WO2020055010A1 - Procédé de préparation d'éther heptafluoroisopropyle trifluorovinyle - Google Patents

Procédé de préparation d'éther heptafluoroisopropyle trifluorovinyle Download PDF

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WO2020055010A1
WO2020055010A1 PCT/KR2019/011008 KR2019011008W WO2020055010A1 WO 2020055010 A1 WO2020055010 A1 WO 2020055010A1 KR 2019011008 W KR2019011008 W KR 2019011008W WO 2020055010 A1 WO2020055010 A1 WO 2020055010A1
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heptafluoroisopropyl
ether
fluoride
tetrafluoropropinoyl
trifluorovinyl
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PCT/KR2019/011008
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English (en)
Korean (ko)
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이상구
이수복
박인준
손은호
강홍석
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한국화학연구원
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/34—Separation; Purification; Stabilisation; Use of additives
    • C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
    • C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/14—Unsaturated ethers
    • C07C43/17—Unsaturated ethers containing halogen

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  • the present invention relates to a method for producing heptafluoroisopropyl trifluorovinyl ether.
  • Fluorine-based functional materials are attracting worldwide attention as a key material for next-generation technologies in the high-tech industries such as optical communications, optoelectronics, semiconductors, automobiles, and computers, and in particular, pre-oxidation resistance (non-flammability) and ultraviolet rays of rapidly increasing various displays such as liquid crystal displays It has very good properties such as resistance (weatherability).
  • fluorine-containing polymers have been widely used in various fields due to their excellent heat resistance and chemical resistance.
  • the amorphous fluorine-containing polymer has excellent transparency in addition, it has been continuously used and studied in the field of optical fibers and resist compositions.
  • various optical plastic materials are used as optical transmission mediums in automobiles, OA devices, and various sensors, but all commonly used methyl methacrylate resins, styrene resins, carbonate resins, norbornene resins, etc. have polymers with CH bonds.
  • methyl methacrylate resins, styrene resins, carbonate resins, norbornene resins, etc. have polymers with CH bonds.
  • a polymer material based on CH bonding is used as an optical fiber, there is a problem that light transmittance is lowered, resulting in light loss.
  • many researches have been made on the use of the fluorine-based polymer as a material for optical fibers, etc.
  • heptafluoroisopropyl trifluorovinyl ether represented by the following formula is
  • Vinyl fluoride (VF; Vinylfluoride; CH 2 CHF ), vinylidene fluoride (VDF; Vinylidenefluoride; CH 2 CF 2), ethylene trifluoroacetate (TrFE; Trifluoroethylene; CHFCF 2) , tetrafluoroethylene (TFE; Tetrafluoroethylene; CF 2 CF 2 ) can be copolymerized with partial or total fluorine-based ethylene, and a polymer of a fluorine-based copolymer or terpolymer can be synthesized during polymerization.
  • a copolymer of tetrafluorethylene and carbon fluoride ether can be used to prepare a cation exchange membrane used to electrolyze salt to produce caustic soda and chlorine.
  • a cation exchange membrane used to electrolyze salt to produce caustic soda and chlorine.
  • it can be applied to a wide range of fields such as the environment, energy, such as used to manufacture membranes such as cation exchange membranes for fuel cells, dialysis membranes for wastewater treatment, pervaporation membranes, and the like.
  • Patent Document 1 U.S. Patent No. 3,250,808 (1996.05.10.)
  • Non-Patent Document 1 Gmelin Handbook: F: PerFHalOrg.SVol. 1, 1.2, page 1-15
  • An object of the present invention is to provide a method for producing high conversion and high purity heptafluoroisopropyl trifluorovinyl ether.
  • Another object of the present invention is a method for preparing a final material, heptafluoroisopropyl trifluorvinyl ether, with high yield and high purity by using a method for preparing heptafluoroisopropyl tetrafluoropropinoyl fluoride, an intermediate having high yield. Is to provide.
  • Another object of the present invention is to provide an apparatus for producing heptafluoroisopropyl trifluorovinyl ether.
