CN101844981B - Method for carrying out hydroesterification by using ionic liquid - Google Patents
Method for carrying out hydroesterification by using ionic liquid Download PDFInfo
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- CN101844981B CN101844981B CN201010178921.9A CN201010178921A CN101844981B CN 101844981 B CN101844981 B CN 101844981B CN 201010178921 A CN201010178921 A CN 201010178921A CN 101844981 B CN101844981 B CN 101844981B
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Abstract
The invention relates to a method for making olefin compound, carbon monoxide and alcohol to carry out hydroesterification under the catalysis of system of the metal complex catalyst system and the promotion of promoter of ionic liquid so as to generate corresponding carboxylic ester. The ionic liquid has the function of inhibiting the polymerization of the reactants so as to ensure the high reactant conversion rate and the controllable stereoselectivity of the products of hydroesterification, and the ionic liquid and the metal complex catalyst can be reused, thus the method has low total cost and wide industrial application prospect.
Description
Technical field
The present invention relates under ionic liquid existence, ethylenically unsaturated compounds and carbon monoxide and low carbon fat alcohol hydroesterification reaction are produced the novel method of carboxylicesters.
Background technology
At alcohol with comprise 8,9 Huo10 family the metals for example catalyst system of palladium and phosphine part for example under the existence of alkylphosphines, cycloalkyl phosphine, aryl phosphine, pyridyl phosphine or bidentate phosphine, use carbon monoxide to carry out the carbonylation of alefinically unsaturated compounds, in many patents, be described, for example EP-A-04489472, EP-A-0499329, EP-A-0495547, US2005085671A1, US6284919B1, US2001051745A1, US6476255B1, WO2007057640A1.Especially US6476255B1 disclose one group of bidentate phosphine compound with substituted aryl bridge can provide remarkable must be higher than the previous speed of reaction of those disclosed catalyzer, and produce a little or do not produce impurity, and thering is high conversion.WO01/68583 discloses the speed obtaining when for high olefin and while externally adding aprotic solvent with WO96/19434 same procedure.
But, in above-mentioned patent, by changing the mode of catalyst ligand, improving reaction-ure conversion-age, bidentate phosphine part is expensive and extremely unstable in air; And the branched carboxylic acids ester generating when alkene used is aryl olefin or long-chain fat alkene and the ratio of straight-chain carboxylic acid's ester are uncontrollable, and for these problems, existing patent does not all propose effective terms of settlement.The present invention adopts in reaction system and adds a small amount of ionic liquid to improve the stereoselectivity of transformation efficiency and the product of reactant.
Summary of the invention
The reaction that the novel method that the present invention proposes makes ethylenically unsaturated compounds, carbon monoxide and alcohol hydroesterification produce carboxylicesters is carried out under ionic liquid exists, and reaction conversion ratio and selectivity are high; When alkene used is aryl olefin or long-chain fat alkene, the double stereoselectivity reagent of doing product of ionic liquid, the three-dimensional arrangement of product is controlled; The noble metal complexes catalyst levels using in reaction is few, and reusable with ionic liquid, and total cost is low, and prospects for commercial application is wide.
The concrete embodiment of the present invention is that catalyzer, ionic liquid and reactant are added in reactor, pours carbon monoxide, and alkene and alcohol react and generates carboxylicesters under suitable temperature and pressure condition.After having reacted, product and the unreacted raw material mode by distillation realizes separated with catalyzer and ionic liquid, and catalyzer and ionic liquid can continue to recycle.
The ionic liquid that the present invention uses is [BMIM] [BF
4], [BMIM] [PF
6], [BMIM] [GaCl
6], [EMIM] [BF
4], [EMIM] [PF
6], [EMIM] [GaCl
6], [Acetonyl-MIM] [BF
4], [Cyanobutyl-MIM] [BF
4], [Dodecyl-MIM] [BF
4], [Butylene-MIM
2] [BF
4]
2, [Benzyl-MIM] [BF
4], [Acetonyl-MIM] [PF
6], [Cyanobutyl-MIM] [PF
6], [Dodecyl-MIM] [PF
6] etc. a kind of or several mixtures wherein in glyoxaline ion liquid.
