JP2007262228A - Method for producing fluorine-containing polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a fluorine-containing polymer having a ring structure having no hydrogen atom. <P>SOLUTION: The fluorine-containing polymer is produced by polymerizing a compound represented by general formula (I) to obtain a polymer having a structural unit represented by general formulas (II-A)-(II-D), and then by fluoridizing the polymer. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a novel method for producing a fluorine-containing polymer.

  The fluorine-containing polymer is excellent in chemical stability, low dielectric constant, low refractive index, low viscosity, lubricity, water repellency, non-adhesiveness, etc., and is applied to various materials. In particular, fluorine-containing polymers having substantially no hydrogen atoms are particularly superior in chemical stability, low dielectric constant, and low refractive index compared to fluorine-containing polymers having hydrogen atoms. Has been made actively. Furthermore, among the fluoropolymers, the fluoropolymer having a cyclic structure in the main chain has excellent solubility in a solvent, transparency (amorphous), etc. in addition to the above-mentioned performance. Used as a protective film.

One method for producing a fluorine-containing polymer having a cyclic structure and having substantially no hydrogen atom is cyclopolymerization of a fluorine-containing diene. The fluorinated polymer produced by cyclic polymerization, for _{example, CF 2 = CFO- (CF 2} ) n CF = CF 2 (n = 1,2) ( Patent Document _{1), CF 2 = CF- (} CF 2 _{) m -CF = CF 2 (m} = 1~5) ( non-Patent Document _{1), CF 2 = CF-} CF 2 CFClCF 2 -CF = CF 2 ( non-patent Document _{1), CF 2 = CFO-} CF 2 CF ₂ -OCF = CF ₂ (Patent Document _{2), CF 2 = CFO-} CF 2 -OCF = CF 2 ( Patent Document 3) have been reported. However, since these synthesis | combination is very difficult, it was difficult to synthesize | combine cheaply. In addition, cyclopolymerization has a problem of requiring a high pressure as high as 1000 MPa and dilution conditions.

  As an example of fluorination of a polymer, an example of fluorination of a polymer having a perfluoroalkyl group has been reported (see Patent Document 4). However, since the polymer that can be synthesized by this method is limited to a structure having an ester group in the polymer side chain, a fluorine-containing polymer having a cyclic structure in the main chain cannot be synthesized.

JP-A-1-131214 British Patent No. 1,106,344 US Pat. No. 5,589,557 International Publication No. WO2002 / 079,274 Pamphlet Journal of Polymer Science, Polymer Physics Edition. 1969, 7 (4), 601-608.

  Accordingly, an object of the present invention is to provide an inexpensive and efficient method for producing a fluorine-containing polymer having substantially no hydrogen atom, which has been difficult to produce. Moreover, it aims at providing the manufacturing method of the polymer which consists of a repeating unit which has a cyclic structure.

  As a result of various studies to solve the above problems, the present inventor has found that the present invention can be achieved by the following means.

(1) A polymer having at least one of structural units represented by general formulas (II-A) to (II-D) is produced by polymerizing a compound represented by general formula (I), and then A method for producing a fluorine-containing polymer having at least one of the structural units represented by any one of the general formulas (III-A) to (III-D), characterized by performing a fluorination treatment.

In general formula (I), X ₁ , X ₂ , X ₃ , X ₄ , X ₅ and X ₆ represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group or an alkoxy group. Y is an alkylene group or a cycloalkylene group which may have an oxygen atom in the main chain.

In general formulas (II-A) to (II-D), X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and Y are X ₁ , X ₂ , X _{3 in} general formula (I). , X ₄ , X ₅ , X ₆ and Y are synonymous.

In general formulas (III-A) to (III-D), X _1F , X _2F , X _3F , X _4F , X _5F and X _6F are halogen atoms, fluorine-containing alkyl groups substantially free of hydrogen, fluorine-containing Represents a cycloalkyl group and a fluorine-containing alkoxy group. However, when X _n (n = 1 to 6) is not changed before and after the fluorination treatment, X _nF is synonymous with X _n in the general formula (I). Y _F is a fluorine-containing alkylene group or cycloalkylene group which has substantially no hydrogen atom and may have an oxygen atom in the main chain. However, when Y does not change before and after the fluorination treatment, Y _F has the same meaning as Y in general formula (I).
(2) A method for producing a fluorine-containing polymer having a structural unit represented by the general formula (III) according to (1), wherein the fluorine source for the fluorination treatment is fluorine gas.
(3) The polymerization reaction is a homopolymerization (refers to a polymerization that produces a polymer having a constitutional unit composed only of any one of the general formulas (II-A) to (II-D)). A fluoropolymer having at least one of the structural units represented by any one of the general formulas (III-A) to (III-D) according to any one of (1) and (2) Production method.
(4) X ₁ , X ₂ , X ₃ , X ₄ , X ₅ and X ₆ are hydrogen atoms or fluorine atoms, at least one contains a hydrogen atom, and X _1F , X _2F , X _3F , X _4F , _X5F and _X6F are fluorine atoms, The structure represented by the general formulas (III-A) to (III-D) according to any one of (1) to (3) A method for producing a fluoropolymer having at least one of units.
(5) Y is represented by any one of general formulas (IV-A), (IV-B), or (IV-C), and Y _F is represented by general formulas (VA), ( (V-B) or (V-C) is represented by any one of the general formulas (III-A) to (III-) according to any one of (1) to (4), A method for producing a fluoropolymer having at least one of the structural units represented by D).

In general formulas (IV-A), (IV-B), and (IV-C), A, B, and C each independently represent one selected from —CR ₁ R ₂ — or —O—. R ₁ and R ₂ each independently represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an alkynyl group.

In the general formulas (V-A), (V-B) and (V-C), A _F , B _F and C _F are each independently one selected from -CR _1F R _2F -or -O-. To express. R _1F and R _2F each independently have a halogen atom, a fluorine-containing alkyl group having substantially no hydrogen atom, a fluorine-containing cycloalkyl group having substantially no hydrogen atom, or substantially a hydrogen atom. Represents no fluorine-containing alkoxy group. However, when A, B and C do not change before and after the fluorination treatment, A _F , B _F and C _F are synonymous with R ₁ and R _{2 in the} general formulas (IV-A) and (IV-B). is there.

  The production method of the present invention makes it possible to produce a fluoropolymer having a cyclic structure in the structural unit at a low cost and efficiently. According to the present invention, a fluoropolymer having a cyclic structure (in which the carbon atoms constituting the cyclic structure are incorporated in the main chain of the polymer) can be produced without complicated processes.

  Hereinafter, the present invention will be described in more detail.

The compound represented by the general formula (I) of the present invention is described in detail below.
In general formula (I), X ₁ , X ₂ , X ₃ , X ₄ , X ₅ and X ₆ represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group or an alkoxy group. The halogen atoms in X ₁ , X ₂ , X ₃ , X ₄ , X ₅ and X ₆ are a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The alkyl group in X ₁ , X ₂ , X ₃ , X ₄ , X ₅ and X ₆ is a linear or branched alkyl group, and even if it is an unsubstituted alkyl group, it is an alkyl group having a substituent. May be. The alkyl group is preferably an alkyl group having 1 to 30 carbon atoms excluding the carbon atoms of the substituent, more preferably an alkyl group having 1 to 20 carbon atoms, and particularly preferably an alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, t-butyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl and the like.

  Examples of the substituent of the alkyl group having a substituent include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, and a carboxyl group. Group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, amino group (including alkylamino group and anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, Aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfino group, sulfo group, alkyl or arylsulfi Group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group And a silyl group.

The said substituent of the alkyl group which has a substituent is demonstrated still in detail below.
Halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group (straight chain or branched substituted or unsubstituted alkyl group, preferably 1-30 carbon atoms, more preferably carbon atoms 1-10 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), cycloalkyl groups (preferably carbon atoms) Examples thereof include substituted or unsubstituted cycloalkyl groups having 3 to 30 carbon atoms, more preferably 3 to 10 carbon atoms, such as cyclohexyl and cyclopentyl, and polycycloalkyl groups such as bicycloalkyl groups (preferably having a carbon atom number). 5-30, more preferably substituted or unsubstituted bicycloalkyl having 5 to 15 carbon atoms Examples thereof include groups having a polycyclic structure such as bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl) and tricycloalkyl groups. A monocyclic cycloalkyl group and a bicycloalkyl group, and a monocyclic cycloalkyl group is particularly preferred.), And the cycloalkyl group is preferably a 3- to 10-membered ring.

  Alkenyl groups (straight-chain or branched substituted or unsubstituted alkenyl groups, preferably alkenyl groups having 2 to 30 carbon atoms, more preferably 2 to 10 carbon atoms, such as vinyl, allyl, prenyl, geranyl , Oleyl), a cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, more preferably 3 to 10 carbon atoms, such as 2-cyclopenten-1-yl, 2- Cyclohexen-1-yl), and a polycycloalkenyl group such as a bicycloalkenyl group (preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, more preferably 5 to 15 carbon atoms). For example, bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2,2] oct-2 En-4-yl)], or tri cycloalkenyl group, a bicycloalkenyl group, cycloalkenyl group of one ring is particularly preferred. ) An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, more preferably 2 to 15 carbon atoms, such as ethynyl, propargyl, trimethylsilylethynyl group),

  An aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, more preferably 6 to 12 carbon atoms, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylamino; Phenyl), a heterocyclic group (preferably a 5- or 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed heterocyclic group, more preferably a ring-constituting atom. Is a heterocyclic group selected from a carbon atom, a nitrogen atom and a sulfur atom, and having at least one heteroatom of any one of a nitrogen atom, an oxygen atom and a sulfur atom, more preferably 3 to 30 carbon atoms, Preferred is a 5- or 6-membered aromatic heterocyclic group having 5 to 12 carbon atoms, for example, 2-furyl, 2-thienyl, 2-pyridy. , 4-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl), a cyano group, a hydroxyl group, a nitro group, a carboxyl group,

  An alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, more preferably 1 to 10 carbon atoms, such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy) and aryloxy groups (preferably substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, more preferably 6 to 12 carbon atoms, such as phenoxy, 2-methylphenoxy, 2 , 4-di-t-amylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), a silyloxy group (preferably 3 to 20 carbon atoms, more preferably carbon atoms) 3 to 10 silyloxy groups such as trimethylsilyloxy, t-butyldimethylsilyloxy ), A heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, more preferably 5 to 12 carbon atoms, and the heterocyclic portion is explained by the aforementioned heterocyclic group. Heterocycles are preferred, such as 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy),

  An acyloxy group (preferably formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, more preferably 2 to 10 carbon atoms, 6 to 30 carbon atoms, more preferably 6 carbon atoms). To 12 substituted or unsubstituted arylcarbonyloxy groups such as formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), carbamoyloxy groups (preferably having 1 carbon atom) To 30 and more preferably a substituted or unsubstituted carbamoyloxy group having 1 to 10 carbon atoms, such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di -N-octylaminocarbo Ruoxy, Nn-octylcarbamoyloxy), an alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, more preferably 2 to 10 carbon atoms, such as methoxycarbonyloxy , Ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), aryloxycarbonyloxy group (preferably substituted or unsubstituted aryl having 7 to 30 carbon atoms, more preferably 7 to 15 carbon atoms) An oxycarbonyloxy group, for example, phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy),

  An amino group (preferably an amino group, 1 to 30 carbon atoms, more preferably a substituted or unsubstituted alkylamino group having 1 to 10 carbon atoms, 6 to 30 carbon atoms, more preferably 6 to 6 carbon atoms); 12 substituted or unsubstituted arylamino groups and heterocyclic amino groups having 0 to 30 carbon atoms, such as amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, N-1, 3,5-triazin-2-ylamino), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, more preferably 1 to 10 carbon atoms, carbon atom A substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, more preferably 6 to 12 carbon atoms. Myramino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino group (preferably having 1 to 30 carbon atoms, more preferably carbon atoms) A substituted or unsubstituted aminocarbonylamino group of 1 to 10, for example, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), alkoxycarbonylamino group (preferably carbon A substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 atoms, more preferably 2 to 10 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octa Decyloxycarbonylamino, N-methyl-methoxycarbonylamino),

