CN112745191A - Method for catalyzing dimerization reaction of hexafluoropropylene by ionic liquid - Google Patents
Method for catalyzing dimerization reaction of hexafluoropropylene by ionic liquid Download PDFInfo
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- CN112745191A CN112745191A CN202011635261.2A CN202011635261A CN112745191A CN 112745191 A CN112745191 A CN 112745191A CN 202011635261 A CN202011635261 A CN 202011635261A CN 112745191 A CN112745191 A CN 112745191A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
- C07C17/278—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons
- C07C17/281—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons of only one compound
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0279—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the cationic portion being acyclic or nitrogen being a substituent on a ring
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for preparing hexafluoropropylene dimerization reaction by ionic liquid catalysis, which uses green ionic liquid as hexafluoropropylene dimerization catalyst, has mild reaction condition, high production efficiency, simple product separation, no need of adding expensive crown ether and other cosolvents, greatly reduces the production cost, has simple synthesis method of the ionic liquid catalyst, cheap and easily obtained raw materials, lower production cost and wide industrial application prospect.
Description
Technical Field
The invention belongs to the field of fine chemical engineering, and particularly relates to a method for catalyzing dimerization reaction of hexafluoropropylene by using an ionic liquid.
Background
The hexafluoropropylene dimer has good thermodynamic stability and chemical stability, and is an important intermediate for synthesizing fluorine-containing surfactants and derivative products, medical active substance intermediates, pesticides, fire extinguishing products and the like. The hexafluoropropylene dimer is a compound with six perfluorocarbons and a double bond, and has a cis-trans isomer D1 and a dimer D2 with a branched chain structure, and is generally prepared by hexafluoropropylene oligomerization, and the synthesis method comprises a gas phase method and a liquid phase method. The gas phase method is a method in which hexafluoropropylene gas is continuously reacted through a catalyst layer, and the reaction is generally carried out in a tubular reactor without using a solvent, but the reaction needs to be carried out at a high temperature. The liquid phase method generally adds a catalyst, a cosolvent and an aprotic polar solvent into a closed pressure-resistant reaction kettle, and then introduces hexafluoropropylene gas to carry out batch reaction or continuous reaction, and the method does not need to adopt high-temperature reaction and is more commonly used.
US4377717 discloses a gas phase synthesis of hexafluoropropylene dimer, which is carried out at a higher temperature by adsorbing metal fluoride on activated carbon as a catalyst, and has a lower reaction selectivity and conversion rate. U.S. Pat. No. 3M CN93121609 uses hexafluoropropylene as a starting material, in a polar aprotic solvent, as catalysts such as quaternary ammonium, quaternary phosphonium, alkali metal cyanide, cyanate and thiocyanate, to obtain hexafluoropropylene dimer in high yield; chinese patent CN200610059035 discloses hexafluoropropylene dimer prepared by using hexafluoropropylene as raw material, acetonitrile as solvent and potassium thiocyanate as catalyst and through stirring reaction at proper temperature. However, in the above patents, cyanide or cyanate is used as a catalyst, the catalyst has strong toxicity, and the product after the reaction is not soluble in a solvent, and can be directly separated after the reaction is finished, but a small amount of solvent and catalyst remain in the product, and further rectification and washing are still needed, and the subsequent purification of the product is relatively complex. Chinese patent CN201710616035 discloses the use of solvents such as acetonitrile, N-dimethylformamide, etc., catalysts such as CsF, NaF, KF and RbF to synthesize hexafluoropropylene dimer, and crown ether as a cocatalyst, wherein crown ether is relatively expensive and is not easily recycled, resulting in higher cost. The related report of using ionic liquid as a catalyst or a cocatalyst for synthesizing hexafluoropropylene dimer does not appear in the prior art.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide the preparation method of the ionic liquid catalyzed hexafluoropropylene dimer, which is green and environment-friendly, low in cost, simple in synthetic route and higher in production efficiency.
The method selects the ionic liquid as the catalyst for the hexafluoropropylene dimerization reaction, does not need to add extra expensive catalyst and auxiliary agent, and can control the relatively high conversion rate of the obtained raw materials and the high selectivity of the target product. A method for catalyzing hexafluoropropylene dimerization reaction by using ionic liquid as a catalyst comprises the following steps:
adding a certain amount of ionic liquid catalyst and organic solvent into a high-pressure reaction kettle, uniformly stirring, introducing suitable inert gas, bubbling for 10 minutes, vacuumizing, repeating the operation for 3 times, introducing hexafluoropropylene gas with a certain pressure under a vacuum condition, and stirring at a constant temperature for reaction to obtain the hexafluoropropylene dimer.
