Separation method

Abstract

Provided is a method capable of separating 1-functional and 2-functional fluorine-containing ether compounds having a polyfluoropolyether chain and a prescribed functional group with good yield and high separation capacity. A separation method is a separation method for separating a compound represented by formula (1) and a compound represented by formula (2) from a mixture containing them using a chromatograph using a stationary phase and a mobile phase, wherein the mobile phase contains at least one specific solvent selected from the group consisting of hydrofluoroolefins, hydrochlorofluoroolefins, chlorofluoroolefins, cyclic hydrofluoroolefins, cyclic hydrochlorofluoroolefins, cyclic chlorofluoroolefins, cyclic hydrofluorocarbons, cyclic hydrochlorofluorocarbons, cyclic chlorofluorocarbons, and perfluoroketones.A‑(OX) m ‑O‑Z‑(R) n1 Formula (1) (R) n2 ‑Z‑(OX) m ‑O‑Z‑(R) n3 Formula (2)

Description

Technical Field

[0001] This invention relates to a separation method. Background Technology

[0002] Fluorinated ether compounds containing polyfluoropolyether chains and reactive silyl groups are suitable for use as surface treatment agents because they can form a surface layer with high lubricity, water and oil repellency, etc., on the surface of a substrate. Surface treatment agents containing fluorinated ether compounds are used for applications requiring the long-term maintenance of the following properties, such as components constituting the finger touch surface of touch panels, eyeglass lenses, and displays of wearable terminals. These properties include: the ability to resist water and oil repellency even with repeated rubbing of the surface layer with fingers (abrasion resistance); and the ability to easily remove fingerprints adhering to the surface layer by wiping (fingerprint removal).

[0003] In the synthesis of such fluorinated ether compounds, fluorinated ether compounds with polyfluorinated polyether chains and functional groups such as -OH, -CH=CH2, -CH3, -NH2, -SH, -Ph (phenyl), -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 starting materials or intermediates.

[0004] It is generally desirable for starting materials or intermediates to have higher purity. This is because higher purity makes the purification of the product obtained from the reaction easier, thereby reducing the formation of byproducts or unidentified substances that may occur during the reaction, and resulting in a target product with better properties. Starting materials or intermediates are typically manufactured as a mixture of a monofunctionalized body (hereinafter also referred to as "monofunctionalized body") having a defined functional group at only one end and a difunctionalized body (hereinafter also referred to as "difunctionalized body") having defined functional groups at both ends. Therefore, a method is required that can easily separate the monofunctionalized body and the difunctionalized body from the mixture of starting materials or intermediates with high purity.

[0005] The separation method described in Patent Document 1 can separate monohydric alcohol compounds containing perfluoro(poly)ether groups and dihydric alcohol compounds containing perfluoro(poly)ether groups by using one solvent selected from the group consisting of hydrofluorocarbons, hydrochlorofluorocarbons, hydrofluoroethers, fluorinated ester solvents, and aromatic solvents containing fluorine atoms as the mobile phase.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent No. 6330960 Summary of the Invention

[0009] The problem the invention aims to solve

[0010] In the separation method described in Patent Document 1, HCFC-225 (CF3CF2CHCl2, CClF2CF2CHClF) is preferably used as the mobile phase.

[0011] However, recently, there has been a demand for further improvement in the separation performance of the monofunctional and difunctional forms of fluorinated ether compounds. For the technique described in Patent Document 1, which uses HCFC-225 as the mobile phase, it has been clarified that the separation performance of the monofunctional and difunctional forms is insufficient.

[0012] The present invention was made in view of the above-mentioned problems, and its objective is to provide a method for separating 1-functionalized and 2-functionalized fluorinated ether compounds having polyfluoropolyether chains and specified functional groups with good yield and high separation capability.

[0013] Solution for solving the problem

[0014] The present invention has the following solution.

[0015] [1] A separation method that uses a chromatograph with a mobile phase and a stationary phase to separate the compound represented by formula (1) and the compound represented by formula (2) from a mixture containing them.

[0016] The separation method has the following characteristics:

[0017] The process of supplying the aforementioned mixture to the stationary phase of a chromatograph and allowing it to be adsorbed onto the stationary phase; and

[0018] The step of supplying a mobile phase to a stationary phase adsorbed with the aforementioned mixture, wherein the mobile phase comprises at least one specific solvent selected from the group consisting of hydrofluoroolefins, hydrochlorofluoroolefins, chlorofluoroolefins, cyclic hydrofluoroolefins, cyclic hydrochlorofluoroolefins, cyclic chlorofluoroolefins, cyclic hydrofluorocarbons, cyclic chlorofluorocarbons, and perfluoroketones.

[0019] A-(OX) m -OZ-(R) n1 Equation (1)

[0020] (R) n2 -Z-(OX) m -OZ-(R) n3 Equation (2)

[0021] in,

[0022] A is an alkyl or fluoroalkyl group.

[0023] X is an alkylene group, or a fluoroalkylene group having one or more fluorine atoms.

[0024] m is an integer greater than or equal to 2.

[0025] Z is a linker group with a valence of (n1+1), (n2+1), or (n3+1).

[0026] R is selected from -OH and -CR. 1 =CR 2 R 3 (where R) 1 R is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 2 and R 3 Each can be independently a hydrogen atom or a fluorine atom. Any functional group from the group consisting of -CH3, -NH2, -SH, -Ph, -F, -Cl, -Br, -I, -C≡CH, and -N3.

[0027] n1 is an integer greater than or equal to 1, and n2 is an integer greater than or equal to 1.

[0028] n3 is an integer greater than or equal to 1.

[0029] [2] According to the separation method described in [1] above, A in the aforementioned formula (1) and formula (2) is a fluoroalkyl group and X is a fluoroalkylene group having one or more fluorine atoms.

[0030] [3] According to the separation method described in [1] or [2] above, n1, n2 and n3 are the same integer in the aforementioned formulas (1) and (2).

[0031] [4] According to any one of [1] to [3] above, the separation method further comprises the compound shown in formula (3) below, wherein the separation method is used to separate the compound shown in formula (1), the compound shown in formula (2) and the compound shown in formula (3).

[0032] A-(OX) m -OA formula (3)

[0033] In this context, A, X, and m have the same meanings as in the aforementioned equations (1) and (2).

[0034] [5] The separation method according to any one of [1] to [4] above, wherein the aforementioned specific solvent is a solvent that does not contain chlorine atoms.

[0035] [6] The separation method according to any one of [1] to [5] above, wherein the aforementioned specific solvent comprises at least one selected from the group consisting of hydrofluoroolefins, cyclic hydrofluoroolefins and cyclic hydrofluorocarbons.

[0036] [7] The separation method according to any one of [1] to [6] above, wherein, in the aforementioned formulas (1), (2), and (3), the aforementioned (OX) m It includes the following structure.

[0037] {(OCF2) m21 ·(OCF2CF2) m22}

[0038] Where m21 is an integer greater than or equal to 1, m22 is an integer greater than or equal to 1, and m21+m22 is an integer from 2 to 500.

[0039] [8] The separation method according to any one of [1] to [7] above, wherein the aforementioned stationary phase is selected from the group consisting of alumina, silica gel, magnesium oxide, aluminum silicate, magnesium silicate, chemically modified silica gel, and diatomaceous earth.

[0040] [9] The separation method according to any one of [1] to [8] above, wherein the aforementioned chromatograph is a column chromatograph.

[0041] The effects of the invention

[0042] According to the present invention, a method can be provided that can achieve the separation of 1-functional and 2-functional forms of fluorinated ether compounds having polyfluoropolyether chains and specified functional groups with good yield and high separation capability, and further, the separation of 0-functional, 1-functional, and 2-functional forms of the aforementioned fluorinated ether compounds. Detailed Implementation

[0043] In this specification, the compound represented by formula (1) is also referred to as compound (1). Compounds represented by other formulas are also referred to accordingly. The group represented by formula (2) is also referred to as group 2. Groups represented by other formulas are also referred to accordingly.

[0044] In this specification, when it is referred to as "alkylene may have an A group", the alkylene may have an A group between carbon-carbon atoms in the alkylene, or it may have an A group at the end as in alkylene-A-group-.

[0045] The "~" sign, which indicates a range of values, refers to the values ​​recorded before and after it as the lower and upper limits.

[0046] (Separated mixture of objects)

[0047] The separation method of the present invention is a method for separating the compound represented by formula (1) and the compound represented by formula (2) from a mixture containing them (hereinafter, sometimes abbreviated as "mixture") using a chromatograph employing a mobile phase and a stationary phase. Specifically, it is a separation method for separating compound (1) and compound (2) using a chromatograph employing a mobile phase and a stationary phase. That is, the separation method of the present invention is suitable as a method for manufacturing compound (1). In addition, the separation method of the present invention is suitable as a method for manufacturing compound (2).

[0048] In this invention, compound (1) has a functional group "R" at a single end, and is therefore called a 1-functional compound, and compound (2) has a functional group "R" at both ends, and is therefore called a 2-functional compound. The ratio of compound (1) to compound (2) in the mixture is not particularly limited, for example, the ratio of compound (1) to compound (2) (by mass) is 20 to 0.05.

[0049] A-(OX) m -OZ-(R) n1 Equation (1)

[0050] (R) n2 -Z-(OX) m -OZ-(R) n3 Equation (2)

[0051] In Equations (1) and (2), the symbols are defined as follows.

[0052] A is an alkyl or fluoroalkyl group.

[0053] X is an alkylene group or a fluoroalkylene group having one or more fluorine atoms, and m is an integer of 2 or more.

[0054] Z is a linker group with a valence of (n1+1), (n2+1), or (n3+1).

[0055] R is selected from -OH and -CR. 1 =CR 2 R 3 (where R) 1 R is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 2 and R 3 Each can be an independent hydrogen or fluorine atom. Any functional group from the group consisting of -CH3, -NH2, -SH, -Ph(phenyl)-F, -Cl, -Br, -I, -C≡CH, and -N3.

[0056] n1 is an integer greater than or equal to 1, n2 is an integer greater than or equal to 1, n3 is an integer greater than or equal to 1, and n1, n2, and n3 represent the same integer.

[0057] The number of carbon atoms in the alkyl 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 or fluoroalkyl group can be straight-chain or branched.

