WO2013154189A1

WO2013154189A1 - Alkoxylation catalyst, method for producing catalyst, and method for producing fatty acid alkyl ester alkoxylate using catalyst

Info

Publication number: WO2013154189A1
Application number: PCT/JP2013/061080
Authority: WO
Inventors: 悠介佐々木; 伊藤　裕; 川名　潤; 翔平小川; 仁志大迫
Original assignee: ライオン株式会社
Priority date: 2012-04-13
Filing date: 2013-04-12
Publication date: 2013-10-17
Also published as: JPWO2013154189A1; KR20150003152A; KR102099676B1; TW201345611A; TWI617351B; SG11201406438WA; CN104245129B; JP6028017B2; CN104245129A

Abstract

Provided is an alkoxylation catalyst for use in a reaction of alkoxylation of fatty acid alkyl ester which is represented by general formula (I), the alkoxylation catalyst being formed when (B) at least one selected from the group consisting of an alkaline-earth metal salt of a carboxylic acid, an alkaline-earth metal salt of a hydroxycarboxylic acid, an oxide of an alkaline-earth metal and a hydroxide of an alkaline-earth metal and (C) sulphuric acid are reacted in (A) a liquid dispersion medium, wherein the molar ratio represented by the component (C)/the component (B) is 0.8 to 1. R¹¹COOR¹² (I) [In the formula (I), R¹¹ is a hydrocarbon group having 1 to 40 carbon atoms and R¹² is a linear alkyl group having 1 to 3 carbon atoms.]

Description

Alkoxylation catalyst, method for producing the catalyst, and method for producing fatty acid alkyl ester alkoxylate using the catalyst

The present invention relates to an alkoxylation catalyst, a method for producing the catalyst, and a method for producing a fatty acid alkyl ester alkoxylate using the catalyst.
This application claims priority based on Japanese Patent Application No. 2012-092161 filed in Japan on April 13, 2012, the contents of which are incorporated herein by reference.

Alkylene oxide adducts of organic compounds having active hydrogen or their derivatives are widely used as solvents, surfactants or various chemical intermediates. In particular, alkylene oxide adducts obtained by adding alkylene oxides such as ethylene oxide and propylene oxide to alcohols, fatty acids, fatty acid alkyl esters, amines or alkylphenols are widely used as nonionic surfactants.
For example, fatty acid alkyl ester alkoxylates obtained by adding alkylene oxides to fatty acid alkyl esters and alcohol alkoxylates obtained by adding alkylene oxides to alcohols are frequently used as cleaning components for liquid detergents.

Examples of the method for producing an alkylene oxide adduct include a method of adding an alkylene oxide to a fatty acid alkyl ester or alcohol in the presence of an alkoxylation catalyst.

Nonionic surfactants of alkylene oxide adducts have many advantages, such as higher foaming power when the distribution of the number of moles of alkylene oxide is narrower than when the distribution of the number of moles of addition is wide. I have.
In addition, when a large amount of unreacted raw material remains in the production of the ionic surfactant, the detergency is reduced, so that it is necessary to remove the unreacted material, and the production process becomes complicated.
On the other hand, when a large amount of alkylene oxide having a narrow distribution of added moles is blended in the liquid detergent, the fluidity of the liquid detergent is likely to be lost.
For this reason, the nonionic surfactant of an alkylene oxide adduct has a narrow distribution and a wide distribution of the number of added moles of alkylene oxide, depending on the application.
Generally, as the alkoxylation catalyst, a homogeneous catalyst such as acid or alkali and / or a heterogeneous catalyst such as solid metal is used. However, the addition reaction (alkoxylation reaction) of an alkylene oxide to a fatty acid alkyl ester having no active hydrogen in the molecule does not proceed with an alkali catalyst such as sodium hydroxide. For this reason, it is necessary to use the said heterogeneous catalyst for the addition reaction of the alkylene oxide to a fatty-acid alkylester.
As a heterogeneous catalyst, for example, a calcined alumina / magnesium hydroxide catalyst whose surface is modified with a metal hydroxide or a metal alkoxide has been proposed (for example, Patent Document 1).
Or the alkoxylation catalyst containing the calcium salt of carboxylic acid and / or hydroxycarboxylic acid, a sulfuric acid, alcohol, and / or ester, or these reaction materials is proposed (for example, patent document 2).

Japanese Patent No. 2940852 International Publication No. 02/38269

However, when the alkoxylation reaction of fatty acid alkyl ester is performed using the catalysts of Patent Documents 1 and 2, by-products such as high molecular weight (weight average molecular weight measured by gel permeation chromatography method is 10,000 or more) polyethylene glycol and the like are generated. . When a fatty acid alkyl ester alkoxylate containing a high molecular weight polyethylene glycol is used as a liquid detergent, there is a problem that the liquid detergent tends to become cloudy. For this reason, it is necessary to provide the process of removing a by-product from the obtained alkylene oxide adduct, and a manufacturing process becomes complicated. Furthermore, if the amount of by-products generated is large, there is a problem that the amount of waste increases.
Therefore, the present invention is directed to an alkoxylation catalyst that can reduce the amount of by-products produced.

