JP2007077141A - Norbornenes having novel fluorosulfonyl group and method for producing the same - Google Patents

Abstract

【選択図】なし
A novel norbornene having a fluorosulfonyl group and a process for producing the norbornene are provided.
A compound represented by the following formula (a), and a compound represented by the following formula (a) in which a compound represented by the following formula (c) and a compound represented by the following formula (b) are subjected to Diels-Alder reaction. is the process for the preparation of compounds (where, X is a methylene group, monomethyl methylene group, dimethylmethylene group, an oxygen atom or a sulfur atom, Q ^F is a divalent fluorinated organic group having 1 to 20 carbon atoms, k is 0 1 or 2 is indicated.)
[Chemical 1]

[Selection figure] None

Description

  The present invention relates to a novel norbornene having a fluorosulfonyl group and a method for producing the norbornene.

  As norbornenes having a fluorosulfonyl group, the following compound (z1) having a structure in which the fluorosulfonyl group is directly bonded to the carbon atom at the 5-position in the norbornene skeleton is known (see Patent Document 1). Moreover, the compound represented by the following Formula (z2) is known as a fluorine-containing tricyclic compound which has a fluoro sulfonyl group (refer patent document 2).

  However, norbornene having a structure in which a fluorosulfonyl group is bonded to a carbon atom in the norbornene skeleton via a chain-like polyfluoro divalent organic group is not known.

Special table 2003-525311 gazette JP-T-2005-535709

  An object of the present invention is to provide norbornenes in which a fluorosulfonyl group is bonded to a carbon atom of a norbornene skeleton via a chain-like divalent fluorine-containing organic group.

That is, the present invention provides the following inventions.
<1> a compound represented by the following formula (a) (provided that, X is a methylene group, monomethyl methylene group, dimethylmethylene group, an oxygen atom or a sulfur atom, Q ^F is a divalent fluorinated C20 A valent organic group, k represents 0, 1 or 2. The same shall apply hereinafter.)
<2> The compound according to <1>, wherein Q ^F is a fluoroalkylene group having 1 to 10 carbon atoms or a fluoroalkylene group having an etheric oxygen atom between 2 to 10 carbon atoms and a carbon atom bond.
<3> The compound according to <1> or <2>, wherein Q ^F is a group represented by the formula — (CH ₂ ) _m OCFY (CF ₂ ) _n — (where Y is a fluorine atom or trifluoromethyl) And m and n each independently represents an integer of 1 to 8, and 2 ≦ m + n ≦ 9.

  <4> A compound represented by the following formula (a) is obtained by subjecting a compound represented by the following formula (c) and a compound represented by the following formula (b) to a Diels-Alder reaction. The manufacturing method of the compound represented by (a).

  The compound of the present invention is a characteristic novel compound in which a fluorosulfonyl group is bonded to a carbon atom of a norbornene skeleton via a chain-like divalent fluorine-containing organic group. A novel fluorine-containing polymer having a fluorosulfonyl group can be produced by radical polymerization of the compound.

  In the present specification, a compound represented by the formula (a) is referred to as a compound (a). The same applies to compounds represented by other formulas.

  The present invention provides the following compound (a).

In the compound (a) of the present invention, the compound in which k is 0 is the following compound (a ⁰ ), the compound in which k is 1 is the following compound (a ¹ ), and the compound in which k is 2 is compound ^{(a 2),} means. The configuration of the group represented by the formula -Q ^F SO ₂ F in the compound (a) may be exo or endo. k is preferably 0, and the compound (a) is preferably the compound (a ⁰ ).

X in the compound (a) is preferably a methylene group. In the compound (a ¹ ) in which two X are present and the compound (a ² ) in which three X are present, X is preferably the same group.

