JPH02276821A - Production of polyethers - Google Patents

Abstract

PURPOSE:To obtain the title polyethers capable of readily carrying out separation and removal of an inactivated catalyst component and treating agent component and useful for a raw material of synthetic resin, etc., by inactivating a catalyst with an alkali metal alcolate as a treating agent. CONSTITUTION:Polyethers obtained by subjecting (iii) >=3C monoepoxide to ring opening addition reaction with (ii) an initiator having at least one OH group in the presence of (i) a plural metals cyan complex compound catalyst and containing the component i are treated with a treating agent consisting of (B) an alkali metal alcolate to inactivate the component i and then the inactivated component i and the component B are removed from the component A to provide the aimed polyethers. Furthermore, when the component i and component B are removed, preferably the component B is added to the component i and then the mixture is heated to inactivate the component i. Thereafter, preferably ethylene oxide is reacted with the component A used as an initiator and then the component i and component B are removed from the component A.

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 initiators with monoepoxides can also be used as initiators.

Polyethers are the following compounds obtained by subjecting the above initiator to a ring-opening addition reaction of a large number of monoepoxides.

A-jr-f-R-ohH].

→R-0←: Ring-opening reaction unit m of monoepoxy guide: Integer 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. In other words, an unsaturated monool produced by isomerization of a monoepoxide, especially propylene oxide, serves as an initiator, and an unsaturated polyether monool (
Hereinafter, this is also referred to as an unsaturated monool).

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 M is 6,500 or more (in the case of trifunctional). Therefore, when propylene oxide is used as the monoepoxide, Synthesis of ethers was virtually impossible.

[Problem to be solved by the invention] On the other hand, it is known that polyethers can be produced using a multimetal cyanide complex as a catalyst (US 32
78457. US 3278458. US 32784
59°US 3427256. US 3427334.
No. 3,427,351° This catalyst produces less of the unsaturated monools mentioned above, and is also capable of producing extremely high molecular weight polyethers.

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.

Therefore, in order to remove this catalyst from polyethers using 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, ionize it, and then It is necessary to remove these decomposition products, residual alkalis, and residual acids by adsorption and filtration.

Secondly, it was difficult to react ethylene oxide to hydroxyl groups using a multimetal cyanide complex as a catalyst. When a multimetal cyanide complex is used as a catalyst and ethylene oxide is subsequently fed to polyethers obtained by a ring-opening reaction of a monoepoxide having 3 or more carbon atoms as an initiator, polyethylene glycol, which is a homopolymer of ethylene oxide, is produced. However, uniform addition of ethylene oxide to the terminal hydroxyl groups of polyethers does not occur.

A method is known in which a multimetal cyanide complex catalyst is treated with an alkali to deactivate the catalyst and remove the catalyst residue, and a method in which ethylene oxide is added after the alkali treatment and then the catalyst residue is removed. As a method for treatment with an alkali, a method using an alkali metal, an alkali metal hydroxide (US 435,518g), or an alkali metal hydride (US 472,181g) is known.

However, simple alkali metals and alkali metal hydrides are dangerous to handle, and alkali metal hydroxides have problems such as the dehydration process taking a long time, especially when polyethers have a high molecular weight. Not realistic.

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

A polyether containing the above catalyst obtained by ring-opening addition reaction of a monoepoxide having 3 or more carbon atoms with an initiator having at least one hydroxyl group in the presence of a multimetal cyanide complex catalyst is prepared from an alkali metal alcoholade. 1. A method for producing polyethers, which comprises treating the catalyst with a treating agent to deactivate the catalyst, and then removing the deactivated catalyst component and the treating agent component from the polyether.

A polyether containing the above catalyst obtained by ring-opening addition reaction of a monoepoxide having 3 or more carbon atoms with an initiator having at least one hydroxyl group in the presence of a multimetal cyanide complex catalyst is prepared from an alkali metal alcoholade. The catalyst is deactivated by treatment with a treating agent, and then ethylene oxide is reacted with the polyether using the polyether as an initiator, and then the deactivated catalyst component and the treating agent component are extracted from the polyether obtained. A method for producing polyethers, which comprises removing polyethers.

The double metal cyanide complex in the present invention is considered to have the structure of the following formula (1), as shown in the above-mentioned known examples.

M, [M', (CN), 1. ()l! 0)c(R)d-
(1) However, M is Zn(II), Fe(■), Fe(
III), Co(II), N1(If), Al([1)
, 5r(II), Mn(II), Cr(I[I), Cu
(If), 5n (II), pb (II), Mo (IV)
, No (Vl), W (IV), etc. W (Ml), and M' is Fe (II), Fe (III), Go (II)
, Go(III), Cr(II).

Cr(III), Mn(II), Mn(III)
, N1 (II), V (IV), V (V), etc., R is an organic ligand, and a.

b, x and y are positive integers that vary depending on the valence and coordination number of the metal, and C and d are positive numbers that vary depending on the coordination number of the metal.

-M in formula (1) is preferably Zn(I[) M'
are Fe(If), Fe(III), Go(II)
, Co(III), etc. are preferred. Examples of organic ligands include ketones, ethers, aldehydes, esters,
Alcohols, amides, etc.

As mentioned above, the double metal cyanide complex represented by the general formula (1) is a metal salt MXa (M, a is the same as above, X is M
anion that forms a salt) and polycyanometalate (salt) z, [g', (cN), lt(M' + X+:
J is the same as above, 2 is hydrogen, alkali metal, alkaline earth metal, etc., e and f are positive integers determined by the valence and coordination number of Z and M') or a mixture of water and an organic solvent. It is produced by mixing solutions of mixed solvents, bringing the resulting double metal cyanide into contact with an organic ligand R, and then removing excess solvent and organic compound R.

Polycyanometalate (salt) z, [x', (cN),
], various metals including hydrogen and alkali metals can be used for Z, but lithium salts, sodium salts, potassium salts, magnesium salts, and calcium salts are preferable.

Particular preference is given to the customary alkali metal salts, namely the sodium and potassium salts.

Polyethers are usually produced by reacting a mixture of a monoepoxide and an initiator in the presence of a catalyst. Alternatively, the reaction can be carried out while gradually adding monoepoxide to the reaction system. Although the reaction occurs at room temperature, the reaction system can be heated or cooled if necessary. The amount of catalyst used is not particularly limited, but is 1 to 5,000 per initiator used.
Approximately ppm is appropriate, and 30 to 11,000 ppm is more preferable. The catalyst may be introduced all at once into the reaction system, or may be introduced in portions in sequence.

By using this double metal cyanide catalyst, it is possible to synthesize polyethers with a low content of unsaturated monols, or with a low content of unsaturated monols and an extremely high molecular weight.

The alkali metal alcoholade in the present invention includes 1
Alcolades of monohydric or polyhydric alcohols are suitable. As the alcohol, an alcohol with a low boiling point is preferable. This is because, after reacting polyethers with alcoholade, it is extremely easy to remove the alcohol produced as a by-product. Therefore, the alcohol is preferably a lower monool, particularly methanol or ethanol, and the alkali metal is preferably sodium or potassium.

Methylates and ethylates of these metals are easy to handle and process, and are easy to use industrially as processing agents.The alcoholades of sodium and potassium used here are either diluted as alcohol solutions or used alone as powders. be able to.

As a method for treating polyethers containing a multimetal cyanide complex, an alkali metal alcoholade is added and heated to preferably 80 to 180°C, particularly 100 to 150°C,
It is preferable to perform vacuum treatment if necessary and then purification. When reacting ethylene oxide, add an alkali metal alcoholide and heat in the same manner, then perform vacuum treatment to remove the by-product alcohol, and then ethylene oxide A method of reacting and then purifying is preferred. In the purification step, after treatment with a neutralizing agent, adsorbent, ion exchange agent, etc., unnecessary substances are separated from the polyethers by filtration or the like. This allows all catalyst residues and alkali residues to be removed from the polyethers. Neutralizing agents include acids and bases, adsorbents include metal oxides such as synthetic magnesium silicate, aluminosilicate, silica, and zeolite, and ion exchange agents include ion exchangers such as anion exchange resins and cation exchange resins. There is resin.

The polyethers obtained by the method of the present invention are preferably polyoxyalkylene polyols, which are obtained by subjecting an initiator having at least two hydroxyl groups to a monoepoxide such as alkylene oxide in a sequential ring-opening addition reaction. It is. As the initiator, polyhydroxy compounds having 2 to 8 hydroxyl groups are particularly preferred. Examples of polyhydroxy compounds include dihydric alcohols such as ethylene glycol and propylene glycol, trihydric alcohols such as glycerin, trimethylolpropane, and hexanetriol, and tetrahydric or higher alcohols such as pentaerythritol, diglycerin, dextrose, sorbitol, and sucrose. There are polyethers that have a lower molecular weight than alcohols and the target products obtained by reacting these alcohols with monoepoxides such as alkylene oxides. Also,
Compounds with phenolic hydroxyl groups and methylol groups such as bisphenol A, resols and novolaks, compounds with hydroxyl groups and other active hydrogens such as ethanolamine and jetanolamine, and compounds obtained by reacting these with monoepoxides such as alkylene oxides. There are polyethers with a lower molecular weight than the target product. Furthermore, there are polyethers having a lower molecular weight than the target product obtained by reacting a monoamine or polyamine having at least two hydrogen atoms bonded to a nitrogen atom with a monoepoxide such as alkylene oxide. Others include phosphoric acid and its derivatives.

Other polyhydroxy compounds can also be used.

Two or more types of these polyhydroxy compounds can also be used in combination.

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 with a monoepoxide.

Examples of monovalent initiators include methanol,
There are polyethers having a lower molecular weight than the target product obtained by reacting ethanol, butanol, hexanol, other monools, phenol, phenol derivatives such as alkyl-substituted phenols, and monoepoxides such as alkylene oxides. Furthermore, there are polyethers having a lower molecular weight than the target product obtained by reacting a monoamine or polyamine having one hydrogen atom bonded to a nitrogen atom with a monoepoxide such as alkylene oxide.

The monoepoxide in the present invention is a monoepoxide having 3 or more carbon atoms, and particularly preferably an alkylene oxide having 3 or more carbon atoms.

More preferably, alkylene oxides having 3 to 4 carbon atoms, such as propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, and epichlorohydrin, are most preferred, and propylene oxide is most preferred. They can be used alone, two or more of them, or in combination with other monoepoxides such as styrene oxide, glycidyl ether, and glycidyl ester. When using two or more alkylene oxides or alkylene oxide and another monoepoxide, they can be added as a mixture or added sequentially to form a random polymer chain or a block polymer chain.

However, even if it is attempted to directly react ethylene oxide with an initiator or polyether using a composite metal cyanide as a catalyst, polyethylene glycol, which is a homopolymer of ethylene oxide, is produced. For this reason,
For example, this catalyst can be used to copolymerize ethylene oxide with other monoepoxides, or polyethers obtained by using composite metal cyanide as a catalyst can be subsequently reacted with ethylene oxide to achieve a high proportion of primary hydroxyl groups. It is not possible to obtain polyethers. however,
As initiators it is possible to use hydroxy compounds having oxyethylene groups, for example polyoxyalkylene polyols having oxyethylene groups.

By the method of the present invention, the hydroxyl groups of polyethers are converted to alcoholades by treatment with sodium alcoholade or potassium alcoholade, and then ethylene oxide is reacted to introduce oxyethylene groups at the molecular terminals, and the catalyst components are separated. This makes it possible to obtain polyethers with a high proportion of primary hydroxyl groups.

The molecular weight of the resulting polyethers is not particularly limited, but products that are liquid at room temperature are preferred from the standpoint of their use. The reaction amount of monoepoxide per mole of initiator is preferably at least about 10 moles, more preferably at least about 50 moles. More preferably, polyethers are obtained by reacting an average of at least about 10 molecules, particularly at least about 30 molecules, per hydroxyl group of the initiator, and in terms of hydroxyl value, a value of 200 or less, particularly 100 or less is suitable. For example, as a raw material for polyurethane, expressed in terms of hydroxyl value, approximately 5
-200, especially 5-60 liquid polyether polyols are preferred. For other uses, such as raw materials for oil such as hydraulic oil, polyether poly(or mono)ols within the above range are preferred.

The polyether polyol obtained by the present invention is most useful as a polyol for polyurethane raw materials used alone or in combination with other polyols. Furthermore, the polyether poly(or mono)ol obtained by the present invention can also be used as a raw material or additive for synthetic resins other than polyurethane. Furthermore, it can be used as a lubricating oil, an insulating oil, a hydraulic oil, and other oils, or as a raw material thereof.

Furthermore, the polyethers obtained according to the present invention can be converted into other compounds such as alkyl ether compounds and acylated compounds and used for various purposes.

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 polyoxypropylene polyol was treated with sodium or potassium alcolade, followed by reaction of ethylene oxide and removal of residue.

The following polyoxypropylene polyol has a molecular weight of 5
00 polyoxypropylene triol as an initiator, a zinc hexacyanocopartate complex catalyst was added thereto, propylene oxide was supplied, and the temperature was heated to about 120°C.
It is a polyoxypropylene triol obtained by reacting until a predetermined molecular weight is reached. This polyoxypropylene triol produced contained the following amount of metal component as a catalyst.

Polyol A: Zinc hexacyanocopartate complex (Z
Polyoxypropylene triol polyol B with a molecular weight of 5000 containing Zn 35 ppm, Co 18 ppm); Zinc hexacyanocopartate complex (Zn 60
ppm, Co 31ppm) with a molecular weight of 70
00 polyoxypropylene triol polyol C;
Zinc hexacyanocopartate complex (Zn 80ppm
Polyoxypropylene triol polyol D with a molecular weight of 9000 containing Zn 1100 ppm, Co
Polyoxypropylene triol with a molecular weight of 15,000 containing o 49 ppa+) Example 1 Sodium methylate (30
% methanol solution) was added, and the demethanol reaction was performed at 70° C. and 1 O Torr for 1 hour, then ethylene oxide 3θOg was introduced and the reaction was performed at 100° C. for 3 hours.

After the reaction, an adsorbent (synthetic magnesium silicate) was added to the product, and the catalyst residue and sodium content were adsorbed onto the adsorbent, followed by filtration to obtain a transparent polyol. The properties of the obtained polyol are as follows.

Comparative Example 1 1000 g of polyol A was directly subjected to an EO reaction in the same manner as in Example 1 without being treated with sodium methylate. A white precipitate was observed in the obtained polyol.

The properties of the polyols obtained in Example 1 and Comparative Example 1 are shown below.
Shown in 1.

Table-1 Example 2 Potassium methylate (30 g
% methanol solution) was added, and the demethanol reaction was carried out at 70°C and 10 Torr for 1 hour. Then, twice the weight of n-hexane and one weight of water were added to the reaction product at 70°C. After treatment for 3 hours, a supernatant consisting of n-hexane and polyol was separated, and n-hexane was separated from the supernatant by distillation to recover the polyol.

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

Moreover, slight turbidity was observed in the obtained polyol.

The properties of the polyols obtained in Example 2 and Comparative Example 2 are shown below.
Shown in 2.

Table-2 Example 3 To 1000 g of polyol C, potassium methylate (30
% methanol solution) was added, and the methanol removal reaction was carried out at 90° C. and 1 O 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 the reaction, add 5 T) IF (tetrahydrofuran) to the raw acid.
After adding 00 g and 100 g of HgO, it was passed through a cation exchange resin and an anion exchange resin, and finally, THF and HgO were added.
,0 was removed under heat and vacuum to give a clear product.

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.

The properties of the polyols obtained in Example 3 and Comparative Example 3 are shown below.
Shown in 3.

Table 3 Example 4 Sodium methylate (30 g
% methanol solution) was added and the demethanol reaction was carried out at 100°C and 10 Torr for 1 hour, then 100g of ethylene oxide was introduced and the mixture was heated at 100°C for 3 hours.
The reaction was carried out.

After the reaction, an adsorbent (synthetic magnesium silicate) was added to the product, and the catalyst residue and sodium content were adsorbed onto the adsorbent, followed by filtration to obtain a transparent polyol. The properties of the obtained polyol are as follows.

Comparative Example 4 9.5 g of potassium hydroxide (48% aqueous solution) was added to 1500 g of Polyol D, and dehydration was carried out at 120°C and 10 To
I went for 3 hours by rr. The water content could not be lowered below 0.2% during the dehydration operation.

This polyol was purified by reacting it with ethylene oxide in the same manner as in Example 4.

The obtained polyol was cloudy.

The properties of the polyols obtained in Example 4 and Comparative Example 4 are shown below.
4.

Table 4 Effects of Invention C: By using an alkali metal alcolade as a treatment agent in the present invention, the composite metal cyanide complex catalyst can be easily deactivated, and the deactivated catalyst component and treatment agent component can be easily deactivated. It also becomes easier to separate and remove the polyethers from the polyethers. Furthermore, after deactivating the multimetal cyanide complex catalyst, it becomes possible to react ethylene oxide with the hydroxyl groups of polyethers, and polyethers with a high proportion of primary hydroxyl groups can be easily obtained.

Claims (1)

[Claims] 1. At least 1 in the presence of a multimetal cyanide complex catalyst
A polyether containing the above-mentioned catalyst obtained by subjecting an initiator having hydroxyl groups to a ring-opening addition reaction of a monoepoxide having 3 or more carbon atoms is treated with a treatment agent consisting of an alkali metal alcoholade to deactivate the above-mentioned catalyst. A method for producing polyethers, which comprises: then removing the deactivated catalyst component and processing agent component from the polyether. 2. Claim 1, wherein a treating agent made of an alkali metal alcoholade is added to polyethers containing a catalyst and heated, and then the catalyst component and the treating agent component are removed from the polyethers.
Section method. 3. At least 1 in the presence of a multimetal cyanide complex catalyst
A polyether containing the above-mentioned catalyst obtained by subjecting an initiator having hydroxyl groups to a ring-opening addition reaction of a monoepoxide having 3 or more carbon atoms is treated with a treatment agent consisting of an alkali metal alcoholade to deactivate the above-mentioned catalyst. , Next, using the polyether as an initiator, it is reacted with ethylene oxide, and then the deactivated catalyst component and the treating agent component are removed from the obtained polyether. . 4. Claim 3, wherein the alkali metal alcoholade is at least one alkali metal alcoholade selected from sodium alcoholade and potassium alcoholade.
Section method. 5. The method according to claim 3, wherein the alkali metal alcoholade is an alcoholade of an alcohol having 4 or less carbon atoms. 6. The method of claim 3, wherein the alkali metal alcoholade is an alcoholade of an alkali metal selected from sodium and potassium and an alcohol selected from methanol and ethanol. 7. The method according to claim 3, wherein the monoepoxide having 3 or more carbon atoms is an alkylene oxide having 3 or 4 carbon atoms. 8. The method according to claim 3, wherein the monoepoxide having 3 or more carbon atoms is propylene oxide. 9. The method according to claim 3, wherein a treating agent consisting of an alkali metal alcoholate is added to the polyether containing the catalyst and heated, the by-product alcohol is removed, and then ethylene oxide is reacted. 10. Claim 9, wherein the heating temperature is 100 to 150°C.
Section method. 11. The method of claim 9, wherein the alcohol is removed by vacuum. 12. The method according to claim 3, wherein the polyether is a polyether obtained by reacting at least 50 moles of a monoepoxide having 3 or more carbon atoms with 1 mole of initiator.