  An aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, more preferably 7 to 10 carbon atoms, such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino; M-n-octyloxyphenoxycarbonylamino), a sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, more preferably 0 to 10 carbon atoms, For example, sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 1 carbon atoms). 10 substituted or unsubstituted alkyl sulfos A ruamino group, a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, more preferably 6 to 10 carbon atoms, such as methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3, 5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto group,

  An alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, more preferably 1 to 10 carbon atoms, such as methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably having a carbon atom number) A substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, more preferably 6 to 12 carbon atoms, such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably having 2 carbon atoms) -30 substituted or unsubstituted heterocyclic thio groups, and the heterocyclic portion is preferably the heterocyclic portion described above for the heterocyclic group, such as 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio ), Sulfamoyl groups (preferably substituted or unsubstituted sulfamoys having 0 to 30 carbon atoms) Groups such as N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N '-Phenylcarbamoyl) sulfamoyl), sulfino group, sulfo group,

  Alkyl and arylsulfino groups (preferably a substituted or unsubstituted alkylsulfino group having 1 to 30 carbon atoms, more preferably 1 to 10 carbon atoms, 6 to 30 carbon atoms, more preferably 6 to 10 carbon atoms). Substituted or unsubstituted arylsulfino groups such as methylsulfino, ethylsulfino, phenylsulfino, p-methylphenylsulfino), alkyl and arylsulfonyl groups (preferably having 1 to 30 carbon atoms) More preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 10 carbon atoms, 6 to 30, more preferably a substituted or unsubstituted arylsulfonyl group having 6 to 10 carbon atoms, such as methylsulfonyl, Ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), acyl groups (preferably Or a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, more preferably 2 to 10 carbon atoms, a substituted or unsubstituted carbon carbonyl group having 7 to 30 carbon atoms, more preferably 7 to 13 carbon atoms. An unsubstituted arylcarbonyl group, for example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl), an aryloxycarbonyl group (preferably having 7 to 30 carbon atoms, Preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 13 carbon atoms, such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl),

  An alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, more preferably 2 to 10 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxy; Carbonyl), a carbamoyl group (preferably a substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, more preferably 1 to 10 carbon atoms, such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N , N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), aryl and heterocyclic azo groups (preferably 6-30 carbon atoms, more preferably 6-12 carbon atoms substituted or unsubstituted) Arylazo group, 3-30 carbon atoms, more preferred Or a substituted or unsubstituted heterocyclic azo group having 3 to 10 carbon atoms (the heterocyclic portion is preferably the heterocyclic portion described in the above heterocyclic group), such as phenylazo, p-chlorophenylazo, 5- Ethylthio-1,3,4-thiadiazol-2-ylazo), an imide group (preferably a substituted or unsubstituted imide group having 2 to 30 carbon atoms, more preferably 2 to 10 carbon atoms, such as N- Succinimide, N-phthalimide), phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, more preferably 2 to 15 carbon atoms, such as dimethylphosphino, diphenylphosphino, methylphenoxy Phosphino), phosphinyl groups (preferably having 2 to 30 carbon atoms, more preferably 2 to 10 carbon atoms). Or unsubstituted phosphinyl group, for example, phosphinyl, dioctyloxyphosphinyl phosphinyl, diethoxyphosphinyl),

  A phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, more preferably 2 to 10 carbon atoms, such as diphenoxyphosphinyloxy, dioctyloxyphos Finyloxy), a phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, more preferably 2 to 10 carbon atoms, such as dimethoxyphosphinylamino Dimethylaminophosphinylamino), a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, more preferably 3 to 10 carbon atoms, such as trimethylsilyl, t-butyldimethylsilyl , Phenyldimethylsilyl).

  Among the above functional groups, those having a hydrogen atom may be substituted with the above groups by removing this. Examples of such functional groups include alkylcarbonylaminosulfonyl group, arylcarbonylaminosulfonyl group, alkylsulfonylaminocarbonyl group, arylsulfonylaminocarbonyl group, specifically methylsulfonylaminocarbonyl, p-methyl. Examples include phenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl groups.

The cycloalkyl group in X ₁ , X ₂ , X ₃ , X ₄ , X ₅ and X ₆ includes a cycloalkyl group having a substituent and an unsubstituted cycloalkyl group. The cycloalkyl group preferably has 3 to 30 carbon atoms, more preferably 3 to 10 carbon atoms, excluding the carbon atoms of the substituent. Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like. Examples of the substituent that these cycloalkyl groups may have include those listed as examples of the substituent of the alkyl group.

The alkoxy group in X ₁ , X ₂ , X ₃ , X ₄ , X ₅ and X ₆ includes an alkoxy group having a substituent and an unsubstituted alkoxy group. The cycloalkyl group is preferably an alkoxy group having 1 to 30 carbon atoms, particularly 1 to 10 carbon atoms, excluding the carbon atoms of the substituent. Examples of the alkoxy group include methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy and the like. Examples of the substituent that these alkoxy groups may have include those listed as examples of the substituent of the alkoxy group.

X ₁ , X ₂ , X ₃ , X ₄ , X ₅ and X ₆ are preferably a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and Although selected from alkoxy groups having 1 to 5 carbon atoms, at least one is preferably a hydrogen atom from the viewpoint of polymerizability, preferably a hydrogen atom and a fluorine atom, and at least one is a hydrogen atom. Particularly preferred. Of X ₁ , X ₂ , X ₃ , X ₄ , X ₅ and X ₆ , 1 to 4 are preferably hydrogen atoms, and 1 to 2 are more preferably hydrogen atoms. X ₃ and / or X ₄ are preferably hydrogen atoms. Of X ₁ , X ₂ , X ₃ , X ₄ , X ₅ and X ₆ , 2 to 6 are preferably fluorine atoms, and 3 to 5 are more preferably fluorine atoms. Moreover, it is preferable that some or all of X ₁ , X ₂ , X ₅ , and X ₆ are fluorine atoms.

  Y is an alkylene group or a cycloalkylene group which may have an oxygen atom in the main chain, and an alkylene group and a cyclohexane which may have an oxygen atom in the main chain having 1 to 10 carbon atoms, particularly 1 to 10 carbon atoms. An alkylene group is preferred, and in particular, Y is preferably a structure represented by the general formulas (IV-A) to (IV-C).

