JP2005068044A - Fluorine-containing divinyl compound and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a compound containing perfluorovinyl groups having different reactivities at both terminals from a readily available compound by a short process. <P>SOLUTION: A compound represented by formula 1:CH<SB>2</SB>=CH(CH<SB>2</SB>)<SB>m</SB>CR<SP>1</SP>R<SP>2</SP>(CH<SB>2</SB>)<SB>n</SB>OCF=CF<SB>2</SB>(R<SP>1</SP>and R<SP>2</SP>are each H, a 1-5C alkyl group, a 1-5C alkoxy group or the like; m and n are each an integer of 0-3; Z<SP>1</SP>, Z<SP>2</SP>, Z<SP>3</SP>and Z<SP>4</SP>are each Cl, Br or I) is obtained from a readily available compound represented by formula 1-1:CH<SB>2</SB>=CH(CH<SB>2</SB>)<SB>m</SB>CR<SP>1</SP>R<SP>2</SP>(CH<SB>2</SB>)<SB>n</SB>OH, halogenated, fluorinated and dehalogenated by turns to produce a compound represented by formula 4:CF<SB>2</SB>=CF(CF<SB>2</SB>)<SB>m</SB>CR<SP>F1</SP>R<SP>F2</SP>(CF<SB>2</SB>)<SB>n</SB>OCF=CF<SB>2</SB>(R<SP>F1</SP>and R<SP>F2</SP>are each a 1-5C polyfluoroalkyl group, a 1-5C polyfluoroalkoxy group or the like). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for producing a fluorinated divinyl compound having a perfluorovinyl group at one end of the main chain and a perfluorovinyloxy group at the other end, and a useful and novel fluorine-containing compound that can be used in the production method. Relates to compounds.

As a fluorine-containing divinyl compound having a perfluorovinyl group at one end of the main chain and having a perfluorovinyloxy group at the other end, a compound represented by the following formula a is known (see Patent Document 1). ).
CF ₂ = CF (CF ₂ ) _k OCF = CF ₂ Formula a
However, k shows the integer of 2-4.
An amorphous polymer obtained by cyclopolymerizing a compound represented by the formula a has a large elastic modulus, yield elongation, elongation at break, excellent impact resistance, and high transparency. Therefore, the amorphous polymer is used as an optical material such as an optical fiber and an optical waveguide. Furthermore, as a monomer of an amorphous polymer having a higher glass transition point and suitable for high temperature use, a compound represented by the following formula b having a trifluoromethyl group in the side chain, and a trifluoromethoxy group: A compound represented by the following formula c in the side chain is known (see Patent Document 2 and Patent Document 3).
CF ₂ = CFCF ₂ CF (CF ₃ ) OCF = CF ₂ ... Formula b
CF ₂ = CFCF (OCF ₃ ) CF ₂ OCF = CF ₂ Formula c
The double bond site of the compound represented by the formula a, the compound represented by the formula b, and the compound represented by the formula c is a dechlorination reaction of -CFClCF ₂ Cl group and / or -CF (COF ) Introduced by thermal decomposition reaction of CF ₃ group or the like.

  The following production route A and the following production route B are known as methods for producing the compound represented by formula a (see Patent Document 1). Production route A is a production route of the compound represented by formula a wherein k is 2 or 4, Production route B is a production route of the compound represented by formula a wherein k is 3. is there. However, s shows 2 or 4. HFPO represents hexafluoropropylene oxide.

  [Production route A]

  [Manufacturing route B]

  Further, the following production route C is known as a method for producing a compound in which k is 2 in the compound represented by the formula a (see Patent Document 4).

  [Manufacturing route C]

  A method for producing a compound represented by the formula b by the following production route D is known (see Patent Document 2).

  [Manufacturing route D]

  A method for producing a compound represented by the formula c by the following production route E is known (see Patent Document 3).

  [Manufacturing route E]

Japanese Patent Laid-Open No. 01-143843 (pages 3 to 4) International Publication No. 01/92194 Pamphlet (pages 13-18) International Publication No. 03/037838 pamphlet (pages 24 to 34) Japanese Patent Laid-Open No. 02-311436 (page 3)

In production route A and production route B, an expensive HFPO, the structure of the product is limited to the structure of _{linear, CF 2 = CFCF 2 OCF =} CF 2 is the starting material in the process of the production route B separately There is a problem that synthesis is necessary and the total number of reaction steps is increased. In the production route C, there are problems such as a method that can be applied only to the production of a compound represented by the formula a in which k is 2 via a fluorooxyhalo compound that is difficult to handle. That is, there is no known production route for producing a compound represented by the formula a in a short process using an inexpensive compound.

Also in production route D, the point of using an expensive _{HFPO, CF 2 ClCFClCF 2 CF =} CF 2 is much total reaction step number is required separately synthesized, that can not be applied to the manufacture of other products of Route D , Etc. Production route E has an advantage that a readily available hydrocarbon alcohol can be used as a raw material. However, there are problems such as a large number of reaction steps, a number of reactions in which hydrogen fluoride is by-produced, a plurality of fluorination reactions, and a limited product. That is, a method for producing the fluorine-containing divinyl compound having various structures from an inexpensive raw material in a short process is not known.

  The present invention has been made for the purpose of solving the above-mentioned problems of conventional methods. Industrially, the fluorine-containing divinyl compound having various structures can be produced industrially in a short process using easily available and inexpensive compounds. There are provided advantageous and practical methods and novel compounds useful in the methods.

In the present invention, the compound represented by the following formula 1 is halogenated using a halogenating agent other than the fluorinating agent to obtain a compound represented by the following formula 2, and then the compound represented by the formula 2 Is fluorinated to obtain a compound represented by the following formula 3, and then the compound represented by the formula 3 is dehalogenated by a dehalogenating agent. A manufacturing method is provided.
CH ₂ = CH (CH ₂ ) _m CR ¹ R ² (CH ₂ ) _n OCF═CF ₂ Formula 1
CH ₂ Z ¹ CHZ ² (CH ₂ ) _m CR ¹ R ² (CH ₂ ) _n OCFZ ³ CF ₂ Z ⁴ ... Formula 2
CF ₂ Z ¹ CFZ ² (CF ₂ ) _m CR ^{F 1} R ^{F 2} (CF ₂ ) _n OCFZ ³ CF ₂ Z ⁴ ... Formula 3
CF ₂ = CF (CF ₂ ) _m CR ^F1 R ^F2 (CF ₂ ) _n OCF = CF ₂ Formula 4
Moreover, this invention provides the manufacturing method of the compound represented by the following Formula 3 characterized by fluorinating the compound represented by the following Formula 2.
CH ₂ Z ¹ CHZ ² (CH ₂ ) _m CR ¹ R ² (CH ₂ ) _n OCFZ ³ CF ₂ Z ⁴ ... Formula 2
CF ₂ Z ¹ CFZ ² (CF ₂ ) _m CR ^{F 1} R ^{F 2} (CF ₂ ) _n OCFZ ³ CF ₂ Z ⁴ ... Formula 3
Furthermore, the present invention provides a compound represented by the following formula 1-A, a compound represented by the following formula 2, and a compound represented by the following formula 3-1.
CH ₂ ═CH (CH ₂ ) _a CR ¹ R ² (CH ₂ ) _b OCF═CF ₂ Formula 1-A
CH ₂ Z ¹ CHZ ² (CH ₂ ) _m CR ¹ R ² (CH ₂ ) _n OCFZ ³ CF ₂ Z ⁴ ... Formula 2
CF ₂ Z ¹ CFZ ² (CF ₂ ) _m C (R ^F10 ) (CF ₃ ) (CF ₂ ) _n OCFZ ³ CF ₂ Z ⁴ ... Formula 3-1.

