JPH0723348B2 - Novel acylated ethylenediamine derivative, production method and use thereof - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel acylated ethylenediamine derivative, specifically, 2-alkyl-2-oxazoline and an organic sulfate or organic sulfonate,
The present invention relates to a novel acylated ethylenediamine derivative obtained by reacting with a nitrogen-containing compound and having surface activity.

[Conventional technology and problems]

It is known that 2-oxazolines are polymerized in the presence of a cationic polymerization catalyst to give a high polymer. (Angew.
Chem, 78 913 (1966)); West German Patent No. 1206585; Belgian Patent No. 666828; Japanese Patent Publication No. 51-10280, etc.) Polymers of 2-alkyl-2-oxazolines are poly (N-
Acrylic ethyleneimine), and the polymerization reaction is considered to follow the following formula.

(J.Polym.Sci.A-1 4 2253 (1966) etc.) (In the formula, R represents a hydrocarbon radical and H ⁺ represents a cationic polymerization catalyst.) Utilizing this reaction, tosylated cellulose or mesylated cellulose diacetate is used as a polymerization initiator
Polymerization of methyl-2-oxazoline to obtain a graft copolymer having cellulose or cellulose diacetate as a trunk polymer (Japanese Patent Application No. 58-17569).
8) Alternatively, a 2-alkyl-2-oxazoline is polymerized with a water-soluble saccharide or a bromoacetic acid ester of a water-soluble saccharide as a polymerization initiator to obtain a graft copolymer having a water-soluble saccharide as a trunk polymer (Japanese Patent Application 59-164612), which are disclosed as having surface-active ability.

However, these chemical substances have a structure in which a large number of alkyl groups corresponding to lipophilic groups are bonded to polymer chemical substances corresponding to hydrophilic groups such as cellulose and sugar, that is, lipophilic groups are included in one block constituting the hydrophilic group. It has a unique chemical structure that many other blocks that make up
It does not always have desirable performance as a surfactant. In general, most of the surfactants have one block that constitutes a hydrophilic group combined with another block that constitutes a lipophilic group to form spherical micelles depending on the concentration thereof in water. Or, it forms a layered micelle. Therefore, it is presumed that if one molecule of oxazoline is allowed to react with another chemical substance without undergoing ring-opening polymerization, a chemical substance having a surfactant structure having one lipophilic group and one hydrophilic group can be obtained. It

[Means for solving problems]

The present inventors earnestly studied to obtain a chemical substance having ethylenediamine, an alkyl group and an acyl group in one molecule, and obtained an acylated ethylenediamine derivative having a specific chemical structure represented by the following general formula (1). The present invention has been completed.

(In the formula, R ¹ , R ² , R ³ and R ⁴ represent hydrogen or an alkyl group having 1 to 20 carbon atoms or a hydroxyalkyl group having 1 to 20 carbon atoms, provided that R ¹ , R ² , R ³ and R ⁴ Only one of them has 4 carbons
Represents a group selected from an alkyl group having .about.20 and a hydroxyalkyl group having 4 to 20 carbon atoms. That is, the present invention provides the chemical substance represented by the general formula (1), and also provides a method for producing the same. The manufacturing method according to the present invention has the following general formula (2): (Wherein R ¹ is the same as R ¹ of the general formula (1)) and a 2-oxazoline compound represented by the following general formula (3) R ² —O—SO ₂ —R ⁵ (3) (Wherein R ² is the same as R ² in the general formula (1), R ⁵ represents —OR ² , an alkyl group having 1 to ² carbon atoms or an aryl group), and an organic sulfur compound represented by the formula: Then general formula (4) (R ³ and R ⁴ respectively in R ³ and R ⁴ are formula formula (1)
Same as. ) By reacting a nitrogen-containing compound represented by
A method for producing an acylated ethylenediamine derivative represented by the above general formula (1).

