JPH05246965A - New amine and its production - Google Patents

Abstract

PURPOSE:To provide a new amine excellent in flexibilizing ability, useful as a flexibilizer with higher biodegradability. CONSTITUTION:The objective amine of formula I (R<1> and R<2> are each 1-4C alkyl or hydroxyalkyl, or combined into a ring through -CH<2>-, -NR-, or O; R IS H or 1-4C alkyl; R<3> is 2-6C alkylene or alkenylene; R<4> is 7-35C alkyl or alkenyl; n is 1-3; m is 2-9). The amine of the formula I can be obtained by the following process: an amine of formula II is hydroxyalkylated into an aminoalcohol, which is, in turn, cyanoethylated and then hydrogenated to produce an amine of formula III; thence, cyanoethylation and hydrogenation are repeated, followed by acylation with a fatty acid or its ester of formula R<4> COOR<5> (R<5> is H or 1-3C alkyl).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel amine and a method for producing the same. More specifically, a surfactant,
Furthermore, the present invention relates to a novel amine used as a softening agent for cloth, hair and the like and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
Compounds used as softeners for cloth and hair are
Although it is a quaternary ammonium salt having an alkyl group, it is necessary to develop a softening agent having higher biodegradability. Therefore, an object of the present invention is to obtain a compound having excellent flexibility and biodegradability, which is suitable as a softening agent.

[0003]

As a result of intensive studies to solve the above problems, the present inventors have found that a specific novel amine is optimal for the above purpose, and completed the present invention. That is, the present invention provides an amine represented by the general formula (I) and a method for producing the same.

[0004]

[Chemical 6]

[Wherein R ¹ and R ^{2 are the} same or different and are an alkyl group or a hydroxyalkyl group having 1 to 4 carbon atoms,
Or R ¹ and R ² together form --CR _2- , --NR--, or --O
A group forming a ring via-is shown. Here, R represents H or an alkyl group having 1 to 4 carbon atoms. R ³ : represents an alkylene group having 2 to 6 carbon atoms or an alkenylene group. R ^{4 represents a} linear or branched alkyl group or alkenyl group having 7 to 35 carbon atoms, and two R ⁴ may be the same or different.

N: Indicates a number from 1 to 3. m: shows the number of 2-9. Examples of the compound represented by the general formula (I) include the following.

[0007]

[Chemical 7]

The compound represented by the general formula (I) of the present invention is produced by the following method. First, the general formula (II)

[0009]

[Chemical 8]

[In the formula, R ¹ , R ² and R ³ have the above-mentioned meanings. ] The amine of formula
I)

[0011]

[Chemical 9]

[In the formula, R ¹ , R ² , R ³ and m have the above-mentioned meanings. ] An amino alcohol represented by the following (hereinafter abbreviated as amino alcohol (III)) is obtained. Subsequently, cyanoethylation reaction is carried out using acrylonitrile, and then hydrogenation reaction using a catalyst is carried out to carry out general formula (IV)

[0013]

[Chemical 10]

[In the formula, R ¹ , R ² , R ³ and m have the above-mentioned meanings. A general formula (V) obtained by repeating a cyanoethylation reaction and a hydrogenation reaction using an acrylonitrile, if necessary, as an amine (hereinafter abbreviated as amine (IV))

[0015]

[Chemical 11]

[In the formula, R ¹ , R ² , R ³ , m, and n have the above-mentioned meanings. ] The amine represented by the following formula (hereinafter abbreviated as amine (V)) is represented by the general formula (VI) R ⁴ COOR ⁵ (VI) [wherein R ⁴ represents the above meaning and R ⁵ represents a hydrogen atom or a carbon atom]. The alkyl groups of the numbers 1 to 3 are shown. ] Acylation is carried out with a fatty acid represented by the following formula or its ester (hereinafter abbreviated as fatty acid or its ester (VI)) to obtain an amine represented by general formula (I) (hereinafter abbreviated as amine (I)) ..

The production of the amine (I) of the present invention will be described in more detail. In the hydroxyalkylation reaction of amine (II) with alkylene oxide, 0.5 to 1.0 times mol of alkylene oxide is added to amine (II), and hydroxyalkylation is carried out in 1 to 2 hours while keeping the temperature at 150 to 170 ° C. The reaction is terminated. When chloroalcohol is used in the hydroxyalkylation reaction, 0.8 to 5 times mole of chloroalcohol to amine (II) and 0.8 to 5 times mole of alkaline substance to amine (II) are added. The reaction is completed at 50-100 ° C for 2-30 hours. Then, the obtained amino alcohol (I
II) to 0.8 to 2 times the molar acrylonitrile of 50 to
It is added while maintaining at 70 ° C. and the reaction is completed over 1 to 5 hours to obtain a cyanoethylated product. The cyanoethylated product is subjected to a hydrogenation reaction in the presence of a catalyst such as Ni at 60 to 120 ° C. for 1 to 12 hours to obtain an amine (IV). If necessary, addition reaction of acrylonitrile and hydrogenation reaction are repeated to obtain amine (V). The obtained amine (V) is used in an amount of 1.8 to 2 times the molar amount of the fatty acid or its ester (VI) with respect to the amine (V) without catalyst or in the presence of a catalyst at 100 to 220 ° C. for 1 to 24 hours. Acylation is carried out under normal pressure or reduced pressure to obtain amine (I).

In the present invention, the alkylene oxide used in the hydroxyalkylation reaction to amine (II) includes ethylene oxide, propylene oxide,
Examples include butylene oxide and the like, or a mixture thereof. Examples of the chloroalcohol include ethylene chlorohydrin, 3-chloropropanol, 4-chlorobutanol, 5-chloropentanol, 6-chlorohexanol, 9-chlorononanol or a mixture thereof, and the alkaline substance includes Examples thereof include sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium carbonate, etc. These may be used alone or in combination.

The fatty acid or its ester (VI) used for acylation in the present invention includes octanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid,
Octadecanoic acid, eicosanoic acid, docosanoic acid, 2-ethylhexanoic acid, 2-butyloctanoic acid, 2-hexyldecanoic acid, 2-octyldodecanoic acid, 2-decyltetradecanoic acid, 2-dodecylhexadecanoic acid, 2-tetradecyloctadecanoic acid , 2-hexadecyl eicosanoic acid or methyl ester, ethyl ester, propyl ester of these fatty acids, or a mixture thereof. Examples of the catalyst used in the acylation of the present invention include sodium methylate, sodium ethylate, potassium ethylate, sodium hydroxide, potassium hydroxide and the like.

The structure of the amine (I) of the present invention can be confirmed by infrared absorption spectrum and nuclear magnetic resonance spectrum. The amine (I) of the present invention is a novel surfactant and is useful as a softening agent base having excellent biodegradability.

[0021]

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

Example 1 N, N was placed in an autoclave equipped with a stirrer, a thermometer and a pressure gauge.
-Add 309g of dimethyl propane diamine, 150-170 ℃
111g ethylene oxide over 1 hour
Was added to carry out addition reaction. Distilled after completion of reaction 1
22 g of amino alcohol was obtained. Boiling point 161-163 ℃ / 54
mmHg. 100 g of the above amino alcohol was placed in a four-necked flask equipped with a stirrer, a thermometer, and a dropping funnel, and the temperature was raised to 60 ° C. 42 g of acrylonitrile was added dropwise over 4 hours while maintaining the liquid temperature at 55 to 65 ° C. After the reaction was completed, the reaction solution was transferred to an autoclave equipped with a stirrer, a thermometer, and a pressure gauge. Subsequently, Raney Ni 6.5 g was added, and the hydrogen pressure was 20 kg / cm.
^The hydrogenation reaction was carried out for 8 hours while keeping the temperature at ² G and 70 ° C. After completion of the reaction, Raney Ni was filtered and the reaction solution was distilled to obtain 86 g of amine. Boiling point 133-135 ℃ / 3mmHg.
64 g of the above amine and 166 g of octadecanoic acid were placed in a four-necked flask equipped with a stirrer, a thermometer, and a dehydration tube, and the temperature was raised to 180 ° C. The acylation reaction was carried out at the same temperature for 18 hours while distilling off the produced water to obtain 206 g of the desired product.
The following structure was confirmed from the NMR spectrum and IR spectrum.

[0023]

[Chemical 12]

NMR spectrum (CDCl ₃ , internal standard TMS) 2.1 ppm (t, 2H) -O-CO-CH _2- , 2.2 ppm (s, 6H) (CH ₃ )
₂ N-

[0025]

[Chemical 13]

