CN105130814B - A kind of method that pyrovinic acid catalysis prepares diethyl sebacate - Google Patents
A kind of method that pyrovinic acid catalysis prepares diethyl sebacate Download PDFInfo
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- CN105130814B CN105130814B CN201510462151.3A CN201510462151A CN105130814B CN 105130814 B CN105130814 B CN 105130814B CN 201510462151 A CN201510462151 A CN 201510462151A CN 105130814 B CN105130814 B CN 105130814B
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- acid
- diethyl sebacate
- pyrovinic
- ethyl alcohol
- absolute ethyl
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
Abstract
The invention discloses the method that a kind of method that pyrovinic acid catalysis prepares diethyl sebacate, category catalyze and synthesize diethyl sebacate.Be raw material with decanedioic acid and absolute ethyl alcohol, catalyst made with pyrovinic acid, hexamethylene makees water entrainer, after reaction terminates, product is neutralized, washing, distillation, purifying, obtain diethyl sebacate.Using hexamethylene as water entrainer, reaction time is short, pyrovinic acid is degradable, product needs not move through vacuum distillation and can obtain the good product of outward appearance, and soda acid consumption is few, the advantages of pollution-free, reaction 1h product yields are more than 94%, low production cost, is a kind of method of efficient, environment-friendly synthesis of sebacic acid diethylester, can realize large-scale industrial production.
Description
Technical field
The present invention relates to the preparation method of diethyl sebacate, particularly a kind of pyrovinic acid catalysis prepares decanedioic acid diethyl
The method of ester.
Background technology
Diethyl sebacate also known as sebum acetoacetic ester, sebum diethyl phthalate is colourless to flaxen liquid, there is grape
Wine, fruit, the fragrance of muskmelon, can be miscible with the organic matter such as ethanol, ether, oils, is mainly used in preparing the edible perfume (or spice) such as grape, pears
Essence and daily chemical essence, can also be commonly used in the middle of plasticizer or organic synthesis as organic solvent, in light, electrochemical sensor
Body.Increasingly perfect with people's environmental consciousness and environmental regulation, Development and Production diethyl sebacate has fabulous development
Prospect.
Diethyl sebacate is typically with decanedioic acid and absolute ethyl alcohol as raw material, in the presence of catalyst, certain
Synthesize under process conditions.Domestic useful p-methyl benzenesulfonic acid, ion exchange resin, solid acid, niter cake, chlorination at present
The catalysis such as iron, heteropoly acid prepare the report of diethyl sebacate, but it is long to there is the reaction time in various degree, and ethanol consumption is big and one
Secondary addition, temperature is raised too soon, and ethanol has neither part nor lot in reaction and just taken out of with by solvent, and catalyst preparation is complicated, high cost, and product is needed
Want vacuum distillation, consume mass energy, dangerous, industrializing implementation difficulty is big, the shortcomings of the three wastes are not effectively addressed.
The content of the invention
It is existing to overcome it is an object of the invention to provide a kind of method that pyrovinic acid catalysis prepares diethyl sebacate
The deficiency of preparation method, takes following several ways and obtains good effect：Absolute ethyl alcohol is added at twice, shortens esterification
Reaction time；The pyrovinic acid separated after reaction has two kinds of purposes：First, can be to reclaim for esterification next time,
In the industrial production, it is capable of achieving to recycle；2nd, it is to extract the decanedioic acid for not participating in reaction completely for neutralizing alkali lye, obtains
Wet decanedioic acid；The complexity of operation is reduced, energy resource consumption is reduced, environmental pollution is reduced significantly, and reduction is produced into
This；By the way of activated carbon purification, reduce because of vacuum distillation（Need high temperature, high pressure）Caused by high energy consumption, yield is low,
The presence of unsafe factor, easy to operate, activated carbon can be reused, and energy consumption is low, low cost；Pyrovinic acid is a kind of catalysis
The active strong, homogeneous catalyst of small toxicity high, acid, it is small to equipment corrosion, biodegradable, environmentally friendly, uses
Amount is small, reusable multiple, low production cost.
Technical scheme is as follows：It is raw material with decanedioic acid and absolute ethyl alcohol, catalyst, hexamethylene is made with pyrovinic acid
Alkane does water entrainer, and after reaction terminates, product is neutralized, washing, distillation, and purifying obtains diethyl sebacate.
