CN1061399A - The production method of polyfluoroolefins - Google Patents

The production method of polyfluoroolefins Download PDF

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CN1061399A
CN1061399A CN91110828A CN91110828A CN1061399A CN 1061399 A CN1061399 A CN 1061399A CN 91110828 A CN91110828 A CN 91110828A CN 91110828 A CN91110828 A CN 91110828A CN 1061399 A CN1061399 A CN 1061399A
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C·G·克雷斯彭
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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
    • 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
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/125—Halogens; Compounds thereof with scandium, yttrium, aluminium, gallium, indium or thallium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
    • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
    • C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C23/00—Compounds containing at least one halogen atom bound to a ring other than a six-membered aromatic ring
    • C07C23/02—Monocyclic halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C23/00—Compounds containing at least one halogen atom bound to a ring other than a six-membered aromatic ring
    • C07C23/02—Monocyclic halogenated hydrocarbons
    • C07C23/08—Monocyclic halogenated hydrocarbons with a five-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/04—Systems containing only non-condensed rings with a four-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

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  • Engineering & Computer Science (AREA)
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Abstract

The present invention relates to a kind of multi-fluoro allyl fluorid catalysis addition fluorinated ethylene and produce the method for multi-fluoro olefins.Form adducts and the F-amylene-2 and the F-amylene-3 of 1: 1 and 1: 2 selectively, further be reduced to dihydro or trihydrogen polyfluoro alkane again, they can be used as the HFC sanitising agent.

