JPH02265921A - 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 specified catalyst, deactivating the catalyst with a treating agent comprising an organic strong base and removing the catalyst component and the treating agent component. CONSTITUTION:An initiator (A) and a 3 C or higher monoepoxide (B) are subjected to a ring opening reaction in the presence of a compound (C) of the formula (wherein M and M' are metals 1 and 2; X is a halogen atom; and R is a 1-18 C acyclic ether) to obtain a mixture of a polyether with component C. A treating agent (D) comprising an organic strong base (e.g. tetraalkyl- ammonium hydroxide in which the alkyls are lower ones) is added to the 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 form 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.

[Conventional technology 1] Polyethers obtained by ring-opening reaction of monoepoxides such as alkylene oxides with 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 (1, 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.) can also be used as initiators. Used as an ether. 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: integer greater than or equal to 1) 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.

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 (as the molecular weight 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 ethers was virtually impossible.

On the other hand, it is known that polyethers can be produced using multimetal cyanide complexes as catalysts (US 32
78457. US 3278458. US 32784
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 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.

Secondly, it was difficult to add ethylene oxide to a multimetal cyanide complex catalyst. When ethylene oxide is fed to polyethers obtained by a ring-opening reaction of a monoepoxide having 3 or more carbon atoms as an initiator using a multimetal cyanide complex as a catalyst, polyethylene glycol, which is a polymeric dish of ethylene oxide, is produced. , uniform addition of ethylene oxide to the terminals of 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 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 treated with a treatment agent selected from strong organic bases. to deactivate the catalyst,
A method for producing polyethers, which comprises then removing the deactivated catalyst component and processing agent component from the polyether.

2. Polyethers containing the above 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 treated with a processing agent selected from strong organic bases. Then, using the polyether as an initiator, the catalyst is subjected to a ring-opening reaction with ethylene oxide, and then the deactivated catalyst component and processing agent component are removed from the obtained polyether. A method for producing polyethers, characterized by the following.

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 (H*0) a ・(R)
-(MX) t[us Pat 32) g457
,3278458,327g459,3427256°3427334.34273351 Using this catalyst, it is also possible to produce extremely high molecular weight polyethers containing less unsaturated monool.

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 other active hydrogen compound having at least one active hydrogen.In particular, ethylene glycol, propylene glycol, Polyoxyalkylene polyols, which are produced by adding alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, and epichlorohydrin, to polyhydroxy compounds such as glycerin, trimethylolpropane, pentaerythritol, dextrose, sucrose, and sucrose are widely used. In this addition reaction, alkali metal hydroxides such as potassium hydroxide and thorium hydroxide are most commonly used as catalysts, and catalysts such as boron trifluoride and tertiary amines are also used. 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, in addition to the method using a composite metal cyanide complex, there is a method using a metal porphyrin (Japanese Patent Application Laid-open No. 1976-197631). Although this method is known, it is not practical due to problems such as coloring of the product polyol.

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 phosphorus, 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 435518g
), 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 specific strong base according to the present invention is easy to handle and process;
It can also be used industrially as a processing agent. As the strong organic base, tetraorganoammonium hydroxide is preferred, and tetraalkylammonium hydroxide having a lower alkyl group is particularly preferred.

As a method for treating polyethers containing composite cyanide complexes, add a strong organic base or its solution and heat at 100 to 150°C.
Heat to and perform depressurization treatment.

If ethylene oxide is added, the addition is carried out after this treatment, followed by purification. In the purification process, all catalyst residues and strong organic base residues can be removed from polyethers by filtration after treatment with a neutralizing agent and adsorbent.

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 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, trivalent alcohols such as glycerin, trimethylolpropane, and hexanetriol. Hydrolic alcohols, alcohols with tetrahydric or higher valences such as pentaerythritol, diglycerin, dextrose, sorbitol, and sucrose.Also, compounds with phenolic hydroxyl groups and methylol groups such as bisphenol A, resols, and novolacs, ethanolamine, Compounds having a hydroxyl group and other active hydrogen such as tanolamine, and polyhydroxy compounds such as compounds obtained by adding an alkylene oxide of the desired lightest weight or less to polyhydroxy compounds and other active hydrogen compounds 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 other epoxy group-containing compounds, they can be added in a mixture or 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.6 According to the method of the present invention, ethylene oxide is added to the initiator by treatment with a strong organic base. This makes it possible 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 a strong organic base consisting of tetraalkylammonium hydroxide to add EO and remove the residue.

Polyol A, polyoxypropylene triol of molecular weight 5000 containing zinc hexacyanocopaltate catalyst residue (Zn 35 ppm, Go 18 ppm) Polyol B of molecular weight 7000 containing zinc hexacyanocopaltate catalyst residue (Zn 60, Go 31 ppm) Oxypropylene triol polyol C zinc hexacyanocopartate catalyst residue (Zn80
Example 1 80 g of tetramethylammonium hydroxide (10% methanol solution) was added to 1000 g of polyol 8, and demethanol was removed at 70° C. and 10 Torr for 1 hour. , 300 g of ethylene oxide was introduced, and 10
The reaction was carried out for 3 hours at 0°C.

After the reaction, the catalyst residue and ammonium salt 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 1 11 g of potassium hydroxide (48% aqueous solution) was added to 1000 g of polyol A, and then in the same manner as in Example 1,
An addition reaction of EO was carried out. 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 90 g of tetrabutylammonium hydroxide (10% methanol solution) was added to 1000 g of polyol B, and methanol was removed at 70° C. and 10' Torr for 1 hour. Add hexane, 150°C, 3) 1r.

After the treatment, the supernatant was separated, and n-hexane was separated from the supernatant by distillation to recover polyether.

Comparative Example 2 The same treatment as in Example 2 was carried out by adding 12 g of potassium hydroxide (48% aqueous solution) to 10QQg 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.

Coloration and turbidity were observed in the obtained polyol.

Example 3 50 g of tetramethylammonium hydroxide (10% methanol solution) was added to 1000 g of polyol C, and methanol was removed at 90° C., 10 Torr, 1
After 100 g of ethylene oxide was introduced,
The reaction was carried out at 0°C for 3 hours.

After the reaction, to the raw acid, T) IF C tetrahydrofuran)
500g! (*After adding 1.OOg of O, pass through a cation exchange resin and an anion exchange resin, and finally, THF,
8.0 was removed under heat and vacuum to give a clear product.

[Effects of the Invention] Using the above multi-metal cyanide complex as a catalyst, a polyneedle containing the above-mentioned catalyst obtained by ring-opening a monoepoxide having 3 or more carbon atoms as an initiator is treated with a strong organic base selected from organic bases. The above-mentioned catalyst component and processing agent component can be completely removed from the polyether by treating the catalyst with an agent to deactivate the catalyst, and then removing the deactivated catalyst component and processing agent component through purification. It has also been revealed that ethylene oxide can be added to the terminals of polyethers by ring-opening reaction of ethylene oxide after treatment with a treatment agent selected from strong organic bases.

Claims (1)

[Claims] 1. Polyethers containing the above catalyst obtained by ring-opening a monoepoxide having 3 or more carbon atoms as an initiator in the presence of a multi-metal cyanide complex catalyst selected from strong organic bases. treatment with a treatment agent to deactivate the catalyst,
A method for producing polyethers, which comprises then removing the deactivated catalyst component and processing agent component from the polyether. 2. Polyethers containing the above 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 treated with a processing agent selected from strong organic bases. Then, using the polyether as an initiator, the catalyst is subjected to a ring-opening reaction with ethylene oxide, and then the deactivated catalyst component and processing agent component are removed from the obtained polyether. A method for producing polyethers, characterized by the following.