CN110156741A - The synthetic method of butylene - Google Patents
The synthetic method of butylene Download PDFInfo
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- CN110156741A CN110156741A CN201810151204.3A CN201810151204A CN110156741A CN 110156741 A CN110156741 A CN 110156741A CN 201810151204 A CN201810151204 A CN 201810151204A CN 110156741 A CN110156741 A CN 110156741A
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- Prior art keywords
- synthetic method
- carbonic acid
- butene esters
- butanediol
- reaction
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings 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
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of synthetic method of butylene, this method is with 1,2- butanediol for raw material, and using carbonic ester as carbonylation agent, under the effect of the catalyst, reaction generates carbonic acid 1,2- butene esters.The useless alcohol of the by-product in coal-ethylene glycol technique is utilized in butylene synthetic method of the invention, and cost is relatively low, and reaction efficiency is high, mild condition.
Description
Technical field
The invention belongs to cyclic carbonate technical fields, and in particular to a kind of synthetic method of butylene.
Background technique
Ethylene glycol is most simple and most important aliphatic dihydroxy alcohol, is that a kind of important large basic organic chemical industry is former
Material, can be used for producing a variety of chemical products, as polyester fiber, antifreezing agent, unsaturated polyester resin, lubricant, plasticizer, it is non-from
Sub- surfactant, explosive, coating and ink etc., wide range of applications.In China, ethylene glycol is mainly as polyester and prevents
Freeze the raw material of liquid.According to statistics, global ethylene glycol aggregate consumption is 22,000,000 tons at present, increases production capacity rapid growth newly.
Currently, the prevailing technology of coal-ethylene glycol is oxalate synthetic method and passes through preparing glycol by hydrogenating oxalate.Grass
Acid esters synthetic method reaction principle is NO and O2Generate N2O3, recycle methanol and N2O3Reaction generates methyl nitrite, is catalyzed in Pd
Agent acts on lower CO and nitrous acid ester oxidative coupling obtains oxalate diester, and oxalate diester produces ethylene glycol through catalytic hydrogenation again.
During preparing glycol by hydrogenating oxalate, it is carried out in two steps.It is generated firstly, dimethyl oxalate is reacted with hydrogen
Methyl glycollate, then methyl glycollate adds hydrogen to obtain ethylene glycol, but when transition adds hydrogen, has a large amount of 1,2- butanediols etc.
The generation of by-product.If reaction gained 1,2- butanediol can use, then can be effectively treated in ethylene glycol synthesis process
By-product.
Carbonic acid 1,2- butene esters are highly important chemical products and chemical intermediate, it has good biological degradability
And dissolubility, it may be used as electrolyte and metal extraction agent of high-energy-density battery and capacitor etc., application prospect is extensive.Mesh
Before, the production of carbonic acid 1,2- butene esters mainly uses epoxy butane and carbon dioxide for the catalysis synthesizing technology of raw material, this method
The shortcomings that be using raw material be epoxy butane, higher cost.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of synthetic method of butylene, so as to
At least one of solve the above problems.
The present invention is achieved through the following technical solutions:
The present invention provides a kind of synthetic method of butylene, the described method comprises the following steps:
Reaction vessel is added in 1,2- butanediol, carbonylating agent and catalyst, and heating generates carbonic acid 1, and 2- butene esters, reaction equation is such as
Under:
Wherein, R includes methyl, ethyl.
Preferably, the carbonylating agent is dimethyl carbonate or diethyl carbonate.
Preferably, the molar ratio of 1,2- butanediol and the carbonylating agent is 1: 1~30.
Preferably, reaction temperature is 20~240 DEG C.
Preferably, the catalyst be calcium oxide, zinc oxide, barium monoxide, magnesia, aluminium oxide, sodium metasilicate, alumina silicate,
One of ferrosilite, calcium silicates, magnesium silicate, potassium silicate, sodium metaaluminate or hydrotalcite.
Preferably, the amount of the catalyst is the 0.1~20% of 1,2- butanediol quality.
Preferably, the reaction time is 0.1~20h.
It can be seen from the above technical proposal that the synthetic method of butylene of the invention has the advantages that
(1) raw material is 1,2- butanediol, the useless alcohol of the by-product being utilized in coal-ethylene glycol technique；
(2) raw material sources are extensive, and cost is relatively low；
(3) reaction efficiency is high, mild condition.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, to this hair
It is bright to be described in further detail.
