WO2019163712A1 - Procédé de production d'un composé acide monocarboxylique contenant un groupe (poly)éther - Google Patents

Procédé de production d'un composé acide monocarboxylique contenant un groupe (poly)éther 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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English (en)
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.

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Abstract

La présente invention concerne un procédé de production d'un composé acide monocarboxylique contenant un groupe (poly)éther comprenant : une étape (I) de séparation d'une composition (a) contenant au moins un composé contenant un groupe (poly)éther représenté par la formule (1), un composé acide monocarboxylique contenant un groupe (poly)éther représenté par la formule (2), et un composé acide dicarboxylique contenant un groupe (poly)éther représenté par la formule (3) ; et une étape (A) d'obtention d'un mélange contenant le composé acide monocarboxylique contenant un groupe (poly)éther représenté par la formule (2) par fluoration du composé acide dicarboxylique contenant un groupe (poly)éther représenté par la formule (3) obtenu par ladite séparation (les symboles dans les formules sont tels que définis dans la description).
PCT/JP2019/005869 2018-02-21 2019-02-18 Procédé de production d'un composé acide monocarboxylique contenant un groupe (poly)éther WO2019163712A1 (fr)

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