JP3005340B2 - Method for producing alkylene oxide adduct - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an alkylene oxide adduct.

[0002]

2. Description of the Related Art Alkylene oxide adducts of organic compounds containing active hydrogen such as higher alcohols are compounds widely used as raw materials for various detergents and chemicals. These alkylene oxide adducts are usually
The compound is produced by reacting an active hydrogen-containing compound such as an alkylene oxide with an alkylene oxide in the presence of an acid or base catalyst. Usually, as the acid catalyst, a mineral acid such as sulfuric acid, hydrochloric acid or phosphoric acid or a metal salt thereof or a metal salt of a carboxylic acid such as acetic acid or oxalic acid is used. As the base catalyst, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide and amines such as diethylamine and triethylamine are used.

[0003]

However, when an alkylene oxide adduct is produced using these acid or base catalysts, for example, with a base catalyst, only one having a wide addition molar number distribution can be obtained, and the reaction product Unreacted raw materials, for example, active hydrogen-containing organic compounds such as alcohol remain therein, which impairs the quality of the formed alkylene oxide adduct. On the other hand, when an acid catalyst is used in place of the base catalyst, the amount of unreacted raw materials in the reaction product decreases, but cyclic ethers such as dioxane or a derivative thereof or polyethylene glycol are by-produced and are also produced. Affects the quality of the alkylene oxide adduct. Therefore, industrially, it has been desired to develop a catalyst having a narrow addition mole number distribution, suppressing the residual unreacted raw materials such as alcohol, and suppressing the by-products such as polyethylene glycol.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, the method for producing an alkylene oxide adduct of the present invention is a method for producing an alkylene oxide adduct from an active hydrogen-containing organic compound and an alkylene oxide, wherein Ba ²⁺ , Si ⁴⁺ , a metal ion selected from Cs ⁺ MgO with one or more added
The reaction is carried out in the presence of a catalyst.

In the present invention, from the active hydrogen-containing organic compound and the alkylene oxide, the distribution of the number of added moles is narrow, the residual amount of the unreacted active hydrogen-containing organic compound such as alcohol is small, and the secondary compounds such as polyethylene glycol and the like. It is possible to produce an alkylene oxide adduct with little production.

The catalyst used in the present invention is obtained by adding Ba ²⁺ , Si ⁴⁺ , Cs ⁺ , B ³⁺ , F ² to MgO (magnesium oxide).
It is one to which one or more metal ions selected from e ³⁺ , Y ³⁺ and Ce ³⁺ are added, and can be prepared by an impregnation method or a coprecipitation method. For example, in the impregnation method, Ba ²⁺ , Cs ⁺ , Fe ³⁺ , Y ³⁺ , and Ce ³⁺
These nitrate, etc. for metal species, boric acid or ammonium borate for B ^3+, also Si ⁴⁺
Is carried out by impregnating and supporting MgO in an aqueous solution using tetraethyl silicate or the like, washing, drying, and finally firing in air.

In the coprecipitation method, after dissolving these metal species in an aqueous solution of magnesium nitrate, a hydroxide is coprecipitated with an alkali such as aqueous ammonia, and then washed, dried and dried in the same manner as in the impregnation method.
Perform baking. B added to MgO of the catalyst of the present invention
a ²⁺ , Si ⁴⁺ , Cs ⁺ , B ³⁺ , Fe ³⁺ , Y ³⁺ and Ce
The amount of ³⁺ is 0.1 to 50% by weight of the catalyst weight, more preferably 1 to 30% by weight. If it is less than 0.1% by weight, sufficient catalytic activity cannot be obtained, and if it is more than 50% by weight, all of the added metal ions are not effectively used.

The active hydrogen-containing organic compound referred to in the present invention is:
Any compound may be used as long as it produces an alkylene oxide adduct by reaction with an alkylene oxide, but alcohols, phenols, polyols, thiols, carboxylic acids, amines , Amides and mixtures thereof.

