JPH03281529A - Production of polyether compound - Google Patents

Abstract

PURPOSE:To obtain the title compound useful as a raw material having excellent workability in producing a polyether by subjecting a cyclic ether compound to ring opening addition polymerization by using a compound having given hydroxyl number as an initiator, by using an amide compound as a solvent. CONSTITUTION:In producing a polyether by subjecting a cyclic ether compound (e.g. propylene oxide) to ring opening addition polymerization in the presence of a binuclear metallic cyanide complex by using a hydroxy compound having >=800 hydroxyl number as an initiator, an amide compound (e.g. DMF: preferably 10-500wt.% based on the amount of the initiator) is used as a solvent to give the objective compound.

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 suitable as raw materials for polyurethane.

[Prior Art] 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 (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-H-R-OhH].

-(R-0+-: Ring-opening reaction unit m of monoepoxide; integer Conventionally, a method of reacting monoepoxide in the presence of an alkali catalyst has been widely used as a method for producing polyethers.As an alkali catalyst, Alkali metal compounds such as potassium hydroxide and sodium hydroxide were used.

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, and this tendency becomes noticeable when the molecular weight is 6,500 or more (in the case of trifunctional), so when propylene oxide is used as the monoepoxide, polyethers with a molecular weight of 6,500 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. US 3278458. US 32784
59US 3427256. US 3427334. U
S 3427335). 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, with methods using these catalysts, it is difficult to obtain high molecular weight polyethers (furthermore, the amount of side reaction products produced is not small, and high molecular weight polyethers with a narrow molecular weight distribution are difficult to obtain). The problem is that the compound cannot be obtained.

In addition, some catalysts are easily affected by water and temperature, and lithium hexafluorophosphate in particular easily reacts with moisture in the air and decomposes to produce hydrofluoric acid, so handling is not always easy. Otherwise, there is a problem.

In addition, conventional double metal cyanide complexes are effective as catalysts for the synthesis of high molecular weight polyether compounds, but they are not suitable for the ring-opening addition polymerization reaction of cyclic ethers to low molecular weight hydroxy compounds with a hydroxyl value of 800 or more. Does not have satisfactory activity.

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

A method characterized by using an amide compound as a solvent in producing a polyether compound by ring-opening addition polymerization of a cyclic ether compound in the presence of a double metal cyanide complex using a hydroxy compound having a hydroxyl value of 800 or more as an initiator. A method for producing a polyether compound.

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

M, [M', (CN), 1. ()120)c(R),
・(1) However, M is Zn(II), Fe(II)
, Fe(III), Co(n), N1(If), AI
(ITJ), 5r(IT), Mn(II), Cr(m)
, C:u(U), 5n(Ill, Pb(1), Mo(I
V) Mo(Vl), W(IV), etc. W(Vl), and M' is Fe(II), Fe(1), CO(■), C
o(III), Cr(II), Cr(III), Mn(
II), Mn (ID), N1 (II), V (■), 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 general formula (1) is preferably Zn (n), and M' is Fe (■), Fe (IIT), Co (II), Co (I
ll) etc. are preferred. Examples of organic ligands include ketones, ethers, aldehydes, esters, alcohols, amides, nitriles, sulfides, and sulfoxides.

Preferred organic ligands are ethers, amides, and ketones. The coordination number α is suitably 0.1 to 6.

As described above, the double metal cyanide complex represented by (-formation (1)) is a metal salt MXa (M, a is the same as above, X is M
and polycyanometalate (salt) Z, [M', (CN), ].

(M' x, y are the same as above. 2 is hydrogen, alkali metal, alkaline earth metal, etc., e, f are positive integers determined by the valence and coordination number of Z, M') It is produced by mixing a solution of a mixed solvent of water and an organic solvent, bringing the resulting double metal cyanide into contact with an organic ligand R, and then removing the excess solvent and organic compound R.

Polycyanometalate (salt) Z, [M', (C
N) For yl t, various metals including hydrogen and alkali metals can be used for 2, 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, and in the present invention, a specific organic solvent is allowed to coexist during this reaction. Furthermore, the reaction can be carried out while gradually adding monoepoxide to the reaction system, or an organic solvent may be added together with the monoepoxide. Although the reaction occurs at room temperature, the reaction system can be heated or cooled if necessary. Usually 50-150°C, preferably 80-150°C
120°C is adopted. The amount of catalyst used is not particularly limited, but 1
~5000ppm is appropriate, and 30~11000ppm
pp is more preferred. The catalyst may be introduced all at once into the reaction system, or may be introduced in portions in sequence.

