JP3068890B2 - Method for producing polyethers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing polyethers using a double metal cyanide complex catalyst.

[0002]

2. Description of the Related Art Polyethers such as polyoxyalkylene polyols obtained by ring-opening reaction of a monoepoxide such as an alkylene oxide with an initiator are used as raw materials for synthetic resins such as polyurethanes, surfactants, lubricants, and other uses. Widely used for The initiator is A-
(H) _n (A: a residue obtained by removing a hydrogen atom from a hydroxyl group of a hydroxyl group-containing compound, n: an integer of 1 or more).

[0003] Examples of the initiator include monohydric alcohol, polyhydric alcohol, monohydric phenol, polyhydric phenol and the like. Further, compounds having a hydroxyalkylamino group (alkanolamines, amines-alkylene oxide adducts, etc.) are also used as initiators. Further, polyethers obtained by reacting the above initiator with a monoepoxide are also used as the initiator.

[0004] Polyethers are the following compounds obtained by subjecting the above initiator to a ring-opening addition reaction of a monoepoxide. A [-(RO) _m -H] _n RO: ring-opened unit of monoepoxide m, n: an integer of 1 or more

Conventionally, as a method for producing polyethers, it has been known to produce polyethers using a double metal cyanide complex as a catalyst (US Pat. No. 3,278,457, US Pat.
3278458, US 3278459). This catalyst is able to produce a polyether unsaturated monol generation is small, also very high have molecular weight. The production method of the double metal cyanide complex catalyst is described in US 3427256, US 3941849, US 4472560,
It is proposed by US 4477589 specification and the like.

[0006]

In a method for producing a polyol using a double metal cyanide complex catalyst, a double metal cyanide complex and an initiator are charged into a reaction vessel, nitrogen replacement is performed, and then a monomer to be polymerized is supplied. And
Are reacting. However, this method has a disadvantage that the amount of monomers that can be polymerized with a certain amount of catalyst is small.

[0007]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems. That is, in a method for producing polyethers by subjecting a monoepoxide to ring-opening polymerization of an initiator in the presence of a double metal cyanide complex catalyst, a polyether characterized in that a surface active solid substance is present in a reaction system. Production method.

The double metal cyanide complex in the present invention is considered to have a structure represented by the following general formula (1). M ¹ _a [M ² _x (CN) _y ] _b (H ₂ O) _c R _d (1)

Where M ¹ is Zn (II), Fe (II), Fe (II)
(III), Co (II), Ni (II), Al (III), Sr (II), M
n (II), Cr (III), Cu (II), Sn (II), Pb (II),
Mo (IV), Mo (VI), W (IV), W (VI), V (V), etc., where M ² is Fe (II), Fe (III), Co (II), Co (I
II), Cr (II), Cr (III), Mn (II), Mn (III),
Ni (II), V (IV), V (V), etc., where R is an organic ligand, and a, b, x and y are positive integers which vary depending on the valence and coordination number of the metal. , C and d are positive numbers depending on the coordination number to the metal.

In the general formula (1), M ¹ is preferably Zn (II), and M ² is Fe (II), Fe (III), Co (II), Co (II).
I) is preferred.

[0011] As the organic ligand, an ether, an ester, an aldehyde, an ester, an alcohol, amide, nitrile, include sulfides, in particular ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, isopropyl alcohol, t-butanol, iso-flop <br / > It is preferable to use at least one ligand selected from propyl ether, n-butanol, and n-pentanol.

The double metal cyanide complex represented by the general formula (1) is composed of a metal salt M ¹ _Xa (M ¹ _and a are the same as described above, X is an anion forming a salt with M ¹ ) and polycyanometallate. (Salt) _Ze [M ² _x (CN) _y ] _f (M ² , x, y are the same as above. Z is hydrogen, alkali metal, alkaline earth metal, etc., and e and f are Z, M ² And a solution of a mixed solvent of water and an organic solvent, and contacting an organic ligand R with the obtained double metal cyanide, It is produced by removing excess solvent and organic ligand R.

The polycyanometallate (salt) _Ze [M ² _x (C
In N) _y ] _f , Z can use various metals including hydrogen and alkali metals, but lithium salts, sodium salts, potassium salts, magnesium salts, and calcium salts are preferred. Particularly preferred are ordinary alkali metal salts, ie, sodium and potassium salts.

The surface-active solid substance of the present invention refers to a solid whose surface is chemically active, and a powder is particularly preferable.
Since these have a hydrophilic group or hydratable ions on the surface, water molecules are likely to be adsorbed or condensed, and thus it is considered that they form a surface which is highly hydrophilic and easily reacts with other foreign molecules.

The surface active solid substance in the present invention includes an inorganic oxide. Examples include activated alumina, silica gel, titanium oxide and zirconium oxide, but are not limited thereto.

Further, the metal alkoxide hydrolyzate may be mentioned as other surface-active solid substances. Examples of metal alkoxides include silane alkoxides and aluminum alkoxides.
Alkoxide and titanium alkoxide
At least one type is preferable. More specifically, examples include, but are not limited to, tetraalkoxysilane, organotrialkoxysilane, diorganodialkoxysilane, tetraalkoxytitanium, organotrialkoxytitanium, trialkoxyaluminum, and the like. . The hydrolysis rate of the metal alkoxide is preferably 10 to 100 mol%.

Other surface active solid substances include zeolite, bentonite, diatomaceous earth and the like. The surface active solid substance of the present invention is not limited to these.

The polyether of the present invention is produced by reacting a mixture of a monoepoxide and an initiator in the presence of a catalyst and a surface-active solid substance. Further, the reaction can be carried out while gradually adding the monoepoxide to the reaction system. The reaction occurs at room temperature, but the reaction system can be heated or cooled if necessary.

The amount of the catalyst used is not particularly limited, but is suitably about 1 to 5000 ppm, more preferably 50 to 1000 ppm, for the initiator used. The catalyst may be introduced into the reaction system in a lump at first, or may be divided and introduced sequentially.

The amount of the surface-active solid substance used is from 0.1 to 150% by weight, especially from 1 to 90% by weight, based on the initiator.
Is preferred. The introduction of a surface-active solid substance into the reaction system
At first, they may be introduced all at once, or they may be introduced sequentially in a divided manner, but it is particularly preferable to use them by adding them to the initiator.

The polyethers obtained in the present invention are preferably polyoxyalkylene polyols. The polyoxyalkylene polyol is obtained by sequentially performing a ring-opening addition reaction of a monoepoxide such as an alkylene oxide to an initiator having at least two hydroxyl groups.

As the initiator, a polyhydroxy compound having 2 to 8 hydroxyl groups is particularly preferable. Examples of the polyhydroxy compound include dihydric alcohols such as ethylene glycol and propylene glycol, trihydric alcohols such as glycerin, trimethylolpropane, and hexanetriol; tetravalent or higher valents such as pentaerythritol, diglycerin, dextrose, sorbitol, and sucrose. There are alcohols and polyethers having a lower molecular weight than the target product obtained by reacting a monoepoxide such as an alkylene oxide with these alcohols.

Compounds having a phenolic hydroxyl group or a methylol group such as bisphenol A, resole and novolak, compounds having a hydroxyl group such as ethanolamine and diethanolamine and other active hydrogens, and monoepoxides such as alkylene oxide are reacted with these compounds. There are polyethers having a lower molecular weight than the target product obtained by the reaction.

Further, there are polyethers having a lower molecular weight than the target product obtained by reacting a monoamine or polyamine having at least two hydrogen atoms bonded to a nitrogen atom with a monoepoxide such as an alkylene oxide. In addition, phosphoric acid, its derivatives, and other polyhydroxy compounds can also be used. These polyhydroxy compounds may be used in combination of two or more.

The present invention is also applicable to a method for producing a polyether monol by subjecting a monovalent initiator to a ring-opening reaction of an alkylene oxide. Examples of the monovalent initiator include phenol derivatives such as methanol, ethanol, butanol, hexanol, other monols, phenols, and alkyl-substituted phenols.
And polyethers having a lower molecular weight than the target product obtained by reacting these with a monoepoxide such as an alkylene oxide.

Furthermore, one hydrogen atom bonded to a nitrogen atom
There are polyethers having a lower molecular weight than a target product obtained by reacting a monoamine or polyamine having one with a monoepoxide such as an alkylene oxide.

The alkylene oxide for producing the polyethers includes alkylene oxides having 2 to 4 carbon atoms, for example, ethylene oxide, propylene oxide,
1,2-butylene oxide, 2,3-butylene oxide and epichlorohydrin are preferred, and propylene oxide is particularly preferred. Two or more of these or other monoepoxides such as styrene oxide, glycidyl ether and glycidyl ester can be used in combination. In the case of using two or more alkylene oxides or using an alkylene oxide and another monoepoxide, they can be mixed and added or sequentially added to form a random polymerized chain or a block polymerized chain.

