JPWO2005121118A1 - Compound having perfluoro (4-methylene-1,3-dioxolane) structure, and novel polymer - Google Patents

Abstract

Provided are a compound having a perfluoro (4-methylene-1,3-dioxolane) structure, which has not been known so far, and a novel polymer. A compound represented by the following formula (a) having a perfluoro (4-methylene-1,3-dioxolane) structure, a method for producing the compound, a novel compound useful for producing the compound, and the following formula (A) (Wherein RF1 to RF4 each independently represents a fluorine atom, a chlorine atom, or a perfluorinated monovalent saturated organic group having 1 to 20 carbon atoms). .).

Description

  The present invention relates to a novel compound having a perfluoro (4-methylene-1,3-dioxolane) structure and a novel polymer.

  As the polymerizable compound having a perfluoro (1,3-dioxolane) structure, a compound represented by the following formula (1) having a perfluoro (2-methylene-1,3-dioxolane) structure (where Q is 2 carbon atoms) Is a polyfluoroalkyl group of ˜7) (see Patent Document 1). Further, Patent Document 1 reports that a polymer containing a monomer unit represented by the following formula (1X) obtained by polymerizing the compound has properties such as amorphous property, solvent solubility, and low refractive index property.

  In addition, as a polymerizable compound having both a perfluoro (2-methylene-1,3-dioxolane) structure and a fluorosulfonyl group, the present applicant has proposed a compound represented by the following formula (2) (Patent Document) 2). A polymer obtained by polymerizing the compound is useful as a material for an ion exchange membrane for salt electrolysis or a polymer electrolyte fuel cell.

JP 05-213929 A International Publication No. 03/037885 Pamphlet

  As a polymerizable compound having a perfluoro (1,3-dioxolane) structure, only a compound having a polymerizable methylene group at the 2-position carbon atom of the 1,3-dioxolane skeleton has been reported. In addition, when changing the structure according to the intended use, attempts have been made to change the substituent of the 1,3-dioxolane skeleton, but no attempt has been made to change the position of the polymerizable methylene group. Even if it was actually attempted to carry out the trial, it was difficult to obtain the compound and it could not be carried out.

  The present invention has been made to solve the above-mentioned problems, and is a novel perfluoro (4-methylene-1,3-dioxolane) compound obtained by introducing a methylene group at the 4-position of a 1,3-dioxolane skeleton, And providing novel polymers.

That is, the present invention provides the following inventions.
<1> A compound represented by the following formula (a) (wherein R ^{F1 to} R ^F4 each independently represents a fluorine atom, a chlorine atom, or a C 1-20 perfluorinated monovalent saturated organic group). .)

<2> A compound represented by the following formula (a1) (wherein R ^F12 is a perfluoroalkyl group having 1 to 4 carbon atoms, or a group represented by the formula — (CF ₂ ) _n1 SO ₂ F (where n1 is Represents an integer of 1 to 4.).

<3> A method for producing a compound represented by the formula (a), wherein the compound represented by the following formula (b) is thermally decomposed to give a compound represented by the following formula (a) (however, R ^{F1 to} R ^F4 Each independently represents a fluorine atom, a chlorine atom, or a C 1-20 perfluorinated monovalent saturated organic group.

  <4> Any compound represented by the following formula:

ただしＲ^Ｆ１〜Ｒ^Ｆ４は、前記と同じ意味を示す。

However, R ^{F1 to} R ^F4 have the same meaning as described above.

R ¹ is ^{R F1, R 2} to ^{R F2, R 3} to ^{R F3, R 4} to ^{R F4,} a corresponding group, ^R 1 ~ corresponding to ^R F1 ^{to R F4} is a chlorine atom R ⁴ is a chlorine atom, ^R 1 to R ⁴ corresponding to ^R F1 ^{to R F4} is a fluorine atom is a hydrogen atom or a fluorine atom, ^{R F1} ~ is a monovalent saturated organic group perfluorinated having 1 to 20 carbon atoms R ^{1 to} R ⁴ corresponding to R ^F4 have the same carbon skeleton having 1 to 20 carbon atoms, and are a monovalent saturated organic group essentially including a hydrogen atom bonded to a carbon atom, or the same as R ^{F1 to} R ^F4 Indicates a group.
R ^EF represents a C 1-10 perfluorinated monovalent saturated organic group.
X represents a hydrogen atom or a fluorine atom.

<5> A polymer containing a repeating unit represented by the following formula (A) (wherein R ^{F1 to} R ^F4 have the same meaning as described above).

<6> A polymer containing a repeating unit represented by the following formula (A1) (provided that R ^F12 has the same meaning as described above).

<7> The polymer according to <5> or <6>, which has a molecular weight of 5 × 10 ² to 1 × 10 ⁶ .

  <8> A method for producing a polymer containing a repeating unit represented by the formula (A), wherein the compound represented by the formula (a) is polymerized to obtain a polymer containing the repeating unit represented by the formula (A).

  According to the present invention, a compound having a novel perfluoro (4-methylene-1,3-dioxolane) structure is provided. The compound of the present invention is useful as a polymerizable compound. Moreover, according to this invention, a novel polymer is provided.

