-methyl-3-ethyl imidazol(e) muriate/aluminum chloride and 1, the 2-dimethyl-3-propyl imidazole muriate/aluminum chloride ionogen as serondary lithium battery.But result of study shows; metallic lithium surface can not form the rete of protectiveness; can not carry out comparatively reversible anode and cathode polarization (Carlin R T; Long H C; Fuller J; et al.Dual intercalating molten electrolyte batteriers.J Electrochemical Society, 1994,141 (4): L73-L76.).
Afterwards, first Jianbin Tang etc. has prepared the ionic liquid that contains carbon-carbon double bond, then obtained ion liquid polymer (Jianbin Tang by the polymerization of carbon-carbon double bond, Huadong Tang, Weilin Sun et al.Low-pressure CO2sorption in ammonium-based poly (ionic liquid) s.Polymer46 (2005): 12460 – 12467), but this method needs polystep reaction, complicated operation, wayward.
CN101786988A discloses a kind of synthetic method of porous ion liquid polymer in addition, wherein relates to a kind of synthetic method of ion liquid polymer: A.1-Methylimidazole and propenyl chloride reaction generate chlorination 1-allyl group-3-Methylimidazole ionic liquid; B. chlorination 1-allyl group-3-Methylimidazole ionic liquid and fluoroboric acid reaction generate 1-allyl group-3-methyl imidazolium tetrafluoroborate ionic liquid; C.1-allyl group-3-methyl imidazolium tetrafluoroborate ionic liquid and acrylonitrile reactor generate ion liquid polymer.The synthetic method of the ion liquid polymer of this invention is also very loaded down with trivial details, complicated operation.
CN102952092A discloses a kind of preparation method of azoles alkanes ionic liquid, comprise the steps: methyl azoles alkane and haloalkane 1:1～1:1.2 mixing in molar ratio post-heating to 60 ℃～80 ℃, stirring reaction obtains alkyl azoles alkane halogenide, wherein, described haloalkane is methoxy ethoxy methyl chloride or methoxy ethoxy monobromethane; Be M by the alkyl azoles alkane halogenide of preparation and general formula
+y
-salt with mol ratio 1:1 mix after add in deionized water, stir occur ion exchange reaction, after separation and purification, obtain azoles alkanes ionic liquid.CN101709055A discloses a kind of synthesis preparation method of ionic liquid, comprise following processing step: (1) synthesis step: by n-propylcarbinyl chloride and N-Methylimidazole by the mixed in molar ratio of 1:1～1.2:1, under return stirring state, react 4～10 hours, temperature of reaction is 70 ℃～90 ℃, obtains reaction product; (2) extracting and separating step: add extraction agent ethyl acetate in the reaction product obtaining, realize separating of ethyl acetate and ionic liquid phase by extraction, obtain ionic liquid.Foregoing invention is all preparations of ionic liquid monomer.
Summary of the invention
One of object of the present invention is to provide a kind of preparation method of ion liquid polymer.Method of the present invention provides a kind of novel method of preparing ion liquid polymer for this area, and preparation method is simple, and reaction is easily controlled.
For reaching above object, the present invention has adopted following technical scheme:
A preparation method for ion liquid polymer, makes ion liquid polymer take bifunctional nitrogenous compound and dihalo hydrocarbon as raw material by quaternary ammonium reaction.
As optimal technical scheme, preparation method of the present invention, bifunctional nitrogenous compound and dihalo hydrocarbon be reaction under heating, obtains crude product, dry after washing.
