TWI659942B - Method for producing fatty acid alkyl ester alkoxylate - Google Patents

Abstract

The invention provides a method for producing a fatty acid alkyl ester alkoxylate, which comprises adding an alkylene oxide to a fatty acid alkyl ester represented by the following general formula (I); and the manufacturing method includes the following steps: An alkoxylation catalyst obtained by reacting a metalloid compound B and at least one acid C selected from the group consisting of sulfuric acid, hydrochloric acid, and phosphoric acid in a liquid dispersion medium A, and the fatty acid alkyl relative to 1 kg Base ester and 0.05 to 0.20 mol, in the presence of at least one alcohol selected from the group consisting of monohydric alcohols and diols, addition of 5 to 1 mol of the fatty acid alkyl ester Mohr ~ 25 Mohr of the alkylene oxide; Mohr ratio (C / B ratio) of the acid C to the alkaline earth metal compound B is 0.8 or more and less than 1.

R ¹¹ COOR ¹² ... (I)

Description

Method for producing fatty acid alkyl ester alkoxylate

The present invention relates to a method for producing a fatty acid alkyl ester alkoxylate.

This application claims priority based on Japanese Patent Application No. 2014-090579 filed in Japan on April 24, 2014, and the contents are incorporated herein by reference.

A fatty acid alkyl ester alkoxylate to which an alkylene oxide is added to a fatty acid alkyl ester is often used as a washing component of a liquid detergent.

Fatty acid alkyl ester alkoxylates are used as nonionic surfactants in laundry detergents and the like. The fatty acid alkyl ester alkoxylate has a small gelation area even if it is formulated at a high concentration, and is therefore effectively used as a concentrated liquid cleaning agent particularly formulated with a surfactant at a high concentration (see Patent Document 1).

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

In general, in the alkoxylation reaction of alcohols, amines, and the like having active hydrogen such as hydrogen in a hydroxyl group, a homogeneous catalyst such as an acid or a base and / or a composite metal oxide are used. Heterogeneous catalysts are used as alkoxylation catalysts. However, the addition reaction of alkylene oxide (also referred to as an alkoxylation reaction) to fatty acid alkyl esters having no active hydrogen in the molecule is caused by an alkali catalyst such as an acid catalyst or a sodium hydroxide which is a homogeneous catalyst. It does not take place under the media. Therefore, a composite metal oxide catalyst or the like is used in the alkoxylation reaction. Examples of the composite metal oxide catalyst include aluminum hydroxide. Aluminum-magnesium-based composite metal oxides such as a magnesium calcined product (see Patent Document 2).

In the case where an alkoxylation reaction of a fatty acid alkyl ester is performed using a composite metal oxide catalyst such as the aluminum-magnesium composite metal oxide, a step such as filtration is required to remove the catalyst after the reaction. In addition, when a composite metal oxide catalyst such as the aluminum-magnesium composite metal oxide is used, a polymer (molecule having a weight average molecular weight of 10,000 or more measured by gel permeation chromatography) is generated during the reaction. When a by-product such as an alkylene glycol is used in a liquid detergent using a fatty acid alkyl ester alkoxylate containing the by-product, there is a problem that the liquid detergent is liable to become cloudy. Therefore, by-products such as the high molecular weight polyalkylene glycol must be removed together with the catalyst. However, the high molecular weight polyalkylene glycol and the like easily cause clogging of the filter cloth. As a result, the filtration speed becomes slow. Therefore, industrially, a large filtering equipment is required, and there is a problem that the equipment burden of the enterprise becomes large.

Therefore, in the alkoxylation reaction of fatty acid alkyl esters, as a catalyst for reducing the yield of the by-products, an alkoxylation catalyst has been proposed, which is selected from the group consisting of an alkaline earth metal salt of a carboxylic acid and a hydroxycarboxylic acid. Acid alkaline earth metal salt, alkaline earth metal oxide and alkaline earth metal hydroxide in a group consisting of at least one alkaline earth metal compound and sulfuric acid reacted in a liquid dispersion medium, and the acid / alkaline earth Metal-like The molar ratio represented by the compound is 0.8 to 1 (see Patent Document 3). Hereinafter, the catalyst obtained by reacting the alkaline earth metal compound and the acid in the liquid dispersion medium as described above is referred to as an acid / alkaline earth metal compound catalyst.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] International Publication No. 2011/007778

[Patent Document 2] International Publication No. 2008/078768

[Patent Document 3] International Publication No. 2013/154189

[Patent Document 4] International Publication No. 2008/001797

However, as a result of research conducted by the present inventors, it was found that if a fatty acid alkyl alkoxylate obtained by using an acid / alkaline earth metal compound catalyst described in Patent Document 3 is used for a liquid detergent, At a low temperature of 0 ° C, the liquid detergent has a problem that it is prone to solidification. The liquid detergent is intended to be kept in a liquid state without being solidified or precipitated at a low temperature in order to be used and stored in a cold area. Therefore, for example, the composition is organized so as to be kept in a liquid state at a storage test of -5 ° C for one month.

Here, it is known that the addition molar number distribution of ethylene oxide of a fatty acid alkyl ester alkoxylate used in a liquid detergent affects the viscosity of the liquid detergent (Patent Document 4).

On the other hand, according to the research by the present inventors, the use of liquid detergents In the case of the fatty acid alkyl ester alkoxylate produced by using the composite metal oxide catalyst at the time, the problem that the liquid detergent is liable to solidify under low temperature conditions lower than 0 ° C does not occur (see the present application Comparative example). However, as described above, in the case where a composite metal oxide catalyst is used, there is a problem that a burden arises when filtering the catalyst and by-products.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for producing a fatty acid alkyl ester alkoxylate in order to reduce the generation of the by-products when producing a fatty acid alkyl ester alkoxylate, The acid / alkaline earth metal compound catalyst is used to produce fatty acid alkyl ester alkoxylates, and the fatty acid alkyl ester alkoxylates can be used as a hard-to-cure under low temperature conditions below 0 ° C. Washing ingredients for liquid detergent.

As a result of intensive studies conducted by the present inventors, the following measures are provided in order to solve the problems.

That is, the method for producing a fatty acid alkyl ester alkoxylate of the present invention is a method for producing a fatty acid alkyl ester alkoxylate by adding an alkylene oxide to a fatty acid alkyl ester represented by the following general formula (I): , Characterized in that it comprises the steps of reacting an alkaline earth metal compound (B) and at least one acid (C) selected from the group consisting of sulfuric acid, hydrochloric acid and phosphoric acid in a liquid dispersion medium (A). An alkoxylation catalyst and at least one alcohol selected from the group consisting of a monohydric alcohol and a dihydric alcohol (hereinafter, also (Referred to as a monohydric alcohol / diol), relative to 1 mole of the fatty acid alkane 5 to 25 moles of the alkylene oxide; and the mole ratio (C / B ratio) of the acid (C) to the alkaline earth metal compound (B) is 0.8 or more And less than 1.

R ¹¹ COOR ¹² ... (I)

[In the formula (I), R ¹¹ is a hydrocarbon group having 7 to 17 carbons, and R ¹² is a linear alkyl group having 1 to 3 carbons]

In addition, the amount of fatty acid alkyl ester, monohydric alcohol / diol, and alkylene oxide can be adjusted according to production equipment and the like, and the ratio is not limited as long as it is the ratio.

In addition, one aspect of the present invention is a method for producing a fatty acid alkyl ester alkoxylate, comprising: a catalyst production step, making the alkaline earth metal compound (B) and a group selected from the group consisting of sulfuric acid, hydrochloric acid, and phosphoric acid At least one of the acids (C) is reacted in a liquid dispersion medium (A) to produce an alkoxylated catalyst; in a catalyst dispersion step, the catalyst and the fatty acid represented by the general formula (I) Alkyl ester mixing; an addition reaction step, in the reaction solution obtained in the catalyst dispersion step, further adding 5 mol to 25 mol of alkylene oxide relative to 1 mol of the fatty acid alkyl ester; and Prior to the addition of the addition alkylene oxide, from 0.05 mol to 0.20 mol of a monohydric / glycol relative to 1 kg of the fatty acid alkyl ester is mixed in the reaction solution.

According to the method for producing a fatty acid alkyl ester alkoxylate according to the present invention, by using a specific amount of a monohydric alcohol / glycol in a reaction system, it is possible to produce a liquid washing which has a suppressed solidification under low temperature conditions and has good fluidity. A useful fatty acid alkyl ester alkoxylate is a detergent ingredient.

(Production method of fatty acid alkyl ester alkoxylate)

The method for producing a fatty acid alkyl ester alkoxylate of the present invention includes the following steps: in the presence of a specific alkoxylation catalyst and a specific amount of a monohydric alcohol / diol, in the following general formula (I) A specific amount of alkylene oxide is added to the fatty acid alkyl ester shown.

<Fatty acid alkyl ester>

R ¹¹ COOR ¹² ... (I)

[In the formula (I), R ¹¹ is a hydrocarbon group having 7 to 17 carbons, and R ¹² is a linear alkyl group having 1 to 3 carbons]

In the formula (I), the lower limit value of the carbon number of R ¹¹ is 7, preferably 9, more preferably 11, the upper limit value is 17, preferably 15, and more preferably 13. In the formula (I), the carbon number of R ¹¹ is preferably 9 to 15, more preferably 11 to 13.

R ¹¹ may be linear or branched. R ^{11 is} preferably a straight chain.

R ¹¹ may be a saturated hydrocarbon group (alkyl group) or an unsaturated hydrocarbon group such as an alkenyl group. R ^{11 is} preferably a saturated hydrocarbon group.

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

Specifically, the fatty acid alkyl ester is preferably a fatty acid methyl ester or a mixture thereof, and more preferably methyl laurate, methyl myristate, or a mixture thereof.

The fatty acid alkyl ester may be used singly or in combination of two or more kinds.

<Alkylene oxide>

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, etc. are preferred. Among these compounds, ethylene oxide is more preferred. alkyl.

The alkylene oxide may be used singly or in combination of two or more kinds.

<Specific amount of monohydric alcohol / glycol>

The specific amount of at least one alcohol selected from the group consisting of a monohydric alcohol and a dihydric alcohol (also referred to as a monohydric alcohol / diol) may be a saturated alcohol or an unsaturated alcohol.

Specific amounts of monohydric alcohols / diols include propanols such as methanol, ethanol, and 2-propanol; butanol, pentanol, hexanol, heptanol, n-octanol, and 2-ethylhexanol; Monohydric alcohols such as nonanol, decanol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, etc. ; Alkylene glycols such as ethylene glycol and propylene glycol; alkoxy alkylene glycols with alkoxylation at one end and the like.

Among these compounds, a specific amount of the monohydric alcohol / diol is preferably a monohydric alcohol, more preferably It is a linear or branched monohydric alcohol having 1 to 18 carbons, particularly preferably a linear or branched monohydric alcohol having 1 to 8 carbons, particularly preferably 2-propanol and 2-ethyl Hexanol.

A specific amount of the monohydric alcohol / diol may be used singly or in combination of two or more kinds.

<Alkoxylation catalyst>

The alkoxylation catalyst in the present invention is an alkaline earth metal compound (B) (hereinafter also referred to as "(B) component") and at least one acid selected from the group consisting of sulfuric acid, hydrochloric acid, and phosphoric acid ( C) (hereinafter also referred to as "(C) component") reacted in a liquid dispersion medium (A) (hereinafter also referred to as "(A) component") (hereinafter also referred to as "catalyst (α)" "). That is, the catalyst (α) contains a reactant of the component (B) and the component (C) (a salt of an alkaline earth metal as a main active component of the catalyst).

The alkoxylation catalyst may be used singly or in combination of two or more kinds.

The catalyst (α) can be produced by mixing the (B) component and the (C) component in the (A) component.

． (A) Ingredient: liquid dispersion medium

(A) The component (A) is capable of maintaining the fluidity of the reaction solution without gelation when the catalyst (α) is produced, and the components (B) and (C) can be reacted in the component (A), It is not particularly limited.

The "liquid" in the component (A) means a liquid in a dispersion step and a mixing step described later.

From a viewpoint of improving the productivity in the manufacturing method of the catalyst ((alpha)) mentioned later, it is preferable that (A) component is a liquid at 30 degreeC.

The component (A) is preferably selected from the group consisting of an alcohol represented by the following general formula (1), an alkylene oxide adduct of an alcohol represented by the formula (1), and Fatty acid alkyl ester represented by the formula, an alkylene oxide adduct of a fatty acid alkyl ester represented by the formula (2), a fatty acid represented by the following general formula (3), and the formula (3) At least one of the group consisting of an alkylene oxide adduct of a fatty acid.

ROH ... (1)

[In formula (1), R is a hydrocarbon group having 3 to 18 carbon atoms]

R ¹ COOR ² ... (2)

[In formula (2), R ¹ is a hydrocarbon group having 3 to 18 carbons, and R ² is a linear alkyl group having 1 to 3 carbons]

R ³ COOH ... (3)

[In formula (3), R ³ is a hydrocarbon group having 3 to 18 carbon atoms]

In the formula (1), the lower limit value of the carbon number of R is 3, and the upper limit value is 18, preferably 12, and more preferably 8. In the formula (1), the carbon number of R is preferably 3 or more and 12 or less, and more preferably 3 or more and 8 or less. If the carbon number of R is less than the lower limit value, when the catalyst (α) is produced, the component (A) thickens into a gel state and loses fluidity, (B) It is difficult for the component to react with the component (C). If the number of carbon atoms of R exceeds the upper limit, the melting point will increase, making it unsuitable as a dispersion medium.

R may be linear or branched.

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

In addition, the alcohol represented by the formula (1) is preferably a monohydric alcohol, more preferably a linear or branched monohydric alcohol having 1 to 18 carbon atoms, and particularly preferably a straight-chain alcohol having 1 to 8 carbon atoms. Or a branched monohydric alcohol. As the alcohol represented by the formula (1), the same amount as the monohydric alcohol / diol can be used.

When the alcohol represented by the formula (1) is used as the component (A), a specific amount of the monohydric alcohol / diol in the production of the fatty acid alkyl ester alkoxylate contains (A ) Ingredients of alcohol.

Examples of the alcohol represented by the formula (1) include 1-hexanol, n-octanol, 2-ethylhexanol, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-decanol Primary alcohols such as octanol, oleyl alcohol, nonanol, undecyl alcohol, and tridecyl alcohol; secondary alcohols such as 2-propanol, 2-octanol, 2-decanol, and 2-dodecanol. Among these alcohols, 2-propanol and 2-ethylhexanol are preferred from the viewpoint of further reducing the yield of by-products such as high molecular polyethylene glycol.

Among the alkylene oxide adducts of the alcohol represented by the formula (1), that is, the alcohol alkoxylates, the alkylene oxides added to the alcohol include alkylene oxides having 2 to 3 carbon atoms.

The average addition mole number of the alkylene oxide of the alkylene oxide adduct of the alcohol represented by the formula (1) is preferably 1 to 7, for example.

In the formula (2), the carbon number of R ¹ is 3 to 18, and it can be arbitrarily selected as long as the fluidity is good under the temperature conditions when the alkoxylation catalyst is produced. In the formula (2), the carbon number of R ¹ is preferably 7 to 17, more preferably 9 to 15, and even more preferably 11 to 13.

R ¹ may be linear or branched. R ^{1 is} preferably a straight chain.

R ¹ may be a saturated hydrocarbon group, that is, an alkyl group, or an unsaturated hydrocarbon group such as an alkenyl group. R ^{1 is} preferably a saturated hydrocarbon group.

In the formula (2), R ² is a linear alkyl group having 1 to 3 carbon atoms, and is preferably a methyl group having 1 carbon atom. When R ² is a linear alkyl group having 1 to 3 carbon atoms, the melting point of the component (A) is low, and the fluidity is good under the temperature conditions when the alkoxylation catalyst is produced.

The fatty acid alkyl ester represented by the formula (2) is preferably a fatty acid methyl ester such as methyl decanoate, methyl laurate, methyl myristate, methyl oleate, or a mixture thereof, and more preferably laurel Methyl ester, methyl myristate, or a mixture thereof. Since the fatty acid alkyl ester represented by the formula (2) has fewer components other than the target, it is preferable to use the same fatty acid alkyl ester represented by the general formula (I).

Among the fatty acid alkyl ester alkylene oxide adducts represented by the formula (2), that is, among the fatty acid alkyl ester alkoxylates, the alkylene oxides to be added include alkylene oxides having 2 to 3 carbon atoms. .

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

In the formula (3), the carbon number of R ³ is 3 to 18, preferably 7 to 17, and more preferably 11 to 17. In the formula (3), the carbon number of R ³ can be arbitrarily selected as long as the fluidity is good under the temperature conditions at the time of 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 represented by the formula (3) include caprylic acid, capric acid, lauric acid, palmitoleic acid, oleic acid, linolenic acid, and linolenic acid. Among them, oleic acid is preferred.

Examples of the alkylene oxide addition product of the fatty acid represented by the formula (3) include an alkylene oxide having 2 to 3 carbon atoms.

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

From the viewpoint of further reducing the yield of by-products, the component (A) is preferably an alcohol represented by the general formula (1) and a fatty acid alkyl ester represented by the general formula (2).

(A) A component may be used individually by 1 type, and may be used in combination of 2 or more type.

． (B) Ingredient: Alkaline earth metal compound

The component (B) is not particularly limited as long as it is a compound containing an alkaline earth metal and reacts with the component (C).

The "alkaline earth metal" in the component (B) contains magnesium, beryllium in addition to calcium, strontium, barium, and radium.

The component (B) is preferably selected from, for example, an alkaline earth metal salt of a carboxylic acid (hereinafter also referred to as "(b1) component"), an alkaline earth metal salt of a hydroxycarboxylic acid (hereinafter also referred to as "(b2) component") Oxides of alkaline earth metals (hereinafter also referred to as "(b3) component"), hydroxides of alkaline earth metals (hereinafter also referred to as "(b4) component"), and alkaline earth metal salts of carbonic acid (hereinafter also referred to as Is at least one of the group consisting of "(b5) component)").

Examples of the component (b1) include calcium acetate (calcium acetate anhydrous, calcium acetate monohydrate, etc.), calcium salts of carboxylic acids such as calcium formate, and barium salts of carboxylic acids such as barium acetate and barium formate. Among these compounds, a carboxylic acid is preferable from the viewpoint of improving the catalytic activity. Calcium salt, more preferably calcium acetate.

Examples of the component (b2) include calcium salts of hydroxycarboxylic acids such as calcium lactate, calcium tartrate, calcium citrate, and calcium malate; and barium salts of hydroxycarboxylic acids such as barium lactate, barium tartrate, barium citrate, and barium malate. Among these compounds, a calcium salt of a hydroxycarboxylic acid is preferable from the viewpoint of improving the catalyst activity.

Examples of the component (b3) include calcium oxide and barium oxide. Among them, calcium oxide is preferred.

Examples of the component (b4) include calcium hydroxide and barium hydroxide. Among them, calcium hydroxide is preferred.

Examples of the component (b5) include calcium carbonate and barium carbonate. Among them, calcium carbonate is preferred.

From the viewpoint of increasing the catalyst activity and further reducing the yield of by-products, the component (B) is preferably the component (b1) and the component (b3), and more preferably the calcium salt of a carboxylic acid and calcium oxide.

(B) A component may be used individually by 1 type, and may be used in combination of 2 or more type.

． (C) Ingredient: acid

The component (C) in the present invention is at least one acid selected from the group consisting of sulfuric acid, hydrochloric acid, and phosphoric acid.

Among the components (C), sulfuric acid is preferred from the viewpoint of stably developing the catalytic activity. Concentrated sulfuric acid can be used in sulfuric acid, or dilute sulfuric acid can be used.

The catalyst (α) can use, for example, a fatty acid alkyl ester represented by the general formula (2) as the component (A), a calcium salt of a carboxylic acid or calcium oxide as the (B) component, and Sulfuric acid was used as the (C) component.

[Manufacturing method of catalyst (α)]

Examples of the method for producing the catalyst (α) include a method including a dispersion step of dispersing the component (B) in the component (A) to obtain a dispersion, and a mixing step of adding the (C) to the dispersion. Component, and (A) component is mixed with (B) component and (C) component.

Step

In the dispersing step, for example, a reactor including a mixing tank including a sleeve and a stirring tank provided with a paddle-type stirring blade is used. In the dispersing step, the components (A) and (B) are put into a stirring tank, and these components are stirred.

The temperature conditions in this step are not particularly limited, and are set to, for example, normal temperature (5 ° C to 35 ° C). The temperature adjustment in the stirring tank is performed by, for example, passing a heat medium (for example, water) having an arbitrary temperature into the sleeve.

The stirring time in this step is not particularly limited, and is set to a time during which the component (B) is substantially uniformly dispersed in the component (A). The stirring time in this step is, for example, 10 minutes to 60 minutes. The term "substantially uniform" refers to a state in which the (B) component does not exist under the visual observation, and the (B) component is uniformly dispersed.

‧ mixing step

In the mixing step, component (C) is added to the dispersion obtained in the dispersion step and mixed to generate a reactant of component (B) and (C), that is, a salt of an alkaline earth metal as a main catalyst active component. An alkoxylation catalyst in which a catalyst active ingredient is dispersed in the component (A) is obtained.

The mixing method in this step is not particularly limited, and for example, a method in which the component (C) is added dropwise while stirring the dispersion in the stirring tank is preferred.

The temperature conditions in this step, that is, the reaction temperature is preferably 10 ° C to 60 ° C, and more preferably 20 ° C to 50 ° C. The lower limit value of the reaction temperature is preferably 10 ° C, more preferably 20 ° C, and the upper limit value is preferably 60 ° C, more preferably 50 ° C. If it is less than the said preferable lower limit, there exists a possibility that the reaction of (B) component and (C) component will become too slow, and the production efficiency of a catalyst ((alpha)) will fall. If the above-mentioned preferable upper limit value is exceeded, there is a concern that the catalyst activity of the obtained catalyst (α) is reduced.

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

The stirring time (i.e., the reaction time) in this step is set to a time when the (B) component and the (C) component can sufficiently react, and the time for heat generation caused by the addition of the (C) component can be controlled. It is 1 to 2 hours. The stirring time in this step refers to the time after the addition of the component (C).

The molar ratio (hereinafter also referred to as "C / B ratio") represented by the (C) component / (B) component in the mixing step is preferably 0.8 or more and less than 1, and more preferably 0.9 to 0.98. The lower limit value of the C / B ratio is preferably 0.8, more preferably 0.9, and the upper limit value is preferably less than 1, and more preferably 0.98.

When the C / B ratio is greater than or equal to the above-mentioned preferred lower limit value, the catalyst (α) obtained in the production step of the fatty acid alkyl ester alkoxylate can favorably reduce the yield of by-products.

When the C / B ratio is 0.9 or more, it is used in the production of fatty acid alkyl ester alkoxylates. In the method, it is easy to expand the distribution of the addition mole number of the alkylene oxide of the obtained fatty acid alkyl ester alkoxylate.

The distribution of the addition mol number of the alkylene oxide of the fatty acid alkyl ester alkoxylate can be determined by gas chromatography (also referred to as GC method). The distribution of the addition mole number of the alkylene oxide of the fatty acid alkyl ester alkoxylate is measured, for example, by gas chromatography (also referred to as the GC method) on the fatty acid alkyl ester alkoxylate. The maximum peak of a fatty acid alkyl ester alkoxylate and the area of the two peaks before and after it are totaled and divided by the total peak area. When a plurality of types of fatty acid alkyl ester alkoxylates are included, for example, it is set to divide the total of the maximum peak of the obtained fatty acid alkyl ester alkoxylate and the sum of the areas of the two peaks before and after by the total Peak area.

In order to increase the distribution of the addition mole number of the alkylene oxide, it is more preferable to set the C / B ratio to 0.93 or more.

When the C / B ratio is equal to or lower than the preferable upper limit value described above, the catalyst activity of the obtained catalyst (α) is improved, and fatty acid alkyl ester alkoxylates can be efficiently produced. If the C / B ratio is less than 1, the catalyst activity of the obtained catalyst (α) is significantly improved.

In addition, the mass ratio represented by [(B) component + (C) component] / (A) component (hereinafter also referred to as "(B + C) / A ratio") in this step is preferably 1/3 to 1, more preferably 1 / 2.5 ~ 1 or less. The lower limit of the (B + C) / A ratio is preferably 1/3, more preferably 1 / 2.5, and the upper limit is preferably 1.

When the (B + C) / A ratio is equal to or lower than the above-mentioned preferable upper limit value, the component can be easily stirred, and the component (B) and the component (C) can be efficiently mixed. If below When the limit value is used, the content of the catalyst active ingredient in the component (A) decreases, and when the fatty acid alkyl ester alkoxylate is produced, the amount of the catalyst (α) added becomes excessive and inefficient.

…… Other steps

After the mixing step, a catalyst curing step of stirring the catalyst (α) at an arbitrary temperature may be provided. The temperature condition of the catalyst curing step is preferably, for example, 10 ° C to 60 ° C, and more preferably 20 ° C to 50 ° C. The lower limit value of the temperature condition is preferably 10 ° C, more preferably 20 ° C, and the upper limit value is preferably 60 ° C, and more preferably 50 ° C. By setting this step, the amount of the unreacted (B) component can be reduced.

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

Furthermore, the catalyst (α) may be subjected to filtration, static separation, or the like, thereby increasing the concentration of the catalyst active component in the catalyst (α).

<Manufacturing method of fatty acid alkyl ester alkoxylate>

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

The method for producing a fatty acid alkyl ester alkoxylate according to this embodiment is in the presence of a specific alkoxylation catalyst (catalyst (α)) and a specific amount of a monohydric alcohol / diol, relative to 1 mole. Examples of the method for adding 5 to 25 mol of alkylene oxide to the fatty acid alkyl ester represented by the general formula (I) include a method for producing the catalyst including a catalyst dispersion step, an addition reaction step, and an aging step. .

《Catalyst Dispersion Steps》

The catalyst dispersion step is a step of dispersing the catalyst (α) in a mixture of a fatty acid alkyl ester represented by the general formula (I) as a starting material and a specific amount of a monohydric alcohol / diol. Step. In this step, a fatty acid alkyl ester, a catalyst (α), and a specific amount of a monohydric / glycol are mixed.

In this step, for example, a stirred tank reactor is used.

The mixing ratio of the fatty acid alkyl ester and the monohydric alcohol / diol in the catalyst dispersing step is: the amount of the monohydric alcohol / diol is 0.05 mol to 0.20 mol, preferably 1 mol relative to 1 kg of the fatty acid alkyl ester. Above 0.06 mol and below 0.10 mol. Relative to 1 kg of the fatty acid alkyl ester, the lower limit of the amount of the monohydric alcohol / diol is 0.05 mole, preferably 0.06 mole, and the upper limit value is 0.20 mole, preferably 0.10 mole. .

When the amount of monohydric alcohol / diol (mole) with respect to 1 kg of fatty acid alkyl ester is equal to or more than the lower limit, fatty acids useful as a washing component of a liquid detergent having good fluidity under low temperature conditions can be produced. Alkyl ester alkoxylate. If the upper limit value is exceeded, the effect reaches the limit. If it is below the upper limit, cost reduction is achieved. In addition, if the above-mentioned upper limit value is exceeded, the addition mole number distribution of the alkylene oxide may become too narrow.

When the catalyst (α) is used, the component (A) is brought along with the catalyst active ingredient.

When the component (A) contains the fatty acid alkyl ester of the formula (I), the amount of the fatty acid alkyl ester as a starting material in this step includes the equivalent of the formula derived from the component (A). (I) A fatty acid alkyl ester. That is, the total amount of the fatty acid alkyl ester equivalent to the formula (I) from the component (A) and the total amount of the fatty acid alkyl ester equivalent to the formula (I) newly added in the catalyst dispersion step. The amount of fatty acid alkyl ester is the amount of fatty acid alkyl ester as a starting material.

When the component (A) contains a monohydric alcohol / diol, the amount of the monohydric alcohol / diol in the specific amount in this step includes the monohydric alcohol / diol from the component (A). That is, based on 1 kg of fatty acid alkyl ester, the total amount of monohydric alcohols / diols derived from the component (A) and the amount of monohydric alcohols / diols re-added in the catalyst dispersion step are monohydric alcohols / diols. The amount of the alcohol is from 0.05 mol to 0.20 mol.

The amount of the catalyst to be added to the raw material can be specified according to the amount of metal in the catalyst (α). The amount of metal is preferably 0.01 mol to 0.25 mol, and more preferably 1 kg of fatty acid alkyl ester as the raw material. 0.02 mol ~ 0.10 mol.

<< addition reaction steps >>

The addition reaction step is in the presence of a specific alkoxylation catalyst (catalyst (α)) and a specific amount of a monohydric alcohol / diol, with respect to 1 mole of the fatty acid represented by the general formula (I) 5 to 25 mol alkylene oxide is added to an alkyl ester to obtain a fatty acid alkyl ester alkoxylate. This step includes a step of performing an operation (condition setting operation) set to arbitrary temperature and pressure conditions for performing an addition reaction; and then performing an alkylene oxide (hereinafter sometimes referred to as AO) and fatty acid alkyl group Step of an operation (AO contact operation) in which an ester, a catalyst (α), and a specific amount of a monohydric / diol mixture are contacted.

Steps for setting conditions: In this step, appropriate temperature and pressure conditions for performing the addition reaction are set. The temperature condition (addition reaction temperature) for performing the addition reaction is, for example, preferably 150 ° C to 180 ° C, and more preferably 160 ° C to 180 ° C.

The pressure conditions for carrying out the addition reaction are appropriately considered in consideration of the addition reaction temperature. It is determined, for example, that it is preferably 0.1 MPa to 1 MPa, and more preferably 0.1 MPa to 0.6 MPa or less. The lower limit value of the pressure condition is preferably 0.1, the upper limit value is preferably 1 MPa, and more preferably 0.6 MPa.

Steps to perform AO contact operation: In this step, the alkylene oxide is contacted with the fatty acid alkyl ester obtained in the catalyst dispersion step, the catalyst (α), and a mixture of a specific amount of a monohydric alcohol / diol. In the AO contact operation, the introduction amount of AO is 5 mol to 25 mol, preferably 10 mol to 20 mol, with respect to the fatty acid alkyl ester represented by the general formula (I). The lower limit of the amount of AO introduced is 5 mol, preferably 10 mol, and the upper limit is 25 mol, preferably 20 mol.

The greater the number of moles of AO added, that is, the greater the amount of AO introduced, the greater the amount of polymer polyethylene glycol produced.

《Mature Steps》

The aging step is a step of stirring the reactant at an arbitrary temperature in the stirring tank after the addition reaction step. By setting this step, the amount of unreacted fatty acid alkyl ester and the amount of unreacted AO can be reduced. The temperature conditions in this step are preferably, for example, 150 ° C to 180 ° C, more preferably 160 ° C to 180 ° C, and more preferably the same as the addition reaction temperature. The stirring time in the aging step is preferably 10 minutes to 20 minutes, and more preferably 30 minutes to 60 minutes.

In addition to the catalyst dispersion step, the addition reaction step, and the aging step, the manufacturing method of this embodiment may include a purification step, if necessary, which purifies the catalyst activity remaining in the fatty acid alkyl ester alkoxylate. Ingredients wait except. Examples of the method for removing the catalyst active ingredient include methods such as washing with water, centrifugation, and filtration.

Among these, washing with water and centrifugation are preferred.

In the purification step, for example, the reactant obtained in the aging step is heated to 70 ° C to 120 ° C to dissolve, and 5 to 30 parts by mass of purified water is added to 100 parts by mass of the reactant, and the mixture is stirred for 30 minutes ~ 120 minutes. Then, it cooled to 50 to 70 degreeC, and stirred for 30 to 120 minutes. Then, the catalyst active ingredient and the like are removed by centrifugation.

In the manufacturing method of the present embodiment, the entire amount of the monohydric alcohol / glycol is blended in the catalyst dispersion step, but it is not limited to this, and may be used in the condition setting operation in the addition reaction step. Blend a specific amount of the entire amount of monohydric alcohol / diol; also dispose a part of the specific amount of monohydric alcohol / diol in the catalyst dispersing step, and deploy the rest in the condition setting operation in the addition reaction step Monohydric alcohols / diols.

In either case, before the AO contact operation, that is, when the alkylene oxide is added to the fatty acid alkyl ester, the mixing ratio of the fatty acid alkyl ester to the monohydric alcohol / diol is set to: relative to 1 kg The fatty acid alkyl ester has a monohydric alcohol / diol content of 0.05 mol to 0.20 mol.

In the method for producing a fatty acid alkyl ester alkoxylate according to the present invention, the specific alkoxylation catalyst and the fatty acid alkyl ester represented by the general formula (I) are 0.05 mol to 1 kg ~ In the presence of 0.20 mol of monohydric alcohol / diol, 5 mol to 25 mol are added to 1 mol of the fatty acid alkyl ester represented by the general formula (I). Ear alkylene oxide. As described above, according to the manufacturing method, the addition reaction step is performed in the presence of a specific amount of a monohydric alcohol / diol, and therefore, it is useful as a washing component for a liquid detergent having good fluidity under low temperature conditions. Fatty acid alkyl ester alkoxylate.

(Fatty acid alkyl ester alkoxylate)

The production method of the present invention is suitable for producing a fatty acid alkyl ester alkoxylate represented by the following general formula (II).

R ¹¹ CO- (R ¹³ O) _m -OR ¹² ... (II)

[In formula (II), R ¹¹ is a hydrocarbon group having 7 to 17 carbons; R ¹² is a linear alkyl group having 1 to 3 carbons; R ¹³ O is an oxyalkylene group having 2 to 4 carbons; m represents R ¹³ O The average number of repetitions, a number from 5 to 25]

In the formula (II), with the same ¹² (I) in which R of the formula R ¹¹ and R ¹¹ and R ^12.

R ¹³ O is oxyethyl, oxypropyl or oxybutyl. (R ¹³ O) _m may be a mixture of two or more kinds of oxyalkylenes among oxyethyl groups, oxypropyl groups, and oxybutyl groups. When two or more kinds of oxyalkylene groups are mixed, the oxyalkylene groups may be mixed in a block form, or may be mixed in a random form. Among them, oxyalkylene is preferably oxyethylene.

m is a number of 5 to 25, and preferably a number of 9 to 20. In addition, m represents the "average" repeat number of the oxyalkylene group. That is, the compound represented by the general formula (II) is an aggregate of molecules having different repeat numbers of oxyalkylene groups. In addition, the fatty acid alkyl ester alkoxylate produced by the method of the present invention may be an aggregate of molecules having different R ¹¹ . The R ¹¹ or R ¹² of each molecule constituting the aggregate of the molecules may be the same or different.

The fatty acid alkyl ester alkoxylate produced by the production method can be used as a washing component of a liquid detergent, and the liquid detergent using the washing component as a washing component has good fluidity under low temperature conditions.

(Liquid detergent)

The fatty acid alkyl ester alkoxylate produced by the production method of the present invention is suitable for use in a liquid detergent. The liquid detergent containing the fatty acid alkyl ester alkoxylate produced by the production method of the present invention can be used as a domestic or industrial use, and is suitable as a liquid detergent for clothes, and particularly suitable as a high concentration surfactant. Liquid detergent for concentrated types of laundry.

In the liquid detergent, the content of the fatty acid alkyl ester alkoxylate is preferably 10% to 50% by mass, and more preferably 30% to 50% by mass relative to the total mass of the liquid detergent. The lower limit is preferably 10% by mass, more preferably 30% by mass, and the upper limit is preferably 50% by mass.

When the content of the fatty acid alkyl ester alkoxylate is at least the above-mentioned preferred lower limit value, the fluidity under low temperature conditions is improved. In addition, the detergency for dirt is improved. On the other hand, if it is below the above-mentioned preferable upper limit value, the viscosity of the liquid detergent under low temperature conditions is increased and further suppressed.

Other ingredients contained in liquid detergents can be used, for example: surfactants, chelating agents, alkaline agents, antioxidants, enzymes, enzyme stabilizers, viscosity reducers or Solubilizers, preservatives, metal oxides or metal salts, hand-improving agents, fluorescent whitening agents, re-pollution preventing agents, soil releasing agents, pearling agents, bleaching agents, flavoring agents ( flavoring agent), colorants, opacifying agents, extracts of natural products, pH adjusters, etc.

A liquid detergent containing a fatty acid alkyl ester alkoxylate produced by the production method of the present invention is unlikely to be cured under low temperature conditions and has good fluidity. Therefore, the liquid detergent can be sold in a wide range of regions as a product on the market. use.

[Example]

Hereinafter, the present invention will be described more specifically with examples and comparative examples, but the present invention is not limited to the following examples. In this embodiment, unless otherwise specified, "%" means "mass%".

The raw materials used in this example are as follows.

． Fatty acid alkyl ester

Methyl laurate: trade name "Pastel M12", manufactured by Lion Chemical Co., Ltd.

Methyl myristate: trade name "Pastel M14", manufactured by Lion King Chemical Co., Ltd.

． Alkylene oxide

Ethylene oxide: manufactured by Air Water Inc.

． Alkoxylation catalyst

Catalyst (α-1), catalyst (α-2), and catalyst synthesized by a manufacturing method described later

(α-3), catalyst (α-4), catalyst (β).

． Monohydric alcohols / diols

2-EH: 2-ethylhexanol, reagent, manufactured by Pure Chemical Co., Ltd.

2-PrOH: 2-propanol, a primary reagent, manufactured by Kanto Chemical Co., Ltd.

． Formulation of liquid detergent

a-1-1 to a-1-12: fatty acid alkyl ester alkoxylates (fatty acid methyl ester ethoxylates) produced by the production methods of Examples 1 to 7 and Comparative Examples 1 to 5 (fatty acid methyl ester ethoxylate (MEE), ethylene oxide (EO) average addition mole number is 15). A mixture of a compound in which R ¹¹ in the general formula (II) is an alkyl group having ¹¹ carbon atoms and a compound in which R ¹¹ in the general formula (II) is an alkyl group having 13 carbon atoms. A compound in which R ¹² is a methyl group, R ¹³ O is an oxyethyl group, and m is 15 in the formula (II).

a-2: For natural alcohol CO-1217 (trade name) manufactured by Procter and Gamble (P & G), an average of 15 mol of ethylene oxide is added.

[Synthesis of a-2]

In a pressure-resistant reaction container, 224.4 g of natural alcohol CO-1270 manufactured by Procter & Gamble and 2.0 g of a 30% by mass NaOH aqueous solution were collected, and the reaction container was replaced with nitrogen. Then, after dehydrating for 30 minutes at a temperature of 100 ° C and a pressure of 2.0 kPa or less, the temperature was raised to 160 ° C. Next, 760.4 g of ethylene oxide (gas form) was slowly added to the alcohol solution while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C. while using a blow pipe while stirring. Addition of ethylene oxide After the bundling, curing was performed at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes. Then, unreacted ethylene oxide was distilled off at a temperature of 180 ° C. and a pressure of 6.0 kPa or less in 10 minutes. After cooling to a temperature of 100 ° C. or lower, 70% by mass of p-toluenesulfonic acid was added to neutralize the pH of the 1% by mass aqueous solution of the reactant to obtain a-2.

b-1: Coconut fatty acid, manufactured by Japan Oil Co., Ltd.

e-1: Methyl Glycine Diacetic Acid Trisodium (MGDA), trade name "Trilon M", manufactured by BASF.

Protease: Trade name "Coronase 48L", manufactured by Novozymes.

SR agent: Detergent, trade name "TexCare SRN-170C", manufactured by Clariant Japan.

LAS-H: linear alkylbenzenesulfonic acid, trade name "Lipon LH-200", manufactured by Lion King Corporation.

MEA: Monoethanolamine, manufactured by Japan Catalyst Co., Ltd.

BHT: Dibutylhydroxytoluene, trade name "SUMILIZER BHT-R", manufactured by Sumitomo Chemical Co., Ltd.

Citric acid: Trade name "citric acid", manufactured by Kanto Chemical Co., Ltd.

Ethanol: Trade name "95% Synthesis of Specific Alcohols", manufactured by Japan Alcohol Trading CO., LTD.

Sodium lactate: Trade name "Sodium Lactate", manufactured by Kanto Chemical Co., Ltd.

Perfume: Perfume composition A described in Tables 11 to 18 of Japanese Patent Laid-Open No. 2002-146399.

Coloring matter: Green No. 3, trade name "Green No. 3", manufactured by Kojima Kasei Co., Ltd.

pH adjuster: sulfuric acid, sodium hydroxide, potassium hydroxide, monoethanolamine.

<Manufacture of alkoxylation catalyst>

The following raw materials (liquid dispersion medium, alkaline earth metal compound, sulfuric acid) were used.

Liquid dispersion medium: a mixed solution of methyl laurate and methyl myristate, a fatty acid methyl ester, trade name Pastel M124, manufactured by Lion King Chemical Co., Ltd.

Alkaline earth metal compounds: calcium acetate monohydrate, special grade reagent, manufactured by Kanto Chemical Co., Ltd.

Calcium Oxide, Special Grade Reagent, Wako Pure Chemical Industries, Ltd.

Barium oxide, premium reagent, Wako Pure Chemical Industries, Ltd.

Sulfuric acid: a special grade reagent with a concentration of 96% by mass, manufactured by Kanto Chemical Co., Ltd.

A catalyst (α-1), a catalyst (α-2), and a catalyst (α-) as alkoxylation catalysts are produced by mixing the alkaline earth metal compound and sulfuric acid in a liquid dispersion medium. 3), catalyst (α-4), catalyst (β). The C / B ratios of catalyst (α-1), catalyst (α-2), catalyst (α-3), catalyst (α-4), and catalyst (β) were 0.90, 0.96, 0.90, 0.90, 0.67, and (B + C) / A ratios were 0.46, 0.47, 0.41, 0.40, and 0.42. In addition, the preparation amount of each component mentioned below is a purity conversion value.

Catalyst (α-1), catalyst (α-2), and method for manufacturing catalyst (β)

Specifically, a fatty acid methyl ester mixed solution and calcium acetate monohydrate were added to a 500 mL beaker and mixed at room temperature (25 ° C) using a paddle-type stirring blade to obtain a dispersion (dispersion step).

While the dispersion was being stirred, 96% by mass of sulfuric acid was added and mixed using a dropping funnel over 10 minutes (mixing step). In the mixing step, heat was generated due to the addition of sulfuric acid. Therefore, the beaker was cooled with a water bath and the reaction temperature was controlled at 20 ° C to 50 ° C while stirring for 1 hour.

After adding sulfuric acid, the mixture was stirred for 2 hours while maintaining the temperature at 20 ° C to 50 ° C, thereby obtaining alkoxylated catalysts (catalyst (α-1), catalyst (α-2), and catalyst (β). ) (Catalyst ripening step).

Manufacturing method of catalyst (α-3)

Specifically, in a 500 mL beaker, a fatty acid methyl ester mixed solution and calcium oxide were added, and mixed at room temperature (25 ° C.) with a paddle-type stirring blade to obtain a dispersion (dispersion step).

While stirring the dispersion, a dropping funnel was used, and sulfuric acid diluted to 76% was added and mixed for 10 minutes (mixing step). In the mixing step, heat was generated due to the addition of sulfuric acid. Therefore, the beaker was cooled with a water bath and the reaction temperature was controlled at 20 ° C to 50 ° C while stirring for 1 hour.

After adding sulfuric acid, the alkoxylation catalyst (catalyst (α-3)) was obtained by stirring for 2 hours while maintaining the temperature at 20 ° C to 50 ° C (catalyst curing step).

Manufacturing method of catalyst (α-4)

The catalyst (α-4) was obtained by the same manufacturing method as the catalyst (α-3), except that barium oxide was used instead of calcium oxide.

The amount of the compound used is as described in Table 1.

<Production of fatty acid alkyl ester alkoxylate>

(Example 1 to Example 7, Comparative Example 3 to Comparative Example 5)

In an autoclave, add 12.5 g of the obtained alkoxylated catalyst (catalyst (α-1), catalyst (α-2), catalyst (α-3), and catalyst (α-4) Or catalyst (β)), 462 g of the methyl laurate, and 166 g of the myristic acid methyl ester, and then add the predetermined amounts of monohydric alcohols / diols as shown in Table 1. (° C) (catalyst dispersion step).

The nitrogen in the autoclave was replaced with stirring. Then, the temperature was raised to the ethylene oxide (EO) addition reaction temperature (160 ° C), and the pressure was adjusted to 0.1 MPa to 0.5 MPa (condition setting operation). Then, under the conditions of the temperature and pressure, 1876 g (15 times mole of the total of methyl laurate and methyl myristate) of ethylene oxide (EO) was introduced, and the reaction was performed while stirring (EO contact). Operation) (the above is the addition reaction step).

Then, it stirred at the said EO addition reaction temperature for 0.5 hour (aging process). Then, it cooled to 80 degreeC, and obtained 2516g of reaction crude.

Next, 29.3 g of purified water was added to 250 g of the reaction crude which was dissolved by heating to 80 ° C., and the mixture was stirred for 30 minutes while maintaining the temperature at 80 ° C. Then, it cooled to 50 degreeC, and stirring was continued for 30 minutes. Then, the catalyst and agglomerates are removed by centrifugation, Purification is performed (purification step).

According to the above manufacturing method, a-1-1 to a-1-7 and a-1-10 to a-1-12 of the target fatty acid methyl ester ethoxylate (MEE) were obtained.

(Comparative example 1)

A-1-8 was obtained as a target fatty acid alkyl ester alkoxylate in the same manner as in Example 1 except that no monohydric alcohol / diol was added.

(Comparative example 2)

Synthesis of an ethylene oxide (15EO adduct of 2-EH) equivalent to an average of 15 mols relative to 2-ethylhexanol.

The obtained alkoxylation catalyst (α-1) was filtered and sufficiently washed with acetone, and then the solid content was dried at 50 ° C. In an autoclave, 2.0 g of the solid content of the obtained alkoxylation catalyst and 285 g of 2-ethylhexanol were added, followed by stirring at room temperature (20 ° C).

The nitrogen in the autoclave was replaced with stirring. Then, the temperature was raised to the ethylene oxide (EO) addition reaction temperature (160 ° C), and the pressure was adjusted to 0.1 MPa to 0.5 MPa (condition setting operation). Then, under the conditions of the temperature and pressure, 1447 g (15 times mole of 2-ethylhexanol) of ethylene oxide (EO) was introduced, and the reaction was performed while stirring.

Then, the mixture was stirred at the EO addition reaction temperature for 0.5 hours. Then, it cooled to 80 degreeC, and obtained 1734 g of reaction crudes.

Next, 250 g of the crude reaction product dissolved at a temperature of 50 ° C. was filtered, the catalyst was removed, and purification was performed to obtain 15E adduct of 2-EH.

Next, a fatty acid alkyl ester alkoxylate produced by the production method of Comparative Example 1 and a 15EO adduct of 2-EH at 0.06 mol per 1 kg of the fatty acid alkyl ester alkoxylate Mixing (15EO adduct of 2-EH was added afterwards) to obtain a-1-9.

<Manufacture of liquid detergent>

(Test example 1)

According to the formulated composition shown in Table 2, 1000 g of a liquid detergent was produced by a conventional method (in the case where an un-dispensed component exists, the component is not blended).

(Test Example 2 to Test Example 12)

1000 g of a liquid detergent was produced in the same manner as in Test Example 1 except that the fatty acid methyl ethoxylate (MEE) was changed from a-1-1 to a-1-2 to a-1-12, respectively.

The unit of the blending amount in Table 2 is mass%, and any component shows the purity conversion amount. In addition, the liquid detergent of each example was prepared so that the sum of each component described in a table might become 100 mass%, and the balance was made with the remainder of water.

By adding an appropriate amount of a pH adjuster to the liquid detergent of each example, the pH value at 25 ° C was adjusted to 7.0. The pH value of the liquid detergent was measured by adjusting the temperature of the liquid detergent to 25 ° C and using a glass electrode pH meter (manufactured by Toa DKK (DKK-TOA) Co., Ltd., product name HM-30G). The glass electrode was directly immersed in the liquid detergent, and the value displayed after 1 minute had elapsed was measured.

<Evaluation>

About the liquid detergent of each case, the fluidity | liquidity of a liquid detergent was evaluated by the evaluation method shown below. The results are shown in Table 2.

[Evaluation of fluidity of liquid detergent]

Take 100mL of liquid detergent for each example and put them into transparent glass bottles (wide mouth In the specification bottle PS-NO.11), cover with a cap to seal. In this state, the sealed glass bottle was placed in a thermostatic bath at -5 ° C and stored for one month.

After the storage, the glass bottle was taken out from a thermostatic bath at -5 ° C, and the glass bottle stored at -5 ° C was leveled, and the change in liquid level was visually observed, based on the following evaluation criteria To evaluate the fluidity of the liquid detergent.

Evaluation benchmark

A: Within 10 seconds after the glass bottle is poured horizontally, the liquid surface becomes horizontal.

B: After pouring the glass bottle to a level, it takes more than 10 seconds until the liquid level becomes horizontal.

C: No fluidity was confirmed at all due to curing.

From the results shown in Table 2, it was confirmed that the liquid detergents of Test Examples 1 to 7 containing fatty acid alkyl ester alkoxylates produced by applying the production methods of Examples 1 to 7 of the present invention were used. Good fluidity at low temperature.

In addition, it was also confirmed that the fatty acid alkyl ester alkoxylate produced by applying the production methods of Examples 1 to 7 of the present invention can be used as a washing component of a liquid detergent.

Hereinafter, using examples and comparative examples, liquid detergents using fatty acid alkyl ester alkoxylates produced using sulfuric acid / alkaline earth metal catalysts and using the composite metal oxide catalysts The low-temperature curability of the produced liquid detergent of fatty acid alkyl ester alkoxylate will be described.

(Example 3, Test Example 3)

For comparison, Example 3 in which a fatty acid alkyl ester alkoxylate is produced using a sulfuric acid / alkaline earth metal-based catalyst, and the fatty acid alkyl ester alkoxylate a-1- obtained in Example 3 is used The liquid detergent of Test Example 3 manufactured by 3 is described in Tables 3 and 4. The fatty acid alkyl ester alkoxylate a-1-3 had an addition mole number distribution of ethylene oxide measured by the following GC method of 54%.

(Comparative Example 6, Test Example 13) Liquid detergent using fatty acid alkyl ester alkoxylate produced by composite metal oxide catalyst

(Comparative Example 6) A fatty acid alkyl ester alkoxylate was produced by a composite metal oxide catalyst.

