Method for producing an olefin-modified fluorine-containing compound, and composition containing the compound.

Abstract

To provide a new method for producing a fluorine-containing compound having an olefin structure (hereinafter referred to as "olefin-modified fluorine-containing compound"), and a composition containing the compound. 【Solution means】A method for producing an olefin-modified fluorine-containing compound, which comprises 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. R 1A -CFY 1 -X 1 ···(1A)[R 1A is a monovalent organic group; Y 1 is H or a halogen; X 1 is a halogen other than fluorine] X 1 -CFY 1 -R 1B -CFY 1 -X 1 ···(1B)[R 1B is a divalent organic group; Y 1 is H or a halogen; X 1 is a halogen other than fluorine] R 2 3Si-(CH2) n1 -CR 4 =CR 5 R 6 ···(2)[R 2 is a monovalent group containing R 21 3Si-; R 21 is H or an alkyl group; n1 is an integer of 1 to 10; R 4 、R 5 and R 6 is H or an alkyl group]

Description

[Technical Field]

[0001] This disclosure relates to a method for producing an olefin-modified fluorine-containing compound, and a composition containing the compound. [Background technology]

[0002] Fluorine-containing compounds, which have fluorine atoms in their molecules, are known to contribute to the formation of layers with physical properties such as water repellency and oil repellency (hereinafter sometimes referred to as "surface treatment layers") (for example, Patent Document 1). Such fluorine-containing compounds are used in many applications. Various studies have been conducted on the synthesis of fluorine-containing compounds. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2021-80448 [Overview of the project] [Problems that the invention aims to solve]

[0004] This disclosure aims to provide a novel method for producing a fluorine-containing compound having an olefin structure (hereinafter sometimes referred to as an "olefin-modified fluorine-containing compound"), and a composition containing said compound. [Means for solving the problem]

[0005] This disclosure provides the following [1] to

[11] : [1] A method for producing an olefin-modified fluorine-containing 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. R 1A -CFY 1 -X 1 ...(1A) [In formula: R 1Ais 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) [wherein: 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) [wherein: R 2 are each independently a monovalent group containing R 21 3Si-; R 21 is each independently a hydrogen atom or a C 1-12 alkyl group; said C 1-12 alkyl group may be substituted by a halogen atom; n1 is an integer from 1 to 10; R 4 , R 5 and R 6 are each independently a hydrogen atom or a C 1-10 alkyl group.] [2] The production method according to [1], wherein the Y 1 is a fluorine atom. [3] The production method according to [1] or [2], wherein the X 1 is a bromine atom or an iodine atom. [4] The R 1A is Rf 1 -RF1 -(O) n21 - Represented by; Rf 1 C may be substituted with one or more fluorine atoms. 1-16 It is an alkyl group; R F1 The formula is: -(OC6F 12 ) a1 -(OC5F 10 ) b1 -(OC4F8) c1 -(OC3R Fa 6) d1 -(OC2F4) e1 -(OCF2) f1 - It is a base represented by; a1, b1, c1, d1, e1, and f1 are each independent integers between 0 and 200, the sum of a1, b1, c1, d1, e1, and f1 is 1 or greater, and the order of existence of each repeating unit enclosed in parentheses with a1, b1, c1, d1, e1, or f1 is arbitrary in the expression; R Fa Each instance is independently a hydrogen atom, a fluorine atom, or a chlorine atom; n21 is either 0 or 1. A manufacturing method described in any one of [1] to [3]. [5] The R 1B is, -(Rf 2 ) n23 -R F1 -(O) n22 - Represented by; Rf 2 It is a divalent organic group; R F1 The formula is: -(OC6F 12 ) a1 -(OC5F 10 ) b1 -(OC4F8) c1 -(OC3R Fa 6) d1 -(OC2F4) e1 -(OCF2) f1 - It is a base represented by; a1, b1, c1, d1, e1, and f1 are each independent integers between 0 and 200, the sum of a1, b1, c1, d1, e1, and f1 is 1 or greater, and the order of existence of each repeating unit enclosed in parentheses with a1, b1, c1, d1, e1, or f1 is arbitrary in the expression; R Fa Each instance is independently a hydrogen atom, a fluorine atom, or a chlorine atom; n22 is either 0 or 1; n23 is either 0 or 1. The manufacturing method described in any one of [1] to [4]. [6] The R 2 Each of them is independent of R 21 It is 3Si-; The aforementioned R 21 Each of these C atoms may be independently substituted with a halogen atom. 1-4 It is an alkyl group; Said C 1-4 Alkyl groups can be linear or branched. A manufacturing method described in any one of [1] to [5]. [7] The R 2 The manufacturing method described in [6], wherein each of them is independently (CH3)3Si-. [8] A method of production according to any one of [1] to [7], wherein a compound represented by formula (1A) or a compound represented by formula (1B) is reacted with a compound represented by formula (2), followed by a purification treatment. [9] The olefin-modified fluorine-containing compound is a compound represented by formula (3A) or a compound represented by formula (3B), the method for producing the compound according to any one of [1] to [8]. R 1A -CFY 1 -CR 5 R 6 -CR 4 =CH-(CH2) n1-1 H ···(3A) [In formula: R 1A , Y 1 n1, R 4 , R 5 and R 6is the same as described 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) [where: R 1B , Y 1 , n1, R 4 , R 5 and R 6 is the same as described in claim 1 respectively.

[10] A composition comprising at least one of the olefin-modified fluorine-containing compound represented by formula (3A) and the olefin-modified fluorine-containing compound represented by formula (3B), and tin of 1 ppm or less based on 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) [where: 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 are each independently, in each occurrence, a hydrogen atom or a C 1-10 alkyl group. 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: R 1B It is a divalent organic group; Y 1 Each of these is independently either a hydrogen atom or a halogen atom; n1 are, independently, integers from 1 to 10; R 4 , R 5 and R 6 In each instance, independently, a hydrogen atom or C 1-10 It is an alkyl group.

[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 formula (3A) and the olefin-modified fluorine-containing compound represented by formula (3B). [Effects of the Invention]

[0006] This disclosure provides a novel method for producing olefin-modified fluorine-containing compounds, and a composition containing such compounds. [Modes for carrying out the invention]

[0007] As used herein, "monovalent organic group" means a monovalent group containing carbon. A monovalent organic group is not particularly limited, but may be a hydrocarbon group or a derivative thereof. A derivative of a hydrocarbon group means a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at the terminal or in the molecular chain of a hydrocarbon group. In this specification, the term "divalent organic group" is not particularly limited, but includes a divalent group obtained by removing one more hydrogen atom from a hydrocarbon group.

[0008] As used herein, "hydrocarbon group" means a group containing carbon and hydrogen, from which one hydrogen atom has been removed from the molecule. Such hydrocarbon groups are not particularly limited, but include hydrocarbon groups having 1 to 20 carbon atoms, which may be substituted with one or more substituents, such as aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The above-mentioned "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. Furthermore, the hydrocarbon group may contain one or more ring structures.

