JP6469091B2 - Process for producing fatty acid alkyl ester alkoxylate - Google Patents

Description

The present invention relates to a method for producing a fatty acid alkyl ester alkoxylate.
This application claims priority on April 24, 2014 based on Japanese Patent Application No. 2014-090579 for which it applied to Japan, and uses the content here.

Fatty acid alkyl ester alkoxylates in which an alkylene oxide is added to a fatty acid alkyl ester are frequently used as a cleaning component of a liquid detergent.
Fatty acid alkyl ester alkoxylates are used as nonionic surfactants in clothing detergents and the like. Fatty acid alkyl ester alkoxylates are utilized as particularly suitable for concentrated liquid detergents containing a surfactant in a high concentration because the gelation region is small even when the concentration is high (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 the fatty acid alkyl ester in the presence of an alkoxylation catalyst.

In general, for alkoxylation reactions such as alcohols and amines that have active hydrogen such as hydrogen in the hydroxyl group in the molecule, as the alkoxylation catalyst, homogeneous catalysts such as acids and alkalis and / or heterogeneous metal oxides are used. System catalysts are used. However, addition reaction of alkylene oxide to fatty acid alkyl ester having no active hydrogen in the molecule (also referred to as alkoxylation reaction) does not proceed with an acid catalyst that is a homogeneous catalyst or an alkali catalyst such as sodium hydroxide. For this reason, a composite metal oxide catalyst or the like is used for the alkoxylation reaction. Examples of the composite metal oxide catalyst include aluminum-magnesium composite metal oxides such as an aluminum hydroxide / magnesium fired product (see Patent Document 2).
When the alkoxylation reaction of a fatty acid alkyl ester is performed using a composite metal oxide catalyst such as the above-described aluminum-magnesium composite metal oxide, a step such as filtration is required for removing the catalyst after the reaction. In addition, when a composite metal oxide catalyst such as the above-mentioned aluminum-magnesium composite metal oxide is used, a polymer (a molecule having a weight average molecular weight of 10,000 or more measured by gel permeation chromatography) during the reaction, polyalkylene glycol, etc. When the fatty acid alkyl ester alkoxylate containing such a by-product is used as a liquid detergent, there is a problem that the liquid detergent tends to become cloudy. Therefore, it is necessary to remove such by-products such as high molecular weight polyalkylene glycol together with the catalyst. However, this high molecular weight polyalkylene glycol or the like easily causes clogging of the filter cloth, resulting in a slow filtration speed. Therefore, a large amount of filtration equipment is required industrially, which increases the equipment burden on the operator. There is a problem.
Therefore, in the alkoxylation reaction of fatty acid alkyl ester, as a catalyst for reducing the amount of such by-products, alkaline earth metal salts of carboxylic acids, alkaline earth metal salts of hydroxycarboxylic acids, alkaline earth metal oxides and At least one alkaline earth metal compound selected from the group consisting of alkaline earth metal hydroxides and sulfuric acid react with each other in a liquid dispersion medium, and are represented by an acid / alkaline earth metal compound. An alkoxylation catalyst having a molar ratio of 0.8 to 1 has been proposed (see Patent Document 3). Hereinafter, a catalyst obtained by reacting such an alkaline earth metal compound and an acid in a liquid dispersion medium is referred to as an acid / alkaline earth metal compound catalyst.

International Publication No. 2011/007778 International Publication No. 2008/078768 International Publication No. 2013/154189 International Publication No. 2008/001797

However, as a result of the study by the present inventors, when the fatty acid alkyl ester alkoxylate obtained using the acid / alkaline earth metal compound catalyst described in Patent Document 3 is used as a liquid detergent, a low temperature condition of less than 0 ° C. Below, it has been found that the liquid detergent has the problem of being prone to solidification. The liquid detergent is desired to be kept in a liquid state without causing solidification or precipitation at a low temperature for use and storage in a cold region. Therefore, for example, the blending composition is set so as to maintain a liquid state in a storage test at −5 ° C. for 1 month.
Here, it is known that the distribution of the number of moles of ethylene oxide of the fatty acid alkyl ester alkoxylate used in the liquid detergent affects the viscosity of the liquid detergent (Patent Document 4).
On the other hand, according to the study by the present inventors, the problem that the liquid detergent is likely to solidify under a low temperature condition of less than 0 ° C. is that the fatty acid produced using the composite metal oxide catalyst for the production of the liquid detergent. It does not occur when an alkyl ester alkoxylate is used (see Comparative Example of the present application). However, as described above, when a composite metal oxide catalyst is used, there is a problem that a burden is imposed on filtration of the catalyst and by-products.
The present invention has been made in view of the above circumstances, and in producing a fatty acid alkyl ester alkoxylate, a fatty acid alkyl ester alkoxylate using the acid / alkaline earth metal compound catalyst in order to reduce the production of the by-product. It is an object of the present invention to provide a method for producing a fatty acid alkyl ester alkoxylate that is useful as a cleaning component of a liquid detergent that hardly causes solidification under low temperature conditions of less than 0 ° C.

As a result of intensive studies, the present inventors provide the following means in order to solve the above 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 in which an alkylene oxide is added to a fatty acid alkyl ester represented by the following general formula (I): 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 the liquid dispersion medium (A), and 0 per 1 kg of the fatty acid alkyl ester. 1 mol of the fatty acid alkyl ester in the presence of at least one alcohol selected from the group consisting of 0.05 to 0.20 mol of monohydric alcohol and dihydric alcohol (hereinafter also referred to as monohydric / dihydric alcohol). A step of adding 5 to 25 mol of the alkylene oxide to the alkaline earth, The molar ratio of metal compound wherein for (B) acid (C) is (C / B ratio), characterized in that it is a 1 less than 0.8 or more.
R ¹¹ COOR ¹² (I)
[In Formula (I), R ¹¹ is a hydrocarbon group having 7 to 17 carbon atoms, and R ¹² is a linear alkyl group having 1 to 3 carbon atoms. ]
In addition, the usage-amount of fatty-acid alkylester, monohydric / dihydric alcohol, and an alkylene oxide can be adjusted with manufacturing equipment etc., If it is said ratio, it will not be limited.
One aspect of the present invention is that the alkaline earth metal compound (B) and at least one acid (C) selected from the group consisting of sulfuric acid, hydrochloric acid and phosphoric acid are reacted in the liquid dispersion medium (A). A catalyst production process for producing an alkoxylation catalyst,
A catalyst dispersion step of mixing the catalyst and the fatty acid alkyl ester represented by the general formula (I);
An addition reaction step of adding 5 to 25 moles of alkylene oxide to 1 mole of the fatty acid alkyl ester to the reaction liquid obtained in the catalyst dispersion step;
The fatty acid alkyl ester alkoxylate comprising 0.05 to 0.20 moles of monohydric / dihydric alcohol to 1 kg of the fatty acid alkyl ester before the addition alkylene oxide is added. It is a manufacturing method.