Description

The production method of polyfluoroolefins
The present invention relates to the method that multi-fluoro allyl fluorid catalysis adds becomes fluorinated ethylene production multi-fluoro olefins.Form the adducts of 1: 1 and 1: 2 such as F-amylene-2 and F-teracrylic acid selectively and further be reduced to dihydro or three hydrogenation polyfluoro paraffinic hydrocarbonss again, they can be used as the HFC sanitising agent.High boiling product (for example boiling point is higher than 100 ℃) can be used as solvent and stabilising liq, especially two keys be hydrogenated fluoridize or the saturated back of chlorination all the more so.
Various catalyzer for multi-fluoro allyl fluorid addition fluorinated ethylene are known.
G.G.Belen ' the Kii of heterocyclic organic compounds institute of Soviet Union academy of sciences (Moscow), E.p.Lur ' e and L.S.German, UDC66,095,253:547 413(1975) uses SbF 5Use perfluoro propylene and 2-H-perfluoro propylene to carry out the alkylation of the fluorine derivative of ethene as catalyzer.
Chang-Ming Hu, Hui Liu and Ze-Qi Xu, studied the reaction of perchloro-fluorine cpd VI, the reaction of the rearrangement of senior perchloro-fluoroolefin and they and nucleophilic reagent and electrophilic reagent is pointed out that the alkali fluoride ion can be induced to form the TFE/HFP adducts.
The present invention uses a kind of fontanelle compound of aluminium that the allyl group fluoride-catalyzed is added becomes fluorinated ethylene.
The invention provides the method that a kind of production has the multi-fluoro olefins of at least 5 carbon atoms, this method comprises first kind of multi-fluoro olefins with following structure
Figure 911108289_IMG4
R wherein 1Be F, Cl, H or R f;
R 2Be F, Cl, H or R f;
R 3Be F, Cl, H or R f;
R fBe C 2-12Perfluoroalkyl, also can contain 1 H or 1 Cl;
R 4Be CF 3Or and R 2Be together-(CF 2) n-, wherein n is 2,3 or 4;
With structure be R 5R 6C=CF 2(R wherein 5Be F, H or Cl; And
R 6Be F or CF 3) second kind of multi-fluoro olefins be AlX at structural formula 3The catalyzer of (wherein X is one or more F, Cl or Br, and regulation X can not be F fully) reacts under existing.
The invention still further relates to the alkene of following structural
(this structure is a raw material In R 4Be CF 3And other variable is by above-mentioned definition)
The invention still further relates to the alkene of following structural
;
Following (the R wherein of the reaction formula of desired addition reaction 4Be CF 3):
Figure 911108289_IMG7
R wherein 1, R 2, R 3, R 5And R 6Above define by the present invention.
Structure shown in the allyl group fluorochemical both can have also can be reset this structure by the fluorochemical migration.
Structure shown in product equally both can have also can have the fluorochemical migration and the structure of formation.
The structure of catalyst system therefor is AlX 3, wherein X is one or more F, Cl or Br, and to require X can not be F fully.Active catalyst can prepare in advance, as the most of example in the table 1, also can prepare with allyl group fluorochemical replacing section halogen F at the scene, as the 5th and the 9th.Preferred catalyzer is AlF xCl y(blended aluminum halide), wherein the total atom number of halogen is x+y=3, and x is from 0～2.95, y is from 3～0.05.Available active C-F compound such as CF 3CF=CF 2, CFCl 3Or CHFCl 2Pre-treatment AlCl 3Prepare AlF xCl y
Temperature range depends on the reactivity of reagent from-20 ℃～150 ℃, but preferred range is 20 ℃～85 ℃.Pressure can change to being higher than in 50 barometric pressure range being lower than 1 normal atmosphere, but preferred 1～20 normal atmosphere.The time of batch reactions was depended on batch weight from 5 minutes～about 2 days.The time of successive reaction was from 1/2～120 minute.Reacting body is depended in the variation in reaction times, temperature, pressure and catalyst amounts.
Reaction is a liquid phase reaction, can carry out by several modes; Batch-type is added to reacted constituent and catalyzer in the cold reactor, is heated to temperature of reaction; Semi-batch is injected a container with one or both reacted constituents (wherein can contain catalyzer) under temperature of reaction, this reactor contain catalyzer and or another kind of reacted constituent; Or continous way, with reactive component (preferably partial liquefaction, and can contain catalyzer) continuously by conversion zone, reaction zone also can contain catalyzer.Catalyzer must be present in the reaction mixture or in the conversion zone, but also can be present in this two places.Allyl group fluorochemical (for example HFP) can be changed to 1: 50 from 5: 1 to the reacted constituent mol ratio of fluoro chain hydrocarbon (for example TFE) (when they are inequality).When expecting 1 to 1 adducts of high yield, use 5: 1～1: 1 ratio usually.Add to be shaped as 1 to 2 and during the adducts of Geng Gao when what want to make fluorinated ethylene, especially when fluoridizing alkene and be tetrafluoroethylene (TFE), use 1: 1 to 1: 50 ratio.Catalyst consumption is 0.5～20(weight of the total charging capacity of reactant in the batch reactions) %, preferred 2～8(weight) %.
Employed solvent is not important, but can use the material such as the phenyl-hexafluoride of relative inertness, F-normal hexane, ClCF 2CF 2Cl, SO 2ClF, CF 3CF 2CHCl 2, ClCF 2CF 2CHFCl, CF 3CHFCHFCF 2CF 3, CF 3CHFCH 2CF 2CF 3, F-amylene-2, CF 3CH 2CHFCF 2CF 3, ClCF 2CFCl 2, CF 3CCl 3, CF 3CCl 2CF 3, CF 3CHCl 2, perfluor-1,2-dimethyl tetramethylene, CCl 2=CCl 2, CCl 2=CHCl, and CF 3CF 2CF 2O (CF(CF 3) CF 2O) nCHFCF 3
Table 1 is depicted as each embodiment and reaction conditions.Can see some records in table 1, use therein tetrafluoroethylene (TFE) has surpassed R 1216 (HFP) in a large number, and obviously condensation of TFE itself as a result produces even number of carbon atoms in the fluoroolefins product.When TFE quantitatively increased the repetition addition of HFP, the branching in the product alkene was just obvious more.Therefore, C 5F 10And C 7F 14Be linear product, C 9F 18Major part is linear, C 11F 22More its (RF) in the high-grade product 2C=CFR fThe quantity of type structure increases.The mixture of these high boiling liquids by hydrogenation, chlorination or fluoridize be converted into have high boiling point more, more stable liquid.