[0009] In the use herein, the substituents of the "hydrocarbon group" are not particularly limited, but include, for example, halogen atoms; C, which may be substituted with one or more halogen atoms. 1-6 Alkyl alkyl group, C 2-6 Alkenyl group, C 2-6 Alkynyl group, C 3-10 Cycloalkyl groups, C 3-10 Unsaturated cycloalkyl group, 5-10 membered heterocyclyl group, 5-10 membered unsaturated heterocyclyl group, C 6-10 Examples include one or more groups selected from aryl groups and 5- to 10-membered heteroaryl groups.

[0010] In this specification, alkyl groups and phenyl groups may be unsubstituted or substituted unless otherwise specified. Substituents for such groups are not particularly limited, but include, for example, halogen atoms and C 1-6 Alkyl alkyl group, C 2-6 Alkenyl group and C 2-6 One or more groups selected from alkynyl groups are examples.

[0011] The following describes one aspect of this disclosure: a method for producing an olefin-modified fluorine-containing compound.

[0012] (Manufacturing method) The method for producing the olefin-modified fluorine-containing compound described herein comprises the following step (I). [Process (I)] Compounds represented by formula (1A) or compounds represented by formula (1B): R 1A -CFY 1 -X 1 ...(1A) X 1 -CFY 1 -R 1B -CFY 1 -X 1 ...(1B) Compounds represented by formula (2): R 2 3Si-(CH2) n1 -CR 4 =CR 5 R 6 ...(2) A step of reacting a compound represented by in the presence of a radical initiator.

[0013] By the above process, a composition containing an olefin-modified fluorine-containing compound represented by formula (3A) or an olefin-modified fluorine-containing compound represented by formula (3B) can be obtained. R 1A -CFY 1 -CR 5 R 6 -CR 4 =CH-(CH2) n1-1 H ···(3A) 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 the following, "olefin-modified fluorine-containing compound" refers to an olefin-modified fluorine-containing compound represented by formula (3A) or an olefin-modified fluorine-containing compound represented by formula (3B).

[0014] By using the above manufacturing method, the selectivity of olefin-modified fluorine-containing compounds in the manufactured compounds is improved.2 3Si- and X 1 Based on the response, -CFY 1 Radicals are generated. In the above manufacturing method, -CFY 1 The rate of radical generation is thought to be moderately controllable, and as a result, the selectivity of the resulting olefin-modified fluorine-containing compounds is expected to improve.

[0015] The following describes each formula.

[0016] (Formula (1A)) R 1A -CFY 1 -X 1 ...(1A)

[0017] 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. In one embodiment, X 1 is a bromine atom. In one embodiment, X 1 This is an iodine atom.

[0018] Y 1 This 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.

[0019] R 1A It is a monovalent organic group.

[0020] In one embodiment, R 1A Rf 1 -R F1 -(O) n21 - represents it.

[0021] Rf 1 C may be substituted with one or more fluorine atoms. 1-16 It is an alkyl group. 1-16 The alkyl group may be linear or branched, preferably linear or branched C 1-6Alkyl groups, especially linear or branched C groups. 1-3 It is an alkyl group, more preferably a linear C 1-6 Alkyl groups, especially C 1-3 It is an alkyl group.

[0022] The above Rf 1 Preferably, C is substituted with one or more fluorine atoms. 1-16 It is an alkyl group, more preferably C 1-16 It is a perfluoroalkyl group. 1-16 The perfluoroalkyl group may be linear or branched, preferably linear or branched C 1-6 Perfluoroalkyl groups, especially linear or branched C13C 1-3 A perfluoroalkyl group, more preferably a linear C 1-6 Perfluoroalkyl groups, especially C 1-3 It is a perfluoroalkyl group.

[0023] In one embodiment, Rf 1 C may be substituted with one or more fluorine atoms. 1-6 It is an alkyl group. 1-6 The alkyl group may be linear or branched, preferably linear or branched C 1-3 It is an alkyl group. In one embodiment, the above C 1-6 The alkyl group is preferably a linear C 1-6 Alkyl groups, especially C 1-3 It is an alkyl group. Rf 1 In one embodiment, it is CF3-; in another embodiment, it is CF3CF2-; and in yet another embodiment, it is CF3CF2CF2-.

[0024] In the above embodiment, Rf 1 Preferably, C is substituted with one or more fluorine atoms. 1-6 It is an alkyl group, more preferably C 1-6 It is a perfluoroalkyl group. In this embodiment, the above C 1-6The perfluoroalkyl group may be linear or branched, and preferably a linear C group. 1-6 Perfluoroalkyl groups, especially C 1-3 It is a perfluoroalkyl group.

[0025] R F1 The formula is: -(OC j R c 2j ) j1 -(OC h R c 2h-2 ) h1 - It is a group represented by -OC. j R c 2j -Each is independently linear or branched, -OC h R c 2h-2 - Each of these is an independent structure containing a ring structure. c Each of these is independently a hydrogen atom, a chlorine atom, or a fluorine atom, except R F1 In at least one R c is a fluorine atom. Each j is an independent integer between 1 and 6, each h is an independent integer between 1 and 7, j1 is a non-negative integer, h1 is a non-negative integer, and the sum of j1 and h1 is 1 or greater. The order of existence of each repeating unit enclosed in parentheses with j1 or h1 is arbitrary in the formula.

[0026] In one embodiment, R F1 The formula is: -(OC6F 12 ) a1 -(OC5F 10 ) b1 -(OC4F8) c1 -(OC3R Fa 6) d1 -(OC2F4) e1 -(OCF2) f1 - It is a base represented by . a1, b1, c1, d1, e1, and f1 are each independent integers between 0 and 200, the sum of a1, b1, c1, d1, e1, and f1 is 1 or greater, and the order of existence of each repeating unit enclosed in parentheses with a1, b1, c1, d1, e1, or f1 is arbitrary in the expression. The above R F1 By having this property, a surface treatment layer can be formed that has water repellency, oil repellency, chemical resistance, and friction durability. In this specification, R F1 The left side is Rf 1 The right side is -(O) n21 -Combine them with each other.

[0027] R Fa In each instance, it is independently a hydrogen atom, a fluorine atom, or a chlorine atom.

[0028] R Fa Preferably, it is a hydrogen atom or a fluorine atom, and more preferably a fluorine atom.

[0029] a1, b1, c1, d1, e1, and f1 may preferably be independent integers between 0 and 100.

[0030] The sum of a1, b1, c1, d1, e1, and f1 is preferably 5 or more, more preferably 10 or more, and may be, 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, and even more preferably 60 or less, and may be, for example, 50 or less or 30 or less.

[0031] R F1 In this structure, these repeating units may be linear, branched, or contain ring structures.

[0032] Examples of the linear or branched repeating units mentioned above include the following structure: -(OC6F 12)- may also 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)-(that is, in the above formula, R Fa (where is a fluorine atom) may be any of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and -(OCF2CF(CF3))-. -(OC2F4)- may be any of -(OCF2CF2)- and -(OCF(CF3))-.

[0033] The above ring structure may be a three-membered ring, a four-membered ring, a five-membered ring, or a six-membered ring. [ka] [In the formula, * indicates a bonding position.]

[0034] In one embodiment, the repeating unit is linear.

[0035] In one embodiment, the repeating unit includes a branched chain structure.

[0036] In one embodiment, the repeating unit includes a ring structure.