In the general formulas (IV-A) to (IV-C), A, B and C each independently represent one selected from —C (R ₁ ) R ₂ — or —O—. R ₁ and R ₂ each independently represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group or an alkoxy group.

The halogen atom in R ₁ and R ₂ is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. The alkyl group in R ₁ and R ₂ includes an alkyl group having a substituent and an unsubstituted alkyl group. The alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, particularly 1 to 10 carbon atoms, excluding the carbon atoms of the substituent. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, t-butyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl and the like. Examples of the substituent that these alkyl groups may have include those listed as examples of the substituent of the alkyl group.

The cycloalkyl group in R ₁ and R ₂ includes a cycloalkyl group having a substituent and an unsubstituted cycloalkyl group. The cycloalkyl group is preferably a cycloalkyl group having 3 to 30 carbon atoms, particularly 1 to 10 carbon atoms, excluding the carbon atoms of the substituent. Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like. Examples of the substituent that these cycloalkyl groups may have include those listed as examples of the substituent of the alkyl group.

The alkenyl group in R ₁ and R ₂ includes an alkenyl group having a substituent and an unsubstituted alkenyl group. The alkenyl group is preferably an alkenyl group having 2 to 30 carbon atoms, particularly 2 to 10 carbon atoms, excluding the carbon atoms of the substituent. Examples of alkenyl groups include vinyl, allyl, prenyl, geranyl, oleyl and the like. Examples of the substituent that these alkenyl groups may have include those listed as examples of the substituent of the alkyl group.

The alkynyl group in R ₁ and R ₂ includes an alkynyl group having a substituent and an unsubstituted alkynyl group. The alkynyl group is preferably an alkynyl group having 2 to 30 carbon atoms, particularly 2 to 10 carbon atoms, excluding the carbon atoms of the substituent. Examples of alkynyl groups include ethynyl, propargyl, trimethylsilylethynyl groups and the like. Examples of the substituent that these alkynyl groups may have include those listed as examples of the substituent of the alkynyl group.

The alkoxy group in R ₁ and R ₂ includes an alkoxy group having a substituent and an unsubstituted alkoxy group. The alkoxy group is preferably an alkoxy group having 1 to 30 carbon atoms, particularly 1 to 10 carbon atoms, excluding the carbon atoms of the substituent. Examples of the alkoxy group include methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy and the like. Examples of the substituent that these alkoxy groups may have include those listed as examples of the substituent of the alkyl group.

As R ₁ and R ₂ , a hydrogen atom, a fluorine atom, a chlorine atom, a fluorine-containing alkyl group, a fluorine-containing cycloalkyl group and a fluorine-containing alkoxy group are preferable. Most preferred are fluorine-containing alkyl groups containing no hydrogen atoms, fluorine-containing cycloalkyl groups having substantially 4 to 10 carbon atoms, and fluorine-containing alkoxy groups having substantially 1 to 5 carbon atoms. preferable.
In the present invention, the term “substantially does not contain (or does not contain) a hydrogen atom” for all groups means that the hydrogen atom of the group is below the measurement limit by ¹ H NMR measurement.

The structural units represented by the general formulas (II-A) to (II-D) of the present invention will be described in detail. General formula (II-A)-(II-D) are the structural units which the polymer formed by superposing | polymerizing general formula (I) has. This polymer has at least one structural unit selected from general formulas (II-A) to (II-D). It is difficult to determine which structure the polymer has depending on the length of the monomer represented by the general formula (I), the substituent, and the polymerization conditions, but it is difficult to determine uniquely (II-A), (II -B) and (II-C) are preferred. In general formulas (II-A) to (II-D), X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and Y are X ₁ , X ₂ , X _{3 in} general formula (I). , X ₄ , X ₅ , X ₆ and Y are synonymous.

The structures represented by the general formulas (III-A) to (III-D) will be described in detail. General formulas (III-A) to (III-D) are structural units possessed by a polymer formed by fluorinating a polymer having at least one structure selected from (II-A) to (II-D). When a polymer having a structural unit of the general formula (II-m) (m = A, B, C and D) is fluorinated, a polymer having a structural unit of the general formula (III-m) is obtained. In the general formulas (III-A) to (III-D), X _1F , X _2F , X _3F , X _4F , X _5F and X _6F are each a halogen atom, a fluorine-containing alkyl group substantially free of a hydrogen atom, A fluorine-containing cycloalkyl group having no hydrogen atom and a fluorine-containing alkoxy group having substantially no hydrogen atom. However, when X _n (n = 1 to 6) is not changed before and after the fluorination treatment, X _nF is synonymous with X _n in the general formula (I).

Examples of the halogen atom in X _1F , X _2F , X _3F , X _4F , X _5F and X _6F include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The fluorine-containing alkyl group substantially free of a hydrogen atom in X _1F , X _2F , X _3F , X _4F , X _5F and X _6F includes a fluorine-containing alkyl group having a substituent and an unsubstituted fluorine-containing alkyl group. included. As the fluorine-containing alkyl group substantially not containing a hydrogen atom, a fluorine-containing alkyl group having 1 to 30 carbon atoms excluding the carbon atoms of the substituent is preferable. Examples of the fluorine-containing alkyl group having substantially no hydrogen atom include trifluoromethyl, pentafluoroethyl, perfluoro-n-propyl, perfluoroisopropyl, perfluoro-t-butyl, perfluoro-sec-butyl, perfluoro-n. -Pentyl, perfluoro-n-hexyl, perfluoro-n-heptyl, perfluoro-n-octyl and the like. Examples of the substituent that the fluorine-containing alkyl group substantially not containing a hydrogen atom may have include those mentioned as examples of the substituent of the alkyl group.