The catalyzer that the present invention uses is homogeneous phase metal complex ML
nx
mcatalyzer, wherein M is 8,9 Huo10 family metals, preferable alloy Pd, Ru, Rh and Pt, more preferably Pd and Rh; L is organism part; X is halogen, carbonate, bicarbonate radical, nitrate radical, carboxylate radical or sulfonate radical; N is the numerical value that is equal to or less than metal-complexing number, and m is 1 or 2 and equal the oxidation state of metal.
The present invention's alkene used can be the fatty alkene such as ethene, propylene, iso-butylene, can be also the aromatic olefins such as vinylbenzene.Alcohol used can be the aliphatic alcohols such as methyl alcohol, ethanol, propyl carbinol, the trimethyl carbinol, can be also the aromatic alcohols such as phenylcarbinol.
In the method for the invention, can in reaction, use the carbon monoxide of pure form; Or under the existence of other gases that is inertia, use, the example of described gas comprises for example argon gas of nitrogen, carbonic acid gas and rare gas; Also can there is small amounts of hydrogen, typically be less than the hydrogen of 5% volume.Gas passes into blistering reaction in reaction system.
In the method for the invention, at the temperature of 20～150 ℃, carry out hydroesterification reaction, preferably, at the temperature of 60～100 ℃, react; Pressure is 0.1～100MPa, preferably, and 1～10MPa.
In the method for the invention, the time length of hydroesterification is had no particular limits, obviously preferably commercially in acceptable time scale, carry out.Hydroesterification in rhythmic reaction can occur maximum 50 hours, and at least 5 minutes, preferably 2～20 hours.
With embodiment, illustrate the present invention below, the selectivity gas Chromatographic Determination of conversion of olefines rate and carboxylicesters, it is defined as follows:
Utilize this method to prepare the preparation method that carboxylicesters mentions with existing patent and compare, have advantages of that transformation efficiency is high, stereoselectivity good, the consumption of catalyzer is few simultaneously, and ionic liquid can be recycled together with catalyzer.
Catalyzer in the present invention is relating in disclosed patent, but in the present invention in ionic liquid the production method of carboxylicesters have no and mention.
Embodiment
Embodiment 1
By 0.0045g ((about 0.02mmol)) palladium, 0.0368g (about 0.14mmol) triphenylphosphine, 0.0173g (about 0.18mmol) methylsulphonic acid, took off 60mL (about 0.51mol) vinylbenzene of gas, took off 90mL (about 2.23mol) methyl alcohol of gas, [BMIM] [BF
4] ionic liquid 10mL joins homemade 200mL with teflon-lined stainless steel reactor, under room temperature, nitrogen replacement is 3 times, fills CO gas (99.99% purity) to 1.0MPa.At 80 ℃, react 10 hours, be chilled to room temperature and emit unreacted CO, the methyl phenylpropionate of preparation and 2-phenylpropionic acid methyl esters and unreacted gas chromatographic analysis, experimental result is in Table 1.
Comparative example 1
0.0091g ((about 0.04mmol)) palladium and 0.0210g (about 0.08mmol) triphenylphosphine are dissolved in 40mL toluene, under room temperature, stirring reaction is 3 hours, stop stirring, add 30mL normal hexane, yellow solid powder is separated out, and pours out upper toluene solution, leach yellow solid, and with normal hexane washing several times, finally with ether washing once, in vacuum drying oven vacuum-drying, obtain catalyzer 1:Pd (PPh
3)
2(OAc)
2.
In reactor, add successively 0.0150g catalyzer 1,0.0263g triphenylphosphine and 0.0173g methylsulphonic acid, and the vinylbenzene 60mL that took off gas, methyl alcohol 90mL, [BMIM] [BF
4] ionic liquid 10mL.Under room temperature, nitrogen replacement is 3 times, fills CO gas (99.99% purity) to 1.0MPa.At 80 ℃, react 10 hours, be chilled to room temperature and emit unreacted CO, experimental result is in Table 1.