Here said synthetic adducts such as the F-amylene-2(CF that can be used for forming 1: 1 and 1: 2 3CF=CFCF 2CF 3) and the F-teracrylic acid, it can be reduced the formation sanitising agent.Chlorination that also can be by two keys, fluoridize or hydrogenation forms more the high-grade adducts as the source of reaction solvent not, steam degreasing agent, and stabilising liq.
Example 1
In 400 milliliters metal tube, charge into 16.4 gram fluorizated AlCl 3(AlCl 3+ CFCl 3), 100 gram (0.5 moles) 1,1,2-three chloro-3,3,3-trifluoro propene and 50 gram (0.50 mole) tetrafluoroethylene stirred 1.5 hours under 25 ℃ of conditions, and this product liquid mixture of fractionation provides the CF that 25.4 grams (25%) reclaim 3CCl=CCl 2, secondly be 42.3 gram (38% productive rate) F-1,1,2-trichlorine amylene-1, boiling point 63-66 ℃ (100mm) is by the IR(infrared spectrum), the NMR(nucleus magnetic resonance) and GC/MS(gas chromatography method) identify.Further fractionate out 23.3 gram (15%) F-1,1,2-tetrachloro amylene-1 and F-1,1, the heterogeneous mixture of 1-2-tetrachloro amylene-2, boiling point 86-89 ℃ (100mm) uses IR equally, and NMR and GC/MS identify.Also there are 2: 1 adductss of some high boiling points.
The reaction formula of reaction is as follows:
Example 2
In the 400ml metal tube, under-20 ℃ of conditions, charge into 8.0 gram AlF 2.8Cl 0.2(from AlCl 3+ CFCl 3Preparation), 75 gram (0.50 mole) R 1216s (HTP) and 50 gram (0.50 mole) tetrafluoroethylene (TFE) shake metal tube 30 minutes, simultaneously temperature are risen to 20 ℃ fast, and pressure is reduced to 8psi.Distill this product and obtain 88.0 gram (70%) F-amylenes-2, boiling point 23-26 ℃, identify with IR, NMR and GC/MS.NMR shows that this product is 89% trans-isomer(ide) and 11% cis-isomeride.
Example 3
CF 3CF=CF 2/ CF 2=CF 2The reaction of carrying out with 1: 2 ratio
Cold feed 3 gram AlF in the 400ml metal tube xCl 3-x(by using CF 3Cl 3Handle aluminum chloride and prepare the fluorizated aluminum chloride catalyst), 40 gram (0.27 mole) R 1216s, with 50 gram (0.50 mole) tetrafluoroethylene, stirred 2 hours down at 25 ℃, stirred 4 hours down, analyze the product liquid of 73 grams with GC and MS at 80 ℃, show and have 28.2 gram (42%) perfluor amylenes-2,42.2 gram (48%) perfluor heptene isomer, 2.7 gram (4%) perfluorinated nonene isomer,＜0.7 gram (1%) C 11F 22Isomer, the higher oligomers of trace also detects very a spot of perfluor hexene and perfluoro caprylene simultaneously.Fractionation obtains 21.9 gram (32%) perfluor amylenes-2, and boiling point 24-26 ℃ then is 34.1 gram (39%) perfluor heptene, boiling point 69.5-71 ℃.Analyze middle portion (70.9 ℃ of boiling points) with IR and NMR, show that most of composition is that trans perfluor teracrylic acid has only a small amount of other isomer to exist.Continue fractionation and obtain 1.2 gram (2%) perfluorinated nonenes, boiling point 66-68 ℃ (150mm) represents that with IR and NMR analysis it mainly is made up of trans perfluorinated nonene-4 and trans perfluorinated nonene-3.
Example 4
CF 3CF=CF 2/ CF 2=CF 2The reaction of carrying out with 1: 4 ratio
Cold feed 5.0 gram AlF in the 400ml metal tube xCl 3-x, 40 gram (0.27 mole) R 1216s and 50 gram (0.50 mole) tetrafluoroethylene shake metal tube 30 minutes at 25 ℃, and pressure is reduced to 0psi simultaneously.Add other 50 gram (0.50 mole) tetrafluoroethylene, this mixture was stirred 4 hours at 25 ℃, pressure is reduced to 0psi more simultaneously.Analyze 122 gram product liquids with GC and MS, show to have 34.5 gram (37% productive rate) perfluor heptene, 59.0 gram (49%) perfluorinated nonenes, 22.2 gram (15%) perfluor undecylenes and 2.0 gram (1%) perfluor tridecylenes.Also detect 0.5～1% perfluor alkene (C with even carbon atom 6F 12, C 8F 16And C 10F 20).Distillation obtains a series of cuts, 66 ℃ of boiling points (1 normal atmosphere)-66 ℃ (18mm), and this is that analysis by GC, IR and NMR obtains.71-72 ℃ of ebullient product show it by straight chain trans-perfluor teracrylic acid and trans-and cis-perfluor heptene-2 form, and exist a small amount of branched-chain alkene (as, CF 3CF 2C(CF 3)=CFCF 2CF 3).Also find boiling point be the product of 74-80 ℃ (200mm) mainly be straight chain trans-perfluorinated nonene-4 and trans-perfluorinated nonene-3, in boiling point is the cut of 74 ℃ (200mm), have 50% side chain perfluorinated nonene, in boiling point is the cut of 76-80 ℃ (200mm), have to be low to moderate about 5% branched-chain alkene.Boiling point is that the mixing perfluor undecylene of 70-77 ℃ (50mm) shows it mainly is (R f) 2C=CFR fType branched structure and a small amount of R fCF=CFR fLinear alkene composition.
Example 5
The CF that equates mole number 3CF=CF 2And CF 2=CF 2With AlCl 3Catalyzer is at CCl 2=CCl 2Reaction in the solvent
Cold feed 5.0 gram aluminum chloride in pipe, 100 milliliters of zellons, 75 gram (0.50 mole) R 1216s and 50 gram (0.50 mole) tetrafluoroethylene shook pipe 4 hours under 25-30 ℃ and pressure is reduced to 69psi.Then with reaction mixture 60 ℃ of down heating 10 hours and pressure is reduced to 45psi.Biphase product liquid distillation is obtained 4ml foreshot, then is 58.4 gram (47%) perfluor amylenes-2, and boiling point 10-25 ℃, it almost is 100% pure being analyzed by GC.
Ethylene tetrachloride is preferred solvent, because under reaction conditions, it has validity and relative inertia, and separates the adducts from lower boiling 1: 1 with 1: 2 easily.
Figure 911108289_IMG8
Figure 911108289_IMG10
Figure 911108289_IMG13
Figure 911108289_IMG14
Although more than narrated the preferred embodiments of the present invention, the structure of the strictness of the present invention that is not limited to here certainly to be disclosed, and can further think and keep right to the contact transformation in the claims limited range of the present invention.

