Method for producing olefin-modified fluorine-containing compound, and composition containing same

Abstract

The present invention pertains to a method for producing an olefin-modified fluorine-containing compound in which a compound represented by formula (1A) or a compound represented by formula (1B) is reacted with a compound represented by formula (2) in the presence of a radical initiator. In the formula, each symbol is as described in the specification. (1), R1A-CFY1-X1... (1A), X1-CFY1-R1B-CFY1-X1... (1B), and R23Si-(CH2) n1-CR4 = CR5R6... (2).

Description

Technical Field

[0001] The present invention relates to a method for producing an olefin-modified fluorine-containing compound and a composition containing the compound. Background Art

[0002] It is known that fluorine-containing compounds having fluorine atoms in the molecule can contribute to the formation of a layer (hereinafter sometimes referred to as a "surface treatment layer") having physical properties such as water repellency and oil repellency (e.g., Patent Document 1). Such fluorine-containing compounds are used in various applications. Various studies have been conducted on the synthesis of fluorine-containing compounds.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2021-80448 Summary of the invention

[0006] Technical problem to be solved by the invention

[0007] An object of the present invention is to provide a novel method for producing a compound having an olefin structure (hereinafter sometimes referred to as an "olefin-modified fluorinated compound") which is a fluorinated compound, and a composition containing the compound.

[0008] Technical solutions for solving technical problems

[0009] The present invention provides the following [1] to

[11] .

[0010] [1] A method for producing an olefin-modified fluorinated compound, comprising reacting a compound represented by formula (1A) or a compound represented by formula (1B) with a compound represented by formula (2) in the presence of a radical initiator.

[0011] R 1A -CFY 1 -X 1 …(1A)

[0012] [Where:

[0013] R 1A is a monovalent organic group;

[0014] Y 1 is a hydrogen atom or a halogen atom;

[0015] X 1 is a halogen atom other than a fluorine atom.]

[0016] X 1 -CFY 1 -R 1B -CFY 1 -X1 …(1B)

[0017] [Where:

[0018] R 1B is a divalent organic group;

[0019] Y 1 are each independently a hydrogen atom or a halogen atom;

[0020] X 1 are each independently a halogen atom other than a fluorine atom.]

[0021] R 2 3Si-(CH2) n1 -CR 4 =CR 5 R 6 …(2)

[0022] [Where:

[0023] R 2 Each independently includes R 21 3Si-monovalent group;

[0024] R 21 Each occurrence is independently a hydrogen atom or a C 1－12 alkyl;

[0025] C 1－12 Alkyl groups may be substituted with halogen atoms;

[0026] n1 is an integer from 1 to 10;

[0027] R 4 , R 5 and R 6 are independently a hydrogen atom or a C 1－10 alkyl.]

[0028] [2] The production method according to [1], wherein the Y 1 A fluorine atom.

[0029] [3] The production method according to [1] or [2], wherein the X 1 is a bromine atom or an iodine atom.

[0030] [4] The production method according to any one of [1] to [3], wherein the R 1A By Rf 1 -R F1 -(O) n21 -express;

[0031] R 1 is C which may be substituted with one or more fluorine atoms1－16 alkyl;

[0032] R F1 Formula: -(OC6F 12 ) a1 -(OC5F 10 ) b1 -(OC4F8) c1 -(OC3R Fa 6) d1 -(OC2F4) e1 -(OCF2) f1 - the group shown;

[0033] a1, b1, c1, d1, e1 and f1 are each independently an integer of 0 to 200, the sum of a1, b1, c1, d1, e1 and f1 is 1 or more, and the order of existence of each repeating unit marked with a1, b1, c1, d1, e1 or f1 and enclosed in brackets in the formula is arbitrary;

[0034] R Fa is independently at each occurrence a hydrogen atom, a fluorine atom or a chlorine atom;

[0035] n21 is 0 or 1.

[0036] [5] The production method according to any one of [1] to [4], wherein the R 1B By - (Rf 2 ) n23 -R F1 -(O) n22 -express;

[0037] R 2 is a divalent organic group;

[0038] R F1 Formula: -(OC6F 12 ) a1 -(OC5F 10 ) b1 -(OC4F8) c1 -(OC3R Fa 6) d1 -(OC2F4) e1 -(OCF2) f1 - the group shown;

[0039] a1, b1, c1, d1, e1 and f1 are each independently an integer of 0 to 200, the sum of a1, b1, c1, d1, e1 and f1 is 1 or more, and the order of existence of each repeating unit marked with a1, b1, c1, d1, e1 or f1 and enclosed in brackets in the formula is arbitrary;

[0040] R Fa is independently at each occurrence a hydrogen atom, a fluorine atom or a chlorine atom;

[0041] n22 is 0 or 1;

[0042] n23 is 0 or 1.

[0043] [6] The production method according to any one of [1] to [5], wherein the R 2 R 21 3Si-;

[0044] The above R 21 are independently C which may be substituted by a halogen atom 1－4 alkyl;

[0045] C 1－4 The alkyl group is linear or branched.

[0046] [7] The production method according to [6], wherein the R 2 Each independently is (CH3)3Si-.

[0047] [8] The production method according to any one of [1] to [7], wherein a purification treatment is performed after the reaction of the compound represented by formula (1A) or the compound represented by formula (1B) with the compound represented by formula (2).

[0048] [9] The production method according to any one of [1] to [8], wherein the olefin-modified fluorinated compound is a compound represented by formula (3A) or a compound represented by formula (3B).

[0049] R 1A -CFY 1 -CR 5 R 6 -CR 4 =CH-(CH2) n1－1 H…(3A)

[0050] [Where:

[0051] R 1A , Y 1 、n1、R 4 , R 5 and R 6 The meanings are the same as those in item [1].]

[0052] H(CH2) n1－1 -CH=CR 4 -CR 5 R 6 -CFY 1 -R 1B -CFY1 -CR 5 R 6 -CR 4 =CH-(CH2) n1－1 H…(3B)

[0053] [Where:

[0054] R 1B , Y 1 、n1、R 4 , R 5 and R 6 The meanings are the same as those in item [1].]

[0055]

[10] A composition comprising: at least one of an olefin-modified fluorine-containing compound represented by formula (3A) and an olefin-modified fluorine-containing compound represented by formula (3B); and tin in an amount of 1 ppm or less relative to the total amount of the olefin-modified fluorine-containing compound represented by formula (3A) and the olefin-modified fluorine-containing compound represented by formula (3B).

[0056] R 1A -CFY 1 -CR 5 R 6 -CR 4 =CH-(CH2) n1－1 H…(3A)

[0057] [Where:

[0058] R 1A is a monovalent organic group;

[0059] Y 1 is a hydrogen atom or a halogen atom;

[0060] n1 is an integer from 1 to 10;

[0061] R 4 , R 5 and R 6 Each occurrence is independently a hydrogen atom or a C 1－10 alkyl.]

[0062] H(CH2) n1－1 -CH=CR 4 -CR 5 R 6 -CFY 1 -R 1B -CFY 1 -CR 5 R 6 -CR 4 =CH-(CH2) n1－1 H…(3B)

[0063] [Where:

[0064] R 1B is a divalent organic group;

[0065] Y 1 are each independently a hydrogen atom or a halogen atom;

[0066] n1 are each independently an integer from 1 to 10;

[0067] R 4 , R 5 and R 6 Each occurrence is independently a hydrogen atom or a C 1－10 alkyl.]

[0068]

[11] The composition according to

[10] , wherein the amount of tin is 1 ppb or less relative to the total amount of the olefin-modified fluorine-containing compound represented by the formula (3A) and the olefin-modified fluorine-containing compound represented by the formula (3B).