[0058] As A, fluoroalkyl is preferred, and perfluoroalkyl is more preferred.

[0059] Examples of alkyl groups include methyl, ethyl, n-propyl, and isopropyl. Examples of fluoroalkyl groups include CHF2-, CH2F-, CF3CH2-, and CF3CH2CH2-.

[0060] Examples of perfluoroalkyl groups include CF3-, CF3CF2-, CF3CF2CF2-, CF3CF2CF2CF2-, CF3CF2CF2CF2CF2-, CF3CF2CF2CF2CF2-, CF3CF(CF3)-, etc.

[0061] As perfluoroalkyl groups, CF3-, CF3CF2-, and CF3CF2CF2- are preferred.

[0062] The number of carbon atoms in the alkylene and fluoroalkylene groups of X is preferably 1 to 6, more preferably 2 to 6, and particularly preferably 2 to 4.

[0063] Alkylenes and fluoroalkylenes can be any of the following: linear, branched, or cyclic.

[0064] In the case of alkylene and fluorinated alkylene in X, the proportion of fluorinated alkylene is preferably 50% or more, more preferably 80% or more, and particularly preferably 100% of the repeating number m.

[0065] The number of fluorine atoms in the fluorine alkyl group is preferably 1 to 2 times the number of carbon atoms, more preferably 1.7 to 2 times.

[0066] The fluoroalkyl group is particularly preferred to be a group in which all hydrogen atoms of the fluoroalkyl group are replaced by fluorine atoms (perfluoroalkyl group).

[0067] Specific examples of (OX) include -OCH2-, -OCHF-, -OCF2CHF-, -OCHFCF2-, -OCF2CH2-, -OCH2CF2-, -OCF2CF2CHF-, -OCHFCF2CF2-, -OCF2CF2CH2-, -OCH2CF2CF2-, -OCF2CF2CF2CH2-, -OCH2CF2CF2CF2-, -OCF2CF2CF2CF2CH2-, -OCH2CF2CF2CF2CF2-, -OCF2 CF2CF2CF2CF2CH2-, -OCH2CF2CF2CF2CF2CF2-, -OCF2-, -OCF2CF2-, -OCF2CF2CF2-, -OCF(CF3)CF2-, -OCF2CF2CF2CF2- , -OCF(CF3)CF2CF2-, -OCF2CF2CF2CF2CF2-, -OCF2CF2CF2CF2CF2CF2-, -O-cycloC4F6-, -O-cycloC5F8-, -O-cycloC6F 10 -

[0068] Here, -cycloC4F6- refers to a perfluorocyclobutane dieryl, and a specific example is perfluorocyclobutane-1,2-diyl. -cycloC5F8- refers to a perfluorocyclopentane dieryl, and a specific example is perfluorocyclopentane-1,3-diyl. -cycloC6F 10 - refers to perfluorocyclohexanediol, and a specific example of it is perfluorocyclohexane-1,4-diol.

[0069] The number of repetitions 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, even more preferably an integer of 5 to 100, and particularly preferably an integer of 10 to 50.

[0070] (OX) as a main chain repeating structure m It can contain only one type (OX) or two or more types (OX). There is no restriction on the bonding order of two or more types (OX), and they can be configured randomly, alternately, or in blocks.

[0071] The presence of two or more (OX) means that in a compound there are two or more (OX) with different numbers of carbon atoms; two or more (OX) with different numbers of hydrogen atoms; two or more (OX) with different positions of hydrogen atoms; and / or two or more (OX) with different presence or absence of side chains, or different types of side chains (number of side chains, number of carbon atoms in side chains, etc.) even if they have the same number of carbon atoms.

[0072] Regarding configurations with more than two (OX) types, for example, {(OCF2)} m21·(OCF2CF2) m22 The structure shown represents m21 (OCF2) and m22 (OCF2CF2) elements arranged randomly. Additionally, (OCF2CF2-OCF2CF2CF2CF2) m25 The structure shown represents an alternating configuration of m25 (OCF2CF2) and m25 (OCF2CF2CF2CF2) units.

[0073] As (OX) m Preferred [(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-cycloC5H mh F (8-mh) ) m18 ·(O-cycloC6H mi F (10-mi) ) m19 ].

[0074] Here, -cycloC4H mg F (6-mg) This indicates a fluorocyclobutanediyl group, preferably a fluorocyclobutane-1,2-diyl group. -cycloC5H mh F (8-mh) This indicates a fluorocyclopentanediyl group, preferably a fluorocyclopentane-1,3-diyl group. -cycloC6H mi F (10-mi) It indicates fluorocyclohexane dimethyl, preferably fluorocyclohexane-1,4-dimethyl.

[0075] 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.

[0076] m11, m12, m13, m14, m15, m16, m17, m18 and m19 are each independently an integer greater than or equal to 0, preferably less than or equal to 100.

[0077] m11+m12+m13+m14+m15+m16+m17+m18+m19 are integers of 2 or more, preferably integers of 2 to 200, more preferably integers of 5 to 150, even more preferably integers of 5 to 100, and particularly preferably integers of 10 to 50.

[0078] Among them, m12 is preferably an integer of 2 or more, and is particularly preferably an integer of 2 to 200.

[0079] Additionally, C3H mc F (6-mc) C4H md F (8-md) C5H me F (10-me) and C6H mf F (12-mf) It can be linear or branched, with linear being preferred.

[0080] It should be noted that m11 (OCH) ma F (2-ma) ), m12 (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-cycloC5H) mh F (8-mh) ), m19 (O-cycloC6H) mi F (10-mi) The order of bonding is not limited.

[0081] When m11 is 2 or higher, multiple (OCH) ma F (2-ma) Choose either the same or different.

[0082] When m12 is 2 or more, multiple (OC2H) mb F (4-mb) Choose either the same or different.

[0083] When m13 is 2 or higher, multiple (OC3H) mc F (6-mc) Choose either the same or different.

[0084] When m14 is 2 or higher, multiple (OC4H) md F (8-md) Choose either the same or different.

[0085] When m15 is 2 or higher, multiple (OC5H) me F (10-me) Choose either the same or different.

[0086] When m16 is 2 or higher, multiple (OC6H) mf F (12-mf) Choose either the same or different.

[0087] When m17 is 2 or higher, multiple (O-cycloC4H) mg F (6-mg) Choose either the same or different.

[0088] When m18 is 2 or higher, multiple (O-cycloC5H) mh F (8-mh) (Optional, either the same or different. When m19 is 2 or more, multiple (O-cycloC6H) mi F (10-mi) Choose either the same or different.

[0089] (OX) m Preferably, it has any of the following structures.

[0090] {(OCF2) m21 ·(OCF2CF2) m22}、

[0091] (OCF2CF2) m23 ,

[0092] (OCF2CF2CF2) m24 ,

[0093] (OCF2CF2-OCF2CF2CF2CF2) m25 ,

[0094] {(OCF2CF2CF2CF2CF2) m26 ·(OCF2) m27}、

[0095] {(OCF2CF2CF2CF2CF2) m26 ·(OCF2CF2) m27}、

[0096] {(OCF2CF2CF2CF2CF2CF2) m26 ·(OCF2) m27}、

[0097] {(OCF2CF2CF2CF2CF2CF2) m26 ·(OCF2CF2) m27}、

[0098] (OCF2CF2CF2CF2CF2-OCF2) m28 ,

[0099] (OCF2CF2CF2CF2CF2-OCF2CF2) m28 ,

[0100] (OCF2CF2CF2CF2CF2CF2-OCF2) m28 ,

[0101] (OCF2CF2CF2CF2CF2CF2-OCF2CF2) m28 ,

[0102] (OCF2-OCF2CF2CF2CF2CF2) m28 ,

[0103] (OCF2-OCF2CF2CF2CF2CF2CF2) m28 ,

[0104] (OCF2CF2-OCF2CF2CF2CF2CF2) m28 ,

[0105] (OCF2CF2-OCF2CF2CF2CF2CF2CF2) m28 .

[0106] Where m21 is an integer greater than or equal to 1, m22 is an integer greater than or equal to 1, m21+m22 is an integer between 2 and 500, m23 and m24 are each an integer between 2 and 500 independently, m25 is an integer between 1 and 250, m26 and m27 are each an integer greater than or equal to 1 independently, m26+m27 is an integer between 2 and 500, and m28 is an integer between 1 and 250.

[0107] (OX) m More preferably, it can be any of the following structures.

[0108] {(OCF2) m21 ·(OCF2CF2) m22}、

[0109] (OCF2CF2CF2)m24 ,

[0110] (OCF2CF2)2{(OCF2) m21 ·(OCF2CF2) m22-2}、

[0111] (OCF2CF2-OCF2CF2CF2CF2) m25-1 OCF2CF2、

[0112] (OCF2CF2CF2CF2CF2-OCF2) m28 ,

[0113] (OCF2CF2CF2CF2CF2CF2-OCF2) m28 ,

[0114] (OCF2CF2-OCF2CF2CF2CF2CF2) m28-1 OCF2CF2, (OCF2CF2-OCF2CF2CF2CF2CF2CF2) m28- 1OCF2CF2.

[0115] Among them, regarding m22-2, m25-1 and m28-1, the quantities of m22, m25 and m28 are selected in such a way that they are integers of 1 or higher.

[0116] Of these, (OX) m For {(OCF2)} m21 ·(OCF2CF2) m22 In the case of}, it is possible to separate compound (1) and compound (2) from the mixture with higher purity, which is therefore preferred.

[0117] {(OCF2) m21 ·(OCF2CF2) m22 In the formula, m22 / m21 is preferably 0.1 to 10, more preferably 0.2 to 5.0, further preferably 0.2 to 2.0, particularly preferably 0.2 to 1.5, and most preferably 0.2 to 0.85.

[0118] (OX) m The number average molecular weight is preferably 1,000 to 20,000, more preferably 2,000 to 15,000, and particularly preferably 2,500 to 10,000.

[0119] Z is a linker group with a valence of (n1+1), (n2+1), or (n3+1). n1, n2, and n3 are each an integer from 1 to 10. Therefore, linkers with valences of 2 to 11 can be cited as Z.

[0120] Z preferably has at least one branch point (hereinafter referred to as "branch point P") selected from the group consisting of organopolysiloxane residues with C, N, Si, ring structures and (n1+1), (n2+1), or (n3+1) valences.

