CN103288634A - A method for catalytic synthesis of diisopropyl maleate - Google Patents
A method for catalytic synthesis of diisopropyl maleate Download PDFInfo
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- CN103288634A CN103288634A CN2013102541801A CN201310254180A CN103288634A CN 103288634 A CN103288634 A CN 103288634A CN 2013102541801 A CN2013102541801 A CN 2013102541801A CN 201310254180 A CN201310254180 A CN 201310254180A CN 103288634 A CN103288634 A CN 103288634A
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Abstract
The present invention discloses a method for catalytic synthesis of diisopropyl maleate by using a dual-core functionalized ionic liquid. The method comprises mixing maleic anhydride and isopropyl alcohol at a molar ratio of (1:3) - (1:8), adding a dual-core functionalized ionic liquid catalyst with an amount of 10%-20% of the mass of the maleic anhydride, reacting at a reaction temperature controlled at 70 DEG C-110 DEG C, stirring and refluxing under condensation for 3-8 h, and after the reaction is completed, standing at room temperature for laying, wherein the ionic liquid of a lower layer is recycled after simple rotary distilling for removing water, and pure diisopropyl maleate is obtained from the product ester of the upper layer through atmospheric distillation, neutralization, liquid separation, and vacuum distillation. According to the invention, the dual-core functionalized ionic liquid adopted has a high catalytic activity, a good selectivity, a stable structure, and good catalytic performance after repeated recycling, not only meeting environmental requirements, but also reducing production costs and improving production efficiency.
Description
Technical field
The present invention relates to the method for a kind of synthetic method of ester, particularly a kind of synthetic isopropyl maleate, belong to
Compound synthesizes technical field.
Background technology
Isopropyl maleate has another name called maleic acid diisopropyl ester (note is made DIPM), is the important intermediate of producing the preparation diisopropyl ester amber acid.Can be widely used in industry such as food, spices, dyestuff, coating, rubber, plastics.The synthetic isopropyl maleate of tradition adopts the sulphuric acid catalysis esterification process, and there are problems such as equipment corrosion, side reaction is many, product is not easily separated in this method.Along with the further investigation of people to catalyst for esterification reaction, engendered that again solid super-strong acid, heteropolyacid, tosic acid, ion exchange resin etc. are as catalyst for reaction, but ubiquity long, drawbacks such as catalyst activity reduction is fast, catalyst recovery difficulty reaction time are restricted its industrial applications.
Ionic liquid (Ionic Liquids, write a Chinese character in simplified form: ILs), claim that again (Room or Ambient Temperature Ionic Liquids RTILs), refers to the salt that is in a liquid state, be made up of zwitterion fully to ionic liquid at room temperature under room temperature or the condition near room temperature.Ionic liquid has caused the extensive concern of researcher as forward position and the focus of international Green Chemistry aspect a lot, especially shown clear superiority at catalytic field.The first, the acid-basicity of ionic liquid (pH value) is adjustable, has guaranteed the catalytic efficiency of catalyzer, and can effectively avoid the etching problem of equipment; The second, the wetting ability of ionic liquid can be regulated, because in esterification reaction process, ionic liquid can absorb the water that generates in the reversible reaction, thereby promotes reaction to carry out to favourable direction, shortens the reaction times; The 3rd, hating of ionic liquid is separating of oil, and after reaction was finished, ionic-liquid catalyst can be realized the AUTOMATIC ZONING with product, had avoided the use of division box, had simplified separating technology, has realized the production that cleans of carboxylicesters synthesis technique; The 4th, the fusing point of ionic liquid is adjustable, and building-up reactions is carried out under low temperature mitigation condition, and the security of operation has obtained greatly ensureing; The 5th, ionic liquid structural stability height has guaranteed recovery and the recycling performance of catalyzer.Therefore, the application of research ionic liquid in compound is synthetic has practical significance.
Summary of the invention
The method that the purpose of this invention is to provide a kind of synthetic isopropyl maleate, it is with double-core imidazoles Br φ nsted(Chinese translation: bronsted) acidic ion liquid is as catalyzer, overcome that the catalytic efficiency that catalyst system therefor exists in the prior art is low, equipment corrosion, catalyzer are difficult for reclaiming, in and problem such as alkali consumption is big, realized the green high-efficient catalytic esterification under the mild conditions, and this technology is simple, with low cost, the recyclable repetition of catalyzer is sharp
With.