[0069] Effects of the Invention

[0070] The present invention can provide a novel method for producing an olefin-modified fluorine-containing compound and a composition containing the compound. DETAILED DESCRIPTION

[0071] As used in this specification, "monovalent organic group" refers to a monovalent group containing carbon. The monovalent organic group is not particularly limited and may be a hydrocarbon group or a derivative thereof. A derivative of a hydrocarbon group refers to a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at the end of the hydrocarbon group or in the molecular chain.

[0072] As used in the present specification, the "divalent organic group" is not particularly limited, and examples thereof include a divalent group obtained by removing one hydrogen atom from a hydrocarbon group.

[0073] When used in this specification, "hydrocarbon group" is a group containing carbon and hydrogen, and refers to a group after removing one hydrogen atom from the molecule. Such a hydrocarbon group is not particularly limited, and examples thereof include hydrocarbon groups having 1 to 20 carbon atoms that can be substituted with one or more substituents, such as aliphatic hydrocarbon groups, aromatic hydrocarbon groups, etc. The above-mentioned "aliphatic hydrocarbon group" can be any of linear, branched or cyclic, and can also be any of saturated or unsaturated. In addition, the hydrocarbon group can also contain one or more ring structures.

[0074] As used in this specification, the substituent of the "hydrocarbon group" is not particularly limited, and examples thereof include: a halogen atom; a C 1－6Alkyl, C 2－6 Alkenyl, C 2－6 Alkynyl, C 3－10 Cycloalkyl, C 3－10 unsaturated cycloalkyl, 5- to 10-membered heterocyclic group, 5- to 10-membered unsaturated heterocyclic group, C 6－10 One or more of an aryl group and a 5- to 10-membered heteroaryl group.

[0075] In this specification, unless otherwise specified, the alkyl group and the phenyl group may be unsubstituted or substituted. The substituents of these groups are not particularly limited, and examples thereof include halogen atoms, C 1－6 Alkyl, C 2－6 Alkenyl and C 2－6 One or more groups in the alkynyl group.

[0076] Hereinafter, one embodiment of the present invention, that is, a method for producing an olefin-modified fluorinated compound will be described.

[0077] (Manufacturing method)

[0078] The method for producing an olefin-modified fluorinated compound of the present invention comprises the following step (I).

[0079] [Step (I)]

[0080] A step of reacting a compound represented by formula (1A) or a compound represented by formula (1B) with a compound represented by formula (2) in the presence of a radical initiator.

[0081] R 1A -CFY 1 -X 1 …(1A)

[0082] X 1 -CFY 1 -R 1B -CFY 1 -X 1 …(1B)

[0083] R 2 3Si-(CH2) n1 -CR 4 =CR 5 R 6 …(2)

[0084] By the above steps, a composition containing an olefin-modified fluorine-containing compound represented by the formula (3A) or an olefin-modified fluorine-containing compound represented by the formula (3B) can be obtained.

[0085] R 1A -CFY 1 -CR5 R 6 -CR 4 =CH-(CH2) n1－1 H…(3A)

[0086] H(CH2) n1－1 -CH=CR 4 -CR 5 R 6 -CFY 1 -R 1B -CFY 1 -CR 5 R 6 -CR 4 =CH-(CH2) n1－1 H…(3B)

[0087] Herein, in the following, the olefin-modified fluorine-containing compound refers to the olefin-modified fluorine-containing compound represented by formula (3A) or the olefin-modified fluorine-containing compound represented by formula (3B).

[0088] By using the above production method, the selectivity of the olefin-modified fluorinated compound in the produced compound is improved. 2 3Si- and X 1 The reaction generates -CFY 1 In the above-mentioned production method, it is believed that -CFY can be appropriately controlled 1 It is considered that the rate of generation of free radicals increases, and as a result, the selectivity of the generated olefin-modified fluorinated compound increases.

[0089] Each formula is described below.

[0090] (Formula (1A))

[0091] R 1A -CFY 1 -X 1 …(1A)

[0092] X 1 is a halogen atom other than a fluorine atom, preferably a chlorine atom, a bromine atom or an iodine atom, more preferably a bromine atom or an iodine atom. 1 is a bromine atom. In one embodiment, X 1 is an iodine atom.

[0093] Y 1 It is a hydrogen atom or a halogen atom, preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and more preferably a fluorine atom.

[0094] R 1A It is a monovalent organic group.

[0095] In one approach, R1A By Rf 1 -R F1 -(O) n21 -express.

[0096] R 1 is C which may be substituted with one or more fluorine atoms 1－16 Alkyl. The above “C 1－16 The "alkyl" may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－6 Alkyl, especially straight-chain or branched C 1－3 Alkyl, more preferably a straight chain C 1－6 Alkyl groups, especially C 1－3 alkyl.

[0097] The above Rf 1 Preferably, C is substituted with one or more fluorine atoms. 1－16 Alkyl, more preferably C 1－16 Perfluoroalkyl. 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, especially linear or branched C 1－3 Perfluoroalkyl, more preferably linear C 1－6 Perfluoroalkyl groups, especially C 1－3 Perfluoroalkyl.

[0098] In one embodiment, Rf 1 is C which may be substituted with one or more fluorine atoms 1－6 Alkyl. The above “C 1－6 The "alkyl" may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－3 As a method, the above C 1－6 The alkyl group is preferably a straight chain C 1－6 Alkyl groups, especially C 1－3 Alkyl. Rf 1 In one embodiment, it is CF3-; in another embodiment, it is CF3CF2-; in still another embodiment, it is CF3CF2CF2-.

[0099] In the above method, Rf 1 Preferably, C is substituted with one or more fluorine atoms. 1－6 Alkyl, more preferably C 1－6 In this embodiment, the above C 1－6 The perfluoroalkyl group may be a straight chain or a branched chain, preferably a straight chain C 1－6 Perfluoroalkyl groups, especially C 1－3 Perfluoroalkyl.

[0100] RF1 Formula: -(OC j R c 2j ) j1 -(OC h R c 2h－2 ) h1 - The group shown. -OC j R c 2j - are independently linear or branched, -OC h R c 2h－2 - are each independently a structure containing a ring structure. c are independently a hydrogen atom, a chlorine atom or a fluorine atom, but in R F1 At least 1 R c is a fluorine atom. j is independently an integer of 1 to 6, h is independently an integer of 1 to 7, j1 is an integer greater than 0, h1 is an integer greater than 0, and the sum of j1 and h1 is greater than 1. The order of existence of each repeating unit marked with j1 or h1 and enclosed in arcs is arbitrary in the formula.

[0101] In one approach, R F1 Formula: -(OC6F 12 ) a1 -(OC5F 10 ) b1 -(OC4F8) c1 -(OC3R Fa 6) d1 -(OC2F4) e1 -(OCF2) f1 - the group shown.

[0102] a1, b1, c1, d1, e1 and f1 are each independently an integer of 0 to 200, the sum of a1, b1, c1, d1, e1 and f1 is greater than 1, and the order of existence of each repeating unit marked with a1, b1, c1, d1, e1 or f1 and enclosed in brackets in the formula is arbitrary.

[0103] By having the above R F1 , which can form a surface treatment layer having water repellency, oil repellency, chemical resistance and friction durability.

[0104] In addition, in this specification, R F1 The left side of Rf 1 Bonded, right side with -(O) n21 - Bonding.

[0105] R Fais independently at each occurrence a hydrogen atom, a fluorine atom or a chlorine atom.

[0106] R Fa It is preferably a hydrogen atom or a fluorine atom, and more preferably a fluorine atom.

[0107] Preferably, a1, b1, c1, d1, e1 and f1 may each independently be an integer of 0 to 100.

[0108] The sum of a1, b1, c1, d1, e1 and f1 is preferably 5 or more, more preferably 10 or more, for example, 15 or more or 20 or more. The sum of a1, b1, c1, d1, e1 and f1 is preferably 200 or less, more preferably 100 or less, further preferably 60 or less, for example, 50 or less or 30 or less.

