CN101659602A - Method for preparing fluorine-containing vinyl ether - Google Patents
Method for preparing fluorine-containing vinyl ether Download PDFInfo
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Abstract
The invention relates to a method for preparing fluorine-containing vinyl ether, which comprises the following steps: 1) reacting a fluorine-containing acyl fluoride shown as formula (shown on the right) and an alkali metal salt/an alkali metal hydroxide in a solvent to prepare a corresponding fluorine-containing carboxylate, wherein Rfx is a fluorine-containing alkane radical which contains perfluorobenzene, O, Br, Cl or I; the weight ratio of the fluorine-containing acyl fluoride to the alkali metal salt/the alkali metal hydroxide is 1:2-3; 2) separating and drying the fluorine-containing carboxylate; and 3) thermally cracking the dried fluorine-containing carboxylate to prepare the fluorine-containing vinyl ether shown in a formula Rfx-O-CF=CF2. The method for preparing the fluorine-containing vinyl ether is suitable for preparing the fluorine-containing vinyl ether with either low boiling point or high boiling point; and the prepared fluorine-containing vinyl ether does not containharmful by-product, namely hydrogen-containing tetrafluoroethane ether, and the subsequent purification cost of a product is reduced greatly.
Description
Technical field
The invention belongs to fluorine-containing fine chemistry field.Be particularly related to a kind of preparation method who contains fluorovinyl ether.
Background technology
Containing fluorovinyl ether is a kind of important fluorine-containing fine chemicals, and the monomer copolymerization with other preparation fluoropolymers can prepare have property, materials such as the fluoro-resin that can use, viton under special conditions.
Containing fluorovinyl ether can be by containing
The fluorine-containing acyl fluorides preparation of structure, as
Deng, many patents and bibliographical information have been arranged this preparation method, the ultimate principle that has document to think to utilize fluorine-containing acyl fluorides to prepare corresponding ether is: perfluoroacyl fluoride generates perfluorocarboxylic acid salt with the salt forming agent reaction earlier, is example with yellow soda ash, and its salification process is:
Elevated temperature then, carboxylate salt decomposites CO
2And NaF, thereby prepare corresponding ether.
The main method that preparation at present contains fluorovinyl ether has two kinds: the first (U.S. Pat 3321532) fluorine-containing acyl fluorides steam through metal oxide (SiO is housed with the nitrogen gas stream band in the nickel pipe reactor
2CaO, ZnO etc.) pipeline, prepare perfluoroalkyl vinyl ether with the Pintsch process that is higher than 300 ℃, the perfluoroalkyl vinyl ether yield has reached 95% in this patent example, its preparation method is simple, the productive rate height, but contain a small amount of hydrogenous Tetrafluoroethane base ether by product in its product, because this material is for the subsequent product that contains fluroxene, the modification meeting of fluoro-resin and viton causes great influence, therefore must purify, but this by product ether be difficult to separate with usual way, so that the cost of subsequent treatment process significantly improve.The fluorine-containing acyl fluorides steam that carries with nitrogen gas stream in this method can only be the lower fluorine-containing acyl fluorides of boiling point in addition, then is not easy to carry out for the fluorine-containing acyl fluorides of high boiling point.
Another kind method is (U.S. Pat 4772756) fluorine-containing acyl fluorides and K in solvent
2CO
3Or Na
2CO
3Salify carries out cracking with about 120 ℃ temperature then in solvent, the perfluoroalkyl vinyl ether that cracking in the solvent is gone out is evaporated at last.This method is by adding N, and dinethylformamide is controlled perfluorovinyl sulfide and generated hydrogenous Tetrafluoroethane base ether.The yield of this patented method further improves, and can reach 96%, but also has following problem: 1) this method is applicable to the lower perfluoroalkyl vinyl ether of preparation boiling point, is unsuitable for preparing high boiling perfluoroalkyl vinyl ether, for example
N 〉=1; 2) can't stop the generation of hydrogenous Tetrafluoroethane base ether; 3) this method is to K
2CO
3Or Na
2CO
3, solvent, catalyzer water-content very strict requirement is arranged, reacted solvent and catalyzer are difficult to reclaim and use, and cause a large amount of solvents, catalyzer waste, cause environmental problem.
Therefore, be necessary to develop a kind of make contain the follow-up cost for purification that does not have hydrogenous Tetrafluoroethane base ether by product in the fluorovinyl ether, reduces product greatly, not only be applicable to lower boiling but also be applicable to that high boiling point contains the preparation method of fluorovinyl ether.
Summary of the invention
The purpose of this invention is to provide the method that a kind of substep preparation contains fluorovinyl ether, may further comprise the steps:
1) with general formula is
Fluorine-containing acyl fluorides and the corresponding fluorine-containing carboxylate salt of an alkali metal salt/oxyhydroxide prepared in reaction;
2) separate also dry fluorine-containing carboxylate salt, make solvent be lower than 20ppm;
3) with the fluorine-containing carboxylate thermal cracking of exsiccant, the preparation general formula is R
Fx-O-CF=CF
2Contain fluorovinyl ether.
R wherein
FxBe to contain perfluor benzene, O, Br, the fluorine-containing alkane group of Cl or I.
Fluorine-containing acyl fluorides and an alkali metal salt or oxyhydroxide react in anhydrous condition, water or organic solvent and generate fluorine-containing carboxylate salt in present method.
According to the stoichiometry mol ratio, the fluorine-containing acyl fluorides of reactant: an alkali metal salt/oxyhydroxide preferred 1: 2～3, more preferably 1: 2.05～2.2, the preferred carbonate of wherein said an alkali metal salt.
Because the reaction of fluorine-containing acyl fluorides and alkaline carbonate/oxyhydroxide is very violent thermopositive reaction, therefore need be at low temperature, have and stir and have under the condition of condensation reflux unit, fluorine-containing acyl fluorides slowly is added drop-wise in alkaline carbonate/oxyhydroxide carries out, when under anhydrous condition, reacting, answer control reaction temperature to be lower than-30 ℃, preferably be lower than-70 ℃; When reacting in solvent, control reaction temperature is not more than 100 ℃, preferably is lower than 50 ℃.Above-mentioned solvent comprises water and organic solvent, and organic solvent is mainly selected pure ether solvent for use, and this kind solvent mainly contains diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dibutyl ethylene glycol ether, diethylene glycol dimethyl ether, diethylene glycol ether, Diethylene Glycol butyl ether or the like; Can be other organic alcohols solvents, for example: methyl alcohol, ethanol, two propyl alcohol or the like; Can be nitrile solvents, as acetonitrile, propionitrile etc.Can use the alkane solvents of halogen atom, for example: chloroform, tetracol phenixin, Freon 113 (F113) etc.The water content of solvent does not have strict the qualification, preferably water-content is controlled at below the 200ppm.
After reaction is finished, filter or centrifugation solvent and fluorine-containing carboxylate salt, the recyclable utilization of organic solvent, with the fluorine-containing carboxylate salt that makes under the condition of decompression, to be not more than 100 ℃ the thorough oven dry of the temperature solvent wherein and the water of trace, water-content will be lower than 20ppm at least, and it is better to be lower than 10ppm, is preferably lower than 5ppm.
Through after dehydration or desolventizing and the drying, with conditioned disjunction in exsiccant nitrogen gas stream the cracking of fluorine-containing carboxylate salt in decompression, split product can adopt and vacuumize or way that nitrogen carries is taken out of from reactor, and collects with cold-trap.The cracking temperature that present method adopts can be selected according to the difference of material, be generally 150～250 ℃, preferred 190～220 ℃, also can progressively improve temperature and carry out the substep cracking, 150 ℃ of beginnings, improve 10 ℃ of cracking then successively, all complete up to cracking, each cracking time period can decide according to practical situation.
Because fluorine-containing carboxylate salt very easily absorbs water, when generally it being transferred to cracking apparatus, may have the part deliquescence, so before cracking, be necessary to dry for some time being not more than under 100 ℃ of temperature, the moisture finish-drying with absorbing carries out scission reaction then again.
The general formula that the present invention adopts is
Fluorine-containing acyl fluorides can be by fluorine-containing carbonyl compound
Addition reaction with Propylene oxide hexafluoride under catalyzer and solvent action prepares, wherein R
FyAnd R
FzCan for-F or fluorine-containing alkyl.As US4035388 described fluorine-containing carbonyl compound in dimethylin difluoro phosphine and diglyme with the method for the fluorine-containing acyl fluorides of Propylene oxide hexafluoride prepared in reaction; It is catalyzer and the fluorine-containing acyl fluorides of Propylene oxide hexafluoride prepared in reaction with the cesium fluoride in the di-alcohol dme that USP3274239 has narrated fluorine-containing carbonyl compound; USP3250808 prepares the Propylene oxide hexafluoride autohemagglutination
Carried out more detailed narration, also generated corresponding simultaneously some other fluorine-containing acyl fluorides and Propylene oxide hexafluoride
Narrate.Therefore, can be relatively easy to obtain to have
The fluorine-containing acyl fluorides of structure.The preparation of fluorine-containing acyl fluorides mainly is by containing among the present invention
The fluorine-containing acyl fluorides of structure, fluorinated ketones contained etc. and Propylene oxide hexafluoride are that the catalyzer addition reaction generates with the metal halide in polar solvent.Wherein polar solvent is anhydrous methanol, anhydrous diethylamine, anhydrous acetonitrile etc.; Catalyzer is a metal halide, and exemplary is: cesium fluoride, Potassium monofluoride, cesium bromide, cupric chloride etc.Table 1 has simply been introduced preparation and the corresponding fluorovinyl ether that contains thereof that preparation contains the part fluorine-containing acyl fluorides of fluorovinyl ether.
Table 1 contains the corresponding raw material of fluorovinyl ether
The present invention utilizes fluorine-containing acyl fluorides to prepare step by step to contain fluorovinyl ether, containing of obtaining do not contain hydrogenous Tetrafluoroethane base ether by product in the fluorovinyl ether, the solvent that uses in the reaction process can be recycled at an easy rate, productive rate is higher, not only is applicable to lower boiling but also be applicable to that high boiling point contains the preparation of fluorovinyl ether.
Embodiment
Following examples are used to illustrate the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
Experimental installation is the 250ml stainless steel cauldron that has condensation reflux unit and stirring, reactor is placed cold-trap, the KOH aqueous solution 150ml that adds 20wt%, under vigorous stirring, slowly splash into perfluor-2-methoxy propyl acyl fluorides 50g (stratographic analysis purity 99%), temperature of reaction is-10 ℃, and reaction times 30min is dried moisture with 90 ℃ in a vacuum with reaction product, get drying solid 75g, record water-content less than 20ppm.
To dry solid and put into the 250ml stainless steel cauldron, reactor has decompression condensation retrieving arrangement and thermometer, 100 ℃ of temperature, secondary drying is 12 hours under the condition of absolute pressure 50mmHg, elevated temperature to 220 ℃ cracking is 1 hour then, condenser is collected product 31g, stratographic analysis perfluoro methyl vinyl ether content 70.6% under the reduced pressure.
Embodiment 2
Experimental installation is the 250ml stainless steel cauldron that has condensation reflux unit and agitator, and reactor is placed cold-trap, adds the K of 35g
2CO
3, under vigorous stirring, slowly splash into perfluor-2-propoxy-propionyl fluoride 80g (stratographic analysis purity 99%), temperature of reaction-30 ℃, reaction times 20min.The centrifugation reaction product will be dried moisture and solvent with 90 ℃ in the reaction product vacuum then, get drying solid 106g, record water-content less than 10ppm.
To dry solid and put into the 250ml stainless steel cauldron, reactor band decompression condensation retrieving arrangement and thermometer, 100 ℃ of temperature, baking is 12 hours under the condition of absolute pressure 50mmHg, elevated temperature to 210 ℃ then, be incubated 1.5 hours, the reduced pressure condenser is collected product 53g, stratographic analysis perfluor n-propyl vinyl ether content 64.3%.
Embodiment 3
Experimental installation is the 250ml stainless steel cauldron that has condensation reflux unit and stirring, and reactor is placed cold-trap, adds the K of 20g
2CO
3And 150ml F113, under vigorous stirring, slowly splashing into perfluor-2-propoxy-propionyl fluoride 80g (stratographic analysis purity 99%), 40 ℃ of temperature of reaction were reacted 30 minutes.Centrifugation solid after reaction is finished, and under vacuum condition, dry moisture and solvent for 90 ℃, get drying solid 107g.
Drying solid is transferred to the 250ml stainless steel cauldron, reactor band decompression condensation retrieving arrangement and thermometer, 100 ℃ of temperature, baking is 12 hours under the condition of absolute pressure 50mmHg, elevated temperature to 190 ℃ then, be incubated 2 hours, condenser is collected product 56g, stratographic analysis perfluor n-propyl vinyl ether content 78.5% under the reduced pressure.
Embodiment 4
Experimental installation is the 250ml stainless steel cauldron that has condensation reflux unit and stirring, and reactor is placed cold-trap, adds KOH and the 150ml chloroform of 30g, slowly splashes into CF under vigorous stirring
3CF
2CF
2-O-CF (CF
3) CF-O-CF (CF
3) CFO 120g (stratographic analysis purity 96%), 50 ℃ of temperature of reaction were reacted 30 minutes.Centrifugation solid after reaction is finished, and vacuum gets drying solid 146g with 90 ℃ of oven dry.
Drying solid is transferred to the 200ml stainless steel cauldron, reactor band decompression condensation retrieving arrangement and thermometer, 100 ℃ of temperature, baking is 12 hours under the condition of absolute pressure 50mmHg, elevated temperature to 240 ℃ then, be incubated 2.2 hours, condenser is collected product 98g, stratographic analysis CF under the reduced pressure
2CF
2-O-CF (CF
3) CF-O-CF=CF
2Content 73.7%.
Embodiment 5
Experimental installation is the 250ml stainless steel cauldron that has condensation reflux unit and stirring, and reactor is placed cold-trap, adds KOH and the 150ml chloroform of 30g, slowly splashes into BrF under vigorous stirring
2CCF
2OCF (CF
3) CFO 80g (stratographic analysis purity 97%), 30 ℃ of temperature of reaction were reacted 15 minutes.Centrifugation solid after reaction is finished, and vacuum gets drying solid 103g with 90 ℃ of oven dry.
Drying solid is put into the 250ml stainless steel cauldron, reactor band decompression condensation retrieving arrangement and thermometer, 100 ℃ of temperature, baking is 12 hours under the condition of absolute pressure 50mmHg, elevated temperature to 200 ℃ then, be incubated 2.5 hours, condenser is collected product 60g, stratographic analysis BrF under the reduced pressure
2C-CF
2-O-CF=CF
2Content 79.4%.
Embodiment 6
Experimental installation is the 250ml stainless steel cauldron that has condensation reflux unit and stirring, and reactor is placed cold-trap, adds KOH and the 150ml diethylene glycol dimethyl ether of 30g, slowly splashes into 80g under intense agitation
(wherein n=0 content 80.5%, n=1 content 12.8%, n=2 content 5.0%), 30 ℃ of temperature of reaction were reacted 18 minutes.Centrifugation solid after reaction is finished, and 90 ℃ of oven dry of vacuum get drying solid 101g.
Drying solid is put into the 250ml stainless steel cauldron, and reactor band decompression condensation retrieving arrangement and thermometer are 100 ℃ of temperature, baking is 12 hours under the condition of absolute pressure 50mmHg, and elevated temperature to 190 ℃ is incubated 3 hours then, condenser is collected product 54g, stratographic analysis under the reduced pressure
Total content 82.6%, wherein n=0 accounts for 68.0%, and n=1 accounts for 10.9%, and n=2 accounts for 3.9%.
Embodiment 7
Experimental installation is the 3000ml stainless steel cauldron that has condensation reflux unit and stirring, and reactor is placed cold-trap, adds the K of 360g
2CO
3And the 1800ml diethylene glycol dimethyl ether, under intense agitation, slowly splashing into perfluor-2-propoxy-propionyl fluoride 1240g (stratographic analysis purity 99%), 30 ℃ of temperature of reaction were reacted 30 minutes.Centrifugation solid after reaction is finished, and 90 ℃ of oven dry of vacuum get drying solid.
It is 50mm that drying solid is put into diameter, long in the 900mm cracking furnace pipe, pyrolyzer pipe racks nitrogengas cylinder, condensation retrieving arrangement and thermometer are 100 ℃ of temperature, baking is 20 hours under the condition of gauge pressure 0.15MPa, elevated temperature to 150 ℃ then, insulation 10min, the speed with 1 ℃/min slowly heats up then, until 210 ℃, be incubated 4 hours, condenser is collected the product 725g that is taken out of by nitrogen, stratographic analysis perfluor n-propyl vinyl ether content 84.4%.
Embodiment 8
Experimental installation is the 3000ml stainless steel cauldron that has condensation reflux unit and stirring, and reactor is placed cold-trap, adds KOH and the 1800ml F113 of 360g, slowly splashes into mixture under intense agitation
(wherein n=0 content 80.5%, n=1 content 12.8%, n=2 content 5.0%), 20 ℃ of temperature of reaction were reacted 30 minutes.The centrifugation solid, and vacuum gets drying solid 1231g with 90 ℃ of oven dry.
It is 50mm that solid is put into diameter, long in the 900mm cracking furnace pipe, pyrolyzer pipe racks vacuum condensation retrieving arrangement and thermometer, 100 ℃ of temperature, baking is 12 hours under the condition of absolute pressure 50mmHg, and elevated temperature to 240 ℃ is incubated 4 hours then, condenser is collected product 706g, stratographic analysis stratographic analysis
Total content 80.2%, wherein n=0 accounts for 62.0%, and n=1 accounts for 12.4%, and n=2 accounts for 5.8%.
The above only is a preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the technology of the present invention principle; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1, a kind of preparation method who contains fluorovinyl ether may further comprise the steps:
1) with general formula is
Fluorine-containing acyl fluorides and an alkali metal salt/oxyhydroxide in solvent, react, prepare corresponding fluorine-containing carboxylate salt, described fluorine-containing acyl fluorides, the ratio of the amount of substance of an alkali metal salt/oxyhydroxide is 1: 2～3;
2) separate also dry fluorine-containing carboxylate salt, make solvent be lower than 20ppm;
3) with the fluorine-containing carboxylate thermal cracking of exsiccant, the preparation general formula is R
Fx-O-CF=CF
2Contain fluorovinyl ether,
R wherein
FxBe to contain perfluor benzene, O, Br, the fluorine-containing alkane group of Cl or I.
2, the method for claim 1 is characterized in that, an alkali metal salt described in the step 1) is an alkaline carbonate.
3, the method for claim 1 is characterized in that, solvent described in the step 1) is water or organic solvent.
4, method as claimed in claim 3 is characterized in that described organic solvent is selected from alcohol ether, alcohol, nitrile or contain in the halocarbon one or more.
5, the method for claim 1 is characterized in that, fluorine-containing acyl fluorides described in the step 1) is 1: 2.05～2.2 with the ratio of the amount of substance of an alkali metal salt/oxyhydroxide.
6, the method for claim 1 is characterized in that, the temperature of reaction of the reaction of described step 1) is below 100 ℃.
7, the method for claim 1 is characterized in that, the described general formula of described step 1) is
Fluorine-containing acyl fluorides and the reaction of an alkali metal salt/oxyhydroxide can under condition of no solvent, carry out, control its temperature of reaction below-30 ℃.
8, the method for claim 1, it is characterized in that, step 2) described separation and drying can followingly be carried out: by filtering or the method for centrifugation is isolated fluorine-containing carboxylate salt from solvent, and in decompression or dry nitrogen air-flow, carry out drying and dehydrating, desolventizing, drying temperature is not more than 100 ℃, is no more than 20ppm until the moisture and quantity of solvent of fluorine-containing carboxylate salt.
9, the method for claim 1 is characterized in that, the described thermo-cracking of step 3) is to carry out heating pyrolyze in decompression or drying nitrogen or helium flow, and cracking temperature is 150～250 ℃.
10, method as claimed in claim 9 is characterized in that, described cracking temperature is 190～220 ℃.
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| CN102516039A (en) * | 2011-11-16 | 2012-06-27 | 中昊晨光化工研究院 | Preparation method of fluorine-containing vinyl ether |
| JP2013060412A (en) * | 2011-08-22 | 2013-04-04 | Unimatec Co Ltd | Method of manufacturing perfluoroalkyl vinyl ether |
| CN103965023A (en) * | 2013-01-31 | 2014-08-06 | 中化蓝天集团有限公司 | Fluoroalkylvinyl ether preparation method |
| CN106146294A (en) * | 2015-04-08 | 2016-11-23 | 中化近代环保化工(西安)有限公司 | A kind of perfluoro methyl vinyl ether and the production method of intermediate thereof |
| CN111116326A (en) * | 2019-12-30 | 2020-05-08 | 天津市长芦化工新材料有限公司 | Polyol type fluorine-containing additive and preparation method thereof |
| CN112778101A (en) * | 2018-03-23 | 2021-05-11 | 金华永和氟化工有限公司 | Method for preparing perfluoroalkyl vinyl ether by taking carboxylate solution as raw material |
| WO2022010204A1 (en) * | 2020-07-07 | 2022-01-13 | 한국화학연구원 | Method for preparing perfluoromethylvinyl ether having high conversion rate |
| CN116178218A (en) * | 2022-12-15 | 2023-05-30 | 福建科润世纪氢能材料有限公司 | Preparation method of novel fluorosulfonyl difluoromethylene trifluoro vinyl ether |
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| US6624328B1 (en) * | 2002-12-17 | 2003-09-23 | 3M Innovative Properties Company | Preparation of perfluorinated vinyl ethers having a sulfonyl fluoride end-group |
| US7176331B2 (en) * | 2005-06-30 | 2007-02-13 | 3M Innovative Properties Company | Method of making fluorinated vinyl ethers |
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| JP2013060412A (en) * | 2011-08-22 | 2013-04-04 | Unimatec Co Ltd | Method of manufacturing perfluoroalkyl vinyl ether |
| CN102516039A (en) * | 2011-11-16 | 2012-06-27 | 中昊晨光化工研究院 | Preparation method of fluorine-containing vinyl ether |
| WO2013071780A1 (en) | 2011-11-16 | 2013-05-23 | 中昊晨光化工研究院有限公司 | Method for preparing fluorine-containing vinyl ether |
| US8981162B2 (en) | 2011-11-16 | 2015-03-17 | Zhonghao Chenguang Research Institute Of Chemical Industry Company Limited | Method for preparing fluorine-containing vinyl ether |
| CN103965023A (en) * | 2013-01-31 | 2014-08-06 | 中化蓝天集团有限公司 | Fluoroalkylvinyl ether preparation method |
| CN103965023B (en) * | 2013-01-31 | 2016-05-11 | 中化蓝天集团有限公司 | A kind of preparation method of fluoro-alkyl vinyl ethers |
| CN106146294B (en) * | 2015-04-08 | 2022-06-21 | 中化近代环保化工(西安)有限公司 | Production method of perfluoromethyl vinyl ether and intermediate thereof |
| CN106146294A (en) * | 2015-04-08 | 2016-11-23 | 中化近代环保化工(西安)有限公司 | A kind of perfluoro methyl vinyl ether and the production method of intermediate thereof |
| CN112778101A (en) * | 2018-03-23 | 2021-05-11 | 金华永和氟化工有限公司 | Method for preparing perfluoroalkyl vinyl ether by taking carboxylate solution as raw material |
| CN112778101B (en) * | 2018-03-23 | 2022-05-10 | 金华永和氟化工有限公司 | Method for preparing perfluoroalkyl vinyl ether by taking carboxylate solution as raw material |
| CN111116326A (en) * | 2019-12-30 | 2020-05-08 | 天津市长芦化工新材料有限公司 | Polyol type fluorine-containing additive and preparation method thereof |
| WO2022010204A1 (en) * | 2020-07-07 | 2022-01-13 | 한국화학연구원 | Method for preparing perfluoromethylvinyl ether having high conversion rate |
| KR20220005777A (en) * | 2020-07-07 | 2022-01-14 | 한국화학연구원 | Method for preparing perfluoromethyl vinyl ether with high conversion rate |
| KR102477162B1 (en) | 2020-07-07 | 2022-12-13 | 한국화학연구원 | Method for preparing perfluoromethyl vinyl ether with high conversion rate |
| CN116178218A (en) * | 2022-12-15 | 2023-05-30 | 福建科润世纪氢能材料有限公司 | Preparation method of novel fluorosulfonyl difluoromethylene trifluoro vinyl ether |
| CN116178218B (en) * | 2022-12-15 | 2023-10-17 | 福建科润世纪氢能材料有限公司 | Preparation method of novel fluorosulfonyl difluoromethylene trifluoro vinyl ether |
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