CN102503767A - Preparation method of hexafluoropropylene dimer - Google Patents
Preparation method of hexafluoropropylene dimer Download PDFInfo
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- CN102503767A CN102503767A CN2011103745328A CN201110374532A CN102503767A CN 102503767 A CN102503767 A CN 102503767A CN 2011103745328 A CN2011103745328 A CN 2011103745328A CN 201110374532 A CN201110374532 A CN 201110374532A CN 102503767 A CN102503767 A CN 102503767A
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Abstract
The invention discloses a preparation method of hexafluoropropylene dimmer. The method comprises the following steps that: complexes formed by cuprous halide and nitrogen-containing ligands are used as catalysts, aprotic polar solvents are used as media, hexafluoropropylene is subjected to oligomerization, and the hexafluoropropylene dimmer is obtained. Because the hexafluoropropylene is an electron-lack monomer and can be activated by the cuprous halide complexed by the nitrogen-containing ligands, so the dimerization reaction is carried out, the complexes formed by cuprous halide and nitrogen-containing ligands are used as the catalysts, and the hexafluoropropylene dimmer is obtained through preparation. Compared with the prior art, the preparation method provided by the invention has the advantages that an environmental-friendly catalyst system is adopted for preparing the hexafluoropropylene dimmer, the adoption of a high-toxicity catalytic system is avoided, the catalyst consumption is low, and the reaction temperature is low.
Description
Technical field
The present invention relates to the hexafluoropropylene dimmer technical field, more particularly, relate to a kind of preparation method of hexafluoropropylene dimmer.
Background technology
The hexafluoropropylene dimmer (HFPD) that is made by R 1216 (HFP) oligomerisation reaction comprises three kinds of isomer usually, respectively suc as formula shown in I (a), formula I (b) and the formula II.Wherein, formula I (a) and formula I (b) are cis-trans-isomer, and its pair key activity is lower; Thermostability and chemicalstability are better; Toxicity is lower, can directly use as end products such as whipping agent, fire-fighting mediums, and can be converted into the isomer shown in the formula II under certain condition.Isomer shown in the formula II does not generally directly use, but its pair key activity is bigger, can with numerous reagent generation nucleophilic additions, be widely used in the preparation of fluorochemical surfactant.
Since Minnesota Mining and Manufacturing Company releases first fluorochemical surfactant in nineteen fifty-one, the history in existing more than 50 year of fluorocarbon surfactant.Because the hydrophobic oleophobic characteristic of branching perfluor carbochain; Fluorochemical surfactant so that hexafluoropropene oligomers derives is compared with general hydrocarbon hydrophobic chain tensio-active agent; Have many excellent physical chemistry, play an important role in a lot of special fields.Simultaneously, not chloride among the HFPD, thereby can not damage atmospheric ozone layer, this makes that HFPD can the replacement fluorine enpara aspect a lot.
The preparation method of hexafluoropropylene dimmer mainly comprises vapor phase process and liquid phase method.Wherein, vapor phase process is loaded on solid catalysts such as Potassium monofluoride in the tubular reactor usually, lets the gasiform R 1216 react through catalyst layer, and temperature of reaction is usually more than 250 ℃.Liquid phase method is dissolved in catalyzer and additive in the polar aprotic solvent usually, feeds R 1216 then and carries out oligomerisation reaction.Compare with vapor phase process, the liquid phase method reaction conditions is gentle, and the hexafluoropropylene dimmer of generation is insoluble to solvent, separate easily.The kind of the catalyzer that liquid phase method is commonly used is a lot, comprises metal halide, metallic hydrogen fluorochemical, quaternary ammonium salt, fluorine-containing aminated compounds, prussiate, cyanate and thiocyanate etc.In the prior art; Application number is that to disclose a kind of be that Primary Catalysts, organic bases are that promotor, polyethers are the method that into agent is urged in catalysis with the alkaline metal fluoride cpd for 200710067489.4 Chinese patent document; In aprotic polar solvent; Carry out stage feeding polymerization at 50～80 ℃ of pressurization 0.1～1Mpa, service temperature and pressure is gentleness relatively, but Primary Catalysts Potassium monofluoride, Sodium Fluoride, cesium fluoride etc. have extremely strong toxicity.Application number is that 200810159977.2 Chinese patent document discloses the method that a kind of liquid phase oligomerization of hexafluoropropylene prepares perfluorinated nonene; Select for use polar aprotic solvent under 0.1～1MPa pressure under 50～150 ℃ of temperature of reaction; With alkali metal cyanate or thiocyanate-is that catalyzer carries out oligomerisation with R 1216, and catalystsystem toxicity is very high.
