JPH1099693A - Catalyst for manufacturing ester alkoxylate and ester alkoxylate manufacture thereby - Google Patents

Abstract

PROBLEM TO BE SOLVED: To narrow additional molar number distribution and to reduce unreacted materials in reacted products by allowing a catalyst with which an ester alkoxylate is manufactured by adding an alkylene oxide to an ester compound to contain a compound of an alkali metal and the like and a metal oxide of Ti and the like. SOLUTION: In a catalyst used for manufacturing an ester alkoxylate having one group represented by the formula II (R is an alcohol or a residue obtained by removing one hydroxyl group from phenol, A is a 2-4 alkylene group and m is a mean additional molar number of an alkylene oxide) by adding an alkylene oxide to an ester compound (methyl laurate or the like) having one group represented by the constitutional formula I, the catalyst is allowed to contain a compound (1) (barium laurate and the like) selected from the group consisting of alkali metals, hydroxides of alkali earth metals or rare earth metals, oxides, organic acid salt or alcholate and a metal oxide (titanium oxide and the like) (2) containing at least one kind of atoms selected from the group consisting of alkali earth metals, Zr, Ti, and Al.

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] Accordingly, an object of the present invention is to provide an ester alkoxylate having a narrow alkylene oxide addition molar distribution and a small amount of unreacted raw materials and by-products, which could not be obtained by using a conventional catalyst. Is to provide a catalyst for use in the process for producing a high reaction rate and a high yield.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above problems can be solved by using a specific 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 to form a group represented by the general formula (II). A catalyst used for producing an ester alkoxylate having at least one compound, which is a compound selected from hydroxides, oxides, organic acid salts and alcoholates of alkali metals, alkaline earth metals or rare earth metals [first component And a metal oxide containing at least one atom selected from the group consisting of alkaline earth metals (excluding the alkaline earth metal of the first component), Zr, Ti and Al (however, Mg and
A second component), and a method for producing an ester alkoxylate using the catalyst. Is what you do.

-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. ]

[0008]

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

[Catalyst] The catalyst used in the present invention comprises a compound [first component] selected from hydroxides, oxides, organic acid salts or alcoholates of alkali metals, alkaline earth metals or rare earth metals; A metal oxide containing at least one atom selected from the group consisting of a class of metals (excluding the alkaline earth metal of the first component), Zr, Ti and Al (however, Mg and
(Excluding the composite metal oxide containing Al) [the second component].

[0010] The first component used in the present invention is N
fatty acid salts of alkali metals such as a and K, preferably fatty acid salts having 1 to 22 carbon atoms (eg, sodium laurate, potassium laurate, sodium stearate, potassium stearate, etc.), and alkali metal alcoholates such as Na and K (For example, sodium methylate, sodium methylate, potassium methylate, potassium methylate, etc.), N
a, a hydroxide of an alkali metal such as K (eg, sodium hydroxide, potassium hydroxide, etc.), a fatty acid salt of an alkaline earth metal such as Mg, Ca, Ba, etc., preferably a fatty acid salt having 1 to 22 carbon atoms (eg, Alkaline earth metal alcoholates such as barium laurate, calcium laurate, magnesium laurate, barium stearate, etc., Mg, Ca, Ba etc. (for example, barium methylate, calcium methylate,
Magnesium methylate, etc.), hydroxides of alkaline earth metals such as Mg, Ca, Ba, etc. (eg, barium hydroxide, calcium hydroxide, magnesium hydroxide, etc.), oxidation of alkaline earth metals such as Mg, Ca, Ba, etc. (E.g., barium oxide, calcium oxide, magnesium oxide, etc.), and fatty acid salts of rare earth metals such as Y and La, preferably those having 1 to 22 carbon atoms (e.g., yttrium stearate).

Among these first components, fatty acid salts of alkali metals or alkaline earth metals and oxides of alkaline earth metals are preferable, and barium compounds such as barium laurate and barium oxide are particularly preferable.

As the second component used in the present invention, M
g, oxides of alkaline earth metals such as Ca and Ba (eg, barium oxide, calcium oxide, magnesium oxide, etc.), Zr
O ₂ , TiO ₂ , Al ₂ O _{3 and the} like, and MgO, CaO, ZrO ₂ , Ti
At least one metal oxide selected from O ₂ and Al ₂ O ₃ is preferred. However, when the first component is an oxide of an alkaline earth metal, the second component is selected from those other than the alkaline earth metal oxide, and the second component contains Mg and
The composite metal oxide containing Al is not included.

[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, and a number of the ester compounds. Although those having an ester group in the molecule may be used, examples thereof include ester compounds represented by the following general formulas (III), (IV) or (V).

