JP2006192375A - Catalyst for alkoxylation - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst which can significantly decrease a ratio of an unreacted material and an odor of a polymerization product caused thereby in a method for producing the catalyst used for adding ethylene oxide and other alkylene oxides to an active hydrogen-containing compound such as higher alcohols, alkyl phenols, fatty acids and alkylamines, and a method for producing an alkylene oxide adduct. <P>SOLUTION: The catalyst for a reaction for adding the alkylene oxide is provided by combining a metal alcoholate comprising at least one of a compound species shown by general formulas (1) to (3) and an acid compound of at least one selected from a group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid, formic acid, acetic acid, oxalic acid, tartaric acid, benzoic acid and p-toluenesulfonic acid. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a catalyst used for adding ethylene oxide and other alkylene oxides to active hydrogen-containing compounds such as higher alcohols, alkylphenols, fatty acids and alkylamines, and a method for producing an alkylene oxide adduct using the same.

  Alkylene oxide adducts such as those described above can freely combine the structure of a hydrophobic group and the structure of a hydrophilic group, so they are widely used as raw materials for household detergents, industrial surfactants, and anionic surfactants. Has been used. In order to produce an alkylene oxide adduct obtained from a compound having these active hydrogens and an alkylene oxide, conventionally, as a catalyst, a basic catalyst such as caustic soda, caustic potash, triethylamine, boron trifluoride, antimony pentachloride, etc. An acidic catalyst is used (for example, Patent Document 1).

  However, these known catalysts have the following disadvantages. That is, when a basic catalyst is used, it is easy to obtain a polymer having a low degree of by-products and a high degree of polymerization. It becomes a mixture containing up to a high degree. If there are many unreacted substances, the odor of the polymer is strong and the value of the petroleum ether soluble matter of the polymer is high, so there is a problem in using it as a surfactant for washing, and the polymerization of alkylene oxide If there are many high-grade ones, the balance between hydrophobicity and hydrophilicity will be lost, and there will be a problem such as deterioration in performance as a surfactant.

  On the other hand, when an acidic catalyst is used, unreacted products of active hydrogen-containing compounds such as higher alcohols are reduced, but many undesirable by-products such as polyethylene glycol and dioxane are generated. Moreover, since an acidic catalyst has strong corrosiveness with respect to a metal, the apparatus to be used is limited and has a fault as an industrial catalyst.

Conventionally, many catalysts for alkoxylation have been proposed as catalysts having a narrow polymerization degree distribution. However, in reality, there are hardly any catalysts capable of sufficiently narrowing the polymerization degree distribution while solving the above problems. .
JP 2002-308811 A

  The present invention has been made in view of the above problems, and in the catalyst for alkylene oxide addition and the method for producing an alkylene oxide adduct using the same, it is caused by residual unreacted substances and excessive spread of the polymerization degree distribution. We try to provide something that can prevent the occurrence of adverse effects.

The catalyst for an alkylene oxide adduct of the present invention is characterized by comprising a combination of a metal alcoholate comprising at least one of the compound types represented by the following general formulas (1) to (3) and an acid compound.

In these general formulas, R ¹ , R ² , R ³ and R ⁴ are each a hydrogen atom, an alkyl group or an alkoxy group, and at least one in each general formula is an alkoxy group. That is, all of the above compounds have at least one alkoxyl group. M ¹ is a magnesium (Mg) or calcium (Ca) atom, M ² is an aluminum (Al) or gallium (Ga) atom, and M ³ is a titanium (Ti) or zirconium (Zr) atom. The alkyl group has 1 to 18 carbon atoms, and the alkoxy group has, for example, 1 to 22 carbon atoms. More preferably, all of R ¹ , R ² , R ³ and R ⁴ are alkoxy groups.

  When the active hydrogen compound to which the alkylene oxide is to be added is an alcohol compound, for example, after adding the above-described metal alcoholate comprising an alkoxy group of the alcohol compound to the alcohol compound to be added, the acid compound is added. In addition, alkylene oxide is subsequently introduced. Here, the alcohol compound is not particularly limited, but is preferably a primary or secondary alcohol having a saturated or unsaturated linear or branched alkyl group having 6 to 30 carbon atoms.