  According to the method for producing a fatty acid alkyl ester alkoxylate of the present invention, by using a specific amount of monohydric / dihydric alcohol in a reaction system, liquid washing with good fluidity in which solidification under low temperature conditions is suppressed. Fatty acid alkyl ester alkoxylate useful as a cleaning component of the agent can be produced.

(Method for producing fatty acid alkyl ester alkoxylate)
The method for producing a fatty acid alkyl ester alkoxylate according to the present invention provides a fatty acid alkyl ester represented by the following general formula (I) in the presence of a specific alkoxylation catalyst and a specific amount of a monohydric / dihydric alcohol. Adding a specific amount of alkylene oxide.

<Fatty acid alkyl ester>
R ¹¹ COOR ¹² (I)
[In Formula (I), R ¹¹ is a hydrocarbon group having 7 to 17 carbon atoms, and R ¹² is a linear alkyl group having 1 to 3 carbon atoms. ]

In the formula (I), the lower limit of the carbon number of R ¹¹ is 7, 9 is more preferable, 11 is more preferable, the upper limit is 17, 15 is preferable, and 13 is more preferable. In the above formula ^(I), the carbon number of ^{R 11} is preferably 9 to 15, 11 to 13 is more preferable.
R ¹¹ may be linear or branched. R ¹¹ is preferably linear.
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 said formula (I), R < ¹² > is a C1-C3 linear alkyl group, and a C1-methyl group is preferable.

Specifically, fatty acid alkyl ester is preferably fatty acid methyl ester, or a mixture thereof, and more preferably methyl laurate, methyl myristate, or a mixture thereof.
Fatty acid alkyl ester may be used individually by 1 type, and 2 or more types may be used in combination.

<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 and the like are preferable, and among these, ethylene oxide is more preferable.
An alkylene oxide may be used individually by 1 type, and may be used in combination of 2 or more type.

<Specific amount of monohydric / dihydric alcohol>
The at least one alcohol selected from the group consisting of a specific amount of monohydric alcohol and dihydric alcohol (also referred to as monohydric / dihydric alcohol) may be a saturated alcohol or an unsaturated alcohol.
Specific amounts of monohydric / dihydric alcohols include propanols such as methanol, ethanol, 2-propanol, butanol, pentanol, hexanol, heptanol, n-octanol, octanol such as 2-ethylhexanol, nonanol, decanol, undecyl Monohydric alcohols such as alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, stearyl alcohol, isostearyl alcohol and oleyl alcohol; alkylene glycols such as ethylene glycol and propylene glycol; alkoxyalkylenes whose one end is alkoxylated Glycol and the like.
Among these, as the specific amount of monohydric / dihydric alcohol, monohydric alcohol is preferable, linear or branched monohydric alcohol having 1 to 18 carbon atoms is more preferable, and straight chain having 1 to 8 carbon atoms. A linear or branched monohydric alcohol is more preferable, and 2-propanol and 2-ethylhexanol are particularly preferable.
The specific amount of monohydric / dihydric alcohol may be used singly or in combination of two or more.

<Alkoxylation catalyst>
The alkoxylation catalyst in the present invention is an alkaline earth metal compound (B) (hereinafter also referred to as “component (B)”) and at least one acid (C) selected from the group consisting of sulfuric acid, hydrochloric acid, and phosphoric acid (hereinafter referred to as “the component (B)”). “(C) component”) reacts in the 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 reaction product of the component (B) and the component (C) (alkaline earth metal salt which is a main catalytic active component).
An alkoxylation catalyst may be used individually by 1 type, and may be used in combination of 2 or more type.

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

-(A) component: liquid dispersion medium (A) component can maintain the fluidity | liquidity of a reaction liquid, without gelatinizing, when manufacturing a catalyst ((alpha)), and in (A) component ( It will not specifically limit if B) component and (C) component can react.
The “liquid” in the component (A) means a liquid in the dispersion step and the mixing step described later.
The component (A) is preferably a liquid at 30 ° C. from the viewpoint of increasing productivity in the method for producing the catalyst (α) described later.

Examples of the component (A) include an alcohol represented by the following general formula (1), an alkylene oxide adduct of the alcohol represented by the above formula (1), and a fatty acid alkyl ester represented by the following general formula (2). , 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 an alkylene oxide adduct of a fatty acid represented by the formula (3) At least one selected from the above is preferred.
ROH (1)
[In Formula (1), R is a C3-C18 hydrocarbon group. ]
R ¹ COOR ² (2)
[In formula (2), ^{R 1} is a hydrocarbon group having 3 to 18 carbon atoms, ^{R 2} is a linear alkyl group having 1 to 3 carbon atoms. ]
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 of the carbon number of R is 3, the upper limit is 18, 12 is preferable, and 8 is more preferable. 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. When the carbon number of R is less than the lower limit, the component (A) thickens in a gel state and loses fluidity when the catalyst (α) is produced, and the component (B) and the component (C) hardly react. . When the carbon number of R exceeds the upper limit value, the melting point becomes high and it is not suitable as a dispersion medium.
R may be a straight chain or a branched chain.
R may be a saturated hydrocarbon group (alkyl group) or an unsaturated hydrocarbon group such as an alkenyl group.
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 a linear chain having 1 to 8 carbon atoms. More preferred are linear or branched monohydric alcohols. As the alcohol represented by the formula (1), the same alcohol as the specific amount of monohydric / dihydric alcohol can be used.
When the alcohol represented by the formula (1) is used as the component (A), the specific amount of monovalent / divalent alcohol in the production of the fatty acid alkyl ester alkoxylate includes alcohol derived from the component (A). Shall be.
Examples of the alcohol represented by the formula (1) include 1-hexanol, n-octanol, 2-ethylhexanol, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, and n-octadecanol. Examples include primary alcohols such as norol, oleyl alcohol, nonanol, undecanol, and tridecanol; secondary alcohols such as 2-propanol, 2-octanol, 2-decanol, and 2-dodecanol. Among these, 2-propanol and 2-ethylhexanol are preferable from the viewpoint of further reducing the amount of by-products such as high molecular weight polyethylene glycol.

