CN101209973A - Bronsted acidic ion liquid using polyamine as cation and preparation method thereof - Google Patents
Bronsted acidic ion liquid using polyamine as cation and preparation method thereof Download PDFInfo
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- CN101209973A CN101209973A CN 200610105395 CN200610105395A CN101209973A CN 101209973 A CN101209973 A CN 101209973A CN 200610105395 CN200610105395 CN 200610105395 CN 200610105395 A CN200610105395 A CN 200610105395A CN 101209973 A CN101209973 A CN 101209973A
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Abstract
The invention discloses a BrPhinsted acidic ionic liquid which takes multi-ammonium as cation and a preparation method thereof; the ionic liquid is one step prepared through neutralization reaction between multi-ammonium and inorganic acid or organic acid. The invention has the advantages of low cost, simple preparation, green process, and suitability for massive production. The ionic liquid has potential practical application prospect in electronic optical and photoelectric material, energy, resource and environment and life science, etc.
Description
Technical field
The present invention relates to a kind of is cationic with polynary ammonium
Acidic ion liquid and preparation method thereof belongs to new chemical material and preparing technical field thereof.
Background technology
Ionic liquid mainly refers to fusing point and is lower than 100 ℃ organic molten salt, and they are made of organic cation with unsymmetrical structure and inorganic or organic anion usually.Normally, because many ionic liquids at room temperature are in a liquid state, therefore be also referred to as ionic liquid at room temperature.In recent years, ionic liquid had been subjected to chemist and material scholar's extensive concern, and its reason has three: (1) worldwide environmental pollution increases the weight of the continuous enhancing with people's environmental consciousness day by day.It is reported the about 6,000,000,000 dollars organic solvent of the annual use value in the world.Because the volatility of organic solvent makes a large amount of organic solvent evaporations in atmosphere, causes the deterioration of Air quality.Obviously, seeking a kind of non-volatile, nonflammable liquid, replace existing organic solvent, is the good method of head it off.A selection that ionic liquid is best just! (2) distinctive designability of ionic liquid and diversity.In the chemical industry field, approximately have only hundreds of surplus kind of molecule-type organic solvents available, and to ionic liquid, have that to surpass hundreds of millions kinds of possible ionic liquids available! Ion liquid multifarious characteristics also make and can find only ionic liquid as reaction medium for specific reaction or catalyzer, thereby make and make up efficiently that reaction system becomes possibility.(3) distinctive ionic internal medium.Before 19th century, the various matter interactions that people obtained and the knowledge of the characteristics of motion all obtain in molecular media; This interaction and rule in being entirely the ionic medium are also understood seldom.Therefore, be necessary to carry out ion liquid research, to obtain some new rule and knowledge.
20th century the mid-80, research institutions such as Britain and France begin systematically to explore the possibility of ionic liquid as " green " medium and catalyzer, indicate the beginning of ionic liquid at room temperature in the chemical field systematic study.In recent years, very active about ion liquid research, western countries government all invested considerable capital to carry out the research of ionic liquid aspect with relevant enterprise.Because ion liquid designability, promptly adjust the suitable functional group of yin, yang ion population or grafting, can obtain the ionic liquid of " target is specific " or " cutting the garment according to the figure ", and demonstrate good prospects for application in recovery, the special optical material field of separation and purification, nuke rubbish.Ionic liquid combines with existing supercutical fluid, electrochemistry, microelectronics etc., makes the further increasing of development space and the function of original these technology more become perfect.At present, ionic liquid research from development " cleaning " or " green " chemical field, expands to functional materials fast, as electric light and photoelectric material, lubricant; The energy is as storage of solar energy, solar cell critical material; Resource environment is as the degraded of natural gas conditioning, xylogen; Life sciences etc. have typically embodied multidisciplinary intersection and comprehensive effect in scientific technological advance.
Because ionic liquid is to be combined by negative ions, this means that it has diversity.Theoretically, exist hundreds of millions kinds of different ionic liquid combinations.And the variation of different zwitterions combination will cause ionic liquid physicochemical property generation change in various degree.Making up the novel ion liquid that obtains to have different performance by the different negative ions of conversion, is the important directions of the liquid research and development of ion.The ionic liquid of report mainly comprises dialkylimidazolium class and alkyl pyridine class ionic liquid at present, and also finding no the pass so far is cationic ion liquid report by polynary ammonium.
Summary of the invention
The object of the present invention is to provide a kind of is cationic with polynary ammonium
Acidic ion liquid and preparation method thereof.
Purpose of the present invention can be achieved through the following technical solutions:
Provided by the invention a kind of be cationic with polynary ammonium
Acidic ion liquid, its structural formula is represented with formula (I) compound:
NH
3 +CH
2CH
2(NH
2 +CH
2CH
2)
nNH
3 +(n+2)X
-
(I)
Wherein, X
-A kind of in chlorine negative ion, bromine negative ion, iodine negative ion, tetrafluoroborate, hexafluoro-phosphate radical, tosic acid root, nitrate radical, formate, sulfur hydrogen anion, dihydrogen phosphate, acetate, methanesulfonic root, trifluoromethayl sulfonic acid root, tosic acid root, p-nitrophenyl sulfonate radical, trifluoracetic acid root or two (perfluoroalkyl group sulfonyl) amido negative ion, n is 0 to 4 integer.
Ionic liquid of the present invention is by making with single step reaction in polyamine and inorganic or the organic acid.
Provided by the invention a kind of be cationic with polynary ammonium
The preparation method of acidic ion liquid is: with the aqueous solution of polyamine and one of hydrochloric acid, Hydrogen bromide, hydroiodic acid HI, Tetrafluoroboric acid, phosphofluoric acid, tosic acid, nitric acid, formic acid, sulphur hydracid, phosphoric acid, acetic acid, methanesulfonic, trifluoromethayl sulfonic acid, tosic acid, p-nitrophenyl sulfonic acid, trifluoroacetic acid or two (perfluoroalkyl group sulfonyl) imines; stir; through acid-base neutralisation, separation, making is cationic with polynary ammonium accordingly
Acidic ion liquid.
Provided by the invention is cationic with polynary ammonium
Acidic ion liquid specifically mainly contains: the nitrate ion liquid of the formate ionic liquid of triethylene tetramine, the acetate ionic liquid of triethylene tetramine, diethylenetriamine, the Tetrafluoroboric acid ionic liquid of diethylenetriamine, the trifluoroacetic acid ionic liquid of tetraethylene pentamine and the trifluoracetic acid ionic liquid of tetraethylene pentamine.
Provided by the invention is cationic with polynary ammonium
Acidic ion liquid compared with prior art
Have following characteristics:
(1) the present invention is to provide a kind of novel ionic liquid, developed the newcomer of ionic liquid family.
(2) cost of material cheaply is easy to get, and synthetic cost is lower.
(3) one step neutralization reactions, preparation process is simple, is fit to scale operation.
(4) the preparation process no coupling product generates, and belongs to atomic economy reaction, the preparation process greenization.
(5) can regulate the potential of hydrogen of product as required, have stronger controllability.
Preparation method of the present invention has that cost is low, preparation is simple, process is green, is fit to advantages such as scale operation.Ionic liquid has the potential actual application prospect in electric light and photoelectric material, the energy, resource environment, life science etc.
Embodiment
In order to further specify details of the present invention, enumerate some embodiment below, but should not be so limited.
Embodiment 1
The formate of triethylene tetramine is ion liquid synthetic
In being furnished with the round-bottomed flask of magnetic agitation, the triethylene tetramine that adds 14.7ml (0.1mol), add the 50ml dehydrated alcohol then, stir 30min under the ice-water bath condition, dropwise add 85% formic acid solution 17.8ml (0.4mol) then while stirring, white precipitate occurs, continue to drip formic acid solution 2ml, after reacting about 10 minutes, suction filtration, the solid matter that leaches are the formate ionic liquid of triethylene tetramine.Temperature of reaction is 0-5 ℃.Productive rate: 85%.Reaction formula is:
Embodiment 2
Synthesizing of the acetate ionic liquid of triethylene tetramine
In being furnished with the round-bottomed flask of magnetic agitation, the triethylene tetramine that adds 14.7ml (0.1mol), add the 50ml dehydrated alcohol then, stir 30min under the ice-water bath condition, dropwise add 99.5% acetic acid 23.0ml (0.3mol) then while stirring, white precipitate occurs, continue to drip acetum 2ml, after reacting about 10 minutes, suction filtration, the solid matter that leaches are the acetate ionic liquid of triethylene tetramine.Temperature of reaction is 0-5 ℃.Productive rate: 79%.Reaction formula is:
Embodiment 3
Synthesizing of the nitrate ion liquid of diethylenetriamine
In being furnished with the round-bottomed flask of magnetic agitation, add 10.8ml (0.1mol) diethylenetriamine, add the 50ml dehydrated alcohol then, stir 30min under the ice-water bath condition, dropwise add 65% nitric acid 29.1g (0.3mol) then while stirring, white precipitate occurs, continue to drip nitric acid 2ml, after reacting about 10 minutes, suction filtration, the solid matter that leaches are the nitrate ion liquid of triethylene tetramine.Temperature of reaction is 0-5 ℃.Productive rate: 82%.Reaction formula is:
Embodiment 4
Synthesizing of the tetrafluoroborate ion liquid of diethylenetriamine
In being furnished with the round-bottomed flask of magnetic agitation, add 10.8ml (0.1mol) diethylenetriamine, add the 50ml dehydrated alcohol then, stir 30min under the ice-water bath condition, dropwise add 40% tetrafluoroborate solution 65.9g then while stirring and (contain HBF
40.3mol), white precipitate appears, continue to drip nitric acid 2ml, react about 10 minutes after, suction filtration, the solid matter that leaches are the tetrafluoroborate ion liquid of triethylene tetramine.Temperature of reaction is 0-5 ℃.Productive rate: 75%.Reaction formula is:
Embodiment 5
The trifluoroacetate of tetraethylene pentamine is ion liquid synthetic
In being furnished with the round-bottomed flask of magnetic agitation, add 17.2ml (0.1mol) tetraethylene pentamine, add the 50ml dehydrated alcohol then, stir 30min under the ice-water bath condition, dropwise add trifluoroacetic acid 57.0g (0.5mol) then while stirring, white precipitate occurs, continue to drip trifluoroacetic acid 2ml, after reacting about 10 minutes, suction filtration, the solid matter that leaches are the trifluoroacetate ionic liquid of tetraethylene pentamine.Temperature of reaction is 0-5 ℃.Productive rate: 79%.Reaction formula is:
Embodiment 6
The formate of tetraethylene pentamine is ion liquid synthetic
In being furnished with the round-bottomed flask of magnetic agitation, adding 0.1mol purity is 98% tetraethylene pentamine, add the 50ml dehydrated alcohol then, stir 30min under the ice-water bath condition, dropwise add formic acid 22.2g (0.5mol) then while stirring, white precipitate occurs, continue to drip formic acid 2ml, after reacting about 10 minutes, suction filtration, the solid matter that leaches are the formate ionic liquid of tetraethylene pentamine.Temperature of reaction is 0-5 ℃.Productive rate: 86%.Reaction formula is:
Claims (2)
1. one kind is cationic with polynary ammonium
Acidic ion liquid, its structural formula is represented with formula (I) compound:
NH
3 +CH
2CH
2(NH
2 +CH
2CH
2)
nNH
3 +(n+2)X
-
(I)
Wherein, X
-A kind of in chlorine negative ion, bromine negative ion, iodine negative ion, tetrafluoroborate, hexafluoro-phosphate radical, tosic acid root, nitrate radical, formate, sulfur hydrogen anion, dihydrogen phosphate, acetate, methanesulfonic root, trifluoromethayl sulfonic acid root, tosic acid root, p-nitrophenyl sulfonate radical, trifluoracetic acid root or two (perfluoroalkyl group sulfonyl) amido negative ion, n is 0 to 4 integer.
2. be cationic with polynary ammonium according to claim 1
The preparation method of acidic ion liquid; it is characterized in that: with the aqueous solution of polyamine and one of hydrochloric acid, Hydrogen bromide, hydroiodic acid HI, Tetrafluoroboric acid, phosphofluoric acid, tosic acid, nitric acid, formic acid, sulphur hydracid, phosphoric acid, acetic acid, methanesulfonic, trifluoromethayl sulfonic acid, tosic acid, p-nitrophenyl sulfonic acid, trifluoroacetic acid or two (perfluoroalkyl group sulfonyl) imines; stir, make through acid-base neutralisation, separation.