Examples of the 2-oxazoline compound represented by the general formula (2), which is a raw material for producing the acylated ethylenediamine derivative according to the present invention, include 2-oxazoline and 2-
Methyl-2-oxazoline, 2-ethyl-2-oxazoline, 2-n-propyl-2-oxazoline, 2-butyl-2-oxazoline, 2-pentyl-2-oxazoline, 2-hexyl-2-oxazoline, 2- Heptyl
2-oxazoline, 2-octyl-2-oxazoline,
2-nonyl-2-oxazoline, 2-decyl-2-oxazoline, 2-undecyl-2-oxazoline, 2-dodecyl-2-oxazoline, 2-tridecyl-2-oxazoline, 2-tetradecyl-2-oxazoline, 2-
Pentadecyl-2-oxazoline, 2-hexadecyl-
2-oxazoline, 2-heptadecyl-2-oxazoline, 2-octadecyl-2-oxazoline, 2-nonadecyl-2-oxazoline, 2-eicosyl-2-oxazoline and 2-hydroxymethyl-2-oxazoline, 2-hydroxyethyl- 2-oxazoline, 2-hydroxypropyl-2-oxazoline, 2-hydroxybutyl-2-oxazoline, 2-hydroxypentyl-
2-oxazoline, 2-hydroxyhexyl-2-oxazoline, 2-hydroxyheptyl-2-oxazoline, 2-hydroxyoctyl-2-oxazoline, 2-
Hydroxynonyl-2-oxazoline, 2-hydroxydecyl-2-oxazoline, 2-hydroxydodecyl-
2-oxazoline, 2-hydroxytetradecyl-2-
Examples thereof include oxazoline, 2-hydroxyhexadecyl-2-oxazoline, 2-hydroxyoctadecyl-2-oxazoline, and 2-hydroxyeicosyl-2-oxazoline. These compounds are, for example, Liebigs An
It is manufactured by the method described in n. Chem.996-1009 (1974).

Examples of the organic sulfur compound represented by the general formula (3) which is another raw material include methyl p-toluenesulfonate and p
-Ethyl toluene sulfonate, butyl p-toluene sulfonate, hexyl p-toluene sulfonate, p-toluene sulfonic acid, decyl p-toluene sulfonate, octyl p-toluene sulfonate, dodecyl p-toluene sulfonate, p-toluene Examples thereof include tetradecyl sulfonate, octadecyl p-toluenesulfonate, eicosyl p-toluenesulfonate, dimethylsulfate, diethylsulfate and ethyl methylsulfonate.

Further, as the nitrogen-containing compound of the general formula (4) which is still another raw material, for example, methylamine, ethylamine,
Hydroxymethylamine, monoethanolamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, eicosylamine, hydroxybutylamine , Hydroxyhexylamine, hydroxyoctylamine, hydroxydecylamine, hydroxydodecylamine, hydroxytetradecylamine, hydroxyhexadecylamine, hydroxystearylamine, hydroxyeicosylamine, methyloctylamine, methylstearylamine, ethyldodecylamine, diethanolamine, Hydroxymethyl nonadecylamine, dimethylamine, methylhydroxyethyl Min and ammonia.

An example of the manufacturing method according to the present invention is represented by a chemical formula as follows.

The acylated ethylenediamine derivative according to the present invention has a structure of a lipophilic group and a structure of a hydrophilic group in the molecule,
Since it has surface activity and has an antistatic function when kneaded into a polymer to form a molded article and an emulsification function when dissolved in water, it can be used as an antistatic agent, an emulsifier, or the like. In order to effectively exhibit such a function, in the general formula (1), only one of R ^{1 to} R ⁴ is an alkyl group having 4 to 20 carbon atoms or a hydroxyalkyl group, and preferably 4 to 4 carbon atoms. It is an alkyl group having 20 or a hydroxyalkyl group having 4 to 12 carbon atoms. The other three of R ^{1 to} R ⁴ are preferably hydrogen, methyl and ethyl. As the surfactant, the most preferable embodiment is that R ² is methyl, R ¹ is methyl or ethyl, R ³ is hydrogen, and R ⁴ has 4 to 4 carbon atoms.
There are also 10 alkyl groups.

As an example of the reaction procedure, a dehydrated and purified solvent is charged into a reaction vessel, and then dehydrated 2-alkyl-2-
Oxazoline and alkyl p-toluenesulfonate were charged in the latter in an equimolar to 3-fold molar amount, for example, 0 ° C or higher.
Keep the temperature below 100 ° C and let it react completely. Then, add ammonia or alkylamine to room temperature or above 150 ℃
After keeping the temperature below and reacting completely, remove the solvent,
Dissolve in acetonitrile and treat with non-aqueous anion exchange resin. Alternatively, ammonia can be blown into the reaction mixture after the reaction to remove the solvent, followed by washing with water to obtain the desired product.