In the alkylene oxide adduct of the alcohol represented by the formula (1), that is, the alcohol alkoxylate, the alkylene oxide added to the alcohol includes an alkylene oxide having 2 to 3 carbon atoms.
As for the average addition mole number of the alkylene oxide of the alkylene oxide addition product of alcohol represented by the said Formula (1), 1-7 are preferable, for example.

In the formula (2), R ¹ has 3 to 18 carbon atoms, and can be arbitrarily selected as long as it has good fluidity in the temperature conditions for producing the alkoxylation catalyst. In the formula (2), the number of carbon atoms in ^{R 1} is preferably 7 to 17, more preferably 9 to 15, 11 to 13 is more preferable.
R ¹ may be a straight chain or a branched chain. R ¹ is preferably linear.
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 above formula (2), R ² is a linear alkyl group having 1 to 3 carbon atoms, preferably a methyl group having one carbon atom. If R ² is a linear alkyl group having 1 to 3 carbon atoms, (A) melting component is low, the temperature conditions during the production of the alkoxylation catalysts, good fluidity.
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, or methyl oleate, or a mixture thereof, such as methyl laurate, myristic acid. Methyl or a mixture thereof is more preferable. As the fatty acid alkyl ester represented by the formula (2), it is preferable to use the same fatty acid alkyl ester as represented by the general formula (I) because components other than the target product are reduced.

In the alkylene oxide adduct of the fatty acid alkyl ester represented by the formula (2), that is, the fatty acid alkyl ester alkoxylate, the alkylene oxide to be added includes alkylene oxides having 2 to 3 carbon atoms.
As for the average addition mole number of alkylene oxide, 1-7 are preferable, for example.

In the formula (3), the number of carbon atoms of ^{R 3} is 3 to 18, preferably from 7 to 17, more preferably from 11 to 17. In the formula (3), the carbon number of R ³ can be arbitrarily selected as long as it has good fluidity in the temperature condition for producing the alkoxylation catalyst.
R ³ may be linear or branched.
R ³ may be a saturated hydrocarbon group (alkyl group) or an unsaturated hydrocarbon group such as an alkenyl group.
Examples of the fatty acid represented by the formula (3) include octanoic acid, decanoic acid, lauric acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, and the like, among which oleic acid is preferable.

In the alkylene oxide adduct of the fatty acid represented by the formula (3), the alkylene oxide to be added includes an alkylene oxide having 2 to 3 carbon atoms.
As for the average addition mole number of alkylene oxide, 1-7 are preferable, for example.

The component (A) is preferably an alcohol represented by the general formula (1) or a fatty acid alkyl ester represented by the general formula (2) from the viewpoint of further reducing the amount of by-products generated.
(A) A component may be used individually by 1 type and may be used in combination of 2 or more type.

-Component (B): 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) includes magnesium and beryllium in addition to calcium, strontium, barium and radium.
As the component (B), for example, an alkaline earth metal salt of a carboxylic acid (hereinafter also referred to as “component (b1)”), an alkaline earth metal salt of a hydroxycarboxylic acid (hereinafter also referred to as “component (b2)”), Alkaline earth metal oxides (hereinafter also referred to as “component (b3)”), alkaline earth metal hydroxides (hereinafter also referred to as “component (b4)”) and carbonic acid alkaline earth metal salts (hereinafter referred to as “( At least one selected from the group consisting of b5) component))) is preferred.

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

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

  Examples of the component (b3) include calcium oxide and barium oxide, and among these, calcium oxide is preferable.

  Examples of the component (b4) include calcium hydroxide and barium hydroxide, among which calcium hydroxide is preferable.

  Examples of the component (b5) include calcium carbonate and barium carbonate, among which calcium carbonate is preferable.

As the component (B), the components (b1) and (b3) are preferable, and the calcium salt and calcium oxide of carboxylic acid are more preferable, from the viewpoint of increasing the catalytic activity and further reducing the amount of by-products generated.
(B) A component may be used individually by 1 type and may be used in combination of 2 or more type.

-(C) component: acid (C) component in this invention is at least 1 sort (s) of acid chosen from the group which consists of a sulfuric acid, hydrochloric acid, and phosphoric acid.
Among the components (C), sulfuric acid is preferable from the viewpoint of stably expressing the catalytic activity. As sulfuric acid, concentrated sulfuric acid or dilute sulfuric acid may be used.

  The catalyst (α) uses, for example, a fatty acid alkyl ester represented by the general formula (2) as the component (A), a calcium salt or calcium oxide of carboxylic acid as the component (B), and sulfuric acid as the component (C). be able to.

[Production method of catalyst (α)]
Examples of the method for producing the catalyst (α) include a dispersion step of dispersing the component (B) in the component (A) to obtain a dispersion, and adding the component (C) to the dispersion (A) component. And a mixing step of mixing the component (B) and the component (C).

-Dispersion process In a dispersion process, the reactor provided with the mixing tank provided with the jacket and the stirring tank provided with the paddle stirring blade, for example is used. In a dispersion | distribution process, (A) component and (B) component are thrown in in a stirring tank, and these are stirred.
Although the temperature conditions in this process are not specifically limited, For example, it shall be normal temperature (5-35 degreeC). The temperature adjustment in the stirring tank is performed, for example, by passing a heat medium (for example, water) having an arbitrary temperature through the jacket.
The stirring time in this step is not particularly limited, and is a time during which the component (B) is dispersed substantially uniformly in the component (A). The stirring time in this step is, for example, 10 to 60 minutes. The term “substantially uniform” refers to a state in which it can be visually determined that the component (B) is free from lumps and the component (B) is uniformly dispersed.

..Mixing step In the mixing step, the component (C) is added to and mixed with the dispersion obtained in the dispersing step, and the reaction product of the component (B) and the component (C), that is, the main catalytically active component. An alkaline earth metal salt is produced to obtain an alkoxylation catalyst having a catalytically active component dispersed in component (A).
Although the mixing method in this process is not specifically limited, For example, the method of dripping (C) component in a dispersion is preferable, stirring the dispersion in a stirring tank.
10-60 degreeC is preferable and, as for the temperature conditions in this process, ie, reaction temperature, 20-50 degreeC is more preferable. The lower limit of the reaction temperature is preferably 10 ° C, more preferably 20 ° C, and the upper limit is preferably 60 ° C, more preferably 50 ° C. If it is less than the preferable lower limit, the reaction between the component (B) and the component (C) becomes too slow, and the production efficiency of the catalyst (α) may be lowered. If it exceeds the preferable upper limit, the catalytic activity of the resulting catalyst (α) may be lowered.
The reaction temperature is adjusted, for example, by passing a heat medium (for example, water) at an arbitrary temperature through the jacket.
The stirring time (that is, reaction time) in this step is a time during which the (B) component and the (C) component can sufficiently react and a time during which the exotherm accompanying the addition of the (C) component can be controlled. 1 to 2 hours. The stirring time in this step refers to the time after the addition of component (C).

