JPH06198169A - Catalyst for producing active hydrogen-containing organic compound alkoxylate - Google Patents

Abstract

PURPOSE:To provide a catalyst for producing an active hydrogen-containing organic compound alkoxylate to allow an active hydrogen-containing organic compound to react with an alkylene oxide. CONSTITUTION:The catalyst for producing the active hydrogen-containing organic compound alkoxylate composed of a multicomponent oxide of at least one kind selected from a group containing titanium and yttrium, and magnesium and to allow the active hydrogen-containing organic compound to react with the aldylene oxide is obtained. Thus, the adantages of the catalyst for producing the alkoxylate are to be narrow in the distribution of degre of polymerization of alkylene oxide addition to the formed active hydrogen-containing organic compound alkylate and small in unreacted active hydrogen-containing organic compound remaining quantity and side reaction product content in the reaction of the active hydrogen-containing organic compound with the slkylene oxide.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for producing an alkoxylate of an active hydrogen-containing organic compound composed of a magnesium-based composite oxide.

[0002]

Alkoxylates obtained by adding alkylene oxides such as ethylene oxide and propylene oxide to active hydrogen-containing compounds such as alcohols and phenols are used as surfactants and chemical intermediates.

The alkoxylation reaction for obtaining such an alkoxylate is represented by the following formula.

[0004] (R: alkyl group, n: 1 or an integer of 1 or more) This reaction is carried out in the presence of an acidic or basic catalyst. Conventionally used catalysts include lithium, sodium, potassium and other alkali metal hydroxides of Group I of the periodic table, soluble strong basic compound catalysts such as alkoxides, and boron, zinc, indium, tin, antimony, etc. There are acidic catalysts such as halides and inorganic acids such as sulfuric acid and phosphoric acid.

[0005]

However, these known catalysts have advantages and disadvantages. The alcohol alkoxylate obtained by using a strongly basic catalyst such as caustic potash or caustic soda has a wide distribution of degree of polymerization of alkylene oxide and a large amount of unreacted raw material alcohol remains. When unreacted alcohol remains, it gives an unpleasant odor to the alkoxylate or its sulfate ester salt (Japanese Patent Publication No. 51-43483), and adversely affects the performance as a surfactant (US Pat. No. 3). No. 682,849), the residual amount of unreacted alcohol is desired to be as small as possible.

On the other hand, when an acidic catalyst is used, these drawbacks are alleviated considerably, but when the number of addition moles of alkylene oxide increases, a side reaction occurs, and a large amount of dioxane, dioxolane, dialkyl ether, polyalkylene glycol. And so on.

Further, JP-A-57-42646 discloses that alcohols having 2 to 36 carbon atoms are based on strontium hydroxide or a hydrate thereof or barium hydroxide or a hydrate thereof, and magnesium oxide is added thereto. It is disclosed that the alkoxylation reaction is carried out at a temperature of 120 ° C. to 260 ° C. by contacting with an alkoxylating agent in the presence of an appropriate amount of a catalyst added.

Japanese Kokai 58-110531 discloses at least one alkanol having 6 to 30 carbon atoms.
A method for producing an alkanol alkoxylate, which comprises reacting a seed with at least one alkylene oxide having 2 to 4 carbon atoms, wherein the first component is at least one basic magnesium compound soluble in alkanol, and A group consisting of aluminum, boron, zinc, titanium, silicon, molybdenum, vanadium, gallium, germanium, yttrium, zirconium, niobium, cadmium, indium, tin, antimony, tungsten, hafnium, tantalum, thallium, lead and bismuth as two components. Reacting in the presence of a cocatalyst containing at least one alkanol-soluble compound of at least one element selected from the group consisting of: Reaction products of um and alcohol, as well as ammonia compounds, amide thiolate, thiophenoxide, and nitride compounds are mentioned.
And the magnesium metals, magnesium oxide and magnesium hydroxide previously contemplated for use as alkoxylation catalysts are substantially insoluble in C ₆ to C ₃₀ alkanols at temperatures suitable for the present invention and thus the present invention. It is specified that it is not directly suitable for the purpose of. JP 58-131930 discloses the preparation of alkanol alkoxylates by reacting at least one alkanol having 6 to 30 carbon atoms with at least one alkylene oxide having 2 to 4 carbon atoms. In the method, at least one basic magnesium compound soluble in alkanol and at least 2.0 mole percent of 1 to 30 C ₂ to C ₄ calculated as the reaction activator based on the moles of alkanol. The presence of at least one alkoxylate of at least one C ₁ to C ₃₀ alkanol having an alkylene oxide moiety of

Japanese Unexamined Patent Publication Nos. 1-164437 and 3-
No. 242421 and JP-A-3-242242 disclose Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , S.
for reacting an organic compound having active hydrogen with an alkylene oxide, which comprises magnesium oxide to which one or more metal ions selected from the group consisting of c ³⁺ , La ³⁺ and Mn ²⁺ are added. A catalyst for alkoxylation is disclosed.