Above-mentioned catalyzer all exists some shortcomings; Like the suction and reduce catalytic efficiency (and it is insoluble in organic solvents such as acetonitrile easily of metal fluoride, metallic hydrogen fluorochemical class catalyzer; Make oligomerisation reaction under higher temperature, higher pressure, to carry out, have only to add to cost an arm and a leg and highly toxic crown ether just can make reaction at room temperature carry out during as promotor; Though the prussiate compounds can make R 1216 under lower temperature, oligomerisation reaction take place as catalyzer, the by product of catalyzed reaction is a highly toxic substance, environmentally safe formation grave danger.Therefore, take all factors into consideration from energy-conservation, energy economy & environment safety equal angles, above-mentioned catalystsystem all is not suitable for the dimeric production of R 1216.
Summary of the invention
In view of this, the technical problem that the present invention will solve is to provide a kind of preparation method of hexafluoropropylene dimmer, and this method adopts environmentally friendly catalystsystem to prepare hexafluoropropylene dimmer.
In order to solve above technical problem, the present invention provides a kind of preparation method of hexafluoropropylene dimmer, may further comprise the steps:
The title complex that forms with cuprous halide and containing n-donor ligand is a catalyzer, is medium with the aprotic polar solvent, and R 1216 is carried out oligomerisation reaction, obtains hexafluoropropylene dimmer.
Preferably, said cuprous halide is cuprous fluoride, cuprous chloride, cuprous bromide or cuprous iodide.
Preferably, the mol ratio of said cuprous halide and containing n-donor ligand is 1: (1～5), the mol ratio of preferred cuprous halide and containing n-donor ligand is 1: 2.
Preferably, the weight ratio of said cuprous halide and R 1216 is 1: (50～500).
Preferably, said containing n-donor ligand be bipyridyliums compound, phenanthroline compounds, the substituted Schiff bases compound of ortho position pyridyl, Tetramethyl Ethylene Diamine, the triamine that connects by ethylidene, the tetramine or the terpyridyl compounds that connect by ethylidene.
Preferably, said containing n-donor ligand is selected from a kind of in the following structural formula,
Wherein, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10And R
11Be respectively substituting group.
Preferably, said aprotic polar solvent is acetonitrile, ETHYLE ACETATE, glycol dimethyl ether, DMSO 99.8MIN. or N, dinethylformamide.
Preferably, the temperature of reaction of said oligomerisation reaction is-10～120 ℃, and the reaction times is 1.5～15 hours.
Preferably, the said step that R 1216 is carried out oligomerisation reaction is specially:
Step a) adds catalyzer and aprotic polar solvent in reaction kettle, freezing, and said catalyzer is the title complex that cuprous halide and containing n-donor ligand form;
Step b) feeds R 1216 in said reaction kettle under nitrogen protection, obtain the dimer of R 1216 behind the oligomerisation reaction.
The invention provides a kind of preparation method of hexafluoropropylene dimmer; May further comprise the steps: the title complex that forms with cuprous halide and containing n-donor ligand is a catalyzer; With the aprotic polar solvent is medium, and R 1216 is carried out oligomerisation reaction, obtains hexafluoropropylene dimmer.Because R 1216 is the electron deficiency monomer, it can be by the cuprous halide activation the containing n-donor ligand complexing under, thereby dimerization reaction takes place, and therefore, the present invention is a catalyzer with the title complex of cuprous halide and containing n-donor ligand formation, prepares hexafluoropropylene dimmer.Compared with prior art, the present invention adopts environmentally friendly catalystsystem to prepare hexafluoropropylene dimmer, has avoided the use of high toxicity catalystsystem, and catalyst levels is few, and temperature of reaction is lower.
Description of drawings
Fig. 1 is the nuclear-magnetism fluorine spectrum of the hexafluoropropylene dimmer of the embodiment of the invention 1 preparation.