The present invention has the following aspects.
[1] In an alkoxylation catalyst used for an alkoxylation reaction of a fatty acid alkyl ester represented by the following general formula (I):
At least one selected from the group consisting of alkaline earth metal salts of carboxylic acids, alkaline earth metal salts of hydroxycarboxylic acids, oxides of alkaline earth metals and hydroxides of alkaline earth metals, and sulfuric acid (C) reacts in the liquid dispersion medium (A),
The alkoxylation catalyst, wherein the molar ratio represented by the component (C) / the component (B) is 0.8-1.
R ¹¹ COOR ¹² (I)
[In the formula (I), R ¹¹ is a hydrocarbon group having 1 to 40 carbon atoms, and R ¹² is a linear alkyl group having 1 to 3 carbon atoms. ]
[2] The component (A) includes an alcohol represented by the following general formula (1), an alkylene oxide adduct of the alcohol, a fatty acid alkyl ester represented by the following general formula (2), and an alkylene of the fatty acid alkyl ester. The alkoxylation catalyst according to [1], which is at least one selected from the group consisting of an oxide adduct, a fatty acid represented by the following general formula (3), and an alkylene oxide adduct of the fatty acid.
ROH (1)
[In the formula (1), R represents a hydrocarbon group having 3 to 18 carbon atoms. ]
R ¹ COOR ² (2)
[In the formula (2), R ¹ is a hydrocarbon group having 3 to 18 carbon atoms, and R ² is a linear alkyl group having 1 to 3 carbon atoms. ]
R ³ COOH (3)
[In the formula (3), R ³ is a hydrocarbon group having 3 to 18 carbon atoms. ]
[3] The alkoxylation catalyst according to [1] or [2], wherein the molar ratio represented by the component (C) / the component (B) is 0.8 or more and less than 1.
[4] The alkoxylation catalyst according to [1] or [2], wherein the molar ratio represented by the component (C) / the component (B) is 0.9 or more and less than 1.
[5] The alkoxylation catalyst according to [1] or [2], wherein the molar ratio represented by the component (C) / the component (B) is 0.9 to 0.98.
[6] The alkoxylation catalyst according to [1] or [2], wherein the molar ratio represented by the component (C) / the component (B) is 0.93 to 0.98.

[7] At least one selected from the group consisting of alkaline earth metal salts of carboxylic acids, alkaline earth metal salts of hydroxycarboxylic acids, oxides of alkaline earth metals and hydroxides of alkaline earth metals (B) And the sulfuric acid (C) are mixed in the liquid dispersion medium (A), the method for producing an alkoxylation catalyst according to [1] or [2],
The method for producing an alkoxylation catalyst, wherein the molar ratio represented by the component (C) / the component (B) is 0.8-1.
[8] The process for producing an alkoxylation catalyst according to [7], wherein the mass ratio represented by [the component (B) + the component (C)] / the component (A) is 1 to 1/3. .
[9] The method for producing an alkoxylation catalyst according to [7] or [8], wherein the molar ratio represented by the component (C) / the component (B) is 0.8 or more and less than 1.
[10] The method for producing an alkoxylation catalyst according to [7] or [8], wherein the molar ratio represented by the component (C) / the component (B) is 0.9 or more and less than 1.
[11] The method for producing an alkoxylation catalyst according to [7] or [8], wherein the molar ratio represented by the component (C) / the component (B) is 0.9 to 0.98.
[12] The method for producing an alkoxylation catalyst according to [7] or [8], wherein the molar ratio represented by the component (C) / the component (B) is 0.93 to 0.98.

[13] A method for producing a fatty acid alkyl ester alkoxylate in which an alkylene oxide is added to a fatty acid alkyl ester in the presence of the alkoxylation catalyst according to any one of [1] to [6].
[14] A method for producing a fatty acid alkyl ester alkoxylate in which an alkylene oxide is added to a fatty acid alkyl ester in the presence of the alkoxylation catalyst according to any one of [1] to [6] and a polyhydric alcohol.
[15] The method for producing a fatty acid alkyl ester alkoxylate according to [14], wherein the polyhydric alcohol is at least one selected from the group consisting of alkylene glycol, polyalkylene glycol, and glycerin.
[16] The method for producing a fatty acid alkyl ester alkoxylate according to [15], wherein the polyhydric alcohol is at least one selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and glycerin.

According to the alkoxylation catalyst of the present invention, the amount of by-products generated can be reduced.

(Alkoxylation catalyst)
The alkoxylation catalyst of the present invention is an alkoxylation catalyst used in an alkoxylation reaction of a fatty acid alkyl ester, and includes an alkaline earth metal salt of a carboxylic acid, an alkaline earth metal salt of a hydroxycarboxylic acid, and an oxide of an alkaline earth metal And at least one selected from the group consisting of hydroxides of alkaline earth metals (B) (hereinafter sometimes referred to as component (B)) and sulfuric acid (C) (hereinafter sometimes referred to as component (C)). ) In the liquid dispersion medium (A) (hereinafter sometimes referred to as component (A)). That is, the alkoxylation catalyst of the present invention contains a reaction product of the component (B) and the component (C) (a alkaline earth metal sulfate which is a main catalytic active component).