Claims (26)

1, a kind of preparation has the method for the multi-fluoro olefins of at least 5 carbon atoms, comprises first kind of multi-fluoro olefins with following structure
Figure 911108289_IMG1
R wherein 1Be F, Cl, H or Rf;
R 2Be F, Cl, H or Rf;
R 3Be F, Cl, H or Rf;
R fBe C 2～C 12Perfluoroalkyl, also can contain 1 H or 1 Cl;
R 4Be CF 3Or and R 2Be together-(CF 2) n-; Wherein n is 2,3, or 4;
With structure be R 5R 6C=CF 2Second kind of polyfluoroolefins (wherein:
R 5Be F, H or Cl;
R 6Be F or CF 3)
In structure is AlX 3The catalyzer of (wherein X is one or more F, Cl or Br, and regulation X can not be F fully) reacts under existing.
2, the method for claim 1 is to carry out in-20 ℃～150 ℃ temperature range.
3, the method for claim 2, wherein temperature is 0 ℃～100 ℃.
4, the method for claim 1 is carried out under 1 atmospheric pressure.
5, the method for claim 1 was carried out with about 5 minutes to about 2 days in batches.
6, the method for claim 1 was carried out continuously with 1/2 minute～120 minutes.
7, the process of claim 1 wherein that reactant and catalyzer put into cold reactor in batches, and then be heated to temperature of reaction.
8, the process of claim 1 wherein one or both reactants are injected the container that contains catalyzer under temperature of reaction that this reaction is that semi-batch is carried out.
9, the process of claim 1 wherein a kind of reactant and catalyzer be injected into the reaction semi-batch is carried out.
10, the process of claim 1 wherein that with reactant by containing the reaction zone of catalyzer, this method is the reaction of operation continuously.
11, the method for claim 10, wherein reactant to small part is a liquid.
12, the process of claim 1 wherein that the reactant of partially liq at least that will contain catalyzer passes through a reaction zone, this method is the reaction of carrying out continuously.
13, the method for claim 11, wherein the partially liq reactant also contains catalyzer at least.
14, the method for claim 1 is carried out in the solvent of relative inertness.
15, the method for claim 14, wherein solvent is selected from phenyl-hexafluoride, F-normal hexane, ClCF 2CF 2Cl, SO 2ClF, CCl 4, CF 3CF 2CHCl 2, ClCF 2CF 2CHFCl, CF 3CHFCHFCF 2CF 3, CF 3CHFCH 2CF 2CF 3, F-amylene-2, CF 3CH 2CHFCF 2CF 3, ClCF 2CFCl 2, CF 3CCl 3, CF 3CCl 2CF 3, CF 3CHCl 2, perfluor-1,2-dimethyl tetramethylene, CCl 2=CCl 2, CCl 2=CHCl, and CF 3CF 2CF 2O (CF(CF 3) CF 2O) n-CHFCF 3
16, the method for claim 2, wherein reactant is
Figure 911108289_IMG2
R wherein 1Be F, Cl, H or R f, and
R 3Be F, Cl, H, or R f
17, the process of claim 1 wherein that first kind of fluoroolefin is R 1216 (HFP), second kind of polyolefine is tetrafluoroethylene (TFE).
18, the method for claim 17, wherein used TFE is excessive with respect to the consumption of HFP.
19, the process of claim 1 wherein that first kind of excessive multi-fluoro olefins of use is excessive with respect to the consumption of second kind of multi-fluoro olefins.
20, the method for claim 17, wherein HFP to the ratio range of TFE from 5: 1～1: 50.
21, the method for claim 17, some of them fluoroolefins product contains even number of carbon atoms.
22, the method for claim 17, some of them fluoroolefins product contains branch.
23, a kind of structural formula is
Figure 911108289_IMG3
Synthetics, R wherein 1, R 3, R 5, R 6With n definition as claimed in claim 1.
24, containing molecular formula is C mF 2mThe liquid phase mixture (wherein m is the integer more than or equal to 11) of perfluorinated olefins, be by the method preparation of claim 17.
25, a kind of structural formula is CF 3CCl=CClCF 2CF 2CF 3Synthetics.
26, a kind of structural formula is CF 3CF 2CF 2CCl=CClCF 2CF 2CF 3Synthetics.
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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
CN113906003A (en) * 2019-04-18 2022-01-07 科慕埃弗西有限公司 Lewis acid catalyzed synthesis of 1, 2-bis (perfluoroalkyl) ethylene

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JP6223345B2 (en) * 2011-10-14 2017-11-01 ハネウェル・インターナショナル・インコーポレーテッドＨｏｎｅｙｗｅｌｌ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｉｎｃ． Method for producing 2,3,3,3-tetrafluoropropene
CN103946193B (en) * 2011-10-14 2015-11-25 霍尼韦尔国际公司 The method of preparation 2,3,3,3-tetrafluoeopropene
US20130098396A1 (en) * 2011-10-19 2013-04-25 E I Du Pont De Nemours And Company Novel 1,1,1,4,4,5,5,6,6,6-decafluorohex-2-ene isomer mixtures and uses thereof
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US3683036A (en) * 1969-10-07 1972-08-08 Air Prod & Chem Method for preparing perfluorocycloolefins
US3662009A (en) * 1969-11-24 1972-05-09 Phillips Petroleum Co Preparation of unsaturated fluorocompounds

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CN113906003A (en) * 2019-04-18 2022-01-07 科慕埃弗西有限公司 Lewis acid catalyzed synthesis of 1, 2-bis (perfluoroalkyl) ethylene
CN112980396A (en) * 2020-11-03 2021-06-18 泉州宇极新材料科技有限公司 Ring skeleton fluorine-containing heat transfer fluid, preparation method and application thereof
CN112980396B (en) * 2020-11-03 2022-04-12 泉州宇极新材料科技有限公司 Ring skeleton fluorine-containing heat transfer fluid, preparation method 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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