JP2003504461A - Metal catalysts complexed with sulfone or sulfoxide compounds - Google Patents

Abstract

  (57) [Summary] The metal cyanide catalyst is complexed with an organic sulfone compound or an organic sulfoxide compound. These catalysts are active alkylene oxide polymerization catalysts that tend to have a short induction period and a mild exotherm.

Description

Detailed Description of the Invention

[0001]   The present invention relates to metal catalysts for the polymerization of alkylene oxides.

Alkylene oxides such as ethylene oxide, propylene oxide, and 1,2-butylene oxide are polymerized to form a wide variety of polyether compounds. For example, polyether polyols are prepared in large quantities in polyurethane applications. Other polyethers are used as lubricants, brake fluids, compressor fluids, and many other applications.

These polyethers are generally prepared by polymerizing one or more alkylene oxides in the presence of an initiator compound and an alkali metal catalyst. The initiator compound is generally a material that has one or more hydroxyl groups, primary or secondary amine groups, carboxyl groups, or thiol groups. The function of the initiator is to determine the nominal functionality (number of hydroxyl groups per molecule) of the product polyether and, optionally, to introduce some desired functionality into the product. Is.

Until recently, the catalyst of choice was an alkali metal hydroxide such as potassium hydroxide. Potassium hydroxide has the advantages that it is inexpensive, compatible with the polymerization of various alkylene oxides, and easily removable from the product polyether.

However, alkali metal hydroxide catalysts, to varying degrees, catalyze the isomerization of propylene oxide to form allyl alcohol. Allyl alcohol is
It acts as a monofunctional initiator during the polymerization of propylene oxide. Thus, when potassium hydroxide is used to catalyze the polymerization of propylene oxide, the product is
It contains monofunctional impurities initiated with allyl alcohol. The isomerization reaction becomes more predominant as the molecular weight of the product polyether increases.
As a result, polypropylene oxide products having equivalent weights of about 800 or higher tend to have very large amounts of monofunctional impurities when prepared using KOH as a catalyst. This tends to lower the average functionality of the product and broaden the molecular weight distribution of the product.

More recently, so-called double metal cyanide (DMC) catalysts have been used commercially as polymerization catalysts for alkylene oxides. These DMC catalysts include, for example, U.S. Patent Nos. 3,278,457, 3,278,458, 3,278,459, among others.
3,404,109, 3,427,256, 3,427,334, 3,427,335, and
5,470,813. Active DMC catalysts usually do not significantly accelerate the isomerization of propylene oxide and prepare polyethers with low unsaturation values and higher molecular weights as compared to potassium hydroxide catalyzed polymerizations. be able to. Recently, developmental and commercial efforts have concentrated almost exclusively on zinc hexcyanocobaltate, with a specific complexing agent (t-butanol).

As described in US Pat. No. 5,470,813, one disadvantage of DMC catalysts is that they require an induction period ranging from nearly an hour to sometimes hours before becoming active. It means that there is a tendency to. Very little polymerization occurs during this induction period, but a violently exothermic reaction follows. Depending on the operation, it may be desirable to shorten this induction period and provide a less pyrogenic reaction.

Therefore, an active catalyst for polymerizing alkylene oxides that exhibits a short induction period before the rapid polymerization of alkylene oxides and provides a more controlled exotherm as this rapid polymerization begins is presented. It would be desirable to provide.

In one embodiment, the present invention provides a metal complexed with an organic sulfone compound (R ⁵ -S (O) ₂ -R ⁵ ) or an organic sulfoxide compound (R ⁵ -S (O) -R ⁵ ). It is a cyanide catalyst.

In another aspect, the present invention is an improvement in a method for polymerizing an epoxide compound in the presence of a catalyst, wherein the catalyst is complexed with an organic sulfone compound or an organic sulfoxide compound. It is a metal cyanide catalyst.

It has been found that the metal cyanide catalyst complex of the present invention has excellent activity as an epoxide polymerization catalyst. In particular, this catalyst exhibits a significantly shorter induction period when used in such polymerizations as compared to, for example, the most commonly used zinc hexacyanocobaltate / t-butanol / polypropylene oxide complex. Often. Furthermore, when rapid alkylene oxide polymerization begins,
A smaller, more controllable exotherm is usually seen.

