JP3102937B2 - 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. When an acid catalyst is used in place of the base catalyst, cyclic ether of dioxane or a derivative thereof or polyethylene glycol is by-produced, which also affects the quality of the formed alkylene oxide adduct. Therefore, industrially, it has been desired to develop a catalyst which has a narrow distribution of the number of added moles, suppresses the residual unreacted raw materials such as alcohol, and suppresses the by-product of 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 the metal ion is selected from Ba ²⁺ , Na ⁺ , and K ^+. The reaction is carried out in the presence of an acid salt catalyst.

In the present invention, the active hydrogen-containing organic compound and the alkylene oxide have an addition mole number distribution narrow, the residue of the unreacted active hydrogen-containing organic compound is small, and the alkylene oxide adduct having little by-product of polyethylene glycol. Generate

The catalyst used in the present invention is Ba ²⁺ , N
a ^+, and K is a aluminate of selected metal ions from the ⁺ generally Ba ^2+, Na ^+, and oxides of a metal ion selected from K ^+, or a carbonate or subjected to heat treatment with aluminum oxide , Ba ²⁺ , Na ⁺ and K ⁺ can be prepared by dissolving aluminum or aluminum hydroxide in a solution of a hydroxide of a metal ion selected from the group consisting of Na ⁺ and K ⁺ , evaporating and concentrating the solution, and then subjecting the solution to heat treatment. , And can be easily purchased as a commercial product.

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.

[0008] Alcohols include n-octano-
N-nonanol, n-decanol, n-dodecano
, N-tridecanol, n-tetradecanol, n-
Pentadecanol, n-hexadecanol, n-heptadecanol, n-octadecanol, n-nonadecanol
Eicanol, 2-methyl-1-nonanol, 2-methyl-1-undecanol, 2-methyl-1-dodecanol, 2-methyl-1-undecanol
Primary alcohols represented by methyl-1-tetradecanol, 2-propanol, 2-heptanol, 3-heptanol
2-octanol, 2-decanol, 2-dodecanol,
4-tetradecanol, 6-heptadecanol, cyclohexanol, cyclopentanol, cycloheptanol,
Secondary alcohols such as cyclopropanol and cyclooctanol, and alkanols formed by an oxo reaction having 8 to 12 carbon atoms.

Commercially available products include Calcol 20 (trade name, manufactured by Kao Corporation) having a C ₁₂ alkanol composition of 95% or more.
C ₁₃ and C ₁₅ alkanol compositions of 60 and 39% D respectively
IADOL135 (trade name, manufactured by Mitsubishi Kasei Corporation), C ₁₂ , C
₁₃ alkanol compositions of 45 and 55% DOBAD respectively
OL23 (trade name, manufactured by Mitsubishi Petrochemical Co., Ltd.), alkanol of C ₁₂ -
Conoco mainly of Le - Le 20 (trade name, manufactured by New Japan Chemical Co., Ltd.), alkanol of C _12, C ₁₃ - Le compositions respectively 40,
NEODOL 23 (trade name, manufactured by Shell Chemical Co., Ltd.) of 60%, alkanol compositions of C ₁₂ and C ₁₄ were 54 and 44, respectively.
% ALFOL1214 (trade name, CONDEA.CH
An alkanol mixture represented by LIAL123 (trade name, manufactured by Enikem Co.) having alkanol compositions of 43 and 57%, respectively, of EMIE), C ₁₂ and C ₁₃ .

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. If the temperature is higher than 230 ° C., the formed adduct is decomposed. The reaction pressure depends on the reaction temperature.
kg / cm ^2, more preferably from 1~6kg / cm ² G.

[0019]

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

EXAMPLE 1 Commercially available barium aluminate (Wako Pure Chemical Industries) was calcined at 600 ° C. for 3 hours in an autoclave with a stirrer having a capacity of 200 ml. After the inside of the autoclave was set to a nitrogen atmosphere by flowing nitrogen gas, the temperature was raised to 135 ° C. while stirring. After 15 minutes, supply of ethylene oxide was started.
The temperature was raised to 0 ° C., 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.

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 1.1% by weight, and polyethylene glycol by-produced.
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 The procedure of Example 1 was repeated, except that the amount of the catalyst was changed to 0.26 g, and then the supply of ethylene oxide was started.
The temperature was raised to 170 ° C. over 1.5 hours, and the reaction was carried out for 4.5 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. The obtained ethylene oxide adduct had an average addition mole number of 7.0, 1.2% by weight of unreacted alcohol, and polyethylene glycol by-produced.
2.0% by weight.

Example 3 4.0 g of aluminum hydroxide was added to 1200 ml of a 0.1 M aqueous barium hydroxide solution, and reacted at 85 ° C. for 1 hour under nitrogen. This was evaporated to dryness and calcined at 600 ° C. for 3 hours to prepare a barium aluminate catalyst.

Next, the same agitator with an agitator as in Example 1 was used.
0.54 g of the above-mentioned catalyst and 20 g of alcohol 20 were charged into the reactor, and a nitrogen gas was flowed into the autoclave to form a nitrogen atmosphere. Then, the temperature was raised to 135 ° C. while stirring. After 15 minutes, supply of ethylene oxide starts, and 1.5
It takes time to raise the temperature to 170 ° C, then 170 ° C, pressure 4k
The reaction was performed for 3.7 hours while maintaining g / cm ² G. During this time, 33 g of ethylene oxide was supplied.

The obtained ethylene oxide adduct had an average number of moles added of 7.0, 1.0% by weight of unreacted alcohol, and 2.0% by weight of polyethylene glycol as a by-product. Also,
The distribution of the number of moles of added ethylene oxide was as shown by curve 2 in FIG.

Example 4 Commercially available sodium aluminate (Wako Pure Chemical Industries) was added at 600 ° C. for 2 hours.
After charging in the same manner as in Example 1 except that 0.53 g of the calcined catalyst was used, the supply of ethylene oxide was started, the temperature was raised to 170 ° C. over 1.0 hour, and then
The reaction was performed for 1.2 hours while maintaining a pressure of 170 ° C. and a pressure of 4 kg / cm ² G. During this time, 36 g of ethylene oxide was supplied. The obtained ethylene oxide adduct has an average addition mole number of 7.6,
The unreacted alcohol was 1.8% by weight and the by-product polyethylene glycol was 1.4% by weight.

Example 5 Aqueous ammonia was added to 1000 ml of a 0.1 M aqueous solution of aluminum chloride to precipitate aluminum hydroxide, and sodium hydroxide was further added. After that, wash, dry, and further
It was calcined at 600 ° C. for 3 hours to prepare a sodium aluminate catalyst.

Next, after charging was conducted in the same manner as in Example 1 except that 0.53 g of the catalyst was used, the supply of ethylene oxide was started, and the temperature was raised to 170 ° C. over 1.5 hours.
Then, the reaction was carried out for 2.0 hours while maintaining the temperature at 170 ° C. and the pressure of 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, 1.8% by weight of unreacted alcohol, and 1.5% by weight of polyethylene glycol as a by-product.

Example 6 The procedure of Example 1 was repeated except that 0.55 g of a commercially available potassium aluminate (Wako Pure Chemical) calcined at 600 ° C. for 2 hours was used, and then ethylene oxide was supplied. Start and raise to 170 ° C over 1.8 hours, then 1
The reaction was carried out for 2.0 hours while maintaining the pressure at 70 ° C. and the pressure of 4 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, 1.3% by weight of unreacted alcohol, and 2.2% by weight of by-produced polyethylene glycol.

COMPARATIVE EXAMPLE 1 In a 200 ml autoclave with a stirrer having the same internal volume as in Example 1, 0.02 g of caustic potassium 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 resulting ethylene oxide adduct had an average addition mole number of 7.0 and unreacted alcohol
And 2.5% by weight of polyethylene glycol as a by-product. Further, the distribution of the added mole number of ethylene oxide was a result shown by a curve 3 in FIG.

[0031]

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 the addition mole number distribution of ethylene oxide in the method for producing an alkylene oxide adduct of the present invention.

Continuation of front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C07C 43/11 B01J 23/02 C07C 41/02 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, comprising the steps of: producing a metal ion selected from Ba ²⁺ , Na ⁺ and K ^{+ in} the presence of an aluminate catalyst; Reacting the alkylene oxide adduct.