JP2005046749A - Catalyst for alkoxylation and method for manufacturing alkylene oxide addition product using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst for alkoxylation with less unreacted product and by-product, capable of narrowing a distribution of polymerization degree of alkylene oxide addition product. <P>SOLUTION: The catalyst for alkoxylation is a catalyst for alkoxylation comprising at least one kind of boron compound selected from the group consisting of boron trifluoride complex salts, borohydrofluoric acid and borohydrofluoric acid salts (for example boron trifluoride ethyl ether complex) and metal alkolate (for example, aluminum alkolate). Further, the method for manufacturing an alkylene oxide addition product comprises the reaction of an active hydrogen atom-containing compound with alkylene oxide in the presence of the catalyst. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

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

  Active hydrogen-containing compounds such as higher alcohols, alkylphenols, fatty acids, and alkylamines can be combined freely with the structure of hydrophobic groups and structures of hydrophilic groups by addition polymerization with alkylene oxide. It is used in a wide range of applications as a raw material for an activator and further an anionic surfactant. In order to produce an alkylene oxide adduct obtained from a compound having these active hydrogens and an alkylene oxide, conventionally, a basic catalyst such as caustic soda, caustic potash, or triethylamine, boron trifluoride, antimony pentachloride, or the like is used as a catalyst. An acidic catalyst is used.

  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. .

  For example, Patent Document 1 listed below proposes an alkoxylation catalyst comprising a halide such as alkyl aluminum fluoride or alkoxy aluminum fluoride, and Patent Document 2 listed below discloses an alkoxylation catalyst for a fluorinated alcohol. As a catalyst, a catalyst composed of a metal alcoholate and hydrogen fluoride has been proposed.

In addition, a catalyst composed of boron trifluoride and a metal alkoxide is described in page 4, lower right column, line 13 and below of Patent Document 2, but in this document, an example of using this in an actual alkoxylation reaction is described. It is not shown and does not suggest any configuration or effect of the present invention.
JP 58-210859 A JP-A-60-149533

  The present invention has been made in view of the above points, and solves the problems of conventional acidic catalysts such as many by-products and strong corrosiveness to metals, and compared with conventional basic catalysts. To provide an alkoxylation catalyst capable of greatly reducing unreacted substances and further narrowing the degree of polymerization distribution of alkylene oxide adducts, and a method for producing alkylene oxide adducts using the same. With the goal.

  As a result of diligent research to solve the above-mentioned problems, the present inventor uses a specific boron compound such as boron trifluoride complex salts and a metal alcoholate in combination, while greatly reducing unreacted substances. The inventors have found that the polymerization degree distribution of the alkylene oxide adduct can be sufficiently narrowed, and that the formation of by-products and the corrosion of the metal can be suppressed, and the present invention has been completed.

  That is, the present invention provides an alkoxylation catalyst comprising at least one boron compound selected from the group consisting of boron trifluoride complex salts, borohydrofluoric acid, and borofluoride salts, and a metal alcoholate. is there.

  The present invention also provides an active hydrogen atom-containing compound and an alkylene oxide comprising at least one boron compound selected from the group consisting of boron trifluoride complex salts, borohydrofluoric acid and borohydrofluoride salts, and a metal alcoholate. The present invention provides a process for producing an alkylene oxide adduct characterized by reacting in the presence.

  According to the present invention, unreacted substances can be greatly reduced and an alkylene oxide adduct having a narrow polymerization degree distribution can be obtained as compared with conventional alkoxylation catalysts. Therefore, the odor of the polymer is weak, and since there are few alkylene oxides with a high degree of polymerization, the balance between hydrophobicity and hydrophilicity is not lost, and performance as a surfactant does not deteriorate. Furthermore, there are few by-products compared with the conventional acidic catalyst, and since the reaction proceeds in the vicinity of neutrality, corrosion of the metal can be suppressed.

The boron compound which is the first component in the alkoxylation catalyst of the present invention is boron trifluoride complex salts, borohydrofluoric acid (tetrafluoroboric acid: HBF ₄ ), or borohydrofluoric acid salts, which are respectively It can be used alone or in combination of two or more.

Examples of the boron trifluoride complex salts include alkyl ether complexes such as boron trifluoride ethyl ether complex ((C ₂ H ₅ ) ₂ O · BF ₃ ), and boron trifluoride phenol complex (2C ₆ H ₅ OH). · BF ₃₎ phenols such complexes, carboxylic acid complexes such as boron trifluoride acetic acid complex _{(2CH 3 COOH · BF 3)} , an alkyl alcohol complexes such as boron trifluoride methyl alcohol complex _{(CH 3} OH · BF 3) Etc.

  Examples of the borohydrofluoride salts include stannous borofluoride, copper borofluoride, lead borofluoride, zinc borofluoride, ferrous borofluoride, antimony borofluoride, indium borofluoride, potassium borofluoride, and boron fluoride. And ammonium fluoride, sodium borofluoride, and magnesium borofluoride.

The second component in the alkoxylation catalyst of the present invention is a metal alcoholate. The metal alcoholate is preferably at least one selected from the group of compounds represented by the following general formula.

In the formula, 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 of each compound is an alkoxy group. That is, all of the above compounds have at least one alkoxyl group. M ¹ is a magnesium or calcium atom, M ² is an aluminum or gallium atom, and M ³ is a titanium or zirconium atom. The alkyl group and alkoxy group preferably have 1 to 18 carbon atoms. Moreover, it is preferable that all of R ¹ , R ² , R ³ and R ⁴ are alkoxy groups.

Specific examples of these divalent metal alcoholates (in the case of M ¹ ) include magnesium diethylate, magnesium methoxyethylate, calcium diethylate, and calcium methoxyethylate.

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. Rate and so on.

Examples of the tetravalent metal alcoholate (in the case of M ³ ) include tetraisopropyl titanate, tetraoctyl titanate, tetramethyl titanate, tetrastearyl 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- butylate _{(Al (tert-C 4 H} 9 O) 3) , and the like.

The alkoxylation catalyst of the present invention is characterized by using the above-described boron compound and metal alcoholate in combination, and by using it together, an alkylene oxide adduct having a narrow polymerization degree distribution as compared with conventional catalysts is obtained. be able to. The reason is not necessarily clear, but it is considered that some complex is formed in the reaction system by mixing the two. That is, as will be shown in Examples below, when the boron compound is used alone, the reaction system is acidic (see Comparative Examples 2 and 5), but when this is combined with a substantially neutral metal alcoholate. Since the reaction proceeds at a pH close to neutrality (see Examples 1 to 7), there is a high possibility that some complex is formed. And it is speculated that excellent catalytic action is exhibited by forming a complex in this way. In the case of using a BF ₃ gas as a boron compound in combination with a metal alcoholate, BF ₃ gas is hardly mixed in the metal alcoholate and uniform since it is a gas, probably because it is difficult to form the complex, the present invention specific for the above The effect cannot be obtained.

  The mixing ratio of the boron compound and the metal alcoholate is preferably a molar ratio A / B = 1/2 to 2/1, where A is the number of moles of the boron compound and B is the number of moles of the metal alcoholate. If the boron compound is too much beyond this range, the polymerization degree distribution tends to be broadened. Moreover, when there is too much said metal alcoholate exceeding the said range, it exists in the tendency for reaction rate to become slow. A more preferable molar ratio is A / B = 1/1 to 1.5 / 1. In other words, mixing so that the boron compound is slightly larger than the metal alcoholate can narrow the polymerization degree distribution. Is preferable.

  In the production method of the present invention, when the alkylene oxide adduct is produced by adding an alkylene oxide to an active hydrogen atom-containing compound, the boron compound and the metal alcoholate are simultaneously used as a catalyst.

  Examples of the active hydrogen-containing compound include alcohols, polyhydric alcohols, phenols, carboxylic acids, 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 1 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 phenol, octylphenol, nonylphenol and the like.

  Examples of the carboxylic acids include fatty acids having a saturated or unsaturated linear or branched alkyl group having 1 to 30 carbon atoms. Specific examples include acetic acid, propionic acid, 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 1 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 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.

  Production of the alkylene oxide adduct by the production method of the present invention can be easily carried out in a pressure reactor such as an autoclave, under ordinary operating procedures and reaction conditions. In that case, it is preferable that reaction temperature is 100-150 degreeC, More preferably, it is 110-130 degreeC. The degree of polymerization distribution of the catalyst of the present invention varies depending on the reaction temperature. By setting the reaction temperature to 100 ° C. or higher, the degree of polymerization distribution can be made narrower. On the other hand, when the reaction temperature exceeds 150 ° C., the boron compound is deactivated and it becomes difficult to obtain a sufficient effect. Such a reaction temperature can be a feature of the conventional reaction using boron trifluoride complex salts alone at a low temperature of 90 ° C. at most.