  The ratio of the unreacted substance and the odor of the polymerization product resulting therefrom can be remarkably reduced. Further, the degree of polymerization distribution can be narrowed. That is, the proportion of the portion having a high degree of polymerization in the alkylene oxide chain can be reduced so that the performance as a surfactant does not deteriorate without losing the balance between hydrophobicity and hydrophilicity.

  The catalyst for addition of an alkylene oxide of the present invention is a combination of a metal alcoholate (metal alkoxide) and an inorganic or organic acid compound, and the metal alcoholate used here is particularly coordinated with at least one alcohol. It is a metal complex having a coordination number of 2 to 4. The metal alcoholate may be a metal alcoholate of a lower alcohol having 1 to 4 carbon atoms, or may be one obtained by replacing this lower alcohol with an active hydrogen compound to be added.

  As will be described later, the compound to which the alkylene oxide is added is not limited to an alcohol compound. However, in the present specification, the term “metal alcoholate” includes those in which an active hydrogen compound other than the alcohol compound is substituted with the alcohol of the metal alcoholate. Such a “metal alcoholate” can also be easily obtained by adding a metal alcoholate of the lower alcohol exemplified below to the active hydrogen compound to be added, followed by dehydration.

Specific examples of the compounds represented by the above general formulas (1) to (3) include divalent metal alcoholates (in the case of M ¹ ) such as magnesium diethylate, magnesium methoxyethylate, calcium diethylate, calcium. Examples include methoxyethylate or the like, or those obtained by replacing the alkoxyl group of these compounds with an active hydrogen compound to be added, which will be described later.

Trivalent metal alcoholates (in the case of M ² ) include aluminum triisopropylate, mono sec-butoxyaluminum diisopropylate, aluminum trisec-butyrate, aluminum tritert-butyrate, aluminum triethylate, gallium triisopropylate. And the like, or those obtained by replacing the alkoxyl group of these compounds with an active hydrogen compound to be added, which will be described later.

Examples of the tetravalent metal alcoholate (in the case of M ³ ) include tetraisopropyl titanate, tetramethyl titanate, and zirconium tetraisopropylate.

Preferred among the above are aluminum alcoholate is a trivalent metal alcoholate, more specifically, aluminum isopropylate _{(Al (iso-C 3 H} 7 O) 3), mono-sec- butoxy aluminum diisopropylate _{(Al (iso-C 3 H} 7 O) 2 (sec-C 4 H 9 O)), aluminum sec- butylate _{(Al (sec-C 4 H} 9 O) 3), aluminum ethylate (Al (O-C ₂ H ₅ O) ₃ ), aluminum tri tert-butyrate (Al (tert-C ₄ H ₉ O) ₃ ), or the like, or those obtained by replacing the alkoxyl group of these compounds with the active hydrogen compound to be added later. It is done.

  As the aluminum alcoholate, a commercially available product can be used, but a mixture of aluminum monoalcolate, dialcolate and trialcolate obtained by reacting aluminum trihalide or trialkylaluminum with alcohol can also be used. In this case as well, it is preferable that the content of the trialcolate is increased.

  In the present invention, as the acid compound combined with the metal alcoholate, a general organic acid or inorganic acid can be appropriately used. Preferable examples include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid, formic acid, acetic acid, oxalic acid, tartaric acid, benzoic acid, and paratoluenesulfonic acid, and use one or any combination thereof. Can do. Particularly preferred are sulfuric acid and phosphoric acid, which have no fear of side reaction such as reaction between a carboxyl group and alkylene oxide, and are less likely to volatilize or corrode the reaction vessel.

  The compounding molar ratio of the acid compound to the metal alcoholate is 0.5 to 4, preferably 1 to 3, and more preferably 1.5 to 2.5. When the compounding amount of the acid compound is less than this range, the effect of the present invention due to the compounding of the acid compound cannot be sufficiently obtained. On the other hand, when the compounding amount of the acid compound is higher than this range, the amount of by-products such as polyethylene glycol and dioxane increases, which is not preferable.

