JPH0549896A - Production of high content polyoxyethylene glyceryl ether fatty acid ester - Google Patents

Abstract

PURPOSE:To obtain the subject compound useful as an emulsifier, a dispersing agent, a detergent, a removing medium for carbon coating, etc., from natural fats or oils in one step of a reaction process. CONSTITUTION:An alkylene oxide is subjected to a direct addition reaction with a mixture consisting of natural fats or oils and oxyalkylamine compound at a mixed ratio of 1:0.01 to <1:1 to obtain the objective high content polyoxyalkylent glycerye ether fatty acid ester.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a polyoxyalkylene glycerin ether fatty acid ester.
More specifically, emulsifiers, dispersants, detergents, dyeing aids,
Used as a fiber treatment agent, deinking agent, penetrant, defoaming agent, wetting agent, antistatic agent, antifogging agent, flotation agent, raw material for cosmetics, etc., and alkylene oxide adducts of fatty acid alkanolamides exist as by-products. No, that is, it relates to a novel production method by which a polyoxyalkylene glycerin ether fatty acid ester having a high content can be directly synthesized.

[0002]

2. Description of the Related Art In the conventional method for producing polyoxyalkylene glycerin ether fatty acid ester, since an alkylene oxide cannot be directly subjected to an addition reaction using an oil or fat having no active hydrogen as a starting material, JP-B-47-
An indirect production method in which a polyether obtained by adding an alkylene oxide to glycerin is esterified with a fatty acid at a high temperature to carry out a dehydration reaction, as disclosed in Japanese Patent No. 40394, is usually adopted.

[0003]

In the case of a raw material having no active hydrogen such as wax and fats and oils, another method is required because alkylene oxide cannot be directly added, and various methods have been proposed. ing. For example, Japanese Patent Publication 35-495
No. 6, in the case of mackerel whale oil, a method of reacting an alkylene oxide with a hydrolyzed product of whale oil, and in Japanese Patent Publication No. 42-13427, for obtaining a polyoxyalkylene ether of glycerin fatty acid ester. There is a method of reacting an alkylene oxide with a monoglyceride or a diglyceride obtained by an esterification reaction of glycerin and a fatty acid. (Mr. Tsuda: Monoglyceride-Manufacturing and Application-Published by Maki Shoten in 1958) All of these are
There is a problem in that it cannot be a one-step manufacturing method (direct synthesis), since it does not directly use wax or fats and oils.

On the other hand, Japanese Patent Laid-Open No. 3-69687 discloses
The mixing molar ratio of oil and fat and alkanolamine is 1: 1 to 1: 1.
A method of reacting alkylene oxide in the range of 2 is disclosed. However, although the nonionic surfactant produced here is obtained by a direct synthetic method, an alkanolamide of a fatty acid is by-produced, and an alkylene oxide adduct thereof is formed. Therefore, there is a problem that the content of the polyoxyalkylene glycerin ether fatty acid ester, which is the target component, is reduced, and its use in various applications is limited.

The object of the present invention is to obtain a polyoxyalkylene glycerin ether fatty acid ester useful for the above-mentioned uses, in which an alkylene oxide can be directly added to a natural fat or oil having no active hydrogen, and the polyoxyalkylene glycerin ether fatty acid ester can be produced. It is an object of the present invention to provide a production method capable of obtaining a polyoxyalkylene glycerin ether fatty acid ester that is a product at a high content rate.

[0006]

The present invention has been made in view of the above circumstances, and as a result of various studies, by specifying the mixing molar ratio of natural fats and oils and oxyalkylamine compounds, the product polyoxyalkylene glycerin is obtained. It has succeeded in obtaining a high content of ether fatty acid ester. That is, in producing a polyoxyalkylene glycerin ether fatty acid ester by directly reacting an alkylene oxide with a mixture of a natural fat and oil and an oxyalkylamine compound, a mixing ratio of the natural fat and oil and the oxyalkylamine compound is 1: 0.01. It is a manufacturing method of the high content polyoxyalkylene glycerin ether fatty acid ester characterized by being less than 1: 1.

The natural fats and oils used in the present invention are coconut oil,
Vegetable oils such as palm oil, olive oil, soybean oil, rapeseed oil, linseed oil and sunflower oil, animal oils such as pork oil, beef tallow, bone oil and tallow and fish oils, or hardened oils of these natural oils, semi-hardened oils, and these Examples include refined oil and recovered oil obtained in the step of refining fats and oils.