  • Hexafluoroacetone and hexafluoropropylene oxide are cross-injected 1 to 50 times to a heptafluoroisopropyl alkoxide metal salt to prepare heptafluoroisopropyl tetrafluoropropinoyl fluoride (step a);
  • step b Separating and discharging the prepared heptafluoroisopropyl tetrafluoropropinoyl fluoride (step b);
  • step c Preparing a heptafluoroisopropyl tetrafluoroacid metal salt by mixing the heptafluoroisopropyl tetrafluoropropinoyl fluoride and a metal carbonate on a solvent (step c);
  • step d Thermally decomposing the prepared heptafluoroisopropyl tetrafluoroacid metal salt to prepare heptafluoroisopropyl trifluorovinyl ether (step d);
  • a method for producing heptafluoroisopropyl trifluorovinyl ether comprising:
  • a heptafluoroisopropyl tetrafluoropropinoyl fluoride supply part organically connected to the reaction part;
  • a solvent supply unit that is organically connected to the reaction unit
  • a metal carbonate supply part that is organically connected to the reaction part
  • heptafluoroisopropyl tetrafluoropropinoyl fluoride which is an intermediate required to prepare heptafluoroisopropyl trifluorovinyl ether, with high conversion and purity.
  • heptafluoroisopropyl trifluorovinyl ether In the method for producing heptafluoroisopropyl trifluorovinyl ether according to the present invention, a useful effect of remarkably improving the conversion rate to a product is achieved through a repeated cross-injection method of reactants, and heptafluoroisopropyl used during the manufacturing process It has the advantage of being able to reuse the alkoxide metal salt repeatedly, so that a continuous production process is possible, and high purity and high yield of heptafluoroisopropyl trifluorovinyl ether can be produced.
  • the heptafluoroisopropyl trifluorvinyl ether prepared by the production method of the present invention can be applied as a comonomer of fluorine-based polymer polymerization by reacting with fluorine-based ethylene.
  • FIG. 1 is a flow chart showing a method for producing heptafluoroisopropyl trifluorvinyl ether according to an embodiment of the present application.
  • Figure 2 is a schematic diagram showing a batch reactor device for the production of heptafluoroisopropyl tetrafluoropropinoyl fluoride according to an embodiment of the present application.
  • Figure 3 is a schematic diagram showing a batch reactor apparatus for the production of heptafluoroisopropyl trifluorvinyl ether according to an embodiment of the present application.
  • Figure 4 is a gas chromatograph confirmed after reacting the heptafluoroisopropyl tetrafluoropropinoyl fluoride obtained through distillation process of heptafluoroisopropyl tetrafluoropropinoyl fluoride prepared according to an embodiment of the present application with methanol It is a graph showing the results of the graph.
  • Example 5 is a graph showing the gas chromatographic results of heptafluoroisopropyl trifluorvinyl ether obtained by distillation of the heptafluoroisopropyl trifluorovinyl ether prepared in Example 1 according to an embodiment of the present application.
  • FIG. 6 is a graph showing the results of 19 F-nuclear magnetic resonance analysis of heptafluoroisopropyl trifluorovinyl ether through a distillation process of the heptafluoroisopropyl trifluorovinyl ether prepared in Example 1 according to an embodiment of the present application. .
  • Hexafluoroacetone and hexafluoropropylene oxide are cross-injected 1 to 50 times to a heptafluoroisopropyl alkoxide metal salt to prepare heptafluoroisopropyl tetrafluoropropinoyl fluoride (step a);
  • step b Separating and discharging the prepared heptafluoroisopropyl tetrafluoropropinoyl fluoride (step b);
  • step c Preparing a heptafluoroisopropyl tetrafluoroacid metal salt by mixing the heptafluoroisopropyl tetrafluoropropinoyl fluoride and a metal carbonate on a solvent (step c);
  • step d Thermally decomposing the prepared heptafluoroisopropyl tetrafluoroacid metal salt to prepare heptafluoroisopropyl trifluorovinyl ether (step d); Containing,
  • a method for the production of heptafluoroisopropyl trifluorovinyl ether is provided.