“Metal cyanide catalyst” means a catalyst represented by the following formula: M _b [M ¹ (CN) _r (X) _t ] _c [M ² (X) ₆ ] _d · zL · aH ₂ O · nM ³ _x A _{y In the} above formula, M is a metal ion that forms an insoluble precipitate together with the M ¹ (CN) _r (X) _t group having at least one water-soluble salt, and M ¹ And M ² are transition metal ions, which may be the same or different, each X independently represents a group other than cyanide, which coordinates with the M ¹ ion or the M ² ion, ³ _x A _y represents a water-soluble salt of the metal ion M ³ and the anion A, where M ³ is M
Same or different from each other, L represents an organic sulfone compound or an organic sulfoxide compound, b and c are positive numbers which together with d give an electrostatically neutral complex, d is zero or a positive number, x and y are numbers that result in an electrostatically neutral salt, r is 4-6, t is 0-2, and z, a , And n are positive numbers (which may be fractions) indicating the relative amounts of the organic sulfone compound or the organic sulfoxide compound, water, and M ³ _x A _y , respectively.

The X groups in M ² (X) ₆ need not all be the same. The molar ratio of c: d is about 1
00: 0 to about 20:80, more preferably about 100: 0 to about 50:50, and even more preferably about
Conveniently it is from 100: 0 to about 80:20.

Similarly, a mixture of two or more different M ¹ (CN) _r (X) _t groups may be used.

[0015]   M and M³Is preferably Zn⁺², Fe⁺², Co⁺², Ni⁺², Mo⁺⁴, Mo⁺⁶, Al⁺³, V ⁺⁴ , V⁺⁵, Sr⁺², W⁺⁴, W⁺⁶, Mn⁺², Sn⁺², Sn⁺⁴, Pb⁺², Cu⁺², La⁺³, And Cr ⁺³ It is a metal ion selected from the group consisting of. M and M³Is more preferably
Zn⁺², Fe⁺², Co⁺², Ni⁺², La⁺³, And Cr⁺³Is. M is most preferably
, Zn⁺²Is.

[0016]   M¹And M²Is preferably Fe⁺³, Fe⁺², Co⁺³, Co⁺², Cr⁺², Cr⁺³, Mn⁺², Mn ⁺³ , Ir⁺³, Ni⁺², Rh⁺³, Ru⁺², V⁺⁴, And V⁺⁵Is. Among the above,
Those in the +3 oxidation state are more preferable. Co⁺³And Fe⁺³But even better
Masu Co⁺³Are most preferred. M¹And M²Are the same, but different
You may stay.

[0017] Preferred groups X are the halides (especially chloride), hydroxide, sulfate, carbonate, oxalate, thiocyanate, isocyanate, isothiocyanate, C _1-4 carboxylate, and nitrite (NO ₂ ^-), etc. And an uncharged species such as CO, H ₂ O, and NO. A particularly preferred group X is
NO, NO ₂ ^-, and a CO.

R is preferably 5 or 6, most preferably 6, and t is preferably 0 or 1, most preferably 0. In most cases r + t will be equal to 6.

Suitable anions A include halides such as chlorides and bromides, nitric acid, sulfates, carbonates, cyanates, oxalates, thiocyanates, isocyanates, isothiocyanates, perchloric acids, and C _1-4 carboxylates. . Chloride ion is especially preferred.

L represents an organic sulfone compound or an organic sulfoxide compound. Suitable sulfone compounds are represented by the general formula R ⁵ -S (O) ₂ -R ⁵ , wherein each R ⁵ is unsubstituted or inertly substituted alkyl, cycloalkyl ,
Aryl or, together with the other R ^5, is linked to the sulfone group (-S (
O) _2- ) forms part of a ring structure containing a sulfur atom. Suitable sulfoxide compounds are represented by the general formula R ⁵ —S (O) —R ⁵ , where each R ⁵ is as just described. In this context, "inertly substituted" means that the group is a substituent which causes a deleterious reaction with the metal cyanide compound, its precursor compound (described below), or an alkylene oxide. Or, it means that it does not contain any substituents that would otherwise hinder the polymerization of the alkylene oxide. Examples of such inert substituents include ether groups, alkoxy groups, hydroxyl groups, nitrile groups, aldehyde groups, ketone groups, amide groups, sulfide groups, further sulfone groups or sulfoxide groups. Each R ⁵ is preferably unsubstituted and is an alkyl group, or together with the other R ⁵ forms a part of the ring structure containing the sulfone group or the sulfoxide group. Is preferred. Particularly preferred R ⁵ groups are alkyl groups having 1 to 4 carbon atoms or, together, form a 5 to 8 membered ring with the sulfur atom of the sulfone or sulfoxide group. More preferred compounds are water-soluble, such as dimethylsulfoxide (DMSO), tetramethylenesulfoxide, 2,2-
Includes sulfonyldiethanol, dimethyl sulfone, and sulfolane (tetramethylene sulfone). DMSO is most preferred because it exhibits a particularly short induction period in the polymerization of propylene oxide.