[0037] In one embodiment, R F1 Each occurrence of is independently represented by one of the following equations (f1) to (f6). -(OC3F6) d1 -(OC2F4) e1 - (f1) [In the formula, d1 is an integer between 1 and 200, and e1 is 0 or 1, preferably 1.] -(OC4F8) c1 -(OC3F6) d1 -(OC2F4) e1 -(OCF2) f1 - (f2) [In the formula, c1 and d1 are independent integers between 0 and 30, and e1 and f1 are independent integers between 1 and 200.] The sum of c1, d1, e1, and f1 is 2 or greater. The order of existence of each repeating unit, denoted by subscripts c1, d1, e1, or f1 and enclosed in parentheses, is arbitrary within the expression. -(R 71 -R 72 ) g1 - (f3) [In the formula, R 71 This is OCF2 or OC2F4, R 72 OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 It is a group selected from these groups, or a combination of two or three groups selected independently from these groups. g1 is an integer between 2 and 100. -(R 71 -R 72 ) g1 -R r -(R 72’ -R 71’ ) g1’ - (f4) [In the formula, R 71 This is OCF2 or OC2F4, R 72 OC2F4, OC3F6, OC4F8, OC5F 10and OC6F 12 It is a group selected from these groups, or a combination of two or three groups selected independently from these groups. R 71’ This is OCF2 or OC2F4, R 72’ OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 It is a group selected from these groups, or a combination of two or three groups selected independently from these groups. g1 is an integer between 2 and 100. g1' is an integer between 2 and 100. R r teeth, [ka] (In the formula, * indicates the bonding position.) That is the case. -(OC6F 12 ) a1 -(OC5F 10 ) b1 -(OC4F8) c1 -(OC3F6) d1 -(OC2F4) e1 -(OCF2) f1 - (f5) [In the formula, e1 is an integer between 1 and 200, a1, b1, c1, d1, and f1 are each independent integers between 0 and 200, the sum of a1, b1, c1, d1, e1, and f1 is at least 1, and the order of existence of each repeating unit enclosed in parentheses with a1, b1, c1, d1, e1, or f1 is arbitrary in the formula.] -(OC6F 12 ) a1 -(OC5F 10 ) b1 -(OC4F8) c1 -(OC3F6) d1 -(OC2F4) e1 -(OCF2) f1 - (f6) [In the formula, f1 is an integer between 1 and 200, a1, b1, c1, d1, and e1 are each independent integers between 0 and 200, the sum of a1, b1, c1, d1, e1, and f1 is at least 1, and the order of existence of the repeating units enclosed in parentheses with a1, b1, c1, d1, e1, or f1 is arbitrary in the formula.]

[0038] In the above formula (f1), d1 is preferably an integer between 5 and 200, more preferably between 10 and 100, and even more preferably between 15 and 50, for example between 25 and 35. In the above formula (f1), (OC3F6) is preferably a group represented by (OCF2CF2CF2) or (OCF(CF3)CF2), and more preferably a group represented by (OCF2CF2CF2). In the above formula (f1), (OC2F4) is preferably a group represented by (OCF2CF2) or (OCF(CF3)), and more preferably a group represented by (OCF2CF2).

[0039] In the above formula (f2), e1 and f1 are each an integer, preferably between 5 and 200, more preferably between 10 and 200. The sum of c1, d1, e1, and f1 is preferably 5 or more, more preferably 10 or more, and may be, 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) f1 - is the base represented by -. In another embodiment, formula (f2) is -(OC2F4) e1 -(OCF2) f1 It may also be represented as a base by -.

[0040] In the above equation (f3), R 71 Preferably, it is OC2F4. In (f3) above, R 72Preferably, the group is 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, but examples include -OC2F4OC3F6-, -OC2F4OC4F8-, -OC3F6OC2F4-, -OC3F6OC3F6-, -OC3F6OC4F8-, -OC4F8OC4F8-, -OC4F8OC3F6-, -OC4F8OC2F4-, and -OC Examples include 2F4OC2F4OC3F6-, -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 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 The chain may be either linear or branched, and is preferably linear. In this embodiment, the above formula (f3) is preferably -(OC2F4-OC3F6) g1 -or-(OC2F4-OC4F8) g1 - is

[0041] In the above equation (f4), R 71 , R 72 And g1 has the same meaning as the description in formula (f3) above and has the same characteristics. 71’ , R 72’ and g1' are R as described in formula (f3) above, respectively. 71 , R 72 And is synonymous with g1 and has a similar appearance. r Preferably, [ka] [In the formula, * indicates a bonding position.] and, more [ka] [In the formula, * indicates a bonding position.] That is the case.

[0042] In the above formula (f5), e1 is preferably an integer between 1 and 100, more preferably between 5 and 100. The sum of a1, b1, c1, d1, e1, and f1 is preferably 5 or more, more preferably 10 or more, for example between 10 and 100.

[0043] In the above equation (f5), R F1 The repeating unit at the end may be -(OCF2CF2OCF2CF2CF2)-.

[0044] In the above formula (f6), f1 is preferably an integer between 1 and 100, more preferably between 5 and 100. The sum of a1, b1, c1, d1, e1 and f1 is preferably 5 or more, more preferably 10 or more, for example between 10 and 100.

[0045] In one embodiment, the above R F1 This is the group represented by the above formula (f1).

[0046] In one embodiment, the above R F1 This is the group represented by the above formula (f2).

[0047] In one embodiment, the above R F1 This is a group represented by the above formula (f3) or (f4).

[0048] In one embodiment, the above R F1 This is the group represented by the above formula (f3).

[0049] In one embodiment, the above R F1 This is the group represented by the above formula (f4).

[0050] In one embodiment, the above R F1 This is the group represented by the above formula (f5).

[0051] In one embodiment, the above R F1 This is the group represented by the above formula (f6).

[0052] In one embodiment, the above R F1 This is a group represented by the above formulas (f1), (f2), (f5), or (f6).

[0053] In one embodiment, the above R F1 This is a group represented by the above formulas (f1), (f2), or (f6).

[0054] The above R F1 In this case, the ratio of e1 to f1 (hereinafter referred to as the "e / f ratio") is, for example, 0.1 or more and 10 or less, preferably 0.2 or more and 5 or less, more preferably 0.2 to 2, even more preferably 0.2 or more and 1.5 or less, even more preferably 0.2 or more and less than 0.9, and particularly preferably 0.2 or more and 0.85 or less. The stability of the resulting fluorine-containing compound is improved by having the e / f ratio within the above range. Here, f1 is an integer of 1 or more.

[0055] In one embodiment, R F1 In this case, the e / f ratio is preferably 1.0 or higher, for example, 1.1 or higher, or 1.3 or higher. F1 In this case, the e / f ratio is preferably 10.0 or less, 9.0 or less, more preferably 5.0 or less, even more preferably 2.0 or less, and particularly preferably 1.5 or less. F1 In this context, the e / f ratio can be, for example, 1.0 to 10.0, more specifically 1.0 to 5.0, more specifically 1.0 to 2.0, and even more specifically 1.0 to 1.5.

[0056] In one embodiment, R F1 In this case, the e / f ratio may be in the range of 1.0 to 1.2.

