JPH03128930A - Production of polyether compound - Google Patents

Abstract

PURPOSE:To produce a high-mol.-wt. polyether compd. using a small amt. of catalyst with the formation of by-products reduced by using a specific catalyst in a process for producing the polyether compd. by the ring-opening addition polymn. of a cyclic ether compd. CONSTITUTION:In a process for producing a polyether compd. by the ring- opening addition polymn. of a cyclic ether compd. (e.g. propylene oxide), a double metal cyanide complex (e.g. zinc hexacyanobaltate) wherein N,N- dialkylamide (e.g. N,N-dimethylacetamide) is coordinated as an org. ligand is used as the catalyst.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a polyether compound using a specific catalyst, and particularly to a method for producing a polyether polyol suitable as a raw material for polyurethane. It is.

[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 for brakes, 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 carrying out a ring-opening addition reaction of a cyclic ether compound to the hydroxyl group of the inishek 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 difficult fields, 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 it 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, as an organic ligand of a double metal cyanide complex, N, N-
We have found that double metal cyanide complexes coordinated with dialkylamides have high catalytic activity.

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 general formula (1) as shown in the above-mentioned known examples.

M, [M', (CN), To(820), (R),
・(1) (M is Zn(II), Fe(II)
, Fe(Ill IGo(Ill, N1(IT),
AI(III), 5r(TI), Mn(IT)C
r[II), Cufll), 5n(TI), P
b(II), Mo(IV), Mo(VN, W(IV)
and W(l, M′ is Fe(H), Fe(II
I 1. (:o(+11.Co(III), C
r(II).

Cr (Ill), Mn (JN, Mn (+11),
V (IV) 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 are It is a positive number that changes depending on the coordination number of the metal. ) The double metal cyanide complex used as the catalyst of the present invention is represented by the general formula (1) as described above, and this compound is manufactured using the metal salt MXa (M, where a is the same as above, and X is M
and polycyatumeclate (salt) Ae [M', (CN), ].

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

Polycyanometalate (salt) A, [y', (cNLL
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 double metal cyanide complex obtained can be various compounds depending on the combination of M and M' in the above-mentioned general formula (1), and among them, M is Zn(II).

Fe(II), Fe(III), Go(II), A1.
(III1 and Cu(II)1M′ are Fe(TI
), Fe(III), Go(II).

Go(III) and Cr(III) are preferred, and furthermore, M is Zn(II), Fe(III), M
' is Fe(III).

(:o(Ill) is preferred; therefore, the first half of the general formula (1) of the double metal cyanide complex is Zn3[Fe(C
N) ad. , zn3[co(cNL]., Fe[F
e(CN)6].

Fe[Co(CN)ad] 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 used is not particularly limited as long as it is compatible with water, but alcohols, aldehydes, ketones, and ethers can be used. 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.

The organic ligand R included in the general formula (], ) of the double metal cyanide complex is N,N-dialkylamide;
Dimethylformamide, N,N-dimethylacetamide, N-methyl-N-ethylacetamide, N-methyl-
N-propylacetamide, NN-diethylacetamide, N,N-dimethylpropionamide, N,N-dialkylamide, N,N-dimethylacetoacetamide, N,
N-dimethylacetopropionamide and the like. Among these N,N-dialkylamides, it is preferable that all the alkyl groups bonded to the nitrogen atom are methyl groups, and N,N-dimethylacetamide and N,N-dimethylacetoacetamide are particularly preferable. . 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. Thereby, d in general formula (1) becomes 0.1 to 6.

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 an organic ligand R or a mixture of an organic ligand R and water, and after thorough stirring, the excess liquid is removed. The operation of removing can also be repeated. Furthermore, when the catalyst is dispersed in the organic ligand R, it is not necessarily necessary to remove the organic ligand R, and a mixture of the double metal cyanide complex and the organic ligand R in the form of a slurry can be used as the catalyst. is also possible.

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 preferably at a temperature 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) alkyl nonoxides are ethylene oxide, butylene oxide, butylene oxide, epichlorohydrin, 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, 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 d-compounds 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, initial condensate of bomaldehyde.

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 to be used is not particularly limited, but it is appropriate to be about 1 to 5000 ppm, and 30 to 5000 ppm based on the hydroxy compound used.
-11000pp 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 preferred. Polyether poly2ols within the above range are also preferred for other uses, such as raw materials for hydraulic oil. 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] Examples 1 to 4, Comparative Example] Double metal cyanide complexes were synthesized using the method described below using the five types of organic ligands shown in Table 1, and their properties as catalysts for polyol synthesis were investigated. did.

Gold cyanide A 0.4 m in a 1.5 mol/42 aqueous solution of zinc iodide
An aqueous solution of potassium cobalt cyanide of ol/J2 was slowly added with stirring. This produced a white precipitate. Add organic ligand and water at a volume ratio of 1:1 to this
After stirring for an hour, the mixture was separated by suction filtration to obtain a white product. This product was dispersed in an organic compound serving as an organic ligand, stirred for 1 hour, and then separated again by suction filtration to obtain a double metal cyanide complex. This stuff at 80℃
After drying in a dryer for 3 hours, it was finely ground and used in the next study of catalyst properties.

Polyether polyol 70 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.
0g and the double metal cyanide complex catalyst Zn3[G synthesized as described above.

(CN) 6] 2- (H□O) c- (organic ligand) (60.25 mg) was charged under a nitrogen atmosphere. This is 1
The temperature was raised to 20° C., and while maintaining this temperature, PO was continued to be introduced until the catalytic effect decreased. After distilling off unreacted PO 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.

[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.Also, since the amount of catalyst used can be reduced, the catalyst removal step after polyol synthesis can be simplified. It also has the effect of reducing costs.

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, N,N-dialkyl acid is coordinated as an organic ligand. 1. A method for producing a polyether compound, comprising using a double metal cyanide complex as a catalyst. 2. The method according to claim 1, wherein the double metal cyanide complex is zinc hexacyanocobaltate, zinc hexacyanoferrate, iron hexacyanocobaltate, or iron hexacyanoferrate. 2. A process according to claim 1, characterized in that the 3,N,N-dialkylamide is N,N-dimethylacetamide. 4. The method according to claim 1, wherein the cyclic ether compound is subjected to ring-opening addition polymerization to a mono- or polyhydroxy compound.