Preferably, bifunctional nitrogenous compound used is 4,4-dipyridyl, 2, the one kind or two or more mixture in 2-dipyridyl, two imidazolyl butane, two imidazolyl pentane, two imidazolyl hexane.The structural formula of above-mentioned substance is as follows:
4,4-joins pyrrole
2,2-dipyridyl
Two imidazolyl butane
Two imidazolyl pentanes
Two imidazolyl hexanes
Preferably, dihalo hydrocarbon used is Isosorbide-5-Nitrae-dichlorobutane, 1,5-dichloropentane, 1,3-propylene dichloride, Dichloroethyl ether, 1, the one kind or two or more mixture in 3-dichloro 2-propyl alcohol, Isosorbide-5-Nitrae-dibromobutane.The structural formula of above-mentioned substance is as follows:
Isosorbide-5-Nitrae-dichlorobutane
1,5-dichloropentane
1,3-propylene dichloride
Dichloroethyl ether
1,3-dichloro 2-propyl alcohol
Isosorbide-5-Nitrae-dibromobutane
Preferably, described bifunctional nitrogenous compound than for 1:0.5-3, for example, is 1:0.7,1:0.9,1:1.3,1:1.8,1:2.0,1:2.3,1:2.6,1:2.9 etc. with the amount of substance of dihalo hydrocarbon, is preferably 1:1.
Preferably, the temperature of described reaction is 50-120 ℃, it is for example 55 ℃, 60 ℃, 63 ℃, 68 ℃, 75 ℃, 86 ℃, 90 ℃, 97 ℃, 106 ℃, 112 ℃, 118 ℃ etc., the time of reaction is 2-120h, for example, be 3h, 5h, 9h, 15h, 30h, 45h, 55h, 60h, 70h, 85h, 90h, 100h, 106h, 115h etc.
Preferably, described washing is used ethyl acetate washing.
Preferably, described washing is carried out more than 1 time, preferably carries out 3 times.
Preferably, described being dried under vacuum carried out.
Preferably, described dry temperature is 60-95 ℃, for example, be 63 ℃, 66 ℃, 69 ℃, 73 ℃, 78 ℃, 81 ℃, 84 ℃, 88 ℃, 92 ℃ etc., is preferably 70-90 institute ℃, more preferably 80 ℃.
Preferably, the described dry time is more than 1h, for example, be 1.5h, 1.8h, 2.5h, 3.1h, 3.6h, 4.0h, 4.5h etc., is preferably 3h.
One of object of the present invention is also to provide the purposes of described ion liquid polymer, described ion liquid polymer is carried out to anionresin and obtains the ion liquid polymer of respective anionic.
For example, carry out as follows: take acetone as solvent, the ion liquid polymer of gained and sodium tetrafluoroborate are reacted to 20-60 hour according to negatively charged ion mol ratio 1:1.1-2 at 40-60 ℃, be cooled to after completion of the reaction room temperature, 40-70 ℃ revolve steam remove acetone, add about 20-50ml CH
2cl
2, suction filtration is removed unreacted NaBF
4with the sodium-chlor generating, liquid phase distilled water wash, preferably 3 times, 50-90 ℃ of vacuum-drying is more than 1 hour.Obtain the ion liquid polymer that negatively charged ion is tetrafluoroborate.
Or: take water as solvent, the ion liquid polymer of gained and Potassium Hexafluorophosphate are reacted to 20-60 hour according to negatively charged ion mol ratio 1:1.1-2 at 40-60 ℃, be cooled to after completion of the reaction room temperature, add about 20-50mlCH
2cl
2, get organic layer, with distilled water wash, preferably 3 times, 50-90 ℃ of vacuum-drying is more than 1 hour.Obtain the ion liquid polymer that negatively charged ion is hexafluoro-phosphate radical.
The present invention compared with prior art, has following beneficial effect:
What 1, use due to the present invention is reactant simple and easy to get, thereby not only for this area provides a kind of novel method of preparing ion liquid polymer, and method is simple, and reaction is easily controlled.
2,, due to method provided by the invention, can, by using different bifunctional nitrogenous compound and dihalo hydrocarbon, obtain diversified ion liquid polymer.
3, the present invention prepares ion liquid polymer excellent performance, and its structure has designability.Thereby can design as required suitable structure, and for expanding it in organic synthesis, extracting and separating, electrochemistry, nano material preparation, Clean Fuel Production, environmental science, the application of the every field such as catalytic science is had laid a good foundation.
Embodiment
Further illustrate technical scheme of the present invention below by embodiment.
Embodiment 1:
Two imidazolyl butane and Isosorbide-5-Nitrae-dichlorobutane are heated 48 hours according to mol ratio 1:1 at 80 ℃, and product washs after 3 times by ethyl acetate, vacuum-drying at 80 ℃.Obtain the ion liquid polymer that negatively charged ion is chlorion.This reaction formula is as follows:
Take acetone as solvent, by this polymkeric substance and sodium tetrafluoroborate according to negatively charged ion mol ratio 1:1.2 50 ℃ of reactions 48 hours, be cooled to after completion of the reaction room temperature, 60 ℃ revolve to steam and remove acetone, add about 20ml CH
2cl
2, suction filtration is removed unreacted NaBF
4with the sodium-chlor generating, distilled water wash 3 times for liquid phase, 80 ℃ of vacuum-drying 3 hours.Obtain the ion liquid polymer that negatively charged ion is tetrafluoroborate.This reaction formula is:
Embodiment 2:
4,4-dipyridyl and Isosorbide-5-Nitrae-dichlorobutane are heated 48 hours according to mol ratio 1:1 at 80 ℃, and product washs after 3 times by ethyl acetate, vacuum-drying at 80 ℃.Obtain the ion liquid polymer that negatively charged ion is chlorion.This reaction formula is as follows:
Take acetone as solvent, the ion liquid polymer that is chlorion by above-mentioned gained negatively charged ion and sodium tetrafluoroborate according to negatively charged ion mol ratio 1:1.2 50 ℃ reaction 48 hours, be cooled to after completion of the reaction room temperature, 60 ℃ revolve steam remove acetone, add about 20ml CH
2cl
2, suction filtration is removed unreacted NaBF
4with the sodium-chlor generating, distilled water wash 3 times for liquid phase, 80 ℃ of vacuum-drying 3 hours.Obtain the ion liquid polymer that negatively charged ion is tetrafluoroborate.This reaction formula is:
Or take water as solvent, the ion liquid polymer that is chlorion by the negatively charged ion of above-mentioned gained and Potassium Hexafluorophosphate 50 ℃ of reactions 48 hours, are cooled to room temperature according to negatively charged ion mol ratio 1:1.2 after completion of the reaction, add about 20ml CH
2cl
2, get organic layer, with distilled water wash 3 times, 80 ℃ of vacuum-drying 3 hours.Obtain the ion liquid polymer that negatively charged ion is hexafluoro-phosphate radical.This reaction formula is:
Embodiment 3:
4,4-dipyridyl and Dichloroethyl ether are heated 48 hours according to mol ratio 1:1 at 80 ℃, and product washs after 3 times by ethyl acetate, vacuum-drying at 80 ℃.Obtain the ion liquid polymer that negatively charged ion is chlorion.This reaction formula is as follows:
Embodiment 4:
4,4-dipyridyl and dichloro 2-propyl alcohol are heated 5 hours according to mol ratio 1:2 at 80 ℃, and product washs after 2 times by ethyl acetate, vacuum-drying at 60 ℃.Obtain the ion liquid polymer that negatively charged ion is chlorion.This reaction formula is as follows:
Embodiment 5:
Two imidazolyl butane and Isosorbide-5-Nitrae-dibromobutane are heated 100 hours according to mol ratio 1:3 at 55 ℃, and product washs after 3 times by ethyl acetate, vacuum-drying at 94 ℃.Obtain the ion liquid polymer that negatively charged ion is bromide anion.This reaction formula is as follows:
Applicant's statement, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, and the selections of the equivalence replacement to the each raw material of product of the present invention and the interpolation of ancillary component, concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (10)
1. a preparation method for ion liquid polymer, is characterized in that, makes ion liquid polymer take bifunctional nitrogenous compound and dihalo hydrocarbon as raw material by quaternary ammonium reaction.
2. preparation method according to claim 1, is characterized in that, bifunctional nitrogenous compound and dihalo hydrocarbon be reaction under heating, obtains crude product, dry after washing.
3. preparation method according to claim 1 and 2, it is characterized in that, bifunctional nitrogenous compound used is 4,4-dipyridyl, 2, the one kind or two or more mixture in 2-dipyridyl, two imidazolyl butane, two imidazolyl pentane, two imidazolyl hexane.
4. according to the preparation method described in claim 1-3 any one, it is characterized in that, dihalo hydrocarbon used is 1,4-dichlorobutane, 1,5-dichloropentane, 1,3-propylene dichloride, Dichloroethyl ether, 1, one kind or two or more mixture in 3-dichloro 2-propyl alcohol, Isosorbide-5-Nitrae-dibromobutane.
5. according to the preparation method described in claim 2-4 any one, it is characterized in that, described bifunctional nitrogenous compound than for 1:0.5-3, is preferably 1:1 with the amount of substance of dihalo hydrocarbon;
Preferably, the temperature of described reaction is 50-120 ℃, and the time of reaction is 2-120h.
6. according to the preparation method described in claim 2-5 any one, it is characterized in that, described washing is used ethyl acetate washing.
7. preparation method according to claim 6, is characterized in that, described washing is carried out more than 1 time, preferably carries out 3 times.
8. according to the preparation method described in claim 2-7 any one, it is characterized in that, described being dried under vacuum carried out.
9. according to the preparation method described in claim 2-8 any one, it is characterized in that, described dry temperature is 60-95 ℃, is preferably 70-90 institute ℃, more preferably 80 ℃;
Preferably, the described dry time is more than 1h, to be preferably 3h.
10. the purposes of the ion liquid polymer that the preparation method described in claim 1-9 any one makes, is characterized in that, described ion liquid polymer is carried out to anionresin and obtains the ion liquid polymer of respective anionic.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107200798A (en) * | 2017-06-12 | 2017-09-26 | 厦门建霖健康家居股份有限公司 | A kind of antiseptic with broad-spectrum antiseptic |
| CN108102092A (en) * | 2018-01-09 | 2018-06-01 | 苏州大学 | cationic organic polymer and its preparation method and application |
| JP7376072B2 (en) | 2019-09-10 | 2023-11-08 | 国立大学法人 岡山大学 | Ionic liquid monomers, polymers and their production methods, and crosslinked polymers |
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| CN101709055A (en) * | 2009-11-21 | 2010-05-19 | 山东海龙股份有限公司 | Method for synthesizing ionic liquid |
| CN102952092A (en) * | 2011-08-30 | 2013-03-06 | 海洋王照明科技股份有限公司 | Oxazolidine ionic liquid and preparation method and application thereof |
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2014
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Patent Citations (3)
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| US4116535A (en) * | 1976-05-10 | 1978-09-26 | U.S. Philips Corporation | Picture display cell with memory effect |
| CN101709055A (en) * | 2009-11-21 | 2010-05-19 | 山东海龙股份有限公司 | Method for synthesizing ionic liquid |
| CN102952092A (en) * | 2011-08-30 | 2013-03-06 | 海洋王照明科技股份有限公司 | Oxazolidine ionic liquid and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| ANANDA S. AMARASEKARA.PREETHI SHANBHAG: "Synthesis and characterization of polymeric ionic liquidpoly(imidazoliumchloride-1,3-Diylbutane-1,4-diyl)", 《POLYMER BULLETIN》, vol. 67, no. 4, 26 November 2010 (2010-11-26), pages 20101126 * |
| BADRI Z. MOMENI等: ""Oxidative addition of some mono, di or tetra haloalkanes to organoplatinum(II)"", 《JOURNAL OF ORGANOMETALLIC CHEMISTRY》, 15 November 2011 (2011-11-15), XP028887364, DOI: doi:10.1016/j.jorganchem.2011.11.018 * |
| RAJENDRA P.SINGH: ""Bridged Tetraquaternary Salts from N,N¢-Polyfluoroalkyl-4,4¢-bipyridine"", 《INORGANIC CHEMISTRY》, 3 October 2003 (2003-10-03) * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107200798A (en) * | 2017-06-12 | 2017-09-26 | 厦门建霖健康家居股份有限公司 | A kind of antiseptic with broad-spectrum antiseptic |
| CN108102092A (en) * | 2018-01-09 | 2018-06-01 | 苏州大学 | cationic organic polymer and its preparation method and application |
| JP7376072B2 (en) | 2019-09-10 | 2023-11-08 | 国立大学法人 岡山大学 | Ionic liquid monomers, polymers and their production methods, and crosslinked polymers |
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Application publication date: 20140528 |