X _1F , X _2F , X _3F , X _4F , X _5F and X _6F include a fluorinated cycloalkyl group having substantially no hydrogen atom, a fluorinated cycloalkyl group having a substituent and an unsubstituted fluorinated cyclohexane. An alkyl group is included. The fluorine-containing cycloalkyl group substantially free of hydrogen atoms is preferably a fluorine-containing cycloalkyl group having 3 to 30 carbon atoms excluding the carbon atoms of the substituent. Examples of the fluorine-containing cycloalkyl group substantially not containing a hydrogen atom include perfluorocyclopentyl, perfluorocyclohexyl, perfluorocycloheptyl, perfluorocyclooctyl and the like. Examples of the substituent that the fluorine-containing cycloalkyl group substantially not containing a hydrogen atom may have include those listed as examples of the substituent of the alkyl group.

The fluorine-containing alkoxy group which does not substantially contain a hydrogen atom in X _1F , X _2F , X _3F , X _4F , X _5F and X _6F includes a fluorine-containing alkoxy group having a substituent and an unsubstituted fluorine-containing alkoxy group. included. The fluorine-containing alkoxy group substantially free of hydrogen atoms is preferably a fluorine-containing alkoxy group having 1 to 30 carbon atoms excluding the carbon atoms of the substituent. Examples of the alkoxy group include trifluoromethoxy, pentafluoroethoxy, perfluoroisopropoxy, perfluoro-t-butoxy, perfluoro-n-octyloxy, perfluoro-2-methoxyethoxy and the like. Examples of the substituent that the alkoxy group substantially not containing a hydrogen atom may have include those listed as examples of the substituent of the alkyl group.
X _1F , X _2F , X _3F , X _4F , X _5F and X _6F are preferably a fluorine atom, a fluorine-containing alkyl group and a fluorine-containing alkoxy group, and particularly preferably a fluorine atom.

Y _F is a fluorine-containing alkylene group or cycloalkylene group which has substantially no hydrogen atom and may have an oxygen atom in the main chain. Among these, a fluorine-containing alkylene group or a cycloalkylene group which does not substantially contain a hydrogen atom and does not have a hydrogen atom having 1 to 10 carbon atoms and may have an oxygen atom in the main chain. preferably, in particular, _{Y F} is preferably a structure represented by formula (V-a) ~ (V -C).

In the general formula (V-A) ~ (V -C), A F, B F and _{C F} are each _{independently, -CR} 1F _{R 2F} - represents one selected from or -O-. R _1F and R _2F each independently represent a halogen atom, a fluorine-containing alkyl group that does not substantially contain a hydrogen atom, a fluorine-containing cycloalkyl group, and a fluorine-containing alkoxy group.

The halogen atoms in R _1F and R _2F are a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The alkyl group substantially free of a hydrogen atom in R _1F and R _2F includes a fluorine-containing alkyl group having a substituent and an unsubstituted fluorine-containing alkyl group. As said fluorine-containing alkyl group which does not contain a hydrogen atom substantially, a C1-C30 alkyl group except the carbon atom of a substituent is preferable. Examples of the fluorine-containing alkyl group substantially free of a hydrogen atom include trifluoromethyl, pentafluoroethyl, perfluoro-n-propyl, perfluoroisopropyl, perfluoro-tetra-butyl, perfluoro-sec-butyl, perfluoro-n- Pentyl, perfluoro-n-hexyl, perfluoro-n-heptyl, perfluoro-n-octyl and the like are included. Examples of the substituent that the fluorine-containing alkyl group substantially not containing a hydrogen atom may have include those mentioned as examples of the substituent of the alkyl group.

The fluorine-containing cycloalkyl group substantially free of a hydrogen atom in R _1F and R _2F includes a fluorine-containing cycloalkyl group having a substituent and an unsubstituted fluorine-containing cycloalkyl group. The fluorine-containing cycloalkyl group substantially free of hydrogen is preferably a fluorine-containing cycloalkyl group having 3 to 30 carbon atoms excluding the carbon atoms of the substituent. Examples of the fluorine-containing cycloalkyl group substantially not containing a hydrogen atom include perfluorocyclopentyl, perfluorocyclohexyl, perfluorocycloheptyl, perfluorocyclooctyl and the like. Examples of the substituent that the fluorine-containing cycloalkyl group substantially not containing a hydrogen atom may have include those listed as examples of the substituent of the alkyl group.

The fluorine-containing alkoxy group containing substantially no hydrogen atom in R _1F and R _2F includes a fluorine-containing alkoxy group having a substituent and an unsubstituted fluorine-containing alkoxy group. As the fluorine-containing alkoxy group which does not substantially contain a hydrogen atom and does not substantially contain a hydrogen atom, a fluorine-containing alkoxy group having 1 to 30 carbon atoms excluding the carbon atoms of the substituent is preferable. Examples of alkoxy groups include trifluoromethoxy, pentafluoroethoxy, perfluoroisopropoxy, perfluoro-tert-butoxy, perfluoro-n-octyloxy, perfluoro-2-methoxyethoxy and the like. Examples of the substituent that the alkoxy group substantially not containing a hydrogen atom may have include those listed as examples of the substituent of the alkyl group.

R _1F and R _2F include a fluorine atom, a chlorine atom, a fluorine-containing alkyl group having substantially 1 to 5 carbon atoms, and a fluorine-containing cyclohexane having substantially 4 to 10 carbon atoms. An alkyl group and a fluorine-containing alkoxy group having 1 to 5 carbon atoms and substantially no hydrogen atom are preferred, and a fluorine atom and a fluorine-containing alkyl group having 1 to 3 carbon atoms and substantially no hydrogen atom are most preferred.

Specific examples of the compound represented by the general formula (I) of the present invention are shown below, but the present invention is not limited thereby.

  Specific examples of the structural unit represented by the general formula (II-A) of the present invention are shown below, but the present invention is not limited thereto. Moreover, general formula (II-B)-general formula (II-D) which are structural isomers of general formula (II-A) mentioned here are also mentioned as an example.

Specific examples of the structure represented by the general formula (III-A) of the present invention are shown below, but the present invention is not limited thereto. Moreover, the general formula (III-B) to the general formula (III-D), which are structural isomers of the general formula (III-A) listed here, are also exemplified.