The acylated ethylenediamine derivative according to the present invention is useful as a nonionic surfactant, and is useful as a polymer modifier, for example, as an antifogging agent for films, an antistatic agent for plastics, or an antistatic agent for fibers. If it is neutralized with an acidic substance or quaternized with a quaternizing agent, it becomes a cationic surfactant and is used as an emulsifier or an antistatic agent.

〔Example〕

The present invention will be specifically described below with reference to examples. In the examples, a HITACHI R20B proton nmr device (manufactured by Hitachi Ltd., 60 MHz) was used to measure the characteristic values, and deuterated chloroform was used as a solvent. Infrared absorption was measured using a Hitachi 260-20 infrared spectrophotometer.

Example 1 N-Methyl 2- according to the method of Polym. J. 4 87 (1973).
Methyl-2-oxazolinium tosylate was synthesized and obtained as a crystal. This method uses 5 mL of diethyl ether.
-Methyl toluenesulfonate 12.8 g (68.7 mmol) was added, and 2-methyl-2-oxazoline 2.04 g (24.0 m
mol) and heat at 35 ° C. for 2 hours. Add 70 mmol of diethyl ether, stir, and filter. The crystals are recrystallized from diethyl ether-acetonitrile. This crystal 0.
Dissolve 390 (1.45 mmol) in 3 ml of acetonitrile, add 0.176 g (2.4 mmol) of n-butylamine at 0 ° C., react at room temperature for 6 hours, and treat with non-aqueous anion exchange resin (Amberlyst A-21) did. After removing the solvent, 0.24 g (yield 96%) of an oily substance was obtained. This product had one peak by TLC (ethyl acetate: methanol = 1: 1) and was purified by a silica gel column (developing solvent, ethyl acetate: methanol = 1: 1).

From the infrared spectrum of this product, an absorption spectrum based on a carbonyl group was confirmed at 1630 cm ^-1, and the following NMR data was obtained. This product was N-acetyl-N-methyl-N'-
It was confirmed to be butylethylenediamine. This N
When the surface tension of an aqueous solution of -acetyl-N-methyl-N'-butylethylenediamine having a concentration of 0.73 wt% was measured, it was 31.8 dyn / cm.

δ (ppm) 0.7 to 1.2 (broad 3H CH ₃ absorption) 1.0 to 1.8 (broad 4H (CH ₂ ) ₂ C absorption) 2.1 (singlet 3H CH ₃ C = O absorption) 2.4 to 2.9 (broad 2H CH ₂ Absorption of N) 2.9 to 4.0 (absorption of broad 4H NCH ₂ CH ₂ N) 3.1 (absorption of singlet 3H CH ₃ N) Example 2 Instead of the raw material N-methyl-2-methyl-2-oxazolinium tosylate And N-methyl-2-ethyl-2-
Oxazolinium tosylate 0.383 g (1.34 mmol), n-
0.187 g of n-octylamine instead of butylamine (1.
45 mmol) and the reaction is carried out in the same manner as in Example 1
25 g (yield 77%) was obtained. From the infrared absorption spectrum of this product, an absorption spectrum based on a carbonyl group was confirmed at 1630 cm ^-1, and the following NMR data was obtained.
It was confirmed to be -propionyl-N-methyl-N'-octylethylenediamine. 0.5w of this N-propionyl-N-methyl-N'-octylethylenediamine
The surface tension was measured as an aqueous solution with a t% concentration of 24.6d.
It was yn / cm.

δ (ppm) 0.7 to 1.2 (broad 3H CH ₃ absorption) 1.0 to 1.8 (broad 12H (CH ₂ ) ₆ C absorption) 2.0 to 2.6 (broad 2H CH ₂ C = O absorption) 2.4 to 2.7 (broad 2H CH ₂ N absorption) 2.9-4.0 (broad 4H NCH ₂ CH ₂ N absorption) 3.1 (singlet 3H CH ₃ N absorption) Example 3 Raw material N-methyl-2-methyl-2-oxazolinium tosylate Was used in an amount of 0.250 g (0.921 mmol), and n-octylamine was 0.182 g (1.41 mmol) instead of n-butylamine.
Was reacted in the same manner as in Example 1 to give 0.19 g of the product.
(Yield 90%) was obtained. 1630 from the infrared spectrum of this product
Confirm the absorption spectrum based on the carbonyl group at cm ^-1 ,
The following NMR data was obtained, and this product was N-acetyl-N
It was confirmed to be -methyl-N'-octylethylenediamine. The surface tension of this N-acetyl-N-methyl-N'-octylethylenediamine was measured as an aqueous solution having a concentration of 0.5 wt% to obtain data of 23.9 dyn / cm.

δ (ppm) 0.7 to 1.2 (broad 3H CH ₃ absorption) 1.0 to 1.8 (broad 12H (CH ₂ ) ₆ C absorption) 2.1 (singlet 3H CH ₂ C = O absorption) 2.4 to 2.7 (broad 2H CH ₂ Absorption of N) 2.9-4.0 (absorption of broad 4H NCH ₂ CH ₂ N) 3.1 (absorption of singlet 3H CH ₃ N) Example 4 201 g of 2- (1-hydroquinisopropyl) -2-oxazoline in 1000 ml of acetonitrile ( 1.56 mmol),
295.9g of methyl p-toluenesulfonate (1.59mmo)
l) was added and heated at 50 ° C. for 1 hour. Then, after cooling to room temperature, 202.7 g (1.57 mmol) of octylamine was added, and the mixture was stirred at room temperature for 5 hours. The reaction mixture was then treated with non-aqueous anion exchange resin Amberlyst A21. After removing the solvent, an oily substance was obtained. From the infrared absorption spectrum of the obtained product, an absorption spectrum based on a carbonyl group was confirmed at 1630 cm ^-1 . The measured molecular weight of this product by the vapor pressure method was 272. The elemental analysis value is C: 0.661 H: 0.
118 N: 0.13 O: 0.117, the obtained characteristic value is N-
(1-Hydroxymethylpropionyl) -N-methyl-
Consistent with N'-octylethylenediamine.

Example 5 Using 2-methyl-2-oxazoline as a 2-oxazoline-based compound, octyl p-toluenesulfonate as an organic sulfur compound, and monoethanolamine as a nitrogen-containing compound, the same number of moles and the same method as in Example 1 were used. I went. The infrared absorption spectrum of the obtained product is 1630 cm.
Absorption was observed at ^-1 , and the molecular weight of this product was 258 g as measured by the vapor pressure method. The elemental analysis value of this product is C: 0.
651 H: 0.117 N: 0.108 O: 0.124 and the characteristic value of this product was in agreement with N-acetyl-N-octyl-N'-hydroxyethylenediamine.

Example 6 Using 2-methyl-2-oxazoline as a 2-oxazoline-based compound, methyl p-toluenesulfonate as an organic sulfur compound, and 1-aminomethylheptanol as a nitrogen-containing compound, the same number of moles and the same as in Example 1 were used. The reaction was carried out by the method. The infrared absorption spectrum of the obtained product
Absorption was observed at 1630 cm ^-1 , and the molecular weight of this product was 244 g as measured by the vapor pressure method. The elemental analysis value of this product is C: 0.630 H: 0.115 N: 0.115 O: 0.131,
The characteristic value of this product is N-acetyl-N-methyl-N'-
Consistent with (2-hydroxyoctyl) ethylenediamine.

Example 7 Using 2-hydroxyethyl-2-oxazoline as a 2-oxazoline-based compound, stearyl p-toluenesulfonate as an organic sulfur compound, and diethanolamine as a nitrogen-containing compound, the reaction was carried out by the same number of moles and the same method as in Example 1. went. The infrared absorption spectrum of the obtained product showed absorption at 1630 cm ^-1 . The molecular weight of this product was measured by the vapor pressure method and found to be 473 g. The elemental analysis value of this product is C: 0.686 H: 0.119 N: 0.059 O: 0.1
35, and the characteristic value of this product is N- (3-hydroxypropionyl) -N-stearyl-N ', N'-bis (2-
Consistent with (hydroxyethyl) ethylenediamine.

