KR19990054750A - Method for producing a cationic surfactant having an ester group in a molecule - Google Patents

Abstract

The present invention relates to a method for producing a cationic surfactant having an ester group in a molecule, and selectively reacting an acrylic derivative with an aqueous ammonia solution and a primary amine to selectively synthesize a tertiary amine, and to prepare an ester derivative using a fatty alcohol. And finally to a method for synthesizing quaternized ester cationic surfactants using alkyl halides.

Description

Method for producing a cationic surfactant having an ester group in a molecule

The present invention relates to a method for producing a cationic surfactant having an ester group in a molecule. More specifically, the present invention synthesizes a tertiary amine selectively by adding an acrylic derivative to an aqueous ammonia solution and a primary amine, and then synthesizes an ester derivative using fatty alcohol and finally quaternized with an alkyl halide. A method for synthesizing an ester cationic surfactant.

In general, conventional cationic surfactants are difficult to biodegrade in nature, so in the developed countries, especially in Europe, the use of such dialkyl dimethyl ammonium chloride (DDAC) and imidazoline-based cationic surfactants is fully regulated. Even if the usage is gradually reducing the situation.

Therefore, as a result of developing a cationic surfactant having excellent biodegradability, when the alkyl group in the molecule contains an ester group, its toxicity and biodegradability are superior to that of the general cationic surfactant, dialkyl diethyl ammonium chloride (DDAC). Already revealed by a number of studies.

Accordingly, an object of the present invention is to provide a novel method for synthesizing cationic surfactants having excellent flexibility and antistatic properties and having low skin toxicity and excellent biodegradation by having an ester group in a molecule.

To date, various derivatives have already been developed for quaternary ammonium salts having ester groups in the molecule. The quaternary ammonium salts already developed and used in the products include monomethyl monoethanol dialkyl ester ammonium sulfate developed by HENKEL and dimethyl dialkyl ester ammonium sulfate developed by P & G and used in fabric softeners. Many types have been developed and applied to products. However, quaternary ammonium salts containing ester groups in previously published molecules use tertiary amines in the synthesis method, which is very expensive in the production of quaternary ammonium due to the high price of tertiary amines. It is necessary. However, in this synthesis, the existing manufacturing cost burden could be reduced by using a relatively inexpensive aqueous ammonia solution and a primary amine as a starting material, instead of using expensive tertiary amines.

In the case of the quaternary ammonium salts having the ester group, the hygroscopicity and the antistatic property were increased in the physical properties of the cationic surfactant while the biodegradability decreased, but the basic performance was poor, and the raw material was very stable, and thus the storage for a long time. As a problem occurs, the stability of the raw material is very important.

Therefore, the present inventors have made diligent efforts to solve the above-mentioned problems. As a result, the acrylic derivatives are selectively added and reacted with ammonia and primary amines using aqueous ammonia solutions and primary amines and acrylic derivatives, which are easily industrially obtained, and fatty alcohols. Synthesis of dipropionic alkyl ester monoalkylamine by esterification using and quaternization with alkyl halide or dimethyl sulfate to synthesize quaternary ammonium salt with excellent storage stability, hypoallergenic and excellent biodegradability And developed the present invention.

The present invention generates a dipropionic carboxylic mono alkyl amine represented by the following formula (2) by reacting an alkyl amine and an acrylic derivative represented by the following formula (1), the product (2) of the higher fatty alcohol and alkali catalyst The present invention relates to a process for preparing a dipropionic alkyl ester mono alkyl amine represented by the following formula (3), characterized by reacting in the presence of:

In the above formula,

R ₁ is H, CH ₂ CH ₂ OH or a C _{1 to} C ₄ alkyl group,

R ₂ is H, Me, Et or M (M = Na, K),

R ₃ is a linear or branched alkyl group C ₈ ~C _24.

The present invention also relates to a method for preparing a quaternized ester derivative represented by the following formula (4), characterized by reacting a dipropionic alkyl ester mono alkyl amine represented by the following formula (3) with an alkyl halide or dimethyl sulfate.

