WO2019163712A1 - Method for producing (poly)ether group-containing monocarboxylic acid compound - Google Patents

Method for producing (poly)ether group-containing monocarboxylic acid compound Download PDF

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WO2019163712A1
WO2019163712A1 PCT/JP2019/005869 JP2019005869W WO2019163712A1 WO 2019163712 A1 WO2019163712 A1 WO 2019163712A1 JP 2019005869 W JP2019005869 W JP 2019005869W WO 2019163712 A1 WO2019163712 A1 WO 2019163712A1
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group
acid compound
poly
dicarboxylic acid
monocarboxylic acid
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PCT/JP2019/005869
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French (fr)
Japanese (ja)
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英樹 中谷
岳臣 平坂
内藤　真人
雅聡 能勢
孝史 野村
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ダイキン工業株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/30—Post-polymerisation treatment, e.g. recovery, purification, drying
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
    • C08G65/323—Polymers modified by chemical after-treatment with inorganic compounds containing halogens

Definitions

  • the present invention relates to a method for producing a (poly) ether group-containing monocarboxylic acid compound.
  • Compounds with perfluoro (poly) ether groups have excellent water repellency, oil repellency, antifouling properties, heat resistance, low temperature properties, oil resistance, solvent resistance, chemical resistance, lubricity, low friction, wear resistance It is known that it can provide the property, releasability, etc.
  • Functional thin films containing a compound having a perfluoro (poly) ether group are used for various substrates such as glass, plastic, fiber, metal, and building materials.
  • a fluorine-based elastomer containing a compound having a perfluoro (poly) ether group is used as a material that maintains durability and reliability in severe environments such as automobiles, aircraft, semiconductors, and space fields.
  • Other compounds having a perfluoro (poly) ether group should be used as intermediate compounds or additives such as acrylic resins, polyurethanes, epoxy resins, polyester resins, laminated resins, and paints and cosmetics. Thus, it is possible to impart and develop excellent performance. Therefore, the search for a method for synthesizing compounds having perfluoro (poly) ether groups having various structures has been energetically performed. In the synthesis of such a compound having a perfluoro (poly) ether group, the perfluoro (poly) ether group-containing carboxylic acid compound is an important compound as a raw material compound or an intermediate.
  • perfluoro (poly) ether group-containing carboxylic acid compound a perfluoro (poly) ether group-containing monocarboxylic acid compound having a carboxylic acid group only at one end, and a perfluoro (poly And ether group-containing dicarboxylic acid compounds.
  • the raw material compound or intermediate has higher purity. Higher purity facilitates purification of the product obtained by the reaction, and further reduces the generation of by-products and unidentified products that can occur in the reaction, resulting in better performance. This is because an object having the above can be obtained. For this reason, various examinations have been made so far as a method for separating a compound used as a raw material compound or an intermediate of a compound having a perfluoro (poly) ether group.
  • Patent Document 1 discloses a perfluoro (poly) ether group-containing compound having no carboxylic acid group at the molecular end, a perfluoro (poly) ether group-containing monocarboxylic acid compound, and a perfluoro (poly) ether group-containing dicarboxylic acid. A method for separating each compound from a mixture containing the compounds is described.
  • a perfluoro (poly) ether group-containing monocarboxylic acid compound is the most usable compound, and an improvement in its yield is desired.
  • An object of the present invention is to improve the yield of a (poly) ether group-containing monocarboxylic acid compound containing a fluorine atom that can be most used among compounds having a (poly) ether group containing a fluorine atom.
  • A is independently at each occurrence R 1 O—CO—W— group, R 1 O—CO—W—O— group, HO—W— group, HO—W—O— group, R 1 O Represents a —W— group, a R 1 O—W—O— group, a V— group, or a V—O— group;
  • R 1 independently represents an alkyl group at each occurrence;
  • W represents a bond or a divalent organic group independently at each occurrence;
  • V independently represents each alkyl group having 1 to 16 carbon atoms in each occurrence;
  • Z independently represents Y—X— or Y—X—O— at each occurrence;
  • Y represents a carboxylic acid group;
  • X independently represents a bond or
  • the yield of the (poly) ether group-containing monocarboxylic acid compound can be improved.
  • 3 is a flowchart of a method according to an embodiment of the present invention.
  • 3 is a flowchart of a method according to an embodiment of the present invention.
  • 3 is a flowchart of a method according to an embodiment of the present invention.
  • 3 is a flowchart of a method according to an embodiment of the present invention.
  • bond means a simple bond having no atom or the like.
  • Z is a —XY group
  • X is a bond
  • Z represents a —Y group.
  • divalent organic group means a divalent group containing carbon. Such a divalent organic group is not particularly limited, and examples thereof include a divalent group obtained by further removing one hydrogen atom from a hydrocarbon group.
  • hydrocarbon group means a group containing carbon and hydrogen, in which one hydrogen atom is eliminated from a molecule.
  • Such hydrocarbon group is not particularly limited, but may be a hydrocarbon group having 1 to 4 carbon atoms which may be substituted by one or more substituents, such as an aliphatic hydrocarbon group, etc. Is mentioned.
  • the “aliphatic hydrocarbon group” may be linear, branched or cyclic, and may be either saturated or unsaturated.
  • the hydrocarbon group may also contain one or more ring structures.
  • Such a hydrocarbon group may have one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy and the like at its terminal or molecular chain.
  • the substituent of the “hydrocarbon group” is not particularly limited, but includes, for example, a halogen atom; C 1-6 alkyl optionally substituted by one or more halogen atoms Group, C 2-6 alkenyl group, C 2-6 alkynyl group, C 3-10 cycloalkyl group, C 3-10 unsaturated cycloalkyl group, 5-10 membered heterocyclyl group, 5-10 membered unsaturated heterocyclyl And one or more groups selected from a group, a C 6-10 aryl group and a 5-10 membered heteroaryl group.
  • an alkyl group and a phenyl group may be unsubstituted or substituted.
  • the substituent of such a group is not particularly limited, and examples thereof include one or more groups selected from a halogen atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. Can be mentioned.
  • the polyether group is independently at each occurrence, - (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 X 1 6) d - (OC 2 F 4) e - (OCF 2) f - It is group represented by these.
  • the (poly) ether group may be referred to as a Pf group.
  • a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1.
  • a, b, c, d, e and f are each independently an integer of 0 or more and 100 or less.
  • the sum of a, b, c, d, e and f is 5 or more, more preferably 10 or more.
  • the sum of a, b, c, d, e, and f is 200 or less, more preferably 100 or less, for example, 10 or more and 200 or less, and more specifically 10 or more and 100 or less.
  • the order of presence of each repeating unit in parentheses with a, b, c, d, e or f is arbitrary in the formula.
  • X 1 is independently a hydrogen atom, a fluorine atom or a chlorine atom at each occurrence, preferably a fluorine atom.
  • the repeating unit may be linear or branched, but is preferably linear.
  • -(OC 6 F 12 )- is-(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 CF 2 CF 2 )-,-(OCF 2 CF (CF 3 ) CF 2 CF 2 CF 2 ) —, — (OCF 2 CF 2 CF (CF 3 ) CF 2 CF 2 ) —, — (OCF 2 CF 2 CF 2 CF (CF 3 ) CF 2 ) — — (OCF 2 CF 2 CF 2 CF (CF 3 )) — or the like may be used, but — (OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 ) — is preferred.
  • — (OC 3 F 6 ) — (that is, X 1 is a fluorine atom) represents — (OCF 2 CF 2 CF 2 ) —, — (OCF (CF 3 ) CF 2 ) — and — (OCF 2 CF (CF 3 )) — may be used, but — (OCF 2 CF 2 CF 2 ) — is preferred.
  • — (OC 2 F 4 ) — may be any of — (OCF 2 CF 2 ) — and — (OCF (CF 3 )) —, preferably — (OCF 2 CF 2 ) —. is there.
  • the Pf group is — (OC 3 F 6 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200). is there.
  • the Pf group is — (OCF 2 CF 2 CF 2 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200) or — (OCF (CF 3 ) CF 2 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200).
  • the Pf group is — (OCF 2 CF 2 CF 2 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200). is there.
  • the Pf group is — (OC 4 F 8 ) c — (OC 3 F 6 ) d — (OC 2 F 4 ) e — (OCF 2 ) f — (wherein c and d are each Each independently represents an integer of 0 to 30; e and f are each independently an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200; c, d, e And the sum of f is at least 5 or more, preferably 10 or more, and the order of presence of each repeating unit in parentheses with the suffix c, d, e or f is optional in the formula) .
  • the Pf group is — (OCF 2 CF 2 CF 2 CF 2 ) c — (OCF 2 CF 2 CF 2 ) d — (OCF 2 CF 2 ) e — (OCF 2 ) f —.
  • the Pf group is — (OC 2 F 4 ) e — (OCF 2 ) f — (wherein e and f are each independently from 1 to 200, preferably from 5 to 200, Preferably, it is an integer of 10 or more and 200 or less, and the order of presence of each repeating unit with the subscript e or f and enclosed in parentheses is arbitrary in the formula).
  • the Pf group is a group represented by-(R 6 -R 7 ) j- .
  • R 6 is OCF 2 or OC 2 F 4 , preferably OC 2 F 4 .
  • R 7 is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 , or is independently selected from these groups Is a combination of 2 or 3 groups.
  • R 7 is a group selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 or from OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12.
  • the combination of 2 or 3 groups independently selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 is not particularly limited.
  • J is 2 or more, preferably 3 or more, more preferably 5 or more, and an integer of 100 or less, preferably 50 or less.
  • OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 may be either linear or branched, preferably linear.
  • the Pf group is preferably — (OC 2 F 4 —OC 3 F 6 ) j — or — (OC 2 F 4 —OC 4 F 8 ) j —.
  • the ratio of e to f (hereinafter referred to as “e / f ratio”) is 0.1 or more and 10 or less, for example, 0.2 or more and 5 or less. 4 or more and 2 or less, more specifically 0.6 or more and 1.5 or less, and more specifically 0.7 or more and 1.4 or less.
  • FIG. 2 shows one embodiment of a method for producing the Pf group-containing monocarboxylic acid compound of the present invention.
  • the method for producing the Pf group-containing monocarboxylic acid compound of this embodiment includes: At least a Pf group-containing compound represented by the following formula (1), a Pf group-containing monocarboxylic acid compound represented by the following formula (2), and a Pf group-containing dicarboxylic acid compound represented by the following formula (3) A step (I-1) of separating the composition (a1) containing, and a fluorination treatment of the Pf group-containing dicarboxylic acid compound represented by the formula (3) obtained by the separation, and represented by the formula (2) A step (A1) of obtaining a mixture containing a Pf group-containing monocarboxylic acid compound including.
  • the Pf group-containing compound represented by the formula (1), the Pf group-containing monocarboxylic acid compound represented by the formula (2), and the Pf group-containing dicarboxylic acid compound represented by the formula (3) are sometimes referred to as “Pf group-containing compound”, “Pf group-containing monocarboxylic acid compound” and “Pf group-containing dicarboxylic acid compound”, respectively.
  • R 1 O—CO—W— group R 1 O—CO—W—O— group, HO—W— group, HO—W—O— group
  • R 1 O Represents a —W— group, a R 1 O—W—O— group, a V— group, or a V—O— group
  • R 1 independently represents an alkyl group at each occurrence
  • W represents a bond or a divalent organic group independently at each occurrence
  • V independently represents each alkyl group having 1 to 16 carbon atoms in each occurrence
  • Z independently represents Y—X— or Y—X—O— at each occurrence
  • Y represents a carboxylic acid group
  • X independently represents a bond or a divalent organic group at each occurrence
  • Pf is independently at each occurrence, the formula: - (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 X 1 6) d - (OC 2 F 4)
  • the step (I-1) and the step (A1) are embodiments of the step (I) and the step (A), respectively.
  • the composition (a1) corresponds to the composition (a).
  • a composition (a1) to be used in step (I-1) is prepared.
  • composition (a1) is not specifically limited, For example, it can obtain by the following reactions.
  • V-Pf-OV (1-c) Decomposition reaction V-Pf-OV (1-c) (Where: V independently represents an alkyl group having 1 to 16 carbon atoms in each occurrence, and preferably, a C 1-16 perfluoroalkyl group, or at least one hydrogen atom consists of a fluorine atom and a chlorine atom Represents a group substituted by at least one atom selected from the group, for example, a group represented by HCF 2 (CF 2 ) g- (g is independently an integer of 0 to 15 at each occurrence) ; Pf is as defined above; Preferred V and g are as described below.
  • the composition (a1) is produced by a hydrolysis reaction of a compound represented by the formula (1-a).
  • the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide, and cesium hydroxide. These may use only 1 type and may use 2 or more types together.
  • the aqueous solution may contain other base such as calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, ammonium hydroxide in addition to the alkali metal hydroxide.
  • the number of equivalents of the base containing the alkali metal hydroxide is 0.1 to 1.5 with respect to 1 mol of the compound represented by the formula (1-a) (2 equivalents as the ester group). Is preferably used in such an amount.
  • the number of equivalents of base is more preferably 0.2 to 1.0, and still more preferably 0.3 to 0.8.
  • the hydrolysis may be carried out in the presence of an organic solvent as necessary.
  • organic solvents include acetonitrile, tetrahydrofuran and the like.
  • the hydrolysis may be performed under conditions where a dispersion aid is further present.
  • examples of the dispersion aid include a fluorine atom-containing solvent which is liquid at ⁇ 10 to 50 ° C. and hardly soluble or insoluble in water.
  • fluorine atom-containing solvent perfluorohexane, xylene hexafluoride and the like are more preferably used.
  • the said fluorine atom containing solvent may be used individually by 1 type, and may use 2 or more types together.
  • the hydrolysis is preferably performed by stirring at -10 ° C. to 50 ° C. for 0.5 to 12 hours.
  • the composition (a1) is formed by fluorination treatment of a Pf group-containing dicarboxylic acid compound. That is, in this embodiment, the composition (a1) is It is obtained by the step (Z1) of obtaining a composition (a1) by subjecting the Pf group-containing dicarboxylic acid compound to a fluorination treatment.
  • the Pf group-containing dicarboxylic acid compound may be a compound obtained by hydrolysis reaction of the compound represented by the formula (1-a).
  • R 1 O—CO—W—Pf—OW—CO—O—R 1 (1-a) (Wherein R 1 , W, and Pf are as defined above)
  • the compound represented by the formula (1-a) may have a number average molecular weight in the range of 1,000 to 10,000, for example, specifically in the range of 3,000 to 5,000. May be.
  • the number average molecular weight is a value determined by 19 F NMR.
  • the step (Z1) is an embodiment of the step (Z).
  • the composition (a1) is obtained by the step (Z1). That is, the composition (a1) is preferably obtained by fluorinating a Pf group-containing dicarboxylic acid compound.
  • the conditions for the fluorination treatment are not particularly limited.
  • the fluorination treatment can be performed by bringing a Pf group-containing dicarboxylic acid compound (or a composition containing a Pf group-containing dicarboxylic acid compound) into contact with a fluorine-containing compound.
  • produces a fluorine radical under fluorination process conditions is mentioned.
  • the fluorine radical source include F 2 , CoF 3 , AgF 2 , UF 6 , OF 2 , N 2 F 2 , CF 3 OF, and halogen fluoride (eg, IF 5 , ClF 3 ).
  • the fluorine radical source such as F 2 may have a concentration of 100%, but is preferably diluted to 5 to 50% by mass, and diluted to 15 to 30% by mass. More preferred.
  • the fluorine radical source can be mixed with an inert gas (specifically, when the fluorine radical source is gaseous)
  • the fluorine radical source and the inert gas are used for safety. It is preferably mixed and diluted to 5 to 50% by mass, more preferably 15 to 30% by mass.
  • the inert gas include nitrogen gas, helium gas, and argon gas. Nitrogen gas is preferable from the economical viewpoint.
  • the fluorination treatment is preferably performed at 50 ° C. to 200 ° C., more preferably 80 ° C. to 150 ° C.
  • the fluorination treatment is generally performed for 0.5 to 50 hours, preferably 1 to 20 hours.
  • the fluorination treatment is preferably performed at 100 to 140 ° C. for 2 to 10 hours.
  • the composition (a1) contains at least a Pf group-containing compound, a Pf group-containing monocarboxylic acid compound, and a Pf group-containing dicarboxylic acid compound.
  • the Pf group-containing compound, the Pf group-containing monocarboxylic acid compound, and the Pf group-containing dicarboxylic acid compound are represented by the following formulas (1), (2), and (3), respectively.
  • A is each independently R 1 O—CO—W— group, R 1 O—CO—W—O— group, HO—W— group, HO—W—O— group, R 1 O—W— group, R 1 O—W—O— group, V— group or V—O— group is represented.
  • R 1 independently represents an alkyl group at each occurrence.
  • the alkyl group is preferably a C 1-4 alkyl group.
  • the C 1-4 alkyl group include a linear or branched C 1-4 alkyl group.
  • Specific examples of the C 1-4 alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 2-butyl group, an isobutyl group, and a t-butyl group.
  • R 1 is more preferably a methyl group or an ethyl group.
  • These alkyl groups may have a substituent. Examples of the substituent include a halogen atom such as a fluorine atom or a chlorine atom, an amino group, a sulfonyl group, and a hydroxyl group.
  • W represents a bond or a divalent organic group independently at each occurrence.
  • the left side is a structure represented by R 1 O—CO—, the HO— or R 1 O— structure
  • the right side is a Pf group, or —O—. Join each one.
  • the divalent organic group preferably contains 1 to 4 carbon atoms.
  • at least one hydrogen atom may be substituted with one or more substituents.
  • a fluorine atom or a chlorine atom can be mentioned.
  • Examples of the divalent organic group having 1 to 4 carbon atoms include a C 1-4 alkylene group, wherein at least one hydrogen atom is substituted with at least one atom selected from the group consisting of a fluorine atom and a chlorine atom. Examples thereof include a C 1-4 alkylene group and a C 1-4 perfluoroalkylene group.
  • the C 1-4 alkylene group includes —CH 2 —, —C 2 H 4 —, —C 3 H 6 —, and —C 4 H 8 —.
  • —C 3 H 6 — and —C 4 H 8 — may be linear or branched.
  • the C 1-4 alkylene group in which the at least one hydrogen atom is substituted with at least one atom selected from the group consisting of a fluorine atom and a chlorine atom includes a part of the hydrogen atoms in the C 1-4 alkylene group.
  • a group substituted by a fluorine atom a group in which part of the hydrogen atom in the C 1-4 alkylene group is substituted by a chlorine atom, or a part of the hydrogen atom in the C 1-4 alkylene group is substituted by a chlorine atom and a fluorine atom Group.
  • Examples of the C 1-4 perfluoroalkylene group include groups in which all the hydrogen atoms in the C 1-4 alkylene group have been substituted with fluorine atoms.
  • the W is preferably a group in which at least one hydrogen atom is substituted with at least one atom selected from the group consisting of a fluorine atom and a chlorine atom.
  • the above W is independently at each occurrence —CJ 2 —, —CJ 2 CJ 2 —, —CJ 2 CJ 2 CJ 2 —, —CJ (CJ 3 ) CJ 2 — or —CJ 2 CJ (CJ 3 ) — is preferred.
  • J independently represents a hydrogen atom, a fluorine atom or a chlorine atom at each occurrence. It is preferable that at least 1 of J is a fluorine atom or a chlorine atom.
  • the W is independently at each occurrence, —CJ ′ 2 —, —CJ ′ 2 CJ ′ 2 —, —CH 2 CJ ′ 2 —, —CJ ′ 2 CH 2 —, —CJ ′.
  • (CJ ′ 3 ) CJ ′ 2 —, —CJ ′ (CJ ′ 3 ) CH 2 —, —CJ ′ 2 CJ ′ 2 CH 2 —, —CH 2 CJ ′ 2 CJ ′ 2 — or —CH 2 CJ ′ ( CJ ′ 3 ) — is preferred.
  • J ′ represents a fluorine atom or a chlorine atom independently at each occurrence.
  • the W is independently at each occurrence —CF 2 —, —CF 2 CF 2 —, —CH 2 CF 2 —, —CF 2 CH 2 —, —CFClCF 2 —, —CF 2 CFCl—, —CF (CF 3 ) CF 2 —, —CF (CF 3 ) CH 2 —, —CF 2 CF 2 CH 2 —, —CH 2 CF 2 CF 2 — or —CH 2 CF (CF 3 ) -.
  • V represents an alkyl group having 1 to 16 carbon atoms independently at each occurrence.
  • the alkyl group having 1 to 16 carbon atoms may be substituted with one or more substituents.
  • substituents a fluorine atom or a chlorine atom can be mentioned.
  • V is preferably a group in which at least one hydrogen atom is substituted with at least one atom selected from the group consisting of a fluorine atom and a chlorine atom.
  • the V is preferably a structure represented by J (CJ 2 ) n —.
  • n is an integer of 1 to 16.
  • J is as defined above. More preferably, at least one of the above J is a fluorine atom or a chlorine atom.
  • V may be a group represented by a C 1-16 perfluoroalkyl group, HCF 2 (CF 2 ) g —, or ClCF 2 (CF 2 ) g —.
  • the C 1-16 perfluoroalkyl group is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms (a group in which all hydrogen atoms in the alkyl group are substituted with fluorine atoms), preferably Is a linear or branched perfluoroalkyl group having 1 to 3 carbon atoms, more specifically CF 3 —, CF 3 CF 2 — or CF 3 CF 2 CF 2 —.
  • the above g is independently an integer of 0 to 15 and more preferably an integer of 1 to 4 at each occurrence.
  • Z represents Y—X— or Y—X—O— independently at each occurrence.
  • Y represents a carboxylic acid group.
  • the above X represents a bond or a divalent organic group independently at each occurrence.
  • the bond and the divalent organic group are as described above. Note that in the structure described as X, the left side is bonded to the structure represented by Y.
  • the divalent organic group is preferably a group containing 1 to 4 carbon atoms.
  • a hydrogen atom may be substituted with one or more fluorine atoms or chlorine atoms.
  • the divalent organic group having 1 to 4 carbon atoms includes a C 1-4 alkylene group, and at least one atom selected from the group consisting of one or more fluorine atoms and chlorine atoms. Examples thereof include a substituted C 1-4 alkylene group or a C 1-4 perfluoroalkylene group.
  • Examples of the C 1-4 alkylene group include —CH 2 —, —C 2 H 4 —, —C 3 H 6 —, and —C 4 H 8 —.
  • —C 3 H 6 — and —C 4 H 8 — may be linear or branched.
  • Examples of the C 1-4 fluoroalkylene group in which a part of the hydrogen atom is substituted with at least one atom selected from the group consisting of one or more fluorine atoms and chlorine atoms include hydrogen in the C 1-4 alkylene group.
  • Examples include a group in which a part of the atoms is substituted with a fluorine atom, a group in which a part of the hydrogen atom is substituted with a chlorine atom, and a group in which a part of the hydrogen atom is substituted with a chlorine atom and a fluorine atom.
  • Examples of the C 1-4 perfluoroalkylene group include groups in which all the hydrogen atoms in the C 1-4 alkylene group have been substituted with fluorine atoms.
  • J is as defined above. It is preferable that at least 1 of J is a fluorine atom or a chlorine atom.
  • Said X is independently at each occurrence, -CJ '2 -, - CJ ' 2 CJ '2 -, - CH 2 CJ' 2 -, - CJ '2 CH 2 -, - CJ' (CJ '3 ) CJ ′ 2 —, —CJ ′ (CJ ′ 3 ) CH 2 —, —CJ ′ 2 CJ ′ 2 CH 2 —, —CH 2 CJ ′ 2 CJ ′ 2 — or —CH 2 CJ ′ (CJ ′ 3 ) -Is more preferable.
  • J ′ is as defined above.
  • the X is independently at each occurrence —CF 2 —, —CF 2 CF 2 —, —CH 2 CF 2 —, —CF 2 CH 2 —, —CFClCF 2 —, —CF 2.
  • Pf means a Pf group.
  • the number average molecular weight of the —Pf— moiety is not particularly limited, but is, for example, 500 to 30,000, preferably 1,500 to 30,000, more preferably 2,000 to 10,000.
  • the number average molecular weight is a value measured by 19 F-NMR.
  • the number average molecular weight of the —Pf— moiety is 500 to 30,000, preferably 1,000 to 20,000, more preferably 1,500 to 15,000, even more preferably 2,000 to It can be 10,000, for example 3,000 to 5,000.
  • the number average molecular weight of the —Pf— moiety can be 4,000 to 30,000, preferably 5,000 to 10,000, more preferably 6,000 to 10,000.
  • Preferred examples of the Pf group-containing compound include, for example, the compounds shown below.
  • R 1 is preferably a C 1-4 alkyl group
  • W is —CF 2 —, —CF 2 CF 2 —, —CFClCF 2 —, —CF 2 CFCl—. Or it is preferably -CF (CF 3 )-.
  • W in the structure described as W, the left side is bonded to —CO—; the Pf group is bonded to the structure represented by W on the left side and —O— on the right side.
  • W represents —CH 2 CF 2 —, —CF 2 CH 2 —, —CFClCF 2 —, —CF 2 CFCl—, —CF 2 CF 2 CH 2 —, —CH 2 CF 2 CF 2 —, —CF (CF 3 ) CH 2 — or —CH 2 CF (CF 3 ) — is preferred.
  • the left side is bonded to HO—; the Pf group is bonded to the structure represented by W on the left side and —O— on the right side.
  • V is —CF 3 , —CF 2 CF 3 , —CFClCF 3 , —CF 2 CF 2 Cl, —CF 2 CF 2 CF 3 , —CF 2 H, —CF 2 CF 2 H or —CF 2 CF 2 CF 2 H is preferred.
  • the Pf group is bonded to the structure represented by V on the left side and —O— on the right side.
  • R 1 is preferably a C 1-4 alkyl group
  • W is —CF 2 —, —CF 2 CF 2 —, —CFClCF 2 —, —CF 2 CFCl—.
  • —CF (CF 3 ) CF 2 — —CH 2 CF 2 —, —CF 2 CH 2 —, —CF 2 CF 2 CH 2 —, —CH 2 CF 2 CF 2 —, —CF (CF 3 ) CH It is preferably 2 — or —CH 2 CF (CF 3 ) —.
  • the structure described as W is bonded to the structure represented by R 1 —O— on the left side; the Pf group has the structure represented by W on the left side and —O— on the right side. To each other.
  • Preferred specific examples of the Pf group-containing monocarboxylic acid compound represented by the above formula (2) include, for example, the compounds shown below.
  • R 1 is preferably a C 1-4 alkyl group
  • W is —CF 2 —, —CF 2 CF 2 —, —CFClCF 2 —, —CF 2 CFCl— Or —CF (CF 3 ) — is preferred
  • X is preferably —CF 2 —, —CF 2 CF 2 — or —CF (CF 3 ) —.
  • the structure represented by W is bonded to —CO— on the left side and the Pf group on the right side; the Pf group is a structure represented on the left side to W and the right side is —
  • Each of the structures represented by X is bonded to O-, and the structure represented by X is bonded to the structure represented by -O- on the left side and Y on the right side.
  • W is —CH 2 CF 2 —, —CFClCF 2 —, —CF 2 CFCl—, —CH 2 CF 2 CF 2 — or —CH 2 CF (CF 3 ) —.
  • X is, -CF 2 -, - CF 2 CF 2 - or -CF (CF 3) - and is preferably.
  • the structure represented by W is bonded to the HO— on the left side and the Pf group on the right side; the Pf group is a structure represented on the left side to the W and —O
  • Each of the structures represented by X is bonded to —O— on the left side and to the structure represented by Y on the right side.
  • V is CF 3 —, CF 3 CF 2 —, CF 3 CF 2 CF 2 —, CF 2 H—, HCF 2 CF 2 —, or HCF 2 CF 2 CF 2 —.
  • the Pf group is bonded to the structure represented by V on the left side and —O— on the right side; the structure represented by X has —O— on the left side and Each bond is bonded to the structure represented by Y.
  • R 1 is preferably a C 1-4 alkyl group
  • W is —CF 2 —, —CF 2 CF 2 —, —CFClCF 2 —, —CF 2 CFCl— , —CF (CF 3 ) CF 2 —, —CH 2 CF 2 —, —CF 2 CH 2 —, —CF 2 CF 2 CH 2 —, —CH 2 CF 2 CF 2 —, —CF (CF 3 ) CH 2 — or —CH 2 CF (CF 3 ) — is preferred;
  • X is —CF 2 —, —CF 2 CF 2 —, —CFClCF 2 —, —CF 2 CFCl—, or —CF (CF 3 )-Is preferred.
  • the structure represented by W is bonded to —O— on the left side and the Pf group on the right side; the Pf group is the structure represented on the left side to W and the right side is —
  • Each of the structures represented by X is bonded to O-, and the structure represented by X is bonded to the structure represented by -O- on the left side and Y on the right side.
  • the terminal CF 3 group ratio of the composition (a1) is preferably 20% or more, and more preferably 40% or more.
  • the terminal CF 3 group ratio may be 80% or less, specifically 60% or less.
  • the terminal CF 3 group ratio is present at the terminal of the compound with respect to the number of moles of terminal groups (total number of terminal moles) present at both terminals of the compound contained in the composition (a1). Means the proportion of moles of —CF 3 groups.
  • Examples of the end groups present at both ends of the compound include —CF 3 , —COOF, —COF, —COOH and the like.
  • the terminal CF 3 group ratio can be measured using 19 F-NMR.
  • the composition (a1) contains 10 to 90 parts by mass of Pf group-containing compound, 100 parts by mass of Pf group-containing compound, 100 parts by mass of Pf group-containing monocarboxylic acid compound, and Pf group-containing dicarboxylic acid compound. It is preferable to contain 20 to 70 parts by mass of the monocarboxylic acid compound containing 10 to 90 parts by mass of the dicarboxylic acid compound containing Pf group; 10 to 60 parts by mass of Pf group containing compound and Pf group containing monocarboxylic acid More preferably, the compound contains 30 to 60 parts by mass and the Pf group-containing dicarboxylic acid compound contains 10 to 60 parts by mass.
  • a Pf group-containing monocarboxylic acid compound has been obtained by separating a composition containing a Pf group-containing monocarboxylic acid compound. Therefore, in order to increase the yield of the Pf group-containing monocarboxylic acid compound, it has been demanded that the content of the Pf group-containing monocarboxylic acid compound contained in the composition before separation is high. However, in the production of a composition having a high content of the Pf group-containing monocarboxylic acid compound, it took time for the fluorination treatment. Furthermore, when the terminal CF 3 group ratio is increased in the fluorination treatment, the content of a compound having no carboxylic acid group (Pf group-containing compound) at the terminal in the composition can be increased. It was difficult to increase only the yield of the contained monocarboxylic acid compound.
  • the Pf group-containing dicarboxylic acid compound obtained in the step (I-1) for separating the composition (a1) is used in the step (A1) performed after the step (I-1). Fluorination treatment is performed to form a Pf group-containing monocarboxylic acid compound.
  • the composition (a1) as described above, a composition having a high content of the Pf group-containing dicarboxylic acid compound (low terminal CF 3 group ratio) can be used. Therefore, according to the method of the present invention, the time required for producing the composition (a1) can be shortened as compared with the conventional method as described above.
  • the number average molecular weight of the Pf group-containing monocarboxylic acid compound contained in the composition (a1) is preferably in the range of 500 to 30,000, more preferably in the range of 1,000 to 20,000, It is more preferably in the range of 1,500 to 15,000, particularly preferably in the range of 1,000 to 10,000, and more preferably in the range of 3,000 to 5,000.
  • the number average molecular weight is a value measured by 19 F NMR.
  • the molecular weight distribution of the Pf group-containing monocarboxylic acid compound contained in the composition (a1) is preferably 2.0 or less, more preferably 1.5 or less, and further preferably 1.3 or less. preferable.
  • the molecular weight distribution is expressed by weight average molecular weight / number average molecular weight, and is calculated using a value measured by gel permeation chromatography (GPC).
  • the step (I-1) is a step of separating the composition (a1).
  • the composition (a1) includes at least a Pf group-containing compound, a Pf group-containing monocarboxylic acid compound, and a Pf group-containing dicarboxylic acid compound as described above.
  • the step (I-1) is preferably a step of separating the Pf group-containing dicarboxylic acid compound and the Pf group-containing monocarboxylic acid compound from the composition (a1).
  • the step (I-1) is more preferably a step of separating the Pf group-containing dicarboxylic acid compound, the Pf group-containing monocarboxylic acid compound, and the Pf group-containing compound from the composition (a1).
  • the Pf group-containing dicarboxylic acid compound, the Pf group-containing monocarboxylic acid compound, and the Pf group-containing compound are separated from the composition (a1) by the step (I-1).
  • the yield of the Pf group-containing monocarboxylic acid compound obtained by the step (I-1) of this embodiment is, for example, 20 to 20 parts per 100 parts by mass of the composition (a1) to be used in the step (I-1). It may be 60 parts by weight, specifically 35-50 parts by weight.
  • Examples of means for separating the Pf group-containing dicarboxylic acid compound, Pf group-containing monocarboxylic acid compound, and Pf group-containing compound from the composition (a1) include filtration, washing, extraction, Soxhlet extraction, and column chromatography. Named, This method Mix the composition (a1); a fluorine atom-containing nonpolar solvent; and a polar stationary phase; Further, a fluorine atom-containing nonpolar solvent is introduced into the column, and then the fluorine stationary phase (for example, silica gel phase) packed in the column is in contact with the top surface of the fluorine atom-containing nonpolar solvent phase. Drain the atom-containing nonpolar solvent. Thereafter, the composition (a1) is charged from the top of the column.
  • a fluorine atom-containing nonpolar solvent for example, silica gel phase
  • a fluorine atom-containing nonpolar solvent is further added to the column, Using a nonpolar mobile phase, the separation means separates the Pf group-containing compound from the polar stationary phase, Then, separating the Pf group-containing monocarboxylic acid compound and the Pf group-containing dicarboxylic acid compound is included.
  • the method may include separating the Pf group-containing monocarboxylic acid compound after separation of the Pf group-containing compound and before separating the Pf group-containing dicarboxylic acid compound.
  • the separated Pf group-containing compound can be reused as a raw material for the hydrolysis reaction.
  • the polar stationary phase is preferably selected from the group consisting of aluminum oxide, silica gel, magnesium oxide, aluminum silicate, magnesium silicate, chemically modified silica gel, and diatomaceous earth.
  • a stationary phase having a polar group such as a group, an alkyl group or a fluoroalkyl group.
  • Examples of the silica gel that is a polar stationary phase include unmodified silica gel, amino group-containing silica gel, and cyano group-containing silica gel.
  • silica gel is preferably used as the polar stationary phase. Such an embodiment is preferable from the viewpoint of narrowing the molecular weight distribution of the obtained Pf group-containing monocarboxylic acid compound.
  • control of molecular weight distribution can be facilitated by using a column packed with silica gel. This is because, in column chromatography using silica gel, the molecular weight affects the movement time in the column, so the molecular weight distribution can be controlled by fractionating the solution discharged from the column and mixing the fractionated solution. This may be possible.
  • a commercial item may be used for the polar stationary phase.
  • a commercially available polar stationary phase for example, silica gel, manufactured by Fuji Silysia Chemical Co., Chromatolex (PSQ-100B), manufactured by Wako Pure Chemical Industries, Ltd., Wakogel (trademark) C-200, manufactured by Merck Co., Ltd., 115111 silica gel 60 Etc.
  • the Pf group-containing compound is less polar than the Pf group-containing monocarboxylic acid compound or the Pf group-containing dicarboxylic acid compound. Therefore, the Pf group-containing compound has a weak holding power with respect to the polar stationary phase, and can be separated by elution or the like in separation using a nonpolar mobile phase (for example, filtration).
  • nonpolar mobile phase a nonpolar mobile phase containing one or more fluorine atom-containing nonpolar solvents can be used.
  • the nonpolar mobile phase is selected from hydrochlorofluorocarbons, hydrofluoromonoethers, fluorine atom-containing aromatic solvents, perfluoroalkanes, hydrofluoroalkanes, hydrofluoroalkenes, and perfluoropolyethers that are fluorine-containing nonpolar solvents. It is more preferable to use at least one selected from the group consisting of hydrofluoromonoether, fluorine atom-containing aromatic solvent, and hydrofluoroalkane.