  • hexafluoroacetone and hexafluoropropylene oxide are preferably cross-injected, but the number of cross-injection of hexafluoroacetone and hexafluoropropylene oxide can be 1 to 50 times, but preferably 2 or more times. It is not particularly limited.
  • the manufacturing method of the present invention may further include the step of performing the above steps a and b at least once more by recycling the residual heptafluoroisopropyl alkoxide metal salt.
  • the residual heptafluoroisopropyl alkoxide metal salt can be understood to be the remaining filtrate after separating and discharging the product, heptafluoroisopropyl tetrafluoropropinoyl fluoride, in step b.
  • the separation and discharge of step b is a method for selectively selectively separating the prepared heptafluoroisopropyl tetrafluoropropinoyl fluoride, and a commonly used separation, discharge method, or the like can be applied, and is not particularly limited. However, it may be a separate discharge through layer separation.
  • the remaining filtrate, or a solution containing the residual heptafluoroisopropyl alkoxide metal salt, etc. without further treatment, or, optionally, a subsequent process of further removing components other than the remaining heptafluoroisopropyl alkoxide metal salt
  • a subsequent process of further removing components other than the remaining heptafluoroisopropyl alkoxide metal salt Those of ordinary skill in the art to which the present invention pertains can further understand that it can be easily performed, and can be selectively applied.
  • the residual heptafluoroisopropyl alkoxide metal salt does not need to be transferred separately, and then, as above, the remaining heptafluoroisopropyl alkoxide metal salt can be recycled to perform steps a and b at least once more, Alternatively, it can be recycled after being transported separately or stored.
  • the production method of the present invention can be performed in a batch process, and as described above, the resource can be recycled, and thus has the advantage of continuously producing heptafluoroisopropyl trifluorovinyl ether.
  • the manufacturing method of the present invention may further include a step of preparing a heptafluoroisopropyl alkoxide metal salt by mixing a metal fluoride and hexafluoroacetone in a solvent.
  • the above step may be understood as a manufacturing step of the heptafluoroisopropyl alkoxide metal salt initially provided in step a, or understood as a heptafluoroisopropyl alkoxide metal salt manufacturing step separately performed to supply in the middle of the process of the above manufacturing method. It may be.
  • the solvent is not particularly limited as long as it can be used to prepare the heptafluoroisopropyl alkoxide metal salt, for example, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dimethyl acetamide, dimethyl formamide, dimethyl sulfoxide Sides, and those containing a solvent selected from the group consisting of combinations can be used, preferably diethylene glycol dimethyl ether.
  • the metal fluoride is not particularly limited as long as it can be used in the production of the heptafluoroisopropyl alkoxide metal salt, for example, may be alkali metal fluoride, alkaline earth metal fluoride, preferably potassium fluoride, Cesium fluoride, or a combination thereof, may be used.
  • the metal fluoride is not particularly limited as long as it can be used for the production of the heptafluoroisopropyl alkoxide metal salt, for example, the metal fluoride and the solvent is 1: 1.0 to 8 weight ratio, 1: 1.2 to 7 weight ratio, or 1: 1.5 to 6 may be mixed in a weight ratio.
  • the metal fluoride is not particularly limited as long as it can be used in the production of the heptafluoroisopropyl alkoxide metal salt, for example, the metal fluoride and heptafluoroacetone is 1: 0.8 to 2 weight ratio, 1: 1.0 to 1.8 weight ratio , Or 1: may be mixed in a weight ratio of 1.0 to 1.5.
  • the weight ratio of hexafluoroacetone and hexafluoropropylene oxide cross-injected into the heptafluoroisopropyl alkoxide metal salt solution is not particularly limited, but, for example, the hexafluoroacetone and hexafluoropropylene oxide may be 1: 0.2 to 2 Weight ratio, 1: 0.3 to 1.5 weight ratio, or 1: 0.5 to 1 weight ratio may be to cross-inject.
