JP3085740B2 - Method for producing polyethers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyether, and more particularly to a method for producing a polyether polyol.

[0002]

2. Description of the Related Art Polyethers such as polyoxyalkylene polyols obtained by a ring-opening addition 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 materials. Widely used for applications. The initiator is a hydroxyl group-containing compound represented by A- (H) _n (A: a residue obtained by removing a hydrogen atom of 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: monoepoxide ring-opened unit m, n: an integer of 1 or more

Hitherto, as a method for producing polyethers, a method of reacting a monoepoxide in the presence of an alkali catalyst represented by an alkali metal compound such as potassium hydroxide or sodium hydroxide has been widely used.

[0006] In the preparation of polyethers using an alkali catalyst unsaturated polyether monool (hereinafter referred to as unsaturated monool) is easily produced, in particular,
This tendency becomes remarkable as the molecular weight of the polyether increases, so that when propylene oxide was used as the monoepoxide, it was practically impossible to synthesize a polyether having a molecular weight of 6500 or more.

On the other hand, it is known to produce polyethers using a double metal cyanide complex as a catalyst (US Pat. Nos. 3,278,457, 3,278,458, and 32).
78459). The catalyst can also be produced polyethers of the unsaturated monol generation is small, also very high have molecular weight.

[0008] However, when ethylene oxide is supplied to the initiator using the above-mentioned double metal cyanide complex catalyst and the initiator is subjected to a ring-opening addition reaction of a monoepoxide having 3 or more carbon atoms, ethylene oxide is homopolymerized. Polyethylene glycol is formed, and no uniform addition of ethylene oxide to polyethers terminal hydroxyl groups occurs.

As a method of uniformly adding the ethylene oxide polyethers terminal obtained using a double metal cyanide complex catalysts are known a method using an alkali metal compound (US4355188, US472181
8, JP-B-59-15336, JP-A-2-27682
1). That is, it is a method of treating with an alkali metal compound to form an alcoholate.

[0010]

From an industrial point of view,
As the alcoholating agent, alkali metal hydroxide (JP-B-59-15336) and alkali metal alcoholate (JP-A-2-276821) are considered to be the most effective.

However, in using the alkali metal hydroxide in the conventional method, the following problems exist in consideration of the quality of the product after the reaction with ethylene oxide. When an alkali metal hydroxide is used, water is generated during alcoholation, but the boiling point of water is as high as 100 ° C.
Be removed until 0.01 wt% or less based on the polyether to affinity higher with polyethers, it is almost impossible, also not constant the residual amount.

Further, although not occur water with the alcoholate of the case of using an alkali metal alcoholate, it absorbs moisture in the air due to the high hygroscopicity of polyethers itself.

[0013] The polyethers after alcoholation are treated with 0.1.
If more than 04% by weight of water is present in the polyethers, this water will act as an initiator in the subsequent ethylene oxide feed to form polyethylene glycol. High molecular weight polyethylene glycol precipitates in polyethers and becomes cloudy.

Not only does the cloud point and turbidity onset temperature of the polyol itself vary greatly depending on the difference in the amount of polyethylene glycol produced, but also when the urethane is produced by reacting with the isocyanate, the reactivity with the isocyanate and the urethane produced Greatly affects the performance of

In an elastomer or the like manufactured using a polyol containing polyethylene glycol,
Cure properties and mechanical properties vary, and in the case of flexible foams, fatal phenomena such as variations in air permeability, rebound resilience, and permanent set under wet heat occur.

[0016]

SUMMARY OF THE INVENTION The present invention is the following invention which has been made to solve the above-mentioned problems.

That is, after a polyether having a hydroxyl group obtained by subjecting an initiator having at least one hydroxyl group to a ring-opening addition reaction with a monoepoxide having 3 or more carbon atoms to form an alcoholate, water in the reaction system is converted into a polyether. After removing 0.04% by weight or less based on ethers, 0.1 to 2 monoepoxides having 3 or more carbon atoms are introduced per one alcoholated hydroxyl group.
This is a method for producing polyethers having a hydroxyl group, which comprises introducing ethylene oxide and then decomposing the alcoholate to convert it to a hydroxyl group.

The present invention also provides an alcoholate of a hydroxyl group-containing polyether obtained by subjecting an initiator having at least one hydroxyl group to a ring-opening addition reaction of a monoepoxide having 3 or more carbon atoms, followed by alcoholation. Removing water until it is less than 0.04% by weight based on polyethers;
Then, a mixture of a monoepoxide having 3 or more carbon atoms and ethylene oxide is introduced in an amount of 0.3 to 10% by weight based on the polyether after alcoholation, and then ethylene oxide is further introduced. Then, the alcoholate is decomposed into hydroxyl groups. This is a method for producing a polyether having a hydroxyl group, which is characterized in that it is changed.

In the present invention, the method for producing the polyether to be alcoholated may be any method,
For example, a production method using an alkali catalyst, a double metal cyanide complex catalyst, a metalloporphyrin, or the like is adopted.
You can use. In particular, a method of producing using a double metal cyanide complex catalyst is preferable.

That is, the present invention provides a polyether having a hydroxyl group by subjecting an initiator having at least one hydroxyl group to a ring-opening addition reaction with a monoepoxide having 3 or more carbon atoms in the presence of a double metal cyanide complex catalyst, After alcoholating the polyethers in the presence of a catalyst, water in the reaction system is removed until the amount becomes 0.04% by weight or less with respect to the polyethers. This is a method for producing hydroxyl group-containing polyethers, which comprises introducing a mixture of ethylene oxide into an alcoholated hydroxyl group, further introducing ethylene oxide, and then decomposing the alcoholate into a hydroxyl group.

It is considered that the double metal cyanide complex in the present invention has a structure represented by the following general formula (1) as shown in the above-mentioned known examples.

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 (III), Co
(II), Ni (II), Al (III), Sr (II), Mn (II), C
r (III), Cu (II), Sn (II), Pb (II), Mo (IV),
Mo (VI), W (IV), W (VI), etc., where M ² is Fe (I
I), Fe (III), Co (II), Co (III), Cr (II), C
r (III), Mn (II), Mn (III), Ni (II), V (IV),
V (V), etc., where R is an organic ligand, a, b, x
And y are positive integers depending on the valence and coordination number of the metal, and 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. Examples of the organic ligand include ketone, ether, aldehyde, ester, alcohol, and amide.

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. e and f are atoms of Z and M ² (A positive integer determined by the valence and the coordination number) or a mixed solvent solution of water and an organic solvent, and contacting the obtained double metal cyanide with the organic ligand R. It is prepared by removing the solvent and excess organic ligand R.

Polycyanometallate (salt) _Ze [M
The ^{_{2 x (CN) y] f}} , although the Z may use a variety of metals, including hydrogen, alkali metal, lithium salt, sodium salt, potassium salt, magnesium salt, calcium salt. Particularly preferred are ordinary alkali metal salts, ie, sodium and potassium salts.

Polyethers produced using a double metal cyanide complex catalyst are usually produced by reacting a mixture of a monoepoxide and an initiator in the presence of a catalyst. 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. Although the amount of the catalyst used is not particularly limited, it is 1 to 5000 based on the initiator used.
ppm is appropriate, and 30 to 1000 ppm is more preferable. The catalyst may be introduced into the reaction system in a lump at first, or may be divided and introduced sequentially.

The polyether to be alcoholated in the method of the present invention is preferably a polyoxyalkylene polyol. 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 polyether monol produced by subjecting a monovalent initiator to a ring-opening addition reaction with a monovalent initiator. Examples of the monovalent initiator include methanol, ethanol, butanol,
There are monools such as hexanol, phenol derivatives such as phenol and alkyl-substituted phenol, and polyethers having a lower molecular weight than the target product obtained by reacting these with a monoepoxide such as an alkylene oxide. Further, 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 an alkylene oxide.

[0032] monoepoxide having 3 or more carbon atoms to be reacted with the initiator in the present invention, especially 3 carbon atoms
The above alkylene oxides are preferred. More preferably, propylene oxide, 1,2-butylene oxide,
It is an alkylene oxide having 3 to 4 carbon atoms such as 2,3-butylene oxide and epichlorohydrin , and most preferably propylene oxide.

These can be used alone or in combination of two or more thereof and other monoepoxides such as styrene oxide, glycidyl ether and glycidyl ester. 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.

In the present invention, as a method for converting a polyether having a hydroxyl group into an alcoholate, a method using an alkali metal compound as described above is preferable. Specifically, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkali metal alcoholates such as sodium alcoholate and potassium alcoholate can be used, but are not limited thereto.

The alkali metal hydroxide may be used alone or diluted as an aqueous solution. The alkali metal alcoholate may be used alone or diluted with an alcohol solution or the like.

In the present invention, the water present in the reaction system after the alcoholation is reduced by 0.00 to the polyethers.
It is removed to 4% by weight or less, preferably 0.03% by weight or less. The method of removing water may be any method.

After the removal of water, a monoepoxide having 3 or more carbon atoms or a mixture thereof with ethylene oxide is introduced into the alcoholated polyether, and then the ethylene oxide is reacted.

When only a monoepoxide having 3 or more carbon atoms is used, 0.1 to 2 per alcoholated hydroxyl group is used.
, Preferably 0.1 to 1 are introduced.

When a mixture of a monoepoxide having 3 or more carbon atoms and ethylene oxide is used, 0.3 to 10% by weight is introduced based on the alcoholated polyether.

The mixing ratio of the mixture of the monoepoxide having 3 or more carbon atoms and ethylene oxide is 10/90 to 90/1.
0 weight ratio is preferable, and especially 20 / 60-80 / 40 weight ratio is preferable.

[0041] monoepoxide having 3 or more carbon atoms referred to herein are the same as those of the previous SL. If the range of the amount of the monoepoxide used is within this range, there is no problem of a decrease in reactivity with isocyanate due to a decrease in the ratio of terminal primary hydroxyl groups.

In the present invention, a polyether is treated with an alkali metal compound or the like to alcoholate a hydroxyl group, and then ethylene oxide is introduced and a ring-opening addition reaction is performed. After the addition of ethylene oxide, the alcoholate is decomposed into hydroxyl groups. Unwanted substances such as a catalyst component and an alkali metal component can be separated by filtration or the like after the ethylene oxide reaction.

When a polyether is produced using a double metal cyanide complex catalyst, after removing water, a neutralizing agent such as an acid or a base, or a metal oxide such as a synthetic magnesium silicate, aluminosilicate, silica or zeolite is used. After treatment with an adsorbent such as a substance or an ion exchanger such as an anion exchange resin or a cation exchange resin, unnecessary substances are separated from polyethers by filtration or the like. This makes it possible to remove all catalyst residues and alkali residues from polyethers.

The molecular weight of the hydroxyl group-containing polyethers obtained in the present invention is not particularly limited.
However, products that are liquid at room temperature are preferred in terms of their use. The reaction amount of the monoepoxide with respect to 1 mol of the initiator is preferably at least about 10 mol, and more preferably at least about 50 mol. More preferably, polyethers obtained by reacting an average of at least about 10 molecules, particularly at least about 30 molecules per hydroxyl group of the initiator are preferred.

In terms of the hydroxyl value, it is suitably 200 or less, particularly 100 or less. For example, as a raw material of polyurethane, about to table ring hydroxyl value of 5 to 200, especially 5
~ 60 liquid polyether polyols are preferred. For other uses, for example, oil raw materials such as hydraulic oil, polyether poly (or mono) ol in the above range is also preferable.

The hydroxyl group-containing polyethers obtained by the present invention are most useful as polyols 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.

[0047]

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.

Table 1 shows polyoxypropylene triols (diols) obtained by reacting propylene oxide at about 120 ° C. using a zinc hexacyanocobaltate complex catalyst. These each had the molecular weight shown in Table 1.

[0049]

[Table 1]

[0050] [Example 1] was added 7.5g of 48% aqueous <br/> solvent solution of potassium hydroxide to the polyol A of 1000 g, 120 ° C., to remove up to 0.025 wt.% Moisture at 30Torr Thereafter, 17.4 g of propylene oxide and then 200 g of ethylene oxide were added and reacted at 120 ° C. for 3 hours. After the reaction, the product A is treated with an adsorbent (synthetic magnesium silicate) and filtered.
-1 was obtained.

[0051] [Comparative Example 1] Polyol A of 1000g were added 7.5g of 48% aqueous <br/> solvent solution of potassium hydroxide, as in Example 1 under the same conditions 0.025
The dehydration reaction was carried out to a weight%, immediately 200 g of ethylene oxide was added, and the reaction was carried out at 120 ° C. for 3 hours. After the reaction, the product A-2 was obtained in the same manner as in Example 1.

[0052] [Example 2] 1000g of polyol B was added 7.3g of 48% aqueous <br/> solvent solution of potassium hydroxide, 120 ° C., after removal of the water up to 0.030 wt% at 20 Torr, Mixture 2 of propylene oxide and ethylene oxide (50/50% by weight)
5.0 g and then 150 g of ethylene oxide are added,
The reaction was performed at 120 ° C. for 3 hours. After the reaction, the mixture was treated with an adsorbent (synthetic magnesium silicate) and filtered to obtain a product B-1.

Comparative Example 2 To 1000 g of polyol B was added 7.3 g of a 48% aqueous solution of potassium hydroxide.
A dehydration reaction was carried out to 0% by weight, immediately 150 g of ethylene oxide was added, and the reaction was carried out at 120 ° C. for 3 hours. After the reaction, the product B-2 was obtained in the same manner as in Example 1.

[0054] [Example 3] 48% sodium hydroxide to Polyol C of 1000g
Was added 5.7g of an aqueous solution, 120 ° C., after removal of the water up to 0.020 wt% at 30 Torr, propylene oxide 16.3 g, was then added ethylene oxide 250 g, the reaction was conducted for 3 hours at 120 ° C.. After the reaction, the product C is treated with an adsorbent (synthetic magnesium silicate) and filtered.
-1 was obtained.

[0055] [Comparative Example 3] 48% sodium hydroxide to Polyol C of 1000g
It was added 5.7g of an aqueous solution, 0.0 under the same conditions as in Example 3
A dehydration reaction was performed up to 20% by weight, and immediately 250 g of ethylene oxide was added, followed by a reaction at 120 ° C. for 3 hours.
After the reaction, the product was treated in the same manner as in Example 3 to obtain product C-2.

Table 2 shows the properties of the polyols obtained in Examples 1 to 3 and Comparative Examples 1 to 3. In Table 2, 1
Grade hydroxyl group (%) indicates the ratio of primary hydroxyl groups to all hydroxyl groups in the obtained polyol.

[0057]

[Table 2]

[Formulation Examples 1-4] Product A-1 is contained in an amount of 72 parts by weight (hereinafter referred to as "parts") and polymer polyol A-1-P (based on product A-1 and containing 20% by weight of an acrylonitrile addition polymer). ) 28 parts, water 3.2 parts, catalyst (Dabco-33LV) 0.6 parts, silicone foam stabilizer SRX-274C (manufactured by Toray Silicone)
1.0 part and a crosslinking agent (sorbitol having a hydroxyl value of 450)
Propylene oxide adduct) A polyol system consisting of 3.2 parts, tolylene diisocyanate T-80 (manufactured by Nippon Polyurethane) and polyphenylpolymethylene polyisocyanate MR-200 (manufactured by Nippon Polyurethane) as isocyanates at a weight ratio of 80/20. After blending the blended material with the index 105, 350 mm x 350
It was poured into a mold of 100 mm × 100 mm (mold temperature 60 ° C.) and cured at room temperature for 6 minutes.

