JP2000095859A - Production of alkylene oxide adduct - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an alkylene oxide adduct by which an alkaline catalyst used for a reaction can efficiently be removed to efficiently produce the high-purity alkylene oxide adduct in relation to the method for producing the alkylene oxide adduct using the alkaline catalyst. SOLUTION: A reactional product obtained by carrying out an addition reaction of an active hydrogen-containing compound with an alkylene oxide in the presence of an alkaline catalyst is mixed with the following substances (b) to (d) in the presence of (a) water in an amount of >=0.1 wt.% based on the total amount of the reactional product and hydrolysis of an alcoholate and neutralizing reaction of the alkaline catalyst are conducted. The resultant reactional mixture is then filtered. (b) 0.1-10 wt.% of a basic aluminum chloride, (c) 0-5 wt.% of a mineral acid and/or an organic acid and (d) 0-5 wt.% of an inorganic adsorbent consisting essentially of at least one of magnesium, aluminum and silica.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing an alkylene oxide adduct using an alkali catalyst, and more particularly, to a method for efficiently removing an alkali catalyst used to efficiently add an alkylene oxide adduct. The present invention relates to a method for producing an alkylene oxide adduct capable of efficiently producing a product.

[0002]

2. Description of the Related Art Conventionally, an alkylene oxide adduct such as polyether polyol is obtained by addition-polymerizing an alkylene oxide to an organic compound having at least one active hydrogen group in a molecule in the presence of an alkali catalyst. It is. Examples of the alkali catalyst used in this addition reaction include sodium hydroxide, potassium hydroxide, sodium methylate, potassium methylate,
There are metallic sodium, potassium carbonate, sodium carbonate and the like.

[0003] These alkali catalysts or neutralized salts (neutralized salts formed when a mineral acid such as phosphoric acid or an organic acid such as acetic acid is added to the crude reaction product) remain in the polyether polyol or the like. In all cases, all uses of alkylene oxide adducts such as polyether polyols, for example, polyurethane resin raw materials, cosmetic raw materials, detergent raw materials,
Since it has an adverse effect on the surfactant raw material and the like, it is usually removed.

[0004] Known methods for removing an alkali catalyst include the following (1) to (9), each of which has the following problems. (1) A method of neutralizing an alkali catalyst with an acid and removing a generated salt by filtration (JP-B-37-5597,
JP-B-41-21237, JP-B-47-3745
No.). In this removal method and the like, the generated salt particles are fine and unstable, making filtration difficult, and halogen-based acids have a problem of corrosion. (2) A method of neutralization or removal using an alkali adsorbent without neutralization (JP-B-38-26158, JP-B-42-13021, JP-B-45-32432, JP-B-45-243) No. 33194, Japanese Patent Publication No. 52-1
0018, JP-B-53-123499).
This removal method and the like have a problem that the load of filtration is large because the alkali adsorption ability is low and a large amount of powder is used, and if the treatment time is long, alkali components are eluted from the adsorbent.

(3) A method of dissolving in a solvent and removing by washing with water (Japanese Patent Publication No. 49-14359). This removal method has a problem that it is not efficient in terms of solvent recovery and waste. (4) Removal method using ion exchange resin
No. 22148). This removal method and the like have a problem that the ion exchange rate is low and organic substances in the ion exchange resin are eluted. (5) A method of filtering a carbonate by neutralizing an alkali catalyst with carbon dioxide (Japanese Patent Publication No. 52-33000). This removal method and the like have a problem that the particle strength of the carbonate is weak and filtration becomes difficult.

(6) An aqueous solution of phosphoric acid having a concentration of 30% or less is added to neutralize the mixture, and after filtration, the excess acid is composed of magnesium silicate or aluminum, magnesium oxide or aluminum, aluminum hydroxide, aluminum carbonate or a mixture thereof. Method for adsorption and removal with an acid adsorbent (JP-A-5
1-101098). This removal method and the like are the same as the above-mentioned method (1) until neutralization and filtration with phosphoric acid, which are known facts. However, there is a problem that the phosphate particles are fine and the filtration load is large. (7) A method using acidic pyrophosphate and disodium dihydrogen pyrophosphate (JP-A-8-176292, JP-A-8-231707, JP-A-3-88823). This removal method has a problem in that its use is limited because phosphate is mixed.

(8) A method of washing a polyether polyol containing an alkali catalyst with water (JP-A-6-157743). This removal method and the like have a problem that it is necessary to treat wastewater containing alkali and a small amount of polyether polyol. (9) A method of using a synthetic magnesium silicate having a low sodium content as an adsorbent after neutralization with a mineral acid (Japanese Unexamined Patent Publication No.
195728). This removal method has a problem in that a commercially available adsorbent usually contains an alkali component of about 1.2 to 2.5% and is not a general adsorbent, and has a low removal efficiency.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned various problems, and is intended to solve the above-mentioned problems. An object of the present invention is to provide a method for producing an alkylene oxide adduct that can efficiently produce an alkylene oxide adduct.

[0009]

Means for Solving the Problems As a result of intensive studies on the above-mentioned conventional problems, the present inventors have found that a specific amount of a reaction product obtained by adding an alkylene oxide to an active hydrogen-containing compound in the presence of an alkali catalyst is added. Water (including water that dissolves the specific substance) and the specific substance are mixed, and the alcoholate is hydrolyzed and the alkali catalyst is neutralized.
Filtration succeeded in obtaining the above-mentioned method for producing an alkylene oxide adduct, and completed the present invention. That is, the method for producing an alkylene oxide adduct of the present invention comprises the steps of: (a) adding water to a reaction product obtained by adding an alkylene oxide to an active hydrogen-containing compound in the presence of an alkali catalyst; In the presence of 1% by weight or more, the following substances (b) to (d) are mixed,
A method for producing an alkylene oxide adduct, comprising conducting hydrolysis of an alcoholate and neutralization of an alkali catalyst, followed by filtration. (B) Basic aluminum chloride 0.1 to 10% by weight (c) Mineral acid and / or organic acid 0 to 5% by weight (d) Inorganic adsorbent containing at least one of magnesium, aluminum and silica as a main component 0 to 5% by weight The "hydrolysis of alcoholate" as defined in the present invention means an alcoholate (alkoxide) which is a compound in which hydrogen of a hydroxyl group of an alcohol is replaced with a metal, for example, CH
Hydrolysis of ₃ OM, C ₂ H ₅ OM, etc. (M is a metal such as Na, K, Ca, Al) (for example, CH ₃ OM + H ₂ O → C
H ₃ OH + MOH, C ₂ H ₅ OM + H ₂ O → C ₂ H ₅ OH + M
OH).

[0010]

Embodiments of the present invention will be described below in detail. The method for producing an alkylene oxide adduct of the present invention comprises first producing a reaction product (crude alkylene oxide adduct) obtained by subjecting an active hydrogen-containing compound to an addition reaction of an alkylene oxide in the presence of an alkali catalyst; The following substances (b) to (d) are mixed in the presence of 0.1% by weight or more of water with respect to the total amount of the product,
After the hydrolysis of the alcoholate and the neutralization reaction of the alkali catalyst are performed, the reaction is filtered. (B) Basic aluminum chloride 0.1 to 10% by weight (c) Mineral acid and / or organic acid 0 to 5% by weight (d) Inorganic adsorbent containing at least one of magnesium, aluminum and silica as a main component According to this production method, CPR (Controlled Polymerization Ra) serving as an index of an alkali catalyst remaining in the reaction product is obtained.
An alkylene oxide adduct capable of reliably reducing te) can be obtained.

In the present invention, a reaction product (crude alkylene oxide adduct) is obtained by adding an alkylene oxide to an active hydrogen-containing compound in the presence of an alkali catalyst. The reaction of the reaction product can be easily performed under well-known operating procedures and reaction conditions. The reaction temperature is, for example, 80 to 230 ° C. The reaction pressure is 0 to 20 depending on the reaction temperature.
atm, preferably 2 to 15 atm, and the addition reaction of the alkylene oxide can be carried out under nitrogen-diluted conditions, if necessary.

The active hydrogen-containing compound used for producing the reaction product of the present invention is not particularly limited as long as it is alkoxylated, and examples thereof include alcohols, polyols, amines, and alkanolamides. And each may be used alone or as a mixture of two or more. As alcohols, for example, n-octanol, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, oleyl alcohol, etocosanol, behenol, nonanol, undecanol, tridecanol and the like A higher aliphatic primary alcohol having a saturated or unsaturated linear alkyl group having 8 to 22 carbon atoms, or a branched alkyl primary alcohol such as a Guerbet alcohol having 16 to 36 carbon atoms; Methyl, 1-dodecanol,
Branched alkyl primary alcohols such as oxo alcohols having 11 to 23 carbon atoms such as 2-methyl and 1-decanol;
Further, secondary alcohols such as 2-octanol, 2-decanol and 2-dodecanol, benzyl alcohol, 2-octyldodecyl alcohol and the like can be mentioned. Examples of the polyols include ethylene glycol, propylene glycol, diethylene glycol, glycerin, sorbitol, trimethylolpropane, and pentaerythritol. Examples of the amines include primary or secondary amines having a saturated or unsaturated alkyl group having 8 to 36 carbon atoms, such as octylamine, dioctylamine, laurylamine, dilaurylamine, stearylamine, distearylamine and the like. And polyamines such as ethylenediamine and diethylenetriamine. Examples of the alkanolamide include lauryl monoethanolamide, lauryl diethanolamide and the like. Among these active hydrogen-containing compounds, a linear or branched saturated or unsaturated alcohol having 8 to 22 carbon atoms is preferable.

The alkylene oxide used for producing the reaction product of the present invention is preferably an alkylene oxide having 2 to 4 carbon atoms. Specifically, ethylene oxide, propylene oxide, butylene oxide, and the like can be used alone or as a mixture of two or more. In the present invention, those obtained by adding 1 to 150 mol of alkylene oxide per 1 mol of the active hydrogen-containing compound are preferable.

The alkali catalyst used for producing the reaction product of the present invention includes, for example, sodium hydroxide, potassium hydroxide, sodium methylate, potassium methylate, metallic sodium, potassium carbonate, sodium carbonate and the like. . The amount of these alkali catalysts used is
The amount of the hydrophobic raw material is preferably 0.01 to 5% by weight, although it varies depending on the type of the alkylene oxide and the hydrophobic raw material such as an active hydrogen atom-containing compound and the number of moles added.

According to the present invention, the reaction product (crude alkylene oxide adduct) obtained above is added to (a) 0.1% by weight or more of water with respect to the total amount of the reaction product, and After mixing the substances (b) to (d), hydrolysis of the alcoholate and neutralization of the alkali catalyst are performed, and then filtration is performed, whereby the target alkylene oxide adduct is produced. (B) Basic aluminum chloride 0.1 to 10% by weight (c) Mineral acid and / or organic acid 0 to 5% by weight (d) Inorganic adsorbent containing at least one of magnesium, aluminum and silica as a main component 0-5% by weight

The water used for the reaction product of the present invention is
It is water for dissolving the alcoholate contained in the reaction product and dissolving the above (ii) to (iv), and industrial water, ion-exchanged water and distilled water are used according to the purpose. The amount of water used is 0.1% by weight or more, preferably 0.1 to 30% by weight, more preferably 0.1% by weight, based on the total amount of the reaction product.
~ 5% by weight. If the amount of water used is less than 0.1% by weight, hydrolysis of the crude alkylene oxide adduct does not sufficiently proceed, and an alkali component remains in the filtrate, which is not preferable.

The basic aluminum chloride (Basic aium inum chloride) used for the reaction product of the present invention is a substance usually used as a coagulant for water treatment, for example, aluminum hydroxychloride, aluminum chlorohydroxide or hydroxy chloride. Polyaluminum chloride, which is an inorganic ionic polymer called aluminum chloride etc. [Also called: PAC (PAC)]
[Al ₂ (OH) _n Cl _6-n ] _m (1 <n <5, m
<10). This basic aluminum chloride is commercially available as polyaluminum chloride in powder and liquid forms. In the present invention, both powdery and liquid forms can be used, and the water content of the liquid is about 20 to 90%. Specific examples of basic aluminum chloride (poly aluminum chloride) include poly aluminum chloride for water supply (JIS K14).
75-1996), TK Flock, PA manufactured by Taki Kagaku Co., Ltd.
C250AD, Van Nol Tan White, Takibain #
Examples include commercially available basic aluminum chloride such as 1500, Takibain # 3000, and PAC # 1000. The amount of the basic aluminum chloride used is 0.1 to 10% by weight, preferably 0.1 to 5% by weight, based on the total amount of the reaction product. When the use amount of the basic aluminum chloride is less than 0.1% by weight, the hydrolysis of the alcoholate and the neutralization reaction of the alkali catalyst do not sufficiently proceed, and the alkali component remains in the alkylene oxide adduct after filtration. It is not preferable. If it exceeds 10% by weight, the hydrolysis of the alcoholate and the neutralization reaction of the alkali catalyst proceed sufficiently, but an excessive amount of basic aluminum chloride remains in the alkylene oxide adduct after filtration, so that it is preferable. Absent.

The mineral acid and / or organic acid used for the reaction product of the present invention is used as a neutralizer.
Examples of the mineral acid include sulfuric acid and phosphoric acid, and examples of the organic acid include acetic acid, citric acid, and lactic acid. The amount of the mineral acid and / or organic acid used is 0 to 5% by weight, preferably 0.1 to 5% by weight, based on the total amount of the reaction product.
01 to 5% by weight. If the amount of the mineral acid and / or organic acid exceeds 5% by weight, the neutralization reaction proceeds sufficiently,
An excessive amount of mineral acid and / or organic acid remains in the filtrate, which is not preferable. In addition, the amount of the mineral acid and / or the organic acid used is 0% by weight, as shown in Table 1 described below, without using the mineral acid and / or the organic acid to be (c). This is because the object of the present invention can be achieved also by a combination of the above (a), (b) and (d).

The inorganic adsorbent containing at least one of magnesium, aluminum and silica used for the reaction product of the present invention is treated with basic aluminum chloride and a mineral acid and / or an organic acid. A method in which a slightly remaining alkali component (catalyst component) is used to remove an alkali component using an inorganic adsorbent, and conversely, an excessive amount of basic aluminum chloride and a mineral acid and / or an organic acid are inorganic-adsorbed. For adsorbing using an agent, for example, M
_{gO, Al (OH) 3 ·} xH 2 O, 1.25Mg (OH)
_{2 · Al (OH) 3 ·} xCO 3 · yH 2 O, Al (OH)
_{3 · NaHCO 3, Mg 6 Al} 2 (OH) 16 CO 3 · 4H
₂ O, 2MgO ₆ SiO ₂ xH ₂ O, Al ₂ O ₃ 9 SiO
₂ H ₂ O, Mg _4.5 · Al ₂ (OH) ₁₃ · CO ₃ · 3.5 H ₂
O and the like and their baked products (baked at 200 to 1500 ° C. for several minutes to several hours) are also included. Furthermore, Mg _0.7 A
_l0.3 · O _{1.15 and the} like, and those not subjected to the water washing treatment are also included. Further, hydrotalcite [natural minerals such as Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O are used. No. Specifically, Kyowa 100 (MgO), Kyowa 200 [A
l (OH) ₃ .xH ₂ O], Kyoward 300 [1.2
5Mg (OH) ₂ · Al (OH) ₃ · xCO ₃ · yH
₂ O], Kyoward 400 [Al (OH) ₃ · NaHC
O ₃ ], Kyoward 500 [Mg ₆ Al ₂ (OH) ₁₆ C
O ₃ .4H ₂ O], Kyoward 600 [2MgO ₆ Si
O ₂ · xH ₂ O], same composition as Kyowaad 600s [Kyoward 600], Kyowaad 700 [Al ₂ O ₃ ·
9SiO ₂ H ₂ O], Kyoward 1000 [Mg _{4.5
Al 2 (OH) 13 · CO3} · 3.5H 2 O ], Kyoward 2000 _{[Mg 4.5 · Al 2 (OH)} 13 · CO 3 · 3.
5H ₂ O]. The amount of the inorganic adsorbent used is 0 to 5% by weight, preferably 0.01 to 5% by weight, based on the total amount of the reaction product. If the amount of the inorganic adsorbent exceeds 5% by weight, the load on the filtration operation is increased, and the amount of the filter cake is also increased. The amount of the inorganic adsorbent used is 0% by weight, as shown in Table 1 below, without using the inorganic adsorbent to become (d), the above (a), ( B)
This is because the object of the present invention is achieved also by the combination of (c) and (c).

The method of the present invention based on the combination of the above (a) to (d) will be specifically described. There are 11 methods shown in Table 1 below.

[Table 1]

As described above, the method (a) is carried out by adding an alkylene oxide to a reaction product of an active hydrogen-containing compound in the presence of an alkali catalyst in the presence of 0.1% by weight or more of water, After adding and mixing the basic aluminum chloride, the mixture is filtered to efficiently remove the alkali catalyst contained in the reaction product. Means for adding and mixing basic aluminum chloride include, for example, i) means for adding and mixing basic aluminum chloride, followed by dehydration and filtration under reduced pressure, and ii) means for adding and mixing basic aluminum chloride, and then adding and mixing under reduced pressure. Means for dehydrating under reduced pressure, and further dehydrating under reduced pressure, iii) means for adding and mixing basic aluminum chloride, treating under pressure or reduced pressure, and performing the operation of i) or ii) above, iv) Means of adding a conventionally known filter aid before the filtration operation means of the above i) to iii), v) means of adding water to powdered basic aluminum chloride as it is or dissolved in water or to crude polyether polyol No.

In the method (b), as described above, the addition product is added to the reaction product in the presence of 0.1% by weight or more of water.
After hydrolysis, a neutralizing agent such as a mineral acid and / or an organic acid is added and mixed, and then the above basic aluminum chloride is added and mixed, followed by filtration to remove an alkali catalyst contained in the reaction product. It removes efficiently. the above
As described above, the method (c) is to hydrolyze the reaction product obtained by the addition reaction in the presence of 0.1% by weight or more of water,
After the inorganic adsorbent is added and mixed, the basic aluminum chloride is added and mixed, followed by filtration to efficiently remove the alkali catalyst contained in the reaction product. In the method (d), a mineral acid serving as a neutralizing agent and / or
Alternatively, after the treatment with an organic acid, the above-mentioned basic aluminum chloride is added and mixed, followed by filtration to efficiently remove the alkali catalyst contained in the reaction product. In the method (e), after treating with a mineral acid and / or an organic acid as a neutralizing agent, adding and mixing an inorganic adsorbent, adding and mixing the basic aluminum chloride, and then filtering. Thereby, the alkali catalyst contained in the reaction product is efficiently removed.

In the method (f), after treatment with a mineral acid and an organic acid as a neutralizing agent, an inorganic adsorbent is added and mixed, and then the above-mentioned basic aluminum chloride is added and mixed, followed by filtration. Thereby, the alkali catalyst contained in the reaction product is efficiently removed. The method of the above (g), after treating with an inorganic adsorbent, adding and mixing the above basic aluminum chloride, and then filtering to efficiently remove the alkali catalyst contained in the reaction product. is there. The method of the above (h), after treating with an inorganic adsorbent, adding and mixing a mineral acid or an organic acid as a neutralizing agent, then adding and mixing the basic aluminum chloride, followed by filtration, The purpose is to efficiently remove the alkali catalyst contained in the product. In the method (i), a basic aluminum chloride aqueous solution is added and mixed, then treated with a mineral acid or an organic acid serving as a neutralizing agent, and then filtered to efficiently remove the alkali catalyst contained in the reaction product. Is to be removed. This method is a post-addition method of the above-mentioned acid used as a neutralizing agent, and is added to surely remove a small amount of an alkali catalyst remaining as a neutralized salt in the treatment with basic aluminum chloride.

In the method (j), the operation up to the filtration (i) is carried out, and then the mixture is further treated with an inorganic adsorbent and then filtered, whereby the alkali contained in the reaction product is removed. It removes the catalyst efficiently. This method
In the method of removing as a neutralized salt by the method (i),
A slight excess of the neutralized salt may be used. In this case, since a small amount of neutralizing agent remains in the filtrate, the excess neutralizing agent is adsorbed and removed by the inorganic adsorbent.
It is also possible to use the above method. In the method (k), as described above, the reaction product obtained by the addition reaction of the alkylene oxide is mixed with basic aluminum chloride in the presence of 0.1% by weight or more of water, and then mixed with an inorganic adsorbent. By filtering after the mixing treatment, the alkali catalyst contained in the reaction product is efficiently removed.
When the basic aluminum chloride used in this method is a water-containing product, the hydrolysis of the alcoholate and the neutralization reaction of the alkali catalyst can be carried out simultaneously with the water contained without any particular addition of water. When powdery basic aluminum chloride is used, the above object can be achieved by adding water.

In the above (a) to (k), dehydration can be performed before and after filtration, and if necessary, a conventionally known filter aid can be added. Further, the filtration in the above (a) to (k), for example, using a two-layer filter of cellulose and polyester as a filter paper, a metal mesh type filter and the like, it is preferable to perform a filtration operation under reduced pressure or pressure, further centrifugation For example, the separation can be performed by a known separator (machine) such as a decanter or a centrifugal clarifier.

In the above methods (a) to (k), it is also possible to blow in an inert gas under a nitrogen atmosphere when operating under normal pressure or when operating under reduced pressure. The processing temperature is 30 to 180 ° C., and the processing time is several minutes to several hours. However, these treatment temperatures and times are temperatures after addition and mixing of basic aluminum chloride. For example, in a nitrogen atmosphere, the processing temperature is from room temperature to 180 ° C.
The treatment time is from 5 minutes to 5 hours. The inorganic ionic polymer is added to the polyether polyol containing an alkaline catalyst under reduced pressure to increased pressure, and the mixture is filtered. (A) to (k) above
In the method, more preferred methods are (a), (b),
(c), (i), (j) and (k), and particularly preferably (a) and (k).

As described above, in the present invention, for example, an active hydrogen-containing compound or the like and an alkali catalyst are charged into an autoclave, and after a dehydration operation under a nitrogen atmosphere, an alkylene oxide is introduced under predetermined temperature and pressure conditions to react. To obtain a reaction product (crude alkylene oxide adduct),
The target purified alkylene oxide adduct can be obtained by removing the alkyl catalyst by treating with any one of the above-mentioned treatment methods (a) to (k).

[0028]

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In addition, CPR (Controlled Polymerizatio
nRate) was measured according to JIS K1557-1970. “%” Is% by weight.

Example 1 Crude polyether polyol obtained by adding propylene oxide (PO) to glycerin [alkali catalyst; potassium hydroxide 0.5% (vs. crude polyether polyol CPR about 2700 glycerin n
PO, n = 5.7) with basic aluminum chloride [Takibaine # 1500 (50% aqueous solution: manufactured by Taki Kagaku)]
%, And the mixture was stirred and mixed at a treatment temperature of 25 ° C. for 30 minutes (3.5% of water vs. reaction product), and then filtered to obtain a purified polyether polyol. The resulting purified polyether polyol had a CPR of 3.

Example 2 A purified polyether polyol was obtained in the same manner as in Example 1 except that the treatment temperature was changed to 80 ° C. CPR of the obtained purified polyether polyol
Was 3.

Example 3 After the treatment in Example 2, before filtration, the water in the system was reduced to 300 p under reduced pressure (5 Torr).
After dehydration (80 to 120 ° C.) until the pressure reached pm, a filtration operation was performed to obtain a purified polyether polyol. The CPR of the obtained purified polyether polyol was 2.

Example 4 The liquid basic aluminum chloride of Example 1 [Takibaine # 1500 (50% aqueous solution:
3.5) instead of powdered basic aluminum chloride [Thaibain # 3000 (manufactured by Taki Kagaku)].
%, And treated in the same manner as in Example 3 except that ion-exchanged water was changed to 3.5% (a reaction product) to obtain a purified polyether polyol. The resulting purified polyether polyol had a CPR of 5.

Example 5 Crude polyether polyol obtained by adding propylene oxide (PO) to glycerin [alkali catalyst; potassium hydroxide 0.5% (vs. crude polyether polyol CPR of about 2700, glycerin
nPO, n = 5.7) was added with 3% of water (a) and hydrolyzed. Next, 7% of basic aluminum chloride [Takibain # 1500 (50% aqueous solution: manufactured by Taki Kagaku)] was added.
The mixture was stirred and mixed at a treatment temperature of 25 ° C. for 30 minutes (water 6.
After pressure filtration (filter paper; double-layer filter of cellulose and polyester, pressure 2K / G, inner diameter 4)
cm) (filtration pressure: 200 cm), and the filtrate obtained by filtration is a silica-magnesium-based Kyoward 600s (manufactured by Kyowa Chemical Industry Co., Ltd.) as an inorganic synthetic adsorbent.
%, And the mixture was stirred and mixed at 80 ° C. for 30 minutes, and then solid matter was removed by a filtration operation to obtain a purified polyether polyol. CPR of the obtained purified polyether polyol was 2.4.

Example 6 After hydrolysis of Example 5, 0.5% of silica-magnesium Kyoward 600s (manufactured by Kyowa Chemical Industry Co., Ltd.) as an inorganic synthetic adsorbent, basic aluminum chloride [Takibain # 1500 ( 50% aqueous solution: manufactured by Taki Kagaku Co.)] was added (5.5% of water to reaction product), and the treatment temperature was 80 ° C, except that the treatment was carried out in the same manner as in Example 5 to obtain a purified polyether polyol. Was. CPR of the obtained purified polyether polyol was 1.5.

Example 7 After the hydrolysis of Example 5, 60% phosphoric acid (reagent primary water dilution) 0.5% as a mineral acid,
Basic aluminum chloride [Takibain # 1500 (50
% Aqueous solution: Taki Chemical Co., Ltd.)] (water 5.5%)
% Of the reaction product) and the same treatment as in Example 5 except that the treatment temperature was 80 ° C., to obtain a purified polyether polyol. CPR of the obtained purified polyether polyol was 2.9.

Example 8 To 500 g of the crude polyether polyol of Example 1 was added 0.4 g of 60% phosphoric acid (reagent first-grade water-diluted product) as a mineral acid.
After mixing for 4 minutes, 4% of basic aluminum chloride [Takibain # 1500 (50% aqueous solution: manufactured by Taki Kagaku)] was added.
(Crude polyether polyol) was added, and the mixture was stirred and mixed at the same temperature for 60 minutes, and then filtered to obtain a purified polyether polyol. The CPR of the obtained purified polyether polyol was 4.

Example 9 To 500 g of the crude polyether polyol of Example 1 was added silica as an inorganic synthetic adsorbent.
After adding 5 g of magnesium-based Kyoward 600s (manufactured by Kyowa Chemical Industry Co., Ltd.) and mixing at a treatment temperature of 100 ° C. for 30 minutes, basic aluminum chloride [Takibaine # 150] was added.
0 (50% aqueous solution: manufactured by Taki Kagaku Co., Ltd.)], 4% (crude polyether polyol) was added, and the mixture was stirred and mixed at the same temperature for 60 minutes, and then filtered to obtain a purified polyether polyol. The resulting purified polyether polyol has a CPR of 3
Met.

Example 10 After adding and mixing an inorganic synthetic adsorbent in the same manner as in Example 5, the pressure was reduced to 10 To
After dehydrating the water in the system at rr until the water content became 300 ppm (80 to 120 ° C), a filtration operation was performed to obtain a purified polyether polyol. The CPR of the obtained purified polyether polyol was 2.

Comparative Example 1 500 g of the crude polyether polyol of Example 1 was mixed with silica as an inorganic synthetic adsorbent.
5 g of magnesium-based Kyoward 600s (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, mixed at a treatment temperature of 25 ° C. for 30 minutes, and filtered to obtain a purified polyether polyol. The resulting purified polyether polyol has a CPR of 1
87.

Comparative Example 2 Silica as an inorganic synthetic adsorbent was added to 500 g of the crude polyether polyol of Example 1.
5 g of magnesium-based Kyoward 600s (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, mixed at a treatment temperature of 80 ° C. for 30 minutes, and filtered to obtain a purified polyether polyol. The resulting purified polyether polyol has a CPR of 1
37.

Comparative Example 3 To 500 g of the crude polyether polyol of Example 1 was added 1.06 moles of sulfuric acid as a mineral acid, followed by mixing at 80 ° C. for 30 minutes. Next, 1% by weight of Kyoward 200 (manufactured by Kyowa Chemical Industry Co., Ltd.) of Al (OH) ₃ .xH ₂ O was added as an inorganic synthetic adsorbent, mixed at a treatment temperature of 80 ° C. for 30 minutes, and then subjected to a filtration operation. But
Filtration was difficult. The purified polyether polyol obtained by filtration in a small amount had a CPR of 10.

Comparative Example 4 To 500 g of the crude polyether polyol of Example 1 was added 1.06 moles of sulfuric acid as a mineral acid, followed by mixing at 80 ° C. for 30 minutes. Next, 1 wt% of Kyoward 200 (manufactured by Kyowa Chemical Industry Co., Ltd.) of Al (OH) ₃ .xH ₂ O was added as an inorganic synthetic adsorbent, and the mixture was mixed at a treatment temperature of 80 ° C. for 300 minutes, followed by filtration. However, filtration was difficult. CPR of the purified polyether polyol obtained by filtration in a small amount was 32, and desorption from the adsorbent was observed because of a long stirring time.

[0043]

According to the present invention, there is provided a method for producing an alkylene oxide adduct capable of efficiently producing an alkylene oxide adduct having high purity by efficiently removing the alkali catalyst used. You.

Claims (1)

[Claims] 1. A reaction product obtained by adding an alkylene oxide to an active hydrogen-containing compound in the presence of an alkali catalyst in the presence of (a) water in an amount of 0.1% by weight or more based on the total amount of the reaction product. And mixing the following substances (b) to (d),
A method for producing an alkylene oxide adduct, comprising conducting hydrolysis of an alcoholate and neutralization of an alkali catalyst, followed by filtration. (B) Basic aluminum chloride 0.1 to 10% by weight (c) Mineral acid and / or organic acid 0 to 5% by weight (d) Inorganic adsorption mainly containing at least one of magnesium, aluminum and silica Agent 0-5% by weight