The alkoxylation catalyst may be a dispersion in which an alkaline earth metal sulfate is dispersed in the component (A), or may be a solid containing an alkaline earth metal sulfate.
When the alkoxylation catalyst is a dispersion, the content of the alkaline earth metal sulfate in the dispersion is not particularly limited, and is, for example, 10 to 30% by mass.

<(A) component>
The component (A) is a liquid dispersion medium. The component (A) is not particularly limited as long as it can maintain fluidity without gelation when the alkoxylation catalyst is produced, and the component (B) and the component (C) can react with each other. The “liquid” in the component (A) means a liquid in the dispersion step and the mixing step described later.
The component (A) is preferably a liquid at 30 ° C. from the viewpoint of increasing productivity in the method for producing an alkoxylation catalyst described later.

Examples of the component (A) include an alcohol represented by the following general formula (1), an alkylene oxide adduct of the alcohol, a fatty acid alkyl ester represented by the following general formula (2), and an alkylene oxide of the fatty acid alkyl ester. At least one selected from the group consisting of an adduct, a fatty acid represented by the following general formula (3), and an alkylene oxide adduct of the fatty acid is preferable.
ROH (1)
[In the formula (1), R represents a hydrocarbon group having 3 to 18 carbon atoms. ]
R ¹ COOR ² (2)
[In the formula (2), R ¹ is a hydrocarbon group having 3 to 18 carbon atoms, and R ² is a linear alkyl group having 1 to 3 carbon atoms. ]
R ³ COOH (3)
[In the formula (3), R ³ is a hydrocarbon group having 3 to 18 carbon atoms. ]

In the above formula (1), R has 3 to 18 carbon atoms, preferably 3 to 12 and more preferably 3 to 8. If it is less than the said lower limit, when manufacturing an alkoxylation catalyst, (A) component thickens to a gel form, loses fluidity | liquidity, and (B) component and (C) component do not react easily. Above the upper limit, the melting point becomes high and is not suitable as a dispersion medium.
R may be a straight chain or a branched chain.
R may be a saturated hydrocarbon group (alkyl group) or an unsaturated hydrocarbon group such as an alkenyl group.
Examples of the alcohol represented by the formula (1) include 1-hexanol, n-octanol, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, oleyl alcohol, and nonanol. Primary alcohols such as undecanol and tridecanol; secondary alcohols such as 2-ethylhexanol, 2-propanol, 2-octanol, 2-decanol and 2-dodecanol. From the viewpoint of further reducing the amount, 2-ethylhexanol is preferable.

In the alkylene oxide adduct of alcohol (ie, alcohol alkoxylate), examples of the alkylene oxide to be added include alkylene oxides having 2 to 3 carbon atoms.
The average number of moles of alkylene oxide added is preferably 1 to 7, for example.

In the above formula (2), R ¹ has 3 to 18 carbon atoms and can be arbitrarily selected as long as it has good fluidity under the temperature conditions for producing the alkoxylation catalyst.
R ¹ may be a straight chain or a branched chain.
R ¹ may be a saturated hydrocarbon group (alkyl group) or an unsaturated hydrocarbon group such as an alkenyl group.

(2) In the formula, R ² is a linear alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group having 1 carbon atom. If it is in the said range, melting | fusing point is low and fluidity | liquidity is good in the temperature conditions at the time of manufacture of an alkoxylation catalyst.

Examples of the fatty acid alkyl ester represented by the formula (2) include fatty acid methyl esters such as methyl decanoate, methyl laurate, methyl myristate, and methyl oleate, and mixtures thereof.

In the alkylene oxide adduct of fatty acid alkyl ester (that is, fatty acid alkyl ester alkoxylate), examples of the alkylene oxide to be added include alkylene oxides having 2 to 3 carbon atoms.
The average number of moles of alkylene oxide added is preferably 1 to 7, for example.

In the above formula (3), R ³ has 3 to 18 carbon atoms and can be arbitrarily selected as long as it has good fluidity in the temperature conditions for producing the alkoxylation catalyst.
R ³ may be linear or branched.
R ³ may be a saturated hydrocarbon group (alkyl group) or an unsaturated hydrocarbon group such as an alkenyl group.
Examples of the fatty acid include octanoic acid, decanoic acid, lauric acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, and the like, among which oleic acid is preferable.

In the alkylene oxide adduct of fatty acids, examples of the alkylene oxide to be added include alkylene oxides having 2 to 3 carbon atoms.
The average number of moles of alkylene oxide added is preferably 1 to 7, for example.

The component (A) described above may be used alone or in combination of two or more.

<(B) component>
Component (B) is an alkaline earth metal salt of carboxylic acid (hereinafter sometimes referred to as (b1) component), an alkaline earth metal salt of hydroxycarboxylic acid (hereinafter sometimes referred to as (b2) component), an alkali It is at least one selected from the group consisting of earth metal oxides (hereinafter sometimes referred to as component (b3)) and alkaline earth metal hydroxides (hereinafter sometimes referred to as component (b4)). .

