JPH03115430A - Production of polyether - Google Patents

Abstract

PURPOSE:To facilitate the removal of a catalyst from a polyether in producing the polyether by the ring-opening reaction of a 3C or higher monoepoxide with an initiator in the presence of a composite metal cyanide complex catalyst by treating the reaction product with a specific treating agent to deactivate the catalyst. CONSTITUTION:A polyester obtd. by the ring-opening reaction of a 3C or higher monoepoxide with an initiator in the presence of a composite metal cyanide complex catalyst and contg. the catalyst is treated with a treating agent selected from the group consisting of a hydride or oxide of calcium and barium to deactivate the catalyst. Then the deactivated catalyst and the treating agent are removed from the polyether. In the above-mentioned process, after the deactivation ethylene oxide is ring opening polymerized using the resulting polyether as the initiator and then the deactivated catalyst and the treating agent are removed to produce a polyether in which ethylene oxide is uniformly added to the molecular ends and which has a high primary OH content.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing polyethers, and particularly to a method for producing polyether polyols.

[Prior art] Polyethers obtained by ring-opening reaction of monoepoxides such as alkylene oxides as initiators are widely used as raw materials for synthetic resins such as polyurethane, surfactants, lubricants, and other uses. . The initiator is a hydroxyl group-containing compound represented by A (H)n (A: a residue obtained by removing the hydrogen atom of the hydroxyl group of the hydroxyl group-containing compound, n: an integer of 1 or more). Examples of initiators include monohydric alcohols, polyhydric alcohols, monohydric phenols,
These include polyhydric phenols. Compounds having a hydroxyalkylamino group (alkanolamines, amines-alkylene oxide adducts, etc.) are also used as initiators. Furthermore, polyethers obtained by reacting the above-mentioned initiators with monoepoxides can also be used as initiators.

Polyethers are the following compounds obtained by subjecting the above initiator to a ring-opening reaction of monoepoxide.

A-[(R-Oh, Hl.

R: ring-opened unit of monoepoxide n, m: an integer of 1 or more Conventionally, as a method for producing polyethers, a method of reacting monoepoxide in the presence of an alkali catalyst has been widely used. Alkali metal compounds such as potassium hydroxide and sodium hydroxide have been used as alkali catalysts.

As alkali catalysts, sodium and potassium hydroxides are most commonly used in the production of polyethers, and alcoholades, hydrides, and elemental metals may also be used for special applications.

However, polyethers obtained using an alkali catalyst have the following problems. That is, an unsaturated monool produced by isomerization of monoepoxide, particularly propylene oxide, serves as an initiator, and an unsaturated monoether to which monoepoxide is added is produced.

The rate of isomerization increases as the molecular weight of polyethers increases, and this tendency becomes noticeable when the molecular weight is 5,000 or more (in the case of trifunctional), so when propylene oxide is used as the monoepoxide, polyethers with a molecular weight of 6,000 or more Synthesis of this type was virtually impossible.

On the other hand, it is known that polyethers can be produced using multimetal cyanide complexes as catalysts (US 32
78457. LIS 3278458. US 3278
459).

This catalyst produces less of the above-mentioned unsaturated monools and is also capable of producing extremely high molecular weight polyethers.

[Problems to be Solved by the Invention] However, the above-mentioned multimetal cyanide complex catalyst has the following two problems. First, it was difficult to remove the catalyst from polyethers obtained by ring-opening reaction of a monoeboside having 3 or more carbon atoms as an initiator using a multimetal cyanide complex as a catalyst. It is not possible to separate the catalyst by filtration or by adsorption with adsorbents such as activated carbon.

Second, it was difficult to add ethylene oxide using a multimetal cyanide complex as a catalyst. When ethylene oxide is fed to polyethers obtained by ring-opening a monoepoxide having 3 or more carbon atoms as an initiator using a multi-metal cyanide complex as a catalyst, polyethylene glycol, which is a high molecular weight form of ethylene oxide, is produced. Uniform addition of terminal hemoethylene oxide to polyethers does not occur.

[Means for Solving the Problems] The present invention provides the following inventions that have been made to solve the above-mentioned problems.

1. Polyethers containing the above-mentioned catalyst obtained by subjecting an initiator to a ring-opening reaction of a monoepoxide having 3 or more carbon atoms in the presence of a multimetal cyanide complex catalyst are selected from hydrides or oxides of calcium and barium. 1. A method for producing polyethers, which comprises deactivating the catalyst by treatment with a treatment agent, and then removing the deactivated catalyst component and treatment agent component from the polyether.

2. Polyethers containing the above catalyst obtained by ring-opening a monoepoxide having 3 or more carbon atoms with an initiator in the presence of a multimetal cyanide complex catalyst are selected from hydrides or oxides of calcium and barium. The above-mentioned catalyst is deactivated by treatment with a treating agent, and then the above-mentioned polyether is used as an initiator to cause a ring-opening reaction with ethylene oxide, and then the deactivated above-mentioned catalyst component and the above-mentioned catalyst component are treated with the obtained polyether. A method for producing polyethers, which comprises removing a processing agent component.

The multimetal cyanide complex used here generally has the following structure, and it is also known that polyethers can be obtained using this complex.

Ma-M'(CN)b(Had)-'(R)-(MX)
t [US Pat 3278457, 3278458.
3278459, 3427256゜3427334.3
427335] Using this catalyst, it is also possible to produce very high molecular weight polyethers with a low content of unsaturated monols.

Polyoxyalkylene polyols are used together with polyisocyanate compounds as raw materials for the production of polyurethanes. Moreover, this polyoxyalkylene polyol is used alone or with additives added as a raw material for functional oils and surfactants.

This polyoxyalkylene polyol contains polyhydroxy compounds, amine compounds, and other active hydrogens with a small amount (both 1
It is produced by adding a monoepoxide, particularly an alkylene oxide, to an active hydrogen compound. In particular, polyhydroxy compounds such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, dextrose, sucrose, sucrose, etc.
Polyoxyalkylene polyols produced by addition of alkylene oxides such as butylene oxide and epichlorohydrin are widely used. In this addition reaction, alkali metal hydroxides such as potassium hydroxide and sodium hydroxide are most commonly used. is used as a catalyst, and the use of catalysts such as boron trifluoride and tertiary amines has also been proposed.

However, in polyethers obtained by polymerizing propylene oxide using an alkali catalyst, unsaturated monool is produced as a by-product, and the amount of this production increases with the molecular weight of the polyether. The problem was that there was an upper limit.

On the other hand, as a method for producing polyethers with little or no unsaturated monool production, in addition to the method using a composite metal cyanide complex, a method using a metal porphyrin (Japanese Patent Application Laid-Open No. 61-197631) is known. Although,
There are problems such as coloring of the product polyol, making it impractical.

It is known that residual catalysts in polyoxyalkylene polyols used as raw materials for polyurethane have an adverse effect on reactions during polyurethane production or on the physical properties of the polyurethane produced. Therefore, in the production of polyoxyalkylene polyol, it is necessary to perform sufficient purification in the latter half. Conventionally, polyethers using alkali metals as catalysts have been purified by neutralization using phosphoric acid, carbon dioxide, or other neutralizing agents, or adsorption treatment using adsorbents such as magnesium silicate or aluminum silicate.

However, in order to remove this catalyst from polyethers using multi-metal cyanide complexes, it is necessary not only to simply filter it or treat it with an adsorbent, but also to decompose the catalyst with an alkali or acid and ionize it. Thereafter, it is necessary to remove these decomposed products, residual alkalis, and residual acids by adsorption and filtration.

As a method of treatment with alkali, alkali metal, alkali metal hydroxide (US 4355188
), alkali metal hydrides (US 472181
8) is known, but simple alkali metals and alkali metal hydrides are dangerous to handle, and alkali metal hydroxides take a long time to dehydrate, especially when polyethers have a high molecular weight. There are problems such as this,
Not realistic.

The calcium and barium hydride or oxide according to the present invention is easy to handle and can be used industrially as a processing agent. It is easier to handle than alkali metal hydrides and oxides, and easier to process than alkali metal hydroxides.

As a method for treating polyethers containing composite cyanide complexes, hydrides or oxides of calcium and barium are added, heated to 100 to 150°C, stirred for 1 to 5 hours under normal pressure, and then treated under reduced pressure at the same temperature. Do this for 1 to 3 hours. If ethylene oxide is added, the addition is carried out after this treatment, followed by purification. All catalyst residues and alkali residues can be removed from polyethers by treatment with a neutralizing agent and adsorbent in the purification process, followed by filtration.

The polyethers obtained by the method of the present invention are preferably polyoxyalkylene polyols, which are obtained by adding alkylene oxide to an active hydrogen compound having at least one active hydrogen. As the active hydrogen compound, a hydroxy compound having at least one hydroxyl group is particularly preferred. Examples of hydroxy compounds include methanol, ethanol,
Monohydric alcohols such as Buknol, dihydric alcohols such as ethylene glycol and propylene glycol, trihydric alcohols such as glycerin, trimethylolpropane, and hexanetriol, and tetrahydric alcohols such as pentaerythritol, diglycerin, dextrose, sorbitol, and sucrose. Alcohol, etc. In addition, compounds with phenolic hydroxyl groups and methylol groups such as bisphenol A, resol, and novolak, compounds with hydroxyl groups and other active hydrogens such as ethanolamine and jetanolamine, polyhydroxy compounds and other active hydrogen compounds are also used. Polyhydroxy compounds such as those obtained by addition of less than the final amount of alkylene oxide can also be used. In addition, phosphoric acid, its derivatives, amines, and other active hydrogen compounds can also be used. Two or more of these active hydrogen compounds can also be used in combination.

As the alkylene oxide, monoepoxides having 3 or more carbon atoms, i.e. alkylene oxides having 4 or less carbon atoms such as propylene oxide, 1,2-butylene oxide, and epichlorohydrin, are preferable, and these may be used alone, or in combination with styrene oxide or two or more of them. Other epoxy group-containing compounds such as glycidyl ether can be used in combination. When using two or more alkylene oxides or alkylene oxide and another epoxy group-containing compound, they can be added in a mixture or added sequentially to form a random polymer chain or a block polymer chain.

However, when ethylene oxide is directly added to the initiator using a composite metal cyanide as a catalyst, a high molecular weight homopolymer of ethylene oxide is produced.
It is impossible to obtain polyethers with high primary OH in which ethylene oxide is uniformly added to the end of the initiator. By the method of the present invention, ethylene oxide is added to the initiator by treatment with calcium and sodium hydrides or oxides to form a primary OH
It becomes possible to obtain polyethers with high

Calcium, paidride, and barium hydride used here can be used alone in the form of powder, or diluted with a solvent that does not have active hydrogen, such as n-hexane.

The present invention can also be applied to a method for producing a polyether monool by subjecting a monovalent initiator to a ring-opening reaction of the monoepoxide described above. Polyether monools are widely used alone or as raw materials as surfactants, lubricants, functional oils, and the like.

Examples of monovalent initiators include methanol,
Phenol derivatives such as ethanol, butanol, hexanol, other monools, phenol, and alkyl-substituted phenols are preferred.

EXAMPLES The present invention will be specifically explained below using Examples and Comparative Examples, but the present invention is not limited only to these Examples.

[Example] The following polyoxyalkylene ether polyol was treated with calcium hydride or barium hydride to add ethylene oxide and remove residue.

Polyol A Polyoxypropylene triol with a molecular weight of 7000 containing zinc hexacyanocopaltate catalyst residues (Zn 50 ppm, Co 26 ppm) Polyol B Zinc hexacyano iron catalyst residues (Zn
Polyoxypropylene monool polyol C zinc hexacyanocopartate catalyst residue (Zn 7
Molecular weight 60 containing 0ppm, Go 37ppm)
00 polyoxypropylene, butylene diol (weight ratio 80/20) Example 1 30 g of calcium hydride (powder) was added to 1200 g of polyol A, and the mixture was stirred at normal pressure at 100° C. for 1 hour.
After stirring under reduced pressure and treating at 20 Torr at 100°C for 1 hour, 250g of ethylene oxide was introduced and the temperature was heated to 110°C.
The reaction was carried out for 2 hours.

After the reaction, the catalyst residue and calcium were treated with an adsorbent (synthetic magnesium silicate and aluminum mixture) and then filtered to obtain a polyol of good quality as shown below.

Comparative Example 1 30g of potassium hydroxide to 1200g of polyol A
(85% pellet form) was added, and treatment and addition of ethylene oxide were performed in the same manner as in Example 1. A white gel-like precipitate was observed in the obtained polyol.

Example 2 Barium hydride (
Add 80g of n-hexane 50% slurry) and make 1.20
After performing IHr treatment at normal pressure IHr 30 Torr at ℃, 3 times the amount of n-hexane was added to the reaction product, and after 2Hr treatment at 120℃, the supernatant was separated. Hexane was recovered by distillation to obtain a polyol product.

Comparative Example 2 Sodium hydroxide (48
% aqueous solution) was added, and the same treatment as in Example 2 was performed. The water content was reduced to less than 0.8% by dehydration, and brown turbidity was observed in the product.

Example 3 80g of calcium oxide (powder) was added to 1,000g of polyol C, stirred under normal pressure at 110°C, stirred under reduced pressure for 5 hours, and stirred at 1.0 Torr at 110°C. I did it.

After the reaction, the raw acid was treated with an adsorbent (synthetic magnesium silicate) to obtain the following polyol.

Comparative Example 3 When attempting to add 56 g of sodium oxide (powder) to Polyol C, it absorbed moisture during the addition and generated heat. It was added as it was to a polyol and treated in the same manner as in Example 3 to obtain the following polyol. A cloudy appearance was observed in the polyol.

[Effect of the invention] Using the above multimetal cyanide complex as a catalyst, a monoepoxide having 3 or more carbon atoms is subjected to a ring-opening reaction as an initiator, and polyethers containing the above catalyst are converted into calcium and barium hydrides or oxides. By treating the catalyst with a treatment agent selected from among the above to deactivate the catalyst, and then removing the deactivated catalyst component and treatment agent component by purification,
The above catalyst components and processing agent components are completely removed from the polyethers, and after treatment with a processing agent selected from calcium and barium hydrides or oxides, ethylene oxide is subjected to a ring-opening reaction. ,
It has become clear that ethylene oxide is added uniformly to the ends of polyethers.

Claims (1)

[Scope of Claims] 1. Calcium and barium hydrides are obtained by subjecting a monoepoxide having 3 or more carbon atoms to a ring-opening reaction using an initiator in the presence of a multimetal cyanide complex catalyst. or a method for producing polyethers, which comprises deactivating the catalyst by treatment with a treatment agent selected from oxides, and then removing the deactivated catalyst component and treatment agent component from the polyether. 2. Polyethers containing the above catalyst obtained by subjecting a monoepoxide having 3 or more carbon atoms to a ring-closing reaction as an initiator in the presence of a multimetal cyanide complex catalyst are selected from hydrides or oxides of calcium and barium. The above-mentioned catalyst is deactivated by treatment with a processing agent, and then subjected to a ring-opening reaction with ethylene oxide using the above-mentioned polyether as an initiator, and then treated with the deactivated catalyst component from the obtained polyether. A method for producing polyethers, which comprises removing agent components.