The amount of the organic solvent is not particularly limited, but it is preferably 0.5% by weight or more based on the amount of the initiator, and the upper limit is preferably 10 times the weight of the initiator. A more preferable amount of organic solvent is 10 to 10% of the initiator.
It is 500% by weight.

Various amide compounds can be used as the organic solvent, but an organic solvent with a relatively low boiling point is preferred in consideration of removal from the polyether after the reaction is completed. Preferably 160
An amide compound having a boiling point of 0.degree. C. or below, particularly 40 to 120.degree. C. is preferred. Specifically, N,N-dialkylamides are preferred, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-N-ethylacetamide, N-methyl-N-propylacetamide, N, N-diethylacetamide, N,N-dimethylpropionamide, N,N-dimethylbutanamide,
NN-dimethylace]acetamide, N,N-dimethylacetopropionamide, etc., preferably N,
N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, and N,N-
There is dimethylacetoacetamide.

It is usually necessary to remove impurities from the resulting polyethers containing catalysts and organic solvents. As this treatment method, for example, a catalyst deactivator such as an alkali metal compound is added, and the temperature is preferably 80 to 180 °C, especially ioo to 1
A preferred method is to perform heating to 50°C and vacuum treatment, followed by purification. In the purification process, after treatment with neutralizing agents, adsorbents, ion exchange agents, etc., unnecessary substances are separated from polyethers by filtration. This allows all catalyst residues, alkali residues, organic solvents, etc. 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;
Examples of ion exchange agents include ion exchange resins such as anion exchange resins and cation exchange resins.

As the polyethers obtained by the method of the present invention, polyoxyalkylene polyols are preferred. Polyoxyalkylene polyol is obtained by subjecting an initiator having at least two hydroxyl groups to a sequential ring-opening addition reaction with a monoepoxide such as alkylene oxide. In the present invention, an initiator with a molecular weight of 1800 or less is used. As the ether, 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; There are polyethers with a molecular weight of 800 or less obtained by reacting tetrahydric or higher alcohols such as pentaerythritol, diglycerin, dextrose, sorbitol, and sucrose, and monoepoxides such as alkylene oxides with these alcohols. In addition, compounds having phenolic hydroxyl groups and methylol groups such as bisphenol A, resols, and novolaks, compounds having hydroxyl groups and other active hydrogens such as ethanolamine and jetanolamine, and monoepoxides such as alkylene oxides are reacted with these. There are polyethers with a molecular weight of 800 or less obtained by reacting a monoepoxide such as an alkylene oxide with a monoamine or polyamine having at least two hydrogen atoms bonded to a nitrogen atom. There are low molecular weight polyethers.

In addition, phosphoric acid, its derivatives, and other polyhydroxy compounds can also be used. These polyhydroxy compounds are 2
It is also possible to use more than one species in combination.

The present invention also uses molecules! It can also be applied to a method of manufacturing polyether monool by subjecting a monoepoxide to a ring-opening reaction with a monovalent initiator of 800 or less. Examples of monovalent initiators include methanol, ethanol, butanol, hexanol, other monools, phenol, phenol derivatives such as alkyl-substituted phenols, and target products obtained by reacting these with monoepoxides such as alkylene oxides. There are also low molecular weight polyethers. Furthermore, there are low molecular weight polyethers with a molecular weight of 800 or less obtained by reacting monoepoxides such as alkylene oxides with monoamines or polyamines having one hydrogen atom bonded to a nitrogen atom.

The molecular weight of the initiator is particularly preferably 400 or less.

Conventionally, monoepoxides with such low molecular weights were difficult to react with at the initial stage of the reaction.

The monoepoxide in the present invention is a monoepoxide having 2 or more carbon atoms, and particularly preferably an alkylene oxide having 2 or more carbon atoms.

More preferably, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, epichlorohydrin, ethylene oxide, and the like having 2 to 2 carbon atoms.
The alkylene oxides of No. 4 are 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. In the case of using two or more alkylene oxides or alkylene oxide and other monoepoxides, they can be added as a mixture or added sequentially to form a random polymer chain or a block polymer chain.

The molecular weight of the obtained polyethers is not particularly limited, but since the purpose of the present invention is to produce particularly high molecular weight polyethers as described above, the lower limit of the molecular weight is expressed by the hydroxyl value. It is preferably 40 or less, particularly 20 or less. There is no particular lower limit to the hydroxyl value, but it is usually about 5. The reaction amount of monoepoxide per mole of vinyl shake is preferably at least about 50 moles, more preferably at least about 100 moles. More preferably, an average of at least about 5
Polyethers obtained by reacting 0 molecules are preferred.

Further, it is preferable that the obtained polyethers be products that are liquid at room temperature from the viewpoint of their use.