In the present specification, a compound represented by the formula (a) is referred to as a compound (a). Other compounds are described in the same manner. The fluorosulfonyl group is also referred to as —SO ₂ F group.
The compound (a) of the present invention is a novel compound having a perfluoro (4-methylene-1,3-dioxolane) structure (provided that R ^{F1 to} R ^F4 have the same meaning as described above).

  1-10 are preferable and, as for carbon number of the C1-C20 perfluorinated monovalent saturated organic group, 1-4 are especially preferable. The monovalent saturated organic group may have a linear structure or a branched structure, and these structures may contain a ring structure.

  A monovalent saturated organic group is a monovalent group essentially comprising a carbon atom and a hydrogen atom bonded to the carbon atom, and when there is a bond between carbon atoms, all of the bonds are saturated. A group that is a bond (single bond). The perfluorinated monovalent saturated organic group refers to a group in which all of hydrogen atoms bonded to carbon atoms in the monovalent saturated organic group are substituted with fluorine atoms. Further, the fluorosulfonylated monovalent saturated organic group means a group in which a fluorosulfonyl group is bonded to a carbon atom in the monovalent saturated organic group.

  Examples of the monovalent saturated organic group include an alkyl group or an alkyl group containing a hetero atom. The alkyl group containing a hetero atom is preferably an alkyl group containing an etheric oxygen atom, an alkyl group containing a fluorosulfonylated etheric oxygen atom, or a fluorosulfonylated alkyl group. The number of etheric oxygen atoms in the alkyl group containing an etheric oxygen atom and the alkyl group containing a fluorosulfonylated etheric oxygen atom may be one or two or more. The etheric oxygen atom may be inserted between the carbon atom-carbon atom bond or may be inserted at the carbon atom bond terminal.

  Examples of the alkyl group containing an etheric oxygen atom include an alkoxy group, an alkoxyalkyl group, and an alkoxyalkoxy group. One or more fluorosulfonyl groups in a fluorosulfonylated alkyl group and an alkyl group containing a fluorosulfonylated etheric oxygen atom are bonded to the non-bonding terminal of the alkyl group or the alkyl group containing an etheric oxygen atom. It is preferable that one is bonded to the non-bonding end.

  As the perfluorinated monovalent saturated organic group, a perfluoroalkyl group, a perfluoroalkoxy group, a perfluoro (alkoxyalkyl) group, a perfluoro (alkoxyalkoxy) group, a fluorosulfonylated perfluoroalkyl group, or a fluorosulfonylated ( Perfluoroalkyl groups containing an etheric oxygen atom) are preferred, these groups having 1 to 10 carbon atoms are particularly preferred, and these groups having 1 to 4 carbon atoms are particularly preferred.

The fluorosulfonylated perfluoroalkyl group is a group represented by the formula — (CF ₂ ) _n1 SO ₂ F (where n1 is an integer of 1 to 20, preferably 1 to 10, preferably 1 to 4). .) Or formula — (CF ₂ ) _n2 CF (SO ₂ F) ₂ (where n2 is an integer of 1 to 19, preferably 1 to 9, and particularly preferably 1 to 3), and formula — ( A group represented by CF ₂ ) _n1 SO ₂ F (where n1 has the same meaning as described above) is particularly preferred.

The fluorosulfonylated (perfluoroalkyl containing an etheric oxygen atom) group has the formula — (CF ₂ ) _n3 OCF ₂ CF ₂ SO ₂ F (where n3 is an integer of 1 to 18, preferably 1 to 8). , 1 or 2 are particularly preferred) or _{-. (CF 2) n4 OCF} 2 CF (SO 2 F) 2 ( provided that n4 is 1 to 18 integer, 1-8 are preferred, 1 or 2 are particularly . a preferred) are preferred, wherein _{-. (CF 2) n3 OCF} 2 CF 2 SO 2 F ( although n3 are as defined above) are particularly preferred.

Specific examples of the perfluoroalkyl group include —CF ₃ , —CF ₂ CF ₃ , —CF ₂ CF ₂ CF ₃ , and —CF ₂ CF (CF ₃ ) ₂ .
Specific examples of the perfluoroalkoxy group include —OCF ₃ , —OCF ₂ CF ₃ , and —OCF ₂ CF ₂ CF ₃ .
Specific examples of perfluoro (alkoxyalkyl) _{group, -CF 2 OCF 3, -CF 2} OCF 2 CF 3, -CF 2 OCF 2 CF 2 CF 3, and _{-CF 2} OCF _{(CF 3)} 2 and the like.
Specific examples of perfluoro (alkoxyalkoxy) _{group, -OCF 2 OCF 3, -OCF 2} OCF 2 CF 3, -OCF 2 OCF 2 CF 2 CF 3, and -OCF ₂ OCF _{(CF 3) 2} and the like.
Examples of fluoro-sulfonylated been perfluoroalkyl _group, -CF ₂ SO _{2 F,} are _{-CF 2 CF 2 CF 2 CF 2} SO 2 F and the like.
Is fluoro sulfonyl as specific examples of the groups (perfluoroalkyl containing an etheric oxygen atom) _{is, -CF 2 OCF 2 CF 2 SO} 2 F, are _{-CF 2 CF 2 OCF 2 CF 2} SO 2 F and the like.
Specific examples of the perfluorinated monovalent saturated organic group other than the above preferred groups include a perfluoro (partial chloroalkyl) group. Specific examples of such groups include -CFClCF ₂ Cl.