However, R < ¹ > and R < ² > in a formula shows a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 alkoxy group each independently. R ^F1 and R ^F2 are atoms in which R ¹ and R ² are fluorinated or a fluorinated group, and are a fluorine atom, a C 1-5 polyfluoroalkyl group, or a C 1-5 polyfluoro An alkoxy group is shown. R ^F10 represents a fluorine atom, a trifluoromethyl group, or a trifluoromethoxy group. m and n each independently represents an integer of 0 to 3. Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a chlorine atom, a bromine atom, or an iodine atom. One of a and b is 1 and the other is 0.

  According to the method of the present invention, compounds having various structures having a perfluorovinyl group at one end and a perfluorovinyloxy group at the other end are industrially advantageous in a short process from readily available and inexpensive compounds. And can be produced by a practical method. The present invention also provides a novel compound useful in the production method.

  In the following description of the present invention, a compound represented by Formula 1 is referred to as Compound 1 unless otherwise specified. The same applies to compounds represented by other formulas. The pressure is expressed as a gauge pressure.

  The outline of the compound and the production method of each compound in the present invention can be shown by the following synthesis route.

[Synthetic route]
^{_{CH 2 = CH (CH 2)}} m CR 1 R 2 (CH 2) n OH ··· formula 1-1
↓ Alkali metal, alkali metal hydride, alkali metal salt, or Ag
CH ₂ = CH (CH ₂ ) _m CR ¹ R ² (CH ₂ ) _n OM Formula 1-2
↓ tetrafluoroethylene CH ₂ ═CH (CH ₂ ) _m CR ¹ R ² (CH ₂ ) _n OCF═CF ₂ Formula 1
↓ halogenating agent _{^{CH 2 Z 1 CHZ 2 (CH}} 2) m CR 1 R 2 (CH 2) n OCFZ 3 CF 2 Z 4 ··· Equation 2
↓ Fluorinated CF ₂ Z ¹ CFZ ² (CF ₂ ) _m CR ^{F 1} R ^{F 2} (CF ₂ ) _n OCFZ ³ CF ₂ Z ⁴ ... Formula 3
↓ Dehalogenating agent CF ₂ = CF (CF ₂ ) _m CR ^F1 R ^F2 (CF ₂ ) _n OCF = CF ₂ .

However, R < ¹ > and R < ² > in a formula shows a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 alkoxy group each independently. R ^F1 and R ^F2 are atoms in which R ¹ and R ² are fluorinated or a fluorinated group, and are a fluorine atom, a C 1-5 polyfluoroalkyl group, or a C 1-5 polyfluoro An alkoxy group is shown. m and n each independently represents an integer of 0 to 3. M represents an alkali metal atom or Ag. Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a chlorine atom, a bromine atom, or an iodine atom.

R ¹ and R ² are each independently preferably a hydrogen atom, a methyl group, or a methoxy group. R ^F1 and R ^F2 are preferably each independently a fluorine atom, a C 1-5 perfluoroalkyl group, or a C 1-5 perfluoroalkoxy group. The perfluoroalkyl group having 1 to 5 carbon atoms is preferably a trifluoromethyl group. The perfluoroalkoxy group having 1 to 5 carbon atoms is preferably a trifluoromethoxy group. M is preferably an alkali metal atom such as Na, Li, Ka, or Cs, with Na being preferred. Z ¹ , Z ² , Z ³ and Z ⁴ are preferably all chlorine atoms.

Hereinafter, it demonstrates in order according to the said synthetic | combination route | root.
As compound 1-1, compounds having many kinds of structures can be easily obtained. That is, compound 1-1 is a compound that can be obtained as a commercial product at a low cost or can be produced from a commercially available compound by a known reaction. R ¹ and R ² in the compound 1-1 are not particularly limited, and the above-described groups are preferable, and a methyl group or a methoxy group is particularly preferable. Further, m and n in the compound 1-1 are not particularly limited, and it is particularly preferable that the sum of m and n is 1.

Specific examples of the compound 1-1 include the following compounds.
Example of compound 1-1 wherein R ¹ and R ² are hydrogen atoms;
_{CH 2 = CHCH 2 OH, CH} 2 = CHCH 2 CH 2 OH, CH 2 = CHCH 2 CH 2 CH 2 OH, CH 2 = CHCH 2 CH 2 CH 2 CH 2 OH and the like.

Example of Compound 1-1 wherein R ¹ or R ² is a group other than a hydrogen atom, and the sum of m and n is 0;
_{CH 2 = CHCH (CH 3)} OH, CH 2 = CHC (CH 3) 2 OH, CH 2 = CHCH (OCH 3) OH, CH 2 = CHC (OCH 3) 2 OH , and the like.

Example of Compound 1-1 wherein R ¹ or R ² is a group other than a hydrogen atom, and the sum of m and n is 1;
_{CH 2 = CHCH 2 CH (CH} 3) OH, CH 2 = CHCH 2 C (CH 3) 2 OH, CH 2 = CHCH 2 CH (OCH 3) OH, CH 2 = CHCH 2 C (OCH 3) 2 OH, _{CH 2 = CHCH (CH 3)} CH 2 OH, CH 2 = CHC (CH 3) 2 CH 2 OH, CH 2 = CHCH (OCH 3) CH 2 OH, CH 2 = CHC (OCH 3) 2 CH 2 OH , etc. .