It is common and preferred that the sulfone or sulfoxide compounds are the only complexing agents.

The complex catalyst is conveniently prepared by first dissolving or dispersing a water soluble metal cyanide compound in an inert solvent such as water or methanol. It is also possible to use mixtures of two or more metal cyanide compounds. The water-soluble metal cyanide compound is represented by the general formula B _u [M ¹ (CN) _r (X) _t ] _v , where B is hydrogen or the above [M ¹ (CN) _r (X) _t ] ion is a metal that forms a water-soluble salt, u and v are integers that give an electrostatically neutral compound, and M ¹ , X, r, and t are the aforementioned On the street. B is preferably hydrogen, sodium or potassium. Compounds where B is hydrogen are conveniently formed by passing an aqueous solution of the corresponding alkali metal salt through a cation exchange resin which is in the hydrogen form.

Furthermore, the solution or dispersion of the metal cyanide compound may also contain a compound having the structure B _u [M ² (X) ₆ ] _v . Where M ² is a transition metal and X, B
, U, and v are as described above. M ² may be the same as or different from M ¹ .

Next, the above solution or dispersion is combined to obtain a solution (a plurality of kinds may be used).
Are combined with an aqueous solution of a water-soluble metal salt in the presence of the sulfone compound or sulfoxide compound. This metal salt is represented by the general formula M _x A _y , where M 1, A 2,
x and y are as defined above. Particularly suitable metal salts include zinc halides, zinc hydroxide, zinc sulfate, zinc carbonate, zinc cyanide, zinc oxalate,
Includes zinc thiocyanate, zinc isocyanate, zinc C _1-4 carboxylate, and zinc nitrate. Zinc chloride is most preferred.

The mixing temperature is not critical as long as the starting materials remain in solution or in a well-dispersed state until mixing is done. Temperatures from about 10 ° C to about the boiling point of the inert solvent, especially 15-40 ° C, are most preferred. Mixing may be performed with rapid stirring. The intimate mixing technique described in US Pat. No. 5,470,813 can also be used, but is not required.

In the precipitation of the catalyst, at least the metal cyanide ion (M ¹ (CN) _r (X
) _t ) and for each equivalent of M ² (X) ₆ ions, if used, 1
Sufficient metal salt is used to provide an equivalent amount of metal ion (M). In general, the more active catalysts were found to have been prepared using an excess of metal salt. It is believed that this excess metal is present in the catalyst complex as a salt in the form M _x A _y or M ³ _x A _y . This excess metal is, for example, not more than about 3 equivalents of metal salt, preferably about 1.1 equivalents per total equivalent of metal cyanide and M ² (X) ₆ ions.
To about 3, more preferably from about 1.5 to about 2.5 equivalents of metal salt,
It can be added in the precipitation step.

An alternative method for adding the excess metal salt is to perform it in a separate step after the precipitation step, as described more fully below. The metal ion in this excess salt may be different than the metal ion in the metal salt used to precipitate the catalyst.

It is preferable to add the solution of the metal cyanide compound to the solution of the metal salt, and it is also preferable to carry out the mixing while stirring. It is preferred to continue stirring for the period after the mixing is complete. The metal cyanide catalyst precipitates, forming a dispersion in the supernatant.

The catalyst complex may be precipitated by mixing the solution or dispersion of the metal salt with the solution or dispersion of the metal cyanide compound in the presence of the sulfone compound or the sulfoxide compound. One way to do this is to add the sulfone or sulfoxide compound to the solution or dispersion of the metal cyanide compound before mixing the solutions. Alternatively, both starting solutions or starting dispersions may be added simultaneously with the sulfone or sulfoxide compound. A third method is to mix the starting solution or dispersion and immediately afterwards add the sulfone compound or sulfoxide compound. Generally, after addition of the initial amount of sulfone or sulfoxide compound, the mixture is stirred for a few minutes to form and precipitate the desired catalyst complex.

