CN101973940B - Continuously synthesizing method of sulfonic acid alkyl group ionic liquid - Google Patents
Continuously synthesizing method of sulfonic acid alkyl group ionic liquid Download PDFInfo
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- CN101973940B CN101973940B CN201010293943A CN201010293943A CN101973940B CN 101973940 B CN101973940 B CN 101973940B CN 201010293943 A CN201010293943 A CN 201010293943A CN 201010293943 A CN201010293943 A CN 201010293943A CN 101973940 B CN101973940 B CN 101973940B
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Abstract
The invention discloses a continuously synthesizing method of a sulfonic acid alkyl group ionic liquid. The used raw materials are as follows: 1-substituted iminazole, substituted pyridine or alkyl tertiary amine, sulfonic acid sultone and Brown acid; water is taken as a reaction medium, and the reaction is carried out under the condition of stirring at the constant pressure to obtain the ionic liquid. Compared with the prior art, the advantages of the invention are as follows: (1) a continuous synthesizing process is adopted to replace the existing substep process, thus simplifying the operation flow, reducing the equipment investment and chemical raw material dosage, and having obvious energy conserving and emission reducing effects; (2) in the synthesizing process, the dosage of the reaction medium water is regulated according to the activities of tertiary amine and the sulfonic acid sultone, thus avoiding the phenomena of bumping and paint spraying generated by the high-activity material reaction at the conditions of the environmental pollution of the organic solvent or no solvent; and the reaction is safe and stable, and is easy to amplify industrially; and (3) the process is widely suitable for preparing various sulfonic acid group ionic liquids, such as imidazoles, pyridine and alkyl tertiary amine and the like, and is an environmentally-friendly chemical process.
Description
One technical field
The present invention relates to the ion liquid method for continuously synthesizing of a kind of sulfonic alkyl, belong to the chemical material preparing technical field.Present method is applicable to that with 1-substituted imidazole, substituted pyridines or alkyl tertiary amine, sultones and Blang's acid be raw material, the synthetic ion liquid occasion of sulfonic alkyl of heated and stirred under normal pressure.
Two background technologies
Ionic liquid is one of representative Green Chemical Technology, the developing direction that composite energy-saving reduces discharging.Wherein, Blang's functionalized acidic ionic liquid has combined the advantage of solid acid and mineral acid, and is similar with solid acid, and such ionic liquid does not have volatility, has eco-friendly advantage; Its acidity can be carried out meticulous adjusting as required, thereby helps the research of catalytic mechanism and the optimization of catalyzer more; Similar with mineral acid, ionic liquid has the advantage of fluent material equally, as: good fluidity, acidic site density height and strength of acid are evenly distributed; Through changing and modified ion liquid yin, yang ionic structure, can realize the optimization of heterogeneous reaction system.Therefore, ionic liquid is the research focus of current chemical field.
The ion liquid cationic moiety of acid function is generally imidazoles, quaternary ammonium 、 quaternary phosphine, pyridine, morphine quinoline, tetramethyleneimine etc. both at home and abroad, and anionicsite is generally inorganic acid radical, organic acid, heteropolyacid root etc.Reported first such as U.S. Cole in 2002 connect preparation (the Novel Bronsted acidic ionic liquids and their use as dual solvent-catalysts.J.Am.Chem.Soc.2002 of the functionalized acidic ionic liquid of fourth sulfonic acid group on the imidazoles 、 quaternary phosphine positively charged ion; 124; 5962-5963), subsequently in China's application patent of invention (CN 1646540A).Wang Tao etc. disclose the functionalized acidic ionic liquid (CN1594280) that connects sulfonic acid group on the pyridylium.Wang Rong etc. disclose a kind of double-functional group ionic liquid and preparation method thereof (CN101058552A).Yu Shitao etc. disclose the preparation of Bronsted-Lewis acid ion liquid and have used (CN 101191935A).Wang Yanji etc. disclose the ion liquid preparation of a kind of quaternary ammonium salt (CN 101182399A).Huang Baohua etc. disclose a kind of pyrrolidone sulfonate ion liquid and preparation method thereof (CN101024625).Yang Jianguo etc. disclose a kind of preparation method (CN 101348487A) (Synthesis of a novel multi-SO of multi-sulfonic functional ion liquid
3H functionalized ionic liquid and its catalytic activities for biodiesel synthesis.Green Chem.2010,12,201-204).
