Method for producing fluoropolyether group-containing compound

Abstract

The purpose of the present invention is to provide a method for producing a fluoropolyether group-containing compound having active groups at both terminals at a lower pressure than in the prior art and at a high yield. A method for producing a fluoropolyether group-containing compound according to the present invention comprises a step in which a compound represented by formula (1) is reacted with a reducing agent in the presence of a reaction medium containing a fluorine-containing alcohol to obtain a compound represented by formula (2). (1), R1-CO-XA-RF2-XA-CO-R2 (1), and R1-CH2-XA-RF2-XA-CH2-R2 (2), and a method for manufacturing the same.

Description

Technical Field

[0001] The present invention relates to a method for producing a compound containing a fluoropolyether group. Background Art

[0002] As a method for producing a compound containing a fluoropolyether group, Patent Document 1 discloses a method for producing a perfluoropolyether, which includes the step of reacting a perfluoropolyether having a carboxyl or ketone terminal group with gaseous hydrogen using Ru or Rh supported on carbon as a hydrogenation catalyst.

[0003] Patent Document 2 discloses that a reducing agent such as LiAlH or NaBH is coexisted when a perfluoropolyether compound having carbonyl groups (—CO—) at both ends is hydrolyzed, salified, or esterified.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2004-339221

[0007] Patent Document 2: U.S. Patent No. 3847978 Summary of the invention

[0008] Problems to be solved by the invention

[0009] In the production method disclosed in Patent Document 1, when producing a fluoropolyether group-containing compound having active groups such as hydroxyl groups and amino groups at both ends, a reduction reaction needs to be carried out under high pressure. In addition, it was found that when a reducing agent such as LiAlH2 or NaBH2 disclosed in Patent Document 2 is used to carry out the reduction reaction, there are defects such as the generation of dimers and gelation, or the desired reduction reaction cannot be fully carried out.

[0010] An object of the present invention is to provide a method for producing a fluoropolyether group-containing compound having active groups at both ends at a lower pressure and a higher yield than in the prior art.

[0011] Technical solutions to solve problems

[0012] The present invention includes the following embodiments.

[0013] [1] A method for producing a compound containing a fluoropolyether group, wherein:

[0014] The method comprises the steps of reacting the compound represented by formula (1) with a reducing agent in the presence of a reaction medium to obtain a compound represented by formula (2),

[0015] R 1 -CO-X A -RF2 -X A -CO-R 2 (1)

[0016] [In formula (1),

[0017] R 1 Indicates - OR 1a or -NR 1b 2.

[0018] R 1a represents a hydrogen atom, which may be substituted by one or more fluorine atoms. 1－16 an alkyl group or a halogen atom.

[0019] R 1b Each occurrence independently represents a hydrogen atom, a C which may be substituted with one or more fluorine atoms 1－16 an alkyl group or a halogen atom.

[0020] R 2 Indicates - OR 2a or -NR 2b 2.

[0021] R 2a represents a hydrogen atom, which may be substituted by one or more fluorine atoms. 1－16 an alkyl group or a halogen atom.

[0022] R 2b Each occurrence independently represents a hydrogen atom, a C which may be substituted with one or more fluorine atoms 1－16 an alkyl group or a halogen atom.

[0023] X A Each occurrence independently represents a single bond or a divalent organic group.

[0024] R F2 Representation - Rf 2 p -R F -O q -

[0025] R 2 It indicates that C may be substituted with one or more fluorine atoms. 1－6 Alkylene.

[0026] R F Each occurrence independently represents a divalent fluoropolyether group.

[0027] p is independently 0 or 1 at each occurrence.

[0028] q is independently 0 or 1 at each occurrence.]

[0029] R1 -CH2-X A -R F2 -X A -CH2-R 2 (2)

[0030] [In formula (2), R 1 , R 2 , X A and R F2 Same meaning as above.]

[0031] The above reaction medium contains fluorine-containing alcohol.

[0032] [2] The manufacturing method according to [1], wherein

[0033] The fluorine-containing alcohol has 1 to 5 carbon atoms.

[0034] [3] The production method according to [1] or [2], wherein

[0035] The reaction medium further contains at least one selected from fluorine-containing solvents other than fluorine-containing alcohols and non-fluorine-containing solvents.

[0036] [4] The production method according to any one of [1] to [3], wherein

[0037] The boiling point of the reaction medium is 70°C to 200°C.

[0038] [5] The production method according to any one of [1] to [4], wherein

[0039] The pressure at which the compound represented by the formula (1) is allowed to react with the reducing agent is 1 MPa or less.

[0040] [6] The production method according to any one of [1] to [5], wherein

[0041] The temperature when the compound represented by the formula (1) is allowed to react with the reducing agent is 100° C. or higher and 150° C. or lower.

[0042] [7] The production method according to any one of [1] to [6], wherein

[0043] The reducing agent contains at least one selected from the group consisting of a metal hydride reducing agent, a metal reducing agent, a hydrazine reducing agent, a phosphine reducing agent, a phosphite reducing agent, a metal alkoxide reducing agent and a rare earth metal halide reducing agent.

[0044] [8] The production method according to any one of [1] to [7], wherein

[0045] The reducing agent includes at least one selected from a boron-based reducing agent, an aluminum-based reducing agent, and a silicon-based reducing agent.