Examples of the component (b1) include calcium acetates such as calcium acetate anhydrate and calcium acetate monohydrate, calcium salts of carboxylic acids such as calcium formate; magnesium salts of carboxylic acids such as magnesium acetate and magnesium formate, and the like. Among them, from the viewpoint of enhancing the catalytic activity, a calcium salt of carboxylic acid is preferable, and calcium acetate is more preferable.

(B2) As the component, calcium salt of hydroxycarboxylic acid such as calcium lactate, calcium tartrate, calcium citrate, calcium malate; magnesium salt of hydroxycarboxylic acid such as magnesium lactate, magnesium tartrate, magnesium citrate, magnesium malate Among them, a calcium salt of hydroxycarboxylic acid is preferable from the viewpoint of enhancing the catalytic activity.

(B3) Examples of the component include calcium oxide and magnesium oxide, among which calcium oxide is preferable.

(B4) Examples of the component include calcium hydroxide and magnesium hydroxide, among which calcium hydroxide is preferable.

The component (B) is preferably the component (b1), more preferably a calcium salt of a carboxylic acid, and still more preferably calcium acetate, from the viewpoint of increasing the catalytic activity and further reducing the amount of by-products generated.
Moreover, the above-mentioned (B) component may be used individually by 1 type, and may be used in combination of 2 or more type.

<(C) component>
Component (C) is sulfuric acid. The component (C) may be concentrated sulfuric acid or diluted sulfuric acid. From the viewpoint of stably expressing the catalytic activity, the component (C) is preferably concentrated sulfuric acid (96 mass% or more).

(Method for producing alkoxylation catalyst)
In the method for producing an alkoxylation catalyst of the present invention, the component (B) and the component (C) are mixed in the component (A).
Examples of the method for producing the alkoxylation catalyst include a dispersion step of dispersing the component (B) in the component (A) to obtain a dispersion, and adding the component (C) to the dispersion and mixing with the component (B). And a mixing step.

In the dispersion step, for example, a reactor equipped with a mixing tank equipped with a jacket and a paddle stirring blade provided in the stirring tank is used, and the components (A) and (B) are charged into the stirring tank. And those that stir these.

The temperature condition in this step is not particularly limited, but is, for example, normal temperature (5 to 35 ° C.). The temperature adjustment in the stirring tank is performed, for example, by passing a heat medium (for example, water) having an arbitrary temperature through the jacket.
The stirring time in this step is not particularly limited, and is a time during which the component (B) is dispersed substantially uniformly in the component (A). The term “substantially uniform” refers to a state in which it can be visually determined that there is no lump of the component (B) and the like is uniformly dispersed.

In the mixing step, the component (C) is added to the dispersion obtained in the dispersing step, the component (B) and the component (C) are mixed, and a reaction product of the component (B) and the component (C) ( That is, an alkaline earth metal sulfate, which is a main catalytically active component, is produced to obtain an alkoxylation catalyst in which the catalytically active component is dispersed in the component (A).
Although the mixing method in this process is not specifically limited, For example, the method of dripping (C) component in a dispersion is preferable, stirring the dispersion in a stirring tank.

The molar ratio represented by component (C) / component (B) in this step (hereinafter sometimes referred to as C / B ratio) is 0.8 to 1, preferably 0.8 or more and less than 1, Is more preferably from 0.9 to less than 1, more preferably from 0.9 to 0.98, particularly preferably from 0.93 to 0.98.
If C / B ratio is more than the said lower limit, the alkoxylation catalyst obtained can reduce the production amount of a by-product favorably in the manufacturing process of fatty acid alkyl ester alkoxylate. If the C / B ratio is 0.9 or more, in the method for producing a fatty acid alkyl ester alkoxylate, the distribution of the number of added moles of alkylene oxide of the obtained fatty acid alkyl ester alkoxylate can be easily widened. In order to broaden the addition mole number distribution of the alkylene oxide, it is more preferable that the C / B ratio is 0.93 or more.
If C / B ratio is below the said upper limit, the catalytic activity of the alkoxylation catalyst obtained will increase, and a fatty-acid alkylester alkoxylate can be manufactured efficiently. If the C / B ratio is less than 1, the catalytic activity of the resulting alkoxylation catalyst can be significantly increased.
In this step, the mass ratio represented by [(B) component + (C) component] / (A) component (hereinafter sometimes referred to as (B + C) / A ratio) is 1 to 1/3. Preferably, 1 to 1 / 2.5 is more preferable. If the (B + C) / A ratio is not more than the above upper limit value, it can be easily stirred and the component (B) and the component (C) can be efficiently mixed. If the amount is less than the above lower limit, the content of the catalytically active component in the component (A) decreases, and when the fatty acid alkyl ester alkoxylate is produced, the amount of addition of the alkoxylation catalyst increases too much, which is inefficient.

The temperature condition (that is, reaction temperature) in this step is preferably 10 to 60 ° C, more preferably 20 to 50 ° C. If it is less than the said lower limit, there exists a possibility that reaction of (B) component and (C) component may become too late, and the production efficiency of an alkoxylation catalyst may become low. If it exceeds the upper limit, the catalytic activity of the resulting alkoxylation catalyst may be lowered.
The reaction temperature is adjusted, for example, by passing a heat medium (for example, water) at an arbitrary temperature through the jacket.

The stirring time (that is, the reaction time) in this step is a time during which the (B) component and the (C) component can sufficiently react and a time during which the exotherm accompanying the addition of the (C) component can be controlled. One to two hours.

After the mixing step, a catalyst aging step of stirring the alkoxylation catalyst at an arbitrary temperature may be provided. The temperature condition in the catalyst ripening step is, for example, preferably 10 to 60 ° C., more preferably 20 to 50 ° C. By providing this step, the amount of the unreacted component (B) can be reduced.
The stirring time in this step is, for example, 0.5 to 3 hours.

Furthermore, the concentration of the catalytically active component in the alkoxylation catalyst may be increased by filtration, stationary separation, etc. of the alkoxylation catalyst.

(Method for producing fatty acid alkyl ester alkoxylate)
In the presence of the alkoxylation catalyst of the present invention, the method for producing a fatty acid alkyl ester alkoxylate of the present invention comprises a fatty acid alkyl ester represented by the following formula (I) (hereinafter sometimes referred to as (α) component): An alkylene oxide is added.

R ¹¹ COOR ¹² (I)
[In the formula (I), R ¹¹ is a hydrocarbon group having 1 to 40 carbon atoms, and R ¹² is a linear alkyl group having 1 to 3 carbon atoms. ]

In the formula (I), the carbon number of R ¹¹ is 1 to 40, preferably 3 to 30, and more preferably 5 to 21.
R ¹¹ may be linear or branched.
R ¹¹ may be a saturated hydrocarbon group (alkyl group) or an unsaturated hydrocarbon group such as an alkenyl group.

In the formula (I), R ¹² is a linear alkyl group having 1 to 3 carbon atoms, more preferably a methyl group having 1 carbon atom.

Examples of the component (α) include fatty acid methyl esters such as methyl decanoate, methyl laurate, methyl myristate, and methyl oleate, and mixtures thereof.
The (α) component may be the same as or different from the fatty acid alkyl ester used as the (A) component.

The alkylene oxide is determined according to the target product. For example, in order to obtain a nonionic surfactant, ethylene oxide, propylene oxide, butylene oxide and the like are preferable, and ethylene oxide and propylene oxide are more preferable. These alkylene oxides may be used individually by 1 type, and may be used in combination of 2 or more type.

Hereinafter, an example of the method for producing the fatty acid alkyl ester alkoxylate of the present invention will be described.
The method for producing a fatty acid alkyl ester alkoxylate according to the present embodiment adds an alkylene oxide to the component (α) in the presence of the alkoxylation catalyst of the present invention, and comprises a catalyst dispersion step, an addition reaction step, and an aging step. A manufacturing method provided with a process is mentioned.

The catalyst dispersion step is a step of dispersing the alkoxylation catalyst in the starting component (α). In this step, for example, a reactor equipped with a mixing tank equipped with a jacket and a paddle stirring blade provided in the stirring tank is used, and the (α) component and the alkoxylation catalyst are stirred in the stirring tank. Can be mentioned.
The mass ratio represented by component (α) / alkoxylation catalyst (hereinafter sometimes referred to as raw material / catalyst ratio) is, for example, preferably 20 to 1000, more preferably 30 to 200. The raw material / catalyst ratio can be arbitrarily set according to the target reaction time. However, when the raw material / catalyst ratio is small, it becomes complicated to separate the catalyst after the reaction.

The temperature condition in this step is not particularly limited, but is, for example, normal temperature (5 to 35 ° C.). The temperature adjustment in the stirring tank is performed, for example, by passing a heat medium (for example, water) having an arbitrary temperature through the jacket.
The stirring time in this step is not particularly limited, and is a time during which the component (α) and the alkoxylation catalyst become substantially uniform.

The addition reaction step is a step in which an alkylene oxide is added to the component (α) to obtain a fatty acid alkyl ester alkoxylate.
This step is performed by contacting an alkylene oxide with a mixture of the component (α) and the alkoxylation catalyst under an arbitrary temperature condition.
In this step, the amount of alkylene oxide introduced relative to component (α) is appropriately determined in consideration of the number of moles of alkylene oxide added to the target product, and is preferably 1 to 100 times mole, and more preferably 5 to 80 times mole. 10 to 50 times mole is more preferable. The greater the number of moles added, that is, the greater the amount of alkylene oxide introduced, the greater the amount of polymer polyethylene glycol produced. For this reason, this invention exhibits a remarkable effect when manufacturing a fatty acid alkyl ester alkoxylate having a large number of added moles.

The temperature condition (addition reaction temperature) in this step is preferably 160 to 180 ° C., for example.
The pressure condition in this step is appropriately determined in consideration of the addition reaction temperature. For example, 0.1 to 1 MPa is preferable, and 0.1 to 0.6 MPa is more preferable.