As R ^{F1 to} R ^F4 in the compound (a) of the present invention, R ^F3 and R ^F4 are fluorine atoms, and R ^F1 and R ^F2 are each independently a perfluorinated monovalent saturation having 1 to 20 carbon atoms. It is preferably an organic group, R ^F3 and R ^F4 are fluorine atoms, R ^F1 is a trifluoromethyl group, and R ^F2 is a perfluorinated monovalent saturated organic group having 1 to 20 carbon atoms. Is particularly preferred.

The compound (a) of the present invention is preferably the following compound (a1) (provided that R ^F12 has the same meaning as described above).

  Specific examples of the compound (a) include the following compounds.

The production method of the compound (a) of the present invention is preferably according to the following method (provided that R ^{F1 to} R ^F4 , R ^{1 to} R ⁴ , R ^EF , and X have the same meaning as described above. M Represents a sodium atom or a potassium atom.)

  That is, the compound (d) is perfluorinated by a liquid phase fluorination reaction to give the compound (c), and then the compound (c) is esterified to give the compound (b). It is preferable to use a method in which compound (b) is thermally decomposed to give compound (a). The liquid phase fluorination reaction and ester decomposition reaction are preferably carried out according to the method described in WO00 / 56694.

  In addition, the reaction of thermally decomposing compound (b) can be carried out by heating compound (b) after converting compound (b) to compound (b1) by a method of directly obtaining compound (a) by heating compound (b). The method of obtaining (a) may be used. These methods are preferably carried out according to the methods described in WO00 / 56694, etc., respectively.

In the production method, R ^{1 to} R ⁴ are preferably groups that are perfluorinated and converted to R ^{F1 to} R ^F4 , respectively. In this case, ^R 1 to R ⁴ which corresponds to a fluorine atom ^R F1 ^{to R F4} is preferably a hydrogen atom, corresponding to ^R F1 ^{to R F4} is a monovalent saturated organic group perfluorinated having 1 to 20 carbon atoms R ^{1 to} R ⁴ are preferably a monovalent saturated organic group having the same carbon skeleton as the perfluorinated monovalent saturated organic group having 1 to 20 carbon atoms and essentially including a hydrogen atom bonded to the carbon atom. X is preferably a hydrogen atom.

R ^EF is preferably a C 1-10 perfluoroalkyl group or a C 2-10 perfluoro (alkyl containing an etheric oxygen atom) group.
Specific examples of R ^EF include the following groups.
_{-CF 2 CF 3, -CF (CF} 3) CF 2 CF 3, -CF (CF 3) 2, -CF (CF 3) O (CF 2) 3 F, -CF (CF 3) OCF 2 CF (CF _{3) O (CF 2) 3} F.

Compound (d), compound (c), compound (b), and compound (b1) in the production method are novel compounds.
Specific examples of the compound (d) include the following compounds.

  Specific examples of the compound (c) include the following compounds.

  Specific examples of the compound (b) include the following compounds.

  Specific examples of the compound (b1) include the following compounds.

The method for obtaining compound (d), which is the starting material of the above method, is not particularly limited, and is preferably according to the following method (provided that R ^{1 to} R ⁴ , R ^EF , and X have the same meaning as described above). The preferred embodiment is the same as described above.

  That is, the compound (i) and the compound (h) are esterified to obtain the compound (g). The compound (g) is converted into the compound (f1) by an epoxidation reaction or the compound (f2) by a diolation reaction. The obtained compound (f1) and compound (f2) can be converted into the compound (d) by cyclization reaction with the compound (e).

  Compound (i) can be obtained from a known compound or a known compound by a known method. The esterification reaction between compound (i) and compound (h) can be carried out according to a known method.

The epoxidation reaction or diolation reaction of the compound (g) can be carried out by an oxidation reaction, specifically by changing the kind of the oxidizing agent to be reacted with the compound (g). For example, when the epoxidation reaction is performed in the compound (g), it is preferable to use a method in which the compound (g) is reacted with H ₂ O ₂ or an organic peracid (such as peracetic acid or m-chloroperbenzoic acid). When the diolation reaction is performed in the compound (g), it is preferable to use a method in which the compound (g) is reacted with KMnO ₄ or OsO ₄ .

  The cyclization reaction of compound (f1) and compound (f2) can be performed by a method in which compound (f1) and compound (f2) are reacted with compound (e) in the presence of an acid catalyst, respectively.

  Examples of the acid catalyst include inorganic acids such as hydrochloric acid and sulfuric acid, Lewis acids such as titanium tetrachloride, boron trifluoride etherate, aluminum chloride, and zinc chloride, and benzfluorosulfonic acid polymers. Examples of the shape of the benzfluorosulfonic acid polymer include a bead shape and a porous nanocomposite supported on amorphous silica. The amount of the acid catalyst is preferably 0.05 to 0.5 moles compared to the compound (f1) and the compound (f2).

