JP2000061304A - Catalyst for alkoxylation, method for producing the same, and method for producing alkylene oxide adduct using the catalyst - Google Patents

Abstract

(57) [Problem] To provide a solid catalyst capable of producing an alkylene adduct having a narrow addition molar distribution while suppressing by-product of a high molecular weight polyalkylene glycol having a molecular weight of about tens of thousands. SOLUTION: Magnesium, aluminum and 6A
A metal oxide containing, as a third component, at least one metal selected from Group 7, 7A and Group 8 is used as a catalyst for alkoxylation. The third component metal is composed of aluminum and a spinel oxide (for example, the third component metal is Mn).
If so, the active site structure of the catalyst is changed by forming MnAl ₂ O ₄ ) or the like, and the by-product of high molecular weight polyalkylene glycol is suppressed.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a catalyst for alkoxylation, a method for producing the same, and a method for producing an alkylene oxide adduct using the catalyst, more specifically, a solid catalyst for alkoxylation comprising a metal oxide, and The present invention relates to a method for producing an alkylene oxide adduct useful as a raw material for chemicals such as surfactants.

[0002]

2. Description of the Related Art Organic compounds having active hydrogen and compounds obtained by adding alkylene oxide to esters are widely used as raw materials for chemicals such as surfactants and solvents.
In particular, alcohols, fatty acids, fatty acid esters, amines,
A polyalkoxylated product of an alkylphenol or the like with an alkylene oxide such as ethylene oxide or propylene oxide is widely used as a nonionic surfactant.

As such an alkylene oxide adduct, an adduct having a narrow addition mole distribution of alkylene oxide has many advantages such as high foaming power as compared with an adduct having a wide distribution. As a method for obtaining an alkylene oxide adduct having a narrow addition mole distribution,
A method using a halide of boron, tin, antimony, iron, aluminum or the like, or an acid catalyst such as phosphoric acid or sulfuric acid is known. However, in the method using such an acid catalyst, the distribution of addition moles is not sufficiently narrowed, a large amount of by-products such as dioxane, dioxolane, and polyethylene glycol are produced, and the corrosiveness to equipment becomes strong.

Therefore, the complex oxides shown below are
It has been proposed as a solid catalyst for producing alkylene oxide adducts with a narrow addition molar distribution. 1) JP-A-1-164437: An alkylene oxide adduct having a narrow addition molar distribution is produced by using magnesium oxide added with a metal ion such as aluminum as a catalyst. The publication discloses a magnesium oxide catalyst containing, for example, 3% by weight of aluminum.

2) JP-A-2-71841: An alkylene oxide adduct having a narrow addition mole distribution is produced by using calcined hydrotalcite as a catalyst.
This calcined hydrotalcite can be obtained by calcining natural or synthetic hydrotalcite.

3) JP-A-7-227540: Zinc,
By using magnesium oxide containing antimony, tin, etc. as a catalyst, an alkylene oxide adduct is produced while suppressing the generation of by-products (polyethylene glycol). When the catalyst composed of this composite oxide is used, the catalytic activity may be lower than when a magnesium oxide catalyst containing aluminum is used, but the by-product amount of polyethylene glycol can be reduced.

4) Japanese Unexamined Patent Publication No. 8-268919: An alkylene oxide adduct having a narrow addition mole distribution is produced by using an aluminum / magnesium composite oxide obtained by firing and activating aluminum hydroxide / magnesium as a catalyst.

[0008]

When each of the above catalysts is used, an alkylene oxide adduct having a narrower addition mole distribution than that when an acid catalyst is used is obtained, and the formation of by-products such as dioxane is suppressed. In particular, a composite oxide of magnesium and aluminum has high activity and is useful,
When this catalyst is used, a by-product of polyalkylene glycol becomes a problem. A catalyst capable of quantitatively suppressing the by-product of polyalkylene glycol is also disclosed in JP-A-7-227540. However, a particularly problematic by-product is a high molecular weight polyalkylene glycol having a molecular weight of tens of thousands. High-molecular-weight polyalkylene glycol causes problems such as difficulty in removing the catalyst and impairing the stability of the compounded product even if the production amount is small. Further, a catalyst for producing an alkylene oxide adduct is required to have practically sufficient catalytic activity.