  • the heptafluoroisopropyl alkoxide metal salt production may be performed at 5 °C to 80 °C, 8 °C to 60 °C, or 10 °C to 50 °C.
  • the preparation of the heptafluoroisopropyl tetrafluoropropinoyl fluoride may be performed at -30 ° C to 60 ° C, -20 ° C to 45 ° C, or -10 ° C to 30 ° C.
  • the manufacturing method of the present invention may further include the step of obtaining high purity heptafluoroisopropyl tetrafluoropropinoyl fluoride through a distillation process.
  • heptafluoroisopropyl tetrafluoropropinoyl fluoride may be separated and discharged, for example, by distillation by transfer to a separate distillation apparatus, from which high-purity heptafluoroiso Propyl tetrafluoropropinoyl fluoride can be obtained.
  • hexafluoroacetone and hexafluropropylene oxide in the heptafluoroisopropyl alkoxide metal salt are, for example, 1: 0.3 to 1.8, 1: 0.4 to 1.5, or 1: 0.5 to 1 in weight ratio It may be a cross-injection.
  • the total weight of the heptafluoroisopropyl alkoxide metal salt and the hexafluoroacetone and hexafluropropylene oxide cross-injected is added at a weight ratio of 1: 0.01 to 0.20, 1: 0.02 to 0.18, or 1: 0.02 to 0.15 It may be.
  • the preparation of the heptafluoroisopropyl tetrafluoropropinoyl fluoride may be performed at -20 ° C to 50 ° C, -15 ° C to 40 ° C, or -10 ° C to 30 ° C.
  • the metal carbonate is not particularly limited as long as it can be used to prepare the heptafluoroisopropyl tetrafluoroacid metal salt, for example, may be alkali metal carbonate, alkaline earth metal carbonate, preferably Sodium carbonate, potassium carbonate, cesium carbonate or a metal carbonate selected from the group consisting of combinations thereof can be used.
  • the solvent is not particularly limited as long as the metal carbonate can be used for the production of the heptafluoroisopropyl tetrafluoroacid metal salt, for example, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dimethyl formamide Or it may be to include a solvent selected from the group consisting of a combination of these, in particular, dimethyl formamide may be used.
  • the metal carbonate is not particularly limited as long as it can be used in the production of the heptafluoroisopropyl tetrafluoroacid metal salt, for example, the metal carbonate and heptafluoroisopropyl tetrafluoropropinoyl fluoride are 1: 0.2 to 2 weight ratio, 1: 0.3 to 1.5 weight ratio, or 1: 0.5 to 1 may be mixed in a weight ratio.
  • the metal carbonate is not particularly limited as long as it can be used to prepare the heptafluoroisopropyl tetrafluoroacid metal salt, for example, the metal carbonate and the solvent 1: 0.2 to 3 weight ratio, 1: 0.3 to 2.5 Weight ratio, or 1: 0.5 to 2 may be mixed in a weight ratio.
  • the solvent is not particularly limited as long as it can be used in the preparation of the heptafluoroisopropyl tetrafluoroacid metal salt, for example, the solvent and the heptafluoroisopropyl tetrafluoropropinoyl fluoride from 1: 0.01 to A weight ratio of 1, a weight ratio of 1: 0.02 to 0.08, or a weight ratio of 1: 0.02 to 0.05.
  • the production of the heptafluoroisopropyl tetrafluoride metal salt may be carried out at 5 °C to 80 °C, 8 °C to 75 °C, or 10 °C to 60 °C.
  • the production of the heptafluoroisopropyl trifluorovinyl ether may be performed at 50 ° C to 180 ° C, 70 ° C to 150 ° C, or 90 ° C to 120 ° C.
  • the production method of the present invention may further include a step of obtaining a high-purity final heptafluoroisopropyl trifluorovinyl ether through a distillation process.
  • heptafluoroisopropyl trifluorovinyl ether may be prepared by thermal decomposition, for example, by distillation by transfer to a separate distillation apparatus, from which high-purity heptafluoroiso Propyl trifluorvinyl ether can be obtained.
