JPH0714907B2 - Aminopropionate derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel aminopropionate derivative.

[Conventional technology]

Surfactants are widely used as the main components of various cleaning agents and finishing agents, and many surfactants have been proposed so far. In particular, aminopropionate derivatives are the mainstream surfactants used in shampoos and the like because of their low skin irritation.

N-alkyl-3-aminopropionate, N- (2-hydroxy) alkyl-N-polyoxyalkylene-3'-aminopropionate and the like are known as aminopropionate derivatives used as the surfactant. ing.

[Problems to be solved by the invention]

However, the above-mentioned compounds are inferior in hard water resistance and penetrating power, and both compounds have low foaming property and foam stability, and conventional cleaning agents using aminopropionate have a drawback that they lack cleaning power.

[Means for solving problems]

As a result of intensive studies to solve the above problems, the present inventors have found that a novel aminopropionate derivative represented by the following formula is useful as a surfactant, and completed the present invention.

The aminopropionate derivative of the present invention has the general formula (Wherein R represents an alkyl or alkenyl group having 8 to 20 carbon atoms, M is an alkali metal, ammonium salt or amine bases, R 'is -CH ₂ -CH ₂ - or Indicated by.

Examples of the aminopropionate derivative of the present invention include 3- [alkyl (2-hydroxyethoxycarbonyl) amino]
Propionic acid alkali metal salt, ammonium salt or amine salt, 3- [alkenyl (2-hydroxyethoxycarbonyl) amino] propionic acid alkali metal salt, ammonium salt or amine salt, or 3- [alkyl (1-methyl-2-hydroxy) Examples thereof include ethoxycarbonyl) amino] propionic acid alkali metal salt, ammonium salt or amine salt, 3- [alkenyl (1-methyl-2-hydroxyethoxycarbonyl) amino] propionic acid alkali metal salt, ammonium salt or amine salt. The alkyl group is an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group,
It is an alkyl group having 8 to 20 carbon atoms such as pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, etc., and alkenyl group is octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group. , Tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, eicosenyl group, and the like, which is an alkenyl group having 8 to 20 carbon atoms, but particularly 8 to 18 carbon atoms
And an alkenyl group having 12 to 18 carbon atoms are preferable. Examples of the alkali metal forming the alkali metal salt include lithium, sodium and potassium, but sodium and potassium are preferable, and amines forming the ammonium salt or amine salt include ammonia, monoethanolamine, diethanolamine and triethanol. Examples thereof include amine and morpholine, but monoethanolamine, diethanolamine and triethanolamine are preferable.

The aminopropionate derivative of the present invention can be produced, for example, by the following method.

First, an alkylamine or alkenylamine represented by the general formula RNH ₂ (1) (where R is an alkyl or alkenyl group having 8 to 20 carbon atoms),
General formula CH ₂ = CHCOOX (2) (where X is hydrogen or an alkyl group) is reacted with acrylic acid or an acrylic ester such as methyl acrylate A compound represented by is obtained. The alkylamines or alkenylamines having different carbon numbers may be mixed and used.

The reaction between the compound (1) and the compound (2) is (2)
It is preferable that the ratio of the compound (1) is 1.0 to 3.0 mol per 1 mol of the compound of (1), and the reaction is carried out at 70 to 90 ° C. for 3 to 4 hours under a nitrogen gas atmosphere. The compound of (3) is obtained by distilling off the compound of 1).

Then, the compound of (3) is reacted with ethylene carbonate or propylene carbonate to give a compound of the general formula (Wherein R 'is -CH ₂ -CH ₂ - or A compound represented by

The reaction of the compound of (3) with ethylene carbonate or propylene carbonate is carried out by adding 1 to 1.2 mol of ethylene carbonate or propylene carbonate per mol of the compound of (3) under a nitrogen gas atmosphere, and after completion of the addition 13
The reaction is preferably carried out at 0 to 150 ° C. for 5 to 7 hours. After completion of the reaction, excess ethylene carbonate or propylene carbonate is distilled off under reduced pressure.

The aminopropionate derivative of the present invention can be obtained by reacting the compound (4) with an alkali metal hydroxide or amines.

〔Example〕

 Hereinafter, the present invention will be described in more detail with reference to examples.

Example 1 Into a four-necked flask equipped with a reflux condenser, 378.4 g of dodecylamine was charged and kept at 100 ° C. and 30 mmHg for 30 minutes,
After cooling to 70 ° C., 87.4 g of methyl acrylate was added dropwise over about 30 minutes while stirring under a nitrogen gas atmosphere. The temperature during the dropping of methyl acrylate was maintained at 70 to 80 ° C. After the dropping is completed, the temperature is raised to 85 ° C and heated for 3 hours until the reflux of unreacted methyl acrylate completely disappears, then 170 ° C, 3mmH.
Unreacted dodecylamine was distilled off at g to obtain methyl N-dodecyl-3-aminopropionate (A reaction product).

279.2 g of the above A reaction product was charged into the same flask as above, and 97.9 g of ethylene carbonate which had been pre-melted with heating and stirring at 120 ° C. was added dropwise under a nitrogen atmosphere over 15 minutes,
After the dropping was completed, the mixture was further heated and stirred at 140 ° C. for about 5 hours. The course of this reaction was traced by infrared absorption spectrum analysis by collecting a sample every predetermined time, and the peak at 1800 cm ^-1 due to ethylene carbonate almost disappeared,
^-1 peak disappears and appears as the reaction progresses The reaction was terminated when the increase in the peak intensity at 1700 cm ⁻¹ due to the structure reached an equilibrium state. Then, unreacted ethylene carbonate was distilled off at 100 ° C. and 8 mmHg to obtain methyl 3- [dodecyl (2-hydroxyethoxycarbonyl) amino] propionate (B reaction product). Infrared absorption spectrum analysis of this B reaction product showed 1
No peak at 800 cm ^-1 was observed.

Then, in the same flask as above, 673 g of 5% potassium hydroxide aqueous solution was charged, and while heating to 80 ° C. and stirring, 216 g of the above reaction product B was added dropwise thereto, and after heating the mixture was heated at 90 ° C. for another hour. The B reaction product was saponified with potassium hydroxide with stirring. After the reaction was completed, 200 g of toluene was added to 100 g of this aqueous solution, and the mixture was heated to 90 to 110 ° C for azeotropic dehydration, further depressurized to 10 mmHg and heated to 100 ° C to completely remove toluene, and then cooled to room temperature. 30.5 g of semi-solid anhydride was obtained.
This anhydride was dissolved in 300 g of isopropyl alcohol, cooled to 5 ° C. and passed, and the solution was distilled under reduced pressure at 70 ° C. and 30 mmHg to remove isopropyl alcohol to purify the anhydride. This anhydride was dissolved again in isopropyl alcohol and the same purification as above was repeated twice more.
The pressure was reduced to mHg and the pressure was maintained for 2 hours to completely remove isopropyl alcohol in the anhydride. Infrared absorption spectrum analysis of the anhydride purified as described above A peak at 1690 cm ^-1 due to the structure was observed. In addition, the peak at 1740 cm ^-1 due to the ester structure disappeared, and
a new peak was observed at cm ^-1 and 1680 cm ^-1, it was confirmed that a potassium salt. Table 1 shows the pH and the elemental analysis values of carbon, hydrogen and nitrogen of a 1% aqueous solution of this anhydride. The potassium content determined by atomic absorption spectrometry after decomposing this anhydride with concentrated hydrochloric acid is also shown in Table 1.

Example 2 263.8 g of octylamine and 87.4 g of methyl acrylate were reacted in the same manner as in Example 1. After the reaction was completed, excess octylamine was distilled off to obtain methyl N-octyl-3-aminopropionate. It was Then, 219.6 g of this compound and 97.9 g of ethylene carbonate were reacted in the same manner as in Example 1 to remove excess ethylene carbonate to give 3- [octyl (2-hydroxyethoxycarbonyl) amino].
Methyl propionate was obtained. 304 g of this compound was saponified with 788 g of a 7% aqueous potassium hydroxide solution in the same manner as in Example 1, and then purified by the same method. Infrared absorption spectrum analysis of the anhydride purified as described above, A peak at 1690 cm ^-1 due to the structure was observed. In addition, the peak at 1740 cm ^-1 due to the ester structure disappeared and disappeared at 1570
a new peak was observed at cm ^-1 and 1680 cm ^-1, it was confirmed that a potassium salt. Table 1 shows the pH, elemental analysis value and potassium content of the 1% aqueous solution of this anhydride, which were determined by atomic absorption spectrometry.

Example 3 Hexadecylamine 40 wt% and Octadecylamine 60 wt%
In the same manner as in Example 1, 385 g of a mixed amine consisting of ## STR1 ## and 87.4 g of methyl acrylate were reacted in the same manner as in Example 1, and 385 g of a compound obtained by distilling off excess amine and 97.9 g of ethylene carbonate were reacted. I'm sorry. Next, 259.4 g of this reaction product was saponified with a 3.8% aqueous sodium hydroxide solution in the same manner as in Example 1, and then purified by the same method. Infrared absorption spectrum analysis of the obtained anhydrous product, A peak at 1690 cm ^-1 due to the structure was observed. The new peak of 1570 cm ^-1 and 1680 cm ^-1 was observed with a peak of 1740 cm ^-1 due to the ester structure disappears, it was confirmed that a sodium salt. 1% of this anhydrous
Table 1 shows the pH of the aqueous solution, the elemental analysis value, and the sodium content determined by atomic absorption spectrometry.

Example 4 407.5 g of heptadecenylamine and 73.5 g of acrylic acid were reacted in the same manner as in Example 1, and 350.8 g of a compound obtained by distilling off excess amine and 113.4 g of propylene carbonate were treated as in Example 1. To react to. This reaction product 45
After 0 g was neutralized with 1490 g of 10% triethanolamine, it was purified in the same manner as in Example 1. Infrared absorption spectrum analysis of the obtained anhydrous product, A peak at 1690 cm ^-1 due to the structure was observed. Also −
The peak at 1710 cm ^-1 due to the COOH structure disappeared to 1570 cm
New peaks were observed at ^-1 and 1680 cm ^-1 , confirming that it was a triethanolamine salt. Table 1 shows the elemental analysis value of this anhydride and the pH of a 1% aqueous solution.

The compounds obtained in Examples 1 to 4 and N-dodecyl-3-
Surface tension, osmotic force, and foaming force tests were conducted on aqueous solutions of sodium aminopropionate (Comparative Example 1), N-hexadecyl (35 wt%) and octadecyl (65 wt%)-3-aminopropionate potassium (Comparative Example 2). The results are shown in Table 2.

The surface tension was measured by the drop number method at 25 ° C for 1.0%, 0.1%, 0.01% aqueous solution, and the penetrating force was measured by the canvas disk method at 25 ° C for 1.0%, 0.1% aqueous solution, and the foaming force was 0.1%. The bubble height of the aqueous solution was measured at 25 ° C by the Los Miles method immediately after falling and after 5 minutes.

EFFECTS OF THE INVENTION The aminopropionate derivative of the present invention is a useful compound which is useful not only as a surfactant but also as a hard water-resistant detergent, penetrant, and shampoo base material.

Claims (1)

[Claims] 1. A general formula (Wherein R represents an alkyl or alkenyl group having 8 to 20 carbon atoms, M is an alkali metal, ammonium salt or amine bases, R 'is -CH ₂ -CH ₂ - or An aminopropionate derivative represented by.