[0109] In R F1 In the above, these repeating units may be linear or branched, and may also contain a ring structure.

[0110] Examples of the linear or branched repeating unit include the following structures. 12 )- can be -(OCF2CF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2CF2)-, -(OCF2CF2CF(CF3)CF2CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3))-, etc. -(OC5F 10 )- may be any of -(OCF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3))-, etc. -(OC4F8)- may be any of -(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 FaThe -(OCF2CF2CF2)- may be any of -(OCF(CF3)CF2)-, -(OCF2CF(CF3))-, and -(OCF2CF(CF3))-. The -(OC2F4)- may be any of -(OCF2CF2)-, and -(OCF(CF3))-.

[0111] The ring structure may be a three-membered ring, a four-membered ring, a five-membered ring or a six-membered ring.

[0112]

[0113] [Wherein, * represents the bonding position.]

[0114] In one embodiment, the repeating unit is linear.

[0115] In one embodiment, the repeating unit includes a branched structure.

[0116] In one embodiment, the repeating unit includes a ring structure.

[0117] In one approach, R F1 Each occurrence is independently a group represented by any of the following formulae (f1) to (f6).

[0118] -(OC3F6) d1 -(OC2F4) e1 - (f1)

[0119] [In the formula, d1 is an integer of 1 to 200, and e1 is 0 or 1, preferably 1.]

[0120] -(OC4F8) c1 -(OC3F6) d1 -(OC2F4) e1 -(OCF2) f1 -(f2)

[0121] [wherein, c1 and d1 are each independently an integer from 0 to 30, e1 and f1 are each independently an integer from 1 to 200,

[0122] The sum of c1, d1, e1 and f1 is greater than 2,

[0123] The order of presence of the repeating units marked with the subscript c1, d1, e1 or f1 and enclosed in parentheses is arbitrary in the formula.]

[0124] -(R 71 -R 72 ) g1 - (f3)

[0125] [Where R 71For OCF2 or OC2F4,

[0126] R 72 is selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of 2 or 3 groups independently selected from these groups,

[0127] g1 is an integer from 2 to 100.]

[0128] -(R 71 -R 72 ) g1 -R r -(R 72’ -R 71’ ) g1’ - (f4)

[0129] [Where R 71 For OCF2 or OC2F4,

[0130] R 72 is selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of 2 or 3 groups independently selected from these groups,

[0131] R 71’ For OCF2 or OC2F4,

[0132] R 72’ is selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of 2 or 3 groups independently selected from these groups,

[0133] g1 is an integer from 2 to 100,

[0134] g1' is an integer from 2 to 100,

[0135] R r for

[0136]

[0137] (Where * represents the bonding position).]

[0138] -(OC6F 12 ) a1 -(OC5F 10 ) b1 -(OC4F8) c1 -(OC3F6) d1-(OC2F4) e1 -(OCF2) f1 - (f5)

[0139] [In the formula, e1 is an integer from 1 to 200, a1, b1, c1, d1 and f1 are each independently an integer from 0 to 200, the sum of a1, b1, c1, d1, e1 and f1 is at least 1, and the order of existence of the repeating units marked with a1, b1, c1, d1, e1 or f1 and enclosed in parentheses is arbitrary in the formula.]

[0140] -(OC6F 12 ) a1 -(OC5F 10 ) b1 -(OC4F8) c1 -(OC3F6) d1 -(OC2F4) e1 -(OCF2) f1 -(f6)

[0141] [In the formula, f1 is an integer from 1 to 200, a1, b1, c1, d1 and e1 are each independently an integer from 0 to 200, the sum of a1, b1, c1, d1, e1 and f1 is at least 1, and the order of existence of each repeating unit marked with a1, b1, c1, d1, e1 or f1 and enclosed in parentheses is arbitrary in the formula.]

[0142] In the above formula (f1), d1 is preferably an integer of 5 to 200, more preferably 10 to 100, further preferably 15 to 50, for example, 25 to 35. (OC3F6) in the above formula (f1) is preferably a group represented by (OCF2CF2CF2) or (OCF(CF3)CF2), more preferably a group represented by (OCF2CF2CF2). (OC2F4) in the above formula (f1) is preferably a group represented by (OCF2CF2) or (OCF(CF3)), more preferably a group represented by (OCF2CF2).

[0143] In the above formula (f2), e1 and f1 are each independently an integer of preferably 5 or more and 200 or less, more preferably an integer of 10 to 200. In addition, the sum of c1, d1, e1 and f1 is preferably 5 or more, more preferably 10 or more, for example, 15 or more or 20 or more. In one embodiment, the above formula (f2) is preferably -(OCF2CF2CF2CF2) c1 -(OCF2CF2CF2) d1 -(OCF2CF2) e1 -(OCF2) f1In another embodiment, formula (f2) may also be -(OC2F4) e1 -(OCF2) f1 - the group shown.

[0144] In the above formula (f3), R 71 Preferably, it is OC2F4. In the above (f3), R 72 It 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. The combination of two or three groups independently selected from OC2F4, OC3F6 and OC4F8 is not particularly limited, and examples thereof include -OC2F4OC3F6-, -OC2F4OC4F8-, -OC3F6OC2F4-, -OC3F6OC3F6-, -OC3F6OC4F8-, -OC4F8OC4F8-, -OC4F8OC3F6-, -OC4F8OC2F4-, -OC2F 4OC2F4OC3F6-, -OC2F4OC2F4OC4F8-, -OC2F4OC3F6OC2F4-, -OC2F4OC3F6OC3F6-, -OC2F4OC4F8OC2F4-, -OC3F6OC2F4OC2F4-, -OC3F6OC2F4OC3F6-, -OC3F6OC3F6OC2F4- and -OC4F8OC2F4OC2F4-. In the above formula (f3), g1 is preferably an integer of 3 or more, more preferably an integer of 5 or more. The above g1 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) g1 -or-(OC2F4-OC4F8) g1 -

[0145] In the above formula (f4), R 71 , R 72 and g1 have the same meanings as those described in the above formula (f3) and have the same aspects. 71’ , R 72’ and g1' respectively have the same meanings as R described in the above formula (f3). 71 , R 72 Same as g1, with the same behavior. r Preferably

[0146]

[0147] [Where * represents the bonding position],

[0148] More preferably

[0149]

[0150] [Wherein, * represents the bonding position].

[0151] In the above formula (f5), e1 is preferably an integer of 1 to 100, more preferably 5 to 100. The sum of a1, b1, c1, d1, e1 and f1 is preferably 5 or more, more preferably 10 or more, for example 10 to 100.

[0152] In the above formula (f5), R F1 The repeating unit at the terminal portion may be -(OCF2CF2OCF2CF2CF2)-.

[0153] In the above formula (f6), f1 is preferably an integer of 1 to 100, more preferably 5 to 100. The sum of a1, b1, c1, d1, e1 and f1 is preferably 5 or more, more preferably 10 or more, for example 10 to 100.

[0154] In one embodiment, the above R F1 It is a group represented by the above formula (f1).

[0155] In one embodiment, the above R F1 It is a group represented by the above formula (f2).

[0156] In one embodiment, the above R F1 It is a group represented by the above formula (f3) or (f4).

[0157] In one embodiment, the above R F1 It is a group represented by the above formula (f3).

[0158] In one embodiment, the above R F1 It is a group represented by the above formula (f4).

[0159] In one embodiment, the above R F1 It is a group represented by the above formula (f5).

[0160] In one embodiment, the above R F1 It is a group represented by the above formula (f6).

[0161] In one embodiment, the above R F1 It is a group represented by the above formula (f1), (f2), (f5) or (f6).

[0162] In one embodiment, the above R F1 It is a group represented by the above formula (f1), (f2) or (f6).