[0121] As a ring structure, it is preferably selected from one of the following groups: aliphatic rings of 3 to 8 members, aromatic rings of 3 to 8 members, heterocyclic rings of 3 to 8 members, and fused rings formed from two or more of these rings. The ring structure listed below is particularly preferred.

[0122] The ring structure can have substituents such as halogen atoms, alkyl groups (which may contain ether oxygen atoms between carbon atoms), cycloalkyl groups, alkenyl groups, allyl groups, alkoxy groups, and oxo groups (=O).

[0123]

[0124] Specific examples of organopolysiloxane residues with (n1+1), (n2+1), or (n3+1) valences include the following groups.

[0125] Wherein, R in the following formula 5 It can be a hydrogen atom, alkyl group, alkoxy group, or phenyl group. R 5 The alkyl and alkoxy groups preferably have 1 to 10 carbon atoms, and more preferably 1.

[0126]

[0127] Z can have a group selected from alkylene, fluoroalkylene, hydroxyalkylene, alkoxyalkylene, carbonyl, amide, ether, thioether, urea, carbamate, carbonate, ester, -SO2NR 6 -、-Si(R 6 )2-、-OSi(R 6 One or more groups in the group consisting of )2-, -Si(CH3)2-Ph-Si(CH3)2- and divalent organopolysiloxane residues.

[0128] Among them, R 6 It consists of a hydrogen atom, an alkyl group or phenyl group having 1 to 6 carbon atoms, 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 to 2, from the perspective of ease of compound production.

[0129] Furthermore, for each bond or group constituting Z, in the case of formula (1), any end can be positioned on the A side. For example, for an amide bond, either the carbon atom or the nitrogen atom can be positioned on the A side. The same applies to other bonds and groups.

[0130] As a specific example of a divalent organopolysiloxane residue, the following group can be cited. Wherein, R in the following formula... 7 It can be a hydrogen atom, alkyl group, alkoxy group, or phenyl group. R 7 The alkyl and alkoxy groups preferably have 1 to 10 carbon atoms, and more preferably 1.

[0131]

[0132] Z also preferably has the selectivity of -C(O)NR 6 -、-C(O)-、-C(O)O-、-NR 6 At least one bond in the group consisting of - and -O-, having -C(O)NR 6 - It is particularly preferred because it can separate compounds (1) and (2) with higher purity.

[0133] For Z, combinations of two or more divalent hydrocarbon groups with one or more branch points P, or combinations of two or more divalent hydrocarbon groups with one or more branch points P and one or more bonds B can be given.

[0134] Specific examples of divalent hydrocarbon groups include divalent aliphatic hydrocarbon groups (alkylene, cycloalkylene, etc.) and divalent aromatic hydrocarbon groups (phenylene, 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.

[0135] In formula (1), Z can be any of the following groups: g2-1 (where d1+d3=1 (i.e., d1 or d3 is 0), n1=d2+d4, d2+d4≥1), g2-2 (where e1=1, n1=e2, e2≥1), g2-3 (where n1=2), g2-4 (where h1=1, n1=h2, h2≥1), g2-5 (where i1=1, n1=i2, i2≥1), g2-6 (where n1=1), g2-7 (where n1=i3+1, i3≥1), g2-8 (where n1=i4, i4≥1), or g2-9 (where n1=i5, i5≥1).

[0136] In formula (2), Z can be independently any of the following groups: g2-1 (where n2 = d2 + d4, n3 = d2 + d4), g2-2 (where e1 = 1, n2 = e2, n3 = e2), g2-3 (where n2 = 2, n3 = 2), g2-4 (where h1 = 1, n2 = h2, n3 = h2), g2-5 (where i1 = 1, n2 = i2, n3 = i2), g2-6 (where n2 = 1, n3 = 1), g2-7 (where n2 = i3 + 1, n3 = i3 + 1), g2-8 (where n2 = i4, n3 = i4), or g2-9 (where n2 = i5, n3 = i5).

[0137]

[0138] (-A 1 -) e1 C(R e2 ) 4-e1-e2 (-Q 22 -) e2 Equation (g2-2)

[0139] -A 1 -N(-Q 23 -)2 Equation (g2-3)

[0140] (-A 1 -) h1 Z 1 (-Q 24 -) h2 Equation (g2-4)

[0141] (-A 1 -) i1 Si(R e3 ) 4-i1-i2 (-Q 25 -) i2 Equation (g2-5)

[0142] -A 1 -Q 26 Equation (g2-6)

[0143] -A 1 -CH(-Q 22 -)-Si(R e3 ) 3-i3 (-Q 25 -) i3 Equation (g2-7)

[0144] -A 1 -[CH2C(R e4 (-Q)27 -)] i4 -R e5 Equation (g2-8)

[0145] -A 1 -Z a (-Q 28 -) i5 Equation (g2-9)

[0146] In equations (g2-1) to (g2-9), A 1 With (OX) m Side connection, Q 22 Q 23 Q 24 Q 25 Q 26 Q 27 and Q 28 Connect to the R side.

[0147] A 1 For single bonds, alkylene groups, and alkylene groups with more than two carbon atoms having a -C(O)NR bond between carbon atoms. 6 -, -C(O)-, -OC(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O-、-SO2NR 6 -or-N(R) 6 The SO2- group, or the -C(O)NR terminal on the side of the alkylene group not connected to A (the side 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 The SO2- group, in each formula, contains two or more A groups. 1 In the case of A above 2 1 The same or different can be chosen. Hydrogen atoms in alkylene groups can be replaced by fluorine atoms.

[0148] Q 11 It is a single bond, -O-, alkylene, or alkylene with -C(O)NR between carbon atoms. 6 -、-C(O)-、-NR 6 - or -O- groups.

[0149] Q 22 It is an alkylene group, and the carbon-carbon atoms of the alkylene group having more than 2 carbon atoms have -C(O)NR. 6 -、-C(O)-、-NR 6- or -O- groups, with -C(O)NR at the A-side end of the alkylene group. 6 -、-C(O)-、-NR 6 - or -O- groups, or -C(O)NR between carbon-carbon atoms in alkylene groups having two or more carbon atoms. 6 -、-C(O)-、-NR 6 -or -O- and has -C(O)NR at the end on side A. 6 -、-C(O)-、-NR 6 - or -O- groups, in each formula, there are more than 2 Q groups. 22 In the case of 2 or more Q 22 Choose either the same or different.

[0150] Q 23 It is an alkylene group, or an alkylene group having -C(O)NR between carbon atoms in the carbon-carbon intervals of two or more carbon atoms. 6 -、-C(O)-、-NR 6 - or -O- groups, 2 Q 23 Choose either the same or different.

[0151] Q 24 It is an alkylene group, or an alkylene group having -C(O)NR between carbon atoms in the carbon-carbon intervals of two or more carbon atoms. 6 -、-C(O)-、-NR 6 - or -O- groups, in each formula, there are more than 2 Q groups. 24 In the case of 2 or more Q 24 Choose either the same or different.

[0152] Q 25 It is an alkylene group, or an alkylene group having -C(O)NR between carbon atoms in the carbon-carbon intervals of two or more carbon atoms. 6 -、-C(O)-、-NR 6 - or -O- groups, in each formula, there are more than 2 Q groups. 25 In the case of 2 or more Q 25 Choose either the same or different.

[0153] Q 26 It is an alkylene group, or an alkylene group having -C(O)NR between carbon atoms in the carbon-carbon intervals of two or more carbon atoms. 6 -、-C(O)-、-NR 6 - or -O- groups.

[0154] R 6 It consists of hydrogen atoms and alkyl or phenyl groups having 1 to 6 carbon atoms.

[0155] Q 27 It is a single bond or an alkylene group.

[0156] Q 28 It is an alkylene group, or a group in which an alkylene group having an ether oxygen atom or a divalent organopolysiloxane residue between carbon atoms.

[0157] Z 1 It is a group with a ring structure having an h1+h2 valence, the ring structure having a similarity to A. 1 Directly bonded carbon or nitrogen atoms and having a Q 24 Directly bonded carbon or nitrogen atoms.

[0158] R e1 The atoms are hydrogen atoms or alkyl groups, and in each formula there are two or more R atoms. e1 In the case of R above 2 e1 Choose either the same or different.

[0159] R e2 It can be a hydrogen atom, hydroxyl group, alkyl group or acyloxy group.

[0160] R e3 It is an alkyl group.

[0161] R e4 The atoms are either hydrogen atoms or alkyl groups; hydrogen atoms are preferred for ease of compound preparation. Each formula contains two or more R atoms. e4 In the case of R above 2 e4 Choose either the same or different.

[0162] R e5 The atom can be either a hydrogen atom or a halogen atom; from the perspective of ease of compound production, a hydrogen atom is preferred.

[0163] d1 is an integer from 0 to 3, preferably 1 or 2. d2 is an integer from 0 to 3, preferably 1 or 2. d1+d2 is an integer from 1 to 3.

[0164] d3 is an integer from 0 to 3, preferably 0 or 1. d4 is an integer from 0 to 3, preferably 2 or 3. d3+d4 is an integer from 1 to 3.

[0165] d1+d3 equals 1.

[0166] For d2+d4, Z in equation (1) is an integer from 1 to 5, preferably 4 or 5, and Z in equation (2) is an integer from 1 to 5, preferably an integer from 3 to 5, and particularly preferably 4 or 5.

[0167] e1+e2 is 3 or 4. e1 is 1. For e2, it is 1 to 3 in Z of equation (1), preferably 2 or 3, and it is 1 to 3 in Z of equation (2), preferably 2 or 3.

[0168] h1 is 1. h2 is an integer greater than or equal to 1 (preferably 2 or 3).

[0169] i1+i2 is 2 to 4 (preferably 3 or 4). i1 is 1. i2 is an integer from 1 to 3 (preferably 2 or 3).

[0170] i3 is an integer from 0 to 3, preferably 1 to 3, and especially preferably 2 or 3.

[0171] i4 is 1 or more in Z of formula (1) (preferably an integer from 2 to 10, especially an integer from 2 to 6), and is 1 or more in Z of formula (2) (preferably an integer from 1 to 10, especially an integer from 1 to 6).

[0172] i5 is 1 or higher (preferably an integer between 2 and 7).

[0173] Q 22 Q 23 Q 24 Q 25 Q 26 Q 27 Q 28 The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, and particularly preferably 1 to 4. The lower limit for the number of carbon atoms in the alkylene group when a specific bond exists between carbon atoms is 2.

[0174] As Z 1 The ring structure in the text can be exemplified by the ring structure described above, and the preferred method is also the same. It should be noted that, due to A... 1 Q 24 Directly bonded to Z 1 The ring structure in the middle will not result in, for example, alkylene groups attached to the ring structure, and A 1 Q 24 The case where it is attached to the alkylene group.

[0175] Z a The organopolysiloxane residues are (i5+1) valence, preferably any of the following groups. Wherein, R in the following formula... a It is an alkyl group (preferably with 1 to 10 carbon atoms) or a phenyl group.

[0176]

[0177] R e1 R e2 R e3 or R e4 The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 to 2.

[0178] R e2 The number of carbon atoms in the alkyl moiety of the acyloxy group is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 3, and particularly preferably 1 to 2.

[0179] h1 is preferably 1 to 6, more preferably 1 to 4, further preferably 1 or 2, and especially preferably 1.

[0180] h2 is preferably 2 to 6, more preferably 2 to 4, and especially preferably 2 or 3.

[0181] Other forms of Z in equation (1) include the following groups: g3-1 (where d1+d3=1 (i.e., d1 or d3 is 0.), n1=d2×r1+d4×r1.), g3-2 (where e1=1, n1=e2×r1.), g3-3 (where n1=2×r1.), g3-4 (where h1=1, n1=h2×r1.), g3-5 (where i1=1, n1=i2×r1.), g3-6 (where g1=r1.), g3-7 (where n1=r1×(i3+1.), g3-8 (where n1=r1×i4.), and g3-9 (where n1=r1×i5.).

[0182] Other forms of Z in equation (2) include groups g3-1 (where n2 = d2×r1 + d4×r1, n3 = d2×r1 + d4×r1.), g3-2 (where n2 = e2×r1, n3 = e2×r1.), g3-3 (where n2 = 2×r1, n3 = 2×r1.), g3-4 (where n2 = h2×r1, n3 = h2×r1.), and groups... g3-5 (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.), group g3-9 (where n2 = r1 × i5, n3 = r1 × i5.).

[0183]

[0184] (-A 1 -) e1 C(R e2 ) 4-e1-e2 (-Q 22 -G 1 ) e2 Equation (g3-2)

[0185] -A 1 -N(-Q 23 -G 1 Equation 2 (g3-3)

[0186] (-A 1 -) h1 Z1 (-Q 24 -G 1 ) h2 Equation (g3-4)

[0187] (-A 1 -) i1 Si(R e3 ) 4-I1-I2 (-Q 25 -G 1 ) i2 Equation (g3-5)

[0188] -A 1 -Q 26 -G 1 Equation (g3-6)

[0189] -A 1 -CH(-Q 22 -G 1 )-Si(R e3 ) 3-i3 (-Q 25 -G 1 ) i3 Equation (g3-7)

[0190] -A 1 -[CH2C(R e4 (-Q) 27 -G 1 )] i4 -R e5 Equation (g3-8)

[0191] -A 1 -Z a (-Q 28 -G 1 ) i5 Equation (g3-9)

[0192] In equations (g3-1) to (g3-9), A 1 With (OX) m Side connection, G 1 Connect to side A.

[0193] G 1 For the group g3, in each formula there are more than two Gs. 1 In the case of more than 2 Gs 1 Choose either the same or different. G 1 The symbols other than those in equations (g2-1) to (g2-9) are the same.

[0194] -Si(R 8 ) 3-r1 (-Q3 -) r1 Formula (g3)

[0195] In equation (g3), Si and Q 22 Q 23 Q 24 Q 25 Q 26 Q 27 and Q 28 Side connection, Q 3 Connect to side A. R 8 It is an alkyl group. Q 3 It is an alkylene group, or an alkylene group having -C(O)NR between carbon atoms in the carbon-carbon intervals of two or more carbon atoms. 6 -、-C(O)-、-NR 6 - or -O- groups, two or more Q 3 Choose either the same or different. r1 is 2 or 3. R 6 It consists of hydrogen atoms and alkyl or phenyl groups having 1 to 6 carbon atoms.

[0196] Q 3 The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, and particularly preferably 1 to 4. The lower limit for the number of carbon atoms in the alkylene group when a specific bond exists between carbon atoms is 2.

[0197] R 8 The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 to 2.

[0198] R 9 The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 to 2.

[0199] R 9 The number of carbon atoms in the alkoxy group is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 to 2.

[0200] p is preferably 0 or 1.

[0201] R is selected from -OH, -CR 1 =CR 2 R 3 Any functional group among -CH3, -NH2, -SH, -Ph(phenyl), -F, -Cl, -Br, -I, -C≡CH, and -N3.

[0202] R 1 It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0203] R 2 and R 3Each can be either a hydrogen atom or a fluorine atom.

[0204] As -CR 1 =CR 2 R 3 Specific examples of the groups shown include -CH=CH2, -C(CH3)=CH2, -C(CF3)=CH2, -CF=CH2, -CH=CHF, -CF=CHF, -CH=CF2, and -CF=CF2.

[0205] As R, -OH and -NH2 can separate compounds (1) and (2) with high purity, and are therefore preferred.

[0206] n1, which represents the number of functional groups R at one end of compound (1), n2, which represents the number of functional groups R at one end of compound (2), and n3, which represents the number of functional groups R at the other end, are all integers from 1 to 10, preferably all representing the same integer.

[0207] n1, n2, and n3 are preferably selected from 1.

[0208] As Z in formulas (1) and (2), it is preferably an alkylene group or a group g2-2 having -O-, -C(O)O- or -C(O)-. The hydrogen atom of the alkylene group may be replaced by a fluorine atom or a hydroxyl group. The number of carbon atoms in the above-mentioned alkylene group is preferably 1 to 10, more preferably 1 to 6.

[0209] It should be noted that, as specific examples of alkylene groups that can have -O-, -C(O)O- or -C(O)-, examples include -alkylene-C(O)O- and -alkylene-C(O)-.

[0210] -OZ-(R) in equations (1) and (2) n1 -OZ-(R) n2 and -OZ-(R) n3 A preferred specific example 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 greater than or equal to 1, preferably 1 to 6, and particularly preferably 1 to 3.

[0211] (Separation methods using chromatography)

[0212] The chromatograph used in the separation method of the present invention is not particularly limited as long as it uses a stationary phase and a mobile phase; any known chromatograph can be used, such as a column chromatograph or a thin-layer chromatograph. A column chromatograph is preferred, and a flash column chromatography or high-performance liquid chromatography (HPLC) is particularly preferred.

[0213] (Stationary phase)

[0214] The preferred stationary phase is composed of free alumina, silica gel, magnesium oxide, aluminum silicate, magnesium silicate, chemically modified silica gel, and diatomaceous earth.

[0215] Silica gel is preferred as the stationary phase. Specific examples of silica gel include unmodified silica gel, amino-containing silica gel, and cyano-containing silica gel.

[0216] Commercially available silicone products can be used. Examples of commercially available silicone products include CHROMATOREX PSQ-100B (product name of Fuji Silysia Chemical Ltd.), Wakogel C-200 (product name of Wako Pure Chemical Industries Co., Ltd.), and 115111Silica gel 60 (product name of Merck).

[0217] The amount of stationary phase used should be appropriately selected based on the compounds being separated, the mobile phase used, and the type of chromatograph. It is preferable to use an amount equal to or greater than the mass of the mixture being separated. Furthermore, if the molecular weight of the compounds being separated is relatively small, it is preferable to use a larger amount of stationary phase.

[0218] (Mobile phase)

[0219] The mobile phase contains the specific solvents shown below.

[0220] Examples of specific solvents include (acyclic) hydrofluoroolefins (hereinafter also called HFO), (acyclic) hydrochlorofluoroolefins (hereinafter also called HCFO), (acyclic) chlorofluoroolefins (hereinafter also called CFO), cyclic hydrofluoroolefins (hereinafter also called cyclic HFO), cyclic hydrochlorofluoroolefins (hereinafter also called cyclic HCFO), cyclic chlorofluoroolefins (hereinafter also called cyclic CFO), cyclic hydrofluorocarbons (hereinafter also called cyclic HFC), cyclic hydrochlorofluorocarbons (hereinafter also called cyclic HCFC), cyclic chlorofluorocarbons (hereinafter also called CFC), and perfluoroketones (hereinafter also called PFK). One of these can be used, or two or more can be used in combination.

[0221] Examples of HFOs include CF3CH2CF=CH2, CF3CH=CHCF3(E), and CF3CH=CHCF3(Z).

[0222] Examples of HCFOs include CF3CF=CCl2, CFCl2CF=CF2, CHF2CF=CHCl, CF3CH=CHCl(Z), CF3CH=CHCl(E), CClF2CF=CHCl, and CHF2CF2CF2CF=CHCl.

[0223] As a CFO, examples include CF3CF=CCl2 and CFCl2CF=CF2.

[0224] Examples of cyclic CFOs include substances represented by the following formula.

[0225]

[0226] Examples of cyclic HFCs include substances represented by the following formula.

[0227]

[0228] Examples of PFKs include CF3CF2COCF(CF3)2, (CF3)2CFCOCF(CF3)2, and CF3CF2CF2OCFCF3COCF(CF3)2.

[0229] As a specific solvent, solvents that do not contain chlorine atoms are preferred because they do not have adverse effects on the Earth's environment. Specifically, HFO, cyclic HFO, cyclic HFC, or PFK are preferred.

[0230] In addition, as a specific solvent, HFO, HCFO, CFO, cyclic HFO, cyclic HCFO, cyclic CFO, cyclic HFC, cyclic HCFC, or cyclic CFC can separate compound (1) and compound (2) with higher purity. Therefore, HFO, CFO, cyclic HFO, cyclic CFO, cyclic HFC, or cyclic CFC are preferred, more preferably, and especially preferred.

[0231] In addition to a specific solvent, the mobile phase may also contain other solvents. Examples of other solvents include hydrocarbons, ethers, ketones, esters, chlorinated hydrocarbons, and fluorinated ethers.

[0232] Examples of hydrocarbons include pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, and xylene.

[0233] Examples of ethers include diethyl ether and tetrahydrofuran.

[0234] Examples of ketones include acetone and 2-butanone.

[0235] Examples of esters include ethyl acetate.

[0236] Examples of chlorinated hydrocarbons include dichloromethane.

[0237] Examples of fluorinated 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.

[0238] The other solvents mentioned above can be mixed with specific solvents and used as a single phase, or specific solvents can be combined with other solvents and used as a gradient elution method.

[0239] The separation method of the present invention includes a step of adsorbing a mixture onto a stationary phase. The method for adsorbing the mixture onto the stationary phase is not particularly limited and can be a method commonly used in chromatographs.

[0240] When using a column chromatograph, the mixture is fed directly, or mixed with a solvent, onto the stationary phase packed in the column, causing the mixture to adsorb onto the stationary phase. In this case, the solvent used is preferably a specific solvent used as the mobile phase.

[0241] Next, a step is performed in which a mobile phase containing a specific solvent is passed through a stationary phase adsorbed with the mixture. When a column chromatograph is used as the chromatograph, a solvent as the mobile phase is injected from the top of the column, and the mobile phase containing the specific solvent is passed through the stationary phase adsorbed with the mixture.

[0242] If a mobile phase containing a specific solvent is passed through, the compound (1) adsorbed in the stationary phase mixture will first dissolve. Therefore, compound (1) in the mixture can be separated. When using a column chromatograph as the chromatograph, a fraction obtained from the bottom of the column can be taken to obtain compound (1) in high purity.

[0243] Next, if a mobile phase containing a specific solvent is passed through, the 2-functional compound (2) adsorbed in the stationary phase mixture dissolves. Therefore, compound (2) in the mixture can be separated. By taking a fraction obtained from the bottom of the column, compound (2) in high purity can be obtained.

[0244] It should be noted that, in order to dissolve compound (2), the type of specific solvent used in the mobile phase can be changed.

[0245] In the separation method of the present invention, the temperature of the stationary phase for separating the compounds is preferably -10°C to 100°C, more preferably 5°C to 50°C, and even more preferably 10°C to 40°C. The temperature of the stationary phase is mostly room temperature (25°C).

[0246] In the separation method of the present invention, the mixture containing compound (1) and compound (2) may also contain the following non-functional compound (3).

[0247] A-(OX) m -OA formula (3)

[0248] In this context, A, X, and m have the same meanings as in equations (1) and (2).

[0249] When the mixture contains compound (3), the ratio of compound (1) to compound (2) to compound (3) in the mixture is not particularly limited. For example, the ratio of compound (1) / compound (2) / compound (3) (by mass) is 1 to 95 / 1 to 95 / 1 to 95.

[0250] In the case where the mixture also contains compound (3), in the mixture adsorbed on the stationary phase, the non-functional compound (3) dissolves before the 1-functional compound (1) dissolves. Therefore, compound (3) in the mixture can be separated.

[0251] In the separation method of the present invention, when a column chromatograph is used as the chromatograph, it is preferable to pressurize the column using inert gases such as nitrogen or argon. 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.

[0252] Example

[0253] The present invention will now be described in detail with examples. Examples 1 to 32 are exemplary embodiments, and Examples 33 to 37 are comparative examples. The present invention is not limited to these examples. It should be noted that the content (%) of each component in Table 1 described below represents a mass standard.

[0254] In addition, the structures of the fluorinated compounds used in the examples are shown below.

[0255] ( (CF2CF2O-CF2CF2CF2CF2O) x Department

[0256] 0 Functional body: CF3-O-(CF2CF2O-CF2CF2CF2CF2O) x1 -CF3

[0257] 1 Functional body: CF3-O-(CF2CF2O-CF2CF2CF2CF2O) x2-CF2CF2OCF2CF2CF2-X

[0258] 2 functional body: X-CF2CF2CF2OCF2CF2-(CF2CF2OCF2CF2CF2CF2O) x3 -CF2CF2OCF2CF2CF2-X

[0259] X is the terminal functional group. The mass-average molecular weight of the structure other than X is 4800. The repeating units are x1 and x2, which are 14.5.

[0260] ( CF2O) n · (CF2CF2O) m system

[0261] 0Functional body: CF3-O-(CF2O) n ·(CF2CF2O) m -CF3

[0262] 1 Functional body: CF3-O-(CF2O) n ·(CF2CF2O) m -X

[0263] 2 functional body X-(CF2O) n ·(CF2CF2O) m -X

[0264] X is the terminal functional group. The mass-average molecular weight of the structure other than X is 4500. The repeating units are n=25 and m=22.

[0265] Synthesis of fluorine-containing compounds

[0266] [Synthesis example 1]

[0267] Synthesis example 1-1

[0268] The following compound (A-1) was obtained by the method described in Example 7 of International Publication No. 2013 / 121984.

[0269] CF3O-(CF2CFHO-CF2CF2CF2CH2O) a1 -H:A-1

[0270] Repeating unit: a1 = 14.5

[0271] Synthesis example 1-2

[0272] In a 200 mL three-necked flask, 30 g of compound (A-1), 1 g of 48% KOH solution, 1.1 g of water, and 0.55 g of tert-butanol were mixed at 80 °C for 10 minutes. 2.4 g of perfluoropropyl vinyl ether was added dropwise to the resulting mixture, and the mixture was stirred at 80 °C for 4 hours. After cooling the mixture to room temperature, it was added to AC-2000 (C6F). 13 H (manufactured by AGC Corporation) 60g, then 6.5g of 2N hydrochloric acid was added dropwise to an ice bath. The mixture was transferred to a 200mL separatory funnel and allowed to stand for 1 hour. The lower phase was removed and transferred to a new 200mL separatory funnel, 87g of water was added, and the mixture was stirred. After standing for 1 hour, the lower phase was recovered and concentrated to obtain the following compound (A-2).

[0273] CF3O-(CF2CFHO-CF2CF2CF2CH2O) a2 -CF2CF2CF3:A-2

[0274] Repeating unit a2 = 14.5

[0275] Synthesis Example 1-3

[0276] Prepare an autoclave (nickel-made, 500 mL internal volume). Connect in series at the autoclave's gas outlet a condenser maintained at 0°C, a NaF granular packing layer, and a condenser maintained at -10°C. Additionally, install a liquid return line to return the liquid condensed in the -10°C condenser back to the autoclave.

[0277] 312 g of R-113 (CF2ClCFCl2) was added to the autoclave and stirred while maintaining the temperature at 25°C. Nitrogen gas was purged into the autoclave at 25°C for 1 hour, followed by purging of 20% fluorine gas at 2.0 L / h for 1 hour at 25°C. Then, while purging 20% ​​fluorine gas at the same flow rate, a liquid prepared by dissolving 8.4 g of compound (A-2) in 84 g of R-113 was injected into the autoclave over 3.6 hours.

[0278] 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). Inside the autoclave, while heating from 25°C to 40°C, 9 mL of a benzene solution containing 0.015 g / mL benzene in R-113 was injected, and the benzene solution inlet of the autoclave was closed. After stirring for 15 minutes, another 6 mL of benzene solution was injected while maintaining 40°C, and the inlet was closed. This same operation was repeated 3 times. The total amount of benzene injected was 0.33 g.

[0279] Then, while blowing 20% ​​fluorine gas into the autoclave at the same flow rate, stirring continued for 1 hour. Next, the pressure inside the autoclave was brought to atmospheric pressure, and nitrogen gas was blown in for 1 hour. The contents of the autoclave were concentrated using an evaporator to obtain 8.8 g of the following non-functional compound (A-3).

[0280] CF3O-(CF2CF2O-CF2CF2CF2CF2O) a3 -CF2CF2O-CF2CF2CF2-CF2-O-CF2CF2CF3:A-3

[0281] Repeating unit a3 = 14.5

[0282] Synthesis Example 1-4

[0283] The following functional compound (B-1) was obtained by the method described in Example 7 of International Publication No. 2013 / 121984.

[0284] CF3O-(CF2CF2O-CF2CF2CF2CF2O) b1 -CF2CF2O-CF2CF2CF2-CH2OH: (B-1)

[0285] Repeating unit b1 = 14.5

[0286] Synthesis Example 1-5

[0287] In a 200 mL round-bottom flask, 16.2 g of HOCH₂CF₂CF₂CH₂OH and 13.8 g of potassium carbonate were added and stirred at 120 °C. Then, 278 g of compound (A-1) obtained in Synthesis Example 1-1 was added, and the mixture was stirred at 120 °C for 2 hours. The temperature was then adjusted to 25 °C, and 50 g each of AC-2000 and hydrochloric acid were added. The mixture was separated, and the organic phase was concentrated. The crude reaction solution was purified using silica gel column chromatography to obtain 117.7 g of compound (C-1).

[0288]

[0289] Repeating unit x1 + x2 = 13.5

[0290] Synthesis Example 1-6

[0291] In a 50 mL 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. The mixture was then stirred at 50°C for 24 hours under a nitrogen atmosphere. After the temperature in the flask was adjusted to 25°C, the sodium fluoride powder was removed by filtration. Excess CF3CF2CF2OCF(CF3)COF and AC-2000 were removed by vacuum distillation to obtain 24 g of compound (C-2).

[0292]

[0293] Repeating unit x1 + x2 = 13.5

[0294] Synthesis Example 1-7

[0295] In a 500 mL metal reactor, 250 mL of ClCF₂CFClCF₂OCF₂CF₂Cl (hereinafter referred to as "CFE-419") was added. After bubbling with nitrogen, 20% by volume fluorine gas diluted with nitrogen was bubbled. A CFE-419 solution of the above-mentioned compound (C-2) (concentration: 10%, compound (C-2): 24 g) was added over 6 hours. The ratio of the fluorine gas introduction rate (mol / h) to the hydrogen atom introduction rate (mol / h) in compound (C-2) was controlled to be 2:1. After the addition of compound (C-2) was completed, a CFE-419 solution of benzene (concentration: 0.1%, benzene: 0.1 g) was intermittently added. After the addition of benzene was completed, fluorine gas was bubbled, and finally, the reactor was completely purged with nitrogen. The solvent was removed by distillation to obtain 25.3 g of the following compound (C-3).

[0296]

[0297] Repeating unit x = 14.5

[0298] Synthesis Example 1-8

[0299] In a 50 mL round-bottom flask, add 25.3 g of compound (C-3), 2.2 g of sodium fluoride, and 25 mL of AC-2000. Stir the mixture in an ice bath. Add 1.7 g of methanol to the resulting mixture and stir at 25 °C for 1 hour. Filter the mixture and purify the filtrate using silica gel column chromatography.

[0300] 15g of the following compound (C-4) was obtained.

[0301]

[0302] Repeating unit x = 14.5

[0303] Synthesis Example 1-9

[0304] In a 50 mL two-necked flask, 0.04 g of lithium aluminum hydride was suspended in 1.6 g of THF (tetrahydrofuran). While cooling the mixture in an ice bath, 6.1 g of the above compound (C-4) was slowly added dropwise using AC-6000 (C6F) solution. 13 A solution of 6.0 g of C2H5 (manufactured by AGC Corporation) was diluted. The ice bath was then removed, and the solution was slowly heated to room temperature while stirring. After stirring at room temperature for 12 hours, hydrochloric acid solution was added dropwise until the solution became acidic. 15 mL of AK-225 was added, and the solution was washed once with water and once with saturated brine to recover the organic phase. The recovered organic phase was concentrated using an evaporator to obtain 5.9 g of the following difunctional compound (C-5).

[0305] HO-CH2-CF2CF2CF2O-(CF2CF2O-CF2CF2CF2CF2O) c5 -CF2CF2O-CF2CF2CF2-CH2OH:C-5

[0306] Repeating unit x = 14.5

[0307] Synthesis Example 1-10

[0308] 5g of the 0-functional compound (A-3), 86g of the 1-functional compound (B-1), and 9g of the 2-functional compound (C-5) were mixed to prepare sample mixtures of Examples 1-16 and 35-37.

[0309] [Synthesis example 2]

[0310] Synthesis example 2-1

[0311] Fomblin M (product name of Solebey Soles) was purified by silica gel column chromatography to obtain the following non-functional compound (D-1).

[0312] CF3-O-(CF2O) n ·(CF2CF2O) m -CF3:D-1

[0313] Repeating units n=25, m=22

[0314] Synthesis example 2-2

[0315] Compound E-1 was obtained by following the method described in Example 1 of Example No. 2017 / 038830 (specifically, Examples 1-1 to 1-4).

[0316] CF3CF2CF2OCF2CF2OCF2CF2[(OCF2) n ·(OCF2CF2) m OCF2C(=O)

[0317] OCH3: E-1

[0318] Repeating units n=25, m=21

[0319] Next, 2.4 g of sodium borohydride powder was added to a 300 cc three-necked round-bottom flask, along with 15 g of AC-2000 (a product name from AGC Corporation). While cooling in an ice bath and stirring, a solution containing 30 g of the aforementioned compound E-1, 4 g of methanol, and 60 g of AC-2000 was slowly added dropwise through a dropping funnel under a nitrogen atmosphere and at an internal temperature not exceeding 10°C. After the total volume was added, another 4 g of methanol was added dropwise. The mixture was then stirred at 10°C for 1 hour. The mixture was cooled again in an ice bath, and hydrochloric acid solution was added dropwise until the solution became acidic. After the reaction was complete, the mixture was washed once with hydrochloric acid solution and once with water to recover the organic phase.

[0320] The recovered organic phase was concentrated using an evaporator. The concentrated solution was then removed by vacuum distillation and purified by column chromatography to obtain 24 g of compound E-2 as described below.

[0321] CF3CF2CF2OCF2CF2OCF2CF2[(OCF2) n ·(OCF2CF2) m OCF2-CH2-OH:E-2

[0322] Repeating units n=25, m=21

[0323] Synthesis example 2-3

[0324] Fomblin D4000 (product name of Sorbeischiss) was purified by silica gel column chromatography to obtain the following difunctional compound (F-1).

[0325] HOCH2-(CF2O){(CF2O) n ·(CF2CF2O) m}-CF2-CH2OH:F-1

[0326] Repeating units n=25, m=22

[0327] Synthesis example 2-4

[0328] 15g of a 0-functional compound (D-1), 55g of a 1-functional compound (E-2), and 30g of a 2-functional compound (F-1) were mixed to prepare mixtures as in Examples 17 to 25.

[0329] Synthesis Example 2-5

[0330] 5g of the 0-functional compound (D-1), 86g of the 1-functional compound (E-2), and 9g of the 2-functional compound (F-1) were mixed to prepare the mixture of Example 32.

[0331] [Synthesis example 3]

[0332] Synthesis example 3-1

[0333] The following compound (G-1) was obtained by the method described in Example 6 of International Publication No. 2013 / 121984.

[0334] CF3-O-(CF2CF2O-CF2CF2CF2CF2O) g1 -CF2CF2OCF2CF2CF2C(=O)OCH3:

[0335] G-1

[0336] Repeating unit g1 = 14.5

[0337] Synthesis example 3-2

[0338] In a 300 mL four-necked flask equipped with a serpentine condenser, dropping funnel, thermometer, and magnetic stirrer, 40 g of compound G-1, 25 g of allyl magnesium bromide diethyl ether solution (bromine concentration 0.05 mol / 100 g), 40 g of 1,3-bis(trifluoromethylbenzene), and 13 g of tetrahydrofuran were added, and the inside of the flask was purged with nitrogen. The resulting mixture was stirred and reacted at an internal temperature of 60 °C for 6 hours, then cooled to room temperature (20 °C). The mixture was then slowly added to a separatory funnel coated with hydrochloric acid solution (a mixture of 6 g of 12N hydrochloric acid and 54 g of water), stirred for 30 minutes, and the lower layer was collected. The solvent components of the recovered solution were removed at 110 °C / 1 mmHg, and purified by silica gel column chromatography to obtain 35 g of the monofunctional compound (G-2).

[0339] CF3O-(CF2CF2O-CF2CF2CF2CF2O) g2 CF2CF2OCF2CF2CF2C(OH)(CH2CH=CH2)2:G-2

[0340] Repeating unit g2 = 14.5

[0341] Synthesis example 3-3

[0342] In a 300 mL four-necked flask equipped with a serpentine condenser, dropping funnel, thermometer, and magnetic stirrer, 40 g of compound (C-4), 50 g of allyl magnesium bromide diethyl ether solution (bromine concentration 0.05 mol / 100 g), 40 g of 1,3-bis(trifluoromethylbenzene), and 13 g of tetrahydrofuran were added. The flask was then purged with nitrogen. The resulting mixture was stirred and reacted at an internal temperature of 60 °C for 6 hours, followed by cooling to room temperature (20 °C). The mixture was then slowly added to a separatory funnel containing hydrochloric acid solution (a mixture of 6 g of 12N hydrochloric acid and 54 g of water), stirred for 30 minutes, and the lower layer was collected. The solvent was removed from the recovered solution at 110 °C / 1 mmHg, and the solution was purified by silica gel column chromatography to obtain 35 g of the difunctional compound (H-1).

[0343]

[0344] Repeating unit x = 14.5

[0345] Synthesis Example 3-4

[0346] The sample mixture of Example 26 was prepared by mixing 5g of the 0-functional compound (A-3), 86g of the 1-functional compound (G-2), and 9g of the 2-functional compound (H-1).

[0347] [Synthesis Example 4]

[0348] Synthesis example 4-1

[0349] 5g of the above-mentioned 0-functional compound A-3, 86g of the above-mentioned 1-functional compound (G-1), and 9g of the above-mentioned 2-functional compound (C-4) were mixed to prepare the sample mixture of Example 27.

[0350] [Synthesis example 5]

[0351] Synthesis example 5-1

[0352] In a 200cc round-bottom flask, 0.67g of HO(C=O)C(CH2CH=CH2)3, 33mL of dichloromethane, and 0.67mL of oxaloyl chloride were added. The mixture was stirred while ice-cold, followed by the addition of 0.0393g of DMF (N,N-dimethylformamide). The mixture was then concentrated at room temperature to obtain 0.6g of Cl(C=O)C(CH2CH=CH2)3.

[0353] In a separate 50cc flask, 7g of compound B-1, 7g of AC-6000, 0.4g of triethylamine, and 0.2g of N,N-dimethyl-4-aminopyridine were added, followed by 0.6g of the aforementioned Cl(C=O)C(CH2CH=CH2)3. The mixture was stirred at 30°C. The resulting mixture was purified by silica gel column chromatography to obtain 5.8g of the monofunctional compound (I-1).

[0354] CF3O(CF2CF2OCF2CF2CF2CF2O) i1 CF2CF2OCF2CF2CF2-CH2O(C=O)C(CH2CH=CH2)3:I-1

[0355] Repeating unit i1 = 14.5

[0356] Synthesis example 5-2

[0357] In a 200cc round-bottom flask, 0.67g of HO(C=O)C(CH2CH=CH2)3, 33mL of dichloromethane, and 0.67mL of oxaloyl chloride were added. The mixture was stirred while ice-cold, followed by the addition of 0.0393g of DMF (N,N-dimethylformamide). The mixture was then concentrated at room temperature to obtain 0.6g of Cl(C=O)C(CH2CH=CH2)3.

[0358] Synthesis example 5-3

[0359] In a separate 50cc flask, 3.5g of compound C-5, 7g of AC-6000, 0.4g of triethylamine, and 0.2g of N,N-dimethyl-4-aminopyridine were added, along with 0.6g of the above Cl(C=O)C(CH2CH=CH2)3. The mixture was stirred at 30°C. The resulting mixture was purified by silica gel column chromatography to obtain 2.4g of the following difunctional compound (J-1).

[0360]

[0361] Repeating unit x = 14.5 (Synthesis Example 8-4)

[0362] Synthesis example 5-4

[0363] 5g of the 0-functional compound (A-3), 86g of the 1-functional compound (I-1), and 9g of the 2-functional compound (J-1) were mixed to prepare the sample mixture of Example 28.

[0364] [Synthesis Example 6]

[0365] Synthesis example 6-1

[0366] The following 1-functional compound (K-1) was obtained by the method described in Example 11 of International Publication No. 2017 / 038830.

[0367] CF3-O-(CF2CF2O-CF2CF2CF2CF2O) k1 (CF2CF2O)-CF2CF2CF2-C(O)NH-CH2-C(CH2CH=CH2)3:K-1

[0368] Repeating unit k1 = 14.5

[0369] Synthesis example 6-2

[0370] In a 50 mL flask, 15 g of compound (C-4), 3.2 g of H2NCH2C(CH2CH=CH2)3, and 15 mL of AC-2000 were added, and the mixture was stirred at 0 °C for 24 hours. The mixture was then purified by silica gel column chromatography. 11.2 g of the following difunctional compound (L-1) was obtained.

[0371]

[0372] Repeating unit x = 14.5

[0373] Synthesis Example 6-3

[0374] 5g of the 0-functional compound (A-3), 86g of the 1-functional compound (K-1), and 9g of the 2-functional compound (L-1) were mixed to prepare the sample mixture of Example 29.

[0375] [Synthesis Example 7]

[0376] Synthesis example 7-1

[0377] In a 100cc pressure-resistant reactor, 15g of compound G-1, 50g of ASAHIKLIN AK-225 (AGC Corporation product name), and 7.5g of 2.0M ammonia-methanol solution were added, and the mixture was stirred at room temperature for 6 hours. Subsequently, the solvent was removed from the mixture by distillation to obtain 14.8g of the target monofunctional compound (M-1).

[0378] CF3(OCF2CF2OCF2CF2CF2CF2) m1 OCF2CF2OCF2CF2CF2-C(=O)NH2:M-1

[0379] Repeating unit m1 = 14.5

[0380] Synthesis example 7-2

[0381] 15g of compound C-4, 50g of ASAHIKLIN AK-225 (AGC Corporation product name), and 15g of 2.0M ammonia-methanol solution were placed in a 100cc pressure reactor and stirred at room temperature for 6 hours. Subsequently, the solvent was removed from the mixture by distillation to obtain 14.8g of the target difunctional compound (N-1).

[0382]

[0383] Repeating unit x = 14.5

[0384] Synthesis Example 7-3

[0385] The sample mixture of Example 30 was prepared by mixing 5g of the 0-functional compound (A-3), 86g of the 1-functional compound (M-1), and 9g of the 2-functional compound (N-1).

[0386] [ Synthesis example 8]

[0387] Synthesis example 8-1

[0388] In a 300cc round-bottom flask, 15g of compound M-1, 75g of AK-225, and 30g of diethyl ether were added, and the mixture was stirred in an ice bath. Then, 0.31g of lithium aluminum hydride was slowly added to the resulting mixture, and the mixture was stirred at room temperature for 20 hours. Subsequently, 0.3cc of a saturated aqueous solution of sodium sulfate was added to the mixture, and the precipitated solids were removed by filtration through a cerium silicate filter. The resulting filtrate was concentrated and purified by silica gel column chromatography to obtain 6.8g of the target compound (O-1).

[0389] CF3(OCF2CF2OCF2CF2CF2CF2) o1 OCF2CF2OCF2CF2CF2-CH2NH2:O-1

[0390] Repeating unit o1 = 14.5

[0391] Synthesis example 8-2

[0392] In a separate 50cc round-bottom flask, add 3.0 g of compound (A-3) and 0.35 mL of triethylamine, along with 0.45 g of Cl(C=O)C(CH2CH=CH2)3 synthesized in Synthesis Example 5-1 and 2 mL of 1,3-bis(trifluoromethylbenzene). Stir the mixture for 1 hour, then remove the solvent by distillation. Purify the crude compound using silica gel column chromatography to obtain 1.7 g of the target monofunctional compound (O-2).

[0393] CF3(OCF2CF2OCF2CF2CF2CF2) o2 OCF2CF2OCF2CF2CF2-CH2NH(C=O)C(CH2CH=CH2)3:O-2

[0394] Repeating unit o2 = 14.5

[0395] Synthesis example 8-3

[0396] In a 300cc round-bottom flask, 15g of compound (N-1), 75g of AK-225, and 30g of diethyl ether were added, and the mixture was stirred in an ice bath. Then, 0.62g of lithium aluminum hydride was slowly added to the mixture, and the mixture was stirred at room temperature for 20 hours. Subsequently, 0.6cc of a saturated aqueous solution of sodium sulfate was added to the mixture, and the precipitated solid was removed by cerium silicate filtration. The resulting filtrate was concentrated and purified by silica gel column chromatography to obtain 6.8g of the target compound (P-1).

[0397]

[0398] Repeating unit x = 14.5

[0399] Synthesis example 8-4

[0400] In a separate 50cc flask, 3.0 g of compound (P-1) and 0.7 mL of triethylamine were added, along with 0.45 g of Cl(C=O)C(CH2CH=CH2)3 synthesized in Synthesis Example 5-3 and 2 mL of 1,3-bis(trifluoromethylbenzene). The mixture was stirred for 1 hour, and the solvent was removed by distillation. The crude compound was purified by silica gel column chromatography to give 1.7 g of the difunctional compound (P-2).

[0401] NMR spectrum of compound X8-6;

[0402]

[0403] Synthesis example 8-5

[0404] 5g of the 0-functional compound (A-3), 86g of the 1-functional compound (O-2), and 9g of the 2-functional compound (P-2) were mixed to prepare the sample mixture of Example 31.

[0405] Synthesis example 9-1

[0406] In a 300 mL flask, 100 g of compound (F-1), 14.9 g of cesium carbonate, and 100 g of 1,3-bis(trifluoromethyl)benzene were added, along with 6.4 g of propyl p-toluenesulfonate. The mixture was stirred at 80 °C for 8 hours under a nitrogen atmosphere. The mixture was washed with dilute hydrochloric acid solution, the organic layer was recovered, concentrated using an evaporator, and purified by silica gel column chromatography to obtain a mixture containing 15.2 g, 55.3 g, and 29.5 g of the following compounds: 0-functional compound (Q-1), 1-functional compound (Q-2), and 2-functional compound (F-1).

[0407] CH3CH2CH2OCH2-(CF2O){(CF2O) n (CF2CF2O) m}-CF2-CH2OCH2CH2CH3:(Q-1)

[0408] HOCH2-(CF2O){(CF2O) n (CF2CF2O) m}-CF2-CH2OCH2CH2CH3:(Q-2)

[0409] HOCH2-(CF2O){(CF2O) n ·(CF2CF2O) m}-CF2-CH2OH:(F-1)

[0410] (Separation Method)

[0411] The sample mixtures of Examples 1 to 37 prepared above were separated by column chromatography.

[0412] A mixture of solvent (200g) and silica gel (50g) used as the mobile phase was placed in a column with a diameter of 2cm and a height of 70cm. Then, 200g of the solvent used as the mobile phase was allowed to flow to prepare the stationary phase.

[0413] Subsequently, a mixture of the sample mixture (10 g) from 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 pushed from the top of the column at a pressure of 0.1 MPa N2 (gauge pressure), and 1000 g of the solution was recovered as the first fraction. This recovered product was concentrated and analyzed using a high-performance liquid chromatograph (HPLC, manufactured by Shimadzu Corporation). Then, a solvent mixture of the previously used mobile phase solvent and acetone at a mass ratio of 1:1 was pushed, and 500 g of the solution was recovered as the second fraction. This fraction was concentrated and analyzed using HPLC.

[0414] The specific solvents used as the mobile phase are shown below.

[0415] Solvent 1: CF3CF=CCl2(CFO)

[0416] Solvent 2: CFCl2CF=CF2(CFO)

[0417] Solvent 3: CF₂HCF = CHCl(HCFO)

[0418] Solvent 4: CF3CH=CHCl(Z)(HCFO)

[0419] Solvent 5: CF3CH=CHCl(E)(HCFO)

[0420] Solvent 6: CClF₂CF = CHCl(HCFO)

[0421] Solvent 7: CHF₂CF₂CF₂CF=CHCl(HCFO)

[0422] Solvent 8: CF3CH2CF=CH2(HFO)

[0423] Solvent 9: CF3CH=CHCF3(E)(HFO)

[0424] Solvent 10: CF3CH=CHCF3(Z)(HFO)

[0425] Solvent 11: Compounds with the following formula (cyclic HFCs)

[0426]

[0427] Solvent 12: Compounds with the following formula (cyclic CFO)

[0428]

[0429] Solvent 13: Compounds with the following formula (cyclic CFO)

[0430]

[0431] Solvent 14: CF3CF2COCF(CF3)2(PFK)

[0432] Solvent 15: (CF3)2CFCOCF(CF3)2(PFK)

[0433] Solvent 16: CF3CF2CF2OCFCF3COCF(CF3)2(PFK)

[0434] Solvent 17: A mixture of 95 wt% CF3CF=CCl2 (CFO) and 5 wt% hexane (hydrocarbon (HC)).

[0435] Solvent 18: C6F 14 (Perfluorocarbons (PFCs))

[0436] Solvent 19: Hexane (hydrocarbon (HC))

[0437] Solvent 20: ASAHIKLIN AK-225 (product name of AGC Corporation, hydrochlorofluorocarbon (HCFC))

[0438] The key points of the separation of the sample mixtures of Examples 1 to 37 above, and the results obtained therein, are shown in Tables 1 to 3 below. It should be noted that the yields in Table 3 represent the recovery rate (mass %) of each fraction relative to the input mass (each component before separation).

[0439] [Table 1]

[0440] example A- -OZ-(R)n Main chain repeating structure 1 fluoroalkyl <![CDATA[-O-(CF2)3-CH2OH]]> <![CDATA[(CF2CF2O-CF2CF2CF2CF2O)x]]> 2 fluoroalkyl <![CDATA[-O-(CF2)3-CH2OH]]> <![CDATA[(CF2CF2O-CF2CF2CF2CF2O)x]]> 3 Fluorine Tomb <![CDATA[-O-(CF2)3-CH2OH]]> <![CDATA[(CF2CF2O-CF2CF2CF2CF2O)x]]> 4 Fluorine Tomb <![CDATA[-O-(CF2)3-CH2OH]]> <![CDATA[(CF2CF2O-CF2CF2CF2CF2O)x]]> 5 fluoroalkyl <![CDATA[-O-(CF2)3-CH2OH]]> <![CDATA[(CF2CF2O-CF2CF2CF2CF2O)x]]> 6 fluoroalkyl <![CDATA[-O-(CF2)3-CH2OH]]> <![CDATA[(CF2CF2O-CF2CF2CF2CF2O)x]]> 7 fluoroalkyl <![CDATA[-O-(CF2)3-CH2OH]]> <![CDATA[(CF2CF2O-CF2CF2CF2CF2O)x]]> 8 fluoroalkyl <![CDATA[-O-(CF2)3-CH2OH]]> <![CDATA[(CF2CF2O-CF2CF2CF2CF2O)x]]> 9 fluoroalkyl <![CDATA[-O-(CF2)3-CH2OH]]> <![CDATA[(CF2CF2O-CF2CF2CF2CF2O)x]]> 10 fluoroalkyl <![CDATA[-O-(CF2)3-CH2OH]]> <![CDATA[(CF2CF2O-CF2CF2CF2CF2O)x]]> 11 fluoroalkyl <![CDATA[-O-(CF2)3-CH2OH]]> <![CDATA[(CF2CF2O-CF2CF2CF2CF2O)x]]> 12 fluoroalkyl <![CDATA[-O-(CF2)3-CH2OH]]> <![CDATA[(CF2CF2O-CF2CF2CF2CF2O)x]]> 13 fluoroalkyl <![CDATA[-O-(CF2)3-CH2OH]]> <![CDATA[(CF2CF2O-CF2CF2CF2CF2O)x <!-- 23 -->]]> 14 fluoroalkyl <![CDATA[-O-(CF2)3-CH2OH]]> <![CDATA[(CF2CF2O-CF2CF2CF2CF2O)x]]> 15 fluoroalkyl <![CDATA[-O-(CF2)3-CH2OH]]> <![CDATA[(CF2CF2O-CF2CF2CF2CF2O)x]]> 16 fluoroalkyl <![CDATA[-O-(CF2)3-CH2OH]]> <![CDATA[(CF2CF2O-CF2CF2CF2CF2O)x]]> 17 fluoroalkyl <![CDATA[-O-(CF2)-CH2OH]]> <![CDATA[(CF2O)n-(CF2CF2O)m]]> 18 fluoroalkyl <![CDATA[-O-(CF2)-CH2OH]]> <![CDATA[(CF2O)n-(CF2CF2O)m]]> 19 fluoroalkyl <![CDATA[-O-(CF2)-CH2OH]]> <![CDATA[(CF2O)n-(CF2CF2O)m]]> 20 Fluorine Tomb <![CDATA[-O-(CF2)-CH2OH]]> <![CDATA[(CF2O)n-(CF2CF2O)m]]> 21 fluoroalkyl <![CDATA[-O-(CF2)-CH2OH]]> <![CDATA[(CF2O)n-(CF2CF2O)m]]> 22 fluoroalkyl <![CDATA[-O-(CF2)-CH2OH]]> <![CDATA[(CF2O)n-(CF2CF2O)m]]> 23 fluoroalkyl <![CDATA[-O-(CF2)-CH2OH]]> <![CDATA[(CF2O)n-(CF2CF2O)m]]> 24 Fluorine Tomb <![CDATA[-C-(CF2)-CH2OH]]> <![CDATA[(CF2O)n-(CF2CF2O)m]]> 25 fluoroalkyl <![CDATA[-O-(CF2)-CH2OH]]> <![CDATA[(CF2O)n-(CF2CF2O)m]]> 26 fluoroalkyl <![CDATA[-O-(CF2)3-C(OH)(CH2CH=CH2)2]]> <![CDATA[(CF2CF2O-CF2CF2CF2CF2O)x]]> 27 fluoroalkyl <![CDATA[-O-(CF 2)3 -COOCH3]]> <![CDATA[(CF2CF2O-CF2CF2CF2CF2O)x]]> 28 Fluorine Tomb <![CDATA[-O-(CF2)3-CH2OC(=O)C(CH2CH=CH2)3]]> <![CDATA[(CF2CF2O-CF2CF2CF2CF2O)x]]> 29 fluoroalkyl <![CDATA[-O-(CF2)3-CONHCH2C(CH2CH=CH2)3]]> <![CDATA[(CF2CF2O-CF2CF2CF2CF2O)x]]> 30 fluoroalkyl <![CDATA[-O-(CF2)3-CONH2]]> <![CDATA[(CF2CF2O-CF2CF2CF2CF2O)x]]> 31 fluoroalkyl <![CDATA[-O-(CF2)3-CH2NHCOC(CH2CH=CH2)3]]> <![CDATA[(CF2CF2O-CF2CF2CF2CF2O)x]]> 32 fluoroalkyl <![CDATA[-O-(CF2)-CH2OH]]> <![CDATA[(CF2O)n-(CF2CF2O)m]]> 33 fluoroalkyl <![CDATA[-O-(CF2)3-CH2OH]]> <![CDATA[(CF2CF2O-CF2CF2CF2CF2O)x]]> 34 alkyl <![CDATA[-O-(CF2)-CH2OH]]> <![CDATA[(CF2O)n-(CF2CF2O)m]]> 35 fluoroalkyl <![CDATA[-O-(CF2)3-CH2OH]]> <![CDATA[(CF2CF2O-CF2CF2CF2CF2O)x]]> 36 Fluorine Tomb <![CDATA[-O-(CF2)3-CH2OH]]> <![CDATA[(CF2CF2O-CF2CF2CF2CF2O)x]]> 37 fluoroalkyl <![CDATA[-O-(CF2)3-CH2OH]]> <![CDATA[(CF2CF2O-CF2CF2CF2CF2O)x]]>

[0441] [Table 2]

[0442]

[0443] [Table 3]

[0444]

[0445] As shown in Tables 1-3, for Examples 1-34 using CFO, HCFO, HFO, cyclic HFC, cyclic CFO, or PFK as the mobile phase, the yield of fluorinated compounds is high, and one functional body can be separated in high purity in the first fraction and two functional bodies can be separated in high purity in the second fraction.

[0446] In Examples 1-13 and 17-25, which used CFO, HCFO, HFO, cyclic HFC, or cyclic CFO, the purity of the monofunctional component in the first fraction was high, and the purity of the difunctional component in the second fraction was high. In Examples 1, 2, 8-13, 17, 18, and 24-25, which used CFO, HFO, cyclic HFC, or cyclic CFO, the purity of the monofunctional component in the first fraction was even higher, and the purity of the difunctional component in the second fraction was even higher. In Examples 8-11, 24, and 25, which used HFO or cyclic HFC, the purity of the monofunctional component in the first fraction was even higher, and the purity of the difunctional component in the second fraction was even higher.

[0447] In Example 33, which uses a mixed solvent of CFO and HC, the first functional body of the first fraction can be separated with high purity, but the yield is reduced.

[0448] If focusing on the main chain of fluorine-containing compounds, then a main chain of (CF2O) is used. n ·(CF2CF2O) m In Examples 17–25, 32, and 34 of the Fomblin-based fluorinated compounds, the separation ability of the monofunctional in the first fraction is high, and the separation ability of the difunctional in the second fraction is high.

[0449] If we focus on the -OZ-(R) of fluorine-containing compounds n In Examples 1-25, 32-37 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, the purity of the monofunctional in the first fraction is high, and the purity of the difunctional in the second fraction is high. Compared with Example 17, where A is a perfluoroalkyl group, the purity and yield of the monofunctional in the first fraction of Example 34, where A is an alkyl group, are slightly lower.

[0450] It should be noted that the entire contents of the specification, claims and abstract of Japanese Patent Application No. 2020-155413, filed on September 16, 2020, are incorporated herein as a disclosure of the specification of this invention.

Claims

1. An isolation method of isolating a compound represented by the following formula (1) and a compound represented by the following formula (2) from a mixture containing them using a chromatograph with a mobile phase and a stationary phase, ###0001### ###0002### the isolation method comprising: a step of supplying the mixture to the stationary phase of the chromatograph and adsorbing the mixture to the stationary phase; and a step of supplying a mobile phase to the stationary phase to which the mixture is adsorbed, the mobile phase containing at least one specific solvent selected from the group consisting of hydrofluoroolefins, hydrochlorofluoroolefins, chlorofluoroolefins, cyclic hydrofluoroolefins, cyclic hydrochlorofluoroolefins, cyclic chlorofluoroolefins, and perfluoroketones, wherein 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, and n1, n2, and n3 are each 1. A is a fluoroalkyl group and X is a fluoroalkylene group having one or more fluorine atoms in the formula (1) and the formula (2). The mixture further contains a compound represented by the following formula (3), and the isolation method isolates the compound represented by the formula (1), the compound represented by the formula (2), and the compound represented by the formula (3), ###0003### wherein A, X, and m have the same meanings as in the formula (1) and the formula (2). The specific solvent is a solvent not containing a chlorine atom. A-(OX) m -O-Z-(R) n1 Formula (1) (R) n2 -Z-(OX) m -O-Z-(R) n3 formula (2) The specific solvent contains at least one selected from the group consisting of hydrofluoroolefins and cyclic hydrofluoroolefins. 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. The stationary phase is selected from the group consisting of alumina, silica gel, magnesia, aluminum silicate, magnesium silicate, and diatomaceous earth. The silica gel is chemically modified silica gel. Z is one or more linking groups selected from the group consisting of an alkylene group, a fluoroalkylene group, a hydroxyalkylene group, an alkoxyalkylene group, an amide bond, an ether bond, a thioether bond, a urea bond, a carbamate bond, a carbonate bond, an ester bond, -SO2NR 6 , -Si(R 6 )2-, -OSi(R 6 )2-, -Si(CH3)2-Ph-Si(CH3)2-, and a divalent organopolysiloxane residue, wherein R 6 is a hydrogen atom, an alkyl group having a carbon number of 1 to 6, or a phenyl group, R is any functional group selected from the group consisting of -OH, -CR 1 =CR 2 R 3 , -CH3, and -NH2, wherein 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, The chromatograph is a column chromatograph.

2. The separation method of claim 1, wherein, ​ 3. The separation method according to claim 1 or 2, wherein, ​ A-(OX) m -O-A Formula (3) ​ 4. The separation method according to claim 1 or 2, wherein, ​ 5. The separation method according to claim 1 or 2, wherein, ​ 6. The separation method of claim 3, wherein, In the formula (1), formula (2), formula (3), the (OX) m comprises the following structure, {(OCF2) m21 • (OCF2CF2) m22} ​ 7. The separation method according to claim 1 or 2, wherein, ​ 8. The separation method of claim 7, wherein, ​ 9. The separation method according to claim 1 or 2, wherein, ​

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