  • a heptafluoroisopropyl tetrafluoropropinoyl fluoride supply part organically connected to the reaction part;
  • a solvent supply unit that is organically connected to the reaction unit
  • a metal carbonate supply part that is organically connected to the reaction part
  • heptafluoroisopropyl trifluorovinyl ether In the production of heptafluoroisopropyl trifluorovinyl ether according to the present invention, heptafluoroisopropyl tetrafluoropropinoyl fluoride, which is an intermediate, can be prepared from the apparatus shown in FIG. 2.
  • a heptafluoroisopropyl alkoxide metal salt supply part that is organically connected to the reaction part;
  • It may be a device comprising a; is separated and discharged portion of the heptafluoroisopropyl tetrafluoropropinoyl fluoride, organically connected to the reaction portion.
  • the reaction unit for the preparation of the heptafluoroisopropyl tetrafluoropropinoyl fluoride may be understood as, but is not limited to, a reaction unit in which hexafluoroacetone and hexafluoropropylene oxide react with a heptafluoroisopropyl alkoxide metal salt. It may be a batch reactor of two (140).
  • the heptafluoroisopropyl alkoxide metal salt supply unit may be understood as a supply unit for supplying a solution of a heptafluoroisopropyl alkoxide metal salt into the reaction unit. It may be understood that the fluoroacetone comprises a second reaction moiety to react.
  • the heptafluoroisopropyl alkoxide metal salt supply unit may be the heptafluoroisopropyl alkoxide metal salt solution supply unit 110 of FIG. 2.
  • the supply portion of the hexafluoroacetone and hexafluoropropylene oxide can be understood as a supply portion supplying hexafluoroacetone and hexafluoropropylene oxide into the reaction portion, and each hexafluoroacetone supply portion and hexafluoropropylene oxide supply
  • the parts may be configured separately, or may be a supply part that cross-feeds hexafluoroacetone and hexafluoropropylene oxide as one supply part.
  • the cross-feeding of hexafluoroacetone and hexafluoropropylene oxide in the hexafluoroacetone and hexafluoropropylene oxide supply portion converts the conversion rate of the intermediate chain heptafluoroisopropyl tetrafluoropropinoyl fluoride. It can be improved, can be understood as the main configuration, for example, from the cross-feeding of the cross-feeding one or more times, two or more times, or 1 to 50 times, or 1 to 10 times, a significant improvement in conversion rate Achieve.
  • the supply portion of the hexafluoroacetone and hexafluoropropylene oxide is not particularly limited as long as cross-feed can be performed, and is included in the present invention, but is not limited thereto, but the hexafluoroacetone supply portion is shown in FIG. 2.
  • the hexafluoroacetone supply unit 120 and the hexafluoropropylene oxide supply unit 130 are separately configured, and hexafluoroacetone and hexafluoropropylene oxide can be alternately supplied, and the number of cross feeds can be selectively adjusted.
  • heptafluoroisopropyl alkoxide metal salt and hexafluoroacetone and hexafluoropropylene oxide are prepared through the supplying portions into the reaction portion
  • heptafluoroisopropyl tetrafluoropropinoyl fluoride may be prepared.
  • Part may optionally further include a stirring motor 150 and a stirring rod 160 as shown in FIG. 2.
  • the reaction unit may optionally further include a temperature indicator 170 as shown in FIG. 2, and may optionally further include a jacket 180 as shown in FIG. 2. .
  • the jacket may further include a constant temperature water supply unit 190 and a constant temperature water discharge unit 200, as shown in FIG. 2, to maintain a constant temperature condition of the reaction unit.
  • the part containing heptafluoroisopropyloxy tetrafluoro propanoyl fluoride is selectively separated and discharged through layer separation. It can be, for example, may further include a reactor outlet 210, as shown in FIG.
  • the product heptafluoroisopropyl tetrafluoropropinoyl fluoride
  • each remaining component is completely removed from the reaction section, and the batch configuration for feed and product production is renewed.