In the cyclization reaction, an ortho acid ester may be used together with the acid catalyst. Ortho acid esters include HC (OCH ₃ ) ₃ , HC (OC ₂ H ₅ ) ₃ , CH ₃ C (OCH ₃ ) ₃ , and CH ₃ C (OC ₂ H ₅ ) ₃ . The amount of the ortho acid ester is preferably 1.0 to 1.5 times the moles of the compound (f1) and the compound (f2).

  The cyclization reaction may be performed in the presence or absence of a solvent, and is preferably performed in the absence of a solvent from the viewpoint of volume efficiency. The lower limit of the reaction temperature in the cyclization reaction is preferably −10 ° C., and the upper limit is preferably the boiling point of the compound (e).

Specific examples of compound (i) in the method for producing compound (d) include CH ₂ ═CHCH ₂ CH ₂ OH, CH ₃ CH ₂ CH═CHCH ₂ CH ₂ OH, and the like.

Specific examples of the compound (h) include CF ₃ CF ₂ COF, CF ₃ CF ₂ CF (CF ₃ ) COF, (CF ₃ ) ₂ CFCOF, F (CF ₂ ) ₃ OCF (CF ₃ ) COF, F (CF ₂ ) ₃ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) COF and the like.

Specific examples of the compound (e) include HC (O) H, CH ₃ C (O) H, CH ₃ C (O) CH ₃ , CH ₃ C (O) CH ₂ CH ₃ , CH ₃ C (O). CH ₂ Cl, and the like.

When the compound (d) is used as a raw material of the compound (a) in which at least one of R ^{F1 to} R ^F4 is a monovalent saturated organic group that is fluorosulfonylated, R ^{1 to} R ⁴ in the compound (d) It is preferable to prepare a compound (d) into which a fluorosulfonyl group has been introduced (hereinafter referred to as compound (ds)) and to use the compound (ds) in the production method of the compound (a).

In this case, as the compound (e), a compound represented by the formula R ¹ C (O) CH ₂ SCN such as CH ₃ C (O) CH ₂ SCN, CH ₃ CH ₂ C (O) CH ₂ SCN (however, R ¹ has the same meaning as described above.) Or a formula R ¹ C such as CH ₃ C (O) CH ₂ SC (S) OCH ₃ , CH ₃ CH ₂ C (O) CH ₂ SC (S) OCH ₃ A compound represented by (O) CH ₂ SC (S) OCH ₃ (wherein R ¹ has the same meaning as described above) can be used. Compound (d) is obtained using these compounds (e), and then the —SCN group or —SC (S) OCH ₃ group in the compound (d) is converted to —SO ₂ F using a known method. The compound (ds) can be prepared by converting to a group.

Compound (ds), a method of -SO ₂ F group or -SO ₂ F group may be converted into groups (-SCN group, -SC (S) OCH ₃ group, etc.) are not present compound (d) is a starting material Can also be prepared. For example, the following compound (dsn-1) is obtained by an exchange reaction between the following compound (d-1) and CH ₃ C (O) CH ₂ SCN, and the compound (dsn-1) is obtained according to a known method. The following method of converting into the following compound (ds-1) after converting into the following compound (dsc-1) is mentioned.

  Since the compound (a) of the present invention has a polymerizable carbon-carbon double bond, it is useful as a monomer. In the present invention, it is preferable to produce a polymer by polymerizing the compound (a). The polymer obtained by polymerizing the compound (a) is a polymer containing the following repeating unit (A) (hereinafter also referred to as polymer (A)).

  Specific examples of the repeating unit (A) include the following examples.

  The polymer (A) may be a homopolymer obtained by homopolymerizing the compound (a), and copolymerizes the compound (a) and a monomer other than the compound (a) (hereinafter referred to as comonomer). It may be a copolymer obtained. The homopolymer is a polymer comprising the repeating unit (A), and the copolymer is a polymer comprising the repeating unit (A) and a repeating repeating unit based on a comonomer (hereinafter referred to as repeating unit (B)).

  The polymer (A) preferably contains the repeating unit (A) more than 0 mol% and 100 mol% or less, more preferably 0.1 mol% to 90 mol%, more preferably 10 to 10 mol% based on all repeating units. It is particularly preferable to contain 40 mol%. When the polymer (A) contains the repeating unit (B), the repeating unit (B) is preferably contained in an amount of more than 0 mol% and less than 100 mol%, and 99.9 mol% to 10 mol% based on all repeating units. It is more preferably contained, and particularly preferably 90 to 60 mol%.

The comonomer may be a comonomer containing no fluorine atom or a comonomer containing a fluorine atom.
Specific examples of the comonomer containing a fluorine atom include CH ₂ ═CHF, CH ₂ ═CF ₂ , CF ₂ ═CFCl, CF ₂ ═CF ₂ , a compound represented by the formula CF ₂ ═CF—W ^F1 (provided that W ^F1 is a monovalent fluorine-containing organic group, the same applies hereinafter (hereinafter referred to as compound m1), a compound represented by the formula CH ₂ = CH—W ^F1 (hereinafter referred to as compound m2), perfluoro (2, 2-dimethyl-1,3-dioxole) or perfluoro (2-methylene-1,3-dioxolane).

