JP2001232210A - Alkoxylation catalyst and method for producing alkylene oxide adduct using the catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alkoxylation catalyst enhanced in its catalytic activity without altering the baking condition and composition of a compound metal oxide. SOLUTION: The surface of a magnesium/aluminum compound oxide catalyst is treated with at least one kind of a coupling agent among a titanate type coupling agent and an aluminum type coupling agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a catalyst for alkoxylation and a method for producing an alkylene oxide adduct using the catalyst for alkoxylation.

[0002]

2. Description of the Related Art Alkylene oxide adducts of organic compounds having active hydrogen or derivatives thereof are widely used as solvents, surfactants and various chemical intermediates. In particular, alkylene oxide adducts obtained by adding ethylene oxide, propylene oxide, or the like to alcohols, fatty acids, fatty acid esters, amines, alkylphenols, and the like are widely used as nonionic surfactants. Among them, an adduct having a narrow alkylene oxide addition molar distribution has advantages such as higher detergency and foaming power and less odor derived from unreacted substances, as compared with an adduct having a wide addition molar distribution. are doing.

As a catalyst for alkoxylation for producing such an alkylene oxide adduct, the following composite metal oxides have been proposed. 1) Magnesium oxide to which metal ions such as aluminum are added (Japanese Patent Laid-Open No. 1-164437: for example,
Magnesium oxide containing aluminum by weight is disclosed. ). 2) A calcined hydrotalcite obtained by calcining a natural or synthetic hydrotalcite (Japanese Patent Laid-Open No. 2-7)
No. 1841). 3) Magnesium oxide containing zinc, antimony, tin, etc. (JP-A-7-227540). 4) Aluminum / magnesium composite oxide obtained by calcining aluminum / magnesium hydroxide (Japanese Patent Application Laid-Open No. 8-268919).

According to the above-mentioned composite metal oxide, an alkoxylation reaction can be catalyzed by a joint effect of an acid site and a base site on the catalyst surface, and an adduct having a narrow alkylene oxide addition molar distribution is produced. be able to.

[0005]

In the production of alkylene oxide adducts, the higher the catalytic activity of the alkoxylation catalyst used, the higher the production efficiency. This is because if the catalyst activity is high, the reaction time can be shortened, and the reaction can be carried out with a small amount of catalyst, so that separation and recovery of the catalyst after the reaction become easy. For this reason, in the catalyst for alkoxylation, further improvement in catalytic activity is required.

An object of the present invention is to provide a catalyst for alkoxylation having high catalytic activity and a method for producing an alkylene oxide adduct using the same.

[0007]

In order to achieve the above object, an alkoxylation catalyst of the present invention is an alkoxylation catalyst containing a composite metal oxide having an alkoxylation catalyst activity, and further comprising a hydrocarbon chain. Wherein the molecule is bonded to the surface of the composite metal oxide.

[0008] Such an alkoxylation catalyst has high catalytic activity. This is presumed to be because the surface of the composite metal oxide is hydrophobized by molecules containing a hydrocarbon chain, so that the dispersibility in a lipophilic reaction solvent is improved. Further, in this alkoxylation catalyst, there is no restriction on the composition of the composite metal oxide and the firing conditions. Therefore, properties dependent on the composition and firing conditions of the composite metal oxide (eg, selectivity of the catalyst, addition molar distribution of the alkylene oxide adduct generated in the catalytic reaction, etc.)
High catalytic activity can be obtained without deteriorating the catalytic activity.

In the above alkoxylation catalyst, the molecule preferably further contains a metal atom, and the metal atom and the metal atom on the surface of the composite metal oxide are preferably bonded via an oxygen atom. . According to this preferred example, a high catalytic activity can be realized more reliably.
It is presumed that this is because the metal atom contained in the molecule functions as a new active site.

In this preferred example, it is particularly preferable that the metal atom contained in the molecule is at least one metal of titanium and aluminum.

In the alkoxylation catalyst, the composite metal oxide preferably contains magnesium and aluminum. According to this preferred example, in addition to ensuring high catalytic activity, it is possible to produce an alkylene oxide adduct having a narrow addition molar distribution.