Next, a method for producing a polymer having at least one of the structural units represented by the general formulas (II-A) to (II-D) by polymerization of the general formula (I) in the present invention will be described in detail. The polymerization reaction in the present invention is not particularly limited, but it is particularly preferably performed by radical polymerization. The radical polymerization includes a method of irradiating with light and a method of using a polymerization initiator, and it is preferable to use a polymerization initiator. As the polymerization initiator, a general radical initiator for radical polymerization can be used. For example, an organic peroxide (for example, diisopropyl peroxydicarbonate, tert-butyl peroxide, lauroyl peroxide, benzoyl peroxide, ( _{C 3 F 7 COO-) 2,} (C 4 F 9 COO-) 2, (C 6 F 5 COO-) 2, (C 6 F 13 COO-) 2, ((CF 3) 3 CO-) 2 , etc. ), Inorganic peroxides (eg, K ₂ S ₂ O ₈ , Na ₂ S ₂ O ₈ , (NH ₄ ) ₂ S ₂ O ₈ ), azo compounds (eg, azobisisobutyronitrile, 2,2 ′ -Azobis (2-aminopropane) dihydrochloride, 4,4'-azobis (4-cyanopentanoic acid), 4,4'-azobis (4-cyanopentanoic acid-2-perfluorooctylethyl), etc.), metal- Peroxidation System (e.g., iron (II) ions - hydrogen peroxide) is preferred.

Examples of the polymerization method include bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and can be used without particular limitation. When a solvent is used for the polymerization reaction, examples of the solvent include water, sulfoxides (for example, dimethyl sulfoxide), ketones (for example, acetone, methyl ethyl ketone), esters (for example, ethyl acetate, butyl acetate, ethyl propionate, etc.) ), Ethers (eg, diethyl ether, dibutyl ether, tetrahydrofuran, etc.), aliphatic hydrocarbons (eg, pentane, hexane, etc.), aromatic hydrocarbons (eg, toluene, xylene, mesitylene, etc.), nitriles ( For example, acetonitrile, propiononitrile, etc.), amides (eg, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, etc.), carboxylic acids (eg, acetic acid, propionic acid, etc.), alcohols ( For example, methanol, ethanol, Propanol, n-butanol, 3-methylbutanol, etc.), fluorine-based solvents (for example, perfluoroalkanes (may be a mixture of structural isomers. For example, perfluoropentane, perfluorohexane, perfluoroheptane, perfluorooctane, etc.), perfluorocycloalkanes) (It may be a structural isomer. For example, perfluorocyclopentane, perfluorocyclohexane, perfluorocycloheptane, perfluorocyclooctane), perfluoroether (may be a structural isomer. For example, Fluorinert ^™ FC-75 (trade name) , manufactured by 3M), Krytox TM ^(trade name, manufactured by DuPont)), perfluoroalkyl amine (may be a structural isomer mixture. For example perfluorotributylamine The solvent used for the mentioned are. Polymerization reaction etc., may be used as a mixture of two or more may be used alone.

  Although there is no restriction | limiting in particular in the temperature in a polymerization reaction, It is preferable to superpose | polymerize at -30 degreeC-200 degreeC, and 0 to 150 degreeC is the most preferable. The pressure (internal pressure) in the polymerization reaction is not particularly limited, but is preferably from normal pressure to 5 MPa, and most preferably from normal pressure to 2 MPa. The polymerization reaction includes homopolymerization (polymerization of only one compound represented by general formula (I)) or copolymerization (polymerization in a system in which two or more types of monomers are present). When the compound represented by the general formula (I) is copolymerized, the other monomer includes other compounds represented by the general formula (I) and hydrocarbon monomers (for example, olefinic (for example, ethylene , Propylene, etc.), vinyl (eg, vinyl chloride, vinyl acetate, etc.), conjugated ester (eg, methyl acrylate, methyl methacrylate, etc.), cyclic olefin (eg, 2-norbornene, cyclopentene, etc.), conjugated diene Systems (butadiene, isobutene, etc.), acetylene systems (acetylene, dimethyl acetylenedicarboxylate, etc.), fluorine-containing monomers (eg, fluorine-containing olefin systems (eg, tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, etc.), Fluorine-containing alkyl vinyl ethers (for example, perfluoropropylene Vinyl ether), cyclic olefin (such as perfluoro (2,2-dimethyl-1,3-Jiokisonoru), etc.)) and the like. Of these, olefins, cyclic olefins, fluorine-containing olefins, and fluorine-containing cyclic olefins are particularly preferable. In the case of copolymerization, the other monomer may be used alone or in combination of two or more. The monomer composition ratio in the copolymerization can be adjusted by the molar ratio of the monomers used, reaction conditions, and the like. As the polymerization reaction, homopolymerization is preferable.

Next, general formulas (III-A) to (III-D) by fluorination treatment of a polymer having at least one of the structural units represented by general formulas (II-A) to (II-D) in the present invention. The method for producing a fluorine-containing polymer having at least one of the structural units represented by
The fluorinating agent can be used without particular limitation as long as it can react with a carbon-hydrogen bond and be converted into a carbon-fluorine bond. Examples of such a fluorinating agent include fluorine gas, XeF ₂ , CoF _{3 and the} like, and fluorine gas is particularly preferable from an economical viewpoint. The fluorination method is not particularly limited, but the following two methods are conceivable.
(Method 1) A method of adding a fluorinating agent to a system containing a polymer.
(Method 2) A method in which a polymer-containing system and a fluorinating agent are simultaneously added to a solvent and reacted.
Of these, method 2 is most preferable from the viewpoint of efficiency. The amount of the fluorinating agent used is preferably 1.0 to 5.0 molar equivalents and most preferably 1.0 to 2.0 molar equivalents relative to the reaction point of the polymer. The reaction temperature for fluorination is preferably -50 to 100 ° C, and most preferably -10 to 50 ° C.

  When the polymer is fluorinated, the polymer is reacted in a solid or molten state with a fluorinating agent, a solution in which a fluorinated polymer is dissolved is reacted with a fluorinating agent, and the fluorinated polymer is dispersed (that is, A method of reacting with a fluorinating agent (in a non-uniform state). Among these, from the viewpoint of reaction efficiency, a method of reacting a solution in which a fluorine-containing polymer is dissolved with a fluorinating agent is particularly preferable.

