JP5072472B2 - Method for producing quaternary ammonium salt using intermediate carboxylic acid residue as counter ion - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a method for producing a quaternary ammonium salt having a counter ion as an intermediate carboxylic acid residue useful as a water-soluble processing oil agent, an aggregating agent such as a water-soluble detergent and a water treatment agent, and a demulsifier.

  Conventionally, various water-soluble processing fluids used in cutting, grinding and plastic working of metals, glass and ceramics, etc. include sliding surface lubricants, hydraulic oils, greases, etc. used in processing machines etc. A demulsifier is added to prevent emulsification due to contamination.

  The applicant has previously provided a quaternary ammonium salt having a intermediate carboxylic acid residue as a counter ion (Patent Document 1). Quaternary ammonium salts with intermediate carboxylic acid residues as counter ions show high demulsibility and do not contain halogen ions, so rusting, corrosion, and burning of metal parts such as machinery caused by halogen ions It is very useful as a demulsifier without problems such as dioxin generation.

  As a method for producing a quaternary ammonium salt having a intermediate carboxylic acid residue as a counter ion, Patent Document 1 discloses that a quaternary ammonium salt having a halogen ion as a counter ion is used as a raw material. A method in which halogen ions are reacted with potassium hydroxide, sodium hydroxide or the like in a polar solution such as methanol or ethanol to precipitate and remove them as potassium halide, sodium halide or the like, and then the treated product is reacted with intermediate carboxylic acid. , And a quaternary ammonium salt having a halogen ion as a counter ion with an anion exchange resin to exchange the halogen ion with a hydroxide ion (developing solvent: water). A method of using and neutralizing is described.

  However, in these methods, the quaternary ammonium gradually decomposes after the treatment with the alkali or anion exchange resin and before the reaction with the intermediate carboxylic acid, and the intermediate carboxylic acid residue is paired with the intermediate carboxylic acid residue. The quaternary ammonium salt used as an ion could not be produced with good yield. In addition, the treatment with an anion exchange resin has a problem of high cost.

Under such circumstances, development of a method for producing a quaternary ammonium salt having a intermediate carboxylic acid residue as a counter ion at a higher yield and lower cost is strongly desired.
Japanese Patent Laid-Open No. 11-181468

  An object of the present invention is to provide a method for producing a quaternary ammonium salt having a intermediate carboxylic acid residue as a counter ion in a high yield and at a low cost.

  As a result of intensive studies in view of the above-mentioned problems of the prior art, the present inventors have reacted a quaternary ammonium salt having a halogen ion as a counter ion and a salt of an intermediate carboxylic acid and an inorganic alkali in a polar solvent. And found that a quaternary ammonium salt having a intermediate carboxylic acid residue as a counter ion can be produced in a high yield, while the halogen ion can be substituted with an intermediate carboxylic acid residue while inhibiting the decomposition of the quaternary ammonium. It was. The present invention is based on such new knowledge.

Accordingly, the present invention provides the following methods:
Item 1. A quaternary ammonium salt having a halogen ion as a counter ion and a salt of an intermediate carboxylic acid and an inorganic alkali are reacted in a polar solvent to replace the halogen ion with an intermediate carboxylic acid residue. And a method for producing a quaternary ammonium salt using a intermediate carboxylic acid residue as a counter ion.
Item 2. The method according to Item 1, further comprising a step of removing an inorganic alkali halide produced in the reaction.
Item 3. The method according to Item 1 or 2, wherein the quaternary ammonium salt having a halogen ion as a counter ion is a salt of at least one of the following polymers (A) to (F) and a halogen ion:
(A) a polymer of a quaternary ammonium salt of a vinyl monomer having at least one cationic nitrogen atom,
(B) Copolymerization of a quaternary ammonium salt of a vinyl monomer having at least one cationic nitrogen atom and a vinyl monomer having at least one basic nitrogen atom or cationic nitrogen atom or a salt thereof. object,
(C) a copolymer of a quaternary ammonium salt of a vinyl monomer having at least one cationic nitrogen atom and a polymerizable monomer having no basic nitrogen atom or no cationic nitrogen atom,
(D) quaternized ammonium salt of polycondensate of polyalkylene polyamine and dihalogenated ethyl ether,
(E) A quaternized ammonium salt of a copolymer of a polyalkylene polyamine and a dihaloalkane and (F) a quaternized ammonium salt of a polycondensate of an alkylene diamine and an epoxy compound.

