Compound, method for producing compound, and method for producing surface treatment agent

Abstract

To provide a novel compound and a method for producing the same, and a method for producing a surface treatment agent having the novel compound as a raw material.　A compound represented by formula (A1) or formula (A2).　G1-(CH2)n-M … formula (A1) M-(CH2)n-G2-(CH2)n-M … formula (A2) Where, each symbol in the formulas is as described in the specification.

Description

[Technical Field]

[0001] The present invention relates to a compound, a method for producing the compound, and a method for producing a surface treatment agent. [Background technology]

[0002] Fluorine-containing compounds are used in a variety of fields, including pesticides, pharmaceuticals, and functional materials. There is a demand for easier methods for synthesizing a variety of structures. For example, synthetic methods for introducing various substituents into compounds with fluoroalkyl groups or (poly)oxyfluoroalkylene chains to impart various functions are being investigated.

[0003] Various studies have been conducted on methods for synthesizing compounds having a structure in which an alkyl group is bonded to a fluoroalkyl group. For example, Patent Document 1 discloses a method for producing a fluorine-containing compound by adding a perfluoroalkyl bromide to an olefin compound by a radical reaction. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2018-43940 A Summary of the Invention [Problem to be solved by the invention]

[0005] The method of Patent Document 1 is unsuitable for synthesizing compounds having a carbon-carbon double bond because it involves the reaction of olefins, and the types of electrophiles that can be used are limited. Furthermore, the product may undergo further radical reaction, resulting in telomerization, which results in the generation of various by-products.

[0006] An object of the present invention is to provide a novel compound and a method for producing the same, as well as a method for producing other compounds and a method for producing surface treatment agents using the novel compound as a raw material. [Means for solving the problem]

[0007] The present invention provides a compound having the following constitutions [1] to [4], a method for producing the same, and a method for producing a surface treatment agent. [1] A compound represented by the following formula (A1) or formula (A2): G 1 -(CH2) n -M formula (A1) M-(CH2) n -G 2 -(CH2) n -M formula (A2) However, in the formula, G 1 is a fluoroalkyl group or a monovalent group having a (poly)oxyfluoroalkylene chain, G 2 is a divalent group having a fluoroalkylene group or a (poly)oxyfluoroalkylene chain, M is BR 1 R 2 and R 1 and R 2 are each independently -OH, -R 5 , -OR 5 , -OC(O)-R 5 , or -NR 5 R 6 is a group represented by R 5 is a hydrocarbon group which may have a substituent and may have a heteroatom in the carbon chain, and two R 5 may be linked to form a ring structure, and R 6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and when there are multiple M's, the M's may be the same or different, n is an integer from 2 to 20. [2] A method for producing the compound according to claim 1, comprising reacting a compound represented by the following formula (B1) or formula (B2) with a compound represented by the following formula (C1): G 1 -(CH2) n-2 -CH=CH2 formula (B1) CH2=CH-(CH2)n-2 -G 2 -(CH2) n-2 -CH=CH2 formula (B2) HBR 1 R 2 Formula (C1) However, in the formula, G 1 is a monovalent group having a (poly)oxyfluoroalkylene chain, G 2 is a divalent group having a (poly)oxyfluoroalkylene chain, R 1 and R 2 are each independently -OH, -R 5 , -OR 5 , -OC(O)-R 5 , or -NR 5 R 6 is a group represented by R 5 is a hydrocarbon group which may have a substituent and may have a heteroatom in the carbon chain, and two R 5 may be linked to form a ring structure, and R 6 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, n is an integer from 2 to 20. [3] A method for producing a compound represented by the following formula (E1) or (E2), comprising reacting the compound of [1] with a compound represented by the following formula (D): R 11 -X 1 Formula (D) G 1 -(CH2) n -R 11 Formula (E1) R 11 -(CH2) n -G 2 -(CH2) n -R 11 Formula (E2) However, in the formula, G 1 is a fluoroalkyl group or a monovalent group having a (poly)oxyfluoroalkylene chain, G 2is a divalent group having a fluoroalkylene group or a (poly)oxyfluoroalkylene chain, n is an integer from 2 to 20, R 11 represents a hydrocarbon group which may have a substituent or may have a hetero atom, X 1 is a halogen atom. [4] A method for producing a surface treatment agent, comprising obtaining a compound represented by formula (E1) or formula (E2) by the production method according to [3], and introducing a reactive silyl group into the compound. [Effects of the Invention]

[0008] The present invention provides a novel compound and a method for producing the same, as well as a method for producing other compounds and a method for producing surface treatment agents using the novel compound as a raw material. DETAILED DESCRIPTION OF THE INVENTION

[0009] In this specification, the compound represented by formula (A1) will be referred to as compound (A1), and the same applies to compounds represented by other formulas. "(Poly)oxyfluoroalkylene" is a general term for oxyfluoroalkylene and polyoxyfluoroalkylene. A fluoroalkyl group is a general term that includes perfluoroalkyl groups and partial fluoroalkyl groups. A perfluoroalkyl group refers to an alkyl group in which all hydrogen atoms have been substituted with fluorine atoms. A partial fluoroalkyl group is an alkyl group in which one or more hydrogen atoms have been substituted with a fluorine atom and which also has one or more hydrogen atoms. That is, a fluoroalkyl group is an alkyl group that contains one or more fluorine atoms. The term "reactive silyl group" refers collectively to a hydrolyzable silyl group and a silanol group (Si-OH), and the term "hydrolyzable silyl group" refers to a group that can undergo a hydrolysis reaction to form a silanol group. The term "surface layer" refers to a layer formed on the surface of a substrate. The symbol "to" indicating a range of values ​​means that the values ​​before and after it are included as the lower and upper limits.

