KR102099676B1 - Alkoxylation catalyst, method for producing catalyst, and method for producing fatty acid alkyl ester alkoxylate using catalyst - Google Patents

Abstract

In the alkoxylation catalyst used for the alkoxylation reaction of the fatty acid alkyl ester represented by the following general formula (I), alkali earth metal salts of carboxylic acids, alkali earth metal salts of hydroxycarboxylic acids, oxides and alkalis of alkaline earth metals At least one (B) and sulfuric acid (C) selected from the group consisting of hydroxides of earth metals are made by reacting in a liquid dispersion medium (A), and the molar ratio represented by the component (C) / the component (B) is 0.8. Alkoxylation catalyst of ∼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 straight chain alkyl group having 1 to 3 carbon atoms]

Description

An alkoxylation catalyst, a method for producing the catalyst, and a method for producing a fatty acid alkyl ester alkoxylate using the catalyst TECHNICAL FIELD

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 for which it applied to Japan on April 13, 2012, and uses the content here.

The alkylene oxide adduct of an organic compound having active hydrogen or a derivative thereof is widely used as a solvent, a surfactant, or various chemical intermediates. In particular, alkylene oxide adducts in which alkylene oxides such as ethylene oxide and propylene oxide are added to alcohols, fatty acids, fatty acid alkyl esters, amines or alkylphenols are widely used as nonionic surfactants.

For example, fatty acid alkyl ester alkoxylates in which alkylene oxide is added to fatty acid alkyl esters, and alcohol alkoxylates in which alkylene oxide is added to alcohols are widely used as cleaning components in liquid detergents.

As a method for producing an alkylene oxide adduct, a method of adding an alkylene oxide to a fatty acid alkyl ester or alcohol in the presence of an alkoxylation catalyst may be mentioned.

The nonionic surfactant of the alkylene oxide adduct has many advantages such as a narrower distribution of the added mole number of the alkylene oxide and a higher foam force compared to a broader distribution of the added mole number.

In addition, in the production of an ionic surfactant, if a large amount of unreacted raw materials remain, the cleaning power is lowered, and thus unreacted substances need to be removed, which makes the manufacturing process complicated.

On the other hand, when the distribution of the added mole number of alkylene oxide is narrow in a large amount of liquid detergent, the liquid detergent is liable to lose fluidity.

For this reason, as for the nonionic surfactant of the alkylene oxide adduct, a narrow distribution and a wide distribution of the number of moles of alkylene oxide added are used depending on the application.

In general, 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 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 in addition reaction of an alkylene oxide to a fatty acid alkyl ester.

As a heterogeneous catalyst, for example, a calcined alumina-magnesium catalyst whose surface is modified with a metal hydroxide or a metal alkoxide has been proposed (for example, Patent Document 1).

Alternatively, an alkoxylation catalyst including a mixture of calcium salt of carboxylic acid and / or hydroxycarboxylic acid with sulfuric acid, alcohol and / or ester, or a reactant thereof has been proposed (for example, Patent Document 2) ).

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

However, when the alkoxylation reaction of the fatty acid alkyl ester is carried out using the catalysts of Patent Documents 1 to 2, by-products such as polymers (weight average molecular weight of 10000 or more measured by gel permeation chromatography method) polyethylene glycol are generated. When a fatty acid alkyl ester alkoxylate containing a polymer polyethylene glycol is used in a liquid detergent, there is a problem that the liquid detergent tends to become cloudy. For this reason, it is necessary to provide a process for removing by-products from the obtained alkylene oxide adduct, which makes the manufacturing process complicated. In addition, there is a problem that the amount of waste increases when the amount of by-products is large.

Thus, the present invention aims at an alkoxylation catalyst capable of reducing the amount of by-products.

The present invention has the following forms.