The molar ratio (hereinafter also referred to as “C / B ratio”) represented by the component (C) / component (B) in the mixing step is preferably 0.8 or more and less than 1, more preferably 0.9 to 0.98. preferable. The C / B ratio preferably has a lower limit of 0.8, more preferably 0.9, and an upper limit of less than 1, more preferably 0.98.
When the C / B ratio is not less than the preferable lower limit, the resulting catalyst (α) can favorably reduce the amount of by-products generated in the fatty acid alkyl ester alkoxylate production process.
If the C / B ratio is 0.9 or more, in the method for producing a fatty acid alkyl ester alkoxylate, the distribution of the number of added moles of alkylene oxide of the obtained fatty acid alkyl ester alkoxylate can be easily widened.

The distribution of the number of added moles of the alkylene oxide of the fatty acid alkyl ester alkoxylate can be determined by a gas chromatography method (also referred to as GC method). The distribution of the number of moles of alkylene oxide added to the fatty acid alkyl ester alkoxylate is measured, for example, by measuring the fatty acid alkyl ester alkoxylate by a gas chromatography method (also referred to as GC method). It is a value obtained by adding up the areas of the maximum peak and the two peaks before and after it and dividing by the total peak area. When multiple types of fatty acid alkyl ester alkoxylates are included, for example, the value obtained by dividing the maximum peak of the peak derived from the obtained fatty acid alkyl ester alkoxylate and the sum of the areas of the two peaks before and after that by the total peak area And
In order to broaden the addition mole number distribution of the alkylene oxide, it is more preferable that the C / B ratio is 0.93 or more.
When the C / B ratio is not more than the above preferable upper limit, the catalytic activity of the resulting catalyst (α) is enhanced, and the fatty acid alkyl ester alkoxylate can be produced efficiently. If the C / B ratio is less than 1, the catalytic activity of the resulting catalyst (α) can be significantly increased.

The mass ratio represented by [(B) component + (C) component] / (A) component in this step (hereinafter also referred to as “(B + C) / A ratio”) is preferably 1/3 to 1. More preferably, it is 1 / 2.5-1 or less. The (B + C) / A ratio is preferably 1/3 as the lower limit, more preferably 1 / 2.5, and 1 as the upper limit.
If the (B + C) / A ratio is equal to or less than the preferable upper limit value, stirring can be easily performed, and the component (B) and the component (C) can be efficiently mixed. If the amount is less than the preferable lower limit, the content of the catalytically active component in the component (A) decreases, and when the fatty acid alkyl ester alkoxylate is produced, the amount of addition of the catalyst (α) increases so that it is inefficient. is there.

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

  Furthermore, you may raise the density | concentration of the catalyst active component in a catalyst ((alpha)) by filtering a catalyst ((alpha)), stationary separation, etc.

<Method for producing fatty acid alkyl ester alkoxylate>
Hereinafter, an embodiment of the method for producing a fatty acid alkyl ester alkoxylate of the present invention will be described.
The method for producing a fatty acid alkyl ester alkoxylate of the present embodiment is represented by the general formula (I) in the presence of a specific alkoxylation catalyst (catalyst (α)) and a specific amount of monohydric / dihydric alcohol. This is a method of adding 5 to 25 mol of alkylene oxide to 1 mol of fatty acid alkyl ester, and includes a production method having a catalyst dispersion step, an addition reaction step, and an aging step.

≪Catalyst dispersion process≫
The catalyst dispersion step is a step of dispersing the catalyst (α) in a mixture of the fatty acid alkyl ester represented by the general formula (I) as a starting material and a specific amount of monohydric / dihydric alcohol. In this step, the fatty acid alkyl ester, the catalyst (α), and a specific amount of monovalent / divalent alcohol are mixed.
In this step, for example, a stirred tank reactor is used.

In the catalyst dispersion step, the mixing ratio of the fatty acid alkyl ester to the monohydric / dihydric alcohol is such that the amount of monohydric / dihydric alcohol is 0.05 to 0.20 moles per 1 kg of the fatty acid alkyl ester. 06 mol or more and 0.10 mol or less are preferable. The lower limit of the amount of the monohydric / dihydric alcohol is 0.05 mol, preferably 0.06 mol, the upper limit is 0.20 mol, and 0.10 mol with respect to 1 kg of the fatty acid alkyl ester. Is preferred.
If the amount of monohydric / dihydric alcohol (mol) per 1 kg of fatty acid alkyl ester is not less than the above lower limit, fatty acid alkyl ester alkoxylates useful as a cleaning component of a liquid detergent having good fluidity under low temperature conditions are produced. it can. This effect reaches its peak when the upper limit is exceeded. If it is less than or equal to the upper limit, cost can be reduced. On the other hand, if it exceeds the upper limit value, the distribution of the number of added moles of alkylene oxide may become too narrow.

In addition, when using a catalyst ((alpha)), (A) component is brought in with a catalyst active component.
When the component (A) contains the fatty acid alkyl ester of the formula (I), the amount of the fatty acid alkyl ester of the starting material in this step includes the fatty acid alkyl ester corresponding to the formula (I) derived from the component (A). Shall be. That is, the total fatty acid alkyl ester amount of the fatty acid alkyl ester amount corresponding to the formula (I) derived from the component (A) and the fatty acid alkyl ester amount corresponding to the formula (I) newly added in the catalyst dispersion step. Is the amount of fatty acid alkyl ester starting material.
When the component (A) contains a monohydric / dihydric alcohol, the specific amount of monohydric / dihydric alcohol in this step includes the monohydric / dihydric alcohol derived from the component (A). . That is, the total amount of monohydric / dihydric alcohol including the amount of monohydric / dihydric alcohol derived from component (A) and the amount of monohydric / dihydric alcohol newly added in the catalyst dispersion step is 1 kg of fatty acid alkyl ester. It becomes 0.05-0.20 mol with respect to.

  The amount of catalyst added to the raw material can be defined from the amount of metal in the catalyst (α), and the amount of metal is preferably 0.01 to 0.25 mol, relative to 1 kg of the fatty acid alkyl ester of the raw material, and 0.02 mol to 0. .10 mole is more preferred.