Therefore, the present invention provides a catalyst capable of producing an alkylene oxide adduct having a narrow addition mole distribution more industrially advantageously, a method for producing the same, and a method for producing the alkylene oxide adduct using this catalyst. The purpose is to do. In particular, an object of the present invention is to provide a catalyst capable of efficiently producing an alkylene oxide adduct having a narrow addition mole distribution while suppressing by-production of high molecular weight polyalkylene glycol.

[0010]

Means for Solving the Problems As a result of intensive investigations by the present inventors regarding an alkoxylation catalyst suitable for the production of alkylene oxide adducts having a narrow alkylene oxide addition molar distribution, the inventors have identified it as a composite oxide of magnesium and aluminum. It was found that the use of the metal-added catalyst can achieve both high catalytic activity and suppression of by-product of high molecular weight polyalkylene glycol.

That is, the first alkoxylation catalyst of the present invention comprises magnesium, aluminum, a 6A group,
It is characterized by comprising a metal oxide containing at least one metal selected from the 7A group and the 8 group.

Here, the above-mentioned metal added to the magnesium-aluminum composite oxide is a group 6A (chromium, molybdenum, tungsten), 7 in the subgroup system periodic table.
It is an element belonging to Group A (manganese, technetium, rhenium) and Group 8 (iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum).

The above catalyst contains magnesium and aluminum which simultaneously contain a base point due to an oxygen atom adjacent to magnesium for activating an organic compound having active hydrogen and an acid point due to aluminum for activating alkylene oxide. The metal as the third component is added to the composite oxide. The composite oxide of magnesium and aluminum is a highly active catalyst capable of producing an alkylene oxide adduct having a narrow addition distribution, as conventionally used. Moreover, in the present invention, by-product of high molecular weight polyalkylene glycol is suppressed by the third component. This is because the active site structure of the by-product reaction is changed by the addition of the metal as the third component.
The active site structure in the catalyst changes, for example, when the metal of the third component and aluminum form a spinel type oxide.

The second catalyst for alkoxylation of the present invention is
It is characterized by comprising a metal oxide containing magnesium, aluminum and a metal M (M is a metal element excluding magnesium and aluminum), and including a spinel type oxide of aluminum and the metal M.

This spinel type oxide has, for example, the chemical formula M
It is represented by Al ₂ O ₄ . As the metal element M, 6A
Group 7, Group 7A or Group 8 metals can be used,
There is no particular limitation. As the metal M, two or more kinds of metals may be used.

The presence of the above spinel type oxide can be confirmed by X-ray diffraction analysis. The catalyst is preferably an oxide in which an X-ray diffraction peak due to a spinel-type oxide and an X-ray diffraction peak due to a magnesium oxide having a rock salt type structure are observed.

As described above, by using the above-mentioned catalyst, it is possible to efficiently produce an alkylene oxide adduct having a narrow addition mole distribution while suppressing the by-production of high molecular weight polyalkylene glycol. That is, the method for producing an alkylene oxide adduct of the present invention is characterized by adding an alkylene oxide to an organic compound using the above-mentioned alkoxylation catalyst.

Further, the method for producing the alkoxylation catalyst of the present invention comprises magnesium, aluminum, 6A group and 7A group.
A step of producing a precipitate containing magnesium, aluminum, and at least one metal selected from groups 6A, 7A, and 8 from a mixed aqueous solution containing at least one metal selected from groups 6 and 8 And a step of firing the precipitate at 300 to 1000 ° C.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The catalyst of the present invention will be specifically described below. Specifically, the metal serving as the third component in the catalyst is preferably chromium, molybdenum, manganese, technetium, iron, cobalt, nickel or ruthenium,
Chromium, manganese and iron are more preferable, and manganese is particularly preferable. As the metal to be the third component, two or more kinds selected from the metals exemplified above may be added.

