CN1600767A - Method for synthesizing aether from olefin and alcohol - Google Patents
Method for synthesizing aether from olefin and alcohol Download PDFInfo
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- CN1600767A CN1600767A CN 03159656 CN03159656A CN1600767A CN 1600767 A CN1600767 A CN 1600767A CN 03159656 CN03159656 CN 03159656 CN 03159656 A CN03159656 A CN 03159656A CN 1600767 A CN1600767 A CN 1600767A
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Abstract
A process for synthesizing ether by alkenes, alcohol, alkyl pyridine end link sulfuric group or ion liquid compose dof 1,3-Dialkyl imidazole positive ion and negative ion as reaction mediator and catalyst includes such steps as taking reaction alkenes and alcohol by catalyst to get ether compound 1-12 hours in 0.1-2.0 MPa at 50-150 deg.C.
Description
Technical field
The present invention relates to a kind of method of alkene and the synthetic ether of alcohol effect of cleaning.
Technical background
In order to adapt to environmental protection requirement, the modified gasoline that contains the oxygen ethers with interpolation replaces the common recognition that doped fuel has become various countries.The ethers modified gasoline is generally obtained by two kinds of methods: the first, in pressure gasoline, directly add more sophisticated ethers gasoline dopes such as methyl tertiary butyl ether, Ethyl Tertisry Butyl Ether, tert amyl methyl ether(TAME) and tertiary amyl ethyl ether; The second, for adapting to the requirement of present China decreasing by gasoline olefin, with the direct etherificate of the alkene in the gasoline for containing the oxygen ethers.These two kinds of methods all need alkene and alcohols etherificate.In the past, mineral acid was once studied widely as this type of catalyst for reaction, for example H
2SO
4, HF and BF
3Deng.Though these catalyzer have been obtained catalytic effect preferably, because alcohols self is dehydrated into ether easily, add etching apparatus, problems such as environmental pollution are difficult to solve, and this catalyst system progressively is eliminated.Recently, multiple solid acid also once was used as the catalyzer of pure and mild alkene effect.But owing to there is the uneven selectivity of product that influences of acidity in solid acid as catalyzer, in addition the easy inactivation of catalyzer, efficient is on the low side etc., and problem makes this catalyst system still be in conceptual phase.The exploitation low toxicity, efficiently alkene and alcohol directly etherification method not only have important economic benefit, but also have good benefits in environment.
In recent years, eco-friendly catalyst system provided more wide space to ionic liquid at room temperature for people explore.Room-temperature ion liquid itself has excellent chemistry and thermodynamic stability, many materials is all had good solvency power, and at room temperature have vapour pressure hardly, and this makes to be applied in and has had the characteristic of being convenient to product separation and catalyst recovery in the catalyzed reaction concurrently.The characteristic that ionic liquid is different from general molecular solvent also has its plasticity-.The length, the function key kind that change ion liquid zwitterion and alkyl group side chain can in very large range be regulated ion liquid physicochemical property.For example, with sulfonic group (SO
3H) be chemically bonded on the ion liquid cationic side chain, can make it to show very strong acidity.Since the ionic liquid of this sulfonic functional have can flow, non-volatile, non-aggressive and with the immiscible special performance of multiple organic solvent, can replace traditional liquid acid and solid acid and be applied in the multiple acid catalyzed reaction.
Summary of the invention
The objective of the invention is to replace the etherificate of traditional liquid acid and solid acid catalyst realization alkene and alcohols, a kind of efficient and eco-friendly reaction medium and catalyzer are provided, under the reaction conditions of gentleness, catalyzed alkene and pure method of synthesizing ether.
The present invention realizes by following measure:
The method of a kind of alkene and the synthetic ether of alcohol is characterized in that adopting terminal bonding that sulfonic group (SO is arranged
3H) alkyl pyridine or 1, the ionic liquid that is liquefaction under the room temperature that 3-dialkylimidazolium positively charged ion and negatively charged ion constitute is simultaneously as reaction medium and catalyzer, at 0.1MPa to 2.0MPa, and 50 to 150 ℃, react under 1 to 12 hour, ether compound is produced in catalyzed alkene and alcohol effect.
The cationic structure of alkyl pyridine is
1, the cationic structure of 3-dialkylimidazolium is
Ionic liquid of the present invention is made up of positively charged ion and negatively charged ion, and wherein negatively charged ion is selected from trifluoromethanesulfonic acid root, tosic acid root, Phenylsulfonic acid root, methanesulfonic root, tetrafluoro and closes borate, hexafluoro and close a kind of in the phosphate radical.
Ionic liquid is 1: 5 to 5: 1 with the mol ratio of alcohol.
Alkene is 1: 5 to 5: 1 with the mol ratio of alcohol.
Alkene used in the present invention is that carbon chain lengths is C
2To C
12Straight chain, side chain or cyclic olefin.
Alcohol used in the present invention is methyl alcohol, ethanol, propyl alcohol or Virahol.
The present invention is 50 to 150 ℃ of temperature of reaction, and under pressure 0.1 to the 2.0MPa condition, ionic liquid can be produced corresponding ether compound with pure effect by catalyzed alkene in 1 to 12 hour time.
Ionic liquid used in the present invention is exactly the sulfonate functional ionic liquid, and its synthetic method can be with reference to reference (A.C.Cole, J.L.Jensen, I.Ntai, K.L.T.Tran, K.J.Weave, D.C.Forbes, J.H.Davis, J.Am.Chem.Soc., 2002,124,5962.).
The following describes the concrete preparation method of trifluoromethayl sulfonic acid 1-octyl group-3-(4-sulfonic group) butyl imidazole ionic liquid:
Get equimolarly 1, after 4-butyl sultone and 1-octyl group imidazoles mix, stirred 72 hours down in normal temperature; In 60 ℃ of maintenances 5 hours, obtain a kind of white gels shape material again; 80 ℃ of vacuum of this material (1mm Hg) were kept 1 to 3 hour down, promptly obtain a kind of limpid liquid that under 80 ℃, is in a liquid state, i.e. 1-octyl group imidazoles-3-fourth acid inner salt; Trifluoromethayl sulfonic acid of its at room temperature equal mole is mixed, and 80 ℃ are stirred down and promptly obtained trifluoromethayl sulfonic acid 1-octyl group-3-(4-sulfonic group) butyl imidazole ionic liquid in 6 hours.
Under lab, our etherification method that adopts is: add alkene, alcohol, ionic liquid and magneton successively in the airtight and inwall of being furnished with magnetic agitation is lined with the stainless steel autoclave of Glass tubing.Wherein, alkene is 1: 5 to 5: 1 with the mol ratio of alcohol, and ionic liquid is 1: 5 to 5: 1 with the mol ratio of alcohol.Then at 50 to 150 ℃, under pressure 0.1 to the 2.0MPa condition, stirring reaction 1 to 12 hour.Stop heating, cool to below 25 ℃.Since the homo-ion liquid of formed ether insoluble and with the ionic liquid natural layering, remove the etherificate product and the responseless alkene on upper strata, after extracting three times with an amount of toluene, remaining ionic liquid finds time under in 80 to 100 ℃ can reuse behind 30 minutes purifying.
The present invention compares its substantial characteristics with traditional liquid acid with solid acid catalysis alkene with pure etherificate:
1. not using that toxicity is big, the catalyzer of severe corrosive, is an eco-friendly reaction process;
2. do not use the solid inorganic material catalyzer, substrate can fully contact with catalyzer, and etherificate is effective and selectivity is high.
3. etherificate product and ionic liquid AUTOMATIC ZONING are separated simple;
4. the ionic liquid that reacted, in 80 to 100 ℃ of following evacuation processes numbers minute after extracting can reuse.
Embodiment
Embodiment 1: the etherificate of 2-methyl-2-butene and methyl alcohol in trifluoromethayl sulfonic acid 1-octyl group-3-(4-sulfonic group) butyl imidazole ionic liquid
Get trifluoromethayl sulfonic acid 1-octyl group-3-(4-sulfonic group) butyl imidazole ionic liquid 22.9g (50mmol), add 2.4g (75mmol) methyl alcohol and 5.3g (75mmol) 2-methyl-2-butene under the room temperature, in 120 ℃ of following stirring reactions after 4 hours, be cooled to-40 ℃, tell the insoluble organism in upper strata, toluene extraction lower floor's ionic liquid (20ml * 3) merges the organism that all obtain, use HP 6890/5973 GC/MS to carry out qualitative analysis, the HP1790 gas chromatograph carries out quantitative analysis.Methanol conversion 99%, tert amyl methyl ether(TAME) selectivity 99%.
Embodiment 2: tertiary amyl ethyl ether is synthetic in tosic acid 1-butyl-3-(3-sulfonic group) propyl imidazole ionic liquid
Replace trifluoromethayl sulfonic acid 1-octyl group-3-(4-sulfonic group) butyl imidazole ionic liquid with tosic acid 1-butyl-3-(3-sulfonic group) propyl imidazole 20.9g (50mmol), ethanol 3.4g (75mmol) replaces methyl alcohol, and all the other are with embodiment 1.Ethanol conversion 98%, tertiary amyl ethyl ether selectivity 100%.
Embodiment 3: different ionic liquid catalysis 2-methyl-2-butene and methanol etherification reactivity worth are relatively
Use trifluoromethayl sulfonic acid 1-octyl group-3-(4-sulfonic group) butyl imidazole, trifluoromethayl sulfonic acid 1-butyl-3-(4-sulfonic group) butyl imidazole, trifluoromethayl sulfonic acid 1-hexyl-3-(4-sulfonic group) butyl imidazole, tosic acid 1-butyl-3-(3-sulfonic group) propyl imidazole, tosic acid 1-hexyl-3-(4 sulfonic group) butyl imidazole as ionic liquid respectively, all the other are with embodiment 1.Reaction result is listed in table 1.
The ionic liquid-catalyzed methyl alcohol of the different sulfonate functionalizations of table 1. and hexene etherification reaction performance are relatively
| Ionic liquid | Methanol conversion (%) | Tert amyl methyl ether(TAME) selectivity (%) |
| Trifluoromethayl sulfonic acid 1-octyl group-3-(4-sulfonic group) butyl imidazole | ??99 | ??99 |
| Trifluoromethayl sulfonic acid 1-butyl-3-(4-sulfonic group) butyl imidazole | ??98 | ??91 |
| Trifluoromethayl sulfonic acid 1-hexyl-3-(4-sulfonic group) butyl imidazole | ??99 | ??95 |
| Tosic acid 1-butyl-3-(3-sulfonic group) propyl imidazole | ??96 | ??97 |
| Tosic acid 1-hexyl-3-(4-sulfonic group) butyl imidazole | ??96 | ??98 |
Embodiment 4: the reaction of 2-methyl-2-butene and methanol etherification is reused in trifluoromethayl sulfonic acid 1-octyl group-3-(4-sulfonic group) butyl imidazole ionic liquid
The ionic liquid that reacted among the embodiment 1 was handled 30 minutes in 100 ℃ of following vacuum (1mm Hg) after extracting, and the reinforced once more etherification reaction that repeats circulates 4 times, the results are shown in table 2.
The result is reused in the reaction of 2-methyl-2-butene and methanol etherification in table 2. trifluoromethayl sulfonic acid 1-octyl group-3-(4-sulfonic group) butyl imidazole ionic liquid
| Cycle index | ????1 | ????2 | ????3 | ????4 | ????5 |
| Methanol conversion (%) | ????99 | ????98 | ????95 | ????96 | ????96 |
| Tert amyl methyl ether(TAME) selectivity (%) | ????99 | ????100 | ????99 | ????97 | ????98 |
Claims (8)
1, the method for a kind of alkene and the synthetic ether of alcohol, it is characterized in that adopting terminal bonding that sulfonic alkyl pyridine or 1 are arranged, the ionic liquid that is liquefaction under the room temperature that 3-dialkylimidazolium positively charged ion and negatively charged ion constitute is simultaneously as reaction medium and catalyzer, at 0.1MPa to 2.0MPa, 50 to 150 ℃, react under 1 to 12 hour, ether compound is produced in catalyzed alkene and alcohol effect.
2, the method for claim 1 is characterized in that the cationic structure of alkyl pyridine is
Wherein s is 2 to 4 integer.
3, the method for claim 1 is characterized in that 1, and the cationic structure of 3-dialkylimidazolium is
Wherein n is 2 to 4 integer, and m is 0 to 12 integer.
4, the method for claim 1 is characterized in that negatively charged ion is selected from trifluoromethanesulfonic acid root, tosic acid root, Phenylsulfonic acid root, methanesulfonic root, tetrafluoro and closes borate, hexafluoro and close a kind of in the phosphate radical.
5, the method for claim 1 is characterized in that the ionic liquid and the mol ratio of alcohol are 1: 5 to 5: 1.
6, the method for claim 1 is characterized in that the alkene and the mol ratio of alcohol are 1: 5 to 5: 1.
7, the method for claim 1 is characterized in that alkene is that carbon chain lengths is C
2To C
12Straight chain, side chain or cyclic olefin.
8, the method for claim 1 is characterized in that alcohol is methyl alcohol, ethanol, propyl alcohol or Virahol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03159656 CN1600767A (en) | 2003-09-25 | 2003-09-25 | Method for synthesizing aether from olefin and alcohol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03159656 CN1600767A (en) | 2003-09-25 | 2003-09-25 | Method for synthesizing aether from olefin and alcohol |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408316A (en) * | 2010-09-21 | 2012-04-11 | 中国石油天然气股份有限公司 | Method for preparing tert-amyl methyl ether |
| CN105566550A (en) * | 2014-10-13 | 2016-05-11 | 中国石化扬子石油化工有限公司 | Preparation method of acidic polystyrene resin catalyst for synthesis of ethyl tert-butyl ether |
| CN106831358A (en) * | 2017-01-18 | 2017-06-13 | 东营市海科新源化工有限责任公司 | A kind of preparation method of dipropylene glycol |
-
2003
- 2003-09-25 CN CN 03159656 patent/CN1600767A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408316A (en) * | 2010-09-21 | 2012-04-11 | 中国石油天然气股份有限公司 | Method for preparing tert-amyl methyl ether |
| CN102408316B (en) * | 2010-09-21 | 2014-08-06 | 中国石油天然气股份有限公司 | Method for preparing tert-amyl methyl ether |
| CN105566550A (en) * | 2014-10-13 | 2016-05-11 | 中国石化扬子石油化工有限公司 | Preparation method of acidic polystyrene resin catalyst for synthesis of ethyl tert-butyl ether |
| CN106831358A (en) * | 2017-01-18 | 2017-06-13 | 东营市海科新源化工有限责任公司 | A kind of preparation method of dipropylene glycol |
| CN106831358B (en) * | 2017-01-18 | 2020-03-03 | 东营市海科新源化工有限责任公司 | Preparation method of dipropylene glycol |
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