[0057] In one correspondence, R F1 In this case, the e / f ratio may be less than 0.9, for example, 0.8 or less, or 0.7 or less. F1 In this case, the e / f ratio is preferably 0.2 or higher, more preferably 0.3 or higher, even more preferably 0.4 or higher, and particularly preferably 0.5 or higher. F1 In this context, the e / f ratio can be, for example, 0.2 or more and less than 0.9, more specifically 0.4 or more and 0.8 or less, and more specifically 0.5 or more and 0.7 or less.

[0058] In one embodiment, d1 is preferably an integer of 1 or more, more preferably 3 or more, even more preferably 6 or more, and may be 200 or less, 120 or less, 60 or less, or 54 or less. In this embodiment, d1 may be between 1 and 200, between 3 and 120, between 3 and 60, or between 6 and 60.

[0059] In one embodiment, R F1 teeth, -(OC3F6) d1 -(OC2F4) e1 - (f1) [In the formula, d1 is an integer between 3 and 60, preferably between 6 and 54; e1 is 1; and OC3F6 and OC2F4 are linear.] It is a base represented by .

[0060] In one embodiment, R F1 teeth, -(OC3F6) d1 -(OC2F4) e1 - (f1) [In the formula, d1 is an integer between 3 and 120, preferably between 6 and 60; e1 is 1; and each OC3F6 and OC2F4 has a branched chain.] This is a base represented by . For example, in equation (f1), the repeating unit is represented by -OCF(CF3)CF2-.

[0061] The above R F1The number-average molecular weight of the part is not particularly limited, but is, for example, 500 to 30,000, preferably 1,500 to 30,000, and more preferably 2,000 to 10,000. In this specification, R F1 The number-average molecular weight is, 19 The value shall be measured by 1F-NMR.

[0062] In another embodiment, R F1 The number-average molecular weight of the part may be 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000, and even more preferably 2,000 to 10,000, for example, 3,000 to 6,000.

[0063] In another embodiment, R F1 The number-average molecular weight of the part may be 4,000 to 30,000, preferably 5,000 to 10,000, and more preferably 6,000 to 10,000.

[0064] n21 is either 0 or 1. In one embodiment, n21 is 0. In one embodiment, n21 is 1.

[0065] (Formula (1B)) X 1 -CFY 1 -R 1B -CFY 1 -X 1 ...(1B)

[0066] X 1 Each of these is independently 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. In one embodiment, X 1 is a bromine atom. In one embodiment, X 1 This is an iodine atom.

[0067] Y 1 Each of these atoms 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.

[0068] R 1B It is a divalent organic group.

[0069] In one embodiment, R 1B is, -(Rf 2 ) n23 -R F1 -(O) n22 - represents it.

[0070] R F1 This is as stated above.

[0071] Rf 2 It is a divalent organic group.

[0072] The above Rf 2 C may preferably be substituted with one or more fluorine atoms. 1-6 It is an alkylene group.

[0073] C may be substituted with one or more fluorine atoms as described above. 1-6 "C" in the alkylene group 1-6 The alkylene group may be linear or branched, preferably linear or branched C 1-3 An alkylene group, more preferably a linear C group 1-3 It is an alkylene group.

[0074] The above Rf 2 Preferably, C is substituted with one or more fluorine atoms. 1-6 It is an alkylene group, and more C 1-6 A perfluoroalkylene group, more preferably C 1-3 It is a perfluoroalkylene group.

[0075] C above 1-6 The perfluoroalkylene group may be linear or branched, preferably linear or branched C 1-3 A perfluoroalkylene group, more preferably a linear C 1-3The perfluoroalkylene group is specifically -CF2-, -CF2CF2-, or -CF2CF2CF2-.

[0076] n22 is either 0 or 1. In one embodiment, n22 is 0. In one embodiment, n22 is 1.

[0077] n23 is either 0 or 1. In one embodiment, n23 is 0. In one embodiment, n23 is 1.

[0078] (Formula (2)) R 2 3Si-(CH2) n1 -CR 4 =CR 5 R 6 ...(2)

[0079] R 2 Each of them is independent of R 21 It is a monovalent group containing 3Si-.

[0080] In one embodiment, the above R 2 R 21 It is a group having a 3Si- and a divalent organic group.

[0081] The above R 2 Preferably, each independently, R 21 It is 3Si-.

[0082] R 21 Each of these is independently a hydrogen atom, or C 1-12 It is an alkyl group. 1-12 The alkyl group may be substituted with a halogen atom. 1-12 Each alkyl group can be independently linear or branched.

[0083] The above R 21 Preferably, each C may be independently substituted with a halogen atom. 1-4 It is an alkyl group. 1-4The alkyl groups are each independently linear or branched. In one embodiment, the C 1-4 alkyl group is linear. In one embodiment, the C 1-4 alkyl group is branched.

[0084] The above R 21 is more preferably each independently a C 1-4 alkyl group.

[0085] The above R 21 is even more preferably a CH3 group. In this case, R 2 is represented by (CH3)3Si-.

[0086] n1 is an integer from 1 to 10, preferably an integer from 1 to 3.

[0087] In one embodiment, n1 is 1. In this case, the terminal of the olefin-modified fluorine-containing compound represented by the formula (3A) or the olefin-modified fluorine-containing compound represented by the formula (3B) formed is -CR 4 =CH2. In this 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 terminal is formed particularly well. -CR 4 =CH2 has less steric hindrance, and it is considered that the reaction proceeds well. When surface treatment is performed using the surface treatment agent containing the above compound, the adhesion to the substrate can be particularly good.

[0088] R 4 , R 5 , and R 6 are each independently a hydrogen atom or a C 1-10 alkyl group at each occurrence.

[0089] The above R 4 is preferably a hydrogen atom or a C 1-6 alkyl group, more preferably a hydrogen atom or a CH3 group. In one embodiment, R 4 is a hydrogen atom. In one embodiment, R4 It is a CH3 group.

[0090] The above R 5 Preferably, a hydrogen atom, or C 1-6 It is an alkyl group, more preferably a hydrogen atom, or a CH3 group, preferably a hydrogen atom.

[0091] The above R 6 Preferably, a hydrogen atom, or C 1-6 It is an alkyl group, more preferably a hydrogen atom, or a CH3 group, preferably a hydrogen atom.

[0092] In one embodiment, R 5 , or R 6 One of them is a CH3 group, and the other is a hydrogen atom.

[0093] In one embodiment, R 5 , and R 6 is a hydrogen atom. In this case, the reactivity between the compound represented by formula (1A) or the compound represented by formula (1B) and the compound represented by formula (2) can be 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 proportion. 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).

[0094] In one embodiment, a compound represented by formula (1A) can be used.

[0095] In one embodiment, a compound represented by formula (1B) can be used.

[0096] In one embodiment, the compound represented by formula (1A) and the compound represented by formula (2) are mixed in a molar ratio in the range of 1:1 to 1:10. Preferably, the compound represented by formula (1A) and the compound represented by formula (2) are mixed in a molar ratio in the range of 1:1 to 1:8, more preferably in a ratio of 1:1 to 1:6, and even more preferably in a ratio of 1:2 to 1:6. By mixing in such molar ratios, the reaction can proceed particularly well.