In the above alkoxylation catalyst, the composite metal oxide may further contain Fe, Ni, Cr,
It is preferable to contain at least one metal selected from the group consisting of Mn, Ti, B, Ga, Ce, Mo and Zr. According to this preferred example, since the selectivity of the catalyst is improved, when used for the production of an alkylene oxide adduct, the production of the polymer polyalkylene glycol as a by-product can be suppressed, and the production efficiency can be improved. it can.

The method for producing an alkylene oxide adduct of the present invention is characterized in that an alkylene oxide is added to an organic compound in the presence of the catalyst for alkoxylation of the present invention.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION In the alkoxylation catalyst of the present invention, a hydrocarbon chain-containing molecule is bonded to the surface of a composite metal oxide having an alkoxylation catalytic activity.

The composite metal oxide is not particularly limited as long as it has an alkoxylation activity.
Preferred composite metal oxides include magnesium / aluminum composite oxides. In this case, the atomic ratio of magnesium to aluminum is Al / (Mg + A
As represented by l), for example, it is 0.1 to 0.7, preferably 0.3 to 0.6, and more preferably 0.4 to 0.5.

Further, the composite metal oxide is preferably a magnesium / aluminum composite oxide containing a third metal. The third metal is, for example, Fe, N
i, Cr, Mn, Ti, B, Ga, Ce, Mo and Z
r, which may be used alone or in combination of two or more. Among these, Fe, Cr, and Mn are preferable, and Mn is particularly preferable. The content of the third metal is, for example, 0.01 to 0.5, preferably 0.05 to 0.3, more preferably 0.1 to 0. 2.

The composite metal oxide is, for example, impregnated,
It can be prepared by a conventionally known method such as a coprecipitation method. Hereinafter, an example of a method for preparing a composite metal oxide powder by a coprecipitation method will be described.

First, a mixed aqueous solution containing ions of each metal is prepared, and a precipitant is added to the mixed aqueous solution. The mixed aqueous solution can be prepared, for example, by mixing aqueous solutions containing metal compounds such as nitrates, sulfates, carbonates, acetates, and chlorides of the respective metals. As the precipitant, for example,
Alkali metal hydroxides, carbonates or mixtures thereof can be used.

The precipitate deposited by the addition of the precipitant is washed with water, dried, and then calcined to obtain a composite metal oxide. The firing temperature is, for example, 300 to 100.
0 ° C., preferably 600-900 ° C., more preferably 7 ° C.
00 to 900 ° C. The firing time is, for example, 0.1.
It is 5 to 10 hours, preferably 1 to 5 hours, more preferably 2 to 4 hours. Further, the firing is preferably performed in an inert gas atmosphere, and more preferably in a nitrogen atmosphere.

The hydrocarbon-containing molecule is not particularly limited as long as it contains a hydrocarbon chain and can bind to the surface of the composite metal oxide.

The hydrocarbon chain contained in the hydrocarbon-containing molecule is not particularly limited, but preferably has a hydrophobic property. For example, carbon number 2-30, preferably 3
To 25, more preferably 8 to 18 hydrocarbon chains.
Further, the hydrocarbon chain may be linear or branched, and may be saturated or unsaturated. Further, it may contain a hetero atom such as O, N, P, and S.

Further, the hydrocarbon chain-containing molecule has a metal atom at one end of the hydrocarbon chain, and this metal atom is bonded to a metal atom of the composite metal oxide via an oxygen atom, whereby a composite metal oxide is formed. It is preferable to be fixed to the surface of the object. Al and Ti are particularly preferred as metal atoms.

Such hydrocarbon chain-containing molecules include:
For example, a coupling agent can be used. In particular, it is preferable to use a titanate coupling agent and an aluminum coupling agent. One type of coupling agent may be used alone, or two or more types may be used in combination.

Examples of the titanate coupling agent include a titanium acylate compound and a titanium chelate compound. Specifically, for example, isopropyl triisostearoyl titanate, isopropyl tri-
n-dodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraisopropyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) ) Bis (ditridecyl phosphite) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearyl titanate, isopropyl tri (dioctyl phosphate) titanate, Isopropyl tricumylphenyl titanate, isopropyl tri (N-aminoethyl-amino Le), such as titanate, and the like. Of these, isopropyl triisostearoyl titanate, isopropyl trioctanoyl titanate, and isopropyl dimethacryl isostearyl titanate are preferred, and isopropyl triisostearoyl titanate is particularly preferred.

As the aluminum-based coupling agent,
For example, an aluminum acylate compound and an aluminum chelate compound are mentioned. Specifically, acetoalkoxyaluminum diisopropylate is preferred.

The method for bonding the hydrocarbon chain-containing molecule to the surface of the composite metal oxide is not particularly limited. For example, when a coupling agent is used, a known method such as a gas phase method, a liquid phase method, an autoclave method, or a mechanochemical method may be employed as a surface treatment method of the inorganic powder with the coupling agent. In particular,
The liquid phase method is preferred because the operation is simple and the apparatus is not restricted.

An example of the treatment of the coupling agent by the liquid phase method will be described. First, an adsorption solution is prepared by dispersing a coupling agent in a solvent, and a composite metal oxide is immersed in the adsorption solution. Thereafter, the catalyst is separated from the adsorbed solution by filtration, washed, and dried to obtain a composite metal oxide having a coupling agent bonded to the surface.

The solvent constituting the adsorption solution is not particularly limited, but for example, benzene, n-hexane, toluene, ethanol, isopropanol, tricrene, methanol, ethyl acetate and the like can be used. Among these, benzene, n-hexane and isopropanol are preferred, and benzene and n-hexane are particularly preferred.

The amount of the coupling agent contained in the adsorption solution is appropriately determined depending on the types of the coupling agent and the composite metal oxide. For example, 1 × 10 ⁻⁶ to 1 mol per 1 g of the composite metal oxide is used. Preferably 1 × 10 ^-5 to 1 mol,
More preferably, it is 1 × 10 ^{-4 to} 5 × 10 ^-1 mol. If the amount of the coupling agent is less than 1 × 10 ⁻⁶ mol, the effect of increasing the catalytic activity may not be easily exhibited. Also,
Even if the amount of the coupling agent is more than 1 mol, the effect of increasing the catalytic activity corresponding to the amount cannot be expected, which may be disadvantageous in cost. This is because the effect of increasing the catalytic activity reaches saturation when the entire surface of the composite metal oxide is covered with the monomolecular film of the coupling agent.

The temperature of the adsorption solution is, for example, 10 to 80 ° C., preferably 15 to 60 ° C., and more preferably 20 to 40 ° C. The immersion time of the catalyst is, for example, 0.5 to 100.
Time, preferably 1 to 50 hours, more preferably 12 to
24 hours.

Next, an example of the method for producing the alkylene oxide adduct of the present invention will be described. The production method of the present invention is carried out by reacting an organic compound with an alkylene oxide in the presence of the catalyst for alkoxylation of the present invention.

The organic compound is not particularly limited as long as it can be alkoxylated. In particular,
Organic compounds having active hydrogen and derivatives thereof are given. Examples include alcohols, phenols, polyols, fatty acids, fatty acid esters, carboxylic acids, thiols, fatty acid amides, aliphatic amines, and mixtures thereof. Of these, alcohols, fatty acid esters, and aliphatic amines are preferred, and alcohols are particularly preferred.

The alcohols include, for example, those having 2 to 30 carbon atoms, preferably 6 to 24 carbon atoms, and more preferably 12 to 24 carbon atoms.
18 saturated or unsaturated alcohols and the like.
In particular, primary and secondary alcohols are preferred, and primary alcohols are more preferred. The alcohols may be used alone or as a mixture of two or more.

The phenols include, for example, mono-, di- or trialkylphenols. Particularly, a mono-, di- or trialkylphenol having an alkyl group having 4 to 12 carbon atoms is preferable.

As the polyols, polyethylene glycol, polypropylene glycol, glycerin, sorbitol and the like are preferable. In the case of polyethylene glycol and polypropylene glycol, the average degree of polymerization is, for example, 2 to 2000, preferably 4 to 500, and more preferably 10 to 200.

The fatty acids include, for example, those having 8 to 8 carbon atoms.
22, preferably 10 to 20, more preferably 12 to 1
8 saturated or unsaturated fatty acids and mixtures thereof. In particular, caprylic acid, capric acid, lauric acid, myristic acid, oleic acid, stearic acid and mixtures thereof are preferred. Such fatty acids can be obtained, for example, by decomposing coconut oil, palm oil, palm kernel oil, soybean oil, sunflower oil, rapeseed oil and fish fat oil. Examples of the fatty acid esters include those obtained by esterifying the fatty acid with an alkyl group having 1 to 4 carbon atoms.

Examples of the aliphatic amines include those having 8 to 44 carbon atoms, preferably 10 to 22 carbon atoms, and more preferably 1 to 22 carbon atoms.
And aliphatic amines having 2 to 18 saturated or unsaturated alkyl groups. In particular, primary aliphatic amines are preferred. Further, as fatty acid amides, for example,
Fatty acid amides having a saturated or unsaturated acyl group having 8 to 22, preferably 10 to 20, and more preferably 12 to 18 carbon atoms are exemplified. In particular, primary or secondary fatty acid amides are preferred.

As the alkylene oxide to be reacted with the organic compound, an alkylene oxide having 2 to 8 carbon atoms is preferably used. In particular, alkylene oxides having 2 to 4 carbon atoms, that is, ethylene oxide, propylene oxide and butylene oxide are preferred.

The reaction conditions for the alkoxylation reaction using the catalyst of the present invention are not particularly limited. For example, the reaction can be carried out under conventional reaction conditions. Hereinafter, preferable reaction conditions will be described. The reaction temperature is, for example, 80 to 230.
° C, preferably 120-200 ° C, more preferably 16 ° C
0-180 ° C. The reaction pressure is appropriately determined depending on the reaction temperature, for example, 0 to 20 atm, preferably 2 to 20 atm.
8 atm, more preferably 2 to 6 atm. Also,
The amount of the catalyst used is appropriately determined depending on the ratio of the organic compound to the reaction and the alkylene oxide. For example, 0.01 to 20 parts by weight, preferably 0.05 to 100 parts by weight, per 100 parts by weight of the organic compound. It is 10 parts by weight, more preferably 0.1 to 5 parts by weight.

Next, an example of a specific reaction operation will be described. First, an organic compound as a starting material and a catalyst are charged into an autoclave, and the inside of the autoclave is replaced with nitrogen. Then, an alkylene oxide is introduced under a predetermined temperature and pressure to cause a reaction. After the completion of the reaction, the product is cooled, and the catalyst is filtered off from the product to obtain an alkylene oxide adduct.

[0041]

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

Example 1 2.5 MgO.Al ₂ O ₃ .m
Aluminum magnesium magnesium represented by the composition formula of H ₂ O (trade name: Kyoward 30 manufactured by Kyowa Chemical Industry Co., Ltd.)
0 "and the same hereinafter. ) Was fired at 700 ° C. for 3 hours in a nitrogen stream to obtain an aluminum / magnesium composite oxide powder. 100 ml of benzene and isopropyl tristearoyl titanate (trade name: "KR TT", manufactured by Ajinomoto Co.)
S "and the same hereinafter. ) 0.0957 g (1.0 × 10 ⁻³ mol) and stirred at room temperature for 10 minutes. 3.0 g of the above-mentioned composite metal oxide powder was added thereto, and the mixture was stirred at room temperature for 30 minutes, and then left overnight. After standing, the composite metal oxide powder filtered off from the solvent was washed with 500 ml of benzene and subsequently with 250 ml of acetone. The washed composite metal oxide powder was vacuum-dried at room temperature for 1 hour as preliminary drying, and further vacuum-dried at 50 ° C. for 3 hours to obtain a catalyst.

Example 2 A catalyst was obtained in the same manner as in Example 1 except that 0.957 g (1.0 × 10 ^-2 mol) of isopropyl tristearoyl titanate was used.