Further, in the above catalyst, the ratio of each metal is set to a range suitable for suppressing the by-production of high molecular weight polyalkylene glycol while maintaining the high catalytic activity of the composite oxide of magnesium and aluminum. It is preferable. Hereinafter, a preferable ratio of each metal will be described.

The atomic ratio of magnesium to aluminum is expressed by Al / (Mg + Al), and is 0.1 to 0.1.
It is preferably 0.7, and more preferably 0.3 to 0.6.

The atomic ratio of the above-mentioned metal added as the third component to all the metals is preferably 0.05 to 0.4, and more preferably 0.1 to 0.25. If the amount of the third component is too small, it becomes difficult to obtain the effect of suppressing the by-production of high molecular weight polyalkylene glycol. On the other hand, if the amount is too large, the catalytic activity may decrease.

The catalyst of the present invention can be obtained by a known method such as an impregnation method or a coprecipitation method for preparing a catalyst composed of a multi-component complex oxide. Here, a method for producing the catalyst of the present invention by the coprecipitation method will be described.

According to the coprecipitation method, first, a mixed aqueous solution containing metal compounds such as nitrates, sulfates, carbonates, acetates and chlorides of respective metals is prepared, and a precipitant is added to this aqueous solution. The precipitate obtained by adding the precipitant is washed with water,
A catalyst composed of a composite oxide is obtained through processes such as drying and firing.

As a specific example of applying this coprecipitation method to the present invention, an aqueous solution containing magnesium, aluminum and a metal compound of a metal to be the third component, and a precipitant,
A method of forming a precipitate by dropping the mixed solution while adjusting the flow rate so that the pH of the mixed solution is within a predetermined range can be mentioned. In this case, the pH of the mixture is 7-11, especially 8
-10 is preferable. When coprecipitation is carried out at a pH outside the above range, the metal may elute and an oxide catalyst having a desired composition or crystal structure may not be obtained. The precipitating agent is preferably an alkaline aqueous solution, particularly an alkaline aqueous solution containing a carbonate such as sodium carbonate. Further, in order to keep the pH within the above range, it is preferable that the precipitant contains an alkali metal hydroxide such as sodium hydroxide.

The composite hydroxide obtained as a precipitate is washed with water to remove water-soluble salts and dried, and then 300 to 10
By calcination at 00 ° C, preferably 600 to 900 ° C, more preferably 700 to 900 ° C, the catalyst of the present invention comprising a complex oxide is converted. The calcination temperature affects the change of the active site structure in the catalyst. If the firing temperature is too low, the spinel of the third component and aluminum may not be formed, and the active sites in the catalyst may not change sufficiently.
On the other hand, if the firing temperature is too high, the sintering proceeds to reduce the surface area and reduce the catalytic activity.

Next, the organic compound to which the alkylene oxide is added by the catalyst of the present invention will be explained. The organic compound is not particularly limited as long as it can be alkoxylated, and specific examples thereof include organic compounds having active hydrogen and esters. More specifically, alcohols, phenols, fatty acids,
Fatty acid esters, fatty amines, fatty acid amides, polyols and mixtures thereof are preferably used.
Typical organic compounds are illustrated below.

As the alcohol, a saturated or unsaturated primary or secondary alcohol having 2 to 30 carbon atoms is preferable, and a primary alcohol having 6 to 24 carbon atoms is more preferable. Further, as the phenols, mono-, di-, or trialkylphenols, particularly, those having 4 carbon atoms in the alkyl group
Compounds containing up to 12 are preferred.