  • a polar mobile phase comprising one or more fluorine atom-containing polar solvents
  • a polar mobile phase comprising a combination of a fluorine atom-containing nonpolar solvent and a fluorine atom-containing polar solvent
  • a polar mobile phase comprising a combination of a fluorine atom-containing nonpolar solvent and a fluorine atom-free polar solvent, Either of these can be used.
  • a Pf group-containing compound and a Pf group-containing dicarboxylic acid compound or a Pf group-containing compound, a Pf group-containing monocarboxylic acid compound, and a Pf group-containing dicarboxylic acid compound, Can be better separated from the polar stationary phase, and the Pf group-containing dicarboxylic acid compound, or the Pf group-containing monocarboxylic acid compound and the Pf group-containing dicarboxylic acid compound requires a heating operation such as reflux. And can be taken out even at room temperature.
  • the concentration of these solvents is changed. It may be used (over a gradient).
  • fluorine atom-containing nonpolar solvent refers to a solvent that contains a fluorine atom and is nonpolar or low in polarity.
  • fluorine atom-containing nonpolar solvent include chlorofluorocarbon, hydrochlorofluorocarbon, hydrofluoromonoether, perfluoromonoether, perfluoroalkane, hydrofluoroalkane, hydrofluoroalkene, perfluoropolyether, perfluoroamine, and fluorine atom. Included alkenes, fluorine atom-containing aromatic solvents, fluorine atom-containing ketones, fluorine atom-containing esters, and the like.
  • chlorofluorocarbon examples include chlorofluorocarbons having 2 to 4 carbon atoms such as R-113 (C 2 F 3 Cl 3 ) and 2,2,3,3-tetrachlorohexafluorobutane.
  • hydrochlorofluorocarbon examples include hydrochlorofluorocarbons having 3 to 6 carbon atoms such as HCFC225 (CF 3 CF 2 CHCl 2 , CClF 2 CF 2 CHClF).
  • hydrofluoroether monoethers for example, C 3 F 7 OCH 3, C 4 F 9 OCH 3, C 4 F 9 OC 2 H 5, C 2 F 5 CF (OCH 3) C 3 F 7, CF 3 CH 2 OCF 2 CHF 2 , CHF 2 CF 2 CF 2 CH 2 OCH 3 , CF 3 CHFCF 2 OCH 2 CF 2 CHF 2 , CHF 2 CF 2 CH 2 OCHFCF 3 , CHF 2 OCH 2 CF 2 CHFCF 3 , CF 3 CHFCF 2 OCH 2 CF 2 CF 3 , CHF 2 OCH 2 CF 2 CHF 2 , CF 3 CHFCF 2 OCH 2 CF 3 , CHF 2 OCH 2 CF 2 CHF 2 , CF 3 CHFCF 2 OCH 2 CF 3 , CHF 2 CF 2 OCH 2 CF 2 CF 3 , CF 3 CH 2 OCH 2 CF 3 , CF 3 CH 2 OCH 2 CHF 2 , CF 3 CHFCF 2 OCH
  • perfluoromonoether examples include perfluoromonopropyl ethers such as perfluorodipropyl ether, perfluorodibutyl ether, perfluoro-2-trifluoromethyl-4-oxanonane, perfluorodipentyl ether, and the like. Is mentioned.
  • perfluoroalkane examples include perfluoroalkanes having 3 to 12 carbon atoms such as perfluorohexane, perfluorooctane perfluoroundecane, and perfluorododecane.
  • hydrofluoroalkane examples include CF 3 CH 2 CF 2 CH 3 , CF 3 CHFCHFC 2 F 5 , 1,1,2,2,3,3,4-heptafluorocyclopentane, CF 3 CF 2 CF 2 CF C 2-8 hydrofluoroalkanes such as 2 CH 2 CH 3 , CF 3 CF 2 CF 2 CF 2 CF 2 CH 2 CH 3 , CF 3 CF 2 CF 2 CF 2 CHF 2 .
  • the perfluoropolyether for example, Galden SV-90, HGalden ZV100 , Galden HT55, Galden HT70, GaldenHT90, Galden HT110, Galden HT135, CF 3 OCF 2 CF 2 OCF 3, CF 3 OCF 2 OCF 2 CF 2 OCF 3 CF 3 OCF 2 CF 2 OCF 2 CF 2 OCF 3 , CF 3 OCF 2 CF 2 OCF 2 OCF 2 CF 2 OCF 3 , CF 3 OCF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 3, etc. 10 perfluoropolyethers.
  • perfluoroamine examples include perfluoroamines having 3 to 15 carbon atoms such as perfluorotriethylamine, perfluorotripropylamine, perfluorotributylamine, and perfluorotriamylamine.
  • fluorine atom-containing alkene examples include fluorine atom-containing alkenes having 3 to 10 carbon atoms such as C 6 F 13 CH ⁇ CH 2 , C 4 F 9 CH ⁇ CH 2 , and C 8 F 15 CH ⁇ CH 2. It is done.
  • fluorine atom-containing aromatic solvent examples include fluorine atom-containing aromatic solvents having 6 to 12 carbon atoms such as m-xylene hexafluoride, perfluorobenzene, trifluorobenzene, and monofluorobenzene.
  • fluorine atom-containing ketone examples include fluorine atom-containing ketones having 2 to 10 carbon atoms such as methyl pentadecafluoroheptyl ketone, trifluoromethyl ethyl ketone, phenylheptafluoropropyl ketone, methylheptafluoropropyl ketone, and phenyltrifluoromethyl ketone. Is mentioned.
  • fluorine atom-containing ester examples include fluorine atom-containing esters having 3 to 10 carbon atoms such as ethyl trifluoroacetate, methyl trifluoroacetate, CF 3 CF 2 COOCH 3 , and CF 3 CF 2 COOCH 2 CH 3. .
  • fluorine atom-containing nonpolar solvents may be used alone or in combination of two or more.
  • Novec (TM) 7200 (C 4 F 9 OC 2 H 5), Novec ( TM), 7300 (C 2 F 5 CF (OCH 3) C 3 F 7), AC-6000 (C 6 F 13 C 2 H 5 ), FC-72 is preferably used.
  • the fluorine atom-containing nonpolar solvent is more preferably one having a boiling point in the range of 20 to 200 ° C.
  • the boiling point of the fluorine atom-containing nonpolar solvent is in the range of 20 to 200 ° C., there is an advantage that the solvent can be easily distilled off after the compound is separated.
  • fluorine atom-containing polar solvent refers to a solvent containing a fluorine atom and having polarity.
  • fluorine atom-containing polar solvent include solvents such as a fluorine atom-containing alcohol, a fluorine atom-containing carboxylic acid, and a fluorine atom-containing sulfonic acid.
  • fluorine atom-containing alcohol examples include CF 3 CH 2 OH, CF 3 CF 2 CH 2 OH, CF 3 CF 2 CF 2 CH 2 OH, hexafluoroisopropanol, HCF 2 CF 2 CH 2 OH, and HCF 2 CH 2 OH.
  • fluorine atom-containing carboxylic acid examples include trifluoroacetic acid, difluoroacetic acid, chlorodifluoroacetic acid, CF 3 CF 2 CO 2 H, CF 3 CF 2 CF 2 CO 2 H, HO 2 C (CF 2 ) 3 CO 2 H , HO 2 C (CF 2 ) 6 CO 2 H, H (CF 2 ) 6 CO 2 H, CF 3 OCF 2 CF 2 OCF 2 CO 2 H, CF 3 OCF 2 CF 2 OCF 2 OCF 2 CO 2 H, CF 3 OCF (CF 3 ) CF 2 OCF (CF 3 ) CO 2 H, CF 3 OCF (CF 3 ) CF 2 OCF 2 OCF (CF 3 ) CO 2 H, CF 3 OCF (CF 3 ) CF 2 OCF 2 OCF (CF 3 ) CO 2 H and other fluorine atom-containing carboxylic acids having 2 to 10 carbon atoms Is mentioned.
  • fluorine atom-containing sulfonic acid examples include fluorine atom-containing sulfonic acids having 1 to 10 carbon atoms such as trifluoromethanesulfonic acid, pentafluorooctanesulfonic acid, and perfluoroethoxyethanesulfonic acid.
  • fluorine atom-containing polar solvents may be used alone or in combination of two or more.
  • the fluorine atom-containing polar solvent preferably has a boiling point in the range of 20 to 200 ° C.
  • the boiling point of the fluorine atom-containing polar solvent is in the range of 20 to 200 ° C., there is an advantage that the solvent can be easily distilled off after the compound is separated.
  • the fluorine atom-containing carboxylic acid used in the fluorine atom-containing polar solvent does not include a Pf group-containing monocarboxylic acid compound and a Pf group-containing dicarboxylic acid compound.
  • a fluorine-atom-free polar solvent is a solvent that has polarity and does not contain a fluorine atom, that is, a solvent that has polarity and does not fall under the above-mentioned fluorine-atom-containing polar solvent.
  • polar solvents not containing fluorine atoms include carboxylic acid solvents such as acetic acid; phenol solvents such as phenol and cresol; sulfonic acid solvents such as methanesulfonic acid; dimethyl sulfoxide, sulfolane, acetonitrile, N, N-dimethylformamide, dimethylacetamide N-methylpyrrolidone and the like.
  • These fluorine atom-free polar solvents may be used alone or in combination of two or more.
  • fluorine atom-free polar solvent it is preferable to use one or more solvents selected from the group consisting of carboxylic acid solvents and sulfonic acid solvents.
  • methanol is not included in the above fluorine atom-free polar solvent.
  • Methanol is an elution solvent generally used as a polar mobile phase in column chromatography using a polar stationary phase.
  • the Pf group-containing monocarboxylic acid compound and the Pf group-containing dicarboxylic acid compound cannot be separated and eluted from the polar stationary phase when using a polar mobile phase containing methanol as a polar solvent. Therefore, the polar mobile phase contains one or more fluorine atom-containing polar solvents, a combination of fluorine atom-containing nonpolar solvents and fluorine atom-containing polar solvents, or fluorine atom-containing nonpolar solvents and fluorine atoms. What uses the combination of the non-containing polar solvent (however, methanol is not included) is used.
  • the polar mobile phase includes one or more fluorine atom-containing polar solvents, or includes a combination of a fluorine atom-containing nonpolar solvent and a fluorine atom-containing polar solvent, more preferably a fluorine atom.
  • a fluorine atom-containing nonpolar solvent and a fluorine atom-containing polar solvent, more preferably a fluorine atom.
  • a combination of a nonpolar solvent containing and a fluorine atom containing polar solvent is included.
  • the fluorine atom-containing nonpolar solvent is preferably at least one selected from the group consisting of a fluorine atom-containing ester, a fluorine atom-containing alkane, and a fluorine atom-containing ether
  • the fluorine atom-containing polar solvent is It is preferably at least one selected from the group consisting of a fluorine atom-containing alcohol and a fluorine atom-containing carboxylic acid.
  • the polar mobile phase includes one or more fluorine atom-containing polar solvents, or includes a combination of a fluorine atom-containing nonpolar solvent and a fluorine atom-containing polar solvent.
  • the fluorine atom-containing nonpolar solvent is preferably at least one selected from hydrochlorofluorocarbons, perfluoroalkanes, hydrofluoromonoethers, fluorine atom-containing aromatic solvents and hydrofluoroalkanes, and contains fluorine atoms.
  • the polar solvent is preferably at least one selected from a fluorine atom-containing alcohol and a fluorine atom-containing carboxylic acid.
  • the fluorine atom-containing nonpolar solvent is a hydrofluoromonoether, a fluorine atom-containing aromatic solvent, or a hydrofluorocarbon. It is preferably at least one selected from alkanes, and the polar solvent not containing fluorine atoms is preferably a carboxylic acid solvent.
  • the polar mobile phase used in the above step (I-1) is obtained by thin-layer chromatography using a Pf group-containing dicarboxylic acid compound, or a Pf group-containing monocarboxylic acid compound and a Pf group-containing dicarboxylic acid compound, using silica gel as a carrier.
  • the polar mobile phase is developed as a developing solvent, the Rf value of the Pf group-containing dicarboxylic acid compound, or the Pf group-containing monocarboxylic acid compound and the Pf group-containing dicarboxylic acid compound is 0.1 or more. It is preferable that the condition is satisfied.
  • the thin layer chromatography is a chromatography performed on a support using a fine powder provided in a thin layer as a stationary phase and a solvent as a mobile phase.
  • silica gel is used as a stationary phase used in thin layer chromatography.
  • examples of the silica gel include Merck's 105715 TLC glass plate silica gel 60F 254 .
  • the support include a glass plate, an aluminum sheet, and a plastic sheet.
  • An example of a specific procedure in thin layer chromatography is as follows.
  • a silica gel thin layer plate having a vertical direction of 5 cm is prepared.
  • a sample solution is prepared by dissolving 0.1 g of a Pf group-containing monocarboxylic acid compound and / or a Pf group-containing dicarboxylic acid compound in 1 ml of the above-mentioned fluorine atom-containing nonpolar solvent (for example, m-xylene hexafluoride).
  • 2 to 10 ⁇ l of sample liquid is spotted using a glass microcapillary at a position 5 mm from the lower end of the thin layer plate. This spot position becomes the development start point (origin).
  • the developing solvent is placed in the developing tank for thin layer chromatography in advance until it reaches a depth of 0.2 to 3.5 mm, and left in the developing tank until the vapor of the developing solvent is saturated. Gently place the thin plate on which the sample is spotted so that the origin is not directly immersed in the developing solvent. Cover the developing tank and let it stand until the tip of the solvent rising on the thin layer plate reaches a position of about 5 mm from the upper end of the thin layer plate. Next, the thin layer plate is taken out from the developing tank, and then heated on a hot plate to sufficiently dry the developing solvent.
  • FIG. 1 is a model diagram of a chromatogram obtained by thin layer chromatography.
  • the Rf value of the Pf group-containing monocarboxylic acid compound and the Pf group-containing dicarboxylic acid compound is 0.1 or more, separation from the polar stationary phase is possible. That is, when the polar mobile phase is developed as a developing solvent, the Pf group-containing monocarboxylic acid compound is separated from the polar stationary phase by the Rf value of the Pf group-containing monocarboxylic acid compound being 0.1 or more. And can be taken out. Moreover, when the Rf value of the Pf group-containing dicarboxylic acid compound is 0.1 or more, the Pf group-containing dicarboxylic acid compound can be separated and taken out from the polar stationary phase.
  • the Rf value is more preferably 0.1 to 0.8.
  • the fluorine atom-containing polar solvent is used alone as the polar mobile phase.
  • the Rf value may be larger.
  • fluorine atom-containing polar solvent promotes elimination of the Pf group-containing dicarboxylic acid compound, or the Pf group-containing monocarboxylic acid compound and the Pf group-containing dicarboxylic acid compound from the polar mobile phase, while fluorine
  • hydrofluoromonoether which is an atom-containing nonpolar solvent, dissolves well because of its high affinity with the Pf group-containing monocarboxylic acid compound and the Pf group-containing dicarboxylic acid compound.
  • the Rf value of the Pf group-containing dicarboxylic acid compound is 0.
  • fills the conditions used as 1 or more is mentioned.
  • the Rf value is more preferably from 0.1 to 0.5, and even more preferably from 0.1 to 0.4.
  • Another preferable embodiment is an embodiment in which the polar mobile phase to be used is changed depending on the separation stage.
  • the Rf value of the Pf group-containing monocarboxylic acid compound is 0.1 or more, and the Rf value of the Pf group-containing dicarboxylic acid compound is less than 0.1.
  • the Pf group-containing monocarboxylic acid compound can be more favorably separated.
  • the Pf group-containing dicarboxylic acid compound can be obtained by using a polar mobile phase in which the Rf value of the Pf group-containing dicarboxylic acid compound is 0.1 or more.
  • the separation of the Pf group-containing monocarboxylic acid compound and the Pf group-containing dicarboxylic acid compound means a state of being taken out in the following state.
  • the separation and removal of the Pf group-containing monocarboxylic acid compound means that the molar ratio of the Pf group-containing monocarboxylic acid compound is the state before separation in the state separated and removed from the mixture by the method of the present invention.
  • the separation and removal of the Pf group-containing dicarboxylic acid compound means that the molar ratio of the Pf group-containing dicarboxylic acid compound in the state separated and removed from the mixture by the method of the present invention is greater than that before the separation.
  • step (A1) will be described.
  • the step (A1) is a step of obtaining a Pf group-containing monocarboxylic acid by fluorinating the Pf group-containing dicarboxylic acid compound separated in the step (I-1).
  • the yield of the Pf group-containing monocarboxylic acid compound can be improved by performing the step (A1).
  • the Pf group-containing dicarboxylic acid compound used in the step (A1) is separated by the step (I-1) as described above. That is, the “Pf group-containing dicarboxylic acid compound” can be provided as a mixture containing a Pf group-containing dicarboxylic acid compound, for example, a mixture containing a Pf group-containing monocarboxylic acid compound and a Pf group-containing dicarboxylic acid compound.
  • the terminal CF 3 group ratio may be 1% or more, or 10% or more.
  • the terminal CF 3 group ratio may be 50% or less, or 30% or less.
  • the terminal CF 3 group ratio is, for example, 1% to 40%, specifically 10% to 30%.
  • the terminal CF 3 group ratio is the ratio of the Pf group-containing monocarboxylic acid compound and the Pf group-containing dicarboxylic acid compound contained in the mixture. It means the ratio of the number of moles of CF 3 groups to the total number of moles of terminal groups present at both ends.
  • the conditions for the fluorination treatment are not particularly limited.
  • the fluorination treatment can be performed by bringing a Pf group-containing dicarboxylic acid compound (or a composition containing a Pf group-containing dicarboxylic acid compound) into contact with a fluorine-containing compound.
  • produces a fluorine radical under fluorination process conditions is mentioned.
  • the fluorine radical source include F 2 , CoF 3 , AgF 2 , UF 6 , OF 2 , N 2 F 2 , CF 3 OF, and halogen fluoride (eg, IF 5 , ClF 3 ).
  • the fluorine radical source such as F 2 may have a concentration of 100%, but is preferably diluted to 5 to 50% by mass, and diluted to 15 to 30% by mass. More preferred.
  • the fluorine radical source can be mixed with an inert gas (specifically, when the fluorine radical source is gaseous)
  • the fluorine radical source and the inert gas are used for safety. It is preferably mixed and diluted to 5 to 50% by mass, more preferably 15 to 30% by mass.
  • the inert gas include nitrogen gas, helium gas, and argon gas. Nitrogen gas is preferable from the economical viewpoint.
  • the fluorination treatment is preferably performed at 50 ° C. to 200 ° C., more preferably 80 ° C. to 150 ° C.
  • the fluorination treatment is generally performed for 0.5 to 50 hours, preferably 1 to 20 hours.
  • the fluorination treatment is preferably performed at 100 to 140 ° C. for 2 to 10 hours.
  • the terminal CF 3 group ratio of the mixture obtained by the fluorination treatment in the step (A1) is preferably 20% or more, and more preferably 40% or more.
  • the terminal CF 3 group ratio may be 80% or less, specifically 60% or less.
  • the terminal CF 3 group ratio is the terminal existing at both ends of the Pf group-containing compound, the Pf group-containing monocarboxylic acid compound and the Pf group-containing dicarboxylic acid compound contained in the mixture. It means the ratio of the number of moles of CF 3 groups to the total number of moles of groups.
  • the measurement conditions for the terminal CF 3 group ratio are as described above.
  • the terminal CF 3 group ratio in the mixture obtained by the fluorination treatment in the step (A1) is preferably 10% or more, and more preferably 20% or more.
  • the terminal CF 3 group ratio is preferably 70% or less, more preferably 60% or less, further preferably 50% or less, and particularly preferably 45% or less.
  • the terminal CF 3 group ratio is preferably 20% to 50%, and more preferably 25% to 45%.
  • the CF 3 group ratio is the total number of moles of terminal groups present at both terminals of the Pf group-containing compound, Pf group-containing monocarboxylic acid compound and Pf group-containing dicarboxylic acid compound contained in the mixture obtained in the step (A1). It means the ratio of the number of moles of CF 3 groups to
  • the Pf group-containing monocarboxylic acid compound contained in the mixture obtained by the step (A1) preferably has a molecular weight distribution of 2 or less, more preferably 1.5 or less, and 1.3 or less. More preferably.
  • the number average molecular weight of the Pf group-containing monocarboxylic acid compound contained in the mixture obtained by the step (A1) is preferably in the range of 500 to 30,000, and in the range of 1,000 to 20,000. Is more preferably in the range of 1,500 to 15,000, more preferably in the range of 1,000 to 10,000, and more preferably in the range of 3,000 to 5,000. preferable.
  • the Pf group-containing dicarboxylic acid compound (or the composition containing the Pf group-containing dicarboxylic acid compound) separated in the step (I-1) is treated.
  • the separation in the step (I-1) the content of the compound having a high molecular weight or a low molecular weight is lowered.
  • the step (A1) is a mixture obtained by fluorinating a Pf group-containing dicarboxylic acid compound (or a composition containing a Pf group-containing dicarboxylic acid compound) (for example, a Pf-containing monocarboxylic acid compound and a Pf-containing dicarboxylic acid compound). It is preferable to further comprise separating at least the Pf-containing monocarboxylic acid compound from the mixture containing
  • the yield of the Pf group-containing monocarboxylic acid compound after the step (A1) is 70 parts by mass or more with respect to 100 parts by mass of the composition (a1) subjected to the step (I-1). Is more preferably 80 parts by mass or more, and particularly preferably 85 parts by mass or more. In this embodiment, the yield of the Pf group-containing monocarboxylic acid compound after the step (A1) is 70 to 100 parts by mass with respect to 100 parts by mass of the composition (a1) subjected to the above step (I-1). It is preferably in the range, and more preferably in the range of 85 to 100 parts by mass.
  • FIG. 3 shows one embodiment of a method for producing the Pf group-containing monocarboxylic acid compound of the present invention.
  • the ether group-containing compound, monocarboxylic acid compound, and dicarboxylic acid compound in FIG. 3 mean a Pf group-containing compound, a Pf group-containing monocarboxylic acid compound, and a Pf group-containing dicarboxylic acid compound, respectively.
  • the method for producing the Pf group-containing monocarboxylic acid compound of this embodiment includes: Separating the composition (a2) (I-2), The Pf group-containing dicarboxylic acid compound obtained by the above separation is fluorinated, and at least a Pf group-containing monocarboxylic acid compound represented by the formula (2) and a Pf group-containing dicarboxylic acid compound represented by the formula (3) And a step (A2) comprising separating a Pf group-containing monocarboxylic acid compound represented by the formula (2) and a Pf group-containing dicarboxylic acid compound represented by the formula (3) from the mixture. And a step (B2) of obtaining a mixture containing the Pf group-containing monocarboxylic acid compound represented by the formula (2) by fluorinating the Pf group-containing dicarboxylic acid compound obtained by the separation in the step (A2).
  • Step (I-2) and Step (A2) are embodiments of Step (I) and Step (A), respectively.
  • the composition (a2) corresponds to the composition (a).
  • composition (a2) may be obtained by a step of fluorinating the Pf group-containing dicarboxylic acid compound. This step can be performed in the same manner as in step (Z1).
  • Step (I-2) can be performed in the same manner as Step (I-1).
  • the composition (a2) has the same meaning as the composition (a1).
  • step (I-2) column chromatography is preferably used.
  • the conditions for column chromatography are as described above.
  • the terminal CF 3 group ratio of the composition obtained in the step (A2) is preferably 10% or more, and more preferably 20% or more.
  • the terminal CF 3 group ratio is preferably 70% or less, more preferably 60% or less, further preferably 50% or less, and particularly preferably 45% or less.
  • the terminal CF 3 group ratio is preferably 25% to 50%, more preferably 30% to 45%.
  • the terminal CF 3 group ratio is present in both ends of the Pf group-containing compound, the Pf group-containing monocarboxylic acid compound and the Pf group-containing dicarboxylic acid compound contained in the composition in the step (A2). It means the ratio of the number of moles of CF 3 group to the total number of moles of terminal groups.
  • Step (A2) may be repeated a plurality of times.
  • the Pf group-containing dicarboxylic acid compound used in the step (B2) is separated by the step (A2) as described above. That is, the “Pf group-containing dicarboxylic acid compound” can be provided as a mixture containing a Pf group-containing dicarboxylic acid compound, for example, a mixture containing a Pf group-containing monocarboxylic acid compound and a Pf group-containing dicarboxylic acid compound.
  • the terminal CF 3 group ratio may be 1% or more, or 10% or more.
  • the terminal CF 3 group ratio may be 50% or less, or 30% or less.
  • the terminal CF 3 group ratio is, for example, 1% to 40%, specifically 10% to 30%.
  • the terminal CF 3 group ratio is the ratio of both the Pf group-containing monocarboxylic acid compound and the Pf group-containing dicarboxylic acid compound contained in the mixture in the mixture containing the Pf group-containing monocarboxylic acid compound and the Pf group-containing dicarboxylic acid compound. It means the ratio of the number of moles of CF 3 groups to the total number of moles of terminal groups present at the terminal.
  • the fluorination treatment in the above step (B2) can be performed in the same manner as the fluorination treatment in the step (A1).
  • the Pf group-containing monocarboxylic acid compound contained in the mixture obtained by the fluorination treatment in the step (B2) is preferably 10% or more, preferably 20% or more, in terms of molar ratio with respect to the mixture. 70% or less, 60% or less, 50% or less, or 45% or less.
  • the Pf group-containing monocarboxylic acid compound may be in the range of 20% to 50% or in the range of 25% to 45% by molar ratio with respect to the mixture.
  • the step (B2) further includes separating at least the Pf group-containing monocarboxylic acid compound from the mixture containing the Pf group-containing dicarboxylic acid compound after the fluorination treatment. Separation in the step (B2) can be performed in the same manner as the separation in the step (A1). For example, column chromatography can be used.
  • the yield of the Pf group-containing monocarboxylic acid compound can be further improved by performing the step (B2).
  • the yield of the Pf group-containing monocarboxylic acid compound is preferably 70 parts by mass or more with respect to 100 parts by mass of the composition (a2) to be used in the step (I-2). More preferably, it is more than 85 parts by mass.
  • FIG. 4 shows one embodiment of a method for producing the Pf group-containing monocarboxylic acid compound of the present invention.
  • an ether group-containing compound, a monocarboxylic acid compound, and a dicarboxylic acid compound mean a Pf group-containing compound, a Pf group-containing monocarboxylic acid compound, and a Pf group-containing dicarboxylic acid compound, respectively.
  • This aspect is characterized in that after the step (B3), the mixture obtained in the step (B3) is further used as at least part of the composition (a3) and reused.
  • the step (B3) and the composition (a3) correspond to the step (B) and the composition (a), respectively.
  • the method for producing the Pf group-containing monocarboxylic acid compound of this embodiment includes: Separating the composition (a3) (I-3), The Pf group-containing dicarboxylic acid compound obtained by the above separation is fluorinated to obtain a mixture containing at least the Pf group-containing monocarboxylic acid compound and the Pf group-containing dicarboxylic acid compound, and the Pf group-containing monocarboxylic acid compound is obtained from the mixture.
  • Step (I-3) and step (A3) are embodiments of step (I) and step (A), respectively.
  • the composition (a3) corresponds to the composition (a).
  • Step (I-3), Step (A3), and Step (B3) can be performed in the same manner as Step (I-1), Step (A1), and Step (B2), respectively.
  • the composition (a3) has the same meaning as the composition (a1).
  • step (I-3) and step (A3) is preferably performed using column chromatography.
  • the cycle of the step (I-3), the step (A3) and the step (B3) using the composition (a3) containing the mixture obtained in the step (B3) is preferably performed a plurality of times.
  • the Pf group-containing monocarboxylic acid is obtained by reusing the Pf group-containing dicarboxylic acid, the yield of the Pf group-containing monocarboxylic acid compound can be improved.
  • Composition (a3) may be a composition obtained by fluorination treatment of a Pf group-containing dicarboxylic acid compound. That is, the method of this aspect may further include a step of fluorinating the Pf group-containing dicarboxylic acid compound to obtain the composition (a3). This step can be performed in the same manner as in step (Z1).
  • FIG. 5 shows one embodiment of a method for producing the Pf group-containing monocarboxylic acid compound of the present invention.
  • an ether group-containing compound, a monocarboxylic acid compound, and a dicarboxylic acid compound mean a Pf group-containing compound, a Pf group-containing monocarboxylic acid compound, and a Pf group-containing dicarboxylic acid compound, respectively.
  • the Pf group-containing dicarboxylic acid compound is reused as at least part of the Pf group-containing dicarboxylic acid compound that is a raw material for forming the composition (a4) in the step (Z4).
  • Step (Z4) is an embodiment of step (Z).
  • the composition (a4) corresponds to the composition (a).
  • the method for producing the Pf group-containing monocarboxylic acid compound of this embodiment includes: Fluorinating the Pf group-containing dicarboxylic acid compound to obtain a composition (a4) (Z4); Separating the composition (a4) (I-4), A fluorination treatment is performed on the Pf group-containing dicarboxylic acid compound to obtain a mixture including at least the Pf group-containing monocarboxylic acid compound and the Pf group-containing dicarboxylic acid compound.
  • a step (A4) including separating the dicarboxylic acid compound, and a raw material for forming the composition (a4) in the step (Z4) from the Pf group-containing dicarboxylic acid compound separated in the step (A4) Using at least a part of the Pf group-containing dicarboxylic acid compound, and performing the step (Z4), the step (I-4), and the step (A4) again.
  • Step (I-4) and Step (A4) are embodiments of Step (I) and Step (A), respectively.
  • the composition (a4) corresponds to the composition (a).
  • Step (Z4), Step (I-4), and Step (A4) can be performed in the same manner as Step (Z1), Step (I-1), and Step (A1), respectively.
  • Composition (a4) contains at least a Pf group-containing compound, a Pf group-containing monocarboxylic acid compound, and a Pf group-containing dicarboxylic acid compound.
  • the terminal CF 3 group ratio of the composition (a4) is preferably 20% or more, and more preferably 40% or more.
  • the terminal CF 3 group ratio may be 80% or less.
  • the terminal CF 3 group ratio exists in both ends of the Pf group-containing compound, the Pf group-containing monocarboxylic acid compound and the Pf group-containing dicarboxylic acid compound contained in the composition (a4) in the composition (a4). It means the ratio of the number of moles of CF 3 groups to the total number of moles of end groups. Examples of the terminal group include —CF 3 , —COOF, —COF, —COOH and the like.
  • the terminal CF 3 group ratio can be measured using 19 F-NMR.
  • the terminal CF 3 group ratio of the composition (a4) is preferably in the range of 20% to 80%, and more preferably in the range of 40% to 60%.
  • the composition (a4) contains 30 to 70 parts by mass of the Pf group-containing monocarboxylic acid compound with respect to 100 parts by mass in total of the Pf group-containing compound, the Pf group-containing monocarboxylic acid compound, and the Pf group-containing dicarboxylic acid compound. It is preferably included, and more preferably 40 to 60 parts by mass.
  • the composition (a4) contains 10 to 50 parts by mass of the Pf group-containing dicarboxylic acid compound with respect to 100 parts by mass in total of the Pf group-containing compound, the Pf group-containing monocarboxylic acid compound, and the Pf group-containing dicarboxylic acid compound.
  • the content is preferably 15 to 45 parts by mass.
  • the composition (a4) comprises 10 to 40 parts by mass of the Pf group-containing compound, 100 parts by mass of the Pf group-containing compound, 100 parts by mass of the Pf group-containing monocarboxylic acid compound, and Pf group-containing dicarboxylic acid compound. It is preferable to contain 30 to 70 parts by mass of the containing monocarboxylic acid compound and 10 to 50 parts by mass of the Pf group-containing dicarboxylic acid compound; 10 to 40 parts by mass of the Pf group-containing compound and Pf group-containing monocarboxylic acid More preferably, the compound contains 40 to 60 parts by mass and the Pf group-containing dicarboxylic acid compound contains 15 to 45 parts by mass.
  • the number average molecular weight of the Pf group-containing monocarboxylic acid compound contained in the composition (a4) is preferably in the range of 500 to 30,000, more preferably in the range of 1,000 to 20,000, It is more preferably in the range of 1,500 to 15,000, particularly preferably in the range of 1,000 to 10,000, and more preferably in the range of 3,000 to 5,000.
  • the number average molecular weight is a value measured by 19 F NMR.
  • the molecular weight distribution of the Pf group-containing monocarboxylic acid compound contained in the composition (a4) is preferably 2.0 or less, more preferably 1.5 or less, and further preferably 1.3 or less. preferable.
  • the molecular weight distribution is expressed by weight average molecular weight / number average molecular weight, and is calculated using a value measured by gel permeation chromatography (GPC).
  • step (I-4) and step (A4) is preferably performed using column chromatography.
  • step (Z4) it is preferable to repeat the cycle of step (Z4), step (I-4) and step (A4) a plurality of times.
  • the Pf group-containing monocarboxylic acid can be obtained by reusing the Pf group-containing dicarboxylic acid, the yield of the Pf group-containing monocarboxylic acid compound can be improved.
  • the terminal CF 3 group ratio was determined using 19 F-NMR. Specifically, the Pf group-containing compound represented by the formula (1), the Pf group-containing monocarboxylic acid compound represented by the formula (2), and the Pf group-containing dicarboxylic acid compound represented by the formula (3) The ratio of the number of moles of terminal CF 3 groups to the total number of moles of terminal groups was determined.
  • Example 1 The (poly) ether group-containing dicarboxylic acid compound (D1) was fluorinated at 120 ° C., and the sample after fluorination was prepared so that the terminal CF 3 group ratio was 50% by 19 F-NMR.
  • the obtained sample after the fluorination treatment was treated as follows using silica gel chromatography. 1500 g of silica gel (PSQ100B; manufactured by Fuji Silysia Chemical Co., Ltd .: average particle size: 100 ⁇ m, polar stationary phase) was placed in a 14 cm diameter column, and passed through HFE7200. Further, 500 g of a sample after fluorination treatment is put, and three kinds of solvents are sequentially circulated as shown below, and a fraction is collected to obtain a (poly) ether compound and a (poly) ether group-containing monocarboxylic acid compound. The sample after the fluorination treatment containing the (poly) ether group-containing dicarboxylic acid compound was purified.
  • the compound containing the (poly) ether group is easily separated from the silica gel in the order of (poly) ether compound, (poly) ether group-containing monocarboxylic acid compound, and (poly) ether group-containing dicarboxylic acid compound.
  • HFE7200 Novec TM 7200; hydrofluoroether C 4 F 9 OC 2 H 5 ): 8755 g
  • HFE7200: 5FP (2,2,3,3,3-pentafluoro-1-propanol ) 9: 1 (volume basis): 8000 g
  • HFE7200: 5FP 1: 1 (volume basis): 8000 g.
  • the fraction was collected by dividing the solution distilled from the column outlet into 30 fractions. The obtained fraction was distilled off for each fraction using a rotary evaporator, and then the remaining liquid was measured using 19 F-NMR. The fraction of the compound having a (poly) ether group in each fraction was measured. Information on type, content and molecular weight was obtained.
  • the liquid remaining after fractionation and distillation was mixed and prepared so that the content of the (poly) ether group-containing monocarboxylic acid compound was 90% or more.
  • the liquid (mixture 1) obtained after the preparation contained 90% of a (poly) ether group-containing monocarboxylic acid compound, and the remainder was a (poly) ether group-containing dicarboxylic acid compound.
  • the molecular weight of the (poly) ether group-containing monocarboxylic acid compound contained in the mixture 1 was 4370, and the molecular weight distribution of the compound was 1.15.
  • the yield of the (poly) ether group-containing monocarboxylic acid compound contained in the mixture 1 with respect to D1 was 40% (molar ratio).
  • the mixture obtained after the fractionation includes a (poly) ether group-containing monocarboxylic acid compound and a (poly) ether group-containing dicarboxylic acid compound, and the (poly) ether group-containing monocarboxylic acid compound contained in the mixture
  • the molecular weight of the compound was 3840, and the molecular weight distribution of the compound was 1.12.
  • the terminal CF 3 group ratio of this mixture was 25%.
  • This mixture was fluorinated at 120 ° C. and prepared such that the terminal CF 3 group ratio in the mixture was 50% by 19 F-NMR. Then, it separated using column chromatography similarly to the above.