The oxyalkylamine compounds used in the present invention include monoethanolamine, diethanolamine and triethanolamine obtained by reacting ammonia with ethylene oxide, and monoisopropanolamine and diisopropanolamine obtained by reacting ammonia with propylene oxide. , Triisopropanolamine, monobutanolamine obtained by reacting ammonia with butylene oxide, dibutanolamine, tributanolamine, and the like. Further, oxyalkylalkylamines which are ethylene oxide adducts and / or propylene oxide adducts to methylamine, ethylamine, propylamine, octylamine, coconut fatty amine and the like can be mentioned.

Examples of the alkylene oxide used in the present invention include ethylene oxide, propylene oxide, butylene oxide and the like, and they may be used alone or in combination of two or more kinds. Since the amount of alkylene oxide can be freely changed, various molecular weights and alkylene oxide species can be adjusted depending on the use.

The molar ratio of the oxyalkylamine compound (B) to the natural oil (A) is (A) :( B) = 1: 0 to obtain a high content of polyoxyalkylene glycerin ether fatty acid ester as a product. .01-1: 1
Less than 1 is required, and preferably from 1: 0.05 to 1: 0.
It is 9. When alkylene oxide is reacted in a mixed system of less than 1 mol of oxyalkylamine compound with respect to 1 mol of natural fat / oil, the fatty acid residue derived from natural fat / oil is more hydroxyl group than the amidation reaction which requires more reaction energy. Selectively moves between ester bonds with weak bonds with
Since only the transesterification reaction is performed, a fatty acid amide, which is a reaction product of a fatty acid derived from a natural fat and oil and an oxyalkylamine compound, is not by-produced, and an alkylene oxide adduct thereof is also not by-produced. This is confirmed by the absence of both the chemical shift of 174.5 ppm for NMR analysis and the amide bond peak at 1660 cm ^-1 for IR analysis. The absence of the alkylene oxide adduct of the fatty acid amide, which is a by-product, inevitably increases the content rate of the polyoxyalkylene glycerin ether fatty acid ester to obtain excellent performance. However, when alkylene oxide is reacted in a mixed system of 1 mol or more of an oxyalkylamine compound with respect to 1 mol of natural fats and oils,
Since the amount of the oxyalkylamine compound becomes excessive, not only the transesterification reaction but also the amidation reaction will be followed, so that a fatty acid amide will be produced as a by-product, and the alkylene oxide adduct thereof will increase. As a result, the content of polyoxyalkylene glycerin ether fatty acid ester is reduced, which is not preferable in terms of performance. Further, if it is less than 0.01 mol, the reaction becomes difficult, which is not preferable.

In carrying out the production method of the present invention, the reaction temperature may be a temperature at which the addition reaction of alkylene oxide and the transesterification reaction are rapidly carried out, but specifically, 120 to 180 ° C. is preferable. Is. The catalyst used in this reaction is an alkaline substance, an alkali metal hydroxide, a carbonate, an organic acid salt or the like usually used in the addition reaction of alkylene oxide, such as sodium methylate, potassium methylate, sodium hydroxide, Examples thereof include potassium hydroxide, potassium carbonate, sodium acetate and potassium lactate. It is preferable to use the catalyst in an amount of about 0.01 to 0.3% by weight based on the product, because it accelerates the reactivity of the alkylene oxide. Further, it is more preferable that the pressure is 10 kg / cm ² G or less than the atmospheric pressure.

Natural fats and oils to which ethylene oxide is added are transparently dissolved in lower alcohols and water, and the aqueous solutions thereof have excellent surface tension lowering ability. Further, those obtained by the addition reaction of propylene oxide are transparently dissolved in mineral oil and lower alcohols, and are excellent in the performance of the oiliness improver. Those to which butylene oxide is further added are excellent as base oils for lubricating oils because they dissolve in mineral oil, have a low viscosity liquid at low temperatures, and have slip characteristics. On the other hand, if the natural oils and fats are not added with ethylene oxide but only the oxyalkylamines are added with ethylene oxide, they will not dissolve in alcohol or become an aqueous solution, and the oils and fats will be separated. Further, it is known that a product obtained by reacting a fatty acid alkanolamide with ethylene oxide is dissolved in water or ethanol and has a surface tension reducing ability. Using an alkylamine compound,
The difference from the one in which alkylene oxide is added in the mixed system in which fatty acid alkanolamide is by-produced is that physical properties, saponification value of product, analysis of fatty acid amount after saponification, molar ratio of fatty acid to glycerin, and further, NMR From the chemical shift of the analysis, it is possible to clarify the molar quantity of the ester bond and the amide bond and the position analysis, and the analysis of the presence or absence of the amide bond in the IR analysis.

[0013]

In the reaction of the present invention, an oxyalkylamine compound is reacted in a molar ratio smaller than the number of moles of natural fats and oils. The transesterification reaction and the addition reaction of alkylene oxide are simultaneously conducted in competition, and the alkylene oxides of fats and oils are simultaneously reacted. A mixture of adduct and alkylene oxide adduct of oxyalkylamine is obtained. In more detail,
In a mixture system of oxyalkylamine compounds with a molar ratio smaller than the number of moles of natural fats and oils, a part of ester bonds of fats and oils move fatty acids, and alkylene oxide is added to some hydroxyl groups of natural fats and oils fluctuation generated here. To do. Subsequently, the alkylene oxide adduct obtained here undergoes transesterification reaction in the molecule, and the alkylene oxide is added to the hydroxyl group of the newly generated natural oil and fat fluctuation. Further, since the reaction is a mixed system, a transesterification reaction and an alkylene oxide addition reaction are further performed between the raw material fat and oil and the above product, and a continuous reaction system is provided, and the reaction proceeds to a polyalkylene oxide adduct. .. In this way, the alkylene oxide addition reaction to natural fats and oils is repeatedly performed, and finally, the hydroxyl group of glycerin and the ester bond of the fatty acid are not left, and the polyether chain length in which the alkylene oxide is contained between the ester bonds of the fat and oil is obtained. An alkylene oxide adduct of natural fats and oils is obtained. In the above-mentioned synthetic product obtained in the present invention, the ratio of the number of moles of glycerin residue to the number of moles of fatty acid residue (based on the amount of fatty acid analyzed by the extraction method after saponification) is almost constant at 1: 3. , Saponification value analysis and NM
From the R and IR analysis, the production method of the present invention performed in a region where the number of moles of oxyalkylamine used is small relative to the fat and oil does not contain a derivative of fatty acid amide, and an alkylene oxide adduct of the fat and oil is obtained at a high content rate. It is characterized by being For this reason, since there are many fatty acids derived from fats and oils that are hydrophobic groups, the performance as a surfactant that cannot be obtained by the conventional one-step reaction is exhibited.

[0014]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. In the examples,% means% by weight.

Example 1 840 g (1 mol) of palm oil in a 5 L autoclave
Then, 14.9 g (0.1 mol) of triethanolamine and 4 g of 100% KOH were charged, and the temperature was raised to 145 ° C. under a mixing condition of a stirring speed of 450 rpm, and then 2200 g (50 mol) of ethylene oxide was added at a temperature of 130 to 150.
The reaction was carried out little by little under the conditions of ° C and a pressure of 2 kg / cm ² G. After the addition reaction of ethylene oxide was completed, the mixture was cooled to 80 ° C and neutralized to PH6 with glacial acetic acid. A pale yellow viscous liquid reaction product was obtained with a yield of 99.0%. This product has a saponification value of 55.0 (theoretical value of 55.1), and the amount of fatty acid analyzed by the extraction method after saponification is 25.7% (theoretical value of 26.3%). You can see that it is progressing. The molar ratio of fatty acid to 1 mol of glycerin residue was 3. In addition, it has water-soluble physical properties, excellent detergency, and low foaming properties, and is suitable as a raw material for detergents. From the above analysis value and surface activity performance, and from the position analysis of the ester bond by NMR analysis, this product has a polyether chain of alkylene oxide between the hydroxyl group of natural fat and oil and the ester bond of fatty acid. I understand. Also, the chemical shift of NMR analysis is 174.5 ppm
The absence of both the amide bond peak of ^{1 and} the amide bond peak of 1660 cm ^{−1 in} the IR analysis shows that the ethylene oxide adduct of the fatty acid alkanolamide as a by-product did not exist.

Example 2 860 g (1 mol) of beef tallow and 6 g of NaOH in 19.1 g (0.1 mol) of triisopropanolamine were charged and dissolved in a 5 L autoclave, and the mixture was mixed at a stirring speed of 450 rpm up to 140 ° C. After the temperature was raised, 2320 g (40 mol) of propylene oxide was added at a temperature of 125-140.
The reaction was carried out little by little under conditions of ° C and a pressure of 3.5 kg / cm ² G. After completion of the propylene oxide addition reaction, the mixture was cooled to 80 ° C, neutralized to PH6 with hydrochloric acid, and further desalted and purified. A pale yellow liquid reaction product was obtained with a yield of 98.0%.
The product has a saponification number of 52.4 (theoretical value of 52.6),
The amount of fatty acid analyzed by the extraction method after saponification was 25.2% (theoretical value: 25.7), and the molar ratio of fatty acid to 1 mol of glycerin residue was 3. In addition, it has a physical property that it is not soluble in water, but it is soluble in mineral oil or ethyl alcohol and has slipperiness, so it is suitable as an additive for lubricating oils. And the effect of improving oiliness was obtained. In addition, an amide bond peak at a chemical shift of 174.5 ppm in NMR analysis and I
The absence of the amide bond peak at 1660 cm ^{−1 in} the R analysis shows that the propylene oxide adduct of the fatty acid alkanolamide as a by-product was not present.

Example 3 In a 5 L autoclave, 943 g (1 mol) of rapeseed oil, 54.9 g (0.9 mol) of monoethanolamine and 10
After charging 8 g of 0% potassium carbonate and raising the temperature to 155 ° C. under a mixing condition of a stirring speed of 450 rpm, 1100 g (25 mol) of ethylene oxide was added at a temperature of 130 to 140.
The reaction was carried out little by little under conditions of ° C and a pressure of 2.0 kg / cm ² G. After completion of the ethylene oxide addition reaction, the temperature is set to 12
Under conditions of 0 to 140 ° C. and a pressure of 3.0 kg / cm ² G, 2030 g (35 mol) of propylene oxide and 72 g (1 mol) of butylene oxide were subjected to a block reaction. Then, it cooled at 80 degreeC and neutralized to pH 6.5 with glacial acetic acid. A pale yellow liquid reaction product was obtained with a yield of 98.2%.
The product has a saponification number of 40.3 (theoretical value of 40.1),
The amount of fatty acid analyzed by the extraction method after saponification was 21.5% (theoretical value: 21.5), and the molar ratio of fatty acid to 1 mol of glycerin residue was 3. In addition, its physical properties are water-soluble and it dissolves transparently. The cloud point of the 5% aqueous solution was 40 ° C, and the surface tension of the 0.1% aqueous solution was 41.6 dynes / cm (20 ° C), indicating excellent permeability.
Further, it has a strong defoaming property and was suitable as an antifoaming agent. Also NMR
The absence of both the amide bond peak at 174.5 ppm for the chemical shift of analysis and the amide bond peak at 1660 cm ⁻¹ for IR analysis indicates that the alkylene oxide adduct of the fatty acid alkanolamide as a by-product did not exist.

Example 4 Palm oil and triethanolamine were added to lard 880, respectively.
g (1 mol) and diethanol monomethylamine 95.2
Under the same conditions as in Example 1 except that the amount was changed to g (0.8 mol), 352 g (8 mol) of ethylene oxide was subjected to an addition reaction. After the reaction is complete, cool to 80 ° C. and add PH with glacial acetic acid
Neutralization to 6.5 gives a pale yellow liquid reaction product in a yield of 9
Obtained at 9.2%. This product had a saponification value of 126.0 (theoretical value of 126.9), and the amount of fatty acid analyzed by the extraction method after saponification was 63.1% (theoretical value of 63.5), which was based on 1 mol of glycerin residues. The molar ratio of fatty acids was 3.
In addition, the absence of the amide bond peak at 174.5 ppm of the chemical shift of the NMR analysis and the peak of the amide bond at 1660 cm ^-1 of the IR analysis indicates that the ethylene oxide adduct of the fatty acid alkanolamide as a by-product did not exist. .. Moreover, the physical properties were suitable for emulsifying and dispersing in water and as an emulsifier for emulsion. Further, when used as a cold rolling oil, the emulsifiability can be stabilized for a long period of time, and the lubricity can be stabilized for a long period of time. Further, it is effective in preventing the generation of oil scum due to the fine iron powder generated in the rolling process, and removing the adhesion of dirt to the steel plate and the rolling roll.

Example 5 Under the conditions of Example 2, 100 parts of 640 g (1 mol) of refined coconut oil and 74.6 g (0.5 mol) of triethanolamine were added.
Propylene oxide (1740 g, 30 mol) and ethylene oxide (2200 g, 50 mol) were mixed under the same conditions except that 4 g of KOH (4 g) was dissolved and charged, and a random addition reaction was performed. After completion of the reaction, the mixture was cooled to 80 ° C., neutralized to pH 6.5 with hydrochloric acid, and further desalted and purified. A pale yellow liquid reaction product was obtained with a yield of 99.4%. This product has a saponification value of 35.8 (theoretical value of 36.2) and the amount of fatty acid analyzed by the extraction method after saponification is 13.0% (theoretical value of 12.
9), and the molar ratio of fatty acid to 1 mol of glycerin residue was 3. In addition, the amide bond peak at a chemical shift of 174.5 ppm in NMR analysis and 16 in IR analysis
The absence of the amide bond peak at 60 cm ⁻¹ indicates that the alkylene oxide adduct of the fatty acid alkanolamide as a by-product did not exist.
The physical properties of this product are transparently soluble in mineral oil, water and alcohol. The cloud point of a 5% aqueous solution is 76.8 ° C.
The surface tension of the aqueous solution at a concentration of 0.1% is 41.0 dynes / cm (20 ° C.), and this product has detergency and rinsing properties as a cosmetic raw material and is suitable as a raw material for shampoos. It is a thing.

Comparative Example 1 Under the conditions of Example 1, the case where triethanolamine was not used was carried out for comparison. Under the same conditions, a small amount of ethylene oxide was introduced into the reactor, but the reaction pressure did not decrease even after 20 hours, and the addition reaction of ethylene oxide could not be performed.

Comparative Example 2 943 g (1 mol) of rapeseed oil and monoethanolamine 6
1.0 g (1.0 mol) and 100% potassium carbonate 8 g
After the temperature was raised to 155 ° C., 1100 g (25 mol) of ethylene oxide, 2030 g (35 mol) of propylene oxide and 72 g (1 mol) of butylene oxide were subjected to a block reaction under the same conditions as in Example 3. This product has a saponification value of 31.8 (theoretical value: 40.0), and the amount of fatty acid analyzed by the extraction method after saponification is 17.2% (theoretical value: 21.
5), and the molar ratio of fatty acid to 1 mol of glycerin residue was 2.4. Further, both an amide bond peak at a chemical shift of 174.5 ppm in NMR analysis and an amide bond peak in IR analysis were observed, and an alkylene oxide adduct of fatty acid monoethanolamide was formed.
From the analysis value, 0.6 mol of fatty acids derived from fats and oils were consumed by the fatty acid amide, and the content of polyoxyalkylene glycerin ether fatty acid ester was reduced. Therefore, although the physical properties were water-soluble, the permeability and defoaming property were inferior to those of Example 3.

Comparative Example 3 Palm oil (1 mol) and monoethanolamine (2 mol)
The catalyst KOH (4 g) was added thereto, the temperature was raised to 140 to 160 ° C., and after 2 hours, ethylene oxide (50 mol) was subjected to an addition reaction under the same conditions as in Example 1. This product has a saponification value of 2
3.0 (theoretical value 53.2), the amount of fatty acid analyzed by the extraction method after saponification was 10.9% (theoretical value 25.4),
The molar ratio of fatty acid to 1 mol of glycerin residue is 1.
It was 3. Also, the chemical shift of NMR analysis 174.
5 ppm amide bond peak and 1660 cm for IR analysis
An amide bond peak of ^-1 was also observed, and from the peak ratio of the chemical shift of 174.5 ppm in the NMR analysis, the ethylene oxide adduct of fatty acid monoethanolamide was produced in an amount of about 2.8 times that at a molar ratio of 1: 1. It was From the analysis value, 1.7 mol of fatty acids derived from fats and oils were consumed by the fatty acid amide, and the composition was composed mainly of polyoxyalkylene fatty acid amide. For this reason, although it is water-soluble in physical properties, it is unsuitable as a raw material for detergents because it has poor detergency against oil stains and has a high foaming property.

[0023]

The high-content polyoxyalkylene glycerin ether fatty acid ester obtained by the present invention is obtained by directly adding alkylene oxide to natural fats and oils, and has a special dryness-terminated surface with a dryness. In a mixed system of molecular structure, since it has few terminal hydroxyl groups, when used as a surfactant, emulsifying property, detergency, dispersibility, foam breaking property,
It has characteristics that it exhibits special functions such as, and physical properties excellent in thermal stability are obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical indication C11C 3/00 2115-4H C11D 1/74 8827-4H (C10M 173/00 101: 04 133: 08 129: 74 145: 18) C10N 30:00 A 8217-4H 40:24 Z 8217-4H

Claims (1)

[Claims] 1. A method for producing a polyoxyalkylene glycerin ether fatty acid ester by directly reacting an alkylene oxide with a mixture of a natural fat and oil and an oxyalkylamine compound, wherein a mixing ratio of the natural fat and oil and the oxyalkylamine compound is 1 in a molar ratio. : 0.01 to less than 1: 1 A method for producing a high content polyoxyalkylene glycerin ether fatty acid ester, which is characterized in that: