CN111484398A - Method for preparing perfluorohexanone - Google Patents
Method for preparing perfluorohexanone Download PDFInfo
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- CN111484398A CN111484398A CN201910321080.3A CN201910321080A CN111484398A CN 111484398 A CN111484398 A CN 111484398A CN 201910321080 A CN201910321080 A CN 201910321080A CN 111484398 A CN111484398 A CN 111484398A
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- perfluoro
- methyl
- pentene
- perfluorohexanone
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing perfluorohexanone, which relates to the technical field of chemical synthesis and comprises the step of respectively introducing perfluoro-2-methyl-2-pentene steam and oxidizing gas into a tubular reactor for gas-phase reaction for 1-5 hours at the temperature of 100-200 ℃ in the presence of amidine catalysts. The invention has the advantages of high production efficiency, low cost and less environmental pollution.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a method for preparing perfluorohexanone.
Background
With the elimination of Halon fire extinguishing agent, hydrofluorocarbon substitutes are emerging in succession. A perfluorohexanone fire extinguishing agent, known under the trade name Novec1230, chemical name 1, 1, 1, 2, 2, 4, 5, 5, 5-nonafluoro-4-trifluoromethyl-pentan-trione, english name 1, 1, 1, 2, 2, 4, 5, 5, 5-nonfluoro-4-trifluoromethenyl-pentan-3-one, is a colorless, odorless, transparent liquid. Since the last 70 s of the century they were synthesized by people, no large-scale production has been carried out. Since 2001, the research on the synthesis technology and application of the product has been increasingly noticed by the American 3M company as a fire extinguishing agent for replacing halon and fluoroalkanes. At present, under the requirements of environmental policy and the influence of climate change caused by global warming, the perfluorohexanone fire extinguishing agent has more excellent performances, and the novel substitute is stored in a liquid state form, overcomes the defects that the first generation halon substitute has the effects of global warming and climate change, and is a novel halon substitute. When the water-based fire extinguishing agent is used for spraying to a protection area, the water-based fire extinguishing agent can be rapidly evaporated and covers the whole protection area, extinguishes fire by using a heat absorption mode, is close to zero in harm to the environment and human bodies, and is a green environment-friendly substance. However, the conversion rate of the product and the purity of the product are to be improved and improved in the production technology, and the product cost is required to be further reduced. Therefore, the development of the green synthesis process of the product is necessary, and the method has important economic and social benefits and wide application prospect.
The prior art proposes a variety of methods for the synthesis of perfluorohexanones. For example, chinese patent application CN103508868A, entitled "blue sky group limited company and" blue sky environmental protection high technology ltd company of zhejiang, proposes that perfluoro-2, 3-oxo-2-methylpentane undergoes catalytic rearrangement reaction at 10-70 ℃ in the presence of fluoride salt and ether compounds to produce perfluorohexanone. The patent uses a composite catalyst, is easy to deactivate, has unstable reaction yield and has partial formula conversion rate lower than 70 percent.
In addition, the existing technology for preparing perfluoro-2-methyl-3-pentanone by taking perfluoro-2-methyl-2-pentene as a raw material through steps of epoxidation, isomerization and the like inevitably needs to use a large amount of toxic solvents such as acetonitrile and the like and corrosive and irritant oxidants such as NaClO and the like, and has the defects of low production efficiency, high cost, environmental pollution and the like.
Disclosure of Invention
Therefore, the technical problems to be solved by the embodiment of the invention are that the preparation method of the perfluorohexanone in the prior art has low production efficiency, high cost and environmental pollution.
To this end, a method of preparing perfluorohexanone according to an embodiment of the present invention includes the steps of:
in the presence of amidine catalyst, at the temperature of 100-200 ℃, introducing perfluoro-2-methyl-2-pentene steam and oxidizing gas into a tubular reactor respectively for gas phase reaction for 1-5 hours;
the amidine-based catalyst comprises DBU;
the dosage of the catalyst accounts for 1 to 10 percent of the mol weight of the perfluoro-2-methyl-2-pentene.
Preferably, the oxidizing gas comprises oxygen, air or N2、He、CO2One or more of oxygen diluted by mixed gas; the mixing volume ratio of the perfluoro-2-methyl-2-pentene and the oxidizing gas is 4-5: 1.
Preferably, the total pressure of the gas phase reaction is 1-10bar, and the space velocity is 50h-1-400h-1。
Preferably, the catalyst is used in an amount of 1.5 to 6% by mole based on the amount of perfluoro-2-methyl-2-pentene.