≪Addition reaction process≫
The addition reaction step is carried out in the presence of a specific alkoxylation catalyst (catalyst (α)) and a specific amount of monohydric / dihydric alcohol with respect to 1 mol of the fatty acid alkyl ester represented by the general formula (I). In this step, 5 to 25 mol of an oxide is added to obtain a fatty acid alkyl ester alkoxylate. This step includes a step of performing an operation (condition setting operation) for setting an arbitrary temperature and pressure condition for the addition reaction, and then a fatty acid alkyl ester, a catalyst (α), and a specific amount of monohydric / dihydric alcohol. And a step of performing an operation (AO contact operation) of bringing the mixture into contact with an alkylene oxide (hereinafter sometimes referred to as AO).

Process for setting conditions:
In this step, appropriate temperature and pressure conditions for the addition reaction are set. The temperature condition (addition reaction temperature) for the addition reaction is preferably, for example, 150 to 180 ° C, and more preferably 160 to 180 ° C.
The pressure condition for the addition reaction is appropriately determined in consideration of the addition reaction temperature. For example, 0.1 to 1 MPa is preferable, and 0.1 MPa to 0.6 MPa or less is more preferable. The lower limit of the pressure condition is preferably 0.1, and the upper limit is preferably 1 MPa, more preferably 0.6 MPa.

Process for performing AO contact operation:
In this step, the alkylene oxide is brought into contact with the mixture of the fatty acid alkyl ester obtained in the catalyst dispersion step, the catalyst (α) and a specific amount of monohydric / dihydric alcohol. In the AO contact operation, the amount of AO introduced with respect to 1 mol of the fatty acid alkyl ester represented by the general formula (I) is 5 to 25 mol, and preferably 10 to 20 mol. The lower limit of the amount of AO introduced is 5 mol, preferably 10 mol, the upper limit is 25 mol, and 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.

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

In addition to the catalyst dispersion step, the addition reaction step, and the aging step, the production method of the present embodiment may include a purification step that removes the catalytically active component remaining in the fatty acid alkyl ester alkoxylate, if necessary. Good. Examples of the method for removing the catalytically active component include water washing, centrifugation, filtration, and the like.
Among these, it is preferable to perform water washing and centrifugation.
In the purification step, for example, the reaction product obtained in the aging step is dissolved by heating to 70 to 120 ° C., 5 to 30 parts by mass of purified water is added to 100 parts by mass of the reaction product, and 30 to 120 minutes. Stir. Subsequently, it cools to 50-70 degreeC, and also stirs for 30-120 minutes. Thereafter, the catalytically active component is removed by centrifugation.

In the production method of the present embodiment described above, the total amount of the specific amount of monohydric / dihydric alcohol is blended in the catalyst dispersion step. However, the present invention is not limited to this, and the specific amount is determined by the condition setting operation in the addition reaction step. The total amount of the monohydric / dihydric alcohol may be blended; a part of the specific monohydric / dihydric alcohol is blended in the catalyst dispersion step, and the remaining monohydric / dihydric alcohol is used in the conditions for the addition reaction You may mix | blend by setting operation.
In any 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 / dihydric alcohol is 1 with respect to 1 kg of the fatty acid alkyl ester. The amount of valence / 2 dihydric alcohol is adjusted to 0.05 to 0.20 mol.

  In the method for producing a fatty acid alkyl ester alkoxylate of the present invention, 0.05 to 0.20 mol of monovalent / 2 with respect to 1 kg of the specific alkoxylation catalyst and the fatty acid alkyl ester represented by the general formula (I). In the presence of a monohydric alcohol, 5 to 25 mol of alkylene oxide is added to 1 mol of the fatty acid alkyl ester represented by the general formula (I). Thus, according to such a production method, the addition reaction step is performed in the presence of a specific amount of monohydric / dihydric alcohol, so that it is useful as a washing component of a liquid detergent having good fluidity under low temperature conditions. Fatty acid alkyl ester alkoxylates can be produced.

(Fatty acid alkyl ester alkoxylate)
The fatty acid alkyl ester alkoxylate represented by the following general formula (II) is preferably produced by the production method of the present invention.
_{^{R 11 CO- (R 13 O)}} m -R 12 ··· (II)
[In Formula (II), R ¹¹ is a hydrocarbon group having 7 to 17 carbon atoms. R ¹² is a linear alkyl group having 1 to 3 carbon atoms. R ¹³ O is an oxyalkylene group having 2 to 4 carbon atoms. m represents the average repeating number of R < ¹³ > O and is a number of 5-25.

In the formula (II), R ¹¹ and R ¹² are the same as R ¹¹ and R ¹² in the formula (I), respectively.
R ¹³ O is an oxyethylene group, an oxypropylene group or an oxybutylene group. (R ¹³ O) _m may be a mixture of two or more oxyalkylene groups among oxyethylene group, oxypropylene group and oxybutylene group. When two or more types of oxyalkylene groups are mixed, the oxyalkylene groups may be mixed in a block shape or may be mixed in a random shape. Among these, an oxyethylene group is preferable as the oxyalkylene group.
m is a number from 5 to 25, and a number from 9 to 20 is preferable. Note that m represents the “average” number of repetitions of the oxyalkylene group. That is, the compound represented by the general formula (II) is an aggregate of molecules having different oxyalkylene group repeating numbers. In addition, the fatty acid alkyl ester alkoxylate produced by the method of the present invention may be an assembly of different molecules of R ¹¹ . R ¹¹ or R ¹² of each molecule of each molecule constituting the molecular assembly may be the same or different.

  The fatty acid alkyl ester alkoxylate produced by the above production method is useful as a cleaning component of a liquid cleaning agent, and a liquid cleaning agent containing this as a cleaning component has good fluidity under low temperature conditions.

(Liquid cleaning agent)
The fatty acid alkyl ester alkoxylate produced by the production method of the present invention is suitably used for 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 for household and industrial uses, and is suitable as a liquid detergent for clothing, and has a surfactant concentration. It is particularly suitable as a high concentration type liquid detergent for clothing.

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 with respect 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 not less than the preferable lower limit, fluidity under low temperature conditions is increased. In addition, the detergency against dirt increases. On the other hand, if it is below the said preferable upper limit, the viscosity increase of the liquid cleaning agent under low temperature conditions will be suppressed more.

  Other components contained in the liquid detergent include, for example, surfactants, chelating agents, alkaline agents, antioxidants, enzymes, enzyme stabilizers, thickeners or solubilizers, preservatives, metal oxides or Metal salts, texture improvers, optical brighteners, anti-staining agents, soil release agents, pearling agents, bleaching agents, flavoring agents, coloring agents, emulsifying agents, natural product extracts, pH adjusters, etc. Can be used.

  The liquid detergent containing the fatty acid alkyl ester alkoxylate produced by the production method of the present invention hardly causes solidification under low temperature conditions and has good fluidity. For this reason, such a liquid cleaning agent can be sold and used in a wide area as a product on the market.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example. In the examples, “%” means “% by mass” unless otherwise specified.
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 Chemical Co., Ltd.

-Alkylene oxide Ethylene oxide: manufactured by Air Water Co., Ltd.

-Alkoxylation catalyst The catalyst ((alpha) -1) ((alpha) -2) ((alpha) -3) ((alpha) -4) ((beta)) synthesize | combined with the below-mentioned manufacturing method.

Monovalent / divalent alcohol 2-EH: 2-ethylhexanol, reagent, manufactured by Junsei Chemical Co., Ltd.
2-PrOH: 2-propanol, primary reagent, manufactured by Kanto Chemical Co., Inc.

-Blending component of liquid detergent a-1-1 to a-1-12: Fatty acid alkyl ester alkoxylate (fatty acid methyl ester ethoxylate (MEE) produced by the production methods of Examples 1 to 7 and Comparative Examples 1 to 5 ), EO average added mole number 15). A mixture of R ¹¹ in the general formula (II) having an alkyl group having 11 carbon atoms and an alkyl group having 13 carbon atoms. In the formula (II), compounds wherein R ¹² is a methyl group, R ¹³ O is an oxyethylene group, and m is 15.

a-2: A product obtained by adding an average of 15 moles of ethylene oxide to natural alcohol CO-1217 (trade name) manufactured by P & G.
[Synthesis of a-2]
In a pressure-resistant reaction vessel, 224.4 g of natural alcohol CO-1270 manufactured by P & G and 2.0 g of 30% by mass NaOH aqueous solution were collected, and the inside of the reaction vessel was purged with nitrogen. Next, 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, while stirring, 760.4 g of ethylene oxide (gaseous) was gradually added to the alcohol liquid while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C. using a blowing tube. After completion of the addition of ethylene oxide, aging was performed at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes. Thereafter, unreacted ethylene oxide was distilled off at a temperature of 180 ° C. and a pressure of 6.0 kPa or less for 10 minutes. Next, after cooling to a temperature of 100 ° C. or lower, neutralization was performed by adding 70% by mass p-toluenesulfonic acid so that the pH of the 1% by mass aqueous solution of the reaction product was about 7, thereby obtaining a-2. .

b-1: Isogo fatty acid, manufactured by NOF Corporation.
e-1: Trisodium methylglycine diacetate (MGDA), trade name “Trilon M”, manufactured by BASF Corporation.
Protease: Trade name “Coronase 48L”, manufactured by Novozymes.
SR agent: Soil release agent, trade name “TexCare SRN-170C”, manufactured by Clariant Japan.
LAS-H: linear alkylbenzene sulfonic acid, trade name “Lypon LH-200”, manufactured by Lion Corporation.
MEA: Monoethanolamine, manufactured by Nippon Shokubai Co., Ltd.
BHT: dibutylhydroxytoluene, trade name “SUMILZER BHT-R”, manufactured by Sumitomo Chemical Co., Ltd.
Citric acid: trade name “citric acid”, manufactured by Kanto Chemical Co., Inc.
Ethanol: trade name “specific alcohol 95 degree synthesis”, manufactured by Nippon Alcohol Sales Co., Ltd.
Sodium lactate: trade name “sodium lactate”, manufactured by Kanto Chemical Co., Inc.
Fragrance | flavor: The fragrance | flavor composition A of Tables 11-18 of Unexamined-Japanese-Patent No. 2002-146399.
Dye: Green No. 3, trade name “Green No. 3”, manufactured by Sakai 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: fatty acid methyl ester mixed solution of lauric acid methyl ester and myristic acid methyl ester, trade name: Pastel M124, manufactured by Lion Chemical Co., Ltd.
Alkaline earth metal compound: calcium acetate monohydrate, special grade reagent, manufactured by Kanto Chemical Co., Inc.
Calcium oxide, special grade reagent, Wako Pure Chemical Industries, Ltd. Barium oxide, special grade reagent, Wako Pure Chemical Industries, Ltd. sulfuric acid: special grade reagent, concentration 96 mass%, manufactured by Kanto Chemical Co., Inc.

By mixing the alkaline earth metal compound and sulfuric acid in a liquid dispersion medium, the catalyst (α-1), the catalyst (α-2), the catalyst (α-3), the catalyst (α -4) and a catalyst (β) were produced. The C / B ratios of the catalyst (α-1), the catalyst (α-2), the catalyst (α-3), the catalyst (α-4), and the catalyst (β) are 0.90, 0.96, and 0.90, respectively. 0.90, 0.67, and the (B + C) / A ratio is 0.46, 0.47, 0.41, 0.40, 0.42. In addition, the compounding quantity of each following component is a pure conversion value.
Production Method of Catalysts (α-1), (α-2), (β) Specifically, a fatty acid methyl ester mixed solution and calcium acetate monohydrate are placed in a 500 mL beaker, and room temperature ( 25 ° C.) to obtain a dispersion (dispersing step).
While stirring this dispersion, 96 mass% sulfuric acid was added over 10 minutes with a dropping funnel and mixed (mixing step). In the mixing step, heat was generated by the addition of sulfuric acid, so the beaker was cooled in a water bath and stirred for 1 hour while controlling the reaction temperature at 20 to 50 ° C.
After adding sulfuric acid, the mixture was further stirred for 2 hours while maintaining the temperature at 20 to 50 ° C. to obtain an alkoxylation catalyst (catalyst (α-1), catalyst (α-2), catalyst (β)) (catalyst aging). Process).
Method for producing catalyst (α-3)

Specifically, the fatty acid methyl ester mixed solution and calcium oxide were put into a 500 mL beaker and mixed at room temperature (25 ° C.) with a paddle stirring blade to obtain a dispersion (dispersing step).
While stirring this dispersion, sulfuric acid diluted to 76% with a dropping funnel was added over 10 minutes and mixed (mixing step). In the mixing step, heat was generated by the addition of sulfuric acid, so the beaker was cooled in a water bath and stirred for 1 hour while controlling the reaction temperature at 20 to 50 ° C.
After adding sulfuric acid, the mixture was further stirred for 2 hours while maintaining the temperature at 20 to 50 ° C. to obtain an alkoxylation catalyst (catalyst (α-3)) (catalyst aging step). Production method of catalyst (α-4) A catalyst (α-4) was obtained by the same production method as the catalyst (α-3) except that barium oxide was used instead of calcium oxide.
The amount of the compound used is as shown in Table 1.

