JPH03733A - Preparation of polyether compound - Google Patents

Abstract

PURPOSE:To obtain easily a high-MW polyether compd. suitable as a raw material of a polyurethane and with a narrow MW distribution by performing ring opening addition polymn. of a cyclic ether using a specified double metal cyanide complex as a catalyst. CONSTITUTION:A double metal cyanide complex of the formula contg. both hexacyanocobaltate ions and hexacyanoferrate ions is provided. In the formula, M is Zn(II), Fe(II), Fe(III), Co(II), Ni(II), Al(III), Sr(II) etc.; R is ether, sulfide, nitrile, ester, etc.; x, y, z, a and b are each a positive number. Then, ring opening addition polymn. of a cyclic ether (e.g. propylene oxide) alone or with a hydroxy compd. (e.g. propylene glycol) as an initiator is performed by using this complex with a high catalitic activity as a catalyst to obtain a polyether compd.

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 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. It is used in hydraulic fluids such as liquids, raw materials for synthetic resins other than polyurethane, and other applications, either directly or by reacting with various compounds.Also, it is obtained by using monovalent incubators such as monoalcohols. The polyether monools used in this process can also be used as surfactants, hydraulic fluids, 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 pentachloride, 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.).

[Problem to be solved by the invention]

However, with methods using these catalysts, it is difficult to obtain high-molecular-weight polyether (and the amount of side reaction products produced is also small (), and it is difficult to obtain high-molecular-weight polyether compounds with a narrow molecular weight distribution. There are problems.

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 satisfactory activity as catalysts for the synthesis of high molecular weight polyether compounds.

[Means for Solving the Problems] The present invention has been made to solve the above-mentioned problems, and as a result of further studies on double metal cyanide complexes, it has been found that metal iodine is 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 a polyether compound using the following double metal cyanide complex as a catalyst.

A method for producing a polyether compound, characterized by ring-opening addition polymerization using a cyclic ether alone or a hydroxy compound as an initiator, using a double metal cyanide complex containing both hexacyanocobaltate ions and hexacyanoferrate ions as a catalyst. .

As shown in the above-mentioned known examples, the double metal cyanide complex is considered to be a complex of an organic compound having a polycyanometallic acid ion and a metal ion, and the double metal cyanide complex in the present invention contains a polycyanometallic acid ion. It is characterized by containing both hexacyanocobaltate ion and hexacyanoferrate ion. This double metal cyanide complex is thought to be represented by the following general formula (1).

M, [Co(CN)aly[Fe(CN)a]-(Hz
O)-(R)b-(1) (where M is Zn(II),
Fe(II), Fe(Ill), Co(II), N1(
I[), Al(III), 5r(II), Mn(I[)
, Cr(III), Cu(II), 5n(II), Pb
(II), Mo (IV), Mo (Vl), W (IV)
and W(Vl), and R is an ether, sulfide, nitrile, ester, alcohol, aldehyde, and ketone.XI yl Zl a and b are positive numbers that vary depending on the valence and coordination number of the metal. ) The double metal cyanide complex used as the catalyst of the present invention is represented by the formula (1) as described above, and the production of this compound is as follows:
A solution of a metal salt that provides a cation of metal M is mixed with a mixed solution of hexanocobaltate and hexacyanoferrate, and after bringing the organic compound R into contact with the resulting double metal cyanide compound, excess solvent and It is produced by removing the organic compound R.

As the solvent for each salt solution, water or a mixed solvent of water and an organic solvent is used. The organic solvent of the mixed solvent is not particularly limited as long as it is compatible with water, and examples include alcohol, aldehyde, ketone, and ether. The mixing ratio of water and these organic solvents is preferably 50% or less, particularly preferably 30% or less by volume.

Any metal salt may be used as long as it dissolves and provides a cation of metal M, but salts of inorganic acids are preferred, and halides of chlorides, bromides, and iodides are particularly preferred. As M, the above-mentioned ones (various ones can be used, but among them, Zn(II), Fe(II), Fe(II)
I), Co(II), AIII and Co(II) are preferred, and furthermore Zn(II), Fe(III)
) is preferred.

Various metal salts including alkali metal salts can be used as the hexacyanocobaltate and hexacyanoferric salt, but lithium salts, sodium salts, potassium salts, magnesium salts and calcium salts are particularly preferred. Further, the cations of the hexacyanocobalt salt and the hexacyanoiron salt may be the same or different.

There are two types of hexacyanocobaltate ions, [Go(II)(CN)-]'- and [C:o(III)(CN)al''-], depending on the valence of the central metal nocobalt, and either one is acceptable. However, [C0(II
I)(CN)6]"- is preferable. Similarly, for hexacyanoferrate ion, [F
e(Il) (CN) sl'- and [Fe(m
) (CN) al ”-, either of which may be used, but a double metal cyanide complex with higher catalytic activity can be obtained [Fe (III) (CN) al
”- is preferred.

The abundance ratio of hexacyanocobaltate ion and hexacyanoferrate ion in the multimetal cyanide complex is such that when 2=0, the reaction rate is slow for 3'lZ in formula (1), and when z
/ (y+ z) is too large, the reaction amount per catalyst decreases, so 0 < z / (y + z)≦0.
8, more preferably 0.05≦z/
It is preferable that (y+z)≦0.6. Particularly preferably, 0.1≦z/(y+z)≦0.5.

