CN103664656A - Synthesis and application of quaternary ammonium salt ionic liquid based on heteropolyacid - Google Patents
Synthesis and application of quaternary ammonium salt ionic liquid based on heteropolyacid Download PDFInfo
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- CN103664656A CN103664656A CN201310729126.8A CN201310729126A CN103664656A CN 103664656 A CN103664656 A CN 103664656A CN 201310729126 A CN201310729126 A CN 201310729126A CN 103664656 A CN103664656 A CN 103664656A
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- heteropolyacid
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Abstract
The invention discloses a quaternary ammonium salt ionic liquid based on heteropolyacid and a synthetic method of the quaternary ammonium salt ionic liquid based on the heteropolyacid, and the quaternary ammonium salt ionic liquid based on the heteropolyacid is used as an acid catalyst for synthetic reaction of ethyl acetate. The heteropolyacid and lauryl amine ethoxylate ether with different chain lengths are used as raw materials, absolute ethyl alcohol is used as a solvent, the synthetic reaction operation is simple, and equipment and technological conditions are mild. The ionic liquid is used as the acid catalyst, the catalytic activity is high, the recycling is easy, problems of serious pollution, difficulty in aftertreatment and corrosion to equipment, caused by a traditional acid catalyst, can be avoided, the process and the technology are environmentally friendly, and a good application prospect is achieved.
Description
Technical field
The present invention relates to quaternary ammonium salt ion liquid and the synthetic method thereof of a class based on heteropolyacid, and this ionic liquid as an acidic catalyst the application method in ethyl acetate is synthetic.
Background technology
Ethyl acetate is a kind of important Organic Chemicals and fabulous industrial solvent, is widely used in the production of cellulose acetate, chlorinated rubber, ethenoid resin, synthetic, coating and paint etc.At present, the prior synthesizing method of ethyl acetate mainly adopts concentrated sulfuric acid catalyst, its technical maturity, productive rate are high, but there is the shortcomings such as etching apparatus, contaminate environment, can not meet the requirement of Green Chemistry, thereby people constantly explore selection new catalyst, so that the greenization more of chemical reaction process and technique.
In recent years, utilize ionic liquid to have much as the report of organic reaction catalyzer, wherein take esterification as focus.The excellent specific property that ionic liquid has comprises: good thermostability and chemical stability, extremely low vapour pressure, and non-volatile, non-combustible, hypotoxicity, zwitterion can design, and is easy to recycling, environmentally friendly etc. for the synthesis of reaction.Ionic liquid is for catalytic esterification, there is good catalytic activity, and ionic liquid based on heteropolyacid can retain heteropolyacid low temperature active high, have good stability, feature that molecular structure is definite, the excellent properties that simultaneously possesses ionic liquid, not only there is acidity and oxidation-reduction quality, also have higher catalytic activity and selectivity, application prospect is very wide simultaneously.
Summary of the invention
The invention provides a series of quaternary ammonium salt ion liquids based on heteropolyacid, and the synthetic method and methods for using them of this ionic liquid is provided.
Quaternary ammonium salt ion liquid structural formula based on heteropolyacid provided by the invention:
Wherein, heteropolyanion A
x-for H
2pW
12o
40 -, H
2pMo
12o
40 -, H
2siW
12o
40 -, PW
12o
40 3-, PMo
12o
40 3-or SiW
12o
40 3-in any one; Cationic amino dodecane Soxylat A 25-7 chain length m+n is 10,15,20 or 30.
The synthesis step of the quaternary ammonium salt ion liquid based on heteropolyacid provided by the invention:
According to heteropolyacid: mol ratio amino dodecane Soxylat A 25-7=1:(1～3), amino dodecane Soxylat A 25-7 is joined in there-necked flask, heteropolyacid is fully dissolved with dehydrated alcohol, with constant pressure funnel, in there-necked flask, drip heteropolyacid ethanolic soln, under agitation condition, reaction system is in 20～100 ℃ of heating reflux reaction 4～48h.
After reaction finishes, be cooled to room temperature, add dehydrated alcohol, standing separatory, repeats 2～4 times, after rotary evaporation 3～6h, in 40～100 ℃ of vacuum-dryings to constant weight, obtains the quaternary ammonium salt ion liquid based on heteropolyacid.
Its reaction equation of quaternary ammonium salt ion liquid based on heteropolyacid provided by the invention is as follows:
X=1 or 3
Quaternary ammonium salt ion liquid based on heteropolyacid provided by the invention, during x=1, A
x-corresponding heteropolyanion is H
2pW
12o
40 -, H
2pMo
12o
40 -or H
2siW
12o
40 -; During x=3, A
x-corresponding heteropolyanion is PW
12o
40 3-, PMo
12o
40 3-or SiW
12o
40 3-.
Quaternary ammonium salt ion liquid based on heteropolyacid provided by the invention, its cationic amino dodecane Soxylat A 25-7 chain length m+n can be 10,15,20 or 30.
The advantage that the technology of preparing of the quaternary ammonium salt ion liquid based on heteropolyacid provided by the invention has is:
Building-up process is simple, easy to operate, and reaction conditions is gentle.
The invention provides the novel ionic liquid of a class, enriched the kind of ionic liquid.
Heteropolyanion, as the negatively charged ion of ionic liquid, has acidity, alternative classical acid catalyzer.
Ionic liquid has retained the character of amino dodecane polyoxyethylene ether surface active agent, is more of value to the Separation and Recovery after the dispersion of catalyzer in esterification and reaction finish.
The application method of ionic liquid provided by the invention:
Using this ionic liquid as an acidic catalyst, reaction for acetic acid ethanol synthesizing ethyl acetate, concrete steps: according to ionic liquid: ethanol: the mol ratio of acetic acid=0.003～0.01:1:1～5 joins in there-necked flask in turn, under agitation condition, reaction system is in 20～120 ℃ of heating reflux reaction 2～8h, reaction finishes to add hexanaphthene in backward system, the add-on of hexanaphthene is 50%～200% of system total mass, isolate catalyzer, the rate of recovery first of catalyzer can reach 80%～95%.
Quaternary ammonium salt ion liquid based on heteropolyacid provided by the invention, catalyzes and synthesizes ethyl acetate, and the transformation efficiency that application gas chromatographic analysis obtains ethanol can reach 58%～93%, and the yield of ethyl acetate can reach 56%～92%.
Ionic-liquid catalyst provided by the invention is compared with the acid catalyst that traditional esterification is used, and advantage is:
Low temperature active is high, and thermal stability is good, non-volatile, non-combustible.
Feed stock conversion and product yield are high.
Be easy to reclaim, reusable.
Avoided the serious pollution of traditional an acidic catalyst, aftertreatment difficulty, and the etching problem to equipment.
Specific embodiments
Below in conjunction with specific embodiment, the present invention is illustrated, these embodiment are just for more clearly openly the present invention, not as limitation of the present invention.
What embodiment 1～6 was ionic liquid provided by the invention is synthetic:
Embodiment 1,
Get 0.01mol amino dodecane Soxylat A 25-7 (m+n=15) in there-necked flask, get 0.01mol phospho-wolframic acid and be dissolved in 25mL dehydrated alcohol, with constant pressure funnel, slowly drip phospho-wolframic acid ethanolic soln, use electric mixer to stir simultaneously, 80 ℃ of temperature of reaction, heating reflux reaction 24h.After reaction finishes, be cooled to room temperature, in system, add appropriate dehydrated alcohol, standing separatory, repeats 3 times, rotary evaporation 4h, and afterwards in 60 ℃ of vacuum-dryings to constant weight, obtaining heteropolyanion is H
2pW
12o
40 -ionic liquid, productive rate approximately 80%.
Embodiment 2,
Get 0.01mol amino dodecane Soxylat A 25-7 (m+n=10) in there-necked flask, get 0.01mol phospho-molybdic acid and be dissolved in 25mL dehydrated alcohol, with constant pressure funnel, slowly drip phosphomolybdic acid ethanol solution, use electric mixer to stir simultaneously, 20 ℃ of temperature of reaction, reaction times 18h.Reaction finishes to enter dehydrated alcohol in backward system, and standing separatory, repeats 4 times, rotary evaporation 5h, and afterwards in 70 ℃ of vacuum-dryings to constant weight, obtaining heteropolyanion is H
2pMo
12o
40 -ionic liquid, productive rate approximately 60%.