The resulting precipitated catalyst complex is then recovered by a suitable technique such as filtration or centrifugation. Preferably, the catalyst is subjected to one or more washes with water, sulfone or sulfoxide compounds, polyether polyols (where used), or combinations thereof. This is conveniently done by reslurrying the catalyst in the liquid with stirring for a few minutes and filtering. Washing is preferably continued at least until all the unwanted ions (especially alkali metal ions and halide ions) have been removed from the complex.

It has been found that treating the catalyst with a polyether polyol having a molecular weight of about 300-4000 may make the catalyst easier to prepare. When a polyether polyol is used in the catalyst complex, the polyether polyol may be added with an initial amount of sulfone or sulfoxide compound or in one or more of the subsequent washes of the complex.

The final catalyst is preferably placed under reduced pressure and at a reasonably high temperature (eg about 50-60).
Conveniently, the excess water and volatile organics are removed by drying (from ° C). Drying is preferably carried out until the catalyst complex reaches a certain mass.

In an alternative technique for forming the above catalyst complex, an aqueous solution containing only the theoretical amount of metal salt with respect to the total amount of metal cyanide compound (and M ² (X) ₆ compound used) is used. , Used in the initial mixing and precipitation steps. After this initial precipitation is complete, the precipitate is washed with water to remove unwanted ions. The precipitate is then combined with water, additional metal salts, and a small amount of a solution containing the sulfone or sulfoxide compound. The metal salt used may be the same as that used in forming the precipitate or it may be a salt of a different metal. The amount of solution added is preferably that absorbed by the precipitate. A typical amount of solution to be used is about 0.5 to about 2, preferably about 0.8 to about 1.5, more preferably about 1 to about 1.5 per gram of isolated precipitate.
It is a solution of mL. The amount of metal salt added with this solution depends on the precipitate 1
Conveniently about 9 to about 30, preferably about 11 to about 25 parts per 00 parts by weight. The sulfone or sulfoxide compound is conveniently present with water in a weight ratio of about 90:10 to about 10:90, preferably about 70:30 to 30:70. If desired, the solution can also include a polyether polyol. The resulting catalyst complex may be dried and used without further treatment, or may be subjected to further washing with water as described above, but with a sulfone compound, a sulfoxide compound or a polyether polyol. It is preferable not to wash.

The catalyst complex of the present invention is used to polymerize an alkylene oxide to produce a polyether. Generally, the method involves mixing a catalytically effective amount of catalyst with an alkylene oxide under polymerization conditions and allowing the polymerization to proceed until the feed amount of alkylene oxide is almost completely consumed. The concentration of catalyst is selected to polymerize the alkylene oxide at the desired rate or within the desired time period. In general, a suitable amount of catalyst is alkylene oxide and, if present, from about 5 to about 10,000 parts by weight metal cyanide catalyst per million parts by total weight of initiator and comonomer. A more preferred catalytic amount is from about 10, especially from about 25 to about 1000, more preferably about 250 ppm, based on the combined weight of alkylene oxide and, if present, initiator and comonomer.

In order to control the molecular weight and give the desired functionality (number of hydroxyl groups per molecule) or the desired terminal functionality, the abovementioned initiator compounds are mixed with the above catalyst complex at the start of the reaction. Preferably. Suitable initiator compounds include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol,
t-butanol, octanol, octadecanol, 3-butyn-1-ol, 3-buten-1-ol, propargyl alcohol, 2-methyl-2-propanol, 2-methyl-3-butyn-2-ol, 2 Includes monoalcohols such as -methyl-3-buten-2-ol, 3-butyn-1-ol, 3-buten-1-ol. Suitable monoalcohol initiator compounds include 2-chloroethanol, 2-bromoethanol, 2-chloro-1-propanol, 3-chloro-1-propanol, 3-bromo-1-propanol, 1,3-dichloro-. 2-Propanol, halogenated alcohols such as 1-chloro-2-methyl-2-propanol, nitro alcohol, keto alcohol, ester alcohol,
Cyano alcohols and other inertly substituted alcohols are included.
Suitable polyalcohol initiators include ethylene glycol, propylene glycol, glycerin, 1,1,1-trimethylolpropane, 1,1,1-trimethylolethane,
1,2,3-trihydroxybutane, pentaerythritol, xylitol, arabitol, mannitol, 2,5-dimethyl-3-hexyne-2,5-diol, 2,4,7,9-tetramethyl-5-decyne- Included are 4,7-diols, sucrose, sorbitol, alkyl glucosides (eg methyl glucoside and ethyl glucoside). Also,
Low molecular weight polyether polyols, especially those having an equivalent weight of about 350 or less, more preferably about 125-250, are also useful initiator compounds.