  • the mixture (mixture 2) obtained after the separation contained 90% of a (poly) ether group-containing monocarboxylic acid compound, and the remainder was a (poly) ether group-containing dicarboxylic acid compound.
  • the molecular weight of the (poly) ether group-containing monocarboxylic acid compound contained in the mixture was 4257, and the molecular weight distribution of the compound was 1.12.
  • the yield of the (poly) ether group-containing monocarboxylic acid compound contained in the mixture 2 with respect to D1 was 40% (molar ratio).
  • a process for producing a (poly) ether group-containing monocarboxylic acid compound A process for producing a (poly) ether group-containing monocarboxylic acid compound.
  • R 1 O—CO—W— group R 1 O—CO—W—O— group, HO—W— group, HO—W—O— group
  • R 1 O Represents a —W— group, a R 1 O—W—O— group, a V— group, or a V—O— group
  • R 1 independently represents an alkyl group at each occurrence
  • W represents a bond or a divalent organic group independently at each occurrence
  • V independently represents each alkyl group having 1 to 16 carbon atoms in each occurrence
  • Z independently represents Y—X— or Y—X—O— at each occurrence
  • Y represents a carboxylic acid group
  • X independently represents a bond or a divalent organic group at each occurrence
  • Pf is independently at each occurrence, the formula: - (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 X 1 6) d - (OC 2 F 4)
  • step (A) the (poly) ether group-containing dicarboxylic acid compound is fluorinated, and represented by at least the (poly) ether group-containing monocarboxylic acid compound represented by formula (2) and formula (3).
  • (Poly) ether group-containing dicarboxylic acid compound is obtained, from which the (poly) ether group-containing monocarboxylic acid compound represented by formula (2) and formula (3) ( Separating the poly) ether group-containing dicarboxylic acid compound, The method further includes a step (B) of obtaining a mixture containing the (poly) ether group-containing monocarboxylic acid compound represented by the formula (2) by fluorinating the (poly) ether group-containing dicarboxylic acid compound obtained by the separation.
  • the mixture obtained in the step (B) is further used as at least part of the composition (a), and again using the composition (a), the step (I) and the step The method according to [4], comprising performing (A) and step (B).
  • the method according to [5] comprising repeating the cycle of the step (I), the step (A) and the step (B) using the composition (a) containing the mixture obtained in the step (B) a plurality of times. the method of.
  • the (poly) ether group-containing dicarboxylic acid compound is fluorinated, and is represented by at least the (poly) ether group-containing monocarboxylic acid compound represented by the formula (2) and the formula (3).
  • step (A) To obtain a mixture containing (poly) ether group-containing dicarboxylic acid compound and to separate at least (poly) ether group-containing monocarboxylic acid compound and (poly) ether group-containing dicarboxylic acid compound from the mixture Including
  • the (poly) ether group-containing dicarboxylic acid compound separated in step (A) is at least a part of the (poly) ether group-containing dicarboxylic acid compound which is a raw material for forming the composition (a) in step (Z).
  • the yield of the Pf group-containing monocarboxylic acid compound can be improved relatively easily.
  • the method of the present invention can contribute to the reduction of the production cost of the Pf group-containing monocarboxylic acid compound.
  • the Pf group-containing monocarboxylic acid compound is a compound that can be used in many fields such as the automobile, aircraft, semiconductor, and space fields.

Abstract

Provided is a method for producing a (poly)ether group-containing monocarboxylic acid compound comprising: a step (I) for separating a composition (a) containing at least a poly(ether) group-containing compound represented by formula (1), a (poly)ether group-containing monocarboxylic acid compound represented by formula (2), and a (poly)ether group-containing dicarboxylic acid compound represented by formula (3); and a step (A)for obtaining a mixture containing the (poly)ether group-containing monocarboxylic acid compound represented by formula (2) by fluorinating the (poly)ether group-containing dicarboxylic acid compound represented by formula (3) obtained by said separation (symbols in the formulas are as defined in the description).

Description

（ポリ）エーテル基含有モノカルボン酸化合物の製造方法Process for producing (poly) ether group-containing monocarboxylic acid compound
　本発明は、（ポリ）エーテル基含有モノカルボン酸化合物の製造方法に関する。 The present invention relates to a method for producing a (poly) ether group-containing monocarboxylic acid compound.
　パーフルオロ（ポリ）エーテル基を有する化合物は、優れた撥水性、撥油性、防汚性、耐熱性、低温特性、耐油性、耐溶剤性、耐薬品性、潤滑性、低摩擦性、耐摩耗性、離型性などを提供し得ることが知られている。パーフルオロ（ポリ）エーテル基を有する化合物を含む機能性薄膜は、例えばガラス、プラスチック、繊維、金属、建築資材など種々多様な基材に使用されている。パーフルオロ（ポリ）エーテル基を有する化合物を含むフッ素系エラストマーは、例えば自動車、航空機、半導体、宇宙分野などの厳しい環境下において、耐久性、信頼性を保つ材料として使用されている。パーフルオロ（ポリ）エーテル基を有する化合物は、他にも、アクリル樹脂、ポリウレタン、エポキシ樹脂、ポリエステル樹脂、積層樹脂などの樹脂、および塗料、化粧品などの中間体化合物、または添加剤として使用することによって、優れた性能を付与させ発現させることが可能となる。そのため、様々な構造を有するパーフルオロ（ポリ）エーテル基を有する化合物を合成する手法の探索が精力的に行われている。このようなパーフルオロ（ポリ）エーテル基を有する化合物の合成において、パーフルオロ（ポリ）エーテル基含有カルボン酸化合物は、原料化合物または中間体として重要な化合物である。パーフルオロ（ポリ）エーテル基含有カルボン酸化合物として、片末端のみにカルボン酸基を有する、パーフルオロ（ポリ）エーテル基含有モノカルボン酸化合物と、両末端にカルボン酸基を有する、パーフルオロ（ポリ）エーテル基含有ジカルボン酸化合物とが挙げられる。 Compounds with perfluoro (poly) ether groups have excellent water repellency, oil repellency, antifouling properties, heat resistance, low temperature properties, oil resistance, solvent resistance, chemical resistance, lubricity, low friction, wear resistance It is known that it can provide the property, releasability, etc. Functional thin films containing a compound having a perfluoro (poly) ether group are used for various substrates such as glass, plastic, fiber, metal, and building materials. A fluorine-based elastomer containing a compound having a perfluoro (poly) ether group is used as a material that maintains durability and reliability in severe environments such as automobiles, aircraft, semiconductors, and space fields. Other compounds having a perfluoro (poly) ether group should be used as intermediate compounds or additives such as acrylic resins, polyurethanes, epoxy resins, polyester resins, laminated resins, and paints and cosmetics. Thus, it is possible to impart and develop excellent performance. Therefore, the search for a method for synthesizing compounds having perfluoro (poly) ether groups having various structures has been energetically performed. In the synthesis of such a compound having a perfluoro (poly) ether group, the perfluoro (poly) ether group-containing carboxylic acid compound is an important compound as a raw material compound or an intermediate. As a perfluoro (poly) ether group-containing carboxylic acid compound, a perfluoro (poly) ether group-containing monocarboxylic acid compound having a carboxylic acid group only at one end, and a perfluoro (poly And ether group-containing dicarboxylic acid compounds.
　原料化合物または中間体は一般に、より高い純度を有していることが望まれる。より高い純度を有していることによって、反応によって得られた生成物の精製が容易となり、さらに、反応において生じうる副生成物・未同定物の生成を低減することができ、より良好な性能を有する目的物を得ることができるためである。このため、パーフルオロ（ポリ）エーテル基を有する化合物の原料化合物または中間体として用いられる化合物の分離方法として、これまでにも様々な検討が行われてきた。 Generally, it is desired that the raw material compound or intermediate has higher purity. Higher purity facilitates purification of the product obtained by the reaction, and further reduces the generation of by-products and unidentified products that can occur in the reaction, resulting in better performance. This is because an object having the above can be obtained. For this reason, various examinations have been made so far as a method for separating a compound used as a raw material compound or an intermediate of a compound having a perfluoro (poly) ether group.
　例えば、特許文献１には、分子末端にカルボン酸基を有しないパーフルオロ（ポリ）エーテル基含有化合物、パーフルオロ（ポリ）エーテル基含有モノカルボン酸化合物およびパーフルオロ（ポリ）エーテル基含有ジカルボン酸化合物を含む混合物から、それぞれの化合物を分離する方法が記載されている。 For example, Patent Document 1 discloses a perfluoro (poly) ether group-containing compound having no carboxylic acid group at the molecular end, a perfluoro (poly) ether group-containing monocarboxylic acid compound, and a perfluoro (poly) ether group-containing dicarboxylic acid. A method for separating each compound from a mixture containing the compounds is described.
特開２０１５－１６４９０８号公報JP 2015-164908 A
　特許文献１に記載されているパーフルオロ（ポリ）エーテル基を有する化合物のうち、パーフルオロ（ポリ）エーテル基含有モノカルボン酸化合物が最も使用され得る化合物であり、その収率の向上が望まれる。 Of the compounds having a perfluoro (poly) ether group described in Patent Document 1, a perfluoro (poly) ether group-containing monocarboxylic acid compound is the most usable compound, and an improvement in its yield is desired. .
　本発明の目的は、フッ素原子を含有する（ポリ）エーテル基を有する化合物の中でも最も使用され得るフッ素原子を含有する（ポリ）エーテル基含有モノカルボン酸化合物の収率を向上させることにある。 An object of the present invention is to improve the yield of a (poly) ether group-containing monocarboxylic acid compound containing a fluorine atom that can be most used among compounds having a (poly) ether group containing a fluorine atom.
　本発明の要旨によれば、以下の方法が提供される。
　少なくとも下記式（１）で表される（ポリ）エーテル基含有化合物、下記式（２）で表される（ポリ）エーテル基含有モノカルボン酸化合物、および、下記式（３）で表される（ポリ）エーテル基含有ジカルボン酸化合物を含む組成物（ａ）を、分離する工程（Ｉ）、および
　上記分離により得られる式（３）で表される（ポリ）エーテル基含有ジカルボン酸化合物をフッ素化処理し、式（２）で表される（ポリ）エーテル基含有モノカルボン酸化合物を含む混合物を得る工程（Ａ）、
を含む、（ポリ）エーテル基含有モノカルボン酸化合物を製造する方法。
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000006
 ［式中：
　Ａは、各出現においてそれぞれ独立して、Ｒ１Ｏ－ＣＯ－Ｗ－基、Ｒ１Ｏ－ＣＯ－Ｗ－Ｏ－基、ＨＯ－Ｗ－基、ＨＯ－Ｗ－Ｏ－基、Ｒ１Ｏ－Ｗ－基、Ｒ１Ｏ－Ｗ－Ｏ－基、Ｖ－基、またはＶ－Ｏ－基を表し；
　Ｒ１は、各出現においてそれぞれ独立して、アルキル基を表し；
　Ｗは、各出現においてそれぞれ独立して、結合手または２価の有機基を表し；
　Ｖは、各出現においてそれぞれ独立して、炭素原子数１～１６のアルキル基を表し；
　Ｚは、各出現においてそれぞれ独立して、Ｙ－Ｘ－、またはＹ－Ｘ－Ｏ－を表し；
　Ｙは、カルボン酸基を表し；
　Ｘは、各出現においてそれぞれ独立して、結合手または２価の有機基を表し；
　Ｐｆは、各出現においてそれぞれ独立して、式：
－（ＯＣ６Ｆ１２）ａ－（ＯＣ５Ｆ１０）ｂ－（ＯＣ４Ｆ８）ｃ－（ＯＣ３Ｘ１ ６）ｄ－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－
（式中、ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して０以上２００以下の整数であって、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は少なくとも１であり、ａ、ｂ、ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意であり、Ｘ１は、各出現においてそれぞれ独立して、水素原子、フッ素原子または塩素原子である。）
で表される基である。］ According to the gist of the present invention, the following method is provided.
At least a (poly) ether group-containing compound represented by the following formula (1), a (poly) ether group-containing monocarboxylic acid compound represented by the following formula (2), and the following formula (3) ( Step (I) for separating the composition (a) containing the poly) ether group-containing dicarboxylic acid compound, and fluorination of the (poly) ether group-containing dicarboxylic acid compound represented by the formula (3) obtained by the separation. A step (A) of treating to obtain a mixture containing a (poly) ether group-containing monocarboxylic acid compound represented by the formula (2),
A process for producing a (poly) ether group-containing monocarboxylic acid compound.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000006
 [Where:
A is independently at each occurrence R 1 O—CO—W— group, R 1 O—CO—W—O— group, HO—W— group, HO—W—O— group, R 1 O Represents a —W— group, a R 1 O—W—O— group, a V— group, or a V—O— group;
R 1 independently represents an alkyl group at each occurrence;
W represents a bond or a divalent organic group independently at each occurrence;
V independently represents each alkyl group having 1 to 16 carbon atoms in each occurrence;
Z independently represents Y—X— or Y—X—O— at each occurrence;
Y represents a carboxylic acid group;
X independently represents a bond or a divalent organic group at each occurrence;
Pf is independently at each occurrence, the formula:
- (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 X 1 6) d - (OC 2 F 4) e - (OCF 2) f -
(Wherein, a, b, c, d, e and f are each independently an integer of 0 to 200, and the sum of a, b, c, d, e and f is at least 1, The order of presence of each repeating unit in parentheses with a, b, c, d, e or f is arbitrary in the formula, and X 1 is independently a hydrogen atom, fluorine An atom or a chlorine atom.)
It is group represented by these. ]
　本発明によれば、（ポリ）エーテル基含有モノカルボン酸化合物の収率を向上することができる。 According to the present invention, the yield of the (poly) ether group-containing monocarboxylic acid compound can be improved.
薄層クロマトグラフィーにより得られるクロマトグラムのモデル図である。It is a model figure of the chromatogram obtained by thin layer chromatography. 本発明の一の実施態様に係る方法のフローチャートである。3 is a flowchart of a method according to an embodiment of the present invention. 本発明の一の実施態様に係る方法のフローチャートである。3 is a flowchart of a method according to an embodiment of the present invention. 本発明の一の実施態様に係る方法のフローチャートである。3 is a flowchart of a method according to an embodiment of the present invention. 本発明の一の実施態様に係る方法のフローチャートである。3 is a flowchart of a method according to an embodiment of the present invention.
　本明細書において用いられる場合、「結合手」とは、原子などを有しない単なる結合を意味する。例えば、Ｚが－Ｘ－Ｙ基である場合において、Ｘが結合手である場合、Ｚは－Ｙ基を表すこととなる。 As used herein, “bond” means a simple bond having no atom or the like. For example, when Z is a —XY group, and X is a bond, Z represents a —Y group.
　本明細書において用いられる場合、「２価の有機基」とは、炭素を含有する２価の基を意味する。かかる２価の有機基としては、特に限定されないが、炭化水素基からさらに１個の水素原子を脱離させた２価の基が挙げられる。 As used herein, “divalent organic group” means a divalent group containing carbon. Such a divalent organic group is not particularly limited, and examples thereof include a divalent group obtained by further removing one hydrogen atom from a hydrocarbon group.
　本明細書において用いられる場合、「炭化水素基」とは、炭素および水素を含む基であって、分子から１個の水素原子を脱離させた基を意味する。かかる炭化水素基としては、特に限定されるものではないが、１つまたはそれ以上の置換基により置換されていてもよい、炭素数１～４の炭化水素基、例えば、脂肪族炭化水素基等が挙げられる。上記「脂肪族炭化水素基」は、直鎖状、分枝鎖状または環状のいずれであってもよく、飽和または不飽和のいずれであってもよい。また、炭化水素基は、１つまたはそれ以上の環構造を含んでいてもよい。尚、かかる炭化水素基は、その末端または分子鎖中に、１つまたはそれ以上のＮ、Ｏ、Ｓ、Ｓｉ、アミド、スルホニル、シロキサン、カルボニル、カルボニルオキシ等を有していてもよい。 As used herein, the “hydrocarbon group” means a group containing carbon and hydrogen, in which one hydrogen atom is eliminated from a molecule. Such hydrocarbon group is not particularly limited, but may be a hydrocarbon group having 1 to 4 carbon atoms which may be substituted by one or more substituents, such as an aliphatic hydrocarbon group, etc. Is mentioned. The “aliphatic hydrocarbon group” may be linear, branched or cyclic, and may be either saturated or unsaturated. The hydrocarbon group may also contain one or more ring structures. Such a hydrocarbon group may have one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy and the like at its terminal or molecular chain.
　本明細書において用いられる場合、「炭化水素基」の置換基としては、特に限定されないが、例えば、ハロゲン原子；１個またはそれ以上のハロゲン原子により置換されていてもよい、Ｃ１－６アルキル基、Ｃ２－６アルケニル基、Ｃ２－６アルキニル基、Ｃ３－１０シクロアルキル基、Ｃ３－１０不飽和シクロアルキル基、５～１０員のヘテロシクリル基、５～１０員の不飽和ヘテロシクリル基、Ｃ６－１０アリール基および５～１０員のヘテロアリール基から選択される１個またはそれ以上の基が挙げられる。 As used herein, the substituent of the “hydrocarbon group” is not particularly limited, but includes, for example, a halogen atom; C 1-6 alkyl optionally substituted by one or more halogen atoms Group, C 2-6 alkenyl group, C 2-6 alkynyl group, C 3-10 cycloalkyl group, C 3-10 unsaturated cycloalkyl group, 5-10 membered heterocyclyl group, 5-10 membered unsaturated heterocyclyl And one or more groups selected from a group, a C 6-10 aryl group and a 5-10 membered heteroaryl group.
　本明細書において、アルキル基およびフェニル基は、特記しない限り、非置換であっても、置換されていてもよい。かかる基の置換基としては、特に限定されないが、例えば、ハロゲン原子、Ｃ１－６アルキル基、Ｃ２－６アルケニル基およびＣ２－６アルキニル基から選択される１個またはそれ以上の基が挙げられる。 In the present specification, unless otherwise specified, an alkyl group and a phenyl group may be unsubstituted or substituted. The substituent of such a group is not particularly limited, and examples thereof include one or more groups selected from a halogen atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. Can be mentioned.
　ポリエーテル基は、各出現において独立して、
－（ＯＣ６Ｆ１２）ａ－（ＯＣ５Ｆ１０）ｂ－（ＯＣ４Ｆ８）ｃ－（ＯＣ３Ｘ１ ６）ｄ－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－
で表される基である。本明細書において、上記（ポリ）エーテル基を、Ｐｆ基と称することがある。式中、ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して０以上２００以下の整数であって、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は少なくとも１である。好ましくは、ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して、０以上１００以下の整数である。好ましくは、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は５以上であり、より好ましくは１０以上である。好ましくは、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は２００以下であり、より好ましくは１００以下であり、例えば１０以上２００以下であり、より具体的には１０以上１００以下である。また、ａ、ｂ、ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。Ｘ１は、各出現においてそれぞれ独立して、水素原子、フッ素原子または塩素原子であり、好ましくはフッ素原子である。 The polyether group is independently at each occurrence,
- (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 X 1 6) d - (OC 2 F 4) e - (OCF 2) f -
It is group represented by these. In the present specification, the (poly) ether group may be referred to as a Pf group. In the formula, a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1. Preferably, a, b, c, d, e and f are each independently an integer of 0 or more and 100 or less. Preferably, the sum of a, b, c, d, e and f is 5 or more, more preferably 10 or more. Preferably, the sum of a, b, c, d, e, and f is 200 or less, more preferably 100 or less, for example, 10 or more and 200 or less, and more specifically 10 or more and 100 or less. Further, the order of presence of each repeating unit in parentheses with a, b, c, d, e or f is arbitrary in the formula. X 1 is independently a hydrogen atom, a fluorine atom or a chlorine atom at each occurrence, preferably a fluorine atom.
　上記Ｐｆ基において、繰り返し単位は、直鎖状であっても、分枝鎖状であってもよいが、好ましくは直鎖状である。例えば、－（ＯＣ６Ｆ１２）－は、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ（ＣＦ３）ＣＦ２ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ（ＣＦ３）ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ（ＣＦ３）ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ（ＣＦ３）ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ（ＣＦ３））－等であってもよいが、好ましくは－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２）－である。－（ＯＣ５Ｆ１０）－は、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ（ＣＦ３）ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ（ＣＦ３）ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ（ＣＦ３）ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ（ＣＦ３））－等であってもよいが、好ましくは－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２）－である。－（ＯＣ４Ｆ８）－は、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ（ＣＦ３）ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ（ＣＦ３）ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ（ＣＦ３））－、－（ＯＣ（ＣＦ３）２ＣＦ２）－、－（ＯＣＦ２Ｃ（ＣＦ３）２）－、－（ＯＣＦ（ＣＦ３）ＣＦ（ＣＦ３））－、－（ＯＣＦ（Ｃ２Ｆ５）ＣＦ２）－および－（ＯＣＦ２ＣＦ（Ｃ２Ｆ５））－のいずれであってもよいが、好ましくは－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２）－である。－（ＯＣ３Ｆ６）－（即ち、Ｘ１はフッ素原子である。）は、－（ＯＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ（ＣＦ３）ＣＦ２）－および－（ＯＣＦ２ＣＦ（ＣＦ３））－のいずれであってもよいが、好ましくは－（ＯＣＦ２ＣＦ２ＣＦ２）－である。また、－（ＯＣ２Ｆ４）－は、－（ＯＣＦ２ＣＦ２）－および－（ＯＣＦ（ＣＦ３））－のいずれであってもよいが、好ましくは－（ＯＣＦ２ＣＦ２）－である。 In the Pf group, the repeating unit may be linear or branched, but is preferably linear. For example,-(OC 6 F 12 )-is-(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 CF 2 CF 2 CF 2 )-,-(OCF 2 CF (CF 3 ) CF 2 CF 2 CF 2 ) —, — (OCF 2 CF 2 CF (CF 3 ) CF 2 CF 2 ) —, — (OCF 2 CF 2 CF 2 CF (CF 3 ) CF 2 ) — , — (OCF 2 CF 2 CF 2 CF 2 CF (CF 3 )) — or the like may be used, but — (OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 ) — is preferred. -(OC 5 F 10 )-is-(OCF 2 CF 2 CF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 CF 2 CF 2 )-,-(OCF 2 CF (CF 3 ) CF 2 CF 2 ) —, — (OCF 2 CF 2 CF (CF 3 ) CF 2 ) —, — (OCF 2 CF 2 CF 2 CF (CF 3 )) — and the like are preferable, but — ( OCF 2 CF 2 CF 2 CF 2 CF 2 ) —. -(OC 4 F 8 )-is-(OCF 2 CF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 CF 2 )-,-(OCF 2 CF (CF 3 ) CF 2 )- ,-(OCF 2 CF 2 CF (CF 3 ))-,-(OC (CF 3 ) 2 CF 2 )-,-(OCF 2 C (CF 3 ) 2 )-,-(OCF (CF 3 ) CF ( CF 3 ))-,-(OCF (C 2 F 5 ) CF 2 )-and-(OCF 2 CF (C 2 F 5 ))-may be used, but preferably-(OCF 2 CF 2 CF 2 CF 2 ) —. — (OC 3 F 6 ) — (that is, X 1 is a fluorine atom) represents — (OCF 2 CF 2 CF 2 ) —, — (OCF (CF 3 ) CF 2 ) — and — (OCF 2 CF (CF 3 )) — may be used, but — (OCF 2 CF 2 CF 2 ) — is preferred. In addition, — (OC 2 F 4 ) — may be any of — (OCF 2 CF 2 ) — and — (OCF (CF 3 )) —, preferably — (OCF 2 CF 2 ) —. is there.
　一の態様において、上記Ｐｆ基は、－（ＯＣ３Ｆ６）ｄ－（式中、ｄは１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数である）である。好ましくは、Ｐｆ基は、－（ＯＣＦ２ＣＦ２ＣＦ２）ｄ－（式中、ｄは１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数である）または－（ＯＣＦ（ＣＦ３）ＣＦ２）ｄ－（式中、ｄは１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数である）である。より好ましくは、Ｐｆ基は、－（ＯＣＦ２ＣＦ２ＣＦ２）ｄ－（式中、ｄは１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数である）である。 In one embodiment, the Pf group is — (OC 3 F 6 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200). is there. Preferably, the Pf group is — (OCF 2 CF 2 CF 2 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200) or — (OCF (CF 3 ) CF 2 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200). More preferably, the Pf group is — (OCF 2 CF 2 CF 2 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200). is there.
　別の態様において、Ｐｆ基は、－（ＯＣ４Ｆ８）ｃ－（ＯＣ３Ｆ６）ｄ－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－（式中、ｃおよびｄは、それぞれ独立して０以上３０以下の整数であり、ｅおよびｆは、それぞれ独立して１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数であり、ｃ、ｄ、ｅおよびｆの和は少なくとも５以上、好ましくは１０以上であり、添字ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である）である。好ましくは、Ｐｆ基は、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２）ｃ－（ＯＣＦ２ＣＦ２ＣＦ２）ｄ－（ＯＣＦ２ＣＦ２）ｅ－（ＯＣＦ２）ｆ－である。一の態様において、Ｐｆ基は、－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－（式中、ｅおよびｆは、それぞれ独立して１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数であり、添字ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である）であってもよい。 In another embodiment, the Pf group is — (OC 4 F 8 ) c — (OC 3 F 6 ) d — (OC 2 F 4 ) e — (OCF 2 ) f — (wherein c and d are each Each independently represents an integer of 0 to 30; e and f are each independently an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200; c, d, e And the sum of f is at least 5 or more, preferably 10 or more, and the order of presence of each repeating unit in parentheses with the suffix c, d, e or f is optional in the formula) . Preferably, the Pf group is — (OCF 2 CF 2 CF 2 CF 2 ) c — (OCF 2 CF 2 CF 2 ) d — (OCF 2 CF 2 ) e — (OCF 2 ) f —. In one embodiment, the Pf group is — (OC 2 F 4 ) e — (OCF 2 ) f — (wherein e and f are each independently from 1 to 200, preferably from 5 to 200, Preferably, it is an integer of 10 or more and 200 or less, and the order of presence of each repeating unit with the subscript e or f and enclosed in parentheses is arbitrary in the formula).
　さらに別の態様において、Ｐｆ基は、－（Ｒ６－Ｒ７）ｊ－で表される基である。式中、Ｒ６は、ＯＣＦ２またはＯＣ２Ｆ４であり、好ましくはＯＣ２Ｆ４である。式中、Ｒ７は、ＯＣ２Ｆ４、ＯＣ３Ｆ６、ＯＣ４Ｆ８、ＯＣ５Ｆ１０およびＯＣ６Ｆ１２から選択される基であるか、あるいは、これらの基から独立して選択される２または３つの基の組み合わせである。好ましくは、Ｒ７は、ＯＣ２Ｆ４、ＯＣ３Ｆ６およびＯＣ４Ｆ８から選択される基であるか、ＯＣ３Ｆ６、ＯＣ４Ｆ８、ＯＣ５Ｆ１０およびＯＣ６Ｆ１２から選択される基であるか、あるいは、これらの基から独立して選択される２または３つの基の組み合わせである。ＯＣ２Ｆ４、ＯＣ３Ｆ６およびＯＣ４Ｆ８から独立して選択される２または３つの基の組み合わせとしては、特に限定されないが、例えば－ＯＣ２Ｆ４ＯＣ３Ｆ６－、－ＯＣ２Ｆ４ＯＣ４Ｆ８－、－ＯＣ３Ｆ６ＯＣ２Ｆ４－、－ＯＣ３Ｆ６ＯＣ３Ｆ６－、－ＯＣ３Ｆ６ＯＣ４Ｆ８－、－ＯＣ４Ｆ８ＯＣ４Ｆ８－、－ＯＣ４Ｆ８ＯＣ３Ｆ６－、－ＯＣ４Ｆ８ＯＣ２Ｆ４－、－ＯＣ２Ｆ４ＯＣ２Ｆ４ＯＣ３Ｆ６－、－ＯＣ２Ｆ４ＯＣ２Ｆ４ＯＣ４Ｆ８－、－ＯＣ２Ｆ４ＯＣ３Ｆ６ＯＣ２Ｆ４－、－ＯＣ２Ｆ４ＯＣ３Ｆ６ＯＣ３Ｆ６－、－ＯＣ２Ｆ４ＯＣ４Ｆ８ＯＣ２Ｆ４－、－ＯＣ３Ｆ６ＯＣ２Ｆ４ＯＣ２Ｆ４－、－ＯＣ３Ｆ６ＯＣ２Ｆ４ＯＣ３Ｆ６－、－ＯＣ３Ｆ６ＯＣ３Ｆ６ＯＣ２Ｆ４－、および－ＯＣ４Ｆ８ＯＣ２Ｆ４ＯＣ２Ｆ４－等が挙げられる。上記ｊは、２以上、好ましくは３以上、より好ましくは５以上であり、１００以下、好ましくは５０以下の整数である。上記式中、ＯＣ２Ｆ４、ＯＣ３Ｆ６、ＯＣ４Ｆ８、ＯＣ５Ｆ１０およびＯＣ６Ｆ１２は、直鎖または分枝鎖のいずれであってもよく、好ましくは直鎖である。この態様において、Ｐｆ基は、好ましくは、－（ＯＣ２Ｆ４－ＯＣ３Ｆ６）ｊ－または－（ＯＣ２Ｆ４－ＯＣ４Ｆ８）ｊ－である。 In still another embodiment, the Pf group is a group represented by-(R 6 -R 7 ) j- . In the formula, R 6 is OCF 2 or OC 2 F 4 , preferably OC 2 F 4 . In which R 7 is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 , or is independently selected from these groups Is a combination of 2 or 3 groups. Preferably, R 7 is a group selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 or from OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12. A selected group or a combination of two or three groups independently selected from these groups. The combination of 2 or 3 groups independently selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 is not particularly limited. For example, —OC 2 F 4 OC 3 F 6 —, —OC 2 F 4 OC 4 F 8 - , - OC 3 F 6 OC 2 F 4 -, - OC 3 F 6 OC 3 F 6 -, - OC 3 F 6 OC 4 F 8 -, - OC 4 F 8 OC 4 F 8 -, - OC 4 F 8 OC 3 F 6 -, - OC 4 F 8 OC 2 F 4 -, - OC 2 F 4 OC 2 F 4 OC 3 F 6 -, - OC 2 F 4 OC 2 F 4 OC 4 F 8 -, - OC 2 F 4 OC 3 F 6 OC 2 F 4 -, - OC 2 F 4 OC 3 F 6 OC 3 F 6 -, - OC 2 F 4 OC 4 F 8 OC 2 F 4 -, -OC 3 F 6 OC 2 F 4 OC 2 F 4 -, - OC 3 F 6 OC 2 F 4 OC 3 F 6 —, —OC 3 F 6 OC 3 F 6 OC 2 F 4 —, —OC 4 F 8 OC 2 F 4 OC 2 F 4 — and the like can be mentioned. J is 2 or more, preferably 3 or more, more preferably 5 or more, and an integer of 100 or less, preferably 50 or less. In the above formula, OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 may be either linear or branched, preferably linear. . In this embodiment, the Pf group is preferably — (OC 2 F 4 —OC 3 F 6 ) j — or — (OC 2 F 4 —OC 4 F 8 ) j —.
　上記Ｐｆ基において、ｆに対するｅの比（以下、「ｅ／ｆ比」という）は、０．１以上１０以下であり、例えば、０．２以上５以下であり、具体的には、０．４以上２以下であり、より具体的には、０．６以上１．５以下であり、さらに具体的には、０．７以上１．４以下である。 In the Pf group, the ratio of e to f (hereinafter referred to as “e / f ratio”) is 0.1 or more and 10 or less, for example, 0.2 or more and 5 or less. 4 or more and 2 or less, more specifically 0.6 or more and 1.5 or less, and more specifically 0.7 or more and 1.4 or less.
　以下において、本発明のＰｆ基含有モノカルボン酸化合物の製造方法を、図面を用いて説明する。 Hereinafter, the method for producing the Pf group-containing monocarboxylic acid compound of the present invention will be described with reference to the drawings.
（実施態様１）
　図２に、本発明のＰｆ基含有モノカルボン酸化合物を製造する方法の一態様を示す。 (Embodiment 1)
FIG. 2 shows one embodiment of a method for producing the Pf group-containing monocarboxylic acid compound of the present invention.
　本態様のＰｆ基含有モノカルボン酸化合物を製造する方法は、
　少なくとも下記式（１）で表されるＰｆ基含有化合物、下記式（２）で表されるＰｆ基含有モノカルボン酸化合物、および、下記式（３）で表されるＰｆ基含有ジカルボン酸化合物を含む組成物（ａ１）を、分離する工程（Ｉ－１）、および
　上記分離により得られる式（３）で表されるＰｆ基含有ジカルボン酸化合物をフッ素化処理し、式（２）で表されるＰｆ基含有モノカルボン酸化合物を含む混合物を得る工程（Ａ１）、
を含む。なお、以下において、式（１）で表されるＰｆ基含有化合物、式（２）で表されるＰｆ基含有モノカルボン酸化合物、および、式（３）で表されるＰｆ基含有ジカルボン酸化合物を、それぞれ「Ｐｆ基含有化合物」、「Ｐｆ基含有モノカルボン酸化合物」および「Ｐｆ基含有ジカルボン酸化合物」と称することがある。
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000009
 ［式中：
　Ａは、各出現においてそれぞれ独立して、Ｒ１Ｏ－ＣＯ－Ｗ－基、Ｒ１Ｏ－ＣＯ－Ｗ－Ｏ－基、ＨＯ－Ｗ－基、ＨＯ－Ｗ－Ｏ－基、Ｒ１Ｏ－Ｗ－基、Ｒ１Ｏ－Ｗ－Ｏ－基、Ｖ－基、またはＶ－Ｏ－基を表し；
　Ｒ１は、各出現においてそれぞれ独立して、アルキル基を表し；
　Ｗは、各出現においてそれぞれ独立して、結合手または２価の有機基を表し；
　Ｖは、各出現においてそれぞれ独立して、炭素原子数１～１６のアルキル基を表し；
　Ｚは、各出現においてそれぞれ独立して、Ｙ－Ｘ－、またはＹ－Ｘ－Ｏ－を表し；
　Ｙは、カルボン酸基を表し；
　Ｘは、各出現においてそれぞれ独立して、結合手または２価の有機基を表し；
　Ｐｆは、各出現においてそれぞれ独立して、式：
－（ＯＣ６Ｆ１２）ａ－（ＯＣ５Ｆ１０）ｂ－（ＯＣ４Ｆ８）ｃ－（ＯＣ３Ｘ１ ６）ｄ－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－
（式中、ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して０以上２００以下の整数であって、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は少なくとも１であり、ａ、ｂ、ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意であり、Ｘ１は、各出現においてそれぞれ独立して、水素原子、フッ素原子または塩素原子である。）
で表される基である。］ The method for producing the Pf group-containing monocarboxylic acid compound of this embodiment includes:
At least a Pf group-containing compound represented by the following formula (1), a Pf group-containing monocarboxylic acid compound represented by the following formula (2), and a Pf group-containing dicarboxylic acid compound represented by the following formula (3) A step (I-1) of separating the composition (a1) containing, and a fluorination treatment of the Pf group-containing dicarboxylic acid compound represented by the formula (3) obtained by the separation, and represented by the formula (2) A step (A1) of obtaining a mixture containing a Pf group-containing monocarboxylic acid compound
including. In the following, the Pf group-containing compound represented by the formula (1), the Pf group-containing monocarboxylic acid compound represented by the formula (2), and the Pf group-containing dicarboxylic acid compound represented by the formula (3) Are sometimes referred to as “Pf group-containing compound”, “Pf group-containing monocarboxylic acid compound” and “Pf group-containing dicarboxylic acid compound”, respectively.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000009
 [Where:
A is independently at each occurrence R 1 O—CO—W— group, R 1 O—CO—W—O— group, HO—W— group, HO—W—O— group, R 1 O Represents a —W— group, a R 1 O—W—O— group, a V— group, or a V—O— group;
R 1 independently represents an alkyl group at each occurrence;
W represents a bond or a divalent organic group independently at each occurrence;
V independently represents each alkyl group having 1 to 16 carbon atoms in each occurrence;
Z independently represents Y—X— or Y—X—O— at each occurrence;
Y represents a carboxylic acid group;
X independently represents a bond or a divalent organic group at each occurrence;
Pf is independently at each occurrence, the formula:
- (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 X 1 6) d - (OC 2 F 4) e - (OCF 2) f -
(Wherein, a, b, c, d, e and f are each independently an integer of 0 to 200, and the sum of a, b, c, d, e and f is at least 1, The order of presence of each repeating unit in parentheses with a, b, c, d, e or f is arbitrary in the formula, and X 1 is independently a hydrogen atom, fluorine An atom or a chlorine atom.)
