JPH10137592A - Catalyst for production of ester alkoxylate and production of ester alkoxylate by using this catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce an ester alkoxylate with little amt. of unreacted source material and by-products with a high reaction rate and high yield by using a catalyst containing an org. acid salt of alkali metal, alkaline-earth metal or rare earth metal and multiple metal oxide of MgO and Al2 O3 . SOLUTION: This catalyst is used for the production of ester alkoxylate having one group expressed by -COO(AO)m R which is produced by adding 2 to 4C alkylene oxide to an ester compd. having one group expressed by -COOR. The catalyst is prepared by incorporating on org. acid salt of alkali metal, alkaline-earth metal or rate earth metal and a multiple metal oxide of MgO and Al2 O3 . In the formula, R is a residue of alcohol or phenol from which one hydroxyl group is removed, A is 2 to 4C alkylene group, and (m) As may be same different, and (m) is the average moles of the alkylene oxide added.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a catalyst used for producing a high-quality ester alkoxylate by adding an alkylene oxide to an ester compound and incorporating the alkylene oxide directly into the ester, and a catalyst used for producing the same. The present invention relates to a method for producing the used ester alkoxylate.

[0002]

BACKGROUND OF THE INVENTION Ester alkoxylates, ie, alkoxylated esters of carboxylic acids, are known for their use in surfactants and other applications. Even if this ester alkoxylate reacts an alkylene oxide with a carboxylic acid ester in the presence of an alkali catalyst or an acid catalyst, the addition polymerization reaction of the alkylene oxide does not proceed at all. After the production of the ether, a two-step reaction by esterification of the polyoxyalkylene alkyl ether with the carboxylic acid is employed.

As a method for producing an ester alkoxylate by a one-step reaction between a carboxylic acid ester and an alkylene oxide, there are the following examples. 1) JP-B-53-24930: zinc, aluminum,
A method for producing an ester alkoxylate from an alkylene oxide and an organic carboxylic acid ester by using a combination of a halide of titanium, tin or iron or an organometallic compound or an amine compound as a catalyst. 2) JP-T-4-505449: Saturated or unsaturated fatty acid alkyl (C _1-
C ₄₎ ester or a method of alkoxylated glycerides of mono-hydroxyl substituted saturated or unsaturated fatty acids. 3) JP-T-6-502139: Hydrophobized double-layered hydroxylated compound, a method for producing the compound by reacting a double-layered hydroxylated compound with a mono- and / or dicarboxylic acid in an organic solvent or a kneader is shown. And use as a catalyst for the alkoxylation of carboxylic acid esters. 4) Japanese Patent Publication No. 6-88944: Trivalent Al, Ga, I
Method for producing ester alkoxylate from fatty acid alkyl ester and alkylene oxide using magnesium oxide catalyst to which at least one metal ion selected from n, Tl, Co, Sc, La ion and divalent Mn ion is added .

[0004] However, in the above method 1), the reaction proceeds while the catalyst is dissolved in the reaction system, and it has been industrially difficult to separate the target substance from the catalyst. In the methods 2) to 4), the target product can be obtained in high yield, but the addition mole number distribution of the alkylene oxide in the product is not necessarily in a narrow range (Narro).
w Range), but there is a problem that a large amount of unreacted carboxylic acid ester is present in the target product.

[0005] Therefore, 5) JP-A-8-169860 and JP-A-8-169861 disclose MgO- having a surface modified with an alkali metal or alkaline earth metal hydroxide or alkoxide such as sodium hydroxide and sodium alkoxide. A method for producing a fatty acid ester alkoxylate having a relatively narrow range using an Al ₂ O ₃ composite metal oxide is exemplified. However, even in this case, if the unreacted raw material remains in the form of an alkylene oxide 6 mol adduct in an amount of 1 to 3% by weight and the odor of the ester alkoxylate is affected even if a small amount of the unreacted raw material remains, Not always satisfactory.