For realizing purpose of the present invention, the technical solution adopted in the present invention is such:
A kind of method of synthetic isopropyl maleate may further comprise the steps:
(1) gets material
Get maleic anhydride and Virahol with amount of substance than (1:3)～(1:8), mix, add double-core class ionic-liquid catalyst, catalyst consumption is 10%～20% of maleic anhydride quality;
(2) reacting by heating
In heating jacket internal heating to 70～110 ℃, stir in the time of heating, condensing reflux 3～8h, reaction is at room temperature left standstill reaction solution after finishing;
(3) catalyst recovery
After reaction finished, reaction solution and catalyzer AUTOMATIC ZONING were toppled over and upper strata ester crude product, lower floor's ionic liquid through vacuum rotary steam except water treatment, can the direct reaction that enter next circulation as raw catalyst;
(4) purifying
Isolated ester crude product is removed excessive Virahol, is neutralized to pH=7 through the normal pressure distillation, and separatory, underpressure distillation are collected and made pure isopropyl maleate.
Among the present invention, the general structure of said double-core class ionic-liquid catalyst is as follows in the step (1):
N in the formula=1～6, along with n increases, the positive charge on the imidazole ring is more concentrated, strengthens the interaction between zwitterion, and the ionic liquid fusing point is raise, and in n=1～6 o'clock, the ionic liquid fusing point is lower, under esterification reaction temperature, realizes homogeneous reaction easily;
In the formula, negatively charged ion X
-Be: bisulfate ion HSO
4 -, dihydrogen phosphate H
2PO
4 -, tetrafluoroborate BF
4 -, thiocyanate ion SCN
-, tosic acid root CH
3PhSO
3 -, wherein a kind of.Negatively charged ion X
-Preferably from one of above-mentioned negatively charged ion, purpose is to make ionic liquid to show as acidity.Because esterification is acid catalyzed reaction, acidic ion liquid is higher to acid alcohol esterification catalytic effect.
The addition sequence of raw material in no particular order in the synthetic method of the present invention, step (1).Because ionic liquid is homogeneous reaction under esterification reaction temperature as catalyzer, feed in raw material and carry out at ambient temperature, the addition sequence of any reactant or catalyzer does not exert an influence to reaction.
Synthetic method of the present invention, the neutralization in the step (4), refer under the room temperature condition that catalyst separating finishes after, adopt NaOH solution or the NaHCO of mass concentration 5%～0%
3Solution neutralization reaction liquid is to pH=7.
Synthetic method of the present invention, the underpressure distillation in the step (4) refers in ester crude product rectifying separation purification process, control pressure (vacuum tightness) 0.05MPa～0.1MPa, 110 ℃～210 ℃ of distillation gas phase temperatures.
The present invention obtains following beneficial effect:
The catalyst that the present invention uses is active high, and consumption is few, and the product selectivity height meets or exceeds existing industrial level; The reaction conditions gentleness of esterification of the present invention, catalyzer and product can be realized AUTOMATIC ZONING, have avoided volatility water liquid benzene, toluene, 1, the use of 2-ethylene dichloride, green degree obtains bigger raising; The catalyst stability that uses is good, and corrodibility is low, and catalyst recovery technology is simple, repeats to apply mechanically repeatedly, and product yield reduces not obvious.
The present invention can be used for synthetic isopropyl maleate suitability for industrialized production.
Following examples are used for explanation the present invention.It may be noted that following examples only are used for explanation the present invention, is not restriction of the present invention.
Embodiment
Embodiment 1
With 200g(2.04mol) maleic anhydride, 367g(6.12mol) Virahol, 36.7g double-core functionalized ion liquid be two-and the two hydrosulfates of (3-methyl isophthalic acid-imidazoles) butylidene add and are equipped with in the four-hole boiling flask of reflux condensation mode, constant temperature stirring reaction 4h under 80 ℃ of conditions, after reaction finished, room temperature left standstill; Topple over and upper strata ester crude product, excessive Virahol is removed in air distillation, adopts concentration 6% NaOH solution to be neutralized to pH ≈ 7, separatory.The ester crude product is purified through vacuum rotary steam (113 ℃, vacuum tightness 0.097MPa), product yield 97.2%, selectivity 100%.
Lower floor's ionic liquid steams except after the water treatment through simply revolving after separating the ester output crude product, can be used as the catalyzer of next circulation again, thereby obtain reusing.
Embodiment 2
With 200g(2.04mol) maleic anhydride, 490g(8.16mol) Virahol, 53.9g double-core functionalized ion liquid be two-and the two hydrosulfates of (3-methyl isophthalic acid-imidazoles) butylidene add and are equipped with in the four-hole boiling flask of reflux condensation mode, constant temperature stirring reaction 4h under 85 ℃ of conditions, after reaction finished, room temperature left standstill; Topple over and upper strata ester crude product, excessive Virahol is removed in air distillation, adopts concentration 6% NaOH solution to be neutralized to pH ≈ 7, separatory.The ester crude product is purified through vacuum rotary steam (114 ℃, vacuum tightness 0.098MPa), product yield 97.8%, selectivity 100%.
Lower floor's ionic liquid steams except after the water treatment through simply revolving after separating the ester output crude product, can be used as the catalyzer of next circulation again, thereby obtain reusing.