Example 3 A catalyst was obtained in the same manner as in Example 1 except that 9.57 g (1.0 × 10 ^-1 mol) of isopropyl tristearoyl titanate was used.

Example 4 A catalyst was obtained in the same manner as in Example 1 except that 47.85 g (5.0 × 10 ^-1 mol) of isopropyl tristearoyl titanate was used.

Example 5 Instead of isopropyl tristearoyl titanate, acetoalkoxy aluminum diisopropylate (trade name: “AL-” manufactured by Ajinomoto Co.)
M ") was used in the same manner as in Example 1 except that a catalyst was obtained. In addition, 4.96 g of acetoalkoxy aluminum diisopropylate was used for 100 ml of benzene.
(1.0 × 10 ⁻¹ mol) was used.

Example 6 Magnesium nitrate hexahydrate 6
8.03 g (0.265 mol) and aluminum nitrate 9
47.69 g (0.127 mol) of hydrate and 24.33 g (0.085 mol) of manganese nitrate hexahydrate in 450
g of deionized water to obtain a solution A. On the other hand, a solution B was prepared by dissolving 13.47 g (0.127 mol) of sodium carbonate in 450 g of deionized water. Solution A and solution B were added to a catalyst preparation tank previously charged with 1800 g of deionized water, and the pH was maintained at 9 with 2M NaOH, and the temperature was adjusted to 40.
The mixture was added dropwise over 1 hour while maintaining the temperature at 0 ° C, and after completion of the addition, the mixture was aged for 1 hour. The precipitate is filtered from the solution, washed with 6 liters of deionized water, and spray-dried to obtain 30 g.
Was obtained. This composite metal hydroxide is
Baking at 800 ° C. for 3 hours in a nitrogen atmosphere, Mg, Al,
19 g of a composite metal oxide powder containing Mn was obtained. A catalyst was obtained in the same manner as in Example 3 except that this composite metal oxide powder was used.

Comparative Example 1 2.5 MgO.Al ₂ O ₃ .m
Aluminum / magnesium hydroxide represented by the composition formula of H ₂ O was calcined at 700 ° C. for 3 hours in a nitrogen stream to obtain a catalyst.

Comparative Example 2 A catalyst was obtained in the same manner as in Example 6, except that no coupling treatment was performed.

Using the catalysts obtained in Examples 1 to 6 and Comparative Examples 1 and 2, an alkylene oxide addition reaction was carried out to evaluate the catalytic activity. Table 1 shows the results. In addition, the reaction conditions, the operation method, and the evaluation method of the catalyst activity are as follows.

[Reaction conditions and operating method] 400 g of lauryl alcohol and 0.4 g of catalyst were placed in an autoclave.
After the inside of the autoclave was replaced with nitrogen, the temperature was increased while stirring. Next, the inside of the autoclave is
C. and 3 atm while maintaining ethylene oxide (E
O) 663 g (7 moles per mole of lauryl alcohol) were introduced, and lauryl alcohol was reacted with EO.

[Evaluation Method of Catalytic Activity] The reaction was carried out under the above reaction conditions and operation method, and E was measured from the time when the inside of the autoclave became constant temperature (180 ° C.) and constant pressure (3 atm).
The O supply rate (g-EO / min) was converted per unit amount of catalyst and used as an evaluation scale of catalytic activity (unit: g-EO / (min · g-ca).
t)). The EO supply speed corresponds to the amount of EO consumed per unit time under a constant temperature and a constant pressure. At the time of this measurement, the catalyst concentration was adjusted to be small enough to correctly evaluate the catalyst activity under the control of the chemical reaction rate.

[Table 1] Catalytic activity [g-EO / min / g-Cat] Example 1 12.23 Example 2 14.56 Example 3 18.84 Example 4 18.80 Example 5 11.09 Example 6 18.83 Comparative Example 1 7.65 Comparative Example 2 6.00

As is clear from the results shown in Table 1, it was confirmed that the catalyst of the present invention can obtain high catalytic activity. In particular, according to the catalyst of Example 3, the catalyst activity was improved to about 2.5 times as compared with the catalyst of Comparative Example 1.

As described above, since the catalyst of the present invention has a high catalytic activity, the time required for the reaction is reduced. For example, in the reaction under the above reaction conditions and operation method, Comparative Example 2
The reaction time when the catalyst of Example 6 was used was 276 minutes, whereas the reaction time when the catalyst of Example 6 was used was 88 minutes.
Minutes.

Next, using the catalysts of Example 6 and Comparative Example 2, a reaction was carried out under the above reaction conditions and operating method, and the amount of by-product high-molecular polyethylene glycol (molecular weight: 20,000 or more) was measured. . As a result, the production amount of the high molecular weight polyethylene glycol was 0.04% by weight when the catalyst of Example 6 was used, and was 0.06% by weight when the catalyst of Comparative Example 2 was used. In addition, these numerical values are weight% with respect to the total amount of products. Thus, according to the present invention, high catalytic activity can be achieved without deteriorating the selectivity of the catalyst.

Using the catalysts of Example 6 and Comparative Example 2, a reaction was carried out under the above reaction conditions and operating method, and the addition molar distribution of the product ethylene oxide adduct was measured. FIG. 1 shows the results obtained when the catalyst of Example 6 was used, and FIG. 2 shows the results obtained when the catalyst of Comparative Example 2 was used.
Shown in As shown in FIGS. 1 and 2, the catalyst of Example 6 can also obtain a narrow additional molar distribution, similarly to the catalyst of Comparative Example 2. Thus, according to the present invention,
Without deteriorating the characteristic of narrowing the addition molar distribution of the alkylene oxide adduct generated by the catalytic reaction,
High catalytic activity can be achieved.

[0058]

As described above, the alkoxylation catalyst of the present invention comprises a composite metal oxide having an alkoxylation catalytic activity and a molecule having a hydrocarbon chain, and the surface of the composite metal oxide is Since the molecules are bonded, high catalytic activity can be obtained.

[Brief description of the drawings]

FIG. 1 is a graph showing an addition molar distribution of an ethylene oxide adduct generated by a reaction using a catalyst of Example 6.

FIG. 2 is a view showing an addition molar distribution of an ethylene oxide adduct generated by a reaction using the catalyst of Comparative Example 2.

Continuation of the front page (72) Inventor Shinno Uemura 1-37 Honjo, Sumida-ku, Tokyo F-term in Lion Corporation (reference) 4G069 AA04 BA01A BA01B BA06A BA06B BA20A BA20B BA27A BA27B BB06A BB06B BC10A BC10B BC16A BC16B BC17A BC23A BC43A BC50A BC50B BC51A BC58A BC59A BC62A BC62B BC66A BC68A BD03A BE06A BE06B BE08A BE08B CB25 CB61 DA05 EA01Y EC28 4H006 AA02 AC43 BA06 BA08 BA09 BA10 BA14 BA16 BA19 BA21 BA30 BA90 GN06 GP01

Claims (6)

[Claims] 1. An alkoxylation catalyst comprising a composite metal oxide having alkoxylation catalytic activity, further comprising:
A catalyst for alkoxylation comprising a molecule having a hydrocarbon chain, wherein the molecule is bonded to the surface of the composite metal oxide. 2. The method according to claim 1, wherein the molecule further includes a metal atom, and the metal atom and the metal atom on the surface of the composite metal oxide are:
The catalyst for alkoxylation according to claim 1, which is bonded via an oxygen atom. 3. The alkoxylation catalyst according to claim 2, wherein the metal atom contained in the molecule is at least one metal of titanium and aluminum. 4. The alkoxylation catalyst according to claim 1, wherein the composite metal oxide contains magnesium and aluminum. 5. The composite metal oxide further comprises Fe, N
i, Cr, Mn, Ti, B, Ga, Ce, Mo and Z
The catalyst for alkoxylation according to claim 4, comprising at least one metal selected from the group consisting of r. 6. A method for producing an alkylene oxide adduct, comprising adding an alkylene oxide to an organic compound in the presence of the alkoxylation catalyst according to any one of claims 1 to 5.