JP5809043B2 - Method for producing quaternary ammonium salt - Google Patents

Description

  The present invention relates to a method for producing a quaternary ammonium salt.

  Quaternary ammonium salts used as bases for clothing detergents, disinfectants, antibacterial agents, fabric softeners, hair treatment agents, antistatic agents, etc. are tertiary amines and quaternizing agents. It is manufactured by a method of reacting using a solvent as necessary. However, the produced quaternary ammonium salt contains impurities such as lower amines produced as a by-product during the reaction and unreacted quaternizing agent. Even if these impurities are contained in a very small amount, they smell and preserve stably. There was a problem of worsening sex.

  Therefore, conventionally, for the purpose of improving odor, hue, and storage stability, removal using a carrier gas under normal pressure or reduced pressure and distillation under reduced pressure are performed after the reaction. For example, in Patent Document 1, quaternization is performed using ethyl alcohol, isopropyl alcohol, or the like as a reaction solvent, and then the hue is improved by distilling out impurities together with the reaction solvent. Patent Document 2 proposes a method of distilling off after adding an antifoaming agent such as silicone as a method of improving the odor that is aggravated by elongating the foaming time under heating. ing.

  Patent Document 3 discloses the production of a quaternary ammonium salt having a good odor and less by-product of impurities by quaternizing a tertiary amine with a dialkyl sulfuric acid using a nonionic surfactant as a solvent. A method is disclosed. Patent Document 4 discloses a method for producing a quaternary ammonium salt in which a tertiary amine compound and a quaternizing agent are reacted in the absence of a solvent.

JP-A-11-106370 Japanese Patent Laid-Open No. 11-279132 JP 2005-179187 A JP 2001-278846 A

  In Patent Document 1, since the quaternary ammonium salt to be produced is obtained as a mixture with a lower alcohol, it is flammable, so the cost of handling equipment is increased, and the odor effect and flash point of the lower alcohol as a product are increased. Problems such as being detected and unusable occur. Further, Patent Document 2 also has a problem that an effective odor improvement effect cannot be obtained. Furthermore, it is difficult for conventional quaternary ammonium salts to sufficiently suppress the generation of odor after being stored under harsh conditions, and Patent Documents 1 to 4 describe this problem and means for solving the problem. There is no specific mention. The method of Patent Document 3 uses dialkyl sulfuric acid as a quaternizing agent.

  An object of the present invention is to provide a production method in which a high-quality quaternary ammonium salt is obtained which has no off-flavor immediately after production and can suppress generation of off-flavor even after being stored under severe conditions. More specifically, an excellent high-quality quaternary ammonium salt that can suppress the generation of off-flavor even after being stored under harsh conditions can be obtained without performing complicated purification such as solvent distillation or deodorizing operation. It is to provide a production method that can be obtained in the form.

  The present invention provides a tertiary amine represented by the following general formula (I) [hereinafter referred to as tertiary amine (I)] and a quaternizing agent selected from alkyl halides having 1 to 3 carbon atoms. The present invention relates to a method for producing a quaternary ammonium salt, which is reacted in water at a molar ratio of quaternizing agent / tertiary amine = 0.90 to 1.03.

(In the formula, R ¹ is a linear or branched alkyl group or alkenyl group having 6 to 30 carbon atoms into which an ester group, an amide group or an ether group may be inserted, and R ² and R ³ are respectively Independently, an alkyl group having 1 to 4 carbon atoms is shown.)

  According to the present invention, it is possible to produce a high-quality quaternary ammonium salt that has no off-flavor immediately after production and can suppress the generation of off-flavor even after being stored under severe conditions. Furthermore, this quaternary ammonium salt can be obtained in the form of an aqueous solution, and in addition to being able to suppress the generation of off-flavors even after being stored under harsh conditions, it has no odor or flammability due to the solvent, It is excellent in handleability and is useful when used as a raw material for preparation of clothing detergents, bactericides, antibacterial agents, textile softeners, hair treatment agents, antistatic agents and the like.

In the tertiary amine (I) used in the present invention, R ¹ in the general formula (I) is an ester group (—COO— or —OCO—), an amide group (—NHCO— or —CONH—), an ether A straight or branched alkyl or alkenyl group having 6 to 30 carbon atoms, preferably 8 to 24 carbon atoms, more preferably 10 to 22 carbon atoms, to which a group (-O-) may be inserted. . R ¹ is preferably a linear or branched alkyl group having 8 to 24 carbon atoms, more preferably a linear or branched alkyl group having 10 to 22 carbon atoms, and even more preferably 10 carbon atoms. More preferably, it is a -18 linear alkyl group.

  The quaternizing agent is an alkyl halide having 1 to 3 carbon atoms, preferably an alkyl halide having 1 to 2 carbon atoms, and more preferably methyl chloride.

  In the present invention, the quaternary ammonium salt is produced by quaternizing the tertiary amine (I) in water. In addition to water, lower alcohols such as methanol, ethanol and isopropyl alcohol (1 to 3 carbon atoms), diols such as ethylene glycol and propylene glycol (2 to 5 carbon atoms), organic solvents such as acetone and acetonitrile. Can be added as appropriate within a range that does not affect the present reaction. As the range of the addition amount having no influence, for example, it can be added within the range where the flash point does not appear in the obtained aqueous solution of quaternary ammonium salt. Specifically, in the case of ethyl alcohol, it can be added at 5% by mass or less. In the present invention, since the quaternization is performed in water, the reaction solvent preferably contains 95% by mass or more of water, and more preferably 95-100% by mass.

  The ratio of the tertiary amine (I) to the water is the time before the first introduction of the quaternizing agent from the viewpoint of securing the fluidity of the resulting quaternary ammonium salt aqueous solution at room temperature and efficient productivity. It is preferable that it is 20-80 mass%, More preferably, it is 25-70 mass%, More preferably, it is 30-60 mass%. This ratio is obtained by [the amount of tertiary amine (I) / the amount of water] × 100.

  In the present invention, the tertiary amine (I) and the quaternizing agent are reacted in water at a molar ratio of quaternizing agent / tertiary amine = 0.90 to 1.03. From the viewpoint of suppressing the generation of off-flavor after storage under harsh conditions, reducing the content of unreacted tertiary amine after quaternization, side reaction of quaternizing agent, discarding of quaternizing agent remaining after reaction, etc. From the viewpoint of reducing the burden on post-treatment, the molar ratio is preferably 0.93 to 1.00, and more preferably 0.950 to 0.995.

  Various combinations of the reaction solvent for producing a quaternary ammonium salt by reacting a tertiary amine with a quaternizing agent and the molar ratio of the tertiary amine to the quaternizing agent have been conventionally known. Yes. However, when the present invention quaternizes a mono-long-chain alkyl or alkenyl-dimethyl type tertiary amine such as tertiary amine (I) in water, It has been found that the molar ratio greatly affects not only the off-flavor immediately after production, but also the suppression of off-flavor generation after storage under severe conditions. The reason why such an off-flavor reduction effect can be obtained by the present invention is not clear, but in the quaternization reaction in water, an odor substance precursor (a precursor that changes to a substance that produces a strong odor after being stored under harsh conditions). It is presumed that the formation is suppressed at a very limited quaternizing agent / tertiary amine molar ratio of the present invention.

  The reaction temperature between the tertiary amine (I) and the quaternizing agent is preferably 30 to 110 ° C., more preferably from the viewpoints of operability and reactivity, and suppression of decomposition of the quaternary ammonium salt, more preferably It is 40-80 degreeC, More preferably, it is 50-75 degreeC. At temperatures in this range, the tertiary amine (I) is present in the reaction system containing water in a state in which it does not dissolve at the beginning of the reaction. In the present invention, the quaternization reaction is started in a heterogeneous system, and after the addition of the quaternizing agent, the proportion of the quaternary ammonium salt in the reaction system increases as the quaternization reaction proceeds, As a whole, it has shifted to a homogeneous system (dissolution).

  The reaction time between the tertiary amine (I) and the quaternizing agent is preferably 0.5 to 3 hours, more preferably 1.0 to 2.5 hours. This reaction time is more preferable when the temperature is within the above range. The starting point of this reaction time can be the time when the total amount of the quaternizing agent is added to the reaction system and the reaction temperature is reached.

  In the present invention, the reaction between the tertiary amine (I) and the quaternizing agent is carried out at 30 to 110 ° C, further 40 to 80 ° C, more preferably 50 to 75 ° C for 0.5 to 3 hours, and further 1.0. It is preferable to carry out for ~ 2.5 hours.

  The quaternary ammonium salt produced by the present invention can be used for various cleaning agents (clothing cleaning agents, body cleaning agents, hair cleaning agents, etc.), hair treatment agents, softeners, and the like.

  Lauryldimethylamine was used as the tertiary amine (I), and methyl chloride was used as the quaternizing agent. Lauryldimethylamine, ion-exchanged water, and methyl chloride were added to the autoclave, and the temperature was raised to 63 ° C. The solution was stirred for 2 hours at the same temperature to obtain an aqueous solution containing a quaternary ammonium salt. Table 1 shows the quaternizing agent / tertiary amine molar ratio, the charged amount, and the results of off-flavor suppression in Examples 1 to 5 and Comparative Examples 1 to 4.

  The molar ratios in Table 1 were calculated assuming that the molecular weight of lauryldimethylamine was 213.41 and the molecular weight of methyl chloride was 50.49.

An aqueous solution immediately after production or an aqueous solution stored at 60 ° C. for 6 months was put in a 100 mL beaker, sensory evaluation was performed by five panelists at room temperature, and the suppression of off-flavors was evaluated according to the following criteria. The aqueous solution is stored in Kyodou Glass Co., Ltd. Hiroguchi Standard Bottle PS-No. 11 (cylinder diameter 51.5 mm, height 95.5 mm, caliber 39.5 mm, made of glass) was filled with 50 mL of an aqueous solution and sealed and shielded from light. The results are shown in Table 1.
◎: 5 people did not feel a bad smell ○: 4 people did not feel a bad odor △: 2 or 3 people did not feel a bad odor ×: 0 people or 1 person did not feel a bad smell (4 people or 5 people felt a strange odor)

Claims (5)

A tertiary amine represented by the following general formula (I) and a quaternizing agent selected from alkyl halides having 1 to 3 carbon atoms are converted into a quaternizing agent / tertiary amine = 0.950 in water. The manufacturing method of the quaternary ammonium salt made to react by the molar ratio of -0.995 .

(In the formula, R ¹ represents a linear or branched alkyl group or alkenyl group having 6 to 30 carbon atoms into which an ester group, an amide group or an ether group may be inserted.) The quaternizing agent is methyl chloride, the production method of the quaternary ammonium salt according to claim 1 Symbol placement. Compound represented by Formula (1) is represented by the general formula (1) R ¹ is the fourth claim 1 or 2 wherein the alkyl or alkenyl group of a straight-chain or branched-chain having 6 to 30 carbon atoms in the A method for producing a quaternary ammonium salt. Wherein the reaction between the tertiary amine and the quaternizing agent, earthenware pots row at 30 to 110 ° C., the manufacturing method of the quaternary ammonium salt of any one of claims 1-3. The method for producing a quaternary ammonium salt according to any one of claims 1 to 4, wherein the reaction between the tertiary amine and the quaternizing agent is carried out for 0.5 to 3 hours.