JPH032136A - Production of double metal cyanide complex and use thereof - Google Patents

Abstract

PURPOSE:To obtain the subject complex suitable to a catalyst for carrying out ring opening addition polymerization of a cyclic ether compound to provide a polyether compound by reacting a polycyanometalate or a salt thereof with a metal iodide in the presence of water and coordinating an organic ligand therewith. CONSTITUTION:A polycyanometalate or a salt thereof, preferably an alkali metal hexacyanocobaltate or hexacyanoferrate is reacted with a metal iodide, preferably zinc iodine in the presence of water and an organic ligand is simultaneously coordinated therewith to afford a double metal cyanide complex, useful as a catalyst for synthesizing a polyether polyol suitable to a raw material for polyether compounds, especially polyurethanes by ring opening addition polymerization of a cyclic ether compound, preferably >=3C alkylene oxide, having high catalyst activity, capable of synthesizing a high-molecular weight polyol by a small amount of the catalyst added and having also effects on hardly any formation of by-products, etc.

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 polyols obtained by adding cyclic ether compounds such as alkylene oxides to polyvalent inishes are widely used as raw materials for polyurethanes. Further, polyether polyols are used as surfactants, hydraulic fluids such as brake fluids, raw materials for synthetic resins other than polyurethane, and other uses, either directly or by reacting with various compounds. In addition, polyether monool obtained by using a monovalent initiator such as a monoalcohol can be similarly used as a surfactant, hydraulic oil, or other raw material.

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.Also, acidic catalysts include boron trifluoride, aluminum chloride, antimony pentoxide, ferric chloride, etc. is known, and boron trifluoride etherate is particularly effective, and this acidic catalyst is used in fields where strong basic catalysts are difficult to use, for example, as a catalyst for ring-opening addition reactions of halogen-containing alkylene oxides. Examples have also 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, with methods using these catalysts, it is difficult to obtain high molecular weight polyethers, and furthermore, the amount of side reaction products produced is small. The problem is that an ether 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. It also has the problem that it is not.

Furthermore, conventional double metal cyanide complexes do not necessarily have satisfactory activity as catalysts for the synthesis of high molecular weight polyether compounds.

Furthermore, conventional double metal cyanide complexes do not necessarily have satisfactory activity as catalysts for the synthesis of high molecular weight polyether compounds.

[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 metal iodine was used as one of the raw materials for double metal cyanide complexes. We have found that double metal cyanide complexes with higher catalytic activity can be obtained by using hydride.

The present invention is a method for producing the following double metal cyanide complex and a method for producing a polyether compound.

1. A method for producing a double metal cyanide complex, which comprises reacting polycyanometalate or a salt thereof with a metal iodide in the presence of water and coordinating an organic ligand.

When manufacturing a polyether compound by ring-opening addition polymerization of a cyclic ether compound in the presence of a double metal cyanide complex catalyst, a polycyanometalate or a salt thereof is reacted with a metal iodide as a double metal cyanide complex catalyst. A method for producing a polyether compound, characterized by using a double metal cyanide complex obtained by.

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

M, [M', (CN), ], (H10), (R),
・(1) (However, M is Zn(II), Fe(II)
), Fe(III), Co(IT), N1(II),
AI(m), 5r(II), Mn(II), Cr(I
II), Cu(II), 5n(II), Pb(II),
Mo(IV), Mo(Vl), W(IV) and w
('vr), and M' is Fe(II), Fe(III
), Go(II), Go(III), Cr(II), C
r(III), Mn(II), Mn(III), V(I
V) and V(V), R is an ether, sulfide, nitrile, ester, alcohol, aldehyde, and ketone, and a, b, x, and y are positive integers that vary depending on the valence and coordination number of the metal. where C and d are positive numbers that vary depending on the coordination number of the metal. ) The double metal cyanide complex used as a catalyst in the present invention is represented by the formula (1) as described above, and this compound is prepared using a metal iodide MI.

(M, a are the same as above) and polycyanometalate (salt)
A, [M', (cN)ylr (M' + X,
y is the same as above. (A is hydrogen, alkali metal, alkaline earth metal, etc., and e and f are positive integers determined by the valence and coordination number of A and M') or a mixed solvent solution of water and organic solvent are mixed. After bringing the organic compound R into contact with the double metal cyanide complex obtained, the excess solvent and organic compound R are removed.