Examples of the fatty acids include fatty acids having 8 to 22 carbon atoms, such as coconut oil, palm oil, palm kernel oil, soybean oil,
It is preferable to use saturated or unsaturated linear fatty acids (eg, caprylic acid, capric acid, lauric acid, mistyric acid, oleic acid, stearic acid) obtained by lipolysis from sunflower oil, rapeseed oil, fish fat, etc. and mixtures thereof. You can As the fatty acid esters, those obtained by esterifying the above fatty acids with an alkyl group having 1 to 4 carbon atoms are preferable.

Suitable fatty amines are primary fatty amines obtained from saturated and unsaturated straight chain fatty acids or the corresponding nitriles of aliphatic alcohols.
As the fatty acid amides, derivatives of saturated or unsaturated linear fatty acids and ammonia or primary fatty amines are preferable.

The polyols have an average degree of polymerization of 2 to
2000 polyethylene glycol, polypropylene glycol, glycerin, sorbitol or the like is preferable.

On the other hand, the alkylene oxide used in the present invention is preferably one having 2 to 8 carbon atoms, and particularly preferably ethylene oxide, propylene oxide or butylene oxide having 2 to 4 carbon atoms.

Hereinafter, preferable reaction conditions in the method for producing an alkylene oxide adduct of the present invention will be described. The reaction temperature is preferably 80 to 230 ° C., more preferably 1
20 to 200 ° C, most preferably 160 to 180 ° C. The reaction pressure depends on the reaction temperature, but is preferably 0 to 2
It is 0 atm, more preferably 2 to 8 atm. The amount of the catalyst used depends on the molar ratio of the alkylene oxide to be used in the reaction and the starting material, but usually 0.01 to 20% by weight of the starting material such as alcohol is preferable, and 0.05 to 5%.
Weight percent is even more preferred.

As a specific reaction operation, for example, a starting material such as alcohol and a catalyst are charged into an autoclave, the inside of the autoclave is replaced with nitrogen, and then a predetermined temperature / temperature is set.
The alkylene oxide is introduced and reacted under pressure. Further, the catalyst may be used as it is in the reaction crude product as it is depending on the intended use, but it is usually filtered after adding water or a filter aid for lowering the viscosity.

[0035]

EFFECTS OF THE INVENTION According to the method for producing an alkylene oxide adduct using the catalyst of the present invention, an alkylene oxide adduct having a very narrow addition mole distribution and a very small by-product of high molecular weight polyethylene glycol can be efficiently produced by high catalytic activity. Can be manufactured in a simple manner. In particular, the by-product of high molecular weight polyalkylene glycol is suppressed, so not only the filterability of the catalyst is improved, but also the characteristics of the chemicals using the obtained alkylene oxide adduct as a raw material (eg low temperature stability) are good. Becomes

[0036]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples.

Example 1 As solution A, magnesium nitrate hexahydrate 68.03 g (0.265 mol), aluminum nitrate nonahydrate 47.69 g (0.127 mol),
Manganese nitrate hexahydrate 24.33 g (0.085 mol)
Was dissolved in 450 g deionized water. On the other hand, as a solution B, 13.47 g (0.127 mol) of sodium carbonate was dissolved in 450 g of deionized water.

Solution A and solution B were added dropwise to a catalyst preparation tank in which 1800 g of deionized water had been charged in advance over 1 hour while keeping the pH at 9 and the temperature at 40 ° C. with 2N NaOH. Aged for 1 hour. The mother liquor was removed by filtration, the precipitate was washed with 6 liters of deionized water and spray-dried to obtain 30 g of composite hydroxide. This composite hydroxide was calcined in a nitrogen atmosphere at 800 ° C. for 3 hours to obtain a composite oxide catalyst of Mg, Al and Mn (Mg: Al:
Mn (atomic ratio) = 0.56: 0.26: 0.18) 19
g was obtained.