[0163] In the above R F1 In the above, the ratio of e1 to f1 (hereinafter referred to as "e / f ratio") is, for example, 0.1 to 10, preferably 0.2 to 5, more preferably 0.2 to 2, further preferably 0.2 to 1.5, further preferably 0.2 to less than 0.9, particularly preferably 0.2 to 0.85. By having the e / f ratio in the above range, the stability of the obtained fluorine-containing compound is improved. Wherein, f1 is an integer greater than 1.

[0164] In one approach, in R F1 In R, the ratio e / f is preferably greater than 1.0, for example, greater than 1.1 or greater than 1.3. F1 The e / f ratio is preferably 10.0 or less, 9.0 or less, more preferably 5.0 or less, further preferably 2.0 or less, and particularly preferably 1.5 or less. F1 The e / f ratio may be, for example, 1.0 to 10.0, specifically 1.0 to 5.0, more specifically 1.0 to 2.0, and even more specifically 1.0 to 1.5.

[0165] In one approach, in R F1 The e / f ratio may be in the range of 1.0 to 1.2.

[0166] In one approach, in R F1 In R, the ratio e / f may be less than 0.9, for example, less than 0.8 or less than 0.7. F1 In the above formula, the ratio e / f is preferably 0.2 or more, more preferably 0.3 or more, further preferably 0.4 or more, and particularly preferably 0.5 or more. F1 The e / f ratio may be, for example, 0.2 or more and less than 0.9, specifically 0.4 or more and 0.8 or less, and more specifically 0.5 or more and 0.7 or less.

[0167] In one embodiment, d1 is preferably an integer greater than 1, more preferably greater than 3, further preferably greater than 6, and may be less than 200, less than 120, less than 60, or less than 54. In this embodiment, d1 may be 1 to 200, 3 to 120, 3 to 60, or 6 to 60.

[0168] In one approach, R F1 For - (OC3F6) d1 -(OC2F4) e1-(f1) [wherein, d1 is an integer of 3 to 60, preferably an integer of 6 to 54; e1 is 1; OC3F6 and OC2F4 are straight-chain. ] represented by a group.

[0169] In one approach, R F1 For - (OC3F6) d1 -(OC2F4) e1 -(f1) [wherein, d1 is an integer of 3 to 120, preferably an integer of 6 to 60; e1 is 1; each of OC3F6 and OC2F4 has a branch. ] For example, in formula (f1), the repeating unit is represented by -OCF(CF3)CF2-.

[0170] The above R F1 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 The number average molecular weight is calculated using 19 The value obtained by F-NMR measurement.

[0171] In another way, R F1 The number average molecular weight of the moiety may be 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000, further preferably 2,000 to 10,000, for example 3,000 to 6,000.

[0172] In another way, R F1 The number average molecular weight of the moiety may be 4,000 to 30,000, preferably 5,000 to 10,000, and more preferably 6,000 to 10,000.

[0173] n21 is 0 or 1. In one embodiment, n21 is 0. In one embodiment, n21 is 1.

[0174] (Formula (1B))

[0175] X 1 -CFY 1 -R 1B -CFY 1 -X 1 …(1B)

[0176] X 1 Each of X and X is independently a halogen atom other than a fluorine atom, preferably a chlorine atom, a bromine atom or an iodine atom, and more preferably a bromine atom or an iodine atom. 1 is a bromine atom. In one embodiment, X 1 is an iodine atom.

[0177] Y 1 Each is independently a hydrogen atom or a halogen atom, preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and more preferably a fluorine atom.

[0178] R 1B It is a divalent organic group.

[0179] In one approach, R 1B By - (Rf 2 ) n23 -R F1 -(O) n22 -express.

[0180] R F1 As mentioned above.

[0181] R 2 It is a divalent organic group.

[0182] The above Rf 2 Preferably, C may be substituted with one or more fluorine atoms. 1－6 Alkylene.

[0183] The above C may be substituted with one or more fluorine atoms 1－6 The "C" in the alkylene 1－6 The "alkylene" may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－3 Alkylene, more preferably a straight chain C 1－3 Alkylene.

[0184] The above Rf 2 Preferably, C is substituted with one or more fluorine atoms. 1－6 Alkylene, more preferably C 1－6 Perfluoroalkylene, more preferably C 1－3 Perfluoroalkylene.

[0185] 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, more preferably linear C 1－3 Perfluoroalkylene is specifically -CF2-, -CF2CF2- or -CF2CF2CF2-.

[0186] n22 is 0 or 1. In one embodiment, n22 is 0. In one embodiment, n22 is 1. n23 is 0 or 1. In one embodiment, n23 is 0. In one embodiment, n23 is 1.

[0187] (Formula (2))

[0188] R 23Si-(CH2) n1 -CR 4 =CR 5 R 6 …(2)

[0189] R 2 Each independently includes R 21 3Si-monovalent group.

[0190] In one embodiment, the above R 2 For R 21 A group consisting of 3Si- and a divalent organic group.

[0191] The above R 2 Preferably, each independently is R 21 3Si-.

[0192] R 21 are independently a hydrogen atom or a C 1－12 Alkyl. 1－12 The alkyl group may be substituted with a halogen atom. 1－12 The alkyl groups are each independently linear or branched.

[0193] The above R 21 Preferably, each independently is C 1－4 Alkyl. 1－4 The alkyl groups are each independently linear or branched. 1－4 The alkyl group is straight chain. 1－4 The alkyl group is branched.

[0194] The above R 21 More preferably, each independently is C 1－4 alkyl.

[0195] The above R 21 More preferably, it is a CH3 group. In this case, R 2 Represented by (CH3)3Si-.

[0196] n1 is an integer of 1-10, and preferably an integer of 1-3.

[0197] In one embodiment, n1 is 1. In this case, the terminal of the olefin-modified fluorinated compound represented by the formula (3A) or the olefin-modified fluorinated compound represented by the formula (3B) is -CR 4 =CH2. In the present production method, the olefin-modified fluorine-containing compound represented by the formula (3A) or the olefin-modified fluorine-containing compound represented by the formula (3B) having the above-mentioned terminal can be particularly well formed. This is considered to be due to -CR 4=CH2 has little steric hindrance and the reaction proceeds well. When the surface is treated with a surface treatment agent containing the above compound, the adhesion to the substrate can be particularly good.

[0198] R 4 , R 5 and R 6 Each occurrence is independently a hydrogen atom or a C 1－10 alkyl.

[0199] The above R 4 Preferably, a hydrogen atom or a C 1－6 An alkyl group is more preferably a hydrogen atom or a CH3 group. 4 is a hydrogen atom. In one embodiment, R 4 It is a CH3 group.

[0200] The above R 5 Preferably, a hydrogen atom or a C 1－6 The alkyl group is more preferably a hydrogen atom or a CH3 group, and is preferably a hydrogen atom.

[0201] The above R 6 Preferably, a hydrogen atom or a C 1－6 The alkyl group is more preferably a hydrogen atom or a CH3 group, and is preferably a hydrogen atom.

[0202] In one approach, R 5 or R 6 One of them is a CH3 group and the other is a hydrogen atom.

[0203] In one approach, R 5 and R 6 is a hydrogen atom. In this case, the reactivity of the compound represented by formula (1A) or the compound represented by formula (1B) with the compound represented by formula (2) can become particularly good. The mixing ratio of the compound represented by formula (1A) and the compound represented by formula (1B) is not particularly limited and can be mixed in any ratio. The mixing ratio of the compound represented by formula (1A) and the compound represented by formula (1B) can be adjusted according to the content of the compound represented by formula (2).

[0204] In one embodiment, a compound represented by formula (1A) can be used.

[0205] In one embodiment, a compound represented by formula (1B) can be used.