Specific examples of the compound m1 include CF ₂ = CFCF ₃ , CF ₂ = CFCF ₂ Br, CF ₂ = CFCF ₂ I, CF ₂ = CFOCF ₃ , CF ₂ = CFOCF ₂ CF ₂ CF ₃ , CF ₂ = CFCF ₂ OCF ₂ CF ₂ CF ₃ , CF ₂ = CFOCF ₂ CF = CF ₂ , CF ₂ = CFOCF ₂ CF ₂ CF = CF ₂ , CF ₂ = CFOCF ₂ CF ₂ OCF = CF ₂ , CF ₂ = CFCF ₂ CF ₂ SO ₂ F CF ₂ = CFOCF ₂ CF ₂ SO ₂ F, CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F, and the like.

Specific examples of the compounds _{m2, CH 2 = CHCF 2 CF} 2 CF 2 CF 2, CH 2 = CHCF 2 CF 2 CF 2 CF 2 H, CH 2 = CHCF 2 CF 2 CF 2 CF 2 Br, CH 2 = CHCF ₂ CF ₂ CF ₂ CF ₂ I, and the like.

Specific examples of the comonomer not containing a fluorine atom include CH ₂ = CH ₂ , CH ₂ = CHCl, CH ₂ = CHBr, CH ₂ = CHI, CH ₂ = CHCH ₃ , CH ₂ = CHCH ₂ Cl, CH ₂ = CHCH. ₂ Br, CH ₂ ═CHCH ₂ I and the like.

  The compound (a) is preferably polymerized in the presence of a polymerization initiator. The polymerization initiator may be added from the beginning of the polymerization or may be added during the polymerization. The polymerization initiator is preferably used in an amount of from 0.0001 to 3% by mass, particularly preferably from 0.001 to 1% by mass, based on the total amount of monomers.

The polymerization initiator is preferably a radical polymerization initiator. As radical polymerization initiators, 2,2-azobis (2-amidinopropane) dihydrochloride, 4,4-azobis (4-cyanopentanoic acid), 2,2-azobis (4-methoxy-2,4-dimethyl) Valeronitrile), azo compounds such as 1,1-azobis (1-cyclohexanecarbonitrile), diisopropyl peroxydicarbonate, benzoyl peroxide, perfluorononanoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxide, (CF ₃ CF ₂ CF ₂ COO) ₂ , (C ₆ F ₅ COO) ₂ , organic peroxides such as ((CH ₃ ) ₂ CO) ₂ , and inorganic peroxides such as K ₂ S ₂ O ₈ and (NH ₄ ) ₂ S ₂ O ₈ .

  The polymerization of the compound (a) may be performed in the presence of a chain transfer agent. Examples of chain transfer agents include alcohols (methanol, ethanol, etc.), chlorofluorohydrocarbons (1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1,1-dichloro-1- Fluoroethane etc.), hydrocarbons (pentane, hexane, cyclohexane etc.), iodofluorohydrocarbons (1,4-diiodoperfluorobutane, 1-bromo-4-iodoperfluorobutane etc.).

  The pressure (gauge pressure) in the polymerization is preferably more than 0 MPa and 20 MPa or less, particularly preferably 0.3 MPa or more and 5 MPa or less. The polymerization temperature is preferably 0 ° C. or higher and 100 ° C. or lower, and particularly preferably 10 ° C. or higher and 80 ° C. or lower. Examples of the polymerization method include known methods such as a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, and a bulk polymerization method.

The molecular weight of the polymer (A) is preferably 5 × 10 ² to 1 × 10 ⁶ . The melting start temperature of the polymer (A) of the present invention is preferably 100 ° C to 400 ° C. However, the definition of the melting start temperature will be described later.

  The polymer (A) is excellent in physical properties such as low refractive index property, water / oil repellency, transparency, heat resistance and mechanical strength. The polymer (A) of the present invention comprises an optical material (for example, an optical waveguide material, an optical fiber material, a pellicle material, a light emitting element sealing material, a lens material, etc.), an electronic material (for example, a semiconductor interlayer insulating film, a high-frequency element protective film, Display surface protective film, etc.), and water and oil repellent materials (for example, oil sealants).

Of the polymers (A), the polymer (A) obtained by polymerizing the compound (a) containing a fluorosulfonyl group is an ion exchange membrane (such as an ion exchange membrane for salt electrolysis) or a solid polymer type. It is suitable as a solid polymer electrolyte for fuel cells. The polymer (A) is particularly suitable as a solid polymer electrolyte for a polymer electrolyte fuel cell operated at 120 ° C. or higher because of its high softening temperature. In this case, the fluorosulfonyl group in the polymer is a polymer containing a group represented by the formula —SO ₂ (OM) (wherein M represents a hydrogen atom, a lithium atom, a potassium atom, or a sodium atom). It is preferable to use after chemical conversion.

