JPH03244632A - Production of polyether - Google Patents

Abstract

PURPOSE:To easily produce a polyether with a high primary hydroxyl content by reacting a polyether with a mixture of ethylene oxide and another monoepoxide in the presence of a composite metal cyanide complex catalyst. CONSTITUTION:A polyether with a high primary hydroxyl content is easily produced by reacting a polyether having at least one hydroxyl group with a mixture of ethylene oxide and a 3C or higher monoepoxide (e.g. propylene oxide) in the presence of a composite metal cyanide complex catalyst of the formula [wherein M is Zn(II), Fe(II), Co(II), Al(III), Mn(II), Mo(IV), etc.; M' is Fe(II), Fe(III), Co(II), Co(III), etc.; R is an org. ligand (e.g. a ketone, ether, aldehyde, ester, alcohol, amide, etc.); and (a), (b), (x), (y), (c), and (d) are each a positive integer].

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. [Prior art] Polyethers obtained by ring-opening reaction of monoepoxides such as alkylene oxides as initiators are widely used as raw materials for synthetic resins such as polyurethane, surfactants, lubricants, and other uses. . The initiator is ASH). 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.) can also be 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 of monoepoxide m: Integer Conventionally, a method of reacting monoepoxide in the presence of an alkali catalyst has been widely used as a method for producing polyethers. Alkali metal compounds such as potassium oxide and sodium hydroxide were used. However, polyethers obtained using alkali catalysts had the following problems: isomerism of monoepoxides, especially propylene oxide; The unsaturated monool produced by the reaction acts as an initiator, and a monoepoxide is added to it by ring-opening to create 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 It was virtually impossible to synthesize this kind. On the other hand, it is known that polyethers can be produced using multimetal cyanide complexes as catalysts (US 32
78457. US 327845g, US 32784
59°US 3427256. US 3427334.
US 3427335). This catalyst produces less of the above-mentioned unsaturated monools and is also capable of producing extremely high molecular weight polyethers.

[Problem to be solved by the invention]

However, the above multimetal cyanide complex catalyst has the following problems. That is, it has been difficult to react ethylene oxide to the terminal hydroxyl group of polyethers using a metal cyanide complex as a catalyst. When a multimetal cyanide complex is used as a catalyst and ethylene oxide is subsequently fed to polyethers obtained by a ring-opening reaction of a monoepoxide having 3 or more carbon atoms as an initiator,
Polyethylene glycol, which is a homopolymer of ethylene oxide, is produced, and ethylene oxide is not uniformly added to the terminal hydroxyl groups of polyethers. A known method is to treat a multimetal cyanide complex catalyst with an alkali to deactivate the catalyst, then add ethylene oxide, and then remove the catalyst residue. In this case, ethylene oxide is added to the terminal hydroxyl group of the polyether by the action of an alkali catalyst. As a method for treatment with an alkali, methods using alkali metals, alkali metal hydroxides (see Japanese Patent Publication No. 59-15336), and alkali metal hydrides (see Japanese Patent Application Laid-open No. 1-229035) are known. However, this method requires the use of two different types of catalysts, making it a complicated production method. Furthermore, simple alkali metals and alkali metal hydrides are dangerous to handle, and alkali metal hydroxides have problems such as the dehydration process taking a long time, especially when polyethers have a high molecular weight. [Means for Solving the Problems] The present invention provides the following inventions to solve the above-mentioned problems. Polyethers having a high proportion of primary hydroxyl groups are prepared by reacting polyethers having at least 19 hydroxyl groups with a mixture of ethylene oxide and a monoepoxide having 3 or more carbon atoms in the presence of a multimetal cyanide complex catalyst. Production method. Conventionally, it has been widely practiced to produce polyoxyalkylene polyols by reacting a mixture of ethylene oxide and a monoepoxide such as propylene oxide with an initiator using an alkali catalyst. Also,
It has also been widely practiced to increase the proportion of primary hydroxyl groups by reacting polyoxyalkylene polyols with a low proportion of primary hydroxyl groups with ethylene oxide in the presence of an alkali catalyst. Ethylene oxide is more reactive than other monoepoxides, so in the former case, ethylene oxide tends to react faster than other monoepoxides;
Therefore, the terminal groups of the resulting polyoxyalkylene polyol have a high proportion of residues of other monoepoxides,
Therefore, the proportion of primary hydroxyl groups is low. In the latter case, when other monoepoxides are mixed and reacted with ethylene oxide, the proportion of primary hydroxyl groups will be much lower than in the case where it is assumed that both react equally. On the other hand, as mentioned above, when attempting to react polyethers with ethylene oxide using a multimetal cyanide complex as a catalyst, polyethylene glycol, which is a homopolymer of ethylene oxide, grows, and the terminal hydroxyl groups of polyethers grow. Uniform addition of ethylene oxide to the ethylene oxide does not occur. The present inventor has discovered that when ethylene oxide and a monoepoxide are mixed and reacted using a multimetal cyanide complex as a catalyst, both react with the terminal hydroxyl group of polyethers. Unlike the case with alkali catalysts, ethylene oxide is not particularly reactive compared to other monoepoxides, and the two react almost uniformly. Therefore, unless the proportion of ethylene oxide is particularly high, an ethylene oxide homopolymer will not be formed, and the proportion of primary hydroxyl groups in the original polyether (this proportion needs to be lower to some extent) will not be produced. Therefore, polyethers having a high proportion of primary hydroxyl groups can be obtained. In addition, in the present invention, the polyethers before reacting the ethylene oxide-containing mixture are not necessarily limited to polyethers obtained using a multimetal cyanide complex as a catalyst. However, polyethers obtained using a multimetal cyanide complex as a catalyst are advantageous because they can be subsequently reacted with an ethylene oxide-containing mixture. The present invention will be explained in more detail below. 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), ], (H20)e(R), -(
1) However, M is Zn(II), Fe(II), Fe
(ITI), Co(II), N1(II), Al(I
II), 5r(II), Mn(II). Cr(III), Cu(■), 5n(TI), Pb(I
I), Mo(IV), Mo(Vl 1. W(IV
), etc. W(Vl), and M′ is Fe(IT)
, Fe(III), Co(II), Co(I
II), Cr(IT), Cr(III), Mn(
II), Mn(III), N1(II), V
(IV) V (V) etc., 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 positive numbers that vary depending on the coordination number of the metal. M in general formula (1) is preferably Zn(II) M'
is Fe(IT), Fe(III 1. Co(II)
, Go(III), etc. are preferred. Examples of organic ligands include ketones, ethers, aldehydes, esters, alcohols, and amides. As mentioned above, the double metal cyanide complex represented by the general formula (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'). Alternatively, after mixing a solution of a mixed solvent of water and an organic solvent and bringing the obtained double metal cyanide into contact with the organic ligand R,
It is produced by removing excess solvent and organic compound R. Polycyanometalate (salt) Z-[M'x(CN)y
In lr, various metals including hydrogen and alkali metals can be used for Z, 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. Alternatively, the reaction can be carried out while gradually adding monoepoxide to the reaction system. Although the reaction occurs at room temperature, the reaction system can be heated or cooled if necessary. The amount of catalyst used is not particularly limited, but is 1 to 5,000 per initiator used.
Approximately ppm is appropriate, and 30 to 11,000 ppm is more preferable. The catalyst may be introduced all at once into the reaction system, or may be introduced in portions in sequence. By using this double metal cyanide catalyst, it is possible to synthesize polyethers with a low content of unsaturated monols, or with a low content of unsaturated monols and an extremely high molecular weight. As the polyether before reacting the ethylene oxide-containing mixture in the present invention, polyoxyalkylene polyol is preferable. A polyoxyalkylene polyol is obtained by subjecting an initiator having at least two hydroxyl groups to a monoepoxide such as an alkylene oxide through a sequential ring-opening addition reaction. As the initiator, 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, and trihydric alcohols such as glycerin, trimethylolpropane, and hexanetriol. , pentaerythritol, diglycerin, dextrose, sorbitol,
There are polyethers having a molecular weight lower than the target product obtained by reacting tetrahydric or higher alcohols such as sucrose and monoepoxides such as alkylene oxides with these alcohols. In addition, compounds with phenolic hydroxyl groups and methylol groups such as bisphenol A, resol, and novolac, compounds with hydroxyl groups and other active hydrogens such as ethanolamine and jetanolamine,
There are also polyethers having a lower molecular weight than the target product obtained by reacting these with monoepoxides such as alkylene oxides. Furthermore, there are polyethers having a lower molecular weight than the target product obtained by reacting a monoepoxide such as an alkylene oxide with a monoamine or polyamine having at least 62 hydrogen atoms bonded to a nitrogen atom. In addition, phosphoric acid, its derivatives, and other polyhydroxy compounds can also be used. These polyhydroxy compounds are 2
More than one species can also be used together. The present invention can also be applied to a method for producing a polyether monool by subjecting a monovalent initiator to a ring-opening reaction with a monoepoxide. Examples of monovalent initiators include methanol,
There are polyethers having a lower molecular weight than the target product obtained by reacting ethanol, butanol, hexanol, other monools, phenol, phenol derivatives such as alkyl-substituted phenols, and monoepoxides such as alkylene oxides. Furthermore, there are polyethers having a lower molecular weight than the target product obtained by reacting a monoamine or polyamine having one hydrogen atom bonded to a nitrogen atom with a monoepoxide such as alkylene oxide. The monoepoxide in the present invention is a monoepoxide having 3 or more carbon atoms, and particularly preferably an alkylene oxide having 3 or more carbon atoms. More preferably, alkylene oxides having 3 to 4 carbon atoms, such as propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, and epichlorohydrin, are most 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. However, as mentioned above, it is difficult to directly react ethylene oxide with an initiator or polyether using a composite metal cyanide as a catalyst. For this reason, for example, in the presence of this catalyst, it is difficult to uniformly react a mixture of ethylene oxide and other monoepoxides using a large amount of ethylene oxide compared to the initiator or polyethers. However, a hydroxy compound having an oxyethylene group, such as a polyoxyalkylene polyol having an oxyethylene group, can be used as an initiator. The molecular weight of the polyethers is not particularly limited, but is preferably about 80 or less in terms of hydroxyl value. The lower limit is preferably about 5. Particularly preferred is polyoxyalkylene bool having a hydroxyl value of 5 to 60. As mentioned above, the polyethers need to have a low proportion of primary hydroxyl groups for the purpose of the present invention. Although not particularly limited, the proportion of primary hydroxyl groups is suitably 50% or less, particularly preferably 30% or less. The proportion of primary hydroxyl groups in polyethers obtained by ring-opening addition polymerization of only propylene oxide using a composite metal cyanide complex is usually 15% or less. Furthermore, the proportion of primary hydroxyl groups in polyethers obtained by applying the present invention by reacting a mixture of ethylene oxide and other monoepoxides is 20% higher than the proportion of primary hydroxyl groups in the above-mentioned original polyethers. It is preferable that the score is higher than the points. For example, if the proportion of primary hydroxyl groups in the original polyether is 10%, the proportion of primary hydroxyl groups in the obtained polyether is 30%.
% or more. Similarly, when the original content is 20%, the obtained product is preferably 40% or more. The proportion of primary hydroxyl groups in the polyethers obtained in the present invention is 30 to 80%.
is appropriate, and 40 to 70% is particularly preferable. As the other monoepoxide in the mixture of ethylene oxide and other monoepoxide to be reacted with polyethers in the presence of a composite metal cyanide complex, alkylene oxide having 3 to 4 carbon atoms is preferable as described above, and propylene oxide is most preferable. It is. Further, the mixing ratio of ethylene oxide and other monoepoxide is preferably 90/10 to 40/60 expressed as a weight ratio of ethylene oxide/other monoepoxide. Particularly preferred is 90/10 to 60/40. The amount of this mixture relative to 100 parts by weight of the polyether is preferably 5 to 50 parts by weight, particularly 10 to 40 parts by weight. After reacting the ethylene oxide-containing mixture, it is usually necessary to remove the multimetal cyanide complex used as a catalyst from the polyethers obtained. As a method for removing the catalyst, methods described in the above-mentioned known documents can be employed. For example, there is a method of adding an alkali to deactivate the catalyst, then treating the deactivated catalyst components and alkali with an adsorbent or ion exchange resin, and removing them by filtration or the like. However, methods for removing the multimetal cyanide complex are not limited to these. The molecular weight of the polyethers finally obtained is not particularly limited, but products that are liquid at room temperature are preferred from the standpoint of their use. The hydroxyl value of this polyether is preferably about 70 or less, particularly preferably from 5 to 40. The number of hydroxyl groups is 1 or more, preferably 2-8, particularly preferably 2-6. 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. 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] The following polyoxypropylene polyol has a molecular weight of 5
00 polyoxypropylene triol as an initiator, a zinc hexacyanocopartate complex catalyst was added thereto, propylene oxide was supplied, and the temperature was heated to about 120°C.
It is a polyoxypropylene triol obtained by reacting until a predetermined molecular weight is reached. The polyoxypropylene triol produced contains the following amounts of catalyst. Polyol A: Zinc hexacyanocopartate complex 20
Polyoxypropylene triol polyol B with a molecular weight of 5000 containing 0 ppm; zinc hexacyanocopartate complex 30
Polyoxypropylene triol polyol C with a molecular weight of 7000 containing 0 ppm; zinc hexacyanocopartate complex 40
Example of polyoxypropylene triol with a molecular weight of 9000 containing 0 ppm! 1,200 g of polyol A was placed in an autoclave, and after sufficient nitrogen substitution, the temperature was raised to 120°C, and the P of propylene oxide (PO) and ethylene oxide (EO) was heated to 120°C.
400 g of a mixture of O10E=20/80 (weight ratio; the same applies hereinafter) was charged, and the reaction was carried out at 120°C for 2 hours. The obtained polyol was transparent, and the proportion of primary hydroxyl groups was 57.5%. Comparative Example 1 Mixture 4 of propylene oxide and ethylene oxide
Polyol A was reacted with ethylene oxide under the same conditions as in Example 1, using 300 g of ethylene oxide instead of 00 g. The obtained polyol was in the form of a cloudy gel, and the proportion of primary hydroxyl groups was 13%. Example 2 81,200 g of polyol was charged into an autoclave, and after sufficient nitrogen substitution, the temperature was raised to 120°C, and the PO10E of propylene oxide and ethylene oxide = 20/
400 g of a mixture of No. 80 was added, and the reaction was carried out at 120° C. for 3 hours. The obtained polyol was transparent, and the proportion of primary hydroxyl groups was 56.0%. Comparative Example 2 Mixture 4 of propylene oxide and ethylene oxide
Polyol B was reacted with ethylene oxide under the same conditions as in Example 2, using 300 g of ethylene oxide instead of 00 g. The obtained polyol was in the form of a cloudy gel, and the proportion of primary hydroxyl groups was 12%. Example 3 1,600 g of polyol C was charged into an autoclave, and after sufficient nitrogen substitution, the temperature was raised to 120°C, and PO10E of propylene oxide and ethylene oxide = 20/
80 was added, and the reaction was carried out at 120° C. for 3 hours. The obtained polyol was transparent, and the proportion of primary hydroxyl groups was 55.0%. Comparative Example 3 Mixture 5 of propylene oxide and ethylene oxide
Polyol C was reacted with ethylene oxide under the same conditions as in Example 3 using 400 g of ethylene oxide instead of 00 g. The obtained polyol was in the form of a cloudy gel, and the proportion of primary hydroxyl groups was 11%. [Effects of the Invention] The present invention makes it possible to primaryize the terminal hydroxyl groups of polyethers, which has been virtually impossible using conventional multimetal cyanide complex catalysts. That is, by reacting polyethers with a d-compound of ethylene oxide and another monoepoxide in the presence of a multimetal cyanide complex catalyst, it became possible to primaryize the terminal hydroxyl group. Therefore, by applying the present invention to the production of polyethers using a multimetal cyanide complex catalyst, 1
Polyethers with a high proportion of hydroxyl groups can be easily produced.

Claims (1)

[Claims] 1. A primary product characterized by reacting a polyether having at least one hydroxyl group with a mixture of ethylene oxide and a monoepoxide having 3 or more carbon atoms in the presence of a multimetal cyanide complex catalyst. A method for producing polyethers with a high proportion of hydroxyl groups. 2. At least 1 in the presence of a multimetal cyanide complex catalyst
Polyethers containing the above catalyst obtained by ring-opening addition reaction of a monoepoxide having 3 or more carbon atoms with an initiator having 3 or more hydroxyl groups, and ethylene oxide and 3 carbon atoms.
2. The method of claim 1, wherein a mixture of the above monoepoxides is reacted. 3. The mixture weight ratio of ethylene oxide/monoepoxide having 3 or more carbon atoms in the mixture of ethylene oxide and monoepoxide having 3 or more carbon atoms is 90/10 to 40/60.
The method according to claim 1, wherein: 4. Monoepoxide with 3 or more carbon atoms has 3 to 4 carbon atoms
The method according to claim 1, 2, or 3, wherein the alkylene oxide is an alkylene oxide. 5. The polyether before reacting the ethylene oxide-containing mixture has a hydroxyl value of 80 or less and a hydroxyl group number of 2 to 8,
It is a polyoxyalkylene polyol with a primary hydroxyl group proportion of 50% or less, and the polyether after reacting with the ethylene oxide-containing mixture has a hydroxyl value of 70 or less, a hydroxyl group number of 2 to 8, and a primary hydroxyl group proportion of the original. 2 than the proportion
% of the polyoxyalkylene polyol that is 0 points or more higher.