Catalyst is made with pyrovinic acid, the present invention is comprised the following steps：
1）Hexamethylene, nothing are added in the three neck round bottom flask of electric blender, thermometer, condenser pipe, water knockout drum is had
Water-ethanol I and pyrovinic acid, stirring is lower to add decanedioic acid, rotating speed to control in 450~500r/min.
2）Esterification：It is heated to reflux to temperature to 84 DEG C, is cooled to 50 DEG C, add absolute ethyl alcohol II, continuation is heated back
84 DEG C are flow to, the water for producing reaction is separated from water knockout drum, treats that three neck round bottom flask is cooled to 50 DEG C, carries out next step；At this
In step, the method for employing secondary addition absolute ethyl alcohol, the purpose of do so is conducive to improving the conversion ratio of decanedioic acid, increases
Plus the yield of purpose product diethyl sebacate.
3）Stand, point sub-cloud pyrovinic acid obtains feed liquid I.
4）To the sodium hydrate aqueous solution that mass percent is 3~5% is added in feed liquid I, stir and neutralize and be unreacted
Decanedioic acid, removes buck layer, obtains feed liquid II；Buck layer step 3）In pyrovinic acid be neutralized to pH=3~4, be filtrated to get
Decanedioic acid；Without drying, can directly bottle, the esterification experiment of diethyl sebacate is prepared for laboratory next time；In industry
In production, the unreacted decanedioic acid that can also obtain the step is added directly into reactor, realizes the circulation of production technology, drop
Low cost of material.
5）Feed liquid II is washed with water to neutrality, and is separated；Separation method is different with the density of water phase according to organic phase,
Separated using separatory funnel.
6）By step 5）The organic phase isolated is put into one and new has electric blender, thermometer, three mouthfuls of condenser pipe
In round-bottomed flask, air-distillation is carried out below 140 DEG C and removes hexamethylene and water, obtain liquid diethyl sebacate.
7）By step 6）The liquid diethyl sebacate for obtaining is cooled to 90 DEG C, adds activated carbon, stirring, at 80~90 DEG C
Insulation 10min, heat filter, obtains diethyl sebacate.
Described absolute ethyl alcohol I and the weight ratio of absolute ethyl alcohol II are 4：1.
Described decanedioic acid and absolute ethyl alcohol mol ratio are 1:6.
The consumption of described catalyst pyrovinic acid is the 3~7% of decanedioic acid weight.
The consumption of hexamethylene is 0.7~1.2 times of decanedioic acid weight.
The consumption of described activated carbon is the 0.5~1% of decanedioic acid weight.
Described decanedioic acid, absolute ethyl alcohol, pyrovinic acid, hexamethylene are 99.5% analysis net product；Activated carbon is medicinal.
The equation of the reaction is as follows：
The beneficial effects of the invention are as follows：
Take following several ways：First, absolute ethyl alcohol is added at twice, shortens reaction time of esterification；2nd, divide after reacting
Separating out the pyrovinic acid for coming has two kinds of purposes：1st, can be to reclaim for esterification next time, in the industrial production, be capable of achieving
Recycle；2nd, it is to extract the decanedioic acid for not participating in reaction completely for neutralizing alkali lye, obtains wet decanedioic acid；Reduce operation
Complexity, reduce energy resource consumption, environmental pollution is reduced significantly, reduce production cost；The side purified using activated carbon
Formula, reduces because of vacuum distillation（Need high temperature, high pressure）Caused by high energy consumption, yield is low, the presence of unsafe factor, operation
Simplicity, energy consumption is low, low cost；Pyrovinic acid is that a kind of catalysis activity is high, the acid strong, homogeneous catalyst of small toxicity, and its pair sets
Standby corrosivity is small, and biodegradable, usage amount is small, reusable multiple, reduces production cost.Using hexamethylene as band water
Agent, reaction condition is gentle, and the reaction time is short, and convenient post-treatment, the advantages of unreacted decanedioic acid is recycled recycling, produces
Product yield can realize large-scale industrial production more than 94%.
Brief description of the drawings
Fig. 1 is present invention process flow chart.
Specific embodiment
With reference to case study on implementation the scheme and effect that the present invention is furture elucidated.
