WO2002026682A1 - Process for producing fluorinated vinyl ethers - Google Patents

Process for producing fluorinated vinyl ethers

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Publication number
WO2002026682A1
WO2002026682A1 PCT/JP2001/008369 JP0108369W WO0226682A1 WO 2002026682 A1 WO2002026682 A1 WO 2002026682A1 JP 0108369 W JP0108369 W JP 0108369W WO 0226682 A1 WO0226682 A1 WO 0226682A1
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WO
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Patent type
Prior art keywords
compound
cf
af
mixture
group
Prior art date
Application number
PCT/JP2001/008369
Other languages
French (fr)
Japanese (ja)
Inventor
Takashi Okazoe
Kunio Watanabe
Masahiro Ito
Daisuke Shirakawa
Shin Tatematsu
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Asahi Glass Company, Limited
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01Preparation of ethers
    • C07C41/18Preparation of ethers by reactions not forming ether-oxygen bonds

Abstract

A process is provided by which fluorinated vinyl ethers can be efficiently produced from more inexpensive raw materials without separating operation in the production process. Specifically, a process for producing fluorinated vinyl ethers (8), characterized by subjecting a mixture of a compound (2F) and a compound (3F) to thermal decomposition: (2F) (3F) (8) wherein RAF is a monovalent organic group stable to thermal decomposition.

Description

Specification

Manufacturing process tools art fluorinated Pinirueteru compounds>

The present invention relates to a process for the production of useful fluorinated Bierue ether compound as the raw material monomer or fluorine resin. More specifically, short steps a fluorine-containing vinyl ether compound, and to a method for efficiently producing a high yield. Ingredients BACKGROUND>

Conventionally, the entire hand C-H moiety of the C one H-containing compound such as a hydrocarbon-based compound as a method of fluorinating a C one F, a method of using a three-cobalt fluoride, directly using the full Tsu-containing gas how to fluorinated, or, in an electrolytic bath, a method of performing fluorination reaction by electrolysis of hydrogen fluoride (hereinafter, £ law (6 1 6 (;. Se 1 ~ 0 ch em icalfluorination) hereinafter) is known the c are, in the case of a method of direct fluorination with fluorine gas, a method of performing in a manner and the liquid phase carried out in the gas phase are known.

How to fluorination with fluorine gas by applying the liquid phase to the compounds of the non-fluorine-based (US P 5 0 9 3 4 3 2 No.) it has also been reported. Also, how to obtain the acid fluoride compound a kind of Perufuruoro of ester compound is subjected to a thermal decomposition reaction is also known, the compounds, the fluorine gas a hydrocarbon-based ester compound of corresponding structures are placing serial and available by direct fluorination in a liquid phase with (J. Am. C h em. S oc., 1 2 0, 7 1 1 7 (1 9 9 8)).

Perufuruoro (alkyl vinyl ether) is useful as a raw material monomer of the heat-resistant and chemical resistance of a fluororesin excellent. The compounds, by dimerization of Perufuruoro epoxides, or, pel full O b alkanoic acid Furuo Li de the in the presence of Al force Li metal fluoride is reacted with pel full O b epoxides Perufuruoro (2- and alkoxy acid) fluoride compounds, by thermal decomposition then, have been industrially produced (US P 3291 843 No.).

However, the conventional method of manufacturing a Perufuruoro (alkyl vinyl ether), it is difficult to control the reaction of the dimerization reaction, the price of raw materials is high, there is a problem it is economically disadvantageous.

An object of the present invention is to solve the above problems, it is to provide a method of the fluorine-containing vinyl ether compound may be prepared short steps, and in high yield efficiently.

<Disclosure of the invention>

We refer to mixtures of the particular starting compound, by subjecting leave the pyrolysis reaction of the mixture was found that the fluorine-containing vinyl ether compound of interest is cut with suitably manufactured. Further, by using the mixture as a raw material, it is economically advantageous as E industry process, and found more about potential that such an efficient continuous process. The present invention is also the in which has been completed based on these findings.

That is, the present invention relates to a method for producing the following fluorinated vinyl ether compounds, Contact and provides novel compounds useful as intermediates in the production process. 1. method for producing the mixture of the following compound (2 F) and the following Compound (3 F), the following fluorine-containing vinyl ether compound, characterized by performing thermal decomposition reaction (8). In the formula, R AF is a monovalent organic group which does not change by a thermal decomposition reaction.

A F OCF (CF 3) COF (2 F) R AF 〇 (CF 2) 2 COF (3 F)

R AF OC F = CF 2 ( 8)

2. the following compound (6), or in a mixture of the following compound (6) the following compound (7), the following compound by performing a decomposition reaction of the ester bond (2 F) and the following compound (3 F) the mixture obtained, the production method c However Shikichu the next following fluorinated vinyl ether compound, characterized by performing the thermal decomposition reaction in the mixture (8), R AF is a monovalent organic group which does not change by the thermal decomposition reaction It is shown.

R AF 0 (CF 2) 3 OCOC F (CF 3) OR AF (6)

R AF O (CF 2) 3 OCOC F 2 CF 2 OR AF (7)

R AF OC F (CF 3) COF (2 F)

A F 0 (CF 2) 2 COF (3 F)

3. compound (6), the following compound (1) and the following compound (2) are reacted esterified to produce the following compounds (4), full Tsu containing then the compound (4) in a liquid phase a reaction product obtained by reacting the compound (6) with the compound mixture of (7), the following compound (1) and the following compound (2) and the following compound (3) and the mixture is reacted following compound of ( 4) to produce a mixture of the following compound (5), said chemical compound (4) with the compound mixture of (5), which is a reaction raw formed product was reacted with fluorine in a liquid phase, in claim 2 the method according.

In the formula, R A, R B, R C are each independently a R AF same monovalent organic group or a monovalent organic group comprising the R AF by reacting with fluorine in a liquid phase, , R AF is a monovalent organic group which does not change by a thermal decomposition reaction, X is a halogen atom.

R A 0 (CH 2) 3 OH (1)

XCOC F (CF 3) OR B (2) XCO (CF 2) 2? OR C (3)

R A O (CH 2) 3 OCOC F (CF 3,) OR 13 (4)

R A O (CH 2) 3 OCO (CF 2) 2 OR C (5)

4. is a compound (4) Fluorine content in the 3 0 wt% or more, the production method according to claim 3 fluorine content in the compound (5) is 3 0 wt% or more.

5. Compound (6) and compound mixtures (7), the following compound (1), under the title compound (2 F) and the following Compound (3 F) mixture and is reacted esterified following compounds of (4 F) and the following compound (5 F) mixture to produce the method according to claim 2 the following to the mixture is a reaction product obtained by reacting with fluorine in a liquid phase. However. Wherein, R A represents a 1 Ataiyu machine group consisting R AF by reacting with fluorine in R AF same 1 Ataiyu machine group or in the liquid phase,, R AF is changed by pyrolysis reaction a monovalent organic group which does not.

R A 0 (CH 2) 3 OH (1)

R AF OC F (CF 3) COF (2 F)

R AF O (CF 2) 2 COF (3 F)

R A O (CH 2) 3 OCOC F (CF 3) OR AF (4 F)

R A O (CH 2) 3 OCOCF 2 CF 2 OR AF (5 F)

6. mixtures of compounds (2 F) and Compound (3 F) is the following compound (6) Contact and the following compound (7) portion of the reaction product obtained by carrying out the decomposition reaction of the ester bond in the mixture or the method according to claim 5 in whole. In the formula, R AF is a monovalent organic group which does not change by a thermal decomposition reaction.

R AF 0 (CF 2) 3 OCOC F (CF 3) OR AF (6)

R AF 0 (CF 2) 3 OCOC F 2 CF 2 OR AF (7)

When fluorine is reacted 7. liquid phase, as a liquid phase, the compound (2 F), compound (3 F), using Compound (6), and compound at least one kind of compound selected from (7) claim 3, 4, 5 or method according to 6,.

8. R AF is Perufuruoro (monovalent saturated hydrocarbon) group, Perufuruoro (partially halogenated monovalent saturated hydrocarbon) group, Perufuruoro (hetero atom-containing monovalent saturated hydrocarbon) group or Perufuruoro (hetero the partially halogenated, the process according to any one of claims 1 to 7 which is atom-containing Atai飽 sum hydrocarbon) group.

9. the following compound (la), to give a mixture of the following compound (2 a) and the following compound (3 a) a mixture and by esterification reaction the following compound of (4 a) and the following compound (5 a), then the compound (4 a) and a mixture of the following compounds by reacting with fluorine in a liquid phase of (5 a) (6 a) and the following compound

To give a mixture of (7 a), then the compound by performing the decomposition of the binding of the ester in (6 a) and a mixture of (7 a), said compound (2 a) and of compound (3 a) to obtain a mixture of higher amount of the compound than the mixture (2 a) and the compound (3 a) with, then compound (2 a) and the compound (3 a) performing thermal decomposition reaction of a mixture of method for producing the following compound (8 a), characterized in.

