CN105315164A - Environment-friendly choline ionic liquid and preparation method therefor - Google Patents
Environment-friendly choline ionic liquid and preparation method therefor Download PDFInfo
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- CN105315164A CN105315164A CN201410375016.0A CN201410375016A CN105315164A CN 105315164 A CN105315164 A CN 105315164A CN 201410375016 A CN201410375016 A CN 201410375016A CN 105315164 A CN105315164 A CN 105315164A
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Abstract
The invention relates to environment-friendly novel choline ionic liquid and a method for preparing the choline ionic liquid. The novel choline ionic liquid contains levulinic acid choline, sorbic acid choline, glutaric acid choline, adipic acid choline, (p-, m- and o-)phthalic acid choline, trifluoromethanesulfonic acid choline, benzenesulfonic acid choline, (p-, m- and o-)toluenesulfonic acid choline, bis(trifluoromethane sulfonimide) choline and the like. The novel choline ionic liquid has the remarkable advantages that the preparation process is simple, the recovery is simple and convenient, the stability of reuse is good, and the like.
Description
Technical field
The present invention relates to a series of eco-friendly new choline ionic liquid and prepare the method for this cholinium ion liquid.Specifically comprise two steps: 1) under basic catalyst existent condition, Lipotril is dissolved in alcoholic solvent, and heating generates choline hydroxide solutions.2) exchanged by choline hydroxide solutions and organic acid ion and obtain new choline class ionic liquid.
Background technology
Along with people are to the raising of environmental protection and Consciousness of Sustainable Development, the green solvent of Development of Novel replaces organic solvent more and more to get more and more people's extensive concerning for the production of fine chemicals.Ionic liquid, with unique physico-chemical property such as " zero " vapour pressure, high stability, dissolving power be strong, becomes one of solvent of most application prospect in Search green chemistry research field.
Choline-like ionic liquid is that a class toxicity is little, hydrophilic ionic-liquid, have a good application prospect, but the kind of cholinium ion liquid is relatively less, limits their application to a certain extent in chemical separating field.Preparing choline-like ionic liquid at present only has Chinese patent CN101260051A to report, and synthesized choline-like ionic liquid only Be very effective in biological degradation.Under above-mentioned background, design and synthesis one class preparation process of the present invention is simple, reclaim easy, to reuse good stability cholinium ion liquid.
Summary of the invention
The object of the invention is to synthesis series of new cholinium ion liquid, take choline as the basic structural unit of ionic liquid, its negatively charged ion is modified, mainly comprise the one in the large series compound of carboxylic acid, dicarboxylic acid or sulfonic acid three.
The eco-friendly cholinium ion liquid of one class, consists of:
Cholinium ion type liquid is: levulinic acid choline, Sorbic Acid choline, pentanedioic acid choline, hexanodioic acid choline, (to, or adjacent) phthalic acid choline, trifluoromethanesulfonic acid choline, Phenylsulfonic acid choline, (to, or adjacent) toluenesulphonic acids choline or two trifluoromethanesulfonimide choline.
For achieving the above object, the present invention realizes by the following technical solutions:
The preparation method of cholinium ion liquid:
1) under basic catalyst existent condition, Lipotril is dissolved in alcoholic solvent, and heating generates bursine first solution;
2) synthesize the second solution by bursine first solution and organic acid, after evaporating solvent, obtain required choline-like ionic liquid.
In step 1) in, described basic catalyst is NaOH, the KOH in solid alkali or one or two or more kinds in 717 strongly basic anion exchange resins;
Described alcoholic solvent is C
nh
2n+1one or two or more kinds in OH alcohol, n=1-5; The mass concentration of Lipotril in solution is 0.1-100%;
Lipotril and basic catalyst mol ratio are 1:1 to 1:5; Temperature of reaction is at 20 DEG C-100 DEG C; Reaction times 0.1h-12h.
Lipotril and basic catalyst preferred molar ratio are 1:1; Preferable temperature is 30 DEG C-60 DEG C; The preferred reaction time is 2h-6h; The mass concentration of Lipotril in solution is 30-60%.
In step 2) in, described organic acid is the one in the large series compound of carboxylic acid, dicarboxylic acid or sulfonic acid three;
Reaction is carried out under liquid condition, can add solvent again or do not add solvent in reaction system, and when adding solvent, solvent is alcoholic solvent or water; The mass concentration of bursine in solution is 0.1-100%.Described alcoholic solvent is C
nh
2n+1one or two or more kinds in OH alcohol, n=1-5;
Bursine and organic acid mol ratio are 1:1 to 1:2; Temperature of reaction is at 20 DEG C-150 DEG C; Reaction times 0.1h-12h; The recyclable recycling of solvent of evaporation.