[0046] [9] The production method according to any one of [1] to [8], wherein

[0047] The reducing agent is used in an amount of 2 mol or more per mol of the compound represented by formula (1).

[0048]

[10] The production method according to any one of [1] to [9], wherein

[0049] The amount of the fluorine-containing alcohol is 0.1 mol or more per 1 mol of the reducing agent.

[0050] Effects of the Invention

[0051] According to the present invention, a fluoropolyether group-containing compound having active groups at both ends can be produced with high yield. DETAILED DESCRIPTION

[0052] The method for producing a fluoropolyether group-containing compound of the present invention comprises the step of reacting a compound represented by formula (1) (hereinafter referred to as "compound (1)") with a reducing agent in the presence of a reaction medium to obtain a compound represented by formula (2) (hereinafter referred to as "compound (2)".

[0053] R 1 -CO-X A -R F2 -X A -CO-R 2 (1)

[0054] [In formula (1),

[0055] R 1 Indicates - OR 1a or -NR 1b 2.

[0056] R 1a represents a hydrogen atom, C which may be substituted with one or more fluorine atoms 1－16 an alkyl group or a halogen atom.

[0057] R 1b Each occurrence independently represents a hydrogen atom, a C which may be substituted with one or more fluorine atoms 1－16 an alkyl group or a halogen atom.

[0058] R 2 Indicates - OR 2a or -NR 2b 2.

[0059] R 2a represents a hydrogen atom, C which may be substituted with one or more fluorine atoms 1－16 an alkyl group or a halogen atom.

[0060] R 2b Each occurrence independently represents a hydrogen atom, a C which may be substituted with one or more fluorine atoms 1－16 an alkyl group or a halogen atom.

[0061] X A Each occurrence independently represents a single bond or a divalent organic group.

[0062] R F2 Representation - Rf 2 p -R F -O q -

[0063] R 2 It indicates that C may be substituted with one or more fluorine atoms. 1－6 Alkylene.

[0064] R F Each occurrence independently represents a divalent fluoropolyether group.

[0065] p is independently 0 or 1 at each occurrence.

[0066] q is independently 0 or 1 at each occurrence.]

[0067] R 1 -CH2-X A -R F2 -X A -CH2-R 2 (2)

[0068] [In formula (2), R 1 , R 2 , X A and R F2 Same meaning as above.]

[0069] The above reaction medium contains fluorine-containing alcohol.

[0070] According to the production method of the present invention, a fluoropolyether group-containing compound having active groups at both ends can be produced at a lower pressure and in a higher yield than in the prior art by reacting with a reducing agent in the presence of a reaction medium containing a fluorine-containing alcohol.

[0071] In formulas (1) and (2), R 1 Indicates - OR 1a or -NR 1b 2.

[0072] R 1a represents a hydrogen atom, C which may be substituted with one or more fluorine atoms 1－16 an alkyl group or a halogen atom.

[0073] R 1b Each occurrence independently represents a hydrogen atom, a C which may be substituted with one or more fluorine atoms 1－16 an alkyl group or a halogen atom.

[0074] R 1a and R 1b The C 1－16 The alkyl groups may be linear or branched, preferably linear or branched. 1－6 Alkyl, especially straight-chain or branched C 1－3 Alkyl, preferably a straight chain C 1－6 Alkyl groups, especially straight-chain C 1－3 alkyl.

[0075] R 1a and R 1b The C 1－16 The alkyl groups are each independently preferably C 1－16 Alkyl, preferably CF2H-C 1－15 Perfluoroalkylene, more preferably C 1－16 Perfluoroalkyl.

[0076] C 1－16 The perfluoroalkyl group may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－6 Perfluoroalkyl groups, especially C 1－3 Perfluoroalkyl, preferably linear C 1－6 Perfluoroalkyl groups, especially C 1－3 Perfluoroalkyl, specifically -CF3, -CF2CF3 or CF2CF2CF3.

[0077] As R 1a and R 1b The halogen atom represented by ' includes, independently, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom and a chlorine atom are preferred.

[0078] In one embodiment, as R 1a A hydrogen atom is preferred.

[0079] In one embodiment, preferably R 1b At least one of them is a hydrogen atom, preferably R 1b All are hydrogen atoms.

[0080] In formulas (1) and (2), R 2 Indicates - OR 2a or -NR 2b 2.

[0081] R 2a represents a hydrogen atom, which may be substituted by one or more fluorine atoms. 1－16 an alkyl group or a halogen atom.

[0082] R 2b Each occurrence independently represents a hydrogen atom, a C which may be substituted with one or more fluorine atoms 1－16 an alkyl group or a halogen atom.

[0083] R 2a and R 2b The C 1－16 The alkyl groups may be linear or branched, preferably linear or branched. 1－6 Alkyl, especially straight-chain or branched C 1－3 Alkyl, preferably a straight chain C 1－6 Alkyl groups, especially straight-chain C 1－3 alkyl.

[0084] R 2a and R 2b The C 1－16 The alkyl groups are each independently preferably C 1－16 Alkyl, preferably CF2H-C 1－15 Perfluoroalkylene, more preferably C 1－16 Perfluoroalkyl.