The same procedure was performed for products B-1, A-2 and B-2. Table 3 shows the evaluations of the flexible foams of Formulation Examples 1 to 4.

[0060]

[Table 3]

[Formulation Examples 5 to 6] 88.0 parts of product C-1, 1,4-butanediol 1
2.0 parts, water 0.50 parts, catalyst (Dabco-33L
V) 1.30 parts, a foam stabilizer SF-1306 (manufactured by Shin-Etsu Chemical) 1.20 parts, and a modified isocyanate (molecular weight 150
0 modified with polyoxypropylene diol 4,4 '
Diphenylmethane diisocyanate, isocyanate content 20% by weight) at a liquid temperature of 30 ° C. in a mixer (4000 r.
pm), the mixture was poured into an aluminum mold (250 mm × 250 mm × 12 mm 2 ) having a mold temperature of 45 ° C., cured in an oven (45 ° C.) for 5 minutes, and then demolded.

The same procedure was performed for product C-2. Table 4 shows the evaluations of the elastomers of Formulation Examples 5 to 6.

[0063]

[Table 4]

[0064]

According to the present invention, ethylene oxide can be introduced into the terminal hydroxyl group of polyethers without producing polyethylene glycol, and polyethers suitable for elastomers and flexible polyurethane foams can be produced.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-1-301713 (JP, A) JP-A-60-199031 (JP, A) JP-A-57-76028 (JP, A) (58) Field (Int. Cl. ⁷ , DB name) C08G 65/00-65/48

Claims (5)

(57) [Claims] An alcohol having a hydroxyl group-containing polyether obtained by subjecting an initiator having at least one hydroxyl group to a ring-opening addition reaction with a monoepoxide having 3 or more carbon atoms is converted into an alcoholate. After removing 0.04% by weight or less based on ethers, 0.1 to 2 monoepoxides having 3 or more carbon atoms are introduced per one alcoholated hydroxyl group, and then ethylene oxide is further introduced. And then converting the alcoholate to a hydroxyl group to produce a hydroxyl group-containing polyether. 2. An alcoholate of a polyether having a hydroxyl group obtained by subjecting an initiator having at least one hydroxyl group to a ring-opening addition reaction of a monoepoxide having 3 or more carbon atoms, and then converting the water in the reaction system to a polyether. Removed to 0.04% by weight or less based on the ethers, and then a mixture of a monoepoxide having 3 or more carbon atoms and ethylene oxide was added to the polyethers after alcoholation in an amount of 0.3 to 10% by weight.
% By weight, ethylene oxide is further introduced,
Thereafter, a method for producing hydroxyl group-containing polyethers, characterized in that alcoholate is decomposed into hydroxyl groups. 3. The mixing ratio of a mixture of a monoepoxide having 3 or more carbon atoms and ethylene oxide is 10/90 to 90/1.
0 is a weight ratio, The method of claim 2 wherein. 4. alcoholation poly ethers, polyethers having a hydroxyl group with the number 3 or more monoepoxides carbon by ring-opening addition reaction to the initiator having the presence of at least one of the hydroxyl groups of the composite metal cyanide complex catalyst 4. The process according to claim 1 , 2 or 3 , wherein the polyethers are obtained by alcoholating the polyethers in the presence of the catalyst. After 5. reacted ethylene oxide, to remove the catalyst component and the alkali metal component from polyethers process according to claim 4, wherein.