Bursine and organic acid preferred molar ratio are 1:1.1; Preferable temperature is 50 DEG C-100 DEG C; The preferred reaction time is 2h-6h; The mass concentration of bursine in solution is 30-60%.
Described organic acid has a carboxylic acid, and its structure comprises, carboxylate compound: carbon chain range between 1 to 10 carbon, as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid or capric acid; Alkylene carboxylic acid compound: as vinylformic acid, butenoic acid, hexenoic acid and phenylformic acid;
Described organic acid has two carboxylic acids, and in structure, carbon chain range is between 2 to 9 carbon, as oxalic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid or phthalic acid;
Described organic acid has a sulfonic acid, as methylsulfonic acid, trifluoromethanesulfonic acid or Phenylsulfonic acid;
Described organic acid has a sulfimide, as two trifluoromethanesulfonimide.
Beneficial effect of the present invention is:
Have preparation process simple, reclaim easy, reuse the remarkable advantages such as good stability.
Accompanying drawing explanation
Fig. 1 is methylsulphonic acid choline structural characterization figure;
Fig. 2 is p-methyl benzenesulfonic acid choline structural characterization figure;
Fig. 3 is trifluoromethanesulfonic acid choline structural characterization figure;
Fig. 4 is levulinic acid choline structural characterization figure;
Fig. 5 is acetic acid choline structural characterization figure.
Embodiment
Embodiment
For methylsulphonic acid choline building-up process: in the flask of 250mL, add Lipotril (Cholinechloride) 50g (0.36mol), the ethanol of sodium hydroxide (NaOH) 14.4g (0.36mol) and 125mL stirs 4 hours at 40 DEG C, reacts.Carry out filtration removing insolubles sodium salt after reaction, reclaim the ethanolic soln containing bursine.Next, recovery solution is cooled to 0 DEG C, then methylsulphonic acid 38g (0.396mol) is added, after stirring 30 minutes, then reaction solution is heated up and be heated to 75 DEG C of back flow reaction 5 hours, after reaction terminates, be cooled to room temperature, by alcohol solvent rotary evaporation removing under the condition of 50 DEG C, the object product methylsulphonic acid choline (micro-yellow) obtained, productive rate is 99%.Product confirms:
Described product is carried out structural characterization, following Fig. 1 of result: methylsulphonic acid choline
1hMR (D
2o) δ: 2.85 (s, 3H), 3.25 (s, 9H), 3.56 (t, 2H), 4.10 (t, 2H).
Other choline dielectric structure characterizes and will contribute to understanding the present invention, preparation method is with methylsulphonic acid choline Example, only change the organic acid (Phenylsulfonic acid, levulinic acid, acetic acid, trifluoromethanesulfonic acid) added, the organic acid added and the mol ratio of Lipotril are 1.1:1.
Described product is carried out structural characterization, and result is as follows:
Fig. 2: p-methyl benzenesulfonic acid choline
1hMR (D
2o) δ: 2.39 (s, 3H), 3.14 (s, 9H), 3.44 (t, 2H), 4.01 (t, 2H), 7.37 (d, 2H), 7.73 (d, 2H);
Fig. 3: trifluoromethanesulfonic acid choline
1hMR (D
2o) δ: 3.15 (s, 9H), 3.46 (t, 2H), 4.00 (t, 2H);
Fig. 4: levulinic acid choline
1hMR (D
2o) δ: 2.22 (s, 3H), 2.49 (t, 2H), 2.81 (t, 2H), 3.19 (s, 3H), 3.51 (t, 2H), 4.05 (m, 2H);
Fig. 5: acetic acid choline
1hMR (D
2o) δ: 1.82 (s, 3H), 3.10 (s, 9H), 3.24 (s, 2H), 3.41 (t, 2H), 3.19 (s, 3H), 3.94 (t, 2H).
Application examples
For wood sugar dehydration synthesis pentahydroxy-methyl furfural: in the flask of 25mL, add cholinium ion liquid 2.5g, the AlCl of wood sugar 0.1g and 0.01g
36H
2o stirs at a certain temperature, is cooled to room temperature, adds mibk and extract 3 times after reaction terminates, and steaming removing mibk, being weighed as total product weight with revolving.The object product pentahydroxy-methyl furfural obtained adopts liquid-phase chromatographic analysis, and reaction result refers to table 1.