Alkylene oxides that can be polymerized using the catalyst complex of the present invention include
Included are ethylene oxide, propylene oxide, 1,2-butylene oxide, styrene oxide, and mixtures thereof. It is also possible to polymerize various alkylene oxides sequentially to produce block copolymers. More preferably, the alkylene oxide is propylene oxide or a mixture of propylene oxide and ethylene oxide and / or butylene oxide. Especially preferred is propylene oxide alone or a mixture of at least 50% by weight propylene oxide and up to about 50% by weight ethylene oxide.

Additionally, modified polyether polyols can be prepared using monomers that copolymerize with the alkylene oxides in the presence of the catalyst complex. Such comonomers include oxetane described in U.S. Pat. Nos. 3,278,457 and 3,404,109, and U.S. Pat. Nos. 5,145,883 and 3,538,043.
Included are the anhydrides described in each of the publications, which yield polyester polyols or polyetherester polyols, respectively. Hydroxyalkanoates (eg, lactic acid, 3-hydroxybutyrate, 3-hydroxyvalerate (and their dimers)), lactones, and carbon dioxide are other suitable compounds that can be polymerized using the catalysts of this invention. Are examples of different monomers.

The polymerization reaction generally proceeds well at temperatures of about 25 to about 150 ° C, preferably about 80 to 130 ° C. A convenient polymerization technique involves mixing the catalyst complex and initiator and pressurizing the reactor with the alkylene oxide. After a short induction period, the polymerization proceeds as indicated by the drop in pressure in the reactor. Once the polymerization has started, additional alkylene oxide is optionally fed to the reactor and sufficient alkylene oxide is added to produce the desired equivalent weight of polymer.

Another convenient polymerization technique is the continuous process. In these continuous processes, the activated initiator / catalyst mixture is continuously fed into a continuous reactor such as a continuous stirred tank reactor (CSTR) or tubular reactor. An alkylene oxide feed is introduced into the reactor and the product is continuously withdrawn.

The catalysts of the present invention are particularly useful in the preparation of homopolymers of propylene oxide and random copolymers of propylene oxide with up to about 15% by weight (based on all monomers) ethylene oxide. Particularly important polymers are about
Hydroxyl equivalents from 800, preferably from about 1000 to about 5000, preferably up to about 4000, more preferably up to about 2500, and unsaturations of 0.02 meq / g or less, preferably about 0.01 meq / g or less. Have.

The product polymer may have a variety of uses due to its molecular weight, equivalent weight, functionality, and the presence of any functional groups. The polyether polyol thus produced is useful as a raw material for producing polyurethane. Polyethers can also be used as surfactants, hydraulic fluids, raw materials for producing surfactants, and as starting materials for producing aminated polyethers, among other applications.

The following examples are provided to illustrate the invention and are not intended to limit the scope of the invention. All parts and percentages are by mass unless stated otherwise.

Example 1 A. Preparation of catalyst Potassium hexacyanocobaltate (8.0 g, 0.024 mol) in 140 mL of distilled water
Prepare a solution of. It is added to a stirred solution of 25 g (0.18 mol) zinc chloride in 40 mL water. 100 mL of dimethyl sulfoxide (DMSO in 100 mL of water
) Solution is added immediately and the resulting mixture is stirred for 10 minutes. A slurry is formed, which is filtered through a Buchner funnel. The collected solids are reslurried in a solution containing 60 mL water and 140 mL DMSO, stirred for 10 minutes and filtered as before. The solid was then reslurried in 200 mL DMSO and
Stir for minutes and filter again. The solid is dried under vacuum at 50 ° C. for 18 hours.

B. 30 g of polyether triol having a polymerization molecular weight of 700 started at high temperature and a catalyst complex obtained from the above-mentioned part A
0.2 g are mixed in a Parr reactor. After purging with nitrogen, the mixture is heated to 100 ° C and pressurized with propylene oxide to about 340 kPa (50 psig). Polymerization begins immediately but no measurable exotherm is seen. As the polymerization proceeded, propylene oxide was continuously fed to the reactor until a total of 140 g of propylene oxide was added, and the pressure was about 340 kPa (50 psig).
). The polymerization of the full charge of propylene oxide takes about 3 hours. The unsaturation of the resulting polyether polyol is 0.013 meq / g and the polydispersity is about 1.29.