[0206] In one embodiment, the compound represented by formula (1A) and the compound represented by formula (2) are mixed in a molar ratio of 1:1 to 1:10. The compound represented by formula (1A) and the compound represented by formula (2) are preferably mixed in a molar ratio of 1:1 to 1:8, more preferably 1:1 to 1:6, and further preferably 1:2 to 1:6. By mixing in such a molar ratio, the reaction can be particularly well performed.

[0207] In one embodiment, the compound represented by formula (1B) and the compound represented by formula (2) are mixed in a molar ratio of 1:2 to 1:20. The compound represented by formula (1B) and the compound represented by formula (2) are preferably mixed in a molar ratio of 1:2 to 1:16, more preferably 1:2 to 1:12, and further preferably 1:4 to 1:12. By mixing in such a molar ratio, the reaction can be particularly well performed.

[0208] (Formula (3A))

[0209] R 1A -CFY 1 -CR 5 R 6 -CR 4 =CH-(CH2) n1－1 H…(3A)

[0210] About R 1A , Y 1 、n1、R 4 , R 5 and R 6 , as described in formula (1A) or formula (2).

[0211] (Formula (3B))

[0212] H(CH2) n1－1 -CH=CR 4 -CR 5 R 6 -CFY 1 -R 1B -CFY 1 -CR 5 R 6 -CR 4 =CH-(CH2) n1－1 H…(3B)

[0213] About R 1B , Y 1 、n1、R 4 , R 5 and R 6 , as described in formula (1B) or formula (2).

[0214] As mentioned above, the compound shown in formula (3A) or the compound shown in formula (3B) (i.e., olefin-modified fluorinated compound) contains olefin. When the surface treatment agent contains the above-mentioned olefin-modified fluorinated compound, the olefin-modified fluorinated compound can be well bonded to the substrate by utilizing the olefin. The above-mentioned olefin-modified fluorinated compound can also be effectively used as a raw material for synthesizing other compounds.

[0215] (Free Radical Initiator)

[0216] As the radical initiator, a compound that undergoes the reaction of step (I) can be used, and examples thereof include azo compounds, dihalogens, and organic peroxides.

[0217] Examples of the azo compound include azobisisobutyronitrile (AIBN), 1,1'-azobis(cyclohexanecarbonitrile) (ABCN), 1-[(1-cyano-1-methylethyl)azo]formamide, 4,4'-azobis(4-cyanovaleric acid), dimethyl-1,1'-azobis(1-cyclohexanecarboxylate), 2,2'-azobis(N-butyl-2-methylpropionamide), and 2,2'-azobis(N-cyclohexyl-2-methylpropionamide). Azo compounds are preferably used because of their good solubility.

[0218] Examples of the dihalogen include chlorine molecules and the like.

[0219] Examples of the organic peroxide include di-tert-butyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, di(3-methylbenzoyl) peroxide, benzoyl(3-methylbenzoyl) peroxide, 1,1-di(tert-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(tert-hexylperoxy)cyclohexane, 1,1-di(tert-butylperoxy)-2-methylcyclohexane, 1,1-di(tert-butylperoxy)cyclohexane, 2,2 -Di(tert-butylperoxy)butane, tert-butylcumyl peroxide, di-tert-hexyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, tert-hexylperoxy-2-ethylhexanoate, tert-butylperoxy-2-ethylhexanoate, tert-hexylperoxyisopropylmonocarbonate, tert-butylperoxyisopropylmonocarbonate, tert-butylperoxy-2-ethylhexylmonocarbonate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, etc.

[0220] In one embodiment, the compound represented by formula (1A) and the radical initiator are preferably mixed in a molar ratio in the range of 1:0.005 to 1:0.2, and more preferably in the range of 1:0.01 to 1:0.1.

[0221] In one embodiment, the compound represented by formula (1B) and the radical initiator are preferably mixed in a molar ratio in the range of 1:0.01 to 1:0.4, and more preferably in the range of 1:0.02 to 1:0.2.

[0222] (Solvent)

[0223] The reaction in step (I) can also be carried out in a solvent.

[0224] The solvent is preferably capable of dissolving the compound represented by formula (1A) or the compound represented by formula (1B) and the compound represented by formula (2). The solvent may be used alone or in combination of two or more.

[0225] The solvent is, for example, a fluorine-based solvent or a non-fluorine-based solvent.

[0226] Fluorine-based solvents are solvents containing one or more fluorine atoms. Examples of fluorine-based solvents include compounds in which at least one hydrogen atom of a hydrocarbon such as a hydrofluorocarbon, a hydrochlorofluorocarbon, or a perfluorocarbon is replaced by a fluorine atom; and hydrofluoroethers. Hydrocarbons refer to compounds containing only carbon atoms and hydrogen atoms.

[0227] Examples of the hydrofluorocarbon include bis(trifluoromethyl)benzene, and specific examples include 1,3-bis(trifluoromethyl)benzene (m-XHF), 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane, C6F 13 CH2CH3 (for example, ASAHIKLIN (registered trademark) AC-6000 manufactured by Asahi Glass Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (for example, ZEORORA (registered trademark) H manufactured by Zeon Corporation), and the like.

[0228] Examples of the hydrochlorofluorocarbon include HCFC-225 (for example, Asahiklinak-225 manufactured by AGC Corporation), and HFO-1233zd(Z) (for example, CELEFIN 1233Z manufactured by Central Glass Co., Ltd.).

[0229] Examples of the perfluorocarbon include perfluorohexane, perfluoromethylcyclohexane, perfluoro-1,3-dimethylcyclohexane, and perfluorobenzene.

[0230] Examples of the hydrofluoroether include alkyl perfluoroalkyl ethers (the perfluoroalkyl group and the alkyl group may be linear or branched) such as perfluoropropyl methyl ether (C3F7OCH3) (e.g., Novec (trademark) 7000 manufactured by Sumitomo 3M Co., Ltd.), perfluorobutyl methyl ether (C4F9OCH3) (e.g., Novec (trademark) 7100 manufactured by Sumitomo 3M Co., Ltd.), perfluorobutyl ethyl ether (C4F9OC2H5) (e.g., Novec (trademark) 7200 manufactured by Sumitomo 3M Co., Ltd.), and perfluorohexyl methyl ether (C2F5CF(OCH3)C3F7) (e.g., Novec (trademark) 7300 manufactured by Sumitomo 3M Co., Ltd.); CF3CH2OCF2CHF2 (e.g., ASAHIKLIN (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.), etc.

[0231] Among the compounds listed above, the fluorine-based solvent is preferably m-XHF, HFE7100, HFE7200, HFE7300, AC-6000, perfluorohexane, and perfluorobenzene.

[0232] Examples of the non-fluorine-based solvent include S atom-containing solvents, amide-based solvents, ether-based solvents, halogen-containing solvents, and hydrocarbon-based solvents.

[0233] Examples of the sulfur atom-containing solvent include dimethyl sulfoxide, sulfolane, dimethyl sulfide, and carbon disulfide.

[0234] Examples of the amide solvent include N-methylpyrrolidone, N,N-dimethylformamide, dimethylacetamide, and hexamethylphosphoric acid triamide.

[0235] Examples of the ether solvent include diethyl ether, tetrahydrofuran, cyclopentyl methyl ether, ethylene glycol, monoglyme, and diglyme.

[0236] Examples of the halogen-containing solvent include dichloromethane and chloroform.

[0237] Examples of the hydrocarbon solvent include pentane, hexane, heptane, benzene, and toluene.

[0238] The solvent is preferably at least one selected from 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane, 1,3-bis(trifluoromethyl)benzene, diethylene glycol dimethyl ether and dimethyl sulfoxide, and more preferably at least one selected from 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane, 1,3-bis(trifluoromethyl)benzene and dimethyl sulfoxide. By using such a solvent, the compound represented by formula (1A) or the compound represented by formula (1B) and the compound represented by formula (2) can be dissolved. In addition, when the above-mentioned solvent is used, the reaction activity of the compound represented by formula (1A) or the compound represented by formula (1B) and the compound represented by formula (2) can be increased. In addition, by using the above-mentioned solvent, the water content in the composition can be reduced.