Embodiment 1
The decanedioic acid of selection, absolute ethyl alcohol, pyrovinic acid, hexamethylene are 99.5% analysis net product；Activated carbon is medicinal；
Added in the three neck round bottom flask of electric blender, thermometer, condenser pipe, water knockout drum is had hexamethylene 50mL,
The 44.22g of absolute ethyl alcohol I and pyrovinic acid 2g, stirring is lower to add decanedioic acid 40.45g, rotating speed to control in 450r/min, heat back
Stream, the water for producing reaction is separated from water knockout drum, and heating is stopped to 84 DEG C, is cooled to 50 DEG C, and the 11.06g of absolute ethyl alcohol II continues
It is heated to reflux stopping heating to 84 DEG C, always flow back 1h, is cooled to 50 DEG C, stands a point demethyl sulfonic acid, obtains feed liquid I, feed liquid I adds
Enter the sodium hydrate aqueous solution stirring that mass fraction is 5% and neutralize unreacted decanedioic acid, remove buck layer, obtain feed liquid II；
The pyrovinic acid that the experiment of buck layer is separated is neutralized to pH=3.0, is filtrated to get decanedioic acid；During feed liquid II is washed with water to
Property, the organic phase isolated first carries out air-distillation, is cooled to 90 DEG C or so, addition activated carbon 0.25g, stirring, on 87 DEG C of left sides
Right insulation 10min, heat filter, obtains diethyl sebacate, is computed obtaining：Yield is 94.64%.
Embodiment 2
The decanedioic acid of selection, absolute ethyl alcohol, pyrovinic acid, hexamethylene are 99.5% analysis net product；Activated carbon is medicinal；
Hexamethylene 50mL, absolute ethyl alcohol I are added in the flask of electric blender, thermometer, condenser pipe, water knockout drum is had
44.22g and fresh pyrovinic acid 0.3g and recovery pyrovinic acid 1.7g, stirring is lower to add decanedioic acid 40.45g, rotating speed control
In 450r/min, it is heated to reflux, the water for producing reaction is separated from water knockout drum, heating is stopped to 84 DEG C, is cooled to 50 DEG C, it is anhydrous
The 11.06g of ethanol II, continues to be heated to reflux to 84 DEG C to stop heating, and always flow back 1h, is cooled to 50 DEG C, stands a point demethyl sulfonic acid,
Feed liquid I is obtained, feed liquid I adds the sodium hydrate aqueous solution stirring that mass fraction is 5% to neutralize unreacted decanedioic acid, except lixiviating
Water layer, obtains feed liquid II；The pyrovinic acid that the experiment of buck layer is separated is neutralized to pH=3.5, is filtrated to get decanedioic acid；Material
Liquid II is washed with water to neutrality, and the organic phase isolated first carries out air-distillation, is cooled to 90 DEG C, adds activated carbon 0.25g, stirs
Mix, 10min is incubated at 85 DEG C or so, heat filter obtains diethyl sebacate, is computed obtaining：Yield is 94.55%.
Embodiment 3
The decanedioic acid of selection, absolute ethyl alcohol, pyrovinic acid, hexamethylene are 99.5% analysis net product；Activated carbon is medicinal；
Hexamethylene 50mL, absolute ethyl alcohol are added in the flask of electric blender, thermometer, condenser pipe, water knockout drum is had
44.22g and pyrovinic acid 2g, stirring is lower to add decanedioic acid 39g, reclaims decanedioic acid 3.0g（Weight in wet base）, rotating speed control is in 450r/
Min, is heated to reflux, and the water for producing reaction is separated from water knockout drum, and heating is stopped to 84 DEG C, is cooled to 50 DEG C, absolute ethyl alcohol
11.06g, continues to be heated to reflux to 84 DEG C to stop heating, and always flow back 1h, is cooled to 50 DEG C, stands a point demethyl sulfonic acid, is expected
Liquid I, feed liquid I adds the sodium hydrate aqueous solution stirring that mass fraction is 5% to neutralize unreacted decanedioic acid, removes buck layer,
Obtain feed liquid II；The pyrovinic acid that the experiment of buck layer is separated is neutralized to pH=4.0, is filtrated to get decanedioic acid；Feed liquid II is used
Water washing to neutrality, the organic phase isolated first carries out air-distillation, is cooled to 90 DEG C, adds activated carbon 0.25g, stirs,
