JPH06322102A - Production of etherified product of polyether polyol - Google Patents

Abstract

PURPOSE:To obtain the subject eterified product, while easily removing at a low cost a large quantity of by-product fine inorganic salt, by ether rification between a polyalkylene ether polyol, a halocompound and an alkali CONSTITUTION:A reaction mixture comprising (A) a polyalkylene ether polyol, (B) a halocompound and (C) an alkali is first treated so as to come to <=1 in alkali value, and the resultant mixture is incorporated with water followed by removing the water through distillatin to effect enlarging the particle size of (C) a by product inorganic salt, which is then removed through filtration, thus affording the objective etherified product of the polyalkylene ether polyol.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing an etherified product of a polyether polyol. More specifically, it relates to a simple method for removing by-produced inorganic salts during the reaction.

[0002]

2. Description of the Related Art A method of reacting a polyalkylene ether polyol, a halogen compound and an alkali to form an ether is known. However, in this method, a large amount of minute inorganic salt is by-produced, so that the inorganic salt is removed. Various methods have been proposed. As a conventionally proposed method, (1) a large amount of water is added to the reaction mixture to completely dissolve the inorganic salt in water, and a target ether of polyalkylene ether polyol and water in which the inorganic salt is dissolved are prepared. And (2) a method of adding an adsorbent such as diatomaceous earth, hydrotalcites and activated alumina or a filter aid to the reaction mixture to remove the inorganic salt by filtration.

[0003]

However, in the method (1), not only a large amount of waste liquid is generated, but also when the desired etherified product of the polyalkylene ether polyol is highly hydrophilic, the liquid separation may take a long time. There are many environmental and quality problems such as incomplete liquid separation.
In addition, the method (2) has a drawback that since the inorganic salt to be removed is extremely minute (for example, 0.5 micron or less), problems such as clogging and filtration leakage occur during filtration and removal.
As a method of improving the problem of (2), a method of adding an aqueous solution of alum to the reaction mixture to enlarge the fine inorganic salt before filtering and removing is also proposed, but the alum itself is also filtered. Not only there is a problem that the amount of the inorganic salt to be removed increases because it needs to be separated, and the yield of the etherified product of the target polyalkylene ether polyol decreases.
During filtration and purification, part of the alum aqueous solution is mixed with the etherified product filtrate of polyalkylene ether polyol,
There was a problem that purification was not performed sufficiently.

[0004]

[Means for Solving the Problems] The present inventors have arrived at the present invention as a result of earnestly studying a production method which can sufficiently remove an inorganic salt by a simple method in view of the above problems. That is, the present invention removes the inorganic salt (D) by-produced during the reaction from the reaction mixture of the polyalkylene ether polyol (A), the halogen compound (B) and the alkali (C) to obtain the polyalkylene ether polyol. In the method for obtaining the etherified product of (A), the reaction mixture is treated so that the alkali number is 1 or less, and then water is added and mixed, and then the water in the reaction mixture is distilled off to produce a by-product. This is a process for producing an etherified product of a polyalkylene ether polyol, which comprises enlarging the particle size of the inorganic salt (D) and filtering and removing it.

Examples of the polyalkylene ether polyol (A) in the present invention include compounds obtained by addition-polymerizing alkylene oxides to active hydrogen-containing compounds such as polyhydric alcohols, polyhydric phenols and amines. Examples of the polyhydric alcohol include ethylene glycol,
Propylene glycol, 1,4-butanediol, 1,
Aliphatic and alicyclic dihydric alcohols such as 6-hexanediol, diethylene glycol, neopentyl glycol, cyclohexanedimethanol and cyclohexylene glycol; glycerin, trimethylolpropane, pentaerythritol, diglycerin, methylglucoside,
Sorbitol, dipentaerythritol, glucose,
Examples thereof include polyhydric alcohols having 3 to 8 valences such as fructose and sucrose.

Examples of polyhydric phenols include monocyclic dihydric phenols such as pyrogallol, hydroquinone and phloroglucin; bisphenols such as bisphenol A and bisphenol sulfone.

Examples of amines include ammonia; C
1-C20 alkyl amines and other aliphatic monoamines;
Aliphatic polyamines such as ethylenediamine and diethylenetriamine; aromatic polyamines such as aniline, phenylenediamine, tolylenediamine and xylylenediamine; and heterocyclic polyamines such as piperazine and N-aminoethylpiperazine.

Examples of the alkylene oxide to be addition-polymerized with the active hydrogen-containing compound include ethylene oxide, propylene oxide, 1,2- or 1,4-
Butylene oxide, styrene oxide, and a combination of two or more of these (block addition or random addition may be used). As the compound (A), a compound obtained by adding an alkylene oxide to the above active hydrogen-containing compound can be used alone or in combination of two or more, and the number of added moles is usually 2 to 500.

(A) is usually obtained by the addition polymerization of the above-mentioned active hydrogen-containing compound with alkylene oxide in the presence of an alkali catalyst under ordinary pressure or pressure at a temperature of 60 to 160 ° C. .

Examples of the halogen compound (B) in the present invention include monohalogenated hydrocarbons, polyhalogenated aliphatic hydrocarbons, polyhalogenated aromatic ring-containing hydrocarbons, polyhalogenated ethers, and polyhalogenated ketones. And halogenated organic compounds.

Examples of monohalogenated hydrocarbons include methyl chloride, ethyl chloride, allyl chloride, allyl bromide, butyl chloride and lauryl chloride.

Examples of polyhalogenated aliphatic hydrocarbons include methylene chloride, methylene bromide, methylene iodide,
Methylene dihalides such as monobromomonochloromethane; alkylene dihalides such as 1,1-dichloroethane and 1,2-dichloroethane; and chloroform, carbon tetrachloride and the like.

Examples of the polyhalogenated aromatic ring-containing hydrocarbons include benzal chloride, benzal bromide, bis (chloromethyl) benzene and the like.

Examples of polyhalogenated ethers include:
Polyhalogenated aliphatic ethers such as bis (chloromethyl) ether and 2,2′-dichloroethyl ether;
Polyhalogenated aromatic ethers such as 4,4′-bis (chloromethyl) diphenyl ether; polyhalogenated aromatic aliphatic ethers such as bis (chloromethoxy) benzene and tris (chloromethoxy) benzene.

Examples of polyhalogenated ketones include bis (chloromethyl) ketone and 4,4'-dichloromethylbenzophenone.

The type and amount of alkali (C) used in the present invention are not particularly limited, but caustic alkalis such as sodium hydroxide and potassium hydroxide; sodium methylate,
Examples thereof include metal alcoholates of lower alcohols such as sodium ethylate and potassium tert-butoxide; alkali metals such as metal sodium and metal potassium; alkali metal hydrides such as sodium hydride and potassium hydride. Ordinarily, an alkali (C) is caused to act on the hydroxyl group of the polyalkylene ether polyol (A) to convert a part or all of the polyalkylene ether polyol (A) into an alkali metal alcoholate and react with the coexisting halogen compound (B). Be used for.

Polyalkylene ether polyol (A)
The reaction between the halogen compound (B) and the alkali (C) is usually carried out by reacting (A) and (C) to convert (A) into an alkali metal alcoholate, or usually at 40 to 160 ° C. This is done by adding (B) at a temperature, but a large amount of an inorganic salt (D) having a very small particle size (predominantly 0.5 μm or less) is by-produced in this reaction. The object of the present invention is a simple method for removing this inorganic salt.

The etherification reaction is usually carried out using an excess amount of alkali (C), and since an excess amount of alkali remains together with the fine inorganic salt (D) in the reaction mixture,
It is necessary to remove the inorganic salt (D) and excess alkali. When the alkali is excessively left in the system, the inorganic salt (D) is enlarged, and the effect of enlargement is impaired when the inorganic salt (D) is removed by filtration, and the particle size of the inorganic salt (D) is not enlarged.
It takes time to remove by filtration. Therefore, it is desirable to remove the alkali as thoroughly as possible, but usually the alkali value (the alkali component present in 1 g is expressed in mg of KOH) is 1 or less, preferably 0.5 or less.

The treatment method for removing the alkali to reduce the alkali value may be a general method, for example, a method of neutralizing with a mineral acid such as hydrochloric acid, nitric acid, sulfuric acid, activated clay, zeolite, hydrotalcites, Examples include a method using an adsorbent such as an ion exchange resin.

The amount of water added to the reaction mixture is usually 0.
It is 5 to 5% by weight, preferably 0.5 to 3% by weight.
If it is less than 0.5% by weight, the effect of enlarging the particle size of the by-product inorganic salt is small, and if it exceeds 5% by weight, the inorganic salt is partially dissolved. Is not preferable because it remains in the system without being enlarged.

After adding water to the reaction mixture, it is necessary to thoroughly mix the water so that the water uniformly diffuses in the system. Mixing is usually performed at 20 to 120 ° C. for 10 minutes to 1 hour.

It is necessary to sufficiently remove the water after the addition of water. The water content in the reaction mixture after evaporation is usually 0.2% by weight or less, preferably 0.15% by weight or less. 0.
If it exceeds 2% by weight, the inorganic salts dissolved in the water in the system cannot be filtered out and the effect of removing the inorganic salts is not sufficient, and the inorganic salts do not grow sufficiently, resulting in clogging and filtration leakage during filtration. Cause problems. Distillation of water may be carried out by a general method and can be easily carried out by heating at 60 to 140 ° C. under reduced pressure.

When the enlarged inorganic salt is filtered off, a filter aid such as diatomaceous earth, activated alumina or hydrotalcite can be used, but the inorganic salt enlarged by the production method of the present invention is It is possible to sufficiently filter using a filter such as a filter paper or a filter cloth without a filter aid.

In the present invention, a solvent may be used, if necessary, at the time of filtering. Suitable solvents are those having a low solubility of salts such as ethers, aliphatic hydrocarbons, halogenated hydrocarbons and aromatic hydrocarbons.

[0024]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Parts and% represent parts by weight and% by weight, respectively.

Example 1 1,000 parts (0.67 mol) of polyoxyethylene monomethyl ether (number average molecular weight of about 1,500) and sodium methylate 25% methanol solution 1 were placed in a closed container.
58 parts (0.73 mol) were charged, and methanol was distilled off under reduced pressure at 120 ° C. with stirring. Then allyl chloride 5
6 parts (0.73 mol) was added dropwise over about 10 minutes, and the temperature was 80 ° C.
And reacted for 1 hour. The solution was neutralized with 1N dilute hydrochloric acid and the alkali value was measured. As a result, it was 0.8 (KOHmg / g). Next, 30 parts of water was added, and the mixture was stirred at 80 ° C. for 30 minutes, and then water was distilled off over about 1 hour at a reduced pressure degree of 20 mmHg or less. The water content in the system measured by the Karl Fischer water content meter was 0.12%. Thus, polyoxyethylene allyl methyl ether containing by-product inorganic salt 1
050 parts were obtained. When this was filtered under a pressure condition of 1.2 kg / cm ² G using a filter paper (No. 2 manufactured by Toyo Roshi Kaisha, Ltd.) as a filter, the filtration was completed in about 10 minutes, and the filtrate was transparent.

Example 2 Polyoxyethylene polyoxypropylene monoallyl ether (number average molecular weight of about 2,300) 1,0 in a closed container
00 parts (0.43 mol) and sodium methylate 25
% 103 methanol solution (0.47 mol) was charged,
Methanol was distilled off under reduced pressure at 120 ° C. with stirring. Then, 24 parts (0.47 mol) of methyl chloride was injected under pressure over about 10 minutes and reacted at 80 ° C. for 1 hour. Activated clay 10
When 30 parts was added and stirred at 80 ° C. for 30 minutes, the alkali value was measured and found to be 0.1 (KOHmg / g). Next, 15 parts of water was added, and after stirring at 80 ° C for 30 minutes, 20m
Water was distilled off at a reduced pressure of mHg or less for about 1 hour.
The water content in the system measured by the Karl Fischer water content meter was 0.08%. Thus, 1010 parts of polyoxyethylene polyoxypropylene allyl methyl ether containing by-product inorganic salt was obtained. 1.2 kg / cm ²
When filtration was performed under a G pressure condition using a filter paper (No. 2 manufactured by Toyo Roshi Kaisha, Ltd.) as a filter, the filtration was completed in about 15 minutes, and the filtrate was transparent.

Example 3 A closed container was charged with 1,000 parts (0.5 mol) of polyoxypropylene glycol (number average molecular weight of about 2,000) and 113 parts (0.53 mol) of a 25% sodium methylate methanol solution. The methanol was distilled off under reduced pressure at 120 ° C. with stirring. Then 45 parts of methylene chloride (0.
(53 mol) was added dropwise over about 10 minutes and reacted at 80 ° C. for 1 hour. After adding 10 parts of activated clay and stirring at 80 ° C. for 30 minutes, the alkali value was measured and found to be 0.1 (KOHm
g / g). Then add 20 parts of water and mix at 80 ° C for 3
After stirring for 0 minutes, water was distilled off under a reduced pressure of 20 mmHg or less for about 1 hour. The water content in the system measured by the Karl Fischer water content meter was 0.11%. Thus, 980 parts of polyoxypropylene glycol containing a by-product inorganic salt was obtained. When this was filtered under a 1.2 kg / cm ² G pressure condition using a filter paper (No. 2 manufactured by Toyo Roshi Kaisha, Ltd.) as a filter, the filtration was completed in about 15 minutes, and the filtrate was transparent.

Comparative Example 1,000 parts (0.67 mol) of polyoxyethylene monomethyl ether (number average molecular weight of about 1,500) and sodium methylate 25% methanol solution 1 were placed in a closed container.
58 parts (0.73 mol) were charged, and methanol was distilled off under reduced pressure at 120 ° C. with stirring. Then allyl chloride 5
6 parts (0.73 mol) was added dropwise over about 10 minutes, and the temperature was 80 ° C.
When the reaction was carried out for 1 hour, the alkali value in the reaction mixture was 1.5 (KOHmg / g). 1. Polyoxyethylene allyl methyl ether containing this by-product inorganic salt
Filter paper under ² kg / cm ² G pressure condition (No.
When filtration was performed using 2) as a filter, clogging occurred in 120 minutes, and filtration was impossible. Furthermore, the filtrate was cloudy.

[0029]

Industrial Applicability According to the production method of the present invention, it is possible to very easily remove minute inorganic salts by-produced in the etherification reaction as compared with the conventional production methods. In particular, compared with the conventional manufacturing method, it is a very excellent manufacturing method because it has the advantages that no waste liquid is produced, there is no need to use a filter aid, and the processing time such as filtration is short. The polyether polyol obtained by the present invention is widely applied as a base material for surfactants, resin modifiers, plasticizers, polyurethane resins, cosmetics, pharmaceuticals, lubricating oils, etc., and the present invention is very useful. is there.

Claims (3)

[Claims] 1. A polyalkylene ether polyol (A), a halogen compound (B), and an alkali salt (C) are removed from the reaction mixture to remove the inorganic salt (D) by-produced during the reaction to obtain the polyalkylene ether polyol. In the method for obtaining the etherified product of (A), the reaction mixture is treated so that the alkali number is 1 or less, and then water is added and mixed, and then the water in the reaction mixture is distilled off to produce a by-product. A process for producing an etherified product of a polyalkylene ether polyol, which comprises enlarging the particle size of an inorganic salt (D) and filtering and removing it. 2. The amount of water added is 0.5 with respect to the reaction mixture.
The production method according to claim 1, wherein the amount is -5% by weight. 3. The method according to claim 1, wherein the water content in the reaction mixture after water is distilled off is 0.2% by weight or less.