Fluorine-containing compound and production method of same and surfactant

Abstract

A compound represented by general formula: R1-R2-X, wherein R1 is -CH3, -CH2F, -CHF2, -CH2I, -CHFI or an anionic group; R2 is an alkylene group formed only with a unit represented by -CFH- or an alkylene group formed only with a unit represented by -CFH- and a unit represented by -CH2-, provided that the alkylene groups may optionally contain an epoxy group, -CH(OH)-, -CHI- or a bivalent cycloalkylene group; and X is -OH, -CH(R21)OH (wherein R21 is H, a non-fluorinated alkyl group or a fluorinated alkyl group), -I, -CFHI, -CH2I, an anionic group or -COOR22 (wherein R22 is a non-fluorinated alkyl group with 1-8 carbon atoms); and the total number of carbon atoms in R1, R2 and X is 2-50.

Description

Fluorine-containing compound, its production method, and surfactant

[0001] The present disclosure relates to a fluorine-containing compound, a method for producing the same, and a surfactant.

[0002] Patent Document 1 describes a compound of the formula Rf-(CH ２ ) ｍ -R'f-COOY, wherein m is 1 to 3, Rf is a perfluoroalkyl or perfluoroalkoxy containing 3 to 8 carbon atoms, R'f is a linear or branched perfluoroalkylene containing 1 to 4 carbon atoms, Y is M or R, and M is NH ４ , Li, Na, K, or H, and R is a linear, branched, or cyclic alkyl containing 1 to 8 carbon atoms.

[0003] Patent Document 2 discloses a compound of formula (I) RfCH ２ OCF (CF ３ )C(O)OM (I) where Rf is a linear or branched perfluoroalkyl group having 2 to 5 carbon atoms and M is H, NH ４ Fluorosurfactants in which the fluorine atom is Li, Na or K are described.

[0004] JP-A-10-212261 Publication Special Publication No. 2012-513531

[0005] However, the compounds described in Patent Documents 1 and 2 both have CF at the molecular terminal. ３ - (trifluoromethyl group) or -CF ２ - (difluoromethylene group) and CF ３ - and -CF ２ There are no fluorine-containing compounds that do not contain units represented by -.

[0006] An object of the present disclosure is to provide a novel fluorine-containing compound that does not contain a trifluoromethyl group or a difluoromethylene group.

[0007] According to the present disclosure, a compound of the general formula: R １ -R ２ -X (wherein, R１ is -CH ３ , -CH ２ F, -CHF ２ , -CH ２ I, -CHFI, or an anionic group, and R ２ represents an alkylene group consisting of only units represented by -CFH-, or a group consisting of units represented by -CFH- and -CH ２ - is an alkylene group consisting only of units represented by -, provided that these alkylene groups may optionally contain an epoxy group, -CH(OH)-, -CHI-, or a divalent cycloalkylene group, and X is -OH, -CH(R ２１ )OH(R ２１ represents H, a non-fluorinated alkyl group or a fluorinated alkyl group), -I, -CFHI, -CH ２ I, an anionic group or -COOR ２２ (R ２２ is a non-fluorinated alkyl group having 1 to 8 carbon atoms, and R １ , R ２ and X has a total of 2 to 50 carbon atoms.

[0008] According to the present disclosure, it is possible to provide a novel fluorine-containing compound that does not contain a trifluoromethyl group or a difluoromethylene group.

[0009] Before specifically describing the present disclosure, some terms used in the present disclosure will be defined or explained.

[0010] In the present disclosure, the term "organic group" refers to a group containing one or more carbon atoms or a group formed by removing one hydrogen atom from an organic compound. Examples of the "organic group" include an alkyl group which may have one or more substituents, an alkenyl group which may have one or more substituents, an alkynyl group which may have one or more substituents, a cycloalkyl group which may have one or more substituents, a cycloalkenyl group which may have one or more substituents, a cycloalkadienyl group which may have one or more substituents, an aryl group which may have one or more substituents, an aralkyl group which may have one or more substituents, a non-aromatic heterocyclic group which may have one or more substituents, a heteroaryl group which may have one or more substituents, a cyano group, a formyl group, RaO-, RaCO-, and RaSO. ２ -, RaCOO-, RaNRaCO-, RaCONRa-, RaOCO-, RaOSO ２ -, and RaNRbSO ２ - (In these formulas, Ra is independently an alkyl group which may have one or more substituents, an alkenyl group which may have one or more substituents, an alkynyl group which may have one or more substituents, a cycloalkyl group which may have one or more substituents, a cycloalkenyl group which may have one or more substituents, a cycloalkadienyl group which may have one or more substituents, an aryl group which may have one or more substituents, an aralkyl group which may have one or more substituents, a non-aromatic heterocyclic group which may have one or more substituents, or a heteroaryl group which may have one or more substituents; and Rb is independently H or an alkyl group which may have one or more substituents). As the organic group, an alkyl group which may have one or more substituents is preferred.

[0011] In the present disclosure, the term "substituent" refers to a substitutable group. Examples of the "substituent" include an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, an aliphatic oxy group, an aromatic oxy group, a heterocyclic oxy group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, a heterocyclic oxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group, an aromatic sulfonyl group, a heterocyclic sulfonyl group, an aliphatic sulfonyloxy group, an aromatic sulfonyloxy group, a heterocyclic sulfonyloxy group, a sulfamoyl group, an aliphatic sulfonamido group, an aromatic sulfonamido group, a heterocyclic sulfonamido group, an amino group, and an aliphatic amino group. groups, aromatic amino groups, heterocyclic amino groups, aliphatic oxycarbonylamino groups, aromatic oxycarbonylamino groups, heterocyclic oxycarbonylamino groups, aliphatic sulfinyl groups, aromatic sulfinyl groups, aliphatic thio groups, aromatic thio groups, hydroxy groups, cyano groups, sulfo groups, carboxy groups, aliphatic oxyamino groups, aromatic oxyamino groups, carbamoylamino groups, sulfamoylamino groups, halogen atoms, sulfamoylcarbamoyl groups, carbamoylsulfamoyl groups, dialiphatic oxyphosphinyl groups, and diaromatic oxyphosphinyl groups.

[0012] The aliphatic group may be saturated or unsaturated and may have a hydroxy group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the aliphatic group include alkyl groups having a total of 1 to 8, preferably 1 to 4, carbon atoms, such as a methyl group, an ethyl group, a vinyl group, a cyclohexyl group, and a carbamoylmethyl group.

[0013] The aromatic group may have, for example, a nitro group, a halogen atom, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the aromatic group include aryl groups having 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms in total, such as a phenyl group, a 4-nitrophenyl group, a 4-acetylaminophenyl group, and a 4-methanesulfonylphenyl group.

[0014] The heterocyclic group may have a halogen atom, a hydroxy group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the heterocyclic group include 5- or 6-membered heterocycles having a total of 2 to 12, preferably 2 to 10, carbon atoms, such as a 2-tetrahydrofuryl group and a 2-pyrimidyl group.

[0015] The acyl group may have an aliphatic carbonyl group, an arylcarbonyl group, a heterocyclic carbonyl group, a hydroxy group, a halogen atom, an aromatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the acyl group include acyl groups having a total of 2 to 8, preferably 2 to 4, carbon atoms, such as an acetyl group, a propanoyl group, a benzoyl group, and a 3-pyridinecarbonyl group.

[0016] The acylamino group may have an aliphatic group, an aromatic group, a heterocyclic group, etc., such as an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propanoylamino group, etc. Examples of the acylamino group include acylamino groups having a total of 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, and alkylcarbonylamino groups having a total of 2 to 8 carbon atoms, such as an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propanoylamino group, etc.

[0017] The aliphatic oxycarbonyl group may be saturated or unsaturated and may have a hydroxy group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the aliphatic oxycarbonyl group include alkoxycarbonyl groups having a total of 2 to 8, preferably 2 to 4, carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, and a (t)-butoxycarbonyl group.

[0018] The carbamoyl group may have an aliphatic group, an aromatic group, a heterocyclic group, etc. Examples of the carbamoyl group include an unsubstituted carbamoyl group, an alkylcarbamoyl group having a total of 2 to 9 carbon atoms, preferably an unsubstituted carbamoyl group, or an alkylcarbamoyl group having a total of 2 to 5 carbon atoms, such as an N-methylcarbamoyl group, an N,N-dimethylcarbamoyl group, or an N-phenylcarbamoyl group.