  Since the decomposition of quaternary ammonium is suppressed, the method of the present invention can produce a quaternary ammonium salt having a intermediate carboxylic acid residue as a counter ion in high yield. In addition, since the method of the present invention does not require expensive equipment, it can be performed at low cost.

  In the method of the present invention, (a) a quaternary ammonium salt having a halogen ion as a counter ion, and (b) a salt of an intermediate carboxylic acid and an inorganic alkali are reacted in a polar solvent to convert the halogen ion to an intermediate carboxyl. It is characterized by substitution with an acid residue.

  Halogen ions include fluoride ions, chloride ions, bromide ions, and iodide ions.

Examples of the quaternary ammonium salt having a halogen ion as a counter ion include at least one of the following polymers (A) to (F):
(A) a polymer of a quaternary ammonium salt of a vinyl monomer having at least one (preferably one) cationic nitrogen atom,
(B) A quaternary ammonium salt of a vinyl monomer having at least one (preferably one) cationic nitrogen atom and at least one (preferably one) basic nitrogen atom or cationic nitrogen atom. A copolymer with a vinyl monomer or a salt thereof,
(C) a quaternary ammonium salt of a vinyl monomer having at least one (preferably one) cationic nitrogen atom and a polymerizable monomer having no basic nitrogen atom or no cationic nitrogen atom Copolymer of
(D) quaternized ammonium salt of polycondensate of polyalkylene polyamine and dihalogenated ethyl ether,
(E) A quaternized ammonium salt of a copolymer of a polyalkylene polyamine and a dihaloalkane and (F) a quaternized ammonium salt of a polycondensate of an alkylene diamine and an epoxy compound.

  As the polymer (A), the formula (1):

[Wherein, R ₁ represents a hydrogen atom or a methyl group, R _{2 to} R ₄ each independently represents an alkyl group having 1 to 5, preferably 1 to 3 carbon atoms, X represents a halogen atom, and n Represents a number of 6 to 60000, preferably 10 to 1000]
A quaternary ammonium salt of an N, N-dialkylaminoethyl (meth) acrylate polymer represented by formula (2):

[Wherein R ₂ , R ₃ , X and n are as defined above]
And cyclized polymers of diallyldialkylammonium halides represented by the formula:

  As the polymer (B), the formula (3):

[Wherein R _{1 to} R ₄ and X are as defined above, R ₁ ′ represents a hydrogen atom or a methyl group, o represents 4 to 60000, preferably 4 to 500, and p represents 4 To 100000, preferably 4 to 500]
A quaternary ammonium salt of a copolymer of N, N-dialkylaminoethyl (meth) acrylate and (meth) acrylamide represented by formula (4):

[Wherein, R _{1 to} R ₃ , X, o and p are as defined above]
And a copolymer of (ally) dialkylammonium halide represented by the formula (meth) acrylamide.

  As the polymer (C), the formula (5):

[Wherein R ₂ , R ₃ and X are as defined above, and s represents a number of 4 to 40000, preferably 4 to 500]
And a copolymer of diallyldialkylammonium halide and sulfur dioxide represented by the formula:

  As the polymer (D), the formula (6):

[Wherein R _{2 to} R ₄ and X are as defined above, R ₅ represents an alkyl group having 1 to ₅ carbon atoms, preferably 1 to 3 carbon atoms, and R ₆ represents 1 to 10 carbon atoms, Preferably an alkylene group of 1 to 6 is shown, and t is a number of 4 to 40,000, preferably 4 to 400]
A copolymer of a tetraalkylalkylenediamine represented by the formula (2) and 2,2-dichloroalkyl ether is exemplified.

  As the polymer (E), the formula (7):

[Wherein R _{2 to} R ₅ and X are as defined above, R ₇ represents an alkylene group having 1 to 4 carbon atoms, preferably 2 or 3 carbon atoms, and R ₈ represents 2 to 10 carbon atoms, Preferably it shows 2-6 alkylene groups, u shows the number of 10-100,000, preferably 10-1000]
The quaternary ammonium salt of the copolymer of the alkylene dichloride and alkylene polyamine represented by these is illustrated.

  As the polymer (F), the formula (8):

[Wherein, R _{2 to} R ₅ , R ₇ , X and u are as defined above]
The quaternary ammonium salt of the copolymer of alkylenediamine and epihalohydrin represented by these is illustrated.

  The average molecular weight of the above polymers (A) to (F) is 300 to 10000000, preferably 300 to 100,000. Particularly preferred polymers are (A), (C) and (D).

  In the present invention, the intermediate carboxylic acid residue means a carboxylic acid having 6 to 12 carbon atoms. For example, hexanoic acid, octanoic acid, nonanoic acid, 3,5,5 trimethylhexanoic acid, decanoic acid, benzoic acid , Nitrobenzoic acid, t-butylbenzoic acid, adipic acid, sebacic acid and the like.

  Accordingly, as the intermediate carboxylic acid residue, a carboxylic acid having 6 to 12 carbon atoms such as hexanoic acid, octanoic acid, nonanoic acid, 3,5,5 trimethylhexanoic acid, decanoic acid, benzoic acid, nitrobenzoic acid, Examples thereof include carboxylic acid residues derived from t-butylbenzoic acid, adipic acid, sebacic acid and the like.

  The salt of intermediate carboxylic acid and inorganic alkali may be prepared by neutralizing the intermediate carboxylic acid with inorganic alkali, or a commercially available product may be used.

  As an inorganic alkali, alkali metal hydroxides, such as potassium hydroxide, sodium hydroxide, lithium hydroxide, are mentioned, for example.

  In the method of the present invention, the ratio of the salt of the intermediate carboxylic acid and inorganic alkali used is 1 to 3 equivalents, preferably 1 as the intermediate carboxylic acid equivalents with respect to the quaternary ammonium salt having a halogen ion as a counter ion. ~ 2 equivalents.

  Examples of the polar solvent include methanol, ethanol, isopropyl alcohol, water, and the like.

  In embodiments where the solubility of the polymer in methanol, ethanol, isopropyl alcohol, etc. is significantly low, mixing a small amount of water with these organic solvents is preferred because the final yield can be improved.

  A polar solvent is used individually by 1 type or in mixture of 2 or more types.

  The usage-amount of a polar solvent is 0.1-100 ml normally with respect to 1g of quaternary ammonium salts which make a halogen ion a counter ion, Preferably it is 0.2-100 ml, More preferably, it is 0.5-50 ml.

  The temperature of the reaction is usually −10 to 80 ° C., preferably 0 to 40 ° C. By making it react in the said temperature range, reaction becomes easy to advance and decomposition | disassembly of a reaction raw material and a product is suppressed.

  In a preferred embodiment, the method of the present invention comprises dissolving a intermediate carboxylic acid and an inorganic alkali in a polar solvent, and adding a quaternary ammonium salt having a halogen ion as a counter ion or a solution thereof to the solution to react. Done.

  In the above reaction, the halogen ion of the quaternary ammonium salt is substituted with a intermediate carboxylic acid to obtain a quaternary ammonium salt having the intermediate carboxylic acid residue as a counter ion, and the halogen ion forms a salt with an inorganic alkali. And precipitated as inorganic alkali halides.

  The target compound obtained by the above reaction formula can be obtained by cooling the reaction mixture, for example, and then separating the crude reaction product by an isolation operation such as filtration, concentration, extraction, etc., and performing normal purification such as column chromatography and recrystallization. By the operation, it can be isolated and purified from the reaction mixture.

  In a preferred embodiment, the method of the present invention includes a step of removing the inorganic alkali halide obtained by the above reaction from the reaction mixture.

  As a method for removing the halide of inorganic alkali, a method commonly used in the art can be widely used, and examples thereof include filtration and centrifugation.

Example 1
40 ml of methanol was put into a 100 ml beaker, 4.4 g of potassium hydroxide was added and dissolved, and the mixture was allowed to cool to 25 ° C. Next, 10.8 g of 3,5,5 trimethylhexanoic acid was added and allowed to cool to 25 ° C. with stirring. Thereafter, 10.0 g of a compound of the following formula (9) [quaternized product of a copolymer of polyethylene polyamine and dichloroethyl ether (molecular weight: about 1500, chlorine content: 18% by weight, 60% aqueous solution)] was added. Stir for 10 minutes. After cooling to 25 ° C., the suspension was filtered through a G4 glass filter to separate the potassium chloride precipitate. The filtrate methanol was distilled off under reduced pressure using a rotary evaporator to obtain 18.5 g of a quaternary ammonium salt compound of the following formula (10) (including water). The yield was calculated from the weight of potassium chloride removed at this time of 3.2 g, and a result of 85% was obtained.