Preferably, the catalyst is used in an amount of 3 to 5% by mole based on the amount of perfluoro-2-methyl-2-pentene.
The technical scheme of the embodiment of the invention has the following advantages:
the product provided by the embodiment of the invention has higher molar yield, is easy to realize low-cost industrial production, greatly improves the reaction yield and selectivity by the whole process method, and has less discharge of three wastes and less environmental pollution.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In describing the present invention, it is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. The terms "comprises" and/or "comprising," when used in this specification, are intended to specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention provides a method for efficiently and selectively preparing perfluorohexanone, which has a reaction process route shown as the following formula:
the method for preparing the perfluorohexanone comprises the step of respectively introducing perfluoro-2-methyl-2-pentene steam and oxidizing gas into a tubular reactor for gas-phase reaction for 1-5 hours at the temperature of 100-200 ℃ in the presence of an amidine catalyst to obtain the perfluorohexanone.
The amidine-based catalyst comprises DBU.
The dosage of the catalyst accounts for 1 to 10 percent of the mol weight of the perfluoro-2-methyl-2-pentene. Preferably, it is 1.5-6%. More preferably, it is 3 to 5%.
Preferably, the oxidizing gas comprises oxygen, air or N2、He、CO2One or more of oxygen diluted by mixed gas; the mixing volume ratio of the perfluoro-2-methyl-2-pentene and the oxidizing gas is 4-5: 1.
Preferably, the total pressure of the gas phase reaction is 1-10bar, and the space velocity is 50h-1-400h-1。
Preferably, the catalyst is also used with a compounding aid, and the catalyst aid comprises KF, BaO and BaF2、CeO2Or Y2O3The content of the catalyst is 1-5 percent of the catalyst.
The method for preparing the perfluorohexanone has the advantages of higher product molar yield, easy realization of low-cost industrial production, great improvement of reaction yield and selectivity by the whole process method, less discharge of three wastes and less environmental pollution.
Objects and advantages of this invention are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this invention and to include other compounds which may be employed in analytical purity unless otherwise specified.
Example 1
Putting amidine catalyst into constant temperature zone of reaction tube, keeping constant temperature at about 100 deg.C with heat-insulating heating jacket, reaction pressure of 0.1MPa, perfluoro-2-methyl-2-pentene steam control flow of 80m L/min, oxidizing gas control flow of 20m L/min, introducing into reaction tube, wherein the oxidizing gas includes trans-formRaw material gas O2And a diluent gas N2The volume ratio is 1:4, the gas phase reaction is carried out for 3 hours, the gas after the reaction is received in a condensation mode and is measured and analyzed, and the result shows that the conversion rate of the perfluoro-2-methyl-2-pentene is 64.3 percent, and the selectivity of the perfluorohexanone is 67.2 percent.
Example 2
Putting amidine catalyst into constant temperature zone of reaction tube, using heat-insulating heating jacket to keep constant temperature at about 200 deg.C, reaction pressure is 0.5MPa, perfluoro-2-methyl-2-pentene steam control flow rate is 80m L/min, introducing into reaction tube, oxidizing gas control flow rate is 20m L/min, introducing into reaction tube, oxidizing gas includes reaction raw material gas O2And a diluent gas N2The volume ratio is 1:4, the gas phase reaction is carried out for 3 hours, the gas after the reaction is received in a condensation mode and is measured and analyzed, and the result shows that the conversion rate of the perfluoro-2-methyl-2-pentene is 75.6 percent, and the selectivity of the perfluorohexanone is 78.4 percent.
Example 3
Putting amidine catalyst and auxiliary agent into a constant temperature region of a reaction tube, adopting KF auxiliary agent with the content of 3 percent of the catalyst, using a heat-preservation heating jacket to keep the constant temperature at about 150 ℃, controlling the reaction pressure at 0.6MPa, controlling the flow of perfluoro-2-methyl-2-pentene steam to be 80m L/min, introducing oxidizing gas into the reaction tube with the control flow of 20m L/min, wherein the oxidizing gas comprises reaction raw material gas O2And a diluent gas N2The volume ratio is 1:4, the gas phase reaction is carried out for 3 hours, the gas after the reaction is received in a condensation mode and is measured and analyzed, and the result shows that the conversion rate of the perfluoro-2-methyl-2-pentene is 80.7 percent, and the selectivity of the perfluorohexanone is 88.3 percent.
