Fluorine-containing compounds, methods for producing the same, and surfactants

Abstract

To provide a novel fluorine-containing compound that does not contain a trifluoromethyl group and a difluoromethylene group. 【Solution means】 General formula: R 1 -R 2 -X (wherein, R 1 is -CH3, -CH2F, -CHF2, -CH2I, -CHFI, or an anionic group, and R 2 is an alkylene group composed only of units represented by -CFH-, or an alkylene group composed only of units represented by -CFH- and units represented by -CH2-, provided that these alkylene groups may optionally 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, -CH2I, an anionic group or -COOR 22 (R 22 is a non-fluorinated alkyl group having 1 to 8 carbon atoms), and a compound represented by (where the total number of carbon atoms of R 1 , R 2 and X is 2 to 50) is provided.

Description

[Technical Field]

[0001] This disclosure relates to fluorine-containing compounds, methods for producing the same, and surfactants. [Background technology]

[0002] Patent Document 1 contains the formula Rf-(CH2) m Compounds are described having -R'f-COOY, where 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, M is NH4, Li, Na, K or H, and R is a linear, branched or cyclic alkyl group containing 1 to 8 carbon atoms.

[0003] Patent Document 2 contains formula (I) RfCH2OCF(CF3)C(O)OM (I) A fluorosurfactant is described that contains the compound, where Rf is a linear or branched perfluoroalkyl group having 2 to 5 carbon atoms, and M is H, NH4, Li, Na, or K. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 10-212261 [Patent Document 2] Special Publication No. 2012-513531 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, the compounds described in Patent Documents 1 and 2 both have a CF3- (trifluoromethyl group) at the molecular terminal or contain a unit (difluoromethylene group) represented by -CF2- in the molecule, and no fluorine-containing compounds that do not contain the units represented by CF3- and -CF2- are described.

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

Means for Solving the Problems

[0007] According to the present disclosure, the general formula: R 1 -R 2 -X (wherein R 1 is -CH3, -CH2F, -CHF2, -CH2I, -CHFI, or an anionic group, R 2 is an alkylene group composed only of units represented by -CFH-, or an alkylene group composed only of units represented by -CFH- and units represented by -CH2-, provided that these alkylene groups may optionally 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, -CH2I, an anionic group or -COOR 22 (R 22 is a non-fluorinated alkyl group having 1 to 8 carbon atoms), and a compound represented by the sum of the carbon numbers of R 1 , R 2 and X being 2 to 50 is provided.

Advantages of the Invention

[0008] According to the present disclosure, a novel fluorine-containing compound that does not contain a trifluoromethyl group and a difluoromethylene group can be provided.

Modes for Carrying Out the Invention

[0009] Before describing this disclosure in detail, we define or explain some of the terms used in this disclosure.

[0010] In this disclosure, "organic group" means a group containing one or more carbon atoms, or a group formed by removing one hydrogen atom from an organic compound. Examples of such "organic groups" are: Alkyl molecules 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, Cyano group, formyl group, RaO-, RaCO-, RaSO2-, RaCOO-, RaNRaCO-, RaCONRa-, RaOCO-, RaOSO2-, and RaNRbSO2- (In these formulas, Ra is independent of, Alkyl molecules 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, Rb is independently an alkyl group which may have H or one or more substituents. It includes. The above organic group is preferably an alkyl group which may have one or more substituents.

[0011] Furthermore, in this disclosure, “substituent” means a substituteable group. Examples of such “substituent” are aliphatic group, aromatic group, heterocyclic group, acyl group, acyloxy group, acylamino group, aliphatic oxy group, aromatic oxy group, heterocyclic oxy group, aliphatic oxycarbonyl group, aromatic oxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, aromatic sulfonyl group, heterocyclic sulfonyl group, aliphatic sulfonyloxy group, aromatic sulfonyloxy group, heterocyclic sulfonyloxy group, sulfamoyl group, aliphatic sulfonamide group, aromatic sulfonamide group, heterocyclic sulfonamide group, amino group, aliphatic amino This includes 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, hydroxyl groups, cyano groups, sulfo groups, carboxyl 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 above aliphatic group may be saturated or unsaturated, and may also include a hydroxyl group, aliphatic oxy group, carbamoyl group, aliphatic oxycarbonyl group, aliphatic thio group, amino group, aliphatic amino group, acylamino group, carbamoylamino group, etc. Examples of the above aliphatic group include alkyl groups having a total of 1 to 8 carbon atoms, preferably 1 to 4, such as a methyl group, ethyl group, vinyl group, cyclohexyl group, carbamoylmethyl group, etc.

[0013] 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, and the like. Examples of the above aromatic group include aryl groups having 6 to 12 carbon atoms, preferably 6 to 10 total carbon atoms, such as a phenyl group, a 4-nitrophenyl group, a 4-acetylaminophenyl group, and a 4-methanesulfonylphenyl group.

[0014] 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, and the like. Examples of the above heterocyclic group include a 5-6 membered heterocycle with a total of 2 to 12 carbon atoms, preferably 2 to 10, such as a 2-tetrahydrofuryl group and a 2-pyrimidyl group.

[0015] The above acyl group may have an aliphatic carbonyl group, an arylcarbonyl 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, and the like. Examples of the above acyl group include acyl groups with a total of 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms, such as an acetyl group, a propanoyl group, a benzoyl group, and a 3-pyridinecarbonyl group.

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

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

[0018] The above carbamoyl group may have an aliphatic group, an aromatic group, a heterocyclic group, etc. Examples of the above 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 above aliphatic sulfonyl group may be saturated or unsaturated, and may also have a hydroxyl group, aromatic group, aliphatic oxy group, carbamoyl group, aliphatic oxycarbonyl group, aliphatic thio group, amino group, aliphatic amino group, acylamino group, carbamoylamino group, etc. Examples of the above aliphatic sulfonyl group include alkyl sulfonyl groups having a total of 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, such as a methanesulfonyl group.

[0020] 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, and the like. Examples of the above aromatic sulfonyl group include aryl sulfonyl groups with a total of 6 to 10 carbon atoms, such as a benzenesulfonyl group.

[0021] The above amino group may also have an aliphatic group, an aromatic group, a heterocyclic group, etc.

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

[0023] The above-mentioned 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 above-mentioned sulfamoyl group may have an aliphatic group, an aromatic group, a heterocyclic group, etc. Examples of the above-mentioned sulfamoyl group include a sulfamoyl group, an alkyl sulfamoyl group having a total of 1 to 9 carbon atoms, a dialkyl sulfamoyl group having a total of 2 to 10 carbon atoms, an aryl sulfamoyl group having a total of 7 to 13 carbon atoms, a heterocyclic sulfamoyl group having a total of 2 to 12 carbon atoms, more preferably a sulfamoyl group, an alkyl sulfamoyl group having a total of 1 to 7 carbon atoms, a dialkyl sulfamoyl group having a total of 3 to 6 carbon atoms, an aryl sulfamoyl group having a total of 6 to 11 carbon atoms, a heterocyclic sulfamoyl group having a total of 2 to 10 carbon atoms, for example, a sulfamoyl group, a methyl sulfamoyl group, an N,N-dimethyl sulfamoyl group, a phenyl sulfamoyl group, a 4-pyridine sulfamoyl group, etc.

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

[0026] The above 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, an aliphatic oxycarbonyl group, preferably an aliphatic group having 1 to 4 total carbon atoms, an aliphatic oxy group having 1 to 4 total carbon atoms, a halogen atom, a carbamoyl group having 1 to 4 total carbon atoms, a nitro group, or an aliphatic oxycarbonyl group having 2 to 4 total carbon atoms.

[0027] The above aliphatic thio group may be saturated or unsaturated, and more preferably an alkyl thio group having a total of 1 to 8 carbon atoms, or more preferably 1 to 6 carbon atoms, such as a methyl thio group, an ethyl thio group, a carbamoyl methyl thio group, or a t-butyl thio group.

[0028] The above-mentioned carbamoylamino group may have an aliphatic group, an aryl group, a heterocyclic group, etc. Examples of the above-mentioned 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, 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. For example, the above-mentioned carbamoylamino group, methylcarbamoylamino group, N,N-dimethylcarbamoylamino group, phenylcarbamoylamino group, 4-pyridinecarbamoylamino group, etc.

[0029] In this disclosure, the ranges represented by endpoints include all numerical values ​​that fall within that range (for example, 1 to 10 includes 1.4, 1.9, 2.33, 5.75, 9.98, etc.).

[0030] In this disclosure, the phrase "at least 1" includes all numbers greater than or equal to 1 (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.).

[0031] The following describes specific embodiments of this disclosure in detail, but this disclosure is not limited to the embodiments described below.

[0032] The compounds disclosed herein have the general formula: R 1 -R 2 -X (In the formula, R 1 is -CH3, -CH2F, -CHF2, -CH2I, -CHFI, or an anionic group, R 2X is an alkylene group consisting only of units represented by -CFH-, or an alkylene group consisting only of units represented by -CFH- and units represented by -CH2-, wherein these alkylene groups may optionally contain epoxy groups, -CH(OH)-, -CHI-, or divalent cycloalkylene groups, and X is -OH, -CH(R 21 )OH(R 21 (H, non-fluorinated alkyl group or fluorinated alkyl group), -I, -CFHI, -CH2I, anionic group or -COOR 22 (R 22 R is a non-fluorinated alkyl group having 1 to 8 carbon atoms. 1 , R 2 The compound is represented by (where the total number of carbon atoms in X is between 2 and 50).

[0033] R 1 The group is -CH3, -CH2F, -CHF2, -CH2I, -CHFI, or an anionic group, preferably -CH2F, -CHF2, or -CHFI, and more preferably -CHF2. One characteristic of the compounds of this disclosure is that they do not have a CF3- (trifluoromethyl group) at the molecular terminus.

[0034] R 2 This refers to an alkylene group composed solely of units represented by -CFH-, or an alkylene group composed solely of units represented by -CFH- and units represented by -CH2-. One characteristic of the compounds of this disclosure is that the molecular chain always contains a unit represented by -CFH- and does not contain a unit represented by -CF2-.

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

[0036] R 2The alkylene group may optionally contain an epoxy group, -CH(OH)-, -CHI-, or a divalent cycloalkylene group. That is, R 2 Some of the alkylene groups may be substituted with epoxy groups (oxirane groups) or cycloalkylene groups, R 2 Either H or F bonded to the carbon atom constituting the alkylene group may be substituted with OH or I.

[0037] R 2 If R is an alkylene group consisting only of units represented by -CFH-, 2 For example, -(CFH) n1 -(where n1 is an integer greater than or equal to 1) is one example, and -(CFH) n1 An alkylene group represented by -(wherein n1 is an integer from 1 to 49) is preferred, and -CHF-(CHF-CHF) n -(n is an integer from 0 to 24) represents an alkylene group, or -(CHF-CHF) n The alkylene group represented by -(n is an integer from 1 to 24) is more preferred. n1 is preferably an integer from 1 to 15, and more preferably an integer from 3 to 11. n is preferably an integer from 1 to 7, and more preferably an integer from 1 to 5.

[0038] R 2 If R is an alkylene group consisting only of units represented by -CFH- and units represented by -CH2-, 2 For example, -CHF-(CHF-CHF) n -(CH2) m -(where n is a non-negative integer and m is a non-negative integer), -(CHF) p -(CH2) q -(p and q are independent integers greater than or equal to 1, the sum of p and q is between 2 and 49, the order of existence of the unit represented by -CFH- and the unit represented by -CH2- is arbitrary in the formula, and either H or F bonded to a carbon atom may be substituted by OH) an alkylene group represented by -CHF-(CHF-CHF) n-CH2-CHI-(CH2) q Examples include alkylene groups represented by -(where n is a non-negative integer and q is a non-negative integer).

[0039] R 2 If R is an alkylene group consisting only of units represented by -CFH- and units represented by -CH2-, 2 For example, -CHF-(CHF-CHF) n -(CH2) m -(where n is an integer between 1 and 24, and m is an integer greater than or equal to 1) is an alkylene group, or -CHF-(CHF-CHF) n -CH2-CHI-(CH2) q An alkylene group represented by -(where n is an integer greater than or equal to 0, and q is an integer greater than or equal to 1) is preferred, such as -CHF-(CHF-CHF) n Alkylene groups represented by -CH2- (where n is an integer from 1 to 24), -CHF- (CHF-CHF) n -CH2CH2-(n is an integer from 1 to 23), or -CHF-(CHF-CHF) n -CH2-CHI-(CH2) q An alkylene group represented by -(where n is an integer greater than or equal to 0, and q is an integer greater than or equal to 1) is more preferred. n is preferably an integer from 0 to 6, more preferably an integer from 0 to 4, and even more preferably an integer from 1 to 3. m is preferably 1 or 2. q is preferably an integer from 1 to 24, more preferably an integer from 1 to 18, and even more preferably an integer from 1 to 12.