[0014]

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. ]

[0016]

Embedded image

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

[0018]

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. 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, coconut oil fatty acid, palm oil fatty acid, and palm kernel oil. Fatty acids, tallow fatty acids, or esters of these hardened fatty acids (eg, methyl esters, ethyl esters) are exemplified.

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, coco oil diester, palm oil diester, palm kernel oil diester, tallow fatty acid diester or the aforementioned Diesters of cured fatty acids obtained by curing fatty acids derived from natural fats and oils are exemplified.

Examples of the ester compound represented by the general formula (V) include fatty acids such as caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and 2-ethylhexanoic acid. Examples include triglycerides, coconut oil, palm oil, palm kernel oil, tallow, lard, and hardened oils obtained by hardening these natural fats and oils.

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

[0023]

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. ]

[0025]

Embedded image

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

[0027]

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. 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 is 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. Not only is it economical to use such a recovery catalyst, but also the ethylene oxide addition mole number distribution in the obtained ester alkoxylate becomes narrower, and a product having a low content of unreacted ester compound can be obtained. preferable.

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

[0033]

Embedded image

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

N _av : a number from 3 to 15 indicating the average number of moles of alkylene oxide added. A surfactant comprising an ester alkoxylate represented by the formula (X), wherein the addition mole number distribution of the alkylene oxide is nmax, where n is the _maximum addition mole number of the alkylene oxide.
Is satisfied, the content of unreacted ester compound is small, and a surfactant having a very narrow ethylene oxide addition molar number distribution can be obtained.

[0036]

(Equation 1)

[Wherein, Yi represents the ratio (% by weight) of the 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.

[0039]

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 In a one-liter four-necked flask, methyl laurate 331.3 was added.
g (1.55 mol) and 14.75 g (0.0275 mol) of Ba laurate
And MgO (trade name: Kyowa Mag 150, manufactured by Kyowa Chemical Co., Ltd.)
After charging 37.0 g, the mixture was stirred at 165 ° C. for 1 hour under a nitrogen atmosphere, cooled to 80 ° C., and filtered to obtain 109.8 g of a cake. This was dispersed in 331.3 g of acetone, stirred at room temperature for 1 hour, filtered, and dried under reduced pressure to obtain 57.8 g of a white powdery MgO catalyst supporting 28.5% Ba laurate.

Ethylene oxide addition reaction In a 1.5 liter autoclave, methyl laurate 300
g (1.4 mol) and 12 g of the above catalyst (4% by weight based on methyl laurate) were charged, heated to 165 ° C., and stirred at the same temperature for 1 hour. Then at the same temperature ethylene oxide 185g
(4.2 mol) was introduced 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 1 hour, the mixture was cooled to 80 ° C., and 116 g of a reaction product was extracted. This was subjected to a vacuum treatment at 500 Torr to remove ethylene oxide, and the catalyst was filtered using No. 2 made by Toyo Roshi Paper Co., Ltd. under a nitrogen pressure of 3 kg / cm ² G using a pressure filter having an inner diameter of 5 cm. Thus, a 3-mol ethylene oxide adduct of methyl laurate was obtained (Example 1).

On the other hand, the reactant left in the autoclave was heated again to 165 ° C., and 145 g of ethylene oxide was added.
(3.3 mol) was introduced 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 2 hours, the mixture was cooled to 80 ° C and the whole amount was extracted. This was subjected to reduced pressure treatment at 500 Torr, and then catalyst filtration was performed using No. 2 made by Toyo Filter Paper with a pressure filter having an inner diameter of 5 cm at a nitrogen pressure of 3 kg / cm ² G. 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 (XI) are shown together. FIG. 1 shows the distribution of the moles of ethylene oxide added.

[0044]

(Equation 2)

[Wherein, n _max and Yi have the above-mentioned meanings. <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.

Preparation of Catalysts 3 and 4 The same operation as in the preparation of catalysts of Examples 1 and 2 was carried out except that TiO ₂ (SSP-20 manufactured by Sakai Chemical Co., Ltd.) was used instead of MgO.
A TiO ₂ catalyst supporting 28.5% Ba laurate was obtained.

Ethylene oxide addition reaction The reaction was carried out in the same manner as in Examples 1 and 2, except that the TiO ₂ catalyst supporting 28.5% of Ba laurate was used, and a 3 mol ethylene oxide adduct of methyl laurate was added. (Example 3) and a 6-mol adduct (Example 4) were obtained. Example 1
Table 1 shows the ethylene oxide addition reaction rate, the ratio of unreacted methyl laurate, and the value represented by the above formula (XI), which were measured in the same manner as in Examples 1 and 2. FIG. 2 shows the distribution of the molar number of addition of ethylene oxide.