Embodiment
Carry out clear, intactly description in the face of the technical scheme in the embodiment of the invention down, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills are not making the every other embodiment that is obtained under the creative work prerequisite, all belong to the scope of the present invention's protection.
The invention discloses a kind of preparation method of hexafluoropropylene dimmer, may further comprise the steps:
The title complex that forms with cuprous halide and containing n-donor ligand is a catalyzer, is medium with the aprotic polar solvent, and R 1216 is carried out oligomerisation reaction, obtains hexafluoropropylene dimmer.
According to the present invention, the above-mentioned step that R 1216 is carried out oligomerisation reaction is specially: step a) adds catalyzer and aprotic polar solvent in reaction kettle, freezing, and said catalyzer is the title complex that cuprous halide and containing n-donor ligand form; Step b) feeds R 1216 in said reaction kettle under nitrogen protection, obtain the dimer of R 1216 behind the oligomerisation reaction.The oligomerisation reaction of above-mentioned R 1216 is shown in following reaction formula:
Catalyzer is the key that R 1216 carries out oligomerisation reaction, when containing n-donor ligand is liquid, with containing n-donor ligand with can obtain title complex after cuprous halide mixes, detailed process can for: containing n-donor ligand and cuprous halide are added in the reaction kettle; In addition, when containing n-donor ligand is solid, need containing n-donor ligand and cuprous halide be ground, make it that sufficient complex reaction take place, be added in the reaction kettle then.
The catalyzer that the present invention adopts is the title complex that cuprous halide and containing n-donor ligand form; Cuprous halide is preferably cuprous fluoride, cuprous chloride, cuprous bromide or cuprous iodide; Wherein, this cuprous chloride can adopt commercial product, also can be through copper halide and copper prepared in reaction are obtained.Containing n-donor ligand in the catalyzer refer to can with the part of cuprous generation complexing action; Can be for containing two parts more than the nitrogen; For example two nitrogen ligands, three nitrogen ligands or four nitrogen ligands etc., the triamine that is preferably bipyridyliums compound, phenanthroline compounds, the substituted Schiff bases compound of ortho position pyridyl, Tetramethyl Ethylene Diamine, connects by ethylidene, the tetramine or the terpyridyl compounds that connect by ethylidene; Concrete, said containing n-donor ligand is selected from a kind of in the following structural formula,
Wherein, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10And R
11Be respectively substituting group.The present invention is for said R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10And R
11Do not have special restriction Deng substituting group.
In above-mentioned catalyzer, the mol ratio of said cuprous halide and containing n-donor ligand is preferably 1: (1～5), more preferably 1: 2.In addition, can control the type and the ratio of isomer of the hexafluoropropylene dimmer of formation through the concentration of control catalyst, when catalyst levels was low, the hexafluoropropylene dimmer of generation was main with formula I (a); When catalyst levels was higher, the hexafluoropropylene dimmer of generation was mainly formula II.The weight ratio of said cuprous halide and R 1216 is preferably 1: (50～500), more preferably 1: (100～300).
Because R 1216 is the electron deficiency monomer, it can be by the cuprous halide activation the containing n-donor ligand complexing under, thereby dimerization reaction takes place, and therefore, the present invention is a catalyzer with the title complex of cuprous halide and containing n-donor ligand formation, prepares hexafluoropropylene dimmer.Compared with prior art, the present invention adopts environmentally friendly catalystsystem to prepare hexafluoropropylene dimmer, has avoided the use of high toxicity catalystsystem.
The preparation method of hexafluoropropylene dimmer of the present invention is a liquid phase process, that is, catalyzer and additive are dissolved in the aprotic polar solvent, feeds R 1216 then and carries out oligomerisation reaction.The aprotic polar solvent that the present invention adopts is preferably acetonitrile, ETHYLE ACETATE, glycol dimethyl ether, DMSO 99.8MIN. or N, dinethylformamide.