Accordingly, an object of the present invention is to provide an ester which has a very narrow alkylene oxide addition molar distribution which cannot be obtained by using a conventional catalyst, and which contains little unreacted raw material and by-products. An object of the present invention is to provide a method for producing an alkoxylate with a high reaction rate and a high yield, and a catalyst used in the method.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that they contain an organic acid salt of an alkali metal, an alkaline earth metal or a rare earth metal, and a composite metal oxide of MgO and Al ₂ O _3. The inventors have found that the above problem can be solved by using a catalyst, and have completed the present invention.

That is, the present invention provides an ester compound having at least one group represented by the following general formula (I) to which an alkylene oxide having 2 to 4 carbon atoms is added.
A catalyst used for producing an ester alkoxylate having at least one group represented by (II), comprising an organic acid salt of an alkali metal, an alkaline earth metal or a rare earth metal [first component]; And a composite metal oxide [second component] of Al ₂ O ₃ and a catalyst for producing an ester alkoxylate, and a method for producing an ester alkoxylate using the catalyst. Things.

-COOR (I) -COO (AO) _m R (II) wherein R represents a residue obtained by removing one hydroxyl group from alcohol or phenol. A: represents an alkylene group having 2 to 4 carbon atoms, and m A's may be the same or different. m: a number indicating the average number of added moles of alkylene oxide. ]

[0010]

Embodiments of the present invention will be described below in detail.

[Catalyst] The catalyst used in the present invention is an organic acid salt of an alkali metal, an alkaline earth metal or a rare earth metal [first component], a composite metal oxide of MgO and Al ₂ O ₃ [second component ] Is contained.

The organic acid constituting the organic acid salt of the first component means the entire organic compound having acidity as described in the Chemical Dictionary 9 published by Kyoritsu Shuppan Co., Ltd. It refers to monovalent or polyvalent carboxylic acids, sulfonic acids, phenols and the like.

When the above-mentioned first component and second component are used alone as catalysts when producing the ester alkoxylate, the ester alkoxylate obtained has a broad alkylene oxide addition mole number distribution, but the first component and the second component are mixed. By using a combination of the two components, an ester alkoxylate with a very narrow distribution can be obtained at a high reaction rate.

The organic acid salt of an alkali metal, alkaline earth metal or rare earth metal as the first component used in the present invention includes alkali metals such as Na and K, alkaline earth metals such as Mg, Ca and Ba, and the like. Or a fatty acid salt of a rare earth metal such as Y or La, and preferably a fatty acid salt having 1 to 22 carbon atoms.
Of these, fatty acid salts of alkaline earth metals are particularly preferred, and barium fatty acids such as barium laurate are more preferred.

The second component used in the present invention comprises MgO and Al
A composite metal oxide of the ₂ O _3, but as the complex metal oxide, natural or synthetic hydro formula _{Mg a · Al b · (OH} ) x · (CO 3) y · zH 2 O Talcite (Kyowa Chemical Co., Ltd., trade name Kyoward 1000, 500 etc.) 400
Those fired at to 1000 ° C., which was fired what the Mg ²⁺ ion and Al ³⁺ ions coprecipitated alkaline with 400 to 1000 ° C., Al ³⁺ to MgO or Mg (OH) ₂ water slurry Those obtained by dropping and depositing ions and firing at 400 to 1000 ° C. can be used.

The mixing ratio of the first component and the second component in the catalyst of the present invention is preferably 1/99 to 80/20 (weight ratio).

[Method for producing ester alkoxylate]
Examples of the ester compound having at least one group represented by the general formula (I) used in the raw material for producing the ester alkoxylate of the present invention include a monoester, a diester, a triester, a tetraester, and the like. Although those having the above number of ester groups in the molecule may be used, for example, the following general formulas (III), (IV), (V) or (V)
The ester compound represented by I) is exemplified.