(Example 2) As a solution A, 68.03 g (0.265 mol) of magnesium nitrate hexahydrate, 47.69 g (0.127 mol) of aluminum nitrate nonahydrate,
Manganese acetate tetrahydrate 20.83 g (0.085 mol)
Was dissolved in 450 g deionized water. On the other hand, as a solution B, 13.47 g (0.127 mol) of sodium carbonate was dissolved in 450 g of deionized water. Hereinafter, by the same method as in Example 1, a composite oxide catalyst of Mg, Al, and Mn (Mg: Al: Mn (atomic ratio) = 0.56: 0.26:
0.18) 19 g was obtained.

Example 3 As solution A, 69.68 g (0.272 mol) of magnesium nitrate hexahydrate, 61.06 g (0.163 mol) of aluminum nitrate nonahydrate,
Manganese nitrate hexahydrate 14.60 g (0.051 mol)
Was dissolved in 450 g deionized water. On the other hand, as a solution B, 17.26 g (0.163 mol) of sodium carbonate was dissolved in 450 g of deionized water. Hereinafter, by the same method as in Example 1, a composite oxide catalyst of Mg, Al, and Mn (Mg: Al: Mn (atomic ratio) = 0.56: 0.34:
21 g of 0.10) was obtained.

(Example 4) As a solution A, 66.72 g (0.260 mol) of magnesium nitrate hexahydrate, 38.98 g (0.104 mol) of aluminum nitrate nonahydrate,
29.82 g (0.104 mol) of manganese nitrate hexahydrate
Was dissolved in 450 g deionized water. On the other hand, as solution B, 11.01 g (0.104 mol) of sodium carbonate was dissolved in 450 g of deionized water. Thereafter, a composite oxide catalyst of Mg, Al, and Mn (Mg: Al: Mn (atomic ratio) = 0.56: 0.22:
0.22) 18 g was obtained.

Example 5 As solution A, 57.26 g (0.223 mol) of magnesium nitrate hexahydrate, 50.06 g (0.133 mol) of aluminum nitrate nonahydrate,
35.60 g (0.089 mol) of chromium nitrate nonahydrate was dissolved in 450 g of deionized water. On the other hand, as the solution B, 23.57 g (0.222 mol) of sodium carbonate was dissolved in 450 g of deionized water. Thereafter, a composite oxide catalyst of Mg, Al and Cr (Mg: Al: Cr (atomic ratio) = 0.50: 0.30:
0.20) 23 g was obtained.

Example 6 As solution A, magnesium nitrate hexahydrate 68.03 g (0.265 mol), aluminum nitrate nonahydrate 47.69 g (0.127 mol),
21.35 g (0.085 mol) of ferrous chloride tetrahydrate was dissolved in 450 g of deionized water. On the other hand, as a solution B, 13.47 g (0.127 mol) of sodium carbonate was dissolved in 450 g of deionized water. Hereinafter, by the same method as in Example 1, a mixed oxide catalyst of Mg, Al, and Fe (Mg: Al: Fe (atomic ratio) = 0.56: 0.26:
0.18) 18 g was obtained.

Example 7 Mg, Al and M were prepared in the same manner as in Example 1 except that 16.82 g (0.085 mol) of manganese chloride tetrahydrate was used as the manganese salt.
n composite oxide catalyst (Mg: Al: Mn (atomic ratio) =
0.56: 0.26: 0.18) 19 g was obtained.

(Example 8) Mg, Al, M was prepared in the same manner as in Example 1 except that 20.49 g (0.085 mol) of manganese sulfate pentahydrate was used as the manganese salt.
n composite oxide catalyst (Mg: Al: Mn (atomic ratio) =
0.56: 0.26: 0.18) 19 g was obtained.

Example 9 Mg, Al and Mn were prepared in the same manner as in Example 1 except that 9.77 g (0.085 mol) of manganese carbonate tetrahydrate was used as the manganese salt.
Composite oxide catalyst (Mg: Al: Mn (atomic ratio) = 0.
56: 0.26: 0.18) 19 g was obtained.

