JPH0459825A - Production of polyether - Google Patents

Abstract

PURPOSE:To obtain the title high-molecular weight polymer by using a low molecular weight initiator by subjecting a monoepoxide to ring opening addition reaction to plural initiators. CONSTITUTION:(A) A monoepoxide (e.g. propylene oxide) is blended with (B) a first initiator having <=1,000 molecular weight per hydroxyl group, (C) a second initiator having >=100 molecular weight per hydroxyl group and molecular weight higher than >= twice the molecular weight of the component B to give the ratio of the component B to the components B+C of 2-95wt.% and (D) 30-5,000 ppm based on the component C and reacted at 50-150 deg.C to give the objective polymer.

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 a hydroxyl group-containing compound represented by ASH)ll (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,
These include polyhydric phenols. Compounds having a hydroxyalkylamino group (alkanolamines, amines-alkylene oxide adducts, etc.) are also 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 -E+-R-0'r-HIn →R-(1: Ring-opening reaction unit of monoepoxide m: Integer Conventionally, as a method for producing polyethers, a method of reacting monoepoxide in the presence of an alkali catalyst has been used. Widely used. Alkali metal compounds such as potassium hydroxide and sodium hydroxide have been used as alkali catalysts.

However, polyethers obtained using an alkali catalyst have the following problems. In other words, an unsaturated monool produced by isomerization of a monoepoxide, especially propylene oxide, serves as an initiator, and 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 3278458. US 32784
59°US 3427256. US 3427334.
(US Pat. No. 3,427,335), this catalyst produces less of the unsaturated monools mentioned above, and is also capable of producing extremely high molecular weight polyethers.

[Problems to be Solved by the Invention] However, when producing polyethers using the above multimetal cyanide complex catalyst, if the initiator has a low molecular weight, the monoepoxide reaction will not occur or the reaction rate will be extremely slow. There is a problem. For this reason, conventionally it has been necessary to use an initiator with a certain degree of high molecular weight or to use a large amount of catalyst. However, the initiator having a high molecular weight is obtained by reacting a monoepoxide with a polyhydric alcohol, and it is difficult to use a multimetal cyanide complex catalyst for this reaction. The use of conventional alkaline catalysts in this reaction produces unsaturated monols, and the use of initiators containing these unsaturated monols offers the advantage of producing polyethers using multimetal cyanide complex catalysts. reduce

[Means for Solving the Problems] The present invention provides the following inventions that have been made to solve the above-mentioned problems.

In a method for producing polyethers by subjecting an initiator having at least one hydroxyl group to a ring-opening addition reaction of a monoepoxide in the presence of a multimetal cyanide complex catalyst, the first initiator has a molecular weight per hydroxyl group of 1000 or less. and a polyether-based second initiator whose molecular weight per hydroxyl group is 100 or more and at least twice the molecular weight per hydroxyl group of the first initiator, and the molecular weight per hydroxyl group is A method for producing polyethers, which comprises producing polyethers having an equivalent or higher quality than that of a second initiator.

According to the study of the present inventor, the catalytic action of the double metal cyanide complex is due to the etheric oxygen atom derived from the ring-opening unit of the monoepoxide in the vinyl shake (hereinafter, unless otherwise specified, the etheric oxygen atom is referred to as this monoepoxide). It is thought that some kind of interaction between the catalyst and the ethereal oxygen atom derived from the ring-opening unit of the epoxide is involved. As described below, a double metal cyanide complex is a complex coordinated with an organic ligand such as an ether. The high catalytic activity of the double metal cyanide complex with respect to an initiator made of a relatively high molecular weight polyether is thought to be due to the interaction between the initiator having an etheric oxygen atom and the catalyst. Therefore, it is thought that if a relatively high molecular weight initiator having this ether oxygen atom is used as a part of the initiator, the catalytic activity of the double metal cyanide complex will be increased, and the catalytic activity for low molecular weight compounds will also be increased.

The present invention has been completed based on this technical idea.

The second initiator in the present invention is a relatively high molecular weight initiator having the above etheric oxygen atom. The first initiator is a relatively low molecular weight initiator that conventionally did not exhibit sufficient catalytic activity with double metal cyanide complexes. This first initiator has no etheric oxygen atoms or a small number of etheric oxygen atoms compared to the second initiator.

When a mixed initiator consisting of a mixture of a first initiator and a second initiator is reacted with a sufficient amount of monoepoxide, polyethers of approximately equal molecular weight are obtained. The reason for this is that the monoepoxide does not react equally with both initiators, but reacts mainly with the first initiator, which has a low molecular weight, and the difference in molecular weight of the polyethers produced from each initiator is reduced, resulting in It is thought that the polyethers have approximately the same molecular weight. Alternatively, it is also conceivable that the telomerization activity of the catalyst is high and that the molecular weights of the produced polyethers are averaged together with the reaction of the monoepoxide, resulting in polyethers having approximately the same molecular weight. Therefore, for example, if both initiators have the same number of hydroxyl groups and the second initiator has the same oxyalkylene chain as the target polyether, it will be difficult to distinguish between the polyethers produced by both initiators. Thus, substantially only one type of polyether is obtained.

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),]l, (N20)c(R),
・(1) However, 1M is Zn(II), Fe(II
), Fe(III), Co(II), N1(II)
, Al(III), 5r(II), Mn(II), Cr
(m), Cu(II), 5n(II), Pb(If),
Mo(rV), Mo(Vl), W(TV), etc. W(
Vl), and M' is Fe(II), Fe(III)
, Co(II), Co(III), Cr(II)
), Cr(III), Mn(II), Mn(III),
N1 (II), v (rv), V (V), etc., and 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'
are Fe(II), Fe(I[[), Co(I[), Co
(III) etc. are preferred. Examples of organic ligands include ketones, ethers, aldehydes, esters, alcohols, amides, nitriles, and sulfides. Preferred are ethers, esters, alcohols, amides, and specific examples include ethylene glycol dimethyl ether, engineered ethylene glycol diethyl ether,
Examples include t-butanol and N,N-dimethylacetamide.

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. Z is hydrogen, alkali metal, alkaline earth metal, etc., e, f are positive integers determined by the valence and coordination number of Z and M'). Alternatively, it can be produced by mixing a solution of a mixed solvent of water and an organic solvent, bringing the obtained double metal cyanide into contact with the organic ligand R, and then removing the excess solvent and organic compound R.

Polycyanometalate (salt) Z-■M'-(CN)
y]-, 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.

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;
Trihydric alcohols such as glycerin, trimethylolpropane, and hexanetriol; tetravalent or higher alcohols such as pentaerythritol, diglycerin, dextrose, sorbitol, and sucrose; and alcohols obtained by reacting these alcohols with monoepoxides such as alkylene oxide. There are polyethers with a lower molecular weight than the target product. In addition, bisphenol A, resol,
Compounds with phenolic hydroxyl groups and methylol groups such as novolak, compounds with hydroxyl groups and other active hydrogens such as ethanolamine and jetanolamine, and amines and polyamines obtained by reacting these with monoepoxides such as alkylene oxides. There are polyethers with a lower molecular weight than the target product obtained by reacting monoepoxides such as alkylene oxides.

The first initiator is an initiator having a molecular weight per hydroxyl group of 1000 or less among the above-mentioned initiators. Preferably, the molecular weight per hydroxyl group is 200
Hereinafter, the initiator is particularly 100 or less. Preferably, this initiator does not have ether oxygen atoms, or even if it does, the number thereof is not more than twice the number of hydroxyl groups. Further, as the compound, monohydric or polyhydric alcohols, phenols, or alkylene oxide adducts thereof (the number of adducts is 2 molecules or less per hydroxyl group) are preferable.

The second initiator has a molecular weight per hydroxyl group of 100
The polyether initiator is above and has a molecular weight per hydroxyl group of at least twice the molecular weight per hydroxyl group of the first initiator. The molecular weight per hydroxyl group of the second initiator is 15
It is preferably 0 or more, particularly preferably 250 or more. The upper limit varies depending on the target polyether,
Usually, the molecular weight is slightly lower than the molecular weight per hydroxyl group of the target polyether. Furthermore, the molecular weight per hydroxyl group of the second initiator must be at least twice the molecular weight per hydroxyl group of the first initiator used together with it, and if the difference between the two molecular weights is small, the characteristics of the present invention are Not demonstrated. Preferably, the difference is 5 times or more, especially 10 times or more. Further, as the compound, monoepoxide adducts such as monohydric or polyhydric alcohols or alkylene oxides of phenols are preferable.

The amount of monoepoxide added is 1 or more per hydroxyl group,
In particular, it is preferable that the number is two or more.

Although the amount of the first initiator in the mixed initiator consisting of the first initiator and the second initiator (each initiator may be two or more types) is not particularly limited, 2-95% by weight, especially 5-8
Preferably, it is 0% by weight. The amount of the multi-metal cyanide complex catalyst used is not particularly limited, but is 30 to 5 ooopp for the second initiator used.
m is appropriate, and 100 to 2000 ppm is more preferable. The catalyst may be introduced all at once into the reaction system, or may be introduced in portions in sequence. but,
As mentioned above, it is thought that the catalyst has some kind of interaction with the second initiator, so it is preferable to use the catalyst and the second initiator mixed together in advance. For example, this mixture may be heated to enhance the interaction, or a second initiator synthesized using this multi-metal cyanide complex catalyst may be added to the main initiator while maintaining the activity of the catalyst contained therein. It is preferable to use it as a mixture of the second initiator and the catalyst in the invention.

In particular, it is preferable to use a second initiator containing an active catalyst obtained by reacting at least a portion of a monoepoxide in the presence of a catalyst.

The monoepoxide in the present invention is a monoepoxide having 2 or more carbon atoms, and particularly preferably an alkylene oxide having 2 or more carbon atoms. More preferably, alkylene oxides having 2 to 4 carbon atoms such as propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, epichlorohydrin, and ethylene oxide are 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.

As the polyethers obtained by the method of the present invention, polyoxyalkylene polyols are preferred. 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.

The molecular weight of the obtained polyethers is not particularly limited, but since the purpose of the present invention is to produce particularly high molecular weight polyethers as described above, the lower limit of the molecular weight is expressed by the hydroxyl value. It is preferably 60 or less, particularly 40 or less. There is no particular lower limit to the hydroxyl value, but it is usually about 5.

Polyethers are made by reacting a mixture of monoepoxide and initiator in the presence of a catalyst. Alternatively, the reaction may be carried out while gradually adding monoepoxide to the reaction system. An organic solvent may be present in the reaction system. Although the reaction occurs at room temperature, the reaction system can be heated or cooled if necessary.

Usually 50-150°C, preferably 80-120°C
will be adopted.

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.

EXAMPLES 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] (Example 1) Polyoxypropylene triol 1 with a weight average molecular weight of 2,000 synthesized using zinc hexacyanocopartate-glyme as a catalyst and containing the catalyst in an amount of I 000 ppm.
00 parts (by weight; the same applies hereinafter) was added with 9210 parts of Gukuse, and propylene oxide was added at 120°C to synthesize a polyoxypropylene triol having a weight average molecular weight of 6000. Looking at the molecular weight distribution of the polyoxypropylene triol after completion of the synthesis, it was found that the polyol had a single peak at a weight average molecular weight of 6,000.

(Example 2) 100 parts of ethylene glycol was added to 100 parts of polyoxypropylene diol with a weight average molecular weight of 1000, which was synthesized using zinc hexacyanocopartate-glyme as a catalyst and contained 800 ppm of the catalyst, and propylene oxide was added at 120°C. was added to synthesize polyoxypropylene diol having a weight average molecular weight of 1500. Looking at the molecular weight distribution of the polyoxypropylene diol after completion of the synthesis, it was found that the polyol had a single peak at a weight average molecular weight of 1,500.

(Example 3) Polyoxypropylene triol 100 with a weight average molecular weight of 1000 synthesized using zinc hexacyanocopartate-glyme as a catalyst and containing 300 ppm of the catalyst.
150 parts of glycerin was added to the mixture, and propylene oxide was added at 120° C. to synthesize polyoxypropylene triol having a weight average molecular weight of 1100. Looking at the molecular weight distribution of the polyoxypropylene triol after completion of the synthesis, it was found that the polyol had a single peak at a weight average molecular weight of 1,100.

(Comparative Example 1) 11,000 pp of zinc hexacyanocopaltate-glyme was added to glycerin, propylene oxide was added, and stirring was continued at 120°C for 2 hours, but the propylene oxide did not substantially react.

(Comparative Example 2) 300 ppm of zinc hexacyanocopartate glyme was added to methyl alcohol, propylene oxide was added, and stirring was continued at 120° C. for 3 hours, but the propylene oxide did not substantially react.

[Effects of the Invention] The present invention makes it possible to use a low molecular weight initiator, which was difficult to use in the past, when producing high molecular weight polyethers using a multimetal cyanide complex catalyst. be. Conventionally, it has been necessary to use polyester with a certain degree of high molecular weight as an initiator, or to use a large amount of catalyst. In the present invention, by using a low molecular weight initiator together with a polyether initiator whose molecular weight has increased to some extent, a high molecular weight polyether in which a monoepoxide is reacted with a low molecular weight initiator can be obtained. Furthermore, since polyethers with almost the same molecular weight as polyethers obtained from polyether initiators can be obtained, if the number of hydroxyl groups in the initiators is the same, it can be regarded as a single polyether. is obtained.

Claims (1)

[Claims] 1. At least 1 in the presence of a multimetal cyanide complex catalyst
In a method for producing polyethers by subjecting an initiator having hydroxyl groups to a ring-opening addition reaction with a monoepoxide, a first initiator having a molecular weight per hydroxyl group of 1000 or less and a first initiator having a molecular weight per hydroxyl group of 100 or more and A mixed initiator with a polyether-based second initiator having a molecular weight per hydroxyl group of at least twice the molecular weight per hydroxyl group of the first initiator is used, and the molecular weight per hydroxyl group of the first initiator is
A method for producing polyethers, characterized by producing polyethers whose initiator is equivalent to or higher than that of the initiator. 2. The first initiator is a monohydric or polyhydric alcohol, a phenol, or an alkylene oxide adduct thereof, and the molecular weight per hydroxyl group is 20
2. The method according to claim 1, wherein the amount is less than or equal to 0. 3. The second initiator is an alkylene oxide adduct of monohydric or polyhydric alcohols or phenols, has one or more oxyalkylene groups per hydroxyl group, and has a molecular weight per hydroxyl group of 150 or more. 2. The method of claim 1, wherein the polyether initiator is a polyether-based initiator. 4. The first initiator and the second initiator have the same number of hydroxyl groups, and the produced polyethers can be considered as a single polyether.
The method according to claim 1. 5. The amount of the first initiator in the mixed initiator is 5 to 80% by weight, and the amount of the multimetal cyanide complex catalyst is 100 to 20% by weight with respect to the second initiator.
2. The method of claim 1, wherein the amount is 00 ppm.