CN110577460A - Preparation method of hexafluoropropylene tripolymer - Google Patents
Preparation method of hexafluoropropylene tripolymer Download PDFInfo
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- CN110577460A CN110577460A CN201910905170.7A CN201910905170A CN110577460A CN 110577460 A CN110577460 A CN 110577460A CN 201910905170 A CN201910905170 A CN 201910905170A CN 110577460 A CN110577460 A CN 110577460A
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- hexafluoropropylene
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- pentene
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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
- B01J31/0201—Oxygen-containing compounds
- B01J31/0204—Ethers
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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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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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
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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
Abstract
The invention discloses a preparation method of hexafluoropropylene trimer. The preparation method comprises the following steps: in an aprotic polar solvent, under the action of a catalyst, perfluoro-2-methyl-2-pentene and hexafluoropropylene are subjected to one-step addition to generate hexafluoropropylene trimer, wherein the catalyst consists of a main catalyst and a cocatalyst in a mass ratio of 0.1-10:1, and the molar ratio of perfluoro-2-methyl-2-pentene to hexafluoropropylene is 0.1-10: 1. By adopting the technology, the perfluoro-2-methyl-2-pentene and hexafluoropropylene are used as raw materials, and under the combined action of the main catalyst and the cocatalyst, the hexafluoropropylene trimer is prepared by a one-step addition method, so that the hexafluoropropylene trimer has the advantages of high selectivity, high conversion rate, high product content, less byproducts and less catalyst consumption.
Description
Technical Field
The invention belongs to the technical field of organic fluorine chemistry, relates to a preparation method of a hexafluoropropylene polymer, and particularly relates to a preparation method of a hexafluoropropylene tripolymer.
Background
Hexafluoropropylene trimer is an important fluorochemical. It is a main raw material for synthesizing fluorine-containing surfactant, and can be used as cleaning agent, solvent and cooling medium, so that it possesses extensive application range.
At present, the synthesis process of hexafluoropropylene trimer is reported, most of Hexafluoropropylene (HFP) is used as a raw material, and is obtained by polymerization in different catalyst and solvent systems, but in the reaction process, a large amount of catalyst is needed, and after the reaction is finished, a large amount of byproducts are generated in the reaction product, so that the use of a large amount of catalyst can increase the production cost, and a large amount of industrial solid wastes are increased.
Disclosure of Invention
in view of the above problems in the prior art, the present invention aims to provide a method for preparing hexafluoropropylene trimer having complete conversion, high raw material utilization rate and low byproduct content.
The preparation method of the hexafluoropropylene tripolymer is characterized in that under the action of a catalyst in an aprotic polar solvent, perfluoro-2-methyl-2-pentene and hexafluoropropylene are subjected to one-step addition to generate the hexafluoropropylene tripolymer.
The preparation method of the hexafluoropropylene tripolymer is characterized in that the molar ratio of the perfluoro-2-methyl-2-pentene to the hexafluoropropylene is 0.1-10:1, preferably 0.5-2: 1.
The preparation method of the hexafluoropropylene trimer is characterized in that the catalyst consists of a main catalyst and a cocatalyst, and the mass ratio of the main catalyst to the cocatalyst is 0.1-10:1, preferably 0.5-2: 1.
The preparation method of the hexafluoropropylene tripolymer is characterized in that the main catalyst is one or a mixture of more than two of potassium fluoride, sodium fluoride, cesium fluoride and aluminum fluoride.
The preparation method of the hexafluoropropylene trimer is characterized in that the cocatalyst is one or a mixture of more than two of 15-crown-5, 18-crown-6, sulfolane and diethyl ether.
the preparation method of the hexafluoropropylene tripolymer is characterized in that the mass ratio of the total mass of the perfluoro-2-methyl-2-pentene and the hexafluoropropylene to the mass of the main catalyst is 20-2000:1, preferably 100-.
the preparation method of the hexafluoropropylene tripolymer is characterized in that the addition reaction temperature is 0-120 ℃, and preferably 30-80 ℃.
The preparation method of the hexafluoropropylene tripolymer is characterized in that the aprotic polar solvent is one or a mixed solvent of more than two of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, propylene glycol dimethyl ether, diethylene glycol dibutyl ether, acetonitrile, benzyl cyanide, N-dimethyl formamide, polyvinylpyrrolidone, dimethyl sulfoxide, sulfolane and tetrahydrofuran.
The preparation method of the hexafluoropropylene tripolymer is characterized in that the mass ratio of the total mass of the perfluoro-2-methyl-2-pentene and the hexafluoropropylene to the solvent is 1-50: 1, preferably 2-10: 1.
By adopting the technology, the invention has the following beneficial effects:
The invention adopts perfluoro-2-methyl-2-pentene and hexafluoropropylene as raw materials, and uses the combined action of a main catalyst and a cocatalyst to prepare hexafluoropropylene trimer by a one-step addition method, and has the advantages of high selectivity, high conversion rate, high content of obtained products, less byproducts and less catalyst consumption.
Detailed Description
The process according to the invention and its use are further illustrated by the following examples, which are intended to be non-limiting illustrations of the invention.
Example 1:
The reaction of perfluoro-2-methyl-2-pentene and hexafluoropropylene to obtain hexafluoropropylene trimer is carried out according to the following steps:
a. Firstly, cleaning a 500ml reaction kettle and drying;
b. Adding 1.5g of anhydrous potassium fluoride and 1.95g of 18-crown-6, covering a kettle cover, and sealing; c. vacuumizing the reaction kettle to be below-0.09 MPa, and sucking 200g of perfluoro-2-methyl-2-pentene and 100ml of acetonitrile;
d. Starting stirring, introducing 120g of hexafluoropropylene, wherein the reaction temperature is not more than 50 ℃;
e. After the reaction is finished, continuously preserving the temperature and reacting for 1.5 h;
f. After the reaction is finished, cooling to room temperature, opening the reaction kettle, and separating the solvent from the fluorinated liquid by using a separating funnel;
g. The obtained fluorinated liquid is sampled and analyzed after being measured;
as a result: the mass of the crude product of the obtained fluorinated liquid was 302.6 g, the content of trimer was 83.2%, the content of by-products was 0.166%, the content of perfluoro-4-methyl-2-pentene was 9.82%, the content of perfluoro-2-methyl-2-pentene was 6.31%, the residue of hexafluoropropylene was 0.00101%, the conversion rate of hexafluoropropylene was 99.99899%, and the yield of trimer was 78.68%.
Example 2:
The same process operation and other conditions as in example 2 were the same except that the amount of anhydrous potassium fluoride as the main catalyst was reduced to 0.5g and the amount of 18-crown-6 as the cocatalyst was reduced to 0.65 g;
As a result: the crude product of the obtained fluorinated liquid has the mass of 305.4g, the content of tripolymer of 84.82 percent, the content of by-products of 0.201 percent, the content of perfluoro-4-methyl-2-pentene of 8.32 percent, the content of perfluoro-2-methyl-2-pentene of 5.83 percent, the residue of hexafluoropropylene of 0.16334 percent, the conversion rate of hexafluoropropylene of 99.83666 percent and the yield of tripolymer of 80.95 percent
Example 3:
The same procedure as in example 1 and other conditions were conducted except that the feed amount of hexafluoropropylene was increased to 150 g.
as a result: the obtained crude fluorinated liquid had a mass of 334.7g, a trimer content of 85.82%, a by-product content of 0.103%, a perfluoro-4-methyl-2-pentene content of 12.32%, a perfluoro-2-methyl-2-pentene content of 0.83%, a hexafluoropropylene residue of 0.00261%, a hexafluoropropylene conversion of 99.99739%, and a trimer yield of 82.07%.
example 4:
The same procedure as in example 1 and other conditions were the same except that the reaction temperature was increased to 70 ℃.
As a result: the obtained crude product of the fluorinated liquid was 303.1g in mass, the trimer content was 89.73%, the by-product content was 0.157%, the perfluoro-4-methyl-2-pentene content was 6.47%, the perfluoro-2-methyl-2-pentene content was 2.84%, the hexafluoropropylene residue was not detected, and the hexafluoropropylene conversion rate was 100%. The trimer yield was 84.99%
comparative example 1:
The trimer was synthesized by direct polymerization with hexafluoropropylene:
a. firstly, a 500ml reaction kettle is cleaned and dried.
b. 1.5g of anhydrous potassium fluoride and 1.95g of 18-crown-6 are added, the kettle cover is covered, and the kettle is sealed.
c. vacuumizing the reaction kettle to below-0.09 MPa, and sucking 100ml of acetonitrile
d. the stirring was started and 320g of hexafluoropropylene were added, the reaction temperature not exceeding 50 ℃.
e. After the reaction is finished, the reaction is continued for 1.5h under the condition of heat preservation.
f. After the reaction is finished, cooling to room temperature, opening the reaction kettle, and separating the solvent from the fluorinated liquid by using a separating funnel.
g. the obtained fluorinated liquid is measured and sampled for analysis.
As a result: the mass of the obtained crude product of the fluorinated liquid is 304.3g, the content of tripolymer is 18.58 percent, and the content of by-products is as follows: 1.23%, the content of perfluoro-4-methyl-2-pentene was 32.70%, the content of perfluoro-2-methyl-2-pentene was 46.05%, the residual amount of hexafluoropropylene was 0.01877%, and the conversion of hexafluoropropylene was 99.98123%. The trimer yield was 17.67%.
Claims (9)
1. a preparation method of hexafluoropropylene tripolymer is characterized in that perfluoro-2-methyl-2-pentene and hexafluoropropylene are subjected to one-step addition to generate the hexafluoropropylene tripolymer in an aprotic polar solvent under the action of a catalyst.
2. The process for producing a hexafluoropropylene trimer according to claim 1, wherein the molar ratio of perfluoro-2-methyl-2-pentene to hexafluoropropylene is 0.1-10:1, preferably 0.5-2: 1.
3. The method for preparing hexafluoropropylene trimer according to claim 1, wherein the catalyst comprises a main catalyst and a cocatalyst, and the mass ratio of the main catalyst to the cocatalyst is 0.1-10:1, preferably 0.5-2: 1.
4. The process according to claim 3, wherein the procatalyst is selected from the group consisting of potassium fluoride, sodium fluoride, cesium fluoride and aluminum fluoride.
5. The process according to claim 3, wherein the cocatalyst is selected from the group consisting of 15-crown-5, 18-crown-6, sulfolane, and diethyl ether.
6. the process for producing a hexafluoropropylene trimer according to claim 3, characterized in that the mass ratio of the total mass of perfluoro-2-methyl-2-pentene and hexafluoropropylene to the mass of the main catalyst is 20-2000:1, preferably 100: 1000: 1.
7. The process according to claim 1, wherein the addition reaction temperature is 0 ℃ to 120 ℃, preferably 30 ℃ to 80 ℃.
8. The method according to claim 1, wherein the aprotic polar solvent is one or a mixed solvent of two or more selected from the group consisting of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, propylene glycol dimethyl ether, diethylene glycol dibutyl ether, acetonitrile, phenylacetonitrile, N-dimethylformamide, polyvinylpyrrolidone, dimethyl sulfoxide, sulfolane and tetrahydrofuran.
9. the process according to claim 1, wherein the mass ratio of the total mass of perfluoro-2-methyl-2-pentene and hexafluoropropylene to the solvent is from 1 to 50: 1, preferably 2-10: 1.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111269081A (en) * | 2020-03-12 | 2020-06-12 | 浙江巨化汉正新材料有限公司 | Preparation method of hexafluoropropylene tripolymer |
| CN111647391A (en) * | 2020-07-15 | 2020-09-11 | 浙江诺亚氟化工有限公司 | Multi-effect organic cooling liquid composition and application thereof |
| CN113548937A (en) * | 2020-04-26 | 2021-10-26 | 浙江蓝天环保高科技股份有限公司 | Continuous preparation method of high-purity perfluoro-2, 4-dimethyl-3-heptene |
| CN113548943A (en) * | 2020-04-26 | 2021-10-26 | 浙江蓝天环保高科技股份有限公司 | Continuous preparation method of hexafluoropropylene tripolymer |
| CN113816824A (en) * | 2021-09-07 | 2021-12-21 | 浙江巨化技术中心有限公司 | Preparation method and application of perfluoroolefin oligomer |
Citations (2)
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| JPH06248014A (en) * | 1993-02-26 | 1994-09-06 | Asahi Glass Co Ltd | Production of fluorinated polymer |
| CN109734552A (en) * | 2018-11-30 | 2019-05-10 | 天津市长芦化工新材料有限公司 | The controllable polymerization method and device of hexafluoropropylene trimer |
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2019
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Patent Citations (2)
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| JPH06248014A (en) * | 1993-02-26 | 1994-09-06 | Asahi Glass Co Ltd | Production of fluorinated polymer |
| CN109734552A (en) * | 2018-11-30 | 2019-05-10 | 天津市长芦化工新材料有限公司 | The controllable polymerization method and device of hexafluoropropylene trimer |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111269081A (en) * | 2020-03-12 | 2020-06-12 | 浙江巨化汉正新材料有限公司 | Preparation method of hexafluoropropylene tripolymer |
| CN113548937A (en) * | 2020-04-26 | 2021-10-26 | 浙江蓝天环保高科技股份有限公司 | Continuous preparation method of high-purity perfluoro-2, 4-dimethyl-3-heptene |
| CN113548943A (en) * | 2020-04-26 | 2021-10-26 | 浙江蓝天环保高科技股份有限公司 | Continuous preparation method of hexafluoropropylene tripolymer |
| CN113548937B (en) * | 2020-04-26 | 2023-09-05 | 浙江蓝天环保高科技股份有限公司 | Continuous preparation method of high-purity perfluoro-2, 4-dimethyl-3-heptene |
| CN113548943B (en) * | 2020-04-26 | 2023-09-05 | 浙江蓝天环保高科技股份有限公司 | Continuous preparation method of hexafluoropropylene trimer |
| CN111647391A (en) * | 2020-07-15 | 2020-09-11 | 浙江诺亚氟化工有限公司 | Multi-effect organic cooling liquid composition and application thereof |
| CN111647391B (en) * | 2020-07-15 | 2022-01-21 | 浙江诺亚氟化工有限公司 | Multi-effect organic cooling liquid composition and application thereof |
| CN113816824A (en) * | 2021-09-07 | 2021-12-21 | 浙江巨化技术中心有限公司 | Preparation method and application of perfluoroolefin oligomer |
| CN113816824B (en) * | 2021-09-07 | 2023-03-10 | 浙江巨化技术中心有限公司 | Preparation method and application of perfluoroolefin oligomer |
| WO2023035876A1 (en) * | 2021-09-07 | 2023-03-16 | 浙江巨化技术中心有限公司 | Preparation method for perfluoroolefin oligomer and application thereof |
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