JP2002201263A - Process for producing polyether - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for efficiently producing a polyether that contains a reduced amount of a catalyst. SOLUTION: The process for producing a polyether comprises treating a catalyst-containing polyether obtained by ring opening polymerization of a 3C or more monoepoxide in the presence of a composite metal cyanide complex catalyst with a treating agent comprising zinc oxide in the presence of water to deactivate the catalyst and then removing the deactivated catalyst and the treating agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a polyether, and more particularly, to a method for producing a polyether having a low catalyst content.

[0002]

2. Description of the Related Art Polyethers are used in large quantities in a wide range of applications such as raw materials for synthetic resins, raw materials for surfactants and raw materials for lubricating oils, and are produced on an industrial scale. The polyether can be produced by subjecting a monoepoxide such as an alkylene oxide to ring-opening polymerization with an initiator having at least one or more hydroxyl groups.

[0003] Conventionally, polyether production methods include:
A method of using an alkali catalyst such as an alkali metal hydroxide or an alkali metal alkoxide for the ring-opening polymerization of a monoepoxide has been generally used. However, the method for producing polyether using an alkali catalyst has some problems.

[0004] Specifically, when the molecular weight distribution of the polyether is widened and the monoepoxide is propylene oxide, a monol having an unsaturated group is formed by isomerization of propylene oxide, and the propylene oxide is opened. Cycloaddition produces unsaturated polyether monools having an unsaturated group at one end, and not only does not provide the desired polyol, but also virtually no high molecular weight polyether. Was.

[0005] In particular, when a polyether containing an unsaturated polyether monol at one end is used as a raw material for a resin, that is, a raw material for polyurethane, the presence of the unsaturated group may cause the desired reaction to be incomplete, resulting in an unsatisfactory reaction. This is a very serious problem in that it has a bad influence on the physical properties of the obtained polyurethane resin.

As a catalyst for solving these problems, a double metal cyanide complex catalyst is known (US Pat. No. 3,278,387).
457, U.S. Pat. No. 3,278,458, U.S. Pat.
59, U.S. Pat. No. 3,427,256, U.S. Pat.
4, U.S. Pat. No. 3,327,335), which is very useful in that the content of unsaturated polyether monol can be significantly reduced and that a polyether having an extremely high molecular weight can be obtained.

However, it is very difficult to remove the catalyst from a crude polyether obtained by ring-opening polymerization of a monoepoxide having 3 or more carbon atoms using a double metal cyanide complex catalyst. The catalyst cannot be removed by the adsorption treatment.

[0008] Removal of the catalyst is very important in practical use because the residual catalyst in the polyether makes it difficult to control the reaction when used as a raw material for polyurethane and adversely affects the physical properties of the obtained polyurethane resin. Technology.

As a method for removing the catalyst, there is known a method in which the catalyst is deactivated by treating with an alkali metal compound, a specific alkaline earth metal compound or a Lewis acid compound, and then treated with an adsorbent or the like. , The amount of catalyst cannot be reduced to the extent that it can be used practically;
Furthermore, there are many problems that need to be solved for practical use, such as complicated handling of treatment agents.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a polyether capable of efficiently producing a polyether having a very small catalyst content.

[0011]

According to the present invention, there is provided a method for treating a catalyst by using zinc oxide in the presence of water as a treating agent for a catalyst.
An object of the present invention is to provide a method for solving the above various practical problems.

That is, the present invention provides a polyether containing a catalyst obtained by subjecting a monoepoxide having 3 or more carbon atoms to ring-opening polymerization in the presence of a double metal cyanide complex catalyst, containing zinc oxide in the presence of water. After the catalyst is deactivated by treating with a treating agent to be treated, the deactivated catalyst (catalyst decomposed product) and the treating agent are removed, and the treating agent removes zinc oxide from water. The present invention relates to the above method for producing a polyether, which is a zinc oxide-water dispersion in the form of a slurry dispersed in water.

[0013]

DETAILED DESCRIPTION OF THE INVENTION In the present invention, a polyether is produced by ring-opening polymerization of a monoepoxide having 3 or more carbon atoms. Examples of the monoepoxide having 3 or more carbon atoms include propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, epichlorohydrin, styrene oxide, glycidyl ethers and the like. Monoepoxides can be used alone or in combination of two or more.

The polyether is preferably a polyoxyalkylene polyol, and a compound having at least two or more active hydrogens is used as an initiator for the ring-opening polymerization of a monoepoxide.

The active hydrogen compound is preferably a polyhydroxy compound having two or more hydroxyl groups. Examples thereof include dihydric alcohols such as ethylene glycol and propylene glycol, trihydric alcohols such as glycerin and trimethylolpropane, and pentaerythryl. , Dextrose, sorbitol, sucrose and the like.

An alkylene oxide is added to a compound having a phenolic hydroxyl group or a methylol group such as bisphenol A, a compound having a hydroxyl group and another active hydrogen such as ethanolamine or diethanolamine, a polyhydroxy compound or another active hydrogen compound. A polyhydroxy compound such as a compound obtained by the above method can also be used.

The molecular weight of the initiator is not particularly limited as long as it is lower in molecular weight than the target polyether. However, in commercial production, it is preferably 2 in terms of the reaction rate and the quality of the initiator. Functional or trifunctional polyethers having a number average molecular weight of 200 to 2000 can be used as initiators.

In the present invention, a double metal cyanide complex is used as a catalyst in the ring-opening polymerization of a monoepoxide. The double metal cyanide complex can be represented, for example, by the formula (1). M _a [M ′ _x (CN) _y ] _b (H ₂ O) _c · (R) _d (1)

In the formula (1), M and M 'are metals, R is an organic ligand, a, b, x and y are positive integers depending on the valence and coordination number of the metal; Is a positive integer depending on the coordination number of the metal.

As the metal M, Zn (II), Fe (I
I), Fe (III), Co (II), Ni (II), Al (II
I), Sr (II), Mn (II), Cr (III), Cu (I
I), Sn (II), Pb (II), Mo (IV), Mo (V
I), W (IV), W (VI), etc.
n (II) is preferably used.

As the metal M ′, Fe (II), Fe (II)
I), Co (II), Co (III), Cr (II), Cr (II
I), Mn (II), Mn (III), Ni (II), V (I
V) and V (V), among which Fe (II),
Fe (III), Co (II) and Co (III) are preferably used.

Examples of the organic ligand R include ketones, ethers, aldehydes, esters, alcohols, amides, nitriles, sulfides and the like, among which ethers, esters, alcohols and amides are preferable.
Specifically, examples of the ether include ethylene glycol dimethyl ether and ethylene glycol diethyl ether, examples of the alcohol include t-butanol, and examples of the amide include N, N-dimethylacetamide.

The double metal cyanide complex is usually used in an amount of 0.005 to 5.0%, preferably 0.02 to 2.0%, based on the reaction raw material (total amount of the monoepoxide and the initiator).
Can be used. If the amount of the double metal cyanide complex is too small, the reaction rate decreases and the reaction step requires a long time, which is not suitable for commercial production. Furthermore, there is a possibility that the quality of the product may be deteriorated due to the high temperature condition for a long time. Conversely, if the amount is too large, not only a large amount of catalyst treating agent is required, but also a long time is required for filtration in the purification step. In addition, the quality of the resulting product may be significantly reduced. Specifically, there is a possibility that a product having a desired molecular weight distribution cannot be obtained, an amount of a by-product increases, a product viscosity increases, and a hue becomes poor.

Monoepoxides are, for example, 80-180
C., preferably 90-150.degree. If the polymerization temperature is too low, the reaction rate decreases and the reaction step requires a long time, which is unsuitable for commercial production. Conversely, if the polymerization temperature is too high, the quality of the resulting product may be significantly reduced. Specifically, there is a possibility that a product having a target molecular weight distribution cannot be obtained, an amount of a by-product increases, and a hue becomes poor. Also,
The double metal cyanide complex catalyst may be thermally decomposed and the catalytic activity may be significantly reduced during the reaction.

In the present invention, for example, a polyether having a number average molecular weight of 500 to 20,000 can be obtained as a reaction crude product.

In the present invention, the catalyst contained in the crude reaction product is decomposed and deactivated using a treating agent containing zinc oxide. In the present invention, the reaction crude is treated in the presence of water. When the treatment is carried out in the absence of water, not only the decomposition of the catalyst becomes incomplete, but also problems such as a decrease in filterability, coloring and turbidity of the product occur. For example,
By using a zinc oxide-water dispersion in the form of slurry in which zinc oxide is dispersed in water as the treatment agent, the treatment can be performed in the presence of water.

The treating agent can be used in an amount of, for example, 0.02 to 30 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the reaction crude product, in terms of zinc oxide. If the amount of the treating agent is too small, the decomposition of the catalyst becomes incomplete, not only the filterability is significantly reduced by the remaining catalyst, but also a problem that a transparent product is not obtained.If the amount is too large, the filterability is adversely affected. In addition to the above, there are problems such as a decrease in product yield and an increase in the amount of filter cake.

Water is, for example, 20 to 1000 parts by weight, preferably 50 to 500 parts by weight, per 100 parts by weight of zinc oxide.
Parts by weight can be present. If the amount of water is too small, the decomposition of the catalyst will be incomplete, and not only will the filterability significantly decrease due to the remaining catalyst, but the color of the product will become poor, and it will cause the product to become turbid, and if it is too much, it will be added. Great effort is required to dewater the water, which is unsuitable for commercial production.

Zinc oxide and water are added to the reaction crude, for example, at 40 to 180 ° C., preferably 80 to 14 ° C.
At 0 ° C., the catalyst can be deactivated by stirring. If the treatment temperature is too low, the decomposition of the catalyst becomes incomplete, not only does the filterability significantly decrease due to the remaining catalyst, but also there is a problem that a transparent product cannot be obtained. It causes increase of impurities, coloring and odor generation due to thermal decomposition of the product. The stirring time can be, for example, 0.5 to 5 hours, preferably 1 to 3 hours. If the stirring time is too short, the decomposition of the catalyst becomes incomplete, and not only does the filterability significantly decrease due to the remaining catalyst, but also there is a problem that a transparent product cannot be obtained. .

By removing the deactivated catalyst and zinc oxide, a polyether having a low catalyst content, for example, a polyether having a metal content of the catalyst of 10 ppm or less, preferably 5 ppm or less can be obtained. The zinc oxide content of the polyether can be, for example, 5 ppm or less, preferably 3 ppm or less in terms of Zn.

If the content of the metal constituting the catalyst of the polyether or the content of Zn derived from zinc oxide is too large, not only does the filterability significantly decrease, but a transparent product cannot be obtained, and the obtained polyale is used as a urethane resin raw material. When used, there is a problem in that it has an adverse effect on the urethane-forming reaction and adversely affects the physical properties of the resulting urethane resin.

The deactivated catalyst and zinc oxide can be removed, for example, by using an adsorbent. For example, adsorbent to polyether containing catalyst,
Preferably, by adding the adsorbent and water and stirring, the deactivated catalyst can be adsorbed on the adsorbent,
After dehydrating under reduced pressure, the adsorbent and the treating agent that have absorbed the deactivated catalyst can be removed by filtration using a filter aid.

As the adsorbent, for example, known ones such as synthetic magnesium silicate and synthetic aluminum silicate can be used. The amount of adsorbent used, for example,
It can be 0.1 to 30 parts by weight based on 100 parts by weight of the reaction crude product. If the amount of the adsorbent is too small, adsorption of the deactivated catalyst becomes incomplete, and not only does the filterability significantly decrease, but there is a problem that a transparent product cannot be obtained.If the amount is too large, the filterability is adversely affected. In addition, there are problems such as a decrease in product yield, an increase in the amount of filter cake, and contamination of the product by the use of a large amount of adsorbent.

[0034]

EXAMPLES <Production of reaction crude product> According to a known method,
Propylene glycol having a molecular weight of 750 was used as an initiator, and zinc hexacyanocobaltate (III) was used as a catalyst in an amount of 0.15% per reaction crude product (total amount of polypropylene glycol and propylene oxide). Oxide is introduced to a predetermined amount, reacted and aged to obtain a molecular weight of 44.
A reaction crude A of 00 was obtained. The reaction crude product A contained 330 ppm of Zn and 206 ppm of Co, which are the constituent metals of the catalyst.

In addition, a polyoxypropylene glyceryl ether having a molecular weight of 900 using glycerin as a starting material was used in place of polypropylene glycol having a molecular weight of 750 as an initiator in the same manner as described above.
A reaction crude B of 00 was obtained. The reaction crude B contained 330 ppm of Zn, which is a metal constituting the catalyst, and 206 ppm of Co.

<Production (Purification) of Polyether> Example 1 20 g of zinc oxide and 20 g of water as a catalyst treating agent were added to 1000 g of the crude reaction product A at a temperature of 70 ° C., and the temperature was raised to 120 ° C. with stirring. C. for 2 hours. After cooling to 80 ° C., 20 g of synthetic magnesium silicate and 30 g of water were added as adsorbents.
Stirred at C for 1 hour. 10 while dehydrating under reduced pressure
After raising the temperature to 5 ° C. to remove the water in the reaction crude product,
The mixture was cooled to 80 ° C. and filtered using a filter aid (Topco No. 31 manufactured by Showa Chemical Industry Co., Ltd.) to obtain 980 g of a colorless and transparent purified product (polyether). Filtration is performed while keeping the temperature of the treatment liquid at 60 ° C., and a Kiriyama type filter as a filter and a Kiriyama filter paper No. as a filter paper. 5
B (95 mm diameter) was used.

Example 2 Zinc oxide 20 was used instead of 20 g of zinc oxide and 20 g of water.
g and 50 g of water were mixed and dispersed in advance.
70 g of an aqueous dispersion was added, and the treatment time of the catalyst was set to 1 hour.
980 g of a colorless and transparent purified product (polyether) was obtained in the same manner as in Example 1 except that only 20 g of synthetic magnesium silicate was added instead of 20 g of synthetic magnesium silicate and 30 g of water.

Comparative Example 1 The procedure of Example 1 was repeated, except that zinc oxide and water were not added, and the treatment time of the catalyst was changed to 4 hours. However, the filterability was very poor, and it took 10 hours to obtain 100 g of a cloudy viscous liquid (polyether).

Comparative Example 2 Zinc oxide 20 was used instead of zinc oxide 20 g and water 20 g.
980 g of a turbid brown viscous liquid (polyether) was obtained in the same manner as in Example 1 except that only g was added.

Comparative Example 3 The procedure of Example 1 was repeated except that only 20 g of water was used instead of 20 g of zinc oxide and 20 g of water. However, the filterability is very poor, and a cloudy viscous liquid (polyether) 100
It took 7 hours to get g.

Comparative Example 4 Example 1 was repeated except that 21 g of a 48% aqueous solution of potassium hydroxide was added instead of 20 g of zinc oxide and 20 g of water, and 30 g of synthetic aluminum silicate was added instead of 20 g of synthetic magnesium silicate. 970 g of a cloudy viscous liquid (polyether) was obtained in the same manner as described above.

Comparative Example 5 The catalyst was treated by adding 21 g of a 48% aqueous solution of potassium hydroxide in place of 20 g of zinc oxide and 20 g of water.
At a temperature of 0 ° C., add 40 g of sodium acid pyrophosphate,
After the temperature was raised to 120 ° C. with stirring, and the temperature was maintained at 120 ° C. for 1 hour, the water in the crude reaction product was removed under reduced pressure, and the precipitate was filtered with a filter aid (manufactured by Showa Chemical Industry Co., Ltd. It filtered using Topco No. 31). Subsequently, 940 g of a turbid brown viscous liquid (polyether) was obtained in the same manner as in Example 1, except that 10 g of synthetic magnesium silicate and 10 g of water were added as an adsorbent and subjected to an adsorption treatment.

Comparative Example 6 Turbidity was reduced in the same manner as in Example 1 except that 20 g of aluminum chloride was used as a 30% tetrahydrofuran solution in place of 20 g of zinc oxide and 20 g of water, and the added amount of synthetic magnesium silicate was 30 g. 980 g of a brown viscous liquid (polyether) was obtained.

Example 3 A reaction crude product B was used in place of the reaction crude product A,
In the same manner as in Example 1, 970 g of a colorless and transparent purified product (polyether) was obtained.

Comparative Example 7 A reaction crude B was used in place of the reaction crude A,
Cloudy viscous liquid (polyether) as in Comparative Example 4
970 g were obtained.

<Results> A catalyst component metal in a sample prepared by dissolving a predetermined amount of the purified polyether obtained in each of Examples and Comparative Examples using a platinum crucible and dissolving it in dilute hydrochloric acid was prepared. The contents of (Co, Zn, K) and the metal (Zn) derived from the treatment agent were quantified using an ICP emission spectrometer. The results are shown in Table 1. Table 1 shows the results of visually evaluating the appearance of the obtained polyether and the results of evaluating the filterability. The filterability was determined from the filtration rate V (g / cm ² · hr) of the crude reaction product according to the following index.
The evaluation was made on a scale. ◎ V ≧ 4.7 ○ 4.7> V ≧ 2.4 Δ2.4> V ≧ 1.2 × 1.2> V

[0047]

[Table 1]

[0048]

According to the present invention, the content of the catalyst residue can be greatly reduced as compared with the conventional method, and a transparent polyether having a good hue can be produced.

According to the embodiment using a zinc oxide-water dispersion as a treating agent, a polyether having a good hue can be produced in a short treating time.

According to the present invention, the handling of the processing agent and the processing method do not require complicated operations.

According to the present invention, the adsorption treatment after the catalyst treatment,
In the filtration step, conventional techniques can be applied.

Claims (2)

[Claims] 1. A treating agent comprising a polyether containing a catalyst obtained by ring-opening polymerization of a monoepoxide having 3 or more carbon atoms in the presence of a double metal cyanide complex catalyst, and containing zinc oxide in the presence of water. And then removing the deactivated catalyst and the treating agent after deactivating the catalyst by treating with a catalyst. 2. The method for producing a polyether according to claim 1, wherein the treating agent is a slurry-like zinc oxide-water dispersion in which zinc oxide is dispersed in water.