  • the residual heptafluoroisopropyl alkoxide metal salt is reused to continuously produce high conversion and high purity heptafluoroisopropyl tetrafluoropropinoyl fluoride.
  • the manufacturing method and apparatus of the present invention are repeated one or more times, two or more times, 1 to 50 times, or 1 to 10 times, for example, 2 to 5 times, while maintaining the residual heptafluoroisopropyl alkoxide metal salt.
  • Heptafluoroisopropyl tetrafluoropropinoyl fluoride can be prepared continuously.
  • heptafluoroisopropyl tetrafluoropropinoyl fluoride discharged through the reactor outlet 210 may, optionally, further include a reservoir for collecting it (for example, storage 1 (220 in FIG. 2) )), It may further include a distillation column 230 with or without a separate storage unit, it is distilled in the distillation column to obtain a heptafluoroisopropyl tetrafluoropropinoyl fluoride obtained in high purity, It may further include another storage unit (for example, the storage 2 240 of FIG. 2) for storing it.
  • the reaction unit for the production of the heptafluoroisopropyl trifluorovinyl ether it can be understood as a reaction unit to react by mixing the prepared heptafluoroisopropyl tetrafluoropropinoyl fluoride and a metal carbonate on a solvent, although not limited thereto, it may be a batch pyrolysis reactor 140 of FIG. 3.
  • the heptafluoroisopropyl tetrafluoropropinoyl fluoride supply unit may be understood as a supply unit for supplying heptafluoroisopropyl tetrafluoropropinoyl fluoride into the reaction unit, and optionally the supply unit itself, or It may also be understood that prior to the supply, a reactor device (batch reactor device in FIG. 2) is prepared in which heptafluoroisopropyl tetrafluoropropinoyl fluoride is prepared.
  • the heptafluoroisopropyl tetrafluoropropinoyl fluoride supply unit may be the heptafluoroisopropyl tetrafluoropropinoyl fluoride supply unit 110 of FIG. 3.
  • the solvent supply unit and the metal carbonate supply unit may be understood as a supply unit for supplying the solvent and the metal carbonate into the reaction unit, and each solvent supply unit and the metal carbonate supply unit may be configured separately, or as one supply unit. It may be a supply unit for supplying a solvent and a metal carbonate.
  • a heptafluoroisopropyltetrafluoropropinoyl fluoride and the solvent and metal carbonate are prepared through the supply units into the reaction unit, a heptafluoroisopropyltetrafluoroacid metal salt may be prepared, wherein the thermal decomposition process is performed in a pyrolysis reactor. Via heptafluoroisopropyl trifluorovinyl ether can be prepared.
  • the reaction unit may optionally further include a stirring motor 150 and a stirring rod 160 as shown in FIG. 3.
  • the reaction unit may optionally further include a temperature indicator 170 as shown in FIG. 3, and may optionally further include a jacket 180 as shown in FIG. 3. .
  • the jacket may further include a constant temperature water supply unit 190 and a constant temperature water discharge unit 200, as shown in FIG. 3, to maintain a constant temperature condition of the reaction unit.
  • heptafluoroisopropyl trifluorvinyl ether and carbon dioxide may be discharged, for example, the reactor outlet 210 as shown in FIG. 3. It may further include.
  • the product, heptafluoroisopropyl trifluorovinyl ether, may be removed from the reactor through the reactor outlet, each remaining component completely removed from the reactor, and again the batch configuration for feed and product production may be renewed.
  • the heptafluoroisopropyl trifluorvinyl ether discharged through the reactor outlet 210 may be separately stored by separately separating heptafluoroisopropyl trifluorvinyl ether from carbon dioxide through the trap cooler 230.
  • it may further include another storage unit (for example, the storage 260 of FIG. 3) for collecting high-purity heptafluoroisopropyl trifluorvinyl ether.