[0085] C 1－16 The perfluoroalkyl group may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－6 Perfluoroalkyl groups, especially C 1－3 Perfluoroalkyl, preferably linear C 1－6 Perfluoroalkyl groups, especially C 1－3 Perfluoroalkyl group is specifically -CF3, -CF2CF3 or CF2CF2CF3.

[0086] As R 2a and R 2b The halogen atom represented by ' includes, independently, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom and a chlorine atom are preferred.

[0087] In one embodiment, as R 2a A hydrogen atom is preferred.

[0088] In one embodiment, preferably R 2b At least one of them is a hydrogen atom, preferably R 2b All are hydrogen atoms.

[0089] In formulas (1) and (2), R F2 Representation - Rf 2 p -R F -O q -

[0090] R 2 The C 1－6 The alkylene group may be a straight chain or a branched chain, and is preferably a straight chain or a branched chain C 1－3 Alkylene, preferably a straight chain C 1－3 Alkylene.

[0091] R 2 Preferably, C is substituted with one or more fluorine atoms. 1－6 Alkylene, preferably C 1－6 Perfluoroalkylene, more preferably C 1－3 Perfluoroalkylene.

[0092] C 1－6 The perfluoroalkylene group may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－3 Perfluoroalkylene, preferably a linear C 1－3 The perfluoroalkylene group is specifically -CF2-, -CF2CF2- or -CF2CF2CF2-.

[0093] In the above formula, p is independently at each occurrence 0 or 1. In one embodiment, p is 0. In another embodiment, p is 1.

[0094] In the above formula, q is independently at each occurrence 0 or 1. In one embodiment, q is 0. In another embodiment, q is 1.

[0095] In the above formulas (1) and (2), R F Each occurrence independently represents a divalent fluoropolyether group.

[0096] R F Preferred are groups represented by the following formula:

[0097] -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3R Fa 6) d -(OC2F4) e -(OCF2) f -

[0098] [Wherein,

[0099] R Fa Each occurrence independently represents a hydrogen atom, a fluorine atom or a chlorine atom.

[0100] 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 1 or more. The order of the repeating units indicated by a, b, c, d, e or f and enclosed in parentheses in the formula is arbitrary. Fa When it is a hydrogen atom or a chlorine atom, at least one of a, b, c, e and f is 1 or more. ].

[0101] R Fa Preferably, they are hydrogen atoms or fluorine atoms, more preferably fluorine atoms. Fa When it is a hydrogen atom or a chlorine atom, at least one of a, b, c, e and f is 1 or more.

[0102] Preferably, a, b, c, d, e and f may each independently be an integer of 0 to 100.

[0103] The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example, 15 or more or 20 or more. The sum of a, b, c, d, e and f is preferably 200 or less, more preferably 100 or less, more preferably 60 or less, for example, 50 or less or 30 or less.

[0104] These repeating units can be straight-chain or branched, and can also contain ring structures. For example, -(OC6F 12 )- can be -(OCF2CF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2CF2)-, -(OCF2CF2CF(CF3)CF2CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3))-, etc. -(OC5F 10)- may be -(OCF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3))-, etc. -(OC4F8)- may be -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)-, and -(OCF2CF(C2F5))-. -(OC3F6)-(i.e., in the above formula, R Fa The -(OCF2CF2CF2)- may be any of -(OCF(CF3)CF2)-, -(OCF2CF(CF3))-, or -(OCF2CF(CF3))-. The -(OC2F4)- may be any of -(OCF2CF2)-, -(OCF(CF3))-, or -(OCF2CF2)-.

[0105] The ring structure may be a three-membered ring, a four-membered ring, a five-membered ring or a six-membered ring.

[0106]

[0107] [Wherein, * indicates the binding position.]

[0108] The ring structure may be a four-membered ring, a five-membered ring or a six-membered ring, and a four-membered ring or a six-membered ring is more preferred.

[0109] The repeating unit having a ring structure is preferably the following unit.

[0110]

[0111] [Wherein, * indicates the binding position.]

[0112] In one embodiment, the repeating unit is linear.

[0113] In one embodiment, the repeating unit is branched.

[0114] In one embodiment, R F Each occurrence thereof is independently a group represented by any one of the following formulae (f1) to (f6).

[0115] -(OC3F6) d -(OC2F4) e - (f1)

[0116] [Wherein, d is an integer of 1 to 200, and e is 0 or 1.]

[0117] -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f -(f2)

[0118] [wherein, c and d are each independently an integer from 0 to 30, e and f are each independently an integer from 1 to 200,

[0119] The sum of c, d, e and f is greater than 2,

[0120] The order in which the repeating units marked with the subscript c, d, e or f and enclosed in brackets are present in the formula is arbitrary.]

[0121] -(R 6 -R 7 ) g - (f3)

[0122] [Where R 6 For OCF2 or OC2F4,

[0123] R 7 is selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of 2 or 3 groups independently selected from these groups,

[0124] g is an integer from 2 to 100.]