Will contain 2.5MgO. Al ₂ O ₃ . The chemical composition of mH ₂ O is aluminum hydroxide. Magnesium (Kyoward 300 manufactured by Kyowa Chemical Industry Co., Ltd.) was calcined at 900 ° C for 3 hours to obtain magnesium. Aluminum composite metal oxide catalyst powder (catalyst γ).

In a 2000 kL stirred reaction tank, 184.1 kg (859 mol) of methyl laurate (manufactured by Lion King Chemical Co., Pastel M12) and 66.0 kg (272 mol) of myristic acid were added. Methyl ester (manufactured by Lion King Chemical Co., Ltd., Pastel M14), 1.00 kg of the composite metal catalyst, 1.25 kg of glycerol as a polyol, and 0.05 kg of potassium hydroxide was added , Stir for 10 minutes to perform alkaline denaturation of the catalyst. Then, while stirring and mixing, the inside of the reaction tank was purged with nitrogen, heated to 100 ° C, and dehydrated for 30 minutes under reduced pressure conditions of 1.3 kPa or less. Then, the temperature was increased to 180 ° C., and 747.6 kg (16972 mol, 15 times mol of fatty acid methyl ester) of ethylene oxide was introduced under the condition that the pressure upper limit value was 0.49 MPa. After further aging for 0.5 hours, it was cooled to 80 ° C. and taken out, and 999 kg was obtained as a crude reaction product containing an alkylene oxide adduct, that is, fatty acid alkyl ester alkoxylate a-1-13. The average addition mole number of ethylene oxide of the fatty acid alkyl ester alkoxylate a-1-13 was 15, and the addition mole number distribution of ethylene oxide measured by the following GC method was 54%. The fatty acid alkyl ester alkoxylate a-1-13 contains 0.9% by weight of polyethylene glycol as a by-product.

(Test Example 13) A liquid detergent of 1000 g was produced in the same manner as in Example 1 except that the fatty acid methyl ethoxylate (MEE) was changed from a-1-1 to a-1-13.

(Comparative Example 7, Test Example 14) A liquid detergent using a fatty acid alkyl ester alkoxylate produced by a sulfuric acid / alkaline earth metal catalyst without adding a specific amount of a monohydric alcohol / diol.

(Comparative Example 7) Except for the production of fatty acid alkyl ester alkoxylates, 0.06 was added to 1 kg of fatty acid alkyl esters instead of isopropyl alcohol used as a specific amount of monohydric alcohol / diol. A fatty acid alkyl ester alkoxylate a-1-14 was produced in the same manner as in Example 3 of the present application for producing a fatty acid alkyl ester alkoxylate a-1-3, except for Mol. Fatty acid alkyl ester alkoxylate a-1-14 has an average ethylene oxide mole number of 15 and an ethylene oxide addition mole number distribution measured by the following GC method was 54%.

(Test Example 14) A liquid detergent of 1000 g was produced in the same manner as in Example 1 except that the fatty acid methyl ethoxylate (MEE) was changed from a-1-1 to a-1-14.

[Determination and calculation of addition mole number distribution of alkylene oxide by gas chromatography]

The distribution of the addition mol number of ethylene oxide in the reaction crude (also referred to as the EO addition mol distribution) is obtained by a gas chromatography method (also referred to as a GC method).

The reaction sample was prepared by diluting with acetone so that the concentration of the fatty acid alkyl ester alkoxylate became a 1% solution as an analysis sample.

The conditions of the GC method are the following measurement conditions, and the EO addition mole number distribution (also referred to as the GC area%) is calculated by the following calculation method. The smaller the value of the EO addition mole number distribution, the wider the distribution of the EO addition mole number becomes.

(GC method measurement conditions)

． Gas chromatograph: GC-2025 manufactured by Shimadzu Corporation

． Tubular string: DB-1 HT manufactured by Agilent, 30m in length, The inner diameter is 0.25mm and the film thickness is 0.1μm

． Mobile phase: Helium

． Detector: flame ionization detector (FID), 380 ° C

． Note entrance: split, 380 ℃

． Temperature: 100 ℃ → 380 ℃

(Calculation method)

From the peak area of the peak obtained by measuring the sample by the GC method, the EO addition mole distribution was calculated from the following formula.

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

<Evaluation>

About the liquid detergent of each reference example, the fluidity | liquidity of the liquid detergent was evaluated by the same evaluation method as an Example. The results are shown in Table 4.

According to the results shown in Tables 3 and 4, it is clear that the problem that liquid detergents tend to solidify at low temperatures below 0 ° C is the case when using sulfuric acid / alkaline earth metal catalysts to produce liquid detergents. A unique problem that arises can be solved by the invention of the present application in which a specific amount of a monohydric alcohol / diol is added.

In addition, even without adding a specific amount of monohydric alcohol / diol, the distribution of the alkylene oxide addition mole number does not change much compared with the case of adding a specific amount of monohydric alcohol / diol. . It is therefore clear: the use of a specific amount of monohydric alcohol / glycol to make Liquid detergents made from fatty acid alkyl ester alkoxylates become difficult to cure, not due to changes in the mole number distribution of the alkylene oxide addition.

[Industrial availability]

According to the present invention, by using an acid / alkaline earth metal compound catalyst to produce a fatty acid alkyl ester alkoxylate in a reaction system containing a specific amount of a monohydric alcohol / diol, it is possible to produce a fatty acid alkyl alkoxylate that is difficult to cure under low temperature A useful fatty acid alkyl ester alkoxylate as a washing ingredient for liquid detergents.

Claims (3)

A method for producing a fatty acid alkyl ester alkoxylate, comprising adding an alkylene oxide to a fatty acid alkyl ester represented by the general formula (I), wherein the fatty acid alkyl ester alkoxylate is of the general formula (II) Compound represented by), R ¹¹ COOR ¹² ... (I) In formula (I), R ¹¹ is a hydrocarbon group having 7 to 17 carbons, R ¹² is a linear alkyl group having 1 to 3 carbons, and R ¹¹ CO -(R ¹³ O) _m -OR ¹² ... (II) In formula (II), R ¹¹ is a hydrocarbon group having 7 to 17 carbons; R ¹² is a linear alkyl group having 1 to 3 carbons; R ¹³ O Is an oxyalkylene group having 2 to 4 carbon atoms; m represents an average repeating number of R ¹³ O, and is a number of 5 to 25; the method for producing the fatty acid alkyl ester alkoxylate includes the following steps: in alkaline earth metals Compound (B) and an alkoxylation catalyst obtained by reacting at least one acid (C) selected from the group consisting of sulfuric acid, hydrochloric acid and phosphoric acid in a liquid dispersion medium (A), and The fatty acid alkyl ester is 0.05 mol to 0.20 mol in the presence of at least one alcohol selected from the group consisting of a monovalent aliphatic alcohol and a divalent aliphatic alcohol, relative to 1 mol of the Addition of fatty acid alkyl esters from 5 mol to 25 mol Alkylene oxide; the molar ratio (C / B ratio) of the acid (C) to the alkaline earth metal compound (B) is 0.8 or more and less than 1. The method for producing a fatty acid alkyl ester alkoxylate according to item 1 of the scope of patent application, wherein the acid (C) has a molar ratio (C / B ratio) with respect to the alkaline earth metal compound (B). It is 0.9 ~ 0.98. The method for producing a fatty acid alkyl ester alkoxylate according to item 1 of the scope of the patent application, wherein the alcohol is a linear or branched monovalent aliphatic alcohol having 1 to 18 carbon atoms.