CH 2 = CHCH 2 OCH 2 CH 2 CH 2 OH (1 a)

CF 3 CF 2 CF 2 OCF ( CF3) COF (2 a)

CF 3 CF 2 CF 2 OCF 2 CF 2 COF (3 a)

CH 2 = CHCH 2 OCH 2 CH 2 CH 2 OCOCF (CF 3) OCF 2 CF 2 CF 3 (4a)

CH 2 = CHCH 2 OCH 2 CH 2 CH 2 OCOCF 2 CF 2 OCF 2 CF 2 CF 3 (5 a)

CF 3 CF 2 CF 2 OCF 2 CF 2 CF 2 OCOCF (CF 3) OCF 2 CF 2 CF 3 (6 a)

CF 3 CF 2 CF 2 OCF 2 CF 2 CF 2 OCOCF 2 CF 2 OCF 2 CF 2 CF 3 (7 a)

CF 3 CF 2 CF 2 OCF = CF 2 (8 a)

10. the following compound (7A). Here, n in the formula is an integer of 1-10. F (CF 2) n O ( CF 2) 3 OCOCF 2 CF 2 O (CF 2) n F (7 A) ingredients BEST MODE FOR CARRYING OUT THE INVENTION>

In the present invention, R AF is shows the monovalent organic group which does not change by a thermal decomposition reaction. In this specification, the monovalent organic group, Les had a monovalent group essentially comprising carbon atoms, be an organic group may be saturated, organic radical of unsaturation.

The monovalent organic group which does not change by a thermal decomposition reaction in the present invention (R AF), a group that does not contain a functional group or atomic group varies by pyrolysis in the base, compound

In (2 F) and before and after the thermal decomposition reaction in the mixture of Compound (3 F), it refers to a monovalent organic group whose chemical structure does not change. The monovalent organic group said one COO CF 2 C - CX a - ( where, a is a halogen atom), - CF 2 CF 2 CO F, and _CF (CF 3) group partial structures is not present, such as COF , a group under the reaction conditions of the pyrolysis no chemically unstable structure, and the like. For example, monovalent hydrocarbon radical or a halogenated monovalent hydrocarbon group, typically a group that does not change Ri by the thermal decomposition reaction. Hetero atom-containing monovalent hydrocarbon group or a halogenated

(Hetero atom-containing monovalent hydrocarbon) group, if TeroHara child group to heteroatoms or in the group are those which do not change by the thermal decomposition reaction, usually a group which does not change by thermal decomposition.

The R AF in the present invention, the raw material availability ease, usefulness of the object compound, in terms of implementation ease of efficient continuous process to be described later, Perufuruoro (monovalent saturated hydrocarbon) group, Perufuruoro (partially halogenated of monovalent saturated hydrocarbon) group, Perufuruoro (hetero atom-containing monovalent saturated hydrocarbon) group or Perufuruoro,

Is preferably a group (hetero atom-containing monovalent saturated hydrocarbon to the partially halogenated), especially Perufuruoro monovalent saturated hydrocarbon group, Perufuruoro (etheric oxygen atom-containing monovalent saturated hydrocarbon) group, Perufuruoro (partial black port monovalent saturated hydrocarbon) group or Perufuruoro (partial black port (etheric oxygen atom-containing monovalent saturated carbon hydrocarbons)) is preferably a group.

The hydrocarbon group in the present specification, may be also an aromatic hydrocarbon group or an aliphatic hydrocarbon group, an aliphatic hydrocarbon group is preferred. Further, in the aliphatic hydrocarbon group, a carbon - as a carbon bond, a single bond, double bond or triple bond may be present. Aliphatic hydrocarbon group, a linear structure, branched structure, cyclic structure or ring structure may be either a structure having partially.

The saturated hydrocarbon group, refers to a group in which the carbon one carbon bond in the group is consisting of a single bond only. Unsaturated bond other than a carbon one-carbon unsaturated bond in the base (e.g., C = o and so 2, etc.) may be present.

The monovalent saturated hydrocarbon group in the present specification, include alkyl groups, its structure is either a straight chain structure, branched structure, cyclic structure (i.e., a cycloalkyl group) structure is, or partially ring it may be.

The carbon number of the alkyl group is 1 to 1 0 are preferred. It is an alkyl group is a straight chain structure, a methyl group, Echiru group, a propyl group, a butyl group. The alkyl group is a branched structure, an isopropyl group, an isobutyl group, sec- heptyl group, tert one butyl group, and the like. Is an alkyl group is a ring structure, e.g., a cycloalkyl group, a bicycloalkyl group, group of alicyclic spiro structure, and the like, preferably a cycloalkyl group having 3 to 6-membered ring, cycloalkyl pentyl group, a cycloalkyl hexyl group, and the like to.

The alkyl group having a ring moiety substituted with an alkyl group the ring structure (linear structure or branched structure) alkyl group or a cyclic base content of the alkyl group is more, the (linear structure or branched structure) group substituted with an alkyl group, vicinal black alkyl groups include groups having an alicyclic spiro structure, or one water atom in an alkyl group substituted by Sik port alkyl group having 3 to 6-membered ring group rather preferred, cyclopentylmethyl group, Kichiruechiru group cyclohexylene, key Shirumechiru group to Echirushikuro is particularly preferred. Other groups, Al Kill group having an aromatic ring (e.g., benzyl group, Ararukiru group such as phenethyl group), an alkyl group having a heterocyclic (e.g., pyridylmethyl group, furfuryl group, etc.) can be mentioned up.

As the halogen atom in halogenated groups, fluorine atoms, EnsoHara child, a bromine atom or an iodine atom, a fluorine atom, a chlorine atom or odor atom are preferred, especially fluorine atom from the viewpoint of usefulness of the compound, , or fluorine atom and chlorine atom are preferred.

As used herein refers to more than one hydrogen atom is substituted with a halogen atom and a halogenated. Refers to a portion of the hydrogen atoms are substituted by halogen atoms and partially halogenated ', during the base, there is a hydrogen atom. Refers to all of the hydrogen atoms are C port Gen of the perhalogenated, there is no hydrogen atom in the group. Halogenated, partially halogenated, meaning of the terms of perhalogenated indicates the same meaning even when the halogen atom is specified. Halogen atoms present in halogenated groups and perhalogenated groups may be two or more even one.

In the present specification, the halogenated monovalent saturated hydrocarbon group, refers to a monovalent saturated group in which one or more is replaced by a halogen atom hydrocarbon group hydrogen atoms present in a. Even during halogenated monovalent saturated hydrocarbon group existed a hydrogen atom may not exist. Is a halogen atom in a halogenated monovalent saturated hydrocarbon group, a fluorine atom or a fluorine atom and a chlorine atom, are preferred.

In the present specification, the partially halogenated monovalent saturated hydrocarbon group, refers to a group in which some of the hydrogen atoms present in the 1 Atai飽 sum hydrocarbon group substituted by a halogen atom. During partially halogenated monovalent saturated hydrocarbon group, it exists a hydrogen atom.

In the present specification, the perhalogenated monovalent saturated hydrocarbon group, refers to a monovalent substantially all saturated carbon hydrogen atom present in the hydrogen radical is replaced by a halogen atom group. During Beruha port Gen of monovalent saturated hydrocarbon groups absent hydrogen atom.

In this specification, the halogenated monovalent saturated hydrocarbon group may be a branched structure may be straight chain structure, in the ring structure may be a structure having a cyclic structure portion. The halogenated monovalent saturated hydrocarbon group, Furuoroarukiru group or Furuoro (partial black port alkyl) group, and the like. The number of carbon atoms of the halogenated monovalent saturated hydrocarbon group 1-2 0 are preferred.

In this specification, the perhalogenated monovalent saturated hydrocarbon group, Perufu Ruoroarukiru group or Perufuruoro (partial black port alkyl) group (i.e., all of the hydrogen atoms in the partial black port alkyl group is fluorinated group) It is preferred. Incidentally, Perufuruoro (partial Furuoroarukiru) group is the same as the pel full O b alkyl group.

In this specification, the hetero atom-containing monovalent saturated hydrocarbon group, referred to as hetero atom SansoHara child, nitrogen atom or to the like sulfur atom, a carbon atom, a saturated group consisting of a hydrogen atom. The heteroatom may be filed with a hetero atom itself or may be a hetero atom group and to each other or heteroatom hetero atom and another atom bonded. Heteroatom group heteroatoms and to is preferably one that neither changed by pyrolysis reaction. The hetero atom, (O in C one O-C) E one ether acids atom, = 0, and the like, particularly preferably an etheric oxygen atom. The number of carbon atoms of the hetero atom-containing monovalent saturated hydrocarbon groups have preferably is 1-2 0. The hetero atom-containing monovalent saturated hydrocarbon group, the saturated hydrocarbon group of carbon-containing - based hetero atom group is 揷入 heteroatom or a divalent to divalent between carbon atoms or the saturated hydrocarbon group, preferred groups group hetero atom is bonded to a carbon atom or a terrorist atomic group to the saturated heteroatom divalent carbon atom bonded ends of the hydrocarbon group or a divalent, is bound in the.