The inventors of the present invention have been keen on a novel catalyst for producing an active hydrogen-containing organic compound alkoxylate having a narrow degree of polymerization distribution of alkylene oxide, a high conversion rate of the active hydrogen-containing compound as a raw material and a small amount of by-products. As a result of research and search, it has been found that a composite oxide of at least one selected from the group consisting of titanium and yttrium and magnesium has a unique and excellent catalytic effect which is not found in known catalysts. That is, when the magnesium-based composite oxide provided by the present invention is used as a catalyst in a reaction of adding an alkylene oxide to an active hydrogen-containing organic compound, the distribution of the degree of polymerization of the alkylene oxide is narrow, and the conversion of the raw material active hydrogen-containing compound is The inventors have found that an alkoxylate having a high rate and a small amount of by-products is provided, and completed the present invention.

[0011]

DISCLOSURE OF THE INVENTION The present invention provides titanium as a catalyst for alkoxylate production for alkoxylating an organic compound having active hydrogen with an alkylene oxide to obtain an alkylene oxide adduct of an active hydrogen-containing compound. And an active hydrogen-containing organic compound alkoxylate for reacting an active hydrogen-containing organic compound with an alkylene oxide, characterized by comprising a composite oxide of at least one selected from the group consisting of and yttrium and magnesium. A catalyst for use is provided.

The alkoxylate produced by the addition-polymerization reaction of an active hydrogen-containing compound such as alcohol or phenol with an alkylene oxide by the catalyst for producing an alkoxylate of the present invention has a content of unreacted active hydrogen-containing compound or by-product. And a narrow distribution of addition degree of alkylene oxide is obtained.

The active hydrogen-containing organic compound used in the present invention may be any one as long as it can be alkoxylated, but it is composed of alcohols, phenols, polyols, carboxylic acids, thiols and amines. One kind or a mixture of two or more kinds selected from the group is preferably used. Alcohols having 1 to 30 carbon atoms
The linear or side chain monohydric and polyhydric alcohols are preferred, and monohydric alcohols having 6 to 24 carbon atoms are more preferred. Specific examples include linear monohydric alcohols such as 1-hexanol, 1-octanol, 1-decanol, 1-dodecanol, 1-tetradecanol and the like. Examples of phenols include phenol, cresol, nonylphenol and bisphenol A. Examples of the polyols include glycerin, sorbitol, hexanetriol, sorbit, monoethylene glycol, diethylene glycol, triethylene glycol and the like. Examples of the carboxylic acids include acetic acid, stearic acid, acrylic acid, oleic acid, benzoic acid, maleic acid and terephthalic acid. Examples of the thiols include methyl mercaptan and lauryl mercaptan. Examples of amines include tert-butylamine, ethylenediamine, aniline and the like.

The alkylene oxide used in the present invention may be any epoxide-containing substance in view of its properties. For example, ethylene oxide, propylene oxide, butylene oxide or a mixture of two or more thereof is used. In particular ethylene oxide and propylene oxide are used.

As a source of titanium and yttrium for producing a catalyst for producing an alkoxylate containing an active hydrogen containing a complex oxide of at least one selected from the group consisting of titanium and yttrium of the present invention and magnesium. A compound containing at least one element selected from the group consisting of titanium and yttrium can be used. The compound used is not particularly limited as long as it is a compound containing at least one element selected from titanium and yttrium, but chlorides, nitrates, sulfates and the like of titanium and yttrium are preferably used.

Various magnesium compounds can be used as the magnesium source for producing the catalyst of the present invention. Magnesium oxide, hydroxide, chloride, nitrate, sulfate and the like are preferably used.

In the catalyst used in the present invention, the amount of titanium and yttrium oxides complexed with magnesium oxide is preferably 0.1 to 30% by weight, based on the catalytic amount of titanium and yttrium, and 0.5 to 20. Weight percent is more preferred.