Formula 3

In the above formula,

R ₁ is H, CH ₂ CH ₂ OH or a C _{1 to} C ₄ alkyl group,

R ₂ is H, Me, Et or M (M = Na, K),

R ₃ is a C ₈ to C ₂₄ linear or branched alkyl group,

R ₄ is a C ₁ to C ₄ alkyl group,

X is Cl, Br or CH ₃ SO ₄ .

According to the present invention, as a reactant, dipropionic carboxylic monoalkyl amine, which is an intermediate of the preparation material as shown in the following formula (2), is used, using an aqueous ammonia solution, a primary amine and an acryl-based derivative, which are readily available industrially. It can manufacture.

Formula 2

In the above formula,

R ₁ and R ₂ are as described above.

The dipropionic carboxylic monoalkyl amine (2) thus prepared is subjected to esterification reaction with a higher fatty alcohol in the presence of an alkali metal catalyst to form dipropionic alkyl ester monoalkyl amine, which is an intermediate of the following preparation material. Can be prepared.

Formula 3

In the above formula,

R ₁ , R ₂ and R ₃ are each as described above.

The dipropionic alkyl ester mono alkylamine (3) thus prepared and the alkyl halide or dimethyl sulphate are water, methanol, ethanol, propyl alcohol, isopropyl alcohol, butanol, sorbitol, ethylene glycol, glycerin, propylene glycol, polyethylene glycol, and the like. The quaternized ester derivative of formula (4), which is the final product, may be prepared by reacting with an alkyl halide or dimethyl sulfate under solvent conditions of monovalent, divalent, trivalent or polyhydric alcohols.

Formula 4

In the above formula,

R ₁ is H, CH ₂ CH ₂ OH or a C _{1 to} C ₄ alkyl group,

R ₃ is a C ₈ to C ₂₄ linear or branched alkyl group,

R ₄ is a C ₁ to C ₄ alkyl group,

X is Cl, Br or CH ₃ SO ₄ .

According to the present invention, in preparing a quaternary ammonium salt having an ester group in a molecule, 2 equivalents of an acrylic derivative is optionally added to mono alkylamine and ammonia, followed by esterification using fatty alcohol, and finally alkyl Reaction with halide or dimethyl sulphate produces quaternized ammonium salt derivatives.

The production method according to the present invention consists of a total of three reaction steps and the overall process diagram is as follows.

In the reaction step, the first step is a step of producing dipropionic carboxylic monoalkyl amine (2), and the reaction is as follows. The alkylamine used in the reaction includes ammonia, mono methylamine, mono ethylamine, mono propylamine, mono butylamine, mono ethanolamine, etc., which are readily available industrially, and as the acrylic derivative (1), methyl acryl Latex, ethyl acrylate, acrylic acid, acrylic acid sodium and the like. In this case, the amount of the starting material is used in an amount of 2 to 4 times the molar ratio of the acrylic derivative in order to reduce the residual amount of unreacted alkylamine, and more preferably 2.5 to 3 times the molar ratio. If small, a large amount of unreacted alkylamine is produced, and if it is more than 4 times too large, polymer material is produced by polymerization of unreacted acrylic derivative during the reaction, and it is inappropriate because a large amount of time is required in the purification process after the reaction. Moreover, reaction temperature is 10-70 degreeC. More preferably, it is good to set it as 30-50 degreeC. In the case of reaction temperature, when the temperature is too low below 10 ° C, the reaction time takes a long time. When the reaction temperature is too high above 70 ° C, the acryl-based derivatives polymerize with each other to produce the desired dipropionic carboxylic mono. The yield of alkyl amines is significantly lower. In the case of acrylonitrile in the acryl-based derivative, first, the nitrile group of acrylonitrile is hydrolyzed under water and an alkali metal to make an acrylic acid alkali salt and then reacted with an alkylamine. At this time, the temperature of hydrolysis is 30-100 degreeC, More preferably, it is 60-80 degreeC.

In the second step, the dipropionic carboxylic mono alkylamine (2) thus prepared is esterified with fatty alcohol to prepare a dipropionic alkyl ester mono alkyl amine of formula (3). This reaction process is as follows. As the fatty alcohol used in the reaction, it is preferable to use 2 to 2.5 moles, preferably 2 to 2.2 moles of the dipropionic carboxylic mono alkylamine (2). At this time, if the molar ratio of the used fatty alcohol is less than 2 times or less, the residual amount of unreacted dipropionic carboxylic monoalkyl amine (2) is large and if the molar ratio is too large, more than 2.5 times, the residual amount of unreacted fatty alcohol is It is inadequate because a lot of time is required in the purification process after completion of the reaction. In the case of the fatty alcohol used in the reaction, a fatty alcohol having a linear or branched alkyl group having 8 to 22 carbon atoms was used. For example, octyl alcohol, decyl alcohol, dodecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, Octadecyl alcohol, eicosanol, docosanol and the like are used.

As an alkali catalyst, sodium carbonate, potassium carbonate, sodium methoxide, potassium hydroxide, sodium hydroxide, etc. are used. The amount of the alkali catalyst is preferably 0.1 to 5% by weight, more preferably 0.5 to 2% by weight based on the total weight of the dipropionic carboxylic mono alkylamine (2) and the fatty alcohol. When the amount of the catalyst used is less than 0.1% by weight, the reaction rate is slow, so that the yield is not good, and when the amount is more than 5% by weight, no further increase in yield can be expected. At this time, the reaction temperature is 100 to 180 ℃, more preferably 120 to 150 ℃. The alcohol produced during the reaction is continuously removed and the vacuum degree during the reaction is 100 to 600 torr, preferably 200 to 300 torr. In the case of the reaction temperature, when the temperature is low, the reaction rate is lowered. When the reaction temperature is too high, not only a lot of side reactants are generated but also the color of the product is bad.

The third step is to prepare a quaternized ester derivative (4) using equimolar moles of dipropionic alkyl ester mono alkyl amine (3) and alkyl halide or dimethyl sulfate synthesized in the second step, wherein the alkyl halide For example, methyl chloride, ethyl chloride, propyl chloride, butyl chloride, methyl bromide, ethyl bromide, propyl bromide, butyl bromide and the like are used.

The solvent used in the reaction includes monohydric, dihydric, trihydric, or polyhydric alcohols such as water, methanol, ethanol, propyl alcohol, butyl alcohol, isopropyl alcohol, sorbitol, ethylene glycol, glycerin, propylene glycol, and polyethylene glycol. In this case, the reaction temperature is 50 to 150 ℃, more preferably in the range of 60 to 100 ℃. When the reaction temperature is lower than 50 ℃, the reaction rate is low and sometimes the reaction does not proceed at all, too high above 150 ℃ not only generates a lot of side reactions but also the color of the product is bad.

According to the present invention, acrylic derivatives and primary amines, which are inexpensive raw materials, were used as starting materials used in the manufacturing process, and these raw materials can be purified by a relatively simple method even after the completion of the reaction. A totally different manufacturing method can synthesize cationic surfactants having excellent economical efficiency, high purity, biodegradability and storage stability in the production of quaternary ammonium salts, and the intermediates (1,2) produced during preparation are amphoteric in addition to intermediates of quaternary ammonium salts. Since it can be used as an intermediate in the preparation of surfactants and anionic surfactants, the ripple effect is greatly expected.

Hereinafter, although this invention is demonstrated concretely based on an Example, the technical scope of this invention is not restrict | limited to these.

Example 1

Into a four-necked flask equipped with a mechanical stirrer, a reflux condenser, a temperature gauge, and a dropping device, add 65 mL (28%) of ammonia water and react with 213 g (2.47 mol) of methyl acrylate gradually dropping while maintaining the reactor temperature at 10 ° C. . After the dropping of methyl acrylate is completed, the reaction is continued for 3 to 4 hours when the temperature of the reactor reaches 30 ° C. At the end of the reaction, the water and unreacted methyl acrylate in the reactant are removed under reduced pressure while gradually raising the temperature.

Thus, 196 g (yield: 93%) of colorless slightly viscous dipropionic methyl ester amines were obtained. 100 g (0.53 mol) and 175.8 g (1.1 mol) of decyl alcohol were added together with 2 g of sodium methoxide as a catalyst, and the temperature of the reactor was slowly heated to 150 ° C. As the temperature of the reactor exceeds 100 ° C., the methanol in the reactant is distilled out gradually. At this time, the reactor is depressurized to facilitate the distillation of methanol. The temperature of the reactor is maintained at 120 to 150 ° C. and the reduced pressure is continued for 2 hours at 200 to 300 torr.

Upon completion of the reaction, unreacted decyl alcohol was distilled off to obtain 235 g (yield: 94%) of viscous yellow dipropionic decyl ester amine. 100 g of the reaction product obtained as described above was reacted with 50 g of normal propyl alcohol solvent in equimolar ratio in a high pressure reactor. At this time, the reaction temperature is maintained at 60 ~ 80 ℃ and reacted for 2 to 3 hours. Upon completion of the reaction, the reaction product was subjected to KS analysis to obtain an aqueous solution of cationic surfactant having a reaction yield of 92%.

Example 2

Into a four-necked flask equipped with a mechanical stirrer, a reflux condenser, a temperature gauge, and a dropping device, 70 ml (40%) of monomethyl amine was added, and 162 g (1.99 mol) of methyl acrylate was slowly added while maintaining the reactor temperature at 10 ° C. React. After the dropping of methyl acrylate is completed, the reaction is continued for 3 to 4 hours when the temperature of the reactor reaches 30 ° C. At the end of the reaction, slowly increase the temperature and remove the liquid and unreacted methyl acrylate under reduced pressure.

This gave 180.5 g (yield: 94%) of colorless, slightly viscous dipropionic methyl ester mono methyl amine. 100 g (0.53 mol) and 171 g (1.07 mol) of decyl alcohol were added together with 2 g of sodium methoxide as a catalyst, and the temperature of the reactor was slowly heated to 150 ° C. As the temperature of the reactor exceeds 100 ° C., the methanol in the reactant is distilled out slowly, at which time the reactor is depressurized to facilitate the distillation of methanol. The temperature of the reactor is maintained at 120 to 150 ° C. and the reduced pressure is continued for 2 hours at 200 to 300 torr.

At the end of the reaction, unreacted decyl alcohol was distilled off to obtain 237 g (yield: 95%) of viscous yellow dipropionic decyl ester mono methyl amine. 100 g of the reaction product obtained as described above was reacted with 50 g of normal propyl alcohol solvent in equimolar ratio in a high pressure reactor. At this time, the reaction temperature is maintained for 60 to 80 ℃ and further reacted for 2 to 3 hours. Upon completion of the reaction, the reaction product was subjected to KS analysis to obtain an aqueous solution of cationic surfactant having a reaction yield of 93%.

Example 3

Into a four-necked flask equipped with a mechanical stirrer, a reflux condenser, a temperature gauge, and a dropping device, 60 g (0.98 mol) of monoethanolamine was added, and then 185 g (2.16 mol) of methyl acrylate was slowly added while maintaining the temperature of the reactor at 30 to 40 ° C. To react. After the dropping of methyl acrylate is completed, the reaction is continued for 3 to 4 hours when the temperature of the reactor reaches 50 ° C. When the reaction is complete, the unreacted methyl acrylate is removed under reduced pressure while gradually raising the temperature.

Thus, 230.3 g of a colorless slightly viscous dipropionic methyl ester mono ethylamine (yield: 94%) was obtained. 100 g (0.43 mol) and 136 g (0.86 mol) of decyl alcohol were added together with 2 g of sodium methoxide as a catalyst, and the temperature of the reactor was slowly heated to 150 ° C. As the temperature of the reactor exceeds 100 ° C., the methanol in the reactants is slowly distilled out, whereby the reactor is depressurized to facilitate distillation. The temperature of the reactor is maintained at 120 to 150 ° C. and the reduced pressure is continued for 2 hours at 200 to 300 torr.

Upon completion of the reaction, unreacted decyl alcohol was distilled off to obtain 237 g (yield: 95%) of viscous yellow dipropionic decyl ester mono ethyl amine. 100 g of the reaction product obtained as described above is reacted with 50 g of normal propyl alcohol solvent in equimolar ratio in a high pressure reactor. At this time, the reaction temperature is maintained for 60 to 80 ℃ and further reacted for 2 to 3 hours. Upon completion of the reaction, the reaction product was subjected to KS analysis to obtain an aqueous solution of cationic surfactant having a reaction yield of 93%.

Example 4

Into a four-necked flask equipped with a mechanical stirrer, a reflux condenser, a temperature gauge, and a dropping device, 60 g (0.98 mol) of monoethanolamine was added, and 205.8 g (2.05 mol) of ethyl acrylate was gradually added while maintaining the temperature of the reactor at 30 to 40 ° C. It reacts by dripping. After the dropping of ethyl acrylate is completed, the reaction is continued for 3 to 4 hours when the temperature of the reactor reaches 40 ° C. When the reaction is finished, unreacted ethyl acrylate is removed under reduced pressure while gradually raising the temperature.

This gave 249.8 g of a colorless slightly viscous dipropionic ethyl ester mono ethylamine (yield: 94%). 100 g (0.4 mol) and 139 g (0.88 mol) of decyl alcohol were added together with 2 g of sodium methoxide as a catalyst, and the temperature of the reactor was slowly heated to 150 ° C. As the temperature of the reactor exceeds 100 ° C., the ethanol in the reactant is distilled out slowly, at which time the reactor is depressurized to facilitate the distillation of ethanol. The temperature of the reactor is maintained at 120 to 150 ° C. and the reduced pressure is continued for 2 hours at 200 to 300 torr.

Upon completion of the reaction, unreacted decyl alcohol was distilled off to obtain 178 g (yield: 94%) of viscous yellow dipropionic decyl ester mono ethyl amine. 100 g of the reaction product obtained as described above is reacted with 50 g of normal propyl alcohol solvent in equimolar ratio in a high pressure reactor. At this time, the reaction temperature is maintained for 70 to 90 ℃ and further reacted for 2 to 3 hours. Upon completion of the reaction, the reaction product was subjected to KS analysis to obtain an aqueous solution of cationic surfactant having a reaction yield of 93%.

Example 5

70 mL (40%) of mono methylamine was added to a four-necked flask equipped with a mechanical stirrer, a reflux cooler, a temperature gauge, and a dropping device. React. After the dropping of ethyl acrylate is completed, the reaction is continued for 3 to 4 hours when the temperature of the reactor reaches 30 to 40 ° C. When the reaction is finished, the water and unreacted acrylate in the reactant are removed under reduced pressure while gradually raising the temperature.

Thus, 204.5 g (yield: 93%) of colorless, slightly viscous dipropionic ethyl ester mono methylamine was obtained. 100 g (0.45 mol) and 157 g (0.99 mol) of decyl alcohol were added together with 2.5 g of sodium methoxide as a catalyst, and the reactor was slowly heated to 150 ° C. As the temperature of the reactor exceeds 100 ° C., the ethanol in the reactant is distilled out slowly, at which time the reactor is depressurized to facilitate the distillation of ethanol. The temperature of the reactor is maintained at 120 to 150 ° C. and the reduced pressure is continued for 2 hours at 200 to 300 torr.

At the end of the reaction, unreacted decyl alcohol was distilled off to obtain 237 g (yield: 95%) of viscous yellow dipropionic decyl ester mono methyl amine. 100 g of the reaction product obtained as described above is reacted with 50 g of normal propyl alcohol solvent in equimolar ratio in a high pressure reactor. At this time, the reaction temperature is maintained for 60 to 80 ℃ and further reacted for 2 to 3 hours. Upon completion of the reaction, the reaction product was subjected to KS analysis to obtain an aqueous solution of cationic surfactant having a reaction yield of 93%.

Example 6

Into a four-necked flask equipped with a mechanical stirrer, a reflux condenser, a temperature gauge, and a dropping device, 60 g (0.98 mol) of monoethanolamine was added, and then gradually 410 g (50%) of an acrylic acid sodium salt solution was maintained at a temperature of 30 to 40 ° C. ) Is added dropwise. After the dropwise addition of the acrylic acid sodium salt solution is completed, the reaction is continued for 3 to 4 hours when the temperature of the reactor reaches 40 ° C.

This gave 252 g (yield: 94%) of colorless slightly viscous dipropionic acrylic acid sodium salt mono ethanolamine. 100 g (0.37 mol) of the reaction product obtained above was added dropwise with dilute hydrochloric acid solution (5%) until the pH of the whole reactant was 3-4, dipropionic neutralized with amino dipropionic acrylic acid sodium salt monoethanolamine. After acryl acid was obtained, 130 g (0.82 mol) of decyl alcohol mono ethanol amine and 2 g of sodium methoxide as a catalyst were added together, and the temperature of the reactor was slowly heated to 150 ° C. As the temperature of the reactor exceeds 100 ° C., the ethanol in the reactant is distilled out slowly, at which time the reactor is depressurized to facilitate the distillation of ethanol. The temperature of the reactor is maintained at 120 to 150 ° C. and the reduced pressure is continued for 2 hours at 200 to 300 torr.

Upon completion of the reaction, unreacted decyl alcohol was distilled off to obtain 178 g (yield: 94%) of viscous yellow dipropionic decyl ester mono ethyl amine. 100 g of the reaction product obtained as described above was reacted with 50 g of normal prop alcohol alcohol in equimolar ratio in a high pressure reactor. At this time, the reaction temperature is maintained for 70 to 90 ℃ and further reacted for 2 to 3 hours. Upon completion of the reaction, the reaction product was subjected to KS analysis to obtain an aqueous solution of cationic surfactant having a reaction yield of 93%.

Example 7

100 g (0.4 mol) of dipropionic ethyl ester mono ethylamine synthesized in the same manner as in Example 4 and 139 g (0.88 mol) of decyl alcohol were added together with 2 g of sodium hydroxide as a catalyst, and the temperature of the reactor was gradually heated to 150 ° C. . As the temperature of the reactor exceeds 100 ° C, ethanol in the reactant is distilled out slowly, at which time the reactor is depressurized to facilitate the distillation of ethanol. The temperature of the reactor is maintained at 120 to 150 ° C. and the reduced pressure is continued for 2 hours at 200 to 300 torr.

Upon completion of the reaction, unreacted decyl alcohol was distilled off to obtain 176 g (yield: 93%) of viscous yellow dipropionic decyl ester mono ethyl amine. 100 g of the reaction product obtained as described above was reacted with 50 g of normal propyl alcohol solvent in equimolar ratio in a high pressure reactor. At this time, the reaction temperature is maintained for 70 to 90 ℃ and further reacted for 2 to 3 hours. Upon completion of the reaction, the reaction product was subjected to KS analysis to obtain an aqueous solution of cationic surfactant having a reaction yield of 93%.

Example 8

100 g (0.4 mol) of dipropionic ethyl ester mono ethylamine synthesized in the same manner as in Example 4 and 139 g (0.88 mol) of decyl alcohol were added together with 2 g of potassium hydroxide as a catalyst, and the reactor was slowly heated to 150 ° C. . As the temperature of the reactor exceeds 100 ° C., the ethanol in the reactant is distilled out slowly, at which time the reactor is depressurized to facilitate the distillation of ethanol. The temperature of the reactor is maintained at 120 to 150 ° C. and the reduced pressure is continued for 2 hours at 200 to 300 torr.

Upon completion of the reaction, unreacted decyl alcohol was distilled off to give 176 g (yield: 93%) of viscous yellow dipropionic decyl ester mono ethyl amine. 100 g of the reaction product obtained as described above was reacted with 50 g of normal propyl alcohol solvent in equimolar ratio in a high pressure reactor. At this time, the reaction temperature is maintained for 70 to 90 ℃ and further reacted for 2 to 3 hours. Upon completion of the reaction, the reaction product was subjected to KS analysis to obtain an aqueous solution of cationic surfactant having a reaction yield of 93%.

Example 9

100 g (0.4 mol) of dipropionic ethyl ester mono ethylamine synthesized in the same manner as in Example 4 and 139 g (0.88 mol) of decyl alcohol were added together with 2 g of potassium carbonate as a catalyst, and the temperature of the reactor was gradually heated to 150 ° C. . As the temperature of the reactor exceeds 100 ℃ ethanol in the reactant is distilled out slowly, at which time the reactor is depressurized to facilitate the distillation of ethanol. The temperature of the reactor is maintained at 120 to 150 ° C. and the reduced pressure is continued for 2 hours at 200 to 300 torr.

Upon completion of the reaction, unreacted decyl alcohol was distilled off to obtain 176 g (yield: 93%) of viscous yellow dipropionic decyl ester mono ethyl amine. 100 g of the reaction product obtained as described above was reacted with 50 g of normal propyl alcohol solvent in equimolar ratio in a high pressure reactor. At this time, the reaction temperature is maintained for 70 to 90 ℃ and further reacted for 2 to 3 hours. Upon completion of the reaction, the reaction product was subjected to KS analysis to obtain an aqueous solution of cationic surfactant having a reaction yield of 93%.

Example 10

100 g (0.4 mol) of dipropionic ethyl ester mono ethylamine and 163 g (0.88 mol) of dodecyl alcohol synthesized in the same manner as in Example 4 were added together with 2 g of sodium methoxide as a catalyst. Heat. As the temperature of the reactor exceeds 100 ° C, ethanol in the reactant is distilled out gradually. At this time, the reactor is depressurized to facilitate the distillation of ethanol. The temperature of the reactor is maintained at 120 to 150 ° C. and the reduced pressure is continued for 2 hours at 200 to 300 torr.

Upon completion of the reaction, unreacted dodecyl alcohol was distilled off and 199 g (yield: 92%) of viscous yellow dipropionic dodecyl ester mono ethyl amine was obtained. 100 g of the reaction product obtained as described above was reacted with 50 g of normal propyl alcohol solvent in equimolar ratio in a high pressure reactor. At this time, the reaction temperature is maintained for 70 to 90 ℃ and further reacted for 2 to 3 hours. Upon completion of the reaction, the reaction product was subjected to KS analysis to obtain an aqueous solution of cationic surfactant having a reaction yield of 93%.

Example 11

100 g (0.4 mol) of dipropionic ethyl ester mono ethylamine and 188 g (0.88 mol) of tetradecyl alcohol synthesized in the same manner as in Example 4 were added together with 2 g of sodium methoxide as a catalyst, and the temperature of the reactor was gradually increased to 150 ° C. Heat. As the temperature of the reactor exceeds 100 ° C., the ethanol in the reactant is distilled out slowly, at which time the reactor is depressurized to facilitate the distillation of ethanol. The temperature of the reactor is maintained at 120 to 150 ° C. and the reduced pressure is continued for 2 hours at 200 to 300 torr.

Upon completion of the reaction, unreacted decyl alcohol was distilled off to obtain 221 g (yield: 93%) of viscous yellow dipropionic tetradecyl ester mono ethyl amine. 100 g of the reaction product obtained as described above was reacted with 50 g of normal propyl alcohol solvent in equimolar ratio in a high pressure reactor. At this time, the reaction temperature is maintained for 70 to 90 ℃ and further react for 2 to 3 hours. Upon completion of the reaction, the reaction product was subjected to KS analysis to obtain an aqueous solution of cationic surfactant having a reaction yield of 93%.

Example 12

100 g (0.4 mol) of dipropionic ethyl ester mono ethylamine and 204 g (0.88 mol) of hexadecyl alcohol synthesized in the same manner as in Example 4 were added together with 2 g of sodium methoxide as a catalyst, and the temperature of the reactor was gradually increased to 150 ° C. Heat. As the temperature of the reactor exceeds 100 ℃ ethanol in the reactant is distilled out slowly, at which time the reactor is depressurized to facilitate the distillation of ethanol. The temperature of the reactor is maintained at 120 to 150 ° C. and the reduced pressure is continued for 2 hours at 200 to 300 torr.

Upon completion of the reaction, unreacted hexadecyl alcohol was distilled off to obtain 239 g (yield: 93%) of viscous yellow dipropionic hexadecyl ester mono ethyl amine. 100 g of the reaction product obtained as described above was reacted with 50 g of normal propyl alcohol solvent in equimolar ratio in a high pressure reactor. At this time, the reaction temperature is maintained for 70 to 90 ℃ and further reacted for 2 to 3 hours. Upon completion of the reaction, the reaction product was subjected to KS analysis to obtain an aqueous solution of cationic surfactant having a reaction yield of 93%.