Specific examples of the polymer (A) containing a group represented by the formula —SO ₂ (OM) include a polymer (A) containing any one of the following repeating units.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these.
CF ₂ ClCF ₂ CHClF is indicated as R-225cb, CCl ₂ FCClF ₂ as R-113, CH ₃ CCl ₂ F as R-141b, and gas chromatography as GC. The purity was determined from the peak area ratio by GC analysis. The yield was determined by ¹⁹ F-NMR using perfluorobenzene as an internal standard.

  [Example 1] Production example of compound (d-1)

[Example 1-1] Production Example of Compound (g-1) A flask equipped with a thermometer, a dropping funnel and a stirrer was cooled in an ice bath, and CH ₂ = CHCH ₂ CH ₂ OH (10 g), NaF ( 7 g) and R-225cb (40 g) were added. Next, while maintaining the internal temperature of the flask at 10 ° C. or lower, the solution was stirred while dropping a solution prepared by dissolving F (CF ₂ ) ₃ OCF (CF ₃ ) COF (50.7 g) in R-225cb (20 g). . Subsequently, the internal temperature was set to 25 ° C., and the mixture was further stirred for 2 hours.

After adding R-225cb (50 mL) to the flask, the content liquid of the flask was subjected to pressure filtration, and a saturated aqueous sodium hydrogen carbonate solution (100 mL) was added to separate the organic layer and the aqueous layer. The aqueous layer was extracted with R-225cb (50 mL) to obtain an extract. The organic layer and the aqueous layer were mixed, dehydrated with anhydrous sodium sulfate, and then concentrated by an evaporator to obtain a product (44.3 g). As a result of analyzing the product by NMR and GC, it was confirmed that the compound (g-1) (purity: 99.3%) was produced. The NMR data of the compound (g-1) are shown below.
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 5.8 (1H), 5.1 (2H), 4.4 (2H), 2.5 (2H) .
¹⁹ F-NMR (282.6 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): −80 (1F), −81.9 (3F), −82.7 (3F), −86.8 (1F), -130.2 (2F), -132.2 (1F).

[Example 1-2] Production Example of Compound (f-1) In a flask equipped with a thermometer and a reflux condenser, the product (35.2 g) obtained in Example 1-1, CH ₂ Cl ₂ (240 g), And R-225cb (120 g) was added, followed by stirring while adding m-chloroperbenzoic acid (25.6 g) little by little. After completion of dropping, the mixture was further stirred for 26 hours. The contents of the flask were filtered under pressure to obtain a filtrate. The filtration residue was extracted with R-225cb (twice with 50 mL) to obtain an extract. The filtrate and the extract were mixed to obtain a mixed solution.

Next, the mixture was washed with a 10% by mass aqueous sodium thiosulfate solution (50 mL) and washed with a saturated aqueous sodium bicarbonate solution (40 mL) four times, and then dehydrated with anhydrous sodium sulfate. Furthermore, it concentrated by the evaporator and obtained the product (29g). As a result of analyzing the product by NMR and GC, it was confirmed that the compound (f-1) (purity 86%) was produced. The NMR data of the compound (f-1) are shown below.
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 4.5 to 4.6 (2H), 3.0 (1H), 2.8 (1H), 2. 5 (1H), 1.9 to 2.1 (2H).
¹⁹ F-NMR (282.6 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): −80 (1F), −81.8 (3F), −82.6 (3F), −86.8 (1F), -130.2 (2F), -132.1 (1F).

[Example 1-3] Production Example of Compound (d-1) In a flask equipped with a thermometer, a reflux condenser, and a dropping funnel, dehydrated CH ₃ C (O) CH ₃ (40 mL) and boron trifluoride etherate (1.1 g) was added, and then a solution obtained by dissolving the product (29 g) obtained in Example 1-2 in CH ₃ C (O) CH ₃ (20 mL) was stirred dropwise. After completion of the dropwise addition, the mixture was further stirred for 2 hours, and a saturated aqueous sodium hydrogen carbonate solution (100 mL) was added to the flask to obtain a reaction crude liquid. The reaction crude liquid was extracted with R-225cb (4 × 50 mL), washed with water (50 mL), dehydrated with anhydrous sodium sulfate, and concentrated with an evaporator to obtain a crude product. The crude product was distilled to obtain a fraction (17.7 g) of 116 ° C./4.0 kPa (absolute pressure). As a result of analyzing the fraction by NMR and GC, it was confirmed that the compound (d-1) (purity 98.6%) was produced. The NMR data of the compound (d-1) are shown below.
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 4.4 to 4.6 (2H), 4.0 to 4.2 (2H), 3.5 to 3 .6 (1H), 2.0 (2H), 1.4 (3H), 1.3 (3H).
¹⁹ F-NMR (282.6 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): −80.2 (1F), −81.8 (3F), −82.6 (3F), −86 .8 (1F), -130.2 (2F), -132.2 (1F).