In this specification, the hetero atom-containing group, an etheric oxygen atom-containing group in view of usefulness of the compound is particularly preferable. In particular the ease of availability, production ease, and from the viewpoint of usefulness of the products, alkyl group (e.g., alkoxyalkyl group.) Containing an etheric oxygen atom is preferred. Further, the monovalent aliphatic hydrocarbon group having a ring portion having an etheric oxygen atom inserted between carbon Ichisumi MotoHara child, for example, Ru include alkyl group having Jiokisoran skeleton.

As the alkoxyalkyl group herein, group in which one is substituted with an alkoxy group hydrogen atoms present in the alkyl group described in the monovalent aliphatic hydrocarbon group is preferred. The number of carbons of the alkoxy group 1 to 1 0 are preferred. The Al Kokishiarukiru group, ethoxymethyl group, 1 one Puropokishechiru group, 2-Puropokishechiru group and the like.

Halogenated herein as a (hetero atom-containing 1. valent saturated hydrocarbon) group, Furuoro (hetero atom-containing monovalent saturated hydrocarbon) group or Furuoro (part minute black port (hetero atom-containing monovalent saturated hydrocarbon )) group is preferred. Halogenated carbon atoms (hetero atom-containing monovalent saturated hydrocarbon) group is 1 to 2 0 is preferable. The perhalogenated (hetero atom-containing monovalent saturated hydrocarbon) group herein may be straight-chain structure may be branched structure, (hetero atom-containing monovalent saturated hydrocarbon to) Perufuruoro group or Perufuruoro (partial black port (terrorist atom-containing monovalent saturated hydrocarbon) to) is preferably a group, Perufuruoro (hetero atom-containing alkyl) group or Perufuruoro (partial black port (hetero atom-containing alkyl Le)) particularly preferably a group, Perufuruoro (alkoxyl) group or Perufuru O b (partial black port (alkoxyl)) group is especially preferred.

Specific examples of these groups include those described in the following examples. In the present invention, it is converted to compound (2 F) and compound mixture was subjected to thermal decomposition reaction fluorinated vinyl ether compound of (3 F) (8). Compound (2 F) and Compound (3 F) are all converted to heat decomposition reaction Te Yodzu the same including full Mmoto vinyl ether compound (8). That is, in this method, compound (2 F) and the compound is one object of compound having a structure corresponding to (3 F) (8) is produced. R AF in the fluorine-containing vinyl ether compound (8) is the same as R AF in the compound (2 F) and Compound (3 F). Examples of the fluorine-containing vinyl ether compound (8) include the following compounds, compounds (8 a) is preferred.

CF 3 CF 2 CF 2 OCF = CF 2 (8 a)

CF 3 OCF CF 2 (8 b )

CF 3 CF 2 OC F = CF 2 (8 c)

CF 3 (CF 2) 5 OCF = CF 2 (8 d)

CF 3 (CF 2) g OCF = CF 2 (8 e)

Further, the following compounds may be mentioned as examples of the compound (2 F), compound from the usefulness of the object compound (2 a) are preferred.

CF 3 CF 2 CF 2 OCF ( CF 3) COF (2 a)

CF 3 OCF (CF 3) COF (2 b)

CF 3 CF 2 OCF (CF 3 ) COF (2 c)

CF 3 (CF 2) 5 OCF (CF 3) COF (2 d)

CF 3 (CF 2) 9 OCF (CF 3) COF (2 e)

Compound (3 F) the following compounds may be mentioned as an example, useful or found compounds of the object compound (3 a) it is preferred.

CF 3 CF 2 CF 2 OCF 2 CF 2 CO F (3 a)

CF 3 OCF 2 CF 2 C_〇_F (3 b)

CF 3 CF 2 OCF 2 CF 2 CO F (3 c)

CF 3 (CF 2) 5 OCF 2 CF 2 COF (3 d)

CF 3 (CF,) 9 OCF 2 CF 2 CO F (3 e)

Furthermore, mixtures of the compounds of the present invention (2 F) and Compound (3 F) (hereinafter, the mixture (2 F- 3 F) and referred.), The compound (2 F) and the compound

Each ratio of (3 F) is not particularly limited, a method of manufacturing a light present onset be any ratio can be performed. If you carried out in a continuous manner described below a production method of the present invention, the mixture in the starting phase of the process (2 F- 3 F) compound in

(2 F) is 40 to 60 wt%, the compound (3 F) is preferably from 40 to 60 wt%. Mixture ratio of each compound (2 F- 3 F) is not particularly limited, in the case of repeated continuous process to be described later, gradually decreases the content of the compound (2 F), compound (3 F) the content of the increases gradually.

Thermal decomposition of mixture (2 F- 3 F) is can in carried out in the gas phase reaction or liquid phase reaction, to carry out a gas phase reaction is efficient preferred. The method and the reaction temperature of the pyrolysis reaction is good preferable to select the boiling point and stability of the mixture (2 F- 3 F). Then, the mixture (2 F- 3 F) is to give order for thermal decomposition reaction in the gas phase reaction, preferably having a boiling point at normal pressure is below 350 ° C. Further, the boiling point of the mixture (2 F- 3 F) is preferably at 50 ° C or higher. Gas phase reaction is preferably carried out in a continuous reaction. Continuous reaction, the mixture was passed through the vaporized in a heated reaction tube (2 F- 3 F), the fluorine-containing vinyl ether compound generated

(8) as an outlet gas, condense them, preferably carried out by a method of continuously recovered. The reaction temperature in the case of performing thermal decomposition at the vapor phase reaction, but may be appropriately changed by the structure of the compound (2 F) and Compound (3 F), generally it is preferably at least 1 50 ° C for ~ at 200 500 ° C are particularly preferred, especially 2 50 ° (:.. When ~ 450 ° C is the preferred reaction temperature is too high, there is a possibility that the decomposition reaction occurs yield of the product decreases also, if the reaction temperature is too low, compound (2 F) and the respective reaction conversion of the compound (3 F) is cause personal lowered.

Further, when the thermal decomposition reaction in the gas phase reaction, to use a tubular reactor favorable preferable. The residence time in the case of using tubular reactor, 0.1 of about 1 second to 1 0 minute superficial basis is preferred. The reaction pressure is not particularly limited. Further, when the mixture (2 F- 3 F) is a high boiling point, the reaction is preferably carried out in vacuo. Further, when the mixture (2 F- 3 F) is a low boiling point is decomposed suppression of product, and because the reaction rate is high, it is preferred to carry out the reaction under pressure. Also, when the mixture (2 F-3 F) has a high boiling point, good fc performing pyrolysis in the liquid phase reaction.

When performing gas phase reactions using a tubular reactor, used to promote the reaction, the glass in the reaction tube, is preferably loaded alkali metal salts or alkaline earth metal salts. The alkali metal salts or aralkyl force Li earth metal salt, a carbonate or a fluoride is preferred. The glass, include common soda glass, glass beads are preferably raised fluidity particularly beaded. The alkali metal salts, sodium carbonate, sodium fluoride, and potassium carbonate © beam or lithium carbonate, is. The alkaline earth metal salts, calcium carbonate, calcium fluoride, and barium carbonate or magnesium carbonate and the like. Further, the glass in the reaction tube, an alkali metal salt or in the case of filling the § alkaline earth metal salts, or glass beads, a light ash or the like of sodium carbonate, the particle size is 1 from 00 to 250 m approximately, with not more, particularly preferable because it can employ a reaction system of a fluidized bed type.

In the gas phase reaction, for the purpose of accelerating the vaporization of the mixture (2 F- 3 F), directly to the thermal decomposition reaction is preferably present with an inert gas which does not participate, as the inert gas, nitrogen gas, carbon dioxide gas, helium gas, argon gas and the like. Inert gas amount is 0.0 1 to 50% by volume based on the mixture (2 F- 3 F) is preferred. When the inert gas amount is too large, there is a possibility that the recovery of the product is lowered undesirably.

In the production method of the present invention, the products according to the thermal decomposition reaction is substantially only contains fluorine vinyl ether compound (8). The product is preferably separated and purified by conventional ways depending on the purpose. The separation and purification methods, distillation method, silica gel column chromatography, and the like. The fluorine-containing vinyl ether of compound (8), the compound is a low molecular weight than (2 F) and Compound (3 F), usually from becoming a compound of low boiling point, the unreacted compound (2 F) and mixtures of compounds (3 F) is preferably efficiently removed by distillation.

Mixture (2 F- 3 F) but in not particularly limited as how to obtain, Oite the present invention, the compound (6), or compound (6) and the mixture in the decomposition reaction of E ester bonds (7) subjected to the reaction product obtained is preferably. The ester bond of the decomposition reaction of the compound (6), stoichiometrically 2 moles of the compound (2 F) to produce the compound (6). In the decomposition reaction of Es ether bond of the compound (7), the compound (7), stoichiometrically equi-magnification mole of compound (2 F) a stoichiometric equi-magnification mole of compound (3 F ) is generated.

Examples of compounds (6) include the following compounds, arbitrary compound (6 a) is preferred.

CF 3 CF 2 CF 2 OCF 2 CF 2 CF 2 OCOC F (CF 3) OCF 2 CF 2 CF 3 (6 a), CF 3 OC F 2 CF 2 CF 2 OCOCF (CF 3) OCF 3 (6 b), CF 3 CF 2 OC F 2 CF 2 CF 2 OCOCF (CF 3) OCF 2 CF 3 (6 c),

CF 3 (CF 2) 5 OC F 2 CF 2 CF 2 OCOCF (CF 3) O (CF 2) 5 CF 3 (6 d),

CF 3 (CF 2) 9 OCF 2 CF 2 CF 2 OCOCF (CF 3) O (CF 2) 9 CF 3 (6 e).

As examples of the compound (7) is the following compound and the like, also, of the compound (7), the following compound (7A) is a novel compound. The following compound (7 A) are useful compounds that can lead to useful Bae Rufuruoro (alkyl vinyl ether) as a raw material monomer of a fluororesin by a process described later. Compound (7A) The compound (7 a) it is preferred. However, where, n is 1; represents an integer of L 0.

F (CF 2) n O ( CF 2) 3 〇_COCF 2 CF 2 O (CF 2) n F (7 A),

CF 3 CF 2 CF 2 OCF 2 CF 2 CF 2 OCOC F 2 CF 2 OC F 2 CF 2 CF 3 (7 a),

CF 3 OC F 2 CF 2 CF 2 OCOCF 2 CF 2 OC F 3 (7 b)

CF 3 CF 2 OCF 2 CF 2 CF 2 OCOCF 2 CF 2 OC F 2 CF 3 (7 c),

CF 3 (CF 2) 5 〇_CF 2 CF 2 CF 2 OCOCF, CF 2 O (CF 2) 5 CF 3 (7 d),

CF a (CF 2) 9 OC F 2 CF 2 CF 2 OCOCF 2 CF 2 O (CF 2) 9 CF 3 (7 e),

Compound (6) or the mixture (6 7) if subjected to the decomposition reaction of the ester bond, the thermal decomposition reaction or carried out by a decomposition reaction carried out in the presence of a nucleophilic agent or an electrophilic agent in a liquid phase it is preferable to.

When performing a decomposition reaction of the ester bond in the thermal decomposition reaction, the compound (6), were or can be performed by heating the mixture (6 7). Anti 応形 type thermal decomposition reaction is preferably selected according to the boiling point and its stability of the compound (6) or a mixture (6 7). For example, when subjecting vaporized easily mixture (6- 7) to the ester thermal decomposition reaction is continuously decomposed in a gas phase, resulting mixture (2 F - 3 F) condensing an outlet gas containing , it may employ the gas phase thermal decomposition method to recover. The reaction temperature of the gas phase pyrolysis method is preferably from 5 0~ 3 5 0 ° C, particularly preferably 5 0~ 3 0 0 ° C, especially 1 5 0~2 5 0 ° C is preferred. Further, the reaction may be allowed to coexist an inert gas is not directly Kumishi related to the reaction system. As the inert gas, nitrogen gas, carbon dioxide gas and the like. The inert gas, compound (6) or a mixture (6 7) with respect to 0. 0 virtuous preferable to add 1-5 about 0% by volume. If the amount of the inert gas is large, Ru Kotogaa the recovery of the product is reduced.

On the other hand, the compound (6), or thermal decomposition of ester le bond when the boiling point is high in the mixture (6 7) is preferably carried out in the reactor liquid phase thermal decomposition method of heat remains liquid at. The reaction pressure in this case is not limited. In the usual case, the product comprising a mixture (2 F- 3 F), since a lower boiling, liquid phase thermal decomposition reaction was carried out the reaction while distilling in a reactor having a distillation column, the product preferably carried out by a method of extracting continuously to vaporize. Furthermore, after the thermal decomposition reaction without distillation, may be withdrawn and the product in a batch from the product. The reaction temperature of this liquid phase pyrolysis method is preferably from 5 0~3 0 0 ° C, in particular 1 0 0~2 5 0 ° C is preferred.

When performing a decomposition reaction of the ester bond in the liquid phase thermal decomposition method, even carried out in the absence of a solvent, it may be carried out in the presence of a solvent. As the solvent not react with both compounds (6) and the compound (7), and certain of these compounds compatible, resulting compound (2 F) and Compound (3 F) and do not react if not limited to especially. As the solvent, Compound (2 F) and the compound preferably selected ones easily separated during purification of the mixture of (3 F). Specific examples of the solvent, Perufuruoro Bok Riarukiruamin, inert solvent such Perufuruorode force Li down, a high boiling point among such black hole Furuorokabon acids click Rollo triflate Ruo ii ethylene oligomers (e.g., trade name: Freon loop), compound (2 F), compound (3 F) and the like are preferable. The amount of the solvent mixture

L 000% by mass; 1 0 against (6-7).

Furthermore, where the compounds (6) or the mixture (6 7) performing a decomposition reaction of the ester bond by reacting with a nucleophilic agent or Motomeden child agent in the liquid phase, the reaction is also carried out in the absence of a solvent it may be carried out in the presence of a solvent. As the solvent, it is the same thing as the solvent used in the liquid phase thermal decomposition method. The nucleophile, F_ are preferred, especially from the alkali metal fluoride F- is preferred. The alkali metal fluoride, NaF, NaHF 2, KF, C s F C., particularly preferably N a F in terms of economy of these. The amount of the nucleophilic agent such F_ is preferably 1 to 500 mol% relative to I spoon compound (6) or a mixture (6 7), particularly preferably 10 to 100 mol%, especially 5 to 50 mol % is preferred. The lower limit of the reaction temperature, - 30 ° is preferably at least C, the upper limit of the boiling point of the solvent, compound

Lowest temperature of preferably of boiling point and the boiling point of (6), and the compound (7), - it is particularly preferred 20 ° Celsius to ten 250.

Even when the liquid-phase method performs a decomposition reaction of the ester bond, using a reactor having a distillation column, while distilling the reaction was carried out, preferably taken product is vaporized continuously the. As a method to obtain a compound (6) Compound (1) Compound (2) compound with ester Le reaction with (4), then the by how the compound (4) Ru reacted in the liquid phase It is preferred. Also, mixtures of compounds (6) and the compound (7)

(Hereinafter, referred to as the mixture (6 7).), The compound (1), a mixture of Compound (2) with the compound (3) (hereinafter, referred to as the mixture (2-3).) And ester Kahan response by, compound (4) with the compound (5) a mixture of (hereinafter referred to as the mixture (4 one 5).), and then Rukoto the mixture (4 one 5) is reacted with fluorine in a liquid phase It can be obtained by. As used here mixture (2-3), compound

(2) the amount ratio of the compound (3) is not particularly limited.

Compounds in the method (1) is, R A OCH 2 CH (CH 3) OH [ hereinafter referred to as the compound (1 ') is a compound available cheaper than. Therefore, the use cheaper compounds to (1), which was esterified fluorinated, to give mixture by carrying out a decomposition reaction of the ester linkage (2 F- 3 F), the mixture is a solution heat content the method of the present invention to obtain single useful fluorine-containing vinyl ether compound (8) by is a industrial production process efficient superior method as. Compound (1) used in the esterification reaction with the compound, is either a compound (2) and either a mixture (2 F- 3 F), be determined in consideration of Chasse of availability, economical efficiency, etc. It may be Re, using any effect of the present invention is exhibited.

Or a mixture (6 7) may be obtained by the fluorination reaction described later mixture (4 F- 5 F). A method of using a mixture (4 F- 5 F) is an advantageous method when carried out as a continuous manufacturing how.

The concept of the production process of the present invention, including the acquisition route and later continuous production method of a mixture (2 F- 3 F) is shown below. However [] compound in, generated when using the mixture (2-3), in the case of using the compound (2) shows the generated without compound.

R AF OCF = CF 2 (8 )

Here, R A, R B or R c each independently, a monovalent group formed in 'R AF by reacting with fluorine in R AF same group or in the liquid phase, <X is a halogen atom it is. R A is a group having a carbon skeleton corresponding to R AF, 1 or more fluorine atoms in R AF, preferably all, it is preferably a monovalent group that is substitution of a hydrogen atom. Also, R B, R c is preferably the same group as R AF.

R A, R B, and R c each independently represents a monovalent saturated hydrocarbon group, halogenation monovalent saturated hydrocarbon group or the Ru hetero atom-containing monovalent saturated hydrocarbon group der to is preferred. Or it may be filed under the Natsuta unsaturated carbon one-carbon unsaturated bonds, such as one or more carbon one-carbon single bonds in these groups double bonds or triple bonds. The group of the unsaturated, monovalent unsaturated hydrocarbon group, a halogenated monovalent unsaturated hydrocarbon group or a hetero atom-containing monovalent unsaturated hydrocarbon group, is exemplified et be. Specific examples of the group of the unsaturated, alkenyl, cycloalkenyl, partial click every mouth alkenyl group, partially chlorinated alkenyl O alkoxyalkyl group, and the like. Groups of unsaturation may be added fluorine to the carbon Motoichi carbon double bond to a carbon one-carbon single bond by fluorination in a liquid phase. Also, if there is double bond carbon Ichisumi containing Ξ in the organic radical can be added fluorine to the carbon Motoichi carbon triple bond by fluorination in a liquid phase, carbon one-carbon single bond or carbon one carbon double bond is formed.

Examples of compounds (1) are the following compounds can be mentioned, compound (la) is good preferable. Compound (1) is a compound which can be easily and inexpensively synthesized by easily and inexpensively available or known methods.

CH 2 = CHCH 2 OCH 2 CH 2 CH 2 OH (1 a),

CH 3 OCH 2 CH 2 CH 2 OH (lb),

CH CH single OCH 2 CH 2 CH 2 OH ( 1 c), CH 3 (CH 2) 5 OCH 2 CH 2 CH 2 OH (1 d), CH 3 (CH 2) 9 OCH 2 CH 2 CH 2 OH (1 e).

Compounds similar compounds and the compound Examples of (2) (2 F), compound (2 F) compounds which became one COF gar COC 1 in the compound (2 F) C one F in the C one compound becomes H and the like, the following compound (2 a) it is preferred.

FCOCF (CF 3) OCF 2 CF 2 CF 3 (2 a) 0

The compounds Examples of compounds (3) (3 F) and similar compounds, compounds (3 F) in - compound COF becomes COC 1, C one compound (3 F) in

F can be mentioned compounds become C one H, the following compound (3 a) is preferred.

FCOCF 2 CF 2 OCF 2 CF 2 CF 3 (3 a).

Examples of compounds (4) include the following compounds, arbitrary compound (4 a) is preferred.

CH 2 = CHCH 2 OCH 2 CH 2 CH 2 OCOCF (CF 3) 〇_CF 2 CF 2 CF 3 (4 a ),

CH 3 OCH 2 CH 2 CH 2 OCOCF (CF 3) OCF 3 (4 b), CH 3 CH 2 OCH 2 CH 2 CH 2 OCOCF (CF 3) OCF 2 CF 3 (4 c),

CH 3 (CH 2) 5 OCH 2 CH 2 CH 2 OCOCF (CF 3) 〇 (CF 2) 5 CF 3 ( 4 d),

CH 3 (CH 2) 9 OCH 2 CH 2 CH 2 OCOCF (CF 3) O (CF 2) 9 CF 3 (4 e),

Examples of compounds (5) may be mentioned the following compounds, arbitrary compound (5 a) is preferred.

CH 2 = CHCH 2 O CH 2 CH 2 CH 2 OCOC F 2 CF 2 OCF 2 CF 2 CF 3 (5 a), CH 3 OCH 2 CH 2 CH 2 OCOCF 2 CF 2 OC F 3 (5 b), CH 3 CH 2 OCH 2 CH 2 CH 2 OCOC F 2 CF 2 OC F 2 CF 3 (5 c),

CH 3 (CH 2) 5 O CH 2 CH 2 CH 2 〇_COCF 2 CF 2 O (CF

2) 5 CF 3 (5 d ),

CH 3 (CI- I 2) 9 OCH 2 CH 2 CH 2 OCOCF 2 CF 2 O (CF 2) 9 CF 3 (5 e),

Compound (1), an ester Kahan response of the compound (2) or a mixture (2-3) can be carried out by applying the reaction method and conditions of a known esterification reaction. Further, the esterification reaction may be carried out in the presence of a solvent, but to carry out in the absence of a solvent is preferred from the viewpoint of the volume efficiency. When a solvent is used, dichloroethylene Rorometan, black hole Holm, the mixed solvent of Bok Riechiruamin or Toryechiruamin and tetrahydrofuran are preferred. The amount of the solvent, the compound

(1), compound (2), and preferably 50 to 500 mass% based on the total amount of the compound (3).

In the esterification reaction, the acid such as HF are generated, an alkali metal fluoride as a scavenger of HF (NaF, KF is preferred) a and Bok Riarukiruami emission may be present in the reaction system. HF scavengers, Compound (1) Compound

(2), and when the compound (3) are each unstable compounds in acid, it is better to use. Also, when not using the scavenger of HF is preferably discharged HF out of the reaction system was entrained in a stream of nitrogen. The amount of the case of using the alkali metal fluoride is preferably equal to 1-1 0 mol per mol of the mixture (2-3).

The reaction temperature of the esterification reaction of the compound (1) is usually, - 5 0 ° is preferably at C or more, + 1 00 ° C or less or less or solvent boiling point is preferred. Further, the reaction of the reaction time can be appropriately changed depending on the compound amount to be used for the reaction with the raw material feed rate of. Reaction pressure (gauge pressure, hereinafter the same) is 0 (atmospheric pressure) ~ 2MP a is preferable.

Compound formed in the above reaction (4) or a mixture reaction of crude Narubutsu containing (4 one 5), be purified according to the purpose, but it may be used for the next reaction such as the following steps the fluorination reaction in view done safely in, crude compound in the product (4) and the compound (5) is not to want to separate purified from other compounds. The purification method of the crude product, the distillation of the crude product a method of directly distilling a method of separated the crude product was treated with a dilute alkali solution, after extracting the crude product with a suitable organic solvent how to silica gel column chromatography, and the like.

Then, the compound (4) or a mixture (4 one 5) is a mixture is reacted with fluorine in a liquid phase (6 7). This reaction can be carried even ECF method, a cobalt fluorination method is carried out by liquid-phase fluorination method is reacted with fluorine (F 2) in the liquid phase in the present invention.

That is, when performing the fluorination by cobalt fluorination method or ECF method, compound (4) or Compound (5) is isomerization reaction, the compound (4) or compound

(5) cleavage reaction of carbon one-carbon bonds in, and cleavage reactions of carbon one oxygen bonds further recombine reaction of these bonds cleaved, the yield of the mixture of interest (6-7) there is a risk of deterioration. Further, when the fluorinated by vapor phase fluorination reaction, and it is control of the reaction is difficult, occur compound (4) or compound (5) cleavage reaction of carbon one-carbon bonds in, the objective the yield of the mixture (6 -7) may be reduced. According to this with respect to the liquid phase fluorination method, obtained in good yield mixture (6- 7) while preventing adverse reactions. When performing a liquid-phase fluorination method, a method of reacting the compound (4) or the mixture (4 one 5) with fluorine gas is introduced into the liquid phase are preferred. Fluorine gas, be used as it is, or may be used a fluorine gas diluted with an inert gas. As the inert gas, nitrogen gas, helium gas preferably, for economic reasons or we nitrogen gas is particularly preferred. Fluorine gas content in the inert gas is not particularly limited, 1 preferred in view of efficiency to 0% or more, 2 0% or more and particularly preferred arbitrariness is to.

The liquid phase in the liquid phase fluorination method, the fluorination reaction Flip be inactive - are preferred solvents of C-F bond does not include the H bond as essential, further Perufuru Oroarukan such, a known organic solvent Perufuruoro turned into organic solvents are preferred. Furthermore, the solvent As the solvent, which can dissolve the compound (4) and the compound (5) it is preferable to use high solubility solvent for, in particular the compound (4) and the compound (5), respectively 1 wt% or more and particularly preferable to use a solvent medium capable of dissolving at least 5 mass%.

Further, the liquid phase by dissolving the fluorine, and, since it is capable of dissolving the mixture (2-3) is preferred, a mixture (2 - 3) of the compound in order to improve the solubility in a liquid phase (4) fluorine content in the well, the fluorine content in the compound (5), preferably to the 3 0 wt% or more, respectively, preferably in a particular 3 0-7 6 wt%. Examples of the solvent used in the liquid phase fluorination method, Perufuruoroa glucan such (FC- 7 2 etc.), per full O b ethers (FC- 7 5, FC- 7 7 etc.), per full O b polyethers (trade name:. Kuraitotsukusu, Fomblin, Galden, DEMNUM etc.), black hole Furuorokabon acids (trade name: Freon loop), black mouth full O b polyethers, pel full O b alkyl § Min (e.g., Perufuruoro Bok real Kiruamin etc.), inert fluid (trade name: Fluorinert), and the like. Among these, per full-O Lot rear Rukiruamin it is preferable. As the liquid phase, a compound involved in the reaction of the present invention, a compound having a function as a solvent (2 F), compound (3 F), compound (6), or of compound (7) in the case of using at least one is of an advantage post-treatment after the reaction is readily ing.

Amount of liquid phase for performing the fluorination with a liquid phase fluorination method, based on the total amount of the compound (4) and compound (5), preferably at least 5 times by mass, particularly 1 0-1 0 0 weight equivalents It is preferred.

The reaction system of the liquid phase fluorination reaction may be either a patch system or a continuous system. Further, examples of the reaction system is preferably by the following fluorination method 1 or fluorination method 2, in particular from a reaction yield of selectivity point, preferably Ru good below fluorination 2. Fluorine gas, even when carried out batchwise, when implemented in continuous manner also may be used diluted with an inert gas such as nitrogen gas.

In the fluorination method 1] reactor was charged with compound (4) or a mixture (4 one 5) a solvent, and stirring is initiated. Under predetermined reaction temperature and reaction pressure, the method of the fluorine gas, the reaction is performed while continuously supplying.

Charged solvent in the fluorination 2] reactor, and stirring is initiated. At the reaction pressure and a predetermined reaction temperature, solvent and the fluorine gas continuously and method for providing simultaneous compound (4) or a mixture (4 one 5) and a predetermined molar ratio.

In the fluorination method 2, when supplying compound (4) or the mixture (4 one 5) improves the selectivity, by-products amount since it is suppressed, the mixture was diluted with solvent (4 one 5) it may be supplied. Further, the fluorination method 2, when diluted mixed compound (4 one 5) in solvent, to a may preferably be the amount of solvent 5 times by mass or more relative to the mixture, in particular 10 times by mass or more It is preferred. In the liquid phase fluorination reaction, even when carried out on a continuous basis even if the reaction is carried out batchwise, the total number of hydrogen atoms of the compound (4) and the compound (5), the fluorine amount is always preferably to carry out the reaction in a state in which the presence of fluorine so that the excess equivalent, in particular 1.5-fold equivalent or more (i.e., 1.5 fold molar or more) selected for the presence of a fluorine gas so that the preferred rate point (fluorine gas content is preferably that continued to maintain always excess until the end from the start of the reaction.

The reaction temperature of the liquid phase fluorination reaction is usually preferably not more than the boiling point of one 60 ° and at C or more and the compound (4) with the compound (5) and the boiling point or a compound of a mixture of (4), reaction yield, selectivity, and particularly preferably one 5 0 ° Celsius to tens 1 00 ° C from the viewpoint of industrial practice ease, reaction pressure especially preferred fluorination reaction to ten 50 ° C in one 20 is particularly limited not, 0~2MP a is the reaction yield, selection 択率, particularly preferred in view of industrial practice ease.

Furthermore, in order to advance the liquid phase fluorination method efficiently, adding C one H bond-containing compound to the reaction system, or irradiated with ultraviolet rays, it is preferred. This may compound present in the reaction system (4) and the compound (5) can be efficiently fluorinated, dramatically improved reaction rates. UV irradiation time is preferably 0.1 to 3 hours.

The C one H bond-containing compound is a compound (4) and the compound (5) an organic compound other than, in particular aromatic hydrocarbons are preferred, especially benzene, preparative Ruen the like are preferable. The addition amount of the C one H bond-containing compound, Compound (4) Contact and compound (5) 0.1 1 to 10 mol% based on the hydrogen atom the total number and even good Mashiku, particularly from 0.1 to 5 preferably a mol%. C one H bond-containing compound is preferably added in a state where there is a fluorine gas in the reaction system. Furthermore, when added to C-H bond-containing compound is preferably pressurize the reaction system. The pressure of the pressurized, 0 · 01 ~ 5MP a is preferable. In the fluorination reaction, the if the reaction occurs to replace the hydrogen atom with a fluorine atom, HF is by-produced. To remove the by-product HF is coexist scavenger HF in the reaction system, or reactor is preferable to a gas outlet is contacted with HF scavenger and the outlet gas. As the HF scavenger is used the same as those used in the reaction with the compound of the aforementioned (1) a mixture (2-3), Na F are preferred.

The amount in the case of coexistence of HF scavenger in the reaction system is 1 to 20 moles are preferred with respect to the total amount of all hydrogen atoms present in the compounds (4) and the compound (5) from 1 to 5 times mole It is preferred. When placing the HF scavenger in the reactor gas outlet preferably maintained in (a) is preferably held in a cooler (1 0 ° Celsius to room temperature (25 ° C), especially about 20 ° C .) (b) Na F pellet packed layer, and (c) a cooler (- is preferably maintained at 78 ° C~ + 10 ° C, in particular that to hold to an 3 0 ° C~0 ° C the preferred), (a) - (b) - for installation in series is preferred in the order of (c). Also, it may be installed a liquid returning line to return the condensed liquid to the reactor from (c) cooler.

The fluorination reaction, the compound (4) to the fluorinated compound (6), or the compound (5) becomes fluorinated compound (7). Obtained by the fluorination reaction, the compound (6) or a mixture (6 7) crude product containing may be used directly in the decomposition process of the next ester linkage, be purified to a high purity There. The purification method may, for example, how such distilling the crude product as it is under normal pressure or reduced pressure, and the like. Compound (6) or a mixture (6 7), the decomposition reaction of the ester bond, the mixture (2 F- 3 F) capable of generating.

Mixtures (6- 7), the compound (2 F) and the compound (3 F) a mixture of (hereinafter, a mixture (2 F- 3 F) and referred.) Be cowpea the decomposition reaction of the ester bond available. That mixture (6 7), the compound (1) the mixture (2 F- 3 F) and the corresponding mixture is reacted (4 F- 5 F), then the mixture (4 F- 5 F) obtained by reacting with fluorine in a liquid phase. In this method, the fluorination reaction of the compound (1) and the mixture esterification reaction between (2 F- 3 F), and the mixture obtained in the reaction liquid phase of the (4 F- 5 F), the it can be carried out in the way and the same way.

Wherein the compound compounds placing serial in illustration of the compound (4) Specific examples of (4 F) is, compounds described in examples of the compounds as specific examples of the compound (5 F) (5) and the like. Further, as a method to obtain the mixture (2 F- 3 F) is not particularly limited, in the present invention, the compound (6), or, obtained by the decomposition reaction of the ester bond of mixed compounds (6- 7) mixture preferably used part of (2 F-3 F). Mixture (2 F- 3 F) methods of recycling to the esterification reaction with some compound (1) of, only you feed compound (1) from the outside of the reaction system, reasonably efficiently fluorinated can be a continuous process that produced vinyl ether compound (8).

The said continuous process is as follows. That is, the compound (1) as a starting material, the compound (2) or a mixture (2-3) and an esterification reaction means pursuant compound of (4) or a mixture to obtain (4 one 5), then compound ( 4) or to give a mixture (4 one 5) fluorinated compound reaction by performing the (6) or the mixture (6 7), then the ester of the compound (6) or a mixture (6- 7) binding was decomposed to obtain the first mixture (2 F- 3 F). In this initial mixture (2 F- 3 F), and then give the compound (1) mixture was esterified reaction (4 F- 5 F), the mixture (4F-5 F) by fluorination mixture (6 7) was obtained, and then the mixture (6 7) of the initial mixture by performing a decomposition reaction of the ester bond (2 F- 3 F) greater than the amount mixture of Te (2 F- 3 F) is obtained. The mixture (2 F- 3 F) may be subjected to thermal decomposition reaction at, successively more repeating the reaction process of again compound (1), higher amounts mixture of (2 F- 3 F) it can be obtained manner. The method of this uses a simple and inexpensive compound obtained (1), and by reducing the inter-hand product separation, the fluorine-containing bi vinyl ether compound having R AF group corresponding to R A of the compound (1) (8) it is a very efficient process capable of producing. As the compound (1), either commercially available, can be easily synthesized from compounds of diverse structures which are commercially available, it is readily available.

The target compound is a fluorine-containing vinyl ether compound of the present invention a method (8), since it has a polymerizable vinyl fluoride group, fluorine-containing vinyl ether compound

Can be prepared one or more, or a fluorine-containing vinyl ether compound containing fluorine Pinirueteru compound (8) and can be polymerized polymerizable monomer is polymerized useful fluoropolymer and (8) (8) .

The polymerizable monomer can be polymerized fluorinated vinyl ether compound (8) it is not particularly limited, may be selected from known polymerizable monomers. Our method of polymerization reactions, can be applied as a technique known reaction. For example CF 2 = CF 2, CF 2 = CFC 1, CF 2 = Furuoroechiren such as CH 2, full O b propylene such as CF 2 = CF CF 3, CF 3 CF 2 CF 2 CF 2 CH - CH 2 Ya CF 3 CF 2 CF 2 CF 2 CF = CH 2 , etc. pel full O of Russia alkyl group carbon number is 4-12 (per full O b alkyl) ethylenes, include ethylene, propylene Ren, Orefin such as Isobuchiren is It is.

Fluoropolymer obtained by polymerization reaction, is useful as a fluorocarbon resin. Off fluororesin, since it has excellent properties in heat resistance and chemical resistance, it is used in various fields. Ingredients Example> Although detailed explanation of the present invention to the following examples, these by the onset bright is not limited. Incidentally, it marks the gas chromatography and GC, gas chromatography mass spectrometry and GC-MS in the following. Moreover, GC purity purity determined from the peak area ratio of GC, referred to yield a GC yield, the yield determined from the peak area ratio of the NMR spectrum described as NMR yield. Also referred to tetramethyl Sila down TMS, and CC 1 2 FCC 1 F 2 the R- 1 1 3. Further, NMR space Kutorude Isseki showed a chemical shift range of apparent. Reference value of 1 3 reference material CDC 1 3 of definitive to C one NMR was set to 76. 9 p pm. In quantification by 1 9 F- N MR C 6 F 6 was used as the internal standard.

[Example 1] CH 2 = CHCH 2 OCH 2 CH 2 CH 2 OCOCF (CF 3) Preparation of OCF 2 CF 2 CF 3

GC purity of 99% CH 2 = CHCH 2 OCH 2 CH 2 CH 2 OH and (13. 9 g) and Toriechiruamin (25. 4 g) were placed in a flask and stirred in an ice bath. FCOCF (CF 3) was added dropwise over OCF 2 CF 2 CF 3 (41. 7 g) 2 hours while keeping the inner temperature at 1 below. After completion of dropping, the mixture was stirred for 1 hour then to room temperature and added to ice water 50 mL.

The obtained crude liquid was subjected to liquid separation, and the lower layer was washed twice with water 5 OML, dried over sulfate Maguneshiu arm, and filtered to give a crude liquid. It was obtained as a fraction of the vacuum distillation in CH 2 = CHCH 2 〇_CH ¾ CH 2 CH 2 OCOCF (CF 3) OCF 2 CF 2 CF 3 (30. 3 g) of 89~90 ^ / 1. 2 k P a . GC purity was 99%. NMR scan Bae Kutorudeta were as follows.

1 H-NMR (300. 4MH z , solvent: CDC 1 3, reference: TMS) δ (p pm) :. 1. 95~2 03 (m, 2 H), 3. 48 (t, J = 6. 0 H z, 2H), 3. 94 (dt, J = 1. 5, 6. 0Hz, 2 H), 4. 4 2~4. 5 5 (m, 2H), 5. 1 6 (d, J = 1 0. 5 H z, 1 H), 5

24 (d, J = 1 7. l Hz, 1 H), 5. 8 0~ 5. 9 3 (m, 1 H).

1 9 F-NMR (2 8 2. 7MHz, solvent · · CDC 1 3, reference · · CFC 1

3) δ (p pm): - 7 9. 9 (IF), one 8 1. 3 (3 F), one 8 2. 2 (3 F), - 8 6. 6 (IF), - 1 29. 5 (2 F), one 1 3 1.5 (1

F).

[Example 2] CF 3 CF 2 CF 2 OCF 2 CF 2 CF 2 OCOCF (CF 3) Preparation of OCF 2 CF 2 CF 3

To 5 0 OML of nickel autoclave, R- 1 1 3 a (3 1 2 g) was pressurized forte agitation was maintained at 2 5 ° C. The autoclave gas outlet, 20 ° C cooler maintained at, N a F pellet packed layer, and an 1 0 ° and held at C cooler installed in series. Incidentally, one 1 from the held condenser at 0 a liquid returning line was installed to return the condensed liquid to the autoclave. After yelling can the nitrogen gas 1.0 hours blow, a fluorine gas diluted to 2 0% with nitrogen gas, was blown for one hour at a flow rate of 6. 47 LX h.

Then, while blowing the fluorine gas at the same flow rate, CH 2 = CH CH 2 OCH 2 CH 2 CH 2 OCOCF (CF 3) obtained in Example 1 OCF 2 CF 2 CF 3 ( 4. 9 9) a - 1 1 3 dissolved solution was injected over a period 8.0 hours to a (1 0 0 g).

Then, while blowing the fluorine gas at the same flow rate, and 9m L injected while raising the temperature to a benzene concentration is 0. 0 1 gZmL R- 1 1 3 solution from 2 5 ° C to 40 ° C, autoclave close the benzene inlet, further closing the outlet valve of O one Tokurepu, close the fluorine gas inlet valve of the autoclave where the pressure becomes 0. 20 mP a, it was continued for 0.6 h. Then the pressure was brought to atmospheric pressure, while maintaining the reactor temperature at 40 ° C, the above benzene solution was 6 m L injected, closing the benzene injection inlet of the autoclave, further closing the outlet valve of the autoclave, the pressure 0. close the autoclave fluorine gas inlet valve upon reaching the 2 OMP a, it was continued for 8 hours stirring 0.1. In addition, it was repeated once the operation of the same customers.

The total amount of benzene injected in injection amount of 0. 2 1 9 g, R- 1 1 3 was 2 LML. In addition, nitrogen gas was blown for 1.5 hours. Was quantified target compound 1 9 F-NM R, the yield of the standard compounds was 8% 85.. NMR spectral data were as follows.

1 9 F-NMR (37 6. 0MHz, solvent: CDC 1 3, reference: CF C 1 3) δ ( p pm): - 7 9. 9 (IF), - 82. 1 (6 F), one 82 . 3

(3 F), - 83. 9 (2 F), one 84. 7 (2 F), one 86. 9 (IF), - 87. 4 (2 F), - 1 29. 6 (2 F), - 1 30. 2 (2 F), one 1 30. 5 (2 F), - 1 32. 2 (1 F).

[Example 3] Production Example of CF 3 CF 2 CF 2 OCF 2 CF 2 C OF

Example 2 obtained in CF 3 CF 2 CF 2 OCF 2 CF 2 CF 2 OCOCF (CF 3) OCF 2 CF 2 CF 3 a (8 g) was charged to the flasks with NaF powder (0. lg), carried out vigorously stirring heated 1 0 hours pressurized with 1 20 in the oil path in while. At an upper portion of the flask was installed a reflux condenser adjusted at a temperature of 20 ° C. After cooling, it was recovered liquid sample (7 g). The GC- MS, CF 3 CF (OCF 2 CF 2 CF 3) a COF and the title compound is the main product, and 1: it was confirmed that a mixture of 1. NMR scan Bae Kutorudeta of the title compound were as follows.

1 9 F-NMR (376. 0 MH z, solvent: CDC 1, reference: CFC 1 3) δ (p pm) 24. 4 (IF), one 81. 9 (3 F), one 84.7 (2 F), - 85 9 (2 F), - 1 2 1. 7 (2 F), one 130. 4 (2 F).

[Example 4] CH 2 = CHCH 2 OCH 2 CH 2 CH 2 OCOCF (CF 3) OCF 2 CF 2 CF 3 and CH 2 = CHCH 2 O CH 2 CH 2 CH 2 OC OCF 2 CF 2 OCF 2 CF 2 CF 3 preparation of a mixture of

CF 3 CF 2 CF 2 OCF obtained in Example 3 (CF 3) C_〇_F Oyobi CF 3 CF

An aliquot of 2 CF 2 OC F 2 CF 2 COF, CF in Example 1 this

3 CF 2 CF 2 OCF (CF 3) used in place of the COF having conducted the reaction in the same manner. Reduced pressure to give the title mixture by distillation.

[Example 5] CF 3 CF 2 CF 2 OCF 2 CF 2 CF 2 OCOCF (CF 3) OCF 2 CF 2 CF 3 and CF 3 CF 2 CF 2 OC F 2 CF 2 CF 2 OC OC F 2 CF 2 OCF 2 CF preparation of a mixture of 2 CF 3

To give the title mixture by carrying out the reaction in the same manner using the mixture obtained in Example 4 in place of CH 2 = CHCH 2 OCH 2 CH 2 CH 2 OCOCF (CF 3) OC F 2 CF 2 CF 3 in the example 2 .

The presence of CF 3 CF 2 CF 2 OCF 2 CF 2 CF 2 OCO CF 2 CF 2 OCF 2 CF 2 CF 3 in the mixture was confirmed by GC-MS. GC- MS: 645 (M + one F).

[Example 6] Production Example of CF 3 CF 2 CF 2 OCF 2 CF 2 (30? Oyobi? 3 CF 2 CF 2 OCF ( CF 3) mixture of COF

To give the title mixture by carrying out the reaction as the mixture obtained in Example 5 CF 3 CF 2 CF 2 OCF 2 CF 2 CF 2 OCOCF (CF 3) in Example 3 using in place of OCF 2 CF 2 CF 3 .

[Example 7] Production Example of CF 3 CF 2 CF 2 OCF = CF 2

Connect internal diameter 20 mm, and S US column made of 1 m long average particle size 160 im of N a 2 C0 3 and 2 80 g packed with an inner diameter of 45 mm, an S US-made fluidized bed reactor of height 400mm in series It was placed in a salt bath, the temperature adjusted reactor in the nitrogen gas in the salt bath to 270 ° C flowing at 1 52 OmL / min, CF 3 CF obtained in example 6 (〇_CF 2 CF 2 CF 3) Flip 0? Oyobi. 3 CF 2 CF 2 OCF 2 CF 2 60. The mixture of COF with the metering pump 2 g / 1. For 8 hours feed. The anti 応器 outlet established a dry ice / ethanol trap, the product was collected. CF 3 CF 2 CF 2 OCF = CF 2 was produced a yield of 80%.1 9 F -NMR product (564. 6MHz, solvent: CDC 1 3, reference: CFC 1 3) the peak of were consistent with those of the authentic sample.

<Industrial Applicability>

According to the method of the present invention, useful fluorinated Biniruete Le compound as the fluorine resin material, was obtained at low cost easily starting compound (1), a mixture (2 F- 3 F) or al, short steps, and in high yield it can be efficiently produced. The method of the present invention is an advantageous method can be carried out without separating the product in each step. Also a E industrially useful method for continuous production process can achieve a product without the separation in each step. Further, novel compounds useful as a raw material for the production of fluorine-containing vinyl ether compound.

Claims

The scope of the claims
1. method for producing the mixture of the following compound (2 F) and the following Compound (3 F), the following fluorine-containing vinyl ether compound, characterized by performing thermal decomposition reaction (8). In the formula, R AF is a monovalent organic group which does not change by a thermal decomposition reaction.
R AF OC F (CF 3) COF (2 F)
R AF O (CF 2) 2 COF (3 F)
R AF OC F = CF 2 ( 8)
2. the following compound (6), or in a mixture of the following compound (6) the following compound (7), the following compound by performing a decomposition reaction of the ester bond (2 F) and the following compound (3 F) the mixture obtained, the production method c However Shikichu the next following fluorinated vinyl ether compound, characterized by performing the thermal decomposition reaction in the mixture (8), R AF is' monovalent organic unchanged by pyrolysis reaction a group.
R AF O (CF 2) 3 OCOC F (CF 3) OR AF (6)
R AF O (CF 2) 3 OCOC F 2 CF 2 OR AF (7)
R AF OC F (CF 3) COF (2 F)
R AF O (CF 2) 2 COF (3 F)
R AF OC F = CF 2 ( 8)
3. compound (6), the following compound (1) and the following compound (2) are reacted esterified to produce the following compounds (4), full Tsu containing then the compound (4) in a liquid phase a reaction product obtained by reacting the compound (6) with the compound mixture of (7), the following compound (1) and the following compound (2) and the following compound (3) and the mixture is reacted following compound of ( 4) to produce a mixture of the following compound (5), said chemical compound (4) with the compound mixture of (5), which is a reaction raw formed product was reacted with fluorine in a liquid phase, in claim 2 the method according.
In the formula, R A, R B, R c are each independently a R AF same monovalent organic group or a monovalent organic group comprising the R AF by reacting with fluorine in a liquid phase, , R AF is a monovalent organic group which does not change by a thermal decomposition reaction, X is a halogen atom.
R A O (CH 2) 3 OH (1)
XCOCF (CF 3) OR B ( 2)
XCO (CF 2) 2 OR c (3)
AO (CH 2) 3 OCOCF ( CF 3) 〇_R B (4)
R A O (CH 2) a OCO (CF 2) 2 OR c (5)
4. is a compound (4) fluorine content more than 30 mass% in method according to claim 3 fluorine content in the compound (5) is not less than 30 mass%.
5. Compound (6) and compound mixtures (7), the following compound (1), under the title compound (2 F) and the following Compound (3 F) mixture and is reacted esterified following compounds of (4F ) and the following compound (5 F) mixture to produce the method according to claim 2 the following to the mixture is a reaction product obtained by reacting with fluorine in a liquid phase. However. Wherein, RA represents one Ataiyu machine group consisting R AF by reacting with fluorine in R AF same 1 Ataiyu machine group or in the liquid phase,, R AF is not changed by the thermal decomposition reaction a monovalent organic group.
R A O (CH 2) 3 OH (1)
R AF OC F (CF 3) COF (2 F). R AF 0 (CF 2) 2 COF (3 F)
R A O (CH 2) 3 OCOC F (CF 3) OR AF (4 F)
R A O (CH 2) 3 OCOCF 2 CF 2 OR AF (5 F)
6. mixtures of compounds (2 F) and Compound (3 F) is the following compound (6) Contact and the following compound (7) portion of the reaction product obtained by carrying out the decomposition reaction of the ester bond in the mixture or the method according to claim 5 in whole. In the formula, R AF is a monovalent organic group which does not change by a thermal decomposition reaction.
R AF 0 (CF 2) 3 OCOC F (CF 3) OR AF (6)
R AF O (CF 2) 3 OCOC F 2 CF 2 OR AF (7)
When fluorine is reacted 7. liquid phase, as a liquid phase, the compound (2 F), compound (3 F), using Compound (6), and compound at least one kind of compound selected from (7) claim 3, 4, 5 or method according to 6,.
8. R AF is Perufuruoro (monovalent saturated hydrocarbon) group, Perufuruoro (partially halogenated monovalent saturated hydrocarbon) group, Perufuruoro (hetero atom-containing monovalent saturated hydrocarbon) group or Perufuruoro (hetero the partially halogenated, the process according to any one of claims 1 to 7 is atom-containing Atai飽 sum hydrocarbon) group.
9. the following compound (la), to give a mixture of the following compound (2 a) and the following compound (3 a) a mixture and by esterification reaction the following compound of (4 a) and the following compound (5 a), then the compound (4 a) and a mixture of the following compounds by reacting with fluorine in a liquid phase of (5 a) (6 a) and the following compound
To give a mixture of (7 a), then the compound (6 a) and a mixture of (7 a)>
PCT/JP2001/008369 2000-09-26 2001-09-26 Process for producing fluorinated vinyl ethers WO2002026682A1 (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6586626B2 (en) 1999-03-23 2003-07-01 Asahi Glass Company, Limited Process for producing a fluorine-containing compound by liquid phase fluorination
US6956138B2 (en) 2000-07-11 2005-10-18 Asahi Glass Company, Limited Method for producing a fluorine-containing compound
US8232416B2 (en) 2008-02-26 2012-07-31 Fujifilm Corporation Method of manufacturing perfluorinated polyfunctional vinyl ether compound

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Publication number Priority date Publication date Assignee Title
EP0150618A2 (en) * 1983-12-27 1985-08-07 E.I. Du Pont De Nemours And Company Fluorinated vinyl ethers, copolymers thereof, and precursors thereof
JPH02311438A (en) * 1989-05-24 1990-12-27 Asahi Glass Co Ltd Novel fluorine-containing compound, its production and use
WO1995025082A1 (en) * 1994-03-15 1995-09-21 Minnesota Mining And Manufacturing Company Process for converting perfluorinated esters to perfluorinated acyl fluorides and/or ketones
WO2000056694A1 (en) * 1999-03-23 2000-09-28 Asahi Glass Company, Limited Process for producing fluorine compound through liquid-phase fluorination

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Publication number Priority date Publication date Assignee Title
US3291843A (en) * 1963-10-08 1966-12-13 Du Pont Fluorinated vinyl ethers and their preparation
US3326984A (en) * 1965-04-28 1967-06-20 Du Pont Perfluorodivinyl ether
JPS6251943B2 (en) * 1978-02-21 1987-11-02 Asahi Glass Co Ltd
JPH0380145B2 (en) * 1983-12-28 1991-12-24 Tokuyama Soda Kk

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Publication number Priority date Publication date Assignee Title
EP0150618A2 (en) * 1983-12-27 1985-08-07 E.I. Du Pont De Nemours And Company Fluorinated vinyl ethers, copolymers thereof, and precursors thereof
JPH02311438A (en) * 1989-05-24 1990-12-27 Asahi Glass Co Ltd Novel fluorine-containing compound, its production and use
WO1995025082A1 (en) * 1994-03-15 1995-09-21 Minnesota Mining And Manufacturing Company Process for converting perfluorinated esters to perfluorinated acyl fluorides and/or ketones
WO2000056694A1 (en) * 1999-03-23 2000-09-28 Asahi Glass Company, Limited Process for producing fluorine compound through liquid-phase fluorination

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6586626B2 (en) 1999-03-23 2003-07-01 Asahi Glass Company, Limited Process for producing a fluorine-containing compound by liquid phase fluorination
US6951957B2 (en) 1999-03-23 2005-10-04 Asahi Glass Company, Limited Process for producing a fluorine-containing compound by liquid phase fluorination
US7083705B2 (en) 1999-03-23 2006-08-01 Asahi Glass Company, Limited Process for producing a fluorine-containing compound by liquid phase fluorination
US6956138B2 (en) 2000-07-11 2005-10-18 Asahi Glass Company, Limited Method for producing a fluorine-containing compound
US8232416B2 (en) 2008-02-26 2012-07-31 Fujifilm Corporation Method of manufacturing perfluorinated polyfunctional vinyl ether compound

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