The divalent fluorine-containing organic group of Q ^F in the compound (a) is a divalent organic group having at least one carbon atom and one fluorine atom. The divalent fluorine-containing organic group optionally contains a hydrogen atom together with a carbon atom and a fluorine atom. The divalent fluorine-containing organic group may have a hetero atom. Examples of the hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom. In the divalent fluorine-containing organic group containing a hetero atom, the hetero atom may be contained as a hetero atom (—O—, ═N—, —S—, etc.), or a hetero atom group (—C (═O )-, -NH-, -S (= O) _2-, etc.). Further, the divalent fluorine-containing organic group may be a saturated group or an unsaturated group. As for carbon number of a bivalent fluorine-containing organic group, 1-10 are preferable.

Q ^F is preferably a fluoroalkylene group having 1 to 10 carbon atoms or a fluoroalkylene group having an etheric oxygen atom between carbon atom-carbon atom bonds having 2 to 10 carbon atoms. A fluoroalkylene group refers to an alkylene group having one or more fluorine atoms.
When Q ^F is a fluoroalkylene group having 1 to 10 carbon atoms, a group represented by the formula — (CH ₂ ) _p (CF ₂ ) _q — ( _p represents an integer of 0 to 8, and q is Represents an integer of 1 to 8, and 1 ≦ p + q ≦ 10. In the group where p is 1 or more, the —CH ₂ — side is preferably bonded to a carbon atom of the norbornene skeleton.
Formula _{- (CH 2) p (CF} 2) q - group represented _{by, - (CH 2) 2 (} CF 2) 2 -, - (CH 2) 2 (CF 2) 4 -, - (CF 2 ) ₂ - or - _{(CF 2) 4} - are preferred.

When Q ^F is a fluoroalkylene group having an etheric oxygen atom between a carbon atom-carbon atom bond having 2 to 10 carbon atoms, a group represented by the formula — (CH ₂ ) _m OCFY (CF ₂ ) _n — (Y represents a fluorine atom or a trifluoromethyl group, m and n each independently represents an integer of 1 to 8, and 2 ≦ m + n ≦ 9, the same applies hereinafter) or formula — (CF ₂ ) _g A group represented by OCF ₂ CF ₂ — (where g represents an integer of 1 to 6, the same shall apply hereinafter) is preferred, and a group represented by the formula — (CH ₂ ) _m OCFY (CF ₂ ) _n — Particularly preferred.

Y is preferably a fluorine atom. m is preferably an integer of 1 to 6. n is preferably 1. In the group, the —CH ₂ — side is preferably bonded to the carbon atom of the norbornene skeleton.

The group represented by the formula — (CH ₂ ) _m OCFY (CF ₂ ) _n — is preferably a group represented by the formula —CH ₂ OCF ₂ CF ₂ — or —CH ₂ OCF (CF ₃ ) CF ₂ —.
The group represented by the formula — (CF ₂ ) _g OCF ₂ CF ₂ — is preferably a group represented by the formula — (CF ₂ ) ₂ OCF ₂ CF ₂ —.

  Specific examples of the compound (a) include the following compound in which -X- is a methylene group, and a methylene group corresponding to -X- in the compound, a methylmethylene group, a dimethylmethylene group, an oxygen atom or a sulfur atom The compound which changed to is mentioned.

The compound (a) of the present invention can be produced using the following compound (c) and the following compound (b) which is industrially easily available.
The compound (a) of the present invention is preferably produced by reacting the following compound (c) and the following compound (b) with a Diels-Alder reaction.

Specific examples of the compound (c) has the formula _{CH 2 = CH (CH 2)} p (CF 2) q SO compound represented by the ₂ F, wherein _{CH 2 = CH (CH 2)} m OCFY (CF 2) n A compound represented by SO ₂ F, or CH ₂ ═CH (CF ₂ ) _g OCF ₂ CF ₂ SO ₂ F can be given.
Specific examples of the compound (b) include the following compounds.

  The Diels-Alder reaction is preferably carried out according to a known method. In this reaction, 1 to 20 mol of compound (c) is preferably used relative to 1 mol of compound (b), and 1.2 to 10 mol is particularly preferably used.