Embodiment 3,
Get 0.01mol amino dodecane Soxylat A 25-7 (m+n=20) in there-necked flask, get 0.01mol silicotungstic acid and be dissolved in 25mL dehydrated alcohol, with constant pressure funnel, slowly drip silicotungstic acid ethanolic soln, use electric mixer to stir simultaneously, 50 ℃ of temperature of reaction, heating reflux reaction 36h.After reaction finishes, be cooled to room temperature, in system, add appropriate dehydrated alcohol, standing separatory, repeats 4 times, rotary evaporation 5h, and afterwards in 70 ℃ of vacuum-dryings to constant weight, obtaining heteropolyanion is H
2siW
12o
40 -ionic liquid, productive rate approximately 75%.
Embodiment 4,
Get 0.03mol amino dodecane Soxylat A 25-7 (m+n=30) in there-necked flask, get 0.01mol phospho-wolframic acid and be dissolved in 25mL dehydrated alcohol, with constant pressure funnel, slowly drip phospho-wolframic acid ethanolic soln, use electric mixer to stir simultaneously, 70 ℃ of temperature of reaction, heating reflux reaction 48h.After reaction finishes, be cooled to room temperature, in system, add appropriate dehydrated alcohol, standing separatory, repeats 4 times, rotary evaporation 3h, and afterwards in 70 ℃ of vacuum-dryings to constant weight, obtaining heteropolyanion is PW
12o
40 3-ionic liquid, productive rate approximately 75%.
Embodiment 5,
Get 0.03mol amino dodecane Soxylat A 25-7 (m+n=15) in there-necked flask, get 0.01mol phospho-molybdic acid and be dissolved in 25mL dehydrated alcohol, with constant pressure funnel, slowly drip phosphomolybdic acid ethanol solution, use electric mixer to stir simultaneously, 100 ℃ of temperature of reaction, heating reflux reaction 36h.After reaction finishes, be cooled to room temperature, in system, add appropriate dehydrated alcohol, standing separatory, repeats 2 times, rotary evaporation 4h, and afterwards in 70 ℃ of vacuum-dryings to constant weight, obtaining heteropolyanion is PMo
12o
40 3-ionic liquid, productive rate approximately 80%.
Embodiment 6,
Get 0.03mol amino dodecane Soxylat A 25-7 (m+n=20) in there-necked flask, get 0.01mol silicotungstic acid and be dissolved in 25mL dehydrated alcohol, with constant pressure funnel, slowly drip silicotungstic acid ethanolic soln, use electric mixer to stir simultaneously, 60 ℃ of temperature of reaction, heating reflux reaction 24h.After reaction finishes, be cooled to room temperature, in system, add appropriate dehydrated alcohol, standing separatory, repeats 3 times, rotary evaporation 4h, and afterwards in 80 ℃ of vacuum-dryings to constant weight, obtaining heteropolyanion is SiW
12o
40 3-ionic liquid, productive rate approximately 70%.
Embodiment 7～11 is the application of ionic liquid of the present invention in ethyl acetate is synthetic:
Embodiment 7,
By 1mmol with H
2pW
12o
40 -ionic liquid (m+n=15) for heteropolyanion, 4.6g(0.1mol) dehydrated alcohol, 18g(0.3mol) acetic acid joins in there-necked flask in turn, use electric mixer stirs, back flow reaction 5h at 100 ℃, reaction finishes to add 30g hexanaphthene in backward system, isolates catalyzer, the transformation efficiency that gas chromatographic analysis obtains ethanol is 90%, and the yield of ethyl acetate is 87%.
Embodiment 8,
By 0.5mmol with H
2pMo
12o
40 -ionic liquid (m+n=20) for heteropolyanion, 4.6g(0.1mol) dehydrated alcohol, 12g(0.2mol) acetic acid joins in there-necked flask in turn, use electric mixer stirs, back flow reaction 4h at 80 ℃, reaction finishes to add 20g hexanaphthene in backward system, isolates catalyzer, the transformation efficiency that gas chromatographic analysis obtains ethanol is 82%, and the yield of ethyl acetate is 80%.
Embodiment 9,
By 0.3mmol with H
2siW
12o
40 -ionic liquid (m+n=10) for heteropolyanion, 4.6g(0.1mol) dehydrated alcohol, 18g(0.3mol) acetic acid joins in there-necked flask in turn, use electric mixer stirs, back flow reaction 6h at 90 ℃, reaction finishes to add 15g hexanaphthene in backward system, isolates catalyzer, the transformation efficiency that gas chromatographic analysis obtains ethanol is 78%, and the yield of ethyl acetate is 77%.
Embodiment 10,
By 0.4mmol with PW
12o
40 3-ionic liquid (m+n=15) for heteropolyanion, 4.6g(0.1mol) dehydrated alcohol, 6g(0.1mol) acetic acid joins in there-necked flask in turn, use electric mixer stirs, back flow reaction 4h at 100 ℃, reaction finishes to add 10g hexanaphthene in backward system, isolates catalyzer, the transformation efficiency that gas chromatographic analysis obtains ethanol is 66%, and the yield of ethyl acetate is 63%.
Embodiment 11,
By 0.7mmol with PMo
12o
40 3-ionic liquid (m+n=30) for heteropolyanion, 4.6g(0.1mol) dehydrated alcohol, 24g(0.4mol) acetic acid joins in there-necked flask in turn, use electric mixer stirs, back flow reaction 5h at 110 ℃, reaction finishes to add 40g hexanaphthene in backward system, isolates catalyzer, the transformation efficiency that gas chromatographic analysis obtains ethanol is 82%, and the yield of ethyl acetate is 79%.
Embodiment 12,
By 0.8mmol with SiW
12o
40 3-ionic liquid (m+n=20) for heteropolyanion, 4.6g(0.1mol) dehydrated alcohol, 12g(0.2mol) acetic acid joins in there-necked flask in turn, use electric mixer stirs, back flow reaction 3h at 70 ℃, reaction finishes to add 18g hexanaphthene in backward system, isolates catalyzer, the transformation efficiency that gas chromatographic analysis obtains ethanol is 69%, and the yield of ethyl acetate is 68%.
Embodiment 13,
After embodiment 7 reaction finishes, isolated catalyzer is again for 4.6g(0.1mol) dehydrated alcohol and 18g(0.3mol) esterification of acetic acid, operational condition is with embodiment 7, obtains the transformation efficiency of ethanol and the yield of ethyl acetate is respectively 86%, 84%.
Embodiment 14,
After embodiment 11 reaction finishes, isolated catalyzer is again for 4.6g(0.1mol) dehydrated alcohol and 24g(0.4mol) esterification of acetic acid, operational condition is with embodiment 10, obtains the transformation efficiency of ethanol and the yield of ethyl acetate is respectively 78%, 75%.
Claims (3)
1. the quaternary ammonium salt ion liquid of a class based on heteropolyacid, is characterized in that: in molecular composition as negatively charged ion be heteropolyanion, as cationic be amino dodecane Soxylat A 25-7 positively charged ion, structure is:
Wherein, heteropolyanion A
x-for H
2pW
12o
40 -, H
2pMo
12o
40 -, H
2siW
12o
40 -, PW
12o
40 3-, PMo
12o
40 3-, SiW
12o
40 3-in any one; In amino dodecane Soxylat A 25-7 positively charged ion, polyether chain length m+n is 10,15,20 or 30.
2. the preparation method of the quaternary ammonium salt ion liquid of a class claimed in claim 1 based on heteropolyacid, is characterized in that concrete synthesis step is as follows:
The first step, amino dodecane Soxylat A 25-7 is joined in there-necked flask, with dehydrated alcohol, heteropolyacid is fully dissolved, with constant pressure funnel, in there-necked flask, drip phospho-wolframic acid ethanolic soln, the mol ratio of heteropolyacid and amino dodecane Soxylat A 25-7 is heteropolyacid: amino dodecane Soxylat A 25-7=1:1～3, under agitation condition, reaction system is in 20～100 ℃ of heating reflux reaction 4～48h;
Second step, reaction are cooled to room temperature after finishing, and add enough dehydrated alcohols, and standing separatory, repeats 2～4 times, and rotary evaporation 3～6h, in 40～100 ℃ of vacuum-dryings to constant weight, obtains heteropolyacid ionic liquid.
3. the application method of the quaternary ammonium salt ion liquid of a class claimed in claim 1 based on heteropolyacid, it is characterized in that: the quaternary ammonium salt ion liquid using this based on heteropolyacid is as an acidic catalyst, reaction for acetic acid ethanol synthesizing ethyl acetate, concrete steps are: according to ionic liquid: ethanol: the mol ratio of acetic acid=0.003～0.01:1:1～5 joins in there-necked flask in turn, under agitation condition, reaction system is in 20～120 ℃ of heating reflux reaction 2～8h, reaction finishes to add hexanaphthene in backward system, the add-on of hexanaphthene is 50%～200% of system total mass, isolate catalyzer.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104032324A (en) * | 2014-06-04 | 2014-09-10 | 中国科学院过程工程研究所 | Method for electrocatalytic reduction of carbon dioxide using multi-metal oxygen cluster ionic liquid as electrocatalyst |
| CN105016975A (en) * | 2015-06-27 | 2015-11-04 | 青岛科技大学 | Method for preparation of terpineol by alpha-pinene hydration reaction |
| CN105601894A (en) * | 2016-03-17 | 2016-05-25 | 青岛科技大学 | Ultrasonic microwave synthesis method for poly(butanediol itaconate-co-butanediol sebate)copolyester |
| CN105801449A (en) * | 2016-04-12 | 2016-07-27 | 哈尔滨工业大学 | Room-temperature ionic liquid based on heteropoly acid anions and preparation method of room-temperature ionic liquid |
| CN106008206A (en) * | 2016-05-31 | 2016-10-12 | 邵阳学院 | Method for dodecylamine phosphotungstate catalyzed synthesis of long-chain carboxylate |
| CN107188804A (en) * | 2017-07-09 | 2017-09-22 | 邵阳学院 | A kind of method that compound phosphotungstate catalyzes and synthesizes methyl oleate |
| CN111616143A (en) * | 2020-05-06 | 2020-09-04 | 南京威尔生物科技有限公司 | Auxiliary agent for fluorosulfonic water agent and fluorosulfonic water agent prepared by same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1847222A (en) * | 2006-04-20 | 2006-10-18 | 大连理工大学 | Temperature controlled ionic liquid two-phase system and its application in complexing catalytic hydrogenation |
| CN101219995A (en) * | 2008-01-14 | 2008-07-16 | 华东理工大学 | Ion liquid based on heteropoly acid and synthesis thereof |
-
2013
- 2013-12-24 CN CN201310729126.8A patent/CN103664656A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1847222A (en) * | 2006-04-20 | 2006-10-18 | 大连理工大学 | Temperature controlled ionic liquid two-phase system and its application in complexing catalytic hydrogenation |
| CN101219995A (en) * | 2008-01-14 | 2008-07-16 | 华东理工大学 | Ion liquid based on heteropoly acid and synthesis thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李工 等: "新型离子液体型固体酸的合成及其在酯化反应中的应用", 《石油化工》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104032324A (en) * | 2014-06-04 | 2014-09-10 | 中国科学院过程工程研究所 | Method for electrocatalytic reduction of carbon dioxide using multi-metal oxygen cluster ionic liquid as electrocatalyst |
| CN104032324B (en) * | 2014-06-04 | 2016-08-17 | 中国科学院过程工程研究所 | A kind of with multi-metal oxygen cluster ionic liquid be eelctro-catalyst electro-catalysis reduction carbon dioxide method |
| CN105016975A (en) * | 2015-06-27 | 2015-11-04 | 青岛科技大学 | Method for preparation of terpineol by alpha-pinene hydration reaction |
| CN105016975B (en) * | 2015-06-27 | 2016-08-24 | 青岛科技大学 | A kind of method that australene hydration reaction prepares terpineol |
| CN105601894A (en) * | 2016-03-17 | 2016-05-25 | 青岛科技大学 | Ultrasonic microwave synthesis method for poly(butanediol itaconate-co-butanediol sebate)copolyester |
| CN105801449A (en) * | 2016-04-12 | 2016-07-27 | 哈尔滨工业大学 | Room-temperature ionic liquid based on heteropoly acid anions and preparation method of room-temperature ionic liquid |
| CN105801449B (en) * | 2016-04-12 | 2017-11-14 | 哈尔滨工业大学 | Ionic liquid at room temperature based on heteropolyacid anions and preparation method thereof |
| CN106008206A (en) * | 2016-05-31 | 2016-10-12 | 邵阳学院 | Method for dodecylamine phosphotungstate catalyzed synthesis of long-chain carboxylate |
| CN106008206B (en) * | 2016-05-31 | 2018-10-23 | 邵阳学院 | A kind of method that phosphotungstic acid lauryl amine salt catalyzes and synthesizes higher fatty ester |
| CN107188804A (en) * | 2017-07-09 | 2017-09-22 | 邵阳学院 | A kind of method that compound phosphotungstate catalyzes and synthesizes methyl oleate |
| CN111616143A (en) * | 2020-05-06 | 2020-09-04 | 南京威尔生物科技有限公司 | Auxiliary agent for fluorosulfonic water agent and fluorosulfonic water agent prepared by same |
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Application publication date: 20140326 |