JP6945283B2 - Gemini-type surfactant - Google Patents

Description

The present invention relates to a Gemini-type surfactant.

Surfactants generally have one hydrophilic group and one hydrophobic group in the molecule. On the other hand, a dimeric compound called a gemini-type surfactant is a compound having two hydrophilic groups and two hydrophobic groups. The compound having three hydrophilic groups and three hydrophobic groups is called a trimeric type surfactant, and the compound having four hydrophilic groups and four hydrophobic groups is called a tetrameric type surfactant. Then, these multimeric compounds are also treated as a category of Gemini-type surfactants. Such Gemini-type surfactants include cationic, anionic, nonionic and amphoteric agents depending on the nature of the hydrophilic group. Gemini-type surfactants have unique physical properties resulting from the binding of two hydrophilic groups in close proximity and the resulting micellar properties, such as detergents, softeners, emulsifiers, dispersants, surface treatment agents, and antistatic agents. It can be used as a phase transfer catalyst, a bactericide, and as an ingredient in skin care lotions, hair conditioners and cosmetics. Specifically, the Gemini-type surfactants described in Patent Documents 1 to 4 are known.

Since a Gemini-type surfactant is a compound having two or more hydrophilic groups and two or more hydrophobic groups, many steps are required to synthesize it. In addition, the Gemini-type surfactant needs to secure a high yield, which is disadvantageous in terms of cost.

Special Table 2003-505339A Japanese Unexamined Patent Publication No. 2006-298864 JP-A-2007-176844 Japanese Unexamined Patent Publication No. 2012-62246

The present invention has been made in view of the above background art, and an object of the present invention is to provide a Gemini-type surfactant having a novel structure and being easily synthesized.

As a result of diligent studies on the Gemini-type surfactant, the present inventors have found a Gemini-type surfactant having a novel structure and can be easily synthesized, and have completed the present invention.

That is, the present invention relates to a Gemini-type surfactant as shown below.

[1] A Gemini-type surfactant represented by the following formulas (1), (3) or (4).

[In the above formula (1), R _{1 to} R ₄ are independently alkyl groups having 1 to 20 carbon atoms, hydroxyalkyl groups having 1 to 20 carbon atoms, alkyl halide groups having 1 to 20 carbon atoms, or Represents an aromatic hydrocarbon group having 6 to 20 carbon atoms. R represents an alkyl group having 6 to 20 carbon atoms, a hydroxyalkyl group having 6 to 20 carbon atoms, an alkyl halide group having 6 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. Y ₁ and Y ₂ independently represent an alkylene group having 1 to 6 carbon atoms. n represents an integer of 1-2. A ⁻ represents a counter ion. Note that R _{1 to} R ₂ and R _{3 to} R ₄ are always the same combination. -Z- is

(In the above formula (2), _{R 5} represents an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or aromatic having 6 to 20 carbon atoms Represents a group hydrocarbon group.)
Represents. ]

[In the above formula (3), R _{1 to} R ₅ are independently alkyl groups having 1 to 20 carbon atoms, hydroxyalkyl groups having 1 to 20 carbon atoms, alkyl halide groups having 1 to 20 carbon atoms, or Represents an aromatic hydrocarbon group having 6 to 20 carbon atoms. R represents an alkyl group having 6 to 20 carbon atoms, a hydroxyalkyl group having 6 to 20 carbon atoms, an alkyl halide group having 6 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. Y1 and Y2 each independently represent an alkylene group having 1 to 6 carbon atoms. n represents an integer of 1-2. A ⁻ represents a counter ion. Note that R _{1 to} R ₂ and R _{3 to} R ₄ are always the same combination. ]

[In the above formula (4), R _{1 to} R ₅ are independently an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, an alkyl halide group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. Represents an aromatic hydrocarbon group having 6 to 20 carbon atoms. R represents an alkyl group having 6 to 20 carbon atoms, a hydroxyalkyl group having 6 to 20 carbon atoms, an alkyl halide group having 6 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. Y ₁ and Y ₂ independently represent an alkylene group having 1 to 6 carbon atoms. n represents an integer of 2-4. A ⁻ represents a counter ion. Note that R _{1 to} R ₂ and R _{3 to} R ₄ are always the same combination. ]
[2] In the above formula (1), formula (3) or formula (4), R represents an alkyl group having 8 to 16 carbon atoms, and R _{1 to} R ₅ are independent of each other and have 1 to 4 carbon atoms. The gemini-type surfactant according to the above [1], which represents an alkyl group or a hydroxyalkyl group of the above, and A ⁻ represents a fluorine ion, a chlorine ion, a bromine ion, or an iodine ion.

[3] 1,2-bis [methyldodecylammonium] dietandichloride, methyloctylbis [3- (dimethyloctylammonio) propyl] ammonium tribromid, methyldecylbis [3- (dimethyldecylammonio) propyl] ammonium The above [1] selected from the group consisting of tribromid, methyldodecylbis [3- (dimethyldodecylammonio) propyl] ammonium tribromid and methyltetradecylbis [3- (dimethyltetradecylammonio) propyl] ammonium tribromid. ] Or [2], the gemini-type surfactant.

[4] Any of the above [1] to [3], which comprises reacting a tertiary amine compound represented by the following formula (5) with a halogenated hydrocarbon compound represented by the following formula (7). The method for producing a Gemini-type surfactant according to.