[0019] The aliphatic sulfonyl group may be saturated or unsaturated and may have a hydroxy group, an aromatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the aliphatic sulfonyl group include alkylsulfonyl groups having a total of 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, such as a methanesulfonyl group.

[0020] The aromatic sulfonyl group may have a hydroxy group, an aliphatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the aromatic sulfonyl group include arylsulfonyl groups having a total of 6 to 10 carbon atoms, such as a benzenesulfonyl group.

[0021] The amino group may have an aliphatic group, an aromatic group, a heterocyclic group, or the like.

[0022] The acylamino group may have, for example, an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propanoylamino group, etc. Examples of the acylamino group include acylamino groups having a total of 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, and more preferably alkylcarbonylamino groups having a total of 2 to 8 carbon atoms, such as an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propanoylamino group, etc.

[0023] The aliphatic sulfonamide group, aromatic sulfonamide group, and heterocyclic sulfonamide group may be, for example, a methanesulfonamide group, a benzenesulfonamide group, or a 2-pyridinesulfonamide group.

[0024] The sulfamoyl group may have an aliphatic group, an aromatic group, a heterocyclic group, etc. Examples of the sulfamoyl group include a sulfamoyl group, an alkylsulfamoyl group having 1 to 9 carbon atoms in total, a dialkylsulfamoyl group having 2 to 10 carbon atoms in total, an arylsulfamoyl group having 7 to 13 carbon atoms in total, and a heterocyclic sulfamoyl group having 2 to 12 carbon atoms in total, more preferably a sulfamoyl group, an alkylsulfamoyl group having 1 to 7 carbon atoms in total, a dialkylsulfamoyl group having 3 to 6 carbon atoms in total, an arylsulfamoyl group having 6 to 11 carbon atoms in total, and a heterocyclic sulfamoyl group having 2 to 10 carbon atoms in total, such as a sulfamoyl group, a methylsulfamoyl group, an N,N-dimethylsulfamoyl group, a phenylsulfamoyl group, and a 4-pyridine sulfamoyl group.

[0025] The aliphatic oxy group may be saturated or unsaturated and may have a methoxy group, an ethoxy group, an i-propyloxy group, a cyclohexyloxy group, a methoxyethoxy group, etc. Examples of the aliphatic oxy group include alkoxy groups having a total of 1 to 8, preferably 1 to 6, carbon atoms, such as a methoxy group, an ethoxy group, an i-propyloxy group, a cyclohexyloxy group, and a methoxyethoxy group.

[0026] The aromatic amino group and heterocyclic amino group may have an aliphatic group, an aliphatic oxy group, a halogen atom, a carbamoyl group, a heterocyclic group fused with the aryl group, or an aliphatic oxycarbonyl group, preferably an aliphatic group having 1 to 4 carbon atoms in total, an aliphatic oxy group having 1 to 4 carbon atoms in total, a halogen atom, a carbamoyl group having 1 to 4 carbon atoms in total, a nitro group, or an aliphatic oxycarbonyl group having 2 to 4 carbon atoms in total.

[0027] The aliphatic thio group may be saturated or unsaturated and includes alkylthio groups having a total of 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, such as a methylthio group, an ethylthio group, a carbamoylmethylthio group, and a t-butylthio group.

[0028] The carbamoylamino group may have an aliphatic group, an aryl group, a heterocyclic group, etc. Examples of the carbamoylamino group include a carbamoylamino group, an alkylcarbamoylamino group having a total of 2 to 9 carbon atoms, a dialkylcarbamoylamino group having a total of 3 to 10 carbon atoms, an arylcarbamoylamino group having a total of 7 to 13 carbon atoms, and a heterocyclic carbamoylamino group having a total of 3 to 12 carbon atoms, preferably a carbamoylamino group, an alkylcarbamoylamino group having a total of 2 to 7 carbon atoms, a dialkylcarbamoylamino group having a total of 3 to 6 carbon atoms, an arylcarbamoylamino group having a total of 7 to 11 carbon atoms, and a heterocyclic carbamoylamino group having a total of 3 to 10 carbon atoms, such as a carbamoylamino group, a methylcarbamoylamino group, an N,N-dimethylcarbamoylamino group, a phenylcarbamoylamino group, and a 4-pyridinecarbamoylamino group.

[0029] In this disclosure, ranges expressed by endpoints include all numbers subsumed within that range (eg, 1 to 10 includes 1.4, 1.9, 2.33, 5.75, 9.98, etc.).

[0030] In this disclosure, the term "at least 1" includes all numbers greater than or equal to 1 (e.g., at least 2, at least 4, at least 6, at least 8, at least 10, at least 25, at least 50, at least 100, etc.).

[0031] Specific embodiments of the present disclosure will be described in detail below, but the present disclosure is not limited to the following embodiments.

[0032] Compounds of the present disclosure have the general formula: R １ -R ２ -X (wherein, R １ is -CH ３ , -CH ２ F, -CHF２ , -CH ２ I, -CHFI, or an anionic group, and R ２ represents an alkylene group consisting of only units represented by -CFH-, or a group consisting of units represented by -CFH- and -CH ２ - is an alkylene group consisting only of units represented by -, provided that these alkylene groups may optionally contain an epoxy group, -CH(OH)-, -CHI-, or a divalent cycloalkylene group, and X is -OH, -CH(R ２１ )OH(R ２１ represents H, a non-fluorinated alkyl group or a fluorinated alkyl group), -I, -CFHI, -CH ２ I, an anionic group or -COOR ２２ (R ２２ is a non-fluorinated alkyl group having 1 to 8 carbon atoms, and R １ , R ２ and X has a total carbon number of 2 to 50.

[0033] R １ is -CH ３ , -CH ２ F, -CHF ２ , -CH ２ I, -CHFI, or an anionic group, preferably -CH ２ F, -CHF ２ or -CHFI, more preferably -CHF ２ The compound of the present disclosure has CF at the molecular terminal. ３ One of the features is that it does not have a -(trifluoromethyl group).

[0034] R ２ represents an alkylene group consisting of only units represented by -CFH-, or a group consisting of units represented by -CFH- and -CH ２ The compound of the present disclosure always contains a unit represented by -CFH- in the molecular chain, and the compound of the present disclosure always contains a unit represented by -CF ２ One of its features is that it does not contain units indicated by -.

[0035] R ２The number of carbon atoms is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more, and is preferably 49 or less, more preferably 15 or less, and even more preferably 11 or less.

[0036] R ２ The alkylene group of R may optionally contain an epoxy group, —CH(OH)—, —CHI—, or a divalent cycloalkylene group. ２ A part of the alkylene group in R may be substituted with an epoxy group (oxirane group) or a cycloalkylene group, ２ Any of H and F bonded to the carbon atoms constituting the alkylene group may be substituted with OH or I.

[0037] R ２ is an alkylene group consisting only of units represented by -CFH-, R ２ Examples of the group include -(CFH) ｎ１ -(wherein n1 is an integer of 1 or more), -(CFH) ｎ１ An alkylene group represented by the formula - (wherein n1 is an integer of 1 to 49) is preferred, and -CHF- (CHF-CHF) ｎ an alkylene group represented by -(n is an integer of 0 to 24), or -(CHF-CHF) ｎ More preferred is an alkylene group represented by - (n is an integer of 1 to 24). n1 is preferably an integer of 1 to 15, and more preferably an integer of 3 to 11. n is preferably an integer of 1 to 7, and more preferably an integer of 1 to 5.

[0038] R ２ is a unit represented by -CFH- and -CH ２ When the alkylene group is composed only of units represented by -, R ２ Examples of the alkyl group include -CHF-(CHF-CHF) ｎ - (CH ２ ) ｍ an alkylene group represented by -(n is an integer of 0 or more, and m is an integer of 1 or more), -(CHF) ｐ - (CH ２ ) ｑ-(p and q are independently an integer of 1 or more, and the sum of p and q is 2 to 49, and a unit represented by -CFH- and a unit represented by -CH ２ The order of the units represented by - is arbitrary in the formula, and either H or F bonded to a carbon atom may be replaced by OH), an alkylene group represented by -CHF-(CHF-CHF) ｎ -CH ２ -CHI- (CH ２ ) ｑ and alkylene groups represented by the formula -(n is an integer of 0 or more, and q is an integer of 1 or more).

[0039] R ２ is a unit represented by -CFH- and -CH ２ When the alkylene group is composed only of units represented by -, R ２ Examples include -CHF- (CHF-CHF) ｎ - (CH ２ ) ｍ an alkylene group represented by - (n is an integer of 1 to 24, m is an integer of 1 or more), or -CHF- (CHF-CHF) ｎ -CH ２ -CHI- (CH ２ ) ｑ An alkylene group represented by - (n is an integer of 0 or more, q is an integer of 1 or more) is preferred, and -CHF- (CHF-CHF) ｎ -CH ２ an alkylene group represented by -(n is an integer of 1 to 24), -CHF-(CHF-CHF) ｎ -CH ２ CH ２ - (n is an integer from 1 to 23), or -CHF- (CHF-CHF) ｎ -CH ２ -CHI- (CH ２ ) ｑ An alkylene group represented by - (n is an integer of 0 or more, and q is an integer of 1 or more) is more preferred. n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4, and even more preferably an integer of 1 to 3. m is preferably 1 or 2. q is preferably an integer of 1 to 24, more preferably an integer of 1 to 18, and even more preferably an integer of 1 to 12.

[0040] X is —OH, —CH(R ２１ )OH(R ２１ represents H, a non-fluorinated alkyl group or a fluorinated alkyl group), -I, -CFHI, -CH ２ I, an anionic group or -COOR ２２ (R ２２ is a non-fluorinated alkyl group having 1 to 8 carbon atoms. Examples of anionic groups include -COOM and -SO ３ M or -OSO ３ It is preferable that the anionic group contains M. Examples of the anionic group include -COOM and -SO ３ M, -CH(R ２１ )—O—(CH ２ ) ３ -SO ３ M, -OSO ３ M, -CH(R ２１ )-OSO ３ Examples include M.

[0041] M of the anionic group represents a counter cation of the anion. M can be H, a metal atom, NR ７ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium. ７ is preferably H or an organic group.

[0042] The metal atom includes alkali metals (Group 1) and alkaline earth metals (Group 2), and is preferably Na, K or Li.

[0043] M is —H, a metal atom, or NR ７ ４ is preferred, and H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR ７ ４ is more preferred, and H, Na, K, Li or NH ４ is more preferred, and H, Na, K or NH ４ is even more preferred, H, Na or NH ４ is particularly preferred, and H or NH ４ is most preferred.

[0044] R２１ is H, a non-fluorinated alkyl group or a fluorinated alkyl group, preferably H or a non-fluorinated alkyl group having 1 to 3 carbon atoms, and more preferably H.

[0045] R ２２ is a non-fluorinated alkyl group having 1 to 8 carbon atoms, preferably a non-fluorinated alkyl group having 1 to 4 carbon atoms, more preferably —CH ３ or -CH ２ CH ３ is.

[0046] R １ , R ２ and X have a total carbon number of 2 to 50, preferably 2 to 16, more preferably 4 to 14, even more preferably 4 to 12, particularly preferably 4 to 10, and most preferably 4 to 8.

[0047] More specifically, compounds of the present disclosure include compounds of the general formula: CH ２ F-CHF-(CHF-CHF) ｎ -CH(R ２１ )OH (wherein n is an integer of 0 or more, R ２１ is as defined above); a fluorine-containing alcohol represented by the general formula: CH ２ F-CHF-(CHF-CHF) ｎ Fluorine-containing carboxylic acids represented by the general formula: CH ２ F-CHF-(CHF-CHF) ｎ -CH(R ２１ )-OSO ３ M (wherein n is an integer of 0 or more, R ２１ is as described above, and M is a cation); １ -CHF- (CHF-CHF) ｎ -I (wherein, R １ is a first, second, fourth or fifth fluorine-containing alkyl iodide represented by the general formula: R １ -CHF- (CHF-CHF) ｎ -CH２ CH ２ -I (wherein, R １ is as defined above, and n is an integer of 1 or more); １ -CHF- (CHF-CHF) ｎ -CH ２ CH ２ -OH (wherein, R １ is as described above, and n is an integer of 0 or more); １ -CHF- (CHF-CHF) ｎ -CH ２ -COOM (wherein, R １ is as described above, n is an integer of 0 or more, and M is a cation); １ -CHF- (CHF-CHF) ｎ - (CH ２ ) ｍ -COOR ２３ (In the formula, R １ is as described above, n is an integer of 0 or more, m is an integer of 0 to 3, R ２３ is H or an alkyl group having 1 to 8 carbon atoms; ２ F-R ２ -OSO ３ M (wherein, R ２ is -(CFH) ｎ１ -(n1 is an integer of 3 to 49), and M is a cation); ２ (-OSO ３ M) ２ (In the formula, R ２ is -(CFH) ｎ１ - (wherein n1 is an integer of 1 to 49), and M is a cation); ３ -R ２ -COOM (in the formula, R ２ represents an alkylene group consisting of only units represented by -CFH-, or a group consisting of units represented by -CFH- and -CH ２- alkylene groups consisting solely of units represented by the formula: -, whereby these alkylene groups may optionally contain epoxy groups, -CH(OH)- or divalent cycloalkylene groups, and M is a cation; １ -CHF- (CHF-CHF) ｎ -CH ２ -CHI- (CH ２ ) ｑ -X (wherein, R １ Ha-CHF ２ or -CHFI, X is -OH, -COOM (M is a cation), -SO ３ M (M is a cation), -OSO ３ M (M is a cation), -COOR ２２ (R ２２ is a non-fluorinated alkyl group having 1 to 8 carbon atoms), n is an integer of 0 or more, and q is an integer of 1 or more; １ -CHF- (CHF-CHF) ｎ -CH ２ -CH ２ - (CH ２ ) ｑ -X(R １ is -CHF ２ or -CHFI, X is -OH, -COOM (M is a cation), -SO ３ M (M is a cation), -OSO ３ M (M is a cation), -COOR ２２ (R ２２ represents a non-fluorinated alkyl group having 1 to 8 carbon atoms), n is an integer of 0 or more, and q is an integer of 1 or more;

[0048] As described above, the compounds of the present disclosure include fluorine-containing alcohols, fluorine-containing carboxylic acids, fluorine-containing sulfates, fluorine-containing alkyl iodides, oligomers, fluorides of unsaturated fatty acids, iodine-containing compounds, etc. Next, methods for producing these compounds will be described.

[0049] <First Production Method> In the first production method, a compound represented by the general formula: R ２１ -CH ２ -OH (wherein, R ２１is H, a non-fluorinated alkyl group or a fluorinated alkyl group), by adding CHF=CHF to an alkanol represented by the general formula: CH ２ F-CHF-(CHF-CHF) ｎ -CH(R ２１ )OH (wherein n is an integer of 0 or more, R ２１ is as described above) to produce a fluorine-containing alcohol.

[0050] R of alkanol and fluorine-containing alcohol ２１ is H, a non-fluorinated alkyl group or a fluorinated alkyl group, preferably H or a non-fluorinated alkyl group having 1 to 3 carbon atoms, and more preferably H.

[0051] In the fluorine-containing alcohol, n represents the degree of polymerization of CHF=CHF and is an integer of not less than 0. n is, for example, an integer of 0 to 23, preferably an integer of 1 to 7, more preferably an integer of 1 to 5, and even more preferably an integer of 1 to 3.

[0052] The reaction of an alkanol with CHF=CHF can be carried out in the presence of a radical initiator. When the reaction is carried out in the presence of a radical initiator, the radical initiator decomposes to generate a radical, which then abstracts a hydrogen atom from the carbon atom to which the hydroxyl group of the alkanol is bonded, thereby generating an alkanol radical, and a reaction (so-called telomerization reaction) in which CHF=CHF is added to the alkanol radical proceeds.

[0053] The radical initiator is preferably an organic peroxide, and examples thereof include dialkyl peroxycarbonates such as diisopropyl peroxydicarbonate and disec-butyl peroxydicarbonate, peroxyesters such as 2-ethylhexanoyl (tert-butyl) peroxide, t-butyl peroxyisobutyrate and t-butyl peroxypivalate, and dialkyl peroxides such as di-t-butyl peroxide.

[0054] The amount of CHF=CHF used is preferably 0.01 to 100 moles per mole of alkanol.

[0055] The amount of the radical initiator used is preferably 0.01 to 2 moles per mole of alkanol.

[0056] The temperature for the reaction of the alkanol with CHF=CHF can be appropriately selected, but is preferably −78 to 200° C. The temperature for the reaction of the alkanol with CHF=CHF is preferably equal to or higher than the decomposition temperature of the radical polymerization initiator, and is preferably lower than the decomposition temperatures of the substrate and the product.

[0057] The pressure for the reaction of the alkanol with CHF=CHF can be appropriately selected, but is preferably 0 to 5.0 MPaG. The time for the reaction of the alkanol with CHF=CHF can be appropriately selected, but is preferably 0.1 to 96 hours.

[0058] <Second Production Method> In the second production method, a compound of the general formula: CH ２ F-CHF-(CHF-CHF) ｎ -CH(R ２１ )OH (wherein n is an integer of 0 or more, R ２１ is as defined above), and then R ２１ When H, the fluorine-containing alcohol is oxidized to give a compound of the general formula: CH ２ F-CHF-(CHF-CHF) ｎ A fluorine-containing carboxylic acid represented by the formula -COOM (wherein n is an integer of 0 or more, and M is a cation) is produced.

[0059] The value of n in the fluorine-containing carboxylic acid is the same as that of n in the fluorine-containing alcohol, and is an integer of not less than 0. The preferred range of n in the fluorine-containing carboxylic acid is the same as the preferred range of n in the fluorine-containing alcohol.

[0060] M is -COO － The counter cation of X is the same as that of M contained in the anionic group of X, and the preferred cations are also the same.

[0061] The oxidation of the fluorine-containing alcohol can be carried out in the presence of an oxidizing agent. Examples of the oxidizing agent include potassium permanganate. The amount of the oxidizing agent used is preferably 0.01 to 100 moles per mole of the fluorine-containing alcohol.

[0062] The oxidation of the fluorine-containing alcohol can be carried out in a solvent, such as water.

[0063] The temperature for the oxidation of the fluorine-containing alcohol can be appropriately selected but is preferably −78 to 200° C. The pressure for the oxidation of the fluorine-containing alcohol can be appropriately selected but is preferably 0 to 5.0 MPaG. The time for the oxidation of the fluorine-containing alcohol can be appropriately selected but is preferably 0.1 to 96 hours.

[0064] <Third Production Method> In the third production method, a compound of the general formula: CH ２ F-CHF-(CHF-CHF) ｎ -CH(R ２１ )OH (wherein n is an integer of 0 or more, R ２１ is as described above), and then the fluorine-containing alcohol is reacted with sulfonic acid chloride to produce a compound represented by the general formula: CH ２ F-CHF-(CHF-CHF) ｎ -CH(R ２１ )-OSO ３ M (wherein n is an integer of 0 or more, R ２１ As described above, the fluorine-containing sulfate represented by the formula (M is a cation) is produced.

[0065] Fluorine-containing sulfate ester R ２１ is the R of the fluorine-containing alcohol ２１ and is a single bond, a non-fluorinated alkylene group, or a fluorinated alkylene group. ２１ The preferred group is R ２１ are the same as the preferred groups of

[0066] The value of n in the fluorine-containing sulfate ester is the same as that of n in the fluorine-containing alcohol, and is an integer of not less than 0. The preferred range of n in the fluorine-containing sulfate ester is the same as the preferred range of n in the fluorine-containing alcohol.

[0067] M is -OSO ３ － The counter cation of X is the same as that of M contained in the anionic group of X, and the preferred cations are also the same.

[0068] The amount of sulfonic chloride used is preferably 1 to 2 moles per mole of fluorine-containing alcohol.

[0069] The reaction of the fluorine-containing alcohol with sulfonic acid chloride can be carried out in the presence of a base, such as an alkali metal hydroxide, an alkaline earth metal hydroxide, or an amine, with an amine being preferred.

[0070] Examples of the amine include tertiary amines such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, dimethylbenzylamine, and N,N,N',N'-tetramethyl-1,8-naphthalenediamine, heteroaromatic amines such as pyridine, pyrrole, uracil, collidine, and lutidine, and cyclic amines such as 1,8-diaza-bicyclo[5.4.0]-7-undecene and 1,5-diaza-bicyclo[4.3.0]-5-nonene. Of these, triethylamine and pyridine are preferred.

[0071] The amount of the base used is 0.5 to 20 moles per mole of the fluorine-containing alcohol.

[0072] The reaction between the fluorine-containing alcohol and the sulfonic acid chloride can be carried out in a solvent, preferably a polar solvent, more preferably an aprotic polar solvent, and even more preferably an ether.

[0073] Examples of the ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraglyme (tetraethylene glycol dimethyl ether), and crown ethers (15-crown-5,18-crown-6). Of these, diethyl ether is preferred.

[0074] The temperature for the reaction of the fluorine-containing alcohol with the sulfonic chloride can be appropriately selected but is preferably 0 to 40° C. The pressure for the reaction of the fluorine-containing alcohol with the sulfonic chloride can be appropriately selected but is preferably 0.1 to 5 MPaG. The time for the reaction of the fluorine-containing alcohol with the sulfonic chloride can be appropriately selected but is preferably 0.1 to 96 hours.

[0075] <Fourth Production Method> In the fourth production method, CHF=CHF and a compound of the general formula: X １ I (X １ is H or F), to obtain a compound represented by the general formula: R １ -CHF-I (wherein R １ Ha-CH ２ F or -CHF ２ ) to produce a first fluorine-containing alkyl iodide represented by the general formula: R １ -CHF- (CHF-CHF) ｎ -I (wherein, R １ As described above, a second fluorine-containing alkyl iodide represented by the formula (where n is an integer of 1 or more) is produced.

[0076] The amount of the iodide compound used is preferably 0.5 to 2 moles per mole of CHF=CHF.

[0077] The reaction of CHF=CHF with the iodide compound can also be carried out in a solvent.

[0078] The temperature for the reaction of CHF=CHF with the iodide compound can be appropriately selected but is preferably −78 to 200° C. The pressure for the reaction of CHF=CHF with the iodide compound can be appropriately selected but is preferably 0 to 5.0 MPaG. The time for the reaction of CHF=CHF with the iodide compound can be appropriately selected but is preferably 0.1 to 96 hours.

[0079] The reaction of CHF=CHF with an iodide compound gives a compound of the general formula: R １ -CHF-I (wherein R １ Ha-CH ２ F or -CHF ２In the fourth production method, next, CHF=CHF is added to the first fluorine-containing alkyl iodide.

[0080] The reaction between the first fluorine-containing alkyl iodide and CHF=CHF is a telomerization reaction in which the first fluorine-containing alkyl iodide serves as a telogen and CHF=CHF serves as a taxogen, and a second fluorine-containing alkyl iodide is produced by this reaction.

[0081] In the second fluorine-containing alkyl iodide, n represents the degree of polymerization of CHF=CHF and is an integer of not less than 1. n is preferably an integer of 1 to 23, more preferably an integer of 1 to 7, still more preferably an integer of 1 to 5, and particularly preferably an integer of 1 to 3.

[0082] The reaction of the first fluorine-containing alkyl iodide with CHF=CHF can be carried out in the presence of a radical initiator, such as an organic peroxide or an azo compound.

[0083] Examples of organic peroxides include dialkyl peroxycarbonates such as diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate, peroxyesters such as 2-ethylhexanoyl (tert-butyl) peroxide, t-butyl peroxyisobutyrate and t-butyl peroxypivalate, and dialkyl peroxides such as di-t-butyl peroxide.

[0084] Examples of the azo compounds include azobisisobutyronitrile.

[0085] The amount of CHF=CHF used is preferably 0.01 to 100 moles per mole of the fluorine-containing alkyl iodide.

[0086] The amount of the radical initiator used is preferably 0.01 to 2 moles per mole of the fluorine-containing alkyl iodide.

[0087] The temperature for the reaction of the first fluorine-containing alkyl iodide with CHF═CHF can be appropriately selected, but is preferably −78 to 200° C. The temperature for the reaction of the first fluorine-containing alkyl iodide with CHF═CHF is preferably not less than the decomposition temperature of the radical polymerization initiator, and is preferably lower than the decomposition temperatures of the substrate and the product.

[0088] The pressure for the reaction of the first fluorine-containing alkyl iodide with CHF═CHF can be appropriately selected, but is preferably 0 to 5.0 MPaG. The time for the reaction of the first fluorine-containing alkyl iodide with CHF═CHF can be appropriately selected, but is preferably 0.1 to 96 hours.

[0089] <Fifth Production Method> In the fifth production method, after the first or second fluorine-containing alkyl iodide is produced by the fourth production method, ethylene is added to the first or second fluorine-containing alkyl iodide to obtain a compound represented by the general formula: R １ -CHF- (CHF-CHF) ｎ -CH ２ CH ２ -I (wherein, R １ As described above, n is an integer of 0 or more), to produce a third fluorine-containing alkyl iodide represented by the formula:

[0090] R of the third fluorine-containing alkyl iodide １ is R of the first or second fluorine-containing alkyl iodide １ is the same as -CH ２ F or -CHF ２ is.

[0091] n in the third fluorine-containing alkyl iodide is an integer of not less than 0. A suitable range for n in the third fluorine-containing alkyl iodide is an integer of 0 to 23, preferably an integer of 0 to 7, more preferably an integer of 0 to 5, and still more preferably an integer of 0 to 3.

[0092] The reaction of the first or second fluorine-containing alkyl iodide with ethylene can be carried out in the presence of a metal catalyst, such as copper.

[0093] The reaction of the first or second fluorine-containing alkyl iodide with ethylene can be carried out in the presence of a radical-generating compound, such as an organic peroxide or an azo compound.

[0094] Examples of organic peroxides include dialkyl peroxycarbonates such as diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate, peroxyesters such as 2-ethylhexanoyl (tert-butyl) peroxide, t-butyl peroxyisobutyrate and t-butyl peroxypivalate, and dialkyl peroxides such as di-t-butyl peroxide.

[0095] Examples of the azo compounds include azobisisobutyronitrile.

[0096] The amount of ethylene used is preferably 0.01 to 100 moles per mole of the first or second fluorine-containing alkyl iodide.

[0097] The amount of the radical-generating compound used is preferably 0.001 to 1 mole per mole of the first or second fluorine-containing alkyl iodide.

[0098] The temperature for the reaction of the first or second fluorine-containing alkyl iodide with ethylene can be appropriately selected but is preferably 50 to 200° C. The pressure for the reaction of the first or second fluorine-containing alkyl iodide with ethylene can be appropriately selected but is preferably 0.1 to 5 MPaG. The time for the reaction of the first or second fluorine-containing alkyl iodide with ethylene can be appropriately selected but is preferably 0.1 to 96 hours.

[0099] <Sixth Production Method> In the sixth production method, a compound of the general formula: R １ -CHF- (CHF-CHF) ｎ -CH ２ CH ２ -I (wherein, R １is as described above, n is an integer of 0 or more), and then the third fluorine-containing alkyl iodide is reacted with fuming sulfuric acid and hydrolyzed to obtain a compound represented by the general formula: １ -CHF- (CHF-CHF) ｎ -CH ２ CH ２ -OH (wherein, R １ As described above, n is an integer of 0 or more) to produce a fluorine-containing alcohol represented by the formula:

[0100] Fluorine-containing alcohol R １ is R of the third fluorine-containing alkyl iodide １ is the same as -CH ２ F or -CHF ２ is.

[0101] n of the fluorine-containing alcohol is the same as n of the third fluorine-containing alkyl iodide, and is an integer of not less than 0. The preferred range of n of the fluorine-containing alcohol is the same as the preferred range of n of the third fluorine-containing alkyl iodide.

[0102] The sulfur trioxide content of fuming sulfuric acid is not particularly limited, but is preferably 10 to 90% by mass, more preferably 30 to 80% by mass, and even more preferably 50 to 70% by mass.

[0103] The amount of fuming sulfuric acid used is preferably 1 to 50 moles per mole of the third fluorine-containing alkyl iodide, in terms of the amount equivalent to sulfur trioxide in fuming sulfuric acid.

[0104] The temperature for the reaction of the third fluorine-containing alkyl iodide with oleum can be suitably selected, but is preferably 0 to 90° C. The pressure for the reaction of the third fluorine-containing alkyl iodide with oleum can be suitably selected, but is preferably 0 to 10.0 MPaG. The time for the reaction of the third fluorine-containing alkyl iodide with oleum can be suitably selected, but is preferably 0.1 to 96 hours.

[0105] In the sixth production method, a third fluorine-containing alkyl iodide is reacted with fuming sulfuric acid to form a compound represented by the general formula: １ -CHF- (CHF-CHF)ｎ -CH ２ CH ２ -OSO ３ H (wherein, R １ As described above, n is an integer of 0 or more), and then the fluorine-containing alkyl hydrogen sulfate is hydrolyzed to give a compound represented by the general formula: R １ -CHF- (CHF-CHF) ｎ -CH ２ CH ２ -OH (wherein, R １ As described above, n is an integer of 0 or more) to produce a fluorine-containing alcohol represented by the formula:

[0106] The hydrolysis of the fluorine-containing alkyl hydrogen sulfate can be carried out, for example, using water or an aqueous sodium sulfite solution by adding the aqueous sodium sulfite solution dropwise to a solution (a fluorine-containing alkyl hydrogen sulfate-containing solution) obtained by reacting the third fluorine-containing alkyl iodide with fuming sulfuric acid.

[0107] The amount of water or aqueous sodium sulfite solution used is not particularly limited, as long as it is an amount that can neutralize the solution obtained by the reaction of the third fluorine-containing alkyl iodide with fuming sulfuric acid and is also an amount necessary to hydrolyze the fluorine-containing alkyl hydrogen sulfate.

[0108] The hydrolysis temperature can be selected as appropriate, but is preferably 15 to 100° C. The hydrolysis time can be selected as appropriate, but is preferably 0.1 to 96 hours.

[0109] <Seventh Production Method> In the seventh production method, the first, second or third fluorine-containing alkyl iodide is reacted with carbon dioxide or a dialkyl carbonate to form a compound represented by the general formula: R １ -CHF- (CHF-CHF) ｎ - (CH ２ ) ｍ -COOR ２３ (In the formula, R １ is as described above, n is an integer of 0 or more, m is an integer of 0 to 3, R ２３is H or an alkyl group having 1 to 8 carbon atoms),

[0110] The fluorine-containing carboxylic acid derivative can be obtained by reacting the first, second or third fluorine-containing alkyl iodide with carbon dioxide or a dialkyl carbonate in the presence of a base.

[0111] This reaction can be carried out in the presence of a base. Examples of the base include alkali metal hydroxides, alkaline earth metal hydroxides, and amines. Examples of the amine include aliphatic amines such as tributylamine.

[0112] The amount of the base used is 0.5 to 20 moles per mole of the fluorine-containing alkyl iodide.

[0113] The temperature at which the fluorine-containing alkyl iodide is reacted with carbon dioxide can be appropriately selected, but is preferably from -78 to 200°C.

[0114] When a fluorine-containing alkyl iodide is reacted with a dialkyl carbonate, for example, dimethyl carbonate can be used as the dialkyl carbonate. The reaction of the fluorine-containing alkyl iodide with dimethyl carbonate proceeds a methoxycarbonylation reaction to produce the corresponding carboxylic acid ester.

[0115] As the carboxylic acid derivative, R ２３ When a carboxylic acid ester is prepared in which R is an alkyl group, the carboxylic acid ester can be converted into a carboxylic acid or a carboxylic acid salt by hydrolysis.

[0116] <Eighth Production Method> In the eighth production method, CHF=CHF is polymerized in the presence of a persulfate to obtain a compound of the general formula: CH ２ F-R ２ -OSO ３ M (wherein, R ２ is -(CFH) ｎ１ - (wherein n1 is an integer of 1 to 49), and M is a cation), or an oligomer represented by R ２ (-OSO ３ M) ２ (In the formula, R２ is -(CFH) ｎ１ - (wherein n1 is an integer of 1 to 49), and M is a cation) to produce an oligomer represented by the formula:

[0117] R ２ is -(CFH) ｎ１ -, and n1 is an integer of 1 to 49, preferably an integer of 3 to 49. That is, the oligomer obtained by the eighth production method is a low molecular weight compound containing repeating units derived from CHF=CHF, and the number of repeating units derived from CHF=CHF is 1 to 25. The oligomer obtained by the eighth production method may be an oligomer having a molecular weight distribution, and in this case, n1 represents the average number of repeating units of molecules contained in the oligomer.

[0118] M is -OSO ３ － The counter cation of X is the same as that of M contained in the anionic group of X, and the preferred cations are also the same.

[0119] Polymerization of CHF═CHF can be carried out in the presence of a persulfate. The use of a persulfate initiates oligomerization of CHF═CHF, resulting in a main chain formed from repeating units derived from CHF═CHF and terminal -OSO ３ An oligomer having M introduced therein is produced.

[0120] Examples of persulfates include ammonium salts of persulfate, alkali salts of persulfate, alkaline earth metal salts of persulfate, etc. The amount of persulfate used is preferably 0.01 to 1000 mass % based on the amount of the oligomer produced.

[0121] The persulfates may be used in combination with a reducing agent, such as sulfites such as sodium sulfite and sodium hydrogen sulfite, metabisulfites such as sodium hydrogen sulfite and potassium hydrogen sulfite, pyrosulfates, and thiosulfates.

[0122] The polymerization of CHF=CHF can be carried out in an aqueous medium, preferably in the absence of surfactants.

[0123] The temperature for the polymerization of CHF═CHF can be appropriately selected, but is preferably −78 to 200° C. The temperature for the polymerization of CHF═CHF is preferably equal to or higher than the decomposition temperature of the persulfate, and is preferably lower than the decomposition temperatures of the substrate and the product.

[0124] The pressure for the polymerization of CHF=CHF can be appropriately selected, but is preferably 0 to 5.0 MPaG. The time for the polymerization of CHF=CHF can be appropriately selected, but is preferably 0.1 to 96 hours.

[0125] <Ninth Production Method> In the ninth production method, an unsaturated fatty acid and HF or F ２ By reacting with ３ -R ２ -COOM (in the formula, R ２ represents an alkylene group consisting of only units represented by -CFH-, or a group consisting of units represented by -CFH- and -CH ２ and M is a cation).

[0126] The unsaturated fatty acid may be either a monounsaturated fatty acid or a polyunsaturated fatty acid. The number of carbon atoms in the unsaturated fatty acid is preferably 4 to 50, more preferably 4 to 16, and even more preferably 4 to 10.

[0127] R of fluoride of unsaturated fatty acids ２ As the group, -(CHF) ｐ - (CH ２ ) ｑ -(p is an integer of 1 or more, q is an integer of 0 or more, the sum of p and q is 1 to 49, and a unit represented by -CFH- and a unit represented by -CH ２ The units represented by - may be present in any order in the formula, and either H or F bonded to a carbon atom may be substituted with OH) is preferred.

[0128] M is -COO －The counter cation of X is the same as that of M contained in the anionic group of X, and the preferred cations are also the same.

[0129] Examples of unsaturated fatty acids include the following compounds: monounsaturated fatty acids such as crotonic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, and nervonic acid; diunsaturated fatty acids such as linoleic acid, eicosadienoic acid, and docosadienoic acid; triunsaturated fatty acids such as linolenic acid, pinolenic acid, eleostearic acid, mead acid, dihomo-γ-linolenic acid, and eicosatrienoic acid; tetraunsaturated fatty acids such as stearidonic acid, arachidonic acid, eicosatetraenoic acid, and adrenic acid; pentaunsaturated fatty acids such as bosseopentaenoic acid, eicosapentaenoic acid, osbondo acid, sardine acid, and tetracosapentaenoic acid; hexaunsaturated fatty acids such as docosahexaenoic acid and herring acid; epoxidized products of unsaturated fatty acids such as epoxidized oleic acid and epoxidized linoleic acid; eicosanoids such as prostaglandins, leukotrienes, and thromboxanes;

[0130] Unsaturated fatty acids and HF or F ２ The reaction can be carried out by contacting the unsaturated fatty acid with hydrogen fluoride gas or fluorine gas. Alternatively, the reaction can be carried out by contacting the unsaturated fatty acid with hydrofluoric acid (aqueous solution of hydrogen fluoride). This reaction can be carried out efficiently by using a catalyst.

[0131] Unsaturated fatty acids and HF or F ２ The fluorides of unsaturated fatty acids obtained by the tenth production method include fluorides of unsaturated fatty acids in which all of the unsaturated bonds have been fluorinated and fluorides of unsaturated fatty acids in which some of the unsaturated bonds have been fluorinated.

[0132] HF or F ２ The amount used is 0.01 to 100 moles per mole of unsaturated bond in the unsaturated fatty acid.

[0133] Unsaturated fatty acids and HF or F ２ The temperature for the reaction can be appropriately selected, but is preferably −78 to 200° C. ２ The pressure for the reaction can be appropriately selected, but is preferably 0 to 5.0 MPaG. ２ The reaction time can be appropriately selected, but is preferably 0.1 to 96 hours.

[0134] <Tenth Production Method> In the tenth production method, CHF=CHF and I ２ and IF ５ by reacting the compound of the general formula: R １ -CHF-I (wherein R １ Ha-CHF ２ or —CHFI) to produce a fourth fluorine-containing alkyl iodide.

[0135] I ２ and IF ５ The amount of is preferably 0.5 to 2 moles per mole of CHF=CHF.

[0136] CHF = CHF and I ２ and IF ５ The reaction can also be carried out in a solvent.

[0137] CHF = CHF and I ２ and IF ５ The reaction temperature can be appropriately selected, but is preferably −78 to 200° C. ２ and IF ５ The pressure of the reaction can be appropriately selected, but is preferably 0 to 5.0 MPaG. ２ and IF ５ The reaction time can be appropriately selected, but is preferably 0.1 to 96 hours.

[0138] In the tenth production method, CHF=CHF is further added to the fourth fluorine-containing alkyl iodide to obtain a compound of the general formula: R １ -CHF- (CHF-CHF) ｎ -I (wherein, R １As described above, n is an integer of 1 or more), and the fifth fluorine-containing alkyl iodide represented by the formula:

[0139] The reaction between the fourth fluorine-containing alkyl iodide and CHF=CHF is a telomerization reaction in which the fourth fluorine-containing alkyl iodide serves as a telogen and CHF=CHF serves as a taxogen, and a fifth fluorine-containing alkyl iodide is produced by this reaction.

[0140] In the fifth fluorine-containing alkyl iodide, n represents the degree of polymerization of CHF=CHF and is an integer of not less than 1. n is preferably an integer of 1 to 23, more preferably an integer of 1 to 7, still more preferably an integer of 1 to 5, and particularly preferably an integer of 1 to 3.

[0141] The reaction of the fourth fluorine-containing alkyl iodide with CHF=CHF can be carried out in the presence of a radical initiator, such as an organic peroxide or an azo compound.

[0142] Examples of organic peroxides include dialkyl peroxycarbonates such as diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate, peroxyesters such as 2-ethylhexanoyl (tert-butyl) peroxide, t-butyl peroxyisobutyrate and t-butyl peroxypivalate, and dialkyl peroxides such as di-t-butyl peroxide.

[0143] Examples of the azo compounds include azobisisobutyronitrile.

[0144] The amount of CHF=CHF used is preferably 0.01 to 100 moles per mole of the fluorine-containing alkyl iodide.

[0145] The amount of the radical initiator used is preferably 0.01 to 2 moles per mole of the fluorine-containing alkyl iodide.

[0146] The temperature for the reaction of the fourth fluorine-containing alkyl iodide with CHF═CHF can be appropriately selected, but is preferably −78 to 200° C. The temperature for the reaction of the fourth fluorine-containing alkyl iodide with CHF═CHF is preferably not less than the decomposition temperature of the radical polymerization initiator, and is preferably lower than the decomposition temperatures of the substrate and the product.

[0147] The pressure for the reaction of the fourth fluorine-containing alkyl iodide with CHF=CHF can be appropriately selected, but is preferably 0 to 5.0 MPa G. The time for the reaction of the fourth fluorine-containing alkyl iodide with CHF=CHF can be appropriately selected, but is preferably 0.1 to 96 hours.

[0148] <Eleventh Production Method> In the eleventh production method, after the fourth or fifth fluorine-containing alkyl iodide is produced by the tenth production method, the fourth or fifth fluorine-containing alkyl iodide and a compound having the general formula: CH ２ =CH-(CH ２ ) ｑ -X (wherein X is -OH, -COOM (M is a cation), -SO ３ M (M is a cation), -OSO ３ M (M is a cation), -COOR ２２ (R ２２ is a non-fluorinated alkyl group having 1 to 8 carbon atoms), and q is an integer of 1 or more), to obtain an unsaturated compound represented by the general formula: R １ -CHF- (CHF-CHF) ｎ -CH ２ -CHI- (CH ２ ) ｑ -X (wherein, R １ , X and q are as defined above, and n is an integer of 0 or more), to produce an iodine-containing compound represented by the formula (1).

[0149] Iodine-containing compounds R １ is R of the fourth or fifth fluorine-containing alkyl iodide １ is the same as -CHF ２ Or -CHFI.

[0150] X in the iodine-containing compound is the same as X in the unsaturated compound, and may be —OH, —COOM (M is a cation), or —SO３ M (M is a cation), -OSO ３ M (M is a cation), -COOR ２２ (R ２２ is a non-fluorinated alkyl group having 1 to 8 carbon atoms).

[0151] The value n of the iodine-containing compound is an integer of 0 or more. The value n of the iodine-containing compound is preferably an integer of 0 to 23, more preferably an integer of 0 to 7, more preferably an integer of 0 to 5, and even more preferably an integer of 0 to 3.

[0152] The q of the iodine-containing compound is an integer of 1 or greater. The suitable range for q of the iodine-containing compound is an integer of 1 to 24, preferably an integer of 1 to 18, and more preferably an integer of 1 to 12.

[0153] The reaction of the fourth or fifth fluorine-containing alkyl iodide with the unsaturated compound can be carried out in the presence of a compound capable of generating radicals, such as an organic peroxide or an azo compound.

[0154] Examples of organic peroxides include dialkyl peroxycarbonates such as diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate, peroxyesters such as 2-ethylhexanoyl (tert-butyl) peroxide, t-butyl peroxyisobutyrate and t-butyl peroxypivalate, and dialkyl peroxides such as di-t-butyl peroxide.

[0155] Examples of the azo compounds include azobisisobutyronitrile.

[0156] The amount of the unsaturated compound used is preferably 0.01 to 100 moles per mole of the fourth or fifth fluorine-containing alkyl iodide.

[0157] The amount of the radical-generating compound used is preferably 0.001 to 1 mole per mole of the fourth or fifth fluorine-containing alkyl iodide.

[0158] The temperature for the reaction of the fourth or fifth fluorine-containing alkyl iodide with the unsaturated compound can be appropriately selected but is preferably 50 to 200° C. The pressure for the reaction of the fourth or fifth fluorine-containing alkyl iodide with the unsaturated compound can be appropriately selected but is preferably 0.1 to 5 MPaG. The time for the reaction of the fourth or fifth fluorine-containing alkyl iodide with the unsaturated compound can be appropriately selected but is preferably 0.1 to 96 hours.

[0159] The obtained iodine-containing compound is reduced to give a compound of the general formula: R １ -CHF- (CHF-CHF) ｎ -CH ２ -CH ２ - (CH ２ ) ｑ -X (wherein, R １ , X, q and n are as defined above), the reduction can be carried out, for example, using a metal catalyst and hydrogen or using zinc as a reducing agent.

[0160] In any of the above-mentioned production methods, after completion of each step, the purity of the obtained compound may be increased by distilling off the solvent, or by carrying out distillation, purification, etc. Furthermore, if the obtained compound does not contain —COOH, —SO ３ H, -OSO ３ In the case of a compound having an acid-type anionic group such as H, these groups can be converted into salt-type anionic groups by contacting the compound with an alkali such as sodium carbonate or ammonia.

[0161] The compounds of the present disclosure can reduce the surface tension of water. Therefore, the compounds of the present disclosure can be suitably used as surfactants. The surfactants of the present disclosure are the compounds described above, in which X in the general formula is —OH, —CH(R ２１ ) OH, and compounds which are anionic groups.

[0162] That is, the surfactants of the present disclosure have the general formula: １ -R ２ -X (wherein, R １ is -CH ３ , -CH２ F or -CHF ２ and R ２ represents an alkylene group consisting of only units represented by -CFH-, or a group consisting of units represented by -CFH- and -CH ２ - is an alkylene group consisting only of units represented by -, provided that these alkylene groups may optionally contain an epoxy group, -CH(OH)-, or a divalent cycloalkylene group, and X is -OH, -CH(R ２１ )OH(R ２１ is H, a non-fluorinated alkyl group or a fluorinated alkyl group, or an anionic group; R １ , R ２ and X has a total carbon number of 2 to 50. The surfactant of the present disclosure can contain one or more of the above compounds.

[0163] The surfactants of the present disclosure can be suitably used in the polymerization of fluoromonomers. Accordingly, the present disclosure includes a method for producing a fluoropolymer, in which a fluoropolymer is obtained by polymerizing a fluoromonomer in an aqueous medium in the presence of the surfactant. Because the surfactants of the present disclosure contain units represented by -CFH-, they exhibit good surface activity even without having a perfluoroalkyl group or a perfluoroalkylene group.

[0164] Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims.

[0165] The main embodiments of the present disclosure are as follows.

[0166] <1> According to a first aspect of the present disclosure, there is provided a compound represented by the general formula: R １ -R ２ -X (wherein, R １ is -CH ３ , -CH ２ F, -CHF ２ , -CH ２ I, -CHFI, or an anionic group, R ２represents an alkylene group consisting of only units represented by -CFH-, or a group consisting of units represented by -CFH- and -CH ２ - is an alkylene group consisting only of units represented by -, provided that these alkylene groups may optionally contain an epoxy group, -CH(OH)-, -CHI- or a divalent cycloalkylene group, and X is -OH, -CH(R ２１ )OH(R ２１ represents H, a non-fluorinated alkyl group or a fluorinated alkyl group), -I, -CFHI, -CH ２ I, an anionic group or -COOR ２２ (R ２２ is a non-fluorinated alkyl group having 1 to 8 carbon atoms, and R １ , R ２ and X has a total carbon number of 2 to 50. <2> According to a second aspect of the present disclosure, there is provided a compound represented by the formula: ２ <3> According to a third aspect of the present disclosure, there is provided a compound in which R ２ is represented by the general formula: -(CFH) ｎ１ -(wherein n1 is an integer of 1 to 49). <4> According to a fourth aspect of the present disclosure, there is provided a compound according to the first or second aspect, which is a fluoride of an unsaturated fatty acid. <5> According to a fifth aspect of the present disclosure, there is provided a compound according to the first or second aspect, which is an alkylene group represented by the formula: R １ , R ２ and X has a total carbon number of 2 to 18. <6> According to a sixth aspect of the present disclosure, there is provided a compound according to any one of the first to fourth aspects, １ -CHF- (CHF-CHF) ｎ -I (wherein, R １ Ha-CHF ２ , -CHF ２ or —CHFI, n is an integer of 0 or more). <7> According to a seventh aspect of the present disclosure, there is provided a compound according to any one of the first to fifth aspects, wherein the anionic group is —COOM, —SO ３ M or -OSO ３There is provided a compound according to any one of the first to fifth aspects, which contains M (M is a cation). <8> According to an eighth aspect of the present disclosure, there is provided a compound according to any one of the first to fifth aspects, wherein X in the general formula is —OH, —CH(R ２１ ) OH, and a surfactant containing at least one compound selected from the group consisting of anionic groups.

[0167] Next, embodiments of the present disclosure will be described with reference to examples, but the present disclosure is not limited to these examples.

[0168] Example 1 Synthesis of 1,1,2-trifluoro-2-iodoethane In a 300 mL pressure vessel, 37.1 g of iodine, IF ５ After cooling the vessel to -78°C, 10 g of (E)-1,2-difluoroethene was added to the vessel, and the vessel was heated at 80°C for 20 hours. After cooling the vessel with ice water, the contents of the pressure vessel were washed with water and then diluted with 5% Na ２ S ２ O ４ Further washing with aqueous solution gave the title compound in 5.8 g. １９ F NMR (282MHz, CDCl ３ ): δ-169.1 to -169.4 (m, 1F), -124.0 to -124.3 (m, 1F). １ H NMR (400 MHz, CDCl3): δ 6.79 (d with fine coupling, J = 48.0 Hz, 1H), 7.26 (td with fine coupling, J = 54.8, 3.6 Hz, 1H). LRMS (EI 70eV) m / z (%): 210 (M+, 100), 190 (8), 171 (3), 83 (62), 64 (37), 51 (14).

[0169] Example 2: Synthesis of 4,5,5-trifluoro-2-iodopentanol. 1.84 g of 1,1,2-trifluoro-2-iodoethane, 509 mg of allyl alcohol, and 288 mg of azobisisobutyronitrile were placed in a 10 mL pressure vessel. The vessel was then heated at 80°C for 22 hours. After cooling the vessel with ice water, the contents of the pressure vessel were analyzed by gas chromatography-mass spectrometry. The title compound was found to be produced at an area ratio of 75.9% compared to 24.1% for the starting material, 1,1,2-trifluoro-2-iodoethane. LRMS (EI 70 eV) m / z (%): 268 (M+, 1), 251 (1), 185 (2), 141 (95), 73 (100), 51 (38).

[0170] Example 3: Synthesis of 7,8,8-trifluoro-5-iodooctan-1-ol. 1.00 g of 1,1,2-trifluoro-2-iodoethane, 477 mg of 5-hexen-1-ol, and 235 mg of azobisisobutyronitrile were placed in a 10 mL pressure vessel. The vessel was then heated at 80°C for 22 hours. After cooling the vessel with ice water, the contents of the pressure vessel were analyzed by gas chromatography-mass spectrometry. The title compound was found to have an area ratio of 66.8% (total of two isomers) compared to 37.2% for the starting material, 1,1,2-trifluoro-2-iodoethane. LRMS (EI 70 eV) m / z (%): 293 ([M-OH]+, 100), 259 (5), 207 (25), 207 (25), 155 (34).

[0171] Example 4: Synthesis of methyl 7,8,8-trifluoro-5-iodooctanoate. 200 mg of 1,1,2-trifluoro-2-iodoethane, 122 mg of methyl 5-hexenoate, and 46.9 mg of azobisisobutyronitrile were placed in a 10 mL pressure vessel. The vessel was then heated at 80°C for 22 hours. After cooling the vessel with ice water, the contents of the pressure vessel were analyzed by gas chromatography-mass spectrometry. The title compound was found to have been produced in an area ratio of 70.0% (total of two isomers) compared to 30.0% of the starting material, 1,1,2-trifluoro-2-iodoethane. LRMS (EI 70 eV) m / z (%): 307 ([M-OMe]+, 21), 211 (100), 192 (5), 151 (35).

[0172] Example 5 Synthesis of 7,8,8-trifluoro-5-iodooctanoic acid 200 mg of 1,1,2-trifluoro-2-iodoethane, 109 mg of 5-hexenoic acid, and 46.9 mg of azobisisobutyronitrile were placed in a 10 mL pressure vessel. The vessel was then heated at 80°C for 22 hours. After cooling the vessel with ice water, a mixture containing the target compound was obtained. 20 mg of this mixture was transferred to a separate glass container and diluted with 1 mL of tetrahydrofuran and 0.2 mL of methanol. Trimethylsilyldiazomethane (10% hexane solution) was added and the mixture was stirred at room temperature. Analysis of the contents by gas chromatography-mass spectrometry revealed that methyl 7,8,8-trifluoro-5-iodooctanoate, the title compound with methylated carboxylic acid, was produced at an area ratio of 85.7% (total of two isomers), compared to an area ratio of 14.3% for the starting material 1,1,2-trifluoro-2-iodoethane. LRMS (EI 70 eV) m / z (%): 307 ([M-OMe]+, 24), 211 (100), 192 (4), 151 (32).

[0173] Example 6 Synthesis of 7,8,8-trifluorooctan-1-ol 67.5 mg of zinc was added to a 10 mL glass vessel containing a mixture of 200 mg of 7,8,8-trifluoro-5-iodooctan-1-ol and 0.4 mL of methanol. 0.33 mL of 2 M aqueous hydrochloric acid was added. After stirring for 6 hours, the contents were analyzed by gas chromatography-mass spectrometry. The title compound was found to have been produced at an area ratio of 75.6% compared to 24.4% for the starting material 7,8,8-trifluoro-5-iodooctan-1-ol. LRMS (EI 70 eV) m / z (%): 167 ([M-OH]+, 100), 127 (54), 51 (4).

[0174] Example 7 Oligomerization reaction of 1,1,2-trifluoro-2-iodoethane with (E)-1,2-difluoroethene 1.00 g of 1,1,2-trifluoro-2-iodoethane and 0.35 mL of 2-ethylhexanoyl(tert-butyl)peroxide were placed in a 30 mL pressure vessel, and the vessel was sealed and cooled to −78° C., after which 1.5 g of (E)-1,2-difluoroethene was introduced. The vessel was heated at 80° C. for 24 hours. After cooling with ice water, the contents of the pressure vessel were analyzed by gas chromatography-mass spectrometry. Compared to the area ratio of the starting material 1,1,2-trifluoro-2-iodoethane (22.2%), H-CF2CHF-(CHFCHF)-I, H-CF2CHF-(CHFCHF)2-I, and H-CF2CHF-(CHFCHF)3-I were produced at area ratios of 36.1% (total of four isomers), 20.5% (total of eight isomers), and 21.3% (total of multiple isomers), respectively. H-CF2CHF-(CHFCHF)-I: LRMS (EI 70 eV) m / z (%): 274 (M+, 87), 191 (11), 159 (30), 147 (76), 83 (45), 77 (100), 51 (82). H-CF2CHF-(CHFCHF)2-I: LRMS (EI 70eV) m / z (%): 338 (M+, 18), 211 (4), 191 (27), 159 (22), 147 (27), 83 (38), 77 (84), 51 (100). H-CF2CHF-(CHFCHF)3-I: LRMS (EI 70eV) m / z (%): 402 (M+, 2), 191 (23), 159 (34), 147 (18), 83 (36), 77 (89), 51 (100).

[0175] Example 8: In a 500 mL pressure vessel, 300 g of water and Na ２ HPO ４0.31 g of ammonium persulfate and 0.48 g of ammonium persulfate were added, the vessel was sealed, and cooled to -78°C. Then, (E)-1,2-difluoroethene was introduced, and the mixture was heated at 0.5 MPa and 90°C for 30 minutes to react. After cooling, the mixture was sampled and dried at 50°C, revealing that a solid content of 0.77 wt% was produced. This solid was analyzed by gel permeation chromatography (standard molecular weight of polystyrene), confirming that an oligomer with Mn 1020 and Mw 1043 had been obtained. Furthermore, IR analysis revealed a peak at 1742 cm -1 The carbonyl stretching of the solid was hardly observed. This suggests that the solid contains an oligomer with a sulfate ester group as an anionic group. The surface tension of the solid was measured and found to be 51.9 mN / m, confirming its effectiveness as a surfactant.

Claims

1. General formula: R １ -R ２ -X (In the formula, R １ is -CH ３ , -CH ２ F, -CHF ２ , -CH ２ I, -CHFI, or an anionic group; R 2 is An alkylene group represented by the general formula: -(CFH) n1 - (wherein n1 is an integer of 3 to 49), An alkylene group represented by the general formula: -CHF-(CHF-CHF) n -(CH 2 ) m - (n is an integer of 0 or more, and m is an integer of 1 or more), or an alkylene group represented by the general formula: -(CHF)p-(CH2)q- (wherein p and q are independently an integer of 1 or more, the sum of p and q is 2 to 49, the order of the units represented by -CFH- and the units represented by -CH2- may be arbitrary in the formula, and either H or F bonded to the carbon atom may be replaced by OH); X is -OH, -CH(R ２１ )OH(R ２１ represents H, a non-fluorinated alkyl group or a fluorinated alkyl group), -I, -CFHI, -CH ２ I, an anionic group or -COOR ２２ (R ２２ is a non-fluorinated alkyl group having 1 to 8 carbon atoms; R １ , R ２ and X has a total carbon number of 2 to 50. A compound represented by the formula:

2. The compound according to claim 1 which is a fluoride of an unsaturated fatty acid.

3. R １ , R ２ The compound according to claim 1 or 2, wherein the total number of carbon atoms of and X is 2 to 18.

4. General formula: R １ -CHF- (CHF-CHF) ｎ -I (wherein, R １ is -CH2F, -CHF ２ or --CHFI, n being an integer of 1 or more).

5. The anionic group is -COOM, -SO ３ M or -OSO ３ 3. The compound of claim 1 or 2, comprising M, where M is a cation.

6. In the compound according to claim 1 or 2, X in the general formula is -OH, -CH(R ２１ ) OH, and a surfactant comprising at least one compound selected from the group consisting of compounds which are an anionic group.