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

  After completion of the reaction, the catalyst may remain in the reaction product. If it is inconvenient, the catalyst may be filtered as it is, filtered after the adsorption treatment, filtered after the hydrolysis treatment, or It can also be removed by filtration after the coagulation treatment.

  Hereinafter, the present invention will be specifically described by way of examples, but the scope of the present invention is not limited thereto.

[Example 1]
In a stainless steel autoclave, 187 g (1 mol) of lauryl alcohol, 2.2 g (0.015 mol) of boron trifluoride ethyl ether complex salt [BF _3. (C ₂ H ₅ ) ₂ O], and aluminum sec- After adding 2.8 g (0.011 mol) of butyrate (ASDB) [Al (sec-C ₄ H ₉ O) ₃ ], the inside of the autoclave was replaced with nitrogen (the above molar ratio A / B = 1.4). Next, 132 g (3 mol) of ethylene oxide was introduced while maintaining the temperature at 120 ° C. and the pressure of 0.2 MPa, and the reaction was performed. Subsequently, after aging at the same temperature for 1 hour, it was cooled to 60 ° C. The pH of the solution during the reaction was 6.0. The average addition mole number of the obtained alkylene oxide adduct was 3.0. As a result of measuring the molecular weight distribution by gel permeation chromatography (GPC), the amount of unreacted alcohol was 0.7% by weight. The amount of by-produced polyethylene glycol (PEG) measured by liquid chromatography was 2.0% by weight.

[Example 2]
In a stainless steel autoclave, 187 g (1 mol) of lauryl alcohol, 2.2 g (0.015 mol) of boron trifluoride ethyl ether complex salt [BF _3. (C ₂ H ₅ ) ₂ O], and aluminum isopropylate After adding (AIPD) [Al (iso-C ₃ H ₇ O) ₃ ] 2.5 g (0.011 mol), the inside of the autoclave was replaced with nitrogen (the above molar ratio A / B = 1.4). Next, while maintaining the temperature at 120 ° C. and the pressure at 0.2 MPa, 132 g (3 mol) of ethylene oxide was introduced to carry out the reaction. Subsequently, after aging at the same temperature for 1 hour, it was cooled to 60 ° C. The pH of the solution during the reaction was 5.9. The average addition mole number of the obtained alkylene oxide adduct was 3.0. As a result of measuring the molecular weight distribution by GPC, the amount of unreacted alcohol was 0.8% by weight. The amount of byproduct PEG was 2.2% by weight.

[Comparative Example 1]
After adding 187 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, while maintaining the temperature at 120 ° C. and the pressure at 0.2 MPa, 132 g (3 mol) of ethylene oxide was introduced to carry out the reaction. Subsequently, after aging at the same temperature for 1 hour, it was cooled to 60 ° C. The average addition mole number of the obtained alkylene oxide adduct was 3.0. As a result of measuring the molecular weight distribution by GPC, the amount of unreacted alcohol was 8.8% by weight. The amount of byproduct PEG was 0.5% by weight.

[Comparative Example 2]
After adding 187 g (1 mol) of lauryl alcohol and 0.6 g (0.004 mol) of boron trifluoride ethyl ether complex salt [BF _3. (C ₂ H ₅ ) ₂ O] to a stainless steel autoclave, the inside of the autoclave Replaced with nitrogen. Next, while maintaining the temperature at 70 ° C. and the pressure at 0.2 MPa, 132 g (3 mol) of ethylene oxide was introduced to carry out the reaction. Subsequently, after aging at the same temperature for 1 hour, it was cooled to 60 ° C. The pH of the solution during the reaction was 3.8. The average addition mole number of the obtained alkylene oxide adduct was 3.0. As a result of measuring the molecular weight distribution by GPC, the amount of unreacted alcohol was 3.7% by weight. The amount of byproduct PEG was 5.0% by weight.

[Comparative Example 3]
After adding 187 g (1 mol) of lauryl alcohol and 3.2 g of a hydrotalcite heat-treated product to a stainless steel autoclave, the inside of the autoclave was replaced with nitrogen. Next, 132 g (3 mol) of ethylene oxide was introduced while maintaining the temperature at 120 ° C. and the pressure of 0.2 MPa, to carry out the reaction. Subsequently, after aging at the same temperature for 1 hour, it was cooled to 60 ° C. The average addition mole number of the obtained alkylene oxide adduct was 3.0. As a result of measuring the molecular weight distribution by GPC, the amount of unreacted alcohol was 4.5% by weight. The amount of byproduct PEG was 1.5% by weight.

  In FIG. 1, distribution of addition mole number about each alkylene oxide adduct obtained in Example 1 and Comparative Examples 1-3 is shown. As is clear from the figure, in Example 1 in which the boron trifluoride complex salt and aluminum alcoholate were used in combination, the polymerization degree distribution was extremely narrow compared to the catalysts of the comparative examples.

  Table 1 below shows the results of the above examples and comparative examples. As is apparent from the table, the amount of unreacted alcohol was greatly reduced in the catalyst of the example, although the amount of by-product PEG was slightly increased as compared with Comparative Example 1 using KOH. Thus, in this example, although the number of moles of ethylene oxide added is small, it is possible to reduce the amount of unreacted substances, which also shows that the degree of polymerization distribution is narrow. Further, in Comparative Example 2 in which the boron trifluoride complex salt alone was used, the pH of the reaction system was 3.8, whereas in Examples 1 and 2, the reaction was proceeding at a pH closer to neutrality. It was also preferable in terms of corrosiveness to metals.

Example 3
In a stainless steel autoclave, 187 g (1 mol) of lauryl alcohol, 2.9 g (0.020 mol) of boron trifluoride ethyl ether complex salt [BF _3. (C ₂ H ₅ ) ₂ O], and aluminum sec- butyrate _{(ASDB) [Al (sec-} C 4 H 9 O) 3] after adding 3.6 g (0.015 mol), was replaced in the autoclave with nitrogen (the molar ratio a / B = 1.4). Next, while maintaining the temperature at 120 ° C. and the pressure of 0.2 MPa, 220 g (5 mol) of ethylene oxide was introduced to carry out the reaction. Subsequently, after aging at the same temperature for 1 hour, it was cooled to 60 ° C. The pH of the solution during the reaction was 5.8. The average addition mole number of the obtained alkylene oxide adduct was 5.0. As a result of measuring the molecular weight distribution by GPC, the amount of unreacted alcohol was 0.3% by weight. The amount of byproduct PEG was 3.3% by weight.

Example 4
In a stainless steel autoclave, 187 g (1 mol) of lauryl alcohol, 2.1 g (0.015 mol) of boron trifluoride ethyl ether complex salt [BF _3. (C ₂ H ₅ ) ₂ O], and aluminum sec- After adding 3.6 g (0.015 mol) of butyrate (ASDB) [Al (sec-C ₄ H ₉ O) ₃ ], the inside of the autoclave was replaced with nitrogen (the above molar ratio A / B = 1.0). Next, while maintaining the temperature at 120 ° C. and the pressure of 0.2 MPa, 220 g (5 mol) of ethylene oxide was introduced to perform the reaction. Subsequently, after aging at the same temperature for 1 hour, it was cooled to 60 ° C. The pH of the solution during the reaction was 5.7. The average addition mole number of the obtained alkylene oxide adduct was 5.0. As a result of measuring the molecular weight distribution by GPC, the amount of unreacted alcohol was 0.3% by weight. The amount of byproduct PEG was 3.0% by weight.

Example 5
In a stainless steel autoclave, 187 g (1 mol) of lauryl alcohol, 1.0 g (0.007 mol) of boron trifluoride ethyl ether complex salt [BF _3. (C ₂ H ₅ ) ₂ O], and aluminum sec- butyrate _{(ASDB) [Al (sec-} C 4 H 9 O) 3] after adding 3.6 g (0.015 mol), was replaced in the autoclave with nitrogen (the molar ratio a / B = 2.0). Next, while maintaining the temperature at 120 ° C. and the pressure of 0.2 MPa, 220 g (5 mol) of ethylene oxide was introduced to carry out the reaction. Subsequently, after aging at the same temperature for 1 hour, it was cooled to 60 ° C. The pH of the solution during the reaction was 5.8. The average addition mole number of the obtained alkylene oxide adduct was 5.0. As a result of measuring the molecular weight distribution by GPC, the amount of unreacted alcohol was 0.3% by weight. The amount of byproduct PEG was 3.3% by weight [Example 6].
In a stainless steel autoclave, 187 g (1 mol) of lauryl alcohol, 4.1 g (0.029 mol) of boron trifluoride ethyl ether complex salt [BF _3. (C ₂ H ₅ ) ₂ O], and aluminum sec- butyrate (ASDB) after addition of _{[Al (sec-C 4 H} 9 O) 3] 3.6g (0.015 moles), was replaced in the autoclave with nitrogen (the molar ratio a / B = 0.5). Next, while maintaining the temperature at 120 ° C. and the pressure of 0.2 MPa, 220 g (5 mol) of ethylene oxide was introduced to carry out the reaction. Subsequently, after aging at the same temperature for 1 hour, it was cooled to 60 ° C. The pH of the solution during the reaction was 5.6. The average addition mole number of the obtained alkylene oxide adduct was 5.0. As a result of measuring the molecular weight distribution by GPC, the amount of unreacted alcohol was 0.3% by weight. The amount of by-product PEG was 3.1% by weight [Comparative Example 4].
After adding 187 g (1 mol) of lauryl alcohol and 0.8 g (0.015 mol) of KOH to a stainless steel autoclave, the inside of the autoclave was replaced with nitrogen. Next, while maintaining the temperature at 120 ° C. and the pressure of 0.2 MPa, 220 g (5 mol) of ethylene oxide was introduced to carry out the reaction. Subsequently, after aging at the same temperature for 1 hour, it was cooled to 60 ° C. The average addition mole number of the obtained alkylene oxide adduct was 5.0. As a result of measuring the molecular weight distribution by GPC, the amount of unreacted alcohol was 4.7% by weight. The amount of byproduct PEG was 0.5% by weight.

[Comparative Example 5]
After adding 187 g (1 mol) of lauryl alcohol and 0.8 g (0.006 mol) of boron trifluoride ethyl ether complex salt [BF _3. (C ₂ H ₅ ) ₂ O] to a stainless steel autoclave, Replaced with nitrogen. Next, while maintaining the temperature at 70 ° C. and the pressure 0.2 MPa, 220 g (5 mol) of ethylene oxide was introduced to carry out the reaction. Subsequently, after aging at the same temperature for 1 hour, it was cooled to 60 ° C. The pH of the solution during the reaction was 4.2. The average addition mole number of the obtained alkylene oxide adduct was 5.0. As a result of measuring the molecular weight distribution by GPC, the amount of unreacted alcohol was 0.8% by weight. The amount of byproduct PEG was 8.3% by weight.

[Comparative Example 6]
After adding 187 g (1 mol) of lauryl alcohol and 3.6 g (0.015 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 nitrogenated. Replaced with. Next, the reaction was carried out by introducing ethylene oxide while maintaining the temperature at 120 ° C. and the pressure at 0.2 MPa. At this time, an attempt was made to introduce 220 g (5 mol) of ethylene oxide, but only up to 88 g (2 mol) could be introduced, and the introduction was stopped. Subsequently, after aging at the same temperature for 5 hours, it was cooled to 60 ° C. As a result, the average added mole number of the alkylene oxide adduct was 1.0, and sufficient catalytic action was not obtained.

  FIG. 2 shows the addition mole number distribution for each alkylene oxide adduct obtained in Examples 3 to 6 and Comparative Examples 4 and 5. As is clear from the figure, in Examples 3 to 6 in which the boron trifluoride complex salt and aluminum alcoholate were used in combination, the polymerization degree distribution was extremely narrow compared to the catalysts of the comparative examples. In particular, in Examples 3 and 4 in which the molar ratio A / B is within a range of 1/1 to 1.5 / 1, a polymer having a more preferable polymerization degree distribution was obtained.

Example 7
In a stainless steel autoclave, 187 g (1 mol) of lauryl alcohol, 3.6 g (0.015 mol) of zinc borofluoride [Zn (BF ₄ ) ₂ ], and aluminum sec-butyrate (ASDB) [Al (sec-C ₄ H ₉ O) ₃ ] 3.6 g (0.015 mol) was added, and the inside of the autoclave was replaced with nitrogen (the molar ratio A / B = 1.0). Next, while maintaining the temperature at 120 ° C. and the pressure of 0.2 MPa, 220 g (5 mol) of ethylene oxide was introduced to carry out the reaction. Subsequently, after aging at the same temperature for 1 hour, it was cooled to 60 ° C. The pH of the solution during the reaction was 5.8. The average addition mole number of the obtained alkylene oxide adduct was 5.0. As a result of measuring the molecular weight distribution by GPC, the amount of unreacted alcohol was 0.8% by weight. The amount of byproduct PEG was 3.0% by weight.

[Comparative Example 7]
After adding 187 g (1 mol) of lauryl alcohol and 3.6 g (0.015 mol) of zinc borofluoride [Zn (BF ₄ ) ₂ ] to a stainless steel autoclave, the inside of the autoclave was replaced with nitrogen. Next, while maintaining the temperature at 120 ° C. and the pressure of 0.2 MPa, 220 g (5 mol) of ethylene oxide was introduced to carry out the reaction. Subsequently, after aging at the same temperature for 1 hour, it was cooled to 60 ° C. The pH of the solution during the reaction was 3.9. The average addition mole number of the obtained alkylene oxide adduct was 5.0. As a result of measuring the molecular weight distribution by GPC, the amount of unreacted alcohol was 0.9% by weight. The amount of byproduct PEG was 8.0% by weight.

FIG. 3 shows the addition mole number distribution for each alkylene oxide adduct obtained in Example 7 and Comparative Example 7 together with Example 3 and Comparative Examples 4 and 5. As shown in the figure, Example 7 in which borofluoride salts and aluminum alcoholate are used in combination can narrow the polymerization degree distribution to the same extent as Example 3 in which boron trifluoride complex salts and aluminum alcoholate are used in combination. did it.

  According to the present invention, it is possible to produce an alkylene oxide adduct having a narrow polymerization degree distribution and less unreacted raw materials and by-products, and the alkylene oxide adduct obtained thereby can be used for household detergents and industrial products. It can be used in a wide variety of applications as a raw material for surfactants and further anionic surfactants.

It is a graph which shows the addition mole number distribution of the ethylene oxide adduct obtained in Example 1 and Comparative Examples 1-3. It is a graph which shows addition mole number distribution of the ethylene oxide adduct obtained in Examples 3-6 and Comparative Examples 4, 5. It is a graph which shows addition mole number distribution of the ethylene oxide adduct obtained in Examples 3 and 7 and Comparative Examples 4, 5, and 7.

Claims (6)

  An alkoxylation catalyst comprising at least one boron compound selected from the group consisting of boron trifluoride complex salts, borohydrofluoric acid, and borohydrofluoride salts, and a metal alcoholate.   The boron compound is boron trifluoride ethyl ether complex, boron trifluoride phenol complex, boron trifluoride acetic acid complex, boron trifluoride methyl alcohol complex, hydrofluoric acid, stannous borofluoride, copper borofluoride, It is at least one selected from the group consisting of lead borofluoride, zinc borofluoride, ferrous borofluoride, antimony borofluoride, indium borofluoride, potassium borofluoride, ammonium borofluoride, sodium borofluoride, and magnesium borofluoride. 2. The alkoxylation catalyst according to claim 1, wherein the catalyst is an alkoxylation catalyst. 3. The alkoxylation catalyst according to claim 1, wherein the metal alcoholate is at least one selected from the group of compounds represented by the following general formula.

(Wherein 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 of each compound is an alkoxy group, M ¹ is a magnesium or calcium atom, M ² is an aluminum or gallium atom, and M ³ is a titanium or zirconium atom.)   The alkoxylation catalyst according to any one of claims 1 to 3, wherein the molar ratio A / B of the boron compound (A) to the metal alcoholate (B) is 1/2 to 2/1. .   An active hydrogen atom-containing compound and an alkylene oxide are reacted in the presence of a metal alcoholate with at least one boron compound selected from the group consisting of boron trifluoride complex salts, borohydrofluoric acid and borohydrofluoride salts. A process for producing an alkylene oxide adduct characterized by the above.   The method for producing an alkylene oxide adduct according to claim 5, wherein the active hydrogen atom-containing compound and the alkylene oxide are reacted at 100 to 150 ° C.

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