Carry out in the process of oligomerisation reaction at R 1216; The temperature of polyreaction is the important factor that the influence reaction is carried out, and along with the rising of temperature of reaction, reaction rate constant can increase; Oligomerisation reaction speed also improves thereupon; But the temperature rising can cause the concentration of R 1216 in liquid phase to reduce, and is unfavorable for that oligomerisation reaction carries out.The temperature of reaction of oligomerisation reaction according to the invention is preferably-10～120 ℃.More specifically; When temperature of reaction when 20 ℃ rise to 55 ℃; It is less that speed of reaction increases, and can increase with the rising along with temperature of the per-cent of hexafluoropropylene dimmer in product of up-to-date style I (b) structure, and the rising of temperature descends the selectivity of reaction; Therefore, temperature of reaction is more preferably 10～40 ℃.
In addition, in the oligomerisation reaction process, along with the prolongation in reaction times, the hexafluoropropylene dimmer productive rate improves, and the reaction times that the present invention adopts is preferably 1.5～15 hours; After reaction 5 hours, dimer productive rate nearly 90%, therefore, the reaction times of the present invention is preferably 5 hours, under the condition with higher productive rate, has reduced cost.
In sum, the present invention is a catalyzer with the title complex that cuprous halide and containing n-donor ligand form, and the oligomerisation reaction of R 1216 has been prepared the dimer of R 1216, and this reaction can at room temperature be carried out, and catalyst levels is few, and selectivity of product is high.For example, be solvent dimer selectivity >=95% with the acetonitrile, product is main with perfluor-E-(4-methyl-2-amylene).Compare with existing catalyzer, the catalyzer that the present invention adopts has that use temperature is low, efficient, advantages of environment protection.
In order to further specify technical scheme of the present invention; Below in conjunction with embodiment the preferred embodiment of the invention is described; Describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
Embodiment 1
With 0.10 gram cuprous bromide and 0.23 gram 2,2 '-dipyridyl fully grinds, obtain cuprous bromide and 2,2 '-title complex that dipyridyl forms;
In autoclave, add said title complex and 3 milliliters of acetonitriles, freezing;
After said autoclave vacuumized/lead to nitrogen circulation 3 times, import 17.8 gram R 1216 gases, 20 ℃ down reaction stop after 1.5 hours, reclaim unreacted R 1216, isolate lower floor's colourless product, obtain 14.8 gram hexafluoropropylene dimmers.
As shown in Figure 1, for the hexafluoropropylene dimmer of present embodiment preparation
19The F nuclear magnetic spectrogram is 83.1% based on the productive rate of R 1216, and the hexafluoropropylene dimmer of formula I (a) structure accounts for 95.7%.
Embodiment 2
With 0.05 gram cuprous bromide and 0.12 gram 2,2 '-dipyridyl fully grinds, obtain cuprous bromide and 2,2 '-title complex that dipyridyl forms;
In autoclave, add said title complex and 3 milliliters of acetonitriles, freezing;
After said autoclave vacuumized/leads to nitrogen circulation 3 times; Import 16.7 gram R 1216 gases, stop after 1.5 hours, reclaim unreacted R 1216 in reaction under 20 ℃; Isolate lower floor's colourless product; Obtaining 11.4 gram hexafluoropropylene dimmers, is 68.4% based on the productive rate of R 1216, and the hexafluoropropylene dimmer of formula I (a) structure accounts for 95%.
Embodiment 3
With 0.10 gram cuprous bromide and 0.23 gram 2,2 '-dipyridyl fully grinds, obtain cuprous bromide and 2,2 '-title complex that dipyridyl forms;
In autoclave, add said title complex and 3 milliliters of acetonitriles, freezing;
After said autoclave vacuumized/leads to nitrogen circulation 3 times; Import 17.4 gram R 1216 gases, stop after 5 hours, reclaim unreacted R 1216 in reaction under 0 ℃; Isolate lower floor's colourless product; Obtaining 15.5 gram hexafluoropropylene dimmers, is 89.1% based on the productive rate of R 1216, and the hexafluoropropylene dimmer of formula I (a) structure accounts for 96.6%.