The ion liquid method for continuously synthesizing of a kind of sulfonic alkyl that the present invention relates to is different from above-mentioned disclosed compound method; Disclosed method all adopts stepwise reaction: the first step is the preparation inner salt; Be reflected under the condition of no solvent or in solvent and react, stoichiometric number hour did not wait to tens of hours, and midbody is with washings such as absolute ethyl alcohol, toluene, anhydrous diethyl ethers; Vacuum-drying under heating condition then obtains purified inner salt.Second step was that neutralization reaction is carried out in Blang's acid such as the equimolar inner salt and the vitriol oil under condition of no solvent or in the aqueous solution; Stoichiometric number hour vacuum-drying under heating condition after 10 hours; Use washings such as toluene, anhydrous diethyl ether successively; Vacuum-drying under heating condition again obtains purified ionic liquid product.The present invention adopts continuous process, and the midbody inner salt needn't separate, and directly adds equimolar Blang's acid and carries out neutralization reaction.
Three summary of the invention
The object of the present invention is to provide the ion liquid method for continuously synthesizing of a kind of sulfonic alkyl.
The technical solution that realizes the object of the invention is: the ion liquid method for continuously synthesizing of a kind of sulfonic alkyl; Be raw material promptly with 1-substituted imidazole, substituted pyridines or alkyl tertiary amine, sultones, Blang's acid; Water is reaction medium, and heated and stirred realizes that this is ion liquid synthetic under normal pressure.
The used ionic-liquid catalyst structure of the present invention is following:
Methylene radical (CH wherein
2) quantity n can be any in 3 or 4 numerals.R, R
1, R
2, R
3Be C
1-C
12Alkyl.A is Blang's acid such as sulfuric acid, hydrochloric acid, phosphoric acid, trifluoroacetic acid, tosic acid, trifluoromethanesulfonic acid.
The mol ratio of the used material of the present invention is a tertiary amine: sultones: Blang's acid=1: 1: 1, and the consumption of water is 50～500% of a material total mass, described material, water proportionally feed intake to mix and stir.
The temperature of reaction according to the invention is 20～100 ℃.
The time of reaction according to the invention is 0.5～5.0 hour.
The ion liquid method for continuously synthesizing of a kind of sulfonic alkyl according to the invention; It is characterized in that: the present invention adopts continuous process; Activity according to tertiary amine, sultones; The water that adds different amounts is as reaction medium, and the midbody inner salt needn't separate, and directly adds equimolar Blang's acid under stirring and carries out neutralization reaction.Heat is emitted in reaction, and the rate of addition of control acid carries out in making and under 60～80 ℃, and entire reaction is controlled in 0.5～5.0 hour and accomplishes.The ionic liquid aqueous solution that obtains carries out liquid-liquid extraction with ETHYLE ACETATE and purifies.Whether decision dewaters as required, and then reducing pressure like needs dewaters, and vacuum-drying obtains the sulfonic alkyl ionic liquid.
The chemical principle of institute of the present invention foundation is following:
According to the ion liquid method for continuously synthesizing of a kind of sulfonic alkyl provided by the invention; Its key problem in technology is to adopt water as reaction medium; After tertiary amine, sultones quaterisation in water finishes; Midbody need not to separate and purifies, and stirs down directly equimolar slow acid to be added, and last vaccum dewatering obtains sulfonic alkyl quaternary ammonium salt ionic liquid.The present invention compared with prior art, its advantage is: (1) adopts continuous synthesis technique to replace existing minute step process, has simplified operating process, and minimizing equipment drops into and the chemical feedstocks consumption, and the effect of energy-saving and emission-reduction is obvious; (2) in the building-up process according to the activity of tertiary amine, sultones, the consumption of conditioned reaction WATER AS FLOW MEDIUM is avoided the high reactivity material reaction produces under environmental pollution or the condition of no solvent of organic solvent bumping, spray material phenomenon, the reaction safety and steady, industry is amplified easily; (3) this technology extensively is suitable for the ion liquid preparations of multiple sulfonic group such as imidazoles, pyridines, alkyl tertiary amine, is eco-friendly chemical process.