[0125] -(R 6 -R 7 ) g -R r -(R 7’ -R 6’ ) g’ - (f4)

[0126] [Where R 6 For OCF2 or OC2F4,

[0127] R 7 is selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of 2 or 3 groups independently selected from these groups,

[0128] R 6’ For OCF2 or OC2F4,

[0129] R 7’ is selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of 2 or 3 groups independently selected from these groups,

[0130] g is an integer from 2 to 100,

[0131] g' is an integer from 2 to 100,

[0132] R r for

[0133]

[0134] (In the formula, * indicates the binding position.) ]

[0135] -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f5)

[0136] [In the formula, e is an integer from 1 to 200, a, b, c, d and f are each independently an integer from 0 to 200, and the order of existence of each repeating unit marked with a, b, c, d, e or f and enclosed in parentheses is arbitrary in the formula.]

[0137] -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f -(f6)

[0138] [In the formula, f is an integer from 1 to 200, a, b, c, d and e are each independently an integer from 0 to 200, and the order of existence of each repeating unit marked with a, b, c, d, e or f and enclosed in parentheses is arbitrary in the formula.]

[0139] In the above formula (f1), d is preferably an integer of 5 to 200, more preferably an integer of 10 to 100, further preferably an integer of 15 to 50, for example, an integer of 25 to 35. OC3F6 in the above formula (f1) is preferably (OCF2CF2CF2), (OCF(CF3)CF2) or (OCF2CF(CF3)), more preferably (OCF2CF2CF2). (OC2F4) in the above formula (f1) is preferably (OCF2CF2) or (OCF(CF3)), more preferably (OCF2CF2). In one embodiment, e is 0. In another embodiment, e is 1.

[0140] In the above formula (f2), e and f are each independently preferably an integer of 5 to 200, and more preferably an integer of 10 to 200. In addition, the sum of c, d, e and f is preferably 5 or more, and more preferably 10 or more, for example, 15 or more or 20 or more. In one embodiment, the above formula (f2) is preferably -(OCF2CF2CF2CF2) c -(OCF2CF2CF2) d -(OCF2CF2) e -(OCF2) f In another embodiment, formula (f2) may be -(OC2F4) e -(OCF2) f - the group shown.

[0141] In the above formula (f3), R 6 Preferably, it is OC2F4. In the above (f3), R 7It is preferably a group selected from OC2F4, OC3F6 and OC4F8, or a combination of two or three groups independently selected from these groups, and more preferably a group selected from OC3F6 and OC4F8. There is no particular limitation on the combination of two or three groups independently selected from OC2F4, OC3F6 and OC4F8, and examples thereof include -OC2F4OC3F6-, -OC2F4OC4F8-, -OC3F6OC2F4-, -OC3F6OC3F6-, -OC3F6OC4F8-, -OC4F8OC4F8-, -OC4F8OC3F6-, -OC4F8OC2F4-, -OC2 F4OC2F4OC3F6-, -OC2F4OC2F4OC4F8-, -OC2F4OC3F6OC2F4-, -OC2F4OC3F6OC3F6-, -OC2F4OC4F8OC2F4-, -OC3F6OC2F4OC2F4-, -OC3F6OC2F4OC3F6-, -OC3F6OC3F6OC2F4- and -OC4F8OC2F4OC2F4-. In the above formula (f3), g is preferably an integer of 3 or more, and more preferably an integer of 5 or more. The above g is preferably an integer of 50 or less. In the above formula (f3), OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 It may be a straight chain or a branched chain, preferably a straight chain. In this embodiment, the above formula (f3) is preferably -(OC2F4-OC3F6) g -or-(OC2F4-OC4F8) g -

[0142] In the above formula (f4), R 6 , R 7 and g have the same meanings as those described in the above formula (f3), and have the same embodiment. 6’ , R 7’ and g' respectively have the same meanings as R described in the above formula (f3). 6 , R 7 Same as g, in the same way. r Preferably

[0143]

[0144] [Wherein, * indicates the binding position.]

[0145] Preferably

[0146]

[0147] [Wherein, * indicates the binding position. ].

[0148] In the above formula (f5), e is preferably an integer of 1 to 100, more preferably an integer of 5 to 100. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 10 to 100.

[0149] In the above formula (f6), f is preferably an integer of 1 to 100, more preferably an integer of 5 to 100. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 10 to 100.

[0150] In one embodiment, the above R F It is a group represented by the above formula (f1).

[0151] In one embodiment, the above R F It is a group represented by the above formula (f2).

[0152] In one embodiment, the above R F It is a group represented by the above formula (f3) or (f4).

[0153] In one embodiment, the above R F It is a group represented by the above formula (f3).

[0154] In one embodiment, the above R F It is a group represented by the above formula (f4).

[0155] In one embodiment, the above R F It is a group represented by the above formula (f5).

[0156] In one embodiment, the above R F It is a group represented by the above formula (f6).

[0157] The above R F In the formula (hereinafter referred to as "e / f ratio"), the ratio of e to f is 0.1 to 10, preferably 0.2 to 5, more preferably 0.2 to 2, further preferably 0.2 to 1.5, and further more preferably 0.2 to 0.85. On the other hand, by making the e / f ratio greater than 0.1, the stability of the compound can be further improved. The greater the e / f ratio, the higher the stability of the compound.