Example of Compound 1-1 wherein R ¹ or R ² is a group other than a hydrogen atom, and the sum of m and n is 2;
_{CH 2 = CHCH 2 CH 2 CH} (CH 3) OH, CH 2 = CHCH 2 CH 2 C (CH 3) 2 OH, CH 2 = CHCH 2 CH 2 CH (OCH 3) OH, CH 2 = CHCH 2 CH 2 _{CH (OCH 3) 2 OH,} CH 2 = CHCH (CH 3) CH 2 CH 2 OH, CH 2 = CHC (CH 3) 2 CH 2 CH 2 OH, CH 2 = CHCH (OCH 3) CH 2 CH 2 OH _{, CH 2 = CHC (OCH 3} ) 2 CH 2 CH 2 OH, CH 2 = CHCH 2 CH (CH 3) CH 2 OH, CH 2 = CHCH 2 CH (OCH 3) CH 2 OH and the like.

Example of Compound 1-1 wherein R ¹ or R ² is a group other than a hydrogen atom, and the sum of m and n is 3;
_{CH 2 = CHCH 2 CH 2 CH} 2 CH (CH 3) OH, CH 2 = CHCH 2 CH 2 CH 2 C (CH 3) 2 OH, CH 2 = CHCH 2 CH 2 CH 2 CH (OCH 3) OH, CH _{2 = CHCH 2 CH 2 CH 2} C (OCH 3) 2 OH, CH 2 = CHCH (CH 3) CH 2 CH 2 CH 2 OH, CH 2 = CHC (CH 3) 2 CH 2 CH 2 CH 2 OH, CH _{2 = CHCH (OCH 3) CH} 2 CH 2 CH 2 OH, CH 2 = CHC (OCH 3) 2 CH 2 CH 2 CH 2 OH, CH 2 = CHCH 2 CH (CH 3) CH 2 CH 2 OH and the like.

As compound 1-1, the usefulness of compound 4 which is the final product of this production method, that is, compound 4 is a monomer that undergoes cyclopolymerization to give an amorphous polymer, R ¹ or R ² is A compound 1-1 which is a group other than a hydrogen atom and the sum of m and n is 1, and CH ₂ ═CHCH ₂ CH ₂ OH are preferred, and an amorphous polymer having a high glass transition point is particularly preferred. The former compound, which is a monomer that provides the above, is preferred.

  The compound 1 in the present invention is compound 1-2 by reacting compound 1-1 with an alkali metal, or a reactive alkali metal compound (hereinafter collectively referred to as alkali metals), or Ag. Can be produced by reacting the compound 1-2 with tetrafluoroethylene. Compound 1-2 is a compound in which H of —OH group in compound 1-1 produced by reaction of compound 1-1 with alkali metal or Ag is substituted with alkali metal or Ag of alkali metal used in the reaction It is.

  The reaction of reacting compound 1-1 with an alkali metal or Ag to obtain compound 1-2 may be performed in the absence of a solvent or in the presence of a solvent, and may be performed in the presence of a solvent. preferable. The solvent is not particularly limited, and cyclic or acyclic ether solvents and aprotic polar solvents are preferably used. Specifically, diethyl ether, methyl-t-butyl ether, tetrahydrofuran, dioxane, monoglyme , Diglyme, triglyme, tetraglyme, acetonitrile, benzonitrile, sulfolane, dimethylformamide, dimethylacetamide, dimethylsulfoxide, and the like. Further, when a solvent is used for the reaction with alkali metals, it is preferable to use an anhydrous solvent.

  It is preferable to use alkali metals for the reaction with the compound 1-1. Examples of the reactive alkali metal compound include alkali metal hydride, alkali metal hydroxide, alkali metal salt, alkali metal alkoxide and the like. Na, Li, K, or Cs as the alkali metal, lithium hydride or sodium hydride as the alkali metal hydride, sodium hydroxide, potassium hydroxide, etc. as the alkali metal hydroxide, carbonate as the alkali metal salt As the alkali metal alkoxide such as cesium, sodium methoxide, sodium ethoxide and the like are preferably used. Na and sodium hydride are preferably used for the reaction with the compound 1-1.

  In order to allow the reaction to proceed quantitatively, it is preferable to react 0.9 to 1.5 times moles of alkali metal with respect to compound 1-1. The reaction temperature between compound 1-1 and alkali metals is not particularly limited, and is preferably -78 ° C to + 30 ° C, particularly preferably 0 ° C to + 20 ° C. The reaction temperature may be any of pressurization, reduced pressure, and atmospheric pressure, and atmospheric pressure is preferred. The reaction time is not particularly limited, and is preferably 2 to 24 hours, particularly preferably 4 to 10 hours. The produced compound 1-2 may be used as it is as a raw material for the next step without performing a separation operation or a purification operation, and may be post-treated as necessary.

  In the reaction for producing Compound 1 by reacting Compound 1-2 with tetrafluoroethylene (hereinafter abbreviated as TFE), Compound 1-2 is charged in a pressure-resistant reactor and sealed, and then TFE is enclosed. Then, it is preferably performed by pressurization and heating.

  The amount of TFE to be encapsulated is preferably 1.0 to 2.0 times mol and particularly preferably 1.2 to 1.6 times mol for the compound 1-2. TFE may be sealed in the pressure resistant reactor as it is, or diluted with an inert gas and introduced into the pressure resistant reactor. The inert gas is preferably nitrogen gas or argon gas. The sealing pressure of TFE is preferably 0.5 to 3.5 MPa, and particularly preferably 1.0 to 2.2 MPa when TFE is sealed as it is. The TFE sealing pressure is preferably 0.5 to 3.5 MPa, and particularly preferably 1.0 to 2.2 MPa when TFE is diluted with an inert gas and sealed. The sealing temperature of TFE is preferably −10 ° C. to + 50 ° C., particularly preferably 0 ° C. to + 30 ° C. After the encapsulation of TFE is completed, the compound 1-2 and TFE are reacted by heating. The reaction temperature between Compound 1-2 and TFE is preferably + 30 ° C. to + 100 ° C., particularly preferably + 50 ° C. to + 70 ° C. The reaction time is preferably carried out until the pressure drop of TFE stops, specifically 30 minutes to 120 hours is particularly preferable, and 5 hours to 10 hours is particularly preferable.

  TFE may be continuously added to the pressure resistant reactor. In this case, it is preferable to continuously add TFE up to a predetermined amount to the pressure resistant reactor at a constant pressure and a constant temperature. The pressure when continuously added is preferably 0.5 to 3.5 MPa, and particularly preferably 0.8 to 1.0 MPa from the viewpoint of safety. The reaction temperature for continuous addition is preferably + 30 ° C to + 100 ° C, particularly preferably + 50 ° C to + 70 ° C. In addition, the predetermined amount of TFE is preferably 1.0 to 2.0 times mol, particularly preferably 1.2 to 1.6 times mol, relative to compound 1-2. TFE in the case of continuous addition may be added to the pressure resistant reactor as it is, or may be diluted with an inert gas and introduced into the pressure resistant reactor.