The anion of the ionic liquid catalyst is Cl-、Br-、SCN-And the like, wherein the cation is an ionic liquid of imidazolium salt and pyridinium salt, and the structural formula of the cation is as follows:
R0-5typically H atoms or saturated or unsaturated hydrocarbon groups containing 1 to 16 carbon atoms;
the organic solvent is acetonitrile, dimethyl sulfoxide and N, N-dimethylformamide.
Ionic liquid: the mass ratio of the organic solvent is 1: 50-1: 1000.
the inert gas is high-purity nitrogen or high-purity argon.
According to the preparation method, the reaction pressure of hexafluoropropylene gas is controlled to be 0.1-5.0 MPa, the reaction can be continuous or intermittent, and the temperature is controlled to be-20-100 ℃.
The ionic liquid is creatively used as a catalyst for hexafluoropropylene dimerization reaction, the catalyst can replace a cyanide or cyanate catalyst with high toxicity, compared with a conventional alkali metal fluoride catalyst, the ionic liquid has high solubility in an organic solvent, so that the solubility of the alkali metal fluoride catalyst in the organic solvent is improved without adding expensive and virulent crown ether and other auxiliary agents, the dosage of the catalyst can be greatly reduced, the reaction can be carried out under the condition of no additional energy input, the selectivity of an oligomerization product hexafluoropropylene dimer can reach more than 99%, wherein the selectivity of D1 is 94-96%, the selectivity of D2 is 4-6%, the product separation process is simple, and the wide industrial prospect is achieved.
Detailed Description
The invention will be further elucidated with reference to the following specific examples.
Materials, reagents and equipment used in the following examples of the present invention were commercially available. All reagents used were analytical grade. The present invention is described by the following examples, but the present invention is not limited to the following examples, and variations and implementations are included in the technical scope of the present invention without departing from the spirit of the invention described above and below.
Example 1:
adding 0.007g of ionic liquid tetrabutylammonium thiocyanate catalyst and 3ml of acetonitrile organic solvent into a 50ml high-pressure reaction kettle, uniformly stirring, bubbling for 10 minutes by using high-purity nitrogen, vacuumizing, repeating the operation for 3 times, introducing 0.5MPa hexafluoropropylene gas, stirring at constant pressure and 30 ℃ for reaction for 16 hours, closing a valve after the reaction is finished, standing overnight, reducing the pressure to 0.1MPa to obtain 1.5ml of product, and analyzing the selectivity of D1 by gas chromatography to be 96%.
Example 2:
adding 0.006g of ionic liquid chlorinated 1-butyl 3-methylimidazole catalyst and 2ml of acetonitrile organic solvent into a 25ml high-pressure reaction kettle, uniformly stirring, bubbling for 10 minutes by using high-purity nitrogen, vacuumizing, repeating the operation for 3 times, introducing 0.4MPa hexafluoropropylene gas under the vacuum condition, stirring and reacting for 24 hours at constant pressure and 50 ℃, closing a valve after the reaction is finished, standing overnight, obtaining 2ml of product, and analyzing the selectivity of D1 by gas chromatography to be 94%.
Example 3:
0.05g of ionic liquid 1-ethyl-3-methylimidazolium thiocyanate catalyst and 15ml of acetonitrile organic solvent are added into a 250ml high-pressure reaction kettle, after uniform stirring, high-purity nitrogen is applied for bubbling for 10 minutes, then vacuum pumping is carried out, the operation is repeated for 3 times, 0.5MPa hexafluoropropylene gas is introduced, the reaction is carried out for 12 hours under the condition of constant pressure and 25 ℃, 12ml of product can be obtained, and the selectivity of D1 is 96% through gas chromatography analysis. .
Example 4:
0.03g of ionic liquid 1-butyl-3-methylimidazolium thiocyanate catalyst and 4ml of N, N-dimethylformamide organic solvent are added into a high-pressure reaction kettle, after uniform stirring, high-purity nitrogen is used for bubbling for 10 minutes, then vacuum pumping is carried out, the operation is repeated for 3 times, 0.5MPa hexafluoropropylene gas is introduced, stirring reaction is carried out for 12 hours under the condition of constant pressure and 55 ℃, then 1.3ml of product is obtained, and the selectivity of D1 is 36% through gas chromatography analysis.
Example 5:
adding 0.006g of ionic liquid 1-butyl-3-methylimidazolium bromide catalyst and 2ml of acetonitrile organic solvent into a high-pressure reaction kettle, uniformly stirring, bubbling for 10 minutes by using high-purity nitrogen, vacuumizing, repeating the operation for 3 times, introducing 0.5MPa hexafluoropropylene gas, stirring and reacting for 12 hours under the condition of constant pressure of 55 ℃, closing a reaction valve, reducing the pressure to 0.1MPa after overnight to obtain 1.2ml of product, and analyzing the selectivity of D1 by gas chromatography to be 95%.
Example 6:
adding 0.3g of ionic liquid 1-butyl-3-methylimidazolium thiocyanate ionic liquid and 20ml of acetonitrile organic solvent into a 250ml high-pressure reaction kettle, uniformly stirring, bubbling for 10 minutes by using high-purity nitrogen, vacuumizing again, repeating the operation for 3 times, continuously introducing 0.5MPa hexafluoropropylene gas, stirring and reacting for 6 hours at constant pressure and 30 ℃, standing overnight after the reaction is finished, reducing the pressure to the normal pressure to obtain 34ml of product, and analyzing the selectivity of D1 by gas chromatography to be 94%.
Claims (10)
1. A method for catalyzing dimerization reaction of hexafluoropropylene by using ionic liquid is characterized by comprising the following steps:
adding ionic liquid and organic solvent into a high-pressure reaction kettle, stirring uniformly, and introducing nitrogen and/orBubbling inert gas, vacuumizing, introducing hexafluoropropylene gas under the vacuum condition, and stirring for reaction to obtain the hexafluoropropylene dimer, wherein the anion of the ionic liquid is Cl-、Br-、SCN-、BF4 -、PF6 -、CF3COO-、CF3SO3 -At least one of them.
2. The method of claim 1, wherein: the cation of the ionic liquid catalyst is imidazole salt and/or pyridine salt.
3. The method of claim 1, wherein: the organic solvent is at least one of acetonitrile, dimethyl sulfoxide, N-dimethylformamide, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether.
4. The production method according to claim 1 or 3, wherein the organic solvent is acetonitrile.
5. The preparation method according to claim 1, wherein the volume ratio of the ionic liquid to the organic solvent is 1:1 to 1: 1000.
6. The method of claim 1, wherein the inert gas is helium and/or argon.
7. The method according to claim 1, wherein the reaction pressure is 0.1 to 5.0 MPa.
8. The method according to claim 1, wherein the reaction is a continuous constant pressure reaction or a batch reaction.
9. The method according to claim 8, wherein the reaction time of the batch reaction is 1 to 48 hours.
10. The method according to claim 1, wherein the reaction temperature is-20 to 100 ℃.
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| CN202011635261.2A CN112745191B (en) | 2020-12-31 | 2020-12-31 | Method for catalyzing dimerization reaction of hexafluoropropylene by ionic liquid |
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| CN202011635261.2A CN112745191B (en) | 2020-12-31 | 2020-12-31 | Method for catalyzing dimerization reaction of hexafluoropropylene by ionic liquid |
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| CN112745191B CN112745191B (en) | 2022-04-05 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2918501A (en) * | 1958-02-27 | 1959-12-22 | Du Pont | Internally unsaturated perfluoroolefins and preparation thereof |
| US4377717A (en) * | 1981-12-14 | 1983-03-22 | Allied Corporation | Method for the production of perfluoro-2-methylpentene-2 |
| US5387728A (en) * | 1992-08-27 | 1995-02-07 | Hoechst Aktiengesellschaft | Process for the preparation of hexafluoropropene dimers having a high proportion of perfluoro-(4-methyl-2-pentene) |
| CN107473929A (en) * | 2012-10-26 | 2017-12-15 | 浙江蓝天环保高科技股份有限公司 | A kind of method that coproduction prepares the amylene of 2 methyl of perfluor 2 and the amylene of 4 methyl of perfluor 2 |
-
2020
- 2020-12-31 CN CN202011635261.2A patent/CN112745191B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2918501A (en) * | 1958-02-27 | 1959-12-22 | Du Pont | Internally unsaturated perfluoroolefins and preparation thereof |
| US4377717A (en) * | 1981-12-14 | 1983-03-22 | Allied Corporation | Method for the production of perfluoro-2-methylpentene-2 |
| US5387728A (en) * | 1992-08-27 | 1995-02-07 | Hoechst Aktiengesellschaft | Process for the preparation of hexafluoropropene dimers having a high proportion of perfluoro-(4-methyl-2-pentene) |
| CN107473929A (en) * | 2012-10-26 | 2017-12-15 | 浙江蓝天环保高科技股份有限公司 | A kind of method that coproduction prepares the amylene of 2 methyl of perfluor 2 and the amylene of 4 methyl of perfluor 2 |
Non-Patent Citations (3)
| Title |
|---|
| STRONG,L.E.等: "Properties of Electrolytic Solutions.XLV. Conductance of Some Salts in Benzene at Higher Concentrations", 《JACS》 * |
| 高海洋等: "离子液体中催化烯烃齐聚/聚合反应的研究进展", 《现代化工》 * |
| 鲁丹等: "六氟丙烯二聚反应的新催化剂研究", 《中国科学技术大学学报》 * |
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