Polycyanometalate (salt) A-[M'X(CN)y
For lr, various metals including hydrogen and alkali metals can be used for A, 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.

The resulting 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).
I), Go(II), Al(IIT) and Cu(II
), M' is Fe(II), Fe(II), Co(II)
, Go(III) and Cr(FIT) are preferable, and furthermore, M is Zn(II), Fe(III), and M' is F
e(III) and Go(1) are preferred, and therefore the first half of the general formula (1) of the double metal cyanide complex is Zns[
Fe(CN)ala, Zni[C0(CN)+]i,
Fe[Fe(CN)al.

Fe[C:o(CN)al is preferred.

When using a metal iodide and a polycyanometalate salt as a solution of a mixed solvent of water and an organic solvent, the organic solvent used is not particularly limited as long as it is compatible with water, but alcohols, aldehydes, ketones, Ether, etc. The mixing ratio of water and these organic solvents is preferably 50% or less, particularly preferably 30% or less by volume.

The compound R included in the general formula (1) of the double metal cyanide complex is diethyl ether, 1-ethoxybencune, dibutyl ether, ethylpropyl ether, 1.2-
Ethers such as dimethoxyethane, 1,2-jethoxyethane, glyme, diglyme, triglyme, tetraglyme, diethylene glycol ethyl ether, diethylene glycol dibutyl ether, sulfides such as dimethyl sulfide, diethyl sulfide, dibutyl sulfide, acetonitrile, propionitrile, etc. Nitriles, esters such as amyl formate, ethyl acetate, methyl propionate, methanol, ethanol,
propa tool, impropa tool, butanol, ter
These include alcohols such as t-butyl alcohol, aldehydes such as formaldehyde, acetaldehyde, and benzaldehyde, and ketones such as acetone and ethyl methyl ketone. Among these organic compounds, ethers are most preferred, ethers containing two or more oxygen atoms are more preferred, and ethers containing three or more oxygen atoms are particularly preferred. The method of bringing these organic compounds R into contact with a double metal cyanide is to add the organic compound R to a solution in which a double metal cyanide complex is formed by mixing a solution of a metal iodide and a polycyanometalate salt, and This is done by stirring. As a result, d in general formula (1)
is 0.1 to 6.

The vine catalyst used in the present invention is obtained by removing excess solvent and organic compound R from the mixture prepared as described above by suction filtration, centrifugation, heat drying, reduced pressure drying, or a combination thereof. can get.

In order to further increase the activity of the catalyst obtained as described above, this catalyst is dispersed in a mixture of specific compound R or organic compound R and water, and after sufficient stirring, excess liquid is removed. The operation can also be repeated. Further, when the catalyst is dispersed in the organic compound R, it is not necessarily necessary to remove the organic compound R, and it is also possible to use a slurry-like mixture of the double metal cyanide complex and the organic compound R as the catalyst.

The manufacturing process of the double metal cyanide complex represented by the above general formula (1) is preferably carried out at 10°C to 80°C, and more preferably carried out at 25°C to 60°C, except for the heat drying process. Further, heat drying is preferably carried out at a temperature of 150° C. or lower so as not to cause a decrease in the activity of the catalyst, and the temperature is preferably as low as possible within a range that allows excess water and organic compounds 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, epichlorohydrin, 4,4,4-1-lichloro-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, compounds having hydroxyl groups such as polyether polyols and polyester polyols having a lower molecular weight than the target polyol compound obtained by adding alkylene oxide to these compounds 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, sucrose.

Polyhydric phenol; bisphenol A, phenol, formaldehyde initial condensate.

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 with respect to the hydroxy compound used, and about 30 to 1000 ppm.
ppm is more preferred. 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] Example 1, Comparative Examples 1 to 5 Double metal cyanide complexes were synthesized using the method described below using the six types of zinc salts shown in Table 1, and their properties as catalysts for polyol synthesis were investigated. .