Example 8 As a 2-oxazoline compound, 2-oxazoline,
Methyl p-toluenesulfonate as an organic sulfur compound,
Using stearyl hydroxyethylamine as the nitrogen-containing compound, the reaction was carried out by the same number of moles and the same method as in Example 1. The infrared absorption spectrum of the obtained product is 1630 cm.
Absorption based on the carbonyl group was observed at ^-1 . The molecular weight of the obtained product was 398.7 g as measured by the vapor pressure method. The elemental analysis value of this product is C: 0.723 H: 0.126 N:
The characteristic value of this product was 0.070 O: 0.080, which was in agreement with that of N-formyl-N-methyl-N'-hydroxyethyl-N'-stearylethylenediamine.

Example 9 2-Stearyl-2- as 2-oxazoline compound
Using oxazoline, methyl p-toluenesulfonate as the organic sulfur compound, and diethanolamine as the nitrogen-containing compound, the reaction was carried out by the same number of moles and the same method as in Example 1. The infrared absorption spectrum of the obtained product is 1630 cm.
Absorption was observed at ^-1 , and the molecular weight of this product was measured by the vapor pressure method to obtain a value of 443 g. The elemental analysis value of this product was C: 0.705 H: 123 N: 0.063 O: 0.108, and the characteristic value of this product was N-nonadecanoyl-N-methyl-N ', N'-bis (2-hydroxyethyl). ) Consistent with ethylenediamine.

Example 10 Using 2-(-hydroxymethylethyl) -2-oxazoline as a 2-oxazoline-based compound, ethyl p-toluenesulfonate as an organic sulfur compound, and 1-methylaminomethylheptadecanol as a nitrogen-containing compound, The same number of moles as in 4 and the same method were used for the reaction. The infrared absorption spectrum of the obtained product showed absorption at 1630 cm ^-1 , and the molecular weight of this product was measured by the vapor pressure method to obtain a value of 457 g. The elemental analysis value of this product is C:
0.710 H: 0.124 N: 0.061 O: 0.105, and the characteristic value of this product is N- (2-hydroxymethylpropionyl)-
Consistent with N-ethyl-N'-methyl-N '-(2-hydroxystearyl) ethylenediamine.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location C09K 3/16 103 C11D 1/52

Claims (2)

[Claims] 1. The following general formula (Wherein R ¹ represents hydrogen, an alkyl group having 1 to 20 carbon atoms or a hydroxyalkyl group having 1 to 20 carbon atoms), and a 2-oxazoline compound represented by the following general formula R ² —OSO ₂ — R ⁵ (in the formula, R ² represents hydrogen, an alkyl group having 1 to 20 carbon atoms or a hydroxyalkyl group having 1 to 20 carbon atoms, and R ⁵ is —OR ² ,
It represents an alkyl group or an aryl group having 1 to 2 carbon atoms. ) Is reacted with an organic sulfur compound, and then the following general formula (Wherein R ³ and R ⁴ represent hydrogen, an alkyl group having 1 to 20 carbon atoms or a hydroxyalkyl group having 1 to 20 carbon atoms), and a nitrogen-containing compound represented by the following formula is reacted. (In the formula, R ¹ , R ² , R ³ and R ⁴ represent hydrogen, an alkyl group having 1 to 20 carbon atoms or a hydroxyalkyl group having 1 to 20 carbon atoms, provided that R ¹ , R ² , R ³ and R ⁴ Only one of them has 4 carbons
Represents a group selected from an alkyl group having .about.20 and a hydroxyalkyl group having 4 to 20 carbon atoms. ] The acylated ethylenediamine derivative represented by these is obtained, The manufacturing method of the acylated ethylenediamine derivative characterized by the above-mentioned. 2. The following general formula (In the formula, R ¹ , R ² , R ³ and R ⁴ represent hydrogen, an alkyl group having 1 to 20 carbon atoms or a hydroxyalkyl group having 1 to 20 carbon atoms, provided that R ¹ , R ² , R ³ and R ⁴ Only one of them has 4 carbons
Represents a group selected from an alkyl group having .about.20 and a hydroxyalkyl group having 4 to 20 carbon atoms. ) A surfactant comprising an acylated ethylenediamine derivative represented by: