Process for producing an aqueous dispersion of refined polytetrafluoroethylene, process for producing a modified polytetrafluoroethylene powder, process for producing a polytetrafluoroethylene molded article, and composition

Abstract

An object of the present invention is to obtain an aqueous polytetrafluoroethylene dispersion in which the content of fluorine-containing compounds has been removed or reduced. [Solution] The present invention is a method for producing a purified aqueous polytetrafluoroethylene dispersion, which comprises a step of removing or reducing the amount of a compound represented by the following general formula (1) or (2) from an aqueous polytetrafluoroethylene dispersion obtained using a hydrocarbon-based surfactant: General formula (1):(H-(CF2) m -COO) p M 1 General formula (2):(H-(CF2) n -SO3) q M 2

Description

Technical Field

[0001] The present invention relates to a method for producing a purified polytetrafluoroethylene aqueous dispersion, a method for producing a modified polytetrafluoroethylene powder, and a method for producing a polytetrafluoroethylene molded article.

Background Art

[0002] Conventionally, a method for producing polytetrafluoroethylene using a hydrocarbon surfactant has been known (see, for example, Patent Document 1).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] It has been found that when polytetrafluoroethylene is produced using a hydrocarbon surfactant, a specific compound containing fluorine is generated. An object of the present invention is to obtain a polytetrafluoroethylene aqueous dispersion and a polytetrafluoroethylene powder in which the above-mentioned fluorine-containing compound is removed or reduced. Another object is to produce a polytetrafluoroethylene molded article in which the above-mentioned fluorine-containing compound is removed or reduced using polytetrafluoroethylene obtained using a hydrocarbon surfactant. Furthermore, an object is to provide a composition containing polytetrafluoroethylene in which the above-mentioned fluorine-containing compound is removed or reduced.

Means for Solving the Problems

[0005] The present invention is a method for producing a purified aqueous dispersion of polytetrafluoroethylene, characterized by including a step of removing or reducing a compound represented by the following general formula (1) or (2) from an aqueous dispersion of polytetrafluoroethylene obtained using a hydrocarbon-based surfactant. General formula (1): (H-(CF2) m -COO) p M 1 (In the formula, m is 3 to 19, and M 1 is H, a metal atom, NR 5 4 (R 5 may be the same or different and is H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2.) General formula (2): (H-(CF2) n -SO3) q M 2 (In the formula, n is 4 to 20. M 2 is H, a metal atom, NR 5 4 (R 5 may be the same or different and is H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. q is 1 or 2.) The step of removing or reducing the compound represented by the general formula (1) or (2) preferably includes a step of subjecting the aqueous dispersion of polytetrafluoroethylene to ion exchange treatment and / or concentration treatment.

[0006] The present invention is also a method for producing a modified polytetrafluoroethylene powder, characterized by including a step of removing or reducing a compound represented by the following general formula (1) or (2) from a polytetrafluoroethylene powder obtained using a hydrocarbon-based surfactant. General formula (1): (H-(CF2) m -COO) p M 1 (In the formula, m is 3 to 19, and M 1 is H, a metal atom, NR 5 4 (R 5may be the same or different, and is H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2.) General formula (2): (H-(CF2) n -SO3) q M 2 (In the formula, n is 4 to 20. M 2 is H, a metal atom, NR 5 4 (R 5 may be the same or different, and is H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. q is 1 or 2.) The step of removing or reducing the compound represented by the general formula (1) or (2) preferably includes a step of heat-treating the polytetrafluoroethylene powder obtained using a hydrocarbon surfactant at a temperature of 160 °C or higher.

[0007] The present invention further relates to a method for producing a molded article using polytetrafluoroethylene produced using a hydrocarbon surfactant, characterized by including a step of removing or reducing a compound represented by the following general formula (1) or (2). A method for producing a polytetrafluoroethylene molded article. General formula (1): (H-(CF2) m -COO) p M 1 (In the formula, m is 3 to 19, M 1 is H, a metal atom, NR 5 4 (R 5 may be the same or different, and is H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2.) General formula (2): (H-(CF2) n -SO3) q M 2 (In the formula, n is 4 to 20. M 2 is H, a metal atom, NR 5 4 (R5 is either the same or different and is H or an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. q is 1 or 2.) The step of removing or reducing the compound represented by the general formula (1) or (2) preferably includes a heat treatment step at a temperature of 160 °C or higher.

[0008] The present invention also includes a step of contacting a fluorine radical source with polytetrafluoroethylene obtained using a hydrocarbon surfactant at a temperature exceeding 100 °C to remove or reduce a compound represented by the following general formula (1) or (2), and is also a method for producing modified polytetrafluoroethylene. General formula (1): (H-(CF2) m -COO) p M 1 (In the formula, m is 3 to 19, M 1 is H, a metal atom, NR 5 4 (R 5 is either the same or different and is H or an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. p is 1 or 2.) General formula (2): (H-(CF2) n -SO3) q M 2 (In the formula, n is 4 to 20. M 2 is H, a metal atom, NR 5 4 (R 5 is either the same or different and is H or an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. q is 1 or 2.)

[0009] The present invention includes a step of contacting polytetrafluoroethylene obtained using a hydrocarbon-based surfactant with a fluorine radical source to remove or reduce a compound represented by the following general formula (1) or (2), and the addition amount of the fluorine radical source is 0.5 parts by weight or more in terms of fluorine atoms per 100 parts by weight of polytetrafluoroethylene, and it is also a method for producing polytetrafluoroethylene. General formula (1): (H-(CF2) m -COO) p M 1 (In the formula, m is 3 to 19, and M 1 is H, a metal atom, NR 5 4 (R 5 may be the same or different, and is H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2.) General formula (2): (H-(CF2) n -SO3) q M 2 (In the formula, n is 4 to 20. M 2 is H, a metal atom, NR 5 4 (R 5 may be the same or different, and is H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. q is 1 or 2.)

[0010] The present invention is also a composition characterized by containing polytetrafluoroethylene and substantially not containing a compound represented by the following general formula (3). General formula (3): (H-(CF2)8-SO3) q M 2 (In the formula, M 2 is H, a metal atom, NR 5 4 (R 5may be the same or different, and is H, an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. q is 1 or 2.) The content of the compound represented by the general formula (3) is preferably 1000 ppb or less, more preferably 25 ppb or less, based on polytetrafluoroethylene.

[0011] One aspect of the present invention is a composition containing a compound represented by the following general formula (4) in an amount of 1000 ppb or less with respect to polytetrafluoroethylene and containing a nonionic surfactant in an amount of 1% / polytetrafluoroethylene or more. General formula (4): (H-(CF2)7-COO) p M 1 (In the formula, M 1 is H, a metal atom, NR 5 4 (R 5 may be the same or different, and is H, an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2.) One aspect of the present invention is a composition containing at least one of the compound represented by the general formula (4) and the compound represented by the following general formula (4’), wherein the content of the compound represented by the general formula (4) is 1000 ppb or less with respect to polytetrafluoroethylene, the content of the compound represented by the general formula (4’) is 1000 ppb or less with respect to polytetrafluoroethylene, and a nonionic surfactant is contained in an amount of 1% / polytetrafluoroethylene or more. General formula (4’): (H-(CF2)8-COO) p M 1 (In the formula, M 1 is H, a metal atom, NR 5 4 (R 5may be the same or different, and is H, an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. p is 1 or 2.) One aspect of the present invention is a composition containing a compound represented by the following general formula (5) in an amount of 1000 ppb or less with respect to polytetrafluoroethylene and containing a nonionic surfactant in an amount of 1% / polytetrafluoroethylene or more. General formula (5): (H-(CF2) 13 -COO) p M 1 (In the formula, M 1 is H, a metal atom, NR 5 4 (R 5 may be the same or different, and is H, an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. p is 1 or 2.) One aspect of the present invention contains at least one of the compound represented by the above general formula (5) and the compound represented by the following general formula (5’), the content of the compound represented by the above general formula (5) is 1000 ppb or less with respect to polytetrafluoroethylene, the content of the compound represented by the following general formula (5’) is 1000 ppb or less with respect to polytetrafluoroethylene, and a nonionic surfactant is contained in an amount of 1% / polytetrafluoroethylene or more. General formula (5’): (H-(CF2) 14 -COO) p M 1 (In the formula, M 1 is H, a metal atom, NR 5 4 (R 5 may be the same or different, and is H, an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. p is 1 or 2.) These aspects of the present invention are compositions that are aqueous dispersions.

[0012] One aspect of the present invention is a composition containing the compound represented by the general formula (4) in an amount of 1000 ppb or less with respect to polytetrafluoroethylene. Further, it is a composition containing at least one of the compound represented by the general formula (4) and the compound represented by the general formula (4'), wherein the content of the compound represented by the general formula (4) is 1000 ppb or less with respect to polytetrafluoroethylene, and the content of the compound represented by the general formula (4') is 1000 ppb or less with respect to polytetrafluoroethylene. Further, it is a composition containing the compound represented by the general formula (5) in an amount of 1000 ppb or less with respect to polytetrafluoroethylene. One aspect of the present invention is a composition containing at least one of the compound represented by the general formula (5) and the compound represented by the general formula (5'), wherein the content of the compound represented by the general formula (5) is 1000 ppb or less with respect to polytetrafluoroethylene, and the content of the compound represented by the general formula (5') is 1000 ppb or less with respect to polytetrafluoroethylene. Further, one aspect of the present invention is a composition containing the compound represented by the general formula (4) in an amount of 25 ppb or less with respect to polytetrafluoroethylene. One aspect of the present invention is a composition containing at least one of the compound represented by the general formula (4) and the compound represented by the general formula (4'), wherein the content of the compound represented by the general formula (4) is 25 ppb or less with respect to polytetrafluoroethylene, and the content of the compound represented by the general formula (4') is 25 ppb or less with respect to polytetrafluoroethylene. One aspect of the present invention is a composition containing the compound represented by the general formula (5) in an amount of 25 ppb or less with respect to polytetrafluoroethylene. One aspect of the present invention is a composition containing at least one of the compound represented by the general formula (5) and the compound represented by the general formula (5'), wherein the content of the compound represented by the general formula (5) is 25 ppb or less with respect to polytetrafluoroethylene, and the content of the compound represented by the general formula (5') is 25 ppb or less with respect to polytetrafluoroethylene. The above composition may further contain a compound represented by the following general formula (7) in an amount of 1000 ppb or less based on polytetrafluoroethylene. General formula (7): (F-(CF2)7-COO) p M 1 (In the formula, M 1 is H, a metal atom, NR 5 4 (R 5 may be the same or different and is H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2.) One aspect of these of the present invention is a composition in the form of a powder.

[0013] Further, it is preferable that the polytetrafluoroethylene in the composition of the present invention is obtained by polymerization using a hydrocarbon surfactant.

[0014] The present invention is also a molded article comprising the above composition. It is also preferable that the molded article of the present invention is a stretched body.

Advantages of the Invention

[0015] The method for producing a purified aqueous dispersion of polytetrafluoroethylene of the present invention can remove or reduce the compound represented by the general formula (1) or (2) present in the obtained purified PTFE aqueous dispersion. The method for producing a modified polytetrafluoroethylene powder of the present invention can remove or reduce the compound represented by the general formula (1) or (2) present in the obtained modified polytetrafluoroethylene powder. The method for producing a polytetrafluoroethylene molded article of the present invention can remove or reduce the compound represented by the general formula (1) or (2) present in the obtained polytetrafluoroethylene molded article. The composition of the present invention has the compound represented by the general formula (3) removed or reduced.

Embodiments for Carrying Out the Invention

[0016] The method for producing a purified aqueous PTFE dispersion of the present invention includes a step of removing or reducing a compound represented by the general formula (1) or (2) from an aqueous PTFE dispersion (hereinafter sometimes referred to as "PTFE") obtained using a hydrocarbon surfactant (hereinafter also referred to as "removal step"). General formula (1): (H-(CF2) m -COO) p M 1 (In the formula, m is 3 to 19, M 1 is H, a metal atom, NR 5 4 (R 5 may be the same or different and is H or an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. p is 1 or 2.) General formula (2): (H-(CF2) n -SO3) q M 2 (In the formula, n is 4 to 20. M 2 is H, a metal atom, NR 5 4 (R 5 may be the same or different and is H or an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. q is 1 or 2.) Examples of the above metal atom include monovalent and divalent metal atoms, and examples include alkali metals (Group 1) or alkaline earth metals (Group 2), and specifically, Na, K, Li, etc. are exemplified. As the above R 5 , the four Rs 5 may be the same or different. R 5 is preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms. Further, it is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The above regulations apply to all Rs 5 described below. In general formula (1), m may be 5 to 11. In general formula (2), n may be 6 to 12.

[0017] In this specification, unless otherwise specified, "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 the "organic group" include an alkyl group which may have one or more substituents, an alkenyl group which may have one or more substituents, an alkynyl group which may have one or more substituents, a cycloalkyl group which may have one or more substituents, a cycloalkenyl group which may have one or more substituents, a cycloalkadienyl group which may have one or more substituents, an aryl group which may have one or more substituents, an aralkyl group which may have one or more substituents, a non-aromatic heterocyclic group which may have one or more substituents, a heteroaryl group which may have one or more substituents, a cyano group, a formyl group, RaO-, RaCO-, RaSO2-, RaCOO-, RaNRaCO-, RaCONRa-, RaOCO-, and RaOSO2- (In these formulas, Ra independently represents an alkyl group which may have one or more substituents, an alkenyl group which may have one or more substituents, an alkynyl group which may have one or more substituents, a cycloalkyl group which may have one or more substituents, a cycloalkenyl group which may have one or more substituents, A cycloalkadienyl group which may have one or more substituents, An aryl group which may have one or more substituents, An aralkyl group which may have one or more substituents, A non-aromatic heterocyclic group which may have one or more substituents, or A heteroaryl group which may have one or more substituents) is included. As the above organic group, an alkyl group which may have one or more substituents is preferable. In addition, as the above organic group, those exemplified as the following substituents are also included. In this specification, unless otherwise specified, "substituent" means a group that can be substituted. 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 hydroxy group, a cyano group, a sulfo group, a carboxy 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, or a di-aromatic oxyphosphinyl group.

[0018] The above aliphatic group may be saturated or unsaturated, and may also have a hydroxy group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the above aliphatic group include an alkyl group having 1 to 8, preferably 1 to 4 carbon atoms in total, such as a methyl group, an ethyl group, a vinyl group, a cyclohexyl group, a carbamoylmethyl group, etc.

[0019] 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. Examples of the above aromatic group include an aryl group having 6 to 12, preferably 6 to 10 carbon atoms in total, such as a phenyl group, a 4-nitrophenyl group, a 4-acetylaminophenyl group, a 4-methanesulfonylphenyl group, etc.

[0020] The above heterocyclic group may have a halogen atom, a hydroxy group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the above heterocyclic group include a 5- to 6-membered heterocycle having 2 to 12, preferably 2 to 10 carbon atoms in total, such as a 2-tetrahydrofuryl group, a 2-pyrimidyl group, etc.

[0021] The above acyl group may have an aliphatic carbonyl group, an arylcarbonyl group, a heterocyclic carbonyl group, a hydroxy group, a halogen atom, an aromatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the above acyl group include an acyl group having 2 to 8, preferably 2 to 4 carbon atoms in total, such as an acetyl group, a propanoyl group, a benzoyl group, a 3-pyridinecarbonyl group, etc.

[0022] The acylamino group may have an aliphatic group, an aromatic group, a heterocyclic group, etc. For example, it may have an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propanoylamino group, etc. As the acylamino group, an acylamino group having 2 to 12 carbon atoms in total, preferably 2 to 8 carbon atoms in total, an alkylcarbonylamino group having 2 to 8 carbon atoms in total, such as an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propanoylamino group, etc. may be mentioned.

[0023] The aliphatic oxycarbonyl group may be saturated or unsaturated, and may also have a hydroxy group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. As the aliphatic oxycarbonyl group, an alkoxycarbonyl group having 2 to 8 carbon atoms in total, preferably 2 to 4 carbon atoms in total, such as methoxycarbonyl, ethoxycarbonyl, (t)-butoxycarbonyl group, etc. may be mentioned.

[0024] The carbamoyl group may have an aliphatic group, an aromatic group, a heterocyclic group, etc. As the 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. may be mentioned.

[0025] The aliphatic sulfonyl group may be saturated or unsaturated, and may also have a hydroxy group, an aromatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. As the aliphatic sulfonyl group, an alkylsulfonyl group having 1 to 6 carbon atoms in total, preferably 1 to 4 carbon atoms in total, such as methanesulfonyl, etc. may be mentioned.

[0026] The above aromatic sulfonyl group may have a hydroxy group, an aliphatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the above aromatic sulfonyl group include arylsulfonyl groups having 6 to 10 carbon atoms in total, such as benzenesulfonyl.

[0027] The above amino group may have an aliphatic group, an aromatic group, a heterocyclic group, etc.

[0028] The above acylamino group may have, for example, an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propanoylamino group, etc. Examples of the above acylamino group include acylamino groups having 2 to 12 carbon atoms in total, preferably acylamino groups having 2 to 8 carbon atoms in total, more preferably alkylcarbonylamino groups having 2 to 8 carbon atoms in total, such as an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propanoylamino group, etc.

[0029] The above aliphatic sulfonamide group, aromatic sulfonamide group, and heterocyclic sulfonamide group may be, for example, a methanesulfonamide group, a benzenesulfonamide group, a 2-pyridinesulfonamide group, etc.

[0030] The above sulfamoyl group may have an aliphatic group, an aromatic group, a heterocyclic group, etc. Examples of the above sulfamoyl group include a sulfamoyl group, an alkylsulfamoyl group having 1 to 9 carbon atoms in total, a dialkylsulfamoyl group having 2 to 10 carbon atoms in total, an arylsulfamoyl group having 7 to 13 carbon atoms in total, a heterocyclic sulfamoyl group having 2 to 12 carbon atoms in total, more preferably a sulfamoyl group, an alkylsulfamoyl group having 1 to 7 carbon atoms in total, a dialkylsulfamoyl group having 3 to 6 carbon atoms in total, an arylsulfamoyl group having 6 to 11 carbon atoms in total, 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.

[0031] The above aliphatic oxy group may be saturated or unsaturated, and may also have a methoxy group, an ethoxy group, an i-propyloxy group, a cyclohexyloxy group, a methoxyethoxy group, etc. Examples of the above aliphatic oxy group include alkoxy groups 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 i-propyloxy group, a cyclohexyloxy group, a methoxyethoxy group, etc.

[0032] 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 condensed with the aryl group, an aliphatic oxycarbonyl group, preferably an aliphatic group having 1 to 4 carbon atoms in total, an aliphatic oxy group having 1 to 4 carbon atoms in total, a halogen atom, a carbamoyl group having 1 to 4 carbon atoms in total, a nitro group, an aliphatic oxycarbonyl group having 2 to 4 carbon atoms in total.

[0033] The above aliphatic thio group may be saturated or unsaturated, and examples thereof include alkylthio groups 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 t-butylthio group, etc.

[0034] The above carbamoyl amino group may have an aliphatic group, an aryl group, a heterocyclic group, etc. Examples of the above carbamoyl amino group include a carbamoyl amino group, an alkylcarbamoyl amino group having 2 to 9 carbon atoms in total, a dialkylcarbamoyl amino group having 3 to 10 carbon atoms in total, an arylcarbamoyl amino group having 7 to 13 carbon atoms in total, a heterocyclic carbamoyl amino group having 3 to 12 carbon atoms in total, preferably a carbamoyl amino group, an alkylcarbamoyl amino group having 2 to 7 carbon atoms in total, a dialkylcarbamoyl amino group having 3 to 6 carbon atoms in total, an arylcarbamoyl amino group having 7 to 11 carbon atoms in total, a heterocyclic carbamoyl amino group having 3 to 10 carbon atoms in total. For example, a carbamoyl amino group, a methylcarbamoyl amino group, an N,N-dimethylcarbamoyl amino group, a phenylcarbamoyl amino, a 4-pyridinecarbamoyl amino group, etc. may be mentioned.

[0035] The above PTFE may be homopolymer PTFE or modified PTFE. The modified PTFE contains a TFE unit and a modified monomer unit based on a modified monomer copolymerizable with TFE. Also, the above PTFE may be high molecular weight PTFE having non-melt processability and fibrillability, or low molecular weight PTFE having melt processability and no fibrillability. The standard specific gravity (SSG) and melt viscosity (MV) used as indicators of the molecular weight of PTFE are not particularly limited.

[0036] The above modified monomer is not particularly limited as long as it can copolymerize with TFE. For example, perfluoroolefins such as hexafluoropropylene [HFP]; chlorofluoroolefins such as chlorotrifluoroethylene [CTFE]; hydrogen-containing fluoroolefins such as trifluoroethylene and vinylidene fluoride [VDF]; perfluorovinyl ether; perfluoroalkyl ethylene; ethylene; fluorine-containing vinyl ether having a nitrile group, etc. may be mentioned. Also, the modified monomer used may be one kind or a plurality of kinds.

[0037] The perfluorovinyl ether is not particularly limited. For example, the following general formula (X) CF2=CF-ORf (X) (In the formula, Rf represents a perfluoro organic group.) Examples thereof include perfluoro unsaturated compounds represented by the formula. In the present specification, the above-mentioned "perfluoro organic group" means an organic group in which all hydrogen atoms bonded to carbon atoms are substituted with fluorine atoms. The above-mentioned perfluoro organic group may have an ether oxygen.

[0038] As the perfluorovinyl ether, for example, in the above general formula (X), a perfluoro(alkyl vinyl ether) [PAVE] in which Rf represents a perfluoroalkyl group having 1 to 10 carbon atoms can be mentioned. The number of carbon atoms of the above-mentioned perfluoroalkyl group is preferably 1 to 5.

[0039] Examples of the perfluoroalkyl group in the above PAVE include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, etc. However, perfluoromethyl vinyl ether [PMVE] in which the perfluoroalkyl group is a perfluoromethyl group and perfluoropropyl vinyl ether [PPVE] in which the perfluoroalkyl group is a perfluoropropyl group are preferable.

[0040] The perfluoroalkyl ethylene is not particularly limited. For example, perfluorobutyl ethylene (PFBE), perfluorohexyl ethylene (PFHE), perfluorooctyl ethylene (PFOE), etc. can be mentioned.

[0041] The modified monomer in the above modified PTFE is preferably at least one selected from the group consisting of HFP, CTFE, VDF, PMVE, PPVE, PFBE, PFHE, CNVE and ethylene.

[0042] The above-mentioned modified PTFE preferably has a range of 0.0001 to 2 mol% of modified monomer units, more preferably a range of 0.0001 to less than 1 mol%, still more preferably a range of 0.0001 to 0.5 mol%, and particularly preferably a range of 0.001 to 0.2 mol%.

[0043] It is preferable that the average primary particle diameter of the above-mentioned PTFE is 150 nm or more, and more preferably 180 nm or more. The larger the average primary particle diameter of the PTFE composition, the more the increase in the paste extrusion pressure can be suppressed when paste extrusion molding is performed using the powder, and the film-forming property is also excellent. The upper limit is not particularly limited and may be 500 nm. From the viewpoint of productivity in the polymerization process, it is preferably 350 nm. The above-mentioned average primary particle diameter is determined by diluting the PTFE aqueous dispersion with water until the solid content becomes 0.15% by mass, measuring the transmittance of the 550 nm projection light with respect to the unit length of the obtained diluted latex, and measuring the number-average particle diameter of several reference lengths determined by measuring the directional diameter from a transmission electron micrograph, creating a calibration curve, and using this calibration curve to determine from the actually measured transmittance of the 550 nm projection light of each sample.

[0044] The above-mentioned PTFE may have a core-shell structure. Examples of the PTFE having a core-shell structure include modified PTFE containing a core of high molecular weight PTFE and a shell of lower molecular weight PTFE or modified PTFE in the particles. Examples of such modified PTFE include PTFE described in JP-T-2005-527652.

[0045] In this specification, the content of each monomer constituting PTFE can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis according to the type of monomer.

[0046] A method for obtaining a PTFE aqueous dispersion using a hydrocarbon surfactant will be described later. The PTFE aqueous dispersion obtained using a hydrocarbon surfactant contains the compound represented by the above general formula (1) or (2).

[0047] As a method for removing or reducing the compound represented by the general formula (1) or (2) from the above PTFE aqueous dispersion, adsorption treatment, concentration treatment, etc. can be mentioned. In addition, a method of removing or reducing the compound represented by the general formula (1) or (2) by drying and vaporizing the PTFE aqueous dispersion can also be adopted. As the drying temperature, for example, the temperature of the heat treatment described later can be adopted. Furthermore, a method of gasifying the PTFE aqueous dispersion and absorbing the compound represented by the general formula (1) or (2) in the gas into an aqueous liquid using a droplet type absorber and / or a liquid film type absorber can also be mentioned. As the temperature of the aqueous liquid, for example, 10 to 60 °C is preferable.

[0048] Examples of the above adsorption treatment include methods using adsorbents such as ion exchange resins (IER), activated carbon, and zeolites. Specifically, by bringing the compound represented by the general formula (1) or (2) contained in the PTFE aqueous dispersion into contact with the adsorbent, the compound represented by the general formula (1) or (2) can be removed or reduced. The above adsorption treatment can be carried out by adding an ion exchange resin to the PTFE aqueous dispersion and stirring if necessary. It is preferable that the ion exchange treatment adds 1 g or more of the ion exchange resin to 100 g of PTFE. The addition amount of the ion exchange resin is more preferably 10 g or more, preferably 200 g or less, and more preferably 100 g or less.

[0049] Examples of the above concentration treatment include phase separation concentration, electroconcentration, filtration treatment using an ultrafiltration membrane, filtration treatment using a reverse osmosis membrane (RO membrane), nanofiltration treatment, etc. As the above concentration treatment, for example, a method of adding a nonionic surfactant to the PTFE aqueous dispersion so that it is 1% / PTFE or more and leaving it standing can be mentioned. The addition amount of the nonionic surfactant is preferably 40% / PTFE or less, more preferably 30% / PTFE or less, and still more preferably 20% / PTFE or less. The temperature for the above-mentioned placement is not limited, and for example, it may be 20°C or higher and 80°C or lower. The placement time is not limited, and for example, it may be 1 minute or longer and 24 hours or shorter.

[0050] The above-mentioned removal step preferably includes a step of adsorbing and / or concentrating the above-mentioned PTFE aqueous dispersion, and more preferably includes a step of ion-exchanging and / or concentrating the above-mentioned PTFE aqueous dispersion. The step of ion-exchanging and / or concentrating may be a step of ion-exchanging, a step of concentrating, or a step of ion-exchanging and concentrating, and each treatment may be performed multiple times. When performing ion-exchange treatment and concentration treatment, the order of ion-exchange treatment and concentration treatment may be arbitrary, and they may be performed alternately. The step of ion-exchanging and / or concentrating is particularly preferably a step of ion-exchanging and concentrating. It is more preferable to perform concentration treatment after ion-exchange treatment in the above-mentioned step of ion-exchanging and / or concentrating.

[0051] The above-mentioned adsorption treatment and concentration treatment may each be performed multiple times. For example, adsorption treatment or concentration treatment may be performed 2, 3, 4, 5, 6, 7, 8, 9, or 10 times. Also, adsorption treatment and concentration treatment may be combined.

[0052] When a PTFE aqueous dispersion is obtained using a hydrocarbon surfactant, usually, compounds represented by general formulas (1) and (2) in an amount of 1 to 200 ppm with respect to PTFE are generated. By the above-mentioned removal step, the compound represented by general formula (1) or (2) in the PTFE aqueous dispersion is removed or reduced, and a purified PTFE aqueous dispersion can be obtained.

