JPH02265923A - Production of polyether - Google Patents

Abstract

PURPOSE:To make it possible to remove the catalyst from the obtained polyether by reacting an initiator with a monoepoxide in the presence of a compound metal cyanide complex catalyst, deactivating the catalyst with a specified treating agent and removing the catalyst component and the treating agent component from the reaction product. CONSTITUTION:An initiator (a) which is a hydroxy compound of formula I (wherein A is a residue derived by removing the hydrogen atoms from the hydroxyl groups of a hydroxy compound; and n>=1) and a 3C or higher monoepoxide (b) are subjected to a ring opening reaction in the presence of a compound metal cyanide complex catalyst (c) of formula II (wherein M and M' are metals 1 and 2; X is a halogen atom; and R is a 1-18C acyclic ether to obtain a mixture of a polyether of formula III (wherein R is a unit derived by ring-opening the monoepoxide; and n and m are each >=1) with component (c). A treating agent (d) selected from simple metals of Li and Cs and their hydrides, hydroxides and alcoholates is added to the above mixture, the resulting mixture is heated to 100-150 deg.C in a vacuum to deactivate component (c), and component (c) and component (d) are removed from the mixture.

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 (H).

It is a hydroxyl group-containing compound represented by (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, and 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 initial shake with a monoepoxide can also be used as an initial shake.

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

A-F→R-OhHl- R: Ring-opened unit of monoepoxide n, m: Integer greater than or equal to 5 Conventionally, as a method for producing polyethers, a method of reacting monoepoxide in the presence of an alkali catalyst has been widely used. ing. Alkali metal compounds such as potassium hydroxide and sodium hydroxide have been used as alkali catalysts.

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 isomerization rate increases as the number of molecules of polyethers increases, and this tendency becomes noticeable when the number of molecules is 15,000 or more (in the case of trifunctional), so when propylene oxide is used as the monoepoxide, one molecule i is 6,000 or more. The synthesis of polyethers was virtually impossible.

On the other hand, it is known that polyneedle products can be produced using a multimetal cyanide complex as a catalyst (US 32
78457. US 3278458. US 327g4
59).

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 multi-metal cyanide complex catalyst has the following two problems.6 First, when the multi-metal cyanide complex is used as a catalyst and carbon is used as an initiator. It was difficult to remove the catalyst from polyethers obtained by ring-opening reaction of monoebosides of three or more. 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 reaction of monoepoxides having 3 or more carbon atoms using a multimetal cyanide complex as a catalyst, polyethylene glycol, which is a high molecular weight form of ethylene oxide, is produced, and polyethylene glycol, which is a high molecular weight form of ethylene oxide, is produced. Uniform addition of ethylene oxide to the terminals of ethers 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 multi-metal cyanide complex catalyst, to lithium or cesium as an elemental metal, hydride, hydroxide, Alternatively, a method for producing polyethers, which comprises deactivating the catalyst by treatment with a treatment agent selected from alcoholates, 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 multi-metal cyanide complex catalyst are mixed with an elemental metal such as lithium or cesium, hydride, or hydroxide. , or an alcoholate in order not to deactivate the catalyst by treating it with a treatment agent selected from the group consisting of alcoholates.Next, using the polyethers as an initiator, ethylene oxide is subjected to a ring-opening reaction, and then from the polyethers obtained, A method for producing polyethers, which comprises removing the deactivated catalyst component and 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)o(HJ)a・(R)-(MX)
t[US Pat 32784.57, 3278458
．． 327g459,3427256°3427334.
342733Fd With 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. This polyoxyalkylene polyol is produced by adding a monoepoxide, especially an alkylene oxide, to a polyhydroxy compound, an amine compound, or another active hydrogen compound having at least one active hydrogen. In particular, polysaccharides produced by adding alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, and epichlorohydrin to polyhydroxy compounds such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, dextrose, sucrose, and sucrose. Oxyalkylene polyols are widely used. In this addition reaction, alkali metal hydroxides such as potassium hydroxide and sodium hydroxide are most commonly used as catalysts, 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 product 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 Unexamined Patent Application Publication No. 1976-197631) 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.

Methods of treatment with alkali include sodium, potassium, sodium and potassium hydroxide (US
4,355,188) and sodium and potassium hydrides (US 4,721,818). The metal element, hydride, hydroxide, or alcoholate of lithium or cesium according to the present invention is easy to handle and process, and can be used industrially as a processing agent like the above-mentioned sodium and potassium. In addition, as alcoholate, methylate, ethylate, etc. are preferable.

As a method for treating polyethers containing a composite cyanide complex, the above-mentioned lithium, cesium, or a compound thereof is added, heated to 100 to 150°C, and subjected to reduced pressure treatment.
When adding ethylene oxide, the addition is carried out after this treatment, followed by purification. In the purification process, after treatment with a neutralizing agent and adsorbent, filtration is performed to remove catalyst residues and the above-mentioned alkali residues. All can be removed from polyethers.

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 two active hydrogens. The active hydrogen compound is particularly preferably a polyhydroxy compound having at least two hydroxyl groups. Examples of the polyhydroxy compound include dihydric alcohols such as ethylene glycol and propylene glycol, and trihydric alcohols such as glycerin, trimethylolpropane, and hexanetriol. Examples include alcohol, pentaerythritol, diglycerin, dextrose, sorbitol, sucrose, and other alcohols with a hydric content of 4 or higher. 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 alkylene oxides that are commercially available 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 thereof. 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 added directly to the inlet 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. According to the method of the present invention, it is possible to add ethylene oxide to an initiator by treating it with lithium, cesium, or the above-mentioned compounds to obtain polyethers with high primary OH.

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 a monoepoxide as described above. Preferred examples of the monovalent initiator include methanol, ethanol, butanol, hexanol, other monools, phenol, and phenol derivatives such as alkyl-substituted phenols.

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 polybrobylene ether polyol was treated with the above-mentioned treatment agent to add EO and remove residue.

Polyol A, molecules containing zinc hexacyanocopaltate catalyst residues (Zn35 ppm, Go18 ppm) [15000 polyoxypropylene triols Polyol B Molecules containing zinc hexacyanocopaltate catalyst residues (Zn60, C:O31 ppml) 317000 polyoxybrobylene triol polyol C zinc hexacyanocopartate catalyst residue (Zn
Polyoxypro and lentriol with a molecular weight of 9000 containing 1000 g of polyol A and 39 ppm of Go
After adding 30 g of methanol solution and carrying out the demethanol reaction at 70°C and 10 Torr for 1 hour, 300 g of ethylene oxide was introduced and the reaction was carried out at 100°C for 3 hours.

After the reaction, the catalyst residue and lithium were treated with an adsorbent (synthetic magnesium silicate) and filtered to obtain a transparent polyol. The properties of the obtained polyol are as follows.

Comparative Example: To 1000 g of polyol A, 1 g of potassium hydroxide (48% aqueous solution) was added, and then in the same manner as in Example 1,
An addition reaction of EO was performed. In the dehydration operation, water content is 0.
It could not be lowered below 3%. In addition, a white precipitate was observed in the obtained polyol.

Example 2 Cesium methylate (30%
After adding 31 g of methanol solution and carrying out the demethanol reaction at 70°C and 10 Torr for 1 hour, twice the amount of n-hexane relative to the reaction product was added and the mixture was heated at 150°C for 3 hours.
After the treatment, the supernatant was separated, and n-hexane was separated from the supernatant by distillation to recover polyether.

Comparative Example 1 The same treatment as in Example 2 was carried out by adding 12 g of potassium hydroxide (48% aqueous solution) to 1000 g of polyol B. The water content could not be lowered below 0.4% during the dehydration operation.

Moreover, slight turbidity was observed in the obtained polyol.

Comparative Example 3 Sodium metal (dispersed in mineral oil) was added to Polyether C, and the same was subjected to a reaction treatment.

The obtained polyol showed one color and turbidity.

Example 3 Lithium methylate (30 g) was added to 000 g of polyol Cl.
% methanol solution) was added and the methanol removal reaction was carried out at 90° C. and 10 Torr for 1 hour. Then, 100 g of ethylene oxide was introduced and the reaction was carried out at 100° C. for 3 hours.

After adding 500 g of THF (tetrahydrofuran) and 100 g of HJ to the repulsion product, it was passed through a cation exchange resin, then an ion exchange resin, and finally, THF,! (1
0 was removed under heat and vacuum to give a clear product.

[Effect of the invention] Polyethers containing the above-mentioned catalyst obtained by using the multimetal cyanide complex as a catalyst and causing a ring-opening reaction of monoevogide having 3 or more carbon atoms as an initiator can be prepared from lithium, cesium, or a compound thereof. By treating with a selected treatment agent to deactivate the catalyst, and then removing the deactivated catalyst component and treatment agent component through purification, the catalyst component and treatment agent component are completely removed from the polyethers. It was also revealed that ethylene oxide is added to the terminals of polyethers by ring-opening reaction of ethylene oxide after treatment with a processing agent selected from lithium, cesium, or their compounds. became.

Claims (1)

[Claims] 1. Polyethers containing the above-mentioned catalyst obtained by ring-opening a monoepoxide having 3 or more carbon atoms as an initiator in the presence of a multimetal cyanide complex catalyst are used as an elemental metal such as lithium or cesium. , hydride, hydroxide, or alcoholate to deactivate the catalyst, and then remove the deactivated catalyst component and treatment agent component from the polyether. manufacturing method. 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 multi-metal cyanide complex catalyst are mixed with an elemental metal such as lithium or cesium, hydride, or hydroxide. Alternatively, the above catalyst is deactivated by treatment with a processing agent selected from alcoholates, and then ethylene oxide is subjected to a ring-opening reaction using the above polyethers as an initiator, and then the resulting polyethers are deactivated. A method for producing polyethers, which comprises removing the above-mentioned catalyst component and processing agent component.