85 DEG C or so insulation 10min, heat filter obtains diethyl sebacate, is computed obtaining：Yield 94.48%.
Embodiment 4
The decanedioic acid of selection, absolute ethyl alcohol, pyrovinic acid, hexamethylene are 99.5% analysis net product；Activated carbon is medicinal；
Added in the flask of electric blender, thermometer, condenser pipe, water knockout drum is had and reclaim hexamethylene 50mL, anhydrous
Ethanol 44.22g and pyrovinic acid 2g, stirring is lower to add decanedioic acid 39g, reclaims decanedioic acid 3.0g（Weight in wet base）, rotating speed control exist
450r/min, is heated to reflux, and the water for producing reaction is separated from water knockout drum, and heating is stopped to 84 DEG C, is cooled to 50 DEG C, anhydrous second
Alcohol 11.06g, continues to be heated to reflux to 84 DEG C to stop heating, and always flow back 1h, is cooled to 50 DEG C, stands a point demethyl sulfonic acid, expects
To feed liquid I, the addition mass fraction of feed liquid I is the 5% sodium hydrate aqueous solution stirring unreacted decanedioic acid of neutralization, removes buck
Layer, obtains feed liquid II；The pyrovinic acid that the experiment of buck layer is separated is neutralized to pH=3.7, is filtrated to get decanedioic acid；Feed liquid
II is washed with water to neutrality, and the organic phase isolated first carries out air-distillation, is cooled to 90 DEG C, adds activated carbon 0.25g, stirs
Mix, 10min is incubated at 83 DEG C or so, heat filter obtains diethyl sebacate, is computed obtaining：Yield is 94.52%.
Claims (1)
1. a kind of method that pyrovinic acid catalysis prepares diethyl sebacate, it is characterised in that：Catalyst is made with pyrovinic acid, is pressed
It is prepared by following steps：
1）Hexamethylene, anhydrous second are added in the three neck round bottom flask of electric blender, thermometer, condenser pipe, water knockout drum is had
Alcohol I and pyrovinic acid, stirring is lower to add decanedioic acid, rotating speed to control in 450~500r/min；
2）Esterification：Be heated to reflux to temperature to 84 DEG C, be cooled to 50 DEG C, add absolute ethyl alcohol II, continue to be heated to reflux to
84 DEG C, the water for producing reaction is separated from water knockout drum, treats that three neck round bottom flask is cooled to 50 DEG C, carries out next step；
3）Stand, point sub-cloud pyrovinic acid obtains feed liquid I；
4）To the sodium hydrate aqueous solution that mass percent is 3~5% is added in feed liquid I, the unreacted last of the ten Heavenly stems two is stirred and neutralized
Acid, removes buck layer, obtains feed liquid II；Buck layer step 3）In pyrovinic acid be neutralized to pH=3~4, be filtrated to get the last of the ten Heavenly stems two
Acid；
5）Feed liquid II is washed with water to neutrality, and is separated；
6）By step 5）The organic phase isolated be put into it is another have an electric blender, thermometer, three mouthfuls of round bottoms of condenser pipe burn
In bottle, air-distillation is carried out below 140 DEG C and removes hexamethylene and water, obtain liquid diethyl sebacate；
7）By step 6）The liquid diethyl sebacate for obtaining is cooled to 90 DEG C, adds activated carbon, stirring, in 80~90 DEG C of insulations
10min, heat filter, obtains filtrate, i.e.,：Diethyl sebacate；
Described absolute ethyl alcohol I and the weight ratio of absolute ethyl alcohol II are 4：1；
Described decanedioic acid and absolute ethyl alcohol mol ratio are 1:6；
The consumption of described catalyst pyrovinic acid is the 3~7% of decanedioic acid weight；
The consumption of hexamethylene is 0.7~1.2 times of decanedioic acid weight；
The consumption of described activated carbon is the 0.5~1% of decanedioic acid weight；
Described decanedioic acid, absolute ethyl alcohol, pyrovinic acid, hexamethylene are 99.5% analysis net product；Activated carbon is medicinal.
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Inventor after: Li Gan Inventor after: Gao Kun Inventor after: Wang Detang Inventor after: Liu Ying Inventor after: Tian Hua Inventor after: Xia Xianwei Inventor after: Wang Jinxing Inventor before: Li Gan Inventor before: Wang Detang Inventor before: Liu Ying Inventor before: Tian Hua Inventor before: Xia Xianwei Inventor before: Wang Jinxing |
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Effective date of registration: 20171114 Address after: 221000 Qingshan Industrial Park, Qingshan Town, Jiawang District, Xuzhou, Jiangsu Patentee after: Xuzhou Currency Magnetoelectricity Co., Ltd. Address before: 221000 Jiangsu Province, Gulou District of Xuzhou City Xiang Wang Road No. 1 Patentee before: Xuzhou Institute of Industry Technology |