[0097] In one embodiment, the compound represented by formula (1B) and the compound represented by formula (2) are mixed in a molar ratio in the range of 1:2 to 1:20. Preferably, the compound represented by formula (1B) and the compound represented by formula (2) are mixed in a molar ratio in the range of 1:2 to 1:16, more preferably in a ratio of 1:2 to 1:12, and even more preferably in a ratio of 1:4 to 1:12. By mixing in such molar ratios, the reaction can proceed particularly well.

[0098] (Formula (3A)) R 1A -CFY 1 -CR 5 R 6 -CR 4 =CH-(CH2) n1-1 H ···(3A)

[0099] R 1A , Y 1 n1, R 4 , R 5 , and R 6 This is as described in equation (1A) or equation (2).

[0100] (Formula (3B)) 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)

[0101] R 1B , Y 1 n1, R 4 , R 5 , and R 6 This is as described in equation (1B) or equation (2).

[0102] As described above, the compound represented by formula (3A) or the compound represented by formula (3B) (i.e., the olefin-modified fluorine-containing compound) contains an olefin. When the olefin-modified fluorine-containing compound is included in a surface treatment agent, the olefin allows the olefin-modified fluorine-containing compound to adhere well to the substrate. The olefin-modified fluorine-containing compound can also be effectively used as a raw material for synthesizing other compounds.

[0103] (Radical initiator) As radical initiators, those that allow the reaction in step (I) to proceed can be used, such as azo compounds, dihalogens, and organic peroxides.

[0104] Examples of azo compounds include azobisisobutyronitrile (AIBN), 1,1'-azobis(cyclohexanecarbonitride) (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 preferable to use because they have good solubility.

[0105] Examples of dihalogens include chlorine molecules.

[0106] 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(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy)cyclohexane, 1,1-di(t-butylperoxy)-2-methylcyclohexane, 1,1-di(t-butylperoxy)cyclohexane, 2,2-di(t-butylperoxy)butane, t-butyl cumyl peroxide, di-t-hexyl peroxide, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, t-hexyl peroxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, t-hexyl peroxyisopropyl monocarbonate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, and the like.

[0107] In one embodiment, the compound represented by the formula (1A) and the radical initiator are preferably mixed in a molar ratio in the range of 1:0.005 to 1:0.2, more preferably in the range of 1:0.01 to 1:0.1.

[0108] In one embodiment, the compound represented by the formula (1B) and the radical initiator are preferably mixed in a molar ratio in the range of 1:0.01 to 1:0.4, more preferably in the range of 1:0.02 to 1:0.2.

[0109] (Solvent) The reaction of step (I) may be carried out in a solvent.

[0110] The above solvent preferably can dissolve the compound represented by the formula (1A) or the compound represented by the formula (1B) and the compound represented by the formula (2). The above solvent may be used alone or in combination of two or more.

[0111] The solvents mentioned above are, for example, fluorinated solvents or non-fluorinated solvents.

[0112] Fluorinated solvents are solvents containing one or more fluorine atoms. Examples of fluorinated solvents include compounds in which at least one hydrogen atom of a hydrocarbon is substituted with a fluorine atom, such as hydrofluorocarbons, hydrochlorofluorocarbons, and perfluorocarbons; and hydrofluoroethers. Here, hydrocarbons refer to compounds containing only carbon atoms and hydrogen atoms.

[0113] Examples of hydrofluorocarbons include bis(trifluoromethyl)benzene, specifically 1,3-bis(trifluoromethyl)benzene (m-XHF), 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane, and C6F. 13 Examples include CH2CH3 (for example, AsahiClean® AC-6000 manufactured by Asahi Glass Co., Ltd.) and 1,1,2,2,3,3,4-heptafluorocyclopentane (for example, Zeolora® H manufactured by Nippon Zeon Corporation).

[0114] Examples of hydrochlorofluorocarbons include HCFC-225 (e.g., AsahiClean AK-225 manufactured by AGC Inc.) and HFO-1233zd(Z) (e.g., Celefin 1233Z manufactured by Central Glass Co., Ltd.).

[0115] Examples of perfluorocarbons include perfluorohexane, perfluoromethylcyclohexane, perfluoro-1,3-dimethylcyclohexane, and perfluorobenzene.

[0116] Examples of hydrofluoroethers include alkyl perfluoroalkyl ethers such as perfluoropropyl methyl ether (C3F7OCH3) (e.g., Novec® 7000 manufactured by Sumitomo 3M Co., Ltd.), perfluorobutyl methyl ether (C4F9OCH3) (e.g., Novec® 7100 manufactured by Sumitomo 3M Co., Ltd.), perfluorobutyl ethyl ether (C4F9OC2H5) (e.g., Novec® 7200 manufactured by Sumitomo 3M Co., Ltd.), and perfluorohexyl methyl ether (C2F5CF(OCH3)C3F7) (e.g., Novec® 7300 manufactured by Sumitomo 3M Co., Ltd.) (the perfluoroalkyl group and alkyl group may be linear or branched); and CF3CH2OCF2CHF2 (e.g., Asahi Clean® AE-3000 manufactured by Asahi Glass Co., Ltd.).

[0117] Among the fluorinated solvents listed above, m-XHF, HFE7100, HFE7200, HFE7300, AC-6000, perfluorohexane, and perfluorobenzene are preferred.

[0118] Examples of non-fluorinated solvents include sulfur-containing solvents, amide solvents, ether solvents, halogen-containing solvents, and hydrocarbon solvents.

[0119] Examples of sulfur-containing solvents include dimethyl sulfoxide, sulfolane, dimethyl sulfide, and carbon disulfide. Examples of amide solvents include N-methylpyrrolidone, N,N-dimethylformamide, dimethylacetamide, and hexamethylphosphate triamide. Examples of ether-based solvents include diethyl ether, tetrahydrofuran, cyclopentyl methyl ether, ethylene glycol, monoglycerides, and diglymes. Examples of halogenated solvents include dichloromethane and chloroform. Examples of hydrocarbon solvents include pentane, hexane, heptane, benzene, and toluene.

[0120] The solvent is preferably at least one selected from the group consisting of 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane, 1,3-bis(trifluoromethyl)benzene, diglyme, and dimethyl sulfoxide, and more preferably at least one selected from the group consisting of 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 formula (1B) can be dissolved with the compound represented by formula (2). Furthermore, using such a solvent can improve the reaction activity between the compound represented by formula (1A) or formula (1B) and the compound represented by formula (2). In addition, using such a solvent can reduce the water content in the composition.

[0121] While not particularly limited, the above solvent may be present 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). If only one of the compounds represented by formula (1A) or formula (1B) is present, the mass of the compound that is present shall be used.

[0122] The reaction temperature in step (I) is not particularly limited. For example, the reaction temperature may be 0 to 200°C, 10 to 180°C, or 20 to 160°C.

[0123] The method for producing an olefin-modified fluorine-containing compound according to this disclosure may include a purification treatment after step (I).

[0124] Examples of purification processes include liquid-liquid separation.