Comparative example 2
By 0.0091g palladium, 0.0210g triphenylphosphine, 0.0077g tosic acid is dissolved in 40mL toluene; under nitrogen protection; under room temperature, stirring reaction is 3 hours, stops stirring, and adds 30mL normal hexane; instantaneous have yellow solid powder to separate out; pour out upper toluene solution, leach yellow solid, and with normal hexane washing several times; finally with ether washing once, in vacuum drying oven vacuum-drying, obtain catalyzer 2:Pd (PPh
3)
2(OTs)
2.
In reactor, add successively 0.0195g catalyzer 1,0.0263g triphenylphosphine and 0.0135g tosic acid, and the vinylbenzene 60mL that took off gas, methyl alcohol 90mL, [BMIM] [BF
4] ionic liquid 10mL.Under room temperature, nitrogen replacement is 3 times, fills CO gas (99.99% purity) to 1.0MPa.At 80 ℃, react 10 hours, be chilled to room temperature and emit unreacted CO, experimental result is in Table 1.
Comparative example 3
Catalyzer, raw material, ionic liquid and the reaction conditions identical with embodiment 1, just do not add [BMIM] [BF
4] ionic liquid prepares methyl phenylpropionate and 2-phenylpropionic acid methyl esters, experimental result is in Table 1.
Comparative example 4
Catalyzer, raw material, ionic liquid and the reaction conditions identical with embodiment 1, just by [BMIM] used [BF
4] amount of ionic liquid changes 5ml into from 10ml, prepares methyl phenylpropionate and 2-phenylpropionic acid methyl esters, experimental result is in Table 1.
Comparative example 5
Catalyzer, raw material, ionic liquid and the reaction conditions identical with embodiment 1, just by [BMIM] used [BF
4] amount of ionic liquid changes 15ml into from 10ml, prepares methyl phenylpropionate and 2-phenylpropionic acid methyl esters, experimental result is in Table 1.
Embodiment 2
Catalyzer, raw material, ionic liquid and the reaction conditions identical with embodiment 1, just by ionic liquid used [BMIM] [BF
4] replace with [BMIM] [PF
6], prepare methyl phenylpropionate and 2-phenylpropionic acid methyl esters, experimental result is in Table 1.
Comparative example 6
Catalyzer, raw material, ionic liquid and the reaction conditions identical with embodiment 1, just by ionic liquid used [BMIM] [PF
6] amount from 10ml, change 5ml into, prepare methyl phenylpropionate and 2-phenylpropionic acid methyl esters, experimental result is in Table 1.
Comparative example 7
Catalyzer, raw material, ionic liquid and the reaction conditions identical with embodiment 1, just by ionic liquid used [BMIM] [PF
6] amount from 10ml, change 15ml into, prepare methyl phenylpropionate and 2-phenylpropionic acid methyl esters, experimental result is in Table 1.
Embodiment 3
Catalyzer, raw material, ionic liquid and the reaction conditions identical with embodiment 1, just by ionic liquid used [BMIM] [BF
4] replace with [EMIM] [PF
6], prepare methyl phenylpropionate and 2-phenylpropionic acid methyl esters, experimental result is in Table 1.
Embodiment 4
Catalyzer, raw material, ionic liquid and the reaction conditions identical with embodiment 1, just by ionic liquid used [BMIM] [BF
4] replace with [EMIM] [BF
4], prepare methyl phenylpropionate and 2-phenylpropionic acid methyl esters, experimental result is in Table 1.
Embodiment 5
Catalyzer, raw material, ionic liquid and the reaction conditions identical with embodiment 1, just by ionic liquid used [BMIM] [BF
4] replace with [EMIM] [GaCl
6], prepare methyl phenylpropionate and 2-phenylpropionic acid methyl esters, experimental result is in Table 1.
Embodiment 6
Catalyzer, ionic liquid and the reaction conditions identical with embodiment 1, just replace with ethanol by raw materials used methyl alcohol, prepares phenylpropionic acid ethyl ester and 2-phenylpropionic acid ethyl ester, and experimental result is in Table 1.
Embodiment 7
By 0.0045g ((about 0.02mmol)) palladium, 0.0368g (about 0.14mmol) triphenylphosphine, 0.0173g (about 0.18mmol) methylsulphonic acid, 100mL methyl alcohol, ionic liquid [BMIM] [BF
4] 10mL joins the reactor identical with embodiment 1, pass into the gas mixture (mol ratio is 1: 1) of ethene and carbon monoxide, be forced into 1.0MPa, temperature is at 80 ℃, to start reaction, continuously logical gas mixture reaction 10 hours, is chilled to room temperature, and Pressure Drop is to normal pressure, prepare methyl propionate gas chromatographic analysis, experimental result is in Table 2.