[In the above formula (5), R _{1 to} R ₄ are independently an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, an alkyl halide group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. Represents an aromatic hydrocarbon group having 6 to 20 carbon atoms. Y ₁ and Y ₂ independently represent an alkylene group having 1 to 6 carbon atoms. n represents an integer from 0 to 2. Note that R _{1 to} R ₂ and R _{3 to} R ₄ are always the same combination. -Z- is

(In the formula (6), _{R 5} is an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or aromatic having 6 to 20 carbon atoms Represents a group hydrocarbon group.)
Represents. ]

[In the above formula (7), R is an alkyl group having 6 to 20 carbon atoms, a hydroxyalkyl group having 6 to 20 carbon atoms, an alkyl halide group having 6 to 20 carbon atoms, or an aromatic hydrocarbon having 6 to 20 carbon atoms. It represents a hydrogen group and X represents a halogen atom. ]
[5] In the above formulas (5) and (6), R _{1 to} R ₅ are independently methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, respectively. Tetradecyl group, hexadecyl group, octadecyl group, icosyl group, hydroxymethyl group, hydroxyethyl group, hydroxybutyl group, hydroxyhexyl group, hydroxyoctyl group, hydroxydecyl group, hydroxydodecyl group, hydroxytetradecyl group, hydroxyhexadecyl group, From the group consisting of hydroxyicosyl group, phenyl group, benzyl group, phenylethyl group, phenylbutyl group, phenylhexyl group, phenyloctyl group, phenyldecyl group, phenyldodecyl group, phenyltetradecyl group and their structural isomers. The above [4], wherein Y ₁ and Y ₂ are selected from the group consisting of a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and structural isomers thereof. A method for producing a Gemini-type surfactant.

[6] The tertiary amine compound represented by the above formula (5) is N, N, N', N'-tetramethyl-1,2-ethylenediamine, N, N, N', N'-tetramethyl-1. , 3-Diaminopropane, N, N, N', N'-tetramethyl-1,2-diaminopropane, N, N, N', N'-tetramethyl-1,4-diaminobutane, N, N, N', N'-tetramethyl-1,2-diaminobutane, N, N, N', N'-tetramethyl-1,3-diaminobutane, N, N, N', N'-tetramethyl-1 , 6-Diaminohexane, bis (2-dimethylaminoethyl) ether, N, N, N', N ", N" -pentamethyldiethylenetriamine, N, N, N', N ", N" ", N" " -Hexamethyltriethylenetetramine, N, N, N', N ", N"', N "", N ""-Heptamethyltetraethylenepentamine, N, N, N', N ", N"', N "", N "" ", N" "'-Octamethylpentaethylenehexamine, N, N'-dimethylpiperazine, N, N", N "-trimethylaminoethylpiperazine, N-methyl-N'-hydroxyethyl Piperazine, Triethylenediamine, N, N, N'-trimethyl-N'-Hydroxyethylethylenediamine, N, N, N', N', N'-Pentamethyldipropylenetriamine, N, N'-N "-Tris ( The method for producing a gemini-type surfactant according to the above [4] or [5], which is selected from the group consisting of 3-dimethylaminopropyl) hexahydrotriazine and 1,2-dimethylimidazole.

[7] In the above formula (7), R is a hexyl group, an octyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, an icosyl group, a hydroxyhexyl group, a hydroxyoctyl group, a hydroxydecyl group and a hydroxydodecyl. Group, hydroxytetradecyl group, hydroxyhexadecyl group, hydroxyicosyl group, phenyl group, benzyl group, phenylethyl group, phenylbutyl group, phenylhexyl group, phenyloctyl group, phenyldecyl group, phenyldodecyl group, phenyltetradecyl group. The above [4] to [6], wherein X is selected from the group consisting of groups and structural isomers thereof, and X is selected from the group consisting of fluorine atom, chlorine atom, bromine atom, and iodine atom. The method for producing a Gemini-type surfactant according to any one.

[8] The halogenated hydrocarbon compound represented by the above formula (7) is chloromethane, chloroethane, chloropropane, chlorobutane, chloropentane, chlorohexane, chlorooctane, chlorodecane, chlorododecane, chlorotetradecane, chlorohexadecan, chloroicosan, chloro. Fluoromethane, chlorodifluoromethane, chlorotrifluoromethane, 1-chloro-2,2,2-trifluoroethane, 1-chloro-3,3,3-trifluoropropane, 1-chloro-4,4,5-tri Fluorobutane, 1-chloro-6,6,6-trifluorohexane, 1-chloro-8,8,8-trifluorooctane, 1-chloro-10,10,10-trifluorodecane, 1-chloro-12 , 12,12-Trifluorododecane, 1-chloro-16,16,16-trifluorohexadecan, 1-chloro-20,20,20-trifluoroicosan, 1-chloro-1-perfluoroethylmethane, 1- Chloro-2-perfluoroethyl ethane, 1-chloro-3-perfluoroethyl propane, 1-chloro-4-perfluoroethylbutane, 1-chloro-6-perfluoroethyl hexane, 1-chloro-8-perfluoro Ethyloctane, 1-chloro-10-perfluoroethyl decan, 1-chloro-12-perfluoroethyl dodecane, 1-chloro-16-perfluoroethyl hexadecane, 1-chloro-18-perfluoroethyl octadecane, 1-chloro -1-Perfluorobutylmethane, 1-chloro-2-perfluorobutylethane, 1-chloro-3-perfluorobutylpropane, 1-chloro-4-perfluorobutylbutane, 1-chloro-6-perfluorobutyl Hexane, 1-chloro-8-perfluorobutyl octane, 1-chloro-10-perfluorobutyl decane, 1-chloro-12-perfluorobutyl dodecane, 1-chloro-16-perfluorobutyl hexadecane, 1-chloro- 1-Perfluorohexylmethane, 1-chloro-2-perfluorohexylethane, 1-chloro-3-perfluorohexylpropane, 1-chloro-4-perfluorohexylbutane, 1-chloro-6-perfluorohexane hexane , 1-Chloro-8-perfluorohexane octane, 1-chloro-10-perfluorohexane dodecane, 1-chloro-12-perfluorohexane dodecane, 1-chloro-16-perfluorohexane Syltetradecane, 1-chloro-1-perfluorooctylmethane, 1-chloro-2-perfluorooctylethane, 1-chloro-3-perfluorooctylpropane, 1-chloro-4-perfluorooctylbutane, 1-chloro -6-Perfluorooctyl hexane, 1-chloro-8-perfluorooctyl octane, 1-chloro-10-perfluorooctyldecane, 1-chloro-12-perfluorooctyldodecane, chlorobenzene, benzyl chloride, naphthylmethyl chloride, Anthracenylmethyl chloride, 2-fluoro-1-chlorobenzene, 2,4-difluoro-1-chlorobenzene, 2,4,6-trifluoro-1-chlorobenzene, pentafluoro-1-chlorobenzene, 2-fluorobenzyl chloride, 2,4-difluorobenzyl chloride, 2,4,6-trifluorobenzyl chloride, pentafluorobenzyl chloride, dibromoethane, dichloroethane, dibromopropane, dichloropropane, dibromobutane, dichlorobutane, dibromopentane, dichloropentane, dibromohexane, The method for producing a gemini-type surfactant according to any one of the above [4] to [7], which is selected from the group consisting of dichlorohexane and structural isomers thereof.

[9] The method for producing a gemini-type surfactant according to any one of the above [4] to [8], wherein R represents an alkyl group having 8 to 16 carbon atoms in the above formula (7). ..

The Gemini-type surfactant of the present invention is extremely useful industrially because it can be synthesized by a simple method using an inexpensive raw material and is excellent in economy and productivity.

Further, since the Gemini-type surfactant of the present invention has high surfactant ability and is excellent in safety and operability, it is a detergent composition, a dispersant composition, a bactericidal agent composition, an emulsifier composition, and a flexible material. It can be used as a constituent material of material compositions, surface treatment agent compositions, and antistatic agent compositions, and contains detergents, dispersants, bactericides, emulsifiers, softeners, surface treatment agents, and antistatic agents. It can be widely used as an inhibitor and the like.

^{It represents the 1 1} H-NMR spectrum of "2C12PMA" obtained in Example 1 and "2C10ETS" obtained in Example 2. ^{It represents the 1 1} H-NMR spectrum of "2C14ETS" obtained in Example 3 and "2C16ETS" obtained in Example 4. Example obtained in 5 '2C12DMP · 2Br ^- "and obtained in Example 6" 2C12DMP · 2Cl ^{- "1} H-NMR spectrum of the. ¹ H-NMR spectrum of "3C8PMA" obtained in Example 7 and "3C10PMA" obtained in Example 8 is represented. ¹ H-NMR spectra of "3C12PMA" obtained in Example 9 and "3C14PMA" obtained in Example 10 are represented. ¹ H-NMR spectrum of "3C8lin-6-Q" obtained in Example 11 and "3C10lin-6-Q" obtained in Example 12 is shown. ¹ H-NMR spectrum of "3C12lin-6-Q" obtained in Example 13 and "3C14lin-6-Q" obtained in Example 14 is shown. The elemental analysis results of the compounds obtained in Examples 1 (No. 1) to 14 (No. 14) are shown.

The Gemini-type surfactant of the present invention has a structure represented by the above formulas (1), (3) or (4).

Here, the alkyl group having 1 to 20 carbon atoms is not particularly limited, but for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and a nonyl group. , Decyl group, Undecyl group, Dodecyl group, Tridecyl group, Tetradecyl group, Pentadecyl group, Hexadecyl group, Heptadecyl group, Octadecyl group, Nonadecil group, Icosyl group and other linear alkyl groups, their branched alkyl groups and their cyclic groups. Examples thereof include an alkyl group.

The hydroxyalkyl group having 1 to 20 carbon atoms is not particularly limited, and examples thereof include those in which a hydroxyl group is substituted with a hydrocarbon in the above-mentioned alkyl group having 1 to 20 carbon atoms.

The alkyl halide group having 1 to 20 carbon atoms is not particularly limited, and examples thereof include the above-mentioned hydrocarbons in the alkyl groups having 1 to 20 carbon atoms in which a halogen atom is substituted. Taking the case where the halogen atom is a fluorine atom as an example, specifically, a linear halogenated alkyl group such as a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group to a perfluoroicosyl group, and branches thereof. Examples thereof include alkyl halide groups and cyclic alkyl halide groups thereof.

The aromatic hydrocarbon having 6 to 20 carbon atoms is not particularly limited, but for example, a phenyl group, a benzyl group, a styryl group, a 2-phenylethyl group, a 2-phenylvinyl group, 2,4. Examples thereof include a 6-trimethylphenyl group, a naphthyl group, an anthracenyl group, and their positional isomers.

The alkylene group having 1 to 6 carbon atoms is not particularly limited, but for example, a linear alkylene group such as a methylene group, an ethylene group or a pentylene group, an ethylidene group, an isopropylidene group, 1, 1, 2 , 2-Branched alkylene group such as tetramethylethylene group and the like. Of these, an ethylene group, a propylene group, a butylene group, and a hexylene group are preferable.

The alkyl group having 6 to 20 carbon atoms is not particularly limited, but for example, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group and a pentadecyl group. , Hexadecyl group, heptadecyl group, octadecyl group, nonadecil group, eicosyl group and other linear alkyl groups, their branched alkyl groups, their cyclic alkyl groups and the like.

The hydroxyalkyl group having 6 to 20 carbon atoms is not particularly limited, and examples thereof include those in which a hydroxyl group is substituted with a hydrocarbon in the above-mentioned alkyl group having 6 to 20 carbon atoms.

The alkyl halide group having 6 to 20 carbon atoms is not particularly limited, and examples thereof include those in which the hydrocarbon in the alkyl group having 6 to 20 carbon atoms is substituted with a halogen atom. Taking the case where the halogen atom is a fluorine atom as an example, specifically, a linear alkyl halide group such as a perfluoroeicosyl group, a branched alkyl halide group thereof, and a cyclic alkyl halide group thereof Etc. are exemplified.

In the above formulas (1), (3) and (4), the ^{counter ion represented by A −} is not particularly limited, but for example, hydroxide ion, fluorine ion, chlorine ion, bromine ion, and the like. Examples thereof include halide ions such as iodine ions, nitrate ions, formate ions, acetate ions, trifluoroacetate ions, p-toluene sulfonate ions, hexafluorophosphate, tetrafluoroborate and the like.

In the above formulas (1), (3) and (4), the ^{counter ion represented by A −} is from halide ions such as fluorine ion, chlorine ion, bromine ion and iodine ion to nitrate ion, formate ion and acetate ion. , Trifluoroacetate ion, p-toluene sulfonate ion, hexafluorophosphate, tetrafluoroborate and other counter ions may be exchanged. Can be exchanged for.

In the above formulas (1), (3) and (4) ^{, two or more types of counter ions represented by A −} may be combined, and the types and ratios in that case are not particularly limited and may be arbitrarily changed. be able to.

In the above equation (1), n represents an integer of 1 to 2.

Considering the water solubility as a gemini-type surfactant and the critical micelle concentration (cmc), the R in the above formulas (1), (3) and (4) is preferably an alkyl group having 8 to 16 carbon atoms. In particular, an alkyl group having 13 to 16 carbon atoms is preferable. As R1 to R5, an alkyl group or a hydroxyalkyl group having 1 to 4 carbon atoms is preferable independently, and as A-, a fluorine ion, a chlorine ion, a bromine ion, or an iodine ion is preferable.

The Gemini-type surfactant represented by the above formula (1) is not particularly limited, but for example, when R is a dodecyl group and A- is a bromine ion, bis (N-dodecyl-N) is exemplified. , N-dimethylpropylammonium) -N'-methylamine dibromid, bis (N-dodecyl-N, N-dimethylethylammonium) ether dibromid, 1,2-bis [methyldodecylammonium] dietandibromid, methyldodecyl Examples thereof include compounds selected from the group consisting of bis [3- (dimethyldodecyl ammonio) propyl] ammonium tribromid. Further, in the above compound, the dodecyl group of R was replaced with an octyl group, a decyl group, a tetradecyl group, a hexadecyl group, or an octadecyl group, and the bromine atom of A- was replaced with a chlorine atom, a fluorine atom, and an iodine atom. Compounds are also mentioned as Gemini-type surfactants represented by the above formulas (1), (3) and (4).

Of these, bis (N-dodecyl-N, N-dimethylpropylammonium) -N'-methylamine dibromid, bis (N-decyl-N, N-dimethylethylammonium) ether dibromid, bis (N-tetradecyl) -N, N-dimethylethylammonium) ether dibromide, bis (N-hexadecyl-N, N-dimethylethylammonium) ether dibromide, 1,2-bis [methyldodecylammonium] dietandichloride, methyloctylbis [3 -(Dimethyloctylammonio) propyl] ammonium tribromid, methyldecylbis [3- (dimethyldecylammonio) propyl] ammonium tribromid, methyldodecylbis [3- (dimethyldodecylammonio) propyl] ammonium tribromid, methyl Compounds selected from the group consisting of tetradecylbis [3- (dimethyltetradecylammonio) propyl] ammonium tribromid, and in these compounds, the dodecyl group of R is an octyl group, a decyl group, a tetradecyl group, a hexadecyl group. , Or a compound in which the bromine atom of A- is replaced with a chlorine atom, a fluorine atom, or an iodine atom. Suitable as an agent.

The Gemini-type surfactant represented by the above formulas (1), (3) or (4) can be produced, for example, by the following method. That is, it can be produced by reacting the tertiary amine compound represented by the above formula (5) with the halogenated hydrocarbon compound represented by the above formula (7).

In this case, it is preferable to dissolve the tertiary amine compound represented by the above formula (5) in an organic solvent such as acetone, acetonitrile or toluene or water, and add the halogenated hydrocarbon compound to react.

Here, the alkyl group having 1 to 20 carbon atoms is not particularly limited, but for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and a nonyl group. , Decyl group, Undecyl group, Dodecyl group, Tridecyl group, Tetradecyl group, Pentadecyl group, Hexadecyl group, Heptadecyl group, Octadecyl group, Nonadecil group, Icosyl group and other linear alkyl groups, their branched alkyl groups and their cyclic groups. Examples thereof include an alkyl group. Of these, octyl group, nonyl group, decyl group, undecylic group, dodecyl group, tridecylic group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecylic group and icosyl group are preferable, and octyl group and decyl group are preferable. , Dodecyl group, hexadecyl group, octadecyl group and icosyl group are more preferable.

The hydroxyalkyl group having 1 to 20 carbon atoms is not particularly limited, and examples thereof include those in which a hydroxyl group is substituted with a hydrocarbon in the above-mentioned alkyl group having 1 to 20 carbon atoms.

The alkyl halide group having 1 to 20 carbon atoms is not particularly limited, and examples thereof include the above-mentioned hydrocarbons in the alkyl groups having 1 to 20 carbon atoms in which a halogen atom is substituted. Taking the case where the halogen atom is a fluorine atom as an example, specifically, a linear halogenated alkyl group such as a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group to a perfluoroicosyl group, and branches thereof. Examples thereof include alkyl halide groups and cyclic alkyl halide groups thereof.

The aromatic hydrocarbon having 6 to 20 carbon atoms is not particularly limited, but for example, a phenyl group, a benzyl group, a styryl group, a 2-phenylethyl group, a 2-phenylvinyl group, 2,4. Examples thereof include a 6-trimethylphenyl group, a naphthyl group, an anthracenyl group, and their positional isomers.

The alkylene group having 1 to 6 carbon atoms is not particularly limited, but for example, a linear alkylene group such as a methylene group, an ethylene group or a pentylene group, an ethylidene group, an isopropylidene group, 1, 1, 2 , 2-Branched alkylene group such as tetramethylethylene group and the like. Of these, an ethylene group, a propylene group, a butylene group, and a hexylene group are preferable.

Further, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

Considering the water solubility as a gemini-type surfactant and the critical micelle concentration (cmc), R _{1 to} R ₄ in the above formula (5) are independently alkyl groups having 1 to 4 carbon atoms or hydroxy. Alkyl groups are preferred.

The tertiary amine compound represented by the above formula (5) is not particularly limited, but for example, N, N, N', N'-tetramethyl-1,2-ethylenediamine, N, N, N'. , N'-tetramethyl-1,3-diaminopropane, N, N, N', N'-tetramethyl-1,2-diaminopropane, N, N, N', N'-tetramethyl-1,4 -Diaminobutane, N, N, N', N'-tetramethyl-1,2-diaminobutane, N, N, N', N'-tetramethyl-1,3-diaminobutane, N, N, N' , N'-tetramethyl-1,6-diaminohexane, N, N, N', N ", N" -pentamethyldiethylenetriamine, N, N, N', N ", N"', N "'-hexa Methyltriethylenediamine, N, N, N', N ", N"', N "", N ""-Heptamethyltetraethylenepentamine, N, N, N', N ", N"', N " ", N" "', N" "'-Octamethylpentaethylenehexamine, N, N, N'-trimethyl-N'-hydroxyethylethylenediamine, bis (2-dimethylaminoethyl) ether, N, N'-dimethyl Examples thereof include compounds selected from the group consisting of -N, N'-didodecylethylenediamine and N, N, N', N', N'-pentamethyldipropylenetriamine.

Of these, it consists of N, N, N', N ", N" -pentamethyldipropylenetriamine, bis (2-dimethylaminoethyl) ether and N, N'-dimethyl-N, N'-didodecylethylenediamine. Compounds selected from the group are preferred.

As the tertiary amine compound represented by the above formula (5), a commercially available product may be used, but for example, it can also be synthesized by the following method.

That is, a tertiary amine compound represented by the above formula (5) is synthesized from the corresponding primary amine compound or secondary amine compound. The synthesis of the tertiary amine compound can be carried out by a known method and is not particularly limited. For example, in the presence of palladium carbon and hydrogen, the primary amine compound or the secondary amine compound, formaldehyde, acetaldehyde and the like can be used. A tertiary amine compound can be obtained by adding the aldehyde compound of.

The halogenated hydrocarbon compound represented by the above formula (7) is not particularly limited. Examples of compounds in which X is a chlorine atom include chloromethane, chloroethane, chloropropane, chlorobutane, chloropentane, chlorohexane, chlorooctane, chlorodecane, chlorododecane, chlorotetradecane, chlorohexadecan, chloroicosan, chlorofluoromethane, chlorodifluoromethane, Chlorotrifluoromethane, 1-chloro-2,2,2-trifluoroethane, 1-chloro-3,3,3-trifluoropropane, 1-chloro-4,4,5-trifluorobutane, 1-chloro- 6,6,6-trifluorohexane, 1-chloro-8,8,8-trifluorooctane, 1-chloro-10,10,10-trifluorodecane, 1-chloro-12,12,12-trifluoro Dodecane, 1-chloro-16,16,16-trifluorohexadecan, 1-chloro-20,20,20-trifluoroicosan, 1-chloro-1-perfluoroethylmethane, 1-chloro-2-perfluoroethyl Etan, 1-chloro-3-perfluoroethyl propane, 1-chloro-4-perfluoroethylbutane, 1-chloro-6-perfluoroethyl hexane, 1-chloro-8-perfluoroethyl octane, 1-chloro- 10-Perfluoroethyl decane, 1-chloro-12-perfluoroethyl dodecane, 1-chloro-16-perfluoroethyl hexadecane, 1-chloro-18-perfluoroethyl octadecane, 1-chloro-1-perfluorobutylmethane , 1-Chloro-2-perfluorobutylethane, 1-chloro-3-perfluorobutylpropane, 1-chloro-4-perfluorobutylbutane, 1-chloro-6-perfluorobutylhexane, 1-chloro-8 -Perfluorobutyl octane, 1-chloro-10-perfluorobutyl decane, 1-chloro-12-perfluorobutyl dodecane, 1-chloro-16-perfluorobutyl hexadecane, 1-chloro-1-perfluorohexane methane, 1-Chloro-2-perfluorohexyl ethane, 1-chloro-3-perfluorohexylpropane, 1-chloro-4-perfluorohexylbutane, 1-chloro-6-perfluorohexane hexane, 1-chloro-8- Perfluorohexyl octane, 1-chloro-10-perfluorohexyl decane, 1-chloro-12-perfluorohexane dodecane, 1-chloro-16-perfluorohexyl tetradecane, 1-Chloro-1-perfluorooctylmethane, 1-chloro-2-perfluorooctylethane, 1-chloro-3-perfluorooctylpropane, 1-chloro-4-perfluorooctylbutane, 1-chloro-6- Perfluorooctylhexane, 1-chloro-8-perfluorooctyloctane, 1-chloro-10-perfluorooctyldecane, 1-chloro-12-perfluorooctyldodecane, chlorobenzene, benzyl chloride, naphthylmethylchloride, anthracenyl Methyl chloride, 2-fluoro-1-chlorobenzene, 2,4-difluoro-1-chlorobenzene, 2,4,6-trifluoro-1-chlorobenzene, pentafluoro-1-chlorobenzene, 2-fluorobenzyl chloride, 2,4 -Difluorobenzyl chloride, 2,4,6-trifluorobenzyl chloride, pentafluorobenzyl chloride, dibromoethane, dichloroethane, dibromopropane, dichloropropane, dibromobutane, dichlorobutane, dibromopentane, dichloropentane, dibromohexane, dichlorohexane and Examples thereof include structural isomers thereof.

Considering the water solubility as a gemini-type surfactant and the critical micelle concentration (cmc), R in the above formula (7) is preferably an alkyl group or an alkylene group having 8 to 16 carbon atoms. More preferably, it is an alkyl group or an alkylene group having 13 to 16 carbon atoms.

The reaction between the tertiary amine compound represented by the above formula (5) and the halogenated hydrocarbon compound represented by the above formula (7) is preferably carried out at a reaction temperature from room temperature to the boiling point of the solvent. When the boiling point of the raw material is lower than the boiling point of the solvent, the raw material can be returned to the reaction solution by a reflux operation by a known method.

The halogenated hydrocarbon compound represented by the above formula (7) may be added to the place where the tertiary amine compound represented by the above formula (5) is dissolved in the above organic solvent or water, and the above formula (7) may be added. The tertiary amine compound represented by the above formula (5) may be added to the halogenated hydrocarbon compound represented by the above dissolved in the above organic solvent or water, and the tertiary amine compound represented by the above formula (5) may be added. Each of the amine compound and the halogenated hydrocarbon compound represented by the above formula (7) may be dissolved in the above organic solvent or water and mixed, and is not particularly limited. Of these, it is preferable to add the halogenated hydrocarbon compound represented by the above formula (7) to the place where the tertiary amine compound represented by the above formula (5) is dissolved in the above organic solvent or water.

After completion of the reaction, the raw material can be removed by a known method such as washing or distillation. Further, it can be purified by a known method such as recrystallization and crystallization using an organic solvent such as acetone, acetonitrile, toluene, ethers and alcohols, water and the like.

The Gemini-type surfactant represented by the above formulas (1), (3) or (4) is, for example, a detergent composition, a dispersant composition, a bactericidal agent composition, an emulsifier composition, a softener composition, and a surface. It can be used as a constituent substance of treatment agent compositions, antistatic agent compositions, etc., and is widely used as detergents, dispersants, bactericides, emulsifiers, softeners, surface treatment agents, antistatic agents, etc. containing these compositions. Can be used for.

Examples of the detergent composition containing the Gemini-type surfactant represented by the above formulas (1), (3) or (4) include, for example.
(A) Gemini-type surfactant represented by the above formulas (1), (3) or (4),
(B) Polyoxyalkylene amine,
Detergent composition containing (c) alkylamine and (d) nonionic surfactant,
(A) Gemini-type surfactant represented by the above formulas (1), (3) or (4),
(B) Anionic surfactant,
A detergent composition containing (c) an amphoteric surfactant and (d) a polyhydric alcohol, and (a) a Gemini-type surfactant represented by the above formulas (1), (3) or (4).
Examples thereof include (b) a water-soluble metal salt, and (c) a detergent composition containing polyethyleneimine or an alkylamine. The type and ratio of each of these components are not particularly limited.

Examples of the dispersant composition containing the Gemini-type surfactant represented by the above formulas (1), (3) or (4) include, for example.
(A) Gemini-type surfactant represented by the above formulas (1), (3) or (4),
(B) Polyester compounds,
Examples thereof include (c) a polycarboxylic acid-based copolymer and (d) a dispersant composition containing water. The type and ratio of each of these components are not particularly limited.

Examples of the bactericidal composition containing the Gemini-type surfactant represented by the above formulas (1), (3) or (4) include, for example.
(A) A bactericidal composition containing a gemini-type surfactant represented by the above formulas (1), (3) or (4), and (b) triethanolamine.
(A) Gemini-type surfactant represented by the above formulas (1), (3) or (4),
(B) Hypochlorous acids or hypochlorates,
Examples thereof include (c) an organic acid or a salt thereof, and (d) a bactericidal composition containing a rust preventive. The type and ratio of each of these components are not particularly limited.

Examples of the emulsifier composition containing the Gemini-type surfactant represented by the above formulas (1), (3) or (4) include, for example.
(A) Gemini-type surfactant represented by the above formulas (1), (3) or (4),
(B) Glycyrrhetinic acid derivative,
Examples thereof include (c) oils such as tocopherols and fatty acid esters, and (d) emulsifier compositions containing phospholipids. The type and ratio of each of these components are not particularly limited.

Examples of the softener composition containing the Gemini-type surfactant represented by the above formulas (1), (3) or (4) include, for example.
(A) Gemini-type surfactant represented by the above formulas (1), (3) or (4),
A softener composition containing (b) an anionic surfactant and (c) an aminocarboxylic acid-based chelating agent.
(A) Gemini-type surfactant represented by the above formulas (1), (3) or (4),
(B) Alkanolamine,
(C) Urea and its derivatives, and (d) Softener composition containing fragrance,
(A) Gemini-type surfactant represented by the above formulas (1), (3) or (4),
(B) Microcapsules containing fragrances, and (c) Softener compositions containing water-soluble solvents such as alcohol,
(A) Gemini-type surfactant represented by the above formula (1),
(B) Tertiary amine,
Examples thereof include (c) silica particles and (d) a softener composition containing a nonionic surfactant, and the type and ratio of each component are not particularly limited.

Examples of the surface treatment agent composition containing the Gemini-type surfactant represented by the above formulas (1), (3) or (4) include, for example.
(A) Gemini-type surfactant represented by the above formulas (1), (3) or (4),
(B) alkylene glycol alkyl ethers, alcohols, glycols,
Examples thereof include (c) a cleaning agent and (d) a surface treatment agent composition containing water. The type and ratio of each of these components are not particularly limited.

Examples of the antistatic agent composition containing the Gemini-type surfactant represented by the above formulas (1), (3) or (4) include, for example.
(A) Gemini-type surfactant represented by the above formulas (1), (3) or (4),
(B) Aqueous polyolefin wax, and (c) Antistatic composition containing water,
(A) Gemini-type surfactant represented by the above formulas (1), (3) or (4),
(B) Anti-aggregation agents such as polyalkylene glycol derivatives,
An antistatic agent composition containing (c) an inorganic compound containing silicon, calcium, etc., and optionally (d) a thermoplastic resin such as polyethylene, polyvinyl chloride, polystyrene, etc.
Examples thereof include (a) a gemini-type surfactant represented by the above formulas (1), (3) or (4), and (b) an antistatic agent composition containing a carboxy-modified polyolefin. The type and ratio of each of these components are not particularly limited.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

The elemental analysis, NMR, and critical micelle concentration (cmc) in Examples and Comparative Examples were measured by the following methods.

<Elemental analysis>
Measured using a Perkin-Elmer 2400II CHNS / O.

<NMR measurement>
JEOL (JEOL Ltd.) JNM-EX was used.

<Measurement method of critical micelle concentration (cmc)>
An aqueous solution of each surfactant was prepared. An aqueous solution of each surfactant was added dropwise to a cell containing 50 ml of Millipore water kept at 25 ° C., and the electrical conductivity at that time was recorded. The relationship between the concentration of each surfactant and the electrical conductivity was plotted on a graph, and the critical micelle concentration (cmc) was calculated from the bending point.

Example 1 (Synthesis of Gemini Surfactant)
10.0 g (0.050 mol) of N, N, N', N ", N" -pentamethyldipropylene triamine (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight = 201.35) was dissolved in acetonitrile and heated to 80 ° C. , 12.4 g (0.050 mol) of 1-bromododecane (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight = 249.24) was added dropwise thereto over 5 hours. After reacting at 80 ° C. for 50 hours, the solvent was distilled off, and the mixture was washed with hexane and ethyl acetate. After washing, solid-liquid separation by centrifugation and recrystallization are repeated to 9.13 g of bis (N-dodecyl-N, N-dimethylpropylammonium) -N'-methylamine dibromid (referred to as "2C12PMA"). (Yield 52%) was obtained. The structure of the product ^{was confirmed by 1 1} H-NMR and elemental analysis.

Example 2 (Synthesis of Gemini Surfactant)
N, N, N', N ", N" -Bis (2-dimethylaminoethyl) ether (manufactured by Tosoh, TOYOCAT-ETS, molecular weight = 160.26) 10.0 g (0) instead of pentamethyldipropylene triamine .062 mol), 1-bromodecane (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight = 221.18) 36.0 g (0.163 mol) was used in place of 1-bromododecane, as described in Example 1. By the same operation as the operation, 31.5 g (yield 83%) of bis (N-decyl-N, N-dimethylethylammonium) ether dibromid (referred to as "2C10ETS") was obtained. The structure of the product ^{was confirmed by 1 1} H-NMR and elemental analysis.

Example 3 (Synthesis of Gemini Surfactant)
The same operation as that described in Example 2 except that 45.2 g (0.163 mol) of 1-bromotetradecane (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight = 277.29) was used instead of 1-bromodecane. Obtained 41.6 g (yield 93%) of bis (N-tetradecyl-N, N-dimethylethylammonium) ether dibromid (referred to as "2C14ETS"). The structure of the product ^{was confirmed by 1 1} H-NMR and elemental analysis.

Example 4 (Synthesis of Gemini Surfactant)
The same operation as that described in Example 2 except that 49.9 g (0.163 mol) of 1-bromohexadecane (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight = 305.34) was used instead of 1-bromodecane. Obtained 45.0 g (yield 93%) of bis (N-hexadecyl-N, N-dimethylethylammonium) ether dibromid (referred to as "2C16ETS"). The structure of the product ^{was confirmed by 1 1} H-NMR and elemental analysis.

Example 5 (Synthesis of Gemini Surfactant)
N, N'-dimethyl-N, N'-didodecylethylenediamine instead of N, N, N', N ", N" -pentamethyldipropylenetriamine, 1,2-dibromoethane instead of 1-bromododecane except for using by operating the same procedure as described in example 1, 1,2-bis [methyl dodecyl ammonium] Jie Tanji bromide ^- was obtained (referred to as "2C12DMP · 2Br"). The structure of the product ^{was confirmed by 1 1} H-NMR and elemental analysis.

Example 6 (Synthesis of Gemini Surfactant)
6.4 g of 1,2-bis [methyldodecylammonium] dietandibromid obtained in Example 5 was dissolved in methanol, and an ion exchange resin (Muromachi Technos Co., Ltd., Dawex 1 × 8, 50-100, Cl type) was dissolved. ) in two passes, the solvent was distilled off, recrystallized 1,2-bis [methyl dodecyl ammonium] Jie Tanji chloride ( "2C12DMP · 2Cl ^-" hereinafter) was obtained 5.04 g (93% yield). The structure of the product ^{was confirmed by 1 1} H-NMR and elemental analysis.

Example 7 (Synthesis of Gemini Surfactant (Trimeric))
The operation was the same as that described in Example 1 except that 58.0 g (0.300 mol) of 1-bromooctane (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight = 193.13) was used instead of 1-bromododecane. By the operation, 36.7 g (yield 94%) of methyloctylbis [3- (dimethyloctylammonio) propyl] ammonium tribromid (3C8PMA) was obtained. The structure of the product ^{was confirmed by 1 1} H-NMR and elemental analysis.

Example 8 (Synthesis of Gemini Surfactant (Trimeric))
Methyldecylbis [3- (dimethyldecylammonio) was performed in the same manner as in Example 1 except that 66.0 g (0.298 mol) of 1-bromodecane was used instead of 1-bromododecane. ) Propyl] Ammonium tribromid (referred to as "3C10PMA") 40.6 g (yield 94%) was obtained. The structure of the product ^{was confirmed by 1 1} H-NMR and elemental analysis.

Example 9 (Synthesis of Gemini Surfactant (Trimeric))
Methyldodecylbis [3- (dimethyldodecylammonio) propyl] ammonium tribromid was performed in the same manner as in Example 1 except that 75.5 g (0.303 mol) of 1-bromododecane was used. 45.0 g (referred to as "3C12PMA") (yield 94%) was obtained. The structure of the product ^{was confirmed by 1 1} H-NMR and elemental analysis.

Example 10 (Synthesis of Gemini Surfactant (Trimeric))
Methyltetradecylvis [3- (dimethyltetra) was performed in the same manner as in Example 1 except that 83.4 g (0.301 mol) of 1-bromotetradecane was used instead of 1-bromododecane. Decylammonio) Propyl] Ammonium tribromid (referred to as "3C14PMA") 44.9 g (yield 87%) was obtained. The structure of the product ^{was confirmed by 1 1} H-NMR and elemental analysis.