[0125] Liquid-liquid separation facilitates the extraction of a composition containing the target compound (i.e., at least one selected from the group consisting of the compound represented by formula (3A) and the compound represented by formula (3B)). Liquid-liquid separation includes, for example, the steps of adding at least one of water and an organic solvent to the composition obtained in step (I), and separating the resulting water or organic solvent layer.

[0126] The above organic solvents may be used individually or in combination of two or more. Examples of organic solvents include acetone, pentane, hexane, heptane, diethyl ether, tetrahydrofuran, cyclopentyl methyl ether, perfluorohexane, m-XHF, HFE7100, HFE7200, HFE7300, AC-6000, perfluorobenzene, HCFC-225, and the like.

[0127] The amount of the above organic solvent is not particularly limited. In one embodiment, it is added by volume in a ratio of 1.0 to 2.0 to the solvent used in step (I).

[0128] In one embodiment, the organic solvent used has a low water content. By using such an organic solvent, the water content in the composition obtained in step (I) is reduced. The water content of the organic solvent is preferably 5,000 ppm or less by mass, more preferably 1,000 ppm or less, even more preferably 500 ppm or less, and particularly preferably 100 ppm or less.

[0129] In one embodiment, after liquid-liquid extraction, a dehydrating agent may be added to the layer containing the organic solvent to perform dehydration. The layer containing the organic solvent contains an olefin-modified fluorine compound. The above-mentioned dehydrating agent is not particularly limited. In one embodiment, molecular sieves, aluminum oxide, calcium chloride, calcium oxide, calcium sulfate, magnesium oxide, magnesium perchlorate, magnesium sulfate, calcium carbonate, silica gel, sodium sulfate, or mixtures thereof can be used as the dehydrating agent.

[0130] Volatile components may be removed by distillation before or after the liquid-liquid separation treatment.

[0131] (composition) In one embodiment, the compound represented by formula (3A) is present in the composition in a molar ratio of 0.7 or more, preferably 0.8 or more, more preferably 0.9 or more, and even more preferably 0.95 or more, relative to the solid content. For example, the compound represented by formula (3A) may be present in a molar ratio of 0.98 or more, 0.99 or more, or even substantially 1, relative to the solid content.

[0132] In one embodiment, the compound represented by formula (3B) is present in the composition in a molar ratio of 0.7 or more, preferably 0.8 or more, more preferably 0.9 or more, and even more preferably 0.95 or more, relative to the solid content. For example, the compound represented by formula (3B) may be present in a molar ratio of 0.98 or more, 0.99 or more, or even substantially 1, relative to the solid content.

[0133] In one embodiment, the total amount of the compound represented by formula (3A) and the compound represented by formula (3B) is preferably 0.7 or more, more preferably 0.8 or more, more preferably 0.9 or more, and even more preferably 0.95 or more, relative to the solid content in the composition. For example, the above compounds may be present in a molar ratio of 0.98 or more, 0.99 or more, or even substantially 1 relative to the solid content.

[0134] In this specification, "substantially 1" means that, with respect to the solid content, only the compound represented by formula (3A), only the compound represented by formula (3B), or the compound represented by formula (3A) and the compound represented by formula (3B) are included, or even if other compounds are included, 19 This refers to the presence of a substance in an amount that cannot be calculated using 1F NMR.

[0135] The above-mentioned solid content refers, for example, to the above-mentioned composition after it has been concentrated using an evaporator or the like and then dried.

[0136] In one embodiment, the above composition may contain, for example, a compound represented by formula (3A) in a molar ratio of 0.7 or more, 0.8 or more, 0.9 or more, or 0.95 or more. For example, the compound represented by formula (3A) may contain in a molar ratio of 0.98 or more, 0.99 or more, or substantially 1.

[0137] In one embodiment, the above composition may contain, for example, a compound represented by formula (3B) in a molar ratio of 0.7 or more, 0.8 or more, 0.9 or more, or 0.95 or more. For example, the compound represented by formula (3B) may contain in a molar ratio of 0.98 or more, 0.99 or more, or substantially 1.

[0138] In one embodiment, the total amount of the compound represented by formula (3A) and the compound represented by formula (3B) in the above composition may be 0.7 or more, 0.8 or more, 0.9 or more, or 0.95 or more in molar ratio with respect to the composition. For example, the above compound may be 0.98 or more, 0.99 or more, or substantially 1 in molar ratio with respect to the composition.

[0139] In this disclosure, no compounds containing metal atoms are added in the reaction. Therefore, a step to remove compounds containing metal atoms from the composition, for example using silica gel, is not particularly necessary. Accordingly, in this disclosure, the composition can be easily purified. Furthermore, in this disclosure, the time required for purification can be shortened. It is preferable that the composition does not contain compounds containing metals. By not including compounds containing metals, the reaction after step (I) can proceed smoothly. For example, the metal can be prevented from acting as a catalyst. Also, by not including compounds containing metals, the decrease in stability during storage of the composition can be suppressed. Furthermore, a surface treatment layer can be formed well from the composition. The durability of this formed surface treatment layer is maintained.

[0140] Examples of metal atoms include tin, palladium, copper, nickel, platinum, and silver; specifically, tin.

[0141] The content of the above-mentioned metal atoms (e.g., tin) is preferably 1 ppm or less by mass, and particularly preferably 1 ppb or less, relative to the olefin-modified fluorine-containing compound. The content of metal atoms can be measured using an ICP (Inductively Coupled Plasma) emission spectrometer. In this specification, the above-mentioned olefin-modified fluorine-containing compound is at least one selected from the group consisting of compounds represented by formula (3A) and compounds represented by formula (3B).

[0142] In one embodiment, the composition of the present disclosure comprises an olefin-modified fluorine-containing compound and is essentially free of metal atoms (e.g., tin). Here, "essentially free" means in a range that cannot be measured using an ICP emission spectrometer, for example, 1 ppb or less relative to the olefin-modified fluorine-containing compound.

[0143] The above composition may further contain other components. Other components include R 1A -CFY 1 -X 1A , R1A -CFY 1 -H, R 1A -(CFY 1 )2-R 1A Examples include solvents. Each symbol has the same meaning as above. Examples of solvents include the solvents listed above.

[0144] The compositions disclosed herein can be used as additives such as surface treatment agents, raw materials for greases, sealants, and monomers for resins.

[0145] The compositions of this disclosure may further include additives such as nonreactive fluoropolyether group-containing compounds (e.g., compounds referred to as "fluorine-containing oils") or (nonreactive) silicone compounds that can be understood as silicone oils (e.g., compounds referred to as "silicone oils"), catalysts, surfactants, polymerization inhibitors, sensitizers, sol-gels, hydrocarbon polymers, fluorine-containing polymers, radical scavengers, inorganic porous materials, dehydrating agents, or dehalogenated compounds.

