Separation methods

Abstract

Provided is a method by which the monofunctional body, bifunctional body, etc. of a fluorine-containing ether compound having a polyfluoropolyether chain and a predetermined functional group can be separated with excellent yield and a high separation capacity.　This separation method is for separating a compound represented by formula (1) and a compound represented by formula (2) from a mixture containing these compounds through chromatography using a stationary phase and a mobile phase, wherein the mobile phase contains at least one specific solvent selected from among hydrofluoroolefin, hydrochlorofluoroolefin, chlorofluoroolefin, cyclic hydrofluoroolefin, cyclic hydrochlorofluoroolefin, cyclic chlorofluoroolefin, cyclic hydrofluorocarbon, cyclic hydrochlorofluorocarbon, cyclic chlorofluorocarbon, and perfluoroketone.　A-(OX)m-O-Z-(R)n1 formula (1) (R)n2-Z-(OX)m-O-Z-(R)n3 formula (2)

Description

[Technical field]

[0001] The present invention relates to a separation method. [Background technology]

[0002] A fluorine-containing ether compound having a polyfluoropolyether chain and a reactive silyl group is suitable for use as a surface treatment agent since it can form a surface layer exhibiting high lubricity, water- and oil-repellency, etc., on the surface of a substrate. A surface treatment agent containing a fluorine-containing ether compound is used as a surface treatment agent for applications requiring a long-term maintenance of the performance of preventing the water- and oil-repellency from decreasing 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 member constituting the surface of a touch panel that is touched by fingers, a spectacle lens, and a display of a wearable terminal.

[0003] In the synthesis of such fluorine-containing ether compounds, fluorine-containing ether compounds having a polyfluoropolyether chain and functional groups such as -OH, -CH=CH2, -CH3, -NH2, -SH, -Ph (phenyl group), -F, -Cl, -Br, -I, -C(CH3)=CH2, -C(CF3)=CH2, -C≡CH, -CF=CH2, -CH=CHF, -CF=CHF, -CH=CF2, -CF=CF2, and -N3 are important compounds as raw material compounds or intermediates.

[0004] In general, it is desirable for the raw material compound or intermediate to have a high purity. This is because a high purity makes it easier to purify the product obtained by the reaction, and furthermore, it is possible to reduce the generation of by-products or unidentified substances that may occur in the reaction, and it is possible to obtain a target product with better performance. The raw material compound or intermediate is usually produced as a mixture of a monofunctional substance (hereinafter also referred to as a "monofunctional substance") having a specific functional group only at one end, and a bifunctional substance (hereinafter also referred to as a "bifunctional substance") having specific functional groups at both ends. For this reason, a method is required that can easily separate the monofunctional substance and the bifunctional substance from the mixture of the raw material compound or intermediate with high purity.

[0005] The separation method described in Patent Document 1 is capable of separating a perfluoro(poly)ether group-containing monoalcohol compound and a perfluoro(poly)ether group-containing dialcohol compound by using, as a mobile phase, one solvent selected from the group consisting of hydrofluorocarbons, hydrochlorofluorocarbons, hydrofluoroethers, fluorine-containing ester solvents, and fluorine atom-containing aromatic solvents. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent No. 6330960 Summary of the Invention [Problem to be solved by the invention]

[0007] In the separation method described in Patent Document 1, it is preferable to use HCFC-225 (CF3CF2CHCl2, CClF2CF2CHClF) as the mobile phase. However, in recent years, there has been a demand for further improvement in the separation performance between monofunctional and difunctional fluorine-containing ether compounds, and it has become clear that the technique described in Patent Document 1, which uses HCFC-225 as a mobile phase, has insufficient separation performance between monofunctional and difunctional compounds.

[0008] The present invention has been made in consideration of the above problems, and an objective of the present invention is to provide a method capable of separating monofunctional and difunctional compounds, etc. of a fluorinated ether compound having a polyfluoropolyether chain and a specified functional group in good yield and with high separation ability. [Means for solving the problem]

[0009] The present invention has the following aspects. [1] A method for separating a compound represented by the following formula (1) and a compound represented by the following formula (2) from a mixture containing them by chromatography using a mobile phase and a stationary phase, comprising: applying said mixture to a chromatographic stationary phase and allowing it to adsorb onto said stationary phase; supplying a mobile phase containing at least one specific solvent selected from the group consisting of hydrofluoroolefins, hydrochlorofluoroolefins, chlorofluoroolefins, cyclic hydrofluoroolefins, cyclic hydrochlorofluoroolefins, cyclic chlorofluoroolefins, cyclic hydrofluorocarbons, cyclic chlorofluorofluorocarbons, and perfluoroketones to the stationary phase on which the mixture has been adsorbed; The separation method comprising the steps of: A-(OX) m -OZ-(R) n1 Formula (1) (R) n2 -Z-(OX) m -OZ-(R) n3 Formula (2) however, A is an alkyl group or a fluoroalkyl group, X is an alkylene group or a fluoroalkylene group having one or more fluorine atoms; m is an integer of 2 or more, Z is an (n1+1)-, (n2+1)-, or (n3+1)-valent linking group; R is -OH, -CR 1 =CR 2 R 3 (However, R 1 is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group, and R 2 and R 3 are each independently a hydrogen atom or a fluorine atom; is any functional group selected from the group consisting of -CH3, -NH2, -SH, -Ph, -F, -Cl, -Br, -I, -C≡CH, and -N3; n1 is an integer of 1 or more, n2 is an integer of 1 or more, n3 is an integer of 1 or greater.

[0010] [2] The separation method according to the above [1], wherein in the formula (1) and the formula (2), A is a fluoroalkyl group, and X is a fluoroalkylene group having one or more fluorine atoms. [3] The separation method according to the above [1] or [2], wherein in the formula (1) and the formula (2), n1, n2, and n3 are the same integer. [4] The method for separating the mixture according to any one of [1] to [3] above, wherein the mixture further contains a compound represented by the following formula (3), and the mixture is separated into a compound represented by formula (1), a compound represented by formula (2), and a compound represented by formula (3). A-(OX) m -OA formula (3) Here, A, X, and m have the same meanings as in the formula (1) and formula (2). [5] The separation method according to any one of the above [1] to [4], wherein the specific solvent is a solvent that does not contain a chlorine atom. [6] The separation method according to any one of the above [1] to [5], wherein the specific solvent contains at least one selected from the group consisting of hydrofluoroolefins, cyclic hydrofluoroolefins, and cyclic hydrofluorocarbons.

[0011] [7] In the formula (1), formula (2), and formula (3), the (OX) m The method for separation according to any one of the above [1] to [6], wherein the compound has the following structure: {(OCF2) m21 (OCF2CF2) m22} Here, m21 is an integer of 1 or more, m22 is an integer of 1 or more, and m21+m22 is an integer of 2-500. [8] The separation method according to any one of the above [1] to [7], wherein the stationary phase is selected from the group consisting of aluminum oxide, silica gel, magnesium oxide, aluminum silicate, magnesium silicate, chemically modified silica gel, and diatomaceous earth. [9] The separation method according to any one of the above [1] to [8], wherein the chromatography is column chromatography. Effect of the Invention

[0012] According to the present invention, there can be provided a method for separating a monofunctional compound and a difunctional compound of a fluorinated ether compound having a polyfluoropolyether chain and a predetermined functional group, and further separating the zero-functional compound, the monofunctional compound and a difunctional compound of the fluorinated ether compound, in a good yield and with high separation ability. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] In this specification, a compound represented by formula (1) is also referred to as compound (1). Compounds represented by other formulas are also referred to in a similar manner. A group represented by formula (2) is also referred to as group 2. Groups represented by other formulas are also referred to in a similar manner. In this specification, when it says that "the alkylene group may have an A group", the alkylene group may have an A group between carbon atoms in the alkylene group, or may have an A group at the terminal, such as alkylene group-A group-. The symbol "~" indicating a range of numerical values ​​means that the numerical values ​​before and after it are included as the lower limit and upper limit.

[0014] (Mixture to be separated) The separation method of the present invention is a method for separating a compound represented by the following formula (1) and a compound represented by the following formula (2) from a mixture containing them (hereinafter, may be simply referred to as "mixture") by chromatography using a mobile phase and a stationary phase. Specifically, it is a separation method for separating compound (1) and compound (2) by chromatography using a mobile phase and a stationary phase. That is, the separation method of the present invention is suitable as a method for producing compound (1). Moreover, the separation method of the present invention is suitable as a method for producing compound (2). In the present invention, compound (1) is called a monofunctional compound because it has a functional group "R" at one end, and compound (2) is called a bifunctional compound because it has functional groups "R" at both ends. The ratio of compound (1) to compound (2) contained in the mixture is not particularly limited, but for example, the ratio of compound (1) / compound (2) (based on mass) is 20 to 0.05.

[0015] A-(OX) m -OZ-(R) n1 Formula (1) (R) n2 -Z-(OX) m -OZ-(R) n3 Formula (2) In the formulas (1) and (2), the symbols are defined as follows: A is an alkyl group or a fluoroalkyl group. X is an alkylene group or a fluoroalkylene group having one or more fluorine atoms, and m is an integer of 2 or more. Z is a (n1+1)-, (n2+1)-, or (n3+1)-valent linking group. R is -OH, -CR 1 =CR 2 R 3 (However, R 1 is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group, and R 2 and R 3are each independently a hydrogen atom or a fluorine atom. is any functional group selected from the group consisting of -CH3, -NH2, -SH, -Ph (phenyl group), -F, -Cl, -Br, -I, -C≡CH, and -N3. n1 is an integer of 1 or greater, n2 is an integer of 1 or greater, n3 is an integer of 1 or greater, and n1, n2, and n3 represent the same integer.

