TWI617351B - Alkoxylation catalyst, method for producing the same, and method for producing fatty acid alkyl alkoxide using the catalyst - Google Patents

Abstract

An alkoxylation catalyst of the present invention is used in the alkoxylation reaction of fatty acid alkyl esters represented by the following general formula (I). The alkoxylation catalyst is selected from 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 At least one (B) in the group and sulfuric acid (C) reacted in the liquid dispersion medium (A), And the molar ratio expressed by the aforementioned (C) component / the aforementioned (B) component 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. ]

Description

Alkoxylation catalyst, method for producing the aforementioned catalyst, and method for producing fatty acid alkyl ester alkoxy salt using the aforementioned catalyst Technical field

The present invention relates to an alkoxylation catalyst, a method for producing the aforementioned catalyst, and a method for producing the fatty acid alkyl ester alkoxy salt using the aforementioned catalyst.

This application claims priority based on Japanese Patent Application No. 2012-092161 filed on April 13, 2012, and the contents thereof are cited here.

Background technique

The alkylene oxide adducts of organic compounds with active hydrogen or their derivatives are widely used as solvents, surfactants or various chemical intermediates. In particular, alkylene oxide adducts in which alkylene oxides such as ethylene oxide or propylene oxide are added to alcohols, fatty acids, fatty acid alkyl esters, amines, or alkylphenols are widely used as nonionic interface activities剂 使用。 Agent use.

For example, fatty acid alkyl ester alkoxy salt with alkylene oxide added to fatty acid alkyl ester, or alkoxylated alcohol with alkylene oxide added to alcohol is often used as a cleaning component of liquid detergent.

The production method of alkylene oxide adducts can be exemplified by alkoxylation catalysis The method of adding alkylene oxide to fatty acid alkyl ester or alcohol in the presence of an agent is exemplified.

The non-ionic surfactants of alkylene oxide adducts have many advantages, such as those with a small distribution of addition moles of alkylene oxide, having a higher foaming power than those with a larger distribution of addition moles.

In addition, when manufacturing an ionic surfactant, if a large amount of unreacted raw materials remains, the cleaning power will be reduced, so it is necessary to remove unreacted materials, and the manufacturing process becomes cumbersome.

On the other hand, if a large amount of the distribution of alkylene oxide addition mole number is mixed with the liquid detergent, the fluidity of the liquid detergent will be easily lost.

Therefore, among the nonionic surfactants of the alkylene oxide adduct, the distribution of the addition mole number of the alkylene oxide is smaller and the larger one can be used flexibly depending on the application.

Generally, a homogeneous catalyst such as an acid or a base and / or a heterogeneous catalyst such as a solid metal are used as the alkoxylation catalyst. However, with alkaline catalysts such as sodium hydroxide, the addition reaction (alkoxylation reaction) of alkylene oxides to fatty acid alkyl esters without active hydrogen in the molecule cannot be performed. Therefore, the aforementioned heterogeneous catalyst needs to be used for the addition reaction of alkylene oxide of fatty acid alkyl ester.

It has been proposed, for example, to bake alumina hydroxide whose surface is modified with metal hydroxides or metal alkoxides. A magnesium catalyst is used as a heterogeneous catalyst (for example, Patent Document 1).

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

Prior technical literature Patent Literature

Patent Literature 1: Patent No. 2940852

Patent Literature 2: International Publication No. 02/38269

Summary of the invention

However, when the alkoxylation reaction of fatty acid alkyl esters is carried out using the catalysts of Patent Documents 1 to 2, high molecular weight (weight average molecular weight measured by gel permeation chromatography method of 10,000 or more) such as polyethylene glycol product. When using a fatty acid alkyl ester alkoxy salt containing a macromolecular polyethylene glycol as a liquid detergent, there is a problem that the liquid detergent tends to become cloudy. Therefore, a step of removing by-products from the obtained alkylene oxide adduct needs to be provided, and the manufacturing step becomes cumbersome. In addition, when the amount of by-products generated is large, there is a problem that the amount of waste increases.

Therefore, the present invention aims at an alkoxylation catalyst that can reduce the amount of by-product formation.

The present invention has the following aspects.

[1] An alkoxylation catalyst used in the alkoxylation reaction of fatty acid alkyl esters represented by the following general formula (I), the alkoxylation catalyst is selected from 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 At least one (B) in the group and sulfuric acid (C) reacted in the liquid dispersion medium (A), And the molar ratio expressed by the aforementioned (C) component / the aforementioned (B) component 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] The alkoxylation catalyst according to [1], wherein the component (A) is selected from the group consisting of an alcohol represented by the following general formula (1), an alkylene oxide adduct of the alcohol, and the following general At least one of the group consisting of the fatty acid alkyl ester represented by formula (2), the alkylene oxide adduct of the aforementioned fatty acid alkyl ester, the fatty acid represented by the following general formula (3), and the alkylene oxide adduct of the aforementioned fatty acid 1 kind.

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 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 aforementioned (C) component / the aforementioned (B) component is 0.8 or more and less than 1.

[4] The alkoxylation catalyst according to [1] or [2], wherein the molar ratio expressed by the aforementioned (C) component / the aforementioned (B) component is 0.9 or more and less than 1.

[5] The alkoxylation catalyst according to [1] or [2], wherein the molar ratio expressed by the component (C) / component (B) is 0.9 to 0.98.

[6] The alkoxylation catalyst according to [1] or [2], wherein the molar ratio expressed by the component (C) / component (B) is 0.93 to 0.98.

[7] A method for manufacturing an alkoxylation catalyst, which is a method for manufacturing an alkoxylation catalyst as described in [1] or [2], which is in a liquid dispersion medium At least one kind selected from the group consisting of alkaline earth metal salt of carboxylic acid, alkaline earth metal salt of hydroxycarboxylic acid, oxide of alkaline earth metal, and hydroxide of alkaline earth metal is mixed with substance (A) (B) and Sulfuric acid (C), and the molar ratio expressed by the aforementioned (C) component / the aforementioned (B) component is 0.8 to 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 expressed by the aforementioned (C) component / the aforementioned (B) component 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 aforementioned (C) component / the aforementioned (B) component 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 expressed by the component (C) / 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 expressed by the component (C) / component (B) is 0.93 to 0.98.

[13] A method for producing a fatty acid alkyl ester alkoxy salt by adding alkylene oxide to a fatty acid alkyl ester in the presence of the alkoxylation catalyst described in any one of [1] to [6].

[14] A method for producing fatty acid alkyl ester alkoxy salt by adding alkylene oxide to fatty acid alkyl ester in the presence of the alkoxylation catalyst and polyhydric alcohol described in any one of [1] to [6] .

[15] The method for producing fatty acid alkyl ester alkoxy salt according to [14], wherein The aforementioned polyol is at least one selected from the group consisting of alkylene glycols, polyalkylene glycols, and glycerin.

[16] The method for producing fatty acid alkyl ester alkoxy salt according to [15], wherein the polyhydric alcohol is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and glycerin At least one of the group.

The alkoxylation catalyst of the present invention can reduce the amount of by-products produced.

Forms for carrying out the invention

(Alkoxylation catalyst)

The alkoxylation catalyst of the present invention is an alkoxylation catalyst used in the alkoxylation reaction of fatty acid alkyl esters, which is selected from the group consisting of alkaline earth metal salts of carboxylic acids, alkaline earth metal salts of hydroxycarboxylic acids, alkaline earth metals At least one (B) (hereinafter, referred to as (B) component) and sulfuric acid (C) (hereinafter, referred to as (C) component) in the group consisting of oxides and hydroxides of alkaline earth metals are dispersed in the liquid state Those reacted in the medium (A) (hereinafter, referred to as (A) component). In other words, the alkoxylation catalyst of the present invention contains the reactant of component (B) and component (C) (the alkaline earth metal sulfate of the main catalyst active component).

The alkoxylation catalyst may be a dispersion liquid in which sulfates of alkaline earth metals are dispersed in the component (A), or may be a solid containing sulfates of alkaline earth metals.

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

<(A) ingredient>

(A) The component-based liquid dispersion medium. (A) The component is not particularly limited as long as it does not gel when producing the alkoxylation catalyst, can maintain fluidity, and can react with the (B) component and (C) component. (A) "Liquid" in the component means liquid in the dispersing step and mixing step described later.

From the viewpoint of improving the productivity of the method for producing an alkoxylation catalyst described later, the component (A) is preferably a liquid at 30 ° C.

For example, the component (A) is preferably selected from the group consisting of alcohols represented by the following general formula (1), alkylene oxide adducts of the foregoing alcohols, fatty acid alkyl esters represented by the following general formula (2), and the foregoing fatty acids At least one of 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 foregoing 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 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 aforementioned formula (1), the carbon number of R is 3 to 18, preferably 3 to 12, preferably 3 to 8. When it is less than the aforementioned lower limit, when the alkoxylation catalyst is produced, the component (A) will increase its consistency in a gel form, lose fluidity, and will not easily react with the components (B) and (C). When it is greater than the upper limit, the melting point becomes higher, which is not suitable for cooperation It is 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.

The alcohol represented by the formula (1) includes, for example, 1-hexanol, n-octanol, n-decyl alcohol, n-dodecyl alcohol, n-tetradecyl alcohol, n-hexadecyl alcohol, n-octadecyl alcohol, oleyl alcohol and nonyl alcohol Primary alcohols such as alcohol, undecyl alcohol, and tridecyl alcohol; secondary alcohols such as 2-ethylhexanol, 2-propanol, 2-octanol, 2-decyl alcohol, 2-dodecyl alcohol, etc. From the viewpoint of reducing the amount of polymer polyethylene glycol produced, 2-ethylhexanol is preferred.

Among the aforementioned alkylene oxide adducts of alcohols (ie, alkoxylated alcohols), the alkylene oxides to be added may be exemplified by alkylene oxides having 2 to 3 carbon atoms.

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

In the above formula (2), the carbon number of R ¹ is 3 to 18, and it can be arbitrarily selected as long as it has good fluidity under the temperature conditions at the time of manufacturing the alkoxylation catalyst.

R ¹ may be linear or branched.

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, preferably a methyl group having 1 carbon atom. As long as it is within the aforementioned range, the fluidity is good under the temperature conditions where the melting point is low and the alkoxylation catalyst is manufactured.

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

Among the alkylene oxide adducts of fatty acid alkyl esters (ie, fatty acid alkyl ester alkoxy salts), the alkylene oxides to be added may be exemplified by alkylene oxides having 2 to 3 carbon atoms.

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

In the above formula (3), the carbon number of R ³ is 3 to 18, and it can be arbitrarily selected as long as it has good fluidity under the temperature conditions at the time of manufacturing 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.

Fatty acids include, for example, caprylic acid, capric acid, lauric acid, palmitoleic acid, oleic acid, linolenic acid, and linolenic acid. Among them, oleic acid is preferred.

Among the aforementioned alkylene oxide adducts of fatty acids, the alkylene oxides to be added can be exemplified by alkylene oxides having 2 to 3 carbon atoms.

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

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

<(B) ingredient>

(B) The component is selected from the group consisting of alkaline earth metal salts of carboxylic acids (hereinafter referred to as (b1) components), alkaline earth metal salts of hydroxycarboxylic acids (hereinafter referred to as (b2) components), and oxides of alkaline earth metals ( Hereinafter, it is referred to as (b3) component) and alkaline earth metal hydroxide (hereinafter, referred to as (b4) component) at least one of the group.

(b1) Components include, for example, calcium acetate anhydrate, calcium acetate monohydrate and other calcium acetate, calcium formate and other carboxylic acid calcium salts; magnesium acetate and magnesium formate and other carboxylic acid magnesium salts, etc. From the viewpoint of activity, calcium salts of carboxylic acids are preferred, and calcium acetate is preferred.

(b2) Components include, for example, calcium salts of hydroxycarboxylic acids such as calcium lactate, calcium tartrate, calcium citrate and calcium malate; magnesium salts of hydroxycarboxylic acids such as magnesium lactate, magnesium tartrate, magnesium citrate and magnesium malate Etc., where From the viewpoint of catalyst activity, the calcium salt of hydroxycarboxylic acid is also preferred.

The component (b3) can be exemplified by calcium oxide, magnesium oxide, etc. Among them, calcium oxide is also preferred.

The component (b4) can be exemplified by calcium hydroxide, magnesium hydroxide, etc., among which calcium hydroxide is also preferred.

From the viewpoint of improving the catalyst activity and further reducing the amount of by-products produced, the component (B) is preferably the component (b1), preferably the calcium salt of the carboxylic acid, and more preferably calcium acetate.

Therefore, the component (B) may be used alone or in combination of two or more.

<(C) ingredient>

(C) The component system is sulfuric acid. (C) The component may be concentrated sulfuric acid or dilute sulfuric acid. From the viewpoint that the catalyst activity can be stably developed, the component (C) is preferably concentrated sulfuric acid (96% by mass or more).

(Manufacturing method of alkoxylation catalyst)

The method for producing the alkoxylation catalyst of the present invention is a mixture of (B) component and (C) component in (A) component.

The manufacturing method of the alkoxylation catalyst includes, for example, a dispersion step of dispersing (B) component in (A) component to obtain a dispersion, adding (C) component to the dispersion, and mixing with (B) component Of mixed steps.

The dispersing step can be exemplified by using a reactor having a mixing tank with a jacket and broad-leaf stirring blades provided in the stirring tank, putting (A) and (B) components into the stirring tank, and mixing these .

The temperature condition of this step is not particularly limited, and it is, for example, normal temperature (5 to 35 ° C). The temperature in the mixing tank is adjusted by, for example, circulating in the jacket The heating medium (for example, water) of any temperature is performed.

The stirring time in this step is not particularly limited, and is the time during which the component (B) is substantially uniformly dispersed in the component (A). Substantially uniform refers to a state in which the (B) component and the like without lumps are visually observed, and it can be judged that the system is uniformly dispersed.

The mixing step is to add the (C) component to the dispersion obtained in the dispersing step, and mix the (B) component and (C) component to produce a reactant of the (B) component and (C) component (that is, the main catalyst active component Sulfate of alkaline earth metal) to obtain an alkoxylation catalyst in which the catalyst active component is dispersed in the component (A).

The mixing method in this step is not particularly limited, but for example, a method of dropping the (C) component in the dispersion while stirring the dispersion in the stirring tank is preferred.

In this step, the molar ratio (hereinafter referred to as C / B ratio) represented by (C) component / (B) component is 0.8 to 1, preferably 0.8 or more and less than 1, preferably 0.9 or more and less than 1 , More preferably 0.9 ~ 0.98, especially 0.93 ~ 0.98.

If the C / B ratio is equal to or greater than the aforementioned lower limit, the resulting alkoxylation catalyst can satisfactorily reduce the amount of by-products produced in the production step of fatty acid alkyl ester alkoxy salt. If the C / B ratio is 0.9 or more, in the method for producing a fatty acid alkyl ester alkoxy salt, the distribution of the alkylene oxide addition mole number of the fatty acid alkyl ester alkoxy salt obtained tends to increase. In order to expand the addition mole number distribution of alkylene oxide, it is preferable to set the C / B ratio to 0.93 or more.

If the C / B ratio is equal to or less than the aforementioned upper limit, the catalyst activity of the obtained alkoxylation catalyst becomes high, and the fatty acid alkyl ester alkoxy salt can be efficiently produced. If the C / B ratio is less than 1, the catalyst activity of the resulting alkoxylation catalyst will be significantly increased.

Furthermore, in this step, the mass ratio expressed by [(B) component + (C) component] / (A) component (hereinafter, referred to as (B + C) / A ratio) is preferably 1 to 1/3, 1 ~ 1 / 2.5 is better. If the (B + C) / A ratio is equal to or less than the aforementioned upper limit value, it can be easily stirred and the (B) component and (C) component can be efficiently mixed. When it is less than the aforementioned lower limit, the content of the catalyst active component in the component (A) decreases, and when the fatty acid alkyl ester alkoxy salt is produced, the amount of the alkoxylation catalyst added becomes too large to be inefficient.

The temperature condition (ie, reaction temperature) of this step is preferably 10 to 60 ° C, preferably 20 to 50 ° C. When it is less than the aforementioned lower limit, the reaction between the component (B) and the component (C) becomes too slow, and there is a possibility that the production efficiency of the alkoxylation catalyst becomes low. If it is greater than the above upper limit value, the catalyst activity of the obtained alkoxylation catalyst may be lowered.

The adjustment of the reaction temperature is performed, for example, by circulating a heating medium (for example, water) of any temperature in the jacket.

The stirring time (ie, reaction time) in this step is the time during which the (B) component and (C) component can react sufficiently, and the time during which the heat generated by the addition of the (C) component can be controlled, for example, 1 to 2 hours .

After the mixing step, a catalyst aging step of stirring the alkoxylation catalyst at any temperature may also be provided. The temperature condition of the catalyst aging step is, for example, preferably 10 to 60 ° C, preferably 20 to 50 ° C. By setting this step, the amount of unreacted (B) component can be reduced.

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

In addition, the alkoxylation catalyst can also be filtered and left standing to increase the concentration of the active component of the catalyst in the alkoxylation catalyst.

(Production method of fatty acid alkyl ester alkoxy salt)

The production method of the fatty acid alkyl ester alkoxy salt of the present invention is added to a fatty acid alkyl ester (hereinafter, referred to as (α) component) represented by the following formula (I) in the presence of the alkoxylation catalyst of the present invention Alkylene oxide.

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 formula (I), the carbon number of R ¹¹ is 1-40, preferably 3-30, preferably 5-21.

R ¹¹ may be a straight chain or a 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 linear alkyl group having 1 to 3 carbon atoms, preferably a methyl group having 1 carbon atom.

The component (α) includes, for example, fatty acid methyl esters such as methyl caprate, methyl laurate, methyl myristate, and methyl oleate, and mixtures thereof.

The component (α) may be the same as the fatty acid alkyl ester used as the component (A), or may be different.

The alkylene oxide is determined according to the intended product. For example, in order to obtain a nonionic surfactant, ethylene oxide, propylene oxide, butylene oxide, etc. are preferred, and ethylene oxide, epoxy Propane is preferred. These alkylene oxides may be used alone or in combination of two or more.

Hereinafter, an example of the production method of the fatty acid alkyl ester alkoxy salt of the present invention will be described.

The production method of the fatty acid alkyl ester alkoxy salt of this embodiment is, for example, in the presence of the alkoxylation catalyst of the present invention, in the (α) component addition Alkylene oxide, and has a method of manufacturing catalyst dispersion step, addition reaction step and aging step.

The catalyst dispersion step is a step of dispersing the alkoxylation catalyst in the (α) component as a starting material. In this step, for example, a reactor having a mixing tank with a jacket and a broad-leaf stirring blade provided in the stirring tank is used to stir the (α) component and the alkoxylation catalyst in the stirring tank.

The mass ratio expressed as (α) component / alkoxylation catalyst (hereinafter, referred to as raw material / catalyst ratio) is, for example, preferably 20 to 1000, preferably 30 to 200. The raw material / catalyst ratio can be arbitrarily set according to the intended reaction time, but if the raw material / catalyst ratio is small, separating the catalyst after the reaction becomes cumbersome.

The temperature condition of this step is not specifically set, for example, normal temperature (5 ~ 35 ° C). The temperature adjustment in the stirring tank is performed, for example, by circulating a heating medium (for example, water) of any temperature in the jacket.

The stirring time in this step is not particularly limited, and it is assumed that the (α) component and the alkoxylation catalyst are substantially uniform.

The addition reaction step is a step of adding alkylene oxide to the (α) component to obtain an alkoxy salt of fatty acid alkyl ester.

This step is performed by contacting the alkylene oxide with a mixture of the (α) component and the alkoxylation catalyst under any temperature conditions.

In this step, the introduction amount of (α) component alkylene oxide is appropriately determined after considering the number of moles of addition of the alkylene oxide of the target substance, for example, 1 to 100 times the molar amount is 5 to 80 times mole is better, and 10 to 50 times mole is better. The more the added mole number, that is, the more the amount of alkylene oxide introduced, the greater the amount of polymer polyethylene glycol produced. Therefore, the present invention has many Fatty acid alkyl ester alkoxy salt will play a significant effect.

The temperature condition (addition reaction temperature) in this step is preferably, for example, 160 to 180 ° C.

The pressure condition in this step is appropriately determined after considering the addition reaction temperature. For example, 0.1 to 1 MPa is preferred, and 0.1 to 0.6 MPa is preferred.

The aging step is a step of stirring in the reaction layer at any temperature after the addition reaction step. By setting this step, the amount of unreacted (α) component can be reduced.

The temperature condition in this step is, for example, the same as the addition reaction temperature.

In addition, the active components of the catalyst remaining in the fatty acid alkyl ester alkoxy salt may be removed as needed. The method of removing the active component of the catalyst can be exemplified by filtration and the like. Alternatively, the catalyst active ingredient may not be removed from the fatty acid alkyl ester alkoxy salt.

In this embodiment, the addition reaction step may be performed in the presence of the alkoxylation catalyst of the present invention and a polyol (hereinafter, referred to as (β) component). By performing the addition reaction step in the presence of (β) component, the amount of by-product formation 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; and glycerin. The component (β) is preferably a polyol having a molecular weight of 200 or less, preferably alkylene glycol, polyalkylene glycol having a molecular weight of 200 or less, or glycerin, and ethylene glycol, diethylene glycol, triethylene glycol Alcohol, tetraethylene glycol, and glycerin are better.

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

In the addition reaction step, the mass ratio expressed by the (β) component / (α) component is preferably 0.0005 to 0.02, preferably 0.001 to 0.01. When it is less than the lower limit, it is difficult to obtain the effect of adding the (β) component, and when it is greater than the upper limit, the distribution of addition mole number of alkylene oxide may become too small.

According to the alkoxylation catalyst of the present invention, (A) component can react with (B) component and (C) component in a specific C / B ratio, so it can be suppressed when producing alkylene oxide adducts The formation of by-products.

The reason why the effect of the present invention can be exerted is not clear, but it is understood that by setting the C / B ratio within a specific range, the crystal structure of the alkoxylation catalyst will be suitable for suppressing the formation of by-products.

Examples

Hereinafter, examples are shown to explain the present invention in detail, but the present invention is not limited by the following description.

(Using raw materials)

<(A) ingredient>

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

2-Propanol: Guarantee reagent, produced by Kanto Chemical Co., Ltd.

1-Hexanol: Guarantee reagent, produced by Kanto Chemical Co., Ltd.

1-Dodecanol: Guarantee reagent, produced by Kanto Chemical Co., Ltd.

Methyl laurate: PASTELL M12, manufactured by LION Chemical Co., Ltd.

<(B) ingredient>

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

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

<(B ’) component: (B) component comparison product>

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

Calcium carbonate: Guarantee reagent, produced by Kanto Chemical Co., Ltd.

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

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

<(C) ingredient>

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

<(C ’) component: (C) component comparison product>

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

<(β) component>

Ethylene glycol: Guarantee reagent, produced by Kanto Chemical Co., Ltd.

Diethylene glycol: Guarantee reagent, produced by Kanto Chemical Co., Ltd.

Glycerin: Guarantee reagent, produced 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 in Tables 1-2, add component (A) and component (B) or component (B ') to a 500 mL beaker, and mix by a broad-leaf stirring blade at room temperature (25 ° C) to obtain a dispersion (Dispersion step). While stirring the dispersion, the component (C) or the component (C ') was added and mixed by a dropping funnel for 10 minutes (mixing step). In the mixing step, heat is generated due to the addition of sulfuric acid, so the beaker is made into a water bath to cool, and the reaction temperature is controlled at 30-50 ° C. After adding the component (C) or the component (C '), the temperature was maintained at 50 ° C, and the mixture was stirred for 2 hours (catalyst aging step) to obtain the alkoxylation catalysts of the examples.

In addition, the mixing amount of each component in the table is a value converted to a pure content (the same applies hereinafter).

After adding 12.5 g of each alkoxylation catalyst, 462 g of methyl laurate (PASTELL M12, manufactured by LION Chemical Co., Ltd.), and 166 g of methyl myristate (PASTELL M14, manufactured by LION Chemical Co., Ltd.) to the autoclave Stirring (catalyst dispersion step). Nitrogen substitution was performed in the autoclave while stirring, the temperature was raised to 100 ° C, and dehydration was performed for 30 minutes under a reduced pressure condition of 1.3 kPa or less. Next, the temperature was raised to the addition reaction temperature in the table, and 1876 g of ethylene oxide (EO) (15 times the molar amount of the total of methyl laurate and methyl myristate) was introduced under the conditions of 0.1 to 0.5 MPa. In the addition reaction time stirring (addition reaction step). In addition, after stirring at the addition reaction temperature for 0.5 hours (aging step) and cooling to 80 ° C, 2516 g of crude reaction product (fatty acid methyl ester ethoxylate (MEE), EO average addition mole number = 15) was obtained. The content of polymer polyethylene glycol (polymer PEG) in the reaction crude was measured by gel permeation chromatography (GPC) method, 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, Comparative Examples 1-5, 1-7, and 1-8, even if the addition reaction time was set to 24 hours, MEE was not generated, so the polymer PEG content was not carried out Of determination.

<Measurement conditions of GPC method>

‧Pipe: 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)

Will 2.5MgO. Al ₂ O ₃ . Aluminum hydroxide represented by nH ₂ O. Magnesium (kyoward 300, manufactured by Kyowa Chemical Industry Co., Ltd.) was baked at 900 ° C for 3 hours to obtain magnesium. Aluminum composite metal oxide catalyst.

In the autoclave, 2.5 g of the aforementioned composite metal oxide catalyst, 462 g of methyl laurate, 166 g of methyl myristate, and 3 g of glycerin were added, and 1.3 g of potassium hydroxide 10% by mass aqueous solution was added, and the mixture was stirred for 10 minutes (composite metal oxidation Alkaline denaturation treatment of the material catalyst).

Thereafter, 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 kPa or less.

Next, 1876 g of EO was introduced under the conditions of an addition reaction temperature of 180 ° C. and 0.5 MPa, and stirred for 7 hours (addition reaction step). Moreover, after stirring at 180 degreeC for 0.5 hour (aging step), it cooled to 80 degreeC, and obtained 2506g of crude reaction products (MEE, EO average addition mole number = 15). The content of polymer PEG in the crude reaction product was measured by 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 of the present invention is 0.15% by mass or less.

On the other hand, as shown in Table 2, Comparative Examples 1-1, 1-2, 1-7, 1-8 using (B ') component instead of (B) component, and (C) using (C') component In the comparative examples 1-3 of the components and the comparative examples 1-5 in which the C / B ratio was 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% by mass.

From these results, it can be seen that by using the present invention, the amount of polymer PEG produced will 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 composition in Tables 3 to 4, add component (A) and component (B) to a 1000mL detachable flask, and mix by a dispersing stirring blade at room temperature (25 ° C) to obtain a dispersion (dispersion step ). While stirring the dispersion, the component (C) was added and mixed by a dropping funnel for 60 minutes (mixing step). In the mixing step, heat is generated due to the addition of sulfuric acid, so the flask is made into a water bath to cool, and the reaction temperature is controlled at 20 ~ 40 ° C. After adding the component (C), the mixture was stirred at 25 ° C for 2 hours (catalyst aging step) to obtain the alkoxylation catalyst of each example.

According to the "MEE manufacturing conditions" in Tables 3 to 4, MEE is manufactured in the following order.

The alkoxylation catalyst, (β) component, methyl laurate (PASTELL M12, manufactured by LION Chemical Co., Ltd.), and methyl myristate (PASTELL M14, manufactured by LION Chemical Co., Ltd.) are added to the autoclave. After stirring (catalyst dispersion step). Next, EO was introduced under the conditions of the addition reaction temperature and 0.1 to 0.5 MPa in the table, and stirred within the addition reaction time in the table (addition reaction step). In addition, it was stirred at the addition reaction temperature for 0.5 hours (the aging step) and then cooled When the temperature reached 80 ° C, the crude reaction product (MEE, EO average addition mole number = 15) was obtained.

The content of polymer PEG in the crude reaction product was measured by GPC method, and the results are shown in the table.

The distribution of the number of moles of EO added (EO added mole distribution) in the crude reaction product 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 additive mole distribution, the larger the distribution of the EO additive mole number.

In addition, in Comparative Example 2-2, even if the addition reaction time was set to 24 hours, MEE was not generated, so the measurement of the polymer PEG content and the EO addition mole distribution was not performed.

<Measurement conditions of GC method>

‧Gas chromatography: GC-2025 manufactured by Shimadzu Corporation.

‧Column: DB-1 HT made by Agilent, 30m in length, 0.25mm in inner diameter, and 0.1μm in film thickness.

‧Mobile phase: Helium.

‧Detector: Hydrogen Flame Free Detector (FID), 380 ℃.

‧Injection port: shunt, 380 ℃.

‧Temperature: 100 ℃ → 380 ℃.

‧Calculate the EO addition molar distribution from the peak area using the following formula.

<Calculation method>

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

{(Area of maximum peak (P1) from methyl laurate) + (total area of 2 peaks before and after maximum peak P1) + (area of maximum peak (P2) from methyl myristate) + (maximum peak The total area of the two peaks before and after P2)) ÷ total peak area

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

In the comparison between Example 2-1 and Examples 2-6 to 2-8, Examples 2-6 to 2-8 with the addition reaction step were carried out in the presence of (β) component, compared to unused ( Example 2-1 of β), the reaction speed is accelerated, and the content of high molecular PEG can be reduced.

In the comparison of Examples 2-1 to 2-3, the higher the C / B ratio, the larger the EO addition molar distribution system.

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

From these results, it can be seen that by using the present invention, the amount of polymer PEG produced can be significantly reduced, and MEE can be produced.

Industrial availability

The catalyst of the present invention can suppress the formation of by-products when producing fatty acid alkyl ester alkoxy salts. Therefore, the fatty acid alkyl ester alkoxy salt produced using the alkoxylation catalyst of the present invention is suitable for use as a nonionic surfactant for liquid detergents.

Claims (6)

An alkoxylation catalyst is used in the alkoxylation reaction of fatty acid alkyl esters represented by the following general formula (I). The alkoxylation catalyst is selected from the group consisting of alkaline earth metal salts of carboxylic acids and hydroxy carboxy At least one kind (B) of the group consisting of acid alkaline earth metal salt, alkaline earth metal oxide and alkaline earth metal hydroxide reacts with sulfuric acid (C) in the liquid dispersion medium (A), and (C) component / the molar ratio represented by the aforementioned (B) component is 0.8 to 1, R ¹¹ COOR ¹² ‧‧‧ (I) [(I) In the formula, R ¹¹ is a hydrocarbon group having 1 to 40 carbon atoms, R ¹² It is a linear alkyl group having 1 to 3 carbons]. An alkoxylation catalyst according to item 1 of the patent application, wherein the aforementioned (A) component is selected from the group consisting of an alcohol represented by the following general formula (1), an alkylene oxide adduct of the aforementioned alcohol, and the following general formula (2) The fatty acid alkyl ester represented, the alkylene oxide adduct of the aforementioned fatty acid alkyl ester, the fatty acid represented by the following general formula (3), and the alkylene oxide adduct of the aforementioned fatty acid constitute at least 1 Species, ROH‧‧‧ (1) [In the formula (1), R is a hydrocarbon group with a carbon number of 3 to 18]; R ¹ COOR ² ‧‧‧ (2) [In the formula, R ¹ is a carbon number 3 ~ 18 hydrocarbon group, R ² is a linear alkyl group having 1 to 3 carbons]; R ³ COOH‧‧‧‧ (3) [(3) In the formula, R ³ is a hydrocarbon group having 3 to 18 carbons] A method for manufacturing an alkoxylation catalyst, such as the method for manufacturing an alkoxylation catalyst according to item 1 or 2 of the patent application, which is mixed with an alkaline earth metal selected from carboxylic acids in a liquid dispersion medium (A) Salts, alkaline earth metal salts of hydroxycarboxylic acids, oxides of alkaline earth metals, and hydroxides of alkaline earth metals, at least one (B) and sulfuric acid (C) in the group consisting of (C) component / (( B) The molar ratio expressed by the components is 0.8 to 1. For example, the method for manufacturing an alkoxylation catalyst according to item 3 of the patent application, wherein the mass ratio expressed by [the aforementioned (B) component + the aforementioned (C) component] / the aforementioned (A) component is 1 to 1/3. A method for producing fatty acid alkyl ester alkoxy salt is to add alkylene oxide to the aforementioned fatty acid alkyl ester in the presence of the alkoxylation catalyst as described in item 1 or 2 of the patent application. A method for producing fatty acid alkyl ester alkoxy salt is to add alkylene oxide to the aforementioned fatty acid alkyl ester in the presence of the alkoxylation catalyst and polyol in item 1 or 2 of the patent application.