[0146] Examples of fluorinated oils are not limited to those represented by the following general formula (4) (perfluoro(poly)ether compounds). Rf 5 -(OC4F8) a’ -(OC3F6) b’ -(OC2F4) c’ -(OCF2) d’ -Rf 6 ...(4) In the formula, Rf 5 C1-16 alkyl group (preferably C) may be substituted with one or more fluorine atoms. 1―16 Rf represents a perfluoroalkyl group. 6 C1-16 alkyl group (preferably C) may be substituted with one or more fluorine atoms. 1-16 Rf represents a perfluoroalkyl group, a fluorine atom, or a hydrogen atom. 5 and Rf 6 More preferably, each independently, C 1-3It is a perfluoroalkyl group. a', b', c', and d' represent the number of repeating units of the four types of perfluoro(poly)ether that constitute the main backbone of the polymer, and are independent integers between 0 and 300, with the sum of a', b', c', and d' being at least 1, preferably 1 to 300, and more preferably 20 to 300. The order of existence of each repeating unit enclosed in parentheses with the subscripts a', b', c', or d' is arbitrary in the formula. Of 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))-, but preferably -(OCF2CF2CF2CF2)-. -(OC3F6)- may be any of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and (OCF2CF(CF3))-, but preferably -(OCF2CF2CF2)-. -(OC2F4)- may be either -(OCF2CF2)- or (OCF(CF3))-, but is preferably -(OCF2CF2)-.

[0147] Examples of perfluoro(poly)ether compounds represented by the above general formula (4) include compounds represented by either of the following general formulas (4a) and (4b) (which may be one or a mixture of two or more). Rf 5 -(OCF2CF2CF2) b” -Rf 6 ...(4a) Rf 5 -(OCF2CF2CF2CF2) a” -(OCF2CF2CF2) b” -(OCF2CF2) c” -(OCF2) d” -Rf 6 ...(4b) In these equations, Rf 5 and Rf6 As stated above, in equation (4a), b'' is an integer between 1 and 100; in equation (4b), a'' and b'' are independently integers between 0 and 30, and c'' and d'' are independently integers between 1 and 300. The order of existence of each repeating unit enclosed in parentheses with subscripts a'', b'', c'', and d'' is arbitrary within the equation.

[0148] From another perspective, fluorine-containing oils have the general formula Rf 3 -F(where Rf 3 is C 5-16 It may be a compound represented as a perfluoroalkyl group. It may also be a chlorotrifluoroethylene oligomer.

[0149] The above-mentioned fluorine-containing oil may have a number-average molecular weight of 500 to 10,000. The molecular weight of the fluorine-containing oil can be measured using gel permeation chromatography.

[0150] Fluorine-containing oil may be present in the composition of the Disclosure in an amount of, for example, 0 to 50% by mass, preferably 0 to 30% by mass, and more preferably 0 to 5% by mass. In one embodiment, the composition of the Disclosure is substantially free of fluorine-containing oil. Substantially free of fluorine-containing oil means that it is either completely free of fluorine-containing oil or may contain trace amounts of fluorine-containing oil.

[0151] Fluorine-containing oils contribute to improving the surface slipperiness of layers formed by the compositions of this disclosure.

[0152] In one embodiment, the average molecular weight of the fluorinated oil may be greater than the average molecular weight of the olefin-modified fluorinated compound. By using such an average molecular weight, better frictional durability and surface lubricity can be obtained. This embodiment is particularly advantageous when the surface treatment layer is formed by vacuum deposition.

[0153] In one embodiment, the average molecular weight of the fluorinated oil may be smaller than the average molecular weight of the olefin-modified fluorinated compound. By using such an average molecular weight, the composition of this disclosure can form a cured product that has high frictional durability and high surface slipperiness while suppressing a decrease in the transparency of the cured product formed using the composition.

[0154] As the silicone oil mentioned above, for example, a linear or cyclic silicone oil with 2,000 or fewer siloxane bonds may be used. Linear silicone oils may be so-called straight silicone oils and modified silicone oils. Examples of straight silicone oils include dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil. Examples of modified silicone oils include straight silicone oils modified with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol, etc. Examples of cyclic silicone oils include cyclic dimethylsiloxane oil.

[0155] In the compositions of the present disclosure, such silicone oil may be included in an amount of, for example, 0 to 300 parts by mass, preferably 50 to 200 parts by mass, based on 100 parts by mass of the total of the fluorine-containing polyether group-containing compounds of the present disclosure (the sum of these if there are two or more types, and the same applies hereinafter).

[0156] Silicone oil contributes to improving the surface slipperiness of the surface-treated layer.

[0157] Examples of catalysts include acids (e.g., acetic acid, trifluoroacetic acid, etc.) and bases (e.g., ammonia, triethylamine, diethylamine, etc.).

[0158] Although embodiments have been described above, it should be understood that various modifications to the form and details are possible without departing from the spirit and scope of the claims. [Examples]

[0159] The following will provide a more detailed explanation through examples, but this disclosure is not limited to these examples.

[0160] Quantitative analysis of tin in each compound was performed using an ICP emission spectrometer (ICP-OES). Measurements were carried out under conditions of a carrier gas flow rate of 12 L / min during plasma introduction and 0.7 L / min during nebulizer introduction. • ICP-OES: Agilent 5900 ·Measurement wavelength: Sn 188.925nm

[0161] (Example 1) Under an argon atmosphere, CF3CF2CF2O(CF2CF2CF2O) is added to a flask. n CF2CF2-I 0.51 g (n=29, weight-average molecular weight (Mw) 5,100), 1,3-bis(trifluoromethyl)benzene 0.4 mL, azobisisobutyronitrile (AIBN) 2.4 mg, and 1,1,1,3,3,3-hexamethyl-2-(2-propen-1-yl)-2-(trimethylsilyl)trisilane 0.53 mmol were introduced. This reaction solution was stirred at 90°C for 3 hours and then cooled to room temperature. The weight-average molecular weight was: 19 It was determined by 1F NMR.

[0162] Acetone and perfluorohexane were added to the resulting reaction solution and separated the liquids. After removing the volatile components, the resulting composition was obtained. 19 Analysis was performed using 1F NMR. Compound (A) was present in 100 parts by mass per 100 parts by mass of the composition. Compound (A): TIFF2026097974000005.tif1188 NMR analysis results of compound (A): 1 H NMR (D2O, C6F6): δ 2.63 (td, J = 17.42, 6.96 Hz, 2H), 5.11 (d, J = 7.28 Hz, 1H), 5.14 (s, 1H), 5.56 - 5.72 (m, 1H); 19 F NMR (D2O, C6F6; δ -163): δ -80.57 (t, J = 7.57 Hz, 3F), -81.10 - -81.70 (m, 4nF), -82.25 (m, 2F), -82.70 - -82.80 (m, 2F), -85.67 (t, J = 13.41 Hz, 2F), -86.12 (s, 2F), -87.53 - -87.54 (m, 2F), -116.74 (t, J = 11.29 Hz, 2F), -127.70 - -128.15 (m, 2nF), -128.68 (s, 2F).

[0163] (Comparative Example 1) 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.

[0164] The resulting reaction solution was separated by adding acetone and perfluorohexane. After removing the volatile components, the resulting composition was purified using a silica gel column. The volatile components of the resulting distillate were removed under reduced pressure, and the resulting composition was... 19 Analysis was performed using 1F NMR. Compound (A) was present in 97 parts by mass per 100 parts by mass of the composition. Quantitative analysis of tin was performed by ICP-OES. Tin was present at 40 ppm relative to compound (A).

[0165] (Example 2) 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-methyl-2-propen-1-yl)-2-(trimethylsilyl)trisilane.

[0166] Acetone and perfluorohexane were added to the resulting reaction solution and separated the liquids. After removing the volatile components, the resulting composition was... 19Analysis was performed using 1F NMR. Compound (B) was present in 84 parts by mass per 100 parts by mass of the composition. Compound (B): TIFF2026097974000006.tif1287 NMR analysis results of compound (B): 1 H NMR (D2O, C6F6): δ 1.65 (s, 3H), 2.55 (t, J = 18.44 Hz, 1H), 4.69 (s, 1H), 4.82 (t, J = 1.40 Hz, 1H); 19 F NMR (D2O, C6F6; δ -163): δ -80.58 (t, J = 7.57 Hz, 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 = 13.41 Hz, 2F), -87.10 - -87.20 (m, 2F), -115.74 (t, J = 18.48 Hz, 2F), -127.70 - -128.10 (m, 2nF), -128.73 (s, 2F)

[0167] As described above, in Example 1, the selectivity of the olefin-modified fluorine-containing compound formed was improved compared to Comparative Example 1. In Comparative Example 1, the reaction between the tributyltin radical and the iodine radical proceeded rapidly, resulting in CF3CF2CF2O(CF2CF2CF2O) n It is thought that a large number of CF2CF2 radicals are generated. In Comparative Example 1, side reactions caused by these radicals proceeded more easily, and as a result, the selectivity of the olefin-modified fluorine-containing compound was thought to be lower. [Industrial applicability]

[0168] According to this disclosure, a new method for producing olefin-modified fluorine-containing compounds can be obtained. This disclosure may improve the selectivity of olefin-modified fluorine-containing compounds.

Claims

1. A method for producing an olefin-modified fluorine-containing 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. R １Ａ -CFY １ -X １ ・・・(1A) [In the formula: R １Ａ is a monovalent organic group; Y １ is a hydrogen atom or a halogen atom; X １ These are halogen atoms other than fluorine atoms. X １ -CFY １ -R １Ｂ -CFY １ -X １ ・・・(1B) [In the formula: R １Ｂ is a divalent organic group; Y １ Each of these is independently either a hydrogen atom or a halogen atom; X １ These are, independently, halogen atoms other than fluorine atoms. R ２ ３ Si-(CH ２ ) ｎ１ -CR ４ =CR ５ R ６ ・・・(2) [In the formula: R ２ Each of them is independent of R ２１ ３ It is a monovalent group containing Si-; R ２１ In each instance, independently, a hydrogen atom or C １－１２ It is an alkyl group; Said C １－１２ The alkyl group may be substituted with a halogen atom; n1 is an integer between 1 and 10; R ４ , R ５ and R ６ Each of these is independently a hydrogen atom, or C １－１０ It is an alkyl group.

2. The aforementioned Y １ The manufacturing method according to claim 1, wherein is a fluorine atom.

3. The aforementioned X １ The manufacturing method according to claim 1 or 2, wherein is a bromine atom or an iodine atom.

4. The aforementioned R １Ａ Rf １ -R Ｆ１ - (O) ｎ２１ Represented by -; Rf １ C may be substituted with one or more fluorine atoms. １－１６ It is an alkyl group; R Ｆ１ The formula is: -(OC ６ F １２ ) ａ１ -(OC ５ F １０ ) ｂ１ -(OC ４ F ８ ) ｃ１ -(OC ３ R Ｆａ ６ ) ｄ１ -(OC ２ F ４ ) ｅ１ -(OCF ２ ) ｆ１ - It is a base represented by; a1, b1, c1, d1, e1, and f1 are each independent integers between 0 and 200, the sum of a1, b1, c1, d1, e1, and f1 is 1 or greater, and the order of existence of each repeating unit enclosed in parentheses with a1, b1, c1, d1, e1, or f1 is arbitrary in the expression; R Ｆａ In each instance, it is independently a hydrogen atom, a fluorine atom, or a chlorine atom; n21 is either 0 or 1. The manufacturing method according to claim 1 or 2.

5. The aforementioned R １Ｂ is, -(Rf ２ ) ｎ２３ -R Ｆ１ - (O) ｎ２２ Represented by -; Rf ２ is a divalent organic group; R Ｆ１ The formula is: -(OC ６ F １２ ) ａ１ -(OC ５ F １０ ) ｂ１ -(OC ４ F ８ ) ｃ１ -(OC ３ R Ｆａ ６ ) ｄ１ -(OC ２ F ４ ) ｅ１ -(OCF ２ ) ｆ１ - It is a base represented by; a1, b1, c1, d1, e1, and f1 are each independent integers between 0 and 200, the sum of a1, b1, c1, d1, e1, and f1 is 1 or greater, and the order of existence of each repeating unit enclosed in parentheses with a1, b1, c1, d1, e1, or f1 is arbitrary in the expression; R Ｆａ In each instance, it is independently a hydrogen atom, a fluorine atom, or a chlorine atom; n22 is either 0 or 1; n23 is either 0 or 1. The manufacturing method according to claim 1 or 2.

6. The aforementioned R ２ Each of them is independent of R ２１ ３ It is Si-; The aforementioned R ２１ is, independently of each other, a C １－４ alkyl group which may be substituted by a halogen atom; Said C １－４ Alkyl groups can be linear or branched. The manufacturing method according to claim 1 or 2.

7. The aforementioned R ２ Each is independent of the others, (CH ３ ) ３ The manufacturing method according to claim 6, wherein the material is Si-.

8. The manufacturing method according to claim 1 or 2, comprising a reaction between a compound represented by formula (1A) or a compound represented by formula (1B) and a compound represented by formula (2), followed by a purification treatment.

9. The method for producing the olefin-modified fluorine-containing compound according to claim 1 or 2, wherein 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-(CH ２ ) ｎ１－１ H ・・・(3A) [In the formula: R １Ａ , Y １ n1, R ４ , R ５ and R ６ These are the same as those described in claim 1. H(CH ２ ) ｎ１－１ -CH=CR ４ -CR ５ R ６ -CFY １ -R １Ｂ -CFY １ -CR ５ R ６ -CR ４ =CH-(CH ２ ) ｎ１－１ H ・・・(3B) [In the formula: R １Ｂ , Y １ n1, R ４ , R ５ and R ６ These are the same as those described in claim 1.

10. A composition comprising at least one 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-(CH ２ ) ｎ１－１ H ・・・(3A) [In the formula: R １Ａ is a monovalent organic group; Y １ is a hydrogen atom or a halogen atom; n1 is an integer between 1 and 10; R ４ , R ５ and R ６ In each instance, independently, a hydrogen atom or C １－１０ It is an alkyl group. H(CH ２ ) ｎ１－１ -CH=CR ４ -CR ５ R ６ -CFY １ -R １Ｂ -CFY １ -CR ５ R ６ -CR ４ =CH-(CH ２ ) ｎ１－１ H ・・・(3B) [In the formula: R １Ｂ is a divalent organic group; Y １ Each of these is independently either a hydrogen atom or a halogen atom; n1 are each an independent integer between 1 and 10; R ４ , R ５ and R ６ In each instance, independently, a hydrogen atom or C １－１０ It is an alkyl group.

11. The composition according to claim 10, wherein the tin content is 1 ppb 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).

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