Embodiment 4
With 0.5 gram cuprous bromide and 1.15 grams 2,2 '-dipyridyl fully grinds, obtain cuprous bromide and 2,2 '-title complex that dipyridyl forms;
In autoclave, add said title complex and 15 milliliters of acetonitriles, freezing;
After said autoclave vacuumized/lead to nitrogen circulation 3 times, import 17.0 gram R 1216 gases, 20 ℃ down reaction stop after 1.5 hours; Reclaim unreacted R 1216; Isolating lower floor's colourless product, obtain 14.1 gram hexafluoropropylene dimmers, is 82.9% based on the productive rate of R 1216; The hexafluoropropylene dimmer of its Chinese style I (a) structure accounts for 67%, and the hexafluoropropylene dimmer of formula II structure accounts for 33%.
Embodiment 5
With 0.051 gram cuprous fluoride and 0.23 gram 2,2 '-dipyridyl fully grinds, obtain cuprous fluoride and 2,2 '-title complex that dipyridyl forms;
In autoclave, add said title complex and 3 milliliters of acetonitriles, freezing;
After said autoclave vacuumized/leads to nitrogen circulation 3 times; Import 17.6 gram R 1216 gases, stop after 1.5 hours, reclaim unreacted R 1216 in reaction under 20 ℃; Isolate lower floor's colourless product; Obtaining 15.7 gram hexafluoropropylene dimmers, is 89.2% based on the productive rate of R 1216, and the hexafluoropropylene dimmer of formula I (a) structure accounts for 95.5%.
Embodiment 6
0.10 gram cuprous bromide and 0.34 gram terpyridyl are fully ground, obtain the title complex that cuprous bromide and terpyridyl form;
In autoclave, add said title complex and 3 milliliters of acetonitriles, freezing;
After said autoclave vacuumized/leads to nitrogen circulation 3 times; Import 17.5 gram R 1216 gases, stop after 1.5 hours, reclaim unreacted R 1216 in reaction under 20 ℃; Isolate lower floor's colourless product; Obtaining 14.7 gram hexafluoropropylene dimmers, is 84% based on the productive rate of R 1216, and the hexafluoropropylene dimmer of formula I (a) structure accounts for 94.5%.
Embodiment 7
Adding 0.1 gram cuprous bromide and 0.255 gram pentamethyl-diethyl triamine form anti-title complex in autoclave; Import R 1216 18.1 grams, stop after 1.5 hours, reclaim unreacted R 1216 in reaction under 20 ℃; Isolate lower floor's colourless product; Obtaining 14.5 gram hexafluoropropylene dimmers, is 80.1% based on the productive rate of R 1216, and the hexafluoropropylene dimmer of its Chinese style I (a) structure accounts for 95.1%.
Comparative example 1
In autoclave, add Tetrabutyl amonium bromide as catalyzer and 3 milliliters of acetonitriles, freezing;
After said autoclave vacuumized/lead to nitrogen circulation 3 times, import 17.8 gram R 1216 gases, 20 ℃ down reaction stop after 1.5 hours, obtain the hexafluoropropylene dimmer of 0 gram I (a) structure, be 0 based on the productive rate of R 1216.
Comparative example 2
In autoclave, add cupric bromide/2,2 '-bipyridyl complexes is as catalyzer and 3 milliliters of acetonitriles, and is freezing;
After said autoclave vacuumized/lead to nitrogen circulation 3 times, import 17.8 gram R 1216 gases, 20 ℃ down reaction stop after 1.5 hours, obtain the hexafluoropropylene dimmer of 0 gram I (a) structure, be 0 based on the productive rate of R 1216.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments among this paper.Therefore, the present invention will can not be restricted to these embodiment shown in this paper, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.
Claims (10)
1. the preparation method of a hexafluoropropylene dimmer may further comprise the steps:
The title complex that forms with cuprous halide and containing n-donor ligand is a catalyzer, is medium with the aprotic polar solvent, and R 1216 is carried out oligomerisation reaction, obtains hexafluoropropylene dimmer.
2. preparation method according to claim 1 is characterized in that, said cuprous halide is cuprous fluoride, cuprous chloride, cuprous bromide or cuprous iodide.
3. preparation method according to claim 1 is characterized in that, the mol ratio of said cuprous halide and containing n-donor ligand is 1: (1～5).
4. preparation method according to claim 3 is characterized in that, the mol ratio of preferred cuprous halide and containing n-donor ligand is 1: 2.
5. preparation method according to claim 1 is characterized in that, the weight ratio of said cuprous halide and R 1216 is 1: (50～500).