In order to efficiently produce the compound (a ⁰ ), it is preferable to use 0.5 to 4 mol, particularly preferably 1 to 2 mol, of the compound (c) with respect to 1 mol of the compound (b). .
In order to efficiently produce the compound (a ¹ ), it is preferable to use 2 to 12 mol, particularly preferably 2.5 to 8 mol, of the compound (c) with respect to 1 mol of the compound (b). .
In order to efficiently produce the compound (a ² ), it is preferable to use 3 to 18 mol, particularly preferably 4 to 15 mol, of the compound (c) with respect to 1 mol of the compound (b).

100-300 degreeC is preferable and, as for the reaction temperature in Diels-Alder reaction, 150-250 degreeC is especially preferable.
The Diels-Alder reaction may be performed in the presence of a solvent or in the absence of a solvent. The solvent is preferably an organic solvent having a boiling point of 60 to 200 ° C. Solvents include aliphatic hydrocarbon solvents (hexane, heptane, octane, methylcyclohexane, dimethylcyclohexane, ethylcyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, etc.), aromatic hydrocarbon solvents (benzene, toluene, xylene) Etc.).

The reaction product obtained by the production method of the present invention is usually a mixture containing three types of compounds (a), ie, a compound (a ⁰ ), a compound (a ¹ ), and a compound (a ² ). It may contain a compound other than (a) (a raw material compound such as compound (b) or compound (c)). Therefore, it is preferable to obtain the compound (a) having the desired purity and composition by purifying the reaction product as necessary. Examples of the purification method include washing with water, extraction, chromatography, distillation and the like.

  The compound (a) of the present invention is a novel novel compound in which a fluorosulfonyl group is bonded to a carbon atom of a norbornene skeleton via a chain-like divalent fluorine-containing organic group. The compound is useful as a radical polymerizable monomer. A fluorine-containing polymer containing a repeating unit derived from the compound (a) can be produced by radical polymerization of the compound (a) of the present invention.

  The fluorine-containing polymer containing a repeating unit derived from the compound (a) is preferably a fluorine-containing polymer containing a monomer unit represented by the following formula (A).

The monomer unit represented by the following formula (A) is represented by the monomer unit represented by the following formula (A ⁰ ), the monomer unit represented by the following formula (A ¹ ), or the following formula (A ² ). A monomer unit is mentioned.

The weight average molecular weight of the fluoropolymer is preferably 5 × 10 ^{3 to} 5 × 10 ⁶ .

  The fluorine-containing polymer includes a repeating unit derived from the compound (a) and a repeating unit other than the repeating unit derived from the compound (a), even if the polymer includes a repeating unit derived from the compound (a). It may be a polymer. The repeating unit other than the repeating unit derived from the compound (a) is preferably a repeating unit derived from a monomer copolymerizable with the compound (a) (hereinafter also referred to as comonomer). In the latter fluoropolymer, the ratio of the repeating unit derived from the compound (a) to the entire repeating unit is preferably 0.5 to 99.5 mol%, and more preferably 5 to 40 mol%. Particularly preferred.

  As a method for radical polymerization of compound (a), a method in which compound (a) is radically polymerized in the presence of a radical polymerization initiator or a method in which compound (a) and a comonomer are radically polymerized in the presence of a radical polymerization initiator is used. Preferably there is.

  As comonomer, polyfluoroalkene (tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, chlorotrifluoroethylene, etc.), alkene (ethylene, propylene, etc.), polyfluoro (alkyl vinyl ether) (perfluoro (n-methyl vinyl ether) ), Perfluoro (n-propyl vinyl ether), etc.), polyfluoroalkylethylene (pentafluoroethylethylene, nonafluorobutylethylene, etc.), vinyl esters (vinyl acetate, vinyl benzoate, etc.), norbornenes (norbornene, 5 -Norbornene-2-carboxylic acid methyl ester etc.), maleic anhydride, maleimide and the like.