[0158] In the above-mentioned fluorinated polyether group-containing compounds, R F1 and R F2 The number average molecular weight of the moiety is not particularly limited, and is, for example, 500 to 30,000, preferably 1,500 to 30,000, and more preferably 2,000 to 10,000. F1 and R F2The number average molecular weight is 19 Value measured by F-NMR.

[0159] In another way, R F1 and R F2 The number average molecular weight of the moiety is 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000, further preferably 2,000 to 10,000, and for example, may be 3,000 to 6,000.

[0160] In another approach, R F1 and R F2 The number average molecular weight of the moiety is 4,000 to 30,000, preferably 5,000 to 10,000, and more preferably 6,000 to 10,000.

[0161] X A Each occurrence is independently a single bond or a divalent organic group.

[0162] As X A The divalent organic group represented by 1－6 Alkylene, -(CH2) z1 -O-(CH2) z2 -(wherein z1 is an integer of 0 to 6, for example, an integer of 1 to 6, and z2 is an integer of 0 to 6, for example, an integer of 1 to 6) or -(CH2) z3 -phenylene-(CH2) z4 - (wherein z3 is an integer of 0 to 6, for example, an integer of 1 to 6, and z4 is an integer of 0 to 6, for example, an integer of 1 to 6). 1－6 The alkylene group may be a straight chain or a branched chain, preferably a straight chain. 1－6 Alkyl, C 2－6 Alkenyl and C 2－6 One or more substituents in the alkynyl group are substituted, but are preferably unsubstituted.

[0163] In a preferred embodiment, X A The divalent organic group represented by 1－6 Alkylene or -(CH2) z3 -phenylene-(CH2) z4 -, preferably -phenylene-(CH2) z4 -

[0164] In another preferred embodiment, the above X A C 1－3 In one embodiment, X AIt may be a single bond or -CH2CH2CH2-. In another embodiment, X A It can be a single bond or -CH2CH2-.

[0165] In one embodiment, X A For a single key.

[0166] The fluoropolyether group-containing compound represented by formula (1) is not particularly limited, but may have 5×10 2 ~1×10 5 The average molecular weight of the compound is preferably 2,000 to 32,000, and more preferably 2,500 to 12,000. The "average molecular weight" refers to the number average molecular weight. 19 Value measured by F-NMR.

[0167] The reaction medium is a medium for reducing compound (1) and contains a fluorinated alcohol. Although it should not be construed as a specific theory, it is believed that by making the reaction medium contain a fluorinated alcohol, the solubility of compound (2) in the reaction medium becomes good, which promotes the reduction reaction of compound (1), thereby achieving a lower pressure and higher yield than the prior art.

[0168] Examples of the fluorine-containing alcohol include alcohols having fluorine atoms, and preferably compounds in which a hydrocarbon group substituted with one or more fluorine atoms and one or more hydroxyl groups are bonded to each other.

[0169] As used in this specification, "hydrocarbon group" means a group containing carbon and hydrogen, wherein one hydrogen atom is removed from a hydrocarbon. A hydrocarbon group substituted with one or more fluorine atoms means a group in which a hydrogen atom contained in the hydrocarbon group is substituted with a fluorine atom.

[0170] The fluorine-containing alcohol is not particularly limited, but examples thereof include alcohols in which an aliphatic hydrocarbon group substituted with one or more fluorine atoms is bonded to a hydroxyl group; and alcohols in which an aromatic hydrocarbon group substituted with one or more fluorine atoms is bonded to a hydroxyl group. The above-mentioned "aliphatic hydrocarbon group" may be any of a straight chain, a branched chain, or a ring, and may be saturated or unsaturated. In addition, the hydrocarbon group may contain one or more ring structures.

[0171] In one embodiment, the hydrocarbon group substituted with one or more fluorine atoms is preferably a linear or branched C 1－20 Fluoroalkyl, preferably a linear or branched C 1－10 Fluoroalkyl, more preferably a linear or branched C 1－5 Fluoroalkyl, particularly preferably linear C 1－5 Fluoroalkyl.

[0172] The number of carbon atoms of the fluorine-containing alcohol (that is, the number of carbon atoms of the hydrocarbon group substituted with one or more fluorine atoms) is preferably 1-20, more preferably 1-10, and even more preferably 1-5.

[0173] The fluorine-containing alcohol may be a primary alcohol, a secondary alcohol or a tertiary alcohol, preferably a primary alcohol.

[0174] The above-mentioned fluorine-containing alcohol can be, for example, CF3CH2OH, CF3CF2CH2OH, CHF2CF2CH2OH, CHF2CH2OH, CF3CH(OH)CF3, CF3CH(OH)CH3, CHF2CH(OH)CHF2, CH2FCH(OH)CH2F, CF3CF2CF2CH2OH, CF3CHFCF2CH2OH, CHF2CF2CF2CH2OH, CF3CH2CH2CH2OH, (CF3)2CFCH2OH, CF3CF2CH(OH)CF3, CF3CF2CH(OH)CH3, (CF3)3COH, CH3(CF3)2COH, CF3(CH3)2COH , CF3CF2CF2CF2CH2OH, CF3CF2CH2CH2CH2OH, CF3CH2CH2CH2CH2OH, CHF2(CF3)2CFCH2CH2OH, (CF3)3CCH2OH, CF3CF2CF2CH(OH)CF3, CF3CF2CF2CH(OH)CH3 , CF3CF2C(CF3)2OH, CF3CF2C(CH3)2OH, CHF2CF2C(CF3)2OH, CF2CF2CF2CH2OH, etc., preferably CF3CH2OH, CF3CF2CH2OH, CF3CF2CF2CH2OH, CF3CF2CF2CF2CH2OH, etc.