The solvent for dissolving the fluorine-containing polymer is preferably a solvent that does not destroy the ozone layer and does not substantially react with fluorine. Examples thereof include perfluoroalkanes (which may be structural isomer mixtures. Examples include perfluoropentane, perfluorohexane, perfluoroheptane, perfluorooctane), and perfluorocycloalkanes (which may be structural isomers. Examples include , Perfluorocyclopentane, perfluorocyclohexane, perfluorocycloheptane, perfluorocyclooctane), perfluoroether (may be a structural isomer. Examples include Fluorinert ^™ FC-75 (trade name, manufactured by 3M), Krytox ^™ ( (Trade name, manufactured by DuPont)), perfluoroalkylamine (a structural isomer mixture may be used. For example, perfluorotributylamine), perfluoro acid fluoride (a structural isomer mixture) Examples include perfluoro (2-methyl-3-oxahexanoyl) fluoride, perfluoro (2,5,8-trimethyl-3,6,9-trioxadodecanoyl fluoride), fluoride, etc. Examples thereof include hydrogen, water, trifluoroacetic acid, supercritical carbon dioxide, and acetonitrile. Among the solvents listed above, those in which some fluorine is replaced with hydrogen (for example, 6H-tridecafluorohexane, 2,2-bis (trifluoromethyl) propionyl fluoride, etc.), and some fluorine A solvent having a site that partially reacts with fluorine, such as those substituted with halogen (for example, perfluorooctyl iodide, perfluorohexyl bromide, etc.) can also be used. These solvents may be used alone or in combination of two or more. Of the solvents mentioned above, perfluoroalkanes, perfluorocycloalkanes, perfluoroethers, perfluoroalkylamines and perfluoroacid fluorides are most preferred. The amount of the solvent to be used is preferably 0.1 to 500 times the volume of the substrate to be injected, more preferably 1 to 300 times, and even more preferably 3 to 200 times.

  When the fluorination reaction is difficult to proceed, the fluorination reaction can be promoted by carrying out the reaction in the presence of a substrate that proceeds singly as soon as possible. A substrate on which a fluorination reaction proceeds promptly by itself refers to a compound having many sites that can easily react with fluorine. Examples thereof include a straight-chain, branched-chain or cyclic hydrocarbon compound having 5 to 30 carbon atoms which may contain a fluorine atom, an oxygen atom and an unsaturated bond (provided that one or more unsaturated bonds or Having one or more C—H bonds), specifically, pentane, hexane, hexene, cyclohexane, cyclohexene, diethyl ether, tetrahydrofuran, ethyl acetate, hexafluoroisopropyl methyl ether, 1,1, Examples include 2,3,3,3-hexafluoropropyl ethyl ether, benzene, toluene, fluorobenzene, trifluoromethylbenzene, 4-fluorotrimethylbenzene, and hexafluorobenzene. These compounds can be used without particular limitation as long as they can accelerate the reaction, whether they are soluble or insoluble in a solvent, but are preferably soluble in a solvent. A substrate in which a fluorination reaction proceeds promptly alone can be mixed with a solid or melted fluoropolymer, or added to a fluoropolymer solution.

  In the reaction of the present invention, fluorine gas may be used as it is without being diluted, but it is safer to use it mixed with an inert gas. As the inert gas, nitrogen gas or helium gas is preferable, and nitrogen gas is preferable from an economical viewpoint. As a density | concentration of the fluorine gas in an inert gas, Preferably it is 10-50 volume%, More preferably, it is 20-30 volume%.

If the fluorination has not completely progressed after completion of the reaction, the reaction can be terminated by adding the substrate on which the fluorination reaction proceeds alone alone to the reaction system simultaneously with the fluorinating agent. The amount of the substrate used for the rapid fluorination reaction by itself depends on the reactivity of the raw material polymer, so it cannot be determined unconditionally. It is preferable to use it so that the reaction point of the substrate on which the reaction proceeds is 0.010 to 1.0 molar equivalent, and most preferably to be 0.10 to 0.50 molar equivalent. The method of introducing a substrate in which a fluorination reaction proceeds promptly alone may be introduced by dissolving or dispersing in a solvent, or may be introduced neat.
The fluorine-containing polymer obtained by the production method of the present invention can be used as a material such as an optical fiber or an antireflection film.

  Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited thereto.

Synthesis Example 1 Synthesis of Compound A

  To a 10N sodium hydroxide solution (100 mL), 116 g (1.0 mol) of 2-chloro-2,2-difluoroethanol was added under ice cooling, and the mixture was stirred for 30 minutes. Thereafter, 46 mL (600 mmol) of thiophosgene was dissolved in 60 mL of methylene chloride, added dropwise under ice cooling, and stirred for 2 hours. Next, 100 mL of ethyl acetate was added, liquid separation operation was performed, and the organic layer was concentrated. Then, 102.9 g (374 mmol, yield 62%) of Compound A was obtained by distillation under reduced pressure.

The spectrum data of the obtained compound A are described below.
¹ H NMR (300 MHz, solvent CDCl ₃ ) δ 4.93 (t, J = 10.1 Hz, 2H)
¹⁹ F NMR (282 MHz, solvent CDCl ₃ ) δ-61.97 (t, J = 10.1 Hz, 2F)

Synthesis Example 2 Synthesis of Compound B

  Compound A (100.0 g, 363.5 mmol) was added to 200 mL of methylene chloride. Chlorine gas was blown into the solution at room temperature for 6 hours. Thereafter, the reaction solution was filtered using Celite (trade name, manufactured by Wako Pure Chemical Industries, Ltd.), 100 mL of water was added to carry out a liquid separation operation, and the organic layer was concentrated. Then, 97.0 g (309 mmol, yield 85%) of Compound B was obtained by distillation under reduced pressure.

The spectrum data of the obtained compound B are described below.
¹ H NMR (300 MHz, solvent CDCl ₃ ) δ 4.43 (t, J = 10.0 Hz, 2H)
¹⁹ F NMR (282 MHz, solvent CDCl ₃ ) δ-62.12 (t, J = 10.0 Hz, 2F)

Synthesis Example 3 Synthesis of Compound C Compound B (3.16 g, 10 mmol) was added dropwise at room temperature to a mixed solution of SbF ₃ (1.79 g, 10 mmol), acetonitrile 10 mL, and bromine (0.01 g, 0.063 mmol). did. After stirring for 3 hours, 20 mL of ethyl acetate and 20 mL of water were added, liquid separation operation was performed, and the organic layer was concentrated. Then, 2.19 g (7.81 mmol, 78% yield) of Compound C was obtained by distillation at atmospheric pressure.