[0016] The number of carbon atoms in the alkyl group or fluoroalkyl group of A is preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 6, and particularly preferably 1 to 3. The alkyl group or fluoroalkyl group may be linear or branched. A is preferably a fluoroalkyl group, more preferably a perfluoroalkyl group.

[0017] Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, etc. Examples of the fluoroalkyl group include CHF2-, CH2F-, CF3CH2-, CF3CH2CH2-, etc. Examples of perfluoroalkyl groups include CF3-, CF3CF2-, CF3CF2CF2-, CF3CF2CF2CF2-, CF3CF2CF2CF2CF2-, CF3CF2CF2CF2CF2CF2-, CF3CF(CF3)-, and the like. The perfluoroalkyl group is preferably CF3-, CF3CF2-, or CF3CF2CF2-.

[0018] The alkylene group and fluoroalkylene group for X preferably have 1 to 6 carbon atoms, more preferably 2 to 6 carbon atoms, and particularly preferably 2 to 4 carbon atoms. The alkylene group and the fluoroalkylene group may be linear, branched, or cyclic. When X is an alkylene group or a fluoroalkylene group, the proportion of the fluoroalkylene group is preferably 50% or more of the repeat number m, more preferably 80% or more, and particularly preferably 100%. The number of fluorine atoms in the fluoroalkylene group is preferably 1 to 2 times, and more preferably 1.7 to 2 times, the number of carbon atoms. The fluoroalkylene group is particularly preferably a fluoroalkylene group in which all hydrogen atoms have been substituted with fluorine atoms (perfluoroalkylene group).

[0019] Specific examples of (OX) include -OCH2-, -OCHF-, -OCF2CHF-, -OCHFCF2-, -OCF2CH2-, -OCH2CF2-, -OCF2CF2CHF-, -OCHFCF2CF2-, -OCF2CF2CH2-, -OCH2CF2CF2-, -OCF2CF2CF2CH2-, -OCH2CF2CF2-, -OCF2CF2CF2CH2-, -OCH2CF2CF2CF2-, -OCF2CF ...CF2-, -OCF2C F2CF2CF2CF2CH2-, -OCH2CF2CF2CF2CF2CF2-, -OCF2-, -OCF2CF2-, -OCF2CF2CF2-, -OCF(CF3)CF2-, -OCF2CF2CF2CF2- , -OCF(CF3)CF2CF2-, -OCF2CF2CF2CF2CF2-, -OCF2CF2CF2CF2CF2CF2-, -O-cycloC4F6-, -O-cycloC5F8-, -O-cycloC6F 10 -- are some examples. Here, -cycloC4F6- means a perfluorocyclobutanediyl group, and a specific example thereof is a perfluorocyclobutane-1,2-diyl group. -cycloC5F8- means a perfluorocyclopentanediyl group, and a specific example thereof is a perfluorocyclopentane-1,3-diyl group. 10 "-" means a perfluorocyclohexanediyl group, and a specific example thereof is a perfluorocyclohexane-1,4-diyl group.

[0020] The repeat number m of (OX) is an integer of 2 or more, preferably an integer of 2 to 200, more preferably an integer of 5 to 150, further preferably an integer of 5 to 100, and particularly preferably an integer of 10 to 50.

[0021] The main chain repeat structure is (OX) m may contain only one type of (OX), or may contain two or more types of (OX). The bonding order of two or more types of (OX) is not limited, and may be arranged randomly, alternately, or in blocks. Containing two or more types of (OX) means that in a compound, there are two or more types of (OX) with different numbers of carbon atoms, there are two or more types of (OX) with different positions of hydrogen atoms, and / or there are two or more types of (OX) that have the same number of carbon atoms but have different presence or absence of side chains or different types of side chains (number of side chains, number of carbon atoms in the side chain, etc.). For the arrangement of two or more (OX), for example, {(OCF2) m21 (OCF2CF2) m22 The structure represented by} indicates that m21 (OCF2) and m22 (OCF2CF2) are randomly arranged. m25 The structure represented by the formula (1) represents that m25 (OCF2CF2) and m25 (OCF2CF2CF2CF2) are arranged alternately.

[0022] (OX) m As an example, [(OCH ma F (2-ma) ) m11 ·(OC2H mb F (4-mb) ) m12 ·(OC3H mc F (6-mc) ) m13 ·(OC4H md F (8-md) ) m14 ·(OC5H me F (10-me) ) m15 ·(OC6H mf F (12-mf) ) m16 (O-cycloC4H mg F (6-mg) ) m17 (O-cycloCH mh F (8-mh) ) m18 (O-cycloCH miF (10-mi) ) m19 ] is preferred. Where -cycloCH mg F (6-mg) represents a fluorocyclobutanediyl group, and preferably a fluorocyclobutane-1,2-diyl group. mh F (8-mh) represents a fluorocyclopentanediyl group, and preferably a fluorocyclopentane-1,3-diyl group. mi F (10-mi) represents a fluorocyclohexanediyl group, and is preferably a fluorocyclohexane-1,4-diyl group. ma is 0 or 1, mb is an integer from 0 to 3, mc is an integer from 0 to 5, md is an integer from 0 to 7, me is an integer from 0 to 9, mf is an integer from 0 to 11, mg is an integer from 0 to 5, mh is an integer from 0 to 7, and mi is an integer from 0 to 9. m11, m12, m13, m14, m15, m16, m17, m18 and m19 each independently represent an integer of 0 or more and preferably 100 or less. m11+m12+m13+m14+m15+m16+m17+m18+m19 is an integer of 2 or more, preferably an integer of 2 to 200, more preferably an integer of 5 to 150, still more preferably an integer of 5 to 100, and particularly preferably an integer of 10 to 50. Among them, m12 is preferably an integer of 2 or more, and an integer of 2 to 200 is particularly preferable. Also, C3H mc F (6-mc) , C4H md F (8-md) , C5H me F (10-me) and C6H mf F (12-mf) may be linear or branched, and is preferably linear.

[0023] In addition, m11 (OCH ma F (2-ma) ), m12 pieces (OC2H mb F (4-mb) ), m13 (OC3H mc F(6-mc) ), m14 (OC4H md F (8-md) ), m15 (OC5H me F (10-me) ), m16 (OC6H mf F (12-mf) ), m17 (O-cycloC4H mg F (6-mg) ), m18 (O-cycloCH mh F (8-mh) ), m19 (O-cycloCH mi F (10-mi) ) may be joined in any order. If m11 is 2 or more, multiple (OCH ma F (2-ma) ) may be the same or different. If m12 is 2 or more, multiple (OC2H mb F (4-mb) ) may be the same or different. If m13 is 2 or more, multiple (OC3H mc F (6-mc) ) may be the same or different. If m14 is 2 or more, multiple (OC4H md F (8-md) ) may be the same or different. If m15 is 2 or more, multiple (OC5H me F (10-me) ) may be the same or different. If m16 is 2 or more, multiple (OC6H mf F (12-mf) ) may be the same or different. When m17 is 2 or more, multiple (O-cycloC4H mg F (6-mg) ) may be the same or different. When m18 is 2 or more, multiple (O-cycloCH mh F (8-mh) ) may be the same or different. When m19 is 2 or more, multiple (O-cycloCH mi F (10-mi) ) may be the same or different.

[0024] (OX) m It is preferable that the compound has any one of the following structures: {(OCF2) m21 (OCF2CF2) m22}, (OCF2CF2) m23 , (OCF2CF2CF2) m24 , (OCF2CF2-OCF2CF2CF2CF2) m25 , {(OCF2CF2CF2CF2CF2) m26 (OCF2) m27}, {(OCF2CF2CF2CF2CF2) m26 (OCF2CF2) m27}, {(OCF2CF2CF2CF2CF2CF2) m26 (OCF2) m27}, {(OCF2CF2CF2CF2CF2CF2) m26 (OCF2CF2) m27}, (OCF2CF2CF2CF2CF2-OCF2) m28 , (OCF2CF2CF2CF2CF2-OCF2CF2) m28 , (OCF2CF2CF2CF2CF2CF2CF2-OCF2) m28 , (OCF2CF2CF2CF2CF2CF2-OCF2CF2) m28 , (OCF2-OCF2CF2CF2CF2CF2) m28 , (OCF2-OCF2CF2CF2CF2CF2CF2) m28 , (OCF2CF2-OCF2CF2CF2CF2CF2) m28 , (OCF2CF2-OCF2CF2CF2CF2CF2CF2) m28 . Here, m21 is an integer of 1 or more, m22 is an integer of 1 or more, m21+m22 is an integer of 2 to 500, m23 and m24 are each independently an integer of 2 to 500, m25 is an integer of 1 to 250, m26 and m27 are each independently an integer of 1 or more, m26+m27 is an integer of 2 to 500, and m28 is an integer of 1 to 250.