6. preparation method according to claim 1; It is characterized in that the triamine that said containing n-donor ligand is bipyridyliums compound, phenanthroline compounds, the substituted Schiff bases compound of ortho position pyridyl, Tetramethyl Ethylene Diamine, connected by ethylidene, the tetramine or the terpyridyl compounds that connect by ethylidene.
7. preparation method according to claim 1 is characterized in that, said containing n-donor ligand is selected from a kind of in the following structural formula,
Wherein, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10And R
11Be respectively substituting group.
8. preparation method according to claim 1 is characterized in that, said aprotic polar solvent is acetonitrile, ETHYLE ACETATE, glycol dimethyl ether, DMSO 99.8MIN. or N, dinethylformamide.
9. preparation method according to claim 1 is characterized in that, the temperature of reaction of said oligomerisation reaction is-10～120 ℃, and the reaction times is 1.5～15 hours.
10. preparation method according to claim 1 is characterized in that, the said step that R 1216 is carried out oligomerisation reaction is specially:
Step a) adds catalyzer and aprotic polar solvent in reaction kettle, freezing, and said catalyzer is the title complex that cuprous halide and containing n-donor ligand form;
Step b) feeds R 1216 in said reaction kettle under nitrogen protection, obtain the dimer of R 1216 behind the oligomerisation reaction.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103254219A (en) * | 2013-05-09 | 2013-08-21 | 福州大学 | Copper fluoride (I) reagent as well as preparation method and application thereof |
| CN104941508B (en) * | 2015-03-24 | 2016-09-14 | 中国科学院上海有机化学研究所 | Fluorocarbon surfactant containing branch fluorocarbon chain and preparation method thereof |
| CN111056914A (en) * | 2019-12-25 | 2020-04-24 | 浙江巨化汉正新材料有限公司 | Preparation method of high-reactivity D2-structure hexafluoropropylene dimer |
| CN111116308A (en) * | 2019-12-25 | 2020-05-08 | 浙江巨化汉正新材料有限公司 | Preparation method of hexafluoropropylene dimer |
| CN113929554A (en) * | 2021-11-05 | 2022-01-14 | 浙江巨化汉正新材料有限公司 | Preparation method of hexafluoropropylene dimer with D2 structure |
| CN114853583A (en) * | 2022-06-13 | 2022-08-05 | 西安通昱科创集团有限公司 | Method for synthesizing perfluorohexanone by copper catalysis |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103254219A (en) * | 2013-05-09 | 2013-08-21 | 福州大学 | Copper fluoride (I) reagent as well as preparation method and application thereof |
| CN103254219B (en) * | 2013-05-09 | 2015-06-03 | 福州大学 | Copper fluoride (I) reagent as well as preparation method and application thereof |
| CN104941508B (en) * | 2015-03-24 | 2016-09-14 | 中国科学院上海有机化学研究所 | Fluorocarbon surfactant containing branch fluorocarbon chain and preparation method thereof |
| CN111056914A (en) * | 2019-12-25 | 2020-04-24 | 浙江巨化汉正新材料有限公司 | Preparation method of high-reactivity D2-structure hexafluoropropylene dimer |
| CN111116308A (en) * | 2019-12-25 | 2020-05-08 | 浙江巨化汉正新材料有限公司 | Preparation method of hexafluoropropylene dimer |
| CN111116308B (en) * | 2019-12-25 | 2023-07-25 | 浙江巨化汉正新材料有限公司 | Preparation method of hexafluoropropylene dimer |
| CN113929554A (en) * | 2021-11-05 | 2022-01-14 | 浙江巨化汉正新材料有限公司 | Preparation method of hexafluoropropylene dimer with D2 structure |
| CN113929554B (en) * | 2021-11-05 | 2023-10-20 | 浙江巨化汉正新材料有限公司 | Preparation method of hexafluoropropylene dimer with D2 structure |
| CN114853583A (en) * | 2022-06-13 | 2022-08-05 | 西安通昱科创集团有限公司 | Method for synthesizing perfluorohexanone by copper catalysis |
| CN114853583B (en) * | 2022-06-13 | 2024-04-02 | 西安通昱科创集团有限公司 | Method for synthesizing perfluoro-hexanone by copper catalysis |
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Application publication date: 20120620 |