Table 1
Apply the cholinium ion liquid prepared by preparation method of ionic liquid involved in the present invention, be suitable for the reaction solvent being applied in biomass catalyzing conversion and organic synthesis.
Claims (8)
1. the eco-friendly cholinium ion liquid of a class, is characterized in that, consist of:
2. according to cholinium ion liquid according to claim 1, it is characterized in that: cholinium ion type liquid is: levulinic acid choline, Sorbic Acid choline, pentanedioic acid choline, hexanodioic acid choline, (to, or adjacent) phthalic acid choline, trifluoromethanesulfonic acid choline, Phenylsulfonic acid choline, (to, or adjacent) toluenesulphonic acids choline or two trifluoromethanesulfonimide choline.
3. a preparation method for cholinium ion liquid described in claim 1, is characterized in that:
1) under basic catalyst existent condition, Lipotril is dissolved in alcoholic solvent, and heating generates bursine first solution;
2) synthesize the second solution by bursine first solution and organic acid, after evaporating solvent, obtain required choline-like ionic liquid.
4., according to preparation method according to claim 3, it is characterized in that:
In step 1) in, described basic catalyst is NaOH, the KOH in solid alkali or one or two or more kinds in 717 strongly basic anion exchange resins;
Described alcoholic solvent is C
nh
2n+1one or two or more kinds in OH alcohol, n=1-5; The mass concentration of Lipotril in solution is 0.1-100%;
Lipotril and basic catalyst mol ratio are 1:1 to 1:5; Temperature of reaction is at 20 DEG C-100 DEG C; Reaction times 0.1h-12h.
5., according to preparation method according to claim 4, it is characterized in that:
Lipotril and basic catalyst preferred molar ratio are 1:1; Preferable temperature is 30 DEG C-60 DEG C; The preferred reaction time is 2h-6h; The mass concentration of Lipotril in solution is 30-60%.
6., according to preparation method according to claim 3, it is characterized in that:
In step 2) in, described organic acid is the one in the large series compound of carboxylic acid, dicarboxylic acid or sulfonic acid three;
Reaction is carried out under liquid condition, can add solvent again or do not add solvent in reaction system, and when adding solvent, solvent is alcoholic solvent or water; The mass concentration of bursine in solution is 0.1-100%.Described alcoholic solvent is C
nh
2n+1one or two or more kinds in OH alcohol, n=1-5;
Bursine and organic acid mol ratio are 1:1 to 1:2; Temperature of reaction is at 20 DEG C-150 DEG C; Reaction times 0.1h-12h; The recyclable recycling of solvent of evaporation.
7., according to preparation method according to claim 6, it is characterized in that:
Bursine and organic acid preferred molar ratio are 1:1.1; Preferable temperature is 50 DEG C-100 DEG C; The preferred reaction time is 2h-6h; The mass concentration of bursine in solution is 30-60%.
8., according to preparation method according to claim 6, it is characterized in that:
Described organic acid has a carboxylic acid, and its structure comprises, carboxylate compound: carbon chain range between 1 to 10 carbon, as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid or capric acid; Alkylene carboxylic acid compound: as vinylformic acid, butenoic acid, hexenoic acid and phenylformic acid;
Described organic acid has two carboxylic acids, and in structure, carbon chain range is between 2 to 9 carbon, as oxalic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid or phthalic acid;
Described organic acid has a sulfonic acid, as methylsulfonic acid, trifluoromethanesulfonic acid or Phenylsulfonic acid;
Described organic acid has a sulfimide, as two trifluoromethanesulfonimide.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108212212A (en) * | 2018-01-29 | 2018-06-29 | 中国科学院青岛生物能源与过程研究所 | A kind of temperature sensitive acidic ionic liquid and preparation method thereof and the purposes in catalysis microcrystalline cellulose hydrolysis |
| CN109575023A (en) * | 2018-12-03 | 2019-04-05 | 深圳市萱嘉生物科技有限公司 | A kind of matrine long chain fatty acids ionic liquid and the preparation method and application thereof |
| CN109796006A (en) * | 2019-03-21 | 2019-05-24 | 河北科技大学 | A kind of ionic liquid is in the preparation method and application for preparing application and nitrogen-doped carbon quantum dot in nitrogen-doped carbon quantum dot |
| CN110862338A (en) * | 2019-11-21 | 2020-03-06 | 珠海中科先进技术研究院有限公司 | Preparation method and application of stachydrine ionic liquid |
| CN110951517A (en) * | 2019-12-10 | 2020-04-03 | 中国科学院兰州化学物理研究所 | Halogen-free choline chelated boron ionic liquid lubricating additive and application thereof |
| CN112674106A (en) * | 2021-01-06 | 2021-04-20 | 沈阳农业大学 | Soluble agent and preparation method thereof |
| CN112851502A (en) * | 2021-02-02 | 2021-05-28 | 中国科学院过程工程研究所 | Method for catalyzing waste PET polyester to carry out methanol alcoholysis by using choline and terephthalic acid non-metallic ionic liquid |
| CN113967287A (en) * | 2021-11-26 | 2022-01-25 | 广东省科学院微生物研究所(广东省微生物分析检测中心) | Antibacterial low-toxicity tooth/bone repair active material and preparation method thereof |
| CN115232048A (en) * | 2021-04-22 | 2022-10-25 | 南京毓浠医药技术有限公司 | Ionic liquid and preparation method and application thereof |
| CN115322108A (en) * | 2022-08-05 | 2022-11-11 | 河南大学 | Choline 2, 6-dihydroxy benzoic acid ionic liquid, synthesis method and application of ionic liquid as magnesium air battery electrolyte additive |
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Cited By (15)
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| CN108212212A (en) * | 2018-01-29 | 2018-06-29 | 中国科学院青岛生物能源与过程研究所 | A kind of temperature sensitive acidic ionic liquid and preparation method thereof and the purposes in catalysis microcrystalline cellulose hydrolysis |
| CN109575023A (en) * | 2018-12-03 | 2019-04-05 | 深圳市萱嘉生物科技有限公司 | A kind of matrine long chain fatty acids ionic liquid and the preparation method and application thereof |
| CN109796006B (en) * | 2019-03-21 | 2022-03-01 | 河北科技大学 | Application of ionic liquid in preparation of nitrogen-doped carbon quantum dots, and preparation method and application of nitrogen-doped carbon quantum dots |
| CN109796006A (en) * | 2019-03-21 | 2019-05-24 | 河北科技大学 | A kind of ionic liquid is in the preparation method and application for preparing application and nitrogen-doped carbon quantum dot in nitrogen-doped carbon quantum dot |
| CN110862338A (en) * | 2019-11-21 | 2020-03-06 | 珠海中科先进技术研究院有限公司 | Preparation method and application of stachydrine ionic liquid |
| CN110951517A (en) * | 2019-12-10 | 2020-04-03 | 中国科学院兰州化学物理研究所 | Halogen-free choline chelated boron ionic liquid lubricating additive and application thereof |
| CN112674106A (en) * | 2021-01-06 | 2021-04-20 | 沈阳农业大学 | Soluble agent and preparation method thereof |
| CN112674106B (en) * | 2021-01-06 | 2021-12-07 | 沈阳农业大学 | Soluble agent and preparation method thereof |
| CN112851502A (en) * | 2021-02-02 | 2021-05-28 | 中国科学院过程工程研究所 | Method for catalyzing waste PET polyester to carry out methanol alcoholysis by using choline and terephthalic acid non-metallic ionic liquid |
| CN115232048A (en) * | 2021-04-22 | 2022-10-25 | 南京毓浠医药技术有限公司 | Ionic liquid and preparation method and application thereof |
| WO2022222844A1 (en) * | 2021-04-22 | 2022-10-27 | 南京毓浠医药技术有限公司 | Ionic liquid, preparation method therefor, and application thereof |
| CN115232048B (en) * | 2021-04-22 | 2024-02-27 | 南京毓浠医药技术有限公司 | Ionic liquid and preparation method and application thereof |
| CN113967287A (en) * | 2021-11-26 | 2022-01-25 | 广东省科学院微生物研究所(广东省微生物分析检测中心) | Antibacterial low-toxicity tooth/bone repair active material and preparation method thereof |
| CN115322108A (en) * | 2022-08-05 | 2022-11-11 | 河南大学 | Choline 2, 6-dihydroxy benzoic acid ionic liquid, synthesis method and application of ionic liquid as magnesium air battery electrolyte additive |
| CN115322108B (en) * | 2022-08-05 | 2023-05-12 | 河南大学 | Choline 2, 6-dihydroxybenzoic acid ionic liquid, synthesis method and application of choline 2, 6-dihydroxybenzoic acid ionic liquid as magnesium air battery electrolyte additive |
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