As a method of producing a composite oxide of at least one selected from the group consisting of titanium and yttrium of the present invention and magnesium, for example, magnesium oxide is immersed in an aqueous solution of a water-soluble salt of titanium or yttrium. , Evaporate to dryness, then crush and add 400
℃ ~ 1000 ℃, preferably by baking at 500 ℃ ~ 800 ℃ (impregnation method), or an aqueous solution of a water-soluble salt of titanium or yttrium and a water-soluble salt of magnesium mixed aqueous solution with ammonia water, urea or the like. A method of neutralizing and precipitating a hydrate of a hydroxide or complex oxide, filtering, washing and drying this, and then calcining at 400 ° C to 1000 ° C, preferably 500 ° C to 800 ° C (coprecipitation method ) Etc.

The method for adding the active hydrogen-containing organic compound and the alkylene oxide to the composite oxide of at least one selected from the group consisting of titanium and yttrium of the present invention and magnesium is as follows. Although mixing is performed or an addition port is provided independently, in either case, there is a method of adding the entire amount from the beginning or a method of continuously or intermittently adding a fixed amount during the reaction. Furthermore, there is also a method of heating and reacting a mixture of an active hydrogen-containing organic compound and an alkylene oxide in a predetermined amount in a catalyst packed bed. Any method is possible, and in practice, it may be appropriately selected in consideration of the reaction format and the operation method.

[0020]

The reaction system of the alkoxylation of the active hydrogen-containing organic compound and the alkylene oxide using the catalyst of the present invention may be a batch system, a semi-batch system or a continuous system. The reaction temperature is 80 ° C to 250 ° C, preferably 130 ° C.
-220 degreeC, Most preferably, it is 130-200 degreeC. If the reaction temperature is too low, the reaction rate will be slow, and conversely, if it is too high, the generated alkoxylate will be decomposed, so this should be avoided.

The reaction pressure is not particularly limited,
Although it is possible to use either normal pressure or increased pressure, when the reaction pressure is low, the solubility of the alkylene oxide in the active hydrogen-containing reactant is lowered, so that the reaction rate is reduced and the alkylene oxide is dispersed. Industrially, it is desirable to pressurize with an inert gas such as nitrogen. The amount of the catalyst used varies depending on the reaction conditions such as the type of active hydrogen-containing organic compound or alkylene oxide used in the reaction and the alkylene oxide, the molar ratio of the two, the reaction temperature and the reaction pressure, and is usually 0.1% of the amount of the alcohol or the like. -30% by weight is preferable, and 2-
10% by weight is more preferred.

After reacting the active hydrogen-containing organic compound with the alkylene oxide in the presence of the catalyst of the present invention, the catalyst can be filtered off by filtration or the like.

The alkoxylates obtained with the catalysts according to the invention are essentially neutral, and thus such that the addition of acids or alkalis neutralizes the alkoxylates as with conventional catalysts. No action required.

[0024]

The present invention will be described in more detail with reference to the following examples. However, this embodiment is one aspect of the invention and does not limit the invention.

Example 1 Yttrium (III) nitrate hexahydrate (6.4 g) was added to pure water (5).
Magnesium oxide (MgO) powder 48 dissolved in 00 g
After adding g, the mixture was thoroughly stirred and then evaporated to dryness. Then 110
After drying overnight at ℃, it was crushed, gradually heated to evacuated and heated at 600 ℃ for 2 hours to obtain a catalyst.

In order to react 1-dodecanol with 4 moles of ethylene oxide, a stainless steel autoclave having a gas discharge pipe and a gas blowing pipe was used.
-257 g of dodecanol and 26 g of the above catalyst were charged, the inside of the autoclave was replaced with nitrogen, and then the temperature was raised to 175 ° C with stirring. Then, the pressure inside the autoclave was adjusted to 1 kg / cm ² with nitrogen, and then ethylene oxide was gradually introduced while paying attention so that the partial pressure of ethylene oxide inside the autoclave was ½ or less of the total pressure. While maintaining the reaction temperature at 175 ° C., 243 g of ethylene oxide was introduced. The time required to introduce ethylene oxide was 2 hours. The temperature was kept at 175 ° C until the partial pressure of ethylene oxide in the autoclave was lowered (aging step), then the reaction solution was cooled to 70 ° C, and the catalyst was filtered off. The content of unreacted 1-dodecanol of 1-dodecanol ethoxylate thus obtained was 4.6%.
(Gas chromatography area%). The ethylene oxide addition polymerization degree distribution of this ethoxylate was determined by gas chromatography and the results are shown in Table 1 and FIG.
Shown in. Similarly, FIG. 1 shows the ethylene oxide addition polymerization degree distribution of an ethoxylate (Comparative Example 2 described later) obtained using a conventional KOH catalyst. As is clear from the comparison of the two,
The ethoxylates obtained with the catalysts of the invention show a very narrow distribution of ethylene oxide addition degree of polymerization compared to ethoxylates produced with conventional catalysts. The amount of by-product polyethylene glycol contained in this ethoxylate was 1.0% by weight, which was smaller than that of the ethoxylate obtained using the conventional BF ₃ catalyst (Comparative Example 4 described later).

