JPH04145123A - Production of polyether compound - Google Patents

Abstract

PURPOSE:To obtain the subject high-molecular weight compound, having long catalyst life and suitable as a raw material for polyurethanes by subjecting a cyclic ether compound to ring opening addition polymerization in the presence of a specified bimetallic cyanide complex catalyst. CONSTITUTION:A cyclic ether compound is subjected to ring opening addition polymerization in the presence of a bimetallic cyanide complex catalyst in which tertiary butanol is coordinated (preferably zinc hexacyanocobaltate, zinc hexacyanoferrate, iron hexacyanocobaltate or iron hexacyanoferrate as the bimetallic cyanide complex) to afford the objective compound.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for producing a catalyst suitable for producing a polyether compound, and a method for producing a polyether compound using the same. The present invention relates to a method for producing polyether polyols suitable as polyether polyols.

[Prior Art] Polyether polyol obtained by adding a cyclic ether compound such as alkylene oxide to a polyvalent initiator is widely used as a raw material for polyurethane. Polyether polyol is also used as a surfactant, It is used in hydraulic fluids such as brake fluid, raw materials for synthetic resins other than polyurethane, and other applications, either directly or by reacting with various compounds.Also, monovalent initiators such as monoalcohols are used. The polyether monools obtained can also be used as surfactants, hydraulic oils, and other raw materials.

These polyether compounds are produced by subjecting the hydroxyl group of an initiator to a ring-opening addition reaction of a cyclic ether compound in the presence of a catalyst. When one molecule of the cyclic ether compound is ring-opened and added to the hydroxyl group, one new hydroxyl group is generated, and the reaction continues. Strongly basic catalysts such as potassium hydroxide and sodium hydroxide are widely used as catalysts for this reaction. In addition, boron trifluoride, aluminum chloride, antimony pentoxide, ferric chloride, etc. are known as acidic catalysts, and boron trifluoride etherate is particularly effective. It is used in fields where it is difficult to use, for example, as a catalyst for ring-opening addition reactions of halogen-containing alkylene oxides. Furthermore, examples have been reported in which an organometallic compound such as an organotin compound is used as a catalyst, and an example in which lithium hexafluorophosphate is used as a catalyst.

Additionally, certain double metal cyanide complexes have been disclosed as catalysts for synthesizing high molecular weight polyether compounds (U.S. Pat. No. 3,278,457 to U.S. Pat. No. 3,278,459, U.S. Pat. , JP-A-58-185621, JP-A-63-27
7236, etc.).

[Problems to be Solved by the Invention] However, in the methods using these catalysts, it is difficult to obtain high molecular weight polyethers, and furthermore, the amount of side reaction products produced is not small, and high molecular weight polyether compounds with narrow molecular weight distribution are difficult to obtain. The problem is that it is not possible to obtain

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. There is also the problem that it is not.

Furthermore, conventional double metal cyanide complexes do not necessarily have sufficient activity as catalysts for the synthesis of high molecular weight polyether compounds. In particular, the catalyst life is not necessarily sufficient.

[Means for Solving the Problems] The present invention was made to solve the above-mentioned problems, and as a result of further studies on double metal cyanide complexes, it was found that tertiary metal cyanide complexes can be used as organic ligands for double metal cyanide complexes. - It has been found that a double metal cyanide complex coordinated with butanol has a long catalytic life.

The present invention provides a method for producing polyether compounds using this catalyst.

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. (H,0)e(R),
, -(1) (where M is Zn(U), Fe(II)
, Fe(III), Go(II), N1(U), AI
(1,5r(U), Mn(II), Cr(m), Cu(
ff ), 5n (Ir), Pb (U), Mo (IV),
Mo (VT), If (■) and W (VT), and M' is Fe (U), Fe (III), Co (I
I), Go(117), Cr(U), Cr(III
), Mn(n), Mn(III, V(N) and v
(v), R is an organic ligand, a, b, x and y are positive integers that vary depending on the valence and coordination number of the metal, and C and d vary depending on the coordination number of the metal. It is a positive number that changes.