The molecular weight of the above polyethers is not particularly limited, but is preferably about 80 or less in terms of hydroxyl value. The lower limit is preferably about 5. In particular, a hydroxyl value of 5
~ 60 polyoxyalkylene polyols are preferred. The number of hydroxyl groups is 1 or more, preferably 2 to 8, and particularly preferably 2 to 6.

After producing the polyols, it is usually necessary to remove the double metal cyanide complex used as a catalyst from the obtained polyethers. As a method for removing the catalyst, a method described in the above-mentioned known document can be employed. For example, after deactivating the catalyst by adding an alkali,
There is a method of treating a catalyst component or an alkali deactivated with an adsorbent or an ion exchange resin and removing them by filtration or the like. However, the method of removing the double metal cyanide complex is not limited to these.

The polyethers obtained according to the present invention are:
It is most useful as a polyether polyol for polyurethane raw materials used alone or in combination with other polyols. The polyethers obtained according to the present invention are also used as raw materials and additives for synthetic resins other than polyurethane. Further, it can be used as lubricating oil, insulating oil, hydraulic oil, other oils, or as a raw material thereof. Further, the polyethers obtained according to the present invention can be converted into other compounds such as alkyl ether compounds and acyl compounds to be used for various applications.

[0031]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited only to these Examples.

[Complex metal cyanide complex catalyst] Complex metal cyanide complex catalyst A zinc hexacyanocobaltate diethylene glycol dimethyl ether complex catalyst Complex metal cyanide complex catalyst B zinc hexacyanocobaltate ethylene glycol dimethyl ether complex catalyst

Example 1 A polyoxypropylene triol having a molecular weight of about 500 was used as an initiator, and a double metal cyanide complex catalyst A was added at 250 ppm to the initiator. Further, activated alumina was added at 5% by weight to the initiator. Then, when propylene oxide was polymerized, a polyether polyol having a molecular weight of 6,500 was obtained.

Example 2 Polyoxypropylene triol having a molecular weight of about 500 was used as an initiator, and 400 ppm of a double metal cyanide complex catalyst B was added to the initiator. Further, 90 mol % hydrolyzed tetraethoxytitanium was added to the initiator. Then, the propylene oxide was polymerized to obtain a polyether polyol having a molecular weight of 9500.

Example 3 Polyoxypropylene diol having a molecular weight of about 500 was used as an initiator, and a mixed metal cyanide complex catalyst A was added at 300 ppm to the initiator, and triethoxy aluminum hydrolyzed by 85 mol % was further added to the initiator. And then polymerized with propylene oxide to obtain a polyether polyol having a molecular weight of 7,000.

Comparative Example 1 Polyoxypropylene triol having a molecular weight of about 500 was used as an initiator, and a composite metal cyanide complex catalyst A was added to the initiator at a concentration of 300 ppm, and then propylene oxide was polymerized. Only ether polyols were obtained.

[0037]

According to the method for producing polyethers using a double metal cyanide complex catalyst, the disadvantage that there are few monomers that can be polymerized with a certain amount of catalyst is eliminated.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-95217 (JP, A) JP-A-58-185621 (JP, A) European Patent Application 130458 (EP, A1) (58) Field (Int.Cl. ⁷ , DB name) C08G 65/00-65/48 WPI / L

Claims (6)

(57) [Claims] 1. A method for producing a polyether by subjecting an initiator to ring-opening polymerization of a monoepoxide in the presence of a double metal cyanide complex catalyst, wherein a surface-active solid substance is present in a reaction system. For producing polyethers. 2. The method according to claim 1, wherein the surface-active solid substance is a powder of an inorganic oxide. 3. The inorganic oxide is activated alumina, silica gel,
3. The method according to claim 2, wherein the method is at least one selected from titanium oxide and zirconium oxide. 4. The method according to claim 1, wherein the surface-active solid substance is a hydrolyzate of a metal alkoxide. 5. The metal alkoxide is a silane alkoxide,
The method according to claim 4, wherein the method is at least one selected from aluminum alkoxide and titanium alkoxide. 6. The hydrolysis rate of the metal alkoxide is 10-1.
The method according to claim 4 or 5, wherein the amount is 00 mol%.