<Production of fatty acid alkyl ester alkoxylate>
(Examples 1-7, Comparative Examples 3-5)
In an autoclave, 12.5 g of the alkoxylation catalyst (catalyst (α-1), catalyst (α-2), catalyst (α-3), catalyst (α-4), or catalyst (β)) obtained above, After adding 462 g of the methyl laurate and 166 g of the methyl myristate, a predetermined amount of monovalent / divalent alcohol shown in Table 1 was added and stirred at room temperature (20 ° C.) (catalyst dispersion step). .
While stirring, nitrogen substitution in the autoclave was performed. Then, it heated up to ethylene oxide (EO) addition reaction temperature (160 degreeC), and adjusted the pressure to 0.1-0.5 MPa (condition setting operation). Then, under such temperature and pressure conditions, 1876 g of ethylene oxide (EO) (15 times the total of methyl laurate and methyl myristate) was introduced, and the reaction was allowed to proceed with stirring (EO contact operation) (above) , Addition reaction step).
Subsequently, it stirred at the said EO addition reaction temperature for 0.5 hour (ripening process). Thereafter, the reaction mixture was cooled to 80 ° C. to obtain 2516 g of a crude reaction product.
Subsequently, 29.3 g of purified water was added to 250 g of the reaction crude product dissolved by heating to 80 ° C., and stirred for 30 minutes while maintaining 80 ° C. Subsequently, it cooled to 50 degreeC and stirring was further continued for 30 minutes. Thereafter, the catalyst and aggregates were removed by centrifugation, and purification was performed (purification step).
By the above manufacturing method, the target fatty acid methyl ester ethoxylate (MEE) a-1-1-1 to a-1-7 and a-1-10 to a-1-12 were obtained, respectively.

(Comparative Example 1)
The target fatty acid alkyl ester alkoxylate a-1-8 was obtained in the same manner as in Example 1 except that no monohydric or dihydric alcohol was added.

(Comparative Example 2)
An average of 15 moles of ethylene oxide added to 2-ethylhexanol (2-EO H15EO adduct) was synthesized.
The alkoxylation catalyst (α-1) obtained above was filtered and thoroughly 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 alkoxylation catalyst obtained above and 285 g of 2-ethylhexanol were added, followed by stirring at room temperature (20 ° C.).
While stirring, nitrogen substitution in the autoclave was performed. Then, it heated up to ethylene oxide (EO) addition reaction temperature (160 degreeC), and adjusted the pressure to 0.1-0.5 MPa (condition setting operation). Subsequently, 1447 g of ethylene oxide (EO) (15-fold mol of 2-ethylhexanol) was introduced under such temperature and pressure conditions, and the reaction was allowed to proceed while stirring.
Subsequently, it stirred at the said EO addition reaction temperature for 0.5 hour. Thereafter, the reaction mixture was cooled to 80 ° C. to obtain 1734 g of a crude reaction product.
Next, 250 g of the reaction crude product dissolved by heating to 50 ° C. was filtered to remove the catalyst, and purification was performed to obtain a 15EO adduct of 2-EH.
Subsequently, the fatty acid alkyl ester alkoxylate produced by the production method of Comparative Example 1 was mixed with 0.06 mol of 2-EO H15EO adduct with respect to 1 kg of the fatty acid alkyl ester alkoxylate (of 2-EH). 15EO adduct was added later) to obtain a-1-9.

<Manufacture of liquid detergent>
(Test Example 1)
According to the composition shown in Table 2, 1000 g of a liquid detergent was produced by a conventional method (when there is an unblended component, the component is not blended).

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

The unit of the blending amount in Table 2 is mass%, and all the components indicate the amount equivalent to pure content. In addition, the liquid cleaning agent of each example was prepared by balancing with the remainder of water so that the total of each component described in the table was 100% by mass.
In the liquid cleaning agent of each example, the pH at 25 ° C. was adjusted to 7.0 by adding an appropriate amount of a pH adjusting agent. The pH of the liquid detergent is adjusted to 25 ° C., and a glass electrode type pH meter (product name HM-30G, manufactured by Toa DKK Corporation) is used to immerse the glass electrode directly in the liquid detergent. And the value shown after 1 minute passed was measured.

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

[Evaluation of fluidity of liquid detergent]
100 mL of the liquid cleaning agent of each example was taken in a transparent glass bottle (wide-mouth standard bottle PS-NO.11), and the lid was closed and sealed. In this state, the sealed glass bottle was allowed to stand in a thermostatic bath at −5 ° C. and stored for 1 month.
After such storage, the glass bottle is taken out from a -5 ° C constant temperature bath, the glass bottle stored at -5 ° C is tilted horizontally, the change in the liquid level is visually observed, and based on the following evaluation criteria. The fluidity of the liquid detergent was evaluated.
Evaluation criteria A: The liquid level became horizontal within 10 seconds after the glass bottle was tilted horizontally.
B: It took more than 10 seconds for the liquid level to become horizontal after the glass bottle was tilted horizontally.
C: No fluidity was observed at all because of solidification.

From the results shown in Table 2, the liquid detergents of Test Examples 1 to 7 containing fatty acid alkyl ester alkoxylates produced by the production methods of Examples 1 to 7 to which the present invention is applied have fluidity under low temperature conditions. It was confirmed that it was good.
In addition, it was confirmed that the fatty acid alkyl ester alkoxylate produced by the production method of Examples 1 to 7 to which the present invention was applied was useful as a cleaning component of the liquid detergent.

Hereinafter, a liquid detergent using a fatty acid alkyl ester alkoxylate produced with a sulfuric acid / alkaline earth metal catalyst and a liquid detergent using a fatty acid alkyl ester alkoxylate produced with the composite metal oxide catalyst at a low temperature The solidification property is described with reference to examples and comparative examples.

(Example 3, Test Example 3)
For comparison, Example 3 in which a fatty acid alkyl ester alkoxylate was produced with a sulfuric acid / alkaline earth metal catalyst and a test example produced using the fatty acid alkyl ester alkoxylate a-1-3 obtained in Example 3 Table 3 and Table 4 show the three liquid cleaning agents. The addition mole number distribution of ethylene oxide measured by the following GC method of fatty acid alkyl ester alkoxylate a-1-3 was 54%.