[0239] Although not particularly limited, the above solvent may be contained in an amount of, for example, 1 to 200% by mass, more specifically 50 to 150% by mass, relative to the total amount of the compound represented by formula (1A), the compound represented by formula (1B) and the compound represented by formula (2). When only one of the compounds represented by formula (1A) and formula (1B) is present, the mass of the compound present is used.

[0240] The reaction temperature of step (I) is not particularly limited and may be, for example, 0 to 200°C, 10 to 180°C, or 20 to 160°C.

[0241] The method for producing an olefin-modified fluorinated compound of the present invention may include performing a purification treatment after the step (I).

[0242] Examples of the purification treatment include liquid separation treatment and the like.

[0243] If liquid separation is performed, it is easy to extract a composition containing the target compound (i.e., at least one selected from the compound represented by formula (3A) and the compound represented by formula (3B)). The liquid separation process, for example, includes a step of adding at least one of water and an organic solvent to the composition obtained in step (I) and a step of separating the obtained water or organic solvent layer.

[0244] The above organic solvents may be used alone or in combination of two or more thereof. Examples of the organic solvent include acetone, pentane, hexane, heptane, diethyl ether, tetrahydrofuran, cyclopentyl methyl ether, perfluorohexane, m-XHF, HFE7100, HFE7200, HFE7300, AC-6000, perfluorobenzene, and HCFC-225.

[0245] The amount of the organic solvent is not particularly limited. In one embodiment, the organic solvent is added in an amount of 1.0 to 2.0 by volume ratio relative to the solvent used in step (I).

[0246] In one embodiment, the organic solvent uses a solvent with a low water content. By using such an organic solvent, the water content contained in the composition obtained in step (I) becomes low. The water content in the organic solvent is preferably 5,000 ppm or less, more preferably 1,000 ppm or less, further preferably 500 ppm or less, and particularly preferably 100 ppm or less, based on mass.

[0247] In one embodiment, after the liquid separation treatment, a dehydrating agent may be added to the layer containing the organic solvent to perform a dehydration treatment, wherein the layer containing the organic solvent contains an olefin-modified fluorine compound.

[0248] The dehydrating agent is not particularly limited. In one embodiment, the dehydrating agent may be a molecular sieve, alumina, calcium chloride, calcium oxide, calcium sulfate, magnesium oxide, magnesium perchlorate, magnesium sulfate, calcium carbonate, silica gel, sodium sulfate, or a mixture thereof.

[0249] Before or after the liquid separation treatment, the volatile components may be removed by distillation.

[0250] (Composition)

[0251] In one embodiment, the compound represented by formula (3A) contains 0.7 or more, preferably 0.8 or more, more preferably 0.9 or more, and further preferably 0.95 or more relative to the solid content contained in the composition in a molar ratio. For example, the compound represented by formula (3A) may contain 0.98 or more, 0.99 or more, or substantially 1 relative to the solid content in a molar ratio.

[0252] In one embodiment, the compound represented by formula (3B) contains 0.7 or more, preferably 0.8 or more, more preferably 0.9 or more, and further preferably 0.95 or more relative to the solid content contained in the composition in a molar ratio. For example, the compound represented by formula (3B) may contain 0.98 or more, 0.99 or more, or substantially 1 relative to the solid content.

[0253] In one embodiment, the total amount of the compound represented by formula (3A) and the compound represented by formula (3B) relative to the solid content contained in the composition is 0.7 or more, preferably 0.8 or more, more preferably 0.9 or more, and further preferably 0.95 or more. For example, the above-mentioned compound may contain 0.98 or more, 0.99 or more, or substantially 1 in terms of molar ratio relative to the solid content.

[0254] In this specification, the above-mentioned "substantially 1" means that, with respect to the solid content, only the compound represented by formula (3A) is contained, only the compound represented by formula (3B) is contained, or the compound represented by formula (3A) and the compound represented by formula (3B) are contained, or when other compounds are contained, the solid content contains 19 Its content could not be quantified by F NMR.

[0255] The solid content refers to a component obtained by, for example, concentrating the composition using an evaporator or the like and then drying the concentrated composition.

[0256] In one embodiment, in the above composition, for example, the compound represented by formula (3A) may be contained in a molar ratio of 0.7 or more, 0.8 or more, 0.9 or more, or 0.95 or more relative to the composition. For example, the compound represented by formula (3A) may be contained in a molar ratio of 0.98 or more, 0.99 or more, or substantially 1 relative to the composition.

[0257] In one embodiment, in the above composition, for example, the compound represented by formula (3B) may be contained in a molar ratio of 0.7 or more, 0.8 or more, 0.9 or more, or 0.95 or more relative to the composition. For example, the compound represented by formula (3B) may be contained in a molar ratio of 0.98 or more, 0.99 or more, or substantially 1 relative to the composition.

[0258] In one embodiment, in the above composition, for example, the total amount of the compound represented by formula (3A) and the compound represented by formula (3B) may be 0.7 or more, 0.8 or more, 0.9 or more, or 0.95 or more, in terms of molar ratio, relative to the composition. For example, the above compound may be 0.98 or more, 0.99 or more, or substantially 1 in terms of molar ratio relative to the composition.

[0259] In the present invention, no compound containing metal atoms is added during the reaction. Therefore, the process of removing the compound containing metal atoms from the composition using, for example, silica gel, is not particularly necessary. Therefore, in the present invention, the composition can be easily purified. In addition, in the present invention, the time required for purification can be shortened. Among them, the composition preferably does not contain a compound containing metal. By not containing a compound containing metal, the reaction after step (I) can be carried out well. For example, the metal can be prevented from acting as a catalyst. In addition, by not containing a compound containing metal, the stability can be suppressed from decreasing when the composition is stored. Furthermore, a surface treatment layer can be formed well from the composition. The durability of the formed surface treatment layer can be maintained.

[0260] Examples of the metal atom include tin, palladium, copper, nickel, platinum, and silver, and specifically, tin.

[0261] The content of the above-mentioned metal atoms (such as tin) is preferably less than 1 ppm on a mass basis relative to the olefin-modified fluorinated compound, and is particularly preferably less than 1 ppb. The content of the metal atoms can be measured using an ICP (Inductively Coupled Plasma) emission spectrometer. In this specification, the above-mentioned olefin-modified fluorinated compound is at least one selected from the compound represented by formula (3A) and the compound represented by formula (3B).

[0262] In one embodiment, the composition of the present invention contains an olefin-modified fluorinated compound and does not substantially contain metal atoms (e.g., tin). “Substantially free” means that the amount cannot be measured using an ICP emission spectrometer, for example, 1 ppb or less relative to the olefin-modified fluorinated compound.

[0263] The above composition may further contain other components. Examples of other components include R 1A -CFY 1 -X 1A , R 1A -CFY 1 -H, R 1A -(CFY 1 )2-R 1A , solvent, etc. The meanings of the symbols are the same as those described above. As the solvent, the above-mentioned solvents can be cited.

[0264] The composition of the present invention can be used as an additive such as a surface treatment agent, a raw material for lubricating oil (grease), a sealant, a monomer for resin, and the like.

[0265] The composition of the present invention may also contain additives such as non-reactive compounds containing fluorinated polyether groups (for example, compounds called "fluorinated oils"), or (non-reactive) organosilicon compounds that can be understood as silicone oils (for example, compounds called "silicone oils"), catalysts, surfactants, inhibitors, sensitizers, sol-gels, hydrocarbon polymers, fluorinated polymers, free radical scavengers, inorganic porous materials, dehydrating agents, or dehalogenated compounds.

[0266] The fluorine-containing oil is not particularly limited, and examples thereof include compounds represented by the following general formula (4) (perfluoro (poly) ether compound).