The spectral data of Compound C obtained are shown below.
¹ H NMR (300 MHz, solvent CDCl ₃ ) δ 4.13 (t, J = 10.0 Hz, 2H)
¹⁹ F NMR (282 MHz, solvent CDCl ₃ ) δ-62.1 (t, J = 10.0 Hz, 2F)

(Synthesis Example 4) Synthesis of Compound (I-10) Compound C (10.0 g, 35.6 mmol) was added to potassium hydroxide (4.20 g, 75.0 mmol) and dimethyl sulfoxide 5.0 mL, and the external temperature was 100 ° C. Heated. After reacting for 1 hour, 4.12 g (19.7 mmol) of Compound (I-10) was obtained by atmospheric distillation.

The spectral data of the obtained compound (I-10) is shown below.
¹ H NMR (300 MHz, solvent CDCl ₃ ) δ 4.10 (m, 2H)
¹⁹ F NMR (282 MHz, solvent CDCl ₃ ) δ-65.57 (t, J = 2.1 Hz, 2F), −93.54 (m, 2F), −112.32 (m, 2F)

Example 1 Polymerization of Compound (I-10) 0.015 g (0.036 mmol) of perfluorobenzoyl peroxide was added to 4.00 g (19.2 mmol) of Compound (I-10). The mixture was cooled to -196 ° C, sucked with a vacuum pump, purged with nitrogen, and returned to room temperature. This operation was performed twice more. Then, it heated at 50 degreeC for 5 days. The obtained polymer was dissolved in hexafluorobenzene and precipitated in chloroform. As a result, 2.62 g of a polymer having at least one of structural units represented by structures (II-A-10) to (II-D-10) was obtained.

(Example 2) Polymer fluorination 2.00 g of the polymer obtained in Example 1 was dissolved in Fluorinert ^™ FC-75 (trade name, manufactured by 3M) to obtain a 30 mL solution. Next, fluorine gas diluted to 20% with nitrogen was introduced into Fluorinert ^™ FC-75 (175 mL) degassed with helium gas at 100 ml / min. Thereto, 30 mL of the polymer solution was added at 16.6 ml / h. After all the polymer solution was injected, the flow rate of fluorine gas was 50 ml / min. Thereto, 5.0 mL of a Fluorinert ^™ FC-75 solution of 0.12 g (0.64 mmol) of hexafluorobenzene was added at 5.0 mL / h. After completion of the reaction, 1.79 g of polymer was obtained by concentrating FC-75. This polymer had completely lost hydrogen atoms by ¹ H NMR. This polymer was amorphous and transparent and had a weight average molecular weight of 35,000.

Claims (5)

The compound represented by the general formula (I) is polymerized to produce a polymer having at least one of the structural units represented by the general formulas (II-A) to (II-D), and then fluorinated A process for producing a fluorine-containing polymer having at least one of the structural units represented by any one of the general formulas (III-A) to (III-D).

In general formula (I), X ₁ , X ₂ , X ₃ , X ₄ , X ₅ and X ₆ represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group or an alkoxy group. Y is an alkylene group or a cycloalkylene group which may have an oxygen atom in the main chain.

In general formulas (II-A) to (II-D), X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and Y are X ₁ , X ₂ , X _{3 in} general formula (I). , X ₄ , X ₅ , X ₆ and Y are synonymous.

In general formulas (III-A) to (III-D), X _1F , X _2F , X _3F , X _4F , X _5F and X _6F are halogen atoms, fluorine-containing alkyl groups substantially free of hydrogen, fluorine-containing Represents a cycloalkyl group and a fluorine-containing alkoxy group. However, when X _n (n = 1 to 6) is not changed before and after the fluorination treatment, X _nF is synonymous with X _n in the general formula (I). Y _F is a fluorine-containing alkylene group or cycloalkylene group which has substantially no hydrogen atom and may have an oxygen atom in the main chain. However, when Y does not change before and after the fluorination treatment, Y _F has the same meaning as Y in general formula (I).   The fluorine-containing polymer having at least one of the structural units represented by the general formulas (III-A) to (III-D) according to claim 1, wherein the fluorine source for the fluorination treatment is a fluorine gas. Manufacturing method.   The polymerization reaction is homopolymerization, and at least of the structural units represented by any one of the general formulas (III-A) to (III-D) according to any one of claims 1 to 2, A method for producing a fluorine-containing polymer having one. X ₁ , X ₂ , X ₃ , X ₄ , X ₅ and X ₆ are a hydrogen atom or a fluorine atom, at least one contains a hydrogen atom, and X _1F , X _2F , X _3F , X _4F , X _5F and _X6F are fluorine atoms, At least one of the structural units represented by the general formulas (III-A) to (III-D) according to any one of claims 1 to 3 For producing a fluorine-containing polymer having two. Y is represented by any one of general formulas (IV-A), (IV-B), or (IV-C), and Y _F is represented by general formulas (VA), (VB) ) Or (V-C), represented by the general formulas (III-A) to (III-D) according to any one of claims 1 to 4, A method for producing a fluorine-containing polymer having at least one of the structural units.

In general formulas (IV-A), (IV-B), and (IV-C), A, B, and C each independently represent one selected from —CR ₁ R ₂ — or —O—. R ₁ and R ₂ each independently represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an alkynyl group.

In the general formulas (V-A), (V-B) and (V-C), A _F , B _F and C _F are each independently one selected from -CR _1F R _2F -or -O-. To express. R _1F and R _2F each independently have a halogen atom, a fluorine-containing alkyl group having substantially no hydrogen atom, a fluorine-containing cycloalkyl group having substantially no hydrogen atom, or substantially a hydrogen atom. Represents no fluorine-containing alkoxy group. However, when A, B and C do not change before and after the fluorination treatment, A _F , B _F and C _F are synonymous with R ₁ and R _{2 in the} general formulas (IV-A) and (IV-B). is there.