  The alkylene oxide used in the present invention may be any alkylene oxide that can react with a compound having active hydrogen to produce an alkoxylate, but has an oxirane ring such as ethylene oxide, propylene oxide, butylene oxide, and the like. Of these, ethylene oxide is particularly preferable.

  The active hydrogen-containing compound to which the alkylene oxide is added is not particularly limited, but is preferably one that does not substantially evaporate even under reduced pressure. For example, alcohols having 6 or more carbon atoms, polyhydric alcohols, phenols Carboxylic acids having 6 or more carbon atoms, amines and mixtures thereof. Examples of alcohols include primary alcohols, secondary alcohols, and arylalkyl alcohols having a saturated or unsaturated linear or branched alkyl group having 6 to 30 carbon atoms. Specific examples of the primary alcohol include n-octanol, n-decanol, n-dodecanol, oleyl alcohol, and 2-ethylhexanol. Examples of the secondary alcohol include 2-decanol and 2-dodecanol.

  Examples of the polyhydric alcohols include ethylene glycol, propylene glycol, diethylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol and the like. Examples of phenols include octylphenol and nonylphenol. Examples of the carboxylic acids include fatty acids having a saturated or unsaturated linear or branched alkyl group having 6 to 30 carbon atoms. Specific examples include lauric acid, stearic acid, oleic acid and the like. Examples of amines include primary or secondary amines having a saturated or unsaturated alkyl group having 8 to 30 carbon atoms. Specific examples include octylamine, laurylamine, stearylamine, distearylamine and the like.

  Among these active hydrogen atom-containing compounds, primary alcohols and secondary alcohols having a saturated or unsaturated linear or branched alkyl group having 8 to 22 carbon atoms are preferable, and carbon number is particularly preferable. It is a saturated primary or secondary alcohol having 10 to 18 linear or branched structures.

  The addition reaction of alkylene oxide can be easily carried out in a pressure reactor such as an autoclave under normal operating procedures and reaction conditions. In that case, it is preferable that reaction temperature is 60-150 degreeC, More preferably, it is 80-130 degreeC.

  In addition, the usage-amount of a catalyst is although it does not specifically limit, It is preferable that it is 0.1 to 5.0 weight% with respect to an active hydrogen containing compound.

  After completion of the alkylene oxide addition reaction, the catalyst is preferably deactivated and removed as follows. First, water is added and heated to hydrolyze the catalyst. Then, an adsorbent is added to adsorb the catalyst, and the catalyst is removed together with the adsorbent by filtration. As the adsorbent, a composite metal oxide containing magnesium oxide, aluminum oxide, silicon oxide or the like can be used. The adsorbent is preferably in the form of powder, for example, a composite metal oxide containing 20 to 80% by weight of magnesium oxide and 5 to 50% by weight of aluminum oxide. Examples of such commercially available adsorbents include “KYOWARD 300”, “KYOWARD 500”, “KYOWARD 1000”, “KYOWARD 2000” of Kyowa Chemical Industry Co., Ltd., “Toyo Pharmaceutical Co., Ltd.” Tomix AD500 "(the names in brackets are trade names). For example, the adsorbent is added at 2.0 to 10.0% by weight with respect to the crude product, and the treatment is performed at 40 to 100 ° C. for 1 to 5 hours. On the other hand, in order to deactivate and remove the catalyst, water is added and heated to hydrolyze the catalyst, followed by washing with warm water, after which the adsorbent is added and the catalyst is removed by filtration. You can also

  Below, the manufacturing method of Examples 1-2 and Comparative Examples 1-3 and its result are demonstrated.

  In addition, in FIG. 1, the graph of the addition mole number of the alkylene oxide adduct obtained by Examples 1-2 and the comparative example 1 is shown. The measurement of the added mole number distribution and the residual unreacted alcohol content in FIG. 1 are based on GPC measurement (gel filtration chromatography) under the following conditions. Moreover, the measurement of the by-product was performed by HPLC (liquid chromatography) under the following conditions.