Example 2 A. Catalyst Preparation A solution of 4.1 g sodium nitroferricyanide in 50 mL deionized water was added to 25
g hydrogen type macroporous styrene-divinylbenzene strong acid cation exchange resin (Th
e Dowex MSC-1) available from Dow Chemical Company. The eluent (containing 0.014 mol H ₂ [Fe (CN) ₅ (NO)]) was added to 4 ml of 50 ml deionized water.
Add to 0.5 g of another solution of potassium hexacyanocobaltate (0.014 mol). This mixture is then added to a stirred solution of 25g zinc chloride in 40mL deionized water. Following this, a solution of 50/50 by volume of water and DMSO is added immediately. Homogenize the resulting slurry for 10 minutes and pour into a large beaker with stirring. To it is added 200 mL of water, 2 mL of DMSO, and 2 g of a solution of 4000 molecular weight nominally trifunctional polypropylene oxide, followed by stirring for 3 minutes. The slurry is then filtered through a Buchner funnel to isolate solids. The solid is reslurried in a solution containing 60 mL water, 140 mL DMSO, and 2 g of the same polypropylene oxide as above, stirred for 10 minutes, and filtered as before. The solid obtained is then reslurried in a solution of 200 mL DMSO and 1 g of the above polypropylene oxide, stirred for a further 10 minutes and filtered. The product is then vacuum dried overnight at 50 ° C.

B. Polymerization Initiated at Elevated Temperature Polymerization at elevated temperature is carried out as described in Example 1B. After a 10-15 minute induction period,
Polymerization begins with an exotherm of 20 ° C. The polyether polyol obtained has a degree of unsaturation of 0.009 meq / g and a polydispersity of 1.26.

Example 3 A. Preparation of Catalyst A solution of 25 g zinc chloride in 40 mL deionized water is added with mixing to a solution of 8.0 g potassium hexacyanocobaltate in 140 mL water. The mixture is stirred for a few seconds. Then a solution of 20 g of methyl sulfone in 200 mL of water is added.
The mixture is stirred for 10 minutes and vacuum filtered. Add this filter cake to 25 mL of 180 mL water.
Reslurry in a solution of g methyl sulfone and add 1 g trifunctional polypropylene oxide having a molecular weight of 450. The mixture is stirred for 10 minutes and filtered again.
The filter cake is then reslurried under the same conditions as above and filtered again. The product is then vacuum dried at 85 ° C. for 24 hours. Then it is slurried in acetone, centrifuged to remove solids and dried at 100 ° C. for 18 hours under reduced pressure.

B. In a polymerization Parr reactor started at elevated temperature , from 30 g of a 700 molecular weight polyether triol and a sufficient amount of Part A above to provide about 1000 ppm of catalyst to the expected mass of product. Mix with the resulting catalyst complex. After purging with nitrogen, add 100% of this mixture.
Heat to ° C and pressurize to about 340 kPa (50 psig) with propylene oxide. about
Polymerization started after a 16 minute induction period with a very slight (5 ° C) exotherm. As the polymerization progressed, until a total of 123 g of propylene oxide was added,
Propylene oxide is continuously fed to the reactor at a pressure of approximately 240 kPa (35 psig)
To maintain. The polymerization of the full charge of propylene oxide takes about 25 minutes. The unsaturation of the resulting polyether polyol is 0.002 meq / g.

Example 4 A. Catalyst Preparation A solution of 6.25 g zinc chloride in 10 mL deionized water is added with mixing to a solution of 2.0 g potassium hexacyanocobaltate in 35 mL water. The mixture is stirred for a few seconds. Then 20 mL of a 50/50 by volume mixture of tetramethylene sulfoxide and distilled water is added. The mixture is stirred for 10 minutes and filtered. The filter cake is reslurried in a solution of 12 mL methyl sulfone and 1 g molecular weight 450 trifunctional polypropylene oxide and filtered again. The filter cake is then slurried in acetone, filtered to collect solids, and dried at 85 ° C. for 7 hours under reduced pressure.

B. Polymerization Initiated at High Temperature The activity of the catalyst obtained from Part A above is evaluated as described in Example 3B. About 25
After a minute induction period, the polymerization started and a slight (24 ° C) exotherm was observed. The polymerization of the full charge of propylene oxide takes about 26 minutes. The unsaturation of the resulting polyether polyol is 0.007 meq / g.

Example 5 A. Catalyst Preparation A solution of 6.25 g zinc chloride in 10 mL deionized water is added with mixing to a solution of 2.0 g potassium hexacyanocobaltate in 35 mL water. The mixture is stirred for a few seconds. Then, 20 mL of a 50/50 by volume mixture of 2,2-sulfonyldiethanol and distilled water is added. The mixture is stirred for 10 minutes and filtered. The filter cake is reslurried in a solution of 15 mL 2,2-sulfonyldiethanol, 10 mL deionized water, and 2 g of a trifunctional polypropylene oxide having a molecular weight of 450 and filtered again. This filter cake was charged with 2,2-sulfonyldiethanol (37.5 mL) and 0.93 g.
Reslurry in a solution of 450 molecular weight trifunctional polypropylene oxide,
Filter again. The filter cake is then slurried in acetone, filtered to collect solids and dried at 85 ° C. for 18 hours under reduced pressure.

B. Polymerization Initiated at High Temperature The activity of the catalyst obtained from Part A above is evaluated as described in Example 3B using 0.19 g of the above catalyst. Polymerization begins immediately. No measurable exotherm is seen as the propylene oxide polymerizes. The polymerization of the full charge of propylene oxide takes about 103 minutes.

[Procedure for Amendment] Submission for translation of Article 34 Amendment of Patent Cooperation Treaty

[Submission date] September 17, 2001 (2001.17)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 14

[Correction method] Change

[Contents of correction]

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[Document name to be amended] Statement

[Correction target item name] 0001

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[Contents of correction]

The present invention relates to metal catalysts and methods for the polymerization of alkylene oxides.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Contents of correction]

More recently, so-called double metal cyanide (DMC) catalysts have been used commercially as polymerization catalysts for alkylene oxides. These DMC catalysts include, for example, U.S. Patent Nos. 3,278,457, 3,278,458, 3,278,459, among others.
3,404,109, 3,427,256, 3,427,334, 3,427,335, and
5,470,813 and European Patent Application Publication Nos. 0862947 and 743093 . Active DMC catalysts usually do not significantly accelerate the isomerization of propylene oxide and, compared to potassium hydroxide catalyzed polymerizations,
Polyethers with low unsaturation values and higher molecular weights can be prepared. Recently, developmental and commercial efforts have concentrated almost exclusively on zinc hexcyanocobaltate, with a specific complexing agent (t-butanol).

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Contents of correction]

L represents an organic sulfone compound or an organic sulfoxide compound. Suitable sulfone compounds are represented by the general formula R ⁵ —S (O) ₂ —R ⁵ , where each R ⁵ is independently an unsubstituted or inertly substituted alkyl group. , Cycloalkyl, aryl, or together with R ^{5 on the} other side, forms part of the ring structure containing the sulfur atom of the sulfone group (—S (O) ₂ —). Suitable sulfoxide compounds are represented by the general formula R ⁵ —S (O) —R ⁵ , where each R ⁵ is as just described. In this context, "inertly substituted" means that the group is
Contains no metal cyanide compounds, their precursor compounds (described below), or any substituents that cause deleterious reactions with the alkylene oxide or that otherwise interfere with the polymerization of the alkylene oxide. It means not doing. Examples of such inert substituents include ether groups, alkoxy groups,
Included are hydroxyl groups, nitrile groups, aldehyde groups, ketone groups, amide groups, sulfide groups, additional sulfone groups or sulfoxide groups. Each R ⁵ is preferably unsubstituted and is an alkyl group, or together with the other R ⁵ forms a part of the ring structure containing the sulfone group or the sulfoxide group. Is preferred. Particularly preferred R ⁵ groups are alkyl groups having 1 to 4 carbon atoms or, together, form a 5 to 8 membered ring with the sulfur atom of the sulfone or sulfoxide group. More preferred compounds are water soluble and include, for example, dimethyl sulfoxide (DMSO), tetramethylene sulfoxide, 2,2-sulfonyldiethanol, dimethyl sulfone, and sulfolane (tetramethylene sulfone). DMSO is most preferred because it exhibits a particularