JP3195458B2 - Method for producing acylated amine having good hue and odor - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing an acylated amine having good hue and odor useful as a fiber softener and the like.

[0002]

2. Description of the Related Art
As shown in JP-A-4-327270, acylated amine salts are known to be useful as textile softeners. These are produced by reacting a corresponding amine with a fatty acid or a fatty acid ester, Since this reaction usually requires a long time at high temperature, various thermal degradations due to the high reactivity of the amine occur and the deterioration of the hue and odor is inevitable, so the commercial value is reduced and the production method is strongly improved. Is desired. Methods of replacing the conventional reaction system with an inert gas such as nitrogen gas or performing adsorption treatment to improve hue and odor have been attempted, but the improvement of hue and odor is still insufficient.

Accordingly, an object of the present invention is to provide a method for producing an acylated amine having a good hue and odor.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, unexpectedly, a compound having a primary amino group and a fatty acid and / or It has been found that the adjustment of the reaction molar ratio with the fatty acid ester is an important point, and the present invention has been completed. That is, the present invention provides a compound represented by the general formula (I):

[0005]

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Wherein R ₁ is an alkyl or alkenyl group having 1 to 22 carbon atoms, a group represented by the formula —C _x H _2x OH (x is 1 to 10
R ₂ is a group represented by the formula —C _x H _2x OH (x is an integer of 1 to 10), a group represented by the formula —C _y H _2y NH ₂ (y is 1 to 10 R ₃ is an integer of the formula —C _z H _2z NH ₂
(Z is an integer of 1 to 10) or H 2. However
R ₁ , R ₂ and R ₃ cannot all be H at the same time. )
A compound having at least one primary amino group represented by the general formula (II) R ₄ COOR ₅ (II) (wherein R ₄ is a linear or branched alkyl group having 7 to 21 carbon atoms or An alkenyl group, and R ₅ represents H or an alkyl group having 1 to 6 carbon atoms or an alkenyl group.) When a fatty acid and / or a fatty acid ester represented by When the number of functional groups to be acylated in one molecule of the compound represented by the formula (I) is n, the fatty acid represented by the formula (II) and / or Or fatty acid ester
An object of the present invention is to provide a method for producing an acylated amine having a good hue and odor, characterized in that the reaction is carried out in an amount of 0.5 nmol or more and less than nmol.

The compound having at least one primary amino group used in the present invention may be any compound represented by the general formula (I) and having at least one primary amino group in one molecule. And those having a functional group such as a hydroxyl group capable of reacting with a fatty acid or a fatty acid ester in addition to the primary amino group. Specifically, octylamine,
Decylamine, dodecylamine, myristylamine, cetylamine, stearylamine, behenylamine, ethylenediamine, propylenediamine, N-aminoethylethanolamine, 3,3′-diaminodipropylamine,
In addition to N, N-bis (3-aminopropyl) methylamine, diamines represented by the general formula (III) can be mentioned.

[0008]

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(Wherein R ₆ represents an alkyl or alkenyl group having 1 to ₆ carbon atoms, x ′ is an integer of 1 to 6, z ′ is 1 to 6
Indicates an integer. As the diamine represented by the general formula (III), N- (2-
(Hydroxyethyl) -N-methyl-1,3-propylenediamine, N- (2-hydroxyethyl) -N-ethyl-
1,3-propylenediamine, N- (2-hydroxyethyl) -N-isopropyl-1,3-propylenediamine,
N- (2-hydroxyethyl) -N-butyl-1,3-propylenediamine, N- (3-hydroxypropyl)-
N-methyl-1,3-propylenediamine, N- (2-hydroxypropyl) -N-methyl-1,3-propylenediamine, N- (4-hydroxybutyl) -N-methyl-
1,3-propylenediamine, N- (6-hydroxyhexyl) -N-methyl-1,3-propylenediamine, N-
(2-hydroxyethyl) -N-methyl-1,2-ethylenediamine and the like. In particular, a diamine represented by the above general formula (III) is used as a compound represented by the general formula (I), and the compound represented by the general formula (IV) and / or (V)

[0010]

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(Wherein R ₄ , R ₆ , x ′ and z ′ have the same meaning as described above).

The fatty acids or fatty acid esters represented by the general formula (II) include hardened tallow fatty acids, palm fatty acids, coconut fatty acids, behenic acid, stearic acid, myristic acid, lauric acid, oleic acid and the like and their carbon numbers. 1
And 6 alkyl or alkenyl esters.

In the present invention, represented by the general formula (I),
A compound having at least one primary amino group (hereinafter abbreviated as compound (I)) and a fatty acid and / or fatty acid ester represented by the general formula (II) (hereinafter abbreviated as fatty acid and / or fatty acid ester (II)) When the number of functional groups to be acylated in one molecule of the compound (I), for example, the number of functional groups including a hydroxyl group, is n, the reaction ratio with the compound (I)
Fatty acid and / or fatty acid ester (II) per mole
Is required to react with 0.5 n or more and less than n mol ,
0.75 n to 0.95 of fatty acid and / or fatty acid ester (II)
Preferably, the reaction is performed in n moles. If the proportion of the fatty acid and / or fatty acid ester (II) is less than 0.5 nmol, the effect of improving the hue and odor is not so remarkable as expected, unreacted substances remain, and the separation and purification thereof is expensive and industrially necessary. If it is more disadvantageous, and if the amount is more than n mol , the reaction system becomes acidic, which is unfavorable because coloring proceeds rapidly and the odor worsens.

In the present invention, the reaction temperature is from 150 to 250
C., preferably 160-220.degree. Reaction temperature
When the temperature is lower than 150 ° C., the reaction time is extremely long, and the productivity is reduced. On the other hand, when the temperature is higher than 250 ° C., the reaction time can be shortened, but the hue and odor deteriorate at a high rate, and the hue and odor of the reaction product are inevitably deteriorated. When the fatty acid ester (II) is used and an alkali catalyst is used, the reaction temperature can be lowered to 100 to 150 ° C.

In the present invention, the reaction pressure may be any of a range from a pressurized pressure to a reduced pressure. However, since amidation and esterification are dehydration and dealcoholization reactions, the reduced pressure increases the reaction rate and shortens the reaction time. Shorter. Further, since the hue is remarkably deteriorated by contact with oxygen, it is desirable to carry out the reaction under a flow of nitrogen or another inert gas.

After this reaction, a small amount of unreacted amine or partially acylated compound remains, but depending on the use, it is better to use a mixture of these as disclosed in JP-A-4-327270. In some cases, it is excellent in terms of product appearance, performance, and the like. Needless to say, if necessary, purification may be carried out by a usual purification step, for example, distillation, extraction, crystallization, or a chromatographic treatment step.

[0017]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 340.8 g (1.2 mol) of stearic acid, N- (2-hydroxyethyl) -N-methyl-1,3-propylenediamine 1
05.6 g (0.8 mol) was charged into a four-necked flask, and after purging with nitrogen, the temperature was raised to 180 ° C. under a reduced pressure of 200 torr.
For 10 hours. Table 1 shows the evaluation results of the hue and odor of the obtained reaction product.

Example 2 357.8 g (1.26 mol) of stearic acid, N- (2-hydroxyethyl) -N-methyl-1,3-propylenediamine
92.9 g (0.70 mol) was reacted under the same conditions as in Example-1. Table 1 shows the evaluation results of the hue and odor of the obtained reaction product.

Comparative Example 1 340.8 g (1.20 mol) of stearic acid, N- (2-hydroxyethyl) -N-methyl-1,3-propylenediamine
79.2 g (0.60 mol) was reacted under the same conditions as in Example-1. Table 1 shows the evaluation results of the hue and odor of the obtained reaction product.

Example 3 3 Hardened tallow fatty acid 344.9 g (1.26 mol) and N- (2-hydroxyethyl) -N-methyl-1,3-propylenediamine 92.4 g (0.70 mol) were used under the same conditions as in Example 1. Was reacted. Table 1 shows the evaluation results of the hue and odor of the obtained reaction product.

Example 4 4- Stearic acid methyl ester 375.5 g (1.26 mol), 28
% Sodium methylate 4.86 g (0.0252 mol) and N-
92.4 g (0.70 mol) of (2-hydroxyethyl) -N-methyl-1,3-propylenediamine was charged into a four-necked flask, purged with nitrogen, and then heated to 120 ° C. under a reduced pressure of 200 torr.
At 120 ° C. for 5 hours. Table 1 shows the evaluation results of the hue and odor of the obtained reaction product.

EXAMPLE 5 57.8 g (0.70 mol) of stearic acid and 102.2 g (0.70 mol) of N- (2-hydroxyethyl) -N-isopropyl-1,3-propylenediamine were added under the same conditions as in Example 1. Reacted. Table 1 shows the evaluation results of the hue and odor of the obtained reaction product.

Example 6 357.8 g (1.26 mol) of stearic acid and 121.8 g (0.70 mol) of N- (6-hydroxyhexyl) -N-methyl-1,3-propylenediamine were prepared under the same conditions as in Example 1. Reacted. Table 1 shows the evaluation results of the hue and odor of the obtained reaction product.
Shown in

EXAMPLE 7 357.8 g (1.26 mol) of 7 stearic acid, N, N-bis (3
-Aminopropyl) methylamine 101.5 g (0.7 mol) was charged into a four-necked flask, and after purging with nitrogen,
The reaction was carried out at 180 ° C. for 7 hours under a reduced pressure of r. Table 1 shows the evaluation results of the hue and odor of the obtained reaction product.

Comparative Example 2 349.3 g (1.23 mol) of stearic acid, N- (2-hydroxyethyl) -N-methyl-1,3-propylenediamine
79.2 g (0.60 mol) was reacted under the same conditions as in Example-1. Table 1 shows the evaluation results of the hue and odor of the obtained reaction product.

Comparative Example 3 374.9 g (1.32 mol) of 3- stearic acid, N- (2-hydroxyethyl) -N-methyl-1,3-propylenediamine
79.2 g (0.60 mol) was reacted under the same conditions as in Example-1. Table 1 shows the evaluation results of the hue and odor of the obtained reaction product.

COMPARATIVE EXAMPLE 4 366.5 g (1.23 mol) of methyl 4- stearate, N- (2-
79.2 g (0.60 mol) of hydroxyethyl) -N-methyl-1,3-propylenediamine, 28% sodium methylate
4.74 g (0.0246 mol) was reacted under the same conditions as in Example- 4 . Table 1 shows the evaluation results of the hue and odor of the obtained reaction product.

Comparative Example 5 519.7 g (1.83 mol) of stearic acid, N, N-bis (3
-Aminopropyl) methylamine (87.0 g, 0.60 mol) was charged into a four-necked flask and reacted under the same conditions as in Example- 7 . Table 1 shows the evaluation results of the hue and odor of the obtained reaction product.
Shown in

[0030]

[Table 1]

Note) * 1: Reaction molar ratio of fatty acid and / or fatty acid ester represented by general formula (II) to 1 mol of compound represented by general formula (I) * 2: Gardner colorimetric tube Judged. * 3: The odor was subjected to a sensory test and evaluated according to the following three levels. ；: Good odor

△: Smell a little bad ×: Smell bad

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Koshiro Toya 446-26 Nakaguro, Iwade-cho, Naga-gun, Wakayama Prefecture (56) References JP-A-4-327270 (JP, A) JP-B-37-11111 ( JP, B1) (58) Field surveyed (Int. Cl. ⁷ , DB name) C07C 231/02 C07C 233/36 C07C 233/38

Claims (3)

(57) [Claims] 1. A compound of the general formula (I) [Wherein, R ₁ represents an alkyl or alkenyl group having 1 to 22 carbon atoms, a group represented by the formula -C _x H _2x OH (x is an integer of 1 to 10) or H ₂ , and R ₂ represents a group represented by the formula -C groups represented by _x H _2x OH _(x is 1 to 10
), A group represented by the formula -C _y H _2y NH ₂ (y is an integer of 1 to 10) or H, and R ₃ represents a group represented by the formula -C _z H _2z NH ₂ (z
Represents an integer of 1 to 10) or H 2. However, all of R ₁ , R ₂ and R ₃ cannot be H at the same time. And a compound having at least one primary amino group represented by the general formula (I
I) R ₄ COOR ₅ (II) (wherein, R ₄ represents a linear or branched alkyl group or alkenyl group having 7 to 21 carbon atoms, R ₅ represents H or an alkyl group having 1 to 6 carbon atoms or When a fatty acid and / or a fatty acid ester represented by alkenyl group is reacted to produce a corresponding acylated amine, the number of functional groups to be acylated in one molecule of the compound represented by the general formula (I) is determined as follows. When n, the fatty acid and / or fatty acid ester represented by the general formula (II) is added to 1 mol of the compound represented by the general formula (I).
A method for producing an acylated amine having good hue and odor, characterized in that the reaction is carried out in an amount of 0.5 nmol or more and less than nmol . 2. The hue according to claim 1, wherein 0.75 n to 0.95 nm of the fatty acid and / or fatty acid ester represented by the general formula (II) is reacted with 1 mol of the compound represented by the general formula (I). A method for producing an acylated amine having a good odor. 3. The compound represented by the general formula (I) is a compound represented by the general formula (III): (Wherein, R ₆ represents an alkyl group or alkenyl group having 1 to ₆ carbon atoms, x ′ represents an integer of 1 to 6, and z ′ represents an integer of 1 to 6). The resulting acylated amine has the general formula (IV) and / or (V) (Wherein R ₄ , R ₆ , x ′ and z ′ have the same meaning as described above).
A process for producing an acylated amine having a good hue and odor as described.