Examples of radical initiators include azo compounds (azobisisobutyronitrile and the like), diacyl peroxides (isobutyryl peroxide, octanoyl peroxide, benzoyl peroxide, lauroyl peroxide, (CF ₃ COO) _{2 and the} like), peroxydicarbonates. (Diisopropyl peroxydicarbonate, etc.), peroxyesters (tert-butylperoxypivalate, tert-butylperoxyisobutyrate, tert-butylperoxyacetate, etc.), inorganic peroxides (potassium persulfate, sodium persulfate, peroxysulfate) Ammonium sulfate, etc.).

  In radical polymerization, various polymerization forms such as emulsion polymerization, solution polymerization, suspension polymerization, and bulk polymerization can be employed. The polymerization pressure (gauge pressure) in radical polymerization is preferably more than 0 MPa to 20 MPa, particularly preferably 0.3 MPa to 10 MPa. The polymerization temperature in radical polymerization is preferably 0 ° C to 100 ° C, particularly preferably 10 ° C to 80 ° C.

  The fluoropolymer obtained by the production method of the present invention is useful as an ion exchange membrane (a membrane for salt electrolysis or a membrane for a polymer electrolyte fuel cell) or an electrolyte for a polymer electrolyte fuel cell. When the fluoropolymer in the present invention is used for these applications, it is preferable to hydrolyze the fluorosulfonyl group in the fluoropolymer. Examples of the hydrolysis method of the fluorosulfonyl group include a method of treating the fluorosulfonyl group with an alkali metal salt of a sulfonic acid group by alkali hydrolysis. The method is preferably according to the method described in WO 03/37885.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.
GC for gas chromatographic analysis, MS for mass spectral analysis, TMS for tetramethylsilane, and THF for tetrahydrofuran. The THF used was sufficiently dehydrated THF.

Example 1 Production Example of Compound (a1) Dicyclopentadiene (5.1 g) was placed in a round bottom flask (internal volume 50 mL), stirred at 170 ° C., and cyclopentadiene (4 produced by decomposition of dicyclopentadiene (4). 0.0 g) was recovered from the top of the round bottom flask. The resulting cyclopentadiene (4.0 g), CH ₂ ═CHCH ₂ OCF ₂ CF ₂ SO ₂ F (22.0 g) and toluene (3.8 g) were added to a round bottom flask (internal volume 100 mL). The flask inner temperature was maintained at 85 ° C., and the solution in the flask was stirred for 5 hours while refluxing. From the GC analysis and GC-MS analysis of the solution in the flask, the following compound (a1) and dicyclopentadiene are formed, and unreacted CH ₂ ═CHCH ₂ OCF ₂ CF ₂ SO ₂ F is present. It was confirmed.

Next, the solution in the flask was transferred to an autoclave (internal volume 200 mL), sealed, and stirred at 170 ° C. for 4 hours. From the GC analysis and GC-MS analysis of the solution in the autoclave, it was confirmed that dicyclopentadiene had completely disappeared and that the following compound (a1) was produced at a selectivity of 92%. Further, the solution in the autoclave was distilled under reduced pressure to obtain a fraction (10.1 g) of 85 ° C./933 Pa. The production of the following compound (a1) having a purity of 99.8% was confirmed by NMR analysis of the fraction. The endo / exo production ratio of the compound (a1) calculated from ¹ H-NMR was 8/1.

¹ H-NMR and ¹⁹ F-NMR of the compound (a1) are shown below.
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm); 0.54 (1H), 1.06-1.53 (2H), 1.87 (1H), 2. 47 (1H), 2.75 to 2.95 (2H), 3.63 to 4.18 (2H), 5.94 to 6.21 (2H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm); +43.2 (1F), -84.0 (2F), -111.4 (2F).