Example 2 Magnesium chloride (MgCl ₂ ) 85.0 g and titanium tetrachloride (TiCl ₄ ) 9.5 g were each added to 250 ml of pure water.
200 ml of 28% ammonia water was added to the aqueous solution obtained by mixing the solution dissolved in the above to coprecipitate. The precipitated product was filtered and washed with distilled water. AgN for washing liquid
While confirming the presence of Cl ⁻ depending on the presence or absence of a white precipitate of AgCl when the O ₃ aqueous solution was added, the washing was repeated until Cl ⁻ disappeared, then dried at 110 ° C. overnight and ground. This was gradually heated while being evacuated, and heat-treated at 600 ° C. for 2 hours to obtain a catalyst. A reaction was carried out in the same manner as in Example 1 except that 10 g of this catalyst was used, the amount of 1-dodecanol was 514 g, and the amount of ethylene oxide introduced was 243 g. The time required to introduce ethylene oxide was 5 hours. The amount of unreacted 1-dodecanol contained in the obtained ethoxylate was 20.2% (gas chromatography area%). The results of the ethylene oxide addition polymerization degree distribution of this ethoxylate obtained by gas chromatography are shown in Table 1 and FIG. The ethylene oxide addition polymerization degree distribution of the obtained ethoxylate and the ethylene oxide addition polymerization degree distribution of the ethoxylate obtained using the conventional catalyst KOH (Comparative Example 3 described later) are shown in FIG. As is clear from the comparison between the two, the ethoxylate obtained using the catalyst of the present invention has a narrower ethylene oxide addition degree of polymerization distribution than the ethoxylate obtained using the conventional catalyst, and the unreacted 1-dodecanol content is Few.

Comparative Example 1 Magnesium oxide powder alone was heat-treated under vacuum exhaust in the same manner as in Example 1 to obtain 26 g of a catalyst.
It was used to react 1-dodecanol with ethylene oxide as in Example 1. 90 g of ethylene oxide was introduced into the autoclave during the reaction for 40 hours, and the catalytic activity was remarkably low as compared with Examples 1 to 3.
Table 1 shows the results of the distribution of the degree of addition polymerization of ethylene oxide of this ethoxylate determined by the gas chromatography method.

Comparative Example 2 257 g of 1-dodecanol and KO were placed in an autoclave.
H 0.5 g (0.10% by weight based on the product after the reaction) was charged, and KOH was completely dissolved by heating and dehydration under reduced pressure to form potassium alcoholate of 1-dodecanol, and then the temperature was further raised to 155 ° C. The mixture was heated and adjusted with nitrogen so that the internal pressure of the autoclave became 1 kg / cm ^2, and ethylene oxide was gradually introduced while paying attention so that the partial pressure of ethylene oxide in the autoclave became 1/2 or less of the total pressure. While maintaining the reaction temperature at 155 ° C., 243 g of ethylene oxide was introduced. The time required to introduce ethylene oxide was 3 hours. The unreacted 1-dodecanol content of the ethoxylate obtained after aging is about 13%.
(Gas chromatography area%). The ethylene oxide addition polymerization degree distribution of this ethoxylate was determined by gas chromatography and the results are shown in Table 1 and FIG.
And shown in FIG. As is clear from the figure, the ethoxylate obtained using the conventional catalyst has a considerably broader ethylene oxide addition polymerization degree distribution than the ethoxylate obtained using the catalyst of the present invention.

Comparative Example 3 The reaction was carried out in the same manner as in Comparative Example 2 except that the amount of 1-dodecanol was 514 g and the amount of ethylene oxide was 243 g. The time required to introduce ethylene oxide was 1.5 hours. The unreacted 1-dodecanol content of the obtained ethoxylate was 30.5% (gas chromatography area%). The results of the ethylene oxide addition polymerization degree distribution of this ethoxylate obtained by gas chromatography are shown in Table 1 and FIG.

Comparative Example 4 257 g of 1-dodecanol (C
After charging 0.53 g of ₂ H ₅ ) ₂ O.BF ₃ (0.05% by weight as BF ₃ with respect to the reaction product), 50
The temperature inside the autoclave is raised to 1 ° C and the pressure inside the autoclave is 1 kg /
It was adjusted to be cm ² , and ethylene oxide was gradually introduced while paying attention so that the partial pressure of ethylene oxide in the autoclave was 1/2 or less of the total pressure. Reaction temperature 5
While maintaining the temperature at 0 ° C, 243 g of ethylene oxide was introduced. The time required for introduction was 1.5 hours. The unreacted 1-dodecanol content of the obtained ethoxylate was 3.8% (gas chromatography area%).
The results of the ethylene oxide addition polymerization degree distribution of this ethoxylate obtained by the gas chromatography method are shown in Table 1 and FIGS. 1 and 3. The amount of by-product polyethylene glycol contained in this ethoxylate is 4.8% by weight, which is larger than that obtained by using the catalyst of the present invention.

Example 3 Magnesium chloride 85.0 g and titanium tetrachloride 10.8 g
Then, 12.1 g of yttrium chloride hexahydrate was dissolved in 250 ml of pure water, and 225 ml of 25% aqueous ammonia was added to the aqueous solution to obtain a coprecipitate solution. The precipitated product was filtered and washed with distilled water. While confirming the presence of Cl ⁻ by the presence or absence of white precipitation of AgCl when the aqueous AgNO ₃ solution was added to the washing solution,
After repeating washing until Cl ^- is no longer detected, 1
It was dried overnight at 10 ° C. and ground. This was gradually heated while being evacuated, and heat-treated at 600 ° C. for 2 hours to obtain a catalyst. The reaction was performed in the same manner as in Example 1 except that 26 g of this catalyst was used. The time required to introduce ethylene oxide was 1.5 hours. The amount of unreacted 1-dodecanol contained in the obtained ethoxylate was 5.0% (gas chromatography area%). The results of the ethylene oxide addition polymerization degree distribution of this ethoxylate obtained by gas chromatography are shown in Table 1 and FIG. FIG. 3 shows the ethylene oxide addition polymerization degree distribution of the obtained ethoxylate and the ethylene oxide addition polymerization degree distribution of the ethoxylate obtained using the conventional catalyst KOH (Comparative Example 2). As is clear from the comparison between the two, the ethoxylate obtained using the catalyst of the present invention has a narrower ethylene oxide addition polymerization degree distribution than the ethoxylate obtained using the conventional catalyst.

[0033]

[Table 1]

[0034]

INDUSTRIAL APPLICABILITY The catalyst for producing an alkoxylate of the present invention can narrow the distribution of the degree of polymerization of alkylene oxide addition of the active hydrogen-containing organic compound alkoxylate produced in the reaction between the active hydrogen-containing organic compound and the alkylene oxide. Further, the residual amount of unreacted active hydrogen-containing organic compound and the by-product content can be reduced.

[Brief description of drawings]

FIG. 1 is a diagram showing a comparison of ethylene oxide addition polymerization degree distributions of ethoxylates obtained in Example 1 of the present invention and ethylene oxide addition polymerization degree distributions of ethoxylates obtained in Comparative Examples 2 and 4. The vertical axis represents the area% by gas chromatography of each ethoxylate component with respect to the total amount of ethoxylates, and the horizontal axis represents the number of moles of ethylene oxide added.

FIG. 2 is a diagram comparing the ethylene oxide addition polymerization degree distribution of the ethoxylate obtained in Example 2 of the present invention with the ethylene oxide addition polymerization degree distribution of the ethoxylate obtained in Comparative Example 3. The vertical axis represents the area% by gas chromatography of each ethoxylate component with respect to the total amount of ethoxylates, and the horizontal axis represents the number of moles of ethylene oxide added.

FIG. 3 is a diagram showing a comparison of ethylene oxide addition polymerization degree distributions of ethoxylates obtained in Example 3 of the present invention and ethylene oxide addition polymerization degree distributions of ethoxylates obtained in Comparative Examples 2 and 4. The vertical axis represents the area% by gas chromatography of each ethoxylate component with respect to the total amount of ethoxylates, and the horizontal axis represents the number of moles of ethylene oxide added.

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[Procedure amendment]

[Submission date] June 15, 1993

[Procedure Amendment 1]

[Document name to be corrected] Drawing

[Correction target item name] All drawings

[Correction method] Change

[Correction content]

[Figure 1]

[Fig. 2]

[Figure 3]

Claims (1)

[Claims] 1. Active hydrogen for reacting an active hydrogen-containing organic compound with an alkylene oxide, characterized by comprising a composite oxide of at least one selected from the group consisting of titanium and yttrium and magnesium. A catalyst for producing an alkoxylate containing an organic compound.