The organic compound R included in formula (1) is diethyl ether,
1-Ethoxypentane, dibutyl ether, ethylpropyl ether, 1.2-dimethoxyethane, 1.2
- Ethers such as jetoxyethane, glyme, diglyme, triglyme, tetraglyme, diethylene glycol ethyl ether and diethylene glycol dibutyl ether, sulfides such as dimethyl sulfide, diethyl sulfide and dibutyl sulfide, nitriles such as acetonitrile and propionitrile, amyl formate, Esters such as ethyl acetate and methyl propionate,
Alcohols such as methanol, ethanol, propatool, isopropanol, butanol, tert-butyl alcohol, formaldehyde, acetaldehyde,
aldehydes such as benzaldehyde and acetone,
Ketones such as 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 it into contact with the compound complex is to add the organic compound R to a liquid in which a double metal cyanide compound is produced by mixing a metal salt solution, a mixed solution of hexacyanocobalt salt, and hexacyanoferrate, and to thoroughly stir the mixture. It will be done. Thereby, d in general formula (1) becomes 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, the catalyst is dispersed in organic compound R or a mixture of organic compound R and water, stirred thoroughly, and then excess liquid is removed. You can also do it repeatedly. Further, when the catalyst is dispersed in the organic compound R, it is not necessarily necessary to remove the organic compound R (it is also possible to use a mixture of the double metal cyanide complex in the form of a slurry 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 can remove excess water and organic compounds.

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-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 can be used depending on the purpose, but polyhydric hydroxy compounds, that is, polyhydroxy compounds, are used as polyether polyols useful as raw materials for polyurethane. 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, 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 ppn+, and 30 to 110 ppn+ based on the hydroxy compound used.
00pp 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 Example Various double metal cyanide complexes as shown in Table 1 were synthesized by the method described below, and their properties as catalysts for polyol synthesis were investigated.

Cyanide: In a 1.5 mol/42 zinc chloride aqueous solution, hexacyanocobaltate ions and hexacyanoferrate ions are present in the proportions shown in Table 1, and the total salt concentration is 0.4 mol/I.
The mixed solution of potassium hexacyanocobaltate and potassium hexacyanoferrate (potassium ferricyanide) in step 2 was slowly added dropwise without stirring. This produced a precipitate. The precipitate that does not contain hexacyanoferrate ions is white. The color of the precipitate gradually became yellowish as the content of hexacyanoferrate ions increased.

A 50% diglyme 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, stirred for 1 hour, and then filtered by suction filtration.
Further, the mixture was dispersed in diglyme and stirred for 1 hour, and then filtered again by suction-filtration to obtain a double metal cyanide complex. This material was dried in a drying oven at 80° C. for 3 hours, then finely ground and used in the next study of catalyst properties. Representative examples of the produced catalysts are shown in Table 1.

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, P015g, and 27 mg of various catalysts having different ratios of y and 2 synthesized as described above were placed in 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 Figure 1. The maximum temperature during the reaction increases when hexacyanoferrate ions are added (z/ (y+z)
The maximum value was reached at =0.2, and as the hexacyanoferrate ion was further increased, the value gradually decreased.

On the other hand, the time required for the internal pressure of the autoclave to drop to 1 atm represents the reaction rate, but when hexacyanoferrate ions are added, it gradually becomes shorter (z/ (y
The minimum value is reached at +z) = 0.5, and as the amount of cyanoferrate ion is increased further, the time becomes longer (i.e., O
<z/(y+z)≦0.8, a highly active catalyst for polyether synthesis was obtained.

Table-1 Middle 1 y and 2 in formula (1) Book 2 Coordinating water and diglyme were omitted.

Example 2 The following test was conducted using the double metal cyanide complex of Examples INo. 3 as a catalyst.

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. 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.

The amount of reaction PO per gram of catalyst was 14 kg-PO/g-catalyst, and the average molecular weight of the produced polyol was about 600.
It was 0.

Example 3 A double metal cyanide complex was synthesized in the same manner as in Example 1 except that the iron chloride in Examples INo. 3 was changed to ferric chloride. This compound was Fe [Co (CN) -] o ,a
[Fe(CN)s]. a (Hao), (digram), .

Using this double metal cyanide complex as a catalyst, the same synthesis test as in Example 8 was conducted, and as a result, the reaction po
The amount was 8 kg-PO/g-catalyst and the average molecular weight of the polyol produced was about 3900.

[Brief explanation of drawings]

FIG. 1 is a graph showing the relationship between the catalyst and its activity in Example 1 and Comparative Example.

Claims (1)

[Claims] 1. Ring-opening addition polymerization is carried out using a double metal cyanide complex containing both hexacyanocobaltate ion and hexacyanoferrate ion as a catalyst, and a cyclic ether alone or a hydroxy compound as an initiator. A method for producing a polyether compound. 2. The method according to claim 1, wherein the other metal ion of the double metal cyanide complex is a zinc or iron ion. 3. The number of hexacyanoferrate ions relative to the total number of hexacyanocobaltate ions and hexacyanoferrate ions in the double metal cyanide complex is 0.1 to 0.6.
The method according to claim 1.