  [Example 2] Production example of compound (a-1)

[Example 2-1] Production Example of Compound (c-1) An autoclave (made of nickel, internal volume 500 mL) was prepared, and a cooler maintained at 20 ° C, a NaF pellet packed layer, and -10 at the gas outlet of the autoclave A cooler maintained at 0 ° C. was installed in series. Moreover, the liquid return line which returns the liquid aggregated from the cooler hold | maintained at -10 degreeC to an autoclave was installed.

  R-113 (312 g) was added to the autoclave and stirred while maintaining at 25 ° C. As it was, nitrogen gas was blown into the autoclave at 25 ° C. for 1 hour, and then fluorine gas diluted to 20% volume with nitrogen gas (hereinafter referred to as 20% fluorine gas) was 1 at 25 ° C. and a flow rate of 15.89 L / h. Time blown. Next, 20% fluorine gas was blown at the same flow rate, and a solution obtained by dissolving the fraction (17.1 g) obtained in Example 1-3 in R-113 (172 g) was injected over 7.4 hours.

  Next, the internal pressure of the autoclave was increased to 0.15 MPa (gauge pressure) while blowing 20% fluorine gas at the same flow rate, and the R-113 solution having a benzene concentration of 0.01 g / mL was changed from 25 ° C. to 40 ° C. 9 mL was injected while heating until the benzene solution inlet of the autoclave was closed. The total amount of benzene injected was 0.22 g.

Further, stirring was continued for 1 hour while blowing 20% fluorine gas at the same flow rate. Next, the pressure in the reactor was set to atmospheric pressure, and nitrogen gas was blown in for 1 hour. As a result of analyzing the contents of the autoclave by NMR, it was confirmed that the compound (c-1) (reaction yield: 86%) was produced. The NMR data of the compound (c-1) are shown below.
¹⁹ F-NMR (282.6 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): −76.6 (1F), −79.8 to −81.6 (8F), −81.9 to -82.1 (6F), -85.6 to -87.6 (3F), -120.1 (1F), -122.7 (1F), -128.2 to -129.7 (1F), -130.3 (2F), -132.0 (1F).

[Example 2-2] Production example of compound (b-1) In a flask equipped with a reflux condenser and a thermometer, the content (compound (c-1) 23.23) obtained in the same manner as in Example 2-1. 6 g.) And KF (0.43 g) were added and stirred at 100 ° C. for 3 hours. The flask was cooled and distilled under atmospheric pressure to obtain a fraction A (4.6 g) at 56 to 62 ° C. and a fraction B (9.7 g) at 62 to 75 ° C.

As a result of analyzing fraction A using NMR and GC, the above-mentioned compound (b-1) (purity 29.6%) and F (CF ₂ ) ₃ OCF (CF ₃ ) COF (purity 66.5%) were produced. It was confirmed. As a result of analyzing fraction B in the same manner, it was confirmed that the compound (b-1) (purity 66.5%) and F (CF ₂ ) ₃ OCF (CF ₃ ) COF (purity 30.5%) were produced. . The NMR data of the compound (b-1) are shown below.
¹⁹ F-NMR (282.6 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): 24.1 (1F), −76.6 (1F), −79.6 to −81.1 (7F ), -115.7 to -119.7 (3F).

[Example 2-3] Production example of compound (a-1) In a flask equipped with a thermometer, the fraction A (4.6 g) and the fraction B (9.7 g) obtained in Example 2-2 were mixed. The mixture and phenolphthalein were charged. Next, a 10% by mass sodium hydroxide methanol solution (28 g) was dropped into the flask to obtain a red colored solution. The solution was concentrated with an evaporator and then dried at 80 ° C. for 30 hours to obtain a solid (14.4 g).

  A flask equipped with a thermometer and dry eye strap was charged with solids (14.1 g). A trap cooled with liquid nitrogen was installed at the top of the tower of the dry eye strap. When the flask was heated to 380 ° C. while reducing the pressure with a vacuum pump, liquid was distilled into a dry ice strap and a trap cooled with liquid nitrogen, respectively.

As a result of analyzing the liquid (6.9 g) distilled in the dry eye strap by NMR and GC, the above compound (a-1) (purity 35.6%), compound (b-1) (purity 6.9%) were analyzed. ) And F (CF ₂ ) ₃ OCF═CF ₂ (purity 48.8%).

The liquid (2.9 g) distilled in the trap cooled with liquid nitrogen was analyzed by NMR and GC. As a result, the compound (a-1) (purity 20.9%) and the compound (b-1) (purity 4) were analyzed. 0.9%) and F (CF ₂ ) ₃ OCF═CF ₂ (purity 48.8%). NMR of compound (a-1) is shown below.
¹⁹ F-NMR (282.6 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −62.3 (2F), −81.3 (6F), −92.6 (1F), −107 .1 (1F).

[Example 3] Production example of polymer (part 1)
An autoclave (internal volume 30 mL, made by Hastelloy) was charged with perfluorobenzoyl peroxide (60.6 mg), R-225cb, and compound (a-1) (10.29 g), and deaerated while being cooled with liquid nitrogen. From which tetrafluoroethylene (4.6 g) was introduced. Next, while stirring the interior of the autoclave, the polymerization reaction was carried out for 5 hours while maintaining the internal temperature at 80 ° C. and the internal pressure at 1.3 MPaG (gauge pressure).