[0040] X is -OH, -CH(R 21 )OH(R 21 (H, non-fluorinated alkyl group or fluorinated alkyl group), -I, -CFHI, -CH2I, anionic group or -COOR 22 (R 22 ( is a non-fluorinated alkyl group having 1 to 8 carbon atoms). The anionic group preferably contains -COOM, -SO3M, or -OSO3M. Examples of anionic groups include -COOM, -SO3M, and -CH(R 21 )-O-(CH2)3-SO3M, -OSO3M, -CH(R21 Examples include the OSO3M.

[0041] In anionic groups, M represents the anion's countercation. M can be H, a metal atom, or NR. 7 4. Preferably, it is imidazolium which may have substituents, pyridinium which may have substituents, or phosphonium which may have substituents. 7 As such, H or an organic group is preferred.

[0042] Examples of metal atoms include alkali metals (Group 1) and alkaline earth metals (Group 2), with Na, K, or Li being preferred.

[0043] For M, this could be -H, a metal atom, or NR. 7 4 is preferred, and H, alkali metals (Group 1), alkaline earth metals (Group 2), or NR 7 4 is more preferred, H, Na, K, Li or NH4 is even more preferred, H, Na, K or NH4 is even more preferred, H, Na or NH4 is particularly preferred, and H or NH4 is most preferred.

[0044] 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, and more preferably H.

[0045] R 22 This is a non-fluorinated alkyl group having 1 to 8 carbon atoms, preferably a non-fluorinated alkyl group having 1 to 4 carbon atoms, and more preferably -CH3 or -CH2CH3.

[0046] R 1 , R 2 The total number of carbon atoms in X is 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, the following compounds are included as examples of compounds in this disclosure. General formula: CH2F-CHF-(CHF-CHF) n -CH(R 21 )OH (In the formula, n is a non-negative integer, R 21 (as described above) fluorine-containing alcohols; General formula: CH2F-CHF-(CHF-CHF) n -COOM Fluorine-containing carboxylic acids represented by (wherein n is a non-negative integer and M is a cation); General formula: CH2F-CHF-(CHF-CHF) n -CH(R 21 )-OSO3M (In the formula, n is a non-negative integer, R 21 As stated above, M is a fluorine-containing sulfate ester represented by (where M is a cation); General formula: R 1 -CHF-(CHF-CHF) n -I (In the formula, R 1 As described above, n is a first, second, fourth, or fifth fluorine-containing alkyl iodide, where n is an integer greater than or equal to 0 (preferably an integer greater than or equal to 1); General formula: R 1 -CHF-(CHF-CHF) n -CH2CH2-I (In the formula, R 1 As described above, is a third fluorine-containing alkyl iodide represented by n (where n is an integer of 1 or more); General formula: R 1 -CHF-(CHF-CHF) n -CH2CH2-OH (In the formula, R 1 As stated above, n is a fluorine-containing alcohol represented by (where n is a non-negative integer); General formula: R 1 -CHF-(CHF-CHF) n -CH2-COOM (In the formula, R 1 As described above, n is a non-negative integer and M is a cation-containing fluorine-containing carboxylic acid; General formula: R 1-CHF-(CHF-CHF) n -(CH2) m -COOR 23 (where 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); a fluorine-containing carboxylic acid derivative represented by General formula: CH2F-R 2 -OSO3M (where R 2 is an alkylene group represented by -(CFH) n1 -(n1 is an integer of 3 to 49), and M is a cation); an oligomer represented by General formula: R 2 (-OSO3M)2 (where R 2 is an alkylene group represented by -(CFH) n1 -(where n1 is an integer of 1 to 49), and M is a cation); an oligomer represented by General formula: CH3-R 2 -COOM (where R 2 is an alkylene group composed only of units represented by -CFH-, or an alkylene group composed only of units represented by -CFH- and units represented by -CH2-, provided that these alkylene groups may optionally contain an epoxy group, -CH(OH)- or a divalent cycloalkylene group, and M is a cation); a fluoride of an unsaturated fatty acid represented by General formula: R 1 -CHF-(CHF-CHF) n -CH2-CHI-(CH2) q -X (where R 1 is -CHF2 or -CHFI, X is -OH, -COOM (M is a cation), -SO3M (M is a cation), -OSO3M (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, q is an integer of 1 or more); an iodine-containing compound represented by General formula: R 1 -CHF-(CHF-CHF) n -CH2-CH2-(CH2) q-X(R 1 -CHF2 or -CHFI, X is -OH, -COOM (M is a cation), -SO3M (M is a cation), -OSO3M (M is a cation), -COOR 22 (R 22 A compound represented by a non-fluorinated alkyl group having 1 to 8 carbon atoms, where n is an integer greater than or equal to 0 and q is an integer greater than or equal to 1;

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

[0049] <First manufacturing method> In the first manufacturing method, the general formula is R 21 -CH2-OH(wherein, R 21 This is formed by adding CHF=CHF to an alkanol represented by H, a non-fluorinated alkyl group, or a fluorinated alkyl group, resulting in the general formula: CH2F-CHF-(CHF-CHF) n -CH(R 21 )OH(wherein n is a non-negative integer, R 21 This method produces a fluorine-containing alcohol as described above.

[0050] R of alkanols and fluorine-containing alcohols 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 fluorine-containing alcohols, n represents the degree of polymerization of CHF=CHF and is an integer greater than or equal to 0. For example, n is an integer from 0 to 23, preferably from 1 to 7, more preferably from 1 to 5, and even more preferably from 1 to 3.

[0052] The reaction between alkanols and 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 abstracts a hydrogen atom from the carbon atom to which the hydroxyl group of the alkanol is attached, thereby generating an alkanol radical. A reaction then proceeds in which CHF=CHF is added to the alkanol radical (a so-called telomerization reaction).

[0053] As radical initiators, organic peroxides are preferred, including 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 dit-butyl peroxide.

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

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

[0056] The reaction temperature between the alkanol and CHF=CHF can be selected as appropriate, but is preferably -78 to 200°C. Furthermore, the reaction temperature between the alkanol and CHF=CHF is preferably above the decomposition temperature of the radical polymerization initiator, and preferably below the decomposition temperature of the substrate and product.