[0026] 2.7ppm (t, 2H)> N- CH 2 -CH 2 -O-CO-,
3.3ppm (q, 2H) - CH 2 -NHCO- 4.1ppm (t, 2H)> N-CH 2 - CH 2 -O-CO-, 6.8ppm (t, 1H)
-NH-IR spectrum (KBr, tablet) 1725 cm ^-1 , 1644 cm ^-1 , 1542 cm ^-1 , 1470 cm ^-1 Example 2 N- in an autoclave equipped with a stirrer, thermometer, pressure gauge
Add (2-aminoethyl) piperidine 256g,
While maintaining the temperature at 0 ° C, 286 g of 9-chlorononanol was added dropwise over 2 hours, and then 50% aqueous sodium hydroxide solution was added 1
34 g was press-fitted over 5 hours and aged at 100 ° C. for 8 hours to complete the addition reaction. After completion of the reaction, the reaction solution was washed with water until the solution became neutral, and then 216 g of amino alcohol was obtained by distillation. The above amino alcohol was added to a four-necked flask equipped with a stirrer, a thermometer, and a dropping funnel.
g was added and the temperature was raised to 60 ° C. While maintaining the liquid temperature at 55 to 65 ° C., 49 g of acrylonitrile was added dropwise over 4 hours. After the reaction was completed, the reaction solution was transferred to an autoclave equipped with a stirrer, a thermometer, and a pressure gauge. Then add Raney Ni 13.0g,
The hydrogenation reaction was carried out for 8 hours while maintaining the hydrogen pressure at 20 kg / cm ² G and the temperature at 70 ° C. After completion of the reaction, Raney Ni was filtered and the reaction solution was distilled to obtain 157 g of amine. mixer,
The above amine was placed in a 4-neck flask equipped with a thermometer and a dehydration tube.
100 g and 159 g of octadecanoic acid were added, and the temperature was raised to 180 ° C. The acylation reaction was carried out at the same temperature for 18 hours while distilling off the produced water to obtain 232 g of the desired product. The following structure was confirmed from the NMR spectrum and IR spectrum.

[0027]

[Chemical 14]

NMR spectrum (CDCl ₃ , internal standard TMS) 2.1 ppm (t, 2H) -O-CO-CH ₂ -2.25-2.35 ppm (m, 4H)> N-CH ₂ -CH ₂ -N <

[0029]

[Chemical 15]

[0030] 3.3ppm (q, 2H) - CH 2 -NHCO-, 4.1ppm (t,
2H) -CH ₂ -O-CO- IR spectrum (KBr, ^{tablets) 1720cm -1, 1644cm -1, 1538cm} -1, 1465cm -1 Example 3 stirrer, a thermometer, an autoclave equipped with a pressure gauge N-
(3-aminopropyl) morpholine 288g, 90 ~
While maintaining the temperature at 100 ° C, 151 g of 3-chloropropanol was added dropwise over 2 hours, and then 50% aqueous sodium hydroxide solution was added.
134 g was press-fitted over 5 hours and aged at 100 ° C. for 8 hours to complete the addition reaction. After the reaction is complete,
After washing with water until the liquid becomes neutral, 174 g by distillation
Was obtained. The above amino alcohol was added to a four-necked flask equipped with a stirrer, a thermometer, and a dropping funnel.
70 g was put and it heated up to 60 degreeC. While maintaining the liquid temperature at 55 to 65 ° C, 44 g of acrylonitrile was added dropwise over 4 hours. After the reaction was completed, the reaction solution was transferred to an autoclave equipped with a stirrer, a thermometer, and a pressure gauge. Subsequently, Raney Ni 10.7 g was added, and the hydrogenation reaction was carried out for 8 hours while maintaining the hydrogen pressure at 20 kg / cm ² G and the temperature at 70 ° C. After completion of the reaction, Raney Ni was filtered and the reaction solution was distilled to obtain 150 g of amine. 150 g of the above amine was placed in a four-necked flask equipped with a stirrer, a thermometer, and a dropping funnel, and the temperature was raised to 60 ° C. Liquid temperature 55-65
30 g of acrylonitrile was added dropwise over 4 hours while maintaining the temperature at ℃. After the reaction was completed, the reaction solution was transferred to an autoclave equipped with a stirrer, a thermometer, and a pressure gauge. Then Raney Ni 10.
7 g was added, and the hydrogenation reaction was carried out for 8 hours while maintaining the hydrogen pressure at 20 kg / cm ² G and the temperature at 70 ° C. After completion of the reaction, Raney Ni was filtered and the reaction solution was distilled to obtain 126 g of amine. 126 g of the above amine was placed in a four-necked flask equipped with a stirrer, a thermometer, and a dropping funnel, and the temperature was raised to 60 ° C. Acrylonitrile over 4 hours while maintaining the liquid temperature at 55-65 ℃
21 g was added dropwise. After the reaction was completed, the reaction solution was transferred to an autoclave equipped with a stirrer, a thermometer, and a pressure gauge. Then, 7.4 g of Raney Ni was added, the hydrogen pressure was 20 kg / cm ² G, and the temperature was 70 ° C.
The hydrogenation reaction was carried out for 8 hours while maintaining the above. After completion of the reaction, Raney Ni was filtered and the reaction solution was distilled to obtain 103 g of amine. In a 4-neck flask equipped with a stirrer, thermometer, and dehydration tube, 100 g of the above amine and methyl octadecanoate 1
46 g and 0.3 g of sodium methylate were added and the temperature was raised to 180 ° C. At the same temperature for 18 hours, distilling off the produced methanol to carry out the acylation reaction to obtain 225 g of the desired product.
Obtained. The following structure was confirmed from the NMR spectrum and IR spectrum.

[0031]

[Chemical 16]

[0032] NMR spectrum (CDCl _3, internal standard TMS) 2.1ppm (t, 2H) -O-CO-CH 2 - 2.25-2.35ppm (m, 4H)> N- CH 2 -CH 2 - CH 2 -N <2.4-2.6ppm (m, 14H) −NHCO− CH ₂ −, etc

[0033]

[Chemical 17]

[0034] _{4.1ppm (t, 2H) -CH 2} -O-CO- IR spectrum (KBr, ^{tablets) 1725cm -1, 1641cm -1, 1545cm} -1, 1475cm -1 Example 4 stirrer, thermometer, pressure N, N for autoclave with meter
-Add 309g of dimethyl propane diamine, 150-170 ℃
111g ethylene oxide over 1 hour
Was added to carry out addition reaction. Distilled after completion of reaction 1
22 g of amino alcohol was obtained. Boiling point 161-163 ℃ / 54
mmHg. 100 g of the above amino alcohol was placed in a four-necked flask equipped with a stirrer, a thermometer, and a dropping funnel, and the temperature was raised to 60 ° C. 42 g of acrylonitrile was added dropwise over 4 hours while maintaining the liquid temperature at 55 to 65 ° C. After the reaction was completed, the reaction solution was transferred to an autoclave equipped with a stirrer, a thermometer, and a pressure gauge. Subsequently, Raney Ni 6.5 g was added, and the hydrogen pressure was 20 kg / cm.
^The hydrogenation reaction was carried out for 8 hours while keeping the temperature at ² G and 70 ° C. After completion of the reaction, Raney Ni was filtered and the reaction solution was distilled to obtain 86 g of amine. Boiling point 133-135 ℃ / 3mmHg.
64 g of the above amine and 52 g of decanoic acid were placed in a four-necked flask equipped with a stirrer, a thermometer, and a dehydration tube, and the temperature was raised to 180 ° C. An acylation reaction was carried out at the same temperature for 5 hours while distilling off the produced water, and 136 g of triacontanoic acid was further added and reacted for 15 hours to obtain 193 g of the desired product. The following structure was confirmed from the NMR spectrum and IR spectrum.

[0035]

[Chemical 18]

NMR spectrum (CDCl ₃ , internal standard TMS) 2.1 ppm (t, 2H) -O-CO-CH _2- , 2.2 ppm (s, 6H) (CH ₃ )
₂ N-

[0037]

[Chemical 19]

[0038] 2.7ppm (t, 2H)> N- CH 2 -CH 2 -O-CO-,
3.3ppm (q, 2H) - CH 2 -NHCO- 4.1ppm (t, 2H)> N-CH 2 - CH 2 -O-CO-, 6.8ppm (t, 1H)
-NH-IR spectrum (KBr, tablet) 1722 cm ^-1 , 1641 cm ^-1 , 1542 cm ^-1 , 1473 cm ^-1

Claims (2)

[Claims] 1. An amine represented by the general formula (I). [Chemical 1] [In the formula, R ¹ and R ^{2 are the} same or different and are an alkyl group or a hydroxyalkyl group having 1 to 4 carbon atoms, or R ¹ and R ² are taken together to form -CR _2- , -NR-, or- A group forming a ring via O- is shown. Here, R is H or 1 to
4 represents an alkyl group. R ³ : represents an alkylene group having 2 to 6 carbon atoms or an alkenylene group. R ^{4 represents a} linear or branched alkyl group or alkenyl group having 7 to 35 carbon atoms, and two R ⁴ may be the same or different. n: shows the number of 1-3. m: shows the number of 2-9. ] 2. A compound represented by the general formula (II): [In the formula, R ¹ , R ² and R ³ have the above-mentioned meanings. ] The amine represented by the general formula (III): [In the formula, R ¹ , R ² , R ³ and m have the above-mentioned meanings. ] The amino alcohol represented by the formula] is subjected to a cyanoethylation reaction and then a hydrogenation reaction to give a compound represented by the general formula (IV): [In the formula, R ¹ , R ² , R ³ and m have the above-mentioned meanings. ] If necessary, the cyanoethylation reaction and hydrogenation reaction are repeated to obtain an amine represented by the following general formula (V): [In the formula, R ¹ , R ² , R ³ , m, and n have the above-mentioned meanings. ] The amine represented by the general formula (VI) R ⁴ COOR ⁵ (VI) [In the formula, R ⁴ represents the above meaning, and R ⁵ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ] The fatty acid represented by these or its ester is acylated, The manufacturing method of the amine represented by General formula (I) of Claim 1 characterized by the above-mentioned.