[1] 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 alkali earth metal salts of carboxylic acids, alkali earth metal salts of hydroxycarboxylic acids, oxides of alkaline earth metals and hydroxides of alkaline earth metals, and sulfuric acid (C) are liquid dispersion media. It is made by reacting in (A),

The alkoxylation catalyst in which the molar ratio represented by the component (C) / the component (B) is 0.8 to 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 straight chain alkyl group having 1 to 3 carbon atoms]

[2] In [1], the component (A) is 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), the fatty acid At least one alkoxylation catalyst selected from the group consisting of alkylene oxide adducts of alkyl esters, fatty acids represented by the following general formula (3), and alkylene oxide adducts of the fatty acids.

ROH ... (1)

[In the formula (1), R is 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 straight 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 (B) and sulfuric acid (C) selected from the group consisting of alkali earth metal salts of carboxylic acids, alkali earth metal salts of hydroxycarboxylic acids, oxides of alkaline earth metals, and hydroxides of alkaline earth metals. A method for producing the alkoxylation catalyst according to [1] or [2], which is mixed in a liquid dispersion medium (A),

The manufacturing method of the alkoxylation catalyst whose molar ratio represented by the said (C) component / said (B) component is 0.8-1.

[8] The method for producing an alkoxylation catalyst according to [7], wherein the mass ratio represented by [the (B) component + the (C) component] / the (A) component 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 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 member selected from the group consisting of alkylene glycol, polyalkylene glycol and glycerin.

[16] The method of [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.

(Effects of the Invention)

According to the alkoxylation catalyst of the present invention, it is possible to reduce the amount of by-products produced.

(Alkoxylation catalyst)

The alkoxylation catalyst of the present invention is an alkoxylation catalyst used in the alkoxylation reaction of fatty acid alkyl esters, alkali earth metal salts of carboxylic acids, alkali earth metal salts of hydroxycarboxylic acids, oxides of alkali earth metals and alkali earth metals At least one (B) (hereinafter sometimes referred to as (B) component) and sulfuric acid (C) (hereinafter sometimes referred to as (C) component) selected from the group consisting of hydroxides are liquid dispersion media (A ) (Hereinafter sometimes referred to as (A) component). That is, the alkoxylation catalyst of the present invention contains the reactants of the component (B) and the component (C) (sulfate of an alkaline earth metal that is the main catalytically active component).

The alkoxylation catalyst may be a dispersion in which the sulfate of the alkaline earth metal is dispersed in the component (A), or may be a solid containing the sulfate of the alkaline earth metal.

When the alkoxylation catalyst is a dispersion, the content of the sulfate of the alkaline earth metal in the dispersion is not particularly limited, and is, for example, 10 to 30% by mass.

<(A) component>

(A) A component is a liquid dispersion medium. The component (A) is not particularly limited as long as it can maintain the fluidity without gelation when producing the alkoxylation catalyst, and the component (B) and the component (C) can react. (A) "Liquid" in a component means that it is a liquid in the dispersion process and mixing process mentioned later.

(A) As a component, it is preferable that it is a liquid at 30 degreeC from a viewpoint of raising productivity in the manufacturing method of the alkoxylation catalyst mentioned later.

As the component (A), for example, 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), an alkylene oxide of the fatty acid alkyl ester At least one member selected from the group consisting of adducts, fatty acids represented by the following general formula (3), and alkylene oxide adducts of the fatty acids is preferred.

ROH ... (1)

[In the formula (1), R is 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 straight 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 formula (1), R has 3 to 18 carbon atoms, preferably 3 to 12 carbon atoms, and more preferably 3 to 8 carbon atoms. Below the lower limit, when the alkoxylation catalyst is prepared, the component (A) is increased to a gel and loses fluidity, making it difficult for the component (B) and component (C) to react. Above the upper limit, the melting point becomes high and is not suitable as a dispersion medium.

R may be straight chain or 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, and oleyl alcohol , Primary alcohols such as nonanol, undecanol, and tridecanol; And secondary alcohols such as 2-ethylhexanol, 2-propanol, 2-octanol, 2-decanol, and 2-dodecanol. Among them, from the viewpoint of reducing the amount of polymer polyethylene glycol produced, 2 -Ethyl hexanole is preferred.