Example 13

100 g (0.4 mol) of dipropionic ethyl ester mono ethylamine and 237 g (0.88 mol) of octadecyl alcohol synthesized in the same manner as in Example 4 were added together with 2 g of sodium methoxide as a catalyst. Heat. As the temperature of the reactor exceeds 100 ° C, ethanol in the reactant is distilled out gradually. At this time, the reactor is depressurized to facilitate the distillation of ethanol. The temperature of the reactor is maintained at 120 to 150 ° C. and the reduced pressure is continued for 2 hours at 200 to 300 torr.

Upon completion of the reaction, unreacted octadecyl alcohol was distilled off to obtain 260 g (yield: 94%) of viscous yellow dipropionic octadecyl ester mono ethyl amine. 100 g of the reaction product obtained as described above was reacted with 50 g of normal propyl alcohol solvent in equimolar ratio in a high pressure reactor. At this time, the reaction temperature is maintained for 70 to 90 ℃ and further reacted for 2 to 3 hours. Upon completion of the reaction, the reaction product was subjected to KS analysis to obtain an aqueous solution of cationic surfactant having a reaction yield of 93%.

Claims (13)

Reaction of the alkylamine with the acrylic derivative represented by the following Chemical Formula 1 to produce a dipropionic carboxylic mono alkyl amine represented by the following Chemical Formula 2, and then the product (2) is reacted in the presence of a higher fatty alcohol and an alkali catalyst Method for producing a dipropionic alkyl ester mono alkyl amine represented by the following formula (3) characterized in that. Formula 1 Formula 2 Formula 3 In the above formula, R ₁ is H, CH ₂ CH ₂ OH or a C _{1 to} C ₄ alkyl group, R ₂ is H, Me, Et or M (M = Na, k), R ₃ is a linear or branched alkyl group C ₈ ~C _24. The process according to claim 1, wherein the alkylamine is ammonia, monomethylamine, monoethylamine, monopropylamine, monobutylamine or monoethanolamine. The method according to claim 1, wherein the acrylic derivative is methyl acrylate, ethyl acrylate, acrylic acid or acrylic acid sodium salt. The method according to claim 1, wherein the amount of the acrylic derivative is 2 to 4 times more than the amount of the alkylamine. The method according to claim 1, wherein the higher fatty alcohol is a fatty alcohol having a linear or branched alkyl group having 8 to 24 carbon atoms. The method of claim 1, wherein the higher fatty alcohol is octyl alcohol, decyl alcohol, dodecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol, eicosanol or docosanol. 2. The process according to claim 1, wherein the higher fatty alcohol is used at a molar ratio of 2 to 2.5 times with respect to dipropionic carboxylic mono alkyl amine (2). The process according to claim 1, wherein the alkali catalyst uses sodium carbonate, potassium carbonate, sodium methoxide, potassium hydroxide or sodium hydroxide. The production method according to claim 1 or 8, wherein the amount of the alkali catalyst is 0.1 to 5% by weight based on the total weight of the dipropionic carboxylic monoalkyl amine (2) and the fatty alcohol. A process for preparing a quaternized ester derivative represented by the following formula (4), comprising reacting a dipropionic alkyl ester mono alkyl amine represented by the following formula (3) with an alkyl halide or dimethyl sulfate. Formula 3 Formula 4 In the above formula, R ₁ is H, CH ₂ CH ₂ OH or a C _{1 to} C ₄ alkyl group, R ₂ is H, Me, Et or M (M = Na, K), R ₃ is a C ₈ to C ₂₄ linear or branched alkyl group, R ₄ is a C ₁ to C ₄ alkyl group, X is Cl, Br or CH ₃ SO ₄ . The process according to claim 10, wherein the alkyl halide is methyl chloride, ethyl chloride, propyl chloride, butyl chloride, methyl bromide, ethyl bromide, propyl bromide or butyl bromide. The process according to claim 10, wherein water, methanol, ethanol, propyl alcohol, isopropyl alcohol, butyl alcohol, sorbitol, ethylene glycol, glycerin, propylene glycol or polyethylene glycol is used as the solvent. The production method according to claim 11, wherein the reaction temperature is 50 to 150 ° C.