Fluorine-containing compound, method for producing same, and surfactant

Abstract

A compound which is represented by general formula R1-R2-X (in the formula, R1 is-CH3,-CH2F,-CHF2,-CH2I,-CHFI, or an anionic group, R2 is an alkylene group comprising only a unit represented by-CFH-, or an alkylene group comprising only a unit represented by-CFH-and a unit represented by-CH2-(wherein these alkylene groups optionally contain or do not contain an epoxy group,-CH (OH)-,-CHI-, or a divalent cycloalkylene group, and X is an integer of 1-2). X is-OH,-CH (R21) OH (R21 is H, a non-fluorinated alkyl group or a fluorinated alkyl group),-I,-CFHI,-CH2I, an anionic group or-COOR22 (R22 is a non-fluorinated alkyl group having 1-8 carbon atoms), and the total number of carbon atoms of R1, R2 and X is 2-50).

Description

Technical Field

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

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

[0003] Patent Document 2 describes a fluorosurfactant containing a compound of formula (I),

[0004] RfCH 2 OCF(CF 3 )C(O)OM (I)

[0005] In the formula, Rf is a linear or branched perfluoroalkyl group having 2 to 5 carbon atoms, and M is H, NH 4 , Li, Na or K.

[0006] Prior Art Documents

[0007] Patent Documents

[0008] Patent Document 1: Japanese Patent Laid-Open No. 10-212261

[0009] Patent Document 2: Japanese Patent Application Laid-Open No. 2012-513531 Summary of the Invention

[0010] Problems to be Solved by the Invention

[0011] However, the compounds described in Patent Documents 1 and 2 are both compounds having -CF 3 -(trifluoromethyl) at the molecular end or containing a unit (-CF 2 - (difluoromethylene)) in the molecule, and there is no description of a fluorine-containing compound that does not contain -CF 3 - and -CF 2 - shown units.

[0012] An object of the present disclosure is to provide a novel fluorine-containing compound that does not contain trifluoromethyl and difluoromethylene.

[0013] Means for Solving the Problems

[0014] According to 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 2 is an alkylene group composed only of units represented by -CFH-, or an alkylene group composed of units represented by -CFH- and -CH 2 - units, wherein these alkylene groups optionally contain or do not contain an epoxy group, -CH(OH)-, -CHI-, or a divalent cycloalkyl group, X is -OH, -CH(R 21 )OH (R 21 is 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 the total number of carbon atoms of R 1 , R 2 and X is 2 to 50).

[0015] Effects of the Invention

[0016] According to the present disclosure, a novel fluorinated compound not containing a trifluoromethyl group and a difluoromethylene group can be provided. Detailed Description of the Invention

[0017] Before specifically describing the present disclosure, some terms used in the present disclosure are defined or explained.

[0018] In the present disclosure, an "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.

[0019] Examples of such "organic groups" include:

[0020] an alkyl group that may have one or more substituents,

[0021] an alkenyl group that may have one or more substituents,

[0022] an alkynyl group that may have one or more substituents,

[0023] a cycloalkyl group that may have one or more substituents,

[0024] a cycloalkenyl group that may have one or more substituents,

[0025] a cyclo-dienyl group that may have one or more substituents,

[0026] an aryl group which may have one or more substituents,

[0027] an aralkyl group which may have one or more substituents,

[0028] a non-aromatic heterocyclic group which may have one or more substituents,

[0029] a heteroaryl group which may have one or more substituents,

[0030] cyano,

[0031] formyl,

[0032] RaO-,

[0033] RaCO-,

[0034] RaSO 2 -,

[0035] RaCOO-,

[0036] RaNRaCO-,

[0037] RaCONRa-,

[0038] RaOCO-,

[0039] RaOSO 2 -, and,

[0040] RaNRbSO 2 -

[0041] (In these formulas, Ra is independently:

[0042] an alkyl group which may have one or more substituents,

[0043] an alkenyl group which may have one or more substituents,

[0044] an alkynyl group which may have one or more substituents,

[0045] a cycloalkyl group which may have one or more substituents,

[0046] a cycloalkenyl group which may have one or more substituents,

[0047] a cyclo-dienyl group which may have one or more substituents,

[0048] an aryl group which may have one or more substituents,

[0049] an aralkyl group which may have one or more substituents,

[0050] a non-aromatic heterocyclic group which may have one or more substituents, or

[0051] A heteroaryl group that may have more than one substituent

[0052] Rb is independently H or an alkyl group that may have more than one substituent).

[0053] As the above organic group, an alkyl group that may have more than one substituent is preferred.

[0054] In addition, in the present disclosure, a "substituent" refers to a group capable of substitution. 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 sulfonamide group, an aromatic sulfonamide group, a heterocyclic sulfonamide group, an amino group, an aliphatic amino group, an aromatic amino group, a heterocyclic amino group, an aliphatic oxycarbonylamino group, an aromatic oxycarbonylamino group, a heterocyclic oxycarbonylamino group, an aliphatic sulfinyl group, an aromatic sulfinyl group, an aliphatic thio group, an aromatic thio group, a hydroxyl group, a cyano group, a sulfo group, a carboxyl group, an aliphatic oxyamino group, an aromatic oxyamino group, a carbamoylamino group, a sulfamoylamino group, a halogen atom, a sulfamoylcarbamoyl group, a carbamoylsulfamoyl group, a di-aliphatic oxyphosphinyl group, and a di-aromatic oxyphosphinyl group.

[0055] The above aliphatic group may be saturated or unsaturated, and may have a hydroxyl 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. As the above aliphatic group, an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a vinyl group, a cyclohexyl group, a carbamoylmethyl group, etc., can be mentioned.

[0056] The above 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. As the above aromatic group, an aryl group having 6 to 12 carbon atoms, preferably a total of 6 to 10 carbon atoms, such as a phenyl group, a 4-nitrophenyl group, a 4-acetylaminophenyl group, a 4-methylsulfonylphenyl group, etc., can be mentioned.

[0057] The above heterocyclic group may have a halogen atom, a hydroxyl 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. As the above heterocyclic group, a 5- to 6-membered heterocycle having 2 to 12 carbon atoms, preferably 2 to 10 carbon atoms, such as a 2-tetrahydrofuranyl group, a 2-pyrimidinyl group, etc., can be mentioned.

[0058] The above acyl group may have an aliphatic carbonyl group, an aromatic carbonyl group, a heterocyclic carbonyl group, a hydroxyl 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. As the above acyl group, an acyl group having 2 to 8 carbon atoms in total, preferably 2 to 4 carbon atoms, such as an acetyl group, a propionyl group, a benzoyl group, a 3-pyridinecarbonyl group, etc. can be mentioned.

[0059] The above acylamino group may have an aliphatic group, an aromatic group, a heterocyclic group, etc., and for example, it may have an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propionylamino group, etc. As the above acylamino group, an acylamino group having 2 to 12 carbon atoms in total, preferably 2 to 8 carbon atoms, an alkylcarbonylamino group having 2 to 8 carbon atoms in total, such as an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propionylamino group, etc. can be mentioned.

[0060] The above aliphatic oxycarbonyl group may be saturated or unsaturated, and further, it may have a hydroxyl 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. As the above aliphatic oxycarbonyl group, an alkoxycarbonyl group having 2 to 8 carbon atoms in total, preferably 2 to 4 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a (tert) -butoxycarbonyl group, etc. can be mentioned.

[0061] The above carbamoyl group may have an aliphatic group, an aromatic group, a heterocyclic group, etc. As the above carbamoyl group, an unsubstituted carbamoyl group, an alkylcarbamoyl group having 2 to 9 carbon atoms in total, preferably an unsubstituted carbamoyl group, an alkylcarbamoyl group having 2 to 5 carbon atoms in total, such as an N-methylcarbamoyl group, an N,N-dimethylcarbamoyl group, an N-phenylcarbamoyl group, etc. can be mentioned.

[0062] The above aliphatic sulfonyl group may be saturated or unsaturated, and further, it may have a hydroxyl 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. As the above aliphatic sulfonyl group, an alkylsulfonyl group having 1 to 6 carbon atoms in total, preferably 1 to 4 carbon atoms in total, such as a methanesulfonyl group, etc. can be mentioned.

[0063] The above aromatic sulfonyl group may have a hydroxyl 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. As the above aromatic sulfonyl group, an arylsulfonyl group having 6 to 10 carbon atoms in total, such as a benzenesulfonyl group, etc. can be mentioned.

[0064] The above-mentioned amino group may have an aliphatic group, an aromatic group, a heterocyclic group, etc.

[0065] The above-mentioned acylamino group may have, for example, an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propionylamino group, etc. As the above-mentioned acylamino group, an acylamino group having 2 to 12 carbon atoms in total, preferably 2 to 8 carbon atoms in total, more preferably an alkylcarbonylamino group having 2 to 8 carbon atoms in total, such as an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propionylamino group, etc., can be cited.

[0066] The above-mentioned aliphatic sulfonamide group, aromatic sulfonamide group, heterocyclic sulfonamide group may be, for example, a methylsulfonamide group, a benzenesulfonamide group, a 2-pyridinesulfonamide group, etc.

[0067] The above-mentioned sulfamoyl group may have an aliphatic group, an aromatic group, a heterocyclic group, etc. As the above-mentioned sulfamoyl group, 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, a heterocyclic sulfamoyl group having 2 to 12 carbon atoms in total can be cited, and 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, 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, a 4-pyridinesulfamoyl group, etc.

[0068] The above-mentioned aliphatic oxy group may be saturated or unsaturated, and may have, for example, a methoxy group, an ethoxy group, an isopropoxy group, a cyclohexyloxy group, a methoxyethoxy group, etc. As the above-mentioned aliphatic oxy group, an alkoxy group having 1 to 8 carbon atoms in total, preferably 1 to 6 carbon atoms in total, such as a methoxy group, an ethoxy group, an isopropoxy group, a cyclohexyloxy group, a methoxyethoxy group, etc., can be cited.

[0069] The above-mentioned aromatic amino group, 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, an aliphatic oxycarbonyl group, and preferably may have 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, an aliphatic oxycarbonyl group having 2 to 4 carbon atoms in total.

[0070] The above-mentioned aliphatic thio group may be saturated or unsaturated, and may have, for example, an alkylthio group having 1 to 8 carbon atoms in total, more preferably 1 to 6 carbon atoms in total, such as a methylthio group, an ethylthio group, a carbamoylmethylthio group, a tert-butylthio group, etc.

[0071] The above carbamoyl amino group may have an aliphatic group, an aryl group, a heterocyclic group, etc. Examples of the carbamoyl amino group include carbamoyl amino group, alkylcarbamoyl amino group having 2 to 9 carbon atoms in total, dialkylcarbamoyl amino group having 3 to 10 carbon atoms in total, arylcarbamoyl amino group having 7 to 13 carbon atoms in total, and heterocyclic carbamoyl amino group having 3 to 12 carbon atoms in total. Preferred are carbamoyl amino group, alkylcarbamoyl amino group having 2 to 7 carbon atoms in total, dialkylcarbamoyl amino group having 3 to 6 carbon atoms in total, arylcarbamoyl amino group having 7 to 11 carbon atoms in total, and heterocyclic carbamoyl amino group having 3 to 10 carbon atoms in total. Examples include carbamoyl amino group, methylcarbamoyl amino group, N,N-dimethylcarbamoyl amino group, phenylcarbamoyl amino group, 4-pyridinecarbamoyl amino group, etc.

[0072] In the present disclosure, the range represented by the endpoints includes all the values included in the range (for example, 1 to 10 includes 1.4, 1.9, 2.33, 5.75, 9.98, etc.).

[0073] In the present disclosure, the description of "at least 1" includes all the values of 1 or more (for example, 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.).

[0074] Hereinafter, specific embodiments of the present disclosure will be described in detail, but the present disclosure is not limited to the following embodiments.

[0075] The compound of the present disclosure is a compound represented by the general formula: R 1 -R 2 -X.

[0076] (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 composed only of units represented by -CFH-, or an alkylene group composed of units represented by -CFH- and units represented by -CH 2 -. Among them, these alkylene groups may optionally contain or not contain an epoxy group, -CH(OH)-, -CHI-, or a divalent cycloalkylene group. X is -OH, -CH(R 21 )OH (R 21 is 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), R1 , R 2 and X have a total carbon atom number of 2 to 50)

[0077] 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 . One of the characteristics of the compounds of the present disclosure is that they do not have CF 3 -(trifluoromethyl) at the molecular end.

[0078] R 2 is an alkylene group consisting only of units represented by -CFH-, or an alkylene group consisting of units represented by -CFH- and -CH 2 -. One of the characteristics of the compounds of the present disclosure is that the molecular chain must contain units represented by -CFH-, and the molecular chain does not contain units represented by -CF 2 -.

[0079] R 2 preferably has 1 or more carbon atoms, more preferably 2 or more carbon atoms, further preferably 3 or more carbon atoms, preferably 49 or less, more preferably 15 or less, and further preferably 11 or less.

[0080] R 2 's alkylene group can optionally contain an epoxy group, -CH(OH)-, -CHI-, or a divalent cycloalkylene group. That is, a part of the alkylene group of R 2 can be substituted by an epoxy group (oxiranyl) or a cycloalkylene group, and either H or F bonded to the carbon atom constituting the alkylene group of R 2 can be substituted by OH or I.

[0081] When R 2 is an alkylene group consisting only of units represented by -CFH-, as R 2 , for example, -(CFH) n1 -(where n1 is an integer of 1 or more), preferably -(CFH) n1 -(where n1 is an integer of 1 to 49), more preferably an alkylene group represented by -CHF-(CHF-CHF) n -(n is an integer of 0 to 24) or -(CHF-CHF) n- (wherein n is an integer from 1 to 24) the alkylene group. n1 is preferably an integer from 1 to 15, more preferably an integer from 3 to 11. n is preferably an integer from 1 to 7, more preferably an integer from 1 to 5.

[0082] In R 2 is an alkylene group composed only of units represented by -CFH- and -CH 2 - units, as R 2 , for example, -CHF-(CHF-CHF) n -(CH 2 ) m -(where n is an integer of 0 or more, m is an integer of 1 or more) the alkylene group, -(CHF) p -(CH 2 ) q -(where p and q are independently integers of 1 or more, the sum of p and q is 2 to 49, the order of the units represented by -CFH- and -CH 2 - units is arbitrary in the formula, and either H or F bonded to the carbon atom can be replaced by OH) the alkylene group, -CHF-(CHF-CHF) n -CH 2 -CHI-(CH 2 ) q -(where n is an integer of 0 or more, q is an integer of 1 or more) the alkylene group, etc.

[0083] In R 2 is an alkylene group composed only of units represented by -CFH- and -CH 2 - units, as R 2 , preferably -CHF-(CHF-CHF) n -(CH 2 ) m -(where n is an integer from 1 to 24, m is an integer of 1 or more) the alkylene group, or -CHF-(CHF-CHF) n -CH 2 -CHI-(CH 2 ) q -(where n is an integer of 0 or more, q is an integer of 1 or more) the alkylene group, more preferably -CHF-(CHF-CHF) n -CH 2 -(where n is an integer from 1 to 24) the alkylene group, -CHF-(CHF-CHF) n -CH 2 CH 2 -(where n is an integer from 1 to 23), or -CHF-(CHF-CHF) n -CH2 -CHI-(CH 2 ) q - (wherein n is an integer of 0 or more and q is an integer of 1 or more) represents an alkylene group. n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4, and still 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 still more preferably an integer of 1 to 12.

[0084] X is -OH, -CH(R 21 )OH (where R 21 is H, a non-fluorinated alkyl group or a fluorinated alkyl group), -I, -CFHI, -CH 2 I, an anionic group or -COOR 22 (where R 22 is a non-fluorinated alkyl group having 1 to 8 carbon atoms). As the anionic group, -COOM, -SO 3 M or -OSO 3 M is preferably included. As the anionic group, for example, -COOM, -SO 3 M, -CH(R 21 )-O-(CH 2 ) 3 -SO 3 M, -OSO 3 M, -CH(R 21 )-OSO 3 M, etc. can be cited.

[0085] M of the anionic group represents a counter cation of the anion. As M, H, a metal atom, NR 7 4 , imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents is preferably used. As R 7 , H or an organic group is preferably used.

[0086] As the metal atom, an alkali metal (Group 1), an alkaline earth metal (Group 2), etc. can be cited, and Na, K, or Li is preferably used.

[0087] As M, -H, a metal atom or NR 7 4 is preferably used, more preferably H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 7 4 , still more preferably H, Na, K, Li or NH 4 , even more preferably H, Na, K or NH 4 , particularly preferably H, Na or NH 4 , and most preferably H or NH 4 .

[0088] R 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, more preferably H.

[0089] 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 .

[0090] R 1 、R 2 and X have a total carbon atom number of 2 to 50, preferably 2 to 16, more preferably 4 to 14, further preferably 4 to 12, particularly preferably 4 to 10, and most preferably 4 to 8.

[0091] As the compound of the present disclosure, more specifically, the following compounds can be cited.

[0092] General formula: CH 2 F-CHF-(CHF-CHF) n -CH(R 21 )OH (wherein n is an integer of 0 or more, and R 21 is as described above) the fluorinated alcohol shown;

[0093] General formula: CH 2 F-CHF-(CHF-CHF) n -COOM (wherein n is an integer of 0 or more, and M is a cation) the fluorinated carboxylic acid shown;

[0094] 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) the fluorinated sulfate shown;

[0095] General formula: R 1 -CHF-(CHF-CHF) n -I (wherein R 1 is as described above, and n is an integer of 0 or more (n is preferably an integer of 1 or more)) the first fluorinated alkyl iodide, the second fluorinated alkyl iodide, the fourth fluorinated alkyl iodide or the fifth fluorinated alkyl iodide shown;

[0096] General formula: R 1 -CHF-(CHF-CHF) n -CH2 CH 2 -I (wherein, R 1 as described above, n is an integer of 1 or more) the third fluoroalkyl iodide;

[0097] 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) the fluoroalcohol;

[0098] General formula: R 1 -CHF-(CHF-CHF) n -CH 2 -COOM (wherein, R 1 as described above, n is an integer of 0 or more, M is a cation) the fluoro carboxylic acid;

[0099] General formula: R 1 -CHF-(CHF-CHF) n -(CH 2 ) m -COOR 23 (wherein, R 1 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) the fluoro carboxylic acid derivative;

[0100] General formula: CH 2 F-R 2 -OSO 3 M (wherein, R 2 is -(CFH) n1 -(where n1 is an integer of 3 to 49), M is a cation) the oligomer;

[0101] General formula: R 2 (-OSO 3 M) 2 (wherein, R 2 is -(CFH) n1 -(where n1 is an integer of 1 to 49), M is a cation) the oligomer;

[0102] General formula: CH 3 -R 2 -COOM (wherein, R 2 is an alkylene group composed only of units represented by -CFH-, or an alkylene group composed of units represented by -CFH- and -CH 2- An alkylene group composed of the units shown, where these alkylene groups optionally contain or do not contain an epoxy group, -CH(OH)- or a divalent cycloalkylene group, and M is a cation); fluoride of an unsaturated fatty acid shown

[0103] General formula: R 1 -CHF-(CHF-CHF) n -CH 2 -CHI-(CH 2 ) q -X (wherein R 1 is -CHF 2 or -CHFI, and 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) iodine-containing compound shown

[0104] General formula: R 1 -CHF-(CHF-CHF) n -CH 2 -CH 2 -(CH 2 ) q -X (R 1 is -CHF 2 or -CHFI, and 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) compound shown

[0105] As described above, the compounds of the present disclosure include fluoroalcohols, fluorocarboxylic acids, fluorosulfuric acid esters, fluoroalkyl iodides, oligomers, fluorides of unsaturated fatty acids, iodine-containing compounds, etc. Next, the manufacturing methods of these compounds will be described.

[0106] <First Manufacturing Method>

[0107] In the first manufacturing method, by adding CHF=CHF to an alkanol shown by the general formula: R 21 -CH 2 -OH (wherein R 21 is H, a non-fluorinated alkyl group or a fluorinated alkyl group), the general formula: CH 2 F-CHF-(CHF-CHF)n -CH(R 21 )OH (wherein n is an integer of 0 or more, and R 21 is as described above) as shown in the fluorinated alcohol.

[0108] For the alkanol and the fluorinated alcohol, R 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, more preferably H.

[0109] In the fluorinated alcohol, n represents the degree of polymerization of CHF=CHF and is an integer of 0 or more. 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 further preferably an integer of 1 to 3.

[0110] The reaction of the 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 radicals, and the generated radicals abstract the hydrogen atom on the carbon to which the hydroxyl group of the alkanol is bonded, thereby generating an alkanol radical, and a reaction of adding CHF=CHF to the alkanol radical (so-called telomerization reaction) is carried out.

[0111] As the radical initiator, an organic peroxide is preferred, and examples thereof include dialkyl peroxydicarbonates such as diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate, peroxyesters such as 2-ethylhexanoyl (tert-butyl) peroxide, tert-butyl peroxyisobutyrate, and tert-butyl peroxypivalate, and dialkyl peroxides such as di-tert-butyl peroxide.

[0112] The amount of CHF=CHF used is preferably 0.01 mol to 100 mol relative to 1 mol of the alkanol.

[0113] The amount of the radical initiator used is preferably 0.01 mol to 2 mol relative to 1 mol of the alkanol.

[0114] The temperature of the reaction of the alkanol with CHF=CHF can be appropriately selected and is preferably -78°C to 200°C. In addition, the temperature of the reaction of the alkanol with CHF=CHF is preferably equal to or higher than the decomposition temperature of the radical polymerization initiator and preferably lower than the decomposition temperatures of the substrate and the product.

[0115] The pressure of the reaction of the alkanol with CHF=CHF can be appropriately selected and is preferably 0 to 5.0 MPaG. The reaction time of the alkanol with CHF=CHF can be appropriately selected and is preferably 0.1 hour to 96 hours.

[0116] <Second manufacturing method>

[0117] In the second manufacturing method, a general formula: CH is manufactured by the first manufacturing method. 2F-CHF-(CHF-CHF) n -CH(R 21 )OH (wherein, n is an integer of 0 or more, R 21 is as described above) After the fluorinated alcohol shown, when R 21 is H, by oxidizing the fluorinated alcohol, the general formula: CH 2 F-CHF-(CHF-CHF) n -COOM (wherein, n is an integer of 0 or more, M is a cation) The fluorinated carboxylic acid shown.

[0118] The n of the fluorinated carboxylic acid is the same value as n of the fluorinated alcohol and is an integer of 0 or more. The preferred range of n of the fluorinated carboxylic acid is the same as the preferred range of n of the fluorinated alcohol.

[0119] M is a counter cation of -COO - and the same cations as M possessed by the anionic group of X described above can be cited, and the preferred cations are also the same.

[0120] The oxidation of the fluorinated alcohol can be carried out in the presence of an oxidizing agent. As the oxidizing agent, potassium permanganate etc. can be cited. The usage amount of the oxidizing agent is preferably 0.01 mol to 100 mol relative to 1 mol of the fluorinated alcohol.

[0121] The oxidation of the fluorinated alcohol can be carried out in a solvent. As the solvent, water can be cited.

[0122] The temperature of the oxidation of the fluorinated alcohol can be appropriately selected, preferably -78°C to 200°C. The pressure of the oxidation of the fluorinated alcohol can be appropriately selected, preferably 0 to 5.0 MPaG. The time of the oxidation of the fluorinated alcohol can be appropriately selected, preferably 0.1 hour to 96 hours.

[0123] <The 3rd manufacturing method>

[0124] In the 3rd manufacturing method, after manufacturing the fluorinated alcohol 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) by the 1st manufacturing method, the fluorinated alcohol is reacted with chlorosulfonic acid, whereby 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, M is a cation) The fluorinated sulfate shown.

[0125] R of the fluorinated sulfate21 Same as that of the fluoroalcohol, it is a single bond, a non-fluorinated alkylene group or a fluorinated alkylene group. The preferred groups of R of the fluorosulfate 21 are the same as those of the fluoroalcohol. The preferred groups of R of the fluorosulfate 21 are the same as those of the fluoroalcohol. 21 are the same as those of the fluoroalcohol.

[0126] n of the fluorosulfate is the same value as n of the fluoroalcohol and is an integer of 0 or more. The preferred range of n of the fluorosulfate is the same as the preferred range of n of the fluoroalcohol.

[0127] M is a counter cation of -OSO 3 - and the same cations as those of M possessed by the anionic groups of X described above can be cited, and the preferred cations are also the same.

[0128] The usage amount of chlorosulfonic acid is preferably 1 mol to 2 mol relative to 1 mol of the fluoroalcohol.

[0129] The reaction of the fluoroalcohol and chlorosulfonic acid can be carried out in the presence of a base. As the base, alkali metal hydroxides, alkaline earth metal hydroxides, amines, etc. can be cited, and among them, amines are preferred.

[0130] As amines, tertiary amines such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, dimethylbenzylamine, N,N,N’,N’-tetramethyl-1,8-naphthalenediamine, etc., heteroaromatic amines such as pyridine, pyrrole, uracil, trimethylpyridine, dimethylpyridine, etc., cyclic amines such as 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonene, etc. can be cited. Among them, triethylamine and pyridine are preferred.

[0131] The usage amount of the base is 0.5 mol to 20 mol relative to 1 mol of the fluoroalcohol.

[0132] The reaction of the fluoroalcohol and chlorosulfonic acid can be carried out in a solvent. As the solvent, a polar solvent is preferred, a non-protic polar solvent is more preferred, and an ether is further preferred.

[0133] As ethers, ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraethylene glycol dimethyl ether (tetraethylene glycol dimethyl ether), crown ethers (15-crown-5, 18-crown-6), etc. can be cited, and among them, diethyl ether is preferred.

[0134] The reaction temperature of the fluoroalcohol and chlorosulfonic acid can be appropriately selected and is preferably 0 to 40 °C. The reaction pressure of the fluoroalcohol and chlorosulfonic acid can be appropriately selected and is preferably 0.1 MPaG to 5 MPaG. The reaction time of the fluoroalcohol and chlorosulfonic acid can be appropriately selected and is preferably 0.1 hour to 96 hours.

[0135] <Fourth manufacturing method>

[0136] In the fourth manufacturing method, by reacting CHF=CHF with an iodide compound represented by the general formula: X 1 I (X 1 is H or F), a first fluoroalkyl iodide represented by the general formula: R 1 -CHF-I (wherein R 1 is -CH 2 F or -CHF 2 ) is produced. By adding CHF=CHF to the first fluoroalkyl iodide, a second fluoroalkyl iodide represented by the general formula: R 1 -CHF-(CHF-CHF) n -I (wherein R 1 is as described above, and n is an integer of 1 or more) is produced.

[0137] The usage amount of the iodide compound is preferably 0.5 mol to 2 mol relative to 1 mol of CHF=CHF.

[0138] The reaction of CHF=CHF with the iodide compound can also be carried out in a solvent.

[0139] The temperature of the reaction of CHF=CHF with the iodide compound can be appropriately selected, preferably -78°C to 200°C. The pressure of the reaction of CHF=CHF with the iodide compound can be appropriately selected, preferably 0 to 5.0 MPaG. The reaction time of CHF=CHF with the iodide compound can be appropriately selected, preferably 0.1 hour to 96 hours.

[0140] By the reaction of CHF=CHF with the iodide compound, a first fluoroalkyl iodide represented by the general formula: R 1 -CHF-I (wherein R 1 is -CH 2 F or -CHF 2 ) is produced. In the fourth manufacturing method, then, CHF=CHF is added to the first fluoroalkyl iodide.

[0141] The reaction of the first fluoroalkyl iodide with CHF=CHF is a telomerization reaction using the first fluoroalkyl iodide as a telogen and CHF=CHF as a backbone substance, and a second fluoroalkyl iodide is produced by this reaction.

[0142] n in the second fluoroalkyl iodide represents the degree of polymerization of CHF=CHF and is an integer of 1 or more. n is preferably an integer of 1 to 23, more preferably an integer of 1 to 7, further preferably an integer of 1 to 5, and particularly preferably an integer of 1 to 3.

[0143] The reaction of the first fluoroalkyl iodide with CHF=CHF can be carried out in the presence of a radical initiator. Examples of the radical initiator include organic peroxides and azo compounds.

[0144] Examples of the organic peroxides include dialkyl peroxydicarbonates such as diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate, peresters such as 2-ethylhexanoyl (tert-butyl) peroxide, tert-butyl peroxyisobutyrate, and tert-butyl peroxypivalate, and dialkyl peroxides such as di-tert-butyl peroxide.

[0145] Examples of the azo compounds include azobisisobutyronitrile.

[0146] The amount of CHF=CHF used is preferably 0.01 mol to 100 mol relative to 1 mol of the fluoroalkyl iodide.

[0147] The amount of the radical initiator used is preferably 0.01 mol to 2 mol relative to 1 mol of the fluoroalkyl iodide.

[0148] The temperature of the reaction of the first fluoroalkyl iodide with CHF=CHF can be appropriately selected, and is preferably -78°C to 200°C. In addition, the temperature of the reaction of the first fluoroalkyl iodide with CHF=CHF is preferably not less than the decomposition temperature of the radical polymerization initiator and preferably less than the decomposition temperatures of the substrate and the product.

[0149] The pressure of the reaction of the first fluoroalkyl iodide with CHF=CHF can be appropriately selected, and is preferably 0 to 5.0 MPaG. The reaction time of the first fluoroalkyl iodide with CHF=CHF can be appropriately selected, and is preferably 0.1 hour to 96 hours.

[0150] <The Fifth Production Method>

[0151] In the fifth production method, after producing the first fluoroalkyl iodide or the second fluoroalkyl iodide by the fourth production method, ethylene is added to the first fluoroalkyl iodide or the second fluoroalkyl iodide to produce a third fluoroalkyl iodide represented by the general formula: R 1 -CHF-(CHF-CHF) n -CH 2 CH 2 -I (wherein, R 1 is as described above, and n is an integer of 0 or more).

[0152] R of the third fluoroalkyl iodide 1 is the same as R of the first fluoroalkyl iodide or the second fluoroalkyl iodide, and is -CH 1 F or -CHF 2 2 .​

[0153] For the third fluoroalkyl iodide, n is an integer of 0 or more. The preferred range of n for the third fluoroalkyl iodide is an integer of 0 to 23, preferably an integer of 0 to 7, more preferably an integer of 0 to 5, and further preferably an integer of 0 to 3.

[0154] The reaction of the first fluoroalkyl iodide or the second fluoroalkyl iodide with ethylene can be carried out in the presence of a metal catalyst. Examples of the metal catalyst include copper.

[0155] The reaction of the first fluoroalkyl iodide or the second fluoroalkyl iodide with ethylene can be carried out in the presence of a radical-generating compound. Examples of such compounds include organic peroxides and azo compounds.

[0156] Examples of the organic peroxide include dialkyl peroxydicarbonates such as diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate, peresters such as 2-ethylhexanoyl (tert-butyl) peroxide, tert-butyl peroxyisobutyrate, and tert-butyl peroxypivalate, and dialkyl peroxides such as di-tert-butyl peroxide.

[0157] Examples of the azo compound include azobisisobutyronitrile.

[0158] The amount of ethylene used is preferably 0.01 mol to 100 mol relative to 1 mol of the first fluoroalkyl iodide or the second fluoroalkyl iodide.

[0159] The amount of the radical-generating compound used is preferably 0.001 mol to 1 mol relative to 1 mol of the first fluoroalkyl iodide or the second fluoroalkyl iodide.

[0160] The reaction temperature of the first fluoroalkyl iodide or the second fluoroalkyl iodide with ethylene can be appropriately selected, and is preferably 50°C to 200°C. The reaction pressure of the first fluoroalkyl iodide or the second fluoroalkyl iodide with ethylene can be appropriately selected, and is preferably 0.1 MPaG to 5 MPaG. The reaction time of the first fluoroalkyl iodide or the second fluoroalkyl iodide with ethylene can be appropriately selected, and is preferably 0.1 hour to 96 hours.

[0161] <The sixth production method>

[0162] In the sixth production method, the general formula: R 1 -CHF-(CHF-CHF) n -CH 2 CH 2 -I (wherein R 1As described above, after the third fluoroalkyl iodide (where n is an integer of 0 or more) is obtained, hydrolysis is carried out by reacting the third fluoroalkyl iodide with fuming sulfuric acid to produce a compound of 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) of the fluoroalcohol.

[0163] The R of the fluoroalcohol 1 is the same as the R of the third fluoroalkyl iodide, and is -CH 1 F or -CHF 2 2 .

[0164] The n of the fluoroalcohol is the same value as the n of the third fluoroalkyl iodide and is an integer of 0 or more. The preferred range of n of the fluoroalcohol is the same as the preferred range of n of the third fluoroalkyl iodide.

[0165] The content of sulfur trioxide in the fuming sulfuric acid is not particularly limited, and is preferably 10% by mass to 90% by mass, more preferably 30% by mass to 80% by mass, and still more preferably 50% by mass to 70% by mass.

[0166] The amount of fuming sulfuric acid used, in terms of the amount equivalent to sulfur trioxide in the fuming sulfuric acid, is preferably 1 mole to 50 moles relative to 1 mole of the third fluoroalkyl iodide.

[0167] The reaction temperature of the third fluoroalkyl iodide and fuming sulfuric acid can be appropriately selected, and is preferably 0 to 90°C. The reaction pressure of the third fluoroalkyl iodide and fuming sulfuric acid can be appropriately selected, and is preferably 0 to 10.0 MPaG. The reaction time of the third fluoroalkyl iodide and fuming sulfuric acid can be appropriately selected, and is preferably 0.1 hour to 96 hours.

[0168] In the sixth production method, by reacting the third fluoroalkyl iodide with fuming sulfuric acid, a fluoroalkyl hydrogensulfate of the general formula: R 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) is formed, and then the fluoroalkyl hydrogensulfate is hydrolyzed to thereby produce a compound of the general formula: R 1 -CHF-(CHF-CHF) n -CH 2 CH 2 -OH (wherein R 1 ​As described above, a fluoroalcohol represented by n being an integer of 0 or more).

[0169] Hydrolysis of the fluoroalkyl hydrogensulfate can be carried out, for example, using water or an aqueous sodium sulfite solution. Hydrolysis of the fluoroalkyl hydrogensulfate can be carried out, for example, by dropping an aqueous sodium sulfite solution into a solution obtained by reacting a third fluoroalkyl iodide with fuming sulfuric acid (a solution containing a fluoroalkyl hydrogensulfate).

[0170] The amount of water or the aqueous sodium sulfite solution used is not particularly limited as long as it is an amount sufficient to neutralize the solution obtained by reacting the third fluoroalkyl iodide with fuming sulfuric acid and further hydrolyze the fluoroalkyl hydrogensulfate.

[0171] The temperature of hydrolysis can be appropriately selected, and is preferably 15°C to 100°C. The time of hydrolysis can be appropriately selected, and is preferably 0.1 hour to 96 hours.

[0172] <The Seventh Manufacturing Method>

[0173] In the seventh manufacturing method, a fluoroalkyl iodide of the first, second, or third type is reacted with carbon dioxide or a dialkyl carbonate to produce a compound of the general formula: R 1 -CHF-(CHF-CHF) n -(CH 2 ) m -COOR 23 (wherein, R 1 As described above, n is an integer of 0 or more, m is an integer of 0 to 3, and R 23 is H or an alkyl group having 1 to 8 carbon atoms) of a fluoro carboxylic acid derivative.

[0174] The fluoro carboxylic acid derivative can be produced by reacting a fluoroalkyl iodide of the first, second, or third type with carbon dioxide or a dialkyl carbonate in the presence of a base.

[0175] This reaction can be carried out in the presence of a base. Examples of the base include alkali metal hydroxides, alkaline earth metal hydroxides, amines, etc. Examples of the amine include aliphatic amines such as tributylamine.

[0176] The amount of the base used is 0.5 mol to 20 mol relative to 1 mol of the fluoroalkyl iodide.

[0177] The temperature for reacting the fluoroalkyl iodide with carbon dioxide can be appropriately selected, and is preferably -78°C to 200°C.

[0178] In the case of reacting a fluoroalkyl iodide with a dialkyl carbonate, as the dialkyl carbonate, for example, dimethyl carbonate can be used. By reacting the fluoroalkyl iodide with dimethyl carbonate, a methoxycarbonylation reaction proceeds to produce the corresponding carboxylic acid ester.

[0179] In the production of a carboxylic acid ester in which R 23 is an alkyl group as a carboxylic acid derivative, the carboxylic acid ester can be converted to a carboxylic acid or a carboxylate by hydrolysis.

[0180] <The 8th production method>

[0181] In the 8th production method, CHF=CHF is polymerized in the presence of a persulfate to produce a general formula: CH 2 F-R 2 -OSO 3 M (wherein R 2 is an alkylene group represented by -(CFH) n1 -(wherein n1 is an integer of 1 to 49), and M is a cation) or R 2 (-OSO 3 M) 2 (wherein R 2 is an alkylene group represented by -(CFH) n1 -(wherein n1 is an integer of 1 to 49), and M is a cation) oligomer.

[0182] R 2 is an alkylene group represented by -(CFH) n1 -, n1 is an integer of 1 to 49, preferably an integer of 3 to 49. That is, the oligomer obtained by the 8th 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 8th production method may be an oligomer having a molecular weight distribution. In this case, n1 represents the average number of repeating units of the molecules contained in the oligomer.

[0183] M is a counter cation of -OSO 3 - , and the same cations as those of M possessed by the anionic group of X described above can be cited, and the preferred cations are also the same.

[0184] The polymerization of CHF=CHF can be carried out in the presence of a persulfate. By using a persulfate, the oligomerization of CHF=CHF starts, and the main chain is formed by repeating units derived from CHF=CHF, producing an oligomer having -OSO 3 M introduced at the end.

[0185] Examples of the persulfate include ammonium salts of persulfuric acid, alkali metal salts of persulfuric acid, alkaline earth metal salts of persulfuric acid, etc. The amount of the persulfate used is preferably 0.01% by mass to 1000% by mass relative to the amount of the produced oligomer.

[0186] The persulfate may also be used in combination with a reducing agent. Examples of the reducing agent include sulfites such as sodium sulfite and sodium bisulfite, metabisulfites such as sodium bisulfite and potassium metabisulfite, pyrosulfates, thiosulfates, etc.

[0187] The polymerization of CHF=CHF can be carried out in an aqueous medium. The polymerization of CHF=CHF is preferably carried out in the absence of a surfactant.

[0188] The temperature of the polymerization of CHF=CHF can be appropriately selected, and is preferably -78°C to 200°C. In addition, the temperature of the polymerization of CHF=CHF is preferably above the decomposition temperature of the persulfate and preferably less than the decomposition temperatures of the substrate and the product.

[0189] The pressure of the polymerization of CHF=CHF can be appropriately selected, and is preferably 0 to 5.0 MPaG. The time of the polymerization of CHF=CHF can be appropriately selected, and is preferably 0.1 hour to 96 hours.

[0190] <The Ninth Manufacturing Method>

[0191] In the ninth manufacturing method, by reacting an unsaturated fatty acid with HF or F 2 a fluoride of an unsaturated fatty acid represented by the general formula: CH 3 -R 2 -COOM (wherein R 2 is an alkylene group composed only of units represented by -CFH-, or an alkylene group composed of units represented by -CFH- and -CH 2 -, and these alkylene groups may optionally contain or not contain an epoxy group, -CH(OH)- or a divalent cycloalkylene group, and M is a cation) is obtained.

[0192] The unsaturated fatty acid may be either a monounsaturated fatty acid or a polyunsaturated fatty acid. The number of carbon atoms of the unsaturated fatty acid is preferably 4 to 50, more preferably 4 to 16, and further preferably 4 to 10.

[0193] As R of the fluoride of the unsaturated fatty acid 2 , preferably -(CHF) p -(CH 2 ) q -(where 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 the units represented by -CFH- and -CH 2- The order of existence of the units shown is arbitrary in the formula, and either H or F bonded to the carbon atom can be replaced by OH).

[0194] M is -COO - as the counter cation, cations the same as those of M possessed by the above-mentioned anionic group of X can be cited, and the preferred cations are also the same.

[0195] As the unsaturated fatty acids, for example, the following compounds can be cited.

[0196] Monounsaturated fatty acids such as crotonic acid, myristoleic acid, palmitoleic acid, cis-6-hexadecenoic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, nervonic acid, etc.;

[0197] Diolefinic fatty acids such as linoleic acid, eicosadienoic acid, docosadienoic acid, etc.;

[0198] Triolefinic fatty acids such as linolenic acid, pinolenic acid, eleostearic acid, mead acid, dihomo-γ-linolenic acid, eicosatrienoic acid, etc.;

[0199] Tetraolefinic fatty acids such as octadecatetraenoic acid, arachidonic acid, eicosatetraenoic acid, docosatetraenoic acid, etc.;

[0200] Pentaolefinic fatty acids such as eicosapentaenoic acid, docosapentaenoic acid, sardine acid, tetracosapentaenoic acid, etc.;

[0201] Hexaolefinic fatty acids such as docosahexaenoic acid, herring acid, etc.;

[0202] Epoxides of unsaturated fatty acids such as epoxyoleic acid, epoxy linoleic acid, etc.;

[0203] Eicosanoids such as prostaglandins, leukotrienes, thromboxanes, etc.

[0204] The reaction of the unsaturated fatty acid with HF or F 2 can be carried out by bringing the unsaturated fatty acid into contact with hydrogen fluoride gas or fluorine gas. Alternatively, the reaction can also be carried out by bringing the unsaturated fatty acid into contact with hydrofluoric acid (aqueous solution of hydrogen fluoride). This reaction can be carried out efficiently by using a catalyst.

[0205] By the reaction of the unsaturated fatty acid with HF or F 2 all of the unsaturated bonds in the unsaturated fatty acid can be fluorinated, or a part of the unsaturated bonds in the unsaturated fatty acid can be fluorinated. The fluorides of unsaturated fatty acids obtained by the 10th production method include fluorides of unsaturated fatty acids in which all of the unsaturated bonds of the unsaturated fatty acid are fluorinated, and fluorides of unsaturated fatty acids in which a part of the unsaturated bonds of the unsaturated fatty acid are fluorinated.

[0206] HF or F 2 The usage amount of HF or F is 0.01 mol to 100 mol per 1 mol of the unsaturated bond in the unsaturated fatty acid.

[0207] The unsaturated fatty acid and HF or F 2 The reaction temperature can be appropriately selected, preferably -78°C to 200°C. The unsaturated fatty acid and HF or F 2 The reaction pressure can be appropriately selected, preferably 0 to 5.0 MPaG. The unsaturated fatty acid and HF or F 2 The reaction time can be appropriately selected, preferably 0.1 hour to 96 hours.

[0208] <The 10th manufacturing method>

[0209] In the 10th manufacturing method, by reacting CHF=CHF with I 2 and IF 5 a tetrafluoroalkyl iodide represented by the general formula: R 1 -CHF-I (wherein R 1 is -CHF 2 or -CHFI) is produced.

[0210] I 2 and IF 5 The usage amount of I and IF is preferably 0.5 mol to 2 mol per 1 mol of CHF=CHF.

[0211] The reaction of CHF=CHF with I 2 and IF 5 can also be carried out in a solvent.

[0212] The reaction temperature of CHF=CHF with I 2 and IF 5 can be appropriately selected, preferably -78°C to 200°C. The reaction pressure of CHF=CHF with I 2 and IF 5 can be appropriately selected, preferably 0 to 5.0 MPaG. The reaction time of CHF=CHF with I 2 and IF 5 can be appropriately selected, preferably 0.1 hour to 96 hours.

[0213] In the 10th manufacturing method, by further adding CHF=CHF to the tetrafluoroalkyl iodide, a pentafluoroalkyl iodide represented by the general formula: R 1 -CHF-(CHF-CHF) n -I (wherein R 1 is as described above, and n is an integer of 1 or more) can be produced.

[0214] The reaction of the fourth fluoroalkyl iodide with CHF=CHF is a telomerization reaction using the fourth fluoroalkyl iodide as a telogen and CHF=CHF as a backbone substance, and the fifth fluoroalkyl iodide is produced through this reaction.

[0215] In the fifth fluoroalkyl iodide, n represents the degree of polymerization of CHF=CHF and is an integer of 1 or more. 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.

[0216] The reaction of the fourth fluoroalkyl iodide with CHF=CHF can be carried out in the presence of a radical initiator. Examples of the radical initiator include organic peroxides and azo compounds.

[0217] Examples of the organic peroxides include dialkyl peroxydicarbonates such as diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate, peresters such as 2-ethylhexanoyl(t-butyl)peroxide, t-butyl peroxyisobutyrate, and t-butyl peroxypivalate, and dialkyl peroxides such as di-t-butyl peroxide.

[0218] Examples of the azo compounds include azobisisobutyronitrile.

[0219] The usage amount of CHF=CHF is preferably 0.01 mol to 100 mol relative to 1 mol of the fluoroalkyl iodide.

[0220] The usage amount of the radical initiator is preferably 0.01 mol to 2 mol relative to 1 mol of the fluoroalkyl iodide.

[0221] The temperature of the reaction of the fourth fluoroalkyl iodide with CHF=CHF can be appropriately selected and is preferably -78°C to 200°C. In addition, the temperature of the reaction of the fourth fluoroalkyl iodide with CHF=CHF is preferably not less than the decomposition temperature of the radical polymerization initiator and preferably less than the decomposition temperatures of the substrate and the product.

[0222] The pressure of the reaction of the fourth fluoroalkyl iodide with CHF=CHF can be appropriately selected and is preferably 0 to 5.0 MPaG. The reaction time of the fourth fluoroalkyl iodide with CHF=CHF can be appropriately selected and is preferably 0.1 hour to 96 hours.

[0223] <The 11th manufacturing method>

[0224] In the 11th manufacturing method, after producing the fourth fluoroalkyl iodide or the fifth fluoroalkyl iodide by the 10th manufacturing method, the fourth fluoroalkyl iodide or the fifth fluoroalkyl iodide is reacted with 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), q is an integer of 1 or more) to react with an unsaturated compound, thereby producing a general formula: R 1 -CHF-(CHF-CHF) n -CH 2 -CHI-(CH 2 ) q -X (wherein R 1 , X and q are as described above, and n is an integer of 0 or more) of an iodine-containing compound.

[0225] The R of the iodine-containing compound 1 is the same as the R of the fourth or fifth fluoroalkyl iodide, and is -CHF 1 or -CHFI. 2

[0226] The X of the iodine-containing compound is the same as the X of the unsaturated compound, and 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).

[0227] The n of the iodine-containing compound is an integer of 0 or more. The preferred range of n of the iodine-containing compound is an integer of 0 to 23, preferably an integer of 0 to 7, more preferably an integer of 0 to 5, and further preferably an integer of 0 to 3.

[0228] The q of the iodine-containing compound is an integer of 1 or more. The preferred range of 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.

[0229] The reaction of the fourth or fifth fluoroalkyl iodide with the unsaturated compound can be carried out in the presence of a compound that generates free radicals. Examples of such a compound include organic peroxides and azo compounds.

[0230] Examples of the organic peroxide include dialkyl peroxydicarbonates such as diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate, peresters such as 2-ethylhexanoyl (tert-butyl) peroxide, tert-butyl peroxyisobutyrate, and tert-butyl peroxypivalate, and dialkyl peroxides such as di-tert-butyl peroxide.

[0231] Examples of the azo compound include azobisisobutyronitrile and the like.

[0232] The amount of the unsaturated compound used is preferably 0.01 mol to 100 mol relative to 1 mol of the fourth fluoroalkyl iodide or the fifth fluoroalkyl iodide.

[0233] The amount of the compound generating a radical used is preferably 0.001 mol to 1 mol relative to 1 mol of the fourth fluoroalkyl iodide or the fifth fluoroalkyl iodide.

[0234] The reaction temperature between the fourth fluoroalkyl iodide or the fifth fluoroalkyl iodide and the unsaturated compound can be appropriately selected, and is preferably 50°C to 200°C. The reaction pressure between the fourth fluoroalkyl iodide or the fifth fluoroalkyl iodide and the unsaturated compound can be appropriately selected, and is preferably 0.1 MPaG to 5 MPaG. The reaction time between the fourth fluoroalkyl iodide or the fifth fluoroalkyl iodide and the unsaturated compound can be appropriately selected, and is preferably 0.1 hour to 96 hours.

[0235] By reducing the obtained iodine-containing compound, a compound represented by 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 described above) can be produced. The reduction can be carried out, for example, by using a metal catalyst and hydrogen, or by using zinc as a reducing agent.

[0236] In any of the above production methods, after each step is completed, the solvent can be removed by distillation, or distillation, purification, etc. can be carried out to improve the purity of the obtained compound. In addition, when the obtained compound is a compound having an acidic anionic group such as -COOH, -SO 3 H, -OSO 3 H, etc., these groups can be converted into salt-type anionic groups by contacting with a base such as sodium carbonate or ammonia.

[0237] The compound of the present disclosure can reduce the surface tension of water. Therefore, the compound of the present disclosure can be suitably used as a surfactant. The surfactant of the present disclosure preferably contains at least one selected from the group consisting of the compounds in which X in the general formula is -OH, -CH(R 21 )OH and an anionic group.

[0238] That is, the surfactant of the present disclosure contains the general formula: R 1 -R2 -X (wherein R 1 is -CH 3 , -CH 2 F or -CHF 2 , R 2 is an alkylene group composed only of units represented by -CFH-, or an alkylene group composed of units represented by -CFH- and -CH 2 -, and these alkylene groups may optionally contain or not contain an epoxy group, -CH(OH)- or a divalent cycloalkylene group, 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, and the total number of carbon atoms of R 1 , R 2 and X is 2 to 50) of the compound shown. The surfactant of the present disclosure may contain one or two or more of the above compounds.

[0239] The surfactant of the present disclosure can be suitably used for the polymerization of fluoromonomers. Therefore, the present disclosure includes a method for producing a fluoropolymer, which is obtained by polymerizing a fluoromonomer in an aqueous medium in the presence of the above surfactant. Since the surfactant of the present disclosure contains units represented by -CFH-, it exhibits good surface activity even without having a perfluoroalkyl group or a perfluoroalkylene group.

[0240] The above embodiments have been described, but it can be understood that various changes can be made to the embodiments and details without departing from the spirit and scope of the claims.

[0241] The main embodiments of the present disclosure are as follows.

[0242] <1> According to the first aspect of the present disclosure, there is provided a compound represented by the general formula: R 1 -R 2 -X.

[0243] (wherein,

[0244] R 1 is -CH 3 , -CH 2 F, -CHF 2 , -CH 2 I, -CHFI, or an anionic group,

[0245] R 2 is an alkylene group composed only of units represented by -CFH-, or an alkylene group composed of units represented by -CFH- and -CH 2- An alkylene group composed of the units shown, wherein these alkylene groups optionally contain or do not contain an epoxy group, -CH(OH)-, -CHI-, or a divalent cycloalkylene group.

[0246] X is -OH, -CH(R 21 )OH (R 21 is 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).

[0247] R 1 、R 2 and the total number of carbon atoms of X is 2 to 50).

[0248] <2> According to the second aspect of the present disclosure, there is provided a compound based on the first aspect, wherein R 2 is an alkylene group having 2 or more carbon atoms.

[0249] <3> According to the third aspect of the present disclosure, there is provided a compound based on the first aspect or the second aspect, wherein R 2 is an alkylene group represented by the general formula: -(CFH) n1 -.

[0250] (In the formula, n1 is an integer from 1 to 49).

[0251] <4> According to the fourth aspect of the present disclosure, there is provided a compound based on the first aspect or the second aspect, which is a fluoride of an unsaturated fatty acid.

[0252] <5> According to the fifth aspect of the present disclosure, there is provided a compound based on any one of the first aspect to the fourth aspect, wherein R 1 、R 2 and the total number of carbon atoms of X is 2 to 18.

[0253] <6> According to the sixth aspect of the present disclosure, there is provided a compound based on any one of the first aspect to the fifth aspect, which is a fluoroalkyl iodide represented by the general formula: R 1 -CHF-(CHF-CHF) n -I (in the formula, R 1 is -CHF 2 、-CHF 2 or -CHFI, and n is an integer of 0 or more).

[0254] <7> According to the seventh aspect of the present disclosure, there is provided a compound based on any one of the first aspect to the fifth aspect, wherein the above anionic group includes -COOM, -SO 3 M or -OSO3 M (where M is a cation).

[0255] <8>According to the 8th aspect of the present disclosure, there is provided a surfactant comprising at least one selected from the group consisting of compounds in which X in the general formula is -OH, -CH(R 21 )OH and an anionic group, among the compounds according to any one of the 1st to 5th aspects.

[0256] Examples

[0257] Next, examples are given to illustrate the embodiments of the present disclosure, but the present disclosure is not limited to the said examples.

[0258] Example 1 Synthesis of 1,1,2-trifluoro-2-iodoethane

[0259] 37.1 g of iodine and 16.1 g of IF were added to a 300 mL pressure-resistant container, and the above container was sealed. After cooling the container to -78 °C, 10 g of (E)-1,2-difluoroethylene was introduced into the container, and the container was heated at 80 °C for 20 hours. After cooling the container with ice water, the contents of the pressure-resistant container were washed with water, and then further washed with a 5% Na 5 S 2 S 2 O 4 aqueous solution to obtain 5.8 g of the title compound.

[0260] 19 F NMR (282 MHz, CDCl 3 ): δ -169.1 to -169.4 (m, 1F), -124.0 to -124.3 (m, 1F).

[0261] 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).

[0262] LRMS (EI 70 eV) m / z (%) : 210 (M+, 100), 190 (8), 171 (3), 83 (62), 64 (37), 51 (14).

[0263] Example 2 Synthesis of 4,5,5-trifluoro-2-iodopentanol

[0264] In a pressure-resistant container with a capacity of 10 mL, 1.84 g of 1,1,2-trifluoro-2-iodoethane, 509 mg of allyl alcohol, and 288 mg of azobisisobutyronitrile were added. Thereafter, the container was heated at 80 °C for 22 hours. After cooling the container with ice water, the content of the pressure-resistant container was analyzed by gas chromatography-mass spectrometry. As a result, the title compound was formed at an area ratio of 75.9% relative to the area ratio of the raw material 1,1,2-trifluoro-2-iodoethane of 24.1%.

[0265] LRMS(EI 70eV) m / z(%) : 268(M+,1), 251(1), 185(2), 141(95), 73(100), 51(38).

[0266] Example 3 Synthesis of 7,8,8-trifluoro-5-iodooctan-1-ol

[0267] In a pressure-resistant container with a capacity of 10 mL, 1.00 g of 1,1,2-trifluoro-2-iodoethane, 477 mg of 5-hexen-1-ol, and 235 mg of azobisisobutyronitrile were added. Thereafter, the container was heated at 80 °C for 22 hours. After cooling the container with ice water, the content of the pressure-resistant container was analyzed by gas chromatography-mass spectrometry. As a result, the title compound was formed at an area ratio of 66.8% (total of 2 isomers) relative to the area ratio of the raw material 1,1,2-trifluoro-2-iodoethane of 37.2%.

[0268] LRMS(EI 70eV) m / z(%) : 293([M-OH]+,100), 259(5), 207(25), 207(25), 155(34).

[0269] Example 4 Synthesis of methyl 7,8,8-trifluoro-5-iodooctanoate

[0270] In a pressure-resistant container with a capacity of 10 mL, 200 mg of 1,1,2-trifluoro-2-iodoethane, 122 mg of methyl 5-hexenoate, and 46.9 mg of azobisisobutyronitrile were added. Thereafter, the container was heated at 80 °C for 22 hours. After cooling the container with ice water, the content of the pressure-resistant container was analyzed by gas chromatography-mass spectrometry. As a result, the title compound was formed at an area ratio of 70.0% (total of 2 isomers) relative to the area ratio of the raw material 1,1,2-trifluoro-2-iodoethane of 30.0%.

[0271] LRMS(EI 70eV) m / z(%) : 307([M-OMe]+,21), 211(100), 192(5), 151(35).

[0272] Example 5 Synthesis of 7,8,8-trifluoro-5-iodooctanoic acid

[0273] In a 10 mL pressure-resistant container, 200 mg of 1,1,2-trifluoro-2-iodoethane, 109 mg of 5-hexenoic acid, and 46.9 mg of azobisisobutyronitrile were added. Thereafter, the container was heated at 80 °C for 22 hours. After cooling the container with ice water, a mixture containing the target compound was obtained. 20 mg of this mixture was taken into another glass container, diluted with 1 mL of tetrahydrofuran and 0.2 mL of methanol, and then trimethylsilyldiazomethane (10% hexane solution) was added. After stirring at room temperature, the content was analyzed by gas chromatography-mass spectrometry. As a result, the methylated 7,8,8-trifluoro-5-iodooctanoic acid methyl ester of the title compound was formed at an area ratio of 85.7% (total of two isomers) relative to the area ratio of 14.3% of the starting material 1,1,2-trifluoro-2-iodoethane.

[0274] LRMS(EI 70eV) m / z(%) : 307([M-OMe]+, 24), 211(100), 192(4), 151(32).

[0275] Example 6 Synthesis of 7,8,8-trifluorooctan-1-ol

[0276] In a 10 mL glass container, 67.5 mg of zinc was added to a mixed solution of 200 mg of 7,8,8-trifluoro-5-iodooctan-1-ol and 0.4 mL of methanol. 0.33 mL of 2 M hydrochloric acid aqueous solution was added. After stirring for 6 hours, the content was analyzed by gas chromatography-mass spectrometry. As a result, the title compound was formed at an area ratio of 75.6% relative to the area ratio of 24.4% of the starting material 7,8,8-trifluoro-5-iodooctan-1-ol.

[0277] LRMS(EI 70eV) m / z(%) : 167([M-OH]+, 100), 127(54), 51(4).

[0278] Example 7 Oligomerization reaction of 1,1,2-trifluoro-2-iodoethane and (E)-1,2-difluoroethylene

[0279] In a 30 mL pressure-resistant container, 1.00 g of 1,1,2-trifluoro-2-iodoethane and 0.35 mL of 2-ethylhexanoyl(t-butyl)peroxide were added. The above container was sealed and cooled to -78 °C, and then 1.5 g of (E)-1,2-difluoroethylene was introduced. The container was heated at 80 °C for 24 hours. Thereafter, after cooling with ice water, the content of the pressure-resistant container was analyzed by gas chromatography-mass spectrometry. As a result, H-CF was formed at an area ratio of 36.1% (total of four isomers), 20.5% (total of eight isomers), and 21.3% (total of multiple isomers) respectively, relative to the area ratio of 22.2% of the starting material 1,1,2-trifluoro-2-iodoethane. 2CHF-(CHFCHF)-I, H-CF 2 CHF-(CHFCHF) 2 -I and H-CF 2 CHF-(CHFCHF) 3 -I.

[0280] H-CF 2 CHF-(CHFCHF)-I: LRMS (EI 70eV) m / z (%) : 274 (M+, 87), 191 (11), 159 (30), 147 (76), 83 (45), 77 (100), 51 (82).

[0281] H-CF 2 CHF-(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).

[0282] H-CF 2 CHF-(CHFCHF) 3 -I: LRMS (EI 70eV) m / z (%) : 402 (M+, 2), 191 (23), 159 (34), 147 (18), 83 (36), 77 (89), 51 (100).

[0283] Example 8

[0284] Add 300 g of water, 0.31 g of Na 2 HPO 4 to a 500 mL pressure-resistant container, 0.48 g of ammonium persulfate. Seal the above container, cool it to -78 °C, then introduce (E)-1,2-difluoroethylene, and heat it at 0.5 MPa and 90 °C for 30 minutes to react. After cooling, take a sample and dry it at 50 °C. As a result, 0.77 wt% of a solid component was formed. Analyze this solid by gel permeation chromatography (standard molecular weight of polystyrene). As a result, an oligomer with Mn 1020 and Mw 1043 was confirmed. In addition, analyze it by IR. As a result, almost no carbonyl stretching at 1742 cm -1 was observed. From this, it is presumed that an oligomer containing a sulfate group as an anionic group is included. In addition, measure the surface tension of the obtained solid component. As a result, it is 51.9 mN / m, and the effectiveness as a surfactant can be confirmed.

Claims

1. A compound having the general formula: R 1 -R 2 -X means, In the formula, R 1 is -CH 3 、-CH 2 F, -CHF 2 、-CH 2 I, -CHFI, or an anionic group, R 2 an alkylene group consisting only of units represented by -CFH-, or an alkylene group consisting of units represented by -CFH- and units represented by -CH 2 - Wherein, These alkylene groups optionally contain or do not contain an epoxy group, -CH(OH)-, -CHI-, or a divalent cycloalkylene group. X is -OH, -CH(R 21 )OH, -I, -CFHI, -CH 2 I, an anionic group or -COOR 22 , where R 21 is H, a non-fluorinated alkyl group or a fluorinated alkyl group, R 22 is a non-fluorinated alkyl group having 1 to 8 carbon atoms, R 1 、 R 2 and X have a total carbon atom number of 2 to 50.

2. The compound according to claim 1, Wherein, R 2 is an alkylene group having 2 or more carbon atoms.

3. The compound according to claim 1 or 2, Wherein, R 2 is a general formula: -(CFH) n1 - the alkylene group shown, In the formula, n1 is an integer from 1 to 49.

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

5. The compound according to any one of claims 1 to 4, Wherein, R 1 、R 2 and X have a total carbon atom number of 2 to 18.

6. The compound according to any one of claims 1 to 5, which has the general formula: R 1 -CHF-(CHF-CHF) n -I, and is a fluoroalkyl iodide as described above In the formula, R 1 is -CHF 2 、-CHF 2 or -CHFI, and n is an integer of 0 or more.

7. The compound according to any one of claims 1 to 5, Wherein, The anionic group includes -COOM, -SO 3 M or -OSO 3 M, where M is a cation.

8. A surfactant comprising at least one selected from the group consisting of compounds in which X in the general formula is -OH, -CH(R 21 )OH and an anionic group among the compounds described in any one of claims 1 to 5.