JP2830171B2 - Method for producing polyethers - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a polyether, particularly to a method for producing a polyether polyol.

[Prior art] Polyethers obtained by a ring-opening reaction of a monoepoxide such as an alkylene oxide with an initiator are used as raw materials for a synthetic resin such as polyurethane, a surfactant, a lubricant,
Widely used for other applications.

The initiator is a hydroxyl group-containing compound represented by A (H) _n (A: a residue of the hydroxyl group-containing compound excluding the hydrogen atom of the hydroxyl group, n: an integer of 1 or more). Examples of the initiator include a monohydric alcohol, a polyhydric alcohol, a monohydric phenol, and a polyhydric phenol. Further, compounds having a hydroxyalkylamino group (alkanolamines, amines-alkylene oxide adducts, etc.) are also used as initiators. Further, polyethers obtained by reacting the above initiator with a monoepoxide are also used as the initiator.

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

A [(RO) _m H] _n RO: ring-opened unit of monoepoxide n, m: an integer of 1 or more Conventionally, as a method for producing polethers, a method of reacting monoepoxide in the presence of an alkali catalyst has been widely used. ing.

As alkali catalysts, hydroxides of sodium and potassium are most commonly used for producing polyethers, and alcoholates, hydrides, and simple metals may be used for special applications.

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

As the molecular weight of polyethers increases, the ratio of isomerization increases. This tendency becomes remarkable when the molecular weight is 5,000 or more (in the case of trifunctionality). The synthesis of ethers was virtually impossible.

On the other hand, it is known to produce polyethers using a complex metal sionide complex as a catalyst (US327845).
7-9). This catalyst generates little of the above-mentioned unsaturated monool, and is also capable of producing extremely high molecular weight polyethers.

[Problems to be Solved by the Invention] However, the double metal cyanide complex catalyst has the following two problems.

First, it was difficult to remove the catalyst from polyethers obtained by ring-opening a monoepoxide having 3 or more carbon atoms with an initiator using a double metal cyanide complex as a catalyst. Neither can the catalyst be separated by filtration, nor can it be separated by adsorption with an adsorbent such as activated carbon.

Second, it has been difficult to add ethylene oxide using a double metal cyanide complex as a catalyst. When a double metal cyanide complex is used as a catalyst and ethylene oxide is fed to a polyether obtained by a ring-opening reaction of a monoepoxide having 3 or more carbon atoms with an initiator, polyethylene glycol, which is a high molecular weight ethylene oxide, is produced. There is no uniform addition of ethylene oxide to the ends of the polyethers.

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

1) Polyethers containing the catalyst obtained by subjecting an initiator to a ring-opening reaction with a monoepoxide having 3 or more carbon atoms in the presence of a double metal cyanide complex catalyst are selected from hydrides and oxides of calcium and barium. A method for producing polyethers, comprising deactivating the catalyst by treating with a treated treating agent, and removing the deactivated catalyst component and treating agent component from the polyethers.

2) Polyethers containing the catalyst obtained by subjecting an initiator to a ring-opening reaction with a monoepoxide having 3 or more carbon atoms in the presence of a double metal cyanide complex catalyst are selected from hydrides and oxides of calcium and barium. To deactivate the catalyst, treat the polyether as an initiator, and subject it to a ring-opening reaction with ethylene oxide, and then react with the catalyst component deactivated from the resulting polyether. A method for producing a polyether, comprising removing a treating agent component.

The double metal cyanide complex used here generally has the following structure, and it is known that polyethers can be obtained using the same.

_{M a · M '(CN)} b · (H 2 O) d · (R) e · (MX) f M, M': metal 1, metal 2 X: halogen R: acyclic C1-18 Ethers [US3278457-9, 3427256, 3427334-5] With this catalyst, it is also possible to produce very high molecular weight polyethers with a low unsaturated monol content.

Polyoxyalkylene polyol is used together with a polyisocyanate compound as a raw material for producing polyurethane. The polyoxyalkylene polyol is used alone or with an additive as a raw material for functional oils and surfactants.

The polyoxyalkylene polyol is produced by adding a monoepoxide, particularly an alkylene oxide, to a polyhydroxy compound, an amine compound, or another active hydrogen compound having at least one active hydrogen. In particular, poly (ethylene glycol), propylene glycol, glycerin, trimethylolpropane, pentaerythritol, dextrose, saccharose, polyhydroxy compounds such as sucrose, ethylene oxide, propylene oxide, butylene oxide, polyalkylene oxide produced by adding an alkylene oxide such as epichlorohydrin Oxyalkylene polyols are widely used.

In this addition reaction, an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide is most commonly used as a catalyst, and the use of a catalyst such as boron trifluoride or a tertiary amine has been proposed.

However, in the polyethers obtained by polymerizing propylene oxide using an alkali catalyst, unsaturated monool is generated as a by-product, and the generated amount increases with the molecular weight of the polyether. There was a problem that the upper limit could be set.

On the other hand, as a method for producing polyethers with little or no generation of unsaturated monool, a method using a metal porphyrin (JP-A-61-197631) is known in addition to a method using a double metal cyanide complex. However, there are problems such as coloring of the product polyol, which is not practical.

It is known that in a polyoxyalkylene polyol used as a raw material of a polyurethane, the residual catalyst adversely affects the reaction during the production of the polyurethane or the physical properties of the generated polyurethane. Therefore, in the production of the polyoxyalkylene polyol, it is necessary to sufficiently purify the latter half. Conventionally, purification of polyethers using an alkali metal as a catalyst has been performed by neutralization with phosphoric acid, carbon dioxide, or another neutralizing agent, or by adsorption treatment with an adsorbent such as magnesium silicate or aluminum silicate.

However, in order to remove this catalyst from the polyethers produced using the complex metal cyanide complex, it is necessary not only to filter or treat with an adsorbent, but also to decompose the catalyst with an alkali or an acid. It is necessary to ionize and then remove these decomposed products, residual alkali and residual acid by adsorption and filtration.

As a method of treating with an alkali, a method using an alkali metal, an alkali metal hydroxide (US4355188), and an alkali metal hydroxide (US4721818) is known.
Alkali metal simple substance, alkali metal hydride involves danger in handling, and alkali metal hydroxide, especially when polyethers have a high molecular weight, there is a problem that it takes time for dehydration treatment, Not feasible.

The treating agent selected from the hydrides and oxides of calcium and barium according to the present invention is easy to handle and can be used industrially as a treating agent. It is easier to handle than hydrides and oxides of alkali metals, and is easier to treat than alkali metal hydroxides.

As a method for treating a polyether containing a double metal cyanide complex, a treating agent selected from hydrides and oxides of calcium and barium is added, and the mixture is heated to 100 to 150 ° C. and stirred under normal pressure for 1 to 5 hours. A decompression treatment is performed at the same temperature for 1 to 3 hours. When adding ethylene oxide, the addition is performed after this treatment, followed by purification. After treatment with a neutralizing agent and an adsorbent in the purification step, filtration can remove all catalyst residues and alkali residues from the polyethers.

The polyethers obtained by the method of the present invention are preferably polyoxyalkylene polyols, which are obtained by adding an 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 the hydroxy compound include monohydric alcohols such as methanol, ethanol and butanol, dihydric alcohols such as ethylene glycol and propylene glycol, trihydric alcohols such as glycerin, trimethylolpropane and hexanetriol, pentaerythritol, diglycerin, dextrose, and the like. There are four or more valent alcohols such as sorbitol and sucrose.

Compounds having a phenolic hydroxyl group or a methylol group such as bisphenol A, resole, and novolak;
Polyhydroxy compounds such as a compound having a hydroxyl group and another active hydrogen such as ethanolamine and diethanolamine, and a compound obtained by adding a desired amount or less of alkylene oxide to a polyhydroxy compound or another active hydrogen compound can also be used. In addition, amines and other active hydrogen compounds can be used as phosphoric acid and derivatives thereof. Two or more of these active hydrogen compounds can be used in combination.

As the alkylene oxide, a monoepoxide having 3 or more carbon atoms, that is, an alkylene oxide having 4 or less carbon atoms such as propylene oxide, 1,2-butylene oxide and epichlorohydrin is preferable. Other epoxy group-containing compounds such as glycidyl ether can be used in combination. In the case of using two or more alkylene oxides or using an alkylene oxide and another epoxy group-containing compound, they can be mixed and added or sequentially added to form a random polymerized chain or a block polymerized chain.

However, if ethylene oxide is directly added to the initiator using a double metal cyanide complex as a catalyst,
It is impossible to obtain polyethers having a high ratio of primary OH, in which a high molecular weight substance which is a homopolymer of ethylene oxide is generated and ethylene oxide is uniformly added to the terminal of the initiator. According to the method of the present invention, it is possible to obtain polyethers having a high proportion of primary OH in which ethylene oxide is added to an initiator by treating with a treating agent selected from hydrides and oxides of calcium and barium.