(Comparative Example 6, Test Example 13) Liquid detergent using a fatty acid alkyl ester alkoxylate produced by a composite metal oxide catalyst (Comparative Example 6) A fatty acid alkyl ester alkoxylate was produced by a composite metal oxide catalyst.
Aluminum hydroxide-magnesium having a chemical composition consisting of _{2.5MgO · Al 2 O 3 · mH} 2 O ( manufactured by Kyowa Chemical Industry Co., Ltd., Kyowaad 300) to 900 ° C. for 3 hours calcined to magnesium aluminum composite metal oxide catalyst A powder (catalyst γ) was obtained.
In a 2000 kL stirred reaction vessel, methyl laurate (Lion Chemical Co., Ltd., Pastel M12) 184.1 kg (859 mol), methyl myristate (Lion Chemical Co., Ltd., Pastel M14) 66.0 kg (272 mol), After adding 1.00 kg of the composite metal catalyst and 1.25 kg of glycerin as a polyhydric alcohol, 0.05 kg of potassium hydroxide was added, and the mixture was stirred for 10 minutes to carry out alkali modification treatment of the catalyst. Thereafter, while stirring and mixing, the inside of the reaction vessel was purged with nitrogen, heated to 100 ° C., and dehydrated under reduced pressure conditions of 1.3 kPa or less for 30 minutes. Subsequently, it heated up to 180 degreeC and 747.6 kg (16972 mol, 15 times mole of fatty acid methyl ester) of ethylene oxide was introduce | transduced on the conditions whose pressure upper limit is 0.49 MPa. After further aging reaction for 0.5 hour, the reaction mixture was cooled to 80 ° C. and extracted, 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 fatty acid alkyl ester alkoxylate a-1-13 had an average ethylene oxide addition mole number of 15, and the ethylene oxide addition mole number distribution measured by the following GC method was 54%. Further, the fatty acid alkyl ester alkoxylate a-1-13 contained 0.9% by weight of polyethylene glycol as a by-product.
(Test Example 13) A liquid cleaning agent 1000 g was produced in the same manner as in Example 1 except that the fatty acid methyl ester ethoxylate (MEE) was changed from a-1-1 to a-1-13.

(Comparative Example 7, Test Example 14) Liquid detergent using a fatty acid alkyl ester alkoxylate produced by a sulfuric acid / alkaline earth metal catalyst without adding a specific amount of mono- or dihydric alcohol (Comparative Example 7) In the production of fatty acid alkyl ester alkoxylate, the fatty acid alkyl ester was used except that 0.06 mol of glycerin was added to 1 kg of fatty acid alkyl ester without adding isopropanol used as a specific amount of monohydric / dihydric alcohol. Fatty acid alkyl ester alkoxylate a-1-14 was produced in the same manner as Example 3 in which alkoxylate a-1-3 was produced. The fatty acid alkyl ester alkoxylate a-1-14 had an average ethylene oxide addition mole number of 15, and the ethylene oxide addition mole number distribution measured by the following GC method was 54%.
(Test Example 14) A liquid cleaning agent 1000 g was produced in the same manner as in Example 1 except that the fatty acid methyl ester ethoxylate (MEE) was changed from a-1-1 to a-1-14.

[Measurement and calculation of added mole number distribution of alkylene oxide by gas chromatography]
The distribution of the number of moles of ethylene oxide added in the reaction crude product (also referred to as EO addition mole distribution) was determined by a gas chromatography method (also referred to as GC method).
The reaction sample was diluted with acetone so that the fatty acid alkyl ester alkoxylate concentration was 1% solution, and prepared 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 GC area%) is calculated by the following calculation method. The smaller the value of the EO added mole number distribution, the wider the EO added mole number distribution.
(Measurement conditions for the GC method)
-Gas chromatograph: GC-2025 manufactured by Shimadzu Corporation
Column: Agilent DB-1HT, length 30 m, inner diameter 0.25 mm, film thickness 0.1 μm
-Mobile phase: Helium-Detector: Hydrogen flame ion detector (FID), 380 ° C
・ Inlet: 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 molar distribution was calculated from the following formula.
{(Area of maximum peak (P1) derived from lauric acid methyl ester alkoxylate) + (total area of two peaks before and after maximum peak P1) + (area of maximum peak (P2) derived from myristic acid methyl ester alkoxylate) ) + (Total area of two peaks before and after the maximum 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 evaluation method similar to an Example. The results are shown in Table 4.

From the results shown in Tables 3 and 4, the problem that the liquid detergent tends to solidify under a low temperature condition of less than 0 ° C. is a characteristic that occurs when the liquid detergent is produced using a sulfuric acid / alkaline earth metal catalyst. It has become a problem, and it has become clear that this problem is solved by the present invention in which a specific amount of monohydric / dihydric alcohol is added.
Further, even when a specific amount of monohydric / dihydric alcohol was not added, the distribution of the number of added alkylene oxides was not significantly different from that when a specific amount of monohydric / dihydric alcohol was added. Therefore, it is difficult to solidify the liquid detergent using the fatty acid alkyl ester alkoxylate prepared by adding a specific amount of monohydric / dihydric alcohol because it is not due to a change in the distribution of the number of added alkylene oxides. It became clear.

  According to the present invention, fatty acid alkyl ester alkoxylate is produced in a reaction system containing an acid / alkaline earth metal compound catalyst and containing a specific amount of monohydric / dihydric alcohol, so that it is difficult to solidify under low temperature conditions. Fatty acid alkyl ester alkoxylates useful as cleaning components for liquid detergents can be produced.

Claims (3)

In the method for producing a fatty acid alkyl ester alkoxylate in which an alkylene oxide is added to a fatty acid alkyl ester represented by the following general formula (I):
An alkoxylation catalyst obtained by 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 the liquid dispersion medium (A); In the presence of at least one alcohol selected from the group consisting of 0.05 to 0.20 mol of monohydric alcohol and dihydric alcohol with respect to 1 kg of ester, the alkylene oxide with respect to 1 mol of the fatty acid alkyl ester. Adding 5 to 25 moles,
The manufacturing method of the fatty-acid alkylester alkoxylate whose molar ratio (C / B ratio) of the said acid (C) with respect to the said alkaline-earth metal compound (B) is 0.9 or more and less than 1.
R ¹¹ COOR ¹² (I)
[In Formula (I), R ¹¹ is a hydrocarbon group having 7 to 17 carbon atoms, and R ¹² is a linear alkyl group having 1 to 3 carbon atoms. ] The molar ratio of the acid (C) with respect to the alkaline earth metal compound (B) is (C / B ratio), the production of fatty acid alkyl ester alkoxylates according to 0.9-0.98 der Ru請 Motomeko 1 Method. The alcohol production method of the fatty acid alkyl ester alkoxylates according to 請 Motomeko 1 Ah Ru monovalent alcohols linear or branched 1 to 18 carbon atoms.