<GPC / HPLC measurement conditions>
(1) GPC (gel filtration chromatography)
Eluent: Tetrahydrofuran (THF)
Column: Megapak GEL 201F, 25 ° C
Detector: Differential refractometer (RI)
(2) HPLC (liquid chromatography)
Eluent: Acetonitrile / water Column: ODS-H, 25 ° C
Detector: Differential refractometer (RI)
<Example 1>
After adding 186 g (1 mol) of lauryl alcohol and 2.8 g (0.011 mol) of aluminum sec-butyrate (ASDB) [Al (sec-C ₄ H ₉ O) 3] to the stainless steel autoclave, Chisso substitution. Thereafter, the temperature was raised to 80 ° C., the pressure was reduced to 2.6 kPa or less, and butanol in aluminum sec-butyrate (ASDB) was removed to convert to aluminum laurate. Then, 2.2 g (0.022 mol) of sulfuric acid was added to obtain an alkoxylation catalyst in which aluminum laurate and sulfuric acid were combined.

  Next, the temperature was raised to 120 ° C., and the reaction was carried out by gradually introducing 88 g (2 mol) of ethylene oxide into the autoclave while maintaining the temperature at 0.2 MPa. Subsequently, the mixture was aged at the same temperature for 1 hour and then cooled to 80 ° C. Then, after adding 9.5 g of water and stirring at 90 ° C., “Kyoward 500, 700” (trade name of Kyowa Chemical Industry Co., Ltd.) is added for adsorption treatment, and after dehydration under reduced pressure, the catalyst is filtered. Removed. The average addition mole number of the obtained alkylene oxide adduct was 2.0. As a result of measuring the molecular weight distribution by GPC, the amount of unreacted alcohol was 4.2%. Moreover, the division | segmentation whose addition mole number is 4.0 or more was 18.0% of the whole, and the division | segmentation whose addition mole number was 6.0 or more was 3.0% of the whole.

<Example 2>
After adding 186 g (1 mol) of lauryl alcohol and 2.2 g (0.011 mol) of aluminum isopropylate (AIPD) [Al (iso-C ₃ H ₇ O) ₃ ] to the stainless steel autoclave, the inside of the autoclave is Replaced. Thereafter, the temperature was raised to 100 ° C., the pressure was reduced to 2.6 kPa or less, and isopropyl alcohol in aluminum isopropylate (AIPD) was removed to convert to aluminum laurate. Then, 2.2 g (0.022 mol) of phosphoric acid was added to obtain an alkoxylation catalyst in which aluminum laurate and phosphoric acid were combined.

  Next, the temperature was raised to 120 ° C., and the reaction was carried out by gradually introducing 88 g (2 mol) of ethylene oxide into the autoclave while maintaining the temperature at 0.2 MPa. Subsequently, the mixture was aged at the same temperature for 1 hour and then cooled to 80 ° C. Then, after adding 9.5 g of water and stirring at 90 ° C., “Kyoward 500, 700” (trade name of Kyowa Chemical Industry Co., Ltd.) is added for adsorption treatment, and after dehydration under reduced pressure, the catalyst is filtered. Removed. The average addition mole number of the obtained alkylene oxide adduct was 2.0. As a result of measuring the molecular weight distribution by GPC, the amount of unreacted alcohol was 3.8%. Moreover, the division | segmentation whose addition mole number is 4.0 or more was 18.7% of the whole, and the division | segmentation whose addition mole number was 6.0 or more was 3.5% of the whole.

