JP2000095858A - Production of alkylene oxide adduct - Google Patents

Abstract

PROBLEM TO BE SOLVED: To surely remove an alkaline catalyst from a crude polyether polyol, etc., and produce the subject high-purity adduct useful as a raw material, etc., for polyurethane resins by carrying out a mixing treatment of a specific reactional product with a polymer and a polyvalent metal salt. SOLUTION: (A) A reactional product prepared by conducting an addition reaction of an active hydrogen-containing compound [e.g. an 8-22C (un)saturated alcohol] with an alkylene oxide (e.g. ethylene oxide) in the presence of an alkaline catalyst (e.g. sodium hydroxide) is subjected to a mixing treatment with (B) a polymer having neutralizing functions [e.g. (meth)acrylic acid monomer] and a polyvalent metal salt (e.g. calcium carbonate) for making the polymer B form a cross-linked structure. The above addition reaction is preferably carried out under conditions of, e.g. 80-230 deg.C reactional temperature and 0-20 atm reactional pressure.

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 conventional problems, the present inventors have found that a reaction product obtained by adding an alkylene oxide to an active hydrogen-containing compound in the presence of an alkali catalyst is neutralized with a neutralized product. By mixing and processing a specific compound having a function and a specific compound in which the compound forms a crosslinked structure, the above-mentioned method for producing an alkylene oxide adduct was successfully obtained, and the present invention was completed. It has been reached. That is, the method for producing an alkylene oxide adduct of the present invention comprises a reaction product obtained by adding an alkylene oxide to an active hydrogen-containing compound in the presence of an alkali catalyst, a polymer compound having a neutralizing function, and the polymer compound Is mixed with a polyvalent metal salt that forms a crosslinked structure.

[0010]

Embodiments of the present invention will be described below in detail. As shown in FIG. 1, the method for producing an alkylene oxide adduct of the present invention first comprises reacting an active hydrogen-containing compound with an alkylene oxide in the presence of an alkali catalyst to obtain a reaction product (crude alkylene oxide adduct). The reaction product is mixed with a polymer compound having a neutralizing function and a polyvalent metal salt which forms a crosslinked structure with the polymer compound, followed by filtration. . By this production method, CPR (Controlled Pol) which is an index of an alkali catalyst remaining in the reaction product is used.
Thus, an alkylene oxide adduct that can reliably reduce the ymerization rate) 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 molecular weight of the obtained reaction product is preferably from 300 to 30,000.

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.

The present invention provides a method of mixing the reaction product (crude alkylene oxide adduct) obtained above with a polymer compound having a neutralizing function and a polyvalent metal salt which forms a crosslinked structure with the polymer compound. By performing the treatment, the desired alkylene oxide adduct is obtained.

The polymer compound (A) having a neutralizing function used in the present invention neutralizes the alkali catalyst contained in the reaction product (crude alkylene oxide adduct),
For example, a polymer selected from the group consisting of acrylic acid or methacrylic acid monomer or an alkali metal salt thereof and a copolymerizable monomer is mentioned, and the average molecular weight is 500 to 100.
0000 is preferred. Examples of the copolymerizable monomer include unsaturated carboxylic acids such as alkyl (meth) acrylate and itaconic acid, and the proportion of the copolymerizable monomer is 0 to 50 mol%. Is desirable. Preferably, as a main component, a homopolymer or copolymer (copolymer) of acrylic acid or methacrylic acid, a copolymer of acrylic acid or methacrylic acid and another monomer (unsaturated carboxylic acid such as itaconic acid), a homopolymer thereof, or Partially neutralized salt of copolymer (Na, K, NH
₃ , triethanolamine, etc.).

The polymer compound (A) is preferably used in the form of an aqueous solution or an organic solvent solution, and if it is in the form of powder, it is desirable to use it after dissolving it in water or an organic solvent. It is also possible to add water or an organic solvent after the addition. Examples of the organic solvent include lower alcohols such as methanol, ethanol, and isopropyl alcohol. The concentration of the polymer compound solution varies depending on the type of the polymer compound (A), but is preferably 5 to 70% by weight from the handling side. When added as an aqueous solution of the polymer, or diluted with an organic solvent or water. It can also be used as a mixed solution of an organic solvent. Further, the alkali metal salt or the partially neutralized salt of the polymer compound is 0 to 5
It is preferably 0 mol%, and when the ratio of the neutralized salt or the like is increased, the viscosity of the aqueous polymer solution increases, which is not preferable in terms of handling. The amount of the polymer compound (A) added depends on the reaction product (crude polyether polyol, etc.)
0.05 to 10% by weight based on the total amount, preferably
It is 0.05 to 5% by weight. If the amount of the polymer compound (A) is less than 0.05% by weight, the alkali catalyst contained in the reaction product cannot be sufficiently removed.
When the amount exceeds 0% by weight, the catalyst component contained in the crude polyether polyol can be sufficiently removed, but the high molecular compound (A) may remain in the purified polyether polyol after filtration, so that it is preferable. Absent.

The polyvalent metal salt (B) used in the present invention forms a crosslinked structure with the polymer compound having a neutralizing function. For example, Ca, Mg, Al salts (carbonate, sulfate) , Chloride and hydroxide), and specific examples thereof include calcium carbonate, aluminum sulfate and the like, magnesium chloride, calcium chloride, aluminum chloride and the like, and hydroxide. These polyvalent metal salts (B)
It is also possible to add the above-mentioned salt, chloride or hydroxide as it is or to dissolve or disperse it in water and then add it. The addition amount of the polyvalent metal salt (B) is 0.01 to 10 with respect to the total amount of the reaction product (crude polyether polyol or the like).
%, Preferably 0.01 to 5% by weight. When the amount of the polyvalent metal salt (B) is less than 0.01% by weight,
When the crosslinked structure is not sufficiently formed, the polymer compound (A) remains, and when the content exceeds 10% by weight, the crosslinked structure is sufficiently formed, but the polyvalent metal salt remains in the filtrate. May be undesirable.

In the present invention, the alkali catalyst can be easily separated and removed by utilizing the crosslinking formation of the polymer compound (A), and the polymer compound (A) is crosslinked to form a gel. However, the amount of the polyvalent metal salt and the ratio of the partially neutralized salt can be adjusted so that the polyvalent metal salt (B) is insolubilized (floc formation) by the crosslinked structure. The amount of the polyvalent metal salt is 0.01 to 10% by weight and the ratio of the partially neutralized salt is 0 to 50% by weight. The polymer compound (A) of the present invention is removed at the time of filtration, and can be easily removed because it is in the form of a floc. That is, in the present invention, the carboxylic acid (—COO) of the polymer compound (A) is used.
H) etc. to neutralize the alkali catalyst, simultaneously form a counter ion with the alkali metal of the catalyst, and further form a floc by cross-linking the polymer with the polyvalent metal salt (B). It can be separated.

In the present invention, the polymer compound (A)
And the polyvalent metal salt (B) can be mixed in any manner with a reaction product comprising a crude polyether polyol or the like. After mixing the reaction product with the polymer compound (A), It is preferable to add and mix the polyvalent metal salt (B). The treatment temperature is from room temperature to 150 ° C., and the contact time is from several minutes to several hours. The treatment is preferably performed in an inert gas atmosphere, but is not limited thereto. Further, at the time of mixing the polymer compound (A) and the polyvalent metal salt (B) or before the mixing, it is also possible to mix a conventionally known filter aid. The filter aid, for example, aluminum silicate and cellulose-based main component such as Celite 545 contains diatomaceous earth or SiO ₂ about 70 wt% of amorphous silica containing SiO ₂ 80 to 95 wt% filtration Auxiliary agents, activated carbon, synthetic zeolite, silica gel, activated alumina, and clay minerals such as clay or acid clay and activated clay can be used, and each can be used alone or as a mixture of two or more. The use amount of these filter aids is preferably about 0.01 to 5% by weight based on the total amount of the reaction product.

Further, in the present invention, it is possible to further neutralize with a mineral acid and / or an organic acid before the filtration, or to add an inorganic adsorbent or the like. The mineral acid and / or organic acid is used as a neutralizing agent. 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. And the like. The amount of the mineral acid and / or organic acid used is based on the total amount of the reaction product.
It is 0 to 5% by weight, preferably 0.01 to 5% by weight.
Examples of the inorganic adsorbent include those containing at least one of magnesium, aluminum, and silica as main components, for example, MgO, Al (OH) ₃ .xH ₂ O,
1.25Mg (OH) ₂ · Al (OH) ₃ · xCO ₃ · y
H ₂ O, Al (OH) ₃ .NaHCO ₃ , Mg ₆ Al ₂ (O
H) ₁₆ CO ₃ .4H ₂ O, 2Mg ₆ SiO ₂ .xH ₂ O,
_{Al 2 O 3 · 9SiO 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 (200
焼 成 1500 ° C. for several minutes to several hours).
Furthermore, Mg _0.7 · Al _0.3 · O _{1.15 and the} like, and those not subjected to the water washing treatment are also included. Further, hydrotalcite [Mg ₆ Al ₂ (OH) ₁₆ CO ₃
· 4H ₂ O are natural minerals, and the like. The amount of the inorganic adsorbent used is 0 to 5% by weight based on the total amount of the reaction product.
Preferably it is 0.01 to 5% by weight. Further, dehydration can be performed before and after the filtration. For the filtration, for example, it is preferable to carry out filtration under reduced pressure or pressure using, for example, a two-layer filter of cellulose and polyester as a filter paper, a metal mesh filter, and the like. Separation, for example, can be performed by a known separator (machine) such as a decanter or a centrifugal clarifier.

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 reaction product is mixed with a polymer compound (A) having a neutralizing function and a polyvalent metal salt (B) in which the polymer compound (A) forms a crosslinked structure, and the alkyl catalyst is removed by filtration. Thus, the desired purified alkylene oxide adduct can be obtained.

[0023]

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.

[Preparation Example of Crude Polyether Polyol] 4
Into an L autoclave, 276 g of glycerin and 16 g of 40% potassium hydroxide were charged, and after purging with nitrogen, the mixture was heated and dehydrated under reduced pressure with stirring.
g. Then, 1010 g of propylene oxide was introduced under control, and the temperature was adjusted to 120 ° C and 3 kg / c.
m ² . An addition reaction was performed with G to obtain a crude polyether polyol (CPR; about 2700) containing an alkali catalyst.

Example 1 Acrylic acid polymer aqueous solution [solid content 40%, viscosity 59 cps, polymer compound (A)] was added to 100 g of the crude polyether polyol obtained in the preparation example.
pH 2.4 (1% aqueous solution), molecular weight about 6000]
After adding 3.2 g and stirring and mixing at 80 ° C. for 15 minutes, 1.7 g of calcium chloride as a polyvalent metal salt (B) was dissolved in 5 g of ion-exchanged water, and the mixture was contacted at the same temperature for 15 minutes. Next, dehydration was performed under reduced pressure to sufficiently remove water in the system, and then a purified polyether polyol was obtained by a filtration operation. C of the obtained purified polyether polyol
PR was 31. The filtration time was 5 minutes.

Example 2 Acrylic acid polymer aqueous solution [solid content 39.6%, viscosity 430] as polymer compound (A)
cps, pH 2.7 (1% aqueous solution), molecular weight about 200
00-30000], and a purified polyether polyol was obtained according to Example 1 except that aluminum chloride was used as the polyvalent metal salt (B). The resulting purified polyether polyol had a CPR of 29. The filtration time was 3 minutes.

Example 3 Acrylic acid polymer aqueous solution [solid content 40%, viscosity 59 cp] as polymer compound (A)
s, pH 2.4 (1% aqueous solution), molecular weight about 6000]
Was treated according to Example 1 except that the solution was partially neutralized with sodium hydroxide to pH 4.2 of a 1% aqueous solution to obtain a purified polyether polyol. The resulting purified polyether polyol had a CPR of 30.

Comparative Example 1 Instead of the polymer compound (A) and the polyvalent metal salt (B) in Example 1, sulfuric acid and a synthetic adsorbent were used, and sulfuric acid was used in an amount of 0.5 times mol (crude polyether polyol) After the addition)
A purified polyether polyol was obtained in the same manner as in Example 1 except that the temperature was changed to 0 ° C. for 60 minutes. However, clogging occurred during the filtration operation, and the filtration time was as slow as 38 minutes. The CPR at that time was 38. Filtration device: A two-layer filter of cellulose and polyester was used at 80 ° C. and a nitrogen pressure of 2.5 atm with a pressure filter having an inner diameter of 4 cm.

Comparative Example 2 Before the filtration operation, the treatment was performed in the same manner as in Comparative Example 1, and 2% by weight of Kyoward 500SN (manufactured by Kyowa Chemical Industry Co., Ltd.) was added to perform the adsorption treatment. At that time, the filtration time was 55 minutes, and the CPR was 18.

[0030]

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.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram illustrating a manufacturing method of the present invention.

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, a polymer compound having a neutralizing function, and a polyvalent compound in which the polymer compound forms a crosslinked structure. A method for producing an alkylene oxide adduct, comprising mixing and treating with a metal salt.