In the alkylene oxide adduct of the alcohol (i.e., alcohol alkoxylate), examples of the alkylene oxide to be added include alkylene oxides having 2 to 3 carbon atoms.

The average added mole number of the alkylene oxide is preferably 1 to 7, for example.

In the formula (2), the number of carbon atoms in R ¹ is 3 to 18, and can be arbitrarily selected as long as it has good fluidity under temperature conditions when producing an alkoxylation catalyst.

R ¹ may be straight chain or branched chain.

R ¹ may be a saturated hydrocarbon group (alkyl group) or an unsaturated hydrocarbon group such as an alkenyl group.

In the formula (2), R ² is a straight-chain alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group having 1 carbon atom. If it is within the above range, the melting point is low, and fluidity is good under temperature conditions at the time of production of the alkoxylation catalyst.

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

As the alkylene oxide added in the alkylene oxide adduct of the fatty acid alkyl ester (that is, fatty acid alkyl ester alkoxylate), an alkylene oxide having 2 to 3 carbon atoms is mentioned.

The average added mole number of the alkylene oxide is preferably 1 to 7, for example.

In the formula (3), R ³ has ³ to 18 carbon atoms, and it can be arbitrarily selected as long as it has good fluidity under temperature conditions when producing an alkoxylation catalyst.

R ³ may be straight chain or branched chain.

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, palmitic acid, oleic acid, linoleic acid, linolenic acid, and the like, and oleic acid is preferable.

Examples of the alkylene oxide added in the alkylene oxide adduct of the fatty acid include alkylene oxides having 2 to 3 carbon atoms.

The average added mole number of the alkylene oxide is preferably 1 to 7, for example.

The above-mentioned (A) component may be used individually by 1 type, or may be used in combination of 2 or more type.

<(B) component>

(B) component is alkaline earth metal salt of carboxylic acid (hereinafter may be referred to as (b1) component), alkaline earth metal salt of hydroxycarboxylic acid (hereinafter may be referred to as (b2) component), alkali It is at least 1 sort (s) selected from the group which consists of the oxide of earth metal (it may be hereafter referred to as (b3) component) and the hydroxide of alkaline earth metal (hereafter, it may be called (b4) component).

(b1) As a component, For example, calcium salts of carboxylic acids, such as calcium acetate and calcium formate, such as calcium acetate anhydride and calcium acetate-hydrate; And magnesium salts of carboxylic acids such as magnesium acetate and magnesium formate. Among them, calcium salts of carboxylic acids are preferred, and calcium acetate is more preferred from the viewpoint of increasing catalytic activity.

(b2) As a component, calcium salts of hydroxycarboxylic acids, such as calcium lactate, calcium tartrate, calcium citrate, and calcium malate; And magnesium salts of hydroxycarboxylic acids such as magnesium lactate, magnesium stannate, magnesium citrate, and magnesium malate. Among them, calcium salts of hydroxycarboxylic acids are preferred from the viewpoint of increasing catalytic activity.

(b3) As a component, calcium oxide, magnesium oxide, etc. are mentioned, Especially, calcium oxide is preferable.

(b4) As a component, calcium hydroxide, magnesium hydroxide, etc. are mentioned, Especially, calcium hydroxide is preferable.

As the component (B), from the viewpoint of increasing the catalytic activity and further reducing the amount of by-products, the component (b1) is preferable, the calcium salt of the carboxylic acid is more preferable, and calcium acetate is more preferable.

Moreover, the above-mentioned (B) component may be used individually by 1 type, or may be used in combination of 2 or more type.

<(C) component>

(C) The component is sulfuric acid. (C) As a component, concentrated sulfuric acid or dilute sulfuric acid may be sufficient. From the viewpoint of stably expressing the catalytic activity, concentrated sulfuric acid (96% by mass or more) is preferable as the component (C).

(Method for producing alkoxylation catalyst)

The production method of the alkoxylation catalyst of this invention is mixing (B) component and (C) component among (A) component.