[0175] The boiling point of the fluorine-containing alcohol is preferably 30° C. to 200° C., more preferably 50° C. to 200° C., and still more preferably 70° C. to 150° C.

[0176] The amount of the fluorinated alcohol used is preferably 0.1 mol or more, more preferably 0.1 mol or more and 50 mol or less, even more preferably 1 mol or more and 30 mol or less, in one embodiment, more preferably 1 mol or more and 10 mol or less, and in another embodiment, more preferably 10 mol or more and 30 mol or less.

[0177] The amount of the fluorinated alcohol used is preferably 0.1 mol or more, more preferably 0.1 mol or more and 50 mol or less, more preferably 1 mol or more and 10 mol or less relative to 1 mol of the reducing agent. The amount of the fluorinated alcohol used is preferably 0.1 mol or more, more preferably 1 mol or more, preferably 50 mol or less, more preferably 10 mol or less relative to 1 mol of the reducing agent.

[0178] The content of the fluorine-containing alcohol in the reaction medium is preferably from 0.01 mass % to 99.9 mass %, more preferably from 0.05 mass % to 80 mass %, and still more preferably from 0.1 mass % to 70 mass %.

[0179] The reaction medium may further contain at least one selected from fluorinated solvents other than fluorinated alcohols and non-fluorinated solvents.

[0180] As the fluorinated solvent other than the fluorinated alcohol, a solvent having a fluorine atom in the molecule and compatible with the fluorinated alcohol can be used. In one embodiment, as the fluorinated solvent other than the fluorinated alcohol, fluorinated ethers, fluorinated hydrocarbons, and fluorinated aromatic hydrocarbons can be mentioned.

[0181] Examples of the fluoroether include hydrofluoroethers such as perfluorobutyl ethyl ether and perfluorohexyl methyl ether; and hydrofluoroethers such as GALDEN HTPFPE, AE-3000, HFE7100, HFE7200, and HFE7300.

[0182] Examples of the fluorocarbons include perfluorocarbons such as perfluorohexane; hydrofluorocarbons such as ZEORORA H; and hydrochlorofluorocarbons such as 1,1,2-trichloro-1,2,2-trifluoroethane, 1,2-dichloro-1,1,2,2-tetrafluoroethane and 1,1-dichloro-1,2,2,3,3-pentafluoropropane (HCFC225).

[0183] Examples of the fluorine-containing aromatic hydrocarbons include hexafluoro-meta-xylene and hexafluorobenzene.

[0184] In the reaction medium, the fluorinated solvent other than the fluorinated alcohol is preferably 100 to 20,000 parts by mass, more preferably 200 to 15,000 parts by mass, and even more preferably 200 to 10,000 parts by mass, based on 100 parts by mass of the fluorinated alcohol.

[0185] As the above-mentioned non-fluorine solvent, there can be listed aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, mineral spirits, etc.; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, solvent naphtha, etc.; glycol ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, etc.; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, tetrahydropyran, dioxane, etc.; etc.

[0186] In the reaction medium, the non-fluorinated solvent is preferably in an amount of 1 to 100 parts by mass, more preferably 2 to 50 parts by mass, and still more preferably 5 to 20 parts by mass, relative to 100 parts by mass of the fluorinated solvent.

[0187] In one embodiment, the reaction medium preferably contains a fluorinated alcohol, a fluorinated aromatic hydrocarbon as a fluorinated solvent other than the fluorinated alcohol, and a glycol ether as a non-fluorinated solvent.

[0188] The boiling point of the reaction medium is preferably 70°C to 200°C, more preferably 80°C to 175°C, more preferably 100°C to 150°C. The boiling point of the reaction medium is preferably 70°C to 80°C, more preferably 100°C to 200°C, more preferably 175°C to 150°C.

[0189] The amount of the reaction medium is preferably 1 part by mass to 50 parts by mass, more preferably 1 part by mass to 30 parts by mass, and even more preferably 1 part by mass to 10 parts by mass, relative to 1 part by mass of the compound (1).

[0190] As the reducing agent, a compound having a function of reacting with the carbon of the carbonyl group (—CO—) contained in the compound (1) to convert the carbonyl group into a methylene group (—CH 2 —) can be used.

[0191] Specific examples of the reducing agent include metal hydride reducing agents, metal reducing agents, hydrazine reducing agents, phosphine reducing agents, phosphite reducing agents, metal alkoxide reducing agents, rare earth halide reducing agents, formic acid reducing agents, dithiothreitol, Hans esters, and hydrogen iodide.

[0192] The metal hydride reducing agent is typically a reducing agent containing a metal and hydrogen atoms bonded to the metal, and examples thereof include boron-based reducing agents, aluminum-based reducing agents, silicon-based reducing agents, and other metal hydride reducing agents.

[0193] Examples of the boron-based reducing agent include borane-ammonia complexes, borane-tert-butylamine complexes, borane-dimethylamine complexes, borane-dicyclohexylamine complexes, borane-trimethylamine complexes, borane-triethylamine complexes, borane-N,N-diethylaniline complexes, borane-pyridine complexes, borane-2-methylpyridine complexes, borane-morpholine complexes, borane-tetrahydrofuran complexes, borane-methyl sulfide complexes, borane-1,2-bis(tert-butylthio)ethane complexes, and boron hydride compounds such as sodium borohydride, lithium borohydride, potassium borohydride, lithium triethylborohydride, sodium triacetoxyborohydride, sodium cyanoborohydride, tetrabutylammonium borohydride, tetraethylammonium borohydride, benzyltriethylammonium borohydride, tetrabutylammonium borohydride, and tetramethylammonium triacetoxyborohydride.

[0194] Examples of the aluminum-based reducing agent include aluminum hydrides such as lithium aluminum hydride, diisobutylaluminum hydride, and sodium bis(2-methoxyethoxy)aluminum hydride.

[0195] Examples of the silicon-based reducing agent include triethylsilane, tri(trimethylsilyl)silane, triphenylsilane, trihexylsilane, triisopropylsilane, 1,1,2,2-tetraphenyldisilane, methyldiphenylsilane, dimethoxy(methyl)silane, dimethylphenylsilane, diethoxymethylsilane, diphenylsilane, phenylsilane, trichlorosilane, trimethoxysilane, triethoxysilane and other silicon hydrides.

[0196] Examples of other metal hydride reducing agents include alkali metal hydrides such as sodium hydride and potassium hydride; alkali metal hydrides such as calcium hydride; and zirconocene chlorohydride.

[0197] Examples of the metal reducing agent include alkali metals such as sodium metal and potassium metal; alkaline earth metals such as magnesium metal and calcium metal; and zinc metal.

[0198] Examples of the hydrazine reducing agent include hydrazine monohydroxide, anhydrous hydrazine, and N'-isopropylidene-2-nitrobenzenesulfonylhydrazide.

[0199] Examples of the phosphine reducing agent include triphenylphosphine and tri(2-carboxyethyl)phosphine hydrochloride.

[0200] Examples of the phosphite reducing agent include triethylphosphite and trimethylphosphite.

[0201] Examples of the metal alkoxide reducing agent include trialkoxyaluminum such as isopropoxyaluminum.

[0202] Examples of the rare earth metal halide reducing agent include rare earth metal iodides such as samarium iodide and cerium iodide; and rare earth metal chlorides such as samarium chloride and cerium chloride.

[0203] Examples of the formic acid-based reducing agent include formic acid, sodium formate, and triethylamine formate.

[0204] In one embodiment, the reducing agent preferably contains at least one selected from metal hydride reducing agents, metal reducing agents, hydrazine reducing agents, phosphite reducing agents, metal alkoxide reducing agents and rare earth metal halide reducing agents, more preferably contains a metal hydroxide reducing agent, and more preferably is selected from at least one selected from boron-based reducing agents, aluminum-based reducing agents and silicon-based reducing agents.

[0205] In one embodiment, the reducing agent is a boron-based reducing agent. In another embodiment, the reducing agent is an aluminum-based reducing agent.

[0206] The amount of the reducing agent used is preferably 2 mol or more, more preferably 2 mol or more and 20 mol or less, more preferably 3 mol or more and 10 mol or less, relative to 1 mol of the compound (1). The amount of the reducing agent used is preferably 2 mol or more, more preferably 3 mol or more, preferably 20 mol or less, more preferably 10 mol or less, relative to 1 mol of the compound (1). Thus, a fluoropolyether group-containing compound having active groups at both ends can be produced more easily at low pressure and with high yield.

[0207] The temperature at which the compound (1) is allowed to react with the reducing agent is preferably 80°C or higher and 150°C or lower, more preferably 100°C or higher and 150°C or lower, and more preferably 110°C or higher and 140°C or lower. The temperature at which the compound (1) is allowed to react with the reducing agent is preferably 80°C or higher, more preferably 100°C or higher, more preferably 110°C or higher, and preferably 150°C or lower, and more preferably 140°C or lower.

[0208] The pressure when compound (1) is allowed to act with the reducing agent is preferably 1 MPa or less, more preferably 0.05 MPa or more and 0.5 MPa or less, more preferably 0.08 MPa or more and 0.2 MPa or less. In one embodiment, compound (1) can be allowed to act with the reducing agent under normal pressure. The pressure when compound (1) is allowed to act with the reducing agent is preferably 1 MPa or less, more preferably 0.5 MPa or less, more preferably 0.2 MPa or less, preferably 0.05 MPa or more, more preferably 0.08 MPa or more.

[0209] When compound (1) is allowed to react with a reducing agent, a catalyst such as a Lewis acid may be present as necessary.

[0210] Although the embodiments are described above, various changes may be made to the embodiments and details without departing from the spirit and scope of the claims.

[0211] Example

[0212] The production method of the present invention is described below by way of examples, but the present invention is not limited to the following examples. It should be noted that in this example, the order of existence of the repeating units constituting the fluoropolyether is arbitrary, and the chemical formula shown below is an average composition.

[0213] (Test Examples 1 to 13)

[0214] In a 200 ml three-necked flask equipped with a cooling tube and a thermometer, HOOCCF2-O (CF2CF2O) dissolved in 40 ml of hexafluorobenzene was added at normal pressure. m -(CF2O) n To 20.0 g of -CF2COOH (m≒26, n≒24, hereinafter referred to as "Compound (1-A)"), the prescribed amounts of pentafluoropropanol and diglyme 4 ml as shown in Table 1 were added, and the mixture was heated to 80°C. To the solution, a prescribed amount of sodium borohydride was added in several portions, and the mixture was heated to a prescribed temperature and stirred at normal pressure for 3 hours.

[0215] After returning to room temperature, the reaction was quenched with 10% hydrochloric acid water. 19 F-NMR analysis. By HOOCCF2-O(CF2CF2O) m -(CF2O) n -CF2COOH and HOCH2CF2-(CF2CF2O) m -(CF2O) n The respective abundance ratios were determined from the integrated value of -CF2- at the β-position of -CF2CH2OH. The results are shown in Table 1.

[0216] [Table 1]

[0217]

[0218] Table 1 shows that, under the reaction conditions of 110 to 130° C. and 3 hours, by using pentafluoropropanol as a reaction medium, a fluoropolyether group-containing compound having active groups at both ends can be produced at normal pressure and in high yield. In particular, by adding 1 molar equivalent or more of pentafluoropropanol to 1 mole of compound (1), the reduction can be sufficiently promoted compared to the case where no pentafluoropropanol is added. In addition, when 6 molar equivalents or more of sodium borohydride and 15 molar equivalents of pentafluoropropanol are used to 1 mole of compound (1), or when 6.6 molar equivalents or more of sodium borohydride and 10 molar equivalents of pentafluoropropanol are used to 1 mole of compound (1), the reaction can be more fully completed.

Claims

1. A method for producing a compound containing a fluoropolyether group, characterized in that: The method comprises the steps of reacting the compound represented by formula (1) with a reducing agent in the presence of a reaction medium to obtain a compound represented by formula (2), R 1 -CO-X A -R F2 -X A -CO-R 2 (1) R 1 -CH2-X A -R F2 -x A -CH2-R 2 (2) In formula (1), R 1 Indicates - OR 1a or -NR 1b 2, R 1a represents a hydrogen atom, C which may be substituted with one or more fluorine atoms 1－16 an alkyl group or a halogen atom, R 1b Each occurrence independently represents a hydrogen atom, a C which may be substituted with one or more fluorine atoms 1－16 an alkyl group or a halogen atom, R 2 Indicates - OR 2a or -NR 2b 2, R 2a represents a hydrogen atom, C which may be substituted with one or more fluorine atoms 1－16 an alkyl group or a halogen atom, R 2b Each occurrence independently represents a hydrogen atom, a C which may be substituted with one or more fluorine atoms 1－16 an alkyl group or a halogen atom, X A Each occurrence independently represents a single bond or a divalent organic group, R F2 Representation - Rf 2 p -R F -O q - R 2 It indicates that C may be substituted with one or more fluorine atoms. 1－6 Alkylene, R F represents independently a divalent fluoropolyether group at each occurrence, p is independently 0 or 1 at each occurrence, q is independently 0 or 1 at each occurrence; In formula (2), R 1 , R 2 , X A and R F2 Has the same meaning as above; The reaction medium contains a fluorine-containing alcohol.

2. The manufacturing method according to claim 1, characterized in that: The fluorine-containing alcohol has 1 to 5 carbon atoms.

3. The manufacturing method according to claim 1 or 2, characterized in that: The reaction medium further contains at least one selected from fluorine-containing solvents other than fluorine-containing alcohols and non-fluorine solvents.

4. The manufacturing method according to any one of claims 1 to 3, characterized in that: The boiling point of the reaction medium is 70° C. to 200° C.

5. The manufacturing method according to any one of claims 1 to 4, characterized in that: The pressure at which the compound represented by the formula (1) is allowed to react with the reducing agent is 1 MPa or less.

6. The manufacturing method according to any one of claims 1 to 5, characterized in that: The temperature when the compound represented by the formula (1) is allowed to react with the reducing agent is 100° C. or higher and 150° C. or lower.

7. The manufacturing method according to any one of claims 1 to 6, characterized in that: The reducing agent contains at least one selected from the group consisting of a metal hydride reducing agent, a metal reducing agent, a hydrazine reducing agent, a phosphine reducing agent, a phosphite reducing agent, a metal alkoxide reducing agent and a halogenated rare earth metal reducing agent.

8. The manufacturing method according to any one of claims 1 to 7, characterized in that: The reducing agent contains at least one selected from a boron-based reducing agent, an aluminum-based reducing agent, and a silicon-based reducing agent.

9. The manufacturing method according to any one of claims 1 to 8, characterized in that: The reducing agent is used in an amount of 2 mol or more per mol of the compound represented by formula (1).

10. The manufacturing method according to any one of claims 1 to 9, characterized in that: The fluorine-containing alcohol is contained in an amount of 0.1 mol or more per 1 mol of the reducing agent.

Images