[0057] The pressure for the reaction between the alkanol and CHF=CHF can be selected as appropriate, but is preferably 0 to 5.0 MPaG. The reaction time between the alkanol and CHF=CHF can be selected as appropriate, but is preferably 0.1 to 96 hours.

[0058] <Second manufacturing method> In the second manufacturing method, the general formula is CH2F-CHF-(CHF-CHF) n -CH(R 21 )OH(wherein n is a non-negative integer, R 21 After producing the fluorine-containing alcohol shown above, R 21 If H is present, oxidizing a fluorine-containing alcohol produces the general formula: CH2F-CHF-(CHF-CHF) n A fluorine-containing carboxylic acid represented by the formula -COOM (wherein n is a non-negative integer and M is a cation) is produced.

[0059] The value of n for a fluorinated carboxylic acid is the same as the value of n for a fluorinated alcohol, and is a non-negative integer. The preferred range for n of a fluorinated carboxylic acid is the same as the preferred range for n of a fluorinated alcohol.

[0060] M is -COO - The countercation is the same cation as M possessed by the anionic group of X mentioned above, and the preferred cations are also the same.

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

[0062] The oxidation of fluorine-containing alcohols can be carried out in a solvent. Water is one example of such a solvent.

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

[0064] <Third manufacturing method> In the third manufacturing method, the general formula is CH2F-CHF-(CHF-CHF)n -CH(R 21 )OH(wherein n is a non-negative integer, R 21 After producing a fluorine-containing alcohol as shown above, the fluorine-containing alcohol is reacted with a chloride sulfonic acid to produce a compound with the general formula: CH2F-CHF-(CHF-CHF) n -CH(R 21 )-OSO3M(wherein n is a non-negative integer, R 21 As described above, this process produces a fluorine-containing sulfate ester represented by M (where M is a cation).

[0065] R of fluorine-containing sulfate esters 21 R is a fluorine-containing alcohol. 21 It is the same as, and is a single bond, a non-fluorinated alkylene group, or a fluorinated alkylene group. R of fluorinated sulfate esters 21 A suitable group is R of a fluorine-containing alcohol. 21 It is the same as the preferred group.

[0066] The value of n for fluorinated sulfate esters is the same as the value of n for fluorinated alcohols, and is a non-negative integer. The preferred range for n for fluorinated sulfate esters is the same as the preferred range for n for fluorinated alcohols.

[0067] M is -OSO3 - The countercation is the same cation as M possessed by the anionic group of X mentioned above, and the preferred cations are also the same.

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

[0069] The reaction between a fluorinated alcohol and a sulfonic chloride can be carried out in the presence of a base. Examples of bases include alkali metal hydroxides, alkaline earth metal hydroxides, and amines, with amines being preferred.

[0070] Examples of amines 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, colidine, and lutidine; and cyclic amines such as 1,8-diazabicyclo[5.4.0]-7-undecene and 1,5-diazabicyclo[4.3.0]-5-nonene. Among these, triethylamine and pyridine are preferred.

[0071] The amount of base used is 0.5 to 20 moles per mole of fluorinated alcohol.

[0072] The reaction between a fluorinated alcohol and a sulfonic acid chloride can be carried out in a solvent. A polar solvent is preferred, an aprotic polar solvent is more preferred, and an ether is even more preferred.

[0073] Examples of ethers 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 ether (15-crown-5,18-crown-6), with diethyl ether being the most preferred.

[0074] The reaction temperature between the fluorinated alcohol and the sulfonic acid chloride can be selected as appropriate, but is preferably 0 to 40°C. The reaction pressure between the fluorinated alcohol and the sulfonic acid chloride can be selected as appropriate, but is preferably 0.1 to 5 MPaG. The reaction time between the fluorinated alcohol and the sulfonic acid chloride can be selected as appropriate, but is preferably 0.1 to 96 hours.

[0075] <Fourth manufacturing method> In the fourth manufacturing method, CHF=CHF and the general formula:X 1 I(X 1By reacting an iodide compound represented by H or F, the general formula is R 1 -CHF-I (wherein, R 1 A first fluorine-containing alkyl iodide represented by -CH2F or -CHF2 is produced, and by adding CHF=CHF to the first fluorine-containing alkyl iodide, the general formula: R 1 -CHF-(CHF-CHF) n -I (where R 1 As described above, a second fluorine-containing alkyl iodide is produced, represented by n (where n is an integer of 1 or more).

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

[0077] The reaction between CHF=CHF and iodide compounds can also be carried out in a solvent.

[0078] The reaction temperature between CHF=CHF and the iodide compound can be selected as appropriate, but is preferably -78 to 200°C. The reaction pressure between CHF=CHF and the iodide compound can be selected as appropriate, but is preferably 0 to 5.0 MPaG. The reaction time between CHF=CHF and the iodide compound can be selected as appropriate, but is preferably 0.1 to 96 hours.

[0079] The reaction of CHF=CHF with an iodide compound produces the general formula: R 1 -CHF-I (wherein, R 1 A first fluorine-containing alkyl iodide, represented by -CH2F or -CHF2, is produced. In the fourth method of production, CHF=CHF is then 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 acts as the telogen and CHF=CHF acts as the taxogen, and this reaction produces a second fluorine-containing alkyl iodide.

[0081] In the second fluorine-containing alkyl iodide, n represents the degree of polymerization of CHF=CHF and is an integer of 1 or more. n is preferably an integer from 1 to 23, more preferably an integer from 1 to 7, even more preferably an integer from 1 to 5, and particularly preferably an integer from 1 to 3.

[0082] The reaction between the first fluorinated alkyl iodide and CHF=CHF can be carried out in the presence of a radical initiator. Examples of radical initiators include organic peroxides and azo compounds.

[0083] Examples of organic peroxides 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 dit-butyl peroxide.

[0084] Examples of azo compounds include azobisisobutyronitrile.

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

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

[0087] The reaction temperature between the first fluorine-containing alkyl iodide and CHF=CHF can be appropriately selected, but is preferably -78 to 200°C. Furthermore, the reaction temperature between the first fluorine-containing alkyl iodide and CHF=CHF is preferably above the decomposition temperature of the radical polymerization initiator, and preferably below the decomposition temperature of the substrate and product.

[0088] The reaction pressure between the first fluorinated alkyl iodide and CHF=CHF can be appropriately selected, but is preferably 0 to 5.0 MPaG. The reaction time between the first fluorinated alkyl iodide and CHF=CHF can be appropriately selected, but is preferably 0.1 to 96 hours.

[0089] <Fifth manufacturing method> In the fifth manufacturing method, after producing the first or second fluorine-containing alkyl iodide by the fourth manufacturing method, ethylene is added to the first or second fluorine-containing alkyl iodide to produce a product of the general formula: R 1 -CHF-(CHF-CHF) n -CH2CH2-I (wherein, R 1 As described above, a third fluorine-containing alkyl iodide is produced, represented by n (where n is a non-negative integer).

[0090] The third fluorine-containing alkyl iodide R 1 R of the first or second fluorine-containing alkyl iodide 1 It is the same as -CH2F or -CHF2.

[0091] The n of the third fluorine-containing alkyl iodide is an integer greater than or equal to 0. A preferred range for the n of the third fluorine-containing alkyl iodide is an integer from 0 to 23, preferably an integer from 0 to 7, more preferably an integer from 0 to 5, and even more preferably an integer from 0 to 3.

[0092] The reaction between the first or second fluorinated alkyl iodide and ethylene can be carried out in the presence of a metal catalyst. Examples of metal catalysts include copper.

[0093] The reaction between the first or second fluorinated alkyl iodide and ethylene can be carried out in the presence of a radical-generating compound. Examples of such compounds include organic peroxides and azo compounds.

[0094] Examples of organic peroxides 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 dit-butyl peroxide.

[0095] Examples of 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 radical-generating compound used is preferably 0.001 to 1 mole per mole of the first or second fluorine-containing alkyl iodide.

[0098] The reaction temperature between the first or second fluorinated alkyl iodide and ethylene can be appropriately selected, but is preferably 50 to 200°C. The reaction pressure between the first or second fluorinated alkyl iodide and ethylene can be appropriately selected, but is preferably 0.1 to 5 MPaG. The reaction time between the first or second fluorinated alkyl iodide and ethylene can be appropriately selected, but is preferably 0.1 to 96 hours.

[0099] <Sixth manufacturing method> In the sixth manufacturing method, the general formula R is used according to the fifth manufacturing method. 1 -CHF-(CHF-CHF) n -CH2CH2-I (wherein, R 1 As described above, a third fluorine-containing alkyl iodide represented by (n is an integer greater than or equal to 0) is produced, and then the third fluorine-containing alkyl iodide is reacted with fuming sulfuric acid and hydrolyzed to obtain a compound with the general formula: R 1 -CHF-(CHF-CHF) n -CH2CH2-OH (wherein, R 1As described above, this process produces a fluorine-containing alcohol represented by n (where n is a non-negative integer).

[0100] R of fluorine-containing alcohols 1 This is the third fluorine-containing alkyl iodide, R 1 It is the same as -CH2F or -CHF2.

[0101] The value of n for the fluorinated alcohol is the same as the value of n for the third fluorinated alkyl iodide, and is a non-negative integer. The preferred range for n for the fluorinated alcohol is the same as the preferred range for n for the third fluorinated 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 a third fluorine-containing alkyl iodide, which is the amount equivalent to the sulfur trioxide of the fuming sulfuric acid.

[0104] The reaction temperature between the third fluorine-containing alkyl iodide and fuming sulfuric acid can be appropriately selected, but is preferably 0 to 90°C. The reaction pressure between the third fluorine-containing alkyl iodide and fuming sulfuric acid can be appropriately selected, but is preferably 0 to 10.0 MPaG. The reaction time between the third fluorine-containing alkyl iodide and fuming sulfuric acid can be appropriately selected, but is preferably 0.1 to 96 hours.

[0105] In the sixth manufacturing method, the reaction of the third fluorine-containing alkyl iodide with fuming sulfuric acid produces a product of general formula: R 1 -CHF-(CHF-CHF) n -CH2CH2-OSO3H (wherein, R 1 As described above, a fluorine-containing alkyl hydrogen sulfate represented by (n is an integer greater than or equal to 0) is produced, and then, by hydrolysis of the fluorine-containing alkyl hydrogen sulfate, the general formula: R 1-CHF-(CHF-CHF) n -CH2CH2-OH (wherein, R 1 As described above, this process produces a fluorine-containing alcohol represented by n (where n is a non-negative integer).

[0106] Hydrolysis of fluorinated alkyl hydrogen sulfates can be carried out, for example, using water or an aqueous sodium sulfite solution. Hydrolysis of fluorinated alkyl hydrogen sulfates can also be carried out, for example, by adding an aqueous sodium sulfite solution dropwise to a solution (fluorinated alkyl hydrogen sulfate-containing solution) obtained by the reaction of a third fluorinated 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 sufficient to neutralize the solution obtained by the reaction of the third fluorinated alkyl iodide with fuming sulfuric acid, and further to hydrolyze the fluorinated 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 manufacturing method> In the seventh manufacturing method, the first, second, or third fluorine-containing alkyl iodide is reacted with carbon dioxide or dialkyl carbonate to produce a product of the general formula: R 1 -CHF-(CHF-CHF) n -(CH2) m -COOR 23 (In the formula, R 1 As mentioned above, n is a non-negative integer, m is an integer between 0 and 3, and R 23 This method produces fluorine-containing carboxylic acid derivatives represented by H or an alkyl group having 1 to 8 carbon atoms.

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

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

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

[0113] The temperature for the reaction between fluorine-containing alkyl iodide and carbon dioxide can be selected as appropriate, but is preferably -78 to 200°C.

[0114] When reacting a fluorinated alkyl iodide with a dialkyl carbonate, for example, dimethyl carbonate can be used as the dialkyl carbonate. The reaction between the fluorinated alkyl iodide and dimethyl carbonate proceeds to a methoxycarbonylation reaction, producing the corresponding carboxylic acid ester.

[0115] As a carboxylic acid derivative, R 23 If a carboxylic acid ester with an alkyl group is produced, the carboxylic acid ester can be converted to a carboxylic acid or carboxylate salt by hydrolysis.

[0116] <Eighth manufacturing method> In the eighth manufacturing method, CHF=CHF is polymerized in the presence of a persulfate, resulting in a product with the general formula: CH2F-R 2 -OSO3M (where R 2 is, -(CFH) n1 -An oligomer represented by (wherein n1 is an integer from 1 to 49), where n1 is an integer from 1 to 49, and M is a cation, or R 2 (-OSO3M)2(wherein, R 2 is, -(CFH) n1An oligomer represented by -(wherein n1 is an integer from 1 to 49) is produced (wherein n1 is an integer from 1 to 49, and M is a cation).

[0117] R 2 is, -(CFH) n1 The alkylene group is represented by -, and n1 is an integer from 1 to 49, preferably an integer from 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 also be an oligomer having a molecular weight distribution, in which case n1 represents the average number of repeating units of the molecules contained in the oligomer.

[0118] M is -OSO3 - The countercation is the same cation as M possessed by the anionic group of X mentioned above, and the preferred cations are also the same.

[0119] Polymerization of CHF=CHF can be carried out in the presence of persulfate. By using persulfate, oligomerization of CHF=CHF is initiated, and an oligomer is produced in which the main chain is formed of repeating units derived from CHF=CHF and -OSO3M is introduced at the terminal.

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

[0121] Persulfates may be used in combination with reducing agents. Examples of reducing agents include sulfites such as sodium sulfite and sodium bisulfite, metabisulfites such as sodium bisulfite and potassium bisulfite, pyrosulfates, and thiosulfates.

[0122] The polymerization of CHF=CHF can be carried out in an aqueous medium. Preferably, the polymerization of CHF=CHF is carried out in the absence of a surfactant.

[0123] The polymerization temperature of CHF=CHF can be selected as appropriate, but is preferably -78 to 200°C. Furthermore, the polymerization temperature of CHF=CHF is preferably above the decomposition temperature of the persulfate, and preferably below the decomposition temperatures of the substrate and product.

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

[0125] <Ninth manufacturing method> In the ninth manufacturing method, an unsaturated fatty acid is reacted with HF or F2 to produce a product with the general formula: CH3-R 2 -COOM(in the formula, R 2 The alkylene group is composed solely of units represented by -CFH-, or solely of units represented by -CFH- and -CH2-, wherein these alkylene groups may optionally contain epoxy groups, -CH(OH)-, or divalent cycloalkylene groups, and M is a cation) to obtain a fluoride of an unsaturated fatty acid.

[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 For example, -(CHF) p -(CH2) q -(p is an integer greater than or equal to 1, q is an integer greater than or equal to 0, the sum of p and q is between 1 and 49, the order of existence of the unit represented by -CFH- and the unit represented by -CH2- is arbitrary in the formula, and either H or F bonded to a carbon atom may be substituted by OH) is preferred.

[0128] M is -COO- The countercation is the same cation as M possessed by the anionic group of X mentioned above, 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 adrenaline; Pentaunsaturated fatty acids such as boseopentaenoic acid, eicosapentaenoic acid, osbondic acid, sardine acid, and tetracosapentaenoic acid; Hexaussaturated fatty acids such as docosahexaenoic acid and herring acid; Epoxylated unsaturated fatty acids such as epoxidized oleic acid and epoxidized linoleic acid; Eicosanoids such as prostaglandins, leukotrienes, and thromboxanes;

[0130] The reaction between unsaturated fatty acids and HF or F2 can be carried out by contacting the unsaturated fatty acids with hydrogen fluoride gas or fluorine gas. Alternatively, the reaction may be carried out by contacting the unsaturated fatty acids with hydrofluoric acid (an aqueous solution of hydrogen fluoride). This reaction can be carried out efficiently by using a catalyst.

[0131] The reaction between the unsaturated fatty acid and HF or F2 may result in the fluorination of all of the unsaturated bonds in the unsaturated fatty acid, or it may result in the fluorination of some of the unsaturated bonds in the unsaturated fatty acid. The fluoride of unsaturated fatty acid obtained by the 10th production method includes fluoride of unsaturated fatty acid in which all of the unsaturated bonds of the unsaturated fatty acid are fluorinated, and fluoride of unsaturated fatty acid in which some of the unsaturated bonds of the unsaturated fatty acid are fluorinated.

[0132] The amount of HF or F2 used is 0.01 to 100 moles per mole of unsaturated bonds in the unsaturated fatty acid.

[0133] The reaction temperature of the unsaturated fatty acid with HF or F2 can be selected as appropriate, but is preferably -78 to 200°C. The reaction pressure of the unsaturated fatty acid with HF or F2 can be selected as appropriate, but is preferably 0 to 5.0 MPaG. The reaction time of the unsaturated fatty acid with HF or F2 can be selected as appropriate, but is preferably 0.1 to 96 hours.

[0134] <Tenth manufacturing method> In the tenth manufacturing method, CHF=CHF is reacted with I2 and IF5 to produce the general formula: R 1 -CHF-I (wherein, R 1 This produces a fourth fluorine-containing alkyl iodide, represented as -CHF2 or -CHFI.

[0135] The amounts of I2 and IF5 used are preferably 0.5 to 2 moles per mole of CHF = CHF.

[0136] The reaction between CHF=CHF and I2 and IF5 can also be carried out in a solvent.

[0137] The reaction temperature of CHF=CHF with I2 and IF5 can be selected as appropriate, but is preferably -78 to 200°C. The reaction pressure of CHF=CHF with I2 and IF5 can be selected as appropriate, but is preferably 0 to 5.0 MPaG. The reaction time of CHF=CHF with I2 and IF5 can be selected as appropriate, but is preferably 0.1 to 96 hours.

[0138] In the tenth manufacturing method, by further adding CHF=CHF to the fourth fluorine-containing alkyl iodide, the general formula: R 1 -CHF-(CHF-CHF) n -I (where R 1 As described above, a fifth fluorine-containing alkyl iodide represented by n (where n is an integer of 1 or more) can be produced.

[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 acts as the telogen and CHF=CHF acts as the taxogen, and this reaction produces a fifth fluorine-containing alkyl iodide.

[0140] In the fifth fluorine-containing alkyl iodide, n represents the degree of polymerization of CHF=CHF and is an integer of 1 or more. n is preferably an integer from 1 to 23, more preferably an integer from 1 to 7, even more preferably an integer from 1 to 5, and particularly preferably an integer from 1 to 3.

[0141] The reaction between the fourth fluorinated alkyl iodide and CHF=CHF can be carried out in the presence of a radical initiator. Examples of radical initiators include organic peroxides and azo compounds.

[0142] Examples of organic peroxides 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 dit-butyl peroxide.

[0143] Examples of azo compounds include azobisisobutyronitrile.

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

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

[0146] The reaction temperature between the fourth fluorine-containing alkyl iodide and CHF=CHF can be appropriately selected, but is preferably -78 to 200°C. Furthermore, the reaction temperature between the fourth fluorine-containing alkyl iodide and CHF=CHF is preferably above the decomposition temperature of the radical polymerization initiator, and preferably below the decomposition temperature of the substrate and product.

[0147] The reaction pressure between the fourth fluorinated alkyl iodide and CHF=CHF can be appropriately selected, but is preferably 0 to 5.0 MPaG. The reaction time between the fourth fluorinated alkyl iodide and CHF=CHF can be appropriately selected, but is preferably 0.1 to 96 hours.

[0148] <No. 11 Manufacturing Method> In the 11th manufacturing method, after producing the 4th or 5th fluorine-containing alkyl iodide by the 10th manufacturing method, the 4th or 5th fluorine-containing alkyl iodide and the general formula: CH2=CH-(CH2) q -X (wherein X is -OH, -COOM (M is a cation), -SO3M (M is a cation), -OSO3M (M is a cation), -COOR) 22 (R 22 This compound is produced by reacting it with an unsaturated compound represented by a nonfluorinated alkyl group having 1 to 8 carbon atoms (where q is an integer of 1 or more), and the general formula is R 1 -CHF-(CHF-CHF) n -CH2-CHI-(CH2) q -X(where R 1 An iodine-containing compound is produced, represented by (X and q as described above, and n is a non-negative integer).

[0149] R of iodine-containing compounds 1R is the fourth or fifth fluorine-containing alkyl iodide. 1 It is the same as -CHF2 or -CHFI.

[0150] X in iodine-containing compounds is the same as X in unsaturated compounds, and includes -OH, -COOM (M is a cation), -SO3M (M is a cation), -OSO3M (M is a cation), and -COOR. 22 (R 22 (This refers to a non-fluorinated alkyl group having 1 to 8 carbon atoms.)

[0151] The value of n in the iodine-containing compound is an integer greater than or equal to 0. A preferred range for n in the iodine-containing compound is an integer from 0 to 23, preferably an integer from 0 to 7, more preferably an integer from 0 to 5, and even more preferably an integer from 0 to 3.

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

[0153] The reaction between a fourth or fifth fluorinated alkyl iodide and an unsaturated compound can be carried out in the presence of a radical-generating compound. Examples of such compounds include organic peroxides and azo compounds.

[0154] Examples of organic peroxides 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 dit-butyl peroxide.

[0155] Examples of azo compounds include azobisisobutyronitrile.

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

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

[0158] The reaction temperature between the fourth or fifth fluorinated alkyl iodide and the unsaturated compound can be appropriately selected, but is preferably 50 to 200°C. The reaction pressure between the fourth or fifth fluorinated alkyl iodide and the unsaturated compound can be appropriately selected, but is preferably 0.1 to 5 MPaG. The reaction time between the fourth or fifth fluorinated alkyl iodide and the unsaturated compound can be appropriately selected, but is preferably 0.1 to 96 hours.

[0159] The resulting iodine-containing compound is reduced to obtain the general formula: R 1 -CHF-(CHF-CHF) n -CH2-CH2-(CH2) q -X(where R 1 Compounds represented by (X, q, and n are as described above) may be prepared. Reduction can be carried out, for example, by using a metal catalyst and hydrogen, or by using zinc as a reducing agent.

[0160] In any of the above-described manufacturing methods, the purity of the obtained compound may be increased after the completion of each step by removing the solvent by distillation, or by performing distillation or purification. Furthermore, if the obtained compound is a compound having acidic anionic groups such as -COOH, -SO3H, or -OSO3H, these groups can be converted to salt-type anionic groups by contacting them with an alkali such as sodium carbonate or ammonia.

[0161] The compounds of this disclosure can lower the surface tension of water. Therefore, the compounds of this disclosure can be suitably used as surfactants. The surfactants of this disclosure are those compounds described above in which X in the general formula is -OH, -CH(R 21Preferably, it contains at least one compound selected from the group consisting of )OH and anionic groups.

[0162] In other words, the surfactant of this disclosure has the general formula: R 1 -R 2 -X (In the formula, R 1 is -CH3, -CH2F, or -CHF2, and R 2 X is an alkylene group consisting only of units represented by -CFH-, or an alkylene group consisting only of units represented by -CFH- and units represented by -CH2-, wherein 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 The surfactants of this disclosure include compounds represented by (where the total number of carbon atoms in X is 2 to 50). The surfactants of this disclosure may contain one or more of the above compounds.

[0163] The surfactants of this disclosure can be suitably used for the polymerization of fluoromonomers. Accordingly, this disclosure includes a method for producing fluoropolymers by polymerizing fluoromonomers in an aqueous medium in the presence of the above-mentioned surfactants. Since the surfactants of this disclosure contain units represented by -CFH-, they exhibit good surface activity even without having perfluoroalkyl groups or perfluoroalkylene groups.

[0164] Although embodiments have been described above, it should be understood that various modifications to the form and details are possible without departing from the spirit and scope of the claims.

[0165] The main embodiments of this disclosure are as follows:

[0166] <1> According to the first aspect of this disclosure, General formula: R 1 -R 2 -X (In the formula, R 1 is -CH3, -CH2F, -CHF2, -CH2I, -CHFI, or an anionic group. R 2 This refers to an alkylene group consisting only of units represented by -CFH-, or an alkylene group consisting only of units represented by -CFH- and units represented by -CH2-, provided that these alkylene groups may optionally contain epoxy groups, -CH(OH)-, -CHI-, or divalent cycloalkylene groups. X is -OH, -CH(R 21 )OH(R 21 (H, non-fluorinated alkyl group or fluorinated alkyl group), -I, -CFHI, -CH2I, anionic group or -COOR 22 (R 22 (This refers to a non-fluorinated alkyl group having 1 to 8 carbon atoms.) R 1 , R 2 (and the total number of carbon atoms in X is between 2 and 50.) The compound shown is provided. <2> According to the second aspect of this disclosure, R 2 However, compounds according to the first viewpoint are provided, which are alkylene groups having 2 or more carbon atoms. <3> According to the third aspect of this disclosure, R 2 However, the general formula is: -(CFH) n1 -(In the formula, n1 is an integer between 1 and 49) Compounds are provided that are alkylene groups as shown in the first or second view. <4> According to the fourth aspect of this disclosure, Compounds are provided that are fluorides of unsaturated fatty acids, according to a first or second view. <5> According to the fifth aspect of this disclosure, R 1 , R 2A compound is provided in any of the first to fourth views, wherein the total number of carbon atoms in X is 2 to 18. <6> According to the sixth aspect of this disclosure, General formula: R 1 -CHF-(CHF-CHF) n -I (where R 1 A compound is provided that is a fluorine-containing alkyl iodide represented by -CHF2, -CHF2 or -CHFI (where n is an integer greater than or equal to 0). <7> According to the seventh aspect of this disclosure, A compound is provided in any of the first to fifth aspects, wherein the anionic group comprises -COOM, -SO3M, or -OSO3M (where M is a cation). <8> According to the eighth aspect of this disclosure, Among the compounds from any of the first to fifth perspectives, if X in the general formula is -OH, -CH(R 21 A surfactant is provided which comprises at least one compound selected from the group consisting of )OH and an anionic group. [Examples]

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

[0168] Example 1: Synthesis of 1,1,2-trifluoro-2-iodoethane 37.1 g of iodine and 16.1 g of IF5 were added to a 300 mL pressure vessel, and the vessel was sealed. After cooling the vessel to -78 °C, 10 g of (E)-1,2-difluoroethene was introduced into 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 further washed with a 5% Na2S2O4 aqueous solution to obtain 5.8 g of the compound described in the title. 19 F NMR (282MHz, CDCl3): δ-169.1~-169.4(m,1F), -124.0~-124.3(m,1F). 1H NMR(400MHz,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 in ice water, the contents of the pressure vessel were analyzed by gas chromatography-mass spectrometry. The results showed that the title compound was formed at an area ratio of 75.9% compared to 24.1% of the starting material, 1,1,2-trifluoro-2-iodoethane. LRMS (EI 70eV) 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 in ice water, the contents of the pressure vessel were analyzed by gas chromatography-mass spectrometry. The results showed that the title compound was formed at an area ratio of 66.8% (total of two isomers) compared to 37.2% of the starting material 1,1,2-trifluoro-2-iodoethane. LRMS (EI 70eV) 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 in ice water, the contents of the pressure vessel were analyzed by gas chromatography-mass spectrometry. It was found that the title compound was formed at 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 70eV) 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 in 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 trimethylsilyldiazomethane (10% hexane solution) was added. After stirring at room temperature, the contents were analyzed by gas chromatography-mass spectrometry. The area ratio of the starting material 1,1,2-trifluoro-2-iodoethane was 14.3%, while the methylated carboxylic acid of the title compound, 7,8,8-trifluoro-5-iodooctanoate methyl, accounted for 85.7% of the area ratio (total of the two isomers). LRMS (EI 70eV) m / z (%):307([M-OMe]+,24),211(100),192(4),151(32).

[0173] Example 6 Synthesis of 7,8,8-trifluorooctan-1-ol To a glass container with a capacity of 10 mL, 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 2M hydrochloric acid aqueous solution was added. After stirring for 6 hours, the contents were analyzed by gas chromatography-mass spectrometry. As a result, the title compound was produced at an area ratio of 75.6% with respect to the area ratio of 24.4% of the raw material 7,8,8-trifluoro-5-iodooctan-1-ol. LRMS (EI 70eV) 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 To a 30 mL pressure-resistant container, 1.00 g of 1,1,2-trifluoro-2-iodoethane and 0.35 mL of 2-ethylhexanoyl(tert-butyl)peroxide were added. The container was sealed and cooled to -78 °C, and then 1.5 g of (E)-1,2-difluoroethene was introduced. The container was heated at 80 °C for 24 hours. Then, after cooling with ice water, the contents of the pressure-resistant container were analyzed by gas chromatography-mass spectrometry. As a result, with respect to the area ratio of 22.2% of the raw material 1,1,2-trifluoro-2-iodoethane, 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 4 isomers), 20.5% (total of 8 isomers), and 21.3% (total of multiple isomers), respectively. H-CF2CHF-(CHFCHF)-I: LRMS (EI 70eV) 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-resistant container, 300 g of water, 0.31 g of Na2HPO4, and 0.48 g of ammonium persulfate were added. The container was sealed and cooled to -78°C, after which (E)-1,2-difluoroethene was introduced and heated at 0.5 MPa and 90°C for 30 minutes to cause a reaction. After cooling, sampling was performed and drying was carried out at 50°C, and it was found that 0.77 wt% of solid content had been generated. When this solid was analyzed by gel permeation chromatography (standard molecular weight of polystyrene), it was confirmed that oligomers with Mn 1020 and Mw 1043 were obtained. Also, when analyzed by IR, carbonyl stretching at 1742 cm -1 was hardly observed. From this, it is presumed that the oligomers contain sulfate ester groups as anionic groups. Also, when the surface tension of the obtained solid content was measured, it was 51.9 mN / m, confirming the effectiveness as a surfactant.

Claims

1. General formula: R １ -R ２ -X (In the formula, R １ is, -CH ３ ien-CH ２ F, -CHF ２ ien-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 only of units represented by -CFH- and units represented by -CH ２ -. However, these alkylene groups may optionally contain an epoxy group, -CH(OH)-, -CHI- or a divalent cycloalkylene group. X is -OH, -CH(R ２１ )OH(R ２１ (H, non-fluorinated alkyl group or fluorinated alkyl group), -I, -CFHI, -CH ２ I, anionic group or -COOR ２２ (R ２２ (This refers to a non-fluorinated alkyl group having 1 to 8 carbon atoms.) R １ , R ２ (and the total number of carbon atoms in X is between 2 and 50.) The compound shown by [this symbol].

2. R ２ The compound according to claim 1, wherein the alkylene group has two or more carbon atoms.

3. R ２ However, the general formula is: - (CFH) ｎ１ - (In the formula, n1 is an integer between 1 and 49) The compound according to claim 1 or 2, wherein the alkylene group is represented by .

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

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

6. General formula: R １ -CHF- (CHF-CHF) ｎ -I (wherein, R １ ha-CHF ２ ,-CHF ２ The compound according to claim 1 or 2, which is a fluorine-containing alkyl iodide represented by -CHFI (where n is an integer of 0 or more).

7. The aforementioned anionic group is -COOM, -SO ３ M or -OSO ３ The compound according to claim 1 or 2, comprising M (where M is a cation).

8. Among the compounds described in claim 1 or 2, X in the general formula is -OH, -CH(R ２１ A surfactant comprising at least one compound selected from the group consisting of OH and an anionic group.