Example 4
Putting amidine catalyst and auxiliary agent into a constant temperature region of a reaction tube, adopting KF auxiliary agent with the content of 3 percent of the catalyst, introducing into the reaction tube by using a heat-preservation heating jacket at the constant temperature of about 150 ℃, the reaction pressure of 0.2MPa, the control flow of perfluoro-2-methyl-2-pentene steam of 40m L/min, and the control flow of oxidizing gas of 10m L/min, wherein the oxidizing gas comprises reaction raw material gas O2And a diluent gas N2The volume ratio of the reaction solution to the reaction solution is 1:4, the gas phase reaction is carried out for 3 hours, and the gas after the reactionThe product is collected by a condensation mode and is measured and analyzed, and the result shows that the conversion rate of the perfluoro-2-methyl-2-pentene is 72.1 percent, and the selectivity of the perfluorohexanone is 78.5 percent.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (5)
1. A process for the preparation of perfluorohexanone, comprising the steps of:
in the presence of amidine catalyst, at the temperature of 100-200 ℃, introducing perfluoro-2-methyl-2-pentene steam and oxidizing gas into a tubular reactor respectively for gas phase reaction for 1-5 hours;
the amidine-based catalyst comprises DBU;
the dosage of the catalyst accounts for 1 to 10 percent of the mol weight of the perfluoro-2-methyl-2-pentene.
2. The method of claim 1, wherein the oxidizing gas comprises oxygen, air, or N2、He、CO2One or more of oxygen diluted by mixed gas; the mixing volume ratio of the perfluoro-2-methyl-2-pentene and the oxidizing gas is 4-5: 1.
3. The process for preparing perfluorohexanone according to claim 1 or 2, wherein the total pressure of the gas-phase reaction is between 1 and 10bar and the space velocity is 50h-1-400h-1。
4. The process for preparing perfluorohexanone according to any one of claims 1 to 3, wherein the catalyst is used in an amount of 1.5 to 6% by mole based on the amount of perfluoro-2-methyl-2-pentene.
5. The process for preparing perfluorohexanone according to any one of claims 1 to 4, wherein the catalyst is used in an amount of 3 to 5% by mole based on the amount of perfluoro-2-methyl-2-pentene.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910321080.3A CN111484398A (en) | 2019-04-22 | 2019-04-22 | Method for preparing perfluorohexanone |
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| CN201910321080.3A CN111484398A (en) | 2019-04-22 | 2019-04-22 | Method for preparing perfluorohexanone |
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| CN111484398A true CN111484398A (en) | 2020-08-04 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1802338A (en) * | 2003-04-01 | 2006-07-12 | 3M创新有限公司 | Method of removing hexafluoropropylene dimers |
| CN105198719A (en) * | 2015-09-06 | 2015-12-30 | 浙江工业大学 | Preparation method of perfluoro-2-methyl-3-pentanone |
| CN105439835A (en) * | 2015-12-02 | 2016-03-30 | 上海三爱富新材料股份有限公司 | Preparation method of C6-fluoroketone |
| CN107235834A (en) * | 2017-06-28 | 2017-10-10 | 江苏科技大学 | A kind of preparation method of perfluorethyl isopropyl ketone |
| CN107382692A (en) * | 2017-09-06 | 2017-11-24 | 北京天康达科技发展有限公司 | The synthetic method of perfluor hexanone and application |
-
2019
- 2019-04-22 CN CN201910321080.3A patent/CN111484398A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1802338A (en) * | 2003-04-01 | 2006-07-12 | 3M创新有限公司 | Method of removing hexafluoropropylene dimers |
| CN105198719A (en) * | 2015-09-06 | 2015-12-30 | 浙江工业大学 | Preparation method of perfluoro-2-methyl-3-pentanone |
| CN105439835A (en) * | 2015-12-02 | 2016-03-30 | 上海三爱富新材料股份有限公司 | Preparation method of C6-fluoroketone |
| CN107235834A (en) * | 2017-06-28 | 2017-10-10 | 江苏科技大学 | A kind of preparation method of perfluorethyl isopropyl ketone |
| CN107382692A (en) * | 2017-09-06 | 2017-11-24 | 北京天康达科技发展有限公司 | The synthetic method of perfluor hexanone and application |
Non-Patent Citations (1)
| Title |
|---|
| 屈文良: "全氟己酮合成工艺优化研究", 《中国优秀博硕士学位论文全文数据库(硕士)工程科技I辑》 * |
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Application publication date: 20200804 |