[Wherein v is about 6. ]

[Wherein v is about 6. ]
Table 1 shows the physical properties of the compound (10).

Comparative Example 40 ml of methanol was placed in a 100 ml beaker, 4.4 g of potassium hydroxide was added and dissolved, and the mixture was allowed to cool to 25 ° C. Next, 10.0 g of a compound of the formula (9) [quaternized product of a copolymer of polyethylene polyamine and dichloroethyl ether (molecular weight: about 1500, chlorine content: 25% by weight, 60% aqueous solution)] was added for 10 minutes. Stir. Subsequently, 10.8 g of 3,5,5 trimethylhexanoic acid (1.5 equivalents relative to chloride ions) was added, and the mixture was allowed to cool to 25 ° C. with stirring. Then, after cooling to 25 ° C., the suspension was filtered through a G4 glass filter to separate potassium chloride precipitate. The methanol in the filtrate was distilled off under reduced pressure using a rotary evaporator.

  In the above method, the target compound of formula (10) could not be obtained, and a mixture of the decomposed compound of formula (11) and 3,5,5 trimethylhexanoic acid was obtained.

  Table 2 shows the physical properties of the compound (11).

Example 2
Formula (12) as starting material

[Wherein w is about 180. ]
The compound of the formula (12) is decomposed by the same operation as in Example 1 using the compound represented by the formula [quaternary ammonium salt of N, N-dialkylaminoethyl (meth) acrylate polymer]. Equation (13) while suppressing

[Wherein w is about 180. ]
The quaternary ammonium salt compound represented by this was able to be obtained.

Example 3
Formula (14) as starting material

[Wherein x is about 250. ]
And a compound represented by formula (15) while suppressing decomposition of the compound of formula (14) by performing the same operation as in Example 1 using the compound [cyclized polymer of diallyldialkylammonium halide].

[Wherein x is about 250. ]
The quaternary ammonium salt compound represented by this was able to be obtained.

Example 4
Formula (16) as starting material

[Wherein y is about 12. ]
And a compound represented by the formula (17), a copolymer of diallyldialkylammonium halide and sulfur dioxide, by the same operation as in Example 1, while suppressing the decomposition of the compound of formula (16), )

[Wherein y is about 12. ]
The quaternary ammonium salt compound represented by these can be obtained.

  Since the quaternary ammonium salt obtained by the method of the present invention with the intermediate carboxylic acid residue as a counter ion does not contain a halogen, it does not cause rust and corrosion to metal parts and generates dioxins. It is particularly useful as an oil separating agent and a coagulating precipitant, and can be used in the fields of water-soluble processing oils, water-soluble cleaning agents, water treatment agents and the like.

Claims (2)

A reaction between a quaternary ammonium salt having a halogen ion as a counter ion and a salt of an intermediate carboxylic acid having 6 to 12 carbon atoms and an inorganic alkali in a polar solvent, and replacing the halogen ion with an intermediate carboxylic acid residue. A method for producing a quaternary ammonium salt characterized by having an intermediate carboxylic acid residue as a counter ion ,
A method in which the quaternary ammonium salt having a halogen ion as a counter ion is a salt of at least one of the following polymers (A) to (F) and a halogen ion:
(A) a polymer of a quaternary ammonium salt of a vinyl monomer having at least one cationic nitrogen atom,
(B) Copolymerization of a quaternary ammonium salt of a vinyl monomer having at least one cationic nitrogen atom and a vinyl monomer having at least one basic nitrogen atom or cationic nitrogen atom or a salt thereof. object,
(C) a copolymer of a quaternary ammonium salt of a vinyl monomer having at least one cationic nitrogen atom and a polymerizable monomer having no basic nitrogen atom or no cationic nitrogen atom,
(D) quaternized ammonium salt of polycondensate of polyalkylene polyamine and dihalogenated ethyl ether,
(E) a quaternized ammonium salt of a copolymer of a polyalkylene polyamine and a dihaloalkane;
(F) A quaternized ammonium salt of a polycondensate of an alkylene diamine and an epoxy compound . The method according to claim 1, further comprising removing an inorganic alkali halide formed in the reaction.