  • Step 1 Put about 36.4 g of potassium fluoride (KF) and about 180 g of diethylene glycol dimethyl ether (DG) in a jacketed 1L stainless steel reaction vessel, and in the form of a turbine. Using a mechanical stirrer equipped with a stirring rod was mixed for 3 hours at a speed of about 300 rpm.
  • KF potassium fluoride
  • DG diethylene glycol dimethyl ether
  • Step 2 After maintaining the temperature at 20 ° C using an elevated temperature circulation device, about 104 g of hexafluoroacetone is gradually added to the reaction vessel at a pressure of 1 bar.
  • Step 3 After the completion of the input of hexafluoroacetone in step 2, after maintaining the temperature and stirring until the pressure of the reaction vessel goes down to 0 bar, the reactor temperature is lowered to 10 ° C.
  • Step 4 10.4 g of hexafluoroacetone was added to the reactor for 5 minutes in a reactor maintained at a reactor temperature of 10 ° C. and 300 rpm. After 10 minutes, 10.4 g of hexafluoropropylene oxide was introduced into the reactor for 5 minutes and held for 10 minutes.
  • Step 5 After repeating the above step 2 5 times, after maintaining for 1 hour without agitation, the layered heptafluoroisopropyl tetrafluoropropinoyl fluoride (lower layer) is sent to the distillation section through the reactor outlet and subjected to a distillation process. , Store it in the cellar. The purity of distilled heptafluoroisopropyl tetrafluoropropinoyl fluoride was 99.3%, and the yield was confirmed to be 86.6%.
  • Example Device 1 Heptafluoroisopropyl Tetrafluoropropinoyl Fluoride Reactor and distillation equipment for manufacturing
  • the reactor device 101 is a heptafluoroisopropyl alkoxide metal salt solution supply unit 110, a hexafluoroacetone supply unit 120 and a hexafluoropropylene oxide supply unit 130, a batch reactor 140, a layer after reaction
  • a reservoir 240 for storing propyl tetrafluoropropinoyl fluoride.
  • the batch reactor 140 is a 1L stainless steel material equipped with a jacket 180, a stirring rod 160 operated by a turbine-type stirring motor 150, and a temperature indicator 170 for checking the reaction temperature.
  • the reaction vessel further includes a constant temperature water supply unit 190 supplied to the jacket and a constant temperature water discharge unit 200 discharged from the jacket.
  • the distillation unit includes a stainless steel filling column and reflux cooler having an inner diameter of 1 inch and a length of 20 inches.
  • Example Device 2 Heptafluoroisopropyl Trifluorovinyl Reactor and distillation equipment for ether production
  • the reactor device 102 is a heptafluoroisopropyl tetrafluoropropinoyl fluoride supply unit 110, a solvent supply unit 120, a metal carbonate supply unit 130, a batch pyrolysis reactor 140, a pyrolysis process synthesized in the manufacturing example Heptafluoroisopropyl trifluorvinyl ether and carbon dioxide outlets 210 and traps 230, distillation column 250 for obtaining high-purity heptafluoroisopropyl trifluorvinyl ether and distilled heptafluoroisopropyl And a reservoir 260 for storing trifluorovinyl ether.
  • the batch pyrolysis reactor 140 is equipped with a jacket 180, a stirring rod 160 operated by a turbine-type stirring motor 150, and a 1 L stainless steel equipped with a temperature indicator 170 for checking the reaction temperature.
  • the reaction vessel of the material further includes a constant temperature water supply unit 190 supplied to the jacket and a constant temperature water discharge unit 200 discharged from the jacket.
  • the collection unit includes a carbon dioxide discharge unit 220, a collection unit storage 240, and a reflux cooler made of stainless steel with an inner diameter of 1.5 inches and a length of 20 inches.
  • the distillation unit includes a stainless steel filling column and reflux cooler having an inner diameter of 1 inch and a length of 20 inches.
  • Step 1 Add about 36.4 g of anhydrous sodium carbonate (Na 2 CO 3 ) and about 100 g of diethylene glycol dimethyl ether (DG) to a jacketed 1 L pyrolysis reactor, The mixture was mixed for 1 hour at a speed of about 300 rpm using a mechanical stirrer equipped with a turbine-type stirring rod.