[Example 2] Example of radical polymerization of compound (a1) (Part 1)
The compound (a1) (1.0 g) and azobisisobutyronitrile (0.005 g) are added to the autoclave, and radical polymerization is performed at 65 ° C. for 8 hours while stirring in the autoclave. The obtained solution in the autoclave is dropped into hexane (100 mL), and the agglomerated solid is collected by filtration and dried in vacuo at 80 ° C. to obtain a fluoropolymer.

[Example 3] Example of radical polymerization of compound (a1) (Part 2)
Compound (a1) (0.5 g) and azobisisobutyronitrile (0.027 g) were added to a round bottom flask (50 ml), and freeze deaeration in the round bottom flask was performed twice. A dropping funnel containing a THF solution (3 ml) containing maleic anhydride (0.16 g) and azobisisobutyronitrile (0.027 g) was placed in a round bottom flask. The THF solution was slowly dropped into the flask while stirring the inside of the round bottom flask at a temperature of 65 ° C. After completion of the dropping, the flask was stirred for 12 hours at a flask internal temperature of 65 ° C. A white precipitate formed by dropping the solution in the flask into hexane was collected by suction filtration, washed with hexane, and then vacuum-dried. As a result, a white powdery polymer (0.44 g, yield 67%) was obtained.

[Example 4] Example of radical polymerization of compound (a1) (Part 3)
Compound (a1) (0.2 g), norbornene (0.1 g), azobisisobutyronitrile (0.014 g) and THF (0.5 ml) were added to a round bottom flask (50 ml). Freeze deaeration was performed twice. A dropping funnel containing a THF solution (0.5 ml) containing maleic anhydride (0.27 g), norbornene (0.1 g) and azobisisobutyronitrile (0.031 g) was placed in a round bottom flask. The THF solution was slowly dropped into the flask while stirring the inside of the round bottom flask at a temperature of 65 ° C. After completion of the dropping, the flask was stirred for 12 hours at a flask internal temperature of 65 ° C. The white precipitate produced by dropping the solution in the flask into hexane was collected by suction filtration, washed with hexane, and then vacuum dried. As a result, a white powdery polymer (0.61 g, yield 88%) was obtained.

According to the present invention, novel norbornenes in which a fluorosulfonyl group is bonded to a carbon atom of a norbornene skeleton via a chain-like divalent fluorine-containing organic group are provided. By radical polymerization of the compound of the present invention, a fluorine-containing polymer useful as an ion exchange membrane (a membrane for salt electrolysis or a membrane for a polymer electrolyte fuel cell) or an electrolyte for a polymer electrolyte fuel cell can be obtained. Provided.

Claims (4)

Compound represented by the following formula (a) (provided that, X is a methylene group, monomethyl methylene group, dimethylmethylene group, an oxygen atom or a sulfur atom, Q ^F is a divalent fluorinated valent organic group having 1 to 20 carbon atoms , K represents 0, 1 or 2.)

The compound according to claim 1, wherein Q ^F is a fluoroalkylene group having 1 to 10 carbon atoms or a fluoroalkylene group having an etheric oxygen atom between a carbon atom-carbon atom bond having 2 to 10 carbon atoms. Q ^F is a group represented by the formula — (CH ₂ ) _m OCFY (CF ₂ ) _n —, wherein the compound according to claim 1 or 2 (wherein Y represents a fluorine atom or a trifluoromethyl group, m And n each independently represents an integer of 1 to 8, and 2 ≦ m + n ≦ 9. A compound represented by the following formula (a) is obtained by reacting a compound represented by the following formula (c) with a compound represented by the following formula (b) by a Diels-Alder reaction: manufacturing method (although the compound represented by, X is a methylene group, monomethyl methylene group, dimethylmethylene group, an oxygen atom or a sulfur atom, Q ^F is a divalent fluorinated valent organic group having 1 to 20 carbon atoms, k represents 0, 1 or 2.)