The reaction product containing Compound 1 produced by the reaction of Compound 1-2 and TFE is preferably post-treated to obtain purified Compound 1.
The post-treatment method of the reaction is not particularly limited, and it is preferably carried out by any of the following methods.
[Method 1]
After opening the pressure-resistant reactor and setting the inside of the reactor to atmospheric pressure, the alkali metals remaining in the reactor are treated by adding methanol. Next, extraction is performed by adding water and an organic solvent (diethyl ether, methylene chloride, or dichloropentafluoropropane (for example, AK-225, etc., Asahi Glass Co., Ltd.) to recover the organic layer. Is dried over magnesium sulfate, and the solvent is distilled off to obtain compound 1.
[Method 2]
A method in which the pressure-resistant reactor is opened and the inside of the reactor is brought to atmospheric pressure, and then the reaction product is distilled under reduced pressure to obtain Compound 1 and the solvent is recovered. Compound 1 may be further purified by rectification.

Of the compound 1 produced by the reaction of compound 1-2 and TFE, the compound represented by the following formula 1-A is a novel compound not described in any literature.
CH ₂ ═CH (CH ₂ ) _a CR ¹ R ² (CH ₂ ) _b OCF═CF ₂ Formula 1-A
However, R < ¹ > and R < ² > in a formula shows a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 alkoxy group each independently. One of a and b is 1 and the other is 0. Among compounds 1-A, from the viewpoint of the usefulness of compound 4 which is the final product of the production method, R ¹ and R ² are each independently preferably a hydrogen atom, a methyl group, or a methoxy group, It is particularly preferred that one is a methyl group or a methoxy group, or both are hydrogen atoms, particularly preferred that R ¹ is a methyl group and R ² is a hydrogen atom. Specific examples of compound 1-A include the following compounds.
_{CH 2 = CHCH 2 CH 2 OCF} = CF 2,
_{CH 2 = CHCH 2 CH (CH} 3) OCF = CF 2,
_{CH 2 = CHCH 2 C (CH} 3) 2 OCF = CF 2,
_{CH 2 = CHCH (CH 3)} CH 2 OCF = CF 2,
_{CH 2 = CHCH (OCH 3)} CH 2 OCF = CF 2.

Next, compound 1 is halogenated using a halogenating agent to obtain compound 2. The halogenation in the present invention means substantially all of the compounds present in Compound 1 using a halogenating agent other than the fluorinating agent (that is, a chlorinating agent, a brominating agent, or an iodinating agent). A reaction in which a halogen atom is added to a carbon-carbon unsaturated double bond. The halogen atom may be one kind or two or more kinds, and preferably one kind. As a halogen atom, a chlorine atom, a bromine atom, or an iodine atom is preferable, and a chlorine atom is particularly preferable. As a halogenating agent, a well-known halogenating agent is mentioned, It is preferable to use halogen or to use together halogen and divalent copper halide. As the halogenating agent, a chlorinating agent is preferable. As the chlorinating agent, it is preferable to use only chlorine (Cl ₂ ), or it is preferable to use chlorine and cupric chloride in combination, and it is particularly preferable to use chlorine from the viewpoint of handling, cost, and the like.

  Hereinafter, the reaction method of the compound 1 and the chlorinating agent will be described. However, this method can be similarly applied to brominating agents and iodinating agents. As a reaction method of Compound 1 and a chlorinating agent, a method of reacting Compound 1 and a chlorinating agent in the presence or absence of a solvent is preferable, and a method of reacting in the presence of a solvent is particularly preferable.

  Examples of the solvent include alkane solvents such as pentane, hexane, and heptane, aromatic hydrocarbon solvents such as benzene and chlorobenzene, hydrocarbon nitrile solvents such as acetonitrile and benzonitrile, chloromethane, dichloromethane, chloroform, and carbon tetrachloride. Halogenated hydrocarbon solvents such as bromomethane, dibromomethane, bromoform, perfluoroalkanes (trade names: FC-72, etc.), perfluoroethers (trade names: FC-75, FC-77, etc.), perfluoropolyethers (Product names: Krytox, Fomblin, Galden, Demnam, etc.), Chlorofluorocarbons, Hydrochlorofluorocarbons, Hydrofluorocarbons, Chlorofluoropolyethers, Hydrochlorofluoropolyethers, Hydroful Roporieteru acids, perfluoroalkyl amines such as perfluorotrialkylamine, inert fluid (trade name: Fluorinert), and the like. Moreover, the compound 2 and the compound 3 which are mentioned later are also mentioned as a solvent.

  When only chlorine is used as the chlorinating agent, the reaction temperature between chlorine and compound 1 is preferably −78 ° C. to + 200 ° C., particularly preferably −50 ° C. to + 100 ° C., and particularly preferably −20 ° C. to + 20 ° C. Since the reaction is an exothermic reaction, it is preferable to carry out the reaction while cooling. Moreover, 2-10 times mole is preferable with respect to the compound 1, and, as for the quantity of chlorine, 2-5 times mole is especially preferable. Chlorine may be liquid or gaseous, and is preferably gaseous from the viewpoint of reaction control, and chlorine gas diluted with an inert gas is particularly preferred. When diluting chlorine gas with an inert gas, the chlorine concentration is preferably from 0.1 to 80% by volume, particularly preferably from 1 to 50% by volume. The method for introducing chlorine gas is not particularly limited, and the following two methods can be mentioned.

[Method 1]
A method of circulating chlorine gas or chlorine gas diluted with an inert gas through the reactor.

[Method 2]
A method of introducing chlorine gas or chlorine gas diluted with an inert gas into a sealed reactor. In the case of introducing diluted chlorine gas, chlorine gas diluted in advance may be introduced, or chlorine gas may be introduced after introducing inert gas.

  When chlorine and cupric chloride are used in combination as a chlorinating agent, after adding cupric chloride and compound 1 to the reactor and heating the reactor to 80 to 85 ° C. and reacting for 1 to 5 hours, Next, it is preferable to carry out by cooling the reactor to −20 ° C. to + 20 ° C. and introducing chlorine gas into the reactor. The amount of the second copper chloride is preferably at least 1 mole, more preferably 1 to 12 moles relative to Compound 1. Moreover, it is preferable to disperse | distribute 2nd copper chloride to polar solvents, such as acetonitrile of 5-30 times mass with respect to 2nd copper chloride, and to charge to a reactor. The amount of chlorine gas is preferably at least 1 mole, more preferably 1 to 5 moles relative to Compound 1. The chlorine gas in the reaction can be used in the same manner as in the method using only chlorine.

Compound 2 produced by the reaction of compound 1 and a chlorinating agent is a novel compound not described in any literature. As the compound 2, from the viewpoint of the usefulness of the compound 4 which is the final product of this production method, at least one of R ¹ and R ² is a methyl group or a methoxy group, or R ¹ and R ² are hydrogen atoms. And the former group is particularly preferred, and it is particularly preferred that R ¹ is a methyl group and R ² is a hydrogen atom. Specific examples of the compound 2 include the following compounds.
CH ₂ ClCHClCH ₂ OCCFClCF ₂ Cl,
CH ₂ ClCHClCH (CH ₃ ) OCFClCF ₂ Cl,
CH ₂ ClCHClCH ₂ CH ₂ OCCFClCF ₂ Cl,
CH ₂ ClCHClCH ₂ CH (CH ₃ ) OCFClCF ₂ Cl,
CH ₂ ClCHClCH ₂ C (CH ₃ ) ₂ OCCFClCF ₂ Cl,
_{CH 2 ClCHClCH (CH 3) CH} 2 OCFClCF 2 Cl,
_{CH 2 ClCHClCH (OCH 3) CH} 2 OCFClCF 2 Cl.

  Next, compound 3 is obtained by fluorinating compound 2. Examples of the fluorination reaction include an electrochemical fluorination method (ECF method), a cobalt fluorination method, a gas phase fluorination method, and a liquid phase fluorination method. From the viewpoints of yield, reaction apparatus, and reaction operation. A liquid phase fluorination method is preferred. The liquid phase fluorination method refers to a method in which compound 2 and fluorine in a solvent are reacted to replace all hydrogen atoms present in compound 2 with fluorine atoms.

  Examples of the solvent include compound 3, which is a reaction product, perfluoroalkanes (trade name: FC-72, etc.), perfluoroethers (trade names: FC-75, FC-77, etc.), perfluoropolyethers (trade name: Crytox, Fomblin, Galden, Demnam, etc.), chlorofluorocarbons, chlorofluoropolyethers, perfluoroalkylamines (eg, perfluorotrialkylamine), inert fluids (trade name: Florinato), and the like. The amount of the solvent is preferably 5 times or more, particularly preferably 10 to 100 times, the amount of the compound 2.

The fluorine gas may be introduced after being diluted with an inert gas. As the inert gas, nitrogen gas or helium gas is preferable, and nitrogen gas is particularly preferable. In the case of diluting the fluorine gas, it is preferably diluted to 5% by volume or more. In order to suppress the detachment or rearrangement of Z ¹ , Z ² , Z ³ , Z ^{4 in} the compound ² , it is 5 to 30% by volume. It is particularly preferred to dilute to The amount of fluorine used in the liquid phase fluorination method of compound 2 is preferably such that the amount of fluorine (F ₂ ) is always an excess equivalent to the amount of hydrogen atoms in compound 2, and is 1.5 times mol or more. Is particularly preferred.

  In liquid phase fluorination, in order to efficiently fluorinate hydrogen atoms that are difficult to be substituted by fluorine in compound 2, a method of coexisting compound 2 with a C—H bond other than compound 2 and / or It is preferable to adopt a method of performing ultraviolet irradiation. For example, it is particularly preferable to employ a method in which a C—H bond-containing compound is added to the reaction system at a later stage of the fluorination reaction and / or a method in which ultraviolet irradiation is performed. As the C—H bond-containing compound, an aromatic hydrocarbon is preferable, and benzene and toluene are particularly preferable. The amount of the C—H bond-containing compound added is preferably 0.1 to 10 mol%, particularly preferably 0.1 to 5 mol%, relative to the hydrogen atom in compound 2.

The reaction temperature in the liquid phase fluorination method is preferably −60 ° C. to the boiling point temperature of Compound 2, particularly preferably −50 ° C. to + 100 ° C., and elimination of Z ¹ , Z ² , Z ³ , and Z ⁴ in Compound 2 And −20 ° C. to + 50 ° C. is particularly preferable for suppressing dislocation. Moreover, the reaction pressure in a liquid phase fluorination method is not specifically limited, 0-2 Mpa is preferable. The HF produced as a by-product in the fluorination reaction of Compound 2 is preferably removed by allowing the HF scavenger to coexist in the reaction system or by bringing the HF scavenger and the outlet gas into contact at the reactor gas outlet. Examples of the HF scavenger include trialkylamines and alkali metal fluorides, and NaF is preferable. When the HF scavenger is allowed to coexist in the reaction system, the amount of the HF scavenger is preferably 1 to 20 moles, particularly preferably 1 to 5 moles, based on the total amount of hydrogen atoms present in the compound 2.

The compound 3 produced by the fluorination reaction of the compound 2 is not particularly limited, and from the viewpoint of the usefulness of the compound 4 which is the final product of this production method, at least one of R ^F1 and R ^F2 is a trifluoromethyl group. Or a trifluoromethoxy group, or R ^F1 and R ^F2 are preferably fluorine atoms, and particularly preferably the former group.

Of the preferred compounds 3, compound 3-1 is a novel compound not described in any literature.
CF ₂ Z ¹ CFZ ² (CF ₂ ) _m C (R ^F10 ) (CF ₃ ) (CF ₂ ) _n OCFZ ³ CF ₂ Z ⁴ ... Formula 3-1
^{However, Z 1, Z 2, Z} 3 in ^{formula, Z} 4, m, and n are as defined ^{above, R F10} is a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group.

Specific examples of the compound 3 include the following compounds.
CF ₂ ClCFClCF ₂ OCFClCF ₂ Cl,
CF ₂ ClCFClCF ₂ CF ₂ OCCFClCF ₂ Cl,
CF ₂ ClCFClCF (CF ₃ ) OCFClCF ₂ Cl,
CF ₂ ClCFClCF ₂ CF (CF ₃ ) OCFClCF ₂ Cl,
CF ₂ ClCFClCF ₂ C (CF ₃ ) ₂ OCCFClCF ₂ Cl,
CF ₂ ClCFClCF (CF ₃ ) CF ₂ OCFClCF ₂ Cl,
_{CF 2 ClCFClCF (OCF 3) CF} 2 OCFClCF 2 Cl.

Next, compound 3 is dehalogenated to obtain compound 4. The dehalogenating agent in the present invention is a dehalogenating agent other than the defluorinating agent. Dehalogenation is performed by allowing a dehalogenating agent to act in a polar solvent. A dehalogenating agent is a reagent that desorbs Z ¹ , Z ² , Z ³ , and Z ⁴ in compound ³ , and when Z ¹ , Z ² , Z ³ , and Z ⁴ are chlorine atoms The dehalogenating agent is a dechlorinating agent. As the dehalogenating agent, zinc, sodium, magnesium, tin, copper, or iron is preferable, and zinc capable of performing the reaction at a low temperature is particularly preferable. The dehalogenating agent is preferably used in an amount of 1 to 20 times by mole, particularly preferably 2 to 8 times by mole, relative to Compound 3.

  The polar solvent is not particularly limited, and specific examples include organic polar solvents such as dimethylformamide, dimethylacetamide, 1,4-dioxane, diglyme, and methanol, or water. The reaction temperature is preferably + 30 ° C to + 100 ° C, particularly preferably + 40 ° C to + 70 ° C. The dehalogenation reaction of compound 3 is preferably carried out by dropping compound 3 in a dehalogenating agent and a polar solvent. Moreover, it is preferable to obtain the compound 4 purified by distillation by reactive distillation.

Compound 4 produced by the dehalogenation reaction of compound 3 is not particularly limited as long as it is a fluorine-containing compound having a perfluorovinyl group at one end of the main chain and a perfluorovinyloxy group at the other end. As the compound 4, it is preferable that at least one of R ^F1 and R ^F2 is a trifluoromethyl group or a trifluoromethoxy group, or R ^F1 and R ^F2 are fluorine atoms. Since the compound which gives the amorphous polymer which has a point is preferable, it is preferable that R ^F1 and R ^F2 are the former groups. Specific examples of the compound 4 include the following compounds.
CF ₂ = CFCF ₂ OCF = CF ₂ ,
CF ₂ = CFCF ₂ CF ₂ OCF = CF ₂ ,
CF ₂ = CFCF (CF ₃ ) OCF = CF ₂ ,
CF ₂ = CFCF ₂ CF (CF ₃ ) OCF = CF ₂ ,
CF ₂ = CFCF ₂ C (CF ₃ ) ₂ OCF = CF ₂ ,
CF ₂ = CFCF (CF ₃ ) CF ₂ OCF = CF ₂ ,
_{CF 2 = CFCF (OCF 3)} CF 2 OCF = CF 2.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
Example 1 (Example) Synthesis example of CH ₂ ═CHCH ₂ CH (CH ₃ ) OCF═CF ₂ (Part 1)
A four-necked flask (with an internal volume of 500 ml) equipped with a stirrer, dropping funnel and three-way cock was prepared, sodium hydride (30.65 g, 0.766 mol) was charged, and then 1,4-dioxane (250 ml) Was charged. While stirring the flask at an internal temperature of 10 to 15 ° C., CH ₂ ═CHCH ₂ CH (CH ₃ ) OH (60.8 g, 0.706 mol) was added dropwise. Thereafter, the internal temperature was raised to 25 ° C., and the reaction was carried out for 4 to 5 hours as it was.

  The obtained reaction solution was transferred as it was to a pressure resistant reactor (internal volume 500 ml), then nitrogen gas was introduced to increase the internal pressure to 1.0 MPa, and then the operation of returning to atmospheric pressure was performed three times. Then, nitrogen gas was again introduced to adjust the internal pressure to 0.05 MPa and the internal temperature to 10 to 15 ° C. Subsequently, when tetrafluoroethylene (107 g, 1.07 mol) was introduced and the reaction temperature was adjusted to 55 ° C., the internal pressure became 2.2 MPa. When 4 to 5 hours passed as it was, the pressure drop of tetrafluoroethylene stopped and the internal pressure became 1.3 MPa. Next, after cooling the reactor, the inside of the reactor was brought to atmospheric pressure.

Methanol (15.0 g) and hydrochloric acid (1.0 mol / L, 160 g) were added to the obtained reaction solution and stirred. Then extracted with diethyl ether and distilled to _{CH 2 = CHCH 2 CH (CH} 3) was obtained OCF = CF 2 (76.9g, 70 % yield).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm); -123.1 (F ^a , 1 F, J _ab = 103 Hz), −130.9 (F ^c , 1F, J _ca = 55 Hz), −132.0 (F ^b , 1F, J _bc = 107.5 Hz).
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm); 5.77 (H ^g , 1H), 5.13 (H ^h , 2H), 4.17 (H ^d , ^{1H), 2.37 (H f,} 2H), 1.28 (H e, 3H).
Boiling point: 42 ° C./10.7 kPa (absolute pressure).

Example 2 (Example) Synthesis Example of CH ₂ ClCHClCH ₂ CH (CH ₃ ) OCFClCF ₂ Cl (Part 1)
A three-necked flask (internal volume 1 L) equipped with a stirrer and a dry ice condenser was prepared, and CH ₂ ═CHCH ₂ CH (CH ₃ ) OCF═CF ₂ (71 g, 0) obtained by the method of Example 1 was added to the flask. 426 mol), and CCl ₄ (680 g). The flask was cooled with stirring so that the internal temperature was -15 ° C to -10 ° C. Next, 5 vol% chlorine gas diluted with nitrogen gas was introduced into the reactor while stirring the reactor and maintaining the internal temperature at −10 ° C. to −5 ° C. After introducing chlorine gas (85 g, 1.18 mol), only nitrogen gas was introduced to remove chlorine gas from the reactor. The obtained crude product was collected and purified by column chromatography (developing solvent: hexane 100%) to obtain CH ₂ ClCHClCH ₂ CH (CH ₃ ) OCFClCF ₂ Cl (85 g, yield 65%).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm); −65.9 to −67.9 (1F), −69.0 to −69.2 (2F).
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm); 4.85 (m, 1H), 4.10 (m, 1H), 3.73 (m, 2H), 1.75-2.38 (2H), 1.45 (m, 3H).

Example 3 (Example) Synthesis example of CH ₂ ClCHClCH ₂ CH (CH ₃ ) OCFClCF ₂ Cl (part 2)
CH ₂ ═CHCH ₂ CH (CH ₃ ) OCF═CF ₂ (15 g, 0.090 mol), hexane (36 g), and chloroform (540 g) obtained by the method of Example 1 were added to a pressure-resistant reactor (internal volume 1 L). The reactor was charged and replaced with nitrogen gas. Subsequently, the internal temperature is cooled to −15 ° C. to −10 ° C., the internal temperature during the reaction is maintained at −10 ° C. to −5 ° C., and the internal pressure during the reaction is maintained at 0.02 MPa. Introduced. After introducing chlorine gas (85 g, 1.18 mol), only nitrogen gas was introduced to exclude chlorine gas from the reactor. The obtained crude product was collected and purified by column chromatography (developing solvent: hexane 100%) to obtain CH ₂ ClCHClCH ₂ CH (CH ₃ ) OCFClCF ₂ Cl (21 g, yield 74%). The formation of the title compound was confirmed by NMR.

Example 4 (Example) Synthesis example of CH ₂ ClCHClCH ₂ CH (CH ₃ ) OCFClCF ₂ Cl (part 3)
A three-necked flask (internal volume: 100 mL) equipped with a stirrer and a reflux condenser was prepared, and cupric chloride (3.3 g, 0.024 mol), CH ₂ = CHCH ₂ obtained by the method of Example 1, was prepared in the flask. CH (CH ₃ ) OCF═CF ₂ (2.0 g, 0.012 mol) and acetonitrile (35 g) were charged. While stirring the flask, the internal temperature was heated to 80 to 85 ° C. and reacted for 2 hours. The main product at this point _{was CH 2 = CHCH 2 CH (CH} 3) OCFClCF 2 Cl. Subsequently, the reflux condenser was replaced with a dry ice condenser, and the internal temperature was cooled to −15 ° C. to −10 ° C. Next, while the reactor was stirred and maintained at −10 ° C. to −5 ° C., 5% by volume of chlorine gas diluted with nitrogen gas was introduced into the reactor. After introducing chlorine gas (1.3 g, 0.018 mol), only nitrogen gas was introduced to remove chlorine gas from the reactor. The obtained crude product was collected and purified by column chromatography (developing solvent: hexane 100%) to obtain CH ₂ ClCHClCH ₂ CH (CH ₃ ) OCFClCF ₂ Cl (2.2 g, yield 60%). . The formation of the title compound was confirmed by NMR.

Example 5 (Example) Synthesis Example of CF ₂ ClCFClCF ₂ CF (CF ₃ ) OCFClCF ₂ Cl 1,1,2-trichlorotrifluoroethane (312 g) was charged into an autoclave (internal volume 500 ml, made of nickel). Stir and keep at 25 ° C. After introducing nitrogen gas for 1.0 hour, fluorine gas diluted to 20% by volume with nitrogen gas was introduced at a flow rate of 13.43 L / h for 1 hour while maintaining the system at atmospheric pressure. At the gas outlet, a cooler kept at 20 ° C., a NaF pellet packed bed, and a cooler kept at −10 ° C. were installed in series from the gas outlet side. Further, from the cooler maintained at −10 ° C., a liquid return line for returning the aggregated liquid to the autoclave was installed. Next, CH ₂ ClCHClCH ₂ CH (CH ₃ dissolved in 1,1,2-trichlorotrifluoroethane (100 g) while introducing the same 20 vol% fluorine gas at the same flow rate and maintaining the system at normal pressure. ) OCFClCF ₂ Cl (5 g, 16.23 mmol) was charged to the autoclave over 3.8 hours.

Subsequently, while introducing fluorine gas diluted to 20% by volume with nitrogen gas at a flow rate of 13.43 L / h, the reactor pressure was maintained at 0.15 MPa, and a benzene concentration of 0.01 g / ml A 1,2-trichlorotrifluoroethane solution (9 ml) was injected while the reactor was heated from 25 ° C to 40 ° C. Next, the benzene inlet of the autoclave was closed, and stirring was continued for another 0.3 hours. Subsequently, this operation was performed three times, and benzene (0.336 g) and 1,1,2-trichlorotrifluoroethane (57 ml) were injected into the autoclave. Stirring was further continued for 1.0 hour, and then nitrogen gas was introduced for 1.0 hour to eliminate fluorine gas from the reactor. The reaction solution was purified by distillation to obtain CF ₂ ClCFClCF ₂ CF (CF ₃ ) OCFClCF ₂ Cl (2.1 g, yield 34%).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm); −61.0 to −65.0 (2F), −69.7 to −70.1 (2F), -72.9 to -74.6 (1F), -75.5 to -76.6 (3F), -109.2 to -115.0 (2F) -128.3 to -137.0 (2F) .

[Example 6 (Example)] Synthesis example of CF ₂ = CFCF ₂ CF (CF ₃ ) OCF = CF ₂ A glass four-necked flask equipped with a stirrer, a reflux condenser, and a dropping funnel (internal volume 200 ml, glass) Prepared. The flask was charged with zinc (21 g, 325 mmol), and dimethylformamide (50 g). Next, the internal pressure of the flask was adjusted to 10.7 kPa (absolute pressure) and the internal temperature was adjusted to 60 to 65 ° C., and CF ₂ ClCFClCF ₂ CF (CF ₃ ) OCFClCF ₂ Cl (19 g, 41 mmol) obtained in Example 3 was added. The mixture was added dropwise with stirring, and the reaction was carried out while collecting the product by distillation to obtain a crude product. The crude product was fractionated _{CF 2 = CFCF 2 CF (CF} 3) OCF = CF 2 was obtained (9.8 g, 70% yield).

EXAMPLE 7 (Reference _{Example)] CF 2 = CFCF 2 CF} (CF 3) Polymerization Example _{CF 2 = CFCF 2 CF (CF} 3) of _{OCF = CF 2 OCF = CF 2} (2g, 6.1mmol) and diisopropyl peroxydicarbonate Carbonate (6.2 mg) is placed in a glass ampule, frozen in liquid nitrogen, vacuum degassed and sealed. After heating in an oven at 40 ° C. for 20 hours, the solidified content is taken out and dried at 200 ° C. for 1 hour. The yield of the resulting polymer (hereinafter referred to as polymer A1) is 99%. When a part of the polymer A1 is dissolved in perfluoro (2-butyltetrahydrofuran) (hereinafter referred to as PBTHF) and the intrinsic viscosity is measured, it is 0.44 dl / g. The molecular weight of the polymer is 131500 in number average molecular weight (M _n ) and 263000 in weight average molecular weight (M _w ).

  When measured with an Abbe refractometer of the film of polymer A1 produced by press molding, the refractive index is 1.327, and the glass transition temperature measured by dynamic thermomechanical analysis (DMA) is 124 ° C. When the tensile properties of the polymer A1 are measured, the tensile modulus is 1430 MPa, the yield stress is 36 MPa, and the elongation at break is 4.2%. Further, when the zero shear viscosity at 230 ° C. is measured by a rotary melt viscoelasticity measuring apparatus, it is 89000 Pa · s.

Also, when measuring the infrared absorption spectrum of the polymer, the absorption of 1785 cm ^-1 and _CF 2 = CFO- to based 1835Cm ^-1 based on _CF 2 = CF- seen the monomer has disappeared. This polymer A1 has no pendant double bond, does not cause a crosslinking reaction, and is completely dissolved in dichloropentafluoropropane (Asahi Glass AK-225) even at a high reaction rate. . Moreover, it turns out that it is a polymer which has a repeating unit of the following structure by ¹⁹ F-NMR analysis.

[Example 8 _(Example) Synthesis Example of _{CH 2 = CHCH 2 CH 2 OCF} = CF 2 ( Part 2)
Instead of CH ₂ ═CHCH ₂ CH (CH ₃ ) ₂ OH in Example 1, CH ₂ ═CHCH ₂ CH ₂ OH (20 g, 0.28 mol) was used, and other reagents were used in the same proportions as in Example 1. Te performs addition reaction of TFE in the same manner as in example 1 _to obtain _{CH 2 = CHCH 2 CH 2 OCF} = CF 2 (27g, 64% yield).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm); −123.0 (F ^a , 1 F, J _ab = 103 Hz), −130.0 (F ^c , 1F, J _ca = 55 Hz), −134.1 (F ^b , 1F, J _bc = 107 Hz).
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm); 5.77 (H ^f , 1H), 5.10 (H ^g , 2H), 3.98 (H ^d , 2H), 2.44 (H ^e , 2H)

[Example 9 _{(Example)] CH 2 = CHCH (OCH} 3) CH 2 Synthesis Example of OCF = CF ₂ (Part 3)
Instead of Example 1 of _{CH 2 = CHCH 2 CH (CH} 3) 2 OH, CH 2 = CHCH (OCH 3) CH 2 OH (20g, 0.20mol) was used, similar to that of Example 1 other reactants Using the ratio, TFE addition reaction was performed in the same manner as in Example 1 to obtain CH ₂ ═CHCH (OCH ₃ ) CH ₂ OCF═CF ₂ (25 g, yield 70%).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm); -122.8 (F ^a , 1 F, J _ab = 103 Hz), -129.7 (F ^c , 1F, J _ca = 55 Hz), -133.5 (F ^b , 1F, J _bc = 107 Hz).
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm); 5.64 (H ^g , 1H), 5.28 (H ^g , 2H), 4.01 (H ^e , ^{1H), 3.62 (H d,} 2H), 3.31 (H f, 3H)

The production method of the present invention provides an industrially advantageous production method of a fluorine-containing divinyl compound having perfluorovinyl groups having different reactivities at both ends from compound 1 which is an inexpensive and readily available vinyl alcohol. Is done. The production method of the present invention provides a method for producing a fluorine-containing divinyl compound having a linear structure or various fluorine-containing divinyl compounds having a branched structure at an arbitrary position. The present invention also provides novel compounds useful for the method. An amorphous polymer obtained by cyclopolymerizing a fluorine-containing divinyl compound produced by using the method of the present invention has a large elastic modulus, yield elongation, elongation at break and excellent impact resistance. It is a polymer having high properties and a high glass transition point, and the polymer is an optical material having excellent heat resistance.

Claims (6)

The compound represented by the following formula 1 is halogenated using a halogenating agent other than the fluorinating agent to obtain the compound represented by the following formula 2, and then the compound represented by the formula 2 is fluorinated. A method for producing a compound represented by the following formula 4, wherein the compound represented by the following formula 3 is obtained, and then the compound represented by the formula 3 is dehalogenated by a dehalogenating agent.
CH ₂ = CH (CH ₂ ) _m CR ¹ R ² (CH ₂ ) _n OCF═CF ₂ Formula 1
CH ₂ Z ¹ CHZ ² (CH ₂ ) _m CR ¹ R ² (CH ₂ ) _n OCFZ ³ CF ₂ Z ⁴ ... Formula 2
CF ₂ Z ¹ CFZ ² (CF ₂ ) _m CR ^{F 1} R ^{F 2} (CF ₂ ) _n OCFZ ³ CF ₂ Z ⁴ ... Formula 3
CF ₂ = CF (CF ₂ ) _m CR ^F1 R ^F2 (CF ₂ ) _n OCF = CF ₂ Formula 4
However, R < ¹ > and R < ² > in a formula shows a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 alkoxy group each independently. R ^F1 and R ^F2 are atoms in which R ¹ and R ² are fluorinated or a fluorinated group, and are a fluorine atom, a C 1-5 polyfluoroalkyl group, or a C 1-5 polyfluoro An alkoxy group is shown. m and n each independently represents an integer of 0 to 3. Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a chlorine atom, a bromine atom, or an iodine atom. A method for producing a compound represented by the following formula 3, which comprises fluorinating a compound represented by the following formula 2.
CH ₂ Z ¹ CHZ ² (CH ₂ ) _m CR ¹ R ² (CH ₂ ) _n OCFZ ³ CF ₂ Z ⁴ ... Formula 2
CF ₂ Z ¹ CFZ ² (CF ₂ ) _m CR ^{F 1} R ^{F 2} (CF ₂ ) _n OCFZ ³ CF ₂ Z ⁴ ... Formula 3
However, R < ¹ > and R < ² > in a formula shows a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 alkoxy group each independently. R ^F1 and R ^F2 are atoms in which R ¹ and R ² are fluorinated or a fluorinated group, and are a fluorine atom, a C 1-5 polyfluoroalkyl group, or a C 1-5 polyfluoro An alkoxy group is shown. m and n each independently represents an integer of 0 to 3. Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a chlorine atom, a bromine atom, or an iodine atom. A compound represented by the following formula 1-A.
CH ₂ ═CH (CH ₂ ) _a CR ¹ R ² (CH ₂ ) _b OCF═CF ₂ Formula 1-A
However, R < ¹ > and R < ² > in a formula shows a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 alkoxy group each independently. One of a and b is 1 and the other is 0. A compound represented by the following formula 2.
CH ₂ Z ¹ CHZ ² (CH ₂ ) _m CR ¹ R ² (CH ₂ ) _n OCFZ ³ CF ₂ Z ⁴ ... Formula 2
However, R < ¹ > and R < ² > in a formula shows a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 alkoxy group each independently. m and n each independently represents an integer of 0 to 3. Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a chlorine atom, a bromine atom, or an iodine atom. The compound according to claim 3 or 4, wherein R ¹ and R ² are each independently a hydrogen atom, a methyl group, or a methoxy group. A compound represented by the following formula 3-1.
CF ₂ Z ¹ CFZ ² (CF ₂ ) _m C (R ^F10 ) (CF ₃ ) (CF ₂ ) _n OCFZ ³ CF ₂ Z ⁴ ... Formula 3-1
However, m and n in a formula show the integer of 0-3 each independently. Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a chlorine atom, a bromine atom, or an iodine atom. m and n show the integer of 0-3. R ^F10 represents a fluorine atom, a trifluoromethyl group, or a trifluoromethoxy group.