<Example 3>
186 g (1 mol) of lauryl alcohol and 6.4 g (0.011 mol) of aluminum laurate [Al (C ₁₂ H ₂₅ O) ₃ ] are added to a stainless steel autoclave, and then 2.2 g (0 After the addition, the inside of the autoclave was replaced with nitrogen. After the temperature was raised to 120 ° C., 88 g (2 mol) of ethylene oxide was gradually introduced while maintaining the temperature at 120 ° C. and the pressure at 0.2 MPa to carry out the reaction. Subsequently, the mixture was aged at the same temperature for 1 hour and then cooled to 80 ° C. Thereafter, 9.5 g of water was added and stirred at 90 ° C., then Kyoward 500 and 700 were added for adsorption treatment. After dehydration under reduced pressure, the catalyst was removed by filtration. The average addition mole number of the obtained alkylene oxide adduct was 2.0. As a result of measuring molecular weight distribution by GPC, the amount of unreacted alcohol was 4.3%.

<Comparative Example 1>
After adding 186 g (1 mol) of lauryl alcohol and 0.6 g (0.011 mol) of KOH to a stainless steel autoclave, the inside of the autoclave was replaced with nitrogen. Next, the temperature was raised to 120 ° C., and the reaction was carried out by gradually introducing 88 g (2 mol) of ethylene oxide into the autoclave while maintaining the temperature at 0.2 MPa. Subsequently, the mixture was aged at the same temperature for 1 hour and then cooled to 80 ° C. The average addition mole number of the obtained alkylene oxide adduct was 2.0. As a result of measuring molecular weight distribution by GPC, the amount of unreacted alcohol was 20.1%. Moreover, the division | segmentation whose addition mole number is 4.0 or more was 36.2% of the whole, and the division | segmentation whose addition mole number was 6.0 or more was 19.5% of the whole.

<Comparative example 2>
After adding 186 g (1 mol) of lauryl alcohol and sulfuric acid (0.004 mol) to a stainless steel autoclave, the inside of the autoclave was replaced with nitrogen. Next, the temperature was raised to 100 ° C., and while maintaining the temperature at 0.2 MPa, 88 g (2 mol) of ethylene oxide was gradually introduced into the autoclave to carry out the reaction. Subsequently, the mixture was aged at the same temperature for 1 hour and then cooled to 80 ° C. The average addition mole number of the obtained alkylene oxide adduct was as small as 1.0, a large amount of dioxane was produced as a by-product, and a normal alkylene oxide adduct could not be obtained. Moreover, as a result of measuring molecular weight distribution by GPC, the amount of unreacted alcohol was 15.3%.

<Comparative Example 3>
After adding 186 g (1 mol) of lauryl alcohol and 2.8 g (0.011 mol) of aluminum sec-butyrate (ASDB) [Al (sec-C ₄ H ₉ O) ₃ ] to the stainless steel autoclave, the inside of the autoclave is Replaced. Next, the temperature was raised to 120 ° C., and the reaction was carried out by introducing ethylene oxide while maintaining the temperature at 0.2 MPa. At this time, 88 g (2 mol) of ethylene oxide was tried to be introduced, but only 44 g (1 mol) could be introduced, and the introduction was stopped. Subsequently, after aging at the same temperature for 5 hours, it was cooled to 80 ° C. As a result, the average addition mole number of the alkylene oxide adduct was 0.5, and sufficient catalytic action was not obtained.

It is a graph which shows addition mole number distribution of the ethylene oxide adduct obtained in Examples 1-3 and the comparative example 1. FIG.

Claims (2)

A catalyst for alkoxylation comprising a combination of a metal alcoholate comprising at least one of the compound types represented by the following general formulas (1) to (3) and an acid compound.

In the general formulas (1) to (3), R ¹ , R ² , R ³ and R ⁴ are all hydrogen atoms, alkyl groups or alkoxyl groups, and at least one of them is alkoxyl in each general formula It is a group. M ¹ is a magnesium (Mg) or calcium (Ca) atom, M ² is an aluminum (Al) or gallium (Ga) atom, and M ³ is a titanium (Ti) or zirconium (Zr) atom. The acid compound is at least one selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid, formic acid, acetic acid, oxalic acid, tartaric acid, benzoic acid, and paratoluenesulfonic acid. Item 4. The alkoxylation catalyst according to Item 1.

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