Example 10 As solution A, magnesium nitrate hexahydrate 317.48 g (1.24 mol), aluminum nitrate nonahydrate 222.55 g (0.593 mol), manganese acetate tetrahydrate 96.9 g (0.396 mol) was dissolved with 600 g deionized water. On the other hand, solution B
As a solution, 62.88 g (0.593 mol) of sodium carbonate was dissolved in 500 g of deionized water.

The solution A and the solution B were added dropwise to a catalyst adjusting tank previously charged with 480 g of deionized water in 1 hour while keeping the pH at 9 and the temperature at 70 ° C. with 10 N NaOH. Aged for 1 hour. The mother liquor was removed by filtration, the precipitate was washed with 9.6 liters of deionized water, and spray-dried to obtain 92 g of a composite hydroxide. This composite hydroxide was calcined in a nitrogen atmosphere at 800 ° C. for 3 hours to obtain a composite oxide catalyst of Mg, Al and Mn (Mg: A).
l: Mn (atomic ratio) = 0.56: 0.26: 0.18)
60 g was obtained.

Comparative Example 1 As solution A, 57.26 g (0.223 mol) of magnesium nitrate hexahydrate and 66.80 g (0.178 mol) of aluminum nitrate nonahydrate were added to 450 g of deionized water. Dissolved. On the other hand, as solution B, 18.87 g (0.178 mol) of sodium carbonate was dissolved in 450 g of deionized water. Then, a composite oxide catalyst of Mg and Al (Mg:
17 g of Al (atomic ratio) = 0.556: 0.444) was obtained.

(Comparative Example 2) 2.5 MgO.Al ₂ O ₃ .mH ₂
25 g of aluminum-magnesium hydroxide having a chemical composition of O (Kyowaad 300, manufactured by Kyowa Chemical Co., Ltd.) was baked at 800 ° C. for 3 hours in a nitrogen atmosphere to obtain 16 g of a composite oxide catalyst of magnesium and aluminum.

Comparative Example 3 Mg ₆ Al ₂ (OH) ₁₆ CO ₃
25 g of hydrotalcite (Kyowa Chemical Co., Ltd .; Kyoward 500) having a chemical composition of 4H ₂ O under a nitrogen atmosphere,
It was calcined at 500 ° C. for 3 hours to obtain 18 g of a composite oxide catalyst of Mg and Al.

The above Examples 1 to 10 and Comparative Examples 1 to 3
The reaction evaluation of the alkylene oxide addition reaction was carried out on the catalyst obtained in 1. by the following reaction evaluation method I, and reaction examples 1 to 10 and reaction comparative examples 1 to 3 were obtained. Further, the catalytic activity and the amount of by-produced high molecular weight polyethylene glycol (PEG) in each reaction example were evaluated by the following methods. The above results are shown in Table 1.

Further, the catalysts obtained in Example 1 and Comparative Example 1 were subjected to a reaction evaluation of an alkylene oxide addition reaction by the following reaction evaluation method II.
1 and Reaction Comparative Example 4 were set. The results are shown in Table 2.

[Reaction Evaluation Method I] 400 g of lauryl alcohol and 0.
4 g was charged, the inside of the autoclave was replaced with nitrogen, and the temperature was raised with stirring. Next, the temperature is 180 ° C and the pressure is 3a.
ethylene oxide (EO) 663 while maintaining at tm
g (average number of added moles: 7) was introduced, and lauryl alcohol and EO were reacted.

[Reaction Evaluation Method II] 400 g of methyl laurate and 1.2 g of catalyst were placed in a 4 liter autoclave.
g and 0.12 g of 40% KOH aqueous solution were charged, the inside of the autoclave was replaced with nitrogen, and the temperature was raised with stirring. Then, while maintaining the temperature at 180 ° C. and the pressure at 3 atm, E
O494 g (average number of moles added: 6) was introduced, and the reaction between methyl laurate and EO was performed.

[Catalytic activity] In each of the above reaction evaluation methods, the EO supply rate (g-EO / min) from the time when the temperature became constant (180 ° C.) and constant pressure (3 atm) was converted per unit amount of catalyst, It was used as an evaluation scale of activity (unit is g-EO / (min ・
g-catalyst)). The EO supply rate corresponds to the EO consumption amount per unit time in the constant temperature and constant pressure. In this measurement, the catalyst concentration was adjusted so that the catalyst activity under the control of the chemical reaction rate could be correctly evaluated.

[By-produced high molecular weight PEG amount] In each of the above reaction evaluation methods, the amount of high molecular weight polyethylene glycol having a molecular weight of 20,000 or more in the reaction product was quantitatively analyzed by the HPLC method.
The comparison was made by weight.

[0058]   (Table 1)               Reaction Examples 1 to 10 and Reaction Comparative Examples 1 to 3   ――――――――――――――――――――――――――――――――――                 Complex oxide catalyst Catalytic activity By-product High molecular weight PEG amount                               (G-EO / (min ・ g-cat)) (wt%)   ――――――――――――――――――――――――――――――――――               1 Example 1 catalyst 6.0 0.06               2 Example 2 catalyst 11.1 0.04               3 Example 3 catalyst 8.6 0.09               4 Example 4 catalyst 3.4 0.05   Reaction Example 5 Example 5 Catalyst 3.6 0.16               6 Example 6 catalyst 3.0 0.20               7 Example 7 catalyst 6.1 0.05               8 Example 8 catalyst 4.5 0.02               9 Example 9 catalyst 4.7 0.05               10 Example 10 Catalyst 9.2 0.04   ――――――――――――――――――――――――――――――――――               1 Comparative Example 1 catalyst 5.7 0.53   Reaction Comparative Example 2 Comparative Example 2 Catalyst 4.8 0.60               3 Comparative Example 3 catalyst 6.7 1.10   ――――――――――――――――――――――――――――――――――

[0059]   (Table 2)                   Reaction Example 11 and Reaction Comparative Example 4   ――――――――――――――――――――――――――――――――――                 Complex oxide catalyst Catalytic activity By-product High molecular weight PEG amount                               (G-EO / (min ・ g-cat)) (wt%)   ――――――――――――――――――――――――――――――――――   Reaction Example 11 Example 1 Catalyst 2.7 0.06   ――――――――――――――――――――――――――――――――――   Reaction Comparative Example 4 Comparative Example 1 Catalyst 1.9 0.58   ――――――――――――――――――――――――――――――――――

As is clear from the results shown in Tables 1 and 2, it is understood that the catalyst of the present invention suppresses by-production of high molecular weight polyethylene glycol. In particular, according to the Mn-added catalyst of Example 1, the amount of high-molecular-weight polyethylene glycol by-produced was reduced to about 1/10 of that of the catalyst of Comparative Example 1 prepared by the same method and containing no Mn. Diminished.

Further, regarding the EO adducts obtained in Reaction Examples 1 to 6 and 11 and Reaction Comparative Examples 1 to 4, HP
The EO-added molar distribution was measured by the LC method. The result is shown in Figure 1.
~ Shown in FIG. Also, for comparison of the distribution of added moles,
The reaction evaluation of the alkylene oxide addition reaction was carried out by the above reaction evaluation method I using a KOH catalyst which was an alkali catalyst, and the addition molar distribution of the EO adduct obtained by this reaction evaluation was measured in the same manner as above. Results are shown in FIG.

Further, the crystal structures of the catalysts obtained in Examples 1, 3, 4 and Comparative Example 1 were examined by X-ray diffraction. The results are shown in FIGS. 13 and 14. As shown in FIG. 13, in each example, formation of spinel type oxide (MnAl ₂ O ₄ ) composed of aluminum and manganese was confirmed. Further, a peak due to an oxide having a rock salt structure (MgO) was also confirmed together with a peak due to an oxide having a spinel structure. On the other hand, as shown in FIG. 14, in the comparative example, only the peak due to the rock salt structure of magnesium oxide was observed.