Embodiment 3
With 200g(2.04mol) maleic anhydride, 428g(7.14mol) Virahol, 51.4g double-core functionalized ion liquid be two-and (3-methyl isophthalic acid-imidazoles) methylene-bis dihydrogen phosphate adds and is equipped with in the four-hole boiling flask of reflux condensation mode, constant temperature stirring reaction 6h under 100 ℃ of conditions, after reaction finished, room temperature left standstill; Topple over and upper strata ester crude product, excessive Virahol is removed in air distillation, adopts concentration 6% NaOH solution to be neutralized to pH ≈ 7, separatory.The ester crude product is purified through vacuum rotary steam (113 ℃, vacuum tightness 0.1MPa), product yield 95.5%, selectivity 100%.
Lower floor's ionic liquid steams except after the water treatment through simply revolving after separating the ester output crude product, can be used as the catalyzer of next circulation again, thereby obtain reusing.
Embodiment 4
With 200g(2.04mol) maleic anhydride, 612g(10.2mol) Virahol, 61.2g double-core functionalized ion liquid be two-and the two hydrosulfates of (3-methyl isophthalic acid-imidazoles) butylidene add and are equipped with in the four-hole boiling flask of reflux condensation mode, constant temperature stirring reaction 4h under 80 ℃ of conditions, after reaction finished, room temperature left standstill; Topple over and upper strata ester crude product, excessive Virahol is removed in air distillation, adopts concentration 6% NaOH solution to be neutralized to pH ≈ 7, separatory.The ester crude product is purified through vacuum rotary steam (110 ℃, vacuum tightness 0.097MPa), product yield 97.7%, selectivity 100%.
Lower floor's ionic liquid steams except after the water treatment through simply revolving after separating the ester output crude product, can be used as the catalyzer of next circulation again, thereby obtain reusing.
Embodiment 5
With 200g(2.04mol) maleic anhydride, 489g(8.16mol) Virahol, 58.7g double-core functionalized ion liquid be two-and (3-methyl isophthalic acid-imidazoles) propylidene biconjugate tosylate adds and is equipped with in the four-hole boiling flask of reflux condensation mode, constant temperature stirring reaction 5h under 90 ℃ of conditions, after reaction finished, room temperature left standstill; Topple over and upper strata ester crude product, excessive Virahol is removed in air distillation, adopts concentration 7% NaOH solution to be neutralized to pH ≈ 7, separatory.The ester crude product is purified through vacuum rotary steam (113 ℃, vacuum tightness 0.098MPa), product yield 96.3%, selectivity 100%.
Lower floor's ionic liquid steams except after the water treatment through simply revolving after separating the ester output crude product, can be used as the catalyzer of next circulation again, thereby obtain reusing.
Embodiment 6
With 200g(2.04mol) maleic anhydride, 551g(9.18mol) Virahol, 82.6g double-core functionalized ion liquid be two-and (3-methyl isophthalic acid-imidazoles) butylidene Rhodan salt adds and is equipped with in the four-hole boiling flask of reflux condensation mode, constant temperature stirring reaction 7h under 95 ℃ of conditions, after reaction finished, room temperature left standstill; Topple over and upper strata ester crude product, excessive Virahol is removed in air distillation, adopts concentration 6% NaOH solution to be neutralized to pH ≈ 7, separatory.The ester crude product is purified through vacuum rotary steam (113 ℃, vacuum tightness 0.099MPa), product yield 96.1%, selectivity 100%.
Lower floor's ionic liquid steams except after the water treatment through simply revolving after separating the ester output crude product, can be used as the catalyzer of next circulation again, thereby obtain reusing.
Embodiment 7
With 200g(2.04mol) maleic anhydride, 734g(12.24mol) Virahol, 73.4g double-core functionalized ion liquid be two-and the two a tetrafluoro borates of (3-methyl isophthalic acid-imidazoles) butylidene add and are equipped with in the four-hole boiling flask of reflux condensation mode, constant temperature stirring reaction 6h under 98 ℃ of conditions, after reaction finished, room temperature left standstill; Topple over and upper strata ester crude product, excessive Virahol is removed in air distillation, adopts concentration 6% NaOH solution to be neutralized to pH ≈ 7, separatory.The ester crude product is purified through vacuum rotary steam (113 ℃, vacuum tightness 0.097MPa), product yield 96.0%, selectivity 100%.
Lower floor's ionic liquid steams except after the water treatment through simply revolving after separating the ester output crude product, can be used as the catalyzer of next circulation again, thereby obtain reusing.