[0053] The above removal step preferably removes 80% by mass or more of the compounds represented by the general formulas (1) and (2) in the above PTFE aqueous dispersion, more preferably 85% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, particularly preferably 97% by mass or more, especially preferably 98% by mass or more, and most preferably 99% by mass or more.

[0054] The above removal step preferably reduces the content of the compounds represented by the general formulas (1) and (2) in the obtained purified PTFE aqueous dispersion to 500 ppb or less, more preferably 200 ppb or less, still more preferably 100 ppb or less, particularly preferably 50 ppb or less, and most preferably 25 ppb or less, based on PTFE.

[0055] The above PTFE aqueous dispersion can be obtained by a production method including a step of emulsion-polymerizing tetrafluoroethylene in an aqueous medium in the presence of a hydrocarbon surfactant. The above emulsion polymerization can be carried out by a conventionally known method. The above aqueous medium is not particularly limited as long as it is a liquid containing water, and may contain, in addition to water, organic solvents such as alcohols, ethers, ketones, and paraffin waxes.

[0056] As the above hydrocarbon surfactant, for example, those described in JP-T-2013-542308, JP-T-2013-542309, and JP-T-2013-542310 can be used. Details of the hydrocarbon surfactant will be described later.

[0057] The present invention is also a method for producing a modified PTFE powder, characterized by including a step of removing a compound represented by the following general formula (1) or (2) from a PTFE powder obtained using a hydrocarbon surfactant. General formula (1): (H-(CF2) m -COO) p M 1(wherein m is 3 to 19, M 1 is H, a metal atom, NR 5 4 (R 5 may be the same or different and is H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2.) General formula (2): (H-(CF2) n -SO3) q M 2 (wherein n is 4 to 20. M 2 is H, a metal atom, NR 5 4 (R 5 may be the same or different and is H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. q is 1 or 2.) Examples of the metal atom include monovalent and divalent metal atoms, and include alkali metals (Group 1) or alkaline earth metals (Group 2), and specifically, Na, K, Li, etc. are exemplified. As the above R 5 , the four Rs 5 may be the same or different. As R 5 , H or an organic group having 1 to 10 carbon atoms is preferable, and H or an organic group having 1 to 4 carbon atoms is more preferable. In general formula (1), m may be 5 to 11. In general formula (2), n may be 6 to 12.

[0058] The PTFE powder obtained using a hydrocarbon surfactant can be obtained, for example, by coagulating the PTFE aqueous dispersion obtained using the above-described hydrocarbon surfactant. As the PTFE in the above PTFE powder, PTFE such as homopolymer PTFE and modified PTFE described in the production method of the purified PTFE aqueous dispersion can be used.

[0059] As a method for removing or reducing the compound represented by the general formula (1) or (2) from the above PTFE powder, heat treatment, fluorination treatment, washing with water or an organic solvent, etc. can be mentioned. Examples of the above organic solvent include ether, halogenated hydrocarbon, aromatic hydrocarbon, pyridine, nitrile, nitrogen-containing polar organic compound, dimethyl sulfoxide, alcohol, etc. Examples of the above ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc. Examples of the above halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc. Examples of the above aromatic hydrocarbon include benzene, toluene, xylene, etc. Examples of the above nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, etc. Examples of the above nitrogen-containing polar organic compound include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, etc. Examples of the above alcohol include methanol, ethanol, 1-propanol, isopropanol, etc. The above organic solvents may be used in combination.

[0060] The method of the above heat treatment is not particularly limited, and a conventionally known method can be adopted. The temperature of the heat treatment is preferably 150°C or higher. Further, from the viewpoint of removing or reducing the compound represented by the general formula (1) or (2), the temperature of the heat treatment is more preferably 160°C or higher. That is, the above removal step preferably includes a step of heat-treating the PTFE powder obtained using a hydrocarbon-based surfactant at a temperature of 160°C or higher. The temperature of the heat treatment is more preferably 170°C or higher, still more preferably 180°C or higher, still more preferably 200°C or higher, particularly preferably 210°C or higher, most preferably 220°C or higher, and most preferably 230°C or higher. Further, the heat treatment temperature is preferably 310°C or lower, more preferably 300°C or lower, still more preferably 290°C or lower, even more preferably 280°C or lower, and particularly preferably 270°C or lower. The above heat treatment may involve drying of moisture. That is, the above heat treatment may be one for drying the wet PTFE powder containing moisture obtained by coagulating the polymerized PTFE dispersion obtained using a hydrocarbon surfactant. Compounds represented by the general formula (1) or (2) or the compound represented by the general formula (7) described later are reduced during drying. Further, it is preferable to heat-treat the PTFE powder free of moisture after drying again. Specifically, the above wet PTFE powder may be dried to remove moisture, and then the temperature may be continuously raised to the above temperature range for heat treatment. In this case, the above drying may be performed at a temperature lower than each of the above temperature ranges, for example, at a temperature lower than 150°C. The method for producing the modified PTFE powder of the present invention may include a step of coagulating a PTFE dispersion obtained using a hydrocarbon surfactant to obtain a wet PTFE powder containing moisture.

[0061] As the method for the fluorination treatment, a conventionally known method can be adopted. For example, there is a method of exposing the above PTFE powder to a fluorine radical source that generates fluorine radicals under fluorination treatment conditions. As the fluorine radical source, in addition to fluorine gas, CoF3, AgF2, UF6, OF2, N2F2, CF3OF, halogen fluorides (for example, IF such as IF n (n is 1 to 7); ClF, ClF3, BrF3, etc.), fluorides of noble gases (XeF2, XeF4, KrF2, etc.), and nitrogen-containing fluorine compounds (for example, NF3, NF2, etc.) can be mentioned. Among them, fluorine gas is most preferable in terms of handleability, price, the ability to efficiently remove the compounds represented by the general formulas (1) and (2), and the difficulty of giving new impurities such as iodine. Since the reaction with the fluorine radical source is extremely exothermic, the fluorine radical source may be diluted with an inert gas such as nitrogen. The level of the fluorine radical source in the fluorine radical source / inert gas mixture can be from 1 to 100% by volume, but it is preferably about 5 to about 25% by volume because working with pure fluorine is highly dangerous. For fluorinated polymer resins with severe heat-induced discoloration, the fluorine radical source / inert gas mixture may be sufficiently diluted to prevent overheating of the fluorinated polymer and the accompanying risk of fire.

[0062] The method of the above fluorination treatment is not particularly limited, and a conventionally known method can be adopted. The temperature of the fluorination treatment is preferably above 100°C. The temperature of the fluorination treatment is more preferably 110°C or higher, still more preferably 120°C or higher, even more preferably 130°C or higher, particularly preferably 150°C or higher. Also, it is particularly preferably 170°C or higher, more preferably 180°C or higher, even more preferably 200°C or higher, particularly preferably 210°C or higher, most preferably 220°C or higher, and most preferably 230°C or higher. Also, the temperature of the fluorination treatment is preferably 310°C or lower, more preferably 300°C or lower, still more preferably 290°C or lower, even more preferably 280°C or lower, particularly preferably 270°C or lower, most preferably 250°C or lower, and most preferably 240°C or lower. If the temperature is too low, the compound represented by the general formula (7) described below may remain in excess of 1000 ppb with respect to PTFE. If the temperature is too high, due to the friction between PTFE powders, even a small shearing force can easily cause fibrillation and loss of the original particle structure state, which may lead to a decrease in paste extrusion performance. The temperature of the fluorination treatment is preferably 110 to 270°C, more preferably 120 to 270°C, still more preferably 150 to 270°C, and particularly preferably 200 to 270°C.

[0063] In the above fluorination treatment, the addition amount of the fluorine radical source is preferably 0.5 parts by weight or more in terms of fluorine atoms relative to 100 parts by weight of the raw material PTFE. More preferably, it is 0.8 parts by weight or more, still more preferably 1.0 parts by weight or more, more preferably 1.6 parts by weight or more, still more preferably 2.0 parts by weight or more, even more preferably 2.5 parts by weight or more, particularly preferably 3.0 parts by weight or more, and especially preferably 5.0 parts by weight or more. Also, the addition amount of the fluorine radical source is preferably 35.0 parts by weight or less, more preferably 26.0 parts by weight or less, still more preferably 20.0 parts by weight or less, and particularly preferably 15.0 parts by weight or less. If the addition amount of the fluorine radical source is too small, there is a risk that the removal or reduction of the compound represented by the general formula (1) or (2) will be insufficient. Also, there is a risk that the removal or reduction of the unidentified compound will be insufficient. Even if the addition amount of the fluorine radical source is too large, the effect of fluorination will not improve and it may become uneconomical.

[0064] As a suitable combination of the temperature of the fluorination treatment and the addition amount of the fluorine radical source, the temperature of the heat treatment is over 100 °C, and the addition amount of the fluorine radical source is 0.5 parts by weight or more in terms of fluorine atoms relative to 100 parts by weight of the raw material PTFE. As the above combination, over 100 °C and 1.0 parts by weight or more is preferable, over 100 °C and 1.6 parts by weight or more is more preferable, over 100 °C and 2.0 parts by weight or more is still more preferable, over 100 °C and 2.5 parts by weight or more is even more preferable, over 100 °C and 3.0 parts by weight or more is particularly preferable, and over 100 °C and 5.0 parts by weight or more is especially preferable. Also, 110 °C or higher and 0.5 parts by weight or more is preferable, 110 °C or higher and 1.0 parts by weight or more is more preferable, 110 °C or higher and 1.6 parts by weight or more is still more preferable, 110 °C or higher and 2.0 parts by weight or more is even more preferable, 110 °C or higher and 2.5 parts by weight or more is particularly preferable, 110 °C or higher and 3.0 parts by weight or more is especially preferable, and 110 °C or higher and 5.0 parts by weight or more is most preferable. Also, it is preferably 120°C or higher and 0.5 parts by weight or more, more preferably 120°C or higher and 1.0 parts by weight or more, still more preferably 120°C or higher and 1.6 parts by weight or more, even more preferably 120°C or higher and 2.0 parts by weight or more, particularly preferably 120°C or higher and 2.5 parts by weight or more, most preferably 120°C or higher and 5.0 parts by weight or more. Also, it is preferably 130°C or higher and 0.5 parts by weight or more, more preferably 130°C or higher and 1.0 parts by weight or more, still more preferably 130°C or higher and 1.6 parts by weight or more, even more preferably 130°C or higher and 2.0 parts by weight or more, particularly preferably 130°C or higher and 2.5 parts by weight or more, most preferably 130°C or higher and 5.0 parts by weight or more. Also, it is preferably 150°C or higher and 0.5 parts by weight or more, more preferably 150°C or higher and 1.0 parts by weight or more, still more preferably 150°C or higher and 1.6 parts by weight or more, even more preferably 150°C or higher and 2.0 parts by weight or more, particularly preferably 150°C or higher and 2.5 parts by weight or more, most preferably 150°C or higher and 5.0 parts by weight or more. Also, it is preferably 170°C or higher and 0.5 parts by weight or more, more preferably 170°C or higher and 1.0 parts by weight or more, still more preferably 170°C or higher and 1.6 parts by weight or more, even more preferably 170°C or higher and 2.0 parts by weight or more, particularly preferably 170°C or higher and 2.5 parts by weight or more, most preferably 170°C or higher and 5.0 parts by weight or more. Also, it is preferably 180°C or higher and 0.5 parts by weight or more, more preferably 180°C or higher and 1.0 parts by weight or more, still more preferably 180°C or higher and 1.6 parts by weight or more, even more preferably 180°C or higher and 2.0 parts by weight or more, particularly preferably 180°C or higher and 2.5 parts by weight or more, most preferably 180°C or higher and 5.0 parts by weight or more. Also, a temperature of 200°C or higher and 0.5 parts by weight or more is preferable, a temperature of 200°C or higher and 1.0 parts by weight or more is more preferable, a temperature of 200°C or higher and 1.6 parts by weight or more is still more preferable, a temperature of 200°C or higher and 2.0 parts by weight or more is even more preferable, a temperature of 200°C or higher and 2.5 parts by weight or more is particularly more preferable, a temperature of 200°C or higher and 3.0 parts by weight or more is especially preferable, and a temperature of 200°C or higher and 5.0 parts by weight or more is most preferable. Also, a temperature of 210°C or higher and 0.5 parts by weight or more is preferable, a temperature of 210°C or higher and 1.0 parts by weight or more is more preferable, a temperature of 210°C or higher and 1.6 parts by weight or more is still more preferable, a temperature of 210°C or higher and 2.0 parts by weight or more is even more preferable, a temperature of 210°C or higher and 2.5 parts by weight or more is particularly more preferable, a temperature of 210°C or higher and 3.0 parts by weight or more is especially preferable, and a temperature of 210°C or higher and 5.0 parts by weight or more is most preferable. Also, a temperature of 220°C or higher and 0.5 parts by weight or more is preferable, a temperature of 220°C or higher and 1.0 parts by weight or more is more preferable, a temperature of 220°C or higher and 1.6 parts by weight or more is still more preferable, a temperature of 220°C or higher and 2.0 parts by weight or more is even more preferable, a temperature of 220°C or higher and 2.5 parts by weight or more is particularly more preferable, a temperature of 220°C or higher and 3.0 parts by weight or more is especially preferable, and a temperature of 220°C or higher and 5.0 parts by weight or more is most preferable. Also, a temperature of 230°C or higher and 0.5 parts by weight or more is preferable, a temperature of 230°C or higher and 1.0 parts by weight or more is more preferable, a temperature of 230°C or higher and 1.6 parts by weight or more is still more preferable, a temperature of 230°C or higher and 2.0 parts by weight or more is even more preferable, a temperature of 230°C or higher and 2.5 parts by weight or more is particularly more preferable, a temperature of 230°C or higher and 3.0 parts by weight or more is especially preferable, and a temperature of 230°C or higher and 5.0 parts by weight or more is most preferable. The heat treatment temperature in the above combination is preferably 310°C or lower, more preferably 300°C or lower, still more preferably 290°C or lower, even more preferably 280°C or lower, particularly more preferably 270°C or lower, especially preferably 250°C or lower, and most preferably 240°C or lower. The addition amount of the fluorine radical source in the above combination is preferably 35.0 parts by weight or less, more preferably 26.0 parts by weight or less, still more preferably 20.0 parts by weight or less, and particularly preferably 15.0 parts by weight or less, in terms of fluorine atoms, based on 100 parts by weight of the raw material PTFE. In addition, as the combination of the heat treatment temperature and the upper limit of the fluorine radical source, it is preferably 240°C or lower and 35.0 parts by weight or less, more preferably 240°C or lower and 26.0 parts by weight or less, still more preferably 240°C or lower and 20.0 parts by weight or less, and particularly preferably 240°C or lower and 15.0 parts by weight or less.

[0065] The addition amount (parts by weight) of the fluorine radical source with respect to 100 parts by weight of PTFE was calculated according to the following formula. A=(B / F)×100 B=C×D×E C={P / (RT×1000)}×G×H A: Addition amount (parts by weight) of the fluorine radical source with respect to 100 parts by weight of PTFE B: Total addition amount of the fluorine radical source (g) C: Concentration of the fluorine radical source in the mixed gas (g / mL) D: Flow rate of the mixed gas (mL / min) E: Fluorination treatment time (min) F: Sample filling amount (g) G: Molecular weight of the fluorine radical source (g / mol) H: Ratio of the fluorine radical source in the mixed gas In the above formula, P, R, and T are used as follows. P = Pressure (atm) R = 0.082 (atm·L / K·mol) T = Temperature (K)

[0066] As the reactor used for the fluorination treatment, any device equipped with a heating device and capable of sufficiently performing solid-gas contact can be used without problems. Specifically, fluidized bed type and shelf type solid-gas contact reactors can be mentioned.

[0067] In the method for producing the modified PTFE powder, the removal step may be performed a plurality of times. For example, the removal step may be performed 2, 3, 4, 5, 6, 7, 8, 9, or 10 times. The heat treatment and the fluorination treatment may be carried out in combination or simultaneously.

[0068] The method of washing with water or an organic solvent is not particularly limited, and a conventionally known method can be adopted.

[0069] When PTFE powder is obtained using a hydrocarbon surfactant, compounds represented by general formulas (1) and (2) may be generated in an amount of 1 to 200 ppm with respect to PTFE. By the above removal step, the compounds represented by general formula (1) or (2) in the PTFE aqueous dispersion are removed or reduced, and a modified PTFE powder can be obtained.

[0070] The removal step preferably removes 80% by mass or more of the compounds represented by general formulas (1) and (2) in the PTFE powder, more preferably 85% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, particularly preferably 97% by mass or more, especially preferably 98% by mass or more, and most preferably 99% by mass or more. The removal step preferably reduces the content of the compounds represented by general formulas (1) and (2) in the obtained modified PTFE powder to 500 ppb or less, more preferably 200 ppb or less, still more preferably 100 ppb or less, particularly preferably 50 ppb or less, and most preferably 25 ppb or less, with respect to PTFE.

[0071] The present invention is a method for producing a molded article using PTFE produced using a hydrocarbon surfactant, and is characterized by including a step of removing or reducing a compound represented by the following general formula (1) or (2). General formula (1): (H-(CF2) m -COO) p M 1 (In the formula, m is 3 to 19, and M 1 is H, a metal atom, NR 5 4 (R 5 may be the same or different and is H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2.) General formula (2): (H-(CF2) n -SO3) q M 2 (In the formula, n is 4 to 20. M 2 is H, a metal atom, NR 5 4 (R 5 may be the same or different and is H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. q is 1 or 2.) Examples of the above metal atom include monovalent and divalent metal atoms, and examples include alkali metals (Group 1) or alkaline earth metals (Group 2), and specifically, Na, K, Li, etc. are exemplified. As for the above R 5 , the four Rs 5 may be the same or different. As R 5 , H or an organic group having 1 to 10 carbon atoms is preferable, and H or an organic group having 1 to 4 carbon atoms is more preferable. In general formula (1), m may be 5 to 11. In general formula (2), n may be 6 to 12.

[0072] As the PTFE produced using a hydrocarbon surfactant, the PTFE powder obtained using the above-described hydrocarbon surfactant can be used. As the above PTFE, PTFE such as homopolymer PTFE and modified PTFE described in the method for producing a purified PTFE aqueous dispersion can be used.

[0073] In the method for producing the molded body of the present invention, examples of the method for removing or reducing the compound represented by the general formula (1) or (2) include heat treatment and fluorination treatment.

[0074] The method of the heat treatment is not particularly limited, and a conventionally known method can be employed. The temperature of the heat treatment is preferably 150°C or higher. The temperature of the heat treatment is more preferably 160°C or higher. That is, the removal step preferably includes a step of heat treatment at a temperature of 160°C or higher. The temperature of the heat treatment is more preferably 170°C or higher, still more preferably 180°C or higher, even more preferably 200°C or higher, particularly preferably 210°C or higher, especially preferably 220°C or higher, and most preferably 230°C or higher. Also, the temperature of the heat treatment is preferably 310°C or lower, more preferably 300°C or lower, still more preferably 290°C or lower, even more preferably 280°C or lower, and particularly preferably 270°C or lower. The time of the heat treatment is not particularly limited, but for example, it is 1 minute or more and 24 hours or less. The heat treatment may involve drying. The compound represented by the general formula (1) or (2) and the compound represented by the general formula (7) described later are reduced during drying.

[0075] As the method of the fluorination treatment, a conventionally known method can be employed. For example, there is a method of exposing the PTFE powder to a fluorine radical source that generates fluorine radicals under fluorination treatment conditions. Examples of the fluorine radical source include, in addition to fluorine gas, CoF3, AgF2, UF6, OF2, N2F2, CF3OF, and halogen fluorides such as IF5, ClF3, and BrF3. Since the reaction with the fluorine radical source is extremely exothermic, the fluorine radical source may be diluted with an inert gas such as nitrogen. The level of the fluorine radical source in the fluorine radical source / inert gas mixture can be from 1 to 100% by volume, but preferably about 5 to about 25% by volume because working with pure fluorine is highly dangerous. For fluorinated polymer resins with intense heat-induced discoloration, the fluorine radical source / inert gas mixture may be sufficiently diluted to prevent overheating of the fluorinated polymer and the accompanying risk of fire. The above heat treatment and fluorination treatment may be carried out in combination or simultaneously. By the above fluorination treatment, the compound represented by the general formula (1) or (2) and the compound represented by the general formula (7) described later are reduced.

[0076] The method of the above fluorination treatment is not particularly limited, and a conventionally known method can be adopted. The temperature of the fluorination treatment is preferably above 100°C. The temperature of the fluorination treatment is more preferably 110°C or higher, further preferably 120°C or higher, still further preferably 130°C or higher, particularly preferably 150°C or higher. Also, it is particularly preferably 170°C or higher, more preferably 180°C or higher, still further preferably 200°C or higher, particularly preferably 210°C or higher, especially preferably 220°C or higher, and most preferably 230°C or higher. Also, the temperature of the fluorination treatment is preferably 310°C or lower, more preferably 300°C or lower, further preferably 290°C or lower, still further preferably 280°C or lower, particularly preferably 270°C or lower, especially preferably 250°C or lower, and most preferably 240°C or lower. The time of the above fluorination treatment is not particularly limited, but for example, it is 1 minute or more and 24 hours or less.

[0077] In the above fluorination treatment, the addition amount of the fluorine radical source is preferably 0.5 parts by weight or more, more preferably 0.8 parts by weight or more, and still more preferably 1.0 parts by weight or more, in terms of fluorine atoms, based on 100 parts by weight of the raw material PTFE. Further, it is more preferably 1.6 parts by weight or more, still more preferably 2.0 parts by weight or more, even more preferably 2.5 parts by weight or more, particularly preferably 3.0 parts by weight or more, and most preferably 5.0 parts by weight or more. Also, the addition amount of the fluorine radical source is preferably 35.0 parts by weight or less, more preferably 26.0 parts by weight or less, still more preferably 20.0 parts by weight or less, and particularly preferably 15.0 parts by weight or less. If the addition amount of the fluorine radical source is too small, the removal or reduction of the compound represented by the general formula (1) or (2) may be insufficient. Also, the removal or reduction of the compound that cannot be identified may be insufficient. Even if the addition amount of the fluorine radical source is too large, the effect of fluorination will not be improved and it may be uneconomical. In the fluorination treatment in the method for producing the molded article as well, all combinations of the temperature of the fluorination treatment and the content of the fluorine radical source in the method for producing the PTFE powder described above can be adopted.

[0078] As the reactor used for the fluorination treatment, any reactor equipped with a heating device and capable of sufficiently performing solid-gas contact can be used without problems. Specifically, fluidized bed type and tray type solid-gas contact reactors can be mentioned.

[0079] The method for producing the molded article of the present invention may include the above removal step.

[0080] In addition to the above removal step, the method for manufacturing a molded article of the present invention may further include a step (1a) of mixing PTFE powder obtained using a hydrocarbon-based surfactant and an extrusion aid, a step (1b) of subjecting the obtained mixture to paste extrusion molding, a step (1c) of drying the extrudate obtained by the extrusion molding, and a step (1d) of firing the dried extrudate to obtain a molded article. The above removal step may be performed after step (1a) and before step (1b), after step (1b) and before step (1c), or after step (1d). When heat treatment is performed as the removal step after step (1d), the heat treatment temperature can also be a temperature exceeding 310°C, and in that case, it is preferably performed at 500°C or lower. Further, the above removal step may be performed during step (1b), step (1c), or step (1d). The above removal step may be performed multiple times. For example, the removal step may be performed 2, 3, 4, 5, 6, 7, 8, 9, or 10 times. The above heat treatment and fluorination treatment may be performed in combination or simultaneously. Thus, in the method for manufacturing a molded article of the present invention, the removal step may be to remove or reduce the compound represented by the general formula (1) or (2) from the PTFE powder obtained using a hydrocarbon-based surfactant, or to remove or reduce the compound represented by the general formula (1) or (2) from the molded article formed using the PTFE powder obtained using a hydrocarbon-based surfactant.

[0081] The above paste extrusion molding can be performed by a conventionally known method, and the molding conditions can be selected according to the desired shape and size. The above paste extrusion molding can also be performed by adding conventionally known additives such as pigments and fillers to the above PTFE powder.

[0082] The method for manufacturing the molded body of the present invention may further include, in addition to the above removal step, a step (2a) of mixing PTFE powder obtained using a hydrocarbon-based surfactant and an extrusion aid, a step (2b) of extruding and rolling the obtained mixture, a step (2c) of drying the extrudate obtained by extrusion rolling, a step (2d) of uniaxially stretching the dried extrudate, a step (2e) of biaxially stretching the uniaxially stretched product, a step (2f) of firing the biaxially stretched product, and a step (2g) of laminating the fired product with another material. In this case, the above removal step may be performed before step (2b) after step (2a), before step (2c) after step (2b), before step (2d) after step (2c), before step (2e) after step (2d), before step (2f) after step (2e), and before step (2g) after step (2f). Further, the removal step may be performed during any of steps (2a), (2b), (2c), (2d), (2e), (2f), or (2g). The above removal step may be performed multiple times. The heat treatment and the fluorination treatment may be combined and performed, or may be performed simultaneously.

[0083] The above extrusion aid is not particularly limited, and generally known ones can be used. For example, hydrocarbon oil and the like can be mentioned.

[0084] The method for manufacturing the molded body of the present invention may include, in addition to the above removal step, a step of compression molding PTFE powder obtained using a hydrocarbon-based surfactant. In that case, the above removal step may be performed during or after the compression molding step. The above removal step may be performed multiple times. The heat treatment and the fluorination treatment may be combined and performed.

[0085] In the method for producing a molded article of the present invention, it is preferable that the above removal step removes 80% by mass or more of the compounds represented by general formulas (1) and (2) before and after the removal step, more preferably 85% by mass or more, still more preferably 90% by mass or more, even more preferably 95% by mass or more, particularly preferably 97% by mass or more, most preferably 98% by mass or more, and extremely preferably 99% by mass or more. It is preferable that the above removal step reduces the content of the compounds represented by general formulas (1) and (2) in the obtained PTFE molded article to 500 ppb or less, more preferably 200 ppb or less, still more preferably 100 ppb or less, particularly preferably 50 ppb or less, and most preferably 25 ppb or less, based on PTFE.

[0086] As described above, as a method for removing or reducing the compound represented by general formula (1) or (2), fluorination treatment performed at a specific temperature is one preferred form. That is, the present invention also relates to a method for producing modified PTFE, characterized by including a step of bringing a fluorine radical source into contact with PTFE obtained using a hydrocarbon-based surfactant at a temperature exceeding 100 °C to remove or reduce the compound represented by the following general formula (1) or (2). General formula (1): (H-(CF2) m -COO) p M 1 (In the formula, m is 3 to 19, and M 1 is H, a metal atom, NR 5 4 (R 5 may be the same or different, and is H or an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. p is 1 or 2.) General formula (2): (H-(CF2) n -SO3) q M 2 (wherein n is from 4 to 20. M 2 is H, a metal atom, NR 5 4 (R 5 may be the same or different and is H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. q is 1 or 2.) By bringing a fluorine radical source into contact at the above specific temperature (fluorination treatment), the compound represented by the general formula (1) or (2) can be efficiently removed. In addition, PTFE obtained using a hydrocarbon surfactant may contain impurities such as decomposition products of substances used in the polymerization of PTFE in addition to the compound represented by the general formula (1) or (2), but such impurities can also be removed by bringing a fluorine radical source into contact at the above specific temperature. The temperature at which the fluorine radical source is brought into contact is above 100 °C. The temperature at which the fluorine radical source is brought into contact can be adjusted by a conventionally known method, preferably 110 °C or higher, more preferably 120 °C or higher, still more preferably 130 °C or higher, even more preferably 150 °C or higher, particularly preferably 170 °C or higher, more preferably 180 °C or higher, and particularly preferably 200 °C or higher. Further, 210 °C or higher is more preferable, 220 °C or higher is particularly preferable, and 230 °C or higher is most preferable. Also, it is preferably 310 °C or lower, more preferably 300 °C or lower, still more preferably 290 °C or lower, even more preferably 280 °C or lower, particularly preferably 270 °C or lower, and most preferably 240 °C or lower. In this production method, all of the above-described amounts of addition of the fluorine radical source and combinations of temperature and addition amount can be adopted. When bringing a fluorine radical source into contact in the method for producing the modified PTFE described above, various conditions of the fluorination treatment described in the method for producing the modified PTFE powder and the method for producing a molded article (for example, the type of fluorine radical source, the addition amount of the fluorine radical source, the timing and number of times of the fluorination treatment, etc.) can be appropriately employed. Further, in addition to the method of bringing the fluorine radical source into contact, the removal methods described in the removal steps such as heat treatment and washing with water or an organic solvent may be combined. In particular, after the step of bringing the fluorine radical source into contact to remove or reduce the compound represented by the general formula (1) or (2), a heat treatment step may be performed. By performing the heat treatment step, the content of the compounds represented by the general formulas (1) and (2) can be further reduced. Also, the content of the compound represented by the general formula (7) can be further reduced. In the heat treatment step, the temperature and time of the heat treatment can be within the ranges described above. In the method for producing the modified PTFE described above, the PTFE obtained using the hydrocarbon surfactant may be in the form of a powder or a molded article.

[0087] Also, as described above, as a method for removing or reducing the compound represented by the general formula (1) or (2), fluorination treatment using a specific amount of a fluorine radical source is also one of the preferred forms. That is, the present invention includes a step of bringing PTFE obtained using a hydrocarbon surfactant into contact with a fluorine radical source to remove or reduce the compound represented by the following general formula (1) or (2), and the addition amount of the fluorine radical source is 0.5 parts by weight or more per 100 parts by weight of PTFE in terms of fluorine atoms, and it is also a method for producing PTFE. General formula (1): (H-(CF2) m -COO) p M 1 (In the formula, m is 3 to 19, M 1 is H, a metal atom, NR 5 4 (R 5is the same or different and is H or an organic group having 1 to 10 carbon atoms), an optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium. p is 1 or 2.) General formula (2): (H-(CF2) n -SO3) q M 2 (In the formula, n is 4 to 20. M 2 is H, a metal atom, NR 5 4 (R 5 is the same or different and is H or an organic group having 1 to 10 carbon atoms), an optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium. q is 1 or 2.) By bringing the fluorine radical source into contact in the above-specified addition amount (fluorination treatment), the compound represented by the general formula (1) or (2) can be efficiently removed. In addition, PTFE obtained using a hydrocarbon surfactant may contain impurities such as decomposition products of substances used in the polymerization of PTFE, in addition to the compound represented by the general formula (1) or (2). However, such impurities can also be removed by bringing it into contact with the fluorine radical source in the above-specified addition amount. The addition amount of the above fluorine radical source, in terms of fluorine atoms, is 0.5 parts by weight or more with respect to 100 parts by weight of the raw material PTFE. Preferably, it is 0.8 parts by weight or more, more preferably 1.0 parts by weight or more, still more preferably 1.6 parts by weight or more, yet more preferably 2.0 parts by weight or more, still more preferably 2.5 parts by weight or more, even more preferably 3.0 parts by weight or more, and particularly preferably 5.0 parts by weight or more. Also, the addition amount of the fluorine radical source is preferably 35.0 parts by weight or less, more preferably 26.0 parts by weight or less, still more preferably 20.0 parts by weight or less, and particularly preferably 15.0 parts by weight or less. If the addition amount of the fluorine radical source is too small, the removal or reduction of the compound represented by the general formula (1) or (2) may be insufficient. Also, the removal or reduction of the compound that cannot be identified may be insufficient. If the addition amount of the fluorine radical source is too large, the fluorination effect will not improve and it tends to be uneconomical. In this production method, as the temperature of the fluorination treatment and the combination of the temperature and the addition amount, all of those described above can be adopted. In the method for producing the modified PTFE, when bringing the fluorine radical source into contact, various conditions (for example, the type of the fluorine radical source, the temperature of the fluorination treatment, the timing and the number of times of performing the fluorination treatment, etc.) described in the above-described method for producing the modified PTFE powder and the method for producing the molded body can be appropriately adopted. In addition to the method of bringing the fluorine radical source into contact, the removal methods described in the removal steps such as heat treatment, washing with water or an organic solvent, etc. may be combined. In particular, after the step of bringing the fluorine radical source into contact to remove or reduce the compound represented by the general formula (1) or (2), a heat treatment step may be performed. By performing the heat treatment step, the content of the compounds represented by the general formulas (1) and (2) can be further reduced. Also, the content of the compound represented by the general formula (7) can be further reduced. In the heat treatment step, the temperature and time of the heat treatment can be within the ranges described above. In the method for producing the modified PTFE, the PTFE obtained using the above hydrocarbon surfactant may be in the form of a powder or a molded body.

[0088] Specific hydrocarbon surfactants are described below.

[0089] Hydrocarbon surfactants have a hydrophilic part and a hydrophobic part on the same molecule. These may be cationic, nonionic or anionic.

[0090] Cationic surfactants usually have a positively charged hydrophilic part such as alkylated ammonium halides such as alkylated ammonium bromide, and a hydrophobic part such as long-chain fatty acids.

[0091] Anionic surfactants usually have a hydrophilic part such as carboxylate, sulfonate or sulfate, and a hydrophobic part which is a long-chain hydrocarbon part such as alkyl.

[0092] Nonionic surfactants usually do not contain a charged group and have a hydrophobic part which is a long-chain hydrocarbon. The hydrophilic part of nonionic surfactants contains water-soluble functional groups such as chains of ethylene ethers derived from polymerization with ethylene oxide.

[0093] Examples of nonionic hydrocarbon surfactants Polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, glycerol esters, and their derivatives.

[0094] Specific examples of polyoxyethylene alkyl ethers: polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene behenyl ether, etc.

[0095] Specific examples of polyoxyethylene alkyl phenyl ethers: polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, etc.

[0096] Specific examples of polyoxyethylene alkyl esters: polyethylene glycol monolaurate, polyethylene glycol monooleate, polyethylene glycol monostearate, etc.

[0097] Specific examples of sorbitan alkyl esters: polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, etc.

[0098] Specific examples of polyoxyethylene sorbitan alkyl esters: polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, etc.

[0099] Specific examples of glycerol esters: glycerol monomyristate, glycerol monostearate, glycerol monooleate, etc.

[0100] Specific examples of the above derivatives: polyoxyethylene alkylamine, polyoxyethylene alkyl phenyl-formaldehyde condensate, polyoxyethylene alkyl ether phosphate, etc.

[0101] The above ethers and esters may have an HLB value of 10 to 18.

[0102] Examples of nonionic hydrocarbon surfactants include Triton® X series (X15, X45, X100, etc.), Tergitol® 15-S series, Tergitol® TMN series (TMN-6, TMN-10, TMN-100, etc.), Tergitol® L series manufactured by Dow Chemical Company; Pluronic® R series (31R1, 17R2, 10R5, 25R4 (m~22, n~23)), T-Det series (A138), Iconol® TDA series (TDA-6, TDA-9, TDA-10, etc.) manufactured by BASF.

[0103] Examples of anionic hydrocarbon surfactants include Versatic® 10 of Resolution Performance Products, Avanel S series (S-70, S-74, etc.) manufactured by BASF.

[0104] Examples of hydrocarbon surfactants include R-L-M 1 (wherein R is a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent, and when having 3 or more carbon atoms, may contain a monovalent or divalent heterocyclic ring or may be ring-rolled; L is -ArSO3 - , -SO3 - , -SO4-, -PO3 - or -COO - ; and M 1 is H, a metal atom, NR 5 4 (R 5 may be the same or different and is H or an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. -ArSO3 - is an aryl sulfonate.) Also included are anionic surfactants represented by the formula. Specifically, CH3-(CH2) n -L-M 1(wherein n is an integer of 6 to 17; L and M are the same as above) can be mentioned. Mixtures in which R is an alkyl group having 12 to 16 carbon atoms and L is a sulfate or sodium dodecyl sulfate (SDS) can also be used. As the hydrocarbon surfactant, R 6 (-L-M 1 )2 (wherein R 6 is a linear or branched alkylene group having 1 or more carbon atoms which may have a substituent, or a cyclic alkylene group having 3 or more carbon atoms which may have a substituent. When the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocyclic ring or may be ringed. L is -ArSO3 - , -SO3 - , -SO4-, -PO3 - or -COO - and M 1 is H, a metal atom, NR 5 4 (R 5 may be the same or different and is H or an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. -ArSO3 - is an aryl sulfonate.) can also be mentioned as an anionic surfactant. As the hydrocarbon surfactant, R 7 (-L-M 1 )3 (wherein R 7 is a linear or branched alkylidine group having 1 or more carbon atoms which may have a substituent, or a cyclic alkylidine group having 3 or more carbon atoms which may have a substituent. When the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocyclic ring or may be ringed. L is -ArSO3 - , -SO3 - , -SO4-, -PO3 - or -COO - and M 1 is H, a metal atom, NR 5 4 (R 5may be the same or different, and is H or an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. -ArSO3 - is an aryl sulfonate. An anionic surfactant represented by ) is also included.

[0105] Examples of the siloxane hydrocarbon-based surfactant include those described in Silicone Surfactants, R.M. Hill, Marcel Dekker, Inc., ISBN: 0-8247-00104. The structure of the siloxane surfactant includes a distinct hydrophobic part and a hydrophilic part. The hydrophobic part includes one or more dihydrocarbyl siloxane units, where the substituents on the silicone atom are completely hydrocarbons. When the carbon atoms of the hydrocarbyl group can be substituted by a halogen such as fluorine and are completely substituted by hydrogen atoms, these siloxane surfactants can also be regarded as hydrocarbon surfactants, that is, the monovalent substituents on the carbon atoms of the hydrocarbyl group are hydrogen.

[0106] The hydrophilic part of the siloxane surfactant may include one or more polar parts containing ionic groups such as sulfate, sulfonate, phosphonate, phosphate ester, carboxylate, carbonate, sulfosuccinate, taurate (as free acid, salt or ester), phosphine oxide, betaine, betaine copolyol, and quaternary ammonium salt. The ionic hydrophobic part may also include an ionically functionalized siloxane graft. Examples of such siloxane surfactants include polydimethylsiloxane-graft-(meth)acrylate, polydimethylsiloxane-graft-polyacrylate salt, and polydimethylsiloxane-grafted quaternary amine. The polar part of the hydrophilic portion of the siloxane surfactant may include nonionic groups formed by polyethers such as polyethylene oxide (PEO) and mixed polyethylene oxide / propylene oxide polyethers (PEO / PPO); monosaccharides and disaccharides; and water-soluble heterocycles such as pyrrolidinone. The ratio of ethylene oxide to propylene oxide (EO / PO) can be varied in the mixed polyethylene oxide / propylene oxide polyether.

[0107] The hydrophilic portion of the siloxane surfactant may also include a combination of an ionic portion and a nonionic portion. Examples of such portions include ionically end-functionalized or randomly functionalized polyethers or polyols. Preferred for the practice of the present invention are siloxanes having a nonionic portion, i.e., nonionic siloxane surfactants.

[0108] The arrangement of the hydrophobic and hydrophilic portions of the structure of the siloxane surfactant may take the form of a diblock polymer (AB), a triblock polymer (ABA) (where "B" represents the siloxane portion of the molecule), or a multiblock polymer. Alternatively, the siloxane surfactant may include a graft polymer.

[0109] The siloxane surfactant is also disclosed in U.S. Patent No. 6,841,616.

[0110] Examples of siloxane-based anionic hydrocarbon surfactants include SilSense TM PE-100 silicone, SilSense TM CA-1 silicone, and the like.

[0111] Examples of anionic hydrocarbon surfactants include sulfosuccinate surfactants such as Lankropol® K8300 from Akzo Nobel Surface Chemistry LLC. Examples of sulfosuccinate hydrocarbon surfactants include diisodecyl sulfosuccinate Na salt, (Emulsogen® SB10 from Clariant), diisotridecyl sulfosuccinate Na salt (Polirol® TR / LNA from Cesapinia Chemicals), etc.

[0112] Examples of hydrocarbon surfactants include PolyFox® surfactants (PolyFox TM PF-156A, PolyFox TM PF-136A, etc.) from Omnova Solutions, Inc.

[0113] Examples of the above hydrocarbon surfactants include the following general formula (1):

Chemical formula

[0114] The surfactant (1) will be described.

[0115] In the formula, R 1 ~R 5 represents H or a monovalent substituent, provided that at least one of R 1 and R 3 is a group represented by the general formula: -Y-R 6 Among R 2 and R 5 at least one is a group represented by the general formula: -X-A, or a group represented by the general formula: -Y-R 6 represents the group shown. Among R 1 ~R 5 any two of them may be bonded to each other to form a ring.

[0116] R 1 The above-mentioned substituent that the above-mentioned alkyl group as R may have is preferably a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, a hydroxy group, and particularly preferably a methyl group or an ethyl group.

[0117] R 1 The above-mentioned alkyl group as R preferably does not contain a carbonyl group. The above alkyl group may have 75% or less of the hydrogen atoms bonded to carbon atoms substituted by halogen atoms, may have 50% or less of the hydrogen atoms bonded to carbon atoms substituted by halogen atoms, or may have 25% or less of the hydrogen atoms bonded to carbon atoms substituted by halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms. The above alkyl group preferably has no substituents.

[0118] R 1 Preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms that may have substituents or a cyclic alkyl group having 3 to 10 carbon atoms that may have substituents. More preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms that does not contain a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms that does not contain a carbonyl group. Even more preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms that has no substituents. Even more preferably, it is a linear or branched alkyl group having 1 to 3 carbon atoms that has no substituents. Particularly preferably, it is a methyl group (-CH3) or an ethyl group (-C2H5), and most preferably, it is a methyl group (-CH3).

[0119] Examples of the monovalent substituent include a group represented by the general formula: -Y-R 6 a group represented by the general formula: -X-A, -H, a C 1-20 alkyl group, -NH2, -NHR 9 (R 9 is an organic group), -OH, -COOR 9 (R 9 is an organic group) or -OR 9 (R 9 (R

[0120] R 9 Preferably, it is a C 1-10 alkyl group or a C 1-10 alkylcarbonyl group, and more preferably, it is a C 1-4 alkyl group or a C 1-4 alkylcarbonyl group.

[0121] In the formula, X is the same or different in each occurrence and represents a divalent linking group or a bond. R 6 When R does not contain any of a carbonyl group, an ester group, an amide group, and a sulfonyl group, X is preferably a divalent linking group containing at least one selected from the group consisting of a carbonyl group, an ester group, an amide group, and a sulfonyl group.

[0122] Examples of X include a divalent linking group containing at least one bond selected from the group consisting of -CO-, -S(=O)2-, -O-, -COO-, -OCO-, -S(=O)2-O-, -O-S(=O)2-, -CONR 8 -, and -NR 8 CO-, an alkylene group of C 1-10 , or a bond is preferred. R 8 represents H or an organic group.

[0123] R 8 is preferably H or an organic group of C 1-10 , more preferably H or an organic group of C 1-4 , and even more preferably H.

[0124] In the formula, A is the same or different in each occurrence and is -COOM, -SO3M, or -OSO3M (M is H, a metal atom, NR 7 4, an optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, and R 7 is H or an organic group. The four Rs 7 may be the same or different. ).

[0125] R 7 is preferably H or an organic group of C 1-10 , and more preferably H or an organic group of C 1-4 . Examples of the above metal atom include monovalent and divalent metal atoms, such as alkali metals (Group 1), alkaline earth metals (Group 2), etc., and Na, K, or Li is preferred.

[0126] M is preferably H, a metal atom or NR 7 4, 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 NH4, even more preferably Na, K or NH4, particularly preferably Na or NH4, and most preferably NH4.

[0127] In the formula, Y is the same or different at each occurrence and is a divalent linking group selected from the group consisting of -S(=O)2-, -O-, -COO-, -OCO-, -CONR 8 -, and -NR 8 CO-, or a bond, and R 8 represents H or an organic group.

[0128] Preferably, Y is a divalent linking group selected from the group consisting of a bond, -O-, -COO-, -OCO-, -CONR 8 -, and -NR 8 CO-, more preferably a divalent linking group selected from the group consisting of a bond, -COO- and -OCO-.

[0129] R 8 is preferably H or a C 1-10 organic group, more preferably H or a C 1-4 organic group, and still more preferably H.

[0130] In the formula, R 6 is the same or different at each occurrence and represents an alkyl group having 2 or more carbon atoms which may contain at least one selected from the group consisting of a carbonyl group, an ester group, an amide group and a sulfonyl group between carbon-carbon atoms. The carbon number of the above R 6 organic group is preferably 2 to 20, and more preferably 2 to 10.

[0131] R 6 alkyl group of may contain one or more of at least one selected from the group consisting of a carbonyl group, an ester group, an amide group and a sulfonyl group between carbon-carbon atoms, but does not contain these groups at the terminal of the alkyl group. The above R 6The alkyl group may have 75% or less of the hydrogen atoms bonded to the carbon atoms substituted by halogen atoms, may have 50% or less of the hydrogen atoms bonded to the carbon atoms substituted by halogen atoms, or may have 25% or less of the hydrogen atoms bonded to the carbon atoms substituted by halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0132] R 6 Examples include General formula: -R 10 -CO-R 11 a group represented by General formula: -R 10 -COO-R 11 a group represented by General formula: -R 11 a group represented by General formula: -R 10 -NR 8 CO-R 11 a group represented by, or General formula: -R 10 -CONR 8 -R 11 a group represented by (In the formula, R 8 represents H or an organic group. R 10 is an alkylene group, and R 11 is an alkyl group which may have a substituent) is preferred. R 6 Examples of R 10 -CO-R 11 a group represented by are more preferred.

[0133] R 8 Examples of R 1-10 are preferably H or an organic group of C 1-4 more preferably H or an organic group of C

[0134] R 10 The number of carbon atoms of the alkylene group of R 10The number of carbon atoms in the alkylene group is preferably from 1 to 20, more preferably from 1 to 10, and still more preferably from 3 to 10.

[0135] R 11 The number of carbon atoms in the alkyl group may be from 1 to 20, preferably from 1 to 15, more preferably from 1 to 12, still more preferably from 1 to 10, even more preferably from 1 to 8, particularly preferably from 1 to 6, still more preferably from 1 to 3, particularly preferably 1 or 2, and most preferably 1. Further, the above R 11 The alkyl group is preferably composed of only primary carbon, secondary carbon, and tertiary carbon, and particularly preferably composed of only primary carbon and secondary carbon. That is, R 11 is preferably a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and particularly preferably a methyl group.

[0136] As the surfactant (1), a compound represented by the general formula (1-1), a compound represented by the general formula (1-2), or a compound represented by the general formula (1-3) is preferable, and a compound represented by the general formula (1-1) or a compound represented by the general formula (1-2) is more preferable.

[0137] General formula (1-1):

Chemical formula

[0138] General formula (1-2):

Chemical formula

[0139] General formula (1-3):

Chemical formula

[0140] Examples of the group represented by the general formula -X-A include -COOM, -R 12 COOM, -SO3M, -OSO3M, -R 12 SO3M, -R 12 OSO3M, -OCO-R 12 -COOM, -OCO-R 12 -SO3M, -OCO-R 12 -OSO3M -COO-R 12 -COOM, -COO-R 12 -SO3M, -COO-R 12 -OSO3M, -CONR 8 -R 12 -COOM, -CONR 8 -R 12 -SO3M, -CONR 8 -R 12 -OSO3M, -NR 8 CO-R 12 -COOM, -NR 8 CO-R 12 -SO3M, -NR 8 CO-R 12 -OSO3M, -OS(=O)2-R 12 -COOM, -OS(=O)2-R 12 -SO3M, or -OS(=O)2-R 12 -OSO3M (wherein R 8 and M are as described above. R 12 is C 1-10The alkylene group.) is preferred. The above R 12 The alkylene group may have 75% or less of the hydrogen atoms bonded to the carbon atoms substituted by halogen atoms, 50% or less substituted by halogen atoms, or 25% or less substituted by halogen atoms, but is preferably a non-halogenated alkylene group containing no halogen atoms such as fluorine atoms and chlorine atoms.

[0141] General formula: -Y-R 6 The group represented by General formula: -R 10 -CO-R 11 The group represented by General formula: -OCO-R 10 -CO-R 11 The group represented by General formula: -COO-R 10 -CO-R 11 The group represented by General formula: -OCO-R 10 -COO-R 11 The group represented by General formula: -COO-R 11 The group represented by the group represented by General formula: -NR 8 CO-R 10 -CO-R 11 The group represented by, or General formula: -CONR 8 -R 10 -NR 8 CO-R 11 The group represented by (In the formula, R 8 , R 10 and R 11 are as described above.) is preferred.

[0142] In the formula, R 4 and R 5 are each independently preferably H or an alkyl group of C 1-4 . The above R 4 and R 5The alkyl group may have 75% or less of the hydrogen atoms bonded to the carbon atoms substituted by halogen atoms, may have 50% or less of the hydrogen atoms bonded to the carbon atoms substituted by halogen atoms, or may have 25% or less of the hydrogen atoms bonded to the carbon atoms substituted by halogen atoms. However, it is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0143] R in the general formula (1-1) 3 is preferably H or an alkyl group of C 1-20 which may have a substituent, more preferably H or an alkyl group of C 1-20 which does not have a substituent, and even more preferably H. The above-mentioned R 3 The alkyl group may have 75% or less of the hydrogen atoms bonded to the carbon atoms substituted by halogen atoms, may have 50% or less of the hydrogen atoms bonded to the carbon atoms substituted by halogen atoms, or may have 25% or less of the hydrogen atoms bonded to the carbon atoms substituted by halogen atoms. However, it is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0144] R in the general formula (1-3) 2 is preferably H, OH or an alkyl group of C 1-20 which may have a substituent, more preferably H, OH or an alkyl group of C 1-20 which does not have a substituent, and even more preferably H or OH. The above-mentioned R 2 The alkyl group may have 75% or less of the hydrogen atoms bonded to the carbon atoms substituted by halogen atoms, may have 50% or less of the hydrogen atoms bonded to the carbon atoms substituted by halogen atoms, or may have 25% or less of the hydrogen atoms bonded to the carbon atoms substituted by halogen atoms. However, it is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0145] The surfactant (1) is obtained by reacting a carboxylic acid represented by the formula: R 6 -COOH (wherein R 6 is as described above) with a halogenating agent to obtain a compound represented by the formula: R 6 -COZ (wherein R 6As described above. Z is a halogen atom.) to obtain a carboxylic acid halide represented by the formula (11), and reacting the carboxylic acid halide with a compound represented by the formula:

Chemical formula

Chemical formula

[0146] As R 3 in the formula of the above acid compound, a group represented by the general formula: -Z 11 H (wherein Z 11 is as described above.), or -H is preferable. When R 3 is a group represented by the general formula: -Z 11 H, in step (12), the above group reacts with the above carboxylic acid halide to form a group represented by the general formula: -Z 11 -CO-R 6 (wherein R 6 and Z 11 are as described above.).

[0147] Examples of the halogenating agent used in step (11) include oxalyl chloride, thionyl chloride, diethylaminosulfur trifluoride (DAST), Deoxo-Fluor, 1,1,2,2-tetrafluoro-N,N-dimethylethylamine (TFEDMA), and the like.

[0148] As Z, F or Cl is preferable, and Cl is more preferable.

[0149] In step (11), considering the improvement of the yield and the reduction of waste, the reaction ratio of the carboxylic acid to the halogenating agent is preferably 0.6 to 5.0 moles, more preferably 0.8 to 2.0 moles, per 1 mole of the carboxylic acid. Also, it is preferably 0.5 to 10 moles, more preferably 0.6 to 5.0 moles.

[0150] The reaction in step (11) can be carried out in a solvent. Examples of the solvent include esters, ketones, aromatic hydrocarbons, ethers, nitrogen-containing polar organic compounds, halogenated hydrocarbons, nitriles, pyridine, or mixtures thereof.

[0151] Examples of the ester include ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy-2-acetoxypropane), etc. Among them, ethyl acetate is preferred.

[0152] Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, etc. Among them, acetone is preferred.

[0153] Examples of the aromatic hydrocarbon include benzene, toluene, xylene, etc. Among them, benzene and toluene are preferred.

[0154] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc. Among them, diethyl ether and tetrahydrofuran are preferred.

[0155] Examples of the nitrogen-containing polar organic compound include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, etc. Among them, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferred.

[0156] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc. Among them, dichloromethane and chloroform are preferred.

[0157] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, etc. Among them, acetonitrile is preferred.

[0158] The reaction temperature in step (11) is preferably 0 to 150°C, more preferably 20 to 100°C. Also, it is preferably -78 to 150°C, more preferably 0 to 100°C.

[0159] The reaction pressure in step (11) is preferably 0 to 5 MPa, more preferably 0.1 to 1.0 MPa.

[0160] The reaction time in step (11) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0161] In step (12), considering the improvement of the yield and the reduction of waste, the reaction ratio of the carboxylic acid halide to the acid compound is preferably 0.5 to 10 moles, more preferably 0.6 to 5.0 moles, and even more preferably 0.8 to 2.0 moles of the acid compound per 1 mole of the carboxylic acid halide.

[0162] The reaction in step (12) is preferably carried out in the presence of an acid. Examples of the acid include sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, etc. Among them, sulfuric acid is preferred.

[0163] In the process (12), the amount of the acid used is preferably 0.00001 to 1.0 mol, more preferably 0.0001 to 1.0 mol, still more preferably 0.00005 to 0.1 mol, and particularly preferably 0.001 to 0.1 mol, per 1 mol of the carboxylic acid halide, considering the improvement in yield and the reduction of waste.

[0164] As the reaction temperature in the process (12), 0 to 150 °C is preferable, and 20 to 100 °C is more preferable.

[0165] As the reaction pressure in the process (12), 0 to 5 MPa is preferable, and 0.1 to 1.0 MPa is more preferable.

[0166] As the reaction time in the process (12), 0.1 to 72 hours is preferable, and 0.1 to 48 hours is more preferable.

[0167] The surfactant (1) is also a compound represented by the formula:

Chemical formula

Chemical formula

Chemical formula

[0168] As R 2 in the formula of the compound (20), the general formula: -Z 11 H (in the formula, Z 11is preferably a group represented by the above formula, or -H. R 2 is a general formula: -Z 11 When the group represented by H is the above group, in step (21), the above group reacts with the above acid anhydride to form a general formula: -Z 11 -CO-(CH2) n -COOM (wherein Z 11 , M and n are as defined above).) A group represented by is formed. Compound (20) may be a hydrochloride, a sulfate, etc., as long as it contains the structure represented by the above formula.

[0169] In step (21), considering the improvement of the yield and the reduction of waste, the reaction ratio of compound (20) and the above acid anhydride is preferably 0.5 to 10 moles, more preferably 0.6 to 5.0 moles, still more preferably 1.2 to 10 moles, and particularly preferably 1.6 to 4.0 moles of the above acid anhydride per 1 mole of compound (20).

[0170] The reaction in step (21) can be carried out in the presence of a base.

[0171] Examples of the base include amines, potassium hydroxide, sodium hydroxide, potassium carbonate, etc.

[0172] Examples of the amine include tertiary amines such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, dimethylbenzylamine, N,N,N',N'-tetramethyl-1,8-naphthalenediamine, heteroaromatic amines such as pyridine, pyrrole, uracil, collidine, lutidine, and cyclic amines such as 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonene, etc. Pyridine or triethylamine is preferred.

[0173] The reaction temperature in step (21) is preferably 0 to 150°C, more preferably 20 to 80°C. Also, -78 to 150°C is preferred, and 0 to 100°C is more preferred.

[0174] As the pressure of the reaction in step (21), 0 to 5 MPa is preferable, and 0.1 to 1 MPa is more preferable.

[0175] As the reaction time in step (21), 0.1 to 72 hours is preferable, and 0.1 to 48 hours is more preferable.

[0176] The surfactant (1) is also represented by the formula:

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0177] In step (31), considering the improvement of the yield and the reduction of waste, the reaction ratio of the tartaric acid ester to the amine is preferably 0.5 to 10 moles, more preferably 0.6 to 5.0 moles, still more preferably 1.2 to 5 moles, and particularly preferably 1.6 to 5.0 moles per mole of the tartaric acid ester.

[0178] The reaction in step (31) can be carried out in a solvent. The solvent is preferably an organic solvent, more preferably an alcohol, an ether, a halogenated hydrocarbon, a nitrogen-containing polar organic compound or a nitrile.

[0179] Examples of the alcohol include methanol, ethanol, 1-propanol, isopropanol and the like.

[0180] Examples of the ether include tetrahydrofuran, dioxane, diethylene glycol diethyl ether and the like.

[0181] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene and the like.

[0182] Examples of the nitrogen-containing polar organic compound include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like. Among them, N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone are preferred.

[0183] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile and the like.

[0184] The reaction temperature in step (31) is preferably 0 to 150 °C, more preferably 20 to 100 °C.

[0185] As the pressure of the reaction in step (31), 0 to 5 MPa is preferable, and 0.1 to 1 MPa is more preferable.

[0186] As the reaction time in step (31), 0.1 to 72 hours is preferable, and 0.1 to 48 hours is more preferable.

[0187] In step (32), considering the improvement of the yield and the reduction of waste, the reaction ratio of compound (31) to the above-mentioned sulfonic acid chloride is preferably 1.0 to 50 moles, more preferably 1.6 to 20 moles, of the above-mentioned sulfonic acid chloride per 1 mole of compound (31).

[0188] The reaction in step (32) is preferably carried out in the presence of a base. Examples of the base include alkali metal hydroxides, alkaline earth metal hydroxides, amines, etc. Among them, amines are preferable.

[0189] Examples of the amine in step (32) include 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, collidine, lutidine, etc., and cyclic amines such as 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonene, etc. Among them, triethylamine is preferable.

[0190] Considering the improvement of the yield and the reduction of waste, the amount of the base used in step (32) is preferably 0.1 to 50 moles, more preferably 1.0 to 20 moles, per 1 mole of compound (31).

[0191] The reaction in step (32) can be carried out in a solvent. As the solvent, an organic solvent is preferable, a polar aprotic solvent is more preferable, and nitrile, halogenated hydrocarbon, dimethyl sulfoxide, sulfolane, nitrogen-containing polar organic compound or ether is even more preferable.

[0192] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, etc. Among them, acetonitrile is preferred.

[0193] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc. Among them, dichloromethane and chloroform are preferred.

[0194] Examples of the nitrogen-containing polar organic compound include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, etc. Among them, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferred.

[0195] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc. Among them, diethyl ether is preferred.

[0196] The reaction temperature in step (32) is preferably -78 to 150°C, more preferably -78 to 100°C, still more preferably -20 to 100°C, and particularly preferably 10 to 50°C.

[0197] The reaction pressure in step (32) is preferably 0 to 5 MPa, more preferably 0.1 to 1.0 Pa.

[0198] The reaction time in step (32) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0199] Surfactant (1) also has the formula:

Chemical formula

[0200] In step (41), considering the improvement of the yield and the reduction of waste, the reaction ratio of the above alcohol to the above acid anhydride is preferably 0.5 to 10 moles, more preferably 0.6 to 4.0 moles, still more preferably 1.2 to 4.0 moles, and particularly preferably 1.6 to 4.0 moles of the above acid anhydride per 1 mole of the above alcohol.

[0201] The reaction in step (41) can be carried out in the presence of a base.

[0202] Examples of the above base include amines, potassium hydroxide, sodium hydroxide, potassium carbonate and the like.

[0203] Examples of the above amine include tertiary amines such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, dimethylbenzylamine, N,N,N',N'-tetramethyl-1,8-naphthalenediamine, heteroaromatic amines such as pyridine, pyrrole, uracil, collidine, lutidine, and cyclic amines such as 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonene, etc., and pyridine or triethylamine is preferred.

[0204] As the reaction temperature in step (41), -78 to 150 °C is preferred, 0 to 150 °C is more preferred, 0 to 100 °C is even more preferred, and 20 to 80 °C is particularly preferred.

[0205] As the reaction pressure in step (41), 0 to 5 MPa is preferred, and 0.1 to 1 MPa is more preferred.

[0206] As the reaction time in step (41), 0.1 to 72 hours is preferred, and 0.1 to 48 hours is more preferred.

[0207] The surfactant (1) is also represented by the formula:

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0208] In step (51), considering the improvement of the yield and the reduction of waste, the reaction ratio of the compound (31) to the above acid anhydride is preferably 0.5 to 10 moles, more preferably 0.6 to 4.0 moles, still more preferably 1.2 to 4.0 moles, and particularly preferably 1.6 to 4.0 moles of the above acid anhydride per mole of the compound (31).

[0209] The reaction in step (51) can be carried out in the presence of a base.

[0210] Examples of the above base include amines, potassium hydroxide, sodium hydroxide, potassium carbonate, and the like.

[0211] Examples of the above amine include tertiary amines such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, dimethylbenzylamine, N,N,N’,N’-tetramethyl-1,8-naphthalenediamine, heteroaromatic amines such as pyridine, pyrrole, uracil, collidine, lutidine, and cyclic amines such as 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonene, etc. Pyridine or triethylamine is preferred.

[0212] As for the temperature of the reaction in step (51), -78 to 150 °C is preferred, 0 to 150 °C is more preferred, 0 to 100 °C is still more preferred, and 20 to 80 °C is particularly preferred.

[0213] As for the pressure of the reaction in step (51), 0 to 5 MPa is preferred, and 0.1 to 1 MPa is more preferred.

[0214] As for the reaction time in step (51), 0.1 to 72 hours is preferred, and 0.1 to 48 hours is more preferred.

[0215] The surfactant (1) also has the formula: R 6 -OH (wherein R 6As described above, reacting an alcohol represented by ( ) with a fumaric acid halide to obtain a compound (61) represented by the formula: [Chemical formula] (wherein R 6 is as described above), step (61), and reacting the compound (61) with a sulfonating oxidizing agent such as sodium bisulfite to obtain a compound (62) represented by the formula: [Chemical formula] (wherein R 6 and X are as described above). It can be preferably produced by a production method including step (62).

[0216] Examples of the fumaric acid halide used in step (61) include fumaroyl chloride, fumaroyl fluoride, fumaroyl bromide, and the like.

[0217] In step (61), considering the improvement of the yield and the reduction of waste, the reaction ratio of the above alcohol to the above fumaric acid halide is preferably 0.1 to 10 moles, more preferably 0.1 to 2.0 moles, still more preferably 0.1 to 2.0 moles, and particularly preferably 0.2 to 0.7 moles of the fumaric acid halide per 1 mole of the above alcohol.

[0218] The reaction in step (61) can be carried out in a solvent. Examples of the solvent include esters, ketones, aromatic hydrocarbons, ethers, nitrogen-containing polar organic compounds, halogenated hydrocarbons, nitriles, pyridine, or mixtures thereof.

[0219] Examples of the above ester include ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy-2-acetoxypropane), etc. Among them, ethyl acetate is preferred.

[0220] Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, etc., and among them, acetone is preferable.

[0221] Examples of the aromatic hydrocarbon include benzene, toluene, xylene, etc., and among them, benzene and toluene are preferable.

[0222] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc., and among them, diethyl ether and tetrahydrofuran are preferable.

[0223] Examples of the nitrogen-containing polar organic compound include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, etc., and among them, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferable.

[0224] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc., and among them, dichloromethane and chloroform are preferable.

[0225] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, etc., and among them, acetonitrile is preferable.

[0226] The temperature of the reaction in step (61) is preferably -78 to 200°C, more preferably -20 to 150°C.

[0227] The pressure of the reaction in step (61) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0228] As the reaction time in step (61), 0.1 to 72 hours is preferable, and 0.1 to 48 hours is more preferable.

[0229] In step (62), compound (62) is produced by an addition reaction between a compound (61) having a double bond and a sulfonating agent such as sodium bisulfite.

[0230] In step (62), considering the improvement of the yield and the reduction of waste, the reaction ratio of compound (61) to the above sulfonating agent is preferably 0.5 to 20.0 moles, more preferably 0.6 to 10.0 moles, still more preferably 0.8 to 10.0 moles, and particularly preferably 1.2 to 10.0 moles with respect to 1 mole of compound (61).

[0231] Step (62) can be carried out in a solvent. As the above solvent, a water-soluble solvent is preferable, and examples thereof include water, alcohol, ether, nitrile, and the like.

[0232] Examples of the above alcohol include methanol, ethanol, 1-propanol, isopropanol, and the like.

[0233] Examples of the above ether include tetrahydrofuran, dioxane, diethylene glycol diethyl ether, and the like.

[0234] Examples of the above nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, and the like. Among them, acetonitrile is preferable.

[0235] As the reaction temperature in step (62), -78 to 200 °C is preferable, and -20 to 150 °C is more preferable.

[0236] As the reaction pressure in step (62), 0 to 5.0 MPa is preferable, and 0.1 to 1.0 MPa is more preferable.

[0237] As the reaction time in step (62), 0.1 to 72 hours is preferable, and 0.1 to 48 hours is more preferable.

[0238] The surfactant (1) is also a compound represented by the formula:

Chemical formula

Chemical formula

[0239] The sulfation in step (71) can be carried out by reacting the compound (70) with a sulfating reagent. Examples of the sulfating reagent include sulfur trioxide amine complexes such as sulfur trioxide pyridine complex, sulfur trioxide trimethylamine complex, and sulfur trioxide triethylamine complex; sulfur trioxide amide complexes such as sulfur trioxide dimethylformamide complex; sulfuric acid - dicyclohexylcarbodiimide, chlorosulfuric acid, concentrated sulfuric acid, sulfamic acid, etc. The amount of the sulfating reagent used is preferably 0.5 to 10 moles, more preferably 0.5 to 5 moles, and still more preferably 0.7 to 4 moles per 1 mole of the compound (70). By adjusting the amount of the sulfating reagent used, one or both of the two -OH groups of the compound (20) can be sulfated.

[0240] The sulfation in step (71) can be carried out in a solvent. The solvent is preferably an organic solvent, and examples include ether, halogenated hydrocarbon, aromatic hydrocarbon, pyridine, dimethyl sulfoxide, sulfolane, nitrile, etc.

[0241] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc. Among them, diethyl ether and tetrahydrofuran are preferred.

[0242] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc. Among them, dichloromethane and chloroform are preferred.

[0243] Examples of the aromatic hydrocarbon include benzene, toluene, xylene, etc. Among them, benzene and toluene are preferred.

[0244] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, etc. Among them, acetonitrile is preferred.

[0245] The temperature of the sulfuric acid esterification in step (71) is preferably -78 to 200°C, more preferably -20 to 150°C.

[0246] The pressure of the sulfuric acid esterification in step (71) is preferably 0 to 10 MPa, more preferably 0.1 to 5 MPa.

[0247] The time of the sulfuric acid esterification in step (71) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0248] Compound (70) is also a compound of the formula:

Chemical formula

Chemical formula

[0249] R 100 The alkyl group as R 100 As -CH2-, the above-mentioned R 11 constitutes.

[0250] The hydroxylation in step (101) can be carried out, for example, by (1) a method of allowing iron(II) phthalocyanine (Fe(Pc)) and sodium borohydride to act on the compound (100) in an oxygen atmosphere, or (2) a method of allowing isopinocampheylborane (IpcBH2) to act on the compound (100) and then oxidizing the resulting intermediate (dialkylborane).

[0251] In method (1), the amount of iron(II) phthalocyanine may be a catalytic amount and can be used in an amount of 0.001 to 1.2 mol per 1 mol of the compound (100).

[0252] In method (1), sodium borohydride can be used in an amount of 0.5 to 20 mol per 1 mol of the compound (100).

[0253] The reaction of method (1) can be carried out in a solvent. As the above solvent, an organic solvent is preferable, and examples include ether, halogenated hydrocarbon, aromatic hydrocarbon, nitrile, nitrogen-containing polar organic compound, etc.

[0254] Examples of the above ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc. Among them, diethyl ether and tetrahydrofuran are preferable.

[0255] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc. Among them, dichloromethane and chloroform are preferred.

[0256] Examples of the aromatic hydrocarbon include benzene, toluene, xylene, etc. Among them, benzene and toluene are preferred.

[0257] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, etc. Among them, acetonitrile is preferred.

[0258] Examples of the nitrogen-containing polar organic compound include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, etc. Among them, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferred.

[0259] The reaction temperature of method (1) is preferably -78 to 200 °C, more preferably 0 to 150 °C.

[0260] The reaction pressure of method (1) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0261] The reaction time of method (1) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0262] In method (2), isopinocampheylborane can be used in an amount of 0.1 to 10.0 moles per 1 mole of compound (100).

[0263] The reaction between compound (100) and isopinocampheylborane can be carried out in a solvent. The solvent is preferably an organic solvent, and examples thereof include ether, halogenated hydrocarbon, aromatic hydrocarbon, etc.

[0264] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc. Among them, diethyl ether and tetrahydrofuran are preferred.

[0265] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc. Among them, dichloromethane and chloroform are preferred.

[0266] Examples of the aromatic hydrocarbon include benzene, toluene, xylene, etc. Among them, benzene and toluene are preferred.

[0267] The reaction temperature between compound (100) and isopinocampheylborane is preferably -78 to 200°C, more preferably 0 to 150°C.

[0268] The reaction pressure between compound (100) and isopinocampheylborane is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0269] The reaction time between compound (100) and isopinocampheylborane is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0270] The oxidation in method (2) can be carried out by allowing an oxidizing agent to act on the above intermediate. Examples of the oxidizing agent include hydrogen peroxide, etc. The oxidizing agent can be used in an amount of 0.7 to 10 moles per 1 mole of the above intermediate.

[0271] The oxidation in method (2) can be carried out in a solvent. Examples of the solvent include water, methanol, ethanol, etc. Among them, water is preferred.

[0272] The oxidation temperature in method (2) is preferably -78 to 150°C, more preferably 0 to 100°C, and even more preferably 10 to 80°C.

[0273] As the pressure of oxidation in the method (2), 0 to 5.0 MPa is preferable, and 0.1 to 1.0 MPa is more preferable.

[0274] As the time of oxidation in the method (2), 0.1 to 72 hours is preferable, and 0.1 to 48 hours is more preferable.

[0275] In the step (102), examples of the method for oxidizing the compound (101) include (a) a method using Jones reagent (CrO3 / H2SO4) (Jones oxidation), (b) a method using Dess-Martin periodinane (DMP) (Dess-Martin oxidation), (c) a method using pyridinium chlorochromate (PCC), (d) a method in which a bleaching agent (about 5 to 6% aqueous solution of NaOCl) acts in the presence of a nickel compound such as NiCl2, and (e) a method in which a hydrogen acceptor such as an aldehyde or a ketone acts in the presence of an aluminum catalyst such as Al(CH3)3 or Al[OCH(CH3)2]3 (Oppenauer oxidation).

[0276] The oxidation in the step (102) can be carried out in a solvent. As the above solvent, water and an organic solvent are preferable, and examples include water, a ketone, an ether, a halogenated hydrocarbon, an aromatic hydrocarbon, and a nitrile.

[0277] Examples of the above ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, etc., and among them, acetone is preferable.

[0278] Examples of the above ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc., and among them, diethyl ether and tetrahydrofuran are preferable.

[0279] Examples of the above halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc., and among them, dichloromethane and chloroform are preferable.

[0280] Examples of the aromatic hydrocarbon include benzene, toluene, xylene, etc., and among them, benzene and toluene are preferred.

[0281] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, etc., and among them, acetonitrile is preferred.

[0282] The oxidation temperature in step (102) is preferably -78 to 200 °C and can be appropriately selected according to the method adopted.

[0283] The oxidation pressure in step (102) is preferably 0 to 5.0 MPa and can be appropriately selected according to the method adopted.

[0284] The oxidation time in step (102) is preferably 0.1 to 72 hours and can be appropriately selected according to the method adopted.

[0285] Compound (70) can also be produced by a production method including a step (201) of subjecting a compound (200) represented by the formula:

Chemical formula

[0286] R 101 is preferably an alkyl group having 1 to 20 carbon atoms. Four R 101 may be the same or different.

[0287] The ozonolysis in step (201) can be carried out by allowing ozone to act on compound (200) and then performing post-treatment with a reducing agent.

[0288] Ozone can be generated by silent discharge in oxygen gas.

[0289] Examples of the reducing agent used in the post-treatment include zinc, dimethyl sulfide, thiourea, phosphines, etc., and among them, phosphines are preferred.

[0290] The ozonolysis in step (201) can be carried out in a solvent. Preferred solvents include water and organic solvents, and examples thereof include water, alcohols, carboxylic acids, ethers, halogenated hydrocarbons, aromatic hydrocarbons, etc.

[0291] Examples of the alcohol include methanol, ethanol, 1-propanol, isopropanol, etc., and among them, methanol and ethanol are preferred.

[0292] Examples of the carboxylic acids include acetic acid, propionic acid, etc., and among them, acetic acid is preferred.

[0293] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc., and among them, diethyl ether and tetrahydrofuran are preferred.

[0294] Examples of the halogenated hydrocarbons include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc., and among them, dichloromethane and chloroform are preferred.

[0295] Examples of the aromatic hydrocarbons include benzene, toluene, xylene, etc., and among them, benzene and toluene are preferred.

[0296] The temperature of the ozonolysis in step (201) is preferably -78 to 200°C, more preferably 0 to 150°C.

[0297] The pressure of the ozonolysis in step (201) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0298] The time for ozonolysis in the process (201) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0299] Compound (70) is also a compound of the formula:

Chemical formula

Chemical formula

Chemical formula

[0300] R 100 and R 102 The above alkyl group as is composed of R 100 R 102 -CH- as described above for R 11 .

[0301] The two R 100 may be the same or different. The two R 102 may be the same or different.

[0302] Epoxidation in step (301) can be carried out by reacting an epoxidizing agent with compound (300).

[0303] Examples of the epoxidizing agent include peracids such as meta-chloroperbenzoic acid (m-CPBA), perbenzoic acid, hydrogen peroxide, tert-butyl hydroperoxide, dimethyldioxirane, methyltrifluoromethyldioxirane, etc. Among them, peracids are preferred, and meta-chloroperbenzoic acid is more preferred. The epoxidizing agent can be used in an amount of 0.5 to 10.0 moles per mole of compound (300).

[0304] Epoxidation in step (301) can be carried out in a solvent. As the solvent, an organic solvent is preferred, and examples include ketones, ethers, halogenated hydrocarbons, aromatic hydrocarbons, nitriles, pyridine, nitrogen-containing polar organic compounds, dimethyl sulfoxide, etc. Among them, dichloromethane is preferred.

[0305] Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, etc. Among them, acetone is preferred.

[0306] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc. Among them, diethyl ether and tetrahydrofuran are preferred.

[0307] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc. Among them, dichloromethane and chloroform are preferred.

[0308] Examples of the aromatic hydrocarbon include benzene, toluene, xylene, etc. Among them, benzene and toluene are preferred.

[0309] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, etc. Among them, acetonitrile is preferred.

[0310] Examples of the nitrogen-containing polar organic compound include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, etc. Among them, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferred.

[0311] The temperature for epoxidation in step (301) is preferably -78 to 200 °C, more preferably -40 to 150 °C.

[0312] The pressure for epoxidation in step (301) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0313] The time for epoxidation in step (301) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0314] In step (302), the dialkylcopper lithium can be used in an amount of 0.5 to 10.0 moles per 1 mole of compound (301).

[0315] The reaction in step (302) can be carried out in a solvent. The solvent is preferably an organic solvent, and examples thereof include ether, halogenated hydrocarbon, aromatic hydrocarbon, etc.

[0316] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc. Among them, diethyl ether and tetrahydrofuran are preferred.

[0317] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc. Among them, dichloromethane and chloroform are preferred.

[0318] Examples of the aromatic hydrocarbon include benzene, toluene, xylene, etc. Among them, benzene and toluene are preferred.

[0319] The reaction temperature in step (302) is preferably -78 to 200°C, more preferably -40 to 150°C.

[0320] The reaction pressure in step (302) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0321] The reaction time in step (302) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0322] In step (303), examples of the method for oxidizing compound (302) include: (a) a method using Jones reagent (CrO3 / H2SO4) (Jones oxidation); (b) a method using Dess-Martin periodinane (DMP) (Dess-Martin oxidation); (c) a method using pyridinium chlorochromate (PCC); (d) a method in which a bleaching agent (about 5 to 6% aqueous solution of NaOCl) acts in the presence of a nickel compound such as NiCl2; (e) a method in which a hydrogen acceptor such as an aldehyde or a ketone acts in the presence of an aluminum catalyst such as Al(CH3)3 or Al[OCH(CH3)2]3 (Oppenauer oxidation).

[0323] The oxidation in step (303) can be carried out in a solvent. Preferred solvents include water and organic solvents, such as water, ketones, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, nitriles, etc.

[0324] Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, etc. Among them, acetone is preferred.

[0325] Examples of the alcohol include methanol, ethanol, 1-propanol, isopropanol, etc. Among them, methanol and ethanol are preferred.

[0326] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc. Among them, diethyl ether and tetrahydrofuran are preferred.

[0327] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc. Among them, dichloromethane and chloroform are preferred.

[0328] Examples of the aromatic hydrocarbon include benzene, toluene, xylene, etc. Among them, benzene and toluene are preferred.

[0329] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, etc. Among them, acetonitrile is preferred.

[0330] The temperature of the oxidation in step (303) is preferably -78 to 200 °C and can be appropriately selected according to the method employed.

[0331] The pressure of the oxidation in step (303) is preferably 0 to 5.0 MPa and can be appropriately selected according to the method employed.

[0332] The time of the oxidation in step (303) is preferably 0.1 to 72 hours and can be appropriately selected according to the method employed.

[0333] Compound (70) is also of the formula: [Chemical formula] (In the formula, R 10 and Y are as described above. R 100 is an alkyl group.) The compound (70) can be produced by a production method including a step (401) of oxidizing the compound (400) represented by the formula.

[0334] The oxidation in step (401) can be carried out by allowing an oxidizing agent to act on the compound (400) in the presence of water and a palladium compound.

[0335] Examples of the oxidizing agent include monovalent or divalent copper salts such as copper chloride, copper acetate, copper cyanide, and copper trifluoromethanethiolate; iron salts such as iron chloride, iron acetate, iron cyanide, iron trifluoromethanethiolate, and hexacyanoferrate; benzoquinones such as 1,4-benzoquinone, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, tetrachloro-1,2-benzoquinone, and tetrachloro-1,4-benzoquinone; H2O2, MnO2, KMnO4, RuO4, m-chloroperbenzoic acid, oxygen, etc., or combinations thereof. Among them, copper salts, iron salts, and benzoquinones are preferred, and copper chloride, iron chloride, and 1,4-benzoquinone are more preferred. The oxidizing agent can be used in an amount of 0.001 to 10 moles per 1 mole of the compound (400).

[0336] The amount of the water can be used in an amount of 0.5 to 1000 moles per 1 mole of the compound (400).

[0337] Examples of the palladium compound include palladium dichloride. The amount of the palladium compound may be a catalytic amount and can be used in an amount of 0.0001 to 1.0 mole per 1 mole of the compound (400).

[0338] The oxidation in the process (401) can be carried out in a solvent. Examples of the solvent include water, esters, aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, carboxylic acids, ethers, halogenated hydrocarbons, nitrogen-containing polar organic compounds, nitriles, dimethyl sulfoxide, and sulfolane.

[0339] Examples of the ester include ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy-2-acetoxypropane), etc. Among them, ethyl acetate is preferred.

[0340] Examples of the aliphatic hydrocarbon include hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, mineral spirit, etc. Among them, cyclohexane and heptane are preferred.

[0341] Examples of the aromatic hydrocarbon include benzene, toluene, xylene, etc. Among them, benzene and toluene are preferred.

[0342] Examples of the alcohol include methanol, ethanol, 1-propanol, isopropanol, etc.

[0343] Examples of the carboxylic acid include acetic acid, propionic acid, etc. Among them, acetic acid is preferred.

[0344] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc. Among them, diethyl ether and tetrahydrofuran are preferred.

[0345] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc. Among them, dichloromethane and chloroform are preferred.

[0346] Examples of the nitrogen-containing polar organic compound include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, etc. Among them, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferred.

[0347] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, etc. Among them, acetonitrile is preferred.

[0348] The temperature of the oxidation in step (401) is preferably -78 to 200°C, more preferably -20 to 150°C.

[0349] The pressure of the oxidation in step (401) is preferably 0 to 10 MPa, more preferably 0.1 to 5.0 MPa.

[0350] The time of the oxidation in step (401) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0351] Compound (100), compound (300), and compound (400) can be produced by a production method including a step (501) of reacting a reducing agent with an aldehyde represented by the formula:

Chemical formula

[0352] In step (501), the aldehyde dimerizes by a reductive coupling reaction to produce compound (100), compound (300), and compound (400). Examples of the reducing agent used in step (501) include samarium diiodide, titanium dichloride, vanadium trichloride, titanium tetrachloride, bis(cyclooctadiene)nickel, copper, magnesium, zinc, sodium, cerium trichloride, chromium oxide, triphenyltin hydride, etc. The above reducing agents may be used in combination. The amount of the reducing agent used is preferably 0.001 to 10 moles, more preferably 0.01 to 5 moles, and even more preferably 0.1 to 2 moles per 1 mole of the aldehyde.

[0353] The reaction in step (501) can be carried out in a solvent. As the above solvent, an organic solvent is preferred, and ether, halogenated hydrocarbon, pyridine, nitrile, aromatic hydrocarbon, etc. are more preferred.

[0354] Examples of the above ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc. Among them, diethyl ether and tetrahydrofuran are preferred.

[0355] Examples of the above halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc. Among them, dichloromethane and chloroform are preferred.

[0356] Examples of the above nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, etc. Among them, acetonitrile is preferred.

[0357] Examples of the above aromatic hydrocarbon include benzene, toluene, xylene, etc. Among them, benzene and toluene are preferred.

[0358] The reaction in step (501) is preferably carried out in the presence of an alcohol. Examples of the above alcohol include methanol, ethanol, isopropanol, etc.

[0359] As the temperature of the reaction in step (501), -78 to 200 °C is preferable, and -20 to 100 °C is more preferable.

[0360] As the pressure of the reaction in step (501), 0 to 5.0 MPa is preferable, and 0.1 to 1.0 MPa is more preferable.

[0361] As the reaction time in step (501), 0.1 to 72 hours is preferable, and 0.1 to 48 hours is more preferable.

[0362] In any of the above-described production methods, after the completion of each step, the solvent may be distilled off, or distillation, purification, etc. may be carried out to increase the purity of the obtained compound. Further, when the obtained compound is a compound in which M is H, such as -COOH, -SO3H, -OSO3H, etc., these groups can be converted into a salt form by contacting with an alkali such as sodium carbonate or ammonia.

[0363] Examples of the hydrocarbon surfactant also include a hydrocarbon surfactant having one or more carbonyl groups (excluding the carbonyl group in the carboxyl group). In addition, a hydrocarbon surfactant obtained by subjecting a hydrocarbon surfactant having one or more carbonyl groups (excluding the carbonyl group in the carboxyl group) to a radical treatment or an oxidation treatment can also be used. The above radical treatment may be a treatment for generating radicals in a hydrocarbon surfactant having one or more carbonyl groups (excluding the carbonyl group in the carboxyl group). For example, deionized water and a hydrocarbon surfactant are added to a reactor, the reactor is sealed, the system is purged with nitrogen, the reactor is heated and pressurized, a polymerization initiator is charged, and after stirring for a certain period of time, the reactor is depressurized until it reaches atmospheric pressure and then cooled. The above oxidation treatment is a treatment for adding an oxidizing agent to a hydrocarbon surfactant having one or more carbonyl groups (excluding the carbonyl group in the carboxyl group). Examples of the oxidizing agent include oxygen, ozone, hydrogen peroxide solution, manganese(IV) oxide, potassium permanganate, potassium dichromate, nitric acid, sulfur dioxide, and the like.

[0364] Examples of the hydrocarbon surfactant having one or more carbonyl groups (excluding the carbonyl group in the carboxyl group) include a surfactant represented by the formula: R-X (wherein R is a fluorine-free organic group having 1 to 2000 carbon atoms and having one or more carbonyl groups (excluding the carbonyl group in the carboxyl group), and X is -OSO3X 1 , -COOX 1 or -SO3X 1 (X 1 is H, a metal atom, NR 1 4, an optionally substituted imidazolium, an optionally substituted pyridinium or an optionally substituted phosphonium, and R 1 is H or an organic group, and they may be the same or different.)) is preferred. R preferably has 500 or fewer carbon atoms, more preferably 100 or fewer carbon atoms, still more preferably 50 or fewer carbon atoms, and even more preferably 30 or fewer carbon atoms. Examples of the above specific hydrocarbon surfactant include the following formula (a):

Chemical formula

Chemical formula

[0365] The surfactant (a) will be described.

[0366] In formula (a), R 1a is a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms. When the alkyl group has 3 or more carbon atoms, it may contain a carbonyl group (-C(=O)-) between two carbon atoms. Further, when the alkyl group has 2 or more carbon atoms, the terminal of the alkyl group may contain the carbonyl group. That is, an acyl group such as an acetyl group represented by CH3-C(=O)- is also included in the alkyl group. In addition, when the alkyl group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocyclic ring or may form a ring. As the heterocyclic ring, an unsaturated heterocyclic ring is preferable, and an oxygen-containing unsaturated heterocyclic ring is more preferable, and examples thereof include a furan ring. R 1a In, a divalent heterocyclic ring may be inserted between two carbon atoms, a divalent heterocyclic ring may be located at the terminal and bonded to -C(=O)-, or a monovalent heterocyclic ring may be located at the terminal of the alkyl group.

[0367] In this specification, the "number of carbon atoms" of the alkyl group shall include the number of carbon atoms constituting the carbonyl group and the number of carbon atoms constituting the heterocyclic ring. For example, a group represented by CH3-C(=O)-CH2- has 3 carbon atoms, a group represented by CH3-C(=O)-C2H4-C(=O)-C2H4- has 7 carbon atoms, and a group represented by CH3-C(=O)- has 2 carbon atoms.

[0368] The hydrogen atom bonded to the carbon atom of the alkyl group may be substituted by a functional group. For example, it may be substituted by a hydroxy group (-OH) or a monovalent organic group containing an ester bond, but it is preferably not substituted by any functional group. As the monovalent organic group containing an ester bond, a group represented by the formula: -O-C(=O)-R 101a (wherein R 101a is an alkyl group) is exemplified. The above alkyl group may have up to 75% of the hydrogen atoms bonded to carbon atoms substituted by halogen atoms, up to 50% of the hydrogen atoms bonded to carbon atoms substituted by halogen atoms, or up to 25% of the hydrogen atoms bonded to carbon atoms substituted by halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0369] In the formula, R 2a and R 3a are each independently a single bond or a divalent linking group. R 2a and R 3a are each independently preferably a single bond or a linear or branched alkylene group having 1 or more carbon atoms or a cyclic alkylene group having 3 or more carbon atoms. R 2a and R 3a The above alkylene group preferably does not contain a carbonyl group.

[0370] The above alkylene group may have the hydrogen atoms bonded to carbon atoms substituted by a functional group, for example, substituted by a hydroxy group (-OH) or a monovalent organic group containing an ester bond, but is preferably not substituted by any functional group. Examples of the above monovalent organic group containing an ester bond include a group represented by the formula: -O-C(=O)-R 102a (In the formula, R 102a is an alkyl group). The above alkylene group may have up to 75% of the hydrogen atoms bonded to carbon atoms substituted by halogen atoms, up to 50% of the hydrogen atoms bonded to carbon atoms substituted by halogen atoms, or up to 25% of the hydrogen atoms bonded to carbon atoms substituted by halogen atoms, but is preferably a non-halogenated alkylene group that does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0371] R 1a , R 2a and R 3aIt has a total carbon number of 6 or more. As the total carbon number, 8 or more is preferable, 9 or more is more preferable, 10 or more is still more preferable, 20 or less is preferable, 18 or less is more preferable, and 15 or less is still more preferable. R 1a , R 2a and R 3a Any two of them may be bonded to each other to form a ring.

[0372] In formula (a), X a is H, a metal atom, NR 4a 4, an optionally substituted imidazolium, an optionally substituted pyridinium or an optionally substituted phosphonium, and R 4a is H or an organic group. The four Rs 4a may be the same or different. As R 4a , H or an organic group having 1 to 10 carbon atoms is preferable, and H or an organic group having 1 to 4 carbon atoms is more preferable. Examples of the above metal atom include monovalent and divalent metal atoms, such as alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K or Li is preferable. X a is preferably H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 4a 4. Since it is easily soluble in water, H, Na, K, Li or NH4 is more preferable. Since it is even more easily soluble in water, Na, K or NH4 is still more preferable. Since Na or NH4 is particularly preferable and removal is easy, NH4 is most preferable. When X a is NH4, the surfactant has excellent solubility in an aqueous medium, and it is difficult for a metal component to remain in PTFE or the final product.

[0373] R 1a is preferably a linear or branched alkyl group having 1 to 8 carbon atoms and not containing a carbonyl group, a cyclic alkyl group having 3 to 8 carbon atoms and not containing a carbonyl group, a linear or branched alkyl group having 2 to 45 carbon atoms and containing 1 to 10 carbonyl groups, a cyclic alkyl group having 3 to 45 carbon atoms and containing a carbonyl group, or an alkyl group containing a monovalent or divalent heterocyclic ring having 3 to 45 carbon atoms.

[0374] Also, R 1a is represented by the following formula:

Chemical formula

[0375] n 11a is preferably an integer from 0 to 5, more preferably an integer from 0 to 3, and even more preferably an integer from 1 to 3.

[0376] R 11a The above alkyl group as R preferably does not contain a carbonyl group. R 11a The above alkyl group as R may have a hydrogen atom bonded to a carbon atom substituted by a functional group, for example, substituted by a hydroxy group (-OH) or a monovalent organic group containing an ester bond, but it is preferably not substituted by any functional group. Examples of the monovalent organic group containing the above ester bond include a group represented by the formula: -O-C(=O)-R 103a (In the formula, R 103a is an alkyl group). R 11a The above alkyl group as R may have 75% or less of the hydrogen atoms bonded to the carbon atoms substituted by halogen atoms, 50% or less substituted by halogen atoms, or 25% or less substituted by halogen atoms, but it is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0377] R 12ais an alkylene group having 0 to 3 carbon atoms. Among them, 1 to 3 carbon atoms are preferred. R 12a The alkylene group as R may be linear or branched. R 12a The alkylene group as R preferably does not contain a carbonyl group. R 12a More preferably, it is an ethylene group (-C2H4-) or a propylene group (-C3H6-). R 12a The hydrogen atom bonded to the carbon atom of the alkylene group as R may be substituted by a functional group. For example, it may be substituted by a hydroxy group (-OH) or a monovalent organic group containing an ester bond, but preferably it is not substituted by any functional group. Examples of the monovalent organic group containing an ester bond include a group represented by the formula: -O-C(=O)-R 104a (In the formula, R 104a is an alkyl group). R 12a Up to 75% of the hydrogen atoms bonded to the carbon atoms of the alkylene group as R may be substituted by halogen atoms, up to 50% may be substituted by halogen atoms, and up to 25% may be substituted by halogen atoms, but preferably it is a non-halogenated alkylene group that does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0378] R 2a and R 3a Preferably, they are independently alkylene groups having 1 or more carbon atoms that do not contain a carbonyl group, more preferably alkylene groups having 1 to 3 carbon atoms that do not contain a carbonyl group, and even more preferably an ethylene group (-C2H4-) or a propylene group (-C3H6-).

[0379] Examples of the surfactant (a) include the following surfactants. In each formula, X a is as described above.

[0380]

Chemical formula

[0381]

Chem.

[0382]

Chem.

[0383]

Chem.

[0384]

Chem.

[0385]

Chem.

[0386]

Chem.

[0387]

Chem.

[0388] Surfactant (a) is a novel compound and can be produced, for example, by the production methods exemplified below.

[0389] Surfactant (a) has the formula:

Chem.

[0390] R 1a When it contains a furan ring, for example, the furan ring may be opened with an acid and converted into a dicarbonyl derivative. Examples of the acid include acetic acid, hydrochloric acid, p-toluenesulfonic acid, etc., and among them, acetic acid is preferable.

[0391] In step (11a), it is preferable to react lithium and the above chlorosilane compound in advance to obtain a siloxylithium compound, and then react the siloxylithium compound with the compound (10a) to obtain the compound (11a).

[0392] E a represents a leaving group. Examples of the above leaving group include a tert-butyldimethylsilyl (TBS) group, a triethylsilyl (TES) group, a triisopropylsilyl (TIPS) group, a tert-butyldiphenylsilyl (TBDPS) group, a benzyl (Bn) group, etc.

[0393] R 21a is preferably a single bond or a linear or branched alkylene group having 1 or more carbon atoms.

[0394] Examples of the above chlorosilane compound include, for example,

Chemical formula

[0395] Any reaction in step (11a) can be carried out in a solvent. As the above solvent, an organic solvent is preferred, a non-protic polar solvent is more preferred, and an ether is even more preferred. As the above ether, 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), crown ether (15-crown-5, 18-crown-6), etc. can be mentioned. Among them, tetrahydrofuran and diethyl ether are preferred.

[0396] As the temperature of the reaction between lithium and the above chlorosilane compound in step (11a), 10 to 40 °C is preferred, and 20 to 30 °C is more preferred. As the temperature of the reaction between the above siloxylithium compound and compound (10a) in step (11a), -100 to 0 °C is preferred, and -80 to -50 °C is more preferred.

[0397] As the pressure of the reaction between lithium and the above chlorosilane compound in step (11a), 0.1 to 5 MPa is preferred, and 0.1 to 1 MPa is more preferred. As the pressure of the reaction between the above siloxylithium compound and compound (10a) in step (11a), 0.1 to 5 MPa is preferred, and 0.1 to 1 MPa is more preferred.

[0398] As the reaction time between lithium and the above chlorosilane compound in step (11a), 0.1 to 72 hours is preferred, and 6 to 10 hours is more preferred. As the reaction time between the above siloxylithium compound and compound (10a) in step (11a), 0.1 to 72 hours is preferred, and 1 to 2 hours is more preferred.

[0399] In step (12a), considering the improvement of the yield and the reduction of waste, the reaction ratio of compound (11a) to the above olefin is preferably 1 to 2 moles of the above olefin per 1 mole of compound (11a), and more preferably 1 to 1.1 moles.

[0400] The reaction in step (12a) can be carried out in a solvent in the presence of a thiazolium salt and a base.

[0401] Examples of the thiazolium salt include 3-ethyl-5-(2-hydroxyethyl)-4-methylthiazolium bromide, 3-benzyl-5-(2-hydroxyethyl)-4-methylthiazolium chloride, and the like.

[0402] Examples of the base include 1,8-diazabicyclo[5.4.0]-7-undecene, triethylamine, and the like.

[0403] As the solvent, an organic solvent is preferred, a non-protic polar solvent is more preferred, and an alcohol or an ether is even more preferred.

[0404] Examples of the alcohol include methanol, ethanol, 1-propanol, isopropanol, and the like.

[0405] Examples of the ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraglyme (tetraethylene glycol dimethyl ether), crown ether (15-crown-5, 18-crown-6), and the like. Among them, tetrahydrofuran and diethyl ether are preferred.

[0406] The reaction temperature in step (12a) is preferably 40 to 60°C, and more preferably 50 to 55°C.

[0407] As for the pressure of the reaction in step (12a), 0.1 to 5 MPa is preferable, and 0.1 to 1 MPa is more preferable.

[0408] As for the reaction time in step (12a), 0.1 to 72 hours is preferable, and 6 to 10 hours is more preferable.

[0409] The elimination reaction of the leaving group in step (13a) can be carried out by using fluoride ions or an acid. Examples of the method for eliminating the leaving group include a method using hydrofluoric acid, a method using an amine complex of hydrogen fluoride such as pyridine·nHF or triethylamine·nHF, a method using an inorganic salt such as cesium fluoride, potassium fluoride, lithium tetrafluoroborate (LiBF4), or ammonium fluoride, and a method using an organic salt such as tetrabutylammonium fluoride (TBAF).

[0410] The elimination reaction of the leaving group in step (13a) can be carried out in a solvent. As the above solvent, an organic solvent is preferable, an aprotic polar solvent is more preferable, and ether is even more preferable.

[0411] Examples of the above ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraglyme (tetraethylene glycol dimethyl ether), crown ether (15-crown-5, 18-crown-6), etc. Among them, tetrahydrofuran and diethyl ether are preferable.

[0412] As for the reaction temperature in step (13a), 0 to 40 °C is preferable, and 0 to 20 °C is more preferable.

[0413] As for the reaction pressure in step (13a), 0.1 to 5 MPa is preferable, and 0.1 to 1 MPa is more preferable.

[0414] The reaction time in step (13a) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0415] In step (14a), considering the improvement of the yield and the reduction of waste, the reaction ratio of compound (13a) and the above-mentioned sulfonic acid chloride is preferably 1 to 2 moles of the above-mentioned sulfonic acid chloride per 1 mole of compound (13a), and more preferably 1 to 1.1 moles.

[0416] The reaction in step (14a) is preferably carried out in the presence of a base. Examples of the base include alkali metal hydroxides, alkaline earth metal hydroxides, amines, etc. Among them, amines are preferred.

[0417] Examples of the amine in step (14a) include tertiary amines such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, dimethylbenzylamine, N,N,N’,N’-tetramethyl-1,8-naphthalenediamine, heteroaromatic amines such as pyridine, pyrrole, uracil, collidine, lutidine, and cyclic amines such as 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonene. Among them, triethylamine and pyridine are preferred.

[0418] Considering the improvement of the yield and the reduction of waste, the amount of the base used in step (14a) is preferably 1 to 2 moles per 1 mole of compound (13a), and more preferably 1 to 1.1 moles.

[0419] The reaction in step (14a) can be carried out in a polar solvent. The solvent is preferably an organic solvent, more preferably an aprotic polar solvent, and even more preferably an ether.

[0420] Examples of the ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraglyme (tetraethylene glycol dimethyl ether), crown ether (15-crown-5, 18-crown-6), etc. Among them, diethyl ether is preferred.

[0421] The reaction temperature in step (14a) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0422] The reaction pressure in step (14a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0423] The reaction time in step (14a) is preferably 0.1 to 72 hours, more preferably 3 to 12 hours.

[0424] When the reaction in step (14a) is carried out in a solvent, a solution containing compound (14a) can be obtained after the completion of the above reaction. After adding water to the above solution, it is allowed to stand and separated into two phases, the aqueous phase is recovered, and the solvent is distilled off to recover high-purity compound (14a). When compound (14a) has a group represented by -OSO3H (i.e., when X is H), it is also possible to convert -OSO3H to a sulfate group by using an alkaline aqueous solution such as an aqueous sodium hydrogen carbonate solution or aqueous ammonia instead of water.

[0425] After the completion of each step, the solvent may be distilled off, or distillation, purification, etc. may be carried out to increase the purity of the obtained compound.

[0426] Surfactant (a) also has the formula:

Chemical formula

Chem.

Chem.

Chem.

Chem.

Chem.

[0427] R 1aWhen it contains a furan ring, for example, the furan ring may be opened with an acid and converted into a dicarbonyl derivative. Examples of the acid include acetic acid, hydrochloric acid, p-toluenesulfonic acid, etc., and among them, acetic acid is preferable.

[0428] E a represents a leaving group. Examples of the above-mentioned leaving group include a tert-butyldimethylsilyl (TBS) group, a triethylsilyl (TES) group, a triisopropylsilyl (TIPS) group, a tert-butyldiphenylsilyl (TBDPS) group, a benzyl (Bn) group, etc.

[0429] R 22a is preferably a linear or branched alkyl group having 1 or more carbon atoms, and more preferably a methyl group. R 23a is preferably a linear or branched alkyl group having 1 or more carbon atoms, and more preferably a methyl group. R 24a is preferably a linear or branched alkylene group having 1 or more carbon atoms, and more preferably a methylene group (-CH2-).

[0430] The reaction in step (21a) can be carried out in a solvent in the presence of a base.

[0431] Examples of the above-mentioned base include sodium amide, sodium hydride, sodium methoxide, sodium ethoxide, etc.

[0432] As the above-mentioned solvent, an organic solvent is preferable, an aprotic polar solvent is more preferable, and alcohol and ether are even more preferable.

[0433] Examples of the above-mentioned alcohol include methanol, ethanol, 1-propanol, isopropanol, etc.

[0434] Examples of the ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraglyme (tetraethylene glycol dimethyl ether), crown ether (15-crown-5, 18-crown-6), etc. Among them, tetrahydrofuran and diethyl ether are preferred.

[0435] The reaction temperature in step (21a) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0436] The reaction pressure in step (21a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0437] The reaction time in step (21a) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0438] The elimination reaction of the leaving group in step (22a) can be carried out by using fluoride ions or an acid. Examples of the method for eliminating the leaving group include a method using hydrofluoric acid, a method using an amine complex of hydrogen fluoride such as pyridine·nHF or triethylamine·nHF, a method using an inorganic salt such as cesium fluoride, potassium fluoride, lithium tetrafluoroborate (LiBF4), ammonium fluoride, and a method using an organic salt such as tetrabutylammonium fluoride (TBAF).

[0439] The elimination reaction of the leaving group in step (22a) can be carried out in a solvent. The solvent is preferably an organic solvent, more preferably an aprotic polar solvent, and even more preferably an ether.

[0440] Examples of the ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraglyme (tetraethylene glycol dimethyl ether), crown ether (15-crown-5, 18-crown-6), etc. Among them, tetrahydrofuran and diethyl ether are preferred.

[0441] The reaction temperature in step (22a) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0442] The reaction pressure in step (22a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0443] The reaction time in step (22a) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0444] In step (23a), considering the improvement of the yield and the reduction of waste, the reaction ratio of compound (22a) to the above-mentioned sulfonic acid chloride is preferably 1 to 2 moles of the above-mentioned sulfonic acid chloride per 1 mole of compound (22a), more preferably 1 to 1.1 moles.

[0445] The reaction in step (23a) is preferably carried out in the presence of a base. Examples of the base include alkali metal hydroxides, alkaline earth metal hydroxides, amines, etc. Among them, amines are preferred.

[0446] Examples of the amine in step (23a) include tertiary amines such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, dimethylbenzylamine, N,N,N’,N’-tetramethyl-1,8-naphthalenediamine, heteroaromatic amines such as pyridine, pyrrole, uracil, collidine, lutidine, and cyclic amines such as 1,8-diazabicyclo[5.4.0]-7-undecene and 1,5-diazabicyclo[4.3.0]-5-nonene. Among them, triethylamine and pyridine are preferred.

[0447] In consideration of improving the yield and reducing waste, the amount of the base used in step (23a) is preferably 1 to 2 moles, more preferably 1 to 1.1 moles, per 1 mole of compound (22a).

[0448] The reaction in step (23a) can be carried out in a polar solvent. As the solvent, an organic solvent is preferred, a polar aprotic solvent is more preferred, and an ether is even more preferred.

[0449] Examples of the ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraglyme (tetraethylene glycol dimethyl ether), crown ether (15-crown-5, 18-crown-6), etc. Among them, diethyl ether is preferred.

[0450] The reaction temperature in step (23a) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0451] The reaction pressure in step (23a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0452] The reaction time in step (23a) is preferably 0.1 to 72 hours, more preferably 3 to 12 hours.

[0453] When the reaction in step (23a) is carried out in a solvent, a solution containing compound (23a) is obtained after the completion of the above reaction. After adding water to the above solution, it is allowed to stand and separated into two phases, the aqueous phase is recovered, and the solvent is distilled off to recover high-purity compound (23a). When compound (23a) has a group represented by -OSO3H (that is, when X is H), by using an alkaline aqueous solution such as an aqueous sodium hydrogen carbonate solution or aqueous ammonia instead of water, it is also possible to convert -OSO3H to a sulfate group.

[0454] After the completion of each step, the solvent may be distilled off, or distillation, purification, etc. may be carried out to increase the purity of the obtained compound.

[0455] Surfactant (a) is also represented by the formula: Y a -R 3a -OE a (In the formula, R 3a is as described above, Y a is a halogen atom, and E a is a leaving group.) is reacted with an alkyl halide represented by the formula:

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0456] When R 1a contains a furan ring, for example, the furan ring may be opened with an acid and converted into a dicarbonyl derivative. Examples of the acid include acetic acid, hydrochloric acid, p-toluenesulfonic acid, etc., and acetic acid is particularly preferred.

[0457] E a represents a leaving group. Examples of the above leaving group include a tert-butyldimethylsilyl (TBS) group, a triethylsilyl (TES) group, a triisopropylsilyl (TIPS) group, a tert-butyldiphenylsilyl (TBDPS) group, a benzyl (Bn) group, etc.

[0458] In step (31a), considering the improvement of the yield and the reduction of waste, the reaction ratio of the above alkyl halide to the above lithium acetylide is preferably 1 to 2 moles, more preferably 1 to 1.2 moles, of the above lithium acetylide per 1 mole of the above alkyl halide.

[0459] The reaction in step (31a) can be carried out in a solvent. As the above solvent, hexane is preferred.

[0460] As the temperature of the reaction in step (31a), -100 to -40 °C is preferred, and -80 to -50 °C is more preferred.

[0461] As the pressure of the reaction in step (31a), 0.1 to 5 MPa is preferred, and 0.1 to 1 MPa is more preferred.

[0462] As the reaction time of the reaction in step (31a), 0.1 to 72 hours is preferred, and 6 to 10 hours is more preferred.

[0463] The oxidation in step (32a) can be carried out in a nitrile solvent using a complex formed by treating [(Cn * )Ru III (CF3CO2)3]·H2O (wherein Cn * represents 1,4,7-trimethyl-1,4,7-triazabicyclononane) with (NH4)2Ce(NO3)6 and trifluoroacetic acid and then adding sodium perchlorate.

[0464] After completion of the oxidation, it may be neutralized with an alkali, and compound (32a) may be extracted using an organic solvent such as ether.

[0465] As the temperature of the reaction in step (32a), 30 to 100 °C is preferred, and 40 to 90 °C is more preferred.

[0466] As the pressure of the reaction in step (32a), 0.1 to 5 MPa is preferred, and 0.1 to 1 MPa is more preferred.

[0467] As the reaction time of the reaction in step (32a), 0.1 to 72 hours is preferred, and 3 to 8 hours is more preferred.

[0468] The elimination reaction of the leaving group in step (33a) can be carried out by using fluoride ions or an acid. Examples of methods for eliminating the leaving group include a method using hydrofluoric acid, a method using an amine complex of hydrogen fluoride such as pyridine·nHF or triethylamine·nHF, a method using an inorganic salt such as cesium fluoride, potassium fluoride, lithium tetrafluoroborate (LiBF4), or ammonium fluoride, and a method using an organic salt such as tetrabutylammonium fluoride (TBAF).

[0469] The elimination reaction of the leaving group in step (33a) can be carried out in a solvent. As the above solvent, an organic solvent is preferable, an aprotic polar solvent is more preferable, and ether is even more preferable.

[0470] Examples of the above ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraglyme (tetraethylene glycol dimethyl ether), crown ether (15-crown-5, 18-crown-6), etc. Among them, tetrahydrofuran and diethyl ether are preferable.

[0471] As the temperature of the reaction in step (33a), 0 to 40°C is preferable, and 0 to 20°C is more preferable.

[0472] As the pressure of the reaction in step (33a), 0.1 to 5 MPa is preferable, and 0.1 to 1 MPa is more preferable.

[0473] As the reaction time in step (33a), 0.1 to 72 hours is preferable, and 3 to 8 hours is more preferable.

[0474] In step (34a), considering the improvement of the yield and the reduction of waste, the reaction ratio of compound (33a) and the above-mentioned sulfonic acid chloride is preferably 1 to 2 moles, more preferably 1 to 1.1 moles of the above-mentioned sulfonic acid chloride per 1 mole of compound (33a).

[0475] The reaction in step (34a) is preferably carried out in the presence of a base. Examples of the above-mentioned base include alkali metal hydroxides, alkaline earth metal hydroxides, amines, etc. Among them, amines are preferred.

[0476] Examples of the above-mentioned amine in step (34a) include tertiary amines such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, dimethylbenzylamine, N,N,N’,N’-tetramethyl-1,8-naphthalenediamine, heteroaromatic amines such as pyridine, pyrrole, uracil, collidine, lutidine, and cyclic amines such as 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonene. Among them, triethylamine and pyridine are preferred.

[0477] Considering the improvement of the yield and the reduction of waste, the amount of the above-mentioned base used in step (34a) is preferably 1 to 2 moles, more preferably 1 to 1.1 moles per 1 mole of compound (33a).

[0478] The reaction in step (34a) can be carried out in a polar solvent. As the above-mentioned solvent, an organic solvent is preferred, a polar aprotic solvent is more preferred, and ether is even more preferred.

[0479] Examples of the ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraglyme (tetraethylene glycol dimethyl ether), crown ether (15-crown-5, 18-crown-6), etc. Among them, diethyl ether is preferred.

[0480] The reaction temperature in step (34a) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0481] The reaction pressure in step (34a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0482] The reaction time in step (34a) is preferably 0.1 to 72 hours, more preferably 3 to 12 hours.

[0483] When the reaction in step (34a) is carried out in a solvent, a solution containing compound (34a) can be obtained after the completion of the above reaction. After adding water to the above solution, it is allowed to stand and separated into two phases, the aqueous phase is recovered, and the solvent is distilled off to recover high-purity compound (34a). When compound (34a) has a group represented by -OSO3H (that is, when X is H), by using an alkaline aqueous solution such as an aqueous sodium hydrogen carbonate solution or aqueous ammonia instead of water, it is also possible to convert -OSO3H to a sulfate group.

[0484] After the completion of each step, the solvent may be distilled off, or distillation, purification, etc. may be carried out to increase the purity of the obtained compound.

[0485] The surfactant (a) also has the formula:

Chemical formula

Chem.

Chem.

Chem.

Chem.

[0486] When R 1a contains a furan ring, for example, the furan ring may be opened with an acid and converted into a dicarbonyl derivative. Examples of the acid include acetic acid, hydrochloric acid, p-toluenesulfonic acid, etc., and acetic acid is preferred among them.

[0487] As R 21a , a single bond or a linear or branched alkylene group having 1 or more carbon atoms is preferred.

[0488] In the step (41a), considering the improvement of the yield and the reduction of waste, the reaction ratio of the above-mentioned alkene to the above-mentioned alkyne is preferably 0.5 to 2 moles of the above-mentioned alkene per 1 mole of the above-mentioned alkyne, and more preferably 0.6 to 1.2 moles.

[0489] The reaction in step (41a) is preferably carried out in the presence of a metal catalyst. Examples of the above metal include ruthenium and the like.

[0490] Considering the improvement of yield and the reduction of waste, the amount of the above metal catalyst used in step (41a) is preferably 0.01 to 0.4 mol, more preferably 0.05 to 0.1 mol, per 1 mol of the above alkene.

[0491] The reaction in step (41a) can be carried out in a polar solvent. Examples of the above solvent include water, acetonitrile, dimethylacetamide, and dimethylformamide, which are preferred.

[0492] As the reaction temperature in step (41a), 20 to 160 °C is preferred, and 40 to 140 °C is more preferred.

[0493] As the reaction pressure in step (41a), 0.1 to 5 MPa is preferred, and 0.1 to 1 MPa is more preferred.

[0494] As the reaction time in step (41a), 0.1 to 72 hours is preferred, and 4 to 8 hours is more preferred.

[0495] In step (42a), considering the improvement of yield and the reduction of waste, the reaction ratio of compound (41a) to the above sulfonyl chloride is preferably 1 to 2 mol, more preferably 1 to 1.1 mol, of the above sulfonyl chloride per 1 mol of compound (41a).

[0496] The reaction in step (42a) is preferably carried out in the presence of a base. Examples of the above base include alkali metal hydroxides, alkaline earth metal hydroxides, amines, etc., and among them, amines are preferred.

[0497] Examples of the amine in step (42a) include tertiary amines such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, dimethylbenzylamine, N,N,N’,N’-tetramethyl-1,8-naphthalenediamine, heteroaromatic amines such as pyridine, pyrrole, uracil, collidine, lutidine, and cyclic amines such as 1,8-diazabicyclo[5.4.0]-7-undecene and 1,5-diazabicyclo[4.3.0]-5-nonene. Among them, triethylamine and pyridine are preferred.

[0498] Considering the improvement of yield and the reduction of waste, the amount of the base used in step (42a) is preferably 1 to 2 moles, more preferably 1 to 1.1 moles, per 1 mole of compound (41a).

[0499] The reaction in step (42a) can be carried out in a polar solvent. As the solvent, an organic solvent is preferred, a aprotic polar solvent is more preferred, and ether is even more preferred.

[0500] Examples of the ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraglyme (tetraethylene glycol dimethyl ether), crown ether (15-crown-5, 18-crown-6), etc. Among them, diethyl ether is preferred.

[0501] The reaction temperature in step (42a) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0502] The reaction pressure in step (42a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0503] The reaction time in step (42a) is preferably 0.1 to 72 hours, more preferably 3 to 12 hours.

[0504] When the reaction in step (42a) is carried out in a solvent, a solution containing compound (42a) can be obtained after the completion of the above reaction. After adding water to the above solution, it is allowed to stand and separated into two phases, the aqueous phase is recovered, and the solvent is distilled off, whereby high-purity compound (42a) may be recovered. When compound (42a) has a group represented by -OSO3H (i.e., when X is H), it is also possible to convert -OSO3H to a sulfate group by using an alkaline aqueous solution such as an aqueous sodium hydrogen carbonate solution or aqueous ammonia instead of water.

[0505] After the completion of each step, the solvent may be distilled off, or distillation, purification, etc. may be carried out to increase the purity of the obtained compound.

[0506] Next, surfactant (b) will be described.

[0507] In formula (b), R 1b is a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent. When the above alkyl group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocyclic ring, or may form a ring. As the above heterocyclic ring, an unsaturated heterocyclic ring is preferable, and an oxygen-containing unsaturated heterocyclic ring is more preferable, and examples thereof include a furan ring. In R 1b , a divalent heterocyclic ring may be inserted between two carbon atoms, a divalent heterocyclic ring may be located at the terminal and bonded to -C(=O)-, or a monovalent heterocyclic ring may be located at the terminal of the above alkyl group.

[0508] In the present specification, the "number of carbon atoms" of the above alkyl group shall include the number of carbon atoms constituting the above heterocyclic ring.

[0509] R 1bThe above-mentioned substituent which the above-mentioned alkyl group may have is preferably a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, or a hydroxy group, and particularly preferably a methyl group or an ethyl group.

[0510] R 1b The above-mentioned alkyl group is preferably free of a carbonyl group. Up to 75% of the hydrogen atoms bonded to the carbon atoms of the above-mentioned alkyl group may be substituted by halogen atoms, up to 50% may be substituted by halogen atoms, and up to 25% may be substituted by halogen atoms, but it is preferably a non-halogenated alkyl group free of halogen atoms such as fluorine atoms and chlorine atoms. The above-mentioned alkyl group preferably has no substituents.

[0511] R 1b Preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent or a cyclic alkyl group having 3 to 10 carbon atoms which may have a substituent, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms free of a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms free of a carbonyl group, still more preferably a linear or branched alkyl group having 1 to 10 carbon atoms having no substituents, still more preferably a linear or branched alkyl group having 1 to 3 carbon atoms having no substituents, particularly preferably a methyl group (-CH3) or an ethyl group (-C2H5), and most preferably a methyl group (-CH3).

[0512] In formula (b), R 2b and R 4b are each independently H or a substituent. A plurality of R 2b and R 4b may be the same or different from each other.

[0513] R 2b and R 4bAs the above-mentioned substituents, a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, or a hydroxy group is preferable, and a methyl group or an ethyl group is particularly preferable.

[0514] R 2b and R 4b As the above-mentioned alkyl group, it is preferably free of a carbonyl group. Up to 75% of the hydrogen atoms bonded to the carbon atoms of the above-mentioned alkyl group may be substituted by halogen atoms, up to 50% may be substituted by halogen atoms, and up to 25% may be substituted by halogen atoms, but it is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms. The above-mentioned alkyl group preferably has no substituents.

[0515] R 2b and R 4b As the above-mentioned alkyl group, a linear or branched alkyl group having 1 to 10 carbon atoms that does not contain a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms that does not contain a carbonyl group is preferable, a linear or branched alkyl group having 1 to 10 carbon atoms that does not contain a carbonyl group is more preferable, a linear or branched alkyl group having 1 to 3 carbon atoms that has no substituents is still more preferable, and a methyl group (-CH3) or an ethyl group (-C2H5) is particularly preferable.

[0516] R 2b and R 4b Independently, H or a linear or branched alkyl group having 1 to 10 carbon atoms that does not contain a carbonyl group is preferable, H or a linear or branched alkyl group having 1 to 3 carbon atoms that has no substituents is more preferable, H, a methyl group (-CH3) or an ethyl group (-C2H5) is even more preferable, and H is particularly preferable.

[0517] In formula (b), R 3b is an alkylene group having 1 to 10 carbon atoms which may have substituents. R 3bWhen multiple are present, they may be the same or different.

[0518] The alkylene group preferably does not contain a carbonyl group. The alkylene group may have 75% or less of the hydrogen atoms bonded to carbon atoms substituted with halogen atoms, 50% or less of the hydrogen atoms substituted with halogen atoms, or 25% or less of the hydrogen atoms substituted with halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms. The alkylene group preferably does not have any substituents.

[0519] The alkylene group is preferably a linear or branched alkylene group having 1 to 10 carbon atoms which may have a substituent, or a cyclic alkylene group having 3 to 10 carbon atoms which may have a substituent, more preferably a linear or branched alkylene group having 1 to 10 carbon atoms which does not contain a carbonyl group, or a cyclic alkylene group having 3 to 10 carbon atoms which does not contain a carbonyl group, and even more preferably a linear or branched alkylene group having 1 to 10 carbon atoms which does not have a substituent, and even more preferably a methylene group (-CH2-), an ethylene group (-C2H4-), an isopropylene group (-CH(CH3)CH2-) or a propylene group (-C3H6-).

[0520] R 1b , R 2b , R 3b and R 4b may be bonded to each other to form a ring, but it is preferable that they do not form a ring.

[0521] In formula (b), n is an integer of 1 or more. n is preferably an integer of 1 to 40, more preferably an integer of 1 to 30, still more preferably an integer of 5 to 25, and particularly preferably an integer of 5 to 9 or 11 to 25.

[0522] In formula (b), p and q are each independently an integer of 0 or more. As p, an integer of 0 to 10 is preferable, and 0 or 1 is more preferable. As q, an integer of 0 to 10 is preferable, and an integer of 0 to 5 is more preferable.

[0523] n, p and q are preferably integers whose total is 5 or more. The total of n, p and q is more preferably an integer of 8 or more. The total of n, p and q is also preferably an integer of 60 or less, more preferably an integer of 50 or less, and still more preferably an integer of 40 or less.

[0524] In formula (b), X b is H, a metal atom, NR 5b 4, an optionally substituted imidazolium, an optionally substituted pyridinium or an optionally substituted phosphonium, and R 5b is H or an organic group. The four Rs 5b may be the same or different. As R 5b , H or an organic group having 1 to 10 carbon atoms is preferable, and H or an organic group having 1 to 4 carbon atoms is more preferable. Examples of the above metal atom include monovalent and divalent metal atoms, such as alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K or Li is preferable. X b is a metal atom or NR 5b 4 (R 5b is as described above) may be. X b is preferably H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 5b 4. Since it is easily soluble in water, H, Na, K, Li or NH4 is more preferable. Since it is more easily soluble in water, Na, K or NH4 is still more preferable. Since Na or NH4 is particularly preferable and removal is easy, NH4 is most preferable. When X b is NH4, the surfactant has excellent solubility in an aqueous medium, and metal components are less likely to remain in PTFE or the final product.

[0525] In formula (b), L is a single bond, -CO2-B-*, -OCO-B-*, -CONR6b -B-*, -NR 6b CO-B-*, or, -CO- (however, -CO2-B-, -OCO-B-, -CONR 6b -B-, -NR 6 excluding the carbonyl group contained in CO-B-.), where B is an alkylene group having 1 to 10 carbon atoms which may have a single bond or a substituent, and R 6b is H or an alkyl group having 1 to 4 carbon atoms which may have a substituent. The alkylene group preferably has 1 to 5 carbon atoms. Also, the above R 6 is more preferably H or a methyl group. * indicates the side bonded to -OSO3X b in the formula.

[0526] L is preferably a single bond.

[0527] As the surfactant (b), the following formula:

Chemical formula

[0528] The above surfactant (b) 1 In the 1H-NMR spectrum, the integrated value of the total peak intensity observed in the region of chemical shift 2.0 to 5.0 ppm is preferably 10% or more.

[0529] The above surfactant (b) 1 In the 1H-NMR spectrum, the integrated value of the total peak intensity observed in the region of chemical shift 2.0 to 5.0 ppm is preferably within the above range. In this case, the above surfactant preferably has a ketone structure in the molecule.

[0530] In the above surfactant (b), the integrated value is more preferably 15 or more, preferably 95 or less, more preferably 80 or less, and even more preferably 70 or less

[0531] The above integral value is measured at room temperature in a heavy water solvent. The heavy water is set to 4.79 ppm.

[0532] As the surfactant (b), for example, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2OSO3Na, (CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2OSO3Na, CH3CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2OSO3Na, CH3CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2OSO3Na, CH3CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2OSO3Na, CH3CH2CH2CH2CH2CH2CH2CH2CH2C(O)CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OCH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OC(O)CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3H, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Li, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3K, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3NH4, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH(CH3)2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, (CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OCH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OC(O)CH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3H, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Li, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3K, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3NH4, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na etc. can be mentioned.

[0533] Surfactant (b) is a novel compound and can be produced, for example, by the production methods exemplified below.

[0534] Surfactant (b) has the following formula: R 11b-CH=CH-(CR 2b 2) n -(OR 3b ) p -(CR 4b 2) q -L-OH (In the formula, R 2b ~R 4b , n, p, and q are as described above. R 11b is H, a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent. When the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocyclic ring or form a ring. L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6b -B-*, -NR 6b CO-B-*, or -CO- (however, excluding the carbonyl groups contained in -CO2-B-, -OCO-B-, -CONR 6b -B-, -NR 6b CO-B-). B is a single bond or an alkylene group having 1 to 10 carbon atoms which may have a substituent, and R 6b is H or an alkyl group having 1 to 4 carbon atoms which may have a substituent. * indicates the side bonded to -OH in the formula.) Hydroxylating the compound (10b) represented by the following formula:

Chemical formula

Chemical formula

Chemical formula

[0535] R 11b The above alkyl group as R preferably does not contain a carbonyl group. R 11b Up to 75% of the hydrogen atoms bonded to the carbon atoms of the above alkyl group as R may be substituted by halogen atoms, up to 50% may be substituted by halogen atoms, and up to 25% may be substituted by halogen atoms, but it is preferably a non-halogenated alkyl group not containing halogen atoms such as fluorine atoms and chlorine atoms. The above alkyl group preferably has no substituents.

[0536] R 11b As R, H, a linear or branched alkyl group having 1 to 9 carbon atoms which may have a substituent, or a cyclic alkyl group having 3 to 9 carbon atoms which may have a substituent is preferable, H, a linear or branched alkyl group having 1 to 9 carbon atoms not containing a carbonyl group or a cyclic alkyl group having 3 to 9 carbon atoms not containing a carbonyl group is more preferable, H, or a linear or branched alkyl group having 1 to 9 carbon atoms having no substituent is even more preferable, H, a methyl group (-CH3) or an ethyl group (-C2H5) is even more preferable, H or a methyl group (-CH3) is particularly preferable, and H is most preferable.

[0537] The hydroxylation in the step (11b) can be carried out, for example, by (1) a method of allowing iron(II) phthalocyanine (Fe(Pc)) and sodium borohydride to act on the compound (10b) in an oxygen atmosphere, or (2) a method of allowing isopinocampheylborane (IpcBH2) to act on the compound (10b) and then oxidizing the resulting intermediate (dialkylborane).

[0538] In method (1), the amount of iron(II) phthalocyanine may be a catalytic amount and can be used in an amount of 0.001 to 1.2 moles per mole of compound (10b).

[0539] In method (1), sodium borohydride can be used in an amount of 0.5 to 20 moles per mole of compound (10b).

[0540] The reaction of method (1) can be carried out in a solvent. As the above solvent, an organic solvent is preferred, and examples thereof include ether, halogenated hydrocarbon, aromatic hydrocarbon, nitrile, nitrogen-containing polar organic compound, etc.

[0541] Examples of the above ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc. Among them, diethyl ether and tetrahydrofuran are preferred.

[0542] Examples of the above halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc. Among them, dichloromethane and chloroform are preferred.

[0543] Examples of the above aromatic hydrocarbon include benzene, toluene, xylene, etc. Among them, benzene and toluene are preferred.

[0544] Examples of the above nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, etc. Among them, acetonitrile is preferred.

[0545] Examples of the above nitrogen-containing polar organic compound include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, etc. Among them, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferred.

[0546] As for the reaction temperature of method (1), -78 to 200 °C is preferable, and 0 to 150 °C is more preferable.

[0547] As for the reaction pressure of method (1), 0 to 5.0 MPa is preferable, and 0.1 to 1.0 MPa is more preferable.

[0548] As for the reaction time of method (1), 0.1 to 72 hours is preferable, and 0.1 to 48 hours is more preferable.

[0549] In method (2), isopinocampheylborane can be used in an amount of 1.0 to 10.0 moles per 1 mole of compound (10b).

[0550] The reaction between compound (10b) and isopinocampheylborane can be carried out in a solvent. As the above solvent, an organic solvent is preferable, and examples thereof include ether, halogenated hydrocarbon, aromatic hydrocarbon, etc.

[0551] Examples of the above ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc. Among them, diethyl ether and tetrahydrofuran are preferable.

[0552] Examples of the above halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc. Among them, dichloromethane and chloroform are preferable.

[0553] Examples of the above aromatic hydrocarbon include benzene, toluene, xylene, etc. Among them, benzene and toluene are preferable.

[0554] As for the reaction temperature between compound (10b) and isopinocampheylborane, -78 to 200 °C is preferable, and 0 to 150 °C is more preferable.

[0555] As for the reaction pressure between compound (10b) and isopinocampheylborane, 0 to 5.0 MPa is preferable, and 0.1 to 1.0 MPa is more preferable.

[0556] As for the reaction time between compound (10b) and isopinocampheylborane, 0.1 to 72 hours is preferable, and 0.1 to 48 hours is more preferable.

[0557] The oxidation in method (2) can be carried out by allowing an oxidizing agent to act on the above intermediate. Examples of the oxidizing agent include hydrogen peroxide. The oxidizing agent can be used in an amount of 0.7 to 10 moles per 1 mole of the above intermediate.

[0558] The oxidation in method (2) can be carried out in a solvent. Examples of the solvent include water, methanol, ethanol, etc., and water is preferable among them.

[0559] As for the temperature of the oxidation in method (2), 0 to 100 °C is preferable, and 0 to 80 °C is more preferable.

[0560] As for the pressure of the oxidation in method (2), 0 to 5.0 MPa is preferable, and 0.1 to 1.0 MPa is more preferable.

[0561] As for the time of the oxidation in method (2), 0.1 to 72 hours is preferable, and 0.1 to 48 hours is more preferable.

[0562] In step (12b), examples of the method for oxidizing compound (11b) include (a) a method using Jones reagent (CrO3 / H2SO4) (Jones oxidation), (b) a method using Dess-Martin periodinane (DMP) (Dess-Martin oxidation), (c) a method using pyridinium chlorochromate (PCC), (d) a method of allowing a bleaching agent (about 5 to 6% aqueous solution of NaOCl) to act in the presence of a nickel compound such as NiCl2, and (e) a method of allowing a hydrogen acceptor such as an aldehyde or a ketone to act in the presence of an aluminum catalyst such as Al(CH3)3 or Al[OCH(CH3)2]3 (Oppenauer oxidation).

[0563] The oxidation in step (12b) can be carried out in a solvent. Preferred solvents include water and organic solvents, such as water, ketones, ethers, halogenated hydrocarbons, aromatic hydrocarbons, nitriles, etc.

[0564] Examples of the ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, etc. Among them, acetone is preferred.

[0565] Examples of the ethers include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc. Among them, diethyl ether and tetrahydrofuran are preferred.

[0566] Examples of the halogenated hydrocarbons include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc. Among them, dichloromethane and chloroform are preferred.

[0567] Examples of the aromatic hydrocarbons include benzene, toluene, xylene, etc. Among them, benzene and toluene are preferred.

[0568] Examples of the nitriles include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, etc. Among them, acetonitrile is preferred.

[0569] The temperature for the oxidation in step (12b) is preferably -78 to 200 °C and can be appropriately selected according to the method adopted.

[0570] The pressure for the oxidation in step (12b) is preferably 0 to 5.0 MPa and can be appropriately selected according to the method adopted.

[0571] The time for the oxidation in step (12b) is preferably 0.1 to 72 hours and can be appropriately selected according to the method adopted.

[0572] The sulfation in step (13b) can be carried out by reacting compound (12b) with a sulfating reagent. Examples of the sulfating reagent include sulfur trioxide amine complexes such as sulfur trioxide pyridine complex, sulfur trioxide trimethylamine complex, and sulfur trioxide triethylamine complex; sulfur trioxide amide complexes such as sulfur trioxide dimethylformamide complex; sulfuric acid - dicyclohexylcarbodiimide, chlorosulfuric acid, concentrated sulfuric acid, sulfamic acid, and the like. The amount of the sulfating reagent used is preferably 0.5 to 10 moles, more preferably 0.5 to 5 moles, and even more preferably 0.7 to 4 moles per mole of compound (12b).

[0573] The sulfation in step (13b) can be carried out in a solvent. The solvent is preferably an organic solvent, and examples thereof include ether, halogenated hydrocarbon, aromatic hydrocarbon, pyridine, dimethyl sulfoxide, sulfolane, nitrile, and the like.

[0574] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc. Among them, diethyl ether and tetrahydrofuran are preferred.

[0575] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, o - dichlorobenzene, etc. Among them, dichloromethane and chloroform are preferred.

[0576] Examples of the aromatic hydrocarbon include benzene, toluene, xylene, etc. Among them, benzene and toluene are preferred.

[0577] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, etc. Among them, acetonitrile is preferred.

[0578] The temperature of the sulfation in step (13b) is preferably - 78 to 200 °C, and more preferably - 20 to 150 °C.

[0579] As the pressure for sulfation in step (13b), 0 to 10 MPa is preferable, and 0.1 to 5 MPa is more preferable.

[0580] As the time for sulfation in step (13b), 0.1 to 72 hours is preferable, and 0.1 to 48 hours is more preferable.

[0581] The surfactant (b) is also a compound represented by the following formula:

Chemical formula

Chemical formula

Chemical formula

[0582] R 101b is preferably an alkyl group having 1 to 20 carbon atoms. Two R 101b may be the same or different.

[0583] The ozonolysis in step (21b) can be carried out by allowing ozone to act on the compound (20b) and then performing post-treatment with a reducing agent.

[0584] Ozone can be generated by silent discharge in oxygen gas.

[0585] Examples of the reducing agent used in the post-treatment include zinc, dimethyl sulfide, thiourea, phosphines, etc. Among them, phosphines are preferred.

[0586] The ozone decomposition in step (21b) can be carried out in a solvent. Preferred solvents include water and organic solvents, such as water, alcohol, carboxylic acids, ethers, halogenated hydrocarbons, aromatic hydrocarbons, etc.

[0587] Examples of the alcohol include methanol, ethanol, 1-propanol, isopropanol, etc. Among them, methanol and ethanol are preferred.

[0588] Examples of the carboxylic acids include acetic acid, propionic acid, etc. Among them, acetic acid is preferred.

[0589] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc. Among them, diethyl ether and tetrahydrofuran are preferred.

[0590] Examples of the halogenated hydrocarbons include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc. Among them, dichloromethane and chloroform are preferred.

[0591] Examples of the aromatic hydrocarbons include benzene, toluene, xylene, etc. Among them, benzene and toluene are preferred.

[0592] The temperature of the ozone decomposition in step (21b) is preferably -78 to 200 °C, more preferably 0 to 150 °C.

[0593] The pressure of the ozone decomposition in step (21b) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0594] As the time for ozonolysis in step (21b), 0.1 to 72 hours is preferable, and 0.1 to 48 hours is more preferable.

[0595] The sulfation in step (22b) can be carried out by reacting compound (21b) with a sulfating reagent, and the same conditions as those in the sulfation in step (13b) can be adopted.

[0596] Surfactant (b) is also represented by the following formula: R 21b -CH=CH-(CR 2b 2) n -(OR 3b ) p -(CR 4b 2) q -L-OH (In the formula, L, R 2b ~R 4b , n, p, and q are as described above. R 21b is H, a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent. When the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocyclic ring or form a ring.) The compound (30b) represented by the formula is epoxidized to obtain a compound (31b) represented by the following formula:

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0597] R 21b The above alkyl group as R preferably does not contain a carbonyl group. R 21b The above alkyl group as R may have 75% or less of the hydrogen atoms bonded to the carbon atoms substituted by halogen atoms, 50% or less substituted by halogen atoms, or 25% or less substituted by halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms. The above alkyl group preferably has no substituents.

[0598] R 21bExamples thereof include H, a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, or a cyclic alkyl group having 3 to 8 carbon atoms which may have a substituent. H, a linear or branched alkyl group having 1 to 8 carbon atoms that does not contain a carbonyl group or a cyclic alkyl group having 3 to 8 carbon atoms that does not contain a carbonyl group are more preferable. H, or a linear or branched alkyl group having 1 to 8 carbon atoms that has no substituent is even more preferable. H or a methyl group (-CH3) is particularly preferable, and H is most preferable.

[0599] R 22b The above alkyl group as [the group represented by R] preferably does not contain a carbonyl group. R 22b Up to 75% of the hydrogen atoms bonded to the carbon atoms of the above alkyl group as [the group represented by R] may be substituted by halogen atoms, up to 50% may be substituted by halogen atoms, and up to 25% may be substituted by halogen atoms, but it is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms. The above alkyl group preferably has no substituents.

[0600] R 22b Examples thereof include a linear or branched alkyl group having 1 to 9 carbon atoms which may have a substituent, or a cyclic alkyl group having 3 to 9 carbon atoms which may have a substituent. A linear or branched alkyl group having 1 to 9 carbon atoms that does not contain a carbonyl group or a cyclic alkyl group having 3 to 9 carbon atoms that does not contain a carbonyl group are more preferable. A linear or branched alkyl group having 1 to 9 carbon atoms that has no substituent is even more preferable. A methyl group (-CH3) or an ethyl group (-C2H5) is particularly preferable, and a methyl group (-CH3) is most preferable.

[0601] Two Rs 22b may be the same or different.

[0602] R 21b and R 22bIt is preferably 1 to 7 in total carbon atoms, more preferably 1 to 2, and most preferably 1.

[0603] Epoxidation in step (31b) can be carried out by allowing an epoxidizing agent to act on compound (30b).

[0604] Examples of the epoxidizing agent include peracids such as m-chloroperbenzoic acid (m-CPBA), perbenzoic acid, hydrogen peroxide, tert-butyl hydroperoxide, dimethyldioxirane, methyltrifluoromethyldioxirane, etc. Among them, peracids are preferred, and m-chloroperbenzoic acid is more preferred. The epoxidizing agent can be used in an amount of 0.5 to 10.0 moles per 1 mole of compound (30b).

[0605] Epoxidation in step (31b) can be carried out in a solvent. As the solvent, an organic solvent is preferred, and examples include ketones, ethers, halogenated hydrocarbons, aromatic hydrocarbons, nitriles, pyridine, nitrogen-containing polar organic compounds, dimethyl sulfoxide, etc. Among them, dichloromethane is preferred.

[0606] Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, etc. Among them, acetone is preferred.

[0607] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc. Among them, diethyl ether and tetrahydrofuran are preferred.

[0608] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc. Among them, dichloromethane and chloroform are preferred.

[0609] Examples of the aromatic hydrocarbon include benzene, toluene, xylene, etc. Among them, benzene and toluene are preferred.

[0610] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, etc. Among them, acetonitrile is preferred.

[0611] Examples of the nitrogen-containing polar organic compound include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, etc. Among them, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferred.

[0612] The temperature of the epoxidation in step (31b) is preferably -78 to 200°C, more preferably -40 to 150°C.

[0613] The pressure of the epoxidation in step (31b) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0614] The time of the epoxidation in step (31b) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0615] In step (32b), the dialkylcopper lithium can be used in an amount of 0.5 to 10.0 moles per 1 mole of compound (31b).

[0616] The reaction in step (32b) can be carried out in a solvent. The solvent is preferably an organic solvent, and examples include ether, halogenated hydrocarbon, aromatic hydrocarbon, etc.

[0617] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc. Among them, diethyl ether and tetrahydrofuran are preferred.

[0618] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc. Among them, dichloromethane and chloroform are preferred.

[0619] Examples of the aromatic hydrocarbon include benzene, toluene, xylene, etc. Among them, benzene and toluene are preferred.

[0620] The reaction temperature in step (32b) is preferably -78 to 200°C, more preferably -40 to 150°C.

[0621] The reaction pressure in step (32b) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0622] The reaction time in step (32b) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0623] In step (33b), examples of the method for oxidizing compound (32b) include: (a) a method using Jones reagent (CrO3 / H2SO4) (Jones oxidation); (b) a method using Dess-Martin periodinane (DMP) (Dess-Martin oxidation); (c) a method using pyridinium chlorochromate (PCC); (d) a method of allowing a bleaching agent (about 5 to 6% aqueous solution of NaOCl) to act in the presence of a nickel compound such as NiCl2; (e) a method of allowing a hydrogen acceptor such as an aldehyde or a ketone to act in the presence of an aluminum catalyst such as Al(CH3)3 or Al[OCH(CH3)2]3 (Oppenauer oxidation).

[0624] The oxidation in step (33b) can be carried out in a solvent. Preferred solvents include water and organic solvents, and examples include water, ketones, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, nitriles, etc.

[0625] Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, etc. Among them, acetone is preferred.

[0626] Examples of the alcohol include methanol, ethanol, 1-propanol, isopropanol, etc. Among them, methanol and ethanol are preferred.

[0627] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc. Among them, diethyl ether and tetrahydrofuran are preferred.

[0628] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc. Among them, dichloromethane and chloroform are preferred.

[0629] Examples of the aromatic hydrocarbon include benzene, toluene, xylene, etc. Among them, benzene and toluene are preferred.

[0630] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, etc. Among them, acetonitrile is preferred.

[0631] The temperature of the oxidation in step (33b) is preferably -78 to 200 °C and can be appropriately selected according to the method employed.

[0632] The pressure of the oxidation in step (33b) is preferably 0 to 5.0 MPa and can be appropriately selected according to the method employed.

[0633] The time of the oxidation in step (33b) is preferably 0.1 to 72 hours and can be appropriately selected according to the method employed.

[0634] The sulfation in step (34b) can be carried out by reacting compound (33b) with a sulfating reagent, and the same conditions as those in step (13b) can be adopted.

[0635] Surfactant (b) can also be represented by the following formula: R 11b -CH=CH-(CR 2b 2) n -(OR 3b ) p -(CR 4b 2) q -L-OH (In the formula, L, R 2b ~R 4b , R 11b , n, p and q are as defined above.) Oxidize compound (10b) to obtain a compound (41b) represented by the following formula:

Chemical formula

Chemical formula

[0636] The oxidation in step (41b) can be carried out by allowing an oxidizing agent to act on compound (10b) in the presence of water and a palladium compound.

[0637] Examples of the above-mentioned oxidizing agent include monovalent or divalent copper salts such as copper chloride, copper acetate, copper cyanide, and copper trifluoromethanethiolate; iron salts such as iron chloride, iron acetate, iron cyanide, iron trifluoromethanethiolate, and hexacyanoferrate; benzoquinones such as 1,4-benzoquinone, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, tetrachloro-1,2-benzoquinone, and tetrachloro-1,4-benzoquinone; H2O2, MnO2, KMnO4, RuO4, m-chloroperbenzoic acid, oxygen, etc. Among them, copper salts, iron salts, and benzoquinones are preferred, and copper chloride, iron chloride, and 1,4-benzoquinone are more preferred. The above-mentioned oxidizing agent can be used in an amount of 0.001 to 10 moles per mole of the compound (10b).

[0638] The above-mentioned water can be used in an amount of 0.5 to 1000 moles per mole of the compound (10b).

[0639] Examples of the above-mentioned palladium compound include palladium dichloride. The amount of the above-mentioned palladium compound may be a catalytic amount and can be used in an amount of 0.0001 to 1.0 mole per mole of the compound (10b).

[0640] The oxidation in step (41b) can be carried out in a solvent. Examples of the above-mentioned solvent include water, ester, aliphatic hydrocarbon, aromatic hydrocarbon, alcohol, carboxylic acid, ether, halogenated hydrocarbon, nitrogen-containing polar organic compound, nitrile, dimethyl sulfoxide, and sulfolane.

[0641] Examples of the above-mentioned ester include ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy-2-acetoxypropane), etc. Among them, ethyl acetate is preferred.

[0642] Examples of the above-mentioned aliphatic hydrocarbon include hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, mineral spirit, etc. Among them, cyclohexane and heptane are preferred.

[0643] Examples of the aromatic hydrocarbon include benzene, toluene, xylene, etc., and among them, benzene and toluene are preferred.

[0644] Examples of the alcohol include methanol, ethanol, 1-propanol, isopropanol, etc.

[0645] Examples of the carboxylic acids include acetic acid, propionic acid, etc., and among them, acetic acid is preferred.

[0646] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc., and among them, diethyl ether and tetrahydrofuran are preferred.

[0647] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc., and among them, dichloromethane and chloroform are preferred.

[0648] Examples of the nitrogen-containing polar organic compound include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, etc., and among them, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferred.

[0649] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, etc., and among them, acetonitrile is preferred.

[0650] The temperature of oxidation in step (41b) is preferably -78 to 200°C, more preferably -20 to 150°C.

[0651] The pressure of oxidation in step (41b) is preferably 0 to 10 MPa, more preferably 0.1 to 5.0 MPa.

[0652] As the oxidation time in step (41b), 0.1 to 72 hours is preferable, and 0.1 to 48 hours is more preferable.

[0653] The sulfation in step (42b) can be carried out by reacting compound (41b) with a sulfating reagent, and the same conditions as those in step (13b) can be adopted.

[0654] Surfactant (b) is also represented by the following formula: R 11b -CH=CH-(CR 2b 2) n -OH (In the formula, R 2b , R 11b and n are as described above.) Reacting compound (50) represented by the formula with a halogenating agent to obtain a compound (51) represented by the following formula: R 11b -CH=CH-(CR 2b 2) n -Z 51b (In the formula, R 2b , R 11b and n are as described above. Z 51b is a halogen atom.) Step (51) of obtaining compound (51), Reacting compound (51) with an alkylene glycol represented by HO-R 3b -L-OH (L, R 3b are as described above.) to obtain a compound (52) represented by the following formula: R 11b -CH=CH-(CR 2b 2) n -O-R 3b -L-OH (In the formula, L, R 2b , R 3b , R 11b and n are as described above.) Step (52) of obtaining compound (52), Oxidizing compound (52) to obtain the following formula:

Chemical formula

Chemical formula

[0655] Z 51b is preferably F, Cl, Br or I, and more preferably Br.

[0656] Examples of the halogenating agent used in the step (51) include N-bromosuccinimide, N-chlorosuccinimide, and the like. The above halogenating agent can be used in an amount of 0.5 to 10.0 moles per 1 mole of the compound (50).

[0657] The reaction of the step (51) can be carried out in the presence of phosphines such as triphenylphosphine. The above phosphines can be used in an amount of 0.5 to 10.0 moles per 1 mole of the compound (50).

[0658] The reaction of the step (51) can be carried out in a solvent. As the above solvent, an organic solvent is preferable, and examples include ether, halogenated hydrocarbon, aromatic hydrocarbon, and the like.

[0659] Examples of the above ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc. Among them, diethyl ether and tetrahydrofuran are preferable.

[0660] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc. Among them, dichloromethane and chloroform are preferred.

[0661] Examples of the aromatic hydrocarbon include benzene, toluene, xylene, etc. Among them, benzene and toluene are preferred.

[0662] The reaction temperature in step (51) is preferably -78 to 200 °C, more preferably -40 to 150 °C.

[0663] The reaction pressure in step (51) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0664] The reaction time in step (51) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0665] In step (52), the alkylene glycol can be used in an amount of 0.5 to 10.0 moles per 1 mole of compound (51).

[0666] The reaction in step (52) can be carried out in the presence of a base. Examples of the base include sodium hydride, sodium hydroxide, potassium hydroxide, etc. The base can be used in an amount of 0.5 to 10.0 moles per 1 mole of compound (51).

[0667] The reaction in step (52) can be carried out in a solvent. The solvent is preferably an organic solvent, and examples thereof include nitrogen-containing polar organic compounds, ethers, halogenated hydrocarbons, aromatic hydrocarbons, etc.

[0668] Examples of the nitrogen-containing polar organic compound include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, etc. Among them, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferred.

[0669] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc. Among them, diethyl ether and tetrahydrofuran are preferred.

[0670] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc. Among them, dichloromethane and chloroform are preferred.

[0671] Examples of the aromatic hydrocarbon include benzene, toluene, xylene, etc. Among them, benzene and toluene are preferred.

[0672] The temperature of the reaction in step (52) is preferably -78 to 200°C, more preferably -40 to 150°C.

[0673] The pressure of the reaction in step (52) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0674] The reaction time of step (52) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0675] The oxidation in step (53) can be carried out by allowing an oxidizing agent to act on compound (52) in the presence of water and a palladium compound, and the same conditions as those in the oxidation in step (41) can be adopted.

[0676] The sulfation with sulfuric acid in step (54) can be carried out by reacting compound (53) with a sulfating reagent, and the same conditions as those in the sulfation with sulfuric acid in step (13) can be adopted.

[0677] In any of the above-described production methods, after the completion of each step, the solvent may be distilled off, or distillation, purification, etc. may be carried out to increase the purity of the obtained compound. Further, when the obtained compound has a group represented by -OSO3H (that is, when X b is H), -OSO3H can be converted to a sulfate group by contacting with an alkali such as sodium carbonate or ammonia.

[0678] Among the production methods of the surfactant (b), the production method including the above steps (41b) and (42b) is preferable.

[0679] The surfactant (c) will be described.

[0680] In formula (c), R 1c is a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms. When the above alkyl group has 3 or more carbon atoms, it may contain a carbonyl group (-C(=O)-) between two carbon atoms. Further, when the above alkyl group has 2 or more carbon atoms, the terminal of the above alkyl group may contain the above carbonyl group. That is, an acyl group such as an acetyl group represented by CH3-C(=O)- is also included in the above alkyl group. Further, when the above alkyl group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocyclic ring, or may form a ring. As the above heterocyclic ring, an unsaturated heterocyclic ring is preferable, and an oxygen-containing unsaturated heterocyclic ring is more preferable, and examples thereof include a furan ring. In R 1c , a divalent heterocyclic ring may be inserted between two carbon atoms, a divalent heterocyclic ring may be located at the terminal and bonded to -C(=O)-, or a monovalent heterocyclic ring may be located at the terminal of the above alkyl group.

[0681] In this specification, the "number of carbon atoms" of the above alkyl group shall include the number of carbon atoms constituting the carbonyl group and the number of carbon atoms constituting the above heterocyclic ring. For example, the group represented by CH3-C(=O)-CH2- has 3 carbon atoms, the group represented by CH3-C(=O)-C2H4-C(=O)-C2H4- has 7 carbon atoms, and the group represented by CH3-C(=O)- has 2 carbon atoms.

[0682] The above alkyl group may have a hydrogen atom bonded to a carbon atom substituted by a functional group. For example, it may be substituted by a hydroxy group (-OH) or a monovalent organic group containing an ester bond, but it is preferably not substituted by any functional group. Examples of the monovalent organic group containing an ester bond include a group represented by the formula: -O-C(=O)-R 101c (wherein R 101c is an alkyl group). Up to 75% of the hydrogen atoms bonded to the carbon atoms of the above alkyl group may be substituted by halogen atoms, up to 50% may be substituted by halogen atoms, and up to 25% may be substituted by halogen atoms, but it is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0683] In formula (c), R 2c and R 3c are each independently a single bond or a divalent linking group. R 2c and R 3c are each independently preferably a single bond or a linear or branched alkylene group having 1 or more carbon atoms or a cyclic alkylene group having 3 or more carbon atoms. R 2c and R 3c The above alkylene group constituting them preferably does not contain a carbonyl group.

[0684] The above-mentioned alkylene group may have a hydrogen atom bonded to a carbon atom substituted by a functional group. For example, it may be substituted by a hydroxy group (-OH) or a monovalent organic group containing an ester bond, but it is preferably not substituted by any functional group. Examples of the monovalent organic group containing an ester bond include a group represented by the formula: -O-C(=O)-R 102c (In the formula, R 102c is an alkyl group). Up to 75% of the hydrogen atoms bonded to the carbon atoms of the above-mentioned alkylene group may be substituted by halogen atoms, up to 50% may be substituted by halogen atoms, and up to 25% may be substituted by halogen atoms. However, it is preferably an unhalogenated alkylene group that does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0685] R 1c 、R 2c and R 3c have a total carbon number of 5 or more. As the total carbon number, 7 or more is preferable, 9 or more is more preferable, 20 or less is preferable, 18 or less is more preferable, and 15 or less is even more preferable. R 1c 、R 2c and R 3c Any two of them may be bonded to each other to form a ring.

[0686] In formula (c), A c is -COOX c or -SO3X c (X c is H, a metal atom, NR 4c 4, an optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, and R 4c is H or an organic group, and they may be the same or different.). R 4cPreferably, it is H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms. Examples of the metal atom include monovalent and divalent metal atoms, such as alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K, or Li is preferable. X c Preferably, it is H, an alkali metal (Group 1), an alkaline earth metal (Group 2), or NR 4c 4, and since it is easily soluble in water, H, Na, K, Li, or NH4 is more preferable. Since it is even more easily soluble in water, Na, K, or NH4 is even more preferable, Na or NH4 is particularly preferable, and since it is easily removable, NH4 is most preferable. X c When X is NH4, the surfactant has excellent solubility in an aqueous medium, and metal components are less likely to remain in PTFE or the final product.

[0687] R 1c Preferably, it is a linear or branched alkyl group having 1 to 8 carbon atoms that does not contain a carbonyl group, a cyclic alkyl group having 3 to 8 carbon atoms that does not contain a carbonyl group, a linear or branched alkyl group having 2 to 45 carbon atoms that contains 1 to 10 carbonyl groups, a cyclic alkyl group having 3 to 45 carbon atoms that contains a carbonyl group, or an alkyl group that contains a monovalent or divalent heterocyclic ring having 3 to 45 carbon atoms.

[0688] Also, R 1c Preferably, it is represented by the following formula:

Chemical formula

[0689] n 11cAs for this, an integer of 0 to 5 is preferable, an integer of 0 to 3 is more preferable, and an integer of 1 to 3 is even more preferable.

[0690] R 11c The above alkyl group as such preferably does not contain a carbonyl group. R 11c The hydrogen atom bonded to the carbon atom of the above alkyl group as such may be substituted by a functional group. For example, it may be substituted by a hydroxy group (-OH) or a monovalent organic group containing an ester bond, but it is preferably not substituted by any functional group. Examples of the monovalent organic group containing the above ester bond include a group represented by the formula: -O-C(=O)-R 103c (In the formula, R 103c is an alkyl group). R 11c Up to 75% of the hydrogen atoms bonded to the carbon atoms of the above alkyl group as such may be substituted by halogen atoms, up to 50% may be substituted by halogen atoms, and up to 25% may be substituted by halogen atoms, but it is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0691] R 12c is an alkylene group having 0 to 3 carbon atoms. The above number of carbon atoms is preferably 1 to 3. R 12c The above alkylene group as such may be linear or branched. R 12c The above alkylene group as such preferably does not contain a carbonyl group. R 12c As for this, an ethylene group (-C2H4-) or a propylene group (-C3H6-) is more preferable. R 12c The hydrogen atom bonded to the carbon atom of the above alkylene group as such may be substituted by a functional group. For example, it may be substituted by a hydroxy group (-OH) or a monovalent organic group containing an ester bond, but it is preferably not substituted by any functional group. Examples of the monovalent organic group containing the ester bond include a group represented by the formula: -O-C(=O)-R 104c (wherein R 104c is an alkyl group). R 12c As the above-mentioned alkylene group, up to 75% of the hydrogen atoms bonded to the carbon atoms may be substituted by halogen atoms, up to 50% may be substituted by halogen atoms, and up to 25% may be substituted by halogen atoms. However, it is preferably a non-halogenated alkylene group that does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0692] R 2c and R 3c are each independently preferably an alkylene group having 1 or more carbon atoms and not containing a carbonyl group, more preferably an alkylene group having 1 to 3 carbon atoms and not containing a carbonyl group, and even more preferably an ethylene group (-C2H4-) or a propylene group (-C3H6-).

[0693] Examples of the surfactant (c) include the following surfactants. In each formula, A c is as described above.

[0694]

Chemical formula

[0695]

Chemical formula

[0696]

Chemical formula

[0697]

Chemical formula

[0698]

Chemical formula

[0699] [Chemical]

[0700] [Chemical]

[0701] [Chemical]

[0702] Surfactant (c) is a novel compound and can be produced, for example, by the production method exemplified below.

[0703] Surfactant (c) has the formula: [Chemical] (wherein R 3c is as described above, E c is a leaving group.) A compound (10c) represented by the formula, lithium, and a formula: R 201c 3Si-Cl (wherein R 201c is independently an alkyl group or an aryl group.) The chlorosilane compound represented by the formula is reacted to obtain a compound (11c) represented by the formula: [Chemical] (wherein R 3c , R 201c and E c are as described above.) Step (11c) of obtaining the compound (11c) represented by the formula, The compound (11c) and a formula: [Chemical] (wherein R 1c is as described above, R 21c is a single bond or a divalent linking group.) The olefin represented by the formula is reacted to obtain a compound represented by the formula: [Chemical formula] (In the formula, R 1c , R 21c , R 3c and E c are as described above.) Step (12c) of obtaining compound (12c) represented by Eliminating the leaving group of compound (12c) to obtain a compound (13c) represented by the formula: [Chemical formula] (In the formula, R 1c , R 21c and R 3c are as described above.) Step (13c), and Oxidizing compound (13c) to obtain a compound (14c) represented by the formula: [Chemical formula] (In the formula, R 1c , R 21c and R 3c are as described above.) Step (14c), can be preferably produced by a production method including

[0704] When R 1c contains a furan ring, for example, the furan ring may be opened with an acid and converted into a dicarbonyl derivative. Examples of the acid include acetic acid, hydrochloric acid, p-toluenesulfonic acid, etc., and acetic acid is preferred.

[0705] In step (11c), it is preferable to react lithium and the above chlorosilane compound in advance to obtain a siloxylithium compound, and then react the siloxylithium compound with compound (10c) to obtain compound (11c).

[0706] E crepresents a leaving group. Examples of the leaving group include a tert-butyldimethylsilyl (TBS) group, a triethylsilyl (TES) group, a triisopropylsilyl (TIPS) group, a tert-butyldiphenylsilyl (TBDPS) group, a benzyl (Bn) group, and the like.

[0707] R 21c is preferably a single bond or a linear or branched alkylene group having 1 or more carbon atoms.

[0708] Examples of the chlorosilane compound include

Chemical formula

[0709] Any reaction in step (11c) can be carried out in a solvent. The solvent is preferably an organic solvent, more preferably an aprotic polar solvent, and even more preferably an ether. Examples of the ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraglyme (tetraethylene glycol dimethyl ether), crown ether (15-crown-5, 18-crown-6), and the like. Among them, tetrahydrofuran and diethyl ether are preferred.

[0710] The reaction temperature of lithium and the chlorosilane compound in step (11c) is preferably -78 to 100 °C, and more preferably 10 to 40 °C. The reaction temperature of the siloxylithium compound and compound (10c) in step (11c) is preferably -100 to 0 °C, and more preferably -80 to -50 °C.

[0711] The reaction pressure of lithium and the chlorosilane compound in step (11c) is preferably 0.1 to 5 MPa, and more preferably 0.1 to 1 MPa. As the pressure for the reaction between the above-mentioned siloxylithium compound and compound (10c) in step (11c), 0.1 to 5 MPa is preferable, and 0.1 to 1 MPa is more preferable.

[0712] As the reaction time between lithium and the above-mentioned chlorosilane compound in step (11c), 0.1 to 72 hours is preferable, and 6 to 10 hours is more preferable. As the reaction time between the above-mentioned siloxylithium compound and compound (10c) in step (11c), 0.1 to 72 hours is preferable, and 1 to 2 hours is more preferable.

[0713] In step (12c), considering the improvement of yield and the reduction of waste, the reaction ratio between compound (11c) and the above-mentioned olefin is preferably such that the olefin is 1 to 2 moles per 1 mole of compound (11c), and more preferably 1 to 1.1 moles.

[0714] The reaction in step (12c) can be carried out in a solvent in the presence of a thiazolium salt and a base.

[0715] Examples of the above-mentioned thiazolium salt include 3-ethyl-5-(2-hydroxyethyl)-4-methylthiazolium bromide, 3-benzyl-5-(2-hydroxyethyl)-4-methylthiazolium chloride, and the like.

[0716] Examples of the above-mentioned base include 1,8-diazabicyclo[5.4.0]-7-undecene, triethylamine, and the like.

[0717] As the above-mentioned solvent, an organic solvent is preferable, a non-protic polar solvent is more preferable, and an alcohol or an ether is even more preferable.

[0718] Examples of the above-mentioned alcohol include methanol, ethanol, 1-propanol, isopropanol, and the like.

[0719] Examples of the ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraglyme (tetraethylene glycol dimethyl ether), crown ether (15-crown-5, 18-crown-6), etc. Among them, tetrahydrofuran and diethyl ether are preferred.

[0720] The reaction temperature in step (12c) is preferably 40 to 60 °C, more preferably 50 to 55 °C.

[0721] The reaction pressure in step (12c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0722] The reaction time in step (12c) is preferably 0.1 to 72 hours, more preferably 6 to 10 hours.

[0723] The elimination reaction of the leaving group in step (13c) can be carried out by using fluoride ions or an acid. Examples of the method for eliminating the leaving group include a method using hydrofluoric acid, a method using an amine complex of hydrogen fluoride such as pyridine·nHF or triethylamine·nHF, a method using an inorganic salt such as cesium fluoride, potassium fluoride, lithium tetrafluoroborate (LiBF4), ammonium fluoride, and a method using an organic salt such as tetrabutylammonium fluoride (TBAF).

[0724] The elimination reaction of the leaving group in step (13c) can be carried out in a polar solvent. As the solvent, an organic solvent is preferred, an aprotic polar solvent is more preferred, and an ether is even more preferred.

[0725] Examples of the ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraglyme (tetraethylene glycol dimethyl ether), crown ether (15-crown-5, 18-crown-6), etc. Among them, tetrahydrofuran and diethyl ether are preferred.

[0726] The reaction temperature in step (13c) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0727] The reaction pressure in step (13c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0728] The reaction time in step (13c) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0729] The oxidation in step (14c) can be carried out in a solvent in the presence of sodium chlorite.

[0730] Examples of the solvent include alcohols such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, tert-butyl alcohol, and water. A disodium hydrogen phosphate solution may be used as the buffer solution.

[0731] Compound (14c) may be contacted with an alkali to convert -COOH into a salt form. Examples of the alkali include sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, etc. An aqueous ammonia solution is preferably used.

[0732] After the completion of each step, the solvent may be distilled off, or distillation, purification, etc. may be carried out to increase the purity of the obtained compound.

[0733] Surfactant (c) also has the formula: [Chemical formula] (wherein, R 3c is as described above, R 22c is a monovalent organic group, and E c is a leaving group.) and a ketone represented by the formula: [Chemical formula] (wherein, R 1c is as described above, R 23c is a monovalent organic group.) and a carboxylic acid ester represented by the formula: [Chemical formula] (wherein, R 1c , R 3c and E c are as described above, and R 24c is a single bond or a divalent linking group.) to obtain a compound (21c) represented by the formula: Eliminating the leaving group of the compound (21c) to obtain a compound (22c) represented by the formula: [Chemical formula] (wherein, R 1c , R 24c and R 3c are as described above.) in step (22c), and Oxidizing the compound (22c) to obtain a compound (23c) represented by the formula: [Chemical formula] (wherein, R 1c , R 24c and R 3c are as described above.) in step (23c), It can be preferably produced by a production method including

[0734] R 1cWhen it contains a furan ring, for example, the furan ring may be opened with an acid and converted into a dicarbonyl derivative. Examples of the acid include acetic acid, hydrochloric acid, p-toluenesulfonic acid, etc., and among them, acetic acid is preferable.

[0735] E c represents a leaving group. Examples of the leaving group include a tert-butyldimethylsilyl (TBS) group, a triethylsilyl (TES) group, a triisopropylsilyl (TIPS) group, a tert-butyldiphenylsilyl (TBDPS) group, a benzyl (Bn) group, etc.

[0736] R 22c is preferably a linear or branched alkyl group having 1 or more carbon atoms, and more preferably a methyl group. R 23c is preferably a linear or branched alkyl group having 1 or more carbon atoms, and more preferably a methyl group. R 24c is preferably a linear or branched alkylene group having 1 or more carbon atoms, and more preferably a methylene group (-CH2-).

[0737] The reaction in step (21c) can be carried out in a solvent in the presence of a base.

[0738] Examples of the base include sodium amide, sodium hydride, sodium methoxide, sodium ethoxide, etc.

[0739] As the solvent, an organic solvent is preferable, a non-protic polar solvent is more preferable, and alcohol and ether are even more preferable.

[0740] Examples of the alcohol include methanol, ethanol, 1-propanol, isopropanol, etc.

[0741] Examples of the ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraglyme (tetraethylene glycol dimethyl ether), crown ether (15-crown-5, 18-crown-6), etc. Among them, tetrahydrofuran and diethyl ether are preferred.

[0742] The temperature of the reaction in step (21c) is preferably 0 to 40°C, more preferably 0 to 20.

[0743] The pressure of the reaction in step (21c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0744] The reaction time in step (21c) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0745] The elimination reaction of the leaving group in step (22c) can be carried out by using fluoride ions or an acid. Examples of the method for eliminating the leaving group include a method using hydrofluoric acid, a method using an amine complex of hydrogen fluoride such as pyridine·nHF or triethylamine·nHF, a method using an inorganic salt such as cesium fluoride, potassium fluoride, lithium tetrafluoroborate (LiBF4), ammonium fluoride, and a method using an organic salt such as tetrabutylammonium fluoride (TBAF).

[0746] The elimination reaction of the leaving group in step (22c) can be carried out in a solvent. As the solvent, an organic solvent is preferred, an aprotic polar solvent is more preferred, and an ether is even more preferred.

[0747] Examples of the ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraglyme (tetraethylene glycol dimethyl ether), crown ether (15-crown-5, 18-crown-6), etc. Among them, tetrahydrofuran and diethyl ether are preferred.

[0748] The reaction temperature in step (22c) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0749] The reaction pressure in step (22c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0750] The reaction time in step (22c) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0751] The oxidation in step (23c) can be carried out in a solvent in the presence of sodium chlorite.

[0752] As the above solvent, alcohol and water can be used. As the buffer solution, a disodium hydrogen phosphate solution may be used.

[0753] Compound (23c) may be contacted with an alkali to convert -COOH into a salt form. Examples of the alkali include sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, etc. An aqueous ammonia solution is preferably used.

[0754] After the completion of each step, the solvent may be distilled off, or distillation, purification, etc. may be carried out to increase the purity of the obtained compound.

[0755] Surfactant (c) also has the formula: Y c -R 3c -CH2-OE c (wherein R 3c is as described above, Y c is a halogen atom, and E c is a leaving group.) The alkyl halide represented by the formula:

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0756] R 1cWhen it contains a furan ring, for example, the furan ring may be opened with an acid and converted into a dicarbonyl derivative. Examples of the acid include acetic acid, hydrochloric acid, p-toluenesulfonic acid, etc., and acetic acid is particularly preferred.

[0757] E c represents a leaving group. Examples of the leaving group include a tert-butyldimethylsilyl (TBS) group, a triethylsilyl (TES) group, a triisopropylsilyl (TIPS) group, a tert-butyldiphenylsilyl (TBDPS) group, a benzyl (Bn) group, etc.

[0758] In step (31c), considering the improvement of the yield and the reduction of waste, the reaction ratio of the above alkyl halide to the above lithium acetylide is preferably 1 to 2 moles, more preferably 1 to 1.2 moles of the above lithium acetylide with respect to 1 mole of the above alkyl halide.

[0759] The reaction in step (31c) can be carried out in a solvent. As the above solvent, hexane is preferred.

[0760] The reaction temperature in step (31c) is preferably -100 to -40 °C, more preferably -80 to -50 °C.

