JP3502680B2 - Method for producing quaternary ammonium salt - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a quaternary ammonium salt. More specifically, the present invention relates to a method for producing a quaternary ammonium salt which is useful as a surfactant and as a base for a softening agent for cloth, hair and the like.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
General formula (I) used as a softener base for fabrics and hair

[0003]

[Chemical 4]

(In the formula, R ¹ is a straight or branched chain having 20 to 20 carbon atoms.
44 alkyl group or alkenyl group, R ² , R ³ and R ⁴
Are the same or different and each represents an alkyl group or a hydroxyalkyl group having 1 to 5 carbon atoms, a represents a number of 1 to 6, and X ⁻ represents an anion. The quaternary ammonium salt represented by) is produced by reacting a corresponding secondary or tertiary amine with a quaternizing agent. During the quaternization reaction, an alcohol such as isopropyl alcohol or ethanol is used. It was general to use 15 to 25% by weight of the system solvent. Such an alcohol solvent has a low flash point and a risk of fire, has a unique odor and adversely affects the odor of products containing these bases, and is a softening active ingredient for cloth and hair. Since it does not work as such, there is a problem that extra cost is required. However, when such a solvent is not used, there is a problem that the quaternary ammonium salt has a high melting point and is difficult to handle.

Therefore, an object of the present invention is to provide a quaternization reaction which does not use such a volatile alcohol solvent or can reduce the amount used as much as possible. The present invention is to find a compound which can be added during the grading reaction and which lowers the melting point of the quaternary ammonium salt represented by the above general formula (I) to be produced and also has the effect of enhancing flexibility. It is an object of the present invention to provide a production method capable of obtaining a quaternary ammonium salt represented by the general formula (I), which has a high enhancing effect.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have made a specific compound coexist during the production of the quaternary ammonium salt represented by the general formula (I). It was found that the above is optimal for the above purpose, and completed the present invention. That is, the present invention provides a method for producing a quaternary ammonium salt represented by the general formula (I) by reacting a corresponding tertiary amine with a quaternizing agent.

[0007]

[Chemical 5]

(In the formula, R ⁵ represents a linear or branched alkyl group or alkenyl group having 7 to 35 carbon atoms, and A ¹ and A ²
Are the same or different and represent an alkylene group having 2 to 4 carbon atoms, n and m are the number average added moles of alkylene oxide, and the same or different are the numbers in which n + m is 0 to 4. The n A ¹ and the m A ² may be the same or different. The present invention provides a method for producing a quaternary ammonium salt, which comprises reacting in the presence of a compound represented by the formula (1).

As the compound represented by the general formula (II) used in the present invention, a compound in which the R ⁵ CO- group is a fatty acid residue derived from natural fat and oil, and n and m are 0 is particularly preferable. The compound represented by the general formula (II) used in the present invention is produced, for example, as follows. That is, it can be obtained by reacting natural fats and oils with diethanolamine in the presence of a basic catalyst to form an amid, and then, if necessary, gradually adding alkylene oxide to react. Lower alcohol esters of fatty acids may be used instead of natural oils and fats. When natural fats and oils are used as the raw material, the compound represented by the general formula (II) includes by-produced glycerin or its alkylene oxide adduct, but can be directly used in the present invention without purification. .

As the natural fats and oils, beef tallow, palm oil, palm stearin oil, palm kernel oil, coconut oil, etc., partially hardened oils thereof, fully hardened oils, or a mixture thereof can be used, preferably beef tallow, palm stearin. oil,
Palm kernel oil or partially hardened or fully hardened oil thereof. Further, as the lower alcohol ester of fatty acid,
Methyl or ethyl esters of C8-C36 fatty acids such as octanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, etc. are preferred, and methyl or ethyl esters of C12-18 fatty acids are preferred. Is.

As the alkylene oxide, ethylene oxide, propylene oxide, butylene oxide, etc., or a mixture thereof can be used, and ethylene oxide is preferably used. If a mixture of alkylene oxides is used, they can be reacted simultaneously or sequentially. As the basic catalyst, potassium hydroxide, sodium hydroxide, sodium methylate or the like can be used.

The amidation reaction temperature of a lower alcohol ester of natural oil or fat and diethanolamine is 60 ° C.
~ 200 ° C, preferably 80 ° C to 150 ° C, and the temperature of the addition reaction of alkylene oxide is 100 ° C to 200 ° C, preferably 140 ° C to 170 ° C. The reaction ratio of the lower alcohol ester of natural oil or fat and the diethanolamine is 0.8 to 1.2 of diethanolamine per 1 mol of ester group of the lower alcohol ester of natural oil or fatty acid.
The molar amount is preferably 0.9 to 1.1 mol. The number of moles of alkylene oxide added is 0 to 4 moles, preferably 0 to 3 moles, relative to 1 mole of diethanolamide.

As the quaternary ammonium salt represented by the above general formula (I) produced in the present invention, any quaternary ammonium salt can be used as long as it is produced from a corresponding tertiary amine and a quaternizing agent. Anything is fine. In the general formula (I), R ¹
Represents a linear or branched alkyl group or alkenyl group having 20 to 44 carbon atoms, preferably

[0014]

[Chemical 6]

(Wherein R ⁶ represents a straight-chain alkyl group having 8 to 20 carbon atoms), which is a group derived from an alcohol called Guerbet alcohol. Conventionally, when a primary alcohol is dehydrated and condensed in the presence of an alkaline substance or in the presence of an alkaline substance and a dehydrogenation catalyst, one molecule of branched dimerized alcohol and one molecule of water are produced from two molecules of the raw material alcohol. Is widely known and is called the Guerbet reaction, and is represented by the following reaction formula.

[0016]

[Chemical 7]

(In the formula, R ⁶ has the above-mentioned meaning.) The branched dimer alcohol obtained by this Guerbet reaction is called Guerbet alcohol. In the group derived from Guerbet alcohol represented by the above formula, R ⁶ has 12 to 16 carbon atoms.
The linear alkyl group of is preferable, and the linear alkyl group having 16 carbon atoms is particularly preferable.

In the above general formula (I), R ² , R ³ and R ⁴
Are the same or different and each represent an alkyl group having 1 to 5 carbon atoms or a hydroxyalkyl group, preferably a methyl group, an ethyl group and a hydroxyethyl group. More preferably, it is a methyl group. Further, a is a number of 1 to 6, but is preferably 1. X ⁻ represents an anion, preferably a halogen ion or an alkyl sulfate ion having 1 to 4 carbon atoms, more preferably Cl ⁻ , Br ⁻ , CH ₃ SO ₄ ^— , particularly preferably Cl ⁻ . .

The fourth of the above general formula (I) of the present invention
The production of the primary ammonium salt can be carried out by the following method. That is, the compound represented by the general formula (II) is 1 to 50% by weight, preferably 5 to 30% by weight based on the total weight of the reactants charged.
Add and react the corresponding tertiary amine with the quaternizing agent. If necessary, an alcohol solvent such as isopropyl alcohol or ethanol may be added in an amount of 20% by weight or less based on the total amount of the reaction products, but addition of more than this is not preferable for the purpose of the present invention. The reaction temperature is 30 to 140 ° C, preferably 50
It is carried out at ~ 100 ° C.

The tertiary amine corresponding to the quaternary ammonium represented by the above general formula (I) produced in the present invention is represented by the general formula (III)

[0021]

[Chemical 8]

(In the formula, R ² and R ³ have the same meanings as described above, and R ⁷ is an alkyl group having 1 to 5 carbon atoms, a hydroxyalkyl group or-(CH ₂ ) _a COOR ¹ (R ¹ and a are A group represented by () has the same meaning as above.) And a quaternizing agent represented by the general formula (IV) X—R ⁸ (IV) , R ⁸ represents an alkyl group having 1 to 5 carbon atoms, a hydroxyalkyl group or a group represented by the formula — (CH ₂ ) _a COOR ¹ (R ¹ and a have the same meanings as described above), and X represents And a compound represented by halogen or an alkyl sulfate having 1 to 4 carbon atoms. Specific examples of the quaternizing agent include chloromethane, dimethylsulfate, formula

[0023]

[Chemical 9]

(R ¹ has the same meaning as described above) and the like. Examples of the quaternary ammonium salt represented by the above general formula (I), which is produced by the reaction of these tertiary amine and quaternizing agent, include the following compounds.

[0025]

[Chemical 10]

The quaternary ammonium salt represented by the general formula (I) obtained by the method of the present invention has both flexibility and odor even if it is used as a softener base in the reaction mixture without purification. It is excellent and very useful as a softener base. Although the reaction mixture obtained by the method of the present invention can be used as it is as a softener base, further softening performance,
Higher alcohols, higher fatty acids, other viscosity modifiers for improving storage stability, lower alcohols as storage stabilizers, and also known cation activators, nonionic activators, inorganic salts, pH adjusters, hydrotropes, fragrances. A softening agent composition can be prepared by adding a defoaming agent, a pigment and the like as necessary and emulsifying the mixture.

[0027]

EXAMPLES The present invention will be described in more detail below with reference to synthetic examples of compounds represented by the general formula (II) and examples of the present invention, but the present invention is not limited to these examples. Absent.

Synthesis Example 1 Diethanolamine (172 g) and 28% NaOCH ₃ methanol solution (5 g) were placed in a four-necked flask equipped with a stirrer and a thermometer, and the mixture was stirred at 100 ° C. and 30 torr for 1 hour, and the methanol was distilled off. Next, 417 g of purified palm stearin oil was added and reacted at 100 ° C. and 30 torr for 2 hours. After cooling to 60 ° C. and aging for 50 hours, diethanolamide derived from palm stearin oil was obtained.

Synthetic Example 2 180 g of diethanolamide derived from palm stearin oil obtained in Synthetic Example 1 was charged into an autoclave, heated to 150 ° C., 66 g of ethylene oxide was added over 2 hours, and then aged for 1 hour to prepare palm stearin. An oil-derived diethanolamide ethylene oxide 3 mol adduct was obtained.

Synthesis Examples 3 to 6 Using the raw materials shown in Table 1, diethanolamide was synthesized in the same manner as in Synthesis Example 1 except for the conditions shown in Table 1.

[0031]

[Table 1]

Example 1 An autoclave equipped with a stirrer and a thermometer was charged with 35 g of the reaction product obtained in Synthesis Example 1, 130 g of dimethylaminoacetic acid 2-hexadecyl eicosyl, and 13 g of chloromethane.
Heated to ° C. React for 6 hours at the same temperature,
The corresponding quaternary ammonium salt was obtained.

Examples 2 to 4 The reaction was carried out under the conditions shown in Table 2 in the same manner as in Example 1 to obtain the corresponding quaternary ammonium salt.

Comparative Examples 1 to 4 The same weight of isopropyl alcohol was used in place of the reaction products obtained in Synthesis Examples 1 to 3 used in Examples 1 to 4, and quaternary ammonium as shown in Table 2 was also used. A salt-based reaction mixture was obtained.

Table 2 shows the reaction conditions of Examples 1 to 4 and Comparative Examples 1 to 4, the structure of the obtained quaternary ammonium salt, and the evaluation results of flexibility and odor evaluated by the following method.

<Flexibility and Odor Evaluation Method> Preparation of Quaternary Ammonium Salt Dispersions The reaction mixtures containing the quaternary ammonium salt as the main component prepared in Examples and Comparative Examples were melted and stirred in water. The mixture was added dropwise to prepare a dispersion liquid having a quaternary ammonium salt concentration of 5% by weight. Treatment method 2 kg of commercially available cotton towel, using a 30 liter washing machine,
After repeatedly washing 5 times with a commercially available detergent attack (registered trademark, manufactured by Kao Corporation) in 3.5 ° DH hard water, the above No. 4
25 ml of the primary ammonium salt dispersion was added and treated with stirring at 25 ° C. for 1 minute.

Softness Evaluation Method The cloth treated by the above method was air-dried at room temperature and then at 25 ° C. and 65% RH.
It was left for 24 hours in a constant temperature and humidity chamber. The softness of these cloths was evaluated. For the evaluation, a pair of comparisons were carried out using the cloth treated with the quaternary ammonium salt of Comparative Example 1 as a control. The evaluation is based on the following criteria. 3; considerably softer than the control 2; softer than the control 1; slightly softer than the control 0; comparable in softness to the control Odor evaluation method The 5 wt% quaternary ammonium salt dispersion prepared by the above method was used to smell the nose. evaluated. The evaluation is based on the following criteria. ×: Alcoholic odor ○: No alcohol odor

[0038]

[Table 2]

As is clear from Table 2, in all cases, the Examples are superior to the Comparative Examples in flexibility and odor.

Examples 5 to 7 The reaction was carried out under the conditions shown in Table 3 in the same manner as in Example 1 to obtain the corresponding quaternary ammonium salt. The reaction conditions of Examples 5 to 7, the structure of the obtained quaternary ammonium salt, and Example 1
The results of evaluation of flexibility and odor evaluated in the same manner as in Table 3 are summarized in Table 3.

[0041]

[Table 3]

Continuation of the front page (56) Reference JP-A-5-132865 (JP, A) JP-A-8-92875 (JP, A) JP-A-2-91050 (JP, A) JP-A-61-194274 (JP , A) US Patent 4237064 (US, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 229/12 C07C 227/18 CA (STN) REGISTRY (STN)

Claims (5)

(57) [Claims] 1. A compound represented by the general formula (I): (In the formula, R ¹ represents a linear or branched alkyl group or alkenyl group having 20 to 44 carbon atoms, and R ² , R ³ and R ⁴ are the same or different and are alkyl groups or hydroxy groups having 1 to 5 carbon atoms. An alkyl group, a is a number of 1 to 6, and X ⁻ is an anion) by reacting a corresponding quaternary ammonium salt with a quaternizing agent. In the method for producing, the compound represented by the general formula (II): (In the formula, R ⁵ represents a linear or branched alkyl group or alkenyl group having 7 to 35 carbon atoms, A ¹ and A ² are the same or different and each represents an alkylene group having 2 to 4 carbon atoms, and n and m represents the number average addition mole number of alkylene oxide, and is the same or different and represents a number such that n + m is 0 to 4. Note that n A ¹ and m A ² may be the same or different. Fourth, characterized by reacting in the presence of the represented compound
Of producing high grade ammonium salt. 2. In the quaternary ammonium salt represented by the general formula (I), R ¹ is represented by the following formula: (In the formula, R ⁶ represents a linear alkyl group having 8 to 20 carbon atoms.)
The production method according to claim 1, which is a group represented by: 3. The production method according to claim 2, wherein R ⁶ is a linear alkyl group having 12 to 16 carbon atoms. 4. The compound represented by the general formula (II), wherein the R ⁵ CO- group is a fatty acid residue derived from natural fats and oils, and n and m are 0. The manufacturing method described in. 5. The method according to claim 1, wherein the compound represented by the general formula (II) is added in an amount of 1 to 50% by weight based on the total weight of the reactants. .