[0010] [Compound (A1), Compound (A2)] The compound according to the present invention (hereinafter also referred to as the present compound) is a compound represented by the following formula (A1) or formula (A2). G 1 -(CH2) n -M formula (A1) M-(CH2) n -G 2 -(CH2) n -M formula (A2) However, in the formula, G 1 is a fluoroalkyl group or a monovalent group having a (poly)oxyfluoroalkylene chain, G 2 is a divalent group having a fluoroalkylene group or a (poly)oxyfluoroalkylene chain, M is BR 1 R 2 and R 1 and R 2 are each independently -OH, -R 5 , -OR 5 , -OC(O)-R 5 , or -NR 5 R 6 is a group represented by R 5 is a hydrocarbon group which may have a substituent and may have a heteroatom in the carbon chain, and two R 5 may be linked to form a ring structure, and R 6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and when there are multiple M's, the M's may be the same or different, n is an integer from 2 to 20.

[0011] This compound has a structure in which a fluoroalkyl chain or a (poly)oxyfluoroalkylene chain and an alkyl chain are linked by a carbon-carbon bond or an oxygen-carbon bond without passing through various bonds such as an ester bond or an amide bond, and the alkyl chain has a boron-based substituent (M). As described above, this compound has excellent chemical stability because the fluoroalkyl chain or (poly)oxyfluoroalkylene chain and the alkyl chain are linked without any type of bond. Furthermore, the alkyl chain of this compound has a substituent M. This compound with such a structure can easily introduce a substituent into the M position through a single-step or multi-step reaction, making it a suitable compound as a raw material for obtaining fluoroalkyl chains or (poly)oxyfluoroalkylene chains imparted with various functionalities.

[0012] G 1 The fluoroalkyl group in the formula (I) may be a linear fluoroalkyl group or a fluoroalkyl group having a branched or cyclic structure. The number of carbon atoms in the fluoroalkyl group may be appropriately adjusted depending on the application of the present compound. From the viewpoints of ease of production of the present compound and high yield in the production of other compounds using the present compound as a raw material, the number of carbon atoms is preferably 1 to 30, more preferably 1 to 20, even more preferably 1 to 10, and particularly preferably 1 to 6. Specific examples of fluoroalkyl groups include CF3-, CHF2-, CF3CF2-, CF3CHF-, CF3CF2CF2-, CF3CHFCF2-, CF3CHFCHF-, CF3CF(CF3)-, CF3CF2CF2CF2-, CF3CHFCF2CF2-, CF3CF(CF3)-CF2-, CF3C(CF3)2-CF2-, CF3CF2CF2CF2CF2-, CF3CF2CF2CF2CF2-, fluorocyclobutyl group, fluorocyclopentyl group, fluorocyclohexyl group, and the like. G 1 The monovalent group having a (poly)oxyfluoroalkylene chain in formula (A1) is a fluoroalkyl group having -O- at the end bonded to CH2, or having -O- between carbon atoms in a carbon chain having two or more carbon atoms, or having both of these. 1 is preferably a structure represented by the following formula (G1-1). R f0 O-[(R f1 O) m1 (R f2 O) m2 (Rf3 O) m3 (R f4 O) m4 (R f5 O) m5 (R f6 O) m6 ]-(R f7 ) m7 - Formula (G1-1) however, R f0 is a fluoroalkyl group having 1 to 20 carbon atoms, R f1 is a fluoroalkylene group having one carbon atom, R f2 is a fluoroalkylene group having 2 carbon atoms, R f3 is a fluoroalkylene group having 3 carbon atoms, R f4 is a fluoroalkylene group having 4 carbon atoms, R f5 is a fluoroalkylene group having 5 carbon atoms, R f6 is a fluoroalkylene group having 6 carbon atoms, R f7 is a fluoroalkylene group having 1 to 6 carbon atoms, m1, m2, m3, m4, m5, and m6 each independently represent an integer of 0 or 1 or more; m7 is an integer of 0 or 1; and m1+m2+m3+m4+m5+m6+m7 is an integer of 0-200. In addition, (R f1 O)~(R f6 O) can be bonded in any order. In formula (G1-1), m1 to m6 are each represented by (R f1 O)~(R f6 O), not the arrangement. For example, (R f5 O) m5 is (R f5 O) is m5, and (R f5 O) m5 It does not represent the block arrangement structure of (R f1 O)~(R f6The order of the units does not represent the bonding order of the units. When m7 is 0, G 1 The end of the bond to CH2 is -O-. When m7 is 1, G 1 The end bonded to CH2 is the carbon atom (R f7 (the terminal carbon atom of The fluoroalkylene group having 3 to 6 carbon atoms may be a straight-chain fluoroalkylene group, or may be a fluoroalkylene group having a branched or cyclic structure.

[0013] For example, when the compound (A1) is used as a raw material for a surface treatment agent, in terms of water and oil repellency and fingerprint removability, it is preferable that m1+m2+m3+m4+m5+m6 is an integer of 1 to 200, i.e., G 1 is preferably a polyoxyfluoroalkylene chain. Furthermore, m7 is preferably 1 from the viewpoint of the chemical stability of the compound (A1), for example.

[0014] R f1 Specific examples include -CF2- and -CHF-. R f2 Specific examples include -CF2CF2-, -CHFCF2-, -CHFCHF-, -CH2CF2-, -CH2CHF-, etc. R f3Specific examples of the alkyl group include -CF2CF2CF2-, -CF2CHFCF2-, -CF2CH2CF2-, -CHFCF2CF2-, -CHFCHFCF2-, -CHFCHFCHF-, -CHFCH2CF2-, -CHFCH2CF2-, -CH2CF2CF2-, -CH2CHFCF2-, -CH2CH2CF2-, -CH2CF2CHF-, -CH2CHFCHF-, -CH2CH2CHF-, -CF(CF3)-CF2-, -CF(CHF2)-CF2-, -CF(CH2F)-CF2-, -CF(CH3)-CF2-, -CF(CF3)-CHF-, -CF(CHF2)- CHF-, -CF(CH2F)-CHF-, -CF(CH3)-CHF-, -CF(CF3)-CH2-, -CF(CHF2)-CH2-, -CF(CH2F)-CH2-, -CF(CH3)-CH2-, -CH(CF3)-CF2-, -CH(CHF2)-CF2-, -CH(CH2F) -CF2-, -CH(CH3)-CF2-, -CH(CF3)-CHF-, -CH(CHF2)-CHF-, -CH(CH2F)-CHF-, -CH(CH3)-CHF-, -CH(CF3)-CH2-, -CH(CHF2)-CH2-, -CH(CH2F)-CH2-, and the like. R f4 Specific examples of the alkyl group include -CF2CF2CF2CF2-, -CHFCF2CF2CF2-, -CH2CF2CF2CF2-, -CF2CHFCF2CF2-, -CHFCHFCF2CF2-, -CH2CHFCF2CF2-, -CF2CH2CF2CF2-, -CHFCH2CF2CF2-, -CH2CH2CF2CF2-, -CHFCF2CHFCF2-, -CH2CF2CHFCF2-, -CF2C Examples include HFCHFCF2-, -CHFCHFCHFCF2-, -CH2CHFCHFCF2-, -CF2CH2CHFCF2-, -CHFCH2CHFCF2-, -CH2CH2CHFCF2-, -CF2CH2CH2CF2-, -CHFCH2CH2CF2-, -CH2CH2CH2CF2-, -CHFCH2CH2CHF-, -CH2CH2CH2CHF-, -cycloC4F6-, and the like. R f5Specific examples of the group include -CF2CF2CF2CF2CF2-, -CHFCF2CF2CF2CF2-, -CH2CHFCF2CF2CF2-, -CF2CHFCF2CF2CF2-, -CHFCHFCF2CF2CF2-, -CH2CHFCF2CF2CF2-, -CF2CH2CF2CF2CF2-, -CHFCH2CF2CF2CF2-, -CH2CH2CF2CF2CF2-, -CF2CF2CHFCF2CF2-, -CHFCF2CHFCF2CF2-, -CF2CF2CHFCF2CF2-, -CHFCF2CHFCF2CF2-, -CH2CF2CHFCF2CF2-, -CH2CF2CF2CHFCF2CF2-, -CH2CF2CF2CF2CH2-, -cycloC5F8-, and the like. R f6 Specific examples of the alkyl group include -CF2CF2CF2CF2CF2CF2-, -CF2CF2CHFCHFCF2CF2-, -CHFCF2CF2CF2CF2CF2-, -CHFCHFCHFCHFCHFCHF-, -CHFCF2CF2CF2CF2CH2-, -CH2CF2CF2CF2CF2CH2-, -cycloCF 10 - and more. Also, R f0 and R f7 Specific examples of R f1 ~R f6 Examples include those similar to those listed above. Here, -cycloC4F6- means a perfluorocyclobutanediyl group, a specific example of which is perfluorocyclobutane-1,2-diyl, -cycloC5F8- means a perfluorocyclopentanediyl group, a specific example of which is perfluorocyclopentane-1,3-diyl, -cycloC6F 10 - means a perfluorocyclohexanediyl group, and a specific example thereof is a perfluorocyclohexane-1,4-diyl group.

[0015] When compound (A1) is used as a raw material for a surface treatment agent, it is preferred to use compound (A1) as a raw material for a surface treatment agent because of its excellent water and oil repellency, abrasion resistance, and fingerprint stain removal properties. 1is preferably a monovalent group having a (poly)oxyfluoroalkylene chain, and more preferably a monovalent group having a polyoxyfluoroalkylene chain. The following formula It is preferable that the compound has a structure represented by the following formula (F1) to (F3). (R f1 O) m1 -(R f2 O) m2 -(R f7 ) m17 Formula (F1) (R f2 O) m2 -(R f4 O) m4 -(R f7 ) m17 Formula (F2) (R f3 O) m3 -(R f7 ) m17 Formula (F3) however, Mode (F1) ~ The symbols in (F3) are the same as those in formula (G1-1).

[0016] In the above formulas (F1) and (F2), (R f1 O) and (R f2 O), (R f2 O) and (R f4 O) can be bonded in any order. For example, (R f1 O) and (R f2 O) may be alternated, and (R f1 O) and (R f2 O) may be arranged in blocks or randomly. The same applies to formula (F3). In formula (F1), m1 is preferably an integer of 1 to 30, more preferably an integer of 1 to 20. Furthermore, m2 is preferably an integer of 1 to 30, more preferably an integer of 1 to 20. In formula (F2), m2 is preferably an integer of 1 to 30, more preferably an integer of 1 to 20. Furthermore, m4 is preferably an integer of 1 to 30, more preferably an integer of 1 to 20. In formula (F3), m3 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20.

[0017] G 2 The fluoroalkylene group in may be linear or may have a branched or cyclic structure. From the viewpoint of increasing the yield of the present production method, the number of carbon atoms in the fluoroalkylene group is preferably 1 to 30, more preferably 1 to 20, even more preferably 1 to 10, and particularly preferably 1 to 6. Specific examples of the fluoroalkylene group include the above-mentioned R f1 ~R f6 Examples include those similar to those listed above.

[0018] G 2 The divalent group having a (poly)oxyfluoroalkylene chain in formula (A2) is a fluoroalkylene group in which two ends bonded to CH2 each independently have -O-, or a carbon-carbon chain having two or more carbon atoms has -O- between carbon atoms, or a combination thereof. 2 is preferably a structure represented by the following formula (G2-1). -(O) m0 -[(R f1 O) m1 (R f2 O) m2 (R f3 O) m3 (R f4 O) m4 (R f5 O) m5 (R f6 O) m6 ]-(R f7 ) m7 - Formula (G2-1) where m0 is an integer of 0 or 1, and R f1 , R f2 , R f3 , R f4 , R f5 , R f6 , R f7 , m1, m2, m3, m4, m5, m6, and m7 are the G 1 It is the same as in the formula (G2-1). f1 O)~(R f6 The bonding order of the groups (O) is arbitrary, as explained in the formula (G1-1) above. When m7 is 0, G 2 The end of one side that is bonded to CH2 is -O-. When m7 is 1, G 2 The one end of the bond to CH2 is the carbon atom (R f7 (The terminal carbon atom of the ) Also, when m0 is 1, G 2 The end of one side that is bonded to CH2 is -O-. When m0 is 0, G 2 The one end of the bond to CH2 is the carbon atom (R f1 ~R f7 (carbon atom at either end of the group, m0 or m7). Note that m0 and m7 each independently represent 0 or 1.

[0019] For example, when the compound (A2) is used as a raw material for a surface treatment agent, in terms of water and oil repellency and fingerprint removability, it is preferable that m0+m1+m2+m3+m4+m5+m6 is an integer of 2 to 200, i.e., G 2 is preferably a polyoxyfluoroalkylene chain. Furthermore, for example, from the viewpoint of the chemical stability of the compound (A2), it is preferable that m0 is 0 or m7 is 1, and it is more preferable that m0 is 0 and m7 is 1.

[0020] When the obtained compound (A2) is used as a surface treatment agent or a raw material thereof, G 2 is especially popular due to its excellent water and oil repellency, abrasion resistance, and fingerprint removal properties. The following formula It is preferable that the compound has a structure represented by the following formula (F4) to (F6). -(O) m0 -(R f1 O) m1 -(R f2 O) m2 -(R f7 ) m7 Formula (F4) -(O) m0 -(R f2 O) m2 -(R f4 O) m4 -(R f7 ) m7 Formula (F5) -(O) m0 -(R f3 O) m3 -(R f7 )m7 Formula (F6) however, Mode (F4) ~ The symbols in (F6) are the same as those in the formula (G2-1).

[0021] In the above formulas (F4) and (F5), (R f1 O) and (R f2 O), (R f2 O) and (R f4 O) can be bonded in any order. For example, (R f1 O) and (R f2 O) may be alternated, and (R f1 O) and (R f2 O) may be arranged in blocks or randomly. In formula (F4), m1 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20. Furthermore, m2 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20. In formula (F5), m2 is preferably an integer of 1 to 30, more preferably an integer of 1 to 20. Furthermore, m4 is preferably an integer of 1 to 30, more preferably an integer of 1 to 20. In formula (F6), m3 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20.

[0022] G 1 and G 2 The proportion of fluorine atoms in the fluoroalkyl chain or (poly)oxyfluoroalkylene chain [{number of fluorine atoms / (number of fluorine atoms+number of hydrogen atoms)}×100(%)] is preferably 40% or more, more preferably 50% or more, and even more preferably 60% or more, in terms of excellent water and oil repellency and fingerprint removability. Furthermore, the molecular weight of the (poly)oxyfluoroalkylene chain portion is preferably from 200 to 30,000, more preferably from 600 to 25,000, even more preferably from 800 to 20,000, and particularly preferably from 1,000 to 8,000, from the viewpoint of abrasion resistance.

[0023] M is a boron-based substituent BR 1 R 2 represents R 1 and R 2are each independently -OH, -R 5 , -OR 5 , -OC(O)-R 5 , or -NR 5 R 6 is a group represented by R 5 is a hydrocarbon group which may have a substituent and may have a heteroatom in the carbon chain, and two R 5 may be linked to form a ring structure, and R 6 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R 5 Examples of the hydrocarbon group in include aliphatic hydrocarbon groups (straight-chain alkyl groups, branched alkyl groups, cycloalkyl groups, etc.). The aliphatic hydrocarbon groups may have a double bond or a triple bond in the carbon chain. Examples of the substituent that the hydrocarbon group may have include a halogen atom, a hydroxy group, an amino group, a nitro group, a sulfo group, an oxo group, etc., and from the viewpoint of the stability of the compound in the present production method, a halogen atom is preferred. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Heteroatoms may be included in the carbon chain alone or in combination with other substituents such as oxo groups. Specific examples of moieties containing heteroatoms include -C(O)NR 25 -, -C(O)O-, -C(O)-, -O-, -NR 25 -, -S-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 25 -,-SO2NR 25 -, -Si(R 25 )2-, -OSi(R 25 )2-, etc. However, R 25 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. The Two R's 5 Examples of structures in which the ring structure is formed by linking include *-R 5 -*, *-OR 5 -*, *-OR 5 -O-*, *-OC(O)-R 5 -C(O)-O-*, *-NR 6 -R 5 -NR6 -*, etc. Here, * is a linking group that bonds to B, and a ring structure including B is formed.

[0024] BR 1 R 2 Specific examples include the following: [ka]

[0025] Specific examples of the compound (A1) and the compound (A2) include the following. [ka] wherein M is as defined above, n11 to n24 represent the number of repeating units and are each independently an integer of 1 to 200, n31 is an integer of 1 to 18, and n32 to n38 are each independently an integer of 0 to 18.

[0026] [Method for producing compound (A1) or compound (A2)] The method for producing the present compound is not particularly limited, but the following production method is preferred in terms of relatively easy availability of raw materials and excellent yield. That is, the method for producing compound (A1) or compound (A2) according to the present invention is characterized by reacting a compound represented by the following formula (B1) or formula (B2) with a compound represented by the following formula (C1): G 1 -(CH2) n-2 -CH=CH2 formula (B1) CH2=CH-(CH2) n-2 -G 2 -(CH2) n-2 -CH=CH2 formula (B2) HBR 1 R 2 Formula (C1) However, in the formula, G 1 , G 2 , R 1 , R 2and n are the same as those in the formula (A1) or (A2), and preferred embodiments are also the same.

[0027] For example, the compound (B1) or (B2), the compound (C1), and optionally a radical polymerization initiator such as an azo-based polymerization initiator are added to a solvent and heated to form a compound. thing ( Compound (A1) or compound (A2) can be obtained by adding compound (C1) to the olefin contained in compound (B1) or compound (B2). The reaction temperature is not particularly limited, but can be, for example, 40 to 120°C. The reaction time is adjusted appropriately depending on the amount of the compound, but can be, for example, 1 to 40 hours.

[0028] Specific examples of the compound (B1) and the compound (B2) include the following.

[0029] [ka] Here, n11 to n24 represent the number of repeating units and are each independently an integer of 1 to 200; n31 is an integer of 1 to 18; and n32 to n38 are each independently an integer of 0 to 18.

[0030] The above compounds (B1) and (B2) can be obtained, for example, by an elimination reaction of a compound represented by the following formula (H1) or (H2). G 1 -X formula (H1) XG 2 -X formula (H2) However, G in the formula 1 and G 2 is as described above, and X is a halogen atom.

[0031] [Method for producing compound (E1) or compound (E2)] The method for producing a compound represented by the following formula (E1) or formula (E2) according to the present invention is characterized by reacting the compound (A1) or compound (A2) with a compound represented by the following formula (D): R 11 -X 1 Formula (D) G 1 -(CH2) n -R 11 Formula (E1) R 11 -(CH2) n -G 2 -(CH2) n -R 11 Formula (E2) However, in the formula, G 1 G 2 , n is as described above, and the preferred embodiments are also the same. R 11 represents a hydrocarbon group which may have a substituent or may have a hetero atom, X 1 is a halogen atom.

[0032] R 11 Examples of the hydrocarbon group in include aliphatic hydrocarbon groups (such as linear alkyl groups, branched alkyl groups, and cycloalkyl groups), aromatic hydrocarbon groups (such as phenyl groups), and groups formed from combinations thereof. The aliphatic hydrocarbon groups may have a double bond or triple bond in the carbon chain. Examples of combinations include groups in which an alkylene group and an aryl group are linked directly or via a heteroatom. Examples of the substituent that the hydrocarbon group may have include a halogen atom, a hydroxy group, an amino group, a nitro group, a sulfo group, and an oxo group. From the viewpoint of the stability of the compound in the present production method, a halogen atom is preferred. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Heteroatoms may be included in the carbon chain alone or in combination with other substituents such as oxo groups. Specific examples of moieties containing heteroatoms include -C(O)NR 26 -, -C(O)O-, -C(O)-, -O-, -NR 26-, -S-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 26 -,-SO2NR 26 -, -Si(R 26 )2-, -OSi(R 26 )2-, -Si(CH3)2-Ph-Si(CH3)2-, and divalent organopolysiloxane residues. 26 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and Ph is a phenylene group. 26 The alkyl group preferably has 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms.

[0033] When other substituents are further introduced into the compound (E1) or the compound (E2), R 11 The hydrocarbon group preferably has a carbon-carbon double bond. When compound (E1) or compound (E2) has a double bond, other substituents can be easily introduced by an addition reaction.

[0034] X 1 In terms of reactivity, the halogen atom in is preferably a chlorine atom, a bromine atom or an iodine atom, more preferably a chlorine atom or a bromine atom, and even more preferably a bromine atom.

[0035] Specific examples of suitable compounds (D) include the following:

[0036] [ka]

[0037] above Record The compound (A1) or the compound (A2) can be reacted with a compound represented by the following formula (D) by, for example, heating in a solvent in the presence of a catalyst and a base. Examples of the catalyst include known metal catalysts, among which transition metal compounds are preferred, and among these, compounds containing Group 8 to Group 11 elements are more preferred, and compounds containing one or more elements selected from copper, nickel, palladium, and cobalt are preferred.

[0038] In the copper-containing metal catalyst, the copper may be zero-valent, monovalent, divalent, or trivalent, but from the viewpoint of catalytic activity, monovalent or divalent copper salts or complex salts are preferred. Furthermore, from the viewpoint of ease of availability, copper chloride is more preferred. As copper chloride, either CuCl or CuCl2 can be suitably used. Note that copper chloride may be anhydrous or hydrated, but from the viewpoint of catalytic activity, copper chloride anhydrous is more preferred.

[0039] In metal catalysts containing nickel, the nickel may be zero-valent, monovalent, divalent, or trivalent. However, from the viewpoint of catalytic activity, salts or complex salts of zero-valent or divalent nickel are preferred. Furthermore, from the viewpoint of ease of availability, nickel chloride (NiCl2) or nickel bromide (NiBr2) are more preferred. Note that nickel chloride may be anhydrous or hydrated, but from the viewpoint of catalytic activity, nickel chloride anhydrous is more preferred. Furthermore, the nickel bromide may be in the form of a complex, such as a nickel(II) bromide 2-methoxyethyl ether complex or a nickel(II) bromide ethylene glycol dimethyl ether complex.

[0040] In a metal catalyst containing palladium, the palladium may be any of zero-valent, monovalent, divalent, and trivalent compounds. However, from the viewpoint of catalytic activity, a salt or complex salt of zero-valent or divalent palladium is preferred. Furthermore, from the viewpoint of ease of availability, tris(dibenzylideneacetone)dipalladium (Pd2(dba)3) and palladium acetate (Pd(OAc)2) are more preferred. Note that tris(dibenzylideneacetone)dipalladium and palladium acetate may be anhydrides or hydrates, but from the viewpoint of catalytic activity, tris(dibenzylideneacetone)dipalladium anhydride and palladium acetate anhydride are more preferred.

[0041] In the reaction of the present production method, a ligand may be used in combination with the metal catalyst as needed. Examples of the ligand include 1,3-butadiene, tricyclohexylphosphine, 1,1-bis(diphenylphosphino)ferrocenephenylpropyne, and tetramethylethylenediamine (TMEDA).

[0042] The base is preferably a strong base with low nucleophilicity, such as potassium tert-butoxide, lithium diisopropylamide, potassium hexamethyldisilazide, or lithium-2,2,6,6-tetramethylpiperidide.

[0043] The solvent may be appropriately selected from solvents inert to this reaction. Examples include ether solvents such as diethyl ether, tetrahydrofuran (THF), and dioxane. When compound (A1) and compound (A2) have a relatively high fluorine atom content, it is preferable to use a fluorine-containing solvent alone or in combination with the above solvents. Examples of fluorine-based solvents include hydrofluorocarbons (1H,4H-perfluorobutane, 1H-perfluorohexane, 1,1,1,3,3-pentafluorobutane, 1,1,2,2,3,3,4-heptafluorocyclopentane, 2H,3H-perfluoropentane, etc.), hydrochlorofluorocarbons (3,3-dichloro-1,1,1,2,2-pentafluoropropane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane (HCFC-225cb), etc.), hydrofluoroethers (CF3CH2OCF2CF2H(AE-3000), (perfluorobutoxy)methane, (perfluorobutoxy)ethane, etc.), hydrochlorofluorocarbons (e.g., ... Examples of suitable fluoroolefins include (Z)-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene (HCFO-1437dycc(Z) form), (E)-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene (HCFO-1437dycc(E) form), (Z)-1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd(Z) form), (E)-1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd(E) form), etc.), and fluorine-containing aromatic compounds such as perfluorobenzene, m-bis(trifluoromethyl)benzene (SR-solvent), and p-bis(trifluoromethyl)benzene.

[0044] [Method of manufacturing surface treatment agent] The method for producing a surface treatment agent according to the present invention is characterized by introducing a reactive silyl group into compound (E1) or compound (E2) obtained by the above-mentioned production method. Compounds having a (poly)oxyfluoroalkylene chain and a hydrolyzable silyl group are suitable for use in surface treatment agents because they can form a surface layer on the surface of a substrate that exhibits high lubricity, water repellency, oil repellency, etc.

[0045] The method for introducing a reactive silyl group into compound (E1) or compound (E2) may be appropriately selected depending on the substituents possessed by compound (E1) or compound (E2). For example, when compound (E1) or compound (E2) has a double bond, the reactive silyl group can be introduced by subjecting the double bond to a hydrosilylation reaction with compound (J1) or (J2) shown below. HSi(R 40 ) 3-c (L) c Formula (J1) HSi(R 41 ) 3-k [-(OSi(R 42 )2) p -O-Si(R 40 ) 3-c (L) c ] k Formula (J2) However, in the formula, R 40 is an alkyl group, and R 40 If there are multiple R 40 may be the same or different, L is a hydrolyzable group or a hydroxyl group, and a plurality of Ls may be the same or different; R 41 is an alkyl group, and R 41 If there are multiple R 41 may be the same or different, R 42 is an alkyl group, a phenyl group, or an alkoxy group, and two R 42 may be the same or different, c is 2 or 3; k is 2 or 3; p is an integer of 0 to 5, and when p is 2 or more, 2 or more (OSi(R 42 )2) may be the same or different. The compound (J1) may be synthesized or may be a commercially available product. The compound (J2) may be produced, for example, by the method described in the specification of Japanese Patent Application No. 2018-085493.

[0046] A reactive silyl group is a group in which either or both of a hydrolyzable group and a hydroxyl group are bonded to a silicon atom. A hydrolyzable group is a group that becomes a hydroxyl group through a hydrolysis reaction. That is, a hydrolyzable silyl group becomes a silanol group (Si-OH) through a hydrolysis reaction. The silanol groups then undergo a dehydration condensation reaction between molecules to form Si-O-Si bonds, and the silanol groups also undergo a dehydration condensation reaction with hydroxyl groups on the surface of the substrate (substrate-OH) to form chemical bonds (substrate-O-Si). Examples of the hydrolyzable group include an alkoxy group, a halogen atom, an acyl group, and an isocyanate group. The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms. The halogen atom is preferably a chlorine atom. As the hydrolyzable group, an alkoxy group or a halogen atom is preferred from the viewpoint of ease of production. As the hydrolyzable group, an alkoxy group having 1 to 4 carbon atoms is preferred from the viewpoint of less outgassing during application and excellent storage stability of the present compound, an ethoxy group is particularly preferred when long-term storage stability of the present compound is required, and a methoxy group is particularly preferred when the reaction time after coating the surface treatment agent on the substrate is to be short.

[0047] According to the above production method, for example, a surface treatment agent represented by the following formula can be obtained.

[0048] [ka] Here, n11 to n22 represent the number of repeating units and are each independently an integer of 1 to 200, and n31 to n37 are each independently an integer of 0 to 18.

[0049] Substrates to which the surface treatment agent is applied include substrates that are required to be imparted with water and oil repellency, such as substrates that may be used by coming into contact with other articles (e.g., a stylus) or human fingers, substrates that may be held with human fingers during operation, and substrates that may be placed on other articles (e.g., a mounting table). The substrate may be made of metal, resin, glass, sapphire, ceramic, stone, or a composite of these materials. The glass may be chemically strengthened. A base film such as a SiO2 film may be formed on the surface of the substrate. The substrate is preferably a substrate for a touch panel, a substrate for a display, or a lens for glasses, and is particularly preferably a substrate for a touch panel.The material of the substrate for a touch panel is preferably glass or a transparent resin. Further, the substrate is preferably a glass or resin film used for the exterior parts (excluding the display part) of devices such as mobile phones (for example, smartphones), personal digital assistants (for example, tablet terminals), game consoles, and remote controls.

[0050] Such a surface treatment agent containing a fluorine-containing compound is preferably used as a surface treatment agent for applications requiring long-term maintenance of the performance of preventing deterioration of water and oil repellency even when the surface layer is repeatedly rubbed with fingers (abrasion resistance) and the performance of easily removing fingerprints attached to the surface layer by wiping (fingerprint stain removability), for example, as a surface treatment agent for members constituting the surfaces of touch panels that are touched with fingers, eyeglass lenses, and displays of wearable devices. [Example]

[0051] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples. Examples 1-2, 1-3, 2-4, 2-5, and 2-6 are examples of production methods.

[0052] [Example 1] <Example 1-1> 44 g of allyltributyltin, 84 g of dodecane, and 7.8 g of tetrakis(triphenylphosphine)palladium were added to a 300 mL recovery flask and mixed with stirring at room temperature, and then 51 g of compound 1-1 was slowly added and stirred for 20 hours at 40° C. The resulting crude liquid was filtered and then purified by distillation to obtain 33 g of compound 1-2.

[0053] [ka]

[0054] [ka]

[0055] <Example 1-2> 15 g of compound 1-2 and 100 g of a 0.5 M THF solution of 9-hydro-9-borabicyclo[2.2.0]nonane were placed in a 200 mL recovery flask and stirred for 15 hours at 60° C. The resulting crude liquid was purified by distillation to obtain 14 g of compound 1-3.

[0056] [ka]

[0057] <Example 1-3> A 50 mL recovery flask was charged with 1.5 g of compound 1-3, 1.2 g of (2-bromoethyl)benzene, 10 g of tetrahydrofuran, 0.6 g of nickel(II) bromide 2-methoxyethyl ether complex, 0.33 g of trans-N,N'-dimethylcyclohexane-1,2-diamine, 0.55 g of potassium t-butoxide, and 0.73 g of isobutyl alcohol, and the mixture was stirred at 60°C for 24 hours. Hydrochloric acid was then added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated aqueous sodium bicarbonate. The resulting organic layer was concentrated and purified by silica gel column chromatography to obtain 0.9 g of compound 1-4. In the formula below, R is CH2CH2Phe, where Phe is a phenyl group.

[0058] [ka]

[0059] [Example 2] <Example 2-1> The following compound 2-1 was obtained according to the method described in Examples 11-1 to 11-3 of the Examples of WO 2013 / 121984. CF3-O-(CF2CF2O-CF2CF2CF2CF2O) nCF2CF2O-CF2CF2CF2-CF2OC(O)CF(CF3)OCF2CF2CF3 Formula 2-1 Average number of units n: 13

[0060] <Example 2-2> 5.8 g of sodium pyrithione and 100 mL of 1,3-bistrifluoromethylbenzene (product name: SR-Solvent) were placed in a 500 mL recovery flask shielded from light with aluminum foil and stirred under ice cooling. Next, 50.0 g of compound 2-1 was slowly added and stirred for 2 hours while still ice-cooled. Next, 12.0 g of iodine and 1.8 g of 2,2-azobis(2-methylbutyronitrile) (product name: V-59) were added, the aluminum foil shielding the light was removed, and the mixture was stirred overnight at 85 °C. The temperature was returned to 25 °C, methanol was added, and the mixture was thoroughly stirred. After that, AC-6000 was added to separate the two layers, and the lower layer was collected and evaporated. The resulting crude product was purified by silica gel column chromatography to obtain 39.8 g of the following compound 2-2.

[0061] [ka] Average number of units n: 13

[0062] <Example 2-3> 47 g of compound 2-2, 20 g of allyltributyltin, 60 g of 1,3-bis(trifluoromethyl)benzene, and 0.32 g of 2,2'-azobis(2-methylbutyronitrile) were added to a 300 mL recovery flask and stirred for 24 hours at 90°C. The resulting crude liquid was concentrated, washed with hexane, and then purified by silica gel chromatography to obtain 42 g of compound 2-3.

[0063] [ka]

[0064] <Example 2-4> 10 g of compound 2-3, 60 g of 1,3-bis(trifluoromethyl)benzene, and 8.3 g of a 0.5 M THF solution of 9-hydro-9-borabicyclo[2.2.0]nonane were added to a 100 mL recovery flask and stirred for 24 hours at 60° C. The resulting crude liquid was concentrated to obtain 11 g of compound 2-4.

[0065] [ka]

[0066] <Example 2-5> A 100 mL recovery flask was charged with 11 g of compound 2-4, 0.61 g of 6-bromo-1-hexene, 40 g of 1,3-bis(trifluoromethyl)benzene, 20 g of tetrahydrofuran, 0.5 g of nickel(II) bromide 2-methoxyethyl ether complex, 0.28 g of trans-N,N'-dimethylcyclohexane-1,2-diamine, 0.51 g of potassium t-butoxide, and 0.69 g of isobutyl alcohol, and the mixture was stirred at 60 °C for 24 hours. Hydrochloric acid was then added, and the mixture was extracted with 1,3-bis(trifluoromethyl)benzene. The organic layer was washed with saturated aqueous sodium bicarbonate. The resulting organic layer was concentrated and purified by silica gel column chromatography to obtain 5.1 g of compound 2-5. In the formula below, R represents CH2CH2CH2CH2CH=CH2.

[0067] [ka]

[0068] <Example 2-6> 10 g of compound 2-3, 60 g of 1,3-bis(trifluoromethyl)benzene, and 0.26 g of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane were added to a 100 mL recovery flask and stirred for 30 hours at 60° C. The resulting crude liquid was concentrated and then purified by column chromatography to obtain 7 g of compound 2-6.

[0069] [ka] [Industrial Applicability]

[0070] According to this production method, it is possible to introduce any substituent into a compound having a fluoroalkylene chain or a (poly)oxyfluoroalkylene chain using a readily available compound under relatively mild reaction conditions. The compound obtained by this production method can be suitably used, for example, as a surface treatment agent or a raw material thereof, capable of forming a surface layer having water and oil repellency, fingerprint wiping removability, etc. on the surface of a substrate.

[0071] This application claims priority based on Japanese Patent Application No. 2021-035096, filed on March 5, 2021, the disclosure of which is incorporated herein in its entirety.

Claims

1. A compound represented by the following formula (A1) or formula (A2): G １ -(CH ２ ) ｎ -M type (A1) M-(CH ２ ) ｎ -G ２ -(CH ２ ) ｎ -M formula (A2) However, in the formula, G １ is a group represented by the following formula (G1-1): G ２ represents a fluoroalkylene group or a group represented by the following formula (G2-1): M is BR １ R ２ and R １ and R ２ are each independently -R ５ , -OR ５ , -O-C(O)-R ５ , or -NR ５ R ６ is a group represented by R ５ is a hydrocarbon group which may have a heteroatom in the carbon chain, and two R ５ may be linked to form a ring structure, and R ６ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and when there are multiple M's, the M's may be the same or different, n is an integer from 2 to 20, R f0 O-[(R f1 O) m1 (R f2 O) m2 (R f3 O) m3 (R f4 O) m4 (R f5 O) m5 (R f6 O) m6 ]-(R f7) m7 - Formula (G1-1) -(O) m0 - [(R f1 O) m1 (R f2 O) m2 (R f3 O) m3 (R f4 O) m4 (R f5 O) m5 (R f6 O) m6 ] - (R f7) m7 - Formula (G2-1) however, R f0 is a fluoroalkyl group having 1 to 20 carbon atoms; R f1 is a fluoroalkylene group having 1 carbon atom; R f2 is a fluoroalkylene group having 2 carbon atoms; R f3 is a fluoroalkylene group having 3 carbon atoms; R f4 is a fluoroalkylene group having 4 carbon atoms; R f5 is a fluoroalkylene group having 5 carbon atoms; R f6 is a fluoroalkylene group having 6 carbon atoms; R f7 is a fluoroalkylene group having 1 to 6 carbon atoms; m1, m2, m3, m4, m5, and m6 each independently represent 0 or an integer of 1 or more; m7 is an integer of 0 or 1, In formula (G1-1), m1+m2+m3+m4+m5+m6 represents an integer of 1 to 200, In formula (G2-1), m1+m2+m3+m4+m5+m6 represents an integer of 2 to 200, m0 is an integer of 0 or 1, In formula (G1-1) and formula (G2-1), the bonding order of (R f1 O) to (R f6 O) is arbitrary; The ratio of fluorine atoms in the fluoroalkyl chain or (poly)oxyfluoroalkylene chain in G 1 and G 2 [{number of fluorine atoms / (number of fluorine atoms+number of hydrogen atoms)}×100(%)] is 40% or more.

2. A method for producing the compound according to claim 1, comprising reacting a compound represented by the following formula (B1) or formula (B2) with a compound represented by the following formula (C1): G １ -(CH ２ ) ｎ－２ -CH=CH ２ Formula (B1) CH ２ =CH-(CH ２ ) ｎ－２ -G ２ -(CH ２ ) ｎ－２ -CH=CH ２ Formula (B2) HBR １ R ２ Formula (C1) However, in the formula, G １ is a group represented by formula (G1-1), G ２ is a group represented by formula (G2-1), R １ and R ２ are each independently -R ５ , -OR ５ , -O-C(O)-R ５ , or -NR ５ R ６ is a group represented by R ５ is a hydrocarbon group which may have a heteroatom in the carbon chain, and two R ５ may be linked to form a ring structure, and R ６ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, n is an integer from 2 to 20.

3. A method for producing a compound represented by the following formula (E1) or (E2), comprising reacting the compound according to claim 1 with a compound represented by the following formula (D): R １１ -X １ Formula (D) G １ -(CH ２ ) ｎ -R １１ Formula (E1) R １１ -(CH ２ ) ｎ -G ２ -(CH ２ ) ｎ -R １１ (Formula (E2)) However, in the formula, G １ is a group represented by formula (G1-1), G ２ is a group represented by formula (G2-1), n is an integer from 2 to 20, R １１ represents a hydrocarbon group which may have a substituent or may have a hetero atom, X １ is a halogen atom.

4. The method according to claim 3, wherein R 11 is a hydrocarbon group having a carbon-carbon double bond and which may have a substituent or a heteroatom.

5. A method for producing a surface treatment agent, comprising obtaining a compound represented by formula (E1) or formula (E2) by the production method according to claim 4 and introducing a reactive silyl group into the compound.

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