  • Na 2 CO 3 anhydrous sodium carbonate
  • DG diethylene glycol dimethyl ether
  • Step 2 The temperature of the thermal decomposition reactor of step 1 was maintained at 20 ° C using an elevated temperature circulator, and then 200 g of heptafluoroisopropyl tetrafluoropropinoyl fluoride synthesized in Preparation Example was supplied for 1 hour through a feed pump. After completion of the input, it is maintained for 1 hour.
  • Step 3 The temperature of the reactor in Step 2 was maintained at 30 ° C. for 2 hours, and at 50 ° C. for 2 hours to prepare a heptafluoroisopropyl tetrafluoroacid metal salt.
  • Step 4 After heating the heptafluoroisopropyltetrafluoroacid metal salt of step 3 to 100 ° C., the heptafluoroisopropyl trifluorvinyl ether produced through thermal decomposition is stored in a storage tank for storage using a cooler maintained at ⁇ 30 ° C. do.
  • Step 5 The heptafluoroisopropyl trifluorovinyl ether of step 4 is sent to the distillation unit through a feed pump, which is subjected to distillation, and then stored in a storage.
  • Example 1 except that the sodium carbonate is potassium carbonate (potassium carbonate, K 2 CO 3 ), it was carried out in the same manner as in Example 1 to prepare heptafluoroisopropyl methyl ether.
  • potassium carbonate potassium carbonate
  • Example 1 except that the diethylene glycol dimethyl ether is tetraethylene glycol dimethyl ether (tetraethylene glycol dimethyl ether, TG), the same method as in Example 1 was carried out to obtain heptafluoroisopropyl trifluorovinyl ether. It was prepared.
  • Example 1 it was prepared in the same manner as in Example 1, except that 6.7 g of dimethylformamide (DMF) was further added to prepare heptafluoroisopropyl trifluorvinyl ether.
  • DMF dimethylformamide
  • Example Heptafluoroisopropyl tetrafluoropropinoyl fluoride (g) Metal carbonate (g) DG (g) Purity (%) Yield (%) One 200 96 (Na 2 CO 3 ) 100 97.1 85.9 2 200 125 (K 2 CO 3 ) 100 96.9 85.2
  • Example Heptafluoroisopropyl tetrafluoropropinoyl fluoride (g) Na 2 CO 3 (g) Solvent (g) Purity (%) Yield (%) One 200 96 100 (DG) 97.1 85.9 3 200 96 100 (TG) 96.8 85.8
  • Example Heptafluoroisopropyl tetrafluoropropinoyl fluoride (g) Na 2 CO 3 (g) DG (g) DMF (g) Purity (%) Yield (%) One 200 96 100 0 97.1 85.9 4 200 96 100 6.7 97.9 86.4

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Abstract

La présente invention concerne un procédé et un dispositif permettant de préparer un éther heptafluoroisopropyle trifluorovinyle. Le procédé et le dispositif fournis par la présente invention sont capables de préparer l'éther heptafluoroisopropyle trifluorovinyle avec une pureté élevée et un haut rendement, et adoptent un procédé de préparation de fluorure heptafluoroisopropyle tétrafluoropropinoyle qui est un intermédiaire ayant un rendement élevé, ce qui a pour effet d'améliorer le rendement de tout le processus notamment de l'éther heptafluoroisopropyle trifluorovinyle qui est un matériau final.
PCT/KR2019/011008 2018-09-11 2019-08-28 Procédé de préparation d'éther heptafluoroisopropyle trifluorovinyle WO2020055010A1 (fr)

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KR1020180108459A KR102031804B1 (ko) 2018-09-11 2018-09-11 헵타플루오르아이소프로필 트리플루오르비닐 에테르의 제조방법

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117945852A (zh) * 2024-03-15 2024-04-30 山东华安新材料有限公司 一种七氟异丙醇的制备方法

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