  Next, the autoclave was cooled and the system gas was purged to terminate the polymerization reaction, and then the autoclave contents were recovered. R-141b was added to the autoclave content diluted with R-225cb to recover the aggregated crude polymer. Further, R-141b was added while stirring the crude polymer in R-225cb, and the agglomerated polymer was collected, dried under reduced pressure at 80 ° C. for 12 hours, and purified polymer (0.66 g) (hereinafter referred to as “reduced polymer”). , Referred to as Polymer 1).

As a result of analyzing polymer 1 by melting ¹⁹ F-NMR, the presence of the following repeating unit (A-1) was confirmed. The ratio of the repeating unit (A-1) to the entire repeating unit of the polymer 1 was 6.6 mol%. Further, a melt extrusion test of polymer 1 (extrusion pressure is 2.94 MPa (gauge pressure)) using a flow tester (manufactured by Shimadzu Corporation, trade name CFT-500D) using a nozzle having a length of 1 mm and an inner diameter of 1 mm. As a result, the melting start temperature of the polymer 1 was 260 ° C.

[Example 4] Production example of polymer (part 2)
A polymer (0) was prepared in the same manner as in Example 3, except that perfluorobenzoic peroxide (37.9 mg) and compound (a-1) (18.95 g) were charged into an autoclave (internal volume 30 mL, manufactured by Hastelloy). .16 g) (hereinafter referred to as polymer 2).

As a result of analyzing polymer 2 by melting ¹⁹ F-NMR, the presence of the repeating unit (A-1) was confirmed. The ratio of the repeating unit (A-1) to the entire repeating unit of the polymer 2 was 15.0 mol%. Moreover, the melting start temperature of the polymer 2 was 120 degreeC.

  The compound of the present invention is useful as a polymerizable compound. The polymer obtained by polymerizing the compound of the present invention is useful as various optical materials, electronic materials, other materials, materials for ion exchange membranes, etc., which are particularly excellent in heat resistance and mechanical strength.

Claims (8)

A compound represented by the following formula (a).

However, R ^{F1 to} R ^F4 each independently represent a fluorine atom, a chlorine atom, or a perfluorinated monovalent saturated organic group having 1 to 20 carbon atoms. A compound represented by the following formula (a1).

R ^F12 is a perfluoroalkyl group having 1 to 4 carbon atoms or a group represented by the formula — (CF ₂ ) _n1 SO ₂ F (where n1 represents an integer of 1 to 4). A method for producing a compound represented by the following formula (a), wherein the compound represented by the following formula (b) is thermally decomposed to obtain a compound represented by the following formula (a).

However, R ^{F1 to} R ^F4 each independently represent a fluorine atom, a chlorine atom, or a perfluorinated monovalent saturated organic group having 1 to 20 carbon atoms. Any compound represented by the following formula.

However, R ^{F1 to} R ^F4 each independently represent a fluorine atom, a chlorine atom, or a perfluorinated monovalent saturated organic group having 1 to 20 carbon atoms.
R ¹ is ^{R F1, R 2} to ^{R F2, R 3} to ^{R F3, R 4} to ^{R F4,} a corresponding group, ^R 1 ~ corresponding to ^R F1 ^{to R F4} is a chlorine atom R ⁴ is a chlorine atom, ^R 1 to R ⁴ corresponding to ^R F1 ^{to R F4} is a fluorine atom is a hydrogen atom or a fluorine atom, ^{R F1} ~ is a monovalent saturated organic group perfluorinated having 1 to 20 carbon atoms R ^{1 to} R ⁴ corresponding to R ^F4 have the same carbon skeleton having 1 to 20 carbon atoms, and are a monovalent saturated organic group essentially including a hydrogen atom bonded to a carbon atom, or the same as R ^{F1 to} R ^F4 Indicates a group.
R ^EF represents a C 1-10 perfluorinated monovalent saturated organic group.
X represents a hydrogen atom or a fluorine atom. The polymer containing the repeating unit represented by the following formula (A).

However, R ^{F1 to} R ^F4 each independently represent a fluorine atom, a chlorine atom, or a perfluorinated monovalent saturated organic group having 1 to 20 carbon atoms. The polymer containing the repeating unit represented by the following formula (A1).

R ^F12 is a perfluoroalkyl group having 1 to 4 carbon atoms or a group represented by the formula — (CF ₂ ) _n1 SO ₂ F (where n1 represents an integer of 1 to 4). The polymer according to claim 5 or 6, which has a molecular weight of 5 x 10 ² to 1 x 10 ⁶ . A polymer containing a repeating unit represented by the following formula (A) is obtained by polymerizing a compound represented by the following formula (a) to obtain a polymer containing a repeating unit represented by the following formula (A): Manufacturing method of coalescence.

However, R ^{F1 to} R ^F4 each independently represent a fluorine atom, a chlorine atom, or a perfluorinated monovalent saturated organic group having 1 to 20 carbon atoms.