It is group represented by these. ]
　上記工程（Ｉ－１）および上記工程（Ａ１）は、それぞれ、工程（Ｉ）および工程（Ａ）の一態様である。組成物（ａ１）は、組成物（ａ）に対応する。 The step (I-1) and the step (A1) are embodiments of the step (I) and the step (A), respectively. The composition (a1) corresponds to the composition (a).
　以下、各工程について説明する。 Hereinafter, each process will be described.
　まず、工程（Ｉ－１）に供する組成物（ａ１）を準備する。 First, a composition (a1) to be used in step (I-1) is prepared.
　上記組成物（ａ１）は、特に限定されないが、例えば下記のような反応によって得ることができる。
・式（１－ａ）で表される化合物の加水分解反応
　　Ｒ１Ｏ－ＣＯ－Ｗ－Ｐｆ－Ｏ－Ｗ－ＣＯ－Ｏ－Ｒ１　　　・・・（１－ａ）
（式中：
　　Ｒ１は、各出現においてそれぞれ独立して、アルキル基を表し；
　　Ｗは、各出現においてそれぞれ独立して、結合手または２価の有機基を表し；
　　Ｐｆは、Ｐｆ基を表し；
　　好ましいＲ１およびＷは後述のとおりである。）
・式（１－ｂ）で表される化合物の酸化反応
　　ＨＯ－Ｗ－Ｐｆ－Ｏ－Ｗ－ＯＨ　　　　　　　　　　　・・・（１－ｂ）
（式中、ＷおよびＰｆは、上記と同意義である。）
・式（３）で表されるＰｆ基含有ジカルボン酸化合物のフッ素化反応
Figure JPOXMLDOC01-appb-C000010
 （式中：
　　Ｚは、各出現においてそれぞれ独立して、Ｙ－Ｘ－、またはＹ－Ｘ－Ｏ－を表し；
　　Ｙは、カルボン酸基を表し；
　　Ｘは、各出現においてそれぞれ独立して、結合手または２価の有機基を表し；
　　Ｐｆは、上記と同意義であり；
　　好ましいＺ、ＹおよびＸは後述のとおりである。）
・上記式（３）で表されるＰｆ基含有ジカルボン酸の脱炭酸反応
・上記式（３）で表されるＰｆ基含有ジカルボン酸の還元反応
・式（１－ｃ）で表される化合物の分解反応
　　Ｖ－Ｐｆ－Ｏ－Ｖ　　　　　　　　　　　　　　　　　・・・（１－ｃ）
（式中：
　　Ｖは、各出現においてそれぞれ独立して、炭素原子数１～１６のアルキル基を表し、好ましくは、Ｃ１－１６パーフルオロアルキル基、または少なくとも１の水素原子が、フッ素原子および塩素原子からなる群より選ばれる少なくとも１の原子により置換された基、例えばＨＣＦ２（ＣＦ２）ｇ－で表される基を表し（ｇは、各出現においてそれぞれ独立して、０～１５の整数である）；
　　Ｐｆは、上記と同意義であり；
　　好ましいＶおよびｇは後述のとおりである。）
・テトラフルオロエチレンおよび酸素を用いた光酸化反応、これにより得られた過酸化物の分解反応および加水分解反応
・テトラフルオロオキセタンのオリゴメリ化反応、これにより得られたオキセタンポリマーのフッ素化反応および加水分解反応
・ポリエチレングリコールのフッ素化反応および加水分解反応
・ヘキサフルオロプロピレンオキサイドのオリゴメリ化反応、これにより得られた生成物の加水分解反応。
　上記の混合物生成反応は、当業者において通常用いられる反応条件などにより、行うことができる。 Although the said composition (a1) is not specifically limited, For example, it can obtain by the following reactions.
Hydrolysis reaction of the compound represented by the formula (1-a) R 1 O—CO—W—Pf—OW—CO—O—R 1 (1-a)
(Where:
R 1 independently represents an alkyl group at each occurrence;
W represents a bond or a divalent organic group independently at each occurrence;
Pf represents a Pf group;
Preferred R 1 and W are as described later. )
・ Oxidation reaction of compound represented by formula (1-b) HO—W—Pf—OW—OH (1-b)
(Wherein, W and Pf are as defined above.)
Fluorination reaction of Pf group-containing dicarboxylic acid compound represented by formula (3)
Figure JPOXMLDOC01-appb-C000010
 (Where:
Z independently represents Y—X— or Y—X—O— at each occurrence;
Y represents a carboxylic acid group;
X independently represents a bond or a divalent organic group at each occurrence;
Pf is as defined above;
Preferred Z, Y and X are as described below. )
・ Decarboxylation reaction of Pf group-containing dicarboxylic acid represented by the above formula (3) ・ Reduction reaction of Pf group-containing dicarboxylic acid represented by the above formula (3) ・ Compound represented by the formula (1-c) Decomposition reaction V-Pf-OV (1-c)
(Where:
V independently represents an alkyl group having 1 to 16 carbon atoms in each occurrence, and preferably, a C 1-16 perfluoroalkyl group, or at least one hydrogen atom consists of a fluorine atom and a chlorine atom Represents a group substituted by at least one atom selected from the group, for example, a group represented by HCF 2 (CF 2 ) g- (g is independently an integer of 0 to 15 at each occurrence) ;
Pf is as defined above;
Preferred V and g are as described below. )
・ Photo-oxidation reaction using tetrafluoroethylene and oxygen, decomposition reaction and hydrolysis reaction of the peroxide obtained ・ Oligomerization reaction of tetrafluorooxetane, fluorination reaction and hydrolysis of the obtained oxetane polymer Decomposition reaction-Polyethylene glycol fluorination reaction and hydrolysis reaction-Hexafluoropropylene oxide oligomerization reaction, hydrolysis reaction of the resulting product.
The above-described mixture formation reaction can be performed according to reaction conditions ordinarily used by those skilled in the art.
　一の態様において、上記組成物（ａ１）は、式（１－ａ）で表される化合物の加水分解反応によって生成される。本態様では、式（１－ａ）で表される化合物を、アルカリ金属水酸化物を含む水溶液の存在下で加水分解することが、より好ましい。
　アルカリ金属水酸化物として、例えば、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、水酸化セシウムが挙げられる。これらは１種のみを用いてもよく、２種以上を併用してもよい。上記水溶液は、アルカリ金属水酸化物に加えて、水酸化カルシウム、水酸化バリウム、水酸化マグネシウム、水酸化ストロンチウム、水酸化アンモニウムなどの他の塩基を含んでもよい。この加水分解において、上記式（１－ａ）で表される化合物　１モル（エステル基としては２当量）に対して、アルカリ金属水酸化物を含む塩基の当量数が０．１～１．５となる量で用いるのが好ましい。塩基の当量数は０．２～１．０であるのがより好ましく、０．３～０．８であるのがさらに好ましい。 In one embodiment, the composition (a1) is produced by a hydrolysis reaction of a compound represented by the formula (1-a). In this embodiment, it is more preferable to hydrolyze the compound represented by the formula (1-a) in the presence of an aqueous solution containing an alkali metal hydroxide.
Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide, and cesium hydroxide. These may use only 1 type and may use 2 or more types together. The aqueous solution may contain other base such as calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, ammonium hydroxide in addition to the alkali metal hydroxide. In this hydrolysis, the number of equivalents of the base containing the alkali metal hydroxide is 0.1 to 1.5 with respect to 1 mol of the compound represented by the formula (1-a) (2 equivalents as the ester group). Is preferably used in such an amount. The number of equivalents of base is more preferably 0.2 to 1.0, and still more preferably 0.3 to 0.8.
　上記加水分解は、必要に応じて、有機溶媒の存在下で行ってもよい。好ましい有機溶媒として、アセトニトリル、テトラヒドロフランなどが挙げられる。上記加水分解は、分散助剤がさらに存在する条件下で行ってもよい。ここで、分散助剤として、－１０～５０℃において液状であって、水に対して難溶性または不溶性であるフッ素原子含有溶媒などが挙げられる。フッ素原子含有溶媒として、パーフルオロヘキサン、キシレンヘキサフルオリドなどがさらに好ましく用いられる。上記フッ素原子含有溶媒は、１種のみを単独で用いてもよく、２種以上を併用してもよい。 The hydrolysis may be carried out in the presence of an organic solvent as necessary. Preferred organic solvents include acetonitrile, tetrahydrofuran and the like. The hydrolysis may be performed under conditions where a dispersion aid is further present. Here, examples of the dispersion aid include a fluorine atom-containing solvent which is liquid at −10 to 50 ° C. and hardly soluble or insoluble in water. As the fluorine atom-containing solvent, perfluorohexane, xylene hexafluoride and the like are more preferably used. The said fluorine atom containing solvent may be used individually by 1 type, and may use 2 or more types together.
　上記加水分解は、例えば－１０℃～５０℃で、０．５～１２時間撹拌して反応させるのが好ましい。 The hydrolysis is preferably performed by stirring at -10 ° C. to 50 ° C. for 0.5 to 12 hours.
　別の態様においては、組成物（ａ１）は、Ｐｆ基含有ジカルボン酸化合物のフッ素化処理によって形成される。すなわち、本態様において、組成物（ａ１）は、
　Ｐｆ基含有ジカルボン酸化合物をフッ素化処理し、組成物（ａ１）を得る工程（Ｚ１）により得られる。
　上記Ｐｆ基含有ジカルボン酸化合物は、式（１－ａ）で表される化合物の加水分解反応によって得られる化合物であり得る。
　　Ｒ１Ｏ－ＣＯ－Ｗ－Ｐｆ－Ｏ－Ｗ－ＣＯ－Ｏ－Ｒ１　　　・・・（１－ａ）
（式中、Ｒ１、Ｗ、およびＰｆは上記と同意義である）
　上記式（１－ａ）で表される化合物は、数平均分子量が、例えば１，０００～１０，０００の範囲にあってもよく、具体的には３，０００～５，０００の範囲にあってもよい。ここで、数平均分子量は、１９Ｆ　ＮＭＲによって求めた値である。
　上記工程（Ｚ１）は、工程（Ｚ）の一態様である。 In another embodiment, the composition (a1) is formed by fluorination treatment of a Pf group-containing dicarboxylic acid compound. That is, in this embodiment, the composition (a1) is
It is obtained by the step (Z1) of obtaining a composition (a1) by subjecting the Pf group-containing dicarboxylic acid compound to a fluorination treatment.
The Pf group-containing dicarboxylic acid compound may be a compound obtained by hydrolysis reaction of the compound represented by the formula (1-a).
R 1 O—CO—W—Pf—OW—CO—O—R 1 (1-a)
(Wherein R 1 , W, and Pf are as defined above)
The compound represented by the formula (1-a) may have a number average molecular weight in the range of 1,000 to 10,000, for example, specifically in the range of 3,000 to 5,000. May be. Here, the number average molecular weight is a value determined by 19 F NMR.
The step (Z1) is an embodiment of the step (Z).
　好ましくは、組成物（ａ１）は、上記工程（Ｚ１）により得られるものである。すなわち、組成物（ａ１）は、Ｐｆ基含有ジカルボン酸化合物をフッ素化処理して得られることが好ましい。 Preferably, the composition (a1) is obtained by the step (Z1). That is, the composition (a1) is preferably obtained by fluorinating a Pf group-containing dicarboxylic acid compound.
　上記フッ素化処理の条件は特に限定されない。フッ素化処理は、Ｐｆ基含有ジカルボン酸化合物（またはＰｆ基含有ジカルボン酸化合物を含む組成物）とフッ素含有化合物とを接触させることにより行うことができる。 The conditions for the fluorination treatment are not particularly limited. The fluorination treatment can be performed by bringing a Pf group-containing dicarboxylic acid compound (or a composition containing a Pf group-containing dicarboxylic acid compound) into contact with a fluorine-containing compound.
　上記フッ素含有化合物としては特に限定されないが、フッ素化処理条件下にてフッ素ラジカルを発生するフッ素ラジカル源が挙げられる。上記フッ素ラジカル源としては、Ｆ２、ＣｏＦ３、ＡｇＦ２、ＵＦ６、ＯＦ２、Ｎ２Ｆ２、ＣＦ３ＯＦ、フッ化ハロゲン（例えばＩＦ５、ＣｌＦ３）等が挙げられる。 Although it does not specifically limit as said fluorine-containing compound, The fluorine radical source which generate | occur | produces a fluorine radical under fluorination process conditions is mentioned. Examples of the fluorine radical source include F 2 , CoF 3 , AgF 2 , UF 6 , OF 2 , N 2 F 2 , CF 3 OF, and halogen fluoride (eg, IF 5 , ClF 3 ).
　上記Ｆ２等のフッ素ラジカル源は、１００％濃度のものであってもよいが、５～５０質量％に希釈して使用することが好ましく、１５～３０質量％に希釈して使用することがより好ましい。例えば、上記フッ素ラジカル源が、不活性ガスと混合し得る場合（具体的には、上記フッ素ラジカル源がガス状である場合）には、安全性の面からフッ素ラジカル源を、不活性ガスと混合し５～５０質量％に希釈して使用することが好ましく、１５～３０質量％に希釈して使用することがより好ましい。上記不活性ガスとしては、窒素ガス、ヘリウムガス、アルゴンガス等が挙げられるが、経済的な面より窒素ガスが好ましい。 The fluorine radical source such as F 2 may have a concentration of 100%, but is preferably diluted to 5 to 50% by mass, and diluted to 15 to 30% by mass. More preferred. For example, when the fluorine radical source can be mixed with an inert gas (specifically, when the fluorine radical source is gaseous), the fluorine radical source and the inert gas are used for safety. It is preferably mixed and diluted to 5 to 50% by mass, more preferably 15 to 30% by mass. Examples of the inert gas include nitrogen gas, helium gas, and argon gas. Nitrogen gas is preferable from the economical viewpoint.
　上記フッ素化処理は、５０℃～２００℃において行うことが好ましく、８０℃～１５０℃において行うことがより好ましい。上記フッ素化処理は、一般に０．５～５０時間、好ましくは１～２０時間行う。上記フッ素化処理は、１００℃～１４０℃にて、２～１０時間行うことが好ましい。 The fluorination treatment is preferably performed at 50 ° C. to 200 ° C., more preferably 80 ° C. to 150 ° C. The fluorination treatment is generally performed for 0.5 to 50 hours, preferably 1 to 20 hours. The fluorination treatment is preferably performed at 100 to 140 ° C. for 2 to 10 hours.
　以下、組成物（ａ１）に含まれる化合物について説明する。 Hereinafter, the compounds contained in the composition (a1) will be described.
　上記組成物（ａ１）は、少なくともＰｆ基含有化合物、Ｐｆ基含有モノカルボン酸化合物、およびＰｆ基含有ジカルボン酸化合物を含む。上記Ｐｆ基含有化合物、上記Ｐｆ基含有モノカルボン酸化合物、および上記Ｐｆ基含有ジカルボン酸化合物は、それぞれ、下記式（１）、（２）および（３）で表される。
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000013
 The composition (a1) contains at least a Pf group-containing compound, a Pf group-containing monocarboxylic acid compound, and a Pf group-containing dicarboxylic acid compound. The Pf group-containing compound, the Pf group-containing monocarboxylic acid compound, and the Pf group-containing dicarboxylic acid compound are represented by the following formulas (1), (2), and (3), respectively.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000013
　式中、Ａは、各出現においてそれぞれ独立して、Ｒ１Ｏ－ＣＯ－Ｗ－基、Ｒ１Ｏ－ＣＯ－Ｗ－Ｏ－基、ＨＯ－Ｗ－基、ＨＯ－Ｗ－Ｏ－基、Ｒ１Ｏ－Ｗ－基、Ｒ１Ｏ－Ｗ－Ｏ－基、Ｖ－基、またはＶ－Ｏ－基を表す。 In the formula, A is each independently R 1 O—CO—W— group, R 1 O—CO—W—O— group, HO—W— group, HO—W—O— group, R 1 O—W— group, R 1 O—W—O— group, V— group or V—O— group is represented.
　式中、Ｒ１は、各出現においてそれぞれ独立して、アルキル基を表す。 In the formula, R 1 independently represents an alkyl group at each occurrence.
　上記Ｒ１において、アルキル基は、Ｃ１－４アルキル基であることが好ましい。Ｃ１－４アルキル基としては、直鎖状または分枝状Ｃ１－４アルキル基が挙げられる。Ｃ１－４アルキル基の具体例としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、２－ブチル基、イソブチル基、ｔ－ブチル基などが挙げられる。Ｒ１は、より好ましくは、メチル基またはエチル基である。なお、これらのアルキル基は、置換基を有していてもよい。置換基として、例えば、フッ素原子または塩素原子などのハロゲン原子、アミノ基、スルホニル基、水酸基などが挙げられる。 In R 1 above, the alkyl group is preferably a C 1-4 alkyl group. Examples of the C 1-4 alkyl group include a linear or branched C 1-4 alkyl group. Specific examples of the C 1-4 alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 2-butyl group, an isobutyl group, and a t-butyl group. R 1 is more preferably a methyl group or an ethyl group. These alkyl groups may have a substituent. Examples of the substituent include a halogen atom such as a fluorine atom or a chlorine atom, an amino group, a sulfonyl group, and a hydroxyl group.
　式中、Ｗは、各出現においてそれぞれ独立して、結合手または２価の有機基を表す。なお、Ｗとして記載している構造において、左側がＲ１Ｏ－ＣＯ－で表される構造、ＨＯ－、またはＲ１Ｏ－で表される構造に、右側がＰｆ基、または－Ｏ－にそれぞれ結合する。 In the formula, W represents a bond or a divalent organic group independently at each occurrence. Note that in the structure described as W, the left side is a structure represented by R 1 O—CO—, the HO— or R 1 O— structure, the right side is a Pf group, or —O—. Join each one.
　上記Ｗにおいて、２価の有機基は、１～４の炭素原子を含有することが好ましい。該２価の有機基は、少なくとも１の水素原子が、１またはそれ以上の置換基により置換されていてもよい。Ｗにおける上記置換基としては、フッ素原子または塩素原子を挙げることができる。 In the above W, the divalent organic group preferably contains 1 to 4 carbon atoms. In the divalent organic group, at least one hydrogen atom may be substituted with one or more substituents. As said substituent in W, a fluorine atom or a chlorine atom can be mentioned.
　上記１～４の炭素原子を有する２価の有機基としては、Ｃ１－４アルキレン基、少なくとも１の水素原子が、フッ素原子および塩素原子よりなる群より選ばれる少なくとも１の原子により置換されたＣ１－４アルキレン基またはＣ１－４パーフルオロアルキレン基などが挙げられる。 Examples of the divalent organic group having 1 to 4 carbon atoms include a C 1-4 alkylene group, wherein at least one hydrogen atom is substituted with at least one atom selected from the group consisting of a fluorine atom and a chlorine atom. Examples thereof include a C 1-4 alkylene group and a C 1-4 perfluoroalkylene group.
　上記Ｗにおいて、上記Ｃ１－４アルキレン基としては、－ＣＨ２－、－Ｃ２Ｈ４－、－Ｃ３Ｈ６－、－Ｃ４Ｈ８－が挙げられる。ここで、－Ｃ３Ｈ６－および－Ｃ４Ｈ８－は、直鎖状であってもよく、分枝状であってもよい。上記少なくとも１の水素原子が、フッ素原子および塩素原子よりなる群より選ばれる少なくとも１の原子により置換されたＣ１－４アルキレン基としては、上記Ｃ１－４アルキレン基における水素原子の一部がフッ素原子に置換された基、Ｃ１－４アルキレン基における水素原子の一部が塩素原子に置換された基、またはＣ１－４アルキレン基における水素原子の一部が塩素原子およびフッ素原子に置換された基が挙げられる。上記Ｃ１－４パーフルオロアルキレン基として、上記Ｃ１－４アルキレン基における全ての水素原子がフッ素原子に置換された基が挙げられる。 In W, the C 1-4 alkylene group includes —CH 2 —, —C 2 H 4 —, —C 3 H 6 —, and —C 4 H 8 —. Here, —C 3 H 6 — and —C 4 H 8 — may be linear or branched. The C 1-4 alkylene group in which the at least one hydrogen atom is substituted with at least one atom selected from the group consisting of a fluorine atom and a chlorine atom includes a part of the hydrogen atoms in the C 1-4 alkylene group. A group substituted by a fluorine atom, a group in which part of the hydrogen atom in the C 1-4 alkylene group is substituted by a chlorine atom, or a part of the hydrogen atom in the C 1-4 alkylene group is substituted by a chlorine atom and a fluorine atom Group. Examples of the C 1-4 perfluoroalkylene group include groups in which all the hydrogen atoms in the C 1-4 alkylene group have been substituted with fluorine atoms.
　上記Ｗは、少なくとも１の水素原子が、フッ素原子および塩素原子からなる群より選ばれる少なくとも１の原子により置換された基であることが好ましい。 The W is preferably a group in which at least one hydrogen atom is substituted with at least one atom selected from the group consisting of a fluorine atom and a chlorine atom.
　一の態様において、上記Ｗは、各出現においてそれぞれ独立して、－ＣＪ２－、－ＣＪ２ＣＪ２－、－ＣＪ２ＣＪ２ＣＪ２－、－ＣＪ（ＣＪ３）ＣＪ２－または－ＣＪ２ＣＪ（ＣＪ３）－であるのが好ましい。Ｊは、各出現においてそれぞれ独立して、水素原子、フッ素原子または塩素原子を表す。上記Ｊの少なくとも１がフッ素原子または塩素原子であることが好ましい。 In one embodiment, the above W is independently at each occurrence —CJ 2 —, —CJ 2 CJ 2 —, —CJ 2 CJ 2 CJ 2 —, —CJ (CJ 3 ) CJ 2 — or —CJ 2 CJ (CJ 3 ) — is preferred. J independently represents a hydrogen atom, a fluorine atom or a chlorine atom at each occurrence. It is preferable that at least 1 of J is a fluorine atom or a chlorine atom.
　本態様において、上記Ｗは、各出現においてそれぞれ独立して、－ＣＪ’２－、－ＣＪ’２ＣＪ’２－、－ＣＨ２ＣＪ’２－、－ＣＪ’２ＣＨ２－、－ＣＪ’（ＣＪ’３）ＣＪ’２－、－ＣＪ’（ＣＪ’３）ＣＨ２－、－ＣＪ’２ＣＪ’２ＣＨ２－、－ＣＨ２ＣＪ’２ＣＪ’２－または－ＣＨ２ＣＪ’（ＣＪ’３）－であるのが好ましい。Ｊ’は、各出現においてそれぞれ独立して、フッ素原子または塩素原子を表す。 In this embodiment, the W is independently at each occurrence, —CJ ′ 2 —, —CJ ′ 2 CJ ′ 2 —, —CH 2 CJ ′ 2 —, —CJ ′ 2 CH 2 —, —CJ ′. (CJ ′ 3 ) CJ ′ 2 —, —CJ ′ (CJ ′ 3 ) CH 2 —, —CJ ′ 2 CJ ′ 2 CH 2 —, —CH 2 CJ ′ 2 CJ ′ 2 — or —CH 2 CJ ′ ( CJ ′ 3 ) — is preferred. J ′ represents a fluorine atom or a chlorine atom independently at each occurrence.
　好ましい実施態様において、上記Ｗは、各出現においてそれぞれ独立して、－ＣＦ２－、－ＣＦ２ＣＦ２－、－ＣＨ２ＣＦ２－、－ＣＦ２ＣＨ２－、－ＣＦＣｌＣＦ２－、－ＣＦ２ＣＦＣｌ－、－ＣＦ（ＣＦ３）ＣＦ２－、－ＣＦ（ＣＦ３）ＣＨ２－、－ＣＦ２ＣＦ２ＣＨ２－、－ＣＨ２ＣＦ２ＣＦ２－または－ＣＨ２ＣＦ（ＣＦ３）－である。 In a preferred embodiment, the W is independently at each occurrence —CF 2 —, —CF 2 CF 2 —, —CH 2 CF 2 —, —CF 2 CH 2 —, —CFClCF 2 —, —CF 2 CFCl—, —CF (CF 3 ) CF 2 —, —CF (CF 3 ) CH 2 —, —CF 2 CF 2 CH 2 —, —CH 2 CF 2 CF 2 — or —CH 2 CF (CF 3 ) -.
　式中、Ｖは、各出現においてそれぞれ独立して、炭素原子数１～１６のアルキル基を表す。上記炭素原子数１～１６のアルキル基は、１またはそれ以上の置換基により置換されていてもよい。上記置換基としては、フッ素原子または塩素原子を挙げることができる。 In the formula, V represents an alkyl group having 1 to 16 carbon atoms independently at each occurrence. The alkyl group having 1 to 16 carbon atoms may be substituted with one or more substituents. As said substituent, a fluorine atom or a chlorine atom can be mentioned.
　上記Ｖは、少なくとも１の水素原子が、フッ素原子および塩素原子からなる群より選ばれる少なくとも１の原子により置換された基であることが好ましい。 V is preferably a group in which at least one hydrogen atom is substituted with at least one atom selected from the group consisting of a fluorine atom and a chlorine atom.
　１の態様において、上記Ｖは、Ｊ（ＣＪ２）ｎ－で表される構造であることが好ましい。ここでｎは１～１６の整数である。Ｊは、上記と同意義である。上記Ｊの少なくとも１がフッ素原子または塩素原子であることがより好ましい。 In one embodiment, the V is preferably a structure represented by J (CJ 2 ) n —. Here, n is an integer of 1 to 16. J is as defined above. More preferably, at least one of the above J is a fluorine atom or a chlorine atom.
　好ましい態様において、Ｖは、Ｃ１－１６パーフルオロアルキル基、ＨＣＦ２（ＣＦ２）ｇ－、またはＣｌＣＦ２（ＣＦ２）ｇ－で表される基であり得る。 In a preferred embodiment, V may be a group represented by a C 1-16 perfluoroalkyl group, HCF 2 (CF 2 ) g —, or ClCF 2 (CF 2 ) g —.
　上記Ｃ１－１６パーフルオロアルキル基は、直鎖状または分枝状の炭素数１～１６のパーフルオロアルキル基（アルキル基における全ての水素原子がフッ素原子に置換された基）であり、好ましくは直鎖状または分枝状の炭素数１～３のパーフルオロアルキル基、より具体的にはＣＦ３－、ＣＦ３ＣＦ２－またはＣＦ３ＣＦ２ＣＦ２－である。 The C 1-16 perfluoroalkyl group is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms (a group in which all hydrogen atoms in the alkyl group are substituted with fluorine atoms), preferably Is a linear or branched perfluoroalkyl group having 1 to 3 carbon atoms, more specifically CF 3 —, CF 3 CF 2 — or CF 3 CF 2 CF 2 —.
　上記ｇは、各出現においてそれぞれ独立して、０～１５の整数であることが好ましく、１～４の整数であることがより好ましい。 The above g is independently an integer of 0 to 15 and more preferably an integer of 1 to 4 at each occurrence.
　式中、Ｚは、各出現においてそれぞれ独立して、Ｙ－Ｘ－、またはＹ－Ｘ－Ｏ－を表す。 In the formula, Z represents Y—X— or Y—X—O— independently at each occurrence.
　上記Ｙは、カルボン酸基を表す。 Y represents a carboxylic acid group.
　上記Ｘは、各出現においてそれぞれ独立して、結合手または２価の有機基を表す。結合手および２価の有機基については上記のとおりである。なお、Ｘとして記載している構造において、左側がＹで表される構造に結合する。 The above X represents a bond or a divalent organic group independently at each occurrence. The bond and the divalent organic group are as described above. Note that in the structure described as X, the left side is bonded to the structure represented by Y.
　上記Ｘにおいて、２価の有機基は、１～４の炭素原子を含有する基であることが好ましい。上記１～４の炭素原子を含有する基においては、水素原子が、１またはそれ以上のフッ素原子または塩素原子により置換されていてもよい。１～４の炭素原子を有する２価の有機基としては、Ｃ１－４アルキレン基、水素原子の一部が１またはそれ以上のフッ素原子および塩素原子からなる群より選ばれる少なくとも１の原子により置換されたＣ１－４アルキレン基またはＣ１－４パーフルオロアルキレン基などが挙げられる。 In X, the divalent organic group is preferably a group containing 1 to 4 carbon atoms. In the group containing 1 to 4 carbon atoms, a hydrogen atom may be substituted with one or more fluorine atoms or chlorine atoms. The divalent organic group having 1 to 4 carbon atoms includes a C 1-4 alkylene group, and at least one atom selected from the group consisting of one or more fluorine atoms and chlorine atoms. Examples thereof include a substituted C 1-4 alkylene group or a C 1-4 perfluoroalkylene group.
　上記Ｃ１－４アルキレン基としては、－ＣＨ２－、－Ｃ２Ｈ４－、－Ｃ３Ｈ６－、－Ｃ４Ｈ８－が挙げられる。ここで、－Ｃ３Ｈ６－および－Ｃ４Ｈ８－は、直鎖状であってもよく、分枝状であってもよい。上記水素原子の一部が１またはそれ以上のフッ素原子および塩素原子からなる群より選ばれる少なくとも１の原子により置換されたＣ１－４フルオロアルキレン基としては、上記Ｃ１－４アルキレン基における水素原子の一部がフッ素原子に置換された基、上記水素原子の一部が塩素原子により置換された基、上記水素原子の一部が塩素原子およびフッ素原子に置換された基が挙げられる。上記Ｃ１－４パーフルオロアルキレン基として、上記Ｃ１－４アルキレン基における全ての水素原子がフッ素原子に置換された基が挙げられる。 Examples of the C 1-4 alkylene group include —CH 2 —, —C 2 H 4 —, —C 3 H 6 —, and —C 4 H 8 —. Here, —C 3 H 6 — and —C 4 H 8 — may be linear or branched. Examples of the C 1-4 fluoroalkylene group in which a part of the hydrogen atom is substituted with at least one atom selected from the group consisting of one or more fluorine atoms and chlorine atoms include hydrogen in the C 1-4 alkylene group. Examples include a group in which a part of the atoms is substituted with a fluorine atom, a group in which a part of the hydrogen atom is substituted with a chlorine atom, and a group in which a part of the hydrogen atom is substituted with a chlorine atom and a fluorine atom. Examples of the C 1-4 perfluoroalkylene group include groups in which all the hydrogen atoms in the C 1-4 alkylene group have been substituted with fluorine atoms.
　上記Ｘは、各出現においてそれぞれ独立して、－ＣＪ２－、－ＣＪ２ＣＪ２－、－ＣＪ（ＣＪ３）ＣＪ２－、－ＣＪ２ＣＪ２ＣＪ２－、または－ＣＪ２ＣＪ（ＣＪ３）－であるのが好ましい。Ｊは上記と同意義である。上記Ｊの少なくとも１がフッ素原子または塩素原子であることが好ましい。 It said X is independently at each occurrence, -CJ 2 -, - CJ 2 CJ 2 -, - CJ (CJ 3) CJ 2 -, - CJ 2 CJ 2 CJ 2 -, or -CJ 2 CJ (CJ 3 )-is preferred. J is as defined above. It is preferable that at least 1 of J is a fluorine atom or a chlorine atom.
　上記Ｘは、各出現においてそれぞれ独立して、－ＣＪ’２－、－ＣＪ’２ＣＪ’２－、－ＣＨ２ＣＪ’２－、－ＣＪ’２ＣＨ２－、－ＣＪ’（ＣＪ’３）ＣＪ’２－、－ＣＪ’（ＣＪ’３）ＣＨ２－、－ＣＪ’２ＣＪ’２ＣＨ２－、－ＣＨ２ＣＪ’２ＣＪ’２－または－ＣＨ２ＣＪ’（ＣＪ’３）－であるのがより好ましい。Ｊ’は上記と同意義である。 Said X is independently at each occurrence, -CJ '2 -, - CJ ' 2 CJ '2 -, - CH 2 CJ' 2 -, - CJ '2 CH 2 -, - CJ' (CJ '3 ) CJ ′ 2 —, —CJ ′ (CJ ′ 3 ) CH 2 —, —CJ ′ 2 CJ ′ 2 CH 2 —, —CH 2 CJ ′ 2 CJ ′ 2 — or —CH 2 CJ ′ (CJ ′ 3 ) -Is more preferable. J ′ is as defined above.
　好ましい態様において、上記Ｘは、各出現においてそれぞれ独立して、－ＣＦ２－、－ＣＦ２ＣＦ２－、－ＣＨ２ＣＦ２－、－ＣＦ２ＣＨ２－、－ＣＦＣｌＣＦ２－、－ＣＦ２ＣＦＣｌ－、－ＣＦ（ＣＦ３）ＣＦ２－、－ＣＦ（ＣＦ３）ＣＨ２－、－ＣＦ２ＣＦ２ＣＨ２－、－ＣＨ２ＣＦ２ＣＦ２－または－ＣＨ２ＣＦ（ＣＦ３）－である。 In a preferred embodiment, the X is independently at each occurrence —CF 2 —, —CF 2 CF 2 —, —CH 2 CF 2 —, —CF 2 CH 2 —, —CFClCF 2 —, —CF 2. CFCl—, —CF (CF 3 ) CF 2 —, —CF (CF 3 ) CH 2 —, —CF 2 CF 2 CH 2 —, —CH 2 CF 2 CF 2 — or —CH 2 CF (CF 3 ) — It is.
　式中、Ｐｆは、Ｐｆ基を意味する。 In the formula, Pf means a Pf group.
　－Ｐｆ－部分の数平均分子量は、特に限定されるものではないが、例えば５００～３０，０００、好ましくは１，５００～３０，０００、より好ましくは２，０００～１０，０００である。上記数平均分子量は、１９Ｆ－ＮＭＲにより測定される値とする。 The number average molecular weight of the —Pf— moiety is not particularly limited, but is, for example, 500 to 30,000, preferably 1,500 to 30,000, more preferably 2,000 to 10,000. The number average molecular weight is a value measured by 19 F-NMR.
　別の態様において、－Ｐｆ－部分の数平均分子量は、５００～３０，０００、好ましくは１，０００～２０，０００、より好ましくは１，５００～１５，０００、さらにより好ましくは２，０００～１０，０００、例えば３，０００～５，０００であり得る。 In another embodiment, the number average molecular weight of the —Pf— moiety is 500 to 30,000, preferably 1,000 to 20,000, more preferably 1,500 to 15,000, even more preferably 2,000 to It can be 10,000, for example 3,000 to 5,000.
　別の態様において、－Ｐｆ－部分の数平均分子量は、４，０００～３０，０００、好ましくは５，０００～１０，０００、より好ましくは６，０００～１０，０００であり得る。 In another embodiment, the number average molecular weight of the —Pf— moiety can be 4,000 to 30,000, preferably 5,000 to 10,000, more preferably 6,000 to 10,000.
　上記Ｐｆ基含有化合物の好ましい具体例として、例えば、以下に示す化合物などが挙げられる。 Preferred examples of the Pf group-containing compound include, for example, the compounds shown below.
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000014
　表１において、Ｐｆ、Ｒ１、ＷおよびＶは、上記定義と同様である。 In Table 1, Pf, R 1 , W and V are as defined above.