Comparative example 8
Catalyzer, raw material, ionic liquid and the reaction conditions identical with embodiment 6, just by ionic liquid used [BMIM] [BF
4] replace with [BMIM] [PF
6], prepare methyl propionate, experimental result is in Table 2.
Embodiment 8
Catalyzer, ionic liquid and the reaction conditions identical with embodiment 7, just replace with ethanol by raw materials used methyl alcohol, prepares ethyl propionate, and experimental result is in Table 2.
Table 1 embodiment and comparative example result
Table 2 embodiment and comparative example result
| Embodiment sequence number | Methanol conversion (%) | Methyl propionate selectivity (%) |
| Embodiment 7 | 73.1 | 98.7 |
| Comparative example 8 | 65.6 | 97.1 |
| Embodiment 8 | 71.9 | 97.3 |
Claims (3)
1. an alkene and carbon monoxide and alcohols hydroesterification reaction generate the method for carboxylicesters, it is characterized by: in hydrogen esterification reaction, complex compound catalyst and glyoxaline ion liquid are dissolved in reactant, under certain reaction conditions, produce carboxylicesters, the stereoselectivity of carboxylicesters is controlled, after having reacted, product and the unreacted raw material mode by distillation realizes separated with catalyzer and ionic liquid, catalyzer and ionic liquid can continue to recycle, and described complex compound catalyst is ML
nx
mform, wherein M is selected from metal Pd, and L is organism part and is selected from triphenylphosphine, and X is selected from carboxylate radical, m=2, n is the appropriate value that is equal to or less than metal-complexing number, and acid source is sulfonic compound, and described alkene is vinylbenzene or ethene.
2. method according to claim 1, ionic liquid is glyoxaline ion liquid [EMIM] [PF
6], [EMIM] [BF
4], [BMIM] [BF
4], [BMIM] [PF
6] in a kind of or several mixtures wherein.
3. method according to claim 1, temperature of reaction is 60-100 ℃, reaction pressure is 1-10MPa.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531890A (en) * | 2010-12-18 | 2012-07-04 | 中国科学院兰州化学物理研究所 | Method for preparing organic carboxylate from olefin through hydroesterification |
| CN105541610B (en) * | 2016-01-13 | 2017-09-26 | 河北工业大学 | A kind of method of utilization carbon dioxide and ethylene synthase methyl propionate |
| CN108003022B (en) * | 2016-11-02 | 2020-01-07 | 中国科学院大连化学物理研究所 | Method for preparing ester compound |
| CN108003023B (en) * | 2016-11-02 | 2019-10-18 | 中国科学院大连化学物理研究所 | A method of preparing methyl propionate |
| CN108003024B (en) * | 2016-11-02 | 2019-10-18 | 中国科学院大连化学物理研究所 | A kind of preparation method of methyl propionate |
| CN108993602B (en) * | 2018-07-23 | 2021-05-07 | 河北工业大学 | Catalytic system for synthesizing methyl propionate and application method thereof |
| CN111087306B (en) * | 2019-12-27 | 2021-08-03 | 南京诚志清洁能源有限公司 | Method for preparing organic carboxylic ester by aryl bidentate phosphine ligand combined catalysis |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1420860A (en) * | 2000-03-14 | 2003-05-28 | 国际壳牌研究有限公司 | Process for carbonylation of ethylenically unsaturated compounds |
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| CN1420860A (en) * | 2000-03-14 | 2003-05-28 | 国际壳牌研究有限公司 | Process for carbonylation of ethylenically unsaturated compounds |
Non-Patent Citations (2)
| Title |
|---|
| 新型环境友好材料—室温离子液的制备及其应用研究;杨雷;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20080315(第03期);第B014-38页 * |
| 杨雷.新型环境友好材料—室温离子液的制备及其应用研究.《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》.2008,(第03期),第B014-38页. * |
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