[0025] (OX) m More preferably, it has any one of the following structures: {(OCF2) m21 (OCF2CF2) m22}, (OCF2CF2CF2) m24 , (OCF2CF2)2{(OCF2) m21 (OCF2CF2) m22-2}, (OCF2CF2-OCF2CF2CF2CF2) m25-1 OCF2CF2, (OCF2CF2CF2CF2CF2-OCF2) m28 , (OCF2CF2CF2CF2CF2CF2CF2-OCF2) m28 , (OCF2CF2-OCF2CF2CF2CF2CF2) m28-1 OCF2CF2, (OCF2CF2-OCF2CF2CF2CF2CF2CF2) m28-1 OCF2CF2. However, the numbers m22, m25 and m28 are selected so that m22-2, m25-1 and m28-1 are integers of 1 or greater. Among these, (OX) m is {(OCF2) m21 (OCF2CF2) m22} is preferable because compound (1) and compound (2) can be separated from the mixture with higher purity. {(OCF2) m21 (OCF2CF2) m22In the formula}, m22 / m21 is preferably from 0.1 to 10, more preferably from 0.2 to 5.0, further preferably from 0.2 to 2.0, particularly preferably from 0.2 to 1.5, and most preferably from 0.2 to 0.85.

[0026] (OX) m The number average molecular weight is preferably from 1,000 to 20,000, more preferably from 2,000 to 15,000, and particularly preferably from 2,500 to 10,000.

[0027] Z is a linking group having a valence of (n1+1), (n2+1), or (n3+1). n1, n2, and n3 are each independently an integer of 1 to 10. Thus, examples of Z include linking groups having a valence of 2 to 11. Z preferably has at least one branch point (hereinafter referred to as "branch point P") selected from the group consisting of C, N, Si, a ring structure, and an (n1+1)-, (n2+1)-, or (n3+1)-valent organopolysiloxane residue.

[0028] The ring structure is preferably one selected from the group consisting of a 3- to 8-membered aliphatic ring, a 3- to 8-membered aromatic ring, a 3- to 8-membered heterocycle, and a fused ring consisting of two or more of these rings, and the ring structure shown in the following formula is particularly preferable. The ring structure may have a substituent such as a halogen atom, an alkyl group (which may contain an ethereal oxygen atom between carbon atoms), a cycloalkyl group, an alkenyl group, an allyl group, an alkoxy group, or an oxo group (=O).

[0029] [ka]

[0030] Specific examples of the (n1+1)-, (n2+1)-, or (n3+1)-valent organopolysiloxane residue include the following groups. However, R in the following formula 5 R is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group. 5The alkyl group and alkoxy group preferably have 1 to 10 carbon atoms, and particularly preferably 1 carbon atom.

[0031] [ka]

[0032] Z is an alkylene group, a fluoroalkylene group, a hydroxyalkylene group, an alkoxyalkylene group, a carbonyl group, an amide bond, an ether bond, a thioether bond, a urea bond, a urethane bond, a carbonate bond, an ester bond, -SONR 6 -, -Si(R 6 )2-, -OSi(R 6 )2-, -Si(CH3)2-Ph-Si(CH3)2-, and a divalent organopolysiloxane residue may have a group containing one or more selected from the group consisting of: -Si(CH3)2-Ph-Si(CH3)2-, and a divalent organopolysiloxane residue. However, R 6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and Ph is a phenylene group. 6 The number of carbon atoms in the alkyl group is preferably 1 to 3, and particularly preferably 1 or 2, from the viewpoint of ease of production of the compound. In addition, in the case of formula (1), each bond or group constituting Z may have either end located on the A side. For example, in the case of an amide bond, the carbon atom may be located on the A side, or the nitrogen atom may be located on the A side. The same applies to other bonds and groups.

[0033] Specific examples of the divalent organopolysiloxane residue include groups of the following formula: 7 R is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group. 7 The alkyl group and alkoxy group preferably have 1 to 10 carbon atoms, and particularly preferably 1 carbon atom.

[0034] [ka]

[0035] Z is -C(O)NR 6 -, -C(O)-, -C(O)O-, -NR 6 It is also preferred that the aryl group has at least one bond selected from the group consisting of - and -O-, and is preferably -C(O)NR 6 It is particularly preferable to have - since this allows compound (1) and compound (2) to be separated with higher purity.

[0036] Z may be a combination of two or more divalent hydrocarbon groups and one or more branch points P, or a combination of two or more divalent hydrocarbon groups, one or more branch points P, and one or more bonds B. Specific examples of the divalent hydrocarbon group include divalent aliphatic hydrocarbon groups (alkylene groups, cycloalkylene groups, etc.) and divalent aromatic hydrocarbon groups (phenylene groups, etc.). The number of carbon atoms in the divalent hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.

[0037] Z in formula (1) may be a group g2-1 (where d1+d3=1 (i.e., d1 or d3 is 0), n1=d2+d4, d2+d4≧1), a group g2-2 (where e1=1, n1=e2, e2≧1), a group g2-3 (where n1=2), a group g2-4 (where h1=1, n1=h2, h2≧1), a group g2-5 (where i1=1, n1=i2, i2≧1), a group g2-6 (where n1=1), a group g2-7 (where n1=i3+1, i3≧1), a group g2-8 (where n1=i4, i4≧1), or a group g2-9 (where n1=i5, i5≧1), as described below.

[0038] In formula (2), Z is independently a group g2-1 (wherein n2=d2+d4, n3=d2+d4), a group g2-2 (wherein e1=1, n2=e2, n3=e2), a group g2-3 (wherein n2=2, n3=2), a group g2-4 (wherein h1=1, n2=h2, n3=h2), a group g2 -5 (wherein i1=1, n2=i2, n3=i2), a group g2-6 (wherein n2=1, n3=1), a group g2-7 (wherein n2=i3+1, n3=i3+1), a group g2-8 (wherein n2=i4, n3=i4), or a group g2-9 (wherein n2=i5, n3=i5).

[0039] [ka]

[0040] (-A 1 -) e1 C(R e2 ) 4-e1-e2 (-Q 22 -) e2 Formula (g2-2) -A 1 -N(-Q 23 -)2 formula (g2-3) (-A 1 -) h1 Z 1 (-Q 24 -) h2 Formula (g2-4) (-A 1 -) i1 Si(R e3 ) 4-i1-i2 (-Q 25 -) i2 Formula (g2-5) -A 1 -Q 26 - Formula (g2-6) -A 1 -CH(-Q 22 -)-Si(R e3 ) 3-i3 (-Q 25 -) i3 Formula (g2-7) -A 1-[CH2C(R e4 )(-Q 27 -)] i4 -R e5 Formula (g2-8) -A 1 -Z a (-Q 28 -) i5 Formula (g2-9)

[0041] However, in formulas (g2-1) to (g2-9), A 1 (OX) m Connect to the Q side. 22 , Q 23 , Q 24 , Q 25 , Q 26 , Q 27 and Q 28 connects to the R side.

[0042] A 1 is a single bond, an alkylene group, or an alkylene group with two or more carbon atoms that has -C(O)NR 6 -, -C(O)-, -OC(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -, -O-, -SO2NR 6 -or-N(R 6 )SO2- or -C(O)NR at the end of the alkylene group not connected to A (opposite to A). 6 -, -C(O)-, -OC(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -, -O-, -SO2NR 6 -or-N(R 6 ) a group having SO2-, 1 If there are two or more, then there are two or more A 1 may be the same or different. A hydrogen atom of the alkylene group may be substituted with a fluorine atom. Q 11 is a single bond, -O-, an alkylene group, or -C(O)NR between carbon atoms of an alkylene group having two or more carbon atoms. 6 -, -C(O)-, -NR 6 - or a group having -O-. Q 22 is an alkylene group, an alkylene group having 2 or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or -O-, -C(O)NR at the terminal of the A side of the alkylene group 6 -, -C(O)-, -NR 6 - or -O-, or -C(O)NR between carbon atoms of an alkylene group having two or more carbon atoms 6 -, -C(O)-, -NR 6 - or -O- and -C(O)NR at the end of the A side 6 -, -C(O)-, -NR 6 - or -O-, 22 If there are two or more, then there are two or more Q 22 may be the same or different. Q 23 is an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or -O-, and two Q 23 may be the same or different. Q 24 is an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or -O-, 24 If there are two or more, then there are two or more Q 24 may be the same or different. Q 25 is an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or -O-, 25 If there are two or more, then there are two or more Q 25 may be the same or different. Q 26is an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or a group having -O-. R 6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. Q 27 is a single bond or an alkylene group. Q 28 is an alkylene group, or a group having an ether oxygen atom or a divalent organopolysiloxane residue between carbon atoms in an alkylene group having two or more carbon atoms.

[0043] Z 1 A 1 has a carbon atom or a nitrogen atom to which Q is directly bonded, 24 is a group having an h1+h2 valent ring structure having a carbon atom or nitrogen atom to which is directly bonded.

[0044] R e1 is a hydrogen atom or an alkyl group, and in each formula, R e1 If there are two or more, there are two or more R e1 may be the same or different. R e2 is a hydrogen atom, a hydroxyl group, an alkyl group, or an acyloxy group. R e3 is an alkyl group. R e4 is a hydrogen atom or an alkyl group, and is preferably a hydrogen atom in terms of ease of production of the compound. e4 If there are two or more, there are two or more R e4 may be the same or different. R e5 is a hydrogen atom or a halogen atom, and is preferably a hydrogen atom in terms of ease of production of the compound.