[Brief description of drawings]

FIG. 1 is a diagram showing an addition mole distribution of an EO adduct obtained in Reaction Example 1 using a catalyst of the present invention.

FIG. 2 is a diagram showing an addition mole distribution of the EO adduct obtained in Reaction Example 2 using the catalyst of the present invention.

FIG. 3 is a diagram showing an addition mole distribution of the EO adduct obtained in Reaction Example 3 using the catalyst of the present invention.

FIG. 4 is a diagram showing an addition mole distribution of the EO adduct obtained in Reaction Example 4 using the catalyst of the present invention.

FIG. 5 is a diagram showing an addition mole distribution of the EO adduct obtained in Reaction Example 5 using the catalyst of the present invention.

FIG. 6 is a view showing an addition mole distribution of the EO adduct obtained in Reaction Example 6 using the catalyst of the present invention.

FIG. 7 is a diagram showing an addition mole distribution of an EO adduct obtained in Reaction Comparative Example 1.

FIG. 8 is a diagram showing an addition mole distribution of an EO adduct obtained in Reaction Comparative Example 2.

FIG. 9 is a diagram showing an addition molar distribution of an EO adduct obtained in Comparative Reaction Example 3.

FIG. 10 is a diagram showing an addition mole distribution of the EO adduct obtained in Reaction Example 11 using the catalyst of the present invention.

FIG. 11 is a diagram showing an addition mole distribution of an EO adduct obtained in Reaction Comparative Example 4.

FIG. 12 is a diagram showing an addition mole distribution of an EO adduct obtained by a reaction example using a KOH catalyst.

FIG. 13 is an X-ray diffraction chart of the catalysts of the present invention obtained in Examples 1, 3 and 4.

FIG. 14 is an X-ray diffraction chart of the conventional catalyst obtained in Comparative Example 1.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) B01J 23/64 B01J 23/64 Z 23/74 23/74 Z 23/745 23/84 Z 23/84 23/89 Z 23/89 C07D 303/04 C07D 303/04 C07B 61/00 300 // C07B 61/00 300 C07C 41/03 C07C 41/03 B01J 23/74 301Z

Claims (8)

[Claims] 1. Magnesium, aluminum and 6A
An alkoxylation catalyst comprising a metal oxide containing at least one metal selected from Group 7, Group 7A and Group 8. 2. The at least one metal selected from the 6A group, 7A group and 8 group includes any metal selected from chromium, molybdenum, manganese, technetium, iron, cobalt, nickel and ruthenium. The alkoxylation catalyst according to 1. 3. The atomic ratio of magnesium to aluminum is 0.1 / 0.1 expressed as Al / (Mg + Al).
The alkoxylation catalyst according to claim 1 or 2, which is 0.7. 4. The atomic ratio of at least one metal selected from the 6A group, 7A group and 8 group to all metal atoms,
The catalyst for alkoxylation according to any one of claims 1 to 3, which is 0.05 to 0.4. 5. The alkoxylation catalyst according to claim 1, which contains a spinel-type oxide of aluminum and at least one metal selected from the groups 6A, 7A, and 8. 6. Magnesium, aluminum and metal M
(M is a metal element except magnesium and aluminum)
A catalyst for alkoxylation comprising a spinel-type oxide of aluminum and the metal M, which is composed of a metal oxide containing 7. Magnesium and aluminum and a group 6A,
A precipitate containing magnesium, aluminum and at least one metal selected from groups 6A, 7A and 8 is produced from a mixed aqueous solution containing at least one metal selected from groups 7A and 8 A method for producing an alkoxylation catalyst, comprising the steps of: calcining the precipitate at 300 to 1000 ° C. 8. A process for producing an alkylene oxide adduct, which comprises adding an alkylene oxide to an organic compound using the alkoxylation catalyst according to claim 1.