Four description of drawings
Accompanying drawing is the schema of the ion liquid method for continuously synthesizing of a kind of sulfonic alkyl of the present invention.
Five embodiments
Below through embodiment the present invention is detailed, these embodiment are only for clear open the present invention, not as limitation of the present invention.
Embodiment 1
In the 25mL round-bottomed flask, add 10mmol triethylamine and 12ml water, 20 ℃ are stirred down; Drip 10mmol (1.22g) propane sultone, react end in 1 hour, slowly add the sulfuric acid of 10mmol massfraction 98%; Under 60 ℃, mix and stirred 2 hours, use the equal volume of ethyl acetate separatory, the water underpressure distillation dewaters; Obtain propanesulfonic acid base triethylammonium salts ionic liquid, productive rate 98% through vacuum-drying.
Embodiment 2
In the 25mL round-bottomed flask, add 10mmol triethylamine and 1.7ml water, 20 ℃ are stirred down; Drip 10mmol (1.34g) butyl sultone, react end in 3 hours, slowly add the sulfuric acid of 10mmol massfraction 98%; Under 80 ℃, mix and stirred 2 hours, use the equal volume of ethyl acetate separatory, the water underpressure distillation dewaters; Obtain propanesulfonic acid base triethylammonium salts ionic liquid, productive rate 98% through vacuum-drying.
Embodiment 3
In the 25mL round-bottomed flask, add 10mmol1-Methylimidazole and 15ml water, 50 ℃ are stirred down; Drip 10mmol (1.22g) propane sultone, react end in 15 minutes, slowly add the phosphoric acid of 10mmol massfraction 85%; Under 80 ℃, mix and stirred 15 minutes hours, use the equal volume of ethyl acetate separatory, the water underpressure distillation dewaters; Obtain Methylimidazole propanesulfonic acid ionic liquid, productive rate 98% through vacuum-drying.
Embodiment 4
In the 25mL round-bottomed flask, add 10mmol1-Methylimidazole and 10ml water, 50 ℃ are stirred down; Drip 10mmol (1.22g) propane sultone, react end in 15 minutes, slowly add the hydrochloric acid of 10mmol massfraction 36%; Under 80 ℃, mix and stirred 1 hour, use the equal volume of ethyl acetate separatory, the water underpressure distillation dewaters; Obtain Methylimidazole propanesulfonic acid ionic liquid, productive rate 98% through vacuum-drying.
Embodiment 5
In the 25mL round-bottomed flask, add 10mmol1-Methylimidazole and 10ml water, 50 ℃ are stirred down; Drip 10mmol (1.22g) propane sultone, react end in 15 minutes, slowly add 10mmol massfraction p-methyl benzenesulfonic acid; Under 80 ℃, mix and stirred 3 hours, use the equal volume of ethyl acetate separatory, the water underpressure distillation dewaters; Obtain Methylimidazole propanesulfonic acid ionic liquid, productive rate 98% through vacuum-drying.
Embodiment 6
In the 25mL round-bottomed flask, add 10mmol1-Methylimidazole and 10ml water, 50 ℃ are stirred down; Drip 10mmol (1.22g) propane sultone; React end in 15 minutes, slowly add 10mmol massfraction trifluoromethyl acetate, mix down in 50 ℃ and stirred 15 minutes hours; Obtain Methylimidazole propanesulfonic acid ionic liquid aqueous solution, productive rate 99%.
Embodiment 7
In the 25mL round-bottomed flask, add 10mmol pyridine and 2.5ml water, 80 ℃ are stirred down; Drip 10mmol (1.22g) propane sultone, react end in 0.5 hour, slowly add the sulfuric acid of 10mmol massfraction 98%; Under 80 ℃, mix and stirred 0.5 hour, use the equal volume of ethyl acetate separatory, the water underpressure distillation dewaters; Obtain pyridine propanesulfonic acid ionic liquid, productive rate 98% through vacuum-drying.
Embodiment 8
In the 25mL round-bottomed flask, add 10mmol dimethyl-12 tertiary amines and 2.5ml water, 100 ℃ are stirred down; Drip 10mmol (1.22g) propane sultone; React end in 0.2 hour, slowly add the sulfuric acid of 10mmol massfraction 98%, mix down in 80 ℃ and stirred 0.3 hour; Obtain propanesulfonic acid base dodecyl quaternary ammonium salt ionic liquid aqueous solution, productive rate 99%.