[0267] R 5 -(OC4F8) a’ -(OC3F6) b’ -(OC2F4) c’-(OCF2) d’ -Rf 6 …(4)

[0268] In the formula, Rf 5 represents an alkyl group having 1 to 16 carbon atoms (preferably C 1―16 perfluoroalkyl), Rf 6 represents an alkyl group having 1 to 16 carbon atoms (preferably C 1－16 perfluoroalkyl), fluorine atom or hydrogen atom, Rf 5 and Rf 6 More preferably, each independently is C 1－3 Perfluoroalkyl.

[0269] a', b', c' and d' respectively represent the number of four repeating units of perfluoro(poly)ether constituting the main skeleton of the polymer, and are independently integers of 0 to 300, and the sum of a', b', c' and d' is at least 1, preferably 1 to 300, and more preferably 20 to 300. The order of existence of each repeating unit marked with the subscript a', b', c' or d' and enclosed in parentheses is arbitrary in the formula. In these repeating units, -(OC4F8)- may be any of -(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))-, and is preferably -(OCF2CF2CF2CF2)-. -(OC3F6)- may be any of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and (OCF2CF(CF3))-, and is preferably -(OCF2CF2CF2)-. -(OC2F4)- may be any of -(OCF2CF2)- and (OCF(CF3))-, but is preferably -(OCF2CF2)-.

[0270] Examples of the perfluoro(poly)ether compound represented by the general formula (4) include compounds represented by any of the following general formulas (4a) and (4b) (the compounds may be one or a mixture of two or more).

[0271] R 5 -(OCF2CF2CF2) b” -Rf 6 …(4a)

[0272] R 5-(OCF2CF2CF2CF2) a” -(OCF2CF2CF2) b” -(OCF2CF2) c” -(OCF2) d” -Rf 6 …(4b)

[0273] In these formulas, Rf 5 and Rf 6 As described above; in formula (4a), b" is an integer greater than 1 and less than 100; in formula (4b), a" and b" are each independently an integer greater than 0 and less than 30, and c" and d" are each independently an integer greater than 1 and less than 300. The order of existence of each repeating unit marked with subscripts a", b", c", d" and enclosed in parentheses is arbitrary in the formula.

[0274] From another perspective, the fluorinated oil may be of the general formula Rf 3 -F(where Rf 3 C 5－16 The compound may be a chlorotrifluoroethylene oligomer.

[0275] The fluorine-containing oil may have a number average molecular weight of 500 to 10,000. The molecular weight of the fluorine-containing oil may be measured using gel permeation chromatography.

[0276] The composition of the present invention may contain, for example, 0 to 50% by mass, preferably 0 to 30% by mass, and more preferably 0 to 5% by mass of fluorinated oil. In one embodiment, the composition of the present invention contains substantially no fluorinated oil. Substantially containing no fluorinated oil means that the composition contains no fluorinated oil at all, or may contain a very small amount of fluorinated oil.

[0277] The fluorine-containing oil contributes to improving the surface smoothness of the layer formed from the composition of the present invention.

[0278] In one embodiment, the average molecular weight of the fluorinated oil can be greater than the average molecular weight of the olefin-modified fluorinated compound. By setting such an average molecular weight, more excellent friction durability and surface smoothness can be obtained. This method is particularly advantageous when the surface treatment layer is formed by vacuum evaporation.

[0279] In one embodiment, the average molecular weight of the fluorinated oil can be made smaller than the average molecular weight of the olefin-modified fluorinated compound. By setting such an average molecular weight, the composition of the present invention can suppress the decrease in transparency of the cured product formed using the composition and form a cured product with high friction durability and high surface smoothness.

[0280] As the above-mentioned silicone oil, for example, a straight-chain or cyclic silicone oil having a siloxane bond of 2,000 or less can be used. The straight-chain silicone oil can be a so-called ordinary silicone oil and a modified silicone oil. As ordinary silicone oil, dimethyl silicone oil, methylphenyl silicone oil, and methyl hydrogen silicone oil can be listed. As modified silicone oil, silicone oil obtained by modifying ordinary silicone oil with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol, etc. can be listed. Examples of cyclic silicone oils include cyclic dimethylsiloxane oil, etc.

[0281] The composition of the present invention may contain, for example, 0 to 300 parts by mass, preferably 50 to 200 parts by mass of the silicone oil per 100 parts by mass of the fluorinated polyether group-containing compound of the present invention (the total of these compounds when two or more are present, the same below).

[0282] Silicone oil helps to improve the surface smoothness of the surface treatment layer.

[0283] Examples of the catalyst include acids (eg, acetic acid, trifluoroacetic acid, etc.), bases (eg, ammonia, triethylamine, diethylamine, etc.), and the like.

[0284] Although the embodiments are described above, it should be understood that various changes can be made in the modes and details without departing from the spirit and scope of the scope of the claims.

[0285] Example

[0286] The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples.

[0287] The quantitative analysis of tin in each compound was performed using an ICP optical emission spectrometer (ICP-OES) and the measurement was performed under the conditions of a carrier gas flow rate of 12 L / min during plasma introduction and a carrier gas flow rate of 0.7 L / min during nebulizer introduction.

[0288] ICP-OES: 5900 manufactured by Agilent

[0289] ·Measurement wavelength: Sn 188.925nm

[0290] (Example 1)

[0291] Into the flask under argon atmosphere, 0.51 g of CF3CF2CF2O (CF2CF2CF2O) was introduced. nCF2CF2-I (n=29, weight average molecular weight (Mw) 5,100), 0.4 mL of 1,3-bis(trifluoromethyl)benzene, 2.4 mg of azobisisobutyronitrile (AIBN) and 0.53 mmol of 1,1,1,3,3,3-hexamethyl-2-(2-propylene-1-yl)-2-(trimethylsilyl)trisilane. The reaction solution was stirred at 90°C for 3 hours and then cooled to room temperature. In addition, the weight average molecular weight was calculated using 19 F NMR was obtained.

[0292] Acetone and perfluorohexane were added to the obtained reaction solution to separate the liquids. After the volatile components were distilled off, the 19 The obtained composition was analyzed by F NMR. The composition contained 100 parts by mass of the compound (A) based on 100 parts by mass of the composition.

[0293] Compound (A):

[0294]

[0295] NMR analysis results of compound (A):

[0296] 1 H NMR (D2O, C6F6): δ2.63 (td, J=17.42, 6.96Hz, 2H), 5.11 (d, J=7.28Hz, 1H), 5.14 (s, 1H), 5.56-5.72 (m, 1H);

[0297] 19 F NMR (D2O, C6F6; δ-163): δ-80.57(t,J=7.57Hz,3F),-81.10--81.70(m,4nF),-82.25(m,2F),-82.70--82.80(m,2F),-85.67(t,J =13.41Hz,2F),-86.12(s,2F),-87.53--87.54(m,2F),-116.74(t,J=11.29Hz,2F),-127.70--128.15(m,2nF),-128.68(s,2F).

[0298] (Comparative Example 1)

[0299] The reaction was carried out under the same conditions as in Example 1 except that 0.32 mmol of allyltributyltin was used instead of 1,1,1,3,3,3-hexamethyl-2-(2-propen-1-yl)-2-(trimethylsilyl)trisilane.

[0300] Acetone and perfluorohexane were added to the obtained reaction solution to separate the liquids. After the volatile components were distilled off, the obtained composition was purified using a silica gel column. The volatile components of the obtained distillate were removed by vacuum distillation, and the obtained composition was purified by using 19 The obtained composition was analyzed by FNMR. The composition contained 97 parts by mass of the compound (A) based on 100 parts by mass. The quantitative analysis of tin was performed by ICP-OES. The composition contained 40 ppm of tin based on the compound (A).