The calcium hydride and barium hydride used here can be used as a powder or a solvent having no active hydrogen such as n-hexane.

The present invention can also be applied to a method for producing a polyether monol by subjecting a monovalent initiator to a ring-opening reaction with a monovalent initiator as described above. Polyether monol is widely used as a surfactant, a lubricant, a functional oil, or the like, or as a raw material.

As a monovalent initiator, for example, methanol,
Phenol derivatives such as ethanol, butanol, hexanol, other monols, phenols and alkyl-substituted phenols are preferred.

Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to only these Examples.

Example The following polyoxyalkylene polyol was treated with calcium hydride or barium hydride to add ethylene oxide and remove residues.

Polyol A: Polyoxypropylene triol having a molecular weight of 7000 and containing zinc hexaanocobaltate catalyst residue (Zn 50 ppm, Co 26 ppm).

Polyol B: zinc hexacyanoiron catalyst residue (Zn 100
ppm, Fe 52ppm) containing 2000 molecular weight polyoxypropylene monol.

Polyol C: a polyoxypropylene oxybutylene diol having a molecular weight of 6000 containing a zinc hexacyanocobaltate catalyst residue (Zn 70 ppm, CO 37 ppm) (weight ratio of oxypropylene groups to oxybutylene groups 80/20).

Example 1 Calcium hydride (powder) 30 g in 1200 g of polyol A
And stirring at normal pressure for 1 hour at 100 ° C and stirring at reduced pressure for 20 Torr.
After the reaction was performed at 100 ° C. for 1 hour, 250 g of ethylene oxide was introduced, and the reaction was performed at 110 ° C. for 2 hours.

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

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

Example 2 To 1200 g of polyol B, 80 g of barium hydride (50% slurry of n-hexane) was added, and the mixture was stirred under normal pressure at 120 ° C. for 1 hour and under reduced pressure at 30 Torr for 1 hour. After adding twice the amount of n-hexane and treating at 120 ° C. for 2 hours, the supernatant was separated, and n-hexane was recovered from the supernatant by distillation to obtain a polyol product.

Comparative Example 2 The same treatment as in Example 2 was performed by adding 50 g of sodium hydroxide (48% aqueous solution) to 1200 g of polyol B. Even after the dehydration operation, the water content did not drop below 0.8%, and the product also showed brown turbidity.

Example 3 80 g of calcium oxide (powder) per 1000 g of polyol C
Add, normal pressure stirring at 110 ° C for 0.5 hour, reduced pressure stirring at 10 Torr
After the reaction was performed at 110 ° C. for 1 hour, 200 g of ethylene oxide was introduced, and the reaction was performed at 120 ° C. for 2 hours.

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

56g of sodium oxide (powder) per 1000g of polyol C
At the time of the addition, moisture was absorbed at the time of addition and heat was generated.
It was added to the polyol as it was and treated in the same manner as in Example 3 to obtain the following polyol. The polyol was cloudy.

[Effects of the Invention] Using a double metal cyanide complex as a catalyst, a polyether containing the catalyst obtained by subjecting an initiator to a ring-opening reaction of a monoepoxide having 3 or more carbon atoms is converted into a hydride and an oxide of calcium and barium. The catalyst component and the treating agent component are completely decomposed from the polyethers by treating with a treating agent selected from the product to deactivate the catalyst, and then removing the deactivated catalyst component and the treating agent component by purification. After treatment with a treating agent selected from hydrides and oxides of calcium and barium,
It was revealed that ethylene oxide was uniformly added to the end of polyethers by ring-opening reaction of ethylene oxide.

Continuation of the front page (56) References JP-A-3-88823 (JP, A) JP-A-61-120831 (JP, A) JP-A-2-242821 (JP, A) JP-A-2-265923 (JP) U.S. Pat. No. 4,718,818 (US, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08G 65/00-65/32 CAS (STN)

Claims (2)

(57) [Claims] 1. A polyether containing said 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 double metal cyanide complex catalyst to obtain a hydride of calcium and barium and oxidation of the polyether containing the catalyst. A method for producing polyethers, comprising deactivating the above catalyst by treating with a treating agent selected from products, and then removing the deactivated catalyst component and treating agent component from the polyethers. 2. A polyether containing said 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 double metal cyanide complex catalyst is converted into a hydride and an oxide of calcium and barium. The catalyst was deactivated by treating with a treating agent selected from the above, and then the above-mentioned polyethers were used as an initiator, and ethylene oxide was subjected to a ring-opening reaction. A method for producing a polyether, comprising removing a catalyst component and a treating agent component.