JPWO2016129606A1 - Method for producing fluoropolymer - Google Patents

Abstract

The present invention relates to a fluorine-containing polymer using as a monomer a compound in which a fluorine atom is directly bonded to both carbons forming a carbon-carbon double bond, a diene compound in which a fluorine atom is bonded to carbon in an allylic position, or the like. An object of the present invention is to provide a method for producing the above. In the present invention, in the presence of a metal-carbene complex compound having olefin metathesis reaction activity, a fluorine-containing diene compound represented by at least one of the following formulas (44) to (47) is polymerized to give 74) to a method for producing a fluoropolymer represented by at least one of the formulas (77). [Chemical 1]

Description

  The present invention relates to a novel method for producing a polymer containing a fluorine atom (fluorinated polymer) using a diene (fluorinated diene) compound containing a fluorine atom as a monomer.

Hydrogenated cycloolefins containing fluorine atoms are known to have excellent chemical resistance, electrical properties, and light resistance in addition to transparency and low water absorption, and various improvements have been attempted. Yes. (Patent Documents 1 to 3)
Non-patent document 1 discloses a diene containing a fluorine atom as a compound that can be a monomer of the ring-opening polymer.

Japanese Unexamined Patent Publication No. 6-206985 Japanese Laid-Open Patent Publication No. 2005-248081 Japanese Unexamined Patent Publication No. 2010-132600

Fustero, S.M. et al. Chem. Rev. 2015, 115, 871-930.

In the diene containing a fluorine atom disclosed in Non-Patent Document 1, one fluorine atom is bonded to one vinyl-position carbon of two carbon-carbon double bonds, and the other vinyl-position carbon is a hydrogen atom. Is a compound to which is bound. In the case of the compound, it is considered that the reactivity of the carbon moiety to which the hydrogen atom is bonded becomes high and the metathesis polymerization reaction is likely to occur.
However, when a fluorine atom is bonded to carbon at both vinyl positions of two carbon-carbon double bonds, it has been considered that the reactivity is low and the metathesis polymerization reaction hardly occurs.
Therefore, in the present invention, among diene compounds, a compound in which a fluorine atom is directly bonded to both carbons forming a carbon-carbon double bond, or a carbon (allyl bonded to a carbon forming a carbon-carbon bond). It is an object of the present invention to provide a method for producing a fluorinated polymer using, as a monomer, a compound in which a fluorine atom is bonded to carbon at a position.

  As a result of earnest study, the present inventors have made an acyclic diene metathesis polymerization reaction from a specific fluorine-containing diene compound which is acyclic in the presence of a metal complex having a ruthenium, molybdenum or tungsten-carbon double bond (Acyclic Diene). A new production method for obtaining a fluoropolymer by Matthesis Polymerization (ADMEP or ADMET) has been found, and the present invention has been completed.

That is, the present invention relates to the following <1> to <8>.
<1> In the presence of the metal-carbene complex compound (10) having olefin metathesis reaction activity, at least one kind of compound selected from the group consisting of fluorine-containing diene compounds represented by the following formulas (44) to (47): A method for producing a fluorine-containing polymer represented by at least one of the following formulas (74) to (77) by polymerizing a fluorine diene compound.

However, the symbols in the above formulas represent the following meanings.
Z is a single bond, an alkylene group having 1 to 25 carbon atoms, or an alkylene group having 1 to 25 carbon atoms including a hetero atom, and 1 to 25 carbon atoms including the alkylene group having 1 to 25 carbon atoms and a hetero atom. The alkylene group may have at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, a carboxyl group and an ester group, and may have a cyclic structure.
R is an atom other than a fluorine atom or an organic group, and a plurality of R may be the same or different.
X ¹⁰ represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 5 carbon atoms, and a plurality of X ¹⁰ may be the same or different.
n is a positive integer representing the number of repeating units.
A ^{11 to} A ¹³ and Af ¹¹ are functional groups represented by the following.

In the above formula, X ¹⁰ , X ¹¹ and X ¹² are each independently a hydrogen atom, a fluorine atom or an alkyl group having 1 to 5 carbon atoms, and A ⁸ and A ⁹ are each independently the following groups (i ), Group (ii), group (iii), and group (iv). A ⁸ and A ⁹ may be bonded to each other to form a ring. R represents an atom other than a fluorine atom or an organic group, and a plurality of R may be the same or different.
Group (i): a hydrogen atom.
Group (ii): a halogen atom.
Group (iii): C1-C20 monovalent hydrocarbon group.
Group (iv): C1-C20 monovalent hydrocarbon group containing 1 or more atoms chosen from the group which consists of a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom.

<2> The production method according to <1>, wherein the metal in the metal-carbene complex compound (10) is ruthenium, molybdenum, or tungsten.
<3> The production method according to <1> or <2>, wherein the metal in the metal-carbene complex compound (10) is ruthenium.
<4> The metal in the metal-carbene complex compound (10) is molybdenum or tungsten, and the metal-carbene complex compound is a ligand [L], and an imide ligand and an oxygen atom are bidentate. The production method according to <1> or <2>, wherein the ligand has a coordinated ligand.
<5> The production method according to any one of <1> to <4>, wherein the fluorine-containing diene compound is a perfluorodiene compound.
<6> Fluorinated diene compound represented by the following formula (44-1), fluorinated diene compound represented by the following formula (44-2), and fluorinated diene compound represented by the following formula (45-1) And a fluorine-containing diene compound represented by the following formula (46-1), a fluorine-containing diene compound represented by the following formula (47-1), and a fluorine-containing diene compound represented by the following formula (47-2). By polymerizing at least one fluorine-containing diene compound selected from the group, the following formula (74-1), the following formula (74-2), the following formula (75-1), the following formula (76-1), In any one of the above items <1> to <4>, wherein a fluoropolymer represented by at least one formula selected from the group consisting of the following formula (77-1) and the following formula (77-2) is produced. The manufacturing method as described.

In the above formula, Z is a single bond, an alkylene group having 1 to 25 carbon atoms, or an alkylene group having 1 to 25 carbon atoms containing a hetero atom, and the carbon containing an alkylene group having 1 to 25 carbon atoms and a hetero atom. The alkylene group of Formula 1 to 25 may further have at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, a carboxyl group, and an ester group. n is a positive integer representing the number of repeating units.
<7> The production method according to any one of <1> to <6>, wherein the polymerization temperature is 0 to 150 ° C.
<8> The production method according to any one of <1> to <7>, wherein no solvent is used.

  According to the method for producing a fluoropolymer according to the present invention, a fluoropolymer can be easily produced by using an acyclic fluorinated diene compound as a monomer by an acyclic diene metathesis polymerization reaction.

Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following embodiments, and can be arbitrarily modified without departing from the gist of the present invention. Further, the present invention relates to the production of a fluorinated polymer by acyclic diene metathesis polymerization reaction of a fluorinated diene compound with a metal catalyst, and description of general features common to the prior art may be omitted.
In the present specification, the “compound represented by the formula (X)” may be simply referred to as “compound (X)”.
In the present specification, the monosubstituted olefin means an olefin in which one hydrogen atom and one organic group are bonded to one carbon atom of a double bond. The 1,2-disubstituted olefin means an olefin in which the same or different organic groups are bonded to each carbon atom of a double bond.
The perhalogenated alkyl group means a group in which all hydrogen atoms of the alkyl group are substituted with halogen atoms. The perhalogenated alkoxy group means a group in which all hydrogen atoms of the alkoxy group are substituted with halogen atoms. The same applies to perhalogenated aryl groups and perhalogenated aryloxy groups.
The term “(per) halogenated alkyl group” is used as a general term that includes a halogenated alkyl group and a perhalogenated alkyl group. That is, the group is an alkyl group having one or more halogen atoms. The same applies to (per) halogenated alkoxy groups, (per) halogenated aryl groups, and (per) halogenated aryloxy groups.
An aryl group means a monovalent group corresponding to a residue obtained by removing one hydrogen atom bonded to any one of carbon atoms forming an aromatic ring in an aromatic compound, and a carbocyclic compound The aryl group derived from is combined with the heteroaryl group derived from a heterocyclic compound.
The number of carbon atoms of the hydrocarbon group means the total number of carbon atoms contained in the whole hydrocarbon group, and when the group has no substituent, the number of carbon atoms forming the hydrocarbon group skeleton is When the group has a substituent, the total number is obtained by adding the number of carbon atoms in the substituent to the number of carbon atoms forming the hydrocarbon group skeleton.
The heteroatom means an atom other than a carbon atom and a hydrogen atom, preferably one or more atoms selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, and a halogen atom. More preferably an oxygen atom or a nitrogen atom.

<Acyclic diene metathesis polymerization reaction>
The present invention relates to a method for producing an acyclic fluorine-containing polymer using a fluorine-containing diene compound as a monomer, and a diene compound containing a fluorine atom (fluorine-containing diene compound) is acyclic in the presence of a metal-carbene complex catalyst. By the diene metathesis polymerization reaction, a fluoropolymer can be obtained, and at the same time, ethylene or an ethylene derivative is also produced.
For example, when a fluorine-containing diene compound represented by the following formula (44) ′ is used as a raw material, a fluorine-containing polymer represented by the following formula (74) ′ and ethylene or an ethylene derivative are produced.

In the present invention, compound (11), compound (12A), compound (12B), compound (13A), compound (13B), compound (13C), compound (14A), compound (15A), compound (15B), The reaction is performed in the presence of at least one metal-carbene complex compound selected from the group consisting of compound (15C) and compound (15D).
As the metal-carbene complex compound, the compound (11) is preferable at the start of the reaction from the viewpoint of availability and reaction efficiency.

<Metal-carbene complex compound (10) having olefin metathesis reaction activity>
The metal-carbene complex compound (10) having olefin metathesis reaction activity plays a role as a catalyst in the production method according to the present invention, but both the one added as a reagent and the one generated during the reaction (catalytically active species) are used. means. Here, the compound (10) is known to show catalytic activity when some of the ligands dissociate under the reaction conditions, and to show catalytic activity without dissociation of the ligands. However, any of them is not limited in the present invention. In general, metathesis polymerization proceeds while repeating coordination and dissociation of the olefin to the catalyst, and therefore it is not always clear how many ligands other than the olefin are coordinated on the catalyst during the reaction. Therefore, in this specification, [L] does not specify the number or type of ligands. The metal in the metal-carbene complex compound (10) is preferably ruthenium, molybdenum, or tungsten.
Examples of the metal-carbene complex compound (10) include a ruthenium-carbene complex, a molybdenum-carbene complex, or a tungsten-carbene complex (hereinafter also collectively referred to as “metal-carbene complex”). A typical example thereof will be described in detail using a compound represented by the following formula (11). In addition to the compound (11), the compound (12A), the compound (12B), the compound (13A), and the compound (13B) described later are used. Compound (13C), Compound (14A), Compound (15A), Compound (15B), Compound (15C), or Compound (15D) may be used, and when any complex compound is used, compound (11 It is considered that the metathesis polymerization reaction proceeds by the same reaction mechanism as when) is used.

In the present specification, symbols in the formula represent the following meanings.
[L] is a ligand.
M is ruthenium, molybdenum or tungsten.
Z is a single bond, an alkylene group having 1 to 25 carbon atoms, or an alkylene group having 1 to 25 carbon atoms including a hetero atom, and 1 to 25 carbon atoms including the alkylene group having 1 to 25 carbon atoms and a hetero atom. The alkylene group may have at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, a carboxyl group and an ester group, and may have a cyclic structure.
R is an atom other than a fluorine atom or an organic group, and a plurality of R may be the same or different.
X ¹⁰ , X ¹¹ and X ¹² are each independently a hydrogen atom, a fluorine atom or an alkyl group having 1 to 5 carbon atoms, and a plurality of X ¹⁰ may be the same or different.
A ¹ , A ² , A ⁸ and A ⁹ are each independently a group selected from the group consisting of the following group (i), group (ii), group (iii) and group (iv). A ¹ and A ² may be bonded to each other to form a ring. A ⁸ and A ⁹ may be bonded to each other to form a ring. However, when ^one of A ¹ and A ² is a halogen atom, the other is a group selected from the group consisting of group (i), group (iii), and group (iv).
Group (i): a hydrogen atom.
Group (ii): a halogen atom.
Group (iii): C1-C20 monovalent hydrocarbon group.
Group (iv): C1-C20 monovalent hydrocarbon group containing 1 or more atoms chosen from the group which consists of a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom.

Hereinafter, the specific compound (11) will be described.
A ¹ and A ² in the compound (11) are respectively the same as defined above. That is, A ¹ and A ² in the compound (11) are each independently a hydrogen atom, a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or an oxygen atom, a nitrogen atom, a sulfur atom, or a phosphorus atom. And a monovalent hydrocarbon group having 1 to 20 carbon atoms containing at least one atom selected from the group consisting of silicon atoms. A ¹ and A ² may be bonded to each other to form a ring. However, the compound (11) is excluded when both A ¹ and A ² are halogen atoms.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom and a chlorine atom are preferable from the viewpoint of availability.
The monovalent hydrocarbon group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 5 to 20 carbon atoms, and may be linear or branched. In addition, a ring may be formed as a divalent hydrocarbon group.
The monovalent hydrocarbon group having 1 to 20 carbon atoms containing at least one atom selected from the group consisting of a halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, and silicon atom preferably includes the atom. Examples thereof include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 5 to 20 carbon atoms containing the atom, and an aryloxy group having 5 to 20 carbon atoms. The monovalent hydrocarbon group may be linear or branched. In addition, a ring may be formed as a divalent hydrocarbon group. In these preferred groups, halogen atoms may be bonded to at least some of the carbon atoms. That is, for example, it may be a (per) fluoroalkyl group or a (per) fluoroalkoxy group. Moreover, these preferable groups may have an etheric oxygen atom between carbon atoms. Further, these preferable groups may further have a substituent containing one or more atoms selected from the group consisting of a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom. Examples of the substituent include hydroxyl group, amino group, imino group, nitrile group, amide group (carbonylamino group), carbamate group (oxycarbonylamino group), nitro group, carboxyl group, ester group (acyloxy group or alkoxycarbonyl group). ), A thioether group, a silyl group, and the like. These groups may be further substituted with an alkyl group or an aryl group. For example, the amino group (—NH ₂ ) is a monoalkylamino group (—NHR ′), a monoarylamino group (—NHAr), a dialkylamino group (—NR ′ ₂ ), or a diarylamino group (—NAr ₂ ). Also good. However, R 'is a C1-C12 alkyl group or a C1-C12 alkyl group which has an etheric oxygen atom between carbon atoms, and Ar is a C5-C12 aryl group. .
Preferred examples of the compound (11) having a combination of A ¹ and A ² include those represented by the following formula from the viewpoint of availability. In the following formula, Cy means a cyclohexyl group.

In the present invention, the metal of the metal carbene complex compound is preferably ruthenium.
Specifically, when M is ruthenium in the compound (11), it can be represented by the following formula (11-A). The ligand [L] in the formula (11) is represented by L ¹ , L ² , L ³ , Z ¹ and Z ² in the formula (11-A). There is no limitation on the positions of L ¹ , L ² , L ³ , Z ¹ and Z ² , and they may be interchanged in the formula (11-A). That is, for example, Z ¹ and Z ² may be in the trans position or in the cis position.

In formula (11-A), L ¹ , L ² and L ³ are each independently a ligand having a neutral charge when being separated from the central metal (neutral electron donating ligand) It is. Specifically, carbonyl group, amines, imines, pyridines, ethers, nitriles, esters, phosphines, thioethers, sulfoxides, sulfones, aromatic compounds, olefins, isocyanides, thiocyanates And hetero atom-containing carbene compounds. Among these, phosphines, pyridines, and heteroatom-containing carbene compounds are preferable, and trialkylphosphine and N-heterocyclic carbene compounds are more preferable.
However, depending on the combination of the ligands, not all ligands can coordinate to the central metal due to steric factors and / or electronic factors, and as a result, some of the coordination sites may be empty. . For example, the following combinations are exemplified as L ¹ , L ² and L ³ .
L ¹ : hetero atom-containing carbene compound, L ² : phosphines, L ³ : none (vacant coordination).
L ¹ : hetero atom-containing carbene compound, L ² : pyridines, L ³ : pyridines.

In formula (11-A), Z ¹ and Z ² are each independently a ligand (anionic ligand) having a negative charge when pulled away from the central metal. Specifically, halogen atom, hydrogen atom, substituted diketonate group, substituted cyclopentadienyl group, alkyl group having 1 to 20 carbon atoms, aryl group having 5 to 20 carbon atoms, substitution having 1 to 20 carbon atoms Alkoxy group, substituted aryloxy group having 5 to 20 carbon atoms, substituted carboxylate group having 1 to 20 carbon atoms, substituted aryl carboxylate group having 6 to 20 carbon atoms, substituted alkylthiolate having 1 to 20 carbon atoms Groups, substituted arylthiolate groups having 6 to 20 carbon atoms, nitrate groups, and the like. Of these, a halogen atom is preferable, and a chlorine atom is more preferable.

Wherein (11-A), ^{A 1} and ^{A 2} are each same as ^{A 1} and ^{A 2} in formula (11).
Alternatively, ^{2 to 6 of} L ¹ , L ² , L ³ , Z ¹ , Z ² , A ¹ and A ² may be bonded to each other to form a multidentate ligand.

  Such catalysts are generally referred to as “ruthenium-carbene complexes” and are described in, for example, Vougioukalakis, G .; C. et al. , Chem. Rev. 2010, 110, 1746-1787. The ruthenium-carbene complex described in 1) can be used. Further, for example, a ruthenium-carbene complex commercially available from Aldrich or Umicore can be used.

Specific examples of the ruthenium-carbene complex include bis (triphenylphosphine) benzylidene ruthenium dichloride, bis (tricyclohexylphosphine) benzylidene ruthenium dichloride, bis (tricyclohexylphosphine) -3-methyl-2-butenylidene ruthenium dichloride, ( 1,3-diisopropylimidazol-2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, (1,3-dicyclohexylimidazole-2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, (1,3-dimesitylimidazole) -2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride, (1,3-dimesityl-4,5-dihydroimidazole) 2-Ilidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, [1,3-bis (2,6-diisopropylphenyl) -4,5-dihydroimidazol-2-ylidene] (tricyclohexylphosphine) benzylideneruthenium dichloride, [1 , 3-bis (2-methylphenyl) -4,5-dihydroimidazol-2-ylidene] (tricyclohexylphosphine) benzylideneruthenium dichloride, [1,3-dicyclohexyl-4,5-dihydroimidazol-2-ylidene] ( Tricyclohexylphosphine) benzylideneruthenium dichloride, bis (tricyclohexylphosphine) ethoxymethylideneruthenium dichloride, (1,3-dimesityl-4,5-dihydroimidazol-2-ylide) ) (Tricyclohexylphosphine) ethoxymethylidene ruthenium dichloride, (1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) [bis (3-bromopyridine)] benzylidene ruthenium dichloride, (1,3-dimesityl- 4,5-dihydroimidazol-2-ylidene) (2-isopropoxyphenylmethylidene) ruthenium dichloride, (1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) [(tricyclohexylphosphoranyl) methylidene ] Dichlororuthenium tetrafluoroborate, Umicore M2, Umicore M51, Umicore M52, Umicore M71 SIMes, Umicore M71 SIPr, Umicore M73 SIMes, Umicore M73 SIPr and the like, (1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride, (1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) ) (2-isopropoxyphenylmethylidene) ruthenium dichloride, (1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) [(tricyclohexylphosphoranyl) methylidene] dichlororuthenium tetrafluoroborate, Umicore M2, Umicore M51, Umicore M52, Umicore M71 SIMes, Umicore M71 SIPr, Umicore M73 SIMes, and Umicore M73 SIPr are particularly preferable. Of the above complexes, the names beginning with “Umicore” are trade names of Umicore products.
In addition, the said ruthenium carbene complex may be used independently and may be used together 2 or more types. Further, if necessary, it may be supported on a carrier such as silica gel, alumina or polymer.

In the compound (11), when M is molybdenum or tungsten, it can be represented by the following formula (11-B) or formula (11-C). As the compound (11), a coordinating solvent (tetrahydrofuran, ethylene glycol dimethyl ether, etc.) may be further coordinated.
When the metal of the metal catalyst is molybdenum or tungsten, the metal catalyst ligand [L] preferably has an imide ligand (R ¹ -N = M). However, examples of R ¹ include an alkyl group and an aryl group. Further, the ligand [L] of the metal catalyst preferably has a ligand in which an oxygen atom is bidentately coordinated. However, the ligand in which the oxygen atom is bidentate is a ligand having two or more oxygen atoms in a ligand having two or more oxygen atoms, and oxygen This includes both cases where two monodentate ligands having atoms are coordinated (in this case, the monodentate ligands may be the same or different).

The ligand [L] in the formula (11) is represented by ═NR ¹ , —R ⁴ , —R ⁵ in the formula (11-B). There is no limitation on the positions of ═NR ¹ , —R ⁴ , and —R ⁵ , and they may be replaced with each other in the formula (11-B). M is molybdenum or tungsten, and examples of R ¹ include an alkyl group and an aryl group. Examples of R ⁴ and R ⁵ include halogen atoms, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, sulfonate groups, amino groups (alkylamino groups, η ¹ -pyrrolide, η ⁵ -pyrrolide, etc.) and the like. R ⁴ and R ⁵ may be linked to form a bidentate ligand.

Further, in the formula (11-C), an olefin (C ₂ (R ⁶ ) ₄ ) is cycloadded to the metal-carbon double bond portion of the compound represented by the formula (11-B) ([2 + 2] cycloaddition). And a compound in which a metallacyclobutane ring is formed. However, four R ⁶ are monovalent groups which may be the same or different from each other, and examples thereof include a hydrogen atom, a halogen atom, an aryl group, an alkoxy group, an aryloxy group and an amino group. The compound represented by the formula (11-C) is considered to be equivalent to the compound represented by the formula (11-B).

In the formula (11-B) and formula (11-C), ^{A 1} and ^{A 2} are each same as ^{A 1} and ^{A 2} in formula (11).

The above catalyst is generally referred to as “molybdenum-carbene complex” or “tungsten-carbene complex”. For example, Grela, K. et al. (Ed) Olefin Metathesis: Theory and Practice, Wiley, 2014. The molybdenum-carbene complex or tungsten-carbene complex described in 1) can be used. For example, a molybdenum-carbene complex or a tungsten-carbene complex commercially available from Aldrich, Strem, and Ximo can be used.
The molybdenum-carbene complex or the tungsten-carbene complex may be used alone or in combination of two or more. Further, if necessary, it may be supported on a carrier such as silica gel, alumina or polymer.

  Specific examples of compound (11-B) are shown below. Me represents a methyl group, i-Pr represents an isopropyl group, t-Bu represents a tertiary butyl group, and Ph represents a phenyl group.

  Specific examples of the compound (11-C) include the following compounds.

<Compounds (12) to (15)>
The compounds (12) to (15) play a role as a catalyst in the production method according to the present invention as in the case of the compound (11), but are added as a reagent and generated in the reaction (catalytically active species). Means both.

<Fluorine-containing diene compound>
In the method for producing a fluoropolymer according to the present invention, at least one fluorine-containing diene compound selected from the group consisting of fluorine-containing diene compounds represented by the following formulas (44) to (47) is used as a raw material.

The symbols in the above formula are the same as defined above, but Z is a single bond, an alkylene group having 1 to 25 carbon atoms, or an alkylene group having 1 to 25 carbon atoms including a hetero atom, The alkylene group having 1 to 25 carbon atoms and the alkylene group having 1 to 25 carbon atoms including a hetero atom may have at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, a carboxyl group and an ester group; It may have an annular structure.
A ^{11 to} A ¹³ and Af ¹¹ are functional groups represented by the following.

In the above formula, X ¹⁰ , X ¹¹ and X ¹² each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 5 carbon atoms, and A ⁸ and A ⁹ each independently represent the following group (i ), Group (ii), group (iii), and group (iv). A ⁸ and A ⁹ may be bonded to each other to form a ring. R represents an atom other than a fluorine atom or an organic group, and a plurality of R may be the same or different.
Group (i): a hydrogen atom.
Group (ii): a halogen atom.
Group (iii): C1-C20 monovalent hydrocarbon group.
Group (iv): C1-C20 monovalent hydrocarbon group containing 1 or more atoms chosen from the group which consists of a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom.

  That is, the compounds (44) to (47) are compounds represented by the following formulas (44) 'to (47)', respectively.

  Z is a single bond, an alkylene group having 1 to 25 carbon atoms, or an alkylene group having 1 to 25 carbon atoms including a hetero atom, and 1 to 25 carbon atoms including the alkylene group having 1 to 25 carbon atoms and a hetero atom. The alkylene group may further have at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, a carboxyl group and an ester group, and may have a cyclic structure.

  Z is a carbon having 1 to 2 and 7 to 20 carbon atoms having at least one substituent selected from the group consisting of a single bond, a halogen atom, a hydroxyl group, a carboxyl group, and an ester group, or a hetero atom. An alkylene group having 2 and 6 to 20 carbon atoms is preferable from the viewpoint of reactivity.

X ¹⁰ , X ¹¹ and X ¹² are each independently a hydrogen atom, a fluorine atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom, a fluorine atom or a methyl group from the viewpoint of reactivity. . When there are a plurality of at least one of X ¹¹ and X ¹² in one molecule, they may be the same or different.

R represents an atom other than a fluorine atom or an organic group, and a plurality of R may be the same or different. Examples of atoms other than fluorine atoms include hydrogen atoms and halogen atoms other than fluorine atoms. Among them, hydrogen atoms and methyl groups are preferable.
Organic groups include alkyl groups, alkoxy groups, aryl groups, aryloxy groups, (per) halogenated alkyl groups, (per) halogenated alkoxy groups, (per) halogenated aryl groups, (per) halogenated aryloxy groups, etc. Is mentioned. The alkyl group, alkoxy group, (per) halogenated alkyl group and (per) halogenated alkoxy group preferably have 1 to 12 carbon atoms, and aryl group, aryloxy group, (per) halogenated aryl group and ( The per-halogenated aryloxy group preferably has 5 to 12 carbon atoms.
The organic group may further have a substituent containing one or more atoms selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom. Specific examples of the substituent include a nitrile group, a carboxyl group, and an ester group (an acyloxy group or an alkoxycarbonyl group). In addition, even if it has this substituent, carbon number of the whole alkyl group, alkoxy group, (per) halogenated alkyl group and (per) halogenated alkoxy group is 1-12, and aryl group, aryloxy group The total number of carbon atoms in the (per) halogenated aryl group and the (per) halogenated aryloxy group is 5 to 20.

  As a C1-C12 alkyl group, the said C1-C8 said group is preferable, and the methyl group, the ethyl group, or the propyl group is specifically preferable from the point of availability. The alkyl group chain may be linear or branched. In addition, a ring may be formed as a divalent group in which one hydrogen atom is removed.

  As a C1-C12 alkoxy group, the said C1-C8 said group is preferable, and a methoxy group, an ethoxy group, or a propoxy group is specifically preferable from the point of availability. The alkoxy group chain may be linear or branched. In addition, a ring may be formed as a divalent group in which one hydrogen atom is removed.

  As a C5-C12 aryl group, the said C5-C12 said group is preferable, and the phenyl group is specifically preferable from the point of availability.

  The aryloxy group having 5 to 12 carbon atoms is preferably the group having 5 to 12 carbon atoms, and particularly preferably an aryloxy group having 5 to 12 carbon atoms. Specifically, a phenyloxy group is preferable from the viewpoint of availability.

  The (per) halogenated alkyl group having 1 to 12 carbon atoms is preferably the group having 1 to 8 carbon atoms, and particularly preferably a (per) fluoroalkyl group having 1 to 8 carbon atoms. Specifically, a trifluoromethyl group, a pentafluoroethyl group, or a heptafluoropropyl group is preferable from the viewpoint of availability. The alkyl group chain may be linear or branched. In addition, a ring may be formed as a divalent group from which one hydrogen atom or halogen atom is removed.

  The (per) halogenated alkoxy group having 1 to 12 carbon atoms is preferably the group having 1 to 8 carbon atoms, and particularly preferably a (per) fluoroalkoxy group having 1 to 8 carbon atoms. Specifically, a trifluoromethoxy group, a pentafluoroethoxy group, a heptafluoropropoxy group, a perfluoro (methoxymethoxy) group, or a perfluoro (propoxypropoxy) group is preferable, and in particular, a trifluoromethoxy group or a perfluoro (propoxypropoxy) group is available. It is preferable from the viewpoint of ease. The alkoxy group chain may be linear or branched. In addition, a ring may be formed as a divalent group from which one hydrogen atom or halogen atom is removed.

  The (per) halogenated aryl group having 5 to 12 carbon atoms is preferably the group having 5 to 12 carbon atoms, and particularly preferably a (per) fluoroaryl group having 5 to 12 carbon atoms. Specifically, a monofluorophenyl group or a pentafluorophenyl group is preferable, and a pentafluorophenyl group is particularly preferable from the viewpoint of availability.

  As the (per) halogenated aryloxy group having 5 to 12 carbon atoms, the group having 5 to 12 carbon atoms is preferable, and (per) fluoroaryloxy group having 5 to 12 carbon atoms is particularly preferable. Specifically, a monofluorophenyloxy group or a pentafluorophenyloxy group is preferable, and a pentafluorophenyloxy group is particularly preferable from the viewpoint of availability.

A ⁸ and A ⁹ are each independently a group selected from the group consisting of the group (i), the group (ii), the group (iii), and the group (iv) described above. That is, A ⁸ and A ⁹ are each independently a hydrogen atom, a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom. It is a C1-C20 monovalent hydrocarbon group containing 1 or more atoms selected from the group.
A ⁸ and A ⁹ may be bonded to each other to form a ring.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom and a chlorine atom are preferable from the viewpoint of availability.

  The monovalent hydrocarbon group having 1 to 20 carbon atoms is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 5 to 20 carbon atoms, or an aryloxy group having 5 to 20 carbon atoms. In particular, methyl group, ethyl group, propyl group, phenyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, tert-butoxy group, (2-ethyl) hexyloxy group, or dodecyloxy group Is preferable from the viewpoint of availability. The hydrocarbon group skeleton may be linear or branched, or may form a ring as a divalent hydrocarbon group from which one hydrogen atom is removed.

  The monovalent hydrocarbon group having 1 to 20 carbon atoms containing at least one atom selected from the group consisting of a halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, and silicon atom preferably includes the atom. Examples thereof include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 5 to 20 carbon atoms containing the atom, and an aryloxy group having 5 to 20 carbon atoms. In these preferred groups, halogen atoms may be bonded to at least some of the carbon atoms. That is, for example, it may be a (per) fluoroalkyl group or a (per) fluoroalkoxy group. Moreover, these preferable groups may have an etheric oxygen atom between carbon atoms. Further, these preferable groups may further have a substituent having an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. Examples of the substituent include an amino group, a nitrile group, a carboxyl group, an ester group (acyloxy group or alkoxycarbonyl group), a thioalkyl group, and a silyl group.

Among them, A ⁸ and A ⁹ are each independently a hydrogen atom, phenyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, tert-butoxy group, (2-ethyl) hexyloxy group, dodecyl. From the viewpoint of availability, an oxy group, an acetyl group, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a perfluorobutyl group, a perfluorohexyl group, or a perfluorooctyl group is preferable.

  Although the number of substituents on the double bond in compound (44) to compound (47) is not particularly limited, ethylene, monosubstituted olefins and 1,2-disubstituted olefins are preferable in that they have high reactivity. The geometric isomerism on the double bond is not particularly limited.

In the compounds (44) to (47), the carbon atoms constituting the main chain preferably have 2 to 27 carbon atoms, excluding the carbon atoms at both ends of the diene, and have 2 to 4 carbon atoms or 9 carbon atoms. More preferably, it is ~ 22. When the main chain contains heteroatoms, the number of atoms containing the heteroatoms is preferably 2 to 27, more preferably 2 to 4 atoms or 9 to 22 atoms.
By setting the above range, the ring distortion of the cycloolefin, which is a product of the ring-closing metathesis reaction that can be considered as a side reaction, is increased, so that the side reaction is suppressed and the acyclic diene metathesis polymerization reaction in the present invention proceeds. It becomes easy to do.
In addition to the two double bonds constituting the diene, the molecule may have a plurality of unsaturated bonds, and the side chain may have a plurality of unsaturated bonds.

  Examples of the compound (44) to the compound (47) include the following compounds. The definition and preferred group of Z in the following formula are the same as those described above.

  More specific examples of the compound (44) to the compound (47) include the compounds shown below.

<Fluoropolymer>
A fluorinated polymer can be obtained by subjecting the above-mentioned fluorinated diene compound to metathesis polymerization.
When compound (44) ′ to compound (47) ′ are used as raw material monomers, polymer (74) to polymer (77) having the repeating units shown below and ethylene or an ethylene derivative are obtained, respectively. In addition, when a plurality of types of compounds are used as monomers, their copolymers are obtained. As described above, compound (44) ′ to compound (47) ′ are the same as compound (44) to compound (47), respectively.

Z in the polymer (74) - Polymer ^{(77), X 10,} R and n are both compound (44) Z in of Compound (47) ^are each and ^{X 10,} R and n synonymous, preferred examples are also It is the same.
In addition, when a metathesis polymerization reaction is performed using the compound (44-1) as a monomer, a polymer (74-1) having a repeating unit shown below is obtained. Similarly, when the compound (44-2), the compound (45-1), the compound (46-1), the compound (47-1), and the compound (47-2) are used as raw materials, A union (74-2), a polymer (75-1), a polymer (76-1), a polymer (77-1) and a polymer (77-2) are obtained.

Among the polymers obtained by the metathesis polymerization of the present invention, the homopolymer is preferably a perfluorodiene compound from the viewpoint of easy availability of monomers as raw materials.
As specific examples, the compound (44-2-1), the compound (44-2-2), the compound (44-2-3), the compound (45-1-1), the compound (46-1-1), Metathesis polymerization using Compound (47-1-1), Compound (47-2-1), Compound (47-2-2), Compound (44-2-3), or Compound (47-2-4) as a monomer When the reaction is carried out, the polymer (74-2-1), polymer (74-2-2), polymer (74-2-3), polymer (75-1- 1), polymer (76-1-1), polymer (77-1-1), polymer (77-2-1), polymer (77-2-2), polymer (77-2-1) 3) A homopolymer of the polymer (77-2-4) is obtained.

  A copolymer is obtained when metathesis polymerization is performed using two or more monomers having different structures as raw materials. As the copolymer, any of alternating copolymer, block copolymer, and random copolymer can be synthesized, and a desired copolymer can be obtained depending on the charge ratio of monomers as raw materials and polymerization conditions. it can.

  As the copolymer, a copolymer of a perfluorodiene compound and a hydrocarbon-based diene compound is preferable from the viewpoint of availability.

The molecular weight of the polymer is preferably 1,000 to 1,000,000 from the viewpoint of mechanical properties and physical properties. The molecular weight is a weight average molecular weight / number average molecular weight, and is measured under conditions of a polymer solution using GPC.
When the polymer is a homopolymer, the number of repeating units represented by n in the formula is preferably 2 to 10,000 from the viewpoint of mechanical properties and physical properties, and more preferably 5 to 6500. More preferably, it is 5-3000. In the case of a copolymer, the total number of repeating units present in a plurality is preferably 2 to 10000, more preferably 5 to 6500, and even more preferably 5 to 3000.

  The resulting polymer has properties such as high heat resistance, low water absorption, high light transmittance (transparency), high chemical durability, high weather resistance, etc. It can be used in various fields such as electronic materials, semiconductor materials, and optical materials.

<Manufacturing method>
The present invention relates to a method for producing a polymer from a fluorinated diene compound by an acyclic diene metathesis polymerization reaction, and typically, by contacting an acyclic fluorinated diene compound with a metal-carbene complex. A metathesis polymerization reaction is performed to obtain a fluoropolymer.

The fluorine-containing diene compound used as a raw material is at least one compound selected from the group consisting of the compounds represented by the above formulas (44) to (47).
From the viewpoint of improving the yield of the target product, it is preferable to use a deaerated and dehydrated fluorine-containing diene compound as a raw material. There is no particular limitation on the deaeration operation, but freeze deaeration and the like may be performed. Although there is no restriction | limiting in particular about dehydration operation, Usually, it is made to contact with a molecular sieve etc. For the fluorine-containing diene compound as a raw material, the degassing and dehydration operations are usually performed before contacting with the metal-carbene complex.
Moreover, since the fluorine-containing diene compound used as a raw material may contain a very small amount of impurities (for example, peroxide), it may be purified from the viewpoint of improving the yield of the target product. There is no particular limitation on the purification method. For example, it can be performed according to the method described in the literature (Armarego, WLF et al., Purification of Laboratory Chemicals (Sixth Edition), 2009, Elsevier).

The raw material fluorine-containing diene compound is charged into the reaction vessel, but when two or more types of fluorine-containing diene compounds are used as monomers, they may be mixed separately into the reaction vessel before being added separately. It doesn't matter.
When two or more kinds of fluorine-containing diene compounds are used as monomers, there is no particular limitation on the molar ratio thereof. About 100 mol is used, preferably about 0.1 to 10 mol.

The metal-carbene complex may be added as a reagent or generated in the system.
When charging as a reagent, a commercially available metal-carbene complex may be used as it is, or a non-commercially available metal-carbene complex synthesized by a known method from a commercially available reagent may be used.
When it is generated in the system, a metal-carbene complex prepared from a metal complex as a precursor by a known method can be used in the present invention.

  Although there is no restriction | limiting in particular as the quantity of the metal-carbene complex to be used, About 0.0001-1 mol is normally used with respect to 1 mol of reference | standard fluorine-containing diene compounds among the fluorine-containing diene compounds used as a raw material, Is used in an amount of about 0.001 to 0.2 mol.

The metal-carbene complex to be used is usually charged into the reaction vessel as a solid, but may be charged after being dissolved or suspended in a solvent. There is no restriction | limiting in particular as a solvent used at this time in the range which does not exert a bad influence on reaction, An organic solvent, a fluorine-containing organic solvent, an ionic liquid, water etc. can be used individually or in mixture. In these solvent molecules, some or all of the hydrogen atoms may be substituted with deuterium atoms.
Further, when the fluorinated diene compound is a liquid (including the case where it is liquefied by heating), it is preferable not to use a solvent. In this case, it is preferable that the metal-carbene complex compound is dissolved in the fluorine-containing diene compound.

Examples of the organic solvent include aromatic hydrocarbon solvents such as benzene, toluene, o-, m-, p-xylene and mesitylene; aliphatic hydrocarbon solvents such as hexane and cyclohexane; dichloromethane, chloroform, 1, 2 -Halogen solvents such as dichloroethane, chlorobenzene, o-dichlorobenzene; ether solvents such as tetrahydrofuran (THF), dioxane, diethyl ether, glyme, diglyme, and the like can be used. Examples of the fluorine-containing organic solvent include hexafluorobenzene, m-bis (trifluoromethyl) benzene, p-bis (trifluoromethyl) benzene, α, α, α-trifluoromethylbenzene, dichloropentafluoropropane, and the like. Can be used. As the ionic liquid, for example, various pyridinium salts, various imidazolium salts and the like can be used. Among the above solvents, benzene, toluene, o-, m-, p-xylene, mesitylene, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, diethyl ether, dioxane, THF in terms of solubility of the metal-carbene complex. Hexafluorobenzene, m-bis (trifluoromethyl) benzene, p-bis (trifluoromethyl) benzene, α, α, α-trifluoromethylbenzene, and the like, and mixtures thereof are preferred.
In addition, it is preferable to use a degassed and dehydrated solvent for improving the yield of the target product. There is no particular limitation on the deaeration operation, but freeze deaeration and the like may be performed. Although there is no restriction | limiting in particular about dehydration operation, Usually, it is made to contact with a molecular sieve etc. The degassing and dehydration operations are usually performed before contacting with the metal-carbene complex.

The atmosphere in which the fluorinated diene compound and the metal-carbene complex are brought into contact with each other is not particularly limited, but is preferably an inert gas atmosphere from the viewpoint of extending the life of the catalyst, and particularly preferably a nitrogen or argon atmosphere. However, when using as a raw material the fluorine-containing diene compound which becomes gas on reaction conditions, such as perfluoro-1, 3- butadiene, it can carry out in these gas atmosphere.
The phase for contacting the fluorine-containing diene compound and the metal-carbene complex is not particularly limited, but a liquid phase is usually used in terms of reaction rate. When the fluorine-containing diene compound as a raw material is a gas under the reaction conditions, it is difficult to carry out in the liquid phase, so that the gas-liquid two phase can also be carried out. In the case of carrying out in the liquid phase, a solvent can be used. As the solvent used at this time, the same solvents as those used for dissolving or suspending the metal-carbene complex can be used. In addition, when the fluorine-containing diene compound used as a raw material includes those that are liquid under the reaction conditions, it may be carried out without a solvent.

  The container for contacting the fluorinated diene compound and the metal-carbene complex is not particularly limited as long as it does not adversely affect the reaction, and for example, a metal container or a glass container can be used. In addition, since the metathesis polymerization reaction concerning this invention may handle the fluorine-containing diene compound of a gaseous state on reaction conditions, the pressure-resistant container in which high airtightness is possible is preferable.

Although there is no restriction | limiting in particular as temperature which makes a fluorine-containing diene compound and a metal carbene complex contact, Usually, it can implement in the range of -100-200 degreeC, and 0-150 degreeC is preferable at the point of reaction rate. Note that the reaction does not start at low temperatures, and the complex may be rapidly decomposed at high temperatures. Therefore, it is necessary to appropriately set the lower limit and the upper limit of the temperature. Usually, it is carried out at a temperature below the boiling point of the solvent used.
Although there is no restriction | limiting in particular as time to contact a fluorine-containing diene compound and a metal carbene complex, Usually, it implements in the range of 1 minute-48 hours.
The pressure for bringing the fluorinated diene compound into contact with the metal-carbene complex is not particularly limited, but may be under pressure, under normal pressure, or under reduced pressure. Usually, it is about 0.001-10 MPa, preferably about 0.01-1 MPa.
The molecular weight of the resulting polymer can be targeted by appropriately adjusting the monomer charge ratio, the reaction conditions such as the reaction temperature, reaction time, and reaction pressure. Furthermore, the end of the obtained fluoropolymer can be converted into a desired group by post-treatment after polymerization.

  When the fluorine-containing diene compound and the metal-carbene complex are brought into contact with each other, an inorganic salt, an organic compound, a metal complex, or the like may coexist within a range that does not adversely influence the reaction. Moreover, you may stir the mixture of a fluorine-containing diene compound and a metal carbene complex in the range which does not have a bad influence on reaction. At this time, a mechanical stirrer, a magnetic stirrer, or the like can be used as a stirring method.

  After completion of the reaction by bringing the fluorinated diene compound and the metal-carbene complex into contact, the polymer as the target product may be isolated by a known method. Examples of the isolation method include distillation, column chromatography, recycle preparative HPLC and the like, and these can be used alone or in combination as necessary.

The target product obtained in this reaction can be identified by a known method similar to that for ordinary polymer compounds. Examples thereof include ¹ H-, ¹⁹ F-, ¹³ C-NMR, GPC, static light scattering, SIMS and GC-MS, and these can be used alone or in combination as required.

In addition, by using two or more kinds of monomers as a copolymer, it is possible to impart various properties as compared with a homopolymer.
When the obtained polymer compound is a copolymer, the ratio of two or more unit structures constituting the copolymer depends on the charge ratio of the monomer, but is usually derived from a fluorine-containing diene compound which is a standard. When the number of units is 1, the number of repeating units derived from other fluorine-containing diene compounds is about 0.01 to 100, preferably about 0.1 to 10.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these.
<Commercially available reagents>
In this example, unless otherwise specified, a commercially available catalyst was used as it was for the reaction. The solvent (m-xylene-d ₁₀ , o-dichlorobenzene-d ₄ ) and the internal standard substance (p-bis (trifluoromethyl) benzene) were pre-freeze degassed in advance, and then dried with molecular sieve 4A. And used for the reaction.
<Evaluation method>
In this example, the structure of the synthesized compound was identified by performing ¹ H-NMR and ¹⁹ F-NMR measurements using a nuclear magnetic resonance apparatus (JNM-AL300) manufactured by JEOL Ltd. Moreover, molecular weight was calculated | required by the electron ionization method (EI) using the Shimadzu Corporation gas chromatograph mass spectrometer (GCMS-QP2010Ultra).

<Example 1>
Metathesis polymerization reaction of perfluoro-1,3-butadiene with second generation Grubbs catalyst Under nitrogen atmosphere, second generation Grubbs catalyst (10 mol%, 0.012 mmol), perfluoro-1,3-butadiene (CF ₂ = CF-CF = CF ₂ , 0.12 mmol, 19.5 mg) and o-dichlorobenzene-d ₄ (0.6 mL) were weighed into an NMR measuring tube. The NMR tube was heated at 180 ° C. and reacted at that temperature for 1 hour. After completion of the reaction, NMR and GC-MS were measured to confirm the progress of the desired reaction.

<Example 2>
Metathesis polymerization reaction of 3,3,4,4,5,5,6,6,7,7,8,8-dodecafluoro-1,9-decadiene with Umicore M73 SIPr catalyst Umicore M73 SIPr catalyst (50 mol%, 0 .05mmol), 3,3,4,4,5,5,6,6,7,7,8,8- dodecafluoro-1,9-decadiene _{(CH 2 = CH- (CF 2} ) 6 -CH = CH _2, 0.10mmol, 0.024mL) and m- xylene _-d 10 a (0.6 mL) was weighed into a NMR measuring tube. The NMR tube was heated to 60 ° C. for 1 hour, then heated to 100 ° C. for 1 hour, and finally heated to 140 ° C. and reacted at that temperature for 1 hour. After completion of the reaction, NMR and GC-MS were measured to confirm the progress of the desired reaction.

<Examples 3 to 6>
Metathesis polymerization reaction of perfluoro-1,3-butadiene with a molybdenum catalyst The second generation Grubbs catalyst of Example 1 was changed to a known molybdenum catalyst D to G represented by the following formula, and the same reaction was carried out. The same reaction product as 1 is obtained.

<Example 7>
Metathesis polymerization reaction of 3,3,4,4,5,5,6,6,7,7,8,8-dodecafluoro-1,9-decadiene with a tungsten catalyst The second generation Grubbs catalyst of Example 1 The reaction is carried out in the same manner by changing to a known tungsten catalyst H represented by the following formula to obtain the same reaction product as in Example 1.

<Examples 8 to 11>
Metathesis polymerization reaction of 3,3,4,4,5,5,6,6,7,7,8,8-dodecafluoro-1,9-decadiene with a molybdenum catalyst The Umicore M73 SIPr catalyst of Example 2 was used as the molybdenum catalyst described above. The reaction product is changed to D to G in the same manner to obtain the same reaction product as in Example 2.

<Example 12>
Metathesis polymerization reaction of 3,3,4,4,5,5,6,6,7,7,8,8-dodecafluoro-1,9-decadiene with a tungsten catalyst The Umicore M73 SIPr catalyst of Example 2 was used as the above tungsten catalyst. The reaction is carried out in the same manner by changing to H to obtain the same reaction product as in Example 2.

  Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application filed on Feb. 9, 2015 (Japanese Patent Application No. 2015-023409), the contents of which are incorporated herein by reference.

  According to the present invention, a fluorine-containing polymer having a desired structure and molecular weight can be easily obtained by a metathesis polymerization reaction of a fluorine-containing diene compound, and the fluorine-containing polymer is an electric / electronic material as a functional polymer. It can be used in various fields such as semiconductor materials and optical materials.

Claims (8)

In the presence of a metal-carbene complex compound (10) having olefin metathesis reaction activity, at least one fluorine-containing diene compound selected from the group consisting of fluorine-containing diene compounds represented by the following formulas (44) to (47) Is a method for producing a fluoropolymer having a repeating unit represented by at least one of the following formulas (74) to (77).

However, the symbols in the above formulas represent the following meanings.
Z is a single bond, an alkylene group having 1 to 25 carbon atoms, or an alkylene group having 1 to 25 carbon atoms including a hetero atom, and 1 to 25 carbon atoms including the alkylene group having 1 to 25 carbon atoms and a hetero atom. The alkylene group may have at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, a carboxyl group and an ester group, and may have a cyclic structure.
R is an atom other than a fluorine atom or an organic group, and a plurality of R may be the same or different.
X ¹⁰ represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 5 carbon atoms, and a plurality of X ¹⁰ may be the same or different.
n is a positive integer representing the number of repeating units.
A ^{11 to} A ¹³ and Af ¹¹ are functional groups represented by the following.

In the above formula, X ¹⁰ , X ¹¹ and X ¹² are each independently a hydrogen atom, a fluorine atom or an alkyl group having 1 to 5 carbon atoms, and A ⁸ and A ⁹ are each independently the following groups (i ), Group (ii), group (iii), and group (iv). A ⁸ and A ⁹ may be bonded to each other to form a ring. R represents an atom other than a fluorine atom or an organic group, and a plurality of R may be the same or different.
Group (i): a hydrogen atom.
Group (ii): a halogen atom.
Group (iii): C1-C20 monovalent hydrocarbon group.
Group (iv): C1-C20 monovalent hydrocarbon group containing 1 or more atoms chosen from the group which consists of a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom.   The manufacturing method according to claim 1, wherein the metal in the metal-carbene complex compound (10) is ruthenium, molybdenum or tungsten.   The method according to claim 1 or 2, wherein the metal in the metal-carbene complex compound (10) is ruthenium.   The metal in the metal-carbene complex compound (10) is molybdenum or tungsten, and the metal-carbene complex compound is a ligand [L], and an imide ligand and an oxygen atom are bidentately coordinated. The manufacturing method of Claim 1 or 2 which has a ligand.   The manufacturing method as described in any one of Claims 1-4 whose said fluorine-containing diene compound is a perfluorodiene compound. Fluorinated diene compound represented by the following formula (44-1), fluorinated diene compound represented by the following formula (44-2), fluorinated diene compound represented by the following formula (45-1), the following formula Selected from the group consisting of a fluorine-containing diene compound represented by (46-1), a fluorine-containing diene compound represented by the following formula (47-1), and a fluorine-containing diene compound represented by the following formula (47-2). By polymerizing at least one fluorine-containing diene compound, the following formula (74-1), the following formula (74-2), the following formula (75-1), the following formula (76-1), the following formula ( The manufacturing method as described in any one of Claims 1-4 which manufactures the fluoropolymer represented by the at least 1 formula chosen from the group which consists of 77-1) and a following formula (77-2).

In the above formula, Z is a single bond, an alkylene group having 1 to 25 carbon atoms, or an alkylene group having 1 to 25 carbon atoms containing a hetero atom, and the carbon containing an alkylene group having 1 to 25 carbon atoms and a hetero atom. The alkylene group of Formula 1 to 25 may further have at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, a carboxyl group, and an ester group. n is a positive integer representing the number of repeating units.   The manufacturing method according to any one of claims 1 to 6, wherein the polymerization temperature is 0 to 150 ° C.   The manufacturing method as described in any one of Claims 1-7 which does not use a solvent.