[0301] (Example 2)

[0302] The reaction was carried out under the same conditions as in Example 1 except that 1,1,1,3,3,3-hexamethyl-2-(2-methyl-2-propen-1-yl)-2-(trimethylsilyl)trisilane was used instead of 1,1,1,3,3,3-hexamethyl-2-(2-propen-1-yl)-2-(trimethylsilyl)trisilane.

[0303] Acetone and perfluorohexane were added to the obtained reaction solution to separate the liquids. After the volatile components were distilled off, the 19 The obtained composition was analyzed by F NMR. The composition contained 84 parts by mass of the compound (B) based on 100 parts by mass of the composition.

[0304] Compound (B):

[0305]

[0306] NMR analysis results of compound (B):

[0307] 1 H NMR (D2O, C6F6): δ1.65 (s, 3H), 2.55 (t, J = 18.44Hz, 1H), 4.69 (s, 1H), 4.82 (t, J = 1.40Hz, 1H);

[0308] 19 F NMR (D2O, C6F6; δ-163): δ-80.58(t,J=7.57Hz,3F),-81.74--81.99(m,4nF),-82.27--82.28(m,2F),-82.76--82.85(m,2F),-86.15 (s,2F),-86.38(t,J=13.41Hz,2F),-87.10--87.20(m,2F),-115.74(t,J=18.48Hz,2F),-127.70--128.10(m,2nF),-128.73(s,2F)

[0309] As described above, in Example 1, the selectivity of the formed olefin-modified fluorinated compound is improved compared with Comparative Example 1. This is considered to be because in Comparative Example 1, the reaction of tributyltin radicals and iodine radicals proceeds quickly, and CF3CF2CF2O (CF2CF2CF2O) n A large amount of CF2CF2 free radicals were generated. This is probably because in Comparative Example 1, the side reaction caused by the free radicals was easy to proceed, and as a result, the selectivity of the olefin-modified fluorine-containing compound became low.

[0310] Industrial Applicability

[0311] The present invention can provide a novel method for producing an olefin-modified fluorine-containing compound. The present invention can improve the selectivity of the olefin-modified fluorine-containing compound.

Claims

1. A method for producing an olefin-modified fluorinated compound, characterized in that: The compound represented by formula (1A) or the compound represented by formula (1B) is reacted with the compound represented by formula (2) in the presence of a free radical initiator. R 1A -CFY 1 -X 1 …(1A) In formula (1A): R 1A is a monovalent organic group; Y 1 is a hydrogen atom or a halogen atom; X 1 is a halogen atom other than a fluorine atom, X 1 -CFY 1 -R 1B -CFY 1 -X 1 …(1B) In formula (1B): R 1B is a divalent organic group; Y 1 are each independently a hydrogen atom or a halogen atom; X 1 are each independently a halogen atom other than a fluorine atom, R 2 3Si-(CH2) n1 -CR 4 =CR 5 R 6 …(2) In formula (2): R 2 Each independently includes R 21 3Si-monovalent group; R 21 Each occurrence is independently a hydrogen atom or a C 1－12 alkyl; The C 1－12 Alkyl groups may be substituted with halogen atoms; n1 is an integer from 1 to 10; R 4 , R 5 and R 6 are independently a hydrogen atom or a C 1－10 alkyl.

2. The manufacturing method according to claim 1, characterized in that: The Y 1 A fluorine atom.

3. The manufacturing method according to claim 1 or 2, characterized in that: The X 1 is a bromine atom or an iodine atom.

4. The manufacturing method according to claim 1 or 2, characterized in that: The R 1A By Rf 1 -R F1 -(O) n21 -express; R 1 is C which may be substituted with one or more fluorine atoms 1－16 alkyl; R F1 Formula: -(OC6F 12 ) a1 -(OC5F 10 ) b1 -(OC4F8) c1 -(OC3R Fa 6) d1 -(OC2F4) e1 -(OCF2) f1 - the group shown; a1, b1, c1, d1, e1 and f1 are each independently an integer of 0 to 200, the sum of a1, b1, c1, d1, e1 and f1 is 1 or more, and the order of existence of each repeating unit marked with a1, b1, c1, d1, e1 or f1 and enclosed in brackets in the formula is arbitrary; R Fa is independently at each occurrence a hydrogen atom, a fluorine atom or a chlorine atom; n21 is 0 or 1.

5. The manufacturing method according to claim 1 or 2, characterized in that: The R 1B By - (Rf 2 ) n23 -R F1 -(O) n22 -express; R 2 is a divalent organic group; R F1 Formula: -(OC6F 12 ) a1 -(OC5F 10 ) b1 -(OC4F8) c1 -(OC3R Fa 6) d1 -(OC2F4) e1 -(OCF2) f1 - the group shown; a1, b1, c1, d1, e1 and f1 are each independently an integer of 0 to 200, the sum of a1, b1, c1, d1, e1 and f1 is 1 or more, and the order of existence of each repeating unit marked with a1, b1, c1, d1, e1 or f1 and enclosed in brackets in the formula is arbitrary; R Fa is independently at each occurrence a hydrogen atom, a fluorine atom or a chlorine atom; n22 is 0 or 1; n23 is 0 or 1.

6. The manufacturing method according to claim 1 or 2, characterized in that: The R 2 R 21 3Si-; The R 21 are independently C which may be substituted by a halogen atom 1－4 alkyl; The C 1－4 The alkyl group is linear or branched.

7. The manufacturing method according to claim 6, characterized in that: The R 2 Each independently is (CH3)3Si-.

8. The manufacturing method according to claim 1 or 2, characterized in that: After the reaction of the compound represented by the formula (1A) or the compound represented by the formula (1B) with the compound represented by the formula (2), a purification treatment is performed.

9. The manufacturing method according to claim 1 or 2, characterized in that: The olefin-modified fluorine-containing compound is a compound represented by formula (3A) or a compound represented by formula (3B), R 1A -CFY 1 -CR 5 R 6 -CR 4 =CH-(CH2) n1－1 H…(3A) In formula (3A): R 1A , Y 1 、n1、R 4 , R 5 and R 6 The same as those in claim 1 respectively; H(CH2) n1－1 -CH=CR 4 -CR 5 R 6 -CFY 1 -R 1B -CFY 1 -CR 5 R 6 -CR 4 =CH-(CH2) n1－1 H…(3B) In formula (3B): R 1B , Y 1 、n1、R 4 , R 5 and R 6 The same as the description of claim 1 respectively.

10. A composition, characterized in that: The invention comprises: at least one of an olefin-modified fluorine-containing compound represented by formula (3A) and an olefin-modified fluorine-containing compound represented by formula (3B); and tin in an amount of 1 ppm or less relative to the total amount of the olefin-modified fluorine-containing compound represented by formula (3A) and the olefin-modified fluorine-containing compound represented by formula (3B), R 1A -CFY 1 -CR 5 R 6 -CR 4 =CH-(CH2) n1－1 H…(3A) In formula (3A): R 1A is a monovalent organic group; Y 1 is a hydrogen atom or a halogen atom; n1 is an integer from 1 to 10; R 4 , R 5 and R 6 Each occurrence is independently a hydrogen atom or a C 1－10 alkyl, H(CH2) n1－1 -CH=CR 4 -CR 5 R 6 -CFY 1 -R 1B -CFY 1 -CR 5 R 6 -CR 4 =CH-(CH2) n1－1 H…(3B) In formula (3B): R 1B is a divalent organic group; Y 1 are each independently a hydrogen atom or a halogen atom; n1 are each independently an integer from 1 to 10; R 4 , R 5 and R 6 Each occurrence is independently a hydrogen atom or a C 1－10 alkyl.

11. The composition according to claim 10, characterized in that: The content of tin is 1 ppb or less based on the total amount of the olefin-modified fluorine-containing compound represented by the formula (3A) and the olefin-modified fluorine-containing compound represented by the formula (3B).

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