CN106831670B - A kind of preparation method of citraconic anhydride - Google Patents
A kind of preparation method of citraconic anhydride Download PDFInfo
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- CN106831670B CN106831670B CN201710030230.6A CN201710030230A CN106831670B CN 106831670 B CN106831670 B CN 106831670B CN 201710030230 A CN201710030230 A CN 201710030230A CN 106831670 B CN106831670 B CN 106831670B
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- itaconic acid
- citraconic anhydride
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/60—Two oxygen atoms, e.g. succinic anhydride
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to citraconic anhydride production technical fields, particularly disclose a kind of preparation method of citraconic anhydride.The preparation method of the citraconic anhydride, using itaconic acid as raw material, it is characterized by: itaconic acid, alkaline metal catalysts and solvent are placed in reactor, then heating divides water to react under reduced vacuum, vacuum distillation recycling for the first time later, recovery product is added in reactor, the itaconic acid of first time additive amount half and the catalyst with first time additive amount equivalent are added again, reduced vacuum heating carries out point water and reacts, after being evaporated under reduced pressure for the second time, heating collects product to get citraconic anhydride.Present invention reaction is simple, and products therefrom hand rate is high, and purity is high, catalyst source is extensive, and price is low, is swift in response, and recycling solution is reusable, and production cost is low.
Description
(1) technical field
The present invention relates to citraconic anhydride production technical field, in particular to a kind of preparation method of citraconic anhydride.
(2) background technique
Citraconic anhydride, chemical name are 2- methyl butene dianhydrides, similar to maleic lemon at important intermediate.Citraconic acid
Acid anhydride is alternatively arranged as the additive of unsaturated-resin, and the polyimide derivative of citraconic anhydride synthesis can be used as composite material or rubber
Additive, citraconic anhydride, which synthesizes double alcohol derivatives via hydrogenation, can be used as the monomer of polyesters.
The method of production citraconic anhydride is mainly cracking process, chemical reagent evaporation, azeotropic dehydration and heat dehydration at present
Method etc..Cracking process synthesize citraconic anhydride technique it is comparatively mature, but the method equipment investment is larger, at high cost, yield compared with
It is low；Chemical reagent evaporation synthesis citraconic anhydride product cost is high, by-product is more, three wastes discharge amount is big.
(3) summary of the invention
The citraconic anhydride that in order to compensate for the shortcomings of the prior art, the present invention provides a kind of conditions is controllable, product quality is high
Preparation method.
The present invention is achieved through the following technical solutions:
A kind of preparation method of citraconic anhydride, using itaconic acid as raw material, it is characterised in that: urge itaconic acid, alkalinous metal
Agent and solvent are placed in reactor, then heating divides water to react under reduced vacuum, and vacuum distillation recycling for the first time, will recycle later
Product is added in reactor, and the itaconic acid of first time additive amount half and the catalysis with first time additive amount equivalent are added again
Agent, reduced vacuum heating carries out point water and reacts, and after being evaporated under reduced pressure for the second time, heating collects product to get citraconic anhydride.
Condition of negative pressure of the present invention, which is lauched, can obtain product citraconic anhydride through catalyst with solvent azeotropic, itaconic acid.This is anti-
Answer that condition is controllable, product quality is high, by-product is few, therefore the application under condition of negative pressure using using alkalinous metal to urge as catalyst
Change itaconic acid and synthesizes citraconic anhydride.
More excellent technical solution of the invention are as follows:
The mass ratio of the itaconic acid and catalyst is 50-300:1, preferably 50-100:1；The quality of itaconic acid and solvent
Than for 1:1-15, preferably 1:1-8.
Vacuum degree in the reactor is 0.1MPa, and reaction temperature is 100-180 DEG C, preferably 100-150 DEG C, when reaction
Between be 2.0-8.0h, preferably 2.0-5.0h.
The catalyst is one of potassium, sodium, magnesium, calcium, barium, lithium.
The solvent is one of dimethylbenzene, o-dichlorohenzene, naphthane.
The first time vacuum distillation condition is vacuum degree 500Pa, and 100 DEG C of temperature, second of vacuum distillation condition is true
Reciprocal of duty cycle 500Pa, 75 DEG C of temperature, then product is collected at 100 DEG C.
Products therefrom is colourless liquid, and for yield up to 88% or more, purity can be up to 95% or more.
Present invention reaction is simple, and products therefrom hand rate is high, and purity is high, catalyst source is extensive, and price is low, is swift in response,
Recycling solution is reusable, and production cost is low.
(4) specific embodiment
Method of the invention is described further below with reference to case study on implementation, is not limitation of the invention.
Embodiment 1:
0.1g calcium, 20g itaconic acid and 20g dimethylbenzene are added to the reaction for being furnished with thermometer, blender and oil water separator
In device, it is heated to 120 DEG C in oil bath pan, divides water to react 1.5h in the case where reduced vacuum degree is 0.1MPa.By reaction product true
Reciprocal of duty cycle 500Pa, recycling is evaporated under reduced pressure at 100 DEG C of temperature.Reactor is added in recovery product, 10g itaconic acid and 0.1g calcium is added
It is heated to 130 DEG C in oil bath pan, divides water to react 0.5h in the case where reduced vacuum degree is 0.1MPa.Reaction product is evaporated under reduced pressure,
At vacuum degree 500Pa, 75 DEG C of temperature, the slightly thin out Huang of the color of efflux has steamed solvent, recyclable to continue to use.100
Product is collected at DEG C, gained is up to colorless liquid product citraconic anhydride, yield 99.3%, purity 99.8%.
Embodiment 2:
0.1g barium, 20g itaconic acid and 20g dimethylbenzene are added to the reaction for being furnished with thermometer, blender and oil water separator
In device, it is heated to 120 DEG C in oil bath pan, divides water to react 1.5h in the case where reduced vacuum degree is 0.1MPa.By reaction product true
Reciprocal of duty cycle 500Pa, recycling is evaporated under reduced pressure at 100 DEG C of temperature.Reactor is added in recovery product, 10g itaconic acid and 0.1g barium is added
It is heated to 130 DEG C in oil bath pan, divides water to react 0.5h in the case where reduced vacuum degree is 0.1MPa.Reaction product is evaporated under reduced pressure,
At vacuum degree 500Pa, 75 DEG C of temperature, the slightly thin out Huang of the color of efflux has steamed solvent, recyclable to continue to use.100
Product is collected at DEG C to get colorless liquid product citraconic anhydride, yield 97.2%, purity 99.4%.
Embodiment 3:
0.1g potassium, 20g itaconic acid and 20g dimethylbenzene are added to the reaction for being furnished with thermometer, blender and oil water separator
In device, it is heated to 120 DEG C in oil bath pan, divides water to react 1.5h in the case where reduced vacuum degree is 0.1MPa.By reaction product true
Reciprocal of duty cycle 500Pa, recycling is evaporated under reduced pressure at 100 DEG C of temperature.Reactor is added in recovery product, 10g itaconic acid and 0.1g potassium is added
It is heated to 130 DEG C in oil bath pan, divides water to react 0.5h in the case where reduced vacuum degree is 0.1MPa.Reaction product is evaporated under reduced pressure,
At vacuum degree 500Pa, 75 DEG C of temperature, the slightly thin out Huang of the color of efflux has steamed solvent, recyclable to continue to use.100
Product is collected at DEG C to get colorless liquid product citraconic anhydride, yield 97.4%, purity 98.7%.
Embodiment 4:
0.1g sodium, 20g itaconic acid and 20g dimethylbenzene are added to the reaction for being furnished with thermometer, blender and oil water separator
In device, it is heated to 120 DEG C in oil bath pan, divides water to react 1.5h in the case where reduced vacuum degree is 0.1MPa.By reaction product true
Reciprocal of duty cycle 500Pa, recycling is evaporated under reduced pressure at 100 DEG C of temperature.Reactor is added in recovery product, 10g itaconic acid and 0.1g sodium is added
Calcium is heated to 130 DEG C in oil bath pan, divides water to react 0.5h in the case where reduced vacuum degree is 0.1MPa.Reaction product is depressurized and is steamed
It evaporates, at vacuum degree 500Pa, 75 DEG C of temperature, the slightly thin out Huang of the color of efflux has steamed solvent, recyclable to continue to use.
Product is collected at 100 DEG C to get colorless liquid product citraconic anhydride, yield 93.8%, purity 96.2%.
Embodiment 5:
0.1g magnesium, 20g itaconic acid and 20g dimethylbenzene are added to the reaction for being furnished with thermometer, blender and oil water separator
In device, it is heated to 120 DEG C in oil bath pan, divides water to react 1.5h in the case where reduced vacuum degree is 0.1MPa.By reaction product true
Reciprocal of duty cycle 500Pa, recycling is evaporated under reduced pressure at 100 DEG C of temperature.Reactor is added in recovery product, 10g itaconic acid and 0.1g magnesium is added
Calcium is heated to 130 DEG C in oil bath pan, divides water to react 0.5h in the case where reduced vacuum degree is 0.1MPa.Reaction product is depressurized and is steamed
It evaporates, at vacuum degree 500Pa, 75 DEG C of temperature, the slightly thin out Huang of the color of efflux has steamed solvent, recyclable to continue to use.
Product is collected at 100 DEG C to get colorless liquid product citraconic anhydride, yield 85.7%, purity 89.1%.
Embodiment 6:
0.1g lithium, 20g itaconic acid and 20g dimethylbenzene are added to the reaction for being furnished with thermometer, blender and oil water separator
In device, it is heated to 120 DEG C in oil bath pan, divides water to react 1.5h in the case where reduced vacuum degree is 0.1MPa.By reaction product true
Reciprocal of duty cycle 500Pa, recycling is evaporated under reduced pressure at 100 DEG C of temperature.Reactor is added in recovery product, 10g itaconic acid and 0.1g lithium is added
Calcium is heated to 130 DEG C in oil bath pan, divides water to react 0.5h in the case where reduced vacuum degree is 0.1MPa.Reaction product is depressurized and is steamed
It evaporates, at vacuum degree 500Pa, 75 DEG C of temperature, the slightly thin out Huang of the color of efflux has steamed solvent, recyclable to continue to use.
Product is collected at 100 DEG C to get colorless liquid product citraconic anhydride, yield 78.6%, purity 82.8%.
Embodiment 7:
The solvent xylene that above-mentioned experiment distills out is collected respectively, in 0.1g calcium, 40g itaconic acid and 80g solvent, in temperature
130 DEG C, divide water reaction 4h to stop experiment under reduced vacuum degree 0.1MPa, the results showed that solvent xylene repeats test 4
Secondary, citraconic anhydride yield is all larger than 88%, and purity is all larger than 95.2%.
Claims (1)
1. a kind of preparation method of citraconic anhydride, using itaconic acid as raw material, it is characterised in that: itaconic acid, alkalinous metal to be catalyzed
Agent and solvent are placed in reactor, then heating divides water to react under reduced vacuum, and vacuum distillation recycling for the first time, recycling is produced later
Object is added in reactor, and the itaconic acid of first time additive amount half and the catalyst with first time additive amount equivalent are added again,
Reduced vacuum heating carries out point water and reacts, and after being evaporated under reduced pressure for the second time, heating collects product to get citraconic anhydride；
The catalyst is calcium；
The solvent is dimethylbenzene；
The first time vacuum distillation condition is vacuum degree 500Pa, and 100 DEG C of temperature, it is vacuum degree that second, which is evaporated under reduced pressure condition,
500Pa, 75 DEG C of temperature, then product is collected at 100 DEG C；
The mass ratio of the itaconic acid and catalyst is 50-100:1, and the mass ratio of itaconic acid and solvent is 1:1-8；
Reaction temperature in the reactor is 100-150 DEG C, reaction time 2.0-5.0h.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995006026A1 (en) * | 1993-08-26 | 1995-03-02 | Akzo Nobel N.V. | Dehydration of itaconic acid |
| CN102464638A (en) * | 2010-11-19 | 2012-05-23 | 财团法人工业技术研究院 | Method for preparing citraconic anhydride and method for isomerizing/dehydrating itaconic acid |
| US8273903B2 (en) * | 2009-12-30 | 2012-09-25 | Industrial Technology Research Institute | Method for preparing the citraconic anhydride and method for isomerizing/dehydrating itaconic acid |
| CN105037301A (en) * | 2015-06-17 | 2015-11-11 | 青岛科技大学 | Preparation method for citraconic anhydride |
-
2017
- 2017-01-17 CN CN201710030230.6A patent/CN106831670B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995006026A1 (en) * | 1993-08-26 | 1995-03-02 | Akzo Nobel N.V. | Dehydration of itaconic acid |
| US8273903B2 (en) * | 2009-12-30 | 2012-09-25 | Industrial Technology Research Institute | Method for preparing the citraconic anhydride and method for isomerizing/dehydrating itaconic acid |
| CN102464638A (en) * | 2010-11-19 | 2012-05-23 | 财团法人工业技术研究院 | Method for preparing citraconic anhydride and method for isomerizing/dehydrating itaconic acid |
| CN105037301A (en) * | 2015-06-17 | 2015-11-11 | 青岛科技大学 | Preparation method for citraconic anhydride |
Non-Patent Citations (4)
| Title |
|---|
| 二元酸酐的合成研究;宋怡鹏;《青岛科技大学硕士学位论文》;20160831;第19-29页 |
| 共沸脱水法制柠康酸酐的研究进展;谢辉辉，等;《广州化工》;20160531;第44卷(第9期);第34-35、85页 |
| 柠康酸酐的合成研究;宋怡鹏，等;《化工科技》;20151231;第23卷(第6期);第59-61页 |
| 柠康酸酐的最佳合成工艺研究;肖英，等;《广州化工》;20150930;第43卷(第17期);第89-91页 |
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