[0761] The reaction pressure in step (31c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0762] The reaction time in step (31c) is preferably 0.1 to 72 hours, more preferably 6 to 10 hours.

[0763] The oxidation in step (32c) is [(Cn * )Ru III (CF3CO2)3]·H2O (wherein Cn *It can be carried out in a nitrile solvent using a complex formed by treating (which represents 1,4,7-trimethyl-1,4,7-triazabicyclononane) with (NH4)2Ce(NO3)6 and trifluoroacetic acid and then adding sodium perchlorate.

[0764] After the oxidation is completed, it may be neutralized with an alkali, and compound (32c) may be extracted using an organic solvent such as ether.

[0765] The reaction temperature in step (32c) is preferably 30 to 100°C, more preferably 40 to 90°C.

[0766] The reaction pressure in step (32c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0767] The reaction time in step (32c) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0768] The elimination reaction of the leaving group in step (33c) can be carried out by using fluoride ions or an acid. Examples of the method for eliminating the leaving group include a method using hydrofluoric acid, a method using an amine complex of hydrogen fluoride such as pyridine·nHF or triethylamine·nHF, a method using an inorganic salt such as cesium fluoride, potassium fluoride, lithium tetrafluoroborate (LiBF4), ammonium fluoride, and a method using an organic salt such as tetrabutylammonium fluoride (TBAF).

[0769] The elimination reaction of the leaving group in step (33c) can be carried out in a solvent. As the above solvent, an organic solvent is preferable, an aprotic polar solvent is more preferable, and ether is even more preferable.

[0770] Examples of the ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraglyme (tetraethylene glycol dimethyl ether), crown ether (15-crown-5, 18-crown-6), etc. Among them, tetrahydrofuran and diethyl ether are preferred.

[0771] The reaction temperature in step (33c) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0772] The reaction pressure in step (33c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0773] The reaction time in step (33c) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0774] The oxidation in step (34c) can be carried out in a solvent in the presence of sodium chlorite.

[0775] As the solvent, alcohol and water can be used. As the buffer solution, a disodium hydrogen phosphate solution may be used.

[0776] Compound (34c) may be contacted with an alkali to convert -COOH into a salt form. Examples of the alkali include sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, etc. An aqueous ammonia solution is preferably used.

[0777] After the completion of each step, the solvent may be distilled off, or distillation, purification, etc. may be carried out to increase the purity of the obtained compound.

[0778] Surfactant (c) also has the formula:

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0779] In step (51c), considering the improvement of the yield and the reduction of waste, the reaction ratio of divinyl ketone to 2-methylfuran is preferably 0.5 to 1 mol, more preferably 0.6 to 0.9 mol of 2-methylfuran per 1 mol of divinyl ketone.

[0780] The reaction in step (51c) is preferably carried out in the presence of an acid. Examples of the above acid include acetic acid, hydrochloric acid, p-toluenesulfonic acid, etc., and among them, acetic acid is preferred.

[0781] In step (51c), considering the improvement of the yield and the reduction of waste, the amount of the acid used is preferably 0.1 to 2 moles, more preferably 0.1 to 1 mole, per mole of divinyl ketone.

[0782] The reaction in step (51c) can be carried out in a polar solvent. Preferred solvents include water and acetonitrile.

[0783] The reaction temperature in step (51c) is preferably 20 to 100 °C, more preferably 40 to 100 °C.

[0784] The reaction pressure in step (51c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0785] The reaction time in step (51c) is preferably 0.1 to 72 hours, more preferably 4 to 8 hours.

[0786] In step (52c), considering the improvement of the yield and the reduction of waste, the reaction ratio of compound (51c) to furan is preferably 1 to 2 moles of furan per mole of compound (51c), more preferably 1 to 1.1 moles.

[0787] The reaction in step (52c) is preferably carried out in the presence of an acid. Examples of the acid include acetic acid, hydrochloric acid, p-toluenesulfonic acid, etc., and among them, acetic acid is preferred.

[0788] In step (52c), considering the improvement of the yield and the reduction of waste, the amount of the acid used is preferably 0.1 to 2 moles, more preferably 0.1 to 1 mole, per mole of compound (51c).

[0789] The reaction in step (52c) can be carried out in a polar solvent. Water is preferred as the solvent.

[0790] The reaction temperature in step (52c) is preferably 20 to 100 °C, more preferably 40 to 100 °C.

[0791] As the pressure of the reaction in step (52c), 0.1 to 5 MPa is preferable, and 0.1 to 1 MPa is more preferable.

[0792] As the reaction time in step (52c), 0.1 to 72 hours is preferable, and 4 to 8 hours is more preferable.

[0793] In step (53c), the furan ring is opened by heating compound (52c) in the presence of an acid.

[0794] As the above acid, hydrochloric acid and sulfuric acid are preferable.

[0795] The reaction in step (53c) can be carried out in a polar solvent. As the above solvent, water is preferable.

[0796] As the reaction temperature in step (53c), 50 to 100 °C is preferable, and 70 to 100 °C is more preferable.

[0797] As the reaction pressure in step (53c), 0.1 to 5 MPa is preferable, and 0.1 to 1 MPa is more preferable.

[0798] As the reaction time in step (53c), 0.1 to 72 hours is preferable, and 1 to 12 hours is more preferable.

[0799] The oxidation in step (54c) can be carried out in a solvent in the presence of sodium chlorite.

[0800] As the above solvent, tert-butyl alcohol and water can be used. As the buffer solution, a disodium hydrogen phosphate solution may be used.

[0801] Compound (54c) may be contacted with an alkali to convert -COOH into a salt form. Examples of the above alkali include sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, etc., and it is preferable to use an aqueous ammonia solution.

[0802] After the completion of each step, the solvent may be distilled off, or distillation, purification, etc. may be carried out to increase the purity of the resulting compound.

[0803] The surfactant (c) is also represented by the formula:

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0804] When R 1c contains a furan ring, for example, the furan ring may be opened with an acid and converted into a dicarbonyl derivative. Examples of the acid include acetic acid, hydrochloric acid, p-toluenesulfonic acid, etc., and acetic acid is preferred among them.

[0805] R 21c is preferably a single bond or a linear or branched alkylene group having 1 or more carbon atoms.

[0806] In step (61c), considering the improvement of the yield and the reduction of waste, the reaction ratio of the above-mentioned alkene to the above-mentioned alkyne is preferably 0.5 to 2 moles of the above-mentioned alkene per 1 mole of the above-mentioned alkyne, and more preferably 0.6 to 1.2 moles.

[0807] The reaction in step (61c) is preferably carried out in the presence of a metal catalyst. Examples of the above-mentioned metal include ruthenium.

[0808] Considering the improvement of the yield and the reduction of waste, the amount of the above-mentioned metal catalyst used in step (61c) is preferably 0.01 to 0.4 moles per 1 mole of the above-mentioned alkene, and more preferably 0.05 to 0.1 moles.

[0809] The reaction in step (61c) can be carried out in a polar solvent. Examples of the above-mentioned solvent include water, acetonitrile, dimethylacetamide, and dimethylformamide.

[0810] The reaction temperature in step (61c) is preferably 20 to 160 °C, and more preferably 40 to 140 °C.

[0811] The reaction pressure in step (61c) is preferably 0.1 to 5 MPa, and more preferably 0.1 to 1 MPa.

[0812] The reaction time in step (61c) is preferably 0.1 to 72 hours, and more preferably 4 to 8 hours.

[0813] In step (62c), considering the improvement of the yield and the reduction of waste, the reaction ratio of compound (61c) to the above-mentioned alkali is preferably 0.6 to 2 moles of the above-mentioned alkali per 1 mole of compound (61c), and more preferably 0.8 to 1.1 moles.

[0814] The amount of the acid used in step (62c) is preferably 1.0 to 20.0 moles, more preferably 1.0 to 10.0 moles, per mole of compound (61c), considering the improvement of the yield and the reduction of waste.

[0815] The reaction in step (62c) can be carried out in a polar solvent. As the above solvent, water is preferred.

[0816] The reaction temperature in step (62c) is preferably 0 to 100 °C, more preferably 20 to 100 °C.

[0817] The reaction pressure in step (62c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0818] The reaction time in step (62c) is preferably 0.1 to 72 hours, more preferably 4 to 8 hours.

[0819] Compound (62c) may be contacted with an alkali to convert -COOH into a salt form. Examples of the above alkali include sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, etc., and an aqueous solution of ammonia is preferably used.

[0820] After the completion of each step, the solvent may be distilled off, or distillation, purification, etc. may be carried out to increase the purity of the obtained compound.

[0821] The surfactant (d) will be described.

[0822] In formula (d), R 1d is a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent. When the above alkyl group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocyclic ring or may form a ring. As the above heterocyclic ring, an unsaturated heterocyclic ring is preferred, and an oxygen-containing unsaturated heterocyclic ring is more preferred. Examples thereof include a furan ring, etc. R 1dIn this case, a divalent heterocyclic ring may be inserted between two carbon atoms, or a divalent heterocyclic ring may be located at the terminal and bonded to -C(=O)-, or a monovalent heterocyclic ring may be located at the terminal of the above alkyl group.

[0823] In addition, in this specification, the "number of carbon atoms" of the above alkyl group shall include the number of carbon atoms constituting the above heterocyclic ring.

[0824] R 1d As the above substituents that the above alkyl group as R may have, a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a hydroxy group are preferable, and a methyl group and an ethyl group are particularly preferable.

[0825] R 1d The above alkyl group as R preferably does not contain a carbonyl group. Up to 75% of the hydrogen atoms bonded to the carbon atoms of the above alkyl group may be substituted by halogen atoms, up to 50% may be substituted by halogen atoms, and up to 25% may be substituted by halogen atoms, but it is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms. The above alkyl group preferably has no substituents.

[0826] R 1d As R, a linear or branched alkyl group having 1 to 10 carbon atoms that may have substituents or a cyclic alkyl group having 3 to 10 carbon atoms that may have substituents is preferable, a linear or branched alkyl group having 1 to 10 carbon atoms that does not contain a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms that does not contain a carbonyl group is more preferable, a linear or branched alkyl group having 1 to 10 carbon atoms that has no substituents is still more preferable, a linear or branched alkyl group having 1 to 3 carbon atoms that has no substituents is even more preferable, a methyl group (-CH3) or an ethyl group (-C2H5) is particularly preferable, and a methyl group (-CH3) is most preferable.

[0827] In formula (d), R 2d and R 4d are each independently H or a substituent. A plurality of R 2d and R 4d may be the same or different from each other.

[0828] As the above substituents for R 2d and R 4d a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, or a hydroxy group is preferable, and a methyl group or an ethyl group is particularly preferable.

[0829] As the above alkyl groups for R 2d and R 4d it is preferable that they do not contain a carbonyl group. Up to 75% of the hydrogen atoms bonded to the carbon atoms of the above alkyl group may be substituted by halogen atoms, up to 50% may be substituted by halogen atoms, and up to 25% may be substituted by halogen atoms, but it is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms. It is preferable that the above alkyl group has no substituents.

[0830] As the above alkyl groups for R 2d and R 4d a linear or branched alkyl group having 1 to 10 carbon atoms that does not contain a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms that does not contain a carbonyl group is preferable, a linear or branched alkyl group having 1 to 10 carbon atoms that does not contain a carbonyl group is more preferable, a linear or branched alkyl group having 1 to 3 carbon atoms that has no substituents is still more preferable, and a methyl group (-CH3) or an ethyl group (-C2H5) is particularly preferable.

[0831] R 2d and R 4dIndependently, a linear or branched alkyl group having 1 to 10 carbon atoms and not containing an H or a carbonyl group is preferred, a linear or branched alkyl group having 1 to 3 carbon atoms and not having an H or a substituent is more preferred, H, a methyl group (-CH3) or an ethyl group (-C2H5) is even more preferred, and H is particularly preferred.

[0832] In formula (d), R 3d is an alkylene group having 1 to 10 carbon atoms which may have a substituent. When there are a plurality of Rs 3d they may be the same or different.

[0833] It is preferred that the above alkylene group does not contain a carbonyl group. Up to 75% of the hydrogen atoms bonded to the carbon atoms of the above alkylene group may be substituted by halogen atoms, up to 50% may be substituted by halogen atoms, up to 25% may be substituted by halogen atoms, but it is preferably a non-halogenated alkyl group not containing halogen atoms such as fluorine atoms and chlorine atoms. It is preferred that the above alkylene group has no substituents.

[0834] As the above alkylene group, a linear or branched alkylene group having 1 to 10 carbon atoms which may have a substituent or a cyclic alkylene group having 3 to 10 carbon atoms which may have a substituent is preferred, a linear or branched alkylene group having 1 to 10 carbon atoms not containing a carbonyl group or a cyclic alkylene group having 3 to 10 carbon atoms not containing a carbonyl group is preferred, a linear or branched alkylene group having 1 to 10 carbon atoms having no substituents is more preferred, and a methylene group (-CH2-), an ethylene group (-C2H4-), an isopropylene group (-CH(CH3)CH2-) or a propylene group (-C3H6-) is even more preferred.

[0835] R 1d and R 2d and R 3d and R 4d Any two of them may be bonded to each other to form a ring.

[0836] In formula (d), n is an integer of 1 or more. As n, an integer of 1 to 40 is preferable, an integer of 1 to 30 is more preferable, and an integer of 5 to 25 is still more preferable.

[0837] In formula (d), p and q are each independently an integer of 0 or more. As p, an integer of 0 to 10 is preferable, and 0 or 1 is more preferable. As q, an integer of 0 to 10 is preferable, and an integer of 0 to 5 is more preferable.

[0838] It is preferable that the sum of n, p and q is an integer of 6 or more. More preferably, the sum of n, p and q is an integer of 8 or more. Also, the sum of n, p and q is preferably an integer of 60 or less, more preferably an integer of 50 or less, and still more preferably an integer of 40 or less.

[0839] In formula (d), A d is -SO3X d or -COOX d (X d is H, a metal atom, NR 5d 4, an optionally substituted imidazolium, an optionally substituted pyridinium or an optionally substituted phosphonium, and R 5d is H or an organic group, and may be the same or different. ). R 5d is preferably H or an organic group having 1 to 10 carbon atoms, and more preferably H or an organic group having 1 to 4 carbon atoms. Examples of the metal atom include monovalent and divalent metal atoms, such as alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K or Li is preferable. X d is a metal atom or NR 5d 4 (R 5d is as described above) may be. X d is H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 5d4 is preferred, and since it is easily soluble in water, H, Na, K, Li or NH4 is more preferred. Since it is even more easily soluble in water, Na, K or NH4 is even more preferred. Na or NH4 is particularly preferred. Since removal is easy, NH4 is most preferred. X d When X is NH4, the surfactant has excellent solubility in the aqueous medium, and it is difficult for metal components to remain in PTFE or the final product.

[0840] In formula (d), L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6d -B-*, -NR 6d CO-B-*, or -CO- (provided that the carbonyl groups contained in -CO2-B-, -OCO-B-, -CONR 6d -B-, -NR 6d CO-B- are excluded). B is a single bond or an alkylene group having 1 to 10 carbon atoms which may have a substituent, and R 6d is H or an alkyl group having 1 to 4 carbon atoms which may have a substituent. The above alkylene group preferably has 1 to 5 carbon atoms. Also, the above R 6d is more preferably H or a methyl group. * refers to the side bonded to A in the formula. d

[0841] L is preferably a single bond.

[0842] The above surfactant 1 In the 1H-NMR spectrum, the integrated value of the total peak intensities observed in the region of chemical shift 2.0 to 5.0 ppm is preferably 10 or more.

[0843] The above surfactant 1 In the 1H-NMR spectrum, the integrated value of the total peak intensities observed in the region of chemical shift 2.0 to 5.0 ppm is preferably within the above range. In this case, the surfactant preferably has a ketone structure in the molecule.

[0844] ​In the above surfactant, the integral value is more preferably 15 or more, preferably 95 or less, more preferably 80 or less, and still more preferably 70 or less.

[0845] The integral value is measured at room temperature in a heavy water solvent. The heavy water is set to 4.79 ppm.

[0846] Examples of the surfactant (d) include CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2COOK, CH3C(O)CH2CH2CH2CH2CH2CH2CH2COONa, CH3C(O)CH2CH2CH2CH2CH2CH2COONa, CH3C(O)CH2CH2CH2CH2CH2COONa, CH3C(O)CH2CH2CH2CH2COONa, CH3C(O)CH2CH2CH2COONa, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2COONa, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2COONa, (CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2COONa, (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2COONa, (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2COONa, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2COONa, CH3CH2CH2C(O)CH2CH2CH2CH2CH2CH2COONa, CH3CH2CH2CH2C(O)CH2CH2CH2CH2CH2COONa, CH3CH2CH2CH2CH2C(O)CH2CH2CH2CH2COONa, CH3CH2CH2CH2CH2CH2C(O)CH2CH2CH2COONa, CH3CH2CH2CH2CH2CH2CH2C(O)CH2CH2COONa, CH3CH2CH2CH2CH2CH2CH2CH2C(O)CH2COONa, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2COONa, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2COOK, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2COOK, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)OCH2COONa, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2OC(O)CH2COONa, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COONa, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COOH, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COOLi, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COONH4, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COONa, CH3C(O)CH2CH2CH2CH2CH2CH2CH2C(CH3)2COOK, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na, (CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na, (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na, (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2SO3Na, CH3C(O)CH2CH2SO3Na, CH3C(O)CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OCH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OC(O)CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3H, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3K, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Li, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3NH4, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(CH3)2SO3Na etc. can be mentioned.

[0847] Surfactant (d) is a novel compound and can be produced, for example, by the production method exemplified below.

[0848] Surfactant (d) has the following formula:

Chemical formula

Chemical formula

[0849] The reaction in step (11d) can be carried out in the presence of a base. Examples of the above base include sodium hydride, sodium hydroxide, potassium hydroxide, triethylamine, etc. The above base can be used in an amount of 0.5 to 20 moles per 1 mole of compound (10d).

[0850] The reaction in step (11d) can be carried out in a solvent. As the above solvent, an organic solvent is preferred, and an aprotic polar solvent is more preferred. Examples of the above organic solvent include ether, aromatic compounds, nitriles, halogenated hydrocarbons, etc. Examples of the above ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc. Among them, diethyl ether and tetrahydrofuran are preferred. Examples of the aromatic compound include benzene, toluene, xylene, etc., and among them, benzene is preferred. Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, etc., and among them, acetonitrile is preferred. Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc., and among them, dichloromethane and chloroform are preferred.

[0851] The reaction temperature in step (11d) is preferably -78 to 150°C, more preferably -20 to 100°C.

[0852] The reaction pressure in step (11d) is preferably 0 to 10 MPa, more preferably 0 to 1.0 MPa.

[0853] The reaction time in step (11d) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0854] Surfactant (d) also has the following formula:

Chemical formula

[0855] The oxidation in step (21d) can be carried out by allowing a nitrosating agent to act on compound (20d).

[0856] As the above nitrosating agent, sodium nitrite, nitrosyl sulfuric acid, isoamyl nitrite, etc. can be used.

[0857] The above nitrosating agent can be used in an amount of 0.5 to 10 moles per 1 mole of compound (20d).

[0858] The oxidation in step (21d) can be carried out in a solvent. As the above solvent, trifluoroacetic acid, acetonitrile, etc. can be used.

[0859] As the temperature of the oxidation in step (21d), -78 to 200 °C is preferable, and -20 to 100 °C is more preferable.

[0860] As the pressure of oxidation in step (21d), 0 to 10 MPa is preferable, and 0 to 1.0 MPa is more preferable.

[0861] As the time of oxidation in step (21d), 0.1 to 72 hours is preferable, and 0.1 to 24 hours is more preferable.

[0862] Compound (10d) and compound (20d) are represented by the following formula: R 11d -CH=CH-Y 1d -OH (In the formula, R 11d is H, a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent. When the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocyclic ring or may form a ring. Y 1d is -(CR 2d 2) n - or -(CR 2d 2) n -(OR 3d ) p -(CR 4d 2) q -L-CH2-(R 2d ~R 4d , n, L, p and q are as described above. L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6d -B-*, -NR 6d CO-B-*, or -CO- (however, excluding the carbonyl group contained in -CO2-B-, -OCO-B-, -CONR 6d -B-, -NR 6d CO-B-). B is a single bond or an alkylene group having 1 to 10 carbon atoms which may have a substituent, and R 6d is H or an alkyl group having 1 to 4 carbon atoms which may have a substituent. * indicates the side bonded to -CH2- in the formula.).) The compound (100d) represented by the formula is hydroxylated to give the following formula:

Chemical formula

Chemical formula

Claims

A method for producing a modified polytetrafluoroethylene powder, which is obtained by a production method including a step of emulsion-polymerizing tetrafluoroethylene in an aqueous medium in the presence of an anionic hydrocarbon surfactant, and which comprises a step of removing or reducing a compound represented by the following general formula (1) from a polytetrafluoroethylene powder having melt processability and no fibrillating property. The method for producing a modified polytetrafluoroethylene powder, wherein the step of removing or reducing the compound represented by the general formula (1) includes a step of heat-treating the polytetrafluoroethylene powder at a temperature of 200°C or higher and 300°C or lower. General formula (1): (H-(CF ２ )) ｍ -COO) ｐ M １ (wherein, m is 3 to 19, M １ is H, a metal atom, NR ５ ４ (R ５ may be the same or different and is H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2.) A method for producing a molded article using a polytetrafluoroethylene powder produced by a production method including a step of emulsion-polymerizing tetrafluoroethylene in an aqueous medium in the presence of an anionic hydrocarbon surfactant, the polytetrafluoroethylene powder having melt processability and no fibrillating property. The method includes a step of removing or reducing a compound represented by the following general formula (1). The method for producing a polytetrafluoroethylene molded article, wherein the step of removing or reducing the compound represented by the general formula (1) includes a step of heat-treating the polytetrafluoroethylene powder at a temperature of 200°C or higher and 300°C or lower. General formula (1): (H-(CF ２ )) ｍ -COO) ｐ M １ (In the formula, m is 3 to 19, M １ is H, a metal atom, NR ５ ４ (R ５ may be the same or different and is H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2.) A method for producing a modified polytetrafluoroethylene powder, which is obtained by a production method including a step of emulsion-polymerizing tetrafluoroethylene in an aqueous medium in the presence of an anionic hydrocarbon surfactant, and which comprises a step of bringing a fluorine radical source into contact with the polytetrafluoroethylene powder having melt processability and no fibrillating property at a temperature exceeding 100°C and 300°C or lower to remove or reduce a compound represented by the following general formula (1). General formula (1): (H-(CF ２ )) ｍ -COO) ｐ M １ (wherein, m is 3 to 19, M １ is H, a metal atom, NR ５ ４ (R ５ may be the same or different and is H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2.) A method for producing a polytetrafluoroethylene powder, which is obtained by a production method including a step of emulsion-polymerizing tetrafluoroethylene in an aqueous medium in the presence of an anionic hydrocarbon surfactant, and which comprises a step of bringing the polytetrafluoroethylene powder having melt processability and no fibrillating property into contact with a fluorine radical source at a temperature of 300°C or lower to remove or reduce a compound represented by the following general formula (1), wherein the addition amount of the fluorine radical source is 0.5 part by weight or more in terms of fluorine atoms per 100 parts by weight of the polytetrafluoroethylene powder. General formula (1): (H-(CF ２ )) ｍ -COO) ｐ M １ (wherein, m is 3 to 19, M １ is H, a metal atom, NR ５ ４ (R ５ may be the same or different and is H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2.) A composition in powder form It contains polytetrafluoroethylene having melt processability and no fibrillating property, the content of the compound represented by the following general formula (3) is 1000 ppb or less with respect to polytetrafluoroethylene, a composition containing the compound represented by the following general formula (5) in an amount of 1000 ppb or less with respect to polytetrafluoroethylene. General formula (3): (H-(CF₂)₈-SO₃)qM₂ (In the formula, M₂ is H, a metal atom, NR₅₄ (R₅ may be the same or different and is H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. q is 1 or 2.) General formula (5): (H-(CF ２ )) １３ -COO) ｐ M １ (In the formula, M １ is H, a metal atom, NR ５ ４ (R ５ may be the same or different and is H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2.)

6. A composition which is a powder, it contains polytetrafluoroethylene having melt processability and no fibrillating property, the content of the compound represented by the following general formula (3) is 1000 ppb or less with respect to polytetrafluoroethylene, it contains at least one of the compound represented by the following general formula (5) and the compound represented by the following general formula (5'), the content of the compound represented by the following general formula (5) is 1000 ppb or less with respect to polytetrafluoroethylene, a composition in which the content of the compound represented by the following general formula (5') is 1000 ppb or less with respect to polytetrafluoroethylene. General formula (3): (H-(CF₂)₈-SO₃)qM₂ (In the formula, M₂ is H, a metal atom, NR₅₄ (R₅ may be the same or different and is H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. q is 1 or 2.) General formula (5): (H-(CF ２ )) １３ -COO) ｐ M １ (In the formula, M １ is H, a metal atom, NR ５ ４ (R ５ may be the same or different and is H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2.) General formula (5'): (H-(CF ２ )) １４ -COO) ｐ M １ (In the formula, M １ is H, a metal atom, NR ５ ４ (R ５ may be the same or different and is H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2.)

7. A composition which is a powder, it contains polytetrafluoroethylene having melt processability and no fibrillating property, the content of the compound represented by the following general formula (3) is 1000 ppb or less with respect to polytetrafluoroethylene, a composition containing the compound represented by the following general formula (5) in an amount of 25 ppb or less with respect to polytetrafluoroethylene. General formula (3): (H-(CF₂)₈-SO₃)qM₂ (In the formula, M2 is H, a metal atom, NR54 (R5 may be the same or different and is H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. q is 1 or 2.) General formula (5): (H-(CF ２ )) １３ -COO) ｐ M １ (In the formula, M １ is H, a metal atom, NR ５ ４ (R ５ may be the same or different and is H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2.)

8. A composition which is a powder, comprising polytetrafluoroethylene having melt processability and not having fibrillating properties, wherein the content of the compound represented by the following general formula (3) is 1000 ppb or less with respect to polytetrafluoroethylene, comprising at least one of the compound represented by the following general formula (5) and the compound represented by the following general formula (5'), wherein the content of the compound represented by the following general formula (5) is 25 ppb or less with respect to polytetrafluoroethylene, A composition wherein the content of the compound represented by the following general formula (5') is 25 ppb or less with respect to polytetrafluoroethylene. General formula (3): (H-(CF2)8-SO3)qM2 (In the formula, M2 is H, a metal atom, NR54 (R5 may be the same or different and is H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. q is 1 or 2.) General formula (5): (H-(CF ２ )) １３ -COO) ｐ M １ (In the formula, M １ is H, a metal atom, NR ５ ４ (R ５ may be the same or different and is H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2.) General formula (5'): (H-(CF ２ )) １４ -COO) ｐ M １ (wherein, M １ is H, a metal atom, NR ５ ４ (R ５ may be the same or different and is H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2.)

9. Furthermore, the composition according to any one of Claims 5 to 8, which contains the compound represented by the following general formula (7) in an amount of 1000 ppb or less with respect to polytetrafluoroethylene. General formula (7): (F-(CF ２ )) ７ -COO) ｐ M １ (In the formula, M １ is H, a metal atom, NR ５ ４ (R ５ may be the same or different and is H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2.)

10. The composition according to any one of Claims 5 to 9, wherein the content of the compound represented by general formula (3) is 25 ppb or less with respect to polytetrafluoroethylene.

11. The composition according to any one of Claims 5 to 10, wherein the polytetrafluoroethylene is obtained by polymerization using an anionic hydrocarbon surfactant.

12. A molded article comprising the composition according to any one of Claims 5 to 11.

13. The molded article according to Claim 12, which is a stretched body.

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