[0018]

Embedded image

[Wherein, E ¹ and G ^{1 are the} same or different and each have a linear or branched carbon number of 1 to 1.
21 represents an alkyl group or an alkenyl group. ]

[0020]

Embedded image

[Wherein, E ¹ and G ^{1 have the} above meanings. ]

[0022]

Embedded image

[Wherein, E ¹ represents the above-mentioned meaning. E ² , E ³ : same or different, linear or branched carbon number 1
21 represents an alkyl group or an alkenyl group. ]

[0024]

Embedded image

[Wherein, E ¹ , E ² , E ³ : have the above-mentioned meanings. E ⁴ : same or different, linear or branched carbon number of 1 to 21
Represents an alkyl group or an alkenyl group. Examples of the ester compound represented by the general formula (III) include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid,
-Ethylhexanoic acid, isostearic acid, coconut oil fatty acid, palm oil fatty acid, palm kernel oil fatty acid, tallow fatty acid, or esters of these hardened fatty acids (eg, methyl ester, ethyl ester).

Examples of the ester compound represented by the general formula (IV) include caproic acid diester of ethylene glycol,
Caprylic diester, capric diester, lauric diester, myristic diester, palmitic diester, stearic diester, oleic diester, 2-ethylhexanoic diester, isostearic diester, coco oil fatty diester, palm oil fatty diester, palm Examples thereof include a diester of a cured fatty acid obtained by curing a fatty acid derived from a natural oil or fat, such as a kernel oil fatty acid diester, a tallow fatty acid diester, or the like.

Examples of the ester compound represented by the general formula (V) include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, 2-ethylhexanoic acid, isostearic acid and the like. And hardened oils obtained by hardening palm oil, palm oil, palm kernel oil, beef tallow, lard or these natural fats and oils.

Examples of the ester compound represented by the general formula (VI) include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, 2-ethylhexanoic acid and isostearic acid. The sorbitan tetraester of a fatty acid is exemplified.

According to the present invention, these general formulas (III),
The ester compound represented by (IV), (V) or (VI) is alkoxylated by adding an alkylene oxide to give the corresponding general formula (VII), (VIII) or (I)
An ester alkoxylate represented by X) or (X) is obtained.

[0030]

Embedded image

[Wherein, E ¹ and G ^{1 have the} above meanings. A: Means as described above, and n A's may be the same or different. n: 1 to 5 indicating the average addition mole number of the alkylene oxide
Number of 0. ]

[0032]

Embedded image

[Wherein, E ¹ , G ¹ , A, n: have the above-mentioned meanings. ]

[0034]

Embedded image

[Wherein, E ¹ , E ² , E ³ : have the above meanings. A: The meaning is as described above, and (n ¹ + n ² + n ³ ) A may be the same or different. n ¹ , n ² , n ³ : the same or different, and is a number from 0 to 50 indicating the average addition mole number of the alkylene oxide. Where n ¹ + n ² +
n ³ > 0. ]

[0036]

Embedded image

[Wherein, E ¹ , E ² , E ³ , E ⁴ : have the above-mentioned meanings. A: Means as described above, and (n ¹ + n ² + n ³ + n ⁴ ) A may be the same or different. n ¹ , n ² , n ³ , n ⁴ : the same or different, and is a number from 0 to 50 indicating the average addition mole number of the alkylene oxide. Where n
^{1 + n 2 + n 3 +} n 4> 0. The alkylene oxide used in the present invention is not particularly limited as long as it can react with an ester compound to form an ester alkoxylate.Ethylene oxide and propylene oxide having an oxirane ring, or a mixture of both are used. preferable.

As a preferred specific example of the method for producing an ester alkoxylate of the present invention, if necessary, an amount of 0.01 to 10% by weight, preferably 0.1 to 2% by weight, based on the ester compound, in a reactor such as an autoclave is used. 0.01 to 10% by weight, preferably 0.1 to 10% by weight, based on the first component, ester compound
In the presence of 5% by weight of the second component, an alkylene oxide is added to the ester compound at 80 to 230 ° C, preferably 120 to 1 ° C.
A method in which the reaction is carried out at a temperature of 80 ° C. is exemplified. Reaction temperature
When the temperature is 80 ° C. or higher, a sufficient reaction rate can be obtained, and when the temperature is 230 ° C. or lower, the raw materials and products are not decomposed, which is preferable. Also,
The catalyst in the present invention may be prepared by previously mixing or supporting a predetermined amount of the first component with the second component.