The present invention provides a kind of synthetic method of butylene, this method with 1,2- butanediol for raw material, with carbonic acid
Ester is as carbonylation agent, and under the effect of the catalyst, reaction generates carbonic acid 1,2- butene esters.The conjunction of butylene of the present invention
The useless alcohol of the by-product in coal-ethylene glycol technique is utilized at method, cost is relatively low, and reaction efficiency is high, mild condition.
Specifically, the present invention provides a kind of synthetic method of butylene, the described method comprises the following steps: 1,2- fourth
Reaction vessel is added in glycol, carbonylating agent and catalyst, heats and generates carbonic acid 1,2- butene esters, and reaction equation is as follows:
Wherein, R includes methyl, ethyl.
Further, the carbonylating agent is dimethyl carbonate or diethyl carbonate.
Further, the molar ratio of 1,2- butanediol and the carbonylating agent is 1:1~30.
Further, reaction temperature is 20~240 DEG C.
Further, the catalyst is calcium oxide, zinc oxide, barium monoxide, magnesia, aluminium oxide, sodium metasilicate, silicic acid
One of aluminium, ferrosilite, calcium silicates, magnesium silicate, potassium silicate, sodium metaaluminate or hydrotalcite.
Further, the amount of the catalyst is the 0.1~20% of 1,2- butanediol quality.
Further, the reaction time is 0.1~20h.
It is further detailed to a kind of synthetic method work of butylene provided by the invention below in conjunction with specific embodiment
It describes in detail bright.
Embodiment 1
Addition 22.5g dimethyl carbonate in a kettle, 4.4g 1,2- butanediol, 0.23g calcium silicates, at 90 DEG C, instead
After answering 7 hours, stops heating stirring, be cooled to room temperature.Appropriate reaction solution is taken, internal standard compound is added, prepares standard liquid through gas phase color
Spectrum analysis.
Embodiment 2
Addition 22.8g dimethyl carbonate in a kettle, 4.5g 1,2- butanediol, 0.25g sodium metasilicate, at 75 DEG C, instead
After answering 7 hours, stops heating stirring, be cooled to room temperature.Appropriate reaction solution is taken, internal standard compound is added, prepares standard liquid through gas phase color
Spectrum analysis.
Embodiment 3
Addition 22.8g dimethyl carbonate in a kettle, 4.5g 1,2- butanediol, 0.45g calcium oxide, at 75 DEG C, instead
After answering 5 hours, stops heating stirring, be cooled to room temperature.Appropriate reaction solution is taken, internal standard compound is added, prepares standard liquid through gas phase color
Spectrum analysis.
Embodiment 4
Addition 22.4g diethyl carbonate in a kettle, 2.3g 1,2- butanediol, 0.22g sodium metasilicate, at 105 DEG C,
After reacting 5 hours, stops heating stirring, be cooled to room temperature.Appropriate reaction solution is taken, internal standard compound is added, prepares standard liquid through gas phase
Chromatography.
Embodiment 5
Addition 22.4g dimethyl carbonate in a kettle, 4.5g 1,2- butanediol, 0.22g aluminium oxide, at 90 DEG C, instead
After answering 5 hours, stops heating stirring, be cooled to room temperature.Appropriate reaction solution is taken, internal standard compound is added, prepares standard liquid through gas phase color
Spectrum analysis.
Embodiment 6
Addition 22.5g dimethyl carbonate in a kettle, 4.5g 1,2- butanediol, 0.44g potassium silicate, at 75 DEG C, instead
After answering 7 hours, stops heating stirring, be cooled to room temperature.Appropriate reaction solution is taken, internal standard compound is added, prepares standard liquid through gas phase color
Spectrum analysis.
Embodiment 7
Addition 22.4g dimethyl carbonate in a kettle, 4.5g 1,2- butanediol, 0.46g aluminium oxide, at 90 DEG C, instead
After answering 7 hours, stops heating stirring, be cooled to room temperature.Appropriate reaction solution is taken, internal standard compound is added, prepares standard liquid through gas phase color
Spectrum analysis.
Embodiment 8
Addition 22.5g diethyl carbonate in a kettle, 4.5g 1,2- butanediol, 0.45g magnesium silicate, at 75 DEG C, instead
After answering 3 hours, stops heating stirring, be cooled to room temperature.Appropriate reaction solution is taken, internal standard compound is added, prepares standard liquid through gas phase color
Spectrum analysis.
Comparative example
Terpyridyl 0.013g (0.05mmol) and 1 is measured respectively, 2- butadiene monoxide 0.361g (5mmol) is added to 25-
In the stainless steel autoclave of mL.After reaction kettle is sealed, the carbon dioxide of 30atm is filled at 25 DEG C.Stirring, is heated to
150℃.Insulation reaction 10h.It then cools to room temperature, deflates.Reaction result: the yield of butylene is 77%.
The test result of embodiment 1-8 and comparative example is summarized in table 1.
The comparison of 1 experimental result of table
It gives up in conclusion the by-product in coal-ethylene glycol technique is utilized in the synthetic method of butylene of the present invention
Alcohol, cost is relatively low, and reaction condition is mild, and reaction efficiency is higher.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical scheme and beneficial effects
Describe in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in protection of the invention
Within the scope of.
Claims (7)
1. a kind of carbonic acid 1, the synthetic method of 2- butene esters, which is characterized in that the described method comprises the following steps:
Reaction vessel is added in 1,2- butanediol, carbonylating agent and catalyst, heating generates carbonic acid 1, and 2- butene esters, reaction equation is such as
Under:
Wherein, R includes methyl, ethyl.
2. carbonic acid 1 according to claim 1, the synthetic method of 2- butene esters, which is characterized in that the carbonylating agent is carbonic acid
Dimethyl ester or diethyl carbonate.
3. carbonic acid 1 according to claim 1, the synthetic method of 2- butene esters, which is characterized in that 1,2- butanediol and described
The molar ratio of carbonylating agent is 1: 1~30.
4. carbonic acid 1 according to claim 1, the synthetic method of 2- butene esters, which is characterized in that reaction temperature be 20~
240℃。
5. carbonic acid 1 according to claim 1, the synthetic method of 2- butene esters, which is characterized in that the catalyst is oxidation
Calcium, zinc oxide, barium monoxide, magnesia, aluminium oxide, sodium metasilicate, alumina silicate, ferrosilite, calcium silicates, magnesium silicate, potassium silicate, inclined aluminium
One of sour sodium or hydrotalcite.
6. carbonic acid 1 according to claim 1, the synthetic method of 2- butene esters, which is characterized in that the amount of the catalyst is
The 0.1~20% of 1,2- butanediol quality.
7. carbonic acid 1 according to claim 1, the synthetic method of 2- butene esters, which is characterized in that the reaction time be 0.1~
20h。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810151204.3A CN110156741B (en) | 2018-02-13 | 2018-02-13 | Method for synthesizing carbonic acid butylene ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810151204.3A CN110156741B (en) | 2018-02-13 | 2018-02-13 | Method for synthesizing carbonic acid butylene ester |
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| Publication Number | Publication Date |
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| CN110156741A true CN110156741A (en) | 2019-08-23 |
| CN110156741B CN110156741B (en) | 2021-02-26 |
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| CN201810151204.3A Active CN110156741B (en) | 2018-02-13 | 2018-02-13 | Method for synthesizing carbonic acid butylene ester |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115594657A (en) * | 2022-12-07 | 2023-01-13 | 中国科学院过程工程研究所（Cn） | Cyclic carbonate and preparation method and application thereof |
| CN116078372A (en) * | 2023-04-06 | 2023-05-09 | 中国科学院过程工程研究所 | Catalyst for synthesizing cyclic carbonate, preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0823997A (en) * | 1994-07-14 | 1996-01-30 | Chisso Corp | Production of optically active 1,2-diol |
-
2018
- 2018-02-13 CN CN201810151204.3A patent/CN110156741B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0823997A (en) * | 1994-07-14 | 1996-01-30 | Chisso Corp | Production of optically active 1,2-diol |
Non-Patent Citations (2)
| Title |
|---|
| SANG-HYUN PYO ET AL.: "Chlorine-Free Synthesis of Organic Alkyl Carbonates and Fiveand Six-Membered Cyclic Carbonates", 《ADVANCED SYNTHESIS & CATALYSIS》 * |
| 郝鹏飞: "五元环状碳酸酯的制备及其应用", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115594657A (en) * | 2022-12-07 | 2023-01-13 | 中国科学院过程工程研究所（Cn） | Cyclic carbonate and preparation method and application thereof |
| CN116078372A (en) * | 2023-04-06 | 2023-05-09 | 中国科学院过程工程研究所 | Catalyst for synthesizing cyclic carbonate, preparation method and application thereof |
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| CN110156741B (en) | 2021-02-26 |
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