As a method for producing an alkoxylation catalyst, for example, a dispersion step of dispersing the component (B) in the component (A) to obtain a dispersion, and a mixing step of adding the component (C) to the dispersion and mixing with the component (B) And having them.

The dispersing process includes, for example, using a mixing tank equipped with a jacket and a reactor equipped with a paddle stirring blade installed in the stirring tank, and adding (A) and (B) components into the stirring tank and stirring them. You can.

The temperature conditions in this step are not particularly limited, but are, for example, room temperature (5 to 35 ° C). The temperature adjustment in the stirring tank is performed, for example, by passing a heat medium (for example, water) at an arbitrary temperature in the jacket.

The stirring time in this step is not particularly limited, and is a time in which the component (B) is substantially uniformly dispersed in the component (A). It is a state in which it can be judged that there is no lump or the like of the component (B) and it is uniformly dispersed when viewed visually.

In the mixing step, the component (C) is added to the dispersion obtained in the dispersing step, and the components (B) and (C) are mixed to react the components (B) and (C) (that is, the main catalytically active component, alkali). Sulfate of earth metal) is produced, and an alkoxylation catalyst in which the catalytically active component is dispersed in the component (A) is obtained.

Although the mixing method in this process is not specifically limited, For example, the method of dropping (C) component in a dispersion is preferable, stirring the dispersion in a stirring tank.

The molar ratio (hereinafter sometimes referred to as C / B ratio) represented by the component (C) / (B) in this step is 0.8 to 1, preferably 0.8 or more and less than 1, and 0.9 or more and less than 1 It is more preferable, 0.9 to 0.98 is more preferable, and 0.93 to 0.98 is particularly preferable.

When the C / B ratio is greater than or equal to the above lower limit, the alkoxylation catalyst obtained can satisfactorily reduce the amount of by-products produced in the production process of a fatty acid alkyl ester alkoxylate. When the C / B ratio is 0.9 or more, it is easy to broaden the distribution of the added mole number of the alkylene oxide of the fatty acid alkyl ester alkoxylate obtained in the method for producing a fatty acid alkyl ester alkoxylate. In order to broaden the addition mole distribution of alkylene oxide, it is more preferable to set the C / B ratio to 0.93 or more.

When the C / B ratio is less than or equal to the above upper limit, the catalytic activity of the resulting alkoxylation catalyst is increased, and fatty acid alkyl ester alkoxylates can be efficiently produced. When the C / B ratio is less than 1, the catalytic activity of the resulting alkoxylation catalyst can be remarkably improved.

In addition, in this process, the mass ratio represented by [(B) component + (C) component] / (A) component (it may be called (B + C) / A ratio hereafter) is 1 to 1/3. This is preferable, and 1 to 1/2 is more preferable. If the (B + C) / A ratio is equal to or less than the above upper limit, it can be easily stirred, and the (B) component and (C) component can be efficiently mixed. Below the 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 the alkoxylation catalyst added is too large, which is inefficient.

10-60 degreeC is preferable and, as for the temperature condition (namely, reaction temperature) in this process, 20-50 degreeC is more preferable. Below the lower limit, the reaction between the (B) component and the (C) component becomes too slow, and there is a fear that the production efficiency of the alkoxylation catalyst is lowered. Above the upper limit, there is a fear that the catalytic activity of the resulting alkoxylation catalyst is lowered.

The reaction temperature is adjusted, for example, by passing a heat medium (for example, water) at an arbitrary temperature in the jacket.

The stirring time (i.e., reaction time) of this process is a time at which the (B) component and (C) component can sufficiently react, and also becomes a time for controlling the exotherm due to the addition of the (C) component. For example, it is 1 to 2 hours.

After the mixing step, a catalyst aging step in which the alkoxylation catalyst is stirred at an arbitrary temperature may be provided. The temperature conditions of the catalyst aging process are, for example, preferably 10 to 60 ° C, and more preferably 20 to 50 ° C. The amount of unreacted (B) component can be reduced by providing this process.

The stirring time in this step is, for example, 0.5 to 3 hours.

Further, the concentration of the catalytically active component in the alkoxylation catalyst may be increased by filtration, static separation, or the like, by filtering the alkoxylation catalyst.

(Method for producing fatty acid alkyl ester alkoxylates)

In the method for producing the fatty acid alkyl ester alkoxylate of the present invention, in the presence of the alkoxylation catalyst of the present invention, an alkylene oxide is added to the fatty acid alkyl ester represented by the following formula (I) (hereinafter, may be referred to as (α) component). Is to add

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 straight chain alkyl group having 1 to 3 carbon atoms]

In the formula (I), R ¹¹ has 1 to 40 carbon atoms, preferably 3 to 30 carbon atoms, and more preferably 5 to ²¹ carbon atoms.

R ¹¹ may be straight chain or branched chain.

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 straight-chain alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group having 1 carbon atom.

Examples of the (α) component 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.

As the alkylene oxide, it is determined according to the intended product, and, for example, ethylene oxide, propylene oxide, butylene oxide, etc. are preferable, and ethylene oxide and propylene oxide are more preferable to obtain a nonionic surfactant. These alkylene oxides may be used alone or in combination of two or more.

Hereinafter, an example of the manufacturing method of the fatty acid alkyl ester alkoxylate of this invention is demonstrated.

The production method of the fatty acid alkyl ester alkoxylate of this embodiment is to add alkylene oxide to the (α) component in the presence of the alkoxylation catalyst of the present invention, and includes a catalyst dispersion process, an addition reaction process, and a aging process. The manufacturing method to be mentioned is mentioned.

The catalyst dispersion process is a process of dispersing an alkoxylation catalyst in the (α) component which is a starting material. This step includes, for example, agitating the (α) component and the alkoxylation catalyst in a stirring tank using a reactor equipped with a jacket and a paddle stirring blade provided in the stirring tank.

(α) The mass ratio (hereinafter, sometimes referred to as raw material / catalyst ratio) represented by the component / alkoxylation catalyst is preferably 20 to 1000, and more preferably 30 to 200. The raw material / catalyst ratio can be arbitrarily set according to the desired reaction time, but when the raw material / catalyst ratio is small, it is complicated to separate the catalyst after the reaction.

The temperature conditions in this step are not particularly limited, but are, for example, room temperature (5 to 35 ° C). The temperature adjustment in the stirring tank is performed, for example, by passing a heat medium (for example, water) at an arbitrary temperature in the jacket.

The stirring time in this step is not particularly limited, and it becomes the time when the (α) component and the alkoxylation catalyst become substantially uniform.

The addition reaction step is a step of obtaining an fatty acid alkyl ester alkoxylate by adding an alkylene oxide to the component (α).

This step is performed by bringing the alkylene oxide into contact with a mixture of the (α) component and an alkoxylation catalyst under arbitrary temperature conditions.

In this step, the amount of alkylene oxide introduced into the component (α) is suitably determined in view of the number of moles of alkylene oxide added to the target product, and, for example, 1 to 100 times mole is preferable, and 5 to 80 times Molar is more preferable, and 10 to 50 times mole is more preferable. The more the number of moles added, that is, the more the alkylene oxide is introduced, the greater the amount of polymer polyethylene glycol produced. For this reason, the present invention exerts a remarkable effect when producing fatty acid alkyl ester alkoxylates having a large number of added moles.

As for the temperature condition (addition reaction temperature) of this process, 160-180 degreeC is preferable, for example.

The pressure conditions in this step are appropriately determined in consideration of the addition reaction temperature, and, for example, 0.1 to 1 MPa is preferable, and 0.1 to 0.6 MPa is more preferable.

The aging process is a process in which the reaction layer is stirred at an arbitrary temperature after the addition reaction process. The amount of unreacted (α) component can be reduced by providing this step.

The temperature conditions in this step are, for example, the same as the addition reaction temperature.

Further, if necessary, the catalytically active component remaining in the fatty acid alkyl ester alkoxylate may be removed. As a method of removing the catalytically active component, for example, filtration and the like. Alternatively, it is not necessary to remove the catalytically active component 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). The amount of by-products can be further reduced by performing an addition reaction step in the presence of the (β) component.

As the (β) component, alkylene glycols such as ethylene glycol and propylene glycol; Polyalkylene glycols such as polyethylene glycol and polypropylene glycol; And glycerin. As the (β) component, polyhydric alcohols having a molecular weight of 200 or less are preferred, alkylene glycols, polyalkylene glycols having a molecular weight of 200 or less, and more preferably ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, or glycerin This is more preferred.

(β) component may coexist with the alkoxylation catalyst in an addition reaction process. 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 with the alkoxylation catalyst in advance.

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

According to the alkoxylation catalyst of the present invention, since (B) component and (C) component of (A) component are reacted at a specific C / B ratio, generation of by-products in production of alkylene oxide adducts can be suppressed. have.

Although the reason why the effect of the present invention is exhibited is not clear, it is considered that the crystal structure of the alkoxylation catalyst becomes suitable for suppressing the formation of by-products by setting the C / B ratio to a specific range.

Example

Hereinafter, the present invention will be described in detail by showing examples, but the present invention is not limited by the following description.

(Used raw materials)

<(A) component>

2-ethylhexanol: a first-class reagent, manufactured by Kanto Chemical Co., Ltd.

2-Propanol: A high-class reagent, manufactured by Kanto Chemical Co., Ltd.

1-hexanol: a high-class reagent, manufactured by Kanto Chemical Co., Ltd.

1-dodecanol: a high-class reagent, manufactured by Kanto Chemical Co., Ltd.

Methyl laurate: Pastel M12, manufactured by Lion Chemicals.

<(B) component>

Calcium acetate monohydrate: a premium reagent, manufactured by Kanto Chemical Co., Ltd.

Calcium oxide: manufactured by Wako Pure Chemical Industries, Ltd.

<(B ') component: Comparative product of (B) component>

Potassium acetate: a premium reagent, manufactured by Kanto Chemical Co., Ltd.

Calcium carbonate: a premium reagent, manufactured by Kanto Chemical Co., Ltd.

Calcium sulfate dihydrate: a first-class reagent, manufactured by Kanto Chemical Co., Ltd.

Calcium sulfate 0.5 hydrate: First-class reagent, manufactured by Kanto Chemical Co., Ltd.

<(C) component>

Sulfuric acid: Special reagent, concentration 96% by mass, manufactured by Kanto Chemical Co., Ltd.

<(C ') component: Comparative product of (C) component>

Phosphoric acid: High-grade reagent, concentration 85% by mass, manufactured by Kanto Chemical Co., Ltd.

<(β) component>

Ethylene glycol: a premium reagent, manufactured by Kanto Chemical Co., Ltd.

Diethylene glycol: a high-class reagent, manufactured by Kanto Chemical Co., Ltd.

Glycerin: A premium reagent, manufactured by Kanto Chemical Co., Ltd.

(Examples 1-1 to 1-7, Comparative Examples 1-1 to 1-5, 1-7, 1-8)

According to the catalyst composition of Tables 1 to 2, (A) component and (B) component or (B ') component were added to a 500 mL beaker, and mixed at room temperature (25 ° C) with a paddle stirring blade to obtain a dispersion (dispersion process ). While stirring the dispersion, (C) component or (C ') component was added over 10 minutes by a dropping lot and mixed (mixing step). In the mixing step, the heat generated by the addition of sulfuric acid, the beaker was cooled by water cooling, and the reaction temperature was controlled to 30 to 50 ° C. After adding the component (C) or the component (C '), the mixture was stirred for another 2 hours while maintaining 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 is a net conversion value (hereafter, it is the same).

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 to the autoclave and stirred. (Catalytic dispersion process). Nitrogen was substituted in the autoclave while stirring, the temperature was raised to 100 ° C, and dehydration was performed for 30 minutes under reduced pressure of 1.3 MPa or less. Subsequently, the temperature was raised to the addition reaction temperature in the table, and 1876 g of ethylene oxide (EO) (15 times the total of methyl laurate and methyl myristate) was introduced under conditions of 0.1 to 0.5 MPa, followed by stirring the addition reaction time in the table. (Additional reaction process). Further, after stirring at an addition reaction temperature for 0.5 hour (aging process), it was cooled to 80 ° C to obtain 2516 g of a reaction preparation (fatty acid methyl ester ethoxylate (MEE), EO average added mole number = 15). The content of the polymer polyethylene glycol (polymer PEG) in the reaction preparation was measured by gel permeation chromatography (GPC), and the results are shown in the table. The GPC method is the following measurement conditions.

In addition, in Comparative Examples 1-1 to 1-3 and Comparative Examples 1-5, 1-7, and 1-8, since the addition reaction time was set to 24 hours, MEE was not generated, and thus the polymer PEG content was not measured.

<Measurement conditions of the GPC method>

Column: Shodex Asahipak GF-310HQ, manufactured by Showa Denko Co., Ltd.

Detector: Differential refractive index detector RID-10A, manufactured by Shimadzu Corporation.

(Comparative Example 1-6)

Alumina-magnesium hydroxide (Kyowad 300, manufactured by Kyowa Kagaku Kogyo Co., Ltd.) represented by 2.5MgO, Al ₂ O ₃ , nH ₂ O was fired at 900 ° C for 3 hours, and a magnesium-aluminum composite metal oxide catalyst was prepared. Got.

To the 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 were added thereto, and 1.3 g of a 10% by mass aqueous solution of potassium hydroxide was added thereto, followed by stirring for 10 minutes (composite) Alkali denaturation treatment of metal oxide catalyst).

Thereafter, the inside of the autoclave was replaced with nitrogen while stirring, the temperature was raised to 100 ° C, and dehydration was performed for 30 minutes under reduced pressure of 1.3 MPa or less.

Subsequently, 1876 g of EO was introduced under conditions of an addition reaction temperature of 180 ° C and 0.5 MPa, followed by stirring for 7 hours (addition reaction step). Moreover, after stirring at 180 degreeC for 0.5 hour (aging process), it cooled to 80 degreeC and obtained 2506g of reaction preparations (average added mole number of MEE, EO = 15). The content of the polymer PEG in this reaction preparation is 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 (B) component (B ') component, Comparative Example 1-1, 1-2, 1-7, 1-8, (C) instead of (C) component ') Comparative Examples 1-3 using components and Comparative Examples 1-5 with a C / B ratio of 1.2 were all unable to produce MEE.

The polymer PEG content of Comparative Example 1-4 with a C / B ratio of 0.45 was 0.53 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 MEE can be produced by significantly reducing the amount of polymer PEG produced by applying the present invention.

(Examples 2-1 to 2-9, Comparative Examples 2-1 to 2-3)

Components (A) and (B) were added to a 1000 mL separable flask according to the catalyst compositions in Tables 3 to 4, and mixed at room temperature (25 ° C) with a disper-shaped stirring blade to obtain a dispersion (dispersion step). While stirring the dispersion, the component (C) was added over a period of 60 minutes with a dropping lot and mixed (mixing step). In the mixing step, the heat was generated by the addition of sulfuric acid, so the flask was cooled by water bath, and the reaction temperature was controlled to 20 to 40 ° C. After adding the component (C), the mixture was stirred for another 2 hours while maintaining at 25 ° C (catalyst aging step) to obtain the alkoxylation catalyst of each example.

MEE was produced in the following procedure according to "MEE production conditions" in Tables 3-4.