　上記式（１－ａ）中、Ｒ１は、Ｃ１－４アルキル基であるのが好ましく、Ｗは、－ＣＦ２－、－ＣＦ２ＣＦ２－、－ＣＦＣｌＣＦ２－、－ＣＦ２ＣＦＣｌ－または－ＣＦ（ＣＦ３）－であるのが好ましい。式（１－ａ）において、Ｗとして記載した構造は、左側が－ＣＯ－に結合し；Ｐｆ基は、左側がＷで表される構造に、右側が－Ｏ－に、それぞれ結合する。
　上記式（１－ｂ）中、Ｗは、－ＣＨ２ＣＦ２－、－ＣＦ２ＣＨ２－、－ＣＦＣｌＣＦ２－、－ＣＦ２ＣＦＣｌ－、－ＣＦ２ＣＦ２ＣＨ２－、－ＣＨ２ＣＦ２ＣＦ２－、－ＣＦ（ＣＦ３）ＣＨ２－または－ＣＨ２ＣＦ（ＣＦ３）－であるのが好ましい。式（１－ｂ）において、Ｗとして記載した構造は、左側がＨＯ－に結合し；Ｐｆ基は、左側がＷで表される構造に、右側が－Ｏ－に、それぞれ結合する。
　上記式（１－ｃ）中、Ｖは、－ＣＦ３、－ＣＦ２ＣＦ３、－ＣＦＣｌＣＦ３、－ＣＦ２ＣＦ２Ｃｌ、－ＣＦ２ＣＦ２ＣＦ３、－ＣＦ２Ｈ、－ＣＦ２ＣＦ２Ｈまたは－ＣＦ２ＣＦ２ＣＦ２Ｈであるのが好ましい。式（１－ｃ）において、Ｐｆ基は、左側がＶで表される構造に、右側が－Ｏ－に、それぞれ結合する。
　上記式（１－ｄ）中、Ｒ１は、Ｃ１－４アルキル基であるのが好ましく、Ｗは、－ＣＦ２－、－ＣＦ２ＣＦ２－、－ＣＦＣｌＣＦ２－、－ＣＦ２ＣＦＣｌ－、－ＣＦ（ＣＦ３）ＣＦ２－、－ＣＨ２ＣＦ２－、－ＣＦ２ＣＨ２－、－ＣＦ２ＣＦ２ＣＨ２－、－ＣＨ２ＣＦ２ＣＦ２－、－ＣＦ（ＣＦ３）ＣＨ２－または－ＣＨ２ＣＦ（ＣＦ３）－であるのが好ましい。式（１－ｄ）において、Ｗとして記載した構造は、左側がＲ１－Ｏ－で表される構造に結合し；Ｐｆ基は、左側がＷで表される構造に、右側が－Ｏ－に、それぞれ結合する。 In the above formula (1-a), R 1 is preferably a C 1-4 alkyl group, and W is —CF 2 —, —CF 2 CF 2 —, —CFClCF 2 —, —CF 2 CFCl—. Or it is preferably -CF (CF 3 )-. In the formula (1-a), in the structure described as W, the left side is bonded to —CO—; the Pf group is bonded to the structure represented by W on the left side and —O— on the right side.
In the above formula (1-b), W represents —CH 2 CF 2 —, —CF 2 CH 2 —, —CFClCF 2 —, —CF 2 CFCl—, —CF 2 CF 2 CH 2 —, —CH 2 CF 2 CF 2 —, —CF (CF 3 ) CH 2 — or —CH 2 CF (CF 3 ) — is preferred. In the formula (1-b), in the structure described as W, the left side is bonded to HO—; the Pf group is bonded to the structure represented by W on the left side and —O— on the right side.
In the above formula (1-c), V is —CF 3 , —CF 2 CF 3 , —CFClCF 3 , —CF 2 CF 2 Cl, —CF 2 CF 2 CF 3 , —CF 2 H, —CF 2 CF 2 H or —CF 2 CF 2 CF 2 H is preferred. In the formula (1-c), the Pf group is bonded to the structure represented by V on the left side and —O— on the right side.
In the above formula (1-d), R 1 is preferably a C 1-4 alkyl group, and W is —CF 2 —, —CF 2 CF 2 —, —CFClCF 2 —, —CF 2 CFCl—. , —CF (CF 3 ) CF 2 —, —CH 2 CF 2 —, —CF 2 CH 2 —, —CF 2 CF 2 CH 2 —, —CH 2 CF 2 CF 2 —, —CF (CF 3 ) CH It is preferably 2 — or —CH 2 CF (CF 3 ) —. In the formula (1-d), the structure described as W is bonded to the structure represented by R 1 —O— on the left side; the Pf group has the structure represented by W on the left side and —O— on the right side. To each other.
　上記式（２）で表されるＰｆ基含有モノカルボン酸化合物の好ましい具体例として、例えば、以下に示す化合物などが挙げられる。 Preferred specific examples of the Pf group-containing monocarboxylic acid compound represented by the above formula (2) include, for example, the compounds shown below.
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000015
　表２において、Ｐｆ、Ｒ１、Ｗ、Ｖ、ＸおよびＹは、上記定義と同様である。 In Table 2, Pf, R 1 , W, V, X and Y are as defined above.
　上記式（２－ａ）中、Ｒ１は、Ｃ１－４アルキル基であるのが好ましく；Ｗは、－ＣＦ２－、－ＣＦ２ＣＦ２－、－ＣＦＣｌＣＦ２－、－ＣＦ２ＣＦＣｌ－または－ＣＦ（ＣＦ３）－であるのが好ましく；Ｘは、－ＣＦ２－、－ＣＦ２ＣＦ２－または－ＣＦ（ＣＦ３）－であるのが好ましい。式（２－ａ）において、Ｗで表される構造は、左側が－ＣＯ－に、右側がＰｆ基に、それぞれ結合し；Ｐｆ基は、左側がＷで表される構造に、右側が－Ｏ－に、それぞれ結合し；Ｘで表される構造は、左側が－Ｏ－に、右側がＹで表される構造に、それぞれ結合する。
　上記式（２－ｂ）中、Ｗは、－ＣＨ２ＣＦ２－、－ＣＦＣｌＣＦ２－、－ＣＦ２ＣＦＣｌ－、－ＣＨ２ＣＦ２ＣＦ２－または－ＣＨ２ＣＦ（ＣＦ３）－であるのが好ましく；Ｘは、－ＣＦ２－、－ＣＦ２ＣＦ２－または－ＣＦ（ＣＦ３）－であるのが好ましい。式（２－ｂ）において、Ｗで表される構造は、左側がＨＯ－に、右側がＰｆ基に、それぞれ結合し；Ｐｆ基は、左側がＷで表される構造に、右側が－Ｏ－に、それぞれ結合し；Ｘで表される構造は、左側が－Ｏ－に、右側がＹで表される構造に、それぞれ結合する。
　上記式（２－ｃ）中、Ｖは、ＣＦ３－、ＣＦ３ＣＦ２－、ＣＦ３ＣＦ２ＣＦ２－、ＣＦ２Ｈ－、ＨＣＦ２ＣＦ２－またはＨＣＦ２ＣＦ２ＣＦ２－であるのが好ましく；Ｘは、－ＣＦ２－、－ＣＦ２ＣＦ２－、－ＣＦＣｌＣＦ２－、－ＣＦ２ＣＦＣｌ－、または－ＣＦ（ＣＦ３）－であるのが好ましい。式（２－ｃ）において、Ｐｆ基は、左側がＶで表される構造に、右側が－Ｏ－に、それぞれ結合し；Ｘで表される構造は、左側が－Ｏ－に、右側がＹで表される構造に、それぞれ結合する。
　上記式（２－ｄ）中、Ｒ１は、Ｃ１－４アルキル基であるのが好ましく；Ｗは、－ＣＦ２－、－ＣＦ２ＣＦ２－、－ＣＦＣｌＣＦ２－、－ＣＦ２ＣＦＣｌ－、－ＣＦ（ＣＦ３）ＣＦ２－、－ＣＨ２ＣＦ２－、－ＣＦ２ＣＨ２－、－ＣＦ２ＣＦ２ＣＨ２－、－ＣＨ２ＣＦ２ＣＦ２－、－ＣＦ（ＣＦ３）ＣＨ２－または－ＣＨ２ＣＦ（ＣＦ３）－であるのが好ましく；Ｘは、－ＣＦ２－、－ＣＦ２ＣＦ２－、－ＣＦＣｌＣＦ２－、－ＣＦ２ＣＦＣｌ－、または－ＣＦ（ＣＦ３）－であるのが好ましい。式（２－ｄ）において、Ｗで表される構造は、左側が－Ｏ－に、右側がＰｆ基に、それぞれ結合し；Ｐｆ基は、左側がＷで表される構造に、右側が－Ｏ－に、それぞれ結合し；Ｘで表される構造は、左側が－Ｏ－に、右側がＹで表される構造に、それぞれ結合する。 In the above formula (2-a), R 1 is preferably a C 1-4 alkyl group; W is —CF 2 —, —CF 2 CF 2 —, —CFClCF 2 —, —CF 2 CFCl— Or —CF (CF 3 ) — is preferred; X is preferably —CF 2 —, —CF 2 CF 2 — or —CF (CF 3 ) —. In the formula (2-a), the structure represented by W is bonded to —CO— on the left side and the Pf group on the right side; the Pf group is a structure represented on the left side to W and the right side is — Each of the structures represented by X is bonded to O-, and the structure represented by X is bonded to the structure represented by -O- on the left side and Y on the right side.
In the above formula (2-b), W is —CH 2 CF 2 —, —CFClCF 2 —, —CF 2 CFCl—, —CH 2 CF 2 CF 2 — or —CH 2 CF (CF 3 ) —. preferably is; X is, -CF 2 -, - CF 2 CF 2 - or -CF (CF 3) - and is preferably. In the formula (2-b), the structure represented by W is bonded to the HO— on the left side and the Pf group on the right side; the Pf group is a structure represented on the left side to the W and —O Each of the structures represented by X is bonded to —O— on the left side and to the structure represented by Y on the right side.
In the above formula (2-c), V is CF 3 —, CF 3 CF 2 —, CF 3 CF 2 CF 2 —, CF 2 H—, HCF 2 CF 2 —, or HCF 2 CF 2 CF 2 —. preferably is; it is X, -CF 2 -, - CF 2 CF 2 -, - CFClCF 2 -, - CF 2 CFCl-, or -CF (CF 3) - and is preferably. In the formula (2-c), the Pf group is bonded to the structure represented by V on the left side and —O— on the right side; the structure represented by X has —O— on the left side and Each bond is bonded to the structure represented by Y.
In the above formula (2-d), R 1 is preferably a C 1-4 alkyl group; W is —CF 2 —, —CF 2 CF 2 —, —CFClCF 2 —, —CF 2 CFCl— , —CF (CF 3 ) CF 2 —, —CH 2 CF 2 —, —CF 2 CH 2 —, —CF 2 CF 2 CH 2 —, —CH 2 CF 2 CF 2 —, —CF (CF 3 ) CH 2 — or —CH 2 CF (CF 3 ) — is preferred; X is —CF 2 —, —CF 2 CF 2 —, —CFClCF 2 —, —CF 2 CFCl—, or —CF (CF 3 )-Is preferred. In the formula (2-d), the structure represented by W is bonded to —O— on the left side and the Pf group on the right side; the Pf group is the structure represented on the left side to W and the right side is — Each of the structures represented by X is bonded to O-, and the structure represented by X is bonded to the structure represented by -O- on the left side and Y on the right side.
　上記組成物（ａ１）の末端ＣＦ３基率は、２０％以上であることが好ましく、４０％以上であることがより好ましい。上記末端ＣＦ３基率は、８０％以下であってもよく、具体的には６０％以下である。組成物（ａ１）においては、上記末端ＣＦ３基率は、組成物（ａ１）に含まれる化合物の両末端に存在する末端基のモル数（全末端モル数）に対する、上記化合物の末端に存在する－ＣＦ３基のモル数の割合を意味する。上記化合物の両末端に存在する末端基としては、－ＣＦ３、－ＣＯＯＦ、－ＣＯＦ、－ＣＯＯＨ等を挙げることができる。上記末端ＣＦ３基率は、１９Ｆ－ＮＭＲを用いて測定できる。 The terminal CF 3 group ratio of the composition (a1) is preferably 20% or more, and more preferably 40% or more. The terminal CF 3 group ratio may be 80% or less, specifically 60% or less. In the composition (a1), the terminal CF 3 group ratio is present at the terminal of the compound with respect to the number of moles of terminal groups (total number of terminal moles) present at both terminals of the compound contained in the composition (a1). Means the proportion of moles of —CF 3 groups. Examples of the end groups present at both ends of the compound include —CF 3 , —COOF, —COF, —COOH and the like. The terminal CF 3 group ratio can be measured using 19 F-NMR.
　組成物（ａ１）は、Ｐｆ基含有化合物、Ｐｆ基含有モノカルボン酸化合物、およびＰｆ基含有ジカルボン酸化合物の合計１００質量部に対して、Ｐｆ基含有化合物を、１０～９０質量部、Ｐｆ基含有モノカルボン酸化合物を、２０～７０質量部、およびＰｆ基含有ジカルボン酸化合物を、１０～９０質量部含むことが好ましく；Ｐｆ基含有化合物を、１０～６０質量部、Ｐｆ基含有モノカルボン酸化合物を、３０～６０質量部、およびＰｆ基含有ジカルボン酸化合物を、１０～６０質量部含むことがより好ましい。 The composition (a1) contains 10 to 90 parts by mass of Pf group-containing compound, 100 parts by mass of Pf group-containing compound, 100 parts by mass of Pf group-containing monocarboxylic acid compound, and Pf group-containing dicarboxylic acid compound. It is preferable to contain 20 to 70 parts by mass of the monocarboxylic acid compound containing 10 to 90 parts by mass of the dicarboxylic acid compound containing Pf group; 10 to 60 parts by mass of Pf group containing compound and Pf group containing monocarboxylic acid More preferably, the compound contains 30 to 60 parts by mass and the Pf group-containing dicarboxylic acid compound contains 10 to 60 parts by mass.
　従来、Ｐｆ基含有モノカルボン酸化合物を含む組成物を分離することにより、Ｐｆ基含有モノカルボン酸化合物が得られてきた。従って、Ｐｆ基含有モノカルボン酸化合物の収率を高くするためには、上記分離前の組成物に含まれる、Ｐｆ基含有モノカルボン酸化合物の含有率が高いことが求められてきた。しかしながら、Ｐｆ基含有モノカルボン酸化合物の含有率の高い組成物の製造においては、フッ素化処理に時間を要していた。さらに、上記フッ素化処理において末端ＣＦ３基率を高くすると、組成物中の末端にカルボン酸基を有しない化合物（Ｐｆ基含有化合物）の含有率が高くなり得ることから、目的とするＰｆ基含有モノカルボン酸化合物の収率のみを高くすることは困難であった。 Conventionally, a Pf group-containing monocarboxylic acid compound has been obtained by separating a composition containing a Pf group-containing monocarboxylic acid compound. Therefore, in order to increase the yield of the Pf group-containing monocarboxylic acid compound, it has been demanded that the content of the Pf group-containing monocarboxylic acid compound contained in the composition before separation is high. However, in the production of a composition having a high content of the Pf group-containing monocarboxylic acid compound, it took time for the fluorination treatment. Furthermore, when the terminal CF 3 group ratio is increased in the fluorination treatment, the content of a compound having no carboxylic acid group (Pf group-containing compound) at the terminal in the composition can be increased. It was difficult to increase only the yield of the contained monocarboxylic acid compound.
　これに対して、本発明の方法では、組成物（ａ１）を分離する工程（Ｉ－１）で得られるＰｆ基含有ジカルボン酸化合物を、工程（Ｉ－１）の後に行う工程（Ａ１）においてフッ素化処理し、Ｐｆ基含有モノカルボン酸化合物を形成する。本発明の方法では、組成物（ａ１）として、上記のようにＰｆ基含有ジカルボン酸化合物の含有率の高い（末端ＣＦ３基率の低い）組成物を用い得る。従って、本発明の方法によると、組成物（ａ１）の製造に要する時間を、上記のような従来法よりも短縮し得る。 In contrast, in the method of the present invention, the Pf group-containing dicarboxylic acid compound obtained in the step (I-1) for separating the composition (a1) is used in the step (A1) performed after the step (I-1). Fluorination treatment is performed to form a Pf group-containing monocarboxylic acid compound. In the method of the present invention, as the composition (a1), as described above, a composition having a high content of the Pf group-containing dicarboxylic acid compound (low terminal CF 3 group ratio) can be used. Therefore, according to the method of the present invention, the time required for producing the composition (a1) can be shortened as compared with the conventional method as described above.
　組成物（ａ１）に含まれるＰｆ基含有モノカルボン酸化合物の数平均分子量は、５００～３０，０００の範囲にあることが好ましく、１，０００～２０，０００の範囲にあることがより好ましく、１，５００～１５，０００の範囲にあることがさらに好ましく、１,０００～１０,０００の範囲にあることが特に好ましく、３,０００～５,０００の範囲にあることがより好ましい。本明細書において、数平均分子量は１９Ｆ　ＮＭＲにより測定された値とする。 The number average molecular weight of the Pf group-containing monocarboxylic acid compound contained in the composition (a1) is preferably in the range of 500 to 30,000, more preferably in the range of 1,000 to 20,000, It is more preferably in the range of 1,500 to 15,000, particularly preferably in the range of 1,000 to 10,000, and more preferably in the range of 3,000 to 5,000. In the present specification, the number average molecular weight is a value measured by 19 F NMR.
　組成物（ａ１）に含まれるＰｆ基含有モノカルボン酸化合物の分子量分布は、２．０以下にあることが好ましく、１．５以下にあることがより好ましく、１．３以下にあることがさらに好ましい。本明細書において、分子量分布は、重量平均分子量／数平均分子量で表されるものであり、ゲル浸透クロマトグラフィー（ＧＰＣ）によって測定した値を用いて計算したものである。 The molecular weight distribution of the Pf group-containing monocarboxylic acid compound contained in the composition (a1) is preferably 2.0 or less, more preferably 1.5 or less, and further preferably 1.3 or less. preferable. In this specification, the molecular weight distribution is expressed by weight average molecular weight / number average molecular weight, and is calculated using a value measured by gel permeation chromatography (GPC).
　以下、工程（Ｉ－１）について説明する。 Hereinafter, the process (I-1) will be described.
　上記工程（Ｉ－１）は、組成物（ａ１）を、分離する工程である。上記組成物（ａ１）は、上記のように、少なくともＰｆ基含有化合物、Ｐｆ基含有モノカルボン酸化合物、および、Ｐｆ基含有ジカルボン酸化合物を含む。 The step (I-1) is a step of separating the composition (a1). The composition (a1) includes at least a Pf group-containing compound, a Pf group-containing monocarboxylic acid compound, and a Pf group-containing dicarboxylic acid compound as described above.
　上記工程（Ｉ－１）は、好ましくは、組成物（ａ１）から、Ｐｆ基含有ジカルボン酸化合物、および、Ｐｆ基含有モノカルボン酸化合物を分離する工程である。上記工程（Ｉ－１）は、より好ましくは、組成物（ａ１）から、Ｐｆ基含有ジカルボン酸化合物、Ｐｆ基含有モノカルボン酸化合物、およびＰｆ基含有化合物を分離する工程である。 The step (I-1) is preferably a step of separating the Pf group-containing dicarboxylic acid compound and the Pf group-containing monocarboxylic acid compound from the composition (a1). The step (I-1) is more preferably a step of separating the Pf group-containing dicarboxylic acid compound, the Pf group-containing monocarboxylic acid compound, and the Pf group-containing compound from the composition (a1).
　一の態様において、上記工程（Ｉ－１）により、組成物（ａ１）から、Ｐｆ基含有ジカルボン酸化合物、Ｐｆ基含有モノカルボン酸化合物、および、Ｐｆ基含有化合物を分離する。本態様の工程（Ｉ－１）により得られるＰｆ基含有モノカルボン酸化合物の収率は、工程（Ｉ－１）に供される組成物（ａ１）１００質量部に対して、例えば、２０～６０質量部であり得、具体的には３５～５０質量部であり得る。 In one embodiment, the Pf group-containing dicarboxylic acid compound, the Pf group-containing monocarboxylic acid compound, and the Pf group-containing compound are separated from the composition (a1) by the step (I-1). The yield of the Pf group-containing monocarboxylic acid compound obtained by the step (I-1) of this embodiment is, for example, 20 to 20 parts per 100 parts by mass of the composition (a1) to be used in the step (I-1). It may be 60 parts by weight, specifically 35-50 parts by weight.
　上記組成物（ａ１）から、Ｐｆ基含有ジカルボン酸化合物、Ｐｆ基含有モノカルボン酸化合物、および、Ｐｆ基含有化合物を分離する手段としては、ろ過、洗浄、抽出、ソックスレイ抽出、カラムクロマトグラフィなどが挙げられ、
　この方法は、
　組成物（ａ１）；フッ素原子含有非極性溶媒；および極性固定相；を混合し、これをカラムに密に詰まるように投入する。さらに、フッ素原子含有非極性溶媒をカラムに投入し、その後、カラムに充填した極性固定相（例えばシリカゲル相）の上面と、該フッ素原子含有非極性溶媒相の上面とが接するように、該フッ素原子含有非極性溶媒を排出する。その後、組成物（ａ１）をカラムの上部から投入する。その後、さらに、フッ素原子含有非極性溶媒をカラムに投入し、
　非極性移動相を用いて、上記分離手段により、極性固定相から、Ｐｆ基含有化合物を分離し、
　次いでＰｆ基含有モノカルボン酸化合物およびＰｆ基含有ジカルボン酸化合物を分離することを包含する。
　上記方法は、Ｐｆ基含有化合物の分離後であって、Ｐｆ基含有ジカルボン酸化合物の分離前に、Ｐｆ基含有モノカルボン酸化合物を分離することを含み得る。
　なお、分離されたＰｆ基含有化合物は加水分解反応の原料として、再利用することができる。 Examples of means for separating the Pf group-containing dicarboxylic acid compound, Pf group-containing monocarboxylic acid compound, and Pf group-containing compound from the composition (a1) include filtration, washing, extraction, Soxhlet extraction, and column chromatography. Named,
This method
Mix the composition (a1); a fluorine atom-containing nonpolar solvent; and a polar stationary phase; Further, a fluorine atom-containing nonpolar solvent is introduced into the column, and then the fluorine stationary phase (for example, silica gel phase) packed in the column is in contact with the top surface of the fluorine atom-containing nonpolar solvent phase. Drain the atom-containing nonpolar solvent. Thereafter, the composition (a1) is charged from the top of the column. Thereafter, a fluorine atom-containing nonpolar solvent is further added to the column,
Using a nonpolar mobile phase, the separation means separates the Pf group-containing compound from the polar stationary phase,
Then, separating the Pf group-containing monocarboxylic acid compound and the Pf group-containing dicarboxylic acid compound is included.
The method may include separating the Pf group-containing monocarboxylic acid compound after separation of the Pf group-containing compound and before separating the Pf group-containing dicarboxylic acid compound.
The separated Pf group-containing compound can be reused as a raw material for the hydrolysis reaction.
　上記極性固定相は、酸化アルミニウム、シリカゲル、酸化マグネシウム、アルミニウムシリケート、マグネシウムシリケート、化学修飾シリカゲル、珪藻土からなる群から選択されることが好ましく、その固定相表面に、－ＯＨ基、アミノ基、シアノ基、アルキル基、フルオロアルキル基などの極性基を有する固定相をいう。極性固定相であるシリカゲルとして、例えば、非修飾シリカゲル、アミノ基含有シリカゲル、シアノ基含有シリカゲルなどが挙げられる。
　本発明において、極性固定相として、シリカゲルを用いるのが好ましい。このような態様は、得られるＰｆ基含有モノカルボン酸化合物の分子量分布を狭くし得る観点から好ましい。また、シリカゲルを充填したカラムを用いることにより、分子量分布の制御が容易になり得る。これは、シリカゲル用いたカラムクロマトグラフィでは、分子量がカラム内の移動時間に影響することから、カラムから排出される溶液を分画し、分画された溶液を混合することによって、分子量分布の制御が可能となり得るためである。 The polar stationary phase is preferably selected from the group consisting of aluminum oxide, silica gel, magnesium oxide, aluminum silicate, magnesium silicate, chemically modified silica gel, and diatomaceous earth. A stationary phase having a polar group such as a group, an alkyl group or a fluoroalkyl group. Examples of the silica gel that is a polar stationary phase include unmodified silica gel, amino group-containing silica gel, and cyano group-containing silica gel.
In the present invention, silica gel is preferably used as the polar stationary phase. Such an embodiment is preferable from the viewpoint of narrowing the molecular weight distribution of the obtained Pf group-containing monocarboxylic acid compound. Moreover, control of molecular weight distribution can be facilitated by using a column packed with silica gel. This is because, in column chromatography using silica gel, the molecular weight affects the movement time in the column, so the molecular weight distribution can be controlled by fractionating the solution discharged from the column and mixing the fractionated solution. This may be possible.
　上記極性固定相は、市販品を用いてもよい。市販の極性固定相として、例えば、シリカゲルである、富士シリシア化学社製、クロマトレックス（ＰＳＱ－１００Ｂ）、和光純薬工業株式会社製、Ｗａｋｏｇｅｌ（商標）Ｃ－２００、Ｍｅｒｃｋ社製、１１５１１１シリカゲル６０などが挙げられる。 A commercial item may be used for the polar stationary phase. As a commercially available polar stationary phase, for example, silica gel, manufactured by Fuji Silysia Chemical Co., Chromatolex (PSQ-100B), manufactured by Wako Pure Chemical Industries, Ltd., Wakogel (trademark) C-200, manufactured by Merck Co., Ltd., 115111 silica gel 60 Etc.
　上記分離方法においては、最初に非極性移動相を用い、次いで極性移動相を用いて、極性固定相からの化合物の分離を行うことが好ましい。Ｐｆ基含有化合物は、Ｐｆ基含有モノカルボン酸化合物またはＰｆ基含有ジカルボン酸化合物と比べて極性が低い。そのため、Ｐｆ基含有化合物は、極性固定相に対する保持力が弱く、非極性移動相を用いた分離（例えばろ過など）において、溶出などによって分離し得る。 In the above separation method, it is preferable to first separate the compound from the polar stationary phase using a nonpolar mobile phase and then using a polar mobile phase. The Pf group-containing compound is less polar than the Pf group-containing monocarboxylic acid compound or the Pf group-containing dicarboxylic acid compound. Therefore, the Pf group-containing compound has a weak holding power with respect to the polar stationary phase, and can be separated by elution or the like in separation using a nonpolar mobile phase (for example, filtration).
　上記非極性移動相としては、１またはそれ以上のフッ素原子含有非極性溶媒を含む非極性移動相を用いることができる。 As the nonpolar mobile phase, a nonpolar mobile phase containing one or more fluorine atom-containing nonpolar solvents can be used.
　上記非極性移動相として、フッ素原子含有非極性溶媒であるハイドロクロロフルオロカーボン、ハイドロフルオロモノエーテル、フッ素原子含有芳香族溶媒、パーフルオロアルカン、ハイドロフルオロアルカン、ハイドロフルオロアルケン、パーフルオロポリエーテルから選択される少なくとも１種を用いるのがより好ましく、ハイドロフルオロモノエーテル、フッ素原子含有芳香族溶媒、ハイドロフルオロアルカンから選択される少なくとも１種を用いるのがさらに好ましい。 The nonpolar mobile phase is selected from hydrochlorofluorocarbons, hydrofluoromonoethers, fluorine atom-containing aromatic solvents, perfluoroalkanes, hydrofluoroalkanes, hydrofluoroalkenes, and perfluoropolyethers that are fluorine-containing nonpolar solvents. It is more preferable to use at least one selected from the group consisting of hydrofluoromonoether, fluorine atom-containing aromatic solvent, and hydrofluoroalkane.
　上記極性移動相として、
・１またはそれ以上のフッ素原子含有極性溶媒を含む極性移動相、
・フッ素原子含有非極性溶媒およびフッ素原子含有極性溶媒の組み合わせを含む極性移動相、または、
・フッ素原子含有非極性溶媒およびフッ素原子非含有極性溶媒の組み合わせを含む極性移動相、
のいずれかを用いることができる。このような非極性移動相および極性移動相を用いることによって、Ｐｆ基含有化合物とＰｆ基含有ジカルボン酸化合物、または、Ｐｆ基含有化合物とＰｆ基含有モノカルボン酸化合物とＰｆ基含有ジカルボン酸化合物とを、極性固定相からより良好に分離させることができ、そしてＰｆ基含有ジカルボン酸化合物、または、Ｐｆ基含有モノカルボン酸化合物およびＰｆ基含有ジカルボン酸化合物を、還流などの加熱操作を必要とすることなく、室温条件下でも取り出すことができる。 As the polar mobile phase,
A polar mobile phase comprising one or more fluorine atom-containing polar solvents,
A polar mobile phase comprising a combination of a fluorine atom-containing nonpolar solvent and a fluorine atom-containing polar solvent, or
A polar mobile phase comprising a combination of a fluorine atom-containing nonpolar solvent and a fluorine atom-free polar solvent,
Either of these can be used. By using such a nonpolar mobile phase and a polar mobile phase, a Pf group-containing compound and a Pf group-containing dicarboxylic acid compound, or a Pf group-containing compound, a Pf group-containing monocarboxylic acid compound, and a Pf group-containing dicarboxylic acid compound, Can be better separated from the polar stationary phase, and the Pf group-containing dicarboxylic acid compound, or the Pf group-containing monocarboxylic acid compound and the Pf group-containing dicarboxylic acid compound requires a heating operation such as reflux. And can be taken out even at room temperature.
　上記極性移動相として、フッ素原子含有非極性溶媒およびフッ素原子含有極性溶媒の組み合わせ、または、フッ素原子含有非極性溶媒およびフッ素原子非含有極性溶媒の組み合わせを用いる場合は、これらの溶媒の濃度を変化させて（グラジエントをかけて）用いてもよい。 When using a combination of a fluorine atom-containing nonpolar solvent and a fluorine atom-containing polar solvent, or a combination of fluorine atom-containing nonpolar solvent and a fluorine atom-free polar solvent as the polar mobile phase, the concentration of these solvents is changed. It may be used (over a gradient).
　本明細書において「フッ素原子含有非極性溶媒」とは、フッ素原子を含み、かつ、非極性または低極性である溶媒をいう。フッ素原子含有非極性溶媒として、例えば、クロロフルオロカーボン、ハイドロクロロフルオロカーボン、ハイドロフルオロモノエーテル、パーフルオロモノエーテル、パーフルオロアルカン、ハイドロフルオロアルカン、ハイドロフルオロアルケン、パーフルオロポリエーテル、パーフルオロアミン、フッ素原子含有アルケン、フッ素原子含有芳香族溶媒、フッ素原子含有ケトン、フッ素原子含有エステルなどが挙げられる。 As used herein, “fluorine atom-containing nonpolar solvent” refers to a solvent that contains a fluorine atom and is nonpolar or low in polarity. Examples of the fluorine atom-containing nonpolar solvent include chlorofluorocarbon, hydrochlorofluorocarbon, hydrofluoromonoether, perfluoromonoether, perfluoroalkane, hydrofluoroalkane, hydrofluoroalkene, perfluoropolyether, perfluoroamine, and fluorine atom. Included alkenes, fluorine atom-containing aromatic solvents, fluorine atom-containing ketones, fluorine atom-containing esters, and the like.
　上記クロロフルオロカーボンとして、例えば、Ｒ－１１３（Ｃ２Ｆ３Ｃｌ３）、２，２，３，３－テトラクロロヘキサフルオロブタンなどの、炭素数２～４のクロロフルオロカーボンが挙げられる。
　上記ハイドロクロロフルオロカーボンとして、ＨＣＦＣ２２５（ＣＦ３ＣＦ２ＣＨＣｌ２、ＣＣｌＦ２ＣＦ２ＣＨＣｌＦ）などの、炭素数３～６のハイドロクロロフルオロカーボンが挙げられる。
　上記ハイドロフルオロモノエーテルとして、例えば、Ｃ３Ｆ７ＯＣＨ３、Ｃ４Ｆ９ＯＣＨ３、Ｃ４Ｆ９ＯＣ２Ｈ５、Ｃ２Ｆ５ＣＦ（ＯＣＨ３）Ｃ３Ｆ７、ＣＦ３ＣＨ２ＯＣＦ２ＣＨＦ２、ＣＨＦ２ＣＦ２ＣＦ２ＣＦ２ＣＨ２ＯＣＨ３、ＣＦ３ＣＨＦＣＦ２ＯＣＨ２ＣＦ２ＣＨＦ２、ＣＨＦ２ＣＦ２ＣＨ２ＯＣＨＦＣＦ３、ＣＨＦ２ＯＣＨ２ＣＦ２ＣＨＦＣＦ３、ＣＦ３ＣＨＦＣＦ２ＯＣＨ２ＣＦ２ＣＦ３、ＣＨＦ２ＯＣＨ２ＣＦ２ＣＨＦ２、ＣＦ３ＣＨＦＣＦ２ＯＣＨ２ＣＦ３、ＣＨＦ２ＣＦ２ＯＣＨ２ＣＦ２ＣＦ３、ＣＦ３ＣＨ２ＯＣＨ２ＣＦ３、ＣＦ３ＣＨ２ＯＣＦ２ＣＨＦ２、ＣＦ３ＣＨＦＣＦ２ＯＣＨ３、ＣＨＦ２ＯＣＨ２ＣＦ２ＣＦ３、ＨＣＦ２ＣＦ２ＯＣ４Ｈ９などの、炭素数３～７のハイドロフルオロモノエーテルが挙げられる。
　上記パーフルオロモノエーテルとして、例えば、パーフルオロジプロピルエーテル、パーフルオロジブチルエーテル、パーフルオロ－２－トリフルオロメチル－４－オキサノナン、パーフルオロジペンチルエーテルなどの、炭素数６～１０のパーフルオロモノエーテルが挙げられる。
　上記パーフルオロアルカンとして、例えば、パーフルオロヘキサン、パーフルオロオクタンパーフルオロウンデカン、パーフルオロドデカンなどの、炭素数３～１２のパーフルオロアルカンが挙げられる。
　上記ハイドロフルオロアルカンとして、例えば、ＣＦ３ＣＨ２ＣＦ２ＣＨ３、ＣＦ３ＣＨＦＣＨＦＣ２Ｆ５、１，１，２，２，３，３，４－ヘプタフルオロシクロペンタン、ＣＦ３ＣＦ２ＣＦ２ＣＦ２ＣＨ２ＣＨ３、ＣＦ３ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＨ２ＣＨ３、ＣＦ３ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＨＦ２などの、炭素数３～８のハイドロフルオロアルカンが挙げられる。
　上記パーフルオロポリエーテルとして、例えば、Ｇａｌｄｅｎ ＳＶ－９０、ＨＧａｌｄｅｎ　ＺＶ１００、Ｇａｌｄｅｎ　ＨＴ５５、Ｇａｌｄｅｎ　ＨＴ７０、ＧａｌｄｅｎＨＴ９０、Ｇａｌｄｅｎ　ＨＴ１１０、Ｇａｌｄｅｎ　ＨＴ１３５、ＣＦ３ＯＣＦ２ＣＦ２ＯＣＦ３、ＣＦ３ＯＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ３、ＣＦ３ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ３、ＣＦ３ＯＣＦ２ＣＦ２ＯＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ３、ＣＦ３ＯＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ３などの、炭素数３～１０のパーフルオロポリエーテルが挙げられる。
　上記パーフルオロアミンとして、例えば、パーフルオロトリエチルアミン、パーフルオロトリプロピルアミン、パーフルオロトリブチルアミン、パーフルオロトリアミルアミンなどの、炭素数３～１５のパーフルオロアミンが挙げられる。
　上記フッ素原子含有アルケンとして、例えば、Ｃ６Ｆ１３ＣＨ＝ＣＨ２、Ｃ４Ｆ９ＣＨ＝ＣＨ２、Ｃ８Ｆ１５ＣＨ＝ＣＨ２などの、炭素数３～１０のフッ素原子含有アルケンが挙げられる。
　上記フッ素原子含有芳香族溶媒として、例えば、ｍ－キシレンヘキサフルオリド、パーフルオロベンゼン、トリフルオロベンゼン、モノフルオロベンゼンなどの、炭素数６～１２のフッ素原子含有芳香族溶媒が挙げられる。
　上記フッ素原子含有ケトンとして、例えば、メチルペンタデカフルオロヘプチルケトン、トリフルオロメチルエチルケトン、フェニルヘプタフルオロプロピルケトン、メチルヘプタフルオロプロピルケトン、フェニルトリフルオロメチルケトンなどの、炭素数２～１０のフッ素原子含有ケトンが挙げられる。
　上記フッ素原子含有エステルとして、例えば、トリフルオロ酢酸エチル、トリフルオロ酢酸メチル、ＣＦ３ＣＦ２ＣＯＯＣＨ３、ＣＦ３ＣＦ２ＣＯＯＣＨ２ＣＨ３などの、炭素数３～１０のフッ素原子含有エステルが挙げられる。 Examples of the chlorofluorocarbon include chlorofluorocarbons having 2 to 4 carbon atoms such as R-113 (C 2 F 3 Cl 3 ) and 2,2,3,3-tetrachlorohexafluorobutane.