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| CN 200610105395 CN101209973A (en) | 2006-12-26 | 2006-12-26 | Bronsted acidic ion liquid using polyamine as cation and preparation method thereof |
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| CN101993378A (en) * | 2010-09-10 | 2011-03-30 | 中国石油大学(北京) | Amido-containing ionic liquid used for absorbing acidic gases and preparation method and application thereof |
| CN102070462A (en) * | 2011-01-20 | 2011-05-25 | 中国科学院过程工程研究所 | Ethylenediamine-nitrophenol type ionic liquids and preparation method thereof |
| CN102416347A (en) * | 2011-08-31 | 2012-04-18 | 中山大桥化工集团有限公司 | Multi-ionic liquid catalyst and application thereof in synthesis of acrylate compounds |
| CN102441312A (en) * | 2010-10-13 | 2012-05-09 | 北京化工大学 | Recyclable ionic liquid type carbon dioxide absorbent and preparation method thereof |
| CN102791675A (en) * | 2009-11-06 | 2012-11-21 | 陶氏环球技术有限责任公司 | Difunctional, amine-based surfactants, and their precursors, preparation, compositions and use |
| CN102898317A (en) * | 2012-10-12 | 2013-01-30 | 四川农业大学 | Organic amino compounds serving as immunopotentiators, metabolic enhancers or roborants and preparation method and use thereof |
| CN102895842A (en) * | 2012-09-14 | 2013-01-30 | 辽宁科技大学 | Preparation method of CO2 gas absorbent for polyamine ionic liquid |
| CN103570561A (en) * | 2013-09-27 | 2014-02-12 | 江南大学 | Synthesis of tetrameric quaternary ammonium salt |
| CN111606814A (en) * | 2020-04-28 | 2020-09-01 | 廊坊师范学院 | Ionic liquid containing citrazinic acid anions and application thereof in iodine absorption |
| CN112062680A (en) * | 2020-08-25 | 2020-12-11 | 南京工业大学 | Organic matter type ionic liquid, two-dimensional perovskite pure-phase quantum well structure film, preparation method and application thereof |
-
2006
- 2006-12-26 CN CN 200610105395 patent/CN101209973A/en active Pending
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| CN102791675B (en) * | 2009-11-06 | 2015-06-17 | 陶氏环球技术有限责任公司 | Difunctional, amine-based surfactants, and their precursors, preparation, compositions and use |
| CN102791675A (en) * | 2009-11-06 | 2012-11-21 | 陶氏环球技术有限责任公司 | Difunctional, amine-based surfactants, and their precursors, preparation, compositions and use |
| CN101993378B (en) * | 2010-09-10 | 2013-05-15 | 中国石油大学(北京) | Amido-containing ionic liquid used for absorbing acidic gases and preparation method and application thereof |
| CN101993378A (en) * | 2010-09-10 | 2011-03-30 | 中国石油大学(北京) | Amido-containing ionic liquid used for absorbing acidic gases and preparation method and application thereof |
| CN102441312A (en) * | 2010-10-13 | 2012-05-09 | 北京化工大学 | Recyclable ionic liquid type carbon dioxide absorbent and preparation method thereof |
| CN102441312B (en) * | 2010-10-13 | 2014-01-08 | 北京化工大学 | Recyclable ionic liquid type carbon dioxide absorbent and preparation method thereof |
| CN102070462A (en) * | 2011-01-20 | 2011-05-25 | 中国科学院过程工程研究所 | Ethylenediamine-nitrophenol type ionic liquids and preparation method thereof |
| CN102416347B (en) * | 2011-08-31 | 2013-11-20 | 中山大桥化工集团有限公司 | Multi-ionic liquid catalyst and application thereof in synthesizing acrylate compounds |
| CN102416347A (en) * | 2011-08-31 | 2012-04-18 | 中山大桥化工集团有限公司 | Multi-ionic liquid catalyst and application thereof in synthesis of acrylate compounds |
| CN102895842A (en) * | 2012-09-14 | 2013-01-30 | 辽宁科技大学 | Preparation method of CO2 gas absorbent for polyamine ionic liquid |
| CN102898317A (en) * | 2012-10-12 | 2013-01-30 | 四川农业大学 | Organic amino compounds serving as immunopotentiators, metabolic enhancers or roborants and preparation method and use thereof |
| CN102898317B (en) * | 2012-10-12 | 2015-04-22 | 四川农业大学 | Organic amino compounds serving as immunopotentiators, metabolic enhancers or roborants and preparation method and use thereof |
| CN103570561A (en) * | 2013-09-27 | 2014-02-12 | 江南大学 | Synthesis of tetrameric quaternary ammonium salt |
| CN111606814A (en) * | 2020-04-28 | 2020-09-01 | 廊坊师范学院 | Ionic liquid containing citrazinic acid anions and application thereof in iodine absorption |
| CN111606814B (en) * | 2020-04-28 | 2023-03-17 | 廊坊师范学院 | Ionic liquid containing citrazinic acid anions and application thereof in iodine absorption |
| CN112062680A (en) * | 2020-08-25 | 2020-12-11 | 南京工业大学 | Organic matter type ionic liquid, two-dimensional perovskite pure-phase quantum well structure film, preparation method and application thereof |
| CN112062680B (en) * | 2020-08-25 | 2021-06-22 | 南京工业大学 | Organic matter type ionic liquid, two-dimensional perovskite pure-phase quantum well structure film, preparation method and application thereof |
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Open date: 20080702 |