The double metal cyanide complex used as the catalyst of the present invention is represented by the general formula (1) as described above, and the production of this compound is the metal salt MXa (M, a is the same as above, X forms a salt with M). anion) and polycyanometalate (salt) A
, [M' CN), ) t (M', x, y are the same as above,
A is hydrogen, alkali metal, alkaline earth metal, etc., e,
f is a positive integer determined by the valence and coordination number of A and M')
After mixing respective aqueous solutions or solutions of mixed solvents of water and an organic solvent, and contacting the obtained double metal cyanide complex with the organic compound R, the excess solvent and organic compound R are removed.

Polycyanometalate (salt) A, [, (cN), L can use various metals including hydrogen and alkali metals for 5A, but lithium salt, sodium salt, potassium salt, magnesium salt, calcium salt Salt is preferred. Particular preference is given to the customary alkali metal salts, namely the sodium and potassium salts.

The obtained double metal cyanide complex can be formed into various compounds depending on the combination of M and M' in the above-mentioned general formula (1).
n), Go(II), Al(III) and Cu
(II), M′ is Fe(Ill, Fe(III),
Co(U), Co(III) and Cr(III) are preferred, and M is preferably Zn(II), Fe(II[)
, M' is preferably Fe(III) or Co(III),
Therefore, the first half of the general formula (1) of the double metal cyanide complex is Zn3[Fe(CN)slz-, Zni[Co(
CN)slz, Fe[Fe(CN)sl.

Fe[Co(CN)-] is preferred.

When using a metal salt and a polycyanometalate salt as a solution of a mixed solvent of water and an organic solvent, the organic solvent that can be used is not particularly limited as long as it is compatible with water, but alcohols, aldehydes, getones, etc. , ether, etc. The mixing ratio of water and these organic solvents is 5% organic solvent by volume.
It is preferably 0% or less, particularly preferably 30% or less.

Note that the desired double metal cyanide complex can be obtained by using tertiary-butanol as the organic solvent. When using another organic solvent or when no organic solvent is used, the double metal cyanide or its complex is once produced and then tertiary butanol is coordinated to obtain the desired double metal cyanide complex.

In the present invention, the general formula (1) of the double metal cyanide complex
The organic ligand R contained in is tertiary-butanol, ie 2-methyl-2-propatol. The method of bringing this organic ligand R into contact with a double metal cyanide compound is to add the organic ligand R to a solution in which a double metal cyanide complex is produced by mixing a solution of a metal salt and a polycyanometalate salt, This is done by stirring thoroughly. This allows the general formula (
d in 1) is 0.1 to 1O.

The mixture used in the present invention can be prepared by removing excess solvent and organic ligand R from the mixture prepared as described above by suction filtration, centrifugation, heat drying, vacuum drying, or a combination thereof. A catalyst is obtained.

In order to further increase the activity of the catalyst obtained as described above, this catalyst is dispersed in the organic ligand R or a mixture of the organic ligand R and water, and after thorough stirring, excess liquid is removed. The removal operation can also be repeated. In addition, when the catalyst is dispersed in the organic ligand R, it is not necessarily necessary to remove the organic ligand R (a mixture of the double metal cyanide complex in the form of a slurry and the tangential compound R may be used as the catalyst). is also possible.

In the manufacturing process of the double metal cyanide complex represented by the above general formula (1), first, the reaction between the metal salt and the polycyanometalate (salt) is preferably carried out at 0°C to 60°C;
It is more preferable to carry out the reaction at a temperature of .degree. C. to 40.degree. When coordinating tertiary-butanol after that, it is preferable to add the tertiary-butanol dropwise to the reaction solution, ripen at 125° C. or lower, and then heat dry. When using an organic ligand or organic solvent other than tertiary-butanol, add it, age and dry it, then add tertiary-butanol and heat to convert the organic ligand to tertiary-butanol. is preferred. Heat drying in these cases should be carried out at 150°C or lower, especially in order to avoid reducing the activity of the catalyst.
The temperature is preferably 125° C. or lower, and is preferably as low as possible within a range that allows excess water and organic ligands to be removed.

As the cyclic ether compound, a compound containing a 3- to 4-membered cyclic ether group having one oxygen atom in the ring is suitable. Particularly preferred compounds are alkylene oxides having 2 to 4 carbon atoms, containing or not containing halogen, and tetrahydrofuran. In addition, alkylene oxide having 5 or more carbon atoms (halogen-containing), styrene oxide,
Glycidyl ethers, glycidyl esters, and other epoxides may also be used. Preferred (halogen-containing) alkylene oxides are ethylene oxide, propylene oxide, butylene oxide, shrimp chlorohydrin, and 4,4.4-trichloro-1,2-epoxybutane. Two or more of these cyclic ether compounds can be used in combination, and in that case, they can be mixed and reacted, or they can be reacted one after another. Particularly preferred cyclic ethers are alkylene oxides having 3 to 4 carbon atoms, especially propylene oxide.

A cyclic ether compound can be reacted alone, but usually a hydroxy compound is used as an initiator,
The hydroxyl group is reacted.

Various hydroxy compounds are used depending on the purpose, and polyether polyols useful as polyurethane raw materials are polyvalent hydroxy compounds, that is, polyhydroxy compounds. Monohydroxy compounds can also be used as surfactants and for other uses. Typical examples of polyhydroxy compounds are polyhydric alcohols and polyhydric phenols. In addition, polyether polyols with a lower molecular weight than the target polyol compound obtained by adding alkylene oxide to these, polyether polyols and polyester polyols with a lower molecular weight than the target polyol compound obtained by adding alkylene oxide to polyamines and monoamines. Compounds with hydroxyl groups such as are used.

Preferred polyhydroxy compounds are polyols such as polyhydric alcohols and polyhydric phenols. These polyhydroxy compounds may also be a mixture of two or more. Specific examples of polyhydroxy compounds include, but are not limited to, the following. Moreover, water is a type of divalent polyhydroxy compound.

Polyhydric alcohols: ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol, siglycerin, sorbitol, dextrol, methyl glucoside, shefrose.

Polyhydric phenol: Bisphenol A, phenol, initial condensate of formaldehyde.

Examples of monohydroxy compounds include methanol, ethanol, propatool, higher aliphatic alcohols, other monohydric alcohols, phenol, alkyl-substituted phenols, and other monohydric phenols.

Polyether compounds are usually produced by reacting a cyclic ether compound or a mixture thereof with a hydroxy compound in the presence of a catalyst. The reaction can also be carried out while gradually adding the cyclic ether to the reaction system. Although the reaction occurs at room temperature, the reaction system can be heated or cooled if necessary. The amount of the catalyst used is not particularly limited, but it is appropriate to be about 1 to 5000 ppm, and 30 to 1100 ppm, based on the hydroxy compound used.
0 pp is more preferable. The catalyst may be introduced all at once into the reaction system, or may be introduced in portions in sequence. After the reaction is completed, the catalyst is removed and other purification is performed to obtain a purified polyether compound.

The molecular weight of the polyether compound obtained is not particularly limited. However, products that are liquid at room temperature are preferred from the viewpoint of their use. For example, as a raw material for polyurethane, a liquid polyether polyol having a hydroxyl value of about 5 to 800, particularly 5 to 60, is preferable.For other uses, such as a raw material for hydraulic oil, polyether polyols having the above range are preferable. The polyether compound obtained by the present invention is most suitable as a polyol for polyurethane raw materials, either alone or in combination with other polyols. In addition, the polyether compound obtained by the present invention can be used for various purposes by itself or by reacting with other compounds such as an alkyl ether compound.

[Example] A double metal cyanide complex was synthesized by the method shown below, and its properties as a catalyst for polyol synthesis were investigated.

, cyan f person reference example 1 15 cc of aqueous solution containing 10 g of zinc chloride, 75 cc of aqueous solution containing 4 g of potassium cobalt cyanate, and 50 wt%
Tertiary-butanol water-soluble? ? 42,100 cc were mixed at room temperature, and the reaction was aged while stirring to obtain a slurry solution. It was then filtered off with suction to obtain a white product. This filter cake was washed with a 30 wt % tertiary-butanol aqueous solution and separated by filtration to obtain a filter cake, which was further washed with tert-butanol and separated by filtration to obtain a filter cake. This filter cake was dried at 40° C. under reduced pressure and pulverized to obtain a double metal cyanide complex.

Reference Example 2 A slurry solution was obtained by reacting and aging 30 cc of an aqueous solution containing Log zinc chloride, 75 cc of an aqueous solution containing 4 g of potassium cobalt cyanate, and 70 cc of a 70% ethylene glycol dimethyl ether aqueous solution. Thereafter, it was filtered to obtain a filter cake. This filter cake was washed with a 30% aqueous solution of diethylene glycol dimethyl ether and then further filtered to obtain a filter cake, which was then washed with diethyl glycol dimethyl ether and filtered. This filter cake was heated to 120℃ in vacuo.
I smoked it and crushed it. Thereafter, tertiary butanol was added and the mixture was left at room temperature for 48 hours.

Reference Example 3 30 cc of an aqueous solution containing 10 g of zinc chloride and 75 cc of an aqueous solution containing 4 g of potassium cobalt cyanate 1.
OOcc was reacted with a 75% diethylene glycol dimethyl ether aqueous solution and aged to obtain a slurry solution. Thereafter, it was filtered to obtain a filter cake. This filter cake was washed with a 40% aqueous solution of diethylene glycol dimethyl ether and filtered twice to obtain a filter cake, which was then washed with diethyl glycol dimethyl ether and filtered. This filter cake was dried in vacuo at 120°C and pulverized. Thereafter, tertiary butanol was added, heat treated at 45°C for 1 hour, dried in air at 80°C for 4 hours, and pulverized.

Comparative Reference Example 1 An aqueous solution of l Occ containing log zinc chloride, 75 cc of an aqueous solution containing 4.17 g of potassium cobalt cyanate, and 100 cc of a 50% diethylene glycol dimethyl ether water bath solution were added at a reaction temperature of 35°C. Made it react. This solution was filtered to obtain a filter cake. 30 pieces of this filter cake
% diethylene glycol dimethyl ether aqueous solution to obtain a filter cake, which was then washed with diethyl glycol dimethyl ether, filtered, dried, and pulverized to obtain a composite metal cyanide complex catalyst.

Comparative Reference Example 2 13 cc of an aqueous solution containing 8 g of zinc chloride, 75 cc of an aqueous solution containing 4 g of potassium cobalt cyanate, and 60 CC of 8
A slurry solution was obtained by reacting with a 0% aqueous ethylene glycol dimethyl ether solution and aging. Thereafter, it was filtered to obtain a filter cake. This filter cake was washed with a 30% aqueous solution of ethylene glycol dimethyl ether and filtered twice to obtain a filter cake, which was then washed with ethylene glycol dimethyl ether and filtered. The filter cake was dried in vacuo at 40°C,
I did the pulverization. Thereafter, diethyl glycol dimethyl ether was added and the mixture was dried in air at 80°C to obtain a composite metal cyanide complex catalyst.

11 In a pressure-resistant autoclave made of stainless steel, 700 g of polyoxypropylene triol with a molecular weight of 600 obtained by adding propylene oxide (hereinafter referred to as PO) to glycerin and the double metal cyanide complex synthesized in the reference example were heated with nitrogen. It was placed in an atmosphere. The temperature was raised to 120° C., and while maintaining this temperature, PO was continued to be introduced until the catalytic action decreased. The double metal cyanide complex of Comparative Reference Example 1 was
．． 25g of the catalyst was used, and other catalysts were used in amounts that made the amount of cobalt the same based on the amount of the catalyst. Table 1 below shows the life of each catalyst based on the life of the catalyst of Comparative Reference Example 1.

Catalyst life was measured in the same manner as above using bisphenol A as the initiator and epichlorohydrin instead of PO. Table 2 below shows the life of each catalyst based on the life of the catalyst of Comparative Reference Example 1. Table 2 also shows the relative selectivity of epichlorohydrin reacted with the initiator.

Table 1 Table 2 [Effects of the Invention] The present invention synthesizes a high molecular weight polyetherol using a double metal cyanide complex having a longer life than conventional ones. Its catalyst life is about 5 to IO times longer than conventional catalysts when reacting propylene oxide. Furthermore, this catalyst has the characteristics of high activity (and long life) even in the reaction of epichlorohydrin.

Claims (1)

[Scope of 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 catalyst, a complex compound in which tert-butanol is coordinated as an organic ligand is used. A method for producing a polyether compound, characterized in that a metal cyanide complex is used as a catalyst. 2. The method of claim 1, wherein the double metal cyanide complex is zinc hexacyanocobaltate, zinc hexacyanoferrate, iron hexacyanocobaltate, or iron hexacyanoferrate. 3. The method according to claim 1, wherein the cyclic ether compound is subjected to ring-opening addition polymerization to a mono- or polyhydroxy compound.