Depending on the application, the product obtained by the above method can be used as it is, but the catalyst is suspended. Usually, the catalyst is removed by a method such as filtration or centrifugation. use.

In the present invention, the catalyst removed and separated by a method such as filtration or centrifugation can be recovered, and the recovered catalyst can be further used for producing an ester alkoxylate. The recovered catalyst is preferably washed with a solvent such as acetone before use. It is economical to use such a recovery catalyst.

According to the production method of the present invention as described above,
General formula (XI)

[0042]

Embedded image

[Wherein, E ¹ , G ¹ , A: have the above-mentioned meanings. n _av : 3 indicating the average number of added moles of alkylene oxide
Is the number of ~ 15. A surfactant consisting of an ester alkoxylate represented by], such distribution of addition mole number of alkylene oxide, when the additional molar number of the most common alkylene oxide was n _max, satisfying formula (XII) Thus, a surfactant having a low content of unreacted ester compound and having a very narrow ethylene oxide addition mole number distribution can be obtained.

[0044]

(Equation 1)

[Wherein, Yi represents the ratio (% by weight) of ester alkoxylate in which the number of moles of ethylene oxide added is i mole. The ester alkoxylate having a narrow addition mole number distribution of the alkylene oxide obtained by the method of the present invention has less unreacted raw material ester than an ester alkoxylate having a broad distribution synthesized using a conventional catalyst. It is improved in smell and has excellent quality. Since the amount of the low addition mole of alkylene oxide is small, water solubility and osmotic power are improved. Further, the alkoxylate of methyl ester is excellent in safety because the amount of methanol produced by hydrolysis and a low addition mole of alkylene oxide of methanol are small.
In addition, since the amount of the high addition mole of alkylene oxide is small, the melting point is low and the solid properties are improved. Furthermore, since the addition mole number distribution of the alkylene oxide is narrow, the active component of the surfactant is increased, so that it has characteristics such as high detergency and a wide range of composition.

Accordingly, the surfactant comprising the ester alkoxylate obtained according to the present invention has very good foaming and odor, has good biodegradability, is environmentally friendly, and can be effectively used as a detergent. Can be.

[0047]

The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. The percentages in the examples are on a weight basis unless otherwise specified.

Examples 1 and 2 Preparation of catalyst Into a 1 liter four-necked flask, 165 g of methyl laurate were added.
7.38 g (0.014 mol) of lauric acid Ba and Kyoward 1000 [Mg _4.5 Al ₂ (OH) ₁₃ (CO ₃ ) .nH ₂ manufactured by Kyowa Chemical Industry Co., Ltd.
O (n = 3 to 3.5)] is sintered at 600 ° C. for 2 hours to obtain MgO.
-Al ₂ O ₃ 18.51 g and 1 at 165 ° C under nitrogen atmosphere
Stirred for hours. Cool to 80 ° C and filter to 58.3 cake
g was obtained. This was dispersed in 165 g of acetone, stirred at room temperature for 1 hour, filtered, and dried under reduced pressure to obtain a white powder.
% Of lauric acid Ba to obtain a loaded with MgO-Al ₂ O ₃ catalyst.

In a 1.5 liter autoclave of ethylene oxide addition reaction , methyl laurate 300
g (1.4 mol) and 12.0 g (4% of methyl laurate) of the above catalyst were charged, and the mixture was heated to 165 ° C and stirred at the same temperature for 1 hour. Thereafter, 185 g (4.2 mol) of ethylene oxide was introduced at the same temperature while maintaining the pressure at 3 to 5 kg / cm ² G, and the reaction was carried out. After aging at the same temperature for 30 minutes, the mixture was cooled to 80 ° C., and 112 g of the reaction product was extracted. This was subjected to a reduced pressure treatment at 500 Torr to remove ethylene oxide, and the catalyst was filtered using No.2 made by Toyo Roshi Paper Co., Ltd. with a pressure filter having an inner diameter of 5 cm and a nitrogen pressure of 3 kg.
/ Cm ² G. Thus, a 3-mol ethylene oxide adduct of methyl laurate was obtained (Example 1).

On the other hand, the temperature of the reactant left in the autoclave was raised again to 165 ° C., and 145 g of ethylene oxide was added.
(3.3 mol) while maintaining the pressure at 3-5 kg / cm ² G,
The reaction was performed. After aging at the same temperature for 30 minutes, the mixture was cooled to 80 ° C and the whole amount was extracted. After decompressing this at 500 Torr,
The catalyst was filtered using No. 2 made of Toyo Roshi Kaisha under a nitrogen pressure of 3 kg / cm ² G with a pressure filter having an inner diameter of 5 cm. Thus, an ethylene oxide 6 mol adduct of methyl laurate was obtained (Example 2).

The ethylene oxide addition reaction rate was measured by the following method, and the ratio of unreacted methyl laurate in the reaction product and the ethylene oxide addition mole number distribution were measured by gas chromatography. Table 1 shows the ethylene oxide addition reaction rate, the ratio of unreacted methyl laurate, and the following formula.
The values represented by (XIII) are shown together. FIG. 1 shows the distribution of the moles of ethylene oxide added.

[0052]

(Equation 2)

[Wherein, n _max and Yi have the same meanings as above. <Ethylene oxide addition reaction rate measuring method> Ethylene oxide is charged in an autoclave and the pressure is 3 kg / cm.
^{Based on the value of 2} , the base is further charged with ethylene oxide to 5 kg / cm ² . The weight of the ethylene oxide charged at that time was measured, and then the pressure was 3 kg / cm ²
The reaction is allowed to take place, and the time during this period is measured. This operation is repeated to add a desired amount of ethylene oxide. The ethylene oxide reaction amount (molar number) per hour was calculated from the charged amount and the reaction time.

Comparative Examples 1 and 2 Kyoward 1000 manufactured by Kyowa Chemical Co., Ltd. was used as a catalyst.
8.58 g (2.86 g) of MgO-Al ₂ O ₃ obtained by firing at
% Relative to methyl laurate), except that 3 moles of ethylene oxide adduct of methyl laurate (Comparative Example 1) and 6 moles of adduct of methyl laurate (Comparative Example 2) were used. Obtained. Table 1 shows the ethylene oxide addition reaction rate, the ratio of unreacted methyl laurate, and the value represented by the above formula (XIII), which were measured in the same manner as in Examples 1 and 2. FIG. 1 shows the distribution of the number of moles of ethylene oxide added.

Comparative Example 3 300 g of methyl laurate was placed in a 1.5-liter autoclave.
(1.4 mol) and 12.00 g of Ba laurate (4% against methyl laurate), and after raising the temperature to 165 ° C, maintaining 370 g (8.4 mol) of ethylene oxide at the same temperature while maintaining a pressure of 3 to 5 kg / cm ² G. The reaction was carried out. Thereafter, the same treatment as in Example 1 was performed to obtain a 6 mol ethylene oxide adduct of methyl laurate. Table 1 shows the ethylene oxide addition reaction rate, the ratio of unreacted methyl laurate, and the value represented by the above (XIII), which were measured in the same manner as in Examples 1 and 2.
It was shown to. FIG. 2 shows the ethylene oxide addition mole number distribution.

[0056]

[Table 1]

As apparent from Table 1 and FIGS. 1 and 2, the ester ethoxylates obtained in Examples 1 and 2 have a very small amount of unreacted methyl laurate remaining and a very narrow distribution of ethylene oxide addition moles. On the other hand, in the case of Comparative Examples 1 to 3 using only MgO-Al ₂ O ₃ as the catalyst and only Ba laurate, a large amount of unreacted methyl laurate remained compared to the example and was obtained. The distribution of moles of ethylene oxide added to the ester ethoxylate was broad.