The alkoxylation catalyst of each example, (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). Subsequently, EO was introduced under the conditions of the addition reaction temperature in the table and 0.1 to 0.5 MPa, and the addition reaction time in the table was stirred (addition reaction step). Moreover, after stirring for 0.5 hours at the addition reaction temperature (aging process), it cooled to 80 degreeC, and obtained the reaction preparation (MEE, EO average added mole number = 15).

The content of the polymer PEG in this reaction preparation is 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 reaction preparation (the 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 the EO addition mole distribution, the wider the distribution of the EO addition mole number.

In addition, in Comparative Example 2-2, since the 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: Agilent DB-1 HT, length 30 m, inner diameter 0.25 mm, film thickness 0.1 µm.

· Mobile phase: Helium.

Detector: Hydrogen salt ion detector (FID), 380 ℃.

· Inlet: Split, 380 ℃.

· Temperature: 100 ℃ → 380 ℃.

EO addition molar distribution is calculated from the following formula from the peak area.

<Calculation method>

The EO addition molar distribution was calculated by the following formula.

{(Area of the maximum peak (P1) derived from methyl laurate) + (total area of the two peaks before and after the maximum peak (P1)) + (area of the maximum peak (P2) derived from methyl myristate) + ( Total area of two peaks before and after the maximum peak (P2)) ÷ total peak area

As shown in Tables 3 to 4, the polymer PEG content of Examples 2-1 to 2-9 to which the present invention was applied was 0.22% by mass or less.

In comparison between Examples 2-1 and Examples 2-6 to 2-8, Examples 2-6 to 2-8 in which an addition reaction step was performed in the presence of (β) component did not use (β) component The reaction rate was faster than in Example 2-1, and the polymer PEG content could be reduced.

In the comparison of Examples 2-1 to 2-3, the molar distribution of EO addition became wider as the C / B ratio increased.

On the other hand, the polymer PEG content of Comparative Examples 2-1 and 2-3 in which the C / B ratio was less than 0.8 was 0.40% by mass or more.

From these results, it was found that MEE can be produced by significantly reducing the amount of polymer PEG produced by applying the present invention.

(Industrial availability)

The catalyst of the present invention can suppress the formation of by-products in preparing fatty acid alkyl ester alkoxylates. For this reason, fatty acid alkyl ester alkoxylates prepared using the alkoxylation catalyst of the present invention are preferred as nonionic surfactants for liquid detergents.

Claims (6)

In the alkoxylation catalyst used in the alkoxylation reaction of a fatty acid alkyl ester represented by the following general formula (I),
At least one (B) and sulfuric acid (C) selected from the group consisting of alkali earth metal salts of carboxylic acids, alkali earth metal salts of hydroxycarboxylic acids, oxides of alkaline earth metals, and hydroxides of alkaline earth metals is a liquid dispersion medium ( It is made by reacting in A),
The alkoxylation catalyst, characterized in that the molar ratio represented by the component (C) / component (B) is 0.8 to 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 straight chain alkyl group having 1 to 3 carbon atoms] According to claim 1,
The component (A) is 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), an alkylene oxide adduct of the fatty acid alkyl ester, An alkoxylation catalyst, characterized in that it is at least one member selected from the group consisting of fatty acids represented by the following general formula (3) and alkylene oxide adducts of the fatty acids.
ROH ... (1)
[In the formula (1), R is 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 straight 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] A liquid dispersion medium containing at least one (B) and sulfuric acid (C) selected from the group consisting of alkali earth metal salts of carboxylic acids, alkali earth metal salts of hydroxycarboxylic acids, oxides of alkaline earth metals, and hydroxides of alkaline earth metals ( A method for producing the alkoxylation catalyst according to claim 1 or 2 to be mixed in A),
The method for producing an alkoxylation catalyst, wherein the molar ratio represented by the component (C) / the component (B) is 0.8 to 1. The method of claim 3,
[The (B) component + the (C) component] / The mass ratio represented by the (A) component is 1 to 1/3, characterized in that the production method of the alkoxylation catalyst. A method for producing a fatty acid alkyl ester alkoxylate, characterized in that 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, characterized in that 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.