Example 11 (Synthesis of Gemini Surfactant (Trimeric))
8.6 g (0.030 mol) of N, N, N', N ", N" -pentamethyldihexylenetriamine was dissolved in acetonitrile, heated to 80 ° C., and then 1-bromooctane 34.8 (0). 180 mol) was added dropwise over 5 hours, followed by heating and stirring for 45 hours. After completion of the reaction, the solvent was distilled off under reduced pressure with an evaporator, the obtained residue was repeatedly washed with hexane and ethyl acetate, and the residue was recrystallized from a mixed solution of ethyl acetate-methanol (6: 1) to form a white solid methyloctyl. 6.60 g (35% yield) of bis [6- (dimethyloctylammonio) hexyl] ammonium tribromide (referred to as "3C8lin-6-Q") was obtained. The structure of the product ^{was confirmed by 1 1} H-NMR and elemental analysis.

N, N, N', N ", N" -pentamethyldihexylenetriamine was synthesized by the following procedure. Bis (hexamethylene) triamine (1.0 equiv), formic acid (17.0 equiv), and 37% formaldehyde (18.0 equiv) dissolved in methanol were mixed and heated under reflux for 5 to 6 hours. After completion of the reaction, 50 mL of hydrochloric acid was added, and the mixture was heated and stirred for 3 hours. The solvent was distilled off under reduced pressure by an evaporator, and the residue was washed twice with acetone and ethyl acetate, respectively, to obtain a white solid N, N, N', N ", N" -pentamethyldihexylenetriamine hydrochloride.

Example 12 (Synthesis of Gemini Surfactant (Trimeric))
10.0 g (0.0350 mol) of N, N, N', N ", N" -pentamethyldihexylenetriamine was used, and 46.4 g (0.210 mol) of 1-bromodecane was used instead of 1-bromooctane. Methyldecylbis [6- (dimethyldecylammonio) hexyl] ammonium tribromide (referred to as "3C10lin-6-Q") 11.9 g (yield) by the same operation as that described in Example 11 except for the above. Rate 61%) was obtained. The structure of the product ^{was confirmed by 1 1} H-NMR and elemental analysis.

Example 13 (Synthesis of Gemini Surfactant (Trimeric))
Methyl dodecylbis [6- (dimethyldodecylammonio) was performed in the same manner as in Example 12 except that 52.3 g (0.210 mol) of 1-bromododecane was used instead of 1-bromodecane. ) Hexil] Ammonium tribromid (referred to as "3C12lin-6-Q") 20.2 g (yield 77%) was obtained. The structure of the product ^{was confirmed by 1 1} H-NMR and elemental analysis.

Example 14 (Synthesis of Gemini Surfactant (Trimeric))
Methyltetradecylbis [6- (dimethyltetradecyl] was performed in the same manner as in Example 12 except that 58.2 g (0.210 mol) of 1-bromotetradecane was used instead of 1-bromodecane. Ammonio) hexyl] ammonium tribromid (referred to as "3C14lin-6-Q") was obtained in an amount of 8.42 g (yield 30%). The structure of the product ^{was confirmed by 1 1} H-NMR and elemental analysis.

Comparative example 1.
Dodecyltrimethylammonium bromide was synthesized as a single-chain surfactant by the following method.

That is, 10.0 g of 1-bromododecane (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in acetonitrile, heated to 80 ° C., and an excess amount of trimethylamine gas (manufactured by Aldrich) was blown into it. After the reaction, the solvent was distilled off, and the mixture was washed with hexane and ethyl acetate. After washing, solid-liquid separation by centrifugation and recrystallization were repeated to obtain 10.0 g (yield 80%) of dodecyltrimethylammonium bromide. The structure of the product ^{was confirmed by 1 1} H-NMR and elemental analysis.

Table 1 shows the critical micelle concentrations (cmc) of the gemini-type surfactants (including trimeric type) synthesized in Examples 1 to 4 and 6 to 14 and the single-chain type surfactants synthesized in Comparative Example 1. Also shown.

From Table 1, it can be seen that the compounds obtained in each example have a smaller cmc than the conventional surfactant of Comparative Example 1 and are excellent as a surfactant.

The Gemini-type surfactant of the present invention comprises, for example, a detergent composition, a dispersant composition, a bactericidal agent composition, an emulsifier composition, a softener composition, a surface treatment agent composition, an antistatic agent composition and the like. It can be used as a substance, and has the potential to be widely used as a detergent, a dispersant, a bactericide, an emulsifier, a softener, a surface treatment agent, an antistatic agent, etc. containing those compositions.

Claims (4)

Gemini-type surfactant represented by the following formula ( 3 ).

[In the above formula (3), R _{1 to} R ₅ represent a methyl group. R represents a tetradecyl group. Y ₁ and Y ₂ independently represent a propylene group, a butylene group, or a hexylene group. n represents an integer of 1-2. A ⁻ represents a counter ion . ] Oite to equation (3), A ^- is fluoride ion, chloride ion, gemini surfactant of claim 1, characterized in that bromine ion, or iodine ion. Gemini surfactant according to claim 1 or 2 represented by the methylation-tetradecyl-bis [3- (dimethyl tetradecyl ammonio) propyl] ammonium tribromide. The Gemini-type surfactant according to any one of claims 1 to 3, wherein the tertiary amine compound represented by the following formula (5) is reacted with the halogenated hydrocarbon compound represented by the following formula (7). A method for producing an activator.

[In the above formula (5), R _{1 to} R ₄ represent a methyl group. Y ₁ and Y ₂ independently represent a propylene group, a butylene group, or a hexylene group. n represents an integer of 1 to 2. -Z- is

(In the formula (6), _{R 5} represents a methyl group.)
Represents. ]

[In the above formula (7), R represents a tetradecyl group and X represents a halogen atom. ]

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