Examples of the hydrochlorofluorocarbon include hydrochlorofluorocarbons having 3 to 6 carbon atoms such as HCFC225 (CF 3 CF 2 CHCl 2 , CClF 2 CF 2 CHClF).
As the hydrofluoroether monoethers, for example, C 3 F 7 OCH 3, C 4 F 9 OCH 3, C 4 F 9 OC 2 H 5, C 2 F 5 CF (OCH 3) C 3 F 7, CF 3 CH 2 OCF 2 CHF 2 , CHF 2 CF 2 CF 2 CF 2 CH 2 OCH 3 , CF 3 CHFCF 2 OCH 2 CF 2 CHF 2 , CHF 2 CF 2 CH 2 OCHFCF 3 , CHF 2 OCH 2 CF 2 CHFCF 3 , CF 3 CHFCF 2 OCH 2 CF 2 CF 3 , CHF 2 OCH 2 CF 2 CHF 2 , CF 3 CHFCF 2 OCH 2 CF 3 , CHF 2 CF 2 OCH 2 CF 2 CF 3 , CF 3 CH 2 OCH 2 CF 3 , CF 3 CH 2 OCF 2 CHF 2 , CF 3 CHFCF 2 OCH 3 , CHF 2 OCH 2 CF 2 Examples thereof include hydrofluoromonoethers having 3 to 7 carbon atoms such as CF 3 and HCF 2 CF 2 OC 4 H 9 .
Examples of the perfluoromonoether include perfluoromonopropyl ethers such as perfluorodipropyl ether, perfluorodibutyl ether, perfluoro-2-trifluoromethyl-4-oxanonane, perfluorodipentyl ether, and the like. Is mentioned.
Examples of the perfluoroalkane include perfluoroalkanes having 3 to 12 carbon atoms such as perfluorohexane, perfluorooctane perfluoroundecane, and perfluorododecane.
Examples of the hydrofluoroalkane include CF 3 CH 2 CF 2 CH 3 , CF 3 CHFCHFC 2 F 5 , 1,1,2,2,3,3,4-heptafluorocyclopentane, CF 3 CF 2 CF 2 CF C 2-8 hydrofluoroalkanes such as 2 CH 2 CH 3 , CF 3 CF 2 CF 2 CF 2 CF 2 CF 2 CH 2 CH 3 , CF 3 CF 2 CF 2 CF 2 CF 2 CHF 2 .
As the perfluoropolyether, for example, Galden SV-90, HGalden ZV100 , Galden HT55, Galden HT70, GaldenHT90, Galden HT110, Galden HT135, CF 3 OCF 2 CF 2 OCF 3, CF 3 OCF 2 OCF 2 CF 2 OCF 3 CF 3 OCF 2 CF 2 OCF 2 CF 2 OCF 3 , CF 3 OCF 2 CF 2 OCF 2 OCF 2 CF 2 OCF 3 , CF 3 OCF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 3, etc. 10 perfluoropolyethers.
Examples of the perfluoroamine include perfluoroamines having 3 to 15 carbon atoms such as perfluorotriethylamine, perfluorotripropylamine, perfluorotributylamine, and perfluorotriamylamine.
Examples of the fluorine atom-containing alkene include fluorine atom-containing alkenes having 3 to 10 carbon atoms such as C 6 F 13 CH═CH 2 , C 4 F 9 CH═CH 2 , and C 8 F 15 CH═CH 2. It is done.
Examples of the fluorine atom-containing aromatic solvent include fluorine atom-containing aromatic solvents having 6 to 12 carbon atoms such as m-xylene hexafluoride, perfluorobenzene, trifluorobenzene, and monofluorobenzene.
Examples of the fluorine atom-containing ketone include fluorine atom-containing ketones having 2 to 10 carbon atoms such as methyl pentadecafluoroheptyl ketone, trifluoromethyl ethyl ketone, phenylheptafluoropropyl ketone, methylheptafluoropropyl ketone, and phenyltrifluoromethyl ketone. Is mentioned.
Examples of the fluorine atom-containing ester include fluorine atom-containing esters having 3 to 10 carbon atoms such as ethyl trifluoroacetate, methyl trifluoroacetate, CF 3 CF 2 COOCH 3 , and CF 3 CF 2 COOCH 2 CH 3. .
　これらのフッ素原子含有非極性溶媒は、１種のみを用いてもよく、２種以上を併用してもよい。 These fluorine atom-containing nonpolar solvents may be used alone or in combination of two or more.
　上記フッ素原子含有非極性溶媒として市販品を用いてもよい。市販品として、例えば、
　３Ｍ社製、Ｎｏｖｅｃ（商標）シリーズのハイドロフルオロモノエーテル、例えばＮｏｖｅｃ（商標）７０００（Ｃ３Ｆ７ＯＣＨ３）、Ｎｏｖｅｃ（商標）７１００（Ｃ４Ｆ９ＯＣＨ３）、Ｎｏｖｅｃ（商標）７２００（Ｃ４Ｆ９ＯＣ２Ｈ５）、Ｎｏｖｅｃ（商標）７３００（Ｃ２Ｆ５ＣＦ（ＯＣＨ３）Ｃ３Ｆ７）、Ｎｏｖｅｃ（商標）７１ＩＰＡなど；
　ＡＧＣ旭硝子社製のハイドロフルオロエーテル、例えばＡＥ－３０００など；
　ＡＧＣ旭硝子社製のハイドロフルオロアルカン、例えばＡＣ－６０００（Ｃ６Ｆ１３Ｃ２Ｈ５）、ＡＣ－２０００（ＣＦ３ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＨＦ２）、ＡＣ－４０００（ＣＦ３ＣＦ２ＣＦ２ＣＦ２ＣＨ２ＣＨ３）など；
　Ｓｏｌｖａｙ社製のパーフルオロポリエーテル、例えばＧａｌｄｅｎＳＶ－９０、ＨＧａｌｄｅｎ　ＺＶ１００、Ｇａｌｄｅｎ　ＨＴ５５、Ｇａｌｄｅｎ　ＨＴ７０、ＧａｌｄｅｎＨＴ９０、Ｇａｌｄｅｎ　ＨＴ１１０、Ｇａｌｄｅｎ　ＨＴ１３５など；
　３Ｍ社製のパーフルオロアルカン、例えばパーフルオロヘキサン、Ｆｌｕｏｒｉｎｅｒｔ（商標）ＦＣ－４０、Ｆｌｕｏｒｉｎｅｒｔ（商標）ＦＣ－７２、Ｆｌｕｏｒｉｎｅｒｔ（商標）ＦＣ－７５、Ｆｌｕｏｒｉｎｅｒｔ（商標）ＦＣ－７７、Ｆｌｕｏｒｉｎｅｒｔ（商標）ＦＣ－８４、Ｆｌｕｏｒｉｎｅｒｔ（商標）ＦＣ－１０４など；
　上記のクロロフルオロカーボン（Ｒ－１１３）およびハイドロクロロフルオロカーボン（ＨＣＦＣ２２５）など；
が挙げられる。上記市販品の中では、Ｎｏｖｅｃ（商標）７２００（Ｃ４Ｆ９ＯＣ２Ｈ５）、Ｎｏｖｅｃ（商標）、７３００（Ｃ２Ｆ５ＣＦ（ＯＣＨ３）Ｃ３Ｆ７）、ＡＣ－６０００（Ｃ６Ｆ１３Ｃ２Ｈ５）、ＦＣ－７２を用いることが好ましい。 Commercially available products may be used as the fluorine atom-containing nonpolar solvent. As a commercial product, for example,
3M, Novec ™ series of hydrofluoromonoethers such as Novec ™ 7000 (C 3 F 7 OCH 3 ), Novec ™ 7100 (C 4 F 9 OCH 3 ), Novec ™ 7200 ( C 4 F 9 OC 2 H 5 ), Novec ( TM) 7300 (C 2 F 5 CF (OCH 3) C 3 F 7), Novec ( TM) 71IPA like;
Hydrofluoroether manufactured by AGC Asahi Glass Co., for example, AE-3000;
Hydrofluoroalkanes manufactured by AGC Asahi Glass Co., for example, AC-6000 (C 6 F 13 C 2 H 5 ), AC-2000 (CF 3 CF 2 CF 2 CF 2 CF 2 CHF 2 ), AC-4000 (CF 3 CF 2 CF 2 CF 2 CH 2 CH 3 ) and the like;
Perfluoropolyethers from Solvay, such as Galden SV-90, HGalden ZV100, Galden HT55, Galden HT70, Galden HT90, Galden HT110, Galden HT135;
Perfluoroalkanes from 3M, such as perfluorohexane, Fluorinert ™ FC-40, Fluorinert ™ FC-72, Fluorinert ™ FC-75, Fluorinert ™ FC-77, Fluorinert ™ FC -84, such as Fluorinert ™ FC-104;
Chlorofluorocarbon (R-113) and hydrochlorofluorocarbon (HCFC225) as described above;
Is mentioned. Among the above commercially available products, Novec (TM) 7200 (C 4 F 9 OC 2 H 5), Novec ( TM), 7300 (C 2 F 5 CF (OCH 3) C 3 F 7), AC-6000 (C 6 F 13 C 2 H 5 ), FC-72 is preferably used.
　また、上記フッ素原子含有非極性溶媒は、沸点が２０～２００℃の範囲内であるものがより好ましい。フッ素原子含有非極性溶媒の沸点が２０～２００℃の範囲内であることによって、上記化合物を分離した後の溶媒留去操作を容易に行うことができる利点がある。 The fluorine atom-containing nonpolar solvent is more preferably one having a boiling point in the range of 20 to 200 ° C. When the boiling point of the fluorine atom-containing nonpolar solvent is in the range of 20 to 200 ° C., there is an advantage that the solvent can be easily distilled off after the compound is separated.
　本明細書において「フッ素原子含有極性溶媒」とは、フッ素原子を含み、かつ、極性を有する溶媒をいう。フッ素原子含有極性溶媒として、例えば、フッ素原子含有アルコール、フッ素原子含有カルボン酸、フッ素原子含有スルホン酸などの溶媒が挙げられる。 In this specification, the “fluorine atom-containing polar solvent” refers to a solvent containing a fluorine atom and having polarity. Examples of the fluorine atom-containing polar solvent include solvents such as a fluorine atom-containing alcohol, a fluorine atom-containing carboxylic acid, and a fluorine atom-containing sulfonic acid.
　上記フッ素原子含有アルコールとして、例えば、ＣＦ３ＣＨ２ＯＨ、ＣＦ３ＣＦ２ＣＨ２ＯＨ、ＣＦ３ＣＦ２ＣＦ２ＣＨ２ＯＨ、ヘキサフルオロイソプロパノール、ＨＣＦ２ＣＦ２ＣＨ２ＯＨ、ＨＣＦ２ＣＨ２ＯＨ、ＣＦ３ＣＦ２ＣＦ２ＣＦ２ＣＨ２ＣＨ２ＯＨ、ＣＦ３ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＨ２ＣＨ２ＯＨ、ＣＦ３ＣＦ２ＣＦ２ＣＨ（ＯＨ）ＣＨ３、ＣＦ３ＯＣＦ２ＣＦ２ＯＣＦ２ＣＨ２ＯＨ、ＣＦ３ＯＣＦ２ＣＦ２ＯＣＦ２ＯＣＦ２ＣＨ２ＯＨ、ＣＦ３ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ（ＣＦ３）ＣＨ２ＯＨ、ＣＦ３ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＯＣＦ（ＣＦ３）ＣＨ２ＯＨ、ＣＦ３Ｃ６Ｈ５ＯＨ、ＨＯＣＨ２（ＣＦ２）６ＣＨ２ＯＨ、Ｃ４Ｆ９ＣＨ２ＣＨ２ＣＨ２ＯＨなどの、炭素数２～１０のフッ素原子含有アルコールが挙げられる。
　上記フッ素原子含有カルボン酸として、例えば、トリフルオロ酢酸、ジフルオロ酢酸、クロロジフルオロ酢酸、ＣＦ３ＣＦ２ＣＯ２Ｈ、ＣＦ３ＣＦ２ＣＦ２ＣＯ２Ｈ、ＨＯ２Ｃ（ＣＦ２）３ＣＯ２Ｈ、ＨＯ２Ｃ（ＣＦ２）６ＣＯ２Ｈ、Ｈ（ＣＦ２）６ＣＯ２Ｈ、ＣＦ３ＯＣＦ２ＣＦ２ＯＣＦ２ＣＯ２Ｈ、ＣＦ３ＯＣＦ２ＣＦ２ＯＣＦ２ＯＣＦ２ＣＯ２Ｈ、ＣＦ３ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ（ＣＦ３）ＣＯ２Ｈ、ＣＦ３ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＯＣＦ（ＣＦ３）ＣＯ２Ｈなどの、炭素数２～１０のフッ素原子含有カルボン酸が挙げられる。
　上記フッ素原子含有スルホン酸として、トリフルオロメタンスルホン酸、ペンタフルオロオクタンスルホン酸、パーフルオロエトキシエタンスルホン酸などの、炭素数１～１０のフッ素原子含有スルホン酸が挙げられる。 Examples of the fluorine atom-containing alcohol include CF 3 CH 2 OH, CF 3 CF 2 CH 2 OH, CF 3 CF 2 CF 2 CH 2 OH, hexafluoroisopropanol, HCF 2 CF 2 CH 2 OH, and HCF 2 CH 2 OH. , CF 3 CF 2 CF 2 CF 2 CH 2 CH 2 OH, CF 3 CF 2 CF 2 CF 2 CF 2 CF 2 CH 2 CH 2 OH, CF 3 CF 2 CF 2 CH (OH) CH 3, CF 3 OCF 2 CF 2 OCF 2 CH 2 OH, CF 3 OCF 2 CF 2 OCF 2 OCF 2 CH 2 OH, CF 3 OCF (CF 3) CF 2 OCF (CF 3) CH 2 OH, CF 3 OCF (CF 3) CF 2 OCF 2 OCF (CF 3) CH 2 OH, CF 3 C 6 H 5 OH, HOCH 2 (CF 2) 6 CH 2 H, such as C 4 F 9 CH 2 CH 2 CH 2 OH, include fluorine-containing alcohols of 2-10 carbon atoms.
Examples of the fluorine atom-containing carboxylic acid include trifluoroacetic acid, difluoroacetic acid, chlorodifluoroacetic acid, CF 3 CF 2 CO 2 H, CF 3 CF 2 CF 2 CO 2 H, HO 2 C (CF 2 ) 3 CO 2 H , HO 2 C (CF 2 ) 6 CO 2 H, H (CF 2 ) 6 CO 2 H, CF 3 OCF 2 CF 2 OCF 2 CO 2 H, CF 3 OCF 2 CF 2 OCF 2 OCF 2 CO 2 H, CF 3 OCF (CF 3 ) CF 2 OCF (CF 3 ) CO 2 H, CF 3 OCF (CF 3 ) CF 2 OCF 2 OCF (CF 3 ) CO 2 H and other fluorine atom-containing carboxylic acids having 2 to 10 carbon atoms Is mentioned.
Examples of the fluorine atom-containing sulfonic acid include fluorine atom-containing sulfonic acids having 1 to 10 carbon atoms such as trifluoromethanesulfonic acid, pentafluorooctanesulfonic acid, and perfluoroethoxyethanesulfonic acid.
　これらのフッ素原子含有極性溶媒は、１種のみを用いてもよく、２種以上を併用してもよい。 These fluorine atom-containing polar solvents may be used alone or in combination of two or more.
　上記フッ素原子含有極性溶媒は、沸点が２０～２００℃の範囲内であるものがより好ましい。フッ素原子含有極性溶媒の沸点が２０～２００℃の範囲内であることによって、上記化合物を分離した後の溶媒留去操作を容易に行うことができる利点がある。 The fluorine atom-containing polar solvent preferably has a boiling point in the range of 20 to 200 ° C. When the boiling point of the fluorine atom-containing polar solvent is in the range of 20 to 200 ° C., there is an advantage that the solvent can be easily distilled off after the compound is separated.
　なお、フッ素原子含有極性溶媒において用いられるフッ素原子含有カルボン酸には、Ｐｆ基含有モノカルボン酸化合物、およびＰｆ基含有ジカルボン酸化合物は含まれないものとする。 The fluorine atom-containing carboxylic acid used in the fluorine atom-containing polar solvent does not include a Pf group-containing monocarboxylic acid compound and a Pf group-containing dicarboxylic acid compound.
　本明細書において「フッ素原子非含有極性溶媒」とは、極性を有する溶媒であって、かつフッ素原子を含まない溶媒、すなわち、極性を有する溶媒であって上記フッ素原子含有極性溶媒に該当しないもの、をいう。フッ素原子非含有極性溶媒として、例えば、酢酸などのカルボン酸溶媒；フェノール、クレゾールなどのフェノール溶媒；メタンスルホン酸などのスルホン酸溶媒；ジメチルスルホキシド、スルホラン、アセトニトリル、Ｎ，Ｎ－ジメチルホルムアミド、ジメチルアセトアミド、Ｎ－メチルピロリドンなどが挙げられる。これらのフッ素原子非含有極性溶媒は、１種のみを用いてもよく、２種以上を併用してもよい。 In this specification, “a fluorine-atom-free polar solvent” is a solvent that has polarity and does not contain a fluorine atom, that is, a solvent that has polarity and does not fall under the above-mentioned fluorine-atom-containing polar solvent. Say. Examples of polar solvents not containing fluorine atoms include carboxylic acid solvents such as acetic acid; phenol solvents such as phenol and cresol; sulfonic acid solvents such as methanesulfonic acid; dimethyl sulfoxide, sulfolane, acetonitrile, N, N-dimethylformamide, dimethylacetamide N-methylpyrrolidone and the like. These fluorine atom-free polar solvents may be used alone or in combination of two or more.
　上記フッ素原子非含有極性溶媒として、カルボン酸溶媒およびスルホン酸溶媒からなる群から選択される溶媒を１種またはそれ以上で用いるのが好ましい。 As the fluorine atom-free polar solvent, it is preferable to use one or more solvents selected from the group consisting of carboxylic acid solvents and sulfonic acid solvents.
　なお、上記フッ素原子非含有極性溶媒において、メタノールは含まれない。メタノールは、極性固定相を用いるカラムクロマトグラフィにおいて、極性移動相として一般的に用いられる溶出溶媒である。一方で、Ｐｆ基含有モノカルボン酸化合物およびＰｆ基含有ジカルボン酸化合物は、極性溶媒としてメタノールを含む極性移動相を用いる場合においては、極性固定相から分離させ溶出させることができない。そのため上記極性移動相として、１またはそれ以上のフッ素原子含有極性溶媒を含むか、フッ素原子含有非極性溶媒およびフッ素原子含有極性溶媒の組み合わせを含むか、または、フッ素原子含有非極性溶媒およびフッ素原子非含有極性溶媒（但しメタノールは含まれない）の組み合わせを含むものを用いることを特徴とする。 Note that methanol is not included in the above fluorine atom-free polar solvent. Methanol is an elution solvent generally used as a polar mobile phase in column chromatography using a polar stationary phase. On the other hand, the Pf group-containing monocarboxylic acid compound and the Pf group-containing dicarboxylic acid compound cannot be separated and eluted from the polar stationary phase when using a polar mobile phase containing methanol as a polar solvent. Therefore, the polar mobile phase contains one or more fluorine atom-containing polar solvents, a combination of fluorine atom-containing nonpolar solvents and fluorine atom-containing polar solvents, or fluorine atom-containing nonpolar solvents and fluorine atoms. What uses the combination of the non-containing polar solvent (however, methanol is not included) is used.
　好ましい態様において、上記極性移動相は、１またはそれ以上のフッ素原子含有極性溶媒を含むものであるか、または、フッ素原子含有非極性溶媒およびフッ素原子含有極性溶媒の組み合わせを含み、より好ましくは、フッ素原子含有非極性溶媒およびフッ素原子含有極性溶媒の組み合わせを含む。本態様において、上記フッ素原子含有非極性溶媒は、フッ素原子含有エステル、フッ素原子含有アルカン、およびフッ素原子含有エーテルからなる群より選ばれる少なくとも１であることが好ましく、上記フッ素原子含有極性溶媒は、フッ素原子含有アルコール、およびフッ素原子含有カルボン酸からなる群より選ばれる少なくとも１であることが好ましい。 In a preferred embodiment, the polar mobile phase includes one or more fluorine atom-containing polar solvents, or includes a combination of a fluorine atom-containing nonpolar solvent and a fluorine atom-containing polar solvent, more preferably a fluorine atom. A combination of a nonpolar solvent containing and a fluorine atom containing polar solvent is included. In this embodiment, the fluorine atom-containing nonpolar solvent is preferably at least one selected from the group consisting of a fluorine atom-containing ester, a fluorine atom-containing alkane, and a fluorine atom-containing ether, and the fluorine atom-containing polar solvent is It is preferably at least one selected from the group consisting of a fluorine atom-containing alcohol and a fluorine atom-containing carboxylic acid.
　別の好ましい態様において、上記極性移動相は、１またはそれ以上のフッ素原子含有極性溶媒を含むものであるか、または、フッ素原子含有非極性溶媒およびフッ素原子含有極性溶媒の組み合わせを含む。ここで、フッ素原子含有非極性溶媒は、ハイドロクロロフルオロカーボン、パーフルオロアルカン、ハイドロフルオロモノエーテル、フッ素原子含有芳香族溶媒およびハイドロフルオロアルカンから選択される少なくとも１種であるのが好ましく、フッ素原子含有極性溶媒は、フッ素原子含有アルコールおよびフッ素原子含有カルボン酸から選択される少なくとも１種であるのが好ましい。また上記極性移動相が、フッ素原子含有非極性溶媒およびフッ素原子非含有極性溶媒の組み合わせを含むものである場合は、フッ素原子含有非極性溶媒は、ハイドロフルオロモノエーテル、フッ素原子含有芳香族溶媒およびハイドロフルオロアルカンから選択される少なくとも１種であるのが好ましく、フッ素原子非含有極性溶媒がカルボン酸溶媒であるのが好ましい。 In another preferred embodiment, the polar mobile phase includes one or more fluorine atom-containing polar solvents, or includes a combination of a fluorine atom-containing nonpolar solvent and a fluorine atom-containing polar solvent. Here, the fluorine atom-containing nonpolar solvent is preferably at least one selected from hydrochlorofluorocarbons, perfluoroalkanes, hydrofluoromonoethers, fluorine atom-containing aromatic solvents and hydrofluoroalkanes, and contains fluorine atoms. The polar solvent is preferably at least one selected from a fluorine atom-containing alcohol and a fluorine atom-containing carboxylic acid. When the polar mobile phase contains a combination of a fluorine atom-containing nonpolar solvent and a fluorine atom-free polar solvent, the fluorine atom-containing nonpolar solvent is a hydrofluoromonoether, a fluorine atom-containing aromatic solvent, or a hydrofluorocarbon. It is preferably at least one selected from alkanes, and the polar solvent not containing fluorine atoms is preferably a carboxylic acid solvent.
　上記極性移動相のより好ましい具体的な態様として、下記例が挙げられる。
Figure JPOXMLDOC01-appb-T000016
 The following example is mentioned as a more preferable specific aspect of the said polar mobile phase.
Figure JPOXMLDOC01-appb-T000016
　上記工程（Ｉ－１）において用いられる極性移動相は、Ｐｆ基含有ジカルボン酸化合物、または、Ｐｆ基含有モノカルボン酸化合物およびＰｆ基含有ジカルボン酸化合物を、シリカゲルを担体とする薄層クロマトグラフィーによって、極性移動相を展開溶媒として用いて展開した場合、上記Ｐｆ基含有ジカルボン酸化合物、または、上記Ｐｆ基含有モノカルボン酸化合物および上記Ｐｆ基含有ジカルボン酸化合物のＲｆ値が０．１以上となる条件を満たすものであることが好ましい。 The polar mobile phase used in the above step (I-1) is obtained by thin-layer chromatography using a Pf group-containing dicarboxylic acid compound, or a Pf group-containing monocarboxylic acid compound and a Pf group-containing dicarboxylic acid compound, using silica gel as a carrier. When the polar mobile phase is developed as a developing solvent, the Rf value of the Pf group-containing dicarboxylic acid compound, or the Pf group-containing monocarboxylic acid compound and the Pf group-containing dicarboxylic acid compound is 0.1 or more. It is preferable that the condition is satisfied.
　上記薄層クロマトグラフィーは、支持体上に、薄い層状に設けられた微粉末を固定相とし、溶媒を移動相として用いて行う、クロマトグラフィーである。本明細書においては、薄層クロマトグラフィーに使用する固定相として、シリカゲルを用いる。シリカゲルとして、例えば、Ｍｅｒｃｋ社製、１０５７１５　ＴＬＣガラスプレートシリカゲル６０Ｆ２５４などが挙げられる。
　前記薄層クロマトグラフィーに使用する支持体としては、特に制限はなく、目的に応じて適宜選択することができる。支持体として、例えば、ガラス板、アルミシート、プラスチックシートなどが挙げられる。 The thin layer chromatography is a chromatography performed on a support using a fine powder provided in a thin layer as a stationary phase and a solvent as a mobile phase. In the present specification, silica gel is used as a stationary phase used in thin layer chromatography. Examples of the silica gel include Merck's 105715 TLC glass plate silica gel 60F 254 .
There is no restriction | limiting in particular as a support body used for the said thin layer chromatography, According to the objective, it can select suitably. Examples of the support include a glass plate, an aluminum sheet, and a plastic sheet.
　薄層クロマトグラフィーにおける具体的な手順の一例は、以下の通りである。薄層クロマトグラフィーの固定相として、縦方向５ｃｍを有する、シリカゲル薄層プレートを準備する。Ｐｆ基含有モノカルボン酸化合物および／またはＰｆ基含有ジカルボン酸化合物０．１ｇを、上述したフッ素原子含有非極性溶媒（例えば、ｍ－キシレンヘキサフルオリド）１ｍｌに溶解して、サンプル液を調製する。次いで、薄層プレートの下端から５ｍｍの位置に、ガラスマイクロキャピラリを用いて、２～１０μｌのサンプル液をスポットする。このスポット位置が、展開スタート地点（原点）となる。サンプル液をスポットした後、しばらく放置するなどして、薄層プレートを十分に乾燥させる。
　薄層クロマトグラフィー用展開槽に、展開溶媒を、０．２～３．５ｍｍの深さになるまで予め入れておき、展開槽中において展開溶媒の蒸気が飽和するまで放置しておく。
　サンプルをスポットした薄層プレートを、原点が展開溶媒に直接浸らないように静かに入れる。展開槽に蓋をし、薄層プレート上に上昇してくる溶媒の先端が、薄層プレートの上端から約５ｍｍの位置に到達するまで静置する。
　次いで、薄層プレートを展開槽から取りだし、その後、ホットプレート上で加熱し、展開溶媒を十分に乾燥させる。乾燥した薄層プレートを、５％過マンガン酸カリウム水溶液中に浸漬し、その後、ホットプレート上で再度加熱する。
　５％過マンガン酸カリウム水溶液は赤紫色であるため、この水溶液中に薄層プレートを浸漬することによって、薄層プレート全体が赤紫色となる。その中で、この操作によって、Ｐｆ基含有モノカルボン酸化合物および／またはＰｆ基含有ジカルボン酸化合物のスポットは白色となる。
　図１は、薄層クロマトグラフィーにより得られるクロマトグラムのモデル図である。本明細書における、上記Ｒｆ値は、原点から、化合物のスポットの中心までの距離Ｌｘを、溶媒の展開距離Ｌで除した値である。
Ｒｆ値＝Ｌｘ／Ｌ An example of a specific procedure in thin layer chromatography is as follows. As a stationary phase for thin layer chromatography, a silica gel thin layer plate having a vertical direction of 5 cm is prepared. A sample solution is prepared by dissolving 0.1 g of a Pf group-containing monocarboxylic acid compound and / or a Pf group-containing dicarboxylic acid compound in 1 ml of the above-mentioned fluorine atom-containing nonpolar solvent (for example, m-xylene hexafluoride). . Next, 2 to 10 μl of sample liquid is spotted using a glass microcapillary at a position 5 mm from the lower end of the thin layer plate. This spot position becomes the development start point (origin). After spotting the sample solution, leave the plate for a while to dry the thin layer plate sufficiently.
The developing solvent is placed in the developing tank for thin layer chromatography in advance until it reaches a depth of 0.2 to 3.5 mm, and left in the developing tank until the vapor of the developing solvent is saturated.
Gently place the thin plate on which the sample is spotted so that the origin is not directly immersed in the developing solvent. Cover the developing tank and let it stand until the tip of the solvent rising on the thin layer plate reaches a position of about 5 mm from the upper end of the thin layer plate.
Next, the thin layer plate is taken out from the developing tank, and then heated on a hot plate to sufficiently dry the developing solvent. The dried thin plate is immersed in a 5% aqueous potassium permanganate solution and then heated again on a hot plate.
Since the 5% potassium permanganate aqueous solution is reddish purple, immersing the thin layer plate in this aqueous solution turns the entire thin layer plate reddish purple. Among them, the spot of the Pf group-containing monocarboxylic acid compound and / or the Pf group-containing dicarboxylic acid compound becomes white by this operation.
FIG. 1 is a model diagram of a chromatogram obtained by thin layer chromatography. In the present specification, the Rf value is a value obtained by dividing the distance L x from the origin to the center of the compound spot by the development distance L of the solvent.
Rf value = L x / L
　Ｐｆ基含有モノカルボン酸化合物、Ｐｆ基含有ジカルボン酸化合物の上記Ｒｆ値について、Ｒｆ値が０．１以上であれば、極性固定相からの分離が可能である。つまり、極性移動相を展開溶媒として用いて展開した場合において、Ｐｆ基含有モノカルボン酸化合物のＲｆ値が０．１以上であることによって、Ｐｆ基含有モノカルボン酸化合物を、極性固定相から分離し取り出すことができる。また、Ｐｆ基含有ジカルボン酸化合物のＲｆ値が０．１以上であることによって、Ｐｆ基含有ジカルボン酸化合物を、極性固定相から分離し取り出すことができる。なお上記Ｒｆ値は０．１～０．８であるのがより好ましい。 When the Rf value of the Pf group-containing monocarboxylic acid compound and the Pf group-containing dicarboxylic acid compound is 0.1 or more, separation from the polar stationary phase is possible. That is, when the polar mobile phase is developed as a developing solvent, the Pf group-containing monocarboxylic acid compound is separated from the polar stationary phase by the Rf value of the Pf group-containing monocarboxylic acid compound being 0.1 or more. And can be taken out. Moreover, when the Rf value of the Pf group-containing dicarboxylic acid compound is 0.1 or more, the Pf group-containing dicarboxylic acid compound can be separated and taken out from the polar stationary phase. The Rf value is more preferably 0.1 to 0.8.
　本発明において、例えば、極性移動相として、フッ素原子含有非極性溶媒であるハイドロフルオロモノエーテルとフッ素原子含有極性溶媒とを組み合わせて用いる場合は、フッ素原子含有極性溶媒を単独で極性移動相として用いる場合と比べて、Ｒｆ値がより大きくなることがある。これは、フッ素原子含有極性溶媒が、上記Ｐｆ基含有ジカルボン酸化合物、または、上記Ｐｆ基含有モノカルボン酸化合物および上記Ｐｆ基含有ジカルボン酸化合物の極性移動相からの脱離を促し、一方でフッ素原子含有非極性溶媒であるハイドロフルオロモノエーテルが、上記Ｐｆ基含有モノカルボン酸化合物および上記Ｐｆ基含有ジカルボン酸化合物との親和性が高いことから良好に溶解させるためであると考えられる。そしてこのような組み合わせの極性移動相を用いることによって、Ｐｆ基含有モノカルボン酸化合物、Ｐｆ基含有ジカルボン酸化合物をより良好に分離することができるという利点がある。
　好ましい一態様として、Ｐｆ基含有ジカルボン酸化合物を、シリカゲルを担体とする薄層クロマトグラフィーによって、前記極性移動相を展開溶媒として用いて展開した場合、上記Ｐｆ基含有ジカルボン酸化合物のＲｆ値が０．１以上となる条件を満たす態様が挙げられる。この条件を満たす極性移動相を用いることによって、上記Ｐｆ基含有ジカルボン酸化合物を、極性固定相から良好に分離し取り出すことができる。なお上記Ｒｆ値は０．１～０．５であるのがより好ましく、０．１～０．４であるのがさらに好ましい。 In the present invention, for example, when a hydrofluoromonoether that is a fluorine atom-containing nonpolar solvent and a fluorine atom-containing polar solvent are used in combination as the polar mobile phase, the fluorine atom-containing polar solvent is used alone as the polar mobile phase. Compared to the case, the Rf value may be larger. This is because the fluorine atom-containing polar solvent promotes elimination of the Pf group-containing dicarboxylic acid compound, or the Pf group-containing monocarboxylic acid compound and the Pf group-containing dicarboxylic acid compound from the polar mobile phase, while fluorine This is considered to be because hydrofluoromonoether, which is an atom-containing nonpolar solvent, dissolves well because of its high affinity with the Pf group-containing monocarboxylic acid compound and the Pf group-containing dicarboxylic acid compound. By using a polar mobile phase in such a combination, there is an advantage that the Pf group-containing monocarboxylic acid compound and the Pf group-containing dicarboxylic acid compound can be separated more favorably.
As a preferred embodiment, when the Pf group-containing dicarboxylic acid compound is developed by thin layer chromatography using silica gel as a carrier using the polar mobile phase as a developing solvent, the Rf value of the Pf group-containing dicarboxylic acid compound is 0. The aspect which satisfy | fills the conditions used as 1 or more is mentioned. By using a polar mobile phase that satisfies this condition, the Pf group-containing dicarboxylic acid compound can be satisfactorily separated and extracted from the polar stationary phase. The Rf value is more preferably from 0.1 to 0.5, and even more preferably from 0.1 to 0.4.
　好ましい他の一態様として、分離段階に応じて、用いる極性移動相を変える態様が挙げられる。例えば、極性移動相を展開溶媒として用いて展開した場合、Ｐｆ基含有モノカルボン酸化合物のＲｆ値が０．１以上となり、かつ、Ｐｆ基含有ジカルボン酸化合物のＲｆ値が０．１未満となる条件を満たす極性移動相を用いることによって、Ｐｆ基含有モノカルボン酸化合物をより良好に分離することができる。次いで、Ｐｆ基含有ジカルボン酸化合物のＲｆ値が０．１以上となる極性移動相を用いることによって、Ｐｆ基含有ジカルボン酸化合物を得ることができる。 Another preferable embodiment is an embodiment in which the polar mobile phase to be used is changed depending on the separation stage. For example, when developed using a polar mobile phase as a developing solvent, the Rf value of the Pf group-containing monocarboxylic acid compound is 0.1 or more, and the Rf value of the Pf group-containing dicarboxylic acid compound is less than 0.1. By using a polar mobile phase that satisfies the conditions, the Pf group-containing monocarboxylic acid compound can be more favorably separated. Next, the Pf group-containing dicarboxylic acid compound can be obtained by using a polar mobile phase in which the Rf value of the Pf group-containing dicarboxylic acid compound is 0.1 or more.