As alcohols, n-octano-
N-nonanol, n-decanol, n-dodecano
, N-tridecanol, n-tetradecanol, n-
Pentadecanol, n-hexadecanol, n-hepta
Decanol, n-octadecanol, n-nonadecano
, Eicosanol, 2-methyl-1-nonanol, 2-methyl
1-undecanol, 2-methyl-1-dodecanol, 2-
Primary alcohol represented by methyl-1-tetradecanol
-, 2-propanol, 2-heptanol, 3-heptanol
2-octanol, 2-decanol, 2-dodecanol,
4-tetradecanol, 6-heptadecanol, cyclohexyl
Sanol, cyclopentanol, cycloheptanol,
Cyclopropanol represented by cyclooctanol
Secondary alcohol, formed by an oxo reaction having 8 to 12 carbon atoms
Alkanols, commercially available C₁₂Alkano
20 with a composition of 95% or more (trademark, Kao Corporation)
Made), C ₁₃, C₁₅Of which the alkanol composition is 60, 39 respectively
% DIADOL135 (trademark, manufactured by Mitsubishi Kasei Corporation),
C₁₂, C₁₃Having an alkanol composition of 45% and 55%, respectively.
OBADOL23 (trademark, manufactured by Mitsubishi Yuka), C₁₂Al
Conocoll 20 (trademark, Shin-Nihon) mainly composed of canol
Rikasha), C₁₂, C₁₃The alkanol composition of
40, 60% NEODOL23 (trademark, Shell Chemical)
Company), C₁₂, C₁₄The alkanol composition of each is 54,
44% ALFOL1214 (trademark, CONDEA CH
EMIE), C₁₂, C₁₃The alkanol composition of
43% and 57% LIAL123 (trademark, manufactured by Enikhem)
Alkanol mixtures represented by

Phenols include phenol and p-
Methyl phenol, p-ethyl phenol, p-butyl phenol, p-hexyl phenol, p-heptyl phenol, p-nonyl phenol, p-decyl phenol
, Dinonyl phenol, didecyl phenol, vinyl phenol, allyl phenol, m-dihydroxy benzene, p-dihydroxy benzene, 2,4-toluene di-
, 1,3,5-benzenetriol, 2,2-bis (4'-hydroxyphenyl) propane and the like.

As the polyols, ethylene glycol is used.
Propylene glycol, hexylene glycol, decylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, glycerin, sorbitol, trimethylolpropane, etc. is there.

As thiols, 1-butanethiol,
Primary thiol represented by 1-hexanethiol, 1-dodecanethiol, 1-tetradecanethiol, 2-methyl-1-tridecanethiol, 2-propanethiol, 2-butanethiol , 3-pentanethiol, 2-decanethiol, 3-
Decanethiol, 4-decanethiol, 5-decanethiol
2-hexadecanethiol, 5-hexadecanethio-
Secondary thio- represented by 8-octadecanethiol
And tertiary thiol.

Examples of the carboxylic acids include acetic acid, propionic acid, octanoic acid, lacnic acid, valeric acid, caproic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, rosin acid, oleic acid and acrylic acid. Acids, methacrylic acid, vinyl acetic acid, crotonic acid, maleic acid, fumaric acid, adipic acid, aliphatic carboxylic acids represented by 1,2,3-propanetricarboxylic acid, terephthalic acid, benzoic acid, vinylbenzoic acid, phenylacetic acid And aromatic carboxylic acids represented by toluic acid and 1,2,4-benzenetricarboxylic acid.

The amines include aliphatic amines such as tert-butylamine, laurylamine, ethylenediamine and diethylenetriamine, and aromatic amines such as aniline and N-methylaniline.

The amides include formamide, N, N
-Dimethylformamide, N, N-dimethylacetamide, octylamide, decylamide, laurylamide,
Stearylamide, acrylamide, N, N-dimethylacrylamide, oxamide, benzamide, p-methoxybenzamide, p-hydroxybenzamide and the like.

On the other hand, the alkylene oxide may be any one having an oxirane ring and reacting with an active hydrogen-containing organic compound to form an adduct. Among them, ethylene oxide and propylene oxide are most commonly used. These may be used as a mixture.

The amount of the catalyst of the present invention depends on the amount of the alkylene oxide to be added to the active hydrogen-containing organic compound, but is usually 0.01 to 10% by weight based on the adduct formed. More preferably, it is 0.1 to 5% by weight. If the amount is less than 0.01% by weight, a sufficient reaction rate cannot be obtained, and if the amount is more than 10% by weight, a side reaction proceeds, and it becomes difficult to separate the catalyst from the reaction solution after the reaction.

[0018] The reaction temperature of the present invention is from 90 to 230 ° C, more preferably from 120 to 180 ° C. If the temperature is lower than 90 ° C, a sufficient reaction rate cannot be obtained, and if the temperature is higher than 230 ° C, the formed adduct is decomposed. The reaction pressure depends on the reaction temperature.
kg / cm ² G, more preferably 1 to 6 Kg / cm ² G.

[0019]

The present invention will be described below in more detail with reference to examples.

Example 1 20 g of MgO was dispersed in 146 ml of an aqueous 0.1 M barium nitrate solution, and the mixture was stirred at room temperature for 24 hours.
Dry at 0 ° C. for 24 hours. This was calcined in air at 600 ° C. for 2 hours to prepare an MgO catalyst to which 10% by weight of Ba ²⁺ was added.

Next, in an autoclave with a stirrer having an inner volume of 200 ml, 0.62 g of the above catalyst and 20 alcohol of alcohol were added.
The autoclave was charged with 20.0 g of nitrogen, and the inside of the autoclave was set to a nitrogen atmosphere by flowing nitrogen gas. After 15 minutes, start supplying ethylene oxide,
The temperature was raised to 170 ° C. over 1.0 hour, and then the reaction was performed for 2.5 hours while maintaining the pressure at 170 ° C. and the pressure of 4 kg / cm ² G. During this time, 33 g of ethylene oxide were supplied.

When the obtained ethylene oxide adduct was analyzed by gas chromatography and liquid chromatography, the average number of moles added was 7.0, unreacted alcohol was 1.0% by weight, and polyethylene glycol produced as a by-product.
1.4% by weight. Further, the distribution of the added mole number of ethylene oxide was a result shown by a curve 1 in FIG. In FIG. 1, the horizontal axis indicates the number of moles of ethylene oxide added, and the vertical axis indicates the weight% of each mole adduct with respect to the weight of the ethylene oxide adduct formed.

Example 2 M was prepared in the same manner as in Example 1 ^except that 5% by weight of Ba ²⁺ was added.
A gO catalyst was prepared. Next, after charging was performed in the same manner as in Example 1 except that the amount of the catalyst was changed to 0.53 g, the supply of ethylene oxide was started, and it took 1.4 hours to raise the temperature to 170 ° C. While maintaining a pressure of 4 kg / cm ² G
The reaction was performed for 7.0 hours. 33g of ethylene oxide during this time
Was supplied. The resulting ethylene oxide adduct had an average addition mole number of 7.0, 1.3% by weight of unreacted alcohol, and 2.0% by weight of polyethylene glycol by-produced.

Example 3 M prepared by adding Ba ²⁺ by 30% by weight in the same preparation method as in Example 1.
A gO catalyst was prepared. Next, after charging was carried out in the same manner as in Example 1 except that the amount of the catalyst was changed to 0.53 g, the supply of ethylene oxide was started, and it took 1.5 hours to raise the temperature to 170 ° C. While maintaining a pressure of 4 kg / cm ² G
The reaction was performed for 2.1 hours. 33g of ethylene oxide during this time
Was supplied. The resulting ethylene oxide adduct had an average addition mole number of 7.0, 1.2% by weight of unreacted alcohol, and 2.2% by weight of by-produced polyethylene glycol.

Example 4 M prepared by adding Ba ²⁺ by 2% by weight in the same manner as in Example 1.
A gO catalyst was prepared. Next, after charging was performed in the same manner as in Example 3, the supply of ethylene oxide was started,
The temperature was raised to 170 ° C. over 1.1 hours, and then the reaction was carried out for 4.0 hours while maintaining the temperature at 170 ° C. and the pressure at 4 kg / cm ² G. During this time, 33 g of ethylene oxide were supplied. The obtained ethylene oxide adduct had an average addition mole number of 7.0, unreacted alcohol of 1.0% by weight, and polyethylene glycol by-produced by 1.7%.
% By weight.

Example 5 7.4 g of tetraethyl silicate was added to 350 ml of water, and 20 g of MgO was dispersed with vigorous stirring. After stirring at room temperature for 24 hours, the water was evaporated and dried at 110 ° C. for 24 hours. This is fired in air at 600 ° C for 2 hours to ^convert Si ⁴⁺ to 5
A MgO catalyst added by weight% was prepared. Next, the above catalyst 2.15 was placed in the same autoclave with a stirrer as in Example 1.
g of alcohol and 20.1 g of alcohol 20 were charged, and a nitrogen gas was flowed into the autoclave to form a nitrogen atmosphere, and the temperature was raised to 135 ° C. with stirring. After 15 minutes, supply of ethylene oxide was started, and it took 1.5 hours to raise the temperature to 170 ° C. Then, while maintaining the temperature at 170 ° C and the pressure of 4 kg / cm ² G,
The reaction was performed for 7.6 hours. 33g of ethylene oxide during this time
Was supplied. The resulting ethylene oxide adduct had an average addition mole number of 7.0 and unreacted alcohol of 0.6% by weight.
Further, the distribution of the added mole number of ethylene oxide was a result shown by a curve 2 in FIG.

Example 6 M prepared by adding 2% by weight of Si ⁴⁺ by the same preparation method as in Example 5.
A gO catalyst was prepared. Next, after charging was conducted in the same manner as in Example 5 except that the amount of the catalyst was changed to 4.27 g, the supply of ethylene oxide was started, and the temperature was raised to 170 ° C. in 1.1 hours, and then 170 ° C. While maintaining a pressure of 4 kg / cm ² G
The reaction was performed for 3.0 hours. 33g of ethylene oxide during this time
Was supplied. The resulting ethylene oxide adduct had an average addition mole number of 7.0 and unreacted alcohol of 0.9% by weight.

Example 7 20 g of MgO was dispersed in 75 ml of a 0.1 M cesium nitrate aqueous solution, and the mixture was stirred at room temperature for 24 hours.
Dry at 24 ° C. for 24 hours. This was calcined in air at 600 ° C. for 2 hours to prepare a MgO catalyst to which 5% by weight of Cs ⁺ was added.

Next, an Au with an agitator similar to that of Example 1 was used.
The catalyst was charged with 1.10 g of the above-mentioned catalyst and 20.1 g of alcohol 20 alcohol, and the inside of the autoclave was made to have a nitrogen atmosphere by flowing nitrogen gas, and then heated to 135 ° C. with stirring. After 15 minutes, start supplying ethylene oxide,
Raise the temperature to 170 ° C over 1.1 hours, then 170 ° C, pressure 4
The reaction was performed for 3.5 hours while maintaining kg / cm ² G. During this time, 33 g of ethylene oxide was supplied. The obtained ethylene oxide adduct had an average addition mole number of 7.0 and unreacted alcohol of 1.3% by weight.

Example 8 The procedure of Example 7 was repeated except that the amount of the catalyst was changed to 2.50 g, and then the supply of ethylene oxide was started.
The temperature was raised to 170 ° C. over 1.5 hours, and then the reaction was performed for 2.1 hours while maintaining the pressure at 170 ° C. and the pressure of 4 kg / cm ² G. During this time, 33 g of ethylene oxide was supplied. The resulting ethylene oxide adduct had an average addition mole number of 7.0 and unreacted alcohol of 1.6% by weight.

COMPARATIVE EXAMPLE In a 200 ml autoclave with a stirrer having the same internal volume as in Example 1, 0.02 g of potassium hydroxide catalyst and 20 alcohol of alcohol were added.
The autoclave was charged with 20.0 g, and the inside of the autoclave was made to have a nitrogen atmosphere by flowing nitrogen gas, and then the temperature was raised to 135 ° C. while stirring. After 15 minutes have elapsed, start supplying ethylene oxide.
It takes time to raise the temperature to 170 ° C, then 150 ° C, pressure 4k
The reaction was performed for 3.0 hours while maintaining g / cm ² G. During this time, 33 g of ethylene oxide were supplied. The obtained ethylene oxide adduct has an average addition mole number of 7.0 and unreacted alcohol.
The content was 2.5% by weight and 3.4% by weight of by-produced polyethylene glycol. Further, the distribution of the added mole number of ethylene oxide was a result shown by a curve 3 in FIG.

[0032]

According to the method of the present invention, it is possible to produce an alkylene oxide adduct having a narrow addition mole number distribution and having a small amount of unreacted raw materials such as alcohol and by-product polyethylene glycol in the reaction product. It is industrially extremely valuable.

[Brief description of the drawings]

FIG. 1 is a graph showing an addition mole number distribution of ethylene oxide in a method for producing an alkylene oxide adduct.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI B01J 23/04 B01J 23/04 X C07B 61/00 300 C07B 61/00 300

Claims (1)

(57) [Claims] 1. A method for producing an alkylene oxide adduct from an active hydrogen-containing organic compound and an alkylene oxide, the method comprising adding one or more metal ions selected from Ba ²⁺ , Si ⁴⁺ and Cs ^+. A method for producing an alkylene oxide adduct, which comprises reacting in the presence of a catalyst.