The aging step is a step of stirring the reaction layer at an arbitrary temperature after the addition reaction step. By providing this step, the amount of the unreacted (α) component can be reduced.
The temperature conditions in this step are the same as, for example, the addition reaction temperature.

Furthermore, if necessary, the catalytically active component remaining in the fatty acid alkyl ester alkoxylate may be removed. Examples of the method for removing the catalytically active component include filtration. Alternatively, the catalytically active component may not be removed from the fatty acid alkyl ester alkoxylate.

In the present embodiment, the addition reaction step may be performed in the presence of the alkoxylation catalyst of the present invention and a polyhydric alcohol (hereinafter sometimes referred to as (β) component). By performing the addition reaction step in the presence of the component (β), the amount of by-products generated can be further reduced.

Examples of the (β) component include alkylene glycols such as ethylene glycol and propylene glycol; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; glycerin and the like. The (β) component is preferably a polyhydric alcohol having a molecular weight of 200 or less, more preferably an alkylene glycol, a polyalkylene glycol having a molecular weight of 200 or less, or glycerin, and more preferably ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, or glycerin. .

The (β) component may coexist with the alkoxylation catalyst in the addition reaction step. Therefore, the (β) component may be added to the (α) component in the catalyst dispersion step, or may be added to the mixture of the (α) component and the alkoxylation catalyst during the addition reaction step. Alternatively, the (β) component may be mixed in advance with the alkoxylation catalyst.

In the addition reaction step, the mass ratio represented by the (β) component / (α) component is preferably 0.0005 to 0.02, more preferably 0.001 to 0.01. If it is less than the lower limit, the effect of adding the (β) component is difficult to obtain, and if it exceeds the upper limit, the added mole number distribution of the alkylene oxide may be too narrow.

According to the alkoxylation catalyst of the present invention, the alkylene oxide adduct is produced because the component (B) and the component (C) are reacted at a specific C / B ratio in the component (A). At the time, generation of by-products can be suppressed.
The reason why the effect of the present invention is exerted is not clear, but by setting the C / B ratio within a specific range, the crystal structure of the alkoxylation catalyst is suitable for suppressing the formation of by-products. It is considered to be.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following description.

(Raw material)
<(A) component>
2-Ethylhexanol: First grade reagent, manufactured by Kanto Chemical Co., Inc.
2-propanol: Special grade reagent, manufactured by Kanto Chemical Co., Inc.
1-Hexanol: Special grade reagent, manufactured by Kanto Chemical Co., Inc.
1-Dodecanol: Special grade reagent, manufactured by Kanto Chemical Co., Inc.
Methyl laurate: Pastel M12, manufactured by Lion Chemical Co., Ltd.

<(B) component>
Calcium acetate monohydrate: Special grade reagent, manufactured by Kanto Chemical Co., Inc.
Calcium oxide: Wako Pure Chemical Industries, Ltd.
<(B ′) component: Comparative product of component (B)>
Potassium acetate: Special grade reagent, manufactured by Kanto Chemical Co., Inc.
Calcium carbonate: Special grade reagent, manufactured by Kanto Chemical Co., Inc.
Calcium sulfate dihydrate: First grade reagent, manufactured by Kanto Chemical Co., Inc.
Calcium sulfate hemihydrate: first grade reagent, manufactured by Kanto Chemical Co., Inc.

<(C) component>
Sulfuric acid: Special grade reagent, concentration 96% by mass, manufactured by Kanto Chemical Co., Inc.
<(C ′) component: Comparative product of component (C)>
Phosphoric acid: Special grade reagent, concentration 85% by mass, manufactured by Kanto Chemical Co., Inc.

<(Β) component>
Ethylene glycol: Special grade reagent, manufactured by Kanto Chemical Co., Inc.
Diethylene glycol: Special grade reagent, manufactured by Kanto Chemical Co., Inc.
Glycerin: Special grade reagent, manufactured by Kanto Chemical Co., Inc.

(Examples 1-1 to 1-7, Comparative Examples 1-1 to 1-5, 1-7, 1-8)
According to the catalyst compositions in Tables 1 and 2, the components (A) and (B) or (B ′) were placed in a 500 mL beaker and mixed at room temperature (25 ° C.) with a paddle stirring blade to obtain a dispersion ( Dispersion step). While stirring the dispersion, the component (C) or the component (C ′) was added and mixed with a dropping funnel over 10 minutes (mixing step). In the mixing step, heat was generated by the addition of sulfuric acid, so the beaker was cooled in a water bath and the reaction temperature was controlled at 30-50 ° C. After adding the component (C) or the component (C ′), the mixture was further stirred for 2 hours while maintaining the temperature at 50 ° C. (catalyst aging step) to obtain the alkoxylation catalyst of each example.
In addition, the compounding quantity of each component in a table | surface is a pure conversion value (it is the same below).

In an autoclave, 12.5 g of the alkoxylation catalyst of each example, 462 g of methyl laurate (Pastel M12, manufactured by Lion Chemical Co., Ltd.) and 166 g of methyl myristate (Pastel M14, manufactured by Lion Chemical Co., Ltd.) were added and stirred. (Catalyst dispersion step). While stirring, the inside of the autoclave was purged with nitrogen, heated to 100 ° C., and dehydrated under reduced pressure conditions of 1.3 kPa or less for 30 minutes. Next, the temperature was increased to the addition reaction temperature in the table, and 1876 g of ethylene oxide (EO) (15 times mol of the total of methyl laurate and methyl myristate) was introduced under the conditions of 0.1 to 0.5 MPa. During the addition reaction time, the mixture was stirred (addition reaction step). Furthermore, after stirring at the addition reaction temperature for 0.5 hour (aging step), the mixture was cooled to 80 ° C. to obtain 2516 g of a crude reaction product (fatty acid methyl ester ethoxylate (MEE), EO average addition mole number = 15). The content of high molecular weight polyethylene glycol (high molecular weight PEG) in this reaction crude product was measured by gel permeation chromatography (GPC) method, and the results are shown in the table. The GPC method is under the following measurement conditions.
In Comparative Examples 1-1 to 1-3 and Comparative Examples 1-5, 1-7, and 1-8, no MEE was produced even when the addition reaction time was 24 hours. Measurement was not performed.

<GPC measurement conditions>
Column: Shodex Asahipak GF-310HQ, manufactured by Showa Denko KK
-Detector: Differential refractive index detector RID-10A, manufactured by Shimadzu Corporation.

(Comparative Example 1-6)
Alumina / magnesium hydroxide (Kyoward 300, manufactured by Kyowa Chemical Industry Co., Ltd.) represented by 2.5 MgO.Al ₂ O ₃ .nH ₂ O is calcined at 900 ° C. for 3 hours, and the magnesium-aluminum composite metal oxide A catalyst was obtained.

In an autoclave, 2.5 g of the composite metal oxide catalyst, 462 g of methyl laurate, 166 g of methyl myristate, and 3 g of glycerin are added, and 1.3 g of a 10% by mass aqueous solution of potassium hydroxide is added thereto for 10 minutes. Stirring (alkali modification treatment of the composite metal oxide catalyst).
Thereafter, while stirring, the inside of the autoclave was purged with nitrogen, heated to 100 ° C., and dehydrated under reduced pressure conditions of 1.3 kPa or less for 30 minutes.
Next, 1876 g of EO was introduced under the conditions of an addition reaction temperature of 180 ° C. and 0.5 MPa, and the mixture was stirred for 7 hours (addition reaction step). Furthermore, after stirring at 180 ° C. for 0.5 hour (aging step), the mixture was cooled to 80 ° C. to obtain 2506 g of a crude reaction product (MEE, EO average added mole number = 15). The content of the polymer PEG in this reaction crude product was measured by the GPC method, and the results are shown in the table.

As shown in Table 1, the polymer PEG content of Examples 1-1 to 1-7 to which the present invention was applied was 0.15% by mass or less.
On the other hand, as shown in Table 2, instead of the component (B), the comparative examples 1-1, 1-2, 1-7, 1-8 using the component (B ′) were replaced with the component (C). In Comparative Example 1-3 using the component (C ′) and Comparative Example 1-5 having a C / B ratio of 1.2, MEE could not be produced.
The polymer PEG content of Comparative Example 1-4 with a C / B ratio of 0.45 was 0.53% by mass, and the polymer PEG content of Comparative Example 1-6 using a composite metal oxide catalyst Was 1.0 mass%.
From these results, it was found that by applying the present invention, the amount of polymer PEG produced can be significantly reduced and MEE can be produced.

(Examples 2-1 to 2-9, Comparative Examples 2-1 to 2-3)
According to the catalyst compositions in Tables 3 to 4, the components (A) and (B) were placed in a 1000 mL separable flask and mixed at room temperature (25 ° C.) with a disperser type stirring blade to obtain a dispersion (dispersing step). . While stirring the dispersion, component (C) was added and mixed with a dropping funnel over 60 minutes (mixing step). In the mixing step, heat was generated by the addition of sulfuric acid, so the flask was cooled in a water bath and the reaction temperature was controlled at 20-40 ° C. (C) After adding component, it stirred for 2 hours, keeping at 25 degreeC (catalyst ripening process), and obtained the alkoxylation catalyst of each case.

According to the “MEE production conditions” in Tables 3 to 4, MEE was produced by the following procedure.
The alkoxylation catalyst of each example, the (β) component, methyl laurate (Pastel M12, manufactured by Lion Chemical Co., Ltd.) and methyl myristate (Pastel M14, manufactured by Lion Chemical Co., Ltd.) were added to the autoclave and stirred. (Catalyst dispersion step). Next, EO was introduced under the conditions of addition reaction temperature and 0.1 to 0.5 MPa in the table, and stirred for the addition reaction time in the table (addition reaction step). Furthermore, after stirring for 0.5 hour at the addition reaction temperature (aging step), the reaction mixture was cooled to 80 ° C. to obtain a crude reaction product (MEE, EO average addition mole number = 15).
The content of the polymer PEG in this reaction crude product was measured by the GPC method, and the results are shown in the table.
The distribution of the number of moles of EO added in the crude reaction product (EO addition mole distribution) was determined by gas chromatography (GC), and the results are shown in the table. The conditions of the GC method are the following measurement conditions, and the EO addition molar distribution (GC area%) is calculated by the following calculation method. The smaller the value of EO addition mole distribution, the wider the distribution of EO addition moles.
In Comparative Example 2-2, since MEE was not generated even when the addition reaction time was 24 hours, the measurement of the polymer PEG content and the EO addition molar distribution was not performed.

<Measurement conditions of GC method>
Gas chromatograph: GC-2025 manufactured by Shimadzu Corporation.
Column: DB-1 HT manufactured by Agilent, length 30 m, inner diameter 0.25 mm, film thickness 0.1 μm.
-Mobile phase: helium.
-Detector: Hydrogen flame ion detector (FID), 380 degreeC.
Inlet: Split, 380 ° C.
-Temperature: 100 ° C. → 380 ° C.
-From the peak area, calculate the EO addition molar distribution by the following formula.

<Calculation method>
The EO addition molar distribution is calculated by the following formula.
{(Area of maximum peak (P1) derived from methyl laurate) + (A total area of two peaks before and after maximum peak P1) + (Area of maximum peak (P2) derived from methyl myristate) + (Maximum peak P2) Total area of two peaks before and after)} ÷ total peak area

As shown in Tables 3 to 4, the content of the polymer PEG in Examples 2-1 to 2-9 to which the present invention was applied was 0.22% by mass or less.
In comparison between Example 2-1 and Examples 2-6 to 2-8, Examples 2-6 to 2-8 in which the addition reaction step was performed in the presence of the component (β) The reaction rate was increased and the content of the high molecular weight PEG could be reduced as compared with Example 2-1, which did not use.
In the comparison of Examples 2-1 to 2-3, the EO addition molar distribution became wider as the C / B ratio increased.
In contrast, the polymer PEG content of Comparative Examples 2-1 and 2-3 having a C / B ratio of less than 0.8 was 0.40% by mass or more.
From these results, it was found that by applying the present invention, the amount of polymer PEG produced can be significantly reduced and MEE can be produced.

The catalyst of the present invention can suppress the formation of by-products when producing fatty acid alkyl ester alkoxylates. For this reason, the fatty acid alkyl ester alkoxylate produced using the alkoxylation catalyst of the present invention is suitable as a nonionic surfactant for liquid detergents.

Claims

In the alkoxylation catalyst used for the alkoxylation reaction of the fatty acid alkyl ester represented by the following general formula (I):
At least one selected from the group consisting of alkaline earth metal salts of carboxylic acids, alkaline earth metal salts of hydroxycarboxylic acids, oxides of alkaline earth metals and hydroxides of alkaline earth metals, and sulfuric acid (C) reacts in the liquid dispersion medium (A),
The alkoxylation catalyst, wherein the molar ratio represented by the component (C) / the component (B) is 0.8-1.
R 11 COOR 12 (I)
[In the formula (I), R 11 is a hydrocarbon group having 1 to 40 carbon atoms, and R 12 is a linear alkyl group having 1 to 3 carbon atoms. ]
The component (A) includes an alcohol represented by the following general formula (1), an alkylene oxide adduct of the alcohol, a fatty acid alkyl ester represented by the following general formula (2), and an alkylene oxide adduct of the fatty acid alkyl ester. The alkoxylation catalyst according to claim 1, which is at least one selected from the group consisting of a fatty acid represented by the following general formula (3) and an alkylene oxide adduct of the fatty acid.
ROH (1)
[In the formula (1), R represents a hydrocarbon group having 3 to 18 carbon atoms. ]
R 1 COOR 2 (2)
[In the formula (2), R 1 is a hydrocarbon group having 3 to 18 carbon atoms, and R 2 is a linear alkyl group having 1 to 3 carbon atoms. ]
R 3 COOH (3)
[In the formula (3), R 3 is a hydrocarbon group having 3 to 18 carbon atoms. ]
At least one selected from the group consisting of alkaline earth metal salts of carboxylic acids, alkaline earth metal salts of hydroxycarboxylic acids, oxides of alkaline earth metals and hydroxides of alkaline earth metals, and sulfuric acid The method for producing an alkoxylation catalyst according to claim 1 or 2, wherein (C) is mixed in the liquid dispersion medium (A),
The method for producing an alkoxylation catalyst, wherein the molar ratio represented by the component (C) / the component (B) is 0.8-1.
The method for producing an alkoxylation catalyst according to claim 3, wherein a mass ratio represented by [the component (B) + the component (C)] / the component (A) is 1 to 1/3.
A method for producing a fatty acid alkyl ester alkoxylate, wherein an alkylene oxide is added to the fatty acid alkyl ester in the presence of the alkoxylation catalyst according to claim 1 or 2.
A method for producing a fatty acid alkyl ester alkoxylate, wherein an alkylene oxide is added to the fatty acid alkyl ester in the presence of the alkoxylation catalyst according to claim 1 or 2 and a polyhydric alcohol.