Furthermore, since the present invention can use a low molecular weight initiator, it can also be applied to the production of highly hydroxylated polyether polyols. That is, it can be applied to the production of polyether polyols with a high hydroxyl value (ie, low molecular weight) that reach a hydroxyl value of 600. In that case, as the initiator, an initiator having a hydroxyl value of 800 or more is used.

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] Example 1 In a 1.5 mol/42 aqueous solution of cyanide complex zinc iodide, 0.4 m
An aqueous solution of potassium cobalt cyanide of ol/ρ was slowly added with stirring. This produced a white precipitate. After adding 50% N,N-dimethylacetamide aqueous solution and stirring for 1 hour, it was filtered by suction filtration.
A white product was obtained. This product was dispersed in a 50% aqueous solution of N,N-dimethylacetamide, stirred for 1 hour, and filtered using suction filtration.
After dispersing in N-dimethylacetamide and stirring for 1 hour, the mixture was filtered again by suction filtration to obtain a double metal cyanide complex. This product was dried in a dryer at 80° C. for 3 hours, then finely ground and used in the next study of catalyst properties.

1 plate of beans in a stainless steel pressure autoclave, add glycerin
og, 30 g of propylene oxide, 20 g of N,N-dimethylacetamide, and 27 mg of the double metal cyan mirror synthesized as described above as a catalyst were placed in a nitrogen atmosphere. This was immersed in a 120° C. oil bath to react for 3 hours, and the pressure and temperature inside the autoclave during the reaction were measured.

The temperature inside the autoclave was observed to rise due to the heat of reaction, and the internal pressure returned to approximately atmospheric pressure at the end of the reaction.

When the product was analyzed by GPC, it was found that 3 to 6 molecules of PO were added to glycerin, and the initiator glycerin was not detected. Also, P
The reaction rate of O was 95% or more.

Comparative Example 1 Glycerin 1 was placed in a stainless steel pressure autoclave.
0g, Po 30g and catalyst 2 used in Example 1
7 mg was put into a nitrogen atmosphere, and the reaction was carried out in the same manner as in Example.

A clear increase in the temperature inside the autoclave was observed, and the internal pressure at the end of the reaction was about 15 atm. As a result of analysis by GPC, it was found that the main product was glycerin with 1 to 2 molecules of PO added, and that glycerin to which PO was not added also remained. Moreover, the reaction rate of PO was about 25%.

Example 2, Comparative Example 2 A double metal cyanide complex was obtained in the same manner as in Example 1, except that zinc chloride was used instead of zinc iodide and glyme was used instead of N,N-dimethylacetamide. Ta.

[Glycerin 1 liter in a pressure-resistant autoclave made of stainless steel
0 g, propylene oxide 30 g, 27 mg of the double metal cyanide complex synthesized as described above as a catalyst, and N,N-dimethylacetamide in various ratios as shown in Table 1 were charged under a nitrogen atmosphere. A test similar to 1 was conducted.

The results are shown in Table 1.

Example 3 In a stainless steel pressure autoclave, glycerin 10
0g, N,N-dimethylacetamide 300g,
0.5 g of the double metal cyanide complex synthesized in Example 1 was placed in a nitrogen atmosphere. The temperature was raised to 120° C., and while maintaining this temperature, PO was continued to be introduced until the catalytic action decreased. After distilling off unreacted PO under reduced pressure, a suction agent was added and stirred to adsorb the catalyst, followed by filtration and drying to obtain a polyol.

The amount of reacted PO per gram of catalyst was 25 kg, and the average molecular weight determined by GPC analysis of the polyol produced was about 10.000.

Table 1 [Effects of the Invention] The present invention has the effect that not only can high molecular weight bols/ols be synthesized by using a hydroxy compound having a hydroxyl value of 800 or more as an initiator, but also that by-products are hardly generated. Furthermore, since the amount of catalyst used can be reduced, there is also the effect that the cost of the catalyst removal step after polyol synthesis can be reduced.

Claims (1)

[Claims] 1. In producing a polyether compound by ring-opening addition polymerization of a cyclic ether compound in the presence of a double metal cyanide complex using a hydroxy compound having a hydroxyl value of 800 or more as an initiator, as a solvent. A method for producing a polyether compound, characterized by using an amide compound. 2. The method according to claim 1, wherein the amide compound used as a solvent is an N,N-dialkylamide. 3. The method of claim 2, wherein the N,N-dialkylamide is N,N-dimethylamide, N,N-dimethylacetamide, N,N-diethylacetamide, or N,N-dimethylacetoacetamide. . 4. The method according to claim 1, wherein the amount of the amide compound used is 0.5 to 1000 wt% based on the hydroxy compound used.