　本発明において、Ｐｆ基含有モノカルボン酸化合物、およびＰｆ基含有ジカルボン酸化合物を分離する、とは、下記に示す状態で取り出された状態をいう。例えば、Ｐｆ基含有モノカルボン酸化合物を分離し取り出すとは、本発明の方法によって、上記混合物から分離し取り出された状態において、Ｐｆ基含有モノカルボン酸化合物のモル比が、分離する前の状態よりも向上していることをいい、好ましくは、Ｐｆ基含有モノカルボン酸化合物：Ｐｆ基含有ジカルボン酸化合物＝１００：０～９０：１０、より好ましくは１００：０～９５：５、さらに好ましくは１００：０～９８：２、特に好ましくは１００：０～９９：１、より好ましくは１００：０～９９．５：０．５、さらに好ましくは１００：０～９９．９：０．１の範囲内である場合をいう。また例えば、Ｐｆ基含有ジカルボン酸化合物を分離し取り出すとは、本発明の方法によって上記混合物から分離し取り出された状態において、Ｐｆ基含有ジカルボン酸化合物のモル比が、分離する前の状態よりも向上している事をいい、好ましくは、Ｐｆ基含有モノカルボン酸化合物：Ｐｆ基含有ジカルボン酸化合物＝０：１００～１０：９０、より好ましくは０：１００～５：９５、さらに好ましくは０：１００～２：９８、特に好ましくは０：１００～１：９９、より好ましくは０：１００～０．５：９９．５、さらに好ましくは０：１００～０．１：９９．９の範囲内である場合をいう。 In the present invention, the separation of the Pf group-containing monocarboxylic acid compound and the Pf group-containing dicarboxylic acid compound means a state of being taken out in the following state. For example, the separation and removal of the Pf group-containing monocarboxylic acid compound means that the molar ratio of the Pf group-containing monocarboxylic acid compound is the state before separation in the state separated and removed from the mixture by the method of the present invention. Preferably, Pf group-containing monocarboxylic acid compound: Pf group-containing dicarboxylic acid compound = 100: 0 to 90:10, more preferably 100: 0 to 95: 5, still more preferably The range is 100: 0 to 98: 2, particularly preferably 100: 0 to 99: 1, more preferably 100: 0 to 99.5: 0.5, and still more preferably 100: 0 to 99.9: 0.1. When it is within. In addition, for example, the separation and removal of the Pf group-containing dicarboxylic acid compound means that the molar ratio of the Pf group-containing dicarboxylic acid compound in the state separated and removed from the mixture by the method of the present invention is greater than that before the separation. Preferably, Pf group-containing monocarboxylic acid compound: Pf group-containing dicarboxylic acid compound = 0: 100 to 10:90, more preferably 0: 100 to 5:95, still more preferably 0: Within the range of 100 to 2:98, particularly preferably 0: 100 to 1:99, more preferably 0: 100 to 0.5: 99.5, still more preferably 0: 100 to 0.1: 99.9. Say a case.
　以下、工程（Ａ１）について説明する。 Hereinafter, the step (A1) will be described.
　上記工程（Ａ１）は、上記工程（Ｉ－１）により分離されたＰｆ基含有ジカルボン酸化合物をフッ素化処理し、Ｐｆ基含有モノカルボン酸を得る工程である。本態様においては、上記工程（Ａ１）を行うことにより、Ｐｆ基含有モノカルボン酸化合物の収率が向上し得る。 The step (A1) is a step of obtaining a Pf group-containing monocarboxylic acid by fluorinating the Pf group-containing dicarboxylic acid compound separated in the step (I-1). In this embodiment, the yield of the Pf group-containing monocarboxylic acid compound can be improved by performing the step (A1).
　工程（Ａ１）に供されるＰｆ基含有ジカルボン酸化合物は、上記のように工程（Ｉ－１）により分離されたものである。すなわち、上記「Ｐｆ基含有ジカルボン酸化合物」は、Ｐｆ基含有ジカルボン酸化合物を含む混合物、例えば、Ｐｆ基含有モノカルボン酸化合物およびＰｆ基含有ジカルボン酸化合物を含む混合物として供され得る。この場合、モル比で、好ましくは、Ｐｆ基含有モノカルボン酸化合物：Ｐｆ基含有ジカルボン酸化合物＝０：１００～１０：９０、より好ましくは０：１００～５：９５、さらに好ましくは０：１００～２：９８、特に好ましくは０：１００～１：９９、より好ましくは０：１００～０．５：９９．５、さらに好ましくは０：１００～０．１：９９．９の範囲内にある。
　上記Ｐｆ基含有モノカルボン酸化合物およびＰｆ基含有ジカルボン酸化合物を含む混合物において、末端ＣＦ３基率は、１％以上であってもよく、１０％以上であってもよい。上記末端ＣＦ３基率は、５０％以下であってもよく、３０％以下であってもよい。上記末端ＣＦ３基率は、例えば１％～４０％であり、具体的には１０％～３０％である。
　上記末端ＣＦ３基率は、上記Ｐｆ基含有モノカルボン酸化合物およびＰｆ基含有ジカルボン酸化合物を含む混合物においては、該混合物に含まれる、Ｐｆ基含有モノカルボン酸化合物およびＰｆ基含有ジカルボン酸化合物の両末端に存在する末端基の合計モル数に対するＣＦ３基のモル数の割合を意味する。 The Pf group-containing dicarboxylic acid compound used in the step (A1) is separated by the step (I-1) as described above. That is, the “Pf group-containing dicarboxylic acid compound” can be provided as a mixture containing a Pf group-containing dicarboxylic acid compound, for example, a mixture containing a Pf group-containing monocarboxylic acid compound and a Pf group-containing dicarboxylic acid compound. In this case, the molar ratio is preferably Pf group-containing monocarboxylic acid compound: Pf group-containing dicarboxylic acid compound = 0: 100 to 10:90, more preferably 0: 100 to 5:95, and still more preferably 0: 100. To 2:98, particularly preferably 0: 100 to 1:99, more preferably 0: 100 to 0.5: 99.5, still more preferably 0: 100 to 0.1: 99.9. .
In the mixture containing the Pf group-containing monocarboxylic acid compound and the Pf group-containing dicarboxylic acid compound, the terminal CF 3 group ratio may be 1% or more, or 10% or more. The terminal CF 3 group ratio may be 50% or less, or 30% or less. The terminal CF 3 group ratio is, for example, 1% to 40%, specifically 10% to 30%.
In the mixture containing the Pf group-containing monocarboxylic acid compound and the Pf group-containing dicarboxylic acid compound, the terminal CF 3 group ratio is the ratio of the Pf group-containing monocarboxylic acid compound and the Pf group-containing dicarboxylic acid compound contained in the mixture. It means the ratio of the number of moles of CF 3 groups to the total number of moles of terminal groups present at both ends.
　上記フッ素化処理の条件は特に限定されない。フッ素化処理は、Ｐｆ基含有ジカルボン酸化合物（またはＰｆ基含有ジカルボン酸化合物を含む組成物）とフッ素含有化合物とを接触させることにより行うことができる。 The conditions for the fluorination treatment are not particularly limited. The fluorination treatment can be performed by bringing a Pf group-containing dicarboxylic acid compound (or a composition containing a Pf group-containing dicarboxylic acid compound) into contact with a fluorine-containing compound.
　上記フッ素含有化合物としては特に限定されないが、フッ素化処理条件下にてフッ素ラジカルを発生するフッ素ラジカル源が挙げられる。上記フッ素ラジカル源としては、Ｆ２、ＣｏＦ３、ＡｇＦ２、ＵＦ６、ＯＦ２、Ｎ２Ｆ２、ＣＦ３ＯＦ、フッ化ハロゲン（例えばＩＦ５、ＣｌＦ３）等が挙げられる。 Although it does not specifically limit as said fluorine-containing compound, The fluorine radical source which generate | occur | produces a fluorine radical under fluorination process conditions is mentioned. Examples of the fluorine radical source include F 2 , CoF 3 , AgF 2 , UF 6 , OF 2 , N 2 F 2 , CF 3 OF, and halogen fluoride (eg, IF 5 , ClF 3 ).
　上記Ｆ２等のフッ素ラジカル源は、１００％濃度のものであってもよいが、５～５０質量％に希釈して使用することが好ましく、１５～３０質量％に希釈して使用することがより好ましい。例えば、上記フッ素ラジカル源が、不活性ガスと混合し得る場合（具体的には、上記フッ素ラジカル源がガス状である場合）には、安全性の面からフッ素ラジカル源を、不活性ガスと混合し５～５０質量％に希釈して使用することが好ましく、１５～３０質量％に希釈して使用することがより好ましい。上記不活性ガスとしては、窒素ガス、ヘリウムガス、アルゴンガス等が挙げられるが、経済的な面より窒素ガスが好ましい。 The fluorine radical source such as F 2 may have a concentration of 100%, but is preferably diluted to 5 to 50% by mass, and diluted to 15 to 30% by mass. More preferred. For example, when the fluorine radical source can be mixed with an inert gas (specifically, when the fluorine radical source is gaseous), the fluorine radical source and the inert gas are used for safety. It is preferably mixed and diluted to 5 to 50% by mass, more preferably 15 to 30% by mass. Examples of the inert gas include nitrogen gas, helium gas, and argon gas. Nitrogen gas is preferable from the economical viewpoint.
　上記フッ素化処理は、５０℃～２００℃において行うことが好ましく、８０℃～１５０℃において行うことがより好ましい。上記フッ素化処理は、一般に０．５～５０時間、好ましくは１～２０時間行う。上記フッ素化処理は、１００℃～１４０℃にて、２～１０時間行うことが好ましい。 The fluorination treatment is preferably performed at 50 ° C. to 200 ° C., more preferably 80 ° C. to 150 ° C. The fluorination treatment is generally performed for 0.5 to 50 hours, preferably 1 to 20 hours. The fluorination treatment is preferably performed at 100 to 140 ° C. for 2 to 10 hours.
　上記工程（Ａ１）のフッ素化処理によって、式（２）で表されるＰｆ基含有モノカルボン酸化合物を含む混合物が得られる。工程（Ａ１）のフッ素化処理によって得られる混合物の末端ＣＦ３基率は、２０％以上であることが好ましく、４０％以上であることがより好ましい。上記末端ＣＦ３基率は、８０％以下であってもよく、具体的には６０％以下である。上記末端ＣＦ３基率は、工程（Ａ１）により得られる混合物において、該混合物に含まれる、Ｐｆ基含有化合物、Ｐｆ基含有モノカルボン酸化合物およびＰｆ基含有ジカルボン酸化合物の両末端に存在する末端基の合計モル数に対するＣＦ３基のモル数の割合を意味する。末端ＣＦ３基率の測定条件については、それぞれ上記のとおりである。 By the fluorination treatment in the step (A1), a mixture containing the Pf group-containing monocarboxylic acid compound represented by the formula (2) is obtained. The terminal CF 3 group ratio of the mixture obtained by the fluorination treatment in the step (A1) is preferably 20% or more, and more preferably 40% or more. The terminal CF 3 group ratio may be 80% or less, specifically 60% or less. In the mixture obtained by the step (A1), the terminal CF 3 group ratio is the terminal existing at both ends of the Pf group-containing compound, the Pf group-containing monocarboxylic acid compound and the Pf group-containing dicarboxylic acid compound contained in the mixture. It means the ratio of the number of moles of CF 3 groups to the total number of moles of groups. The measurement conditions for the terminal CF 3 group ratio are as described above.
　上記工程（Ａ１）のフッ素化処理によって得られる混合物における末端ＣＦ３基率は、１０％以上であることが好ましく、２０％以上であることがより好ましい。上記末端ＣＦ３基率は、７０％以下であることが好ましく、６０％以下であることがより好ましく、５０％以下であることがさらに好ましく、４５％以下であることが特に好ましい。上記末端ＣＦ３基率は、２０％～５０％であることが好ましく、２５％～４５％であることがより好ましい。
　上記ＣＦ３基率は、工程（Ａ１）により得られる混合物に含まれる、Ｐｆ基含有化合物、Ｐｆ基含有モノカルボン酸化合物およびＰｆ基含有ジカルボン酸化合物の両末端に存在する末端基の合計モル数に対するＣＦ３基のモル数の割合を意味する。 The terminal CF 3 group ratio in the mixture obtained by the fluorination treatment in the step (A1) is preferably 10% or more, and more preferably 20% or more. The terminal CF 3 group ratio is preferably 70% or less, more preferably 60% or less, further preferably 50% or less, and particularly preferably 45% or less. The terminal CF 3 group ratio is preferably 20% to 50%, and more preferably 25% to 45%.
The CF 3 group ratio is the total number of moles of terminal groups present at both terminals of the Pf group-containing compound, Pf group-containing monocarboxylic acid compound and Pf group-containing dicarboxylic acid compound contained in the mixture obtained in the step (A1). It means the ratio of the number of moles of CF 3 groups to
　上記工程（Ａ１）によって得られる混合物に含まれるＰｆ基含有モノカルボン酸化合物は、分子量分布が、２以下にあることが好ましく、１．５以下にあることがより好ましく、１．３以下にあることがさらに好ましい。 The Pf group-containing monocarboxylic acid compound contained in the mixture obtained by the step (A1) preferably has a molecular weight distribution of 2 or less, more preferably 1.5 or less, and 1.3 or less. More preferably.
　上記工程（Ａ１）によって得られる混合物に含まれるＰｆ基含有モノカルボン酸化合物の数平均分子量は、５００～３０，０００の範囲にあることが好ましく、１，０００～２０，０００の範囲にあることがより好ましく、１，５００～１５，０００の範囲にあることがさらに好ましく、１,０００～１０,０００の範囲にあることが特に好ましく、３,０００～５,０００の範囲にあることがより好ましい。 The number average molecular weight of the Pf group-containing monocarboxylic acid compound contained in the mixture obtained by the step (A1) is preferably in the range of 500 to 30,000, and in the range of 1,000 to 20,000. Is more preferably in the range of 1,500 to 15,000, more preferably in the range of 1,000 to 10,000, and more preferably in the range of 3,000 to 5,000. preferable.
　上記工程（Ａ１）のフッ素化処理では、工程（Ｉ－１）で分離されたＰｆ基含有ジカルボン酸化合物（あるいはＰｆ基含有ジカルボン酸化合物を含む組成物）を処理する。工程（Ｉ－１）の分離を行うことにより、高分子量あるいは低分子量を有する化合物の含有率が低くなる。その結果、工程（Ａ１）において上記のような分子量分布または分子量を有する化合物が得られると考えられる。 In the fluorination treatment in the above step (A1), the Pf group-containing dicarboxylic acid compound (or the composition containing the Pf group-containing dicarboxylic acid compound) separated in the step (I-1) is treated. By performing the separation in the step (I-1), the content of the compound having a high molecular weight or a low molecular weight is lowered. As a result, it is considered that a compound having the molecular weight distribution or molecular weight as described above is obtained in the step (A1).
　上記工程（Ａ１）は、Ｐｆ基含有ジカルボン酸化合物（またはＰｆ基含有ジカルボン酸化合物を含む組成物）をフッ素化処理して得られる混合物（例えば、Ｐｆ含有モノカルボン酸化合物およびＰｆ含有ジカルボン酸化合物を含む混合物）から、少なくともＰｆ含有モノカルボン酸化合物を、分離することをさらに含むことが好ましい。 The step (A1) is a mixture obtained by fluorinating a Pf group-containing dicarboxylic acid compound (or a composition containing a Pf group-containing dicarboxylic acid compound) (for example, a Pf-containing monocarboxylic acid compound and a Pf-containing dicarboxylic acid compound). It is preferable to further comprise separating at least the Pf-containing monocarboxylic acid compound from the mixture containing
　上記分離にはカラムクロマトグラフィを用いることが好ましい。カラムクロマトグラフィを用いる方法としては、工程（Ｉ－１）について記載した方法と同様の方法を用いることができる。 It is preferable to use column chromatography for the above separation. As a method using column chromatography, a method similar to the method described for the step (I-1) can be used.
　本態様においては、工程（Ａ１）後のＰｆ基含有モノカルボン酸化合物の収率は、工程（Ｉ－１）に供した組成物（ａ１）１００質量部に対して、７０質量部以上であることが好ましく、８０質量部以上であることがより好ましく、８５質量部以上であることが特に好ましい。本態様において、工程（Ａ１）後のＰｆ基含有モノカルボン酸化合物の収率は、上記工程（Ｉ－１）に供した組成物（ａ１）１００質量部に対して、７０～１００質量部の範囲にあることが好ましく、８５～１００質量部の範囲にあることがより好ましい。 In this embodiment, the yield of the Pf group-containing monocarboxylic acid compound after the step (A1) is 70 parts by mass or more with respect to 100 parts by mass of the composition (a1) subjected to the step (I-1). Is more preferably 80 parts by mass or more, and particularly preferably 85 parts by mass or more. In this embodiment, the yield of the Pf group-containing monocarboxylic acid compound after the step (A1) is 70 to 100 parts by mass with respect to 100 parts by mass of the composition (a1) subjected to the above step (I-1). It is preferably in the range, and more preferably in the range of 85 to 100 parts by mass.
（実施態様２）
　図３に、本発明のＰｆ基含有モノカルボン酸化合物を製造する方法の一態様を示す。図３のエーテル基含有化合物、モノカルボン酸化合物、およびジカルボン酸化合物は、それぞれ、Ｐｆ基含有化合物、Ｐｆ基含有モノカルボン酸化合物、およびＰｆ基含有ジカルボン酸化合物を意味する。 (Embodiment 2)
FIG. 3 shows one embodiment of a method for producing the Pf group-containing monocarboxylic acid compound of the present invention. The ether group-containing compound, monocarboxylic acid compound, and dicarboxylic acid compound in FIG. 3 mean a Pf group-containing compound, a Pf group-containing monocarboxylic acid compound, and a Pf group-containing dicarboxylic acid compound, respectively.
　本態様のＰｆ基含有モノカルボン酸化合物の製造方法は、
　組成物（ａ２）を、分離する工程（Ｉ－２）、
　上記分離により得られるＰｆ基含有ジカルボン酸化合物をフッ素化処理し、少なくとも式（２）で表されるＰｆ基含有モノカルボン酸化合物と式（３）で表されるＰｆ基含有ジカルボン酸化合物とを含む混合物を得、該混合物から、式（２）で表されるＰｆ基含有モノカルボン酸化合物および式（３）で表されるＰｆ基含有ジカルボン酸化合物を分離することを含む工程（Ａ２）、および
　上記工程（Ａ２）における分離により得られるＰｆ基含有ジカルボン酸化合物をフッ素化処理し、式（２）で表されるＰｆ基含有モノカルボン酸化合物を含む混合物を得る工程（Ｂ２）を含む。 The method for producing the Pf group-containing monocarboxylic acid compound of this embodiment includes:
Separating the composition (a2) (I-2),
The Pf group-containing dicarboxylic acid compound obtained by the above separation is fluorinated, and at least a Pf group-containing monocarboxylic acid compound represented by the formula (2) and a Pf group-containing dicarboxylic acid compound represented by the formula (3) And a step (A2) comprising separating a Pf group-containing monocarboxylic acid compound represented by the formula (2) and a Pf group-containing dicarboxylic acid compound represented by the formula (3) from the mixture. And a step (B2) of obtaining a mixture containing the Pf group-containing monocarboxylic acid compound represented by the formula (2) by fluorinating the Pf group-containing dicarboxylic acid compound obtained by the separation in the step (A2).
　工程（Ｉ－２）、および工程（Ａ２）は、それぞれ、工程（Ｉ）および工程（Ａ）の一態様である。組成物（ａ２）は、組成物（ａ）に対応する。 Step (I-2) and Step (A2) are embodiments of Step (I) and Step (A), respectively. The composition (a2) corresponds to the composition (a).
　組成物（ａ２）は、Ｐｆ基含有ジカルボン酸化合物のフッ素化処理を行う工程により得られたものであってもよい。該工程は、工程（Ｚ１）と同様に行うことができる。 The composition (a2) may be obtained by a step of fluorinating the Pf group-containing dicarboxylic acid compound. This step can be performed in the same manner as in step (Z1).
　工程（Ｉ－２）は、工程（Ｉ－１）と同様に行うことができる。組成物（ａ２）は、組成物（ａ１）と同意義である。 Step (I-2) can be performed in the same manner as Step (I-1). The composition (a2) has the same meaning as the composition (a1).
　工程（Ｉ－２）における分離は、カラムクロマトグラフィを用いることが好ましい。カラムクロマトグラフィの条件は、上記のとおりである。 In the step (I-2), column chromatography is preferably used. The conditions for column chromatography are as described above.
　上記工程（Ａ２）において得られる組成物の末端ＣＦ３基率は、１０％以上であることが好ましく、２０％以上であることがより好ましい。上記末端ＣＦ３基率は、７０％以下であることが好ましく、６０％以下であることがより好ましく、５０％以下であることがさらに好ましく、４５％以下であることが特に好ましい。上記末端ＣＦ３基率は、２５％～５０％であることが好ましく、３０％～４５％であることがより好ましい。
　上記末端ＣＦ３基率は、工程（Ａ２）において得られる組成物において、該組成物に含まれる、Ｐｆ基含有化合物、Ｐｆ基含有モノカルボン酸化合物およびＰｆ基含有ジカルボン酸化合物の両末端に存在する末端基の合計モル数に対するＣＦ３基のモル数の割合を意味する。 The terminal CF 3 group ratio of the composition obtained in the step (A2) is preferably 10% or more, and more preferably 20% or more. The terminal CF 3 group ratio is preferably 70% or less, more preferably 60% or less, further preferably 50% or less, and particularly preferably 45% or less. The terminal CF 3 group ratio is preferably 25% to 50%, more preferably 30% to 45%.
The terminal CF 3 group ratio is present in both ends of the Pf group-containing compound, the Pf group-containing monocarboxylic acid compound and the Pf group-containing dicarboxylic acid compound contained in the composition in the step (A2). It means the ratio of the number of moles of CF 3 group to the total number of moles of terminal groups.
　工程（Ａ２）は、複数回繰り返して実施してもよい。 Step (A2) may be repeated a plurality of times.
　工程（Ｂ２）に供されるＰｆ基含有ジカルボン酸化合物は、上記のように工程（Ａ２）により分離されたものである。すなわち、上記「Ｐｆ基含有ジカルボン酸化合物」は、Ｐｆ基含有ジカルボン酸化合物を含む混合物、例えば、Ｐｆ基含有モノカルボン酸化合物およびＰｆ基含有ジカルボン酸化合物を含む混合物として供され得る。この場合、モル比で、好ましくは、Ｐｆ基含有モノカルボン酸化合物：Ｐｆ基含有ジカルボン酸化合物＝０：１００～１０：９０、より好ましくは０：１００～５：９５、さらに好ましくは０：１００～２：９８、特に好ましくは０：１００～１：９９、より好ましくは０：１００～０．５：９９．５、さらに好ましくは０：１００～０．１：９９．９の範囲内にある。
　上記Ｐｆ基含有モノカルボン酸化合物およびＰｆ基含有ジカルボン酸化合物を含む混合物において、末端ＣＦ３基率は、１％以上であってもよく、１０％以上であってもよい。上記末端ＣＦ３基率は、５０％以下であってもよく、３０％以下であってもよい。上記末端ＣＦ３基率は、例えば１％～４０％であり、具体的には１０％～３０％である。
　上記末端ＣＦ３基率は、上記Ｐｆ基含有モノカルボン酸化合物およびＰｆ基含有ジカルボン酸化合物を含む混合物において、該混合物に含まれる、Ｐｆ基含有モノカルボン酸化合物およびＰｆ基含有ジカルボン酸化合物の両末端に存在する末端基の合計モル数に対するＣＦ３基のモル数の割合を意味する。 The Pf group-containing dicarboxylic acid compound used in the step (B2) is separated by the step (A2) as described above. That is, the “Pf group-containing dicarboxylic acid compound” can be provided as a mixture containing a Pf group-containing dicarboxylic acid compound, for example, a mixture containing a Pf group-containing monocarboxylic acid compound and a Pf group-containing dicarboxylic acid compound. In this case, the molar ratio is preferably Pf group-containing monocarboxylic acid compound: Pf group-containing dicarboxylic acid compound = 0: 100 to 10:90, more preferably 0: 100 to 5:95, and still more preferably 0: 100. To 2:98, particularly preferably 0: 100 to 1:99, more preferably 0: 100 to 0.5: 99.5, still more preferably 0: 100 to 0.1: 99.9. .
In the mixture containing the Pf group-containing monocarboxylic acid compound and the Pf group-containing dicarboxylic acid compound, the terminal CF 3 group ratio may be 1% or more, or 10% or more. The terminal CF 3 group ratio may be 50% or less, or 30% or less. The terminal CF 3 group ratio is, for example, 1% to 40%, specifically 10% to 30%.
The terminal CF 3 group ratio is the ratio of both the Pf group-containing monocarboxylic acid compound and the Pf group-containing dicarboxylic acid compound contained in the mixture in the mixture containing the Pf group-containing monocarboxylic acid compound and the Pf group-containing dicarboxylic acid compound. It means the ratio of the number of moles of CF 3 groups to the total number of moles of terminal groups present at the terminal.
　上記工程（Ｂ２）におけるフッ素化処理は、工程（Ａ１）におけるフッ素化処理と同様に行うことができる。 The fluorination treatment in the above step (B2) can be performed in the same manner as the fluorination treatment in the step (A1).
　工程（Ｂ２）におけるフッ素化処理により得られる混合物に含まれるＰｆ基含有モノカルボン酸化合物は、該混合物に対して、モル比で１０％以上であることが好ましく、２０％以上であることが好ましく；７０％以下であってもよく、６０％以下であってもよく、５０％以下であってもよく、４５％以下であってもよい。Ｐｆ基含有モノカルボン酸化合物は、該混合物に対して、モル比で、２０％～５０％の範囲にあってもよく、２５％～４５％の範囲にあってもよい。 The Pf group-containing monocarboxylic acid compound contained in the mixture obtained by the fluorination treatment in the step (B2) is preferably 10% or more, preferably 20% or more, in terms of molar ratio with respect to the mixture. 70% or less, 60% or less, 50% or less, or 45% or less. The Pf group-containing monocarboxylic acid compound may be in the range of 20% to 50% or in the range of 25% to 45% by molar ratio with respect to the mixture.
　工程（Ｂ２）は、さらに、フッ素化処理後のＰｆ基含有ジカルボン酸化合物を含む混合物から、少なくともＰｆ基含有モノカルボン酸化合物を、分離することをさらに含むことが好ましい。工程（Ｂ２）における分離は、工程（Ａ１）における分離と同様に行うことができ、例えば、カラムクロマトグラフィを用いることができる。 It is preferable that the step (B2) further includes separating at least the Pf group-containing monocarboxylic acid compound from the mixture containing the Pf group-containing dicarboxylic acid compound after the fluorination treatment. Separation in the step (B2) can be performed in the same manner as the separation in the step (A1). For example, column chromatography can be used.
　本態様においては、工程（Ｂ２）を行うことにより、Ｐｆ基含有モノカルボン酸化合物の収率がさらに向上し得る。 In this embodiment, the yield of the Pf group-containing monocarboxylic acid compound can be further improved by performing the step (B2).
　本態様によると、Ｐｆ基含有モノカルボン酸化合物の収率は、工程（Ｉ－２）に供される組成物（ａ２）１００質量部に対して、７０質量部以上であることが好ましく、８０質量部以上であることがより好ましく、８５質量部以上であることが特に好ましい。 According to this embodiment, the yield of the Pf group-containing monocarboxylic acid compound is preferably 70 parts by mass or more with respect to 100 parts by mass of the composition (a2) to be used in the step (I-2). More preferably, it is more than 85 parts by mass.
（実施態様３）
　図４に、本発明のＰｆ基含有モノカルボン酸化合物を製造する方法の一態様を示す。図４において、エーテル基含有化合物、モノカルボン酸化合物、およびジカルボン酸化合物は、それぞれ、Ｐｆ基含有化合物、Ｐｆ基含有モノカルボン酸化合物、およびＰｆ基含有ジカルボン酸化合物を意味する。 (Embodiment 3)
FIG. 4 shows one embodiment of a method for producing the Pf group-containing monocarboxylic acid compound of the present invention. In FIG. 4, an ether group-containing compound, a monocarboxylic acid compound, and a dicarboxylic acid compound mean a Pf group-containing compound, a Pf group-containing monocarboxylic acid compound, and a Pf group-containing dicarboxylic acid compound, respectively.
　本態様は、工程（Ｂ３）の後、さらに工程（Ｂ３）において得られる混合物を、組成物（ａ３）の少なくとも一部として用いて、再利用することを特徴とする。工程（Ｂ３）、組成物（ａ３）は、それぞれ工程（Ｂ）、組成物（ａ）に対応する。 This aspect is characterized in that after the step (B3), the mixture obtained in the step (B3) is further used as at least part of the composition (a3) and reused. The step (B3) and the composition (a3) correspond to the step (B) and the composition (a), respectively.
　具体的には、本態様のＰｆ基含有モノカルボン酸化合物の製造方法は、
　組成物（ａ３）を、分離する工程（Ｉ－３）、
　上記分離により得られるＰｆ基含有ジカルボン酸化合物をフッ素化処理し、少なくともＰｆ基含有モノカルボン酸化合物とＰｆ基含有ジカルボン酸化合物とを含む混合物を得、該混合物から、Ｐｆ基含有モノカルボン酸化合物およびＰｆ基含有ジカルボン酸化合物を、分離することを含む工程（Ａ３）、
　上記工程（Ａ３）における分離で得られるＰｆ基含有ジカルボン酸化合物をフッ素化処理して、Ｐｆ基含有モノカルボン酸化合物を含む混合物を得る工程（Ｂ３）、および
　上記工程（Ｂ３）の後、さらに工程（Ｂ３）で得られる混合物を、組成物（ａ３）の少なくとも一部として用い、再度、前記組成物（ａ３）を用いて工程（Ｉ－３）、工程（Ａ３）および工程（Ｂ３）を行うことを含む。すなわち、本態様においては、工程（Ｂ３）で得られるＰｆ基含有ジカルボン酸化合物を、組成物（ａ３）の一部として再利用することができる。 Specifically, the method for producing the Pf group-containing monocarboxylic acid compound of this embodiment includes:
Separating the composition (a3) (I-3),
The Pf group-containing dicarboxylic acid compound obtained by the above separation is fluorinated to obtain a mixture containing at least the Pf group-containing monocarboxylic acid compound and the Pf group-containing dicarboxylic acid compound, and the Pf group-containing monocarboxylic acid compound is obtained from the mixture. And separating the Pf group-containing dicarboxylic acid compound (A3),
Fluorination treatment of the Pf group-containing dicarboxylic acid compound obtained by the separation in the step (A3) to obtain a mixture containing the Pf group-containing monocarboxylic acid compound, and after the step (B3), Using the mixture obtained in step (B3) as at least part of the composition (a3), again using the composition (a3), steps (I-3), (A3) and (B3) Including doing. That is, in this embodiment, the Pf group-containing dicarboxylic acid compound obtained in the step (B3) can be reused as part of the composition (a3).
　工程（Ｉ－３）、および工程（Ａ３）は、それぞれ、工程（Ｉ）および工程（Ａ）の一態様である。組成物（ａ３）は、組成物（ａ）に対応する。 Step (I-3) and step (A3) are embodiments of step (I) and step (A), respectively. The composition (a3) corresponds to the composition (a).
　工程（Ｉ－３）、工程（Ａ３）、および工程（Ｂ３）は、それぞれ、工程（Ｉ－１）、工程（Ａ１）、および工程（Ｂ２）と同様に行うことができる。組成物（ａ３）は、組成物（ａ１）と同意義である。 Step (I-3), Step (A3), and Step (B3) can be performed in the same manner as Step (I-1), Step (A1), and Step (B2), respectively. The composition (a3) has the same meaning as the composition (a1).
　工程（Ｉ－３）、工程（Ａ３）における分離は、カラムクロマトグラフィを用いて行うことが好ましい。 The separation in step (I-3) and step (A3) is preferably performed using column chromatography.
　本態様においては、工程（Ｂ３）で得られる混合物を含む組成物（ａ３）を用いる工程（Ｉ－３）、工程（Ａ３）および工程（Ｂ３）のサイクルを複数回行うことが好ましい。 In this embodiment, the cycle of the step (I-3), the step (A3) and the step (B3) using the composition (a3) containing the mixture obtained in the step (B3) is preferably performed a plurality of times.
　本態様によると、Ｐｆ基含有ジカルボン酸を再利用してＰｆ基含有モノカルボン酸を得ることから、Ｐｆ基含有モノカルボン酸化合物の収率を向上し得る。 According to this aspect, since the Pf group-containing monocarboxylic acid is obtained by reusing the Pf group-containing dicarboxylic acid, the yield of the Pf group-containing monocarboxylic acid compound can be improved.
　組成物（ａ３）は、Ｐｆ基含有ジカルボン酸化合物のフッ素化処理により得られる組成物であってもよい。すなわち、本態様の方法は、Ｐｆ基含有ジカルボン酸化合物をフッ素化処理し、組成物（ａ３）を得る工程をさらに含んでいてもよい。この工程は、工程（Ｚ１）と同様に行うことができる。 Composition (a3) may be a composition obtained by fluorination treatment of a Pf group-containing dicarboxylic acid compound. That is, the method of this aspect may further include a step of fluorinating the Pf group-containing dicarboxylic acid compound to obtain the composition (a3). This step can be performed in the same manner as in step (Z1).
（実施態様４）
　図５に、本発明のＰｆ基含有モノカルボン酸化合物を製造する方法の一態様を示す。図５において、エーテル基含有化合物、モノカルボン酸化合物、およびジカルボン酸化合物は、それぞれ、Ｐｆ基含有化合物、Ｐｆ基含有モノカルボン酸化合物、およびＰｆ基含有ジカルボン酸化合物を意味する。 (Embodiment 4)
FIG. 5 shows one embodiment of a method for producing the Pf group-containing monocarboxylic acid compound of the present invention. In FIG. 5, an ether group-containing compound, a monocarboxylic acid compound, and a dicarboxylic acid compound mean a Pf group-containing compound, a Pf group-containing monocarboxylic acid compound, and a Pf group-containing dicarboxylic acid compound, respectively.
　本態様は、Ｐｆ基含有ジカルボン酸化合物を、工程（Ｚ４）おける組成物（ａ４）を形成するための原料であるＰｆ基含有ジカルボン酸化合物の少なくとも一部として、再利用することを特徴とする。工程（Ｚ４）は、工程（Ｚ）の一態様である。組成物（ａ４）は、組成物（ａ）に対応する。 In this embodiment, the Pf group-containing dicarboxylic acid compound is reused as at least part of the Pf group-containing dicarboxylic acid compound that is a raw material for forming the composition (a4) in the step (Z4). . Step (Z4) is an embodiment of step (Z). The composition (a4) corresponds to the composition (a).
　具体的には、本態様のＰｆ基含有モノカルボン酸化合物の製造方法は、
　Ｐｆ基含有ジカルボン酸化合物をフッ素化処理し、組成物（ａ４）を得る工程（Ｚ４）、
　上記組成物（ａ４）を分離する工程（Ｉ－４）、
　Ｐｆ基含有ジカルボン酸化合物をフッ素化処理し、少なくともＰｆ基含有モノカルボン酸化合物とＰｆ基含有ジカルボン酸化合物とを含む混合物を得、該混合物から、少なくともＰｆ基含有モノカルボン酸化合物とＰｆ基含有ジカルボン酸化合物とを、分離することを含む工程（Ａ４）、および
　上記工程（Ａ４）で分離されたＰｆ基含有ジカルボン酸化合物を、工程（Ｚ４）における組成物（ａ４）を形成するための原料であるＰｆ基含有ジカルボン酸化合物の少なくとも一部として用い、再度工程（Ｚ４）、工程（Ｉ－４）、および工程（Ａ４）を行うことを含む。 Specifically, the method for producing the Pf group-containing monocarboxylic acid compound of this embodiment includes:
Fluorinating the Pf group-containing dicarboxylic acid compound to obtain a composition (a4) (Z4);
Separating the composition (a4) (I-4),
A fluorination treatment is performed on the Pf group-containing dicarboxylic acid compound to obtain a mixture including at least the Pf group-containing monocarboxylic acid compound and the Pf group-containing dicarboxylic acid compound. A step (A4) including separating the dicarboxylic acid compound, and a raw material for forming the composition (a4) in the step (Z4) from the Pf group-containing dicarboxylic acid compound separated in the step (A4) Using at least a part of the Pf group-containing dicarboxylic acid compound, and performing the step (Z4), the step (I-4), and the step (A4) again.
　工程（Ｉ－４）、および工程（Ａ４）は、それぞれ、工程（Ｉ）および工程（Ａ）の一態様である。組成物（ａ４）は、組成物（ａ）に対応する。 Step (I-4) and Step (A4) are embodiments of Step (I) and Step (A), respectively. The composition (a4) corresponds to the composition (a).
　工程（Ｚ４）、工程（Ｉ－４）、および工程（Ａ４）は、それぞれ、工程（Ｚ１）、工程（Ｉ－１）、および工程（Ａ１）と同様に行うことができる。 Step (Z4), Step (I-4), and Step (A4) can be performed in the same manner as Step (Z1), Step (I-1), and Step (A1), respectively.