Examples 5 and 6 Preparation of catalyst Instead of MgO, Al ₂ O ₃ (DN-1A, manufactured by Mizusawa Chemical Co., Ltd.)
The same operation as in the preparation of the catalysts of Examples 1 and 2 was performed except for using, to obtain an Al ₂ O ₃ catalyst supporting 28.5% of Ba laurate.

Ethylene oxide addition reaction The reaction was carried out in the same manner as in Examples 1 and 2 except that the above Al ₂ O ₃ catalyst supporting 28.5% of Ba laurate was used. An adduct (Example 5) and a 6 molar adduct (Example 6) were obtained. Table 1 shows the ethylene oxide addition reaction rate, the ratio of unreacted methyl laurate, and the value represented by the above formula (XI), which were measured in the same manner as in Examples 1 and 2. FIG. 3 shows the distribution of the number of moles of ethylene oxide added.

Examples 7 and 8 Preparation of catalyst Instead of MgO, ZrO ₂ (CAP manufactured by Daiichi Kagaku Kagaku KK)
The same operation as in the preparation of the catalysts of Examples 1 and 2 was carried out except for using, to obtain a ZrO ₂ catalyst supporting 28.5% of Ba laurate.

Ethylene oxide addition reaction The reaction was carried out in the same manner as in Examples 1 and 2 except that the ZrO ₂ catalyst supporting 28.5% of Ba laurate was used, and 3 moles of ethylene oxide were added to methyl laurate. (Example 7) and a 6-mol adduct (Example 8). Table 1 shows the ethylene oxide addition reaction rate, the ratio of unreacted methyl laurate, and the value represented by the above formula (XI), which were measured in the same manner as in Examples 1 and 2. FIG. 4 shows the distribution of the number of moles of ethylene oxide added.

Comparative Example 1 Preparation of Catalyst The same operation as in the preparation of the catalyst of Examples 1 and 2 was carried out except that activated carbon (Carbofin manufactured by Takeda Pharmaceutical Co., Ltd.) was used instead of MgO. An activated carbon catalyst supporting Ba laurate was obtained.

Ethylene oxide addition reaction The reaction was carried out in the same manner as in Examples 1 and 2, except that the activated carbon catalyst supporting 28.5% of Ba laurate was used, but the ethylene oxide addition reaction rate was 0.12 EOmol. / Hr
And significantly slower than the catalyst systems of the examples.

[0054]

[Table 1]

As is clear from the results of Examples 1 to 8 and Comparative Example 1, Examples 1 to 8 had a higher ethylene oxide addition reaction rate than Comparative Example 1, and the obtained ester ethoxylate was unreacted. It can be seen that the residual amount of methyl laurate is small and a narrow ethylene oxide addition mole number distribution is exhibited.

[0056]

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 graph showing the ethylene oxide addition mole number distribution of the products obtained in Examples 1 and 2.

FIG. 2 is a view showing the ethylene oxide addition mole number distribution of the products obtained in Examples 3 and 4.

FIG. 3 is a view showing the ethylene oxide addition mole number distribution of the products obtained in Examples 5 and 6.

FIG. 4 is a graph showing the ethylene oxide addition mole number distribution of the products obtained in Examples 7 and 8.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C07C 69/30 C07C 69/30 C07D 303/16 C07D 303/16 (72) Inventor Hiroshi Nagumo 1334 Minato 1334 Minato, Wakayama-shi, Wakayama Kao Corporation In the laboratory

Claims (7)

[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 compound, which is a compound selected from alkali metal, alkaline earth metal or rare earth metal hydroxide, oxide, organic acid salt or alcoholate [first component] And a metal oxide containing at least one atom selected from the group consisting of alkaline earth metals (excluding the alkaline earth metal of the first component), Zr, Ti and Al (however, Mg and
(Excluding complex metal oxides containing Al) [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 method according to claim 1, wherein the first component is an alkali metal fatty acid salt,
The catalyst according to claim 1, which is an alcoholate or a hydroxide, or a fatty acid salt of an alkaline earth metal, an alcoholate, a hydroxide or an oxide. 3. The composition of claim 2, wherein the second component is MgO, CaO, ZrO ₂ , TiO ₂ and
At least one of claims 1 or 2 wherein the catalyst is a metal oxide selected from the al ₂ O _3. 4. 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). The method for producing an ester alkoxylate having at least one ester alkoxylate as a catalyst.
A method for producing an ester alkoxylate, comprising using the catalyst according to any one of the above. 5. The method according to claim 4, wherein a recovered catalyst obtained by recovering the catalyst used in the production of the ester alkoxylate is used. 6. The method according to claim 4, wherein the ester compound having at least one group represented by the general formula (I) is a monoester, diester or triester. 7. An ester alkoxylate of the general formula (V
5. The compound represented by the formula (VII), the compound represented by the general formula (VII), or the compound represented by the general formula (VIII).
7. The production method according to any one of claims 6 to 6. 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. ]