Embodiment 8
With 200g(2.04mol) maleic anhydride, 490g(8.16mol) Virahol, 73.4g double-core functionalized ion liquid be two-and the two hydrosulfates of (3-methyl isophthalic acid-imidazoles) pentylidene add and are equipped with in the four-hole boiling flask of reflux condensation mode, constant temperature stirring reaction 4h under 80 ℃ of conditions, after reaction finished, room temperature left standstill; Topple over and upper strata ester crude product, excessive Virahol is removed in air distillation, adopts concentration 6% NaOH solution to be neutralized to pH ≈ 7, separatory.The ester crude product is purified through vacuum rotary steam (113 ℃, vacuum tightness 0.097MPa), product yield 97.9%, selectivity 100%.
Lower floor's ionic liquid steams except after the water treatment through simply revolving after separating the ester output crude product, can be used as the catalyzer of next circulation again, thereby obtain reusing.
Claims (4)
1. the method for a synthetic isopropyl maleate is characterized in that may further comprise the steps:
(1) gets material
Get maleic anhydride and Virahol with amount of substance than (1:3)～(1:8), mix, add double-core class ionic-liquid catalyst, catalyst consumption is 10%～20% of maleic anhydride quality;
(2) reacting by heating
In heating jacket internal heating to 70～110 ℃, stir in the time of heating, condensing reflux 3～8h, reaction is at room temperature left standstill reaction solution after finishing;
(3) catalyst recovery
After reaction finished, reaction solution and catalyzer AUTOMATIC ZONING were toppled over and upper strata ester crude product, and lower floor's ionic liquid removes water treatment through vacuum rotary steam, enters the reaction of next circulation as raw catalyst;
(4) purifying
Isolated ester crude product is removed excessive Virahol, is neutralized to pH=7 through the normal pressure distillation, and separatory, underpressure distillation are collected and made isopropyl maleate.
2. synthetic method according to claim 1 is characterized in that the general structure of said double-core class ionic-liquid catalyst in the step (1) is as follows:
N in the formula=1～6;
Negatively charged ion X
-Be: bisulfate ion HSO
4 -, dihydrogen phosphate H
2PO
4 -, tetrafluoroborate BF
4 -, thiocyanate ion SCN
-, tosic acid root CH
3PhSO
3 -, wherein a kind of.
3. synthetic method according to claim 1, it is characterized in that neutralization in the step (4) refers to that catalyst separating finishes under the room temperature condition after, adopt NaOH solution or the NaHCO of mass concentration 5%～0%
3Solution.
4. synthetic method according to claim 1 is characterized in that the underpressure distillation in the step (4), control pressure 0.05MPa～0.1MPa, 110 ℃～210 ℃ of distillation gas phase temperatures.
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| CN2013102541801A CN103288634A (en) | 2013-06-25 | 2013-06-25 | A method for catalytic synthesis of diisopropyl maleate |
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| CN2013102541801A CN103288634A (en) | 2013-06-25 | 2013-06-25 | A method for catalytic synthesis of diisopropyl maleate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106349473A (en) * | 2015-12-17 | 2017-01-25 | 邯郸学院 | Method for preparing dipolyethylene glycol maleate by using ionic liquid |
| JP2017149702A (en) * | 2016-02-26 | 2017-08-31 | 東京応化工業株式会社 | Method for producing carboxylic acid ester, esterification agent and ring-opening addition catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5648517A (en) * | 1994-07-04 | 1997-07-15 | Bayer Aktiengesellschaft | Process for the preparation of dialkyl maleates |
| CN102757346A (en) * | 2011-04-26 | 2012-10-31 | 中国科学院兰州化学物理研究所 | Preparation method of dimethyl fumarate |
-
2013
- 2013-06-25 CN CN2013102541801A patent/CN103288634A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5648517A (en) * | 1994-07-04 | 1997-07-15 | Bayer Aktiengesellschaft | Process for the preparation of dialkyl maleates |
| CN102757346A (en) * | 2011-04-26 | 2012-10-31 | 中国科学院兰州化学物理研究所 | Preparation method of dimethyl fumarate |
Non-Patent Citations (3)
| Title |
|---|
| H. VALIZADEH ET AL.: "Efficient synthesis of symmetrical phthalate and maleate diesters using phosphinite ionic liquids", 《J IRAN CHEM SOC》 * |
| H. VALIZADEH ET AL.: "Efficient synthesis of symmetrical phthalate and maleate diesters using phosphinite ionic liquids", 《J IRAN CHEM SOC》, vol. 9, 5 January 2012 (2012-01-05), pages 529 - 534 * |
| 赵地顺等: "双核离子液体的合成及其对酯化反应的催化活性", 《有机化学》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106349473A (en) * | 2015-12-17 | 2017-01-25 | 邯郸学院 | Method for preparing dipolyethylene glycol maleate by using ionic liquid |
| JP2017149702A (en) * | 2016-02-26 | 2017-08-31 | 東京応化工業株式会社 | Method for producing carboxylic acid ester, esterification agent and ring-opening addition catalyst |
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Application publication date: 20130911 |