[0045] d1 is an integer of 0 to 3, and preferably 1 or 2. d2 is an integer of 0 to 3, and preferably 1 or 2. d1+d2 is an integer of 1 to 3. d3 is an integer of 0 to 3, and preferably 0 or 1. d4 is an integer of 0 to 3, and preferably 2 or 3. d3+d4 is an integer of 1 to 3. d1+d3 is 1. In Z of formula (1), d2+d4 is an integer of 1 to 5, preferably 4 or 5, and in Z of formula (2), d2+d4 is an integer of 1 to 5, preferably 3 to 5, particularly preferably 4 or 5. e1+e2 is 3 or 4. e1 is 1. e2 is 1 to 3, preferably 2 or 3, in Z of formula (1), and is 1 to 3, preferably 2 or 3, in Z of formula (2). h1 is 1. h2 is an integer of 1 or more (preferably 2 or 3). i1+i2 is 2 to 4 (preferably 3 or 4). i1 is 1. i2 is an integer of 1 to 3 (preferably 2 or 3). i3 is an integer of 0 to 3, preferably 1 to 3, and particularly preferably 2 or 3. i4 is 1 or more in Z of formula (1) (preferably an integer from 2 to 10, particularly preferably an integer from 2 to 6), and is 1 or more in Z of formula (2) (preferably an integer from 1 to 10, particularly preferably an integer from 1 to 6). i5 is 1 or more (preferably an integer from 2 to 7).

[0046] Q 22 , Q 23 , Q 24 , Q 25 , Q 26 , Q 27 , Q 28 The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4. However, the lower limit of the number of carbon atoms in the alkylene group in the case where the alkylene group has a specific bond between carbon atoms is 2.

[0047] Z 1 The ring structure in the formula (I) is the same as that described above, and the preferred forms are also the same. 1 The ring structure in 1 Or Q 24is directly bonded to the ring structure, for example, an alkylene group is connected to the alkylene group, and A 1 Or Q 24 are never linked. Z a is an organopolysiloxane residue having a valence of (i5+1), and is preferably any one of the following groups. a is an alkyl group (preferably having 1 to 10 carbon atoms) or a phenyl group.

[0048] [ka]

[0049] R e1 , R e2 , R e3 or R e4 The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms. R e2 The alkyl group portion of the acyloxy group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms. h1 is preferably 1 to 6, more preferably 1 to 4, further preferably 1 or 2, and particularly preferably 1. h2 is preferably 2 to 6, more preferably 2 to 4, and particularly preferably 2 or 3.

[0050] Other forms of Z in formula (1) include the following group g3-1 (where d1+d3=1 (i.e., d1 or d3 is 0), n1=d2×r1+d4×r1), group g3-2 (where e1=1, n1=e2×r1), group g3-3 (where n1=2×r1), group g3-4 (where h1=1, n1=h2×r1), group g3-5 (where i1=1, n1=i2×r1), group g3-6 (where g1=r1), group g3-7 (where n1=r1×(i3+1)), group g3-8 (where n1=r1×i4), and group g3-9 (where n1=r1×i5). Other forms of Z in formula (2) include a group g3-1 (where n2=d2×r1+d4×r1, n3=d2×r1+d4×r1), a group g3-2 (where n2=e2×r1, n3=e2×r1), a group g3-3 (where n2=2×r1, n3=2×r1), a group g3-4 (where n2=h2×r1, n3=h2×r1), a group g3-5 (where n2=h2×r1, n3=h2×r1), a group g3-6 (where n2=h2×r1, n3=h2×r1), a group g3-7 (where n2=h2×r1, n3=h2×r1), a group g3-8 (where n2=h2×r1, n3=h2×r1), a group g3-9 (where n2=h2×r1, n3=h2×r1), a group g3-10 (where n2=h2×r1, n3=h2×r1), a group g3-11 (where n2=h2×r1, n3=h2×r1), a group g3-12 (where n2=h2×r1, n3=h2×r1), a group g3-13 (where n2=h2×r1, n3=h2×r1), a group g3-14 (where n2=h2×r1, n3=h2×r1), a group g3-15 (where n2=h2×r1, n3=h2×r1), a group g3-16 (where n2=h2×r1, n3=h2×r1), a group g3-17 (where n2=h2×r1, n3=h2×r1), a group g3-18 (where n2=h2×r1, n3=h2×r1), a group g3-19 (where n2=h2 where n2=i2×r1, n3=i2×r1), group g3-6 (where n2=r1, n3=r1), group g3-7 (where n2=r1×(i3+1), n3=r1×(i3+1)), group g3-8 (where n2=r1×i4, n3=r1×i4), and group g3-9 (where n2=r1×i5, n3=r1×i5).

[0051] [ka]

[0052] (-A 1 -) e1 C(R e2 ) 4-e1-e2 (-Q 22 -G 1 ) e2 Formula (g3-2) -A 1 -N(-Q 23 -G 1 )2 formula (g3-3) (-A 1 -) h1 Z 1 (-Q 24 -G 1 ) h2 Formula (g3-4) (-A 1 -) i1 Si(R e3 ) 4-I1-I2 (-Q 25 -G 1 ) i2 Formula (g3-5) -A 1 -Q 26 -G 1 Formula (g3-6) -A 1 -CH(-Q 22 -G1 )-Si(R e3 ) 3-i3 (-Q 25 -G 1 ) i3 Formula (g3-7) -A 1 -[CH2C(R e4 )(-Q 27 -G 1 )] i4 -R e5 Formula (g3-8) -A 1 -Z a (-Q 28 -G 1 ) i5 Formula (g3-9)

[0053] However, in formulas (g3-1) to (g3-9), A 1 (OX) m Connect to the G side. 1 connects to side A.

[0054] G 1 is a group g3, and in each formula, G 1 If there are two or more, there are two or more G 1 may be the same or different. G 1 The symbols other than are the same as those in formulas (g2-1) to (g2-9). -Si(R 8 ) 3-r1 (-Q 3 -) r1 Formula (g3) However, in formula (g3), Si is Q 22 , Q 23 , Q 24 , Q 25 , Q 26 , Q 27 and Q 28 Connect to the Q side. 3 connects to side A. R 8 is an alkyl group. 3 is an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or -O-, and two or more Q3 may be the same or different. r1 is 2 or 3. R 6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.

[0055] Q 3 The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4. However, the lower limit of the number of carbon atoms in the alkylene group in the case where the alkylene group has a specific bond between carbon atoms is 2. R 8 The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms. R 9 The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms. R 9 The alkoxy group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms. p is preferably 0 or 1.

[0056] R is -OH, -CR 1 =CR 2 R 3 , -CH3, -NH2, -SH, -Ph (phenyl group), -F, -Cl, -Br, -I, -C≡CH, and -N3. R 1 is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group, R 2 and R 3 are each independently a hydrogen atom or a fluorine atom. -CR 1 =CR 2 R 3 Specific examples of the group represented by the formula include -CH=CH2, -C(CH3)=CH2, -C(CF3)=CH2, -CF=CH2, -CH=CHF, -CF=CHF, -CH=CF2, and -CF=CF2. As R, -OH and -NH2 are preferable since they allow compound (1) and compound (2) to be separated with higher purity.

[0057] n1, which indicates the number of functional groups R at one end of compound (1), n2, which indicates the number of functional groups R at one end of compound (2), and n3, which indicates the number of functional groups R at the other end, each represent an integer of 1 to 10, and it is preferable that all represent the same integer. Each of n1, n2 and n3 is preferably 1.

[0058] Z in formula (1) and formula (2) is preferably an alkylene group which may have -O-, -C(O)O- or -C(O)-, or a group g2-2. A hydrogen atom of the alkylene group may be substituted with a fluorine atom or a hydroxyl group. The number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 6. Specific examples of the alkylene group which may have -O-, -C(O)O- or -C(O)- include an -alkylene group -C(O)O- and an -alkylene group -C(O)-. -OZ-(R) in formula (1) and formula (2) n1 , -OZ-(R) n2 , and -OZ-(R) n3 A preferred example of the group is -O-(CF2) n4 -CH2OH, -O-(CF2) n4 -C(OH)(CH2CH=CH2)2, -O-(CF2) n4 -COOCH3, -O-(CF2) n4 -CH2OC(=O)C(CH2CH=CH2)3, -O-(CF2) n4 -CONHC(=O)H2C(CH2CH=CH2)3, -O-(CF2) n4 -CONH2, -O-(CF2) n4 -CH2NHCOC(CH2CH=CH2)3. n4 is an integer of 1 or more, preferably 1 to 6, and particularly preferably 1 to 3.

[0059] (Chromatographic separation method) The chromatography in the separation method of the present invention is not particularly limited as long as it uses a stationary phase and a mobile phase, and known chromatography can be used, for example, column chromatography and thin layer chromatography. Column chromatography is preferably used, and flash column chromatography or high performance liquid chromatography (HPLC) is particularly preferably used.

[0060] (stationary phase) The stationary phase is preferably selected from the group consisting of aluminum oxide, silica gel, magnesium oxide, aluminum silicate, magnesium silicate, chemically modified silica gel and diatomaceous earth.

[0061] As the stationary phase, silica gel is more preferable. Specific examples of silica gel include unmodified silica gel, amino group-containing silica gel, and cyano group-containing silica gel.

[0062] Commercially available silica gel can be used, such as Chromatorex PSQ-100B (product name of Fuji Silysia Chemical), Wakogel C-200 (product name of Wako Pure Chemical Industries, Ltd.), and 115111 Silica Gel 60 (product name of Merck).

[0063] The amount of stationary phase used is appropriately selected depending on the compound to be separated, the mobile phase to be used, the type of chromatography, etc. Preferably, the amount used is equal to or greater than the mass of the mixture to be separated. Also, when the molecular weight of the compound to be separated is relatively small, it is preferable to use a larger amount of stationary phase.

[0064] (mobile phase) The mobile phase contains the specific solvents shown below. Examples of specific solvents include (non-cyclic) hydrofluoroolefins (hereinafter also referred to as HFOs), (non-cyclic) hydrochlorofluoroolefins (hereinafter also referred to as HCFOs), (non-cyclic) chlorofluoroolefins (hereinafter also referred to as CFOs), cyclic hydrofluoroolefins (hereinafter also referred to as cyclic HFOs), cyclic hydrochlorofluoroolefins (hereinafter also referred to as cyclic HCFOs), cyclic chlorofluoroolefins (hereinafter also referred to as cyclic CFOs), cyclic hydrofluorocarbons (hereinafter also referred to as cyclic HFCs), cyclic hydrochlorofluorocarbons (hereinafter also referred to as cyclic HCFCs), cyclic chlorofluorocarbons (hereinafter also referred to as CFCs), and perfluoroketones (hereinafter also referred to as PFKs). Of these, one type may be used, or two or more types may be used in combination.

[0065] Examples of HFOs include CF3CH2CF=CH2, CF3CH=CHCF3(E), and CF3CH=CHCF3(Z).

[0066] Examples of HCFOs include CF3CF=CCl2, CFCl2CF=CF2, CHF2CF=CHCl, CF3CH=CHCl(Z), CF3CH=CHCl(E), CClF2CF=CHCl, and CHF2CF2CF2CF=CHCl. Examples of CFO include CF3CF=CCl2 and CFCl2CF=CF2.

[0067] Examples of the cyclic CFO include those represented by the following formula: [ka]

[0068] Examples of cyclic HFCs include those represented by the following formula: [ka]

[0069] Examples of PFK include CF3CF2COCF(CF3)2, (CF3)2CFCOCF(CF3)2, and CF3CF2CF2OCFCF3COCF(CF3)2.

[0070] The specific solvent is preferably one that does not contain chlorine atoms because it does not adversely affect the global environment. Specifically, HFO, cyclic HFO, cyclic HFC, or PFK is preferred. Furthermore, as the specific solvent, HFO, HCFO, CFO, cyclic HFO, cyclic HCFO, cyclic CFO, cyclic HFC, cyclic HCFC, or cyclic CFC is preferable since it enables separation of compound (1) and compound (2) with higher purity, and HFO, CFO, cyclic HFO, cyclic CFO, cyclic HFC, or cyclic CFC is more preferable, and HFO, cyclic HFO, or cyclic HFC is particularly preferable.

[0071] The mobile phase may contain other solvents in addition to the specific solvent, such as hydrocarbons, ethers, ketones, esters, chlorinated hydrocarbons, and fluorine-containing ethers. Examples of the hydrocarbon include pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, and xylene. Examples of the ether include diethyl ether and tetrahydrofuran. Ketones include acetone and 2-butanone. The esters include ethyl acetate and the like. Chlorinated hydrocarbons include methylene chloride and the like. Examples of fluorine-containing ethers include CF3CH2OCF2CF2H, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, and 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-trifluoromethyl-pentane. The other solvent may be mixed with the specific solvent and used as a single phase, or the specific solvent may be combined with the other solvent and used as a gradient elution method.

[0072] The separation method of the present invention includes a step of adsorbing a mixture onto a stationary phase. The method for adsorbing a mixture onto a stationary phase is not particularly limited, and may be a method commonly used in chromatography. When column chromatography is used as the chromatography, the mixture is supplied directly or in a mixture with a solvent onto a stationary phase packed in a column, and the mixture is adsorbed onto the stationary phase. In this case, the solvent used is preferably the specific solvent used as the mobile phase.

[0073] Next, a step of passing a mobile phase containing a specific solvent through the stationary phase to which the mixture is adsorbed is performed. When column chromatography is used as the chromatography, a solvent as a mobile phase is injected from the top of the column, and the mobile phase containing the specific solvent is passed through the stationary phase to which the mixture is adsorbed.

[0074] When a mobile phase containing a specific solvent is passed through the mixture, the monofunctional compound (1) is eluted first from the mixture adsorbed on the stationary phase. Therefore, compound (1) in the mixture can be separated. When column chromatography is used as the chromatography, highly pure compound (1) can be obtained by collecting the fraction obtained from the bottom of the column.

[0075] Next, when a mobile phase containing a specific solvent is passed through the column, the bifunctional compound (2) from the mixture adsorbed on the stationary phase is eluted. Therefore, compound (2) in the mixture can be separated. By collecting the fraction obtained from the bottom of the column, compound (2) in high purity can be obtained. In order to elute compound (2), the type of the specific solvent used in the mobile phase may be changed.

[0076] In the separation method of the present invention, the temperature of the stationary phase when separating the compounds is preferably −10° C. to 100° C., more preferably 5° C. to 50° C., and further preferably 10° C. to 40° C. The temperature of the stationary phase is often room temperature (25° C.).

[0077] In the separation method of the present invention, the mixture containing compound (1) and compound (2) may further contain the following zero-functional compound (3). A-(OX) m -OA formula (3) Here, A, X, and m are the same as in formula (1) and formula (2). When the mixture contains compound (3), the ratio of compound (1), compound (2), and compound (3) contained in the mixture is not particularly limited, and the ratio (by mass) of compound (1) / compound (2) / compound (3) is, for example, 1-95 / 1-95 / 1-95.

[0078] When the mixture further contains compound (3), the compound (3) with zero functionality is eluted before the compound (1) with one functionality is eluted from the mixture adsorbed on the stationary phase, and therefore compound (3) in the mixture can be separated.

[0079] In the separation method of the present invention, when column chromatography is used as the chromatography, it is preferable to pressurize the inside of the column with an inert gas such as nitrogen, argon, etc. The pressure (gauge pressure) during pressurization is preferably 0.1 MPa to 1.0 MPa, and particularly preferably 0.1 MPa to 0.5 MPa. EXAMPLES

[0080] The present invention will be described in detail below with reference to examples. Examples 1 to 32 are working examples, and Examples 33 to 37 are comparative examples. However, the present invention is not limited to these examples. The content (%) of each component in Table 1 described later is based on mass. The structures of the fluorine-containing compounds used in the examples are as shown below. ( CF 2 CF 2 O-CF 2 CF 2 CF 2 CF 2 O) x Tie 0 functional group: CF3-O-(CF2CF2O-CF2CF2CF2CF2O) x1 -CF3 Monofunctional: CF3-O-(CF2CF2O-CF2CF2CF2CF2O) x2 -CF2CF2OCF2CF2CF2-X Bifunctional: X-CF2CF2CF2OCF2CF2-(CF2CF2OCF2CF2CF2CF2CF2O) x3 -CF2CF2OCF2CF2CF2-X X is a terminal functional group, the mass average molecular weight of the structure other than X is 4800, and the repeating units: x1, x2 = 14.5. ( CF 2 O) n · (CF 2 CF 2 O) m Tie 0 functional group: CF3-O-(CF2O) n (CF2CF2O) m -CF3 Monofunctional: CF3-O-(CF2O) n (CF2CF2O) m -X Bifunctional X-(CF2O) n (CF2CF2O) m -X X is a terminal functional group, the mass average molecular weight of the structure other than X is 4500, and the repeating units are n=25 and m=22.

[0081] [Synthesis of fluorine-containing compounds] [Synthesis Example 1] Synthesis example 1-1 The following compound (A-1) was obtained by the method described in Example 7 of WO 2013 / 121984. CF3O-(CF2CFHO-CF2CF2CF2CH2O) a1 -H: A-1 Repeating unit: a1=14.5

[0082] Synthesis example 1-2 In a 200 mL three-neck flask, 30 g of compound (A-1), 1 g of 48% KOH solution, 1.1 g of water, and 0.55 g of tert-butyl alcohol were mixed at 80° C. for 10 minutes. 2.4 g of perfluoropropyl vinyl ether was added dropwise to the resulting mixture and mixed at 80° C. for 4 hours. After cooling the mixture to room temperature, AC-2000 (CF 13 60 g of HCl (H: manufactured by AGC) was added, and 6.5 g of 2N hydrochloric acid was added dropwise in an ice bath. The mixture was transferred to a 200 mL separatory funnel and allowed to stand for 1 hour. The lower phase was removed and placed in a new 200 mL separatory funnel, and 87 g of water was added and stirred. After allowing to stand for 1 hour, the lower phase was collected and concentrated to obtain the following compound (A-2). CF3O-(CF2CFHO-CF2CF2CF2CH2O) a2 -CF2CF2CF3: A-2 Repeating unit a2=14.5

[0083] Synthesis Example 1-3 An autoclave (made of nickel, internal volume 500 mL) was prepared, and a cooler maintained at 0°C, a NaF pellet packed bed, and a cooler maintained at -10°C were installed in series at the gas outlet of the autoclave. In addition, a liquid return line was installed to return the coagulated liquid from the cooler maintained at -10°C to the autoclave. 312 g of R-113 (CF2ClCFCl2) was charged into the autoclave and stirred while maintaining the temperature at 25° C. Nitrogen gas was blown into the autoclave at 25° C. for 1 hour, and then 20% fluorine gas was blown into the autoclave at a flow rate of 2.0 L / hour for 1 hour at 25° C. Next, while blowing in 20% fluorine gas at the same flow rate, a solution in which 8.4 g of compound (A-2) was dissolved in 84 g of R-113 was injected into the autoclave over 3.6 hours. Next, while blowing in 20% fluorine gas at the same flow rate, the internal pressure of the autoclave was increased to 0.15 MPa (gauge pressure). 9 mL of a benzene solution containing 0.015 g / mL of benzene in R-113 was injected into the autoclave while heating it from 25°C to 40°C, and the benzene solution injection port of the autoclave was closed. After stirring for 15 minutes, 6 mL of the benzene solution was again injected while maintaining the temperature at 40°C, and the injection port was closed. The same operation was repeated three more times. The total amount of benzene injected was 0.33 g. Further, 20% fluorine gas was blown into the autoclave at the same flow rate while stirring for 1 hour. Then, the pressure inside the autoclave was adjusted to atmospheric pressure, and nitrogen gas was blown in for 1 hour. The contents of the autoclave were concentrated with an evaporator to obtain 8.8 g of the following 0-functional compound (A-3). CF3O-(CF2CF2O-CF2CF2CF2CF2O) a3 -CF2CF2O-CF2CF2CF2-CF2-O-CF2CF2CF3: A-3 Repeating unit a3=14.5

[0084] Synthesis Example 1-4 The following monofunctional compound (B-1) was obtained by the method described in Example 7 of WO 2013 / 121984. CF3O-(CF2CF2O-CF2CF2CF2CF2O) b1 -CF2CF2O-CF2CF2CF2-CH2OH : (B-1) Repeating unit b1=14.5

[0085] Synthesis Example 1-5 In a 200 mL eggplant flask, 16.2 g of HOCH2CF2CF2CH2OH and 13.8 g of potassium carbonate were placed and stirred at 120°C, and 278 g of compound (A-1) obtained in Synthesis Example 1-1 was added and stirred at 120°C for 2 hours. The temperature in the eggplant flask was brought to 25°C, and 50 g each of AC-2000 and hydrochloric acid were added, separated, and the organic phase was concentrated. The resulting reaction crude liquid was purified by silica gel column chromatography to obtain 117.7 g of the following compound (C-1). [ka] Repeating unit x1+x2=13.5

[0086] Synthesis Example 1-6 In a 50 mL eggplant flask, 20 g of compound (C-1), 7.1 g of sodium fluoride powder, 20 g of AC-2000, and 20 g of CF3CF2CF2OCF(CF3)COF were added. Then, the mixture was stirred at 50°C for 24 hours under a nitrogen atmosphere. After the temperature inside the eggplant flask was brought to 25°C, the sodium fluoride powder was removed by filtration. Excess CF3CF2CF2OCF(CF3)COF and AC-2000 were distilled off under reduced pressure to obtain 24 g of the following compound (C-2). [ka] Repeating unit x1+x2=13.5

[0087] Synthesis Example 1-7 250 mL of ClCF2CFClCF2OCF2CF2Cl (hereinafter referred to as "CFE-419") was placed in a 500 mL metal reactor, and after bubbling with nitrogen gas, 20% by volume of fluorine gas diluted with nitrogen gas was bubbled. The above CFE-419 solution of compound (C-2) (concentration: 10%, compound (C-2): 24 g) was added over 6 hours. The ratio of the introduction rate of fluorine gas (mol / hour) to the introduction rate of hydrogen atoms in compound (C-2) (mol / hour) was controlled to be 2:1. After the introduction of compound (C-2) was completed, a CFE-419 solution of benzene (concentration: 0.1%, benzene: 0.1 g) was intermittently added. After the introduction of benzene was completed, fluorine gas was bubbled, and finally the inside of the reactor was sufficiently replaced with nitrogen gas. The solvent was distilled off to obtain 25.3 g of the following compound (C-3). [ka] Repeating unit x=14.5

[0088] Synthesis Example 1-8 In a 50 mL eggplant flask, 25.3 g of compound (C-3), 2.2 g of sodium fluoride, and 25 mL of AC-2000 were placed and the mixture was stirred in an ice bath. 1.7 g of methanol was added to the resulting mixture and stirred at 25°C for 1 hour. After filtering the mixture, the filtrate was purified by silica gel column chromatography. 15 g of the following compound (C-4) was obtained. [ka] Repeating unit x=14.5

[0089] Synthesis Example 1-9 In a 50 mL two-necked eggplant flask, 0.04 g of lithium aluminum hydride was suspended in 1.6 g of THF (tetrahydrofuran). While the mixture was cooled in an ice bath, 6.1 g of the above compound (C-4) was added to AC-6000 (CF 13 A solution diluted with 6.0 g of C2H5 (manufactured by AGC) was slowly added dropwise. The ice bath was then removed, and stirring was continued while slowly raising the temperature to room temperature. After stirring at room temperature for 12 hours, hydrochloric acid solution was added dropwise until the liquid became acidic. 15 mL of AK-225 was added, and the mixture was washed once with water and once with saturated saline, and the organic phase was recovered. The recovered organic phase was concentrated with an evaporator to obtain 5.9 g of the following bifunctional compound (C-5). HO-CH2-CF2CF2CF2O-(CF2CF2O-CF2CF2CF2CF2O) c5 -CF2CF2O-CF2CF2CF2-CH2OH : C-5 Repeating unit x=14.5

[0090] Synthesis Example 1-10 Sample mixtures of Examples 1-16 and 35-37 were prepared by mixing 5 g of the zero-functional compound (A-3), 86 g of the monofunctional compound (B-1), and 9 g of the difunctional compound (C-5).

[0091] [Synthesis Example 2] Synthesis example 2-1 Fomblin M (a product name of Solvay Solexis) was purified by silica gel column chromatography to obtain the following non-functional compound (D-1). CF3-O-(CF2O) n (CF2CF2O) m -CF3: D-1 Repeating unit n=25, m=22

[0092] Synthesis example 2-2 The following compound E-1 was obtained according to the method described in Example 1 of the Examples of WO 2017 / 038830 (specifically, Examples 1-1 to 1-4). CF3CF2CF2OCF2CF2OCF2CF2[(OCF2) n (OCF2CF2) m ]OCF2C(=O)OCH3: E-1 Repeating units n=25, m=21 Next, 2.4 g of sodium borohydride powder was placed in a 300 cc three-neck round-bottom flask, and 15 g of AC-2000 (AGC product name) was added. The mixture was stirred while being cooled in an ice bath, and a solution of 30 g of the above compound E-1, 4 g of methanol, and 60 g of AC-2000 was slowly dripped from the dropping funnel under a nitrogen atmosphere so that the internal temperature did not exceed 10°C. After the entire amount was dripped, 4 g of methanol was further dripped. Then, the mixture was stirred at 10°C for 1 hour. The mixture was cooled again in an ice bath, and an aqueous hydrochloric acid solution was dripped until the liquid became acidic. After the reaction was completed, the mixture was washed once with a hydrochloric acid solution and once with water, and the organic phase was recovered. The collected organic phase was concentrated using an evaporator. The collected concentrated liquid was distilled under reduced pressure and purified using a column to obtain 24 g of the following compound E-2. CF3CF2CF2OCF2CF2OCF2CF2[(OCF2) n (OCF2CF2) m ]OCF2-CH2-OH: E-2 Repeating units n=25, m=21

[0093] Synthesis example 2-3 Fomblin D4000 (product name of Solvay Solexis) was used for purification by silica gel column chromatography to obtain the following bifunctional compound (F-1). HOCH2-(CF2O){(CF2O) n (CF2CF2O) m}-CF2-CH2OH: F-1 Repeating unit n=25, m=22

[0094] Synthesis example 2-4 Mixtures of Examples 17 to 25 were prepared by mixing 15 g of the zero-functional compound (D-1), 55 g of the monofunctional compound (E-2), and 30 g of the difunctional compound (F-1).

[0095] Synthesis example 2-5 A mixture of Example 32 was prepared by mixing 5 g of the zero-functional compound (D-1), 86 g of the monofunctional compound (E-2), and 9 g of the difunctional compound (F-1).

[0096] [Synthesis Example 3] Synthesis example 3-1 The following compound (G-1) was obtained by the method described in Example 6 of WO 2013 / 121984. CF3-O-(CF2CF2O-CF2CF2CF2CF2O) g1 -CF2CF2OCF2CF2CF2C(=O)OCH3: G-1 Repeat unit g1=14.5

[0097] Synthesis example 3-2 A 300mL four-neck flask equipped with a Dimroth, dropping funnel, thermometer, and magnetic stirrer was charged with 40g of compound G-1, 25g of a diethyl ether solution of allyl magnesium bromide (bromo group concentration 0.05mol / 100g), 40g of 1,3-bistrifluoromethylbenzene, and 13g of tetrahydrofuran, and the inside of the flask was replaced with nitrogen. The resulting mixture was reacted at an internal temperature of 60°C for 6 hours while stirring, and then cooled to room temperature (20°C). The mixture was then slowly added to a separatory funnel containing hydrochloric acid (a mixture of 6g of 12N hydrochloric acid and 54g of water), stirred for 30 minutes, and the lower layer was collected. The collected liquid was subjected to removal of the solvent component under conditions of 110°C / 1mmHg, and purified by silica gel column chromatography to obtain 35g of the following monofunctional compound (G-2). CF3O-(CF2CF2O-CF2CF2CF2CF2O) g2 CF2CF2OCF2CF2CF2C(OH)(CH2CH=CH2)2: G-2 Repeating unit g2 = 14.5

[0098] Synthesis example 3-3 A 300mL four-neck flask equipped with a Dimroth, dropping funnel, thermometer, and magnetic stirrer was charged with 40g of compound (C-4), 50g of a diethyl ether solution of allyl magnesium bromide (bromo group concentration 0.05mol / 100g), 40g of 1,3-bistrifluoromethylbenzene, and 13g of tetrahydrofuran, and the inside of the flask was replaced with nitrogen. The resulting mixture was reacted at an internal temperature of 60°C for 6 hours while stirring, and then cooled to room temperature (20°C). The mixture was then slowly added to a separatory funnel containing hydrochloric acid (a mixture of 6g of 12N hydrochloric acid and 54g of water), stirred for 30 minutes, and the lower layer was collected. The collected liquid was subjected to removal of the solvent component under conditions of 110°C / 1mmHg, and purified by silica gel column chromatography to obtain 35g of the following bifunctional compound (H-1). [ka] Repeating unit x=14.5

[0099] Synthesis Example 3-4 A sample mixture of Example 26 was prepared by mixing 5 g of the zero-functional compound (A-3), 86 g of the monofunctional compound (G-2), and 9 g of the difunctional compound (H-1).

[0100] [Synthesis Example 4] Synthesis example 4-1 A sample mixture of Example 27 was prepared by mixing 5 g of the above zero-functional compound A-3, 86 g of the above monofunctional compound (G-1), and 9 g of the above difunctional compound (C-4).

[0101] [Synthesis Example 5] Synthesis example 5-1 0.67g of HO(C=O)C(CH2CH=CH2)3, 33mL of dichloromethane, and 0.67mL of oxalyl chloride were added to a 200cc eggplant flask and stirred under ice cooling, then 0.0393g of DMF (N,N-dimethylformamide) was added. The mixture was then stirred at room temperature and concentrated to obtain 0.6g of Cl(C=O)C(CH2CH=CH2)3. Separately, 7 g of compound B-1, 7 g of AC-6000, 0.4 g of triethylamine, and 0.2 g of N,N-dimethyl-4-aminopyridine were added to a 50 cc recovery flask, and 0.6 g of the above Cl(C=O)C(CH2CH=CH2)3 was further added, and the mixture was stirred at 30° C. The resulting mixture was purified by silica gel column chromatography to obtain 5.8 g of the following monofunctional compound (I-1). CF3O(CF2CF2OCF2CF2CF2CF2O) i1 CF2CF2OCF2CF2CF2-CH2O(C=O)C(CH2CH=CH2)3: I-1 Repeat unit i1=14.5

[0102] Synthesis example 5-2 0.67g of HO(C=O)C(CH2CH=CH2)3, 33mL of dichloromethane, and 0.67mL of oxalyl chloride were added to a 200cc eggplant flask and stirred under ice cooling, then 0.0393g of DMF (N,N-dimethylformamide) was added. The mixture was then stirred at room temperature and concentrated to obtain 0.6g of Cl(C=O)C(CH2CH=CH2)3.

[0103] Synthesis example 5-3 Separately, 3.5 g of compound C-5, 7 g of AC-6000, 0.4 g of triethylamine, and 0.2 g of N,N-dimethyl-4-aminopyridine were added to a 50 cc recovery flask, and 0.6 g of the above Cl(C=O)C(CH2CH=CH2)3 was added, and the mixture was stirred at 30° C. The resulting mixture was purified by silica gel column chromatography to obtain 2.4 g of the following bifunctional compound (J-1). [ka] Repeating unit x = 14.5 (Synthesis Example 8-4)

[0104] Synthesis example 5-4 A sample mixture of Example 28 was prepared by mixing 5 g of the zero-functional compound (A-3), 86 g of the monofunctional compound (I-1), and 9 g of the difunctional compound (J-1).

[0105] [Synthesis Example 6] Synthesis example 6-1 The following monofunctional compound (K-1) was obtained by the method described in Example 11 of WO 2017 / 038830. CF3-O-(CF2CF2O-CF2CF2CF2CF2O) k1 (CF2CF2O)-CF2CF2CF2-C(O)NH-CH2-C(CH2CH=CH2)3: K-1 Repeating unit k1=14.5

[0106] Synthesis example 6-2 In a 50 mL eggplant flask, 15 g of compound (C-4), 3.2 g of H2NCH2C(CH2CH=CH2)3, and 15 mL of AC-2000 were placed, and the mixture was stirred at 0°C for 24 hours. The mixture was purified by silica gel column chromatography. 11.2 g of the following bifunctional compound (L-1) was obtained. [ka] Repeating unit x=14.5

[0107] Synthesis Example 6-3 A sample mixture of Example 29 was prepared by mixing 5 g of the zero-functional compound (A-3), 86 g of the monofunctional compound (K-1), and 9 g of the difunctional compound (L-1).

[0108] [Synthesis Example 7] Synthesis example 7-1 In a 100cc pressure-resistant reactor, 15g of compound G-1, 50g of Asahiklin AK-225 (AGC product name), and 7.5g of 2.0M ammonia-methanol solution were placed, and the mixture was stirred at room temperature for 6 hours. After that, the solvent was distilled off from the mixture, and 14.8g of the desired monofunctional compound (M-1) was obtained. CF3(OCF2CF2OCF2CF2CF2CF2) m1 OCF2CF2OCF2CF2CF2-C(=O)NH2: M-1 Repeating unit m1 = 14.5

[0109] Synthesis Example 7-2 15g of compound C-4, 50g of Asahiklin AK-225 (AGC product name), and 15g of 2.0M ammonia-methanol solution were placed in a 100cc pressure reactor, and the mixture was stirred at room temperature for 6 hours. After that, the solvent was distilled off from the mixture, and 14.8g of the desired bifunctional compound (N-1) was obtained. [ka] Repeating unit x=14.5

[0110] Synthesis Example 7-3 A sample mixture of Example 30 was prepared by mixing 5 g of the above zero-functional compound (A-3), 86 g of the above monofunctional compound (M-1), and 9 g of the above difunctional compound (N-1).

[0111] [Synthesis Example 8] Synthesis example 8-1 15g of compound M-1, 75g of AK-225, and 30g of diethyl ether were added to a 300cc eggplant flask and stirred in an ice bath. Then, 0.31g of lithium aluminum hydride was slowly added to the resulting mixture and stirred at room temperature for 20 hours. Then, 0.3cc of saturated aqueous sodium sulfate solution was added to the mixture and the precipitated solid was removed by celite filtration. The resulting filtrate was concentrated and purified by silica gel column chromatography to obtain 6.8g of the target compound (O-1). CF3(OCF2CF2OCF2CF2CF2CF2) o1 OCF2CF2OCF2CF2CF2-CH2NH2: O-1 Repeating unit o1=14.5

[0112] Synthesis example 8-2 Separately, 3.0 g of compound (A-3) and 0.35 mL of triethylamine were added to a 50 cc eggplant flask, and 0.45 g of Cl(C=O)C(CH2CH=CH2)3 synthesized in Synthesis Example 5-1 and 2 mL of 1,3-bistrifluoromethylbenzene were added. The mixture was stirred for 1 hour, and the solvent was distilled off. The obtained crude product was purified by silica gel column chromatography, and 1.7 g of the desired monofunctional compound (O-2) was obtained. CF3(OCF2CF2OCF2CF2CF2CF2) o2 OCF2CF2OCF2CF2CF2-CH2NH(C=O)C(CH2CH=CH2)3: O-2 Repeating unit o2=14.5

[0113] Synthesis example 8-3 15g of compound (N-1), 75g of AK-225, and 30g of diethyl ether were added to a 300cc eggplant flask and stirred in an ice bath. Then, 0.62g of lithium aluminum hydride was slowly added to the mixture and stirred at room temperature for 20 hours. Then, 0.6cc of saturated aqueous sodium sulfate solution was added to the mixture and the precipitated solid was removed by celite filtration. The obtained filtrate was concentrated and purified by silica gel column chromatography to obtain 6.8g of the target compound (P-1). [ka] Repeating unit x=14.5

[0114] Synthesis example 8-4 Separately, 3.0 g of compound (P-1) and 0.7 mL of triethylamine were added to a 50 cc eggplant flask, and 0.45 g of Cl(C=O)C(CH2CH=CH2)3 synthesized in Synthesis Example 5-3 and 2 mL of 1,3-bistrifluoromethylbenzene were added. The mixture was stirred for 1 hour, and the solvent was distilled off. The obtained crude product was purified by silica gel column chromatography to obtain 1.7 g of the following bifunctional compound (P-2). NMR spectrum of compound X8-6;

[0115] [ka]

[0116] Synthesis example 8-5 A sample mixture of Example 31 was prepared by mixing 5 g of the zero-functional compound (A-3), 86 g of the monofunctional compound (O-2), and 9 g of the difunctional compound (P-2).

[0117] Synthesis example 9-1 In a 300 mL eggplant flask, 100 g of compound (F-1), 14.9 g of cesium carbonate, and 100 g of 1,3-bis(trifluoromethyl)benzene were placed, and 6.4 g of p-toluenesulfonate propyl was added. The mixture was stirred at 80°C for 8 hours under a nitrogen atmosphere. The organic layer was washed with a dilute hydrochloric acid solution, and the crude material obtained by concentrating it with an evaporator was purified by silica gel chromatography to obtain a mixture containing 15.2 g, 55.3 g, and 29.5 g of the following 0-functional compound (Q-1), 1-functional compound (Q-2), and 2-functional compound (F-1), respectively. CH3CH2CH2OCH2-(CF2O){(CF2O) n (CF2CF2O) m}-CF2-CH2OCH2CH2CH3: (Q-1) HOCH2-(CF2O){(CF2O) n (CF2CF2O) m}-CF2-CH2OCH2CH2CH3: (Q-2) HOCH2-(CF2O){(CF2O) n (CF2CF2O) m}-CF2-CH2OH: (F-1)

[0118] (Separation method) The sample mixtures of Examples 1 to 37 prepared above were separated by column chromatography. A mixture of the solvent (200 g) used as the mobile phase and silica gel (50 g) was placed in a column having a diameter of 2 cm and a height of 70 cm, and then 200 g of the solvent used as the mobile phase was poured into the column to prepare a stationary phase. Then, a mixture of the sample mixture (10 g) of Examples 1 to 37 and the solvent (5 g) used as the mobile phase was adsorbed onto the stationary phase at the top of the column. Next, the solvent used as the mobile phase was flushed from the top of the column with an N2 pressure (gauge pressure) of 0.1 MPa, and 1000 g of the solution was collected as the first fraction. This collected material was concentrated and analyzed using high performance liquid chromatography (HPLC, manufactured by Shimadzu Corporation. Furthermore, a solvent in which the solvent previously used as the mobile phase and acetone were mixed in a mass ratio of 1:1 was flushed, and 500 g of the solution was collected as the second fraction. This was concentrated and analyzed using HPLC.

[0119] The specific solvents used as the mobile phase above are as follows: Solvent 1: CF3CF=CCl2(CFO) Solvent 2: CFCl2CF=CF2(CFO) Solvent 3: CF2HCF=CHCl (HCFO) Solvent 4: CF3CH=CHCl(Z) (HCFO) Solvent 5: CF3CH=CHCl(E) (HCFO) Solvent 6: CClF2CF=CHCl (HCFO) Solvent 7: CHF2CF2CF2CF=CHCl (HCFO) Solvent 8: CF3CH2CF=CH2(HFO) Solvent 9: CF3CH=CHCF3(E) (HFO) Solvent 10: CF3CH=CHCF3(Z) (HFO)

[0120] Solvent 11: Compound of the following formula (cyclic HFC) [ka] Solvent 12: Compound of the following formula (cyclic CFO)

[0121] [ka] Solvent 13: Compound of the following formula (cyclic CFO) [ka]

[0122] Solvent 14: CF3CF2COCF(CF3)2(PFK) Solvent 15: (CF3)2CFCOCF(CF3)2(PFK) Solvent 16: CF3CF2CF2OCFCF3COCF(CF3)2(PFK) Solvent 17: A mixture of 95 wt% CF3CF=CCl2 (CFO) and 5 wt% hexane (hydrocarbon (HC)). Solvent 18: CF14 (Perfluorocarbons (PFCs)) Solvent 19: Hexane (hydrocarbon (HC)) Solvent 20: Asahiklin AK-225 (AGC product name, hydrochlorofluorocarbon (HCFC))

[0123] The main points in the separation of the sample mixtures of Examples 1 to 37 and the results obtained in each are shown in the following Tables 1 to 3. The yields in Table 3 indicate the recovery rates (mass%) of each fraction relative to the charged mass (each component before separation).

[0124] [Table 1]

[0125] [Table 2]

[0126] [Table 3]

[0127] As shown in Tables 1 to 3, in Examples 1 to 34 in which CFO, HCFO, HFO, cyclic HFC, cyclic CFO, or PFK was used as the mobile phase, the yield of the fluorine-containing compound was high, and monofunctional compounds were separated with high purity in the first fraction, and difunctional compounds were separated with high purity in the second fraction. Among them, Examples 1 to 13 and 17 to 25, which used CFO, HCFO, HFO, cyclic HFC, or cyclic CFO, have a high purity of monofunctional compounds in the first fraction and a high purity of difunctional compounds in the second fraction. Examples 1, 2, 8 to 13, 17, 18, and 24 to 25, which used CFO, HFO, cyclic HFC, or cyclic CFO, have a higher purity of monofunctional compounds in the first fraction and a higher purity of difunctional compounds in the second fraction. Examples 8 to 11, 24, and 25, which used HFO or cyclic HFC, have an even higher purity of monofunctional compounds in the first fraction and a even higher purity of difunctional compounds in the second fraction. In Example 33, in which a mixed solvent of CFO and HC was used, the monofunctional compound in the first fraction could be separated with high purity, but the yield was reduced.

[0128] When we look at the main chain of a fluorine-containing compound, the main chain is (CF2O) n (CF2CF2O) m Examples 17 to 25, 32, and 34, which used a Fomblin-based fluorine-containing compound, showed high separation ability for monofunctional compounds in the first fraction, and high separation ability for bifunctional compounds in the second fraction. Fluorine-containing compound -OZ-(R) n Focusing on the above, Examples 1 to 25 and 32 to 37 of -O-(CF2)3-CH2OH, Example 29 of -O-(CF2)3-CONHCH2C(CH2CH=CH2)3, Example 30 of -O-(CF2)3-CONH2, and Example 31 of -O-(CF2)3-CH2NHCOC(CH2CH=CH2)3 have high purity of monofunctional compounds in the first fraction and high purity of bifunctional compounds in the second fraction. Example 34 where A is an alkyl group has slightly lower purity and yield of monofunctional compounds in the first fraction compared to Example 17 where A is a perfluoroalkyl group.

[0129] The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2020-155413, filed on September 16, 2020, are hereby incorporated by reference as the disclosure of the specification of the present invention.

Claims

1. A method for separating a compound represented by the following formula (1) and a compound represented by the following formula (2) from a mixture containing them by chromatography using a mobile phase and a stationary phase, comprising the steps of: applying said mixture to a chromatographic stationary phase and allowing it to adsorb onto said stationary phase; supplying a mobile phase containing at least one specific solvent selected from the group consisting of hydrofluoroolefins, hydrochlorofluoroolefins, chlorofluoroolefins, cyclic hydrofluoroolefins, cyclic hydrochlorofluoroolefins, cyclic chlorofluoroolefins, cyclic hydrofluorocarbons, cyclic chlorofluorofluorocarbons, and perfluoroketones to the stationary phase on which the mixture has been adsorbed; The separation method comprising the steps of: A-(OX) ｍ -O-Z-(R) ｎ１ Formula (1) (R) ｎ２ -Z-(OX) ｍ -O-Z-(R) ｎ３ Formula (2) however, A is an alkyl group or a fluoroalkyl group; X is an alkylene group or a fluoroalkylene group having one or more fluorine atoms; m is an integer of 2 or more, Z is a (n1+1)-, (n2+1)-, or (n3+1)-valent linking group; R is -OH, -CR １ =CR ２ R ３ (However, R １ is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group, R ２ and R ３ are each independently a hydrogen atom or a fluorine atom; ３ , -NH ２ , -SH, -Ph, -F, -Cl, -Br, -I, -C≡CH, and -N ３ is any functional group selected from the group consisting of n1 is an integer of 1 or more, n2 is an integer of 1 or more, n3 is an integer of 1 or more.

2. 2. The method according to claim 1, wherein in the formulas (1) and (2), A is a fluoroalkyl group, and X is a fluoroalkylene group having one or more fluorine atoms.

3. The separation method according to claim 1 or 2, wherein in the formulas (1) and (2), n1, n2, and n3 are the same integer.

4. The method according to any one of claims 1 to 3, wherein the mixture further contains a compound represented by the following formula (3), and is separated into a compound represented by formula (1), a compound represented by formula (2), and a compound represented by formula (3). A-(OX) ｍ -O-A formula (3) Here, A, X, and m have the same meanings as in formula (1) and formula (2).

5. The separation method according to any one of claims 1 to 4, wherein the specific solvent is a solvent that does not contain a chlorine atom.

6. The separation method according to any one of claims 1 to 5, wherein the specific solvent comprises at least one selected from the group consisting of hydrofluoroolefins, cyclic hydrofluoroolefins, and cyclic hydrofluorocarbons.

7. In the formula (1), the (OX) ｍ The method of any one of claims 1 to 6, wherein: {(OCF ２ ) ｍ２１ ・(OCF ２ CF ２ ) ｍ２２ } Here, m21 is an integer of 1 or more, m22 is an integer of 1 or more, and m21+m22 is an integer of 2 to 500.

8. The method according to claim 1, wherein in formula (2), (OX) m comprises the following structure: {(OCF 2 ) m21 ・(OCF 2 CF 2 ) m22} Here, m21 is an integer of 1 or more, m22 is an integer of 1 or more, and m21+m22 is an integer of 2 to 500.

9. The method according to claim 4, wherein in formula (3), (OX) m comprises the following structure: {(OCF 2 ) m21 ・(OCF 2 CF 2 ) m22} Here, m21 is an integer of 1 or more, m22 is an integer of 1 or more, and m21+m22 is an integer of 2 to 500.

10. The method according to any one of claims 1 to 9, wherein the stationary phase is selected from the group consisting of aluminum oxide, silica gel, magnesium oxide, aluminum silicate, magnesium silicate, chemically modified silica gel, and diatomaceous earth.

11. The separation method according to any one of claims 1 to 10, wherein the chromatography is column chromatography.

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