　組成物（ａ４）は、少なくともＰｆ基含有化合物、Ｐｆ基含有モノカルボン酸化合物、およびＰｆ基含有ジカルボン酸化合物を含む。 Composition (a4) contains at least a Pf group-containing compound, a Pf group-containing monocarboxylic acid compound, and a Pf group-containing dicarboxylic acid compound.
　上記組成物（ａ４）の末端ＣＦ３基率は、２０％以上であることが好ましく、４０％以上であることがより好ましい。上記末端ＣＦ３基率は、８０％以下であってもよい。上記末端ＣＦ３基率は、組成物（ａ４）において、該組成物（ａ４）に含まれる、Ｐｆ基含有化合物、Ｐｆ基含有モノカルボン酸化合物およびＰｆ基含有ジカルボン酸化合物の両末端に存在する末端基の合計モル数に対するＣＦ３基のモル数の割合を意味する。上記末端基としては、－ＣＦ３、－ＣＯＯＦ、－ＣＯＦ、－ＣＯＯＨ等を挙げることができる。上記末端ＣＦ３基率は、１９Ｆ－ＮＭＲを用いて測定できる。 The terminal CF 3 group ratio of the composition (a4) is preferably 20% or more, and more preferably 40% or more. The terminal CF 3 group ratio may be 80% or less. The terminal CF 3 group ratio exists in both ends of the Pf group-containing compound, the Pf group-containing monocarboxylic acid compound and the Pf group-containing dicarboxylic acid compound contained in the composition (a4) in the composition (a4). It means the ratio of the number of moles of CF 3 groups to the total number of moles of end groups. Examples of the terminal group include —CF 3 , —COOF, —COF, —COOH and the like. The terminal CF 3 group ratio can be measured using 19 F-NMR.
　上記組成物（ａ４）の末端ＣＦ３基率は、２０％～８０％の範囲にあることが好ましく、４０％～６０％の範囲にあることがより好ましい。 The terminal CF 3 group ratio of the composition (a4) is preferably in the range of 20% to 80%, and more preferably in the range of 40% to 60%.
　組成物（ａ４）は、Ｐｆ基含有化合物、Ｐｆ基含有モノカルボン酸化合物、およびＰｆ基含有ジカルボン酸化合物の合計１００質量部に対して、Ｐｆ基含有モノカルボン酸化合物を、３０～７０質量部含むことが好ましく、４０～６０質量部含むことがより好ましい。 The composition (a4) contains 30 to 70 parts by mass of the Pf group-containing monocarboxylic acid compound with respect to 100 parts by mass in total of the Pf group-containing compound, the Pf group-containing monocarboxylic acid compound, and the Pf group-containing dicarboxylic acid compound. It is preferably included, and more preferably 40 to 60 parts by mass.
　組成物（ａ４）は、Ｐｆ基含有化合物、Ｐｆ基含有モノカルボン酸化合物、およびＰｆ基含有ジカルボン酸化合物の合計１００質量部に対して、Ｐｆ基含有ジカルボン酸化合物を、１０～５０質量部含むことが好ましく、１５～４５質量部含むことがより好ましい。 The composition (a4) contains 10 to 50 parts by mass of the Pf group-containing dicarboxylic acid compound with respect to 100 parts by mass in total of the Pf group-containing compound, the Pf group-containing monocarboxylic acid compound, and the Pf group-containing dicarboxylic acid compound. The content is preferably 15 to 45 parts by mass.
　組成物（ａ４）は、Ｐｆ基含有化合物、Ｐｆ基含有モノカルボン酸化合物、およびＰｆ基含有ジカルボン酸化合物の合計１００質量部に対して、Ｐｆ基含有化合物を、１０～４０質量部、Ｐｆ基含有モノカルボン酸化合物を、３０～７０質量部、およびＰｆ基含有ジカルボン酸化合物を、１０～５０質量部含むことが好ましく；Ｐｆ基含有化合物を、１０～４０質量部、Ｐｆ基含有モノカルボン酸化合物を、４０～６０質量部、およびＰｆ基含有ジカルボン酸化合物を、１５～４５質量部含むことがより好ましい。 The composition (a4) comprises 10 to 40 parts by mass of the Pf group-containing compound, 100 parts by mass of the Pf group-containing compound, 100 parts by mass of the Pf group-containing monocarboxylic acid compound, and Pf group-containing dicarboxylic acid compound. It is preferable to contain 30 to 70 parts by mass of the containing monocarboxylic acid compound and 10 to 50 parts by mass of the Pf group-containing dicarboxylic acid compound; 10 to 40 parts by mass of the Pf group-containing compound and Pf group-containing monocarboxylic acid More preferably, the compound contains 40 to 60 parts by mass and the Pf group-containing dicarboxylic acid compound contains 15 to 45 parts by mass.
　組成物（ａ４）に含まれるＰｆ基含有モノカルボン酸化合物の数平均分子量は、５００～３０，０００の範囲にあることが好ましく、１，０００～２０，０００の範囲にあることがより好ましく、１，５００～１５，０００の範囲にあることがさらに好ましく、１,０００～１０,０００の範囲にあることが特に好ましく、３,０００～５,０００の範囲にあることがより好ましい。本明細書において、数平均分子量は１９Ｆ　ＮＭＲにより測定された値とする。 The number average molecular weight of the Pf group-containing monocarboxylic acid compound contained in the composition (a4) is preferably in the range of 500 to 30,000, more preferably in the range of 1,000 to 20,000, It is more preferably in the range of 1,500 to 15,000, particularly preferably in the range of 1,000 to 10,000, and more preferably in the range of 3,000 to 5,000. In the present specification, the number average molecular weight is a value measured by 19 F NMR.
　組成物（ａ４）に含まれるＰｆ基含有モノカルボン酸化合物の分子量分布は、２．０以下にあることが好ましく、１．５以下にあることがより好ましく、１．３以下にあることがさらに好ましい。本明細書において、分子量分布は、重量平均分子量／数平均分子量で表されるものであり、ゲル浸透クロマトグラフィー（ＧＰＣ）によって測定した値を用いて計算したものである。 The molecular weight distribution of the Pf group-containing monocarboxylic acid compound contained in the composition (a4) is preferably 2.0 or less, more preferably 1.5 or less, and further preferably 1.3 or less. preferable. In this specification, the molecular weight distribution is expressed by weight average molecular weight / number average molecular weight, and is calculated using a value measured by gel permeation chromatography (GPC).
　工程（Ｉ－４）、および工程（Ａ４）における分離は、カラムクロマトグラフィを用いて行うことが好ましい。 The separation in step (I-4) and step (A4) is preferably performed using column chromatography.
　本態様においては、工程（Ｚ４）、工程（Ｉ－４）および工程（Ａ４）のサイクルを複数回繰り返すことが好ましい。 In this embodiment, it is preferable to repeat the cycle of step (Z4), step (I-4) and step (A4) a plurality of times.
　本態様によると、Ｐｆ基含有ジカルボン酸を再利用してＰｆ基含有モノカルボン酸を得ることができることから、Ｐｆ基含有モノカルボン酸化合物の収率を向上し得る。 According to this aspect, since the Pf group-containing monocarboxylic acid can be obtained by reusing the Pf group-containing dicarboxylic acid, the yield of the Pf group-containing monocarboxylic acid compound can be improved.
　以下の実施例により本発明をさらに具体的に説明するが、本発明はこれらに限定されない。実施例中、「部」および「％」は、ことわりのない限り、重量基準による。なお、本実施例において、（ポリ）エーテルを構成する繰り返し単位（ＣＦ２Ｏ）、（ＣＦ２ＣＦ２Ｏ）、（ＣＦ（ＣＦ３）ＣＦ２Ｏ）、（ＣＦ２ＣＦ２ＣＦ２Ｏ）、（ＣＦ２ＣＦ（ＣＦ３）Ｏ）および（ＣＦ２ＣＦ２ＣＦ２ＣＦ２Ｏ）の存在順序は任意である。また、以下に示される化学式はすべて平均組成を示す。 The following examples further illustrate the present invention, but the present invention is not limited thereto. In the examples, “parts” and “%” are based on weight unless otherwise specified. In this example, the repeating unit (CF 2 O), (CF 2 CF 2 O), (CF (CF 3 ) CF 2 O), (CF 2 CF 2 CF 2 O) constituting the (poly) ether is used in this example. , (CF 2 CF (CF 3 ) O) and (CF 2 CF 2 CF 2 CF 2 O) may be present in any order. Moreover, all the chemical formulas shown below show average compositions.
（分子量の測定方法）
　数平均分子量は、１９Ｆ　ＮＭＲを用いて測定した。 (Measurement method of molecular weight)
The number average molecular weight was measured using 19 F NMR.
（分子量分布の測定方法）
　以下の条件で、ＧＰＣを用いて分子量分布を求めた。
装置：ＧＰＣｍａｘ（ＨＰＬＣシステム）および、ＴＤＡ－３０２（Malvern Instruments社製）
カラム：Shodex GPC KF-806L×3（昭和電工製）
検出装置：ＲＩ 示差屈折計
流量：０．７５ｍＬ／ｍｉｎ
測定温度：３０℃ (Measurement method of molecular weight distribution)
The molecular weight distribution was determined using GPC under the following conditions.
Apparatus: GPCmax (HPLC system) and TDA-302 (manufactured by Malvern Instruments)
Column: Shodex GPC KF-806L x 3 (made by Showa Denko)
Detector: RI Differential refractometer Flow rate: 0.75 mL / min
Measurement temperature: 30 ° C
（末端ＣＦ３基率の測定方法）
　末端ＣＦ３基率は、１９Ｆ－ＮＭＲを用いて求めた。具体的には、式（１）で表されるＰｆ基含有化合物、式（２）で表されるＰｆ基含有モノカルボン酸化合物、および式（３）で表されるＰｆ基含有ジカルボン酸化合物の末端基の全モル数に対する、末端のＣＦ３基のモル数の割合を求めた。

Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000019
 (Measurement method of terminal CF 3 group ratio)
The terminal CF 3 group ratio was determined using 19 F-NMR. Specifically, the Pf group-containing compound represented by the formula (1), the Pf group-containing monocarboxylic acid compound represented by the formula (2), and the Pf group-containing dicarboxylic acid compound represented by the formula (3) The ratio of the number of moles of terminal CF 3 groups to the total number of moles of terminal groups was determined.

Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000019
（実施例１）
　（ポリ）エーテル基含有ジカルボン酸化合物（Ｄ１）を１２０℃でフッ素化処理し、フッ素化処理後のサンプルの末端ＣＦ３基率が１９Ｆ－ＮＭＲにて５０％になるように調製した。 Example 1
The (poly) ether group-containing dicarboxylic acid compound (D1) was fluorinated at 120 ° C., and the sample after fluorination was prepared so that the terminal CF 3 group ratio was 50% by 19 F-NMR.
　得られたフッ素化処理後のサンプルを、シリカゲルクロマトグラフィを用いて以下のとおり処理した。
　１４ｃｍ径のカラムに１５００ｇのシリカゲル（ＰＳＱ１００Ｂ；富士シリシア化学製：平均粒径：１００μｍ、極性固定相）を入れ、ＨＦＥ７２００を通した。さらに５００ｇのフッ素化処理後のサンプルを入れ、以下のように、３種類の溶媒を順次流通させ、留分を回収することにより、（ポリ）エーテル化合物、（ポリ）エーテル基含有モノカルボン酸化合物、（ポリ）エーテル基含有ジカルボン酸化合物を含むフッ素化処理後のサンプルを精製した。なお、上記（ポリ）エーテル基を含有する化合物は、（ポリ）エーテル化合物、（ポリ）エーテル基含有モノカルボン酸化合物、（ポリ）エーテル基含有ジカルボン酸化合物の順にシリカゲルから分離されやすい。 The obtained sample after the fluorination treatment was treated as follows using silica gel chromatography.
1500 g of silica gel (PSQ100B; manufactured by Fuji Silysia Chemical Co., Ltd .: average particle size: 100 μm, polar stationary phase) was placed in a 14 cm diameter column, and passed through HFE7200. Further, 500 g of a sample after fluorination treatment is put, and three kinds of solvents are sequentially circulated as shown below, and a fraction is collected to obtain a (poly) ether compound and a (poly) ether group-containing monocarboxylic acid compound. The sample after the fluorination treatment containing the (poly) ether group-containing dicarboxylic acid compound was purified. In addition, the compound containing the (poly) ether group is easily separated from the silica gel in the order of (poly) ether compound, (poly) ether group-containing monocarboxylic acid compound, and (poly) ether group-containing dicarboxylic acid compound.
　上記３種類の溶媒は、ＨＦＥ７２００（Ｎｏｖｅｃ（商標）７２００；ハイドロフルオロエーテル　C4F9OC2H5）：８７５５ｇ、ＨＦＥ７２００：５ＦＰ（２，２，３，３，３－ペンタフルオロ－１－プロパノール）＝９：１（体積基準）：８０００ｇ、ＨＦＥ７２００：５ＦＰ＝１：１（体積基準）：８０００ｇである。留分は、カラムの出口から留出した溶液を３０分画に分けて回収した。得られた留分を、分画毎にロータリーエバポレーターを用いて溶媒を留去した後、残った液体を１９Ｆ－ＮＭＲを用いて測定し、各留分における（ポリ）エーテル基を有する化合物の種類、含有量、分子量の情報を得た。 The above three types of solvents are HFE7200 (Novec ™ 7200; hydrofluoroether C 4 F 9 OC 2 H 5 ): 8755 g, HFE7200: 5FP (2,2,3,3,3-pentafluoro-1-propanol ) = 9: 1 (volume basis): 8000 g, HFE7200: 5FP = 1: 1 (volume basis): 8000 g. The fraction was collected by dividing the solution distilled from the column outlet into 30 fractions. The obtained fraction was distilled off for each fraction using a rotary evaporator, and then the remaining liquid was measured using 19 F-NMR. The fraction of the compound having a (poly) ether group in each fraction was measured. Information on type, content and molecular weight was obtained.
　（ポリ）エーテル基含有モノカルボン酸化合物の含有率が９０％以上になるように、分画および留去後に残った液体を混合し、調製した。調製後に得られた液体（混合物１）は、（ポリ）エーテル基含有モノカルボン酸化合物を９０％含み、残りは（ポリ）エーテル基含有ジカルボン酸化合物であった。混合物１に含まれる（ポリ）エーテル基含有モノカルボン酸化合物の分子量は４３７０、該化合物の分子量分布は１．１５であった。なお、Ｄ１に対する、混合物１に含まれる（ポリ）エーテル基含有モノカルボン酸化合物の収率は、４０％であった（モル比）。 The liquid remaining after fractionation and distillation was mixed and prepared so that the content of the (poly) ether group-containing monocarboxylic acid compound was 90% or more. The liquid (mixture 1) obtained after the preparation contained 90% of a (poly) ether group-containing monocarboxylic acid compound, and the remainder was a (poly) ether group-containing dicarboxylic acid compound. The molecular weight of the (poly) ether group-containing monocarboxylic acid compound contained in the mixture 1 was 4370, and the molecular weight distribution of the compound was 1.15. In addition, the yield of the (poly) ether group-containing monocarboxylic acid compound contained in the mixture 1 with respect to D1 was 40% (molar ratio).
　上記分画以降に得られた混合物は、（ポリ）エーテル基含有モノカルボン酸化合物および（ポリ）エーテル基含有ジカルボン酸化合物を含み、該混合物中に含まれる（ポリ）エーテル基含有モノカルボン酸化合物の分子量は３８４０、該化合物の分子量分布は１．１２であった。この混合物の末端ＣＦ３基率は２５％であった。
　この混合物を１２０℃でフッ素化処理し、混合物に含まれる末端ＣＦ３基率が１９Ｆ－ＮＭＲにて５０％になるように調製した。その後、上記と同様にカラムクロマトグラフィを用いて分離した。分離後に得られた混合物（混合物２）は、（ポリ）エーテル基含有モノカルボン酸化合物を９０％含み、残りは（ポリ）エーテル基含有ジカルボン酸化合物であった。混合物に含まれる（ポリ）エーテル基含有モノカルボン酸化合物の分子量は４２５７、該化合物の分子量分布は１．１２であった。なお、Ｄ１に対する、混合物２に含まれる（ポリ）エーテル基含有モノカルボン酸化合物の収率は、４０％であった（モル比）。 The mixture obtained after the fractionation includes a (poly) ether group-containing monocarboxylic acid compound and a (poly) ether group-containing dicarboxylic acid compound, and the (poly) ether group-containing monocarboxylic acid compound contained in the mixture The molecular weight of the compound was 3840, and the molecular weight distribution of the compound was 1.12. The terminal CF 3 group ratio of this mixture was 25%.
This mixture was fluorinated at 120 ° C. and prepared such that the terminal CF 3 group ratio in the mixture was 50% by 19 F-NMR. Then, it separated using column chromatography similarly to the above. The mixture (mixture 2) obtained after the separation contained 90% of a (poly) ether group-containing monocarboxylic acid compound, and the remainder was a (poly) ether group-containing dicarboxylic acid compound. The molecular weight of the (poly) ether group-containing monocarboxylic acid compound contained in the mixture was 4257, and the molecular weight distribution of the compound was 1.12. The yield of the (poly) ether group-containing monocarboxylic acid compound contained in the mixture 2 with respect to D1 was 40% (molar ratio).
　本発明の開示は以下の態様を含む。
［１］　少なくとも下記式（１）で表される（ポリ）エーテル基含有化合物、下記式（２）で表される（ポリ）エーテル基含有モノカルボン酸化合物、および、下記式（３）で表される（ポリ）エーテル基含有ジカルボン酸化合物を含む組成物（ａ）を、分離する工程（Ｉ）、および
　上記分離により得られる式（３）で表される（ポリ）エーテル基含有ジカルボン酸化合物をフッ素化処理し、式（２）で表される（ポリ）エーテル基含有モノカルボン酸化合物を含む混合物を得る工程（Ａ）、
を含む、（ポリ）エーテル基含有モノカルボン酸化合物を製造する方法。
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000022
 ［式中：
　Ａは、各出現においてそれぞれ独立して、Ｒ１Ｏ－ＣＯ－Ｗ－基、Ｒ１Ｏ－ＣＯ－Ｗ－Ｏ－基、ＨＯ－Ｗ－基、ＨＯ－Ｗ－Ｏ－基、Ｒ１Ｏ－Ｗ－基、Ｒ１Ｏ－Ｗ－Ｏ－基、Ｖ－基、またはＶ－Ｏ－基を表し；
　Ｒ１は、各出現においてそれぞれ独立して、アルキル基を表し；
　Ｗは、各出現においてそれぞれ独立して、結合手または２価の有機基を表し；
　Ｖは、各出現においてそれぞれ独立して、炭素原子数１～１６のアルキル基を表し；
　Ｚは、各出現においてそれぞれ独立して、Ｙ－Ｘ－、またはＹ－Ｘ－Ｏ－を表し；
　Ｙは、カルボン酸基を表し；
　Ｘは、各出現においてそれぞれ独立して、結合手または２価の有機基を表し；
　Ｐｆは、各出現においてそれぞれ独立して、式：
－（ＯＣ６Ｆ１２）ａ－（ＯＣ５Ｆ１０）ｂ－（ＯＣ４Ｆ８）ｃ－（ＯＣ３Ｘ１ ６）ｄ－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－
（式中、ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して０以上２００以下の整数であって、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は少なくとも１であり、ａ、ｂ、ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意であり、Ｘ１は、各出現においてそれぞれ独立して、水素原子、フッ素原子または塩素原子である。）
で表される基である。］
［２］　上記工程（Ｉ）の前に、（ポリ）エーテル基含有ジカルボン酸化合物をフッ素化処理し、組成物（ａ）を得る工程（Ｚ）をさらに含む、［１］に記載の方法。
［３］　工程（Ａ）が、（ポリ）エーテル基含有ジカルボン酸化合物をフッ素化処理して得られた混合物から、少なくとも式（２）で表される（ポリ）エーテル基含有モノカルボン酸化合物を分離することをさらに含む、［１］または［２］に記載の方法。
［４］　工程（Ａ）が、（ポリ）エーテル基含有ジカルボン酸化合物をフッ素化処理し、少なくとも式（２）で表される（ポリ）エーテル基含有モノカルボン酸化合物と式（３）で表される（ポリ）エーテル基含有ジカルボン酸化合物とを含む混合物を得、該混合物から、式（２）で表される（ポリ）エーテル基含有モノカルボン酸化合物および式（３）で表される（ポリ）エーテル基含有ジカルボン酸化合物を、分離することを含み、
　上記分離により得られる（ポリ）エーテル基含有ジカルボン酸化合物をフッ素化処理し、式（２）で表される（ポリ）エーテル基含有モノカルボン酸化合物を含む混合物を得る工程（Ｂ）をさらに含む、［１］または［２］に記載の方法。
［５］　工程（Ｂ）の後、さらに工程（Ｂ）で得られる混合物を、組成物（ａ）の少なくとも一部として用い、再度、前記組成物（ａ）を用いて工程（Ｉ）、工程（Ａ）および工程（Ｂ）を行うことを含む、［４］に記載の方法。
［６］　前記工程（Ｂ）で得られる混合物を含む組成物（ａ）を用いる工程（Ｉ）、工程（Ａ）および工程（Ｂ）のサイクルを複数回繰り返すことを含む、［５］に記載の方法。
［７］　工程（Ａ）が、（ポリ）エーテル基含有ジカルボン酸化合物をフッ素化処理し、少なくとも式（２）で表される（ポリ）エーテル基含有モノカルボン酸化合物と式（３）で表される（ポリ）エーテル基含有ジカルボン酸化合物とを含む混合物を得、該混合物から、少なくとも（ポリ）エーテル基含有モノカルボン酸化合物と（ポリ）エーテル基含有ジカルボン酸化合物とを、分離することを含み、
　工程（Ａ）で分離された（ポリ）エーテル基含有ジカルボン酸化合物を、工程（Ｚ）における組成物（ａ）を形成するための原料である（ポリ）エーテル基含有ジカルボン酸化合物の少なくとも一部として用い、再度、工程（Ｚ）、工程（Ｉ）、および工程（Ａ）を行うことを含む、［２］～［６］のいずれか１に記載の方法。
［８］　前記工程（Ｚ）、工程（Ｉ）および工程（Ａ）のサイクルを複数回繰り返すことを含む、［７］に記載の方法。
［９］　Ｘ１が、フッ素原子である、［１］～［８］のいずれか１に記載の方法。 The disclosure of the present invention includes the following aspects.
[1] At least a (poly) ether group-containing compound represented by the following formula (1), a (poly) ether group-containing monocarboxylic acid compound represented by the following formula (2), and the following formula (3) Step (I) for separating the composition (a) containing the (poly) ether group-containing dicarboxylic acid compound, and the (poly) ether group-containing dicarboxylic acid compound represented by the formula (3) obtained by the separation (A) to obtain a mixture containing a (poly) ether group-containing monocarboxylic acid compound represented by the formula (2):
A process for producing a (poly) ether group-containing monocarboxylic acid compound.
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000022
 [Where:
A is independently at each occurrence R 1 O—CO—W— group, R 1 O—CO—W—O— group, HO—W— group, HO—W—O— group, R 1 O Represents a —W— group, a R 1 O—W—O— group, a V— group, or a V—O— group;
R 1 independently represents an alkyl group at each occurrence;
W represents a bond or a divalent organic group independently at each occurrence;
V independently represents each alkyl group having 1 to 16 carbon atoms in each occurrence;
Z independently represents Y—X— or Y—X—O— at each occurrence;
Y represents a carboxylic acid group;
X independently represents a bond or a divalent organic group at each occurrence;
Pf is independently at each occurrence, the formula:
- (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 X 1 6) d - (OC 2 F 4) e - (OCF 2) f -
(Wherein, a, b, c, d, e and f are each independently an integer of 0 to 200, and the sum of a, b, c, d, e and f is at least 1, The order of presence of each repeating unit in parentheses with a, b, c, d, e or f is arbitrary in the formula, and X 1 is independently a hydrogen atom, fluorine An atom or a chlorine atom.)
It is group represented by these. ]
[2] The method according to [1], further comprising a step (Z) of obtaining a composition (a) by subjecting the (poly) ether group-containing dicarboxylic acid compound to a fluorination treatment before the step (I).
[3] From the mixture obtained by fluorinating the (poly) ether group-containing dicarboxylic acid compound in step (A), at least a (poly) ether group-containing monocarboxylic acid compound represented by formula (2) The method according to [1] or [2], further comprising separating.
[4] In step (A), the (poly) ether group-containing dicarboxylic acid compound is fluorinated, and represented by at least the (poly) ether group-containing monocarboxylic acid compound represented by formula (2) and formula (3). (Poly) ether group-containing dicarboxylic acid compound is obtained, from which the (poly) ether group-containing monocarboxylic acid compound represented by formula (2) and formula (3) ( Separating the poly) ether group-containing dicarboxylic acid compound,
The method further includes a step (B) of obtaining a mixture containing the (poly) ether group-containing monocarboxylic acid compound represented by the formula (2) by fluorinating the (poly) ether group-containing dicarboxylic acid compound obtained by the separation. [1] or [2].
[5] After the step (B), the mixture obtained in the step (B) is further used as at least part of the composition (a), and again using the composition (a), the step (I) and the step The method according to [4], comprising performing (A) and step (B).
[6] The method according to [5], comprising repeating the cycle of the step (I), the step (A) and the step (B) using the composition (a) containing the mixture obtained in the step (B) a plurality of times. the method of.
[7] In the step (A), the (poly) ether group-containing dicarboxylic acid compound is fluorinated, and is represented by at least the (poly) ether group-containing monocarboxylic acid compound represented by the formula (2) and the formula (3). To obtain a mixture containing (poly) ether group-containing dicarboxylic acid compound and to separate at least (poly) ether group-containing monocarboxylic acid compound and (poly) ether group-containing dicarboxylic acid compound from the mixture Including
The (poly) ether group-containing dicarboxylic acid compound separated in step (A) is at least a part of the (poly) ether group-containing dicarboxylic acid compound which is a raw material for forming the composition (a) in step (Z). The method according to any one of [2] to [6], wherein the step (Z), the step (I), and the step (A) are performed again.
[8] The method according to [7], comprising repeating the step (Z), the step (I) and the step (A) a plurality of times.
[9] The method according to any one of [1] to [8], wherein X 1 is a fluorine atom.
　本発明によって、Ｐｆ基含有モノカルボン酸化合物の収率を比較的容易に向上し得る。本発明の方法は、Ｐｆ基含有モノカルボン酸化合物の製造コストの低減などに寄与し得る。上記Ｐｆ基含有モノカルボン酸化合物は、自動車、航空機、半導体、宇宙分野などの多くの分野において使用し得る化合物である。 According to the present invention, the yield of the Pf group-containing monocarboxylic acid compound can be improved relatively easily. The method of the present invention can contribute to the reduction of the production cost of the Pf group-containing monocarboxylic acid compound. The Pf group-containing monocarboxylic acid compound is a compound that can be used in many fields such as the automobile, aircraft, semiconductor, and space fields.

Claims (9)

  1. 　少なくとも下記式（１）で表される（ポリ）エーテル基含有化合物、下記式（２）で表される（ポリ）エーテル基含有モノカルボン酸化合物、および、下記式（３）で表される（ポリ）エーテル基含有ジカルボン酸化合物を含む組成物（ａ）を、分離する工程（Ｉ）、および
    　上記分離により得られる式（３）で表される（ポリ）エーテル基含有ジカルボン酸化合物をフッ素化処理し、式（２）で表される（ポリ）エーテル基含有モノカルボン酸化合物を含む混合物を得る工程（Ａ）、
    を含む、（ポリ）エーテル基含有モノカルボン酸化合物を製造する方法。
    Figure JPOXMLDOC01-appb-C000001
    Figure JPOXMLDOC01-appb-C000002
    Figure JPOXMLDOC01-appb-C000003
     ［式中：
    　Ａは、各出現においてそれぞれ独立して、Ｒ１Ｏ－ＣＯ－Ｗ－基、Ｒ１Ｏ－ＣＯ－Ｗ－Ｏ－基、ＨＯ－Ｗ－基、ＨＯ－Ｗ－Ｏ－基、Ｒ１Ｏ－Ｗ－基、Ｒ１Ｏ－Ｗ－Ｏ－基、Ｖ－基、またはＶ－Ｏ－基を表し；
    　Ｒ１は、各出現においてそれぞれ独立して、アルキル基を表し；
    　Ｗは、各出現においてそれぞれ独立して、結合手または２価の有機基を表し；
    　Ｖは、各出現においてそれぞれ独立して、炭素原子数１～１６のアルキル基を表し；
    　Ｚは、各出現においてそれぞれ独立して、Ｙ－Ｘ－、またはＹ－Ｘ－Ｏ－を表し；
    　Ｙは、カルボン酸基を表し；
    　Ｘは、各出現においてそれぞれ独立して、結合手または２価の有機基を表し；
    　Ｐｆは、各出現においてそれぞれ独立して、式：
    －（ＯＣ６Ｆ１２）ａ－（ＯＣ５Ｆ１０）ｂ－（ＯＣ４Ｆ８）ｃ－（ＯＣ３Ｘ１ ６）ｄ－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－
    （式中、ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して０以上２００以下の整数であって、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は少なくとも１であり、ａ、ｂ、ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意であり、Ｘ１は、各出現においてそれぞれ独立して、水素原子、フッ素原子または塩素原子である。）
    で表される基である。］     At least a (poly) ether group-containing compound represented by the following formula (1), a (poly) ether group-containing monocarboxylic acid compound represented by the following formula (2), and the following formula (3) ( Step (I) for separating the composition (a) containing the poly) ether group-containing dicarboxylic acid compound, and fluorination of the (poly) ether group-containing dicarboxylic acid compound represented by the formula (3) obtained by the separation. A step (A) of treating to obtain a mixture containing a (poly) ether group-containing monocarboxylic acid compound represented by the formula (2),
    A process for producing a (poly) ether group-containing monocarboxylic acid compound.
    Figure JPOXMLDOC01-appb-C000001
    Figure JPOXMLDOC01-appb-C000002
    Figure JPOXMLDOC01-appb-C000003
     [Where:
    A is independently at each occurrence R 1 O—CO—W— group, R 1 O—CO—W—O— group, HO—W— group, HO—W—O— group, R 1 O Represents a —W— group, a R 1 O—W—O— group, a V— group, or a V—O— group;
    R 1 independently represents an alkyl group at each occurrence;
    W represents a bond or a divalent organic group independently at each occurrence;
    V independently represents each alkyl group having 1 to 16 carbon atoms in each occurrence;
    Z independently represents Y—X— or Y—X—O— at each occurrence;
    Y represents a carboxylic acid group;
    X independently represents a bond or a divalent organic group at each occurrence;
    Pf is independently at each occurrence, the formula:
    - (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 X 1 6) d - (OC 2 F 4) e - (OCF 2) f -
    (Wherein, a, b, c, d, e and f are each independently an integer of 0 to 200, and the sum of a, b, c, d, e and f is at least 1, The order of presence of each repeating unit in parentheses with a, b, c, d, e or f is arbitrary in the formula, and X 1 is independently a hydrogen atom, fluorine An atom or a chlorine atom.)
    It is group represented by these. ]
  2. 　上記工程（Ｉ）の前に、（ポリ）エーテル基含有ジカルボン酸化合物をフッ素化処理し、組成物（ａ）を得る工程（Ｚ）をさらに含む、請求項１に記載の方法。 The method according to claim 1, further comprising a step (Z) of obtaining a composition (a) by fluorinating the (poly) ether group-containing dicarboxylic acid compound before the step (I).
  3. 　工程（Ａ）が、（ポリ）エーテル基含有ジカルボン酸化合物をフッ素化処理して得られた混合物から、少なくとも式（２）で表される（ポリ）エーテル基含有モノカルボン酸化合物を、分離することをさらに含む、請求項１または２に記載の方法。 Step (A) separates at least the (poly) ether group-containing monocarboxylic acid compound represented by the formula (2) from the mixture obtained by fluorinating the (poly) ether group-containing dicarboxylic acid compound. The method according to claim 1 or 2, further comprising:
  4. 　工程（Ａ）が、（ポリ）エーテル基含有ジカルボン酸化合物をフッ素化処理し、少なくとも式（２）で表される（ポリ）エーテル基含有モノカルボン酸化合物と式（３）で表される（ポリ）エーテル基含有ジカルボン酸化合物とを含む混合物を得、該混合物から、式（２）で表される（ポリ）エーテル基含有モノカルボン酸化合物および式（３）で表される（ポリ）エーテル基含有ジカルボン酸化合物を分離することを含み、
    　上記分離により得られる（ポリ）エーテル基含有ジカルボン酸化合物をフッ素化処理し、式（２）で表される（ポリ）エーテル基含有モノカルボン酸化合物を含む混合物を得る工程（Ｂ）をさらに含む、請求項１または２に記載の方法。     In step (A), the (poly) ether group-containing dicarboxylic acid compound is fluorinated, and is represented by at least the (poly) ether group-containing monocarboxylic acid compound represented by formula (2) and formula (3) ( A poly) ether group-containing dicarboxylic acid compound is obtained, and a (poly) ether group-containing monocarboxylic acid compound represented by formula (2) and a (poly) ether represented by formula (3) are obtained from the mixture. Separating the group-containing dicarboxylic acid compound,
    The method further includes a step (B) of obtaining a mixture containing the (poly) ether group-containing monocarboxylic acid compound represented by the formula (2) by fluorinating the (poly) ether group-containing dicarboxylic acid compound obtained by the separation. The method according to claim 1 or 2.
  5. 　工程（Ｂ）の後、さらに工程（Ｂ）で得られる混合物を、組成物（ａ）の少なくとも一部として用い、再度、前記組成物（ａ）を用いて工程（Ｉ）、工程（Ａ）および工程（Ｂ）を行うことを含む、請求項４に記載の方法。 After the step (B), the mixture obtained in the step (B) is further used as at least part of the composition (a), and again using the composition (a), the steps (I) and (A) And performing the step (B).
  6. 　前記工程（Ｂ）で得られる混合物を含む組成物（ａ）を用いる工程（Ｉ）、工程（Ａ）および工程（Ｂ）のサイクルを複数回繰り返すことを含む、請求項５に記載の方法。 The method of Claim 5 including repeating the cycle of the process (I), the process (A), and the process (B) using the composition (a) containing the mixture obtained at the said process (B) in multiple times.
  7. 　工程（Ａ）が、（ポリ）エーテル基含有ジカルボン酸化合物をフッ素化処理し、少なくとも式（２）で表される（ポリ）エーテル基含有モノカルボン酸化合物と式（３）で表される（ポリ）エーテル基含有ジカルボン酸化合物とを含む混合物を得、該混合物から、少なくとも（ポリ）エーテル基含有モノカルボン酸化合物と（ポリ）エーテル基含有ジカルボン酸化合物とを、分離することを含み、
    　工程（Ａ）で分離された（ポリ）エーテル基含有ジカルボン酸化合物を、工程（Ｚ）における組成物（ａ）を形成するための原料である（ポリ）エーテル基含有ジカルボン酸化合物の少なくとも一部として用い、再度、工程（Ｚ）、工程（Ｉ）、および工程（Ａ）を行うことを含む、請求項２～６のいずれか１項に記載の方法。     In step (A), the (poly) ether group-containing dicarboxylic acid compound is fluorinated, and is represented by at least the (poly) ether group-containing monocarboxylic acid compound represented by formula (2) and formula (3) ( Obtaining a mixture comprising a poly) ether group-containing dicarboxylic acid compound, and separating at least a (poly) ether group-containing monocarboxylic acid compound and a (poly) ether group-containing dicarboxylic acid compound from the mixture,
    The (poly) ether group-containing dicarboxylic acid compound separated in step (A) is at least a part of the (poly) ether group-containing dicarboxylic acid compound which is a raw material for forming the composition (a) in step (Z). The method according to any one of claims 2 to 6, which comprises performing the step (Z), the step (I) and the step (A) again.
  8. 　前記工程（Ｚ）、工程（Ｉ）および工程（Ａ）のサイクルを複数回繰り返すことを含む、請求項７に記載の方法。 The method of Claim 7 including repeating the cycle of said process (Z), process (I), and process (A) in multiple times.
  9. 　Ｘ１が、フッ素原子である、請求項１～８のいずれか１項に記載の方法。 The method according to any one of claims 1 to 8, wherein X 1 is a fluorine atom.
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