Embodiment 9
In the 1L round-bottomed flask, add 1mol pyridine and 500ml water, 40 ℃ are stirred down; Drip 1mol (122g) propane sultone, react end in 1.5 hours, slowly add the sulfuric acid of 1mol massfraction 98%; Under 80 ℃, mix and stirred 3 hours, use the equal volume of ethyl acetate separatory, the water underpressure distillation dewaters; Obtain propanesulfonic acid yl pyridines ionic liquid, productive rate 98% through vacuum-drying.
Claims (2)
1. ion liquid method for continuously synthesizing of sulfonic alkyl, it is characterized in that: with tertiary amine, sultones is raw material, water is reaction medium; Carry out quaterisation, after reaction finished, midbody need not to separate and purifies; Directly equimolar Blang's slow acid is added under stirring, heat is emitted in reaction, the rate of addition of control acid; Neutralization reaction is carried out under 60～80 ℃, and entire reaction is controlled in 0.5-5 hour and accomplishes, and whether decision dewaters as required; As need then reduce pressure and dewater, vacuum-drying obtains the sulfonic alkyl ionic liquid, and said tertiary amine is 1-substituted imidazole, substituted pyridines or alkyl tertiary amine; Said Blang's acid is sulfuric acid, hydrochloric acid, phosphoric acid, trifluoroacetic acid, tosic acid or trifluoromethanesulfonic acid.
2. the ion liquid method for continuously synthesizing of a kind of sulfonic alkyl according to claim 1; It is characterized in that: the mol ratio of used material is a tertiary amine: sultones: Blang's acid=1: 1: 1; The consumption of water is 50～500% of a material total mass, and wherein said material proportionally feeds intake with water and mixes stirring.
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| CN102229569A (en) * | 2011-04-11 | 2011-11-02 | 新疆大学 | Method for preparing Br[phi]nsted acidic ionic liquid based on benzimidazole cations |
| CN102626656B (en) * | 2012-03-27 | 2013-11-06 | 绍兴文理学院 | Preparation method of acidic ionic liquid hydrothermal carbonization material |
| CN103936677B (en) * | 2013-01-21 | 2016-06-29 | 中国科学院大连化学物理研究所 | A kind of sulfonic acid funtionalized ionic liquid based on perfluoro alkyl sulfonic acid root anion and preparation method thereof |
| CN110078946B (en) * | 2019-05-17 | 2022-06-07 | 南京工业大学 | Method for quickly dissolving chitosan by acidic ionic liquid at low temperature |
| CN111187223B (en) * | 2020-03-09 | 2022-02-22 | 沧州那瑞化学科技有限公司 | Synthetic method of linagliptin intermediate 2-chloromethyl-4-methyl quinazoline |
| CN112250635A (en) * | 2020-11-03 | 2021-01-22 | 淮安信盛新材料科技有限公司 | Large-scale preparation method and reaction system of acidic functionalized ionic liquid |
| CN112968209A (en) * | 2021-02-24 | 2021-06-15 | 珠海中科先进技术研究院有限公司 | Ionic liquid gel electrolyte and preparation method and application thereof |
| CN112968210A (en) * | 2021-02-24 | 2021-06-15 | 珠海中科先进技术研究院有限公司 | Zwitterionic liquid gel electrolyte and preparation method and application thereof |
| CN115094507A (en) * | 2022-07-06 | 2022-09-23 | 武汉天立表面技术有限公司 | Deplating liquid for rack deplating process and deplating method and detection method thereof |
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| CN101058552B (en) * | 2006-04-18 | 2010-12-08 | 上海师范大学 | Double-functional group ionic liquid and preparation method |
| CN101508675B (en) * | 2009-03-26 | 2011-05-25 | 浙江工业大学 | Novel disulfonic acid type alkyl imidazole ionic liquid, preparation and uses thereof |
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Application publication date: 20110216 Assignee: Jiangsu Dahua Chemical Industrial Co., Ltd. Assignor: Yancheng Normal College Contract record no.: 2013320000736 Denomination of invention: Continuously synthesizing method of sulfonic acid alkyl group ionic liquid Granted publication date: 20121003 License type: Exclusive License Record date: 20131101 |
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