[0058]

According to the present invention, it is possible to carry out one-stage alkoxylation of esters, which has been difficult in the past, to produce an ester alkoxylate having a narrow addition mole number distribution and a small amount of unreacted raw materials in the reaction product. Was completed.

[Brief description of the drawings]

FIG. 1 is a diagram showing the ethylene oxide addition mole number distributions of the products obtained in Examples 1 and 2 and Comparative Examples 1 and 2.

FIG. 2 is a view showing the ethylene oxide addition mole number distribution of a product obtained in Comparative Example 3.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hiroshi Nagumo 1334 Minato, Wakayama City, Wakayama Prefecture Kao Corporation Research Center

Claims (6)

[Claims] 1. An alkylene oxide having 2 to 4 carbon atoms is added to an ester compound having at least one group represented by the following general formula (I) to form at least a group represented by the general formula (II). A catalyst used for producing an ester alkoxylate having one, an organic acid salt of an alkali metal, an alkaline earth metal or a rare earth metal [first component], and a composite metal oxide of MgO and Al ₂ O ₃ A catalyst for producing an ester alkoxylate, which comprises [second component]. -COOR (I) -COO (AO) _m R (II) [wherein, R represents a residue obtained by removing one hydroxyl group from alcohol or phenol. A: represents an alkylene group having 2 to 4 carbon atoms, and m A's may be the same or different. m: a number indicating the average number of added moles of alkylene oxide. ] 2. The catalyst according to claim 1, wherein the first component is a fatty acid salt of an alkaline earth metal. 3. An alkylene oxide having 2 to 4 carbon atoms is added to an ester compound having at least one group represented by the general formula (I) to form a group represented by the general formula (II). A method for producing an ester alkoxylate having at least one ester alkoxylate, wherein the catalyst according to claim 1 or 2 is used as a catalyst. 4. The process according to claim 3, wherein a recovered catalyst obtained by recovering the catalyst used in the production of the ester alkoxylate is used. 5. The method according to claim 3, wherein the ester compound having at least one group represented by the general formula (I) is a monoester, diester, triester or tetraester. 6. An ester alkoxylate represented by the general formula (VI)
The compound represented by the formula (VIII), the compound represented by the general formula (IX) or the compound represented by the general formula (X) represented by the formula (I). The production method according to claim 1. Embedded image (Wherein, E ¹ and G ^{1 are the} same or different and each have a linear or branched carbon number of 1 to 1.
21 represents an alkyl group or an alkenyl group. A: Means as described above, and n A's may be the same or different. n: 1 to 5 indicating the average addition mole number of the alkylene oxide
Number of 0. [Chemical formula 2] [Wherein, E ¹ , G ¹ , A, n: have the above meanings. [Chemical formula 3] [Wherein, E ^{1 has} the meaning described above. E ² , E ³ : same or different, linear or branched carbon number 1
21 represents an alkyl group or an alkenyl group. A: The meaning is as described above, and (n ¹ + n ² + n ³ ) A may be the same or different. n ¹ , n ² , n ³ : the same or different, and is a number from 0 to 50 indicating the average addition mole number of the alkylene oxide. Where n ¹ + n ² +
n ³ > 0. [Formula 4] [Wherein, E ¹ , E ² , and E ^{3 have the} above-mentioned meanings. E ⁴ : same or different, linear or branched carbon number of 1 to 21
Represents an alkyl group or an alkenyl group. A: Means as described above, and (n ¹ + n ² + n ³ + n ⁴ ) A may be the same or different. n ¹ , n ² , n ³ , n ⁴ : the same or different, and is a number from 0 to 50 indicating the average addition mole number of the alkylene oxide. Where n
^{1 + n 2 + n 3 +} n 4> 0. ]