Add 0.4 mol to a 1.5 mol/n aqueous solution of human zinc salt of cyanide.
An aqueous solution of potassium cobalt cyanide of /j2 was slowly added with stirring. This produced a white precipitate. A 50% diclime aqueous solution was added thereto, and the mixture was stirred for 1 hour and filtered by suction-filtration to obtain a white product.

This product was dispersed in a 30% diglyme aqueous solution and
After stirring for an hour, the product was filtered by suction filtration, and the obtained product was further dispersed in diglyme, stirred for 1 hour, and filtered again by suction filtration to obtain a double metal cyanide complex.

After drying this in a drying oven at 80°C for 3 hours,
It was finely ground (pulverized and used for the next study of catalyst properties).

Polyether polyol 75 with a molecular weight of 1000 obtained by adding propylene oxide (hereinafter referred to as PO) to glycerin in a stainless steel pressure-resistant autoclave.
g and P015g and the double metal cyanide complex Zn-[Co(ON)-]-1 synthesized as described above as a catalyst.
27 mg of HaO)-.(diglyme) was charged under a nitrogen atmosphere. This was immersed in an oil bath at 120°C, and the pressure and temperature inside the pressure autoclave at this time were measured.

As the reaction progressed, the pressure inside the autoclave gradually decreased due to the consumption of PO, and an increase in temperature was observed due to the heat of reaction.

The results are shown in Table 1. Double metal cyanide complexes synthesized using zinc sulfate (Comparative Example 3), zinc nitrate (Comparative Example 4), and zinc fluoroborate (Comparative Example 5) did not exhibit any reaction activity. All of the double metal cyanide complexes synthesized using zinc halide had reaction activity, but Example 1
The double metal cyanide complex synthesized using zinc iodide has the lowest reaction initiation temperature, the highest temperature reached during the reaction (and the internal pressure decreases faster), and is the highest as a catalyst for polyether synthesis. It had activity.

Examples 2 to 5, Comparative Example 6.7 Double metal cyanide mirrors were synthesized in the same manner as in Example 1 using each zinc salt and hexacyanometalate salt shown in Table 2.

In a pressure-resistant autoclave made of stainless steel, 700 g of a polyether polyol having a molecular weight of 1000 obtained by adding PO to glycerin and 0.25 g of the double metal cyanide complex catalyst synthesized as described above were placed under 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. Unreacted P.

After distilling off under reduced pressure, an adsorbent was added and stirred to adsorb the catalyst, followed by filtration and drying to obtain a polyol.

Table 2 shows the amount of reacted PO per gram of catalyst and the average molecular weight determined by GPC analysis of the polyol produced. The reaction p is higher when a double metal cyanide complex using an iodide is used as a catalyst than when a chloride is used as a metal salt.

Larger amounts of higher molecular weight polyols were obtained.

As described above, the double metal cyanide complex containing water and an organic compound synthesized using a metal iodide and a polycyanometalate salt has high catalytic activity for the synthesis of polyols, and requires less catalyst addition. can synthesize high molecular weight polyols.

[Effects of the Invention] The present invention not only enables the synthesis of high-molecular-weight polyols, but also has the effect of making by-products less likely to be produced. It also has the effect of reducing costs.

Claims (1)

[Claims] 1. A method for producing a double metal cyanide complex, which comprises reacting polycyanometalate or a salt thereof with a metal iodide in the presence of water and coordinating an organic ligand therewith. 2. Claim 1, wherein the polycyanometalate or its salt is an alkali metal salt of hexacyanocobalt or hexacyanoiron, and the metal iodide is zinc iodide.
The method described in section. 3. When producing a polyether compound by ring-opening addition polymerization of a cyclic ether compound in the presence of a double metal cyanide complex catalyst, polycyanometalate or a salt thereof and a metal iodide are used as the double metal cyanide complex catalyst. A method for producing a polyether compound, characterized by using a double metal cyanide complex obtained by reaction. 4. Claim 3, wherein the polycyanometalate or its salt is an alkali metal salt of hexacyanocobalt or hexacyanoiron, and the metal iodide is zinc iodide.
Section method. 5. The method according to claim 3, wherein the cyclic ether compound is subjected to ring-opening addition polymerization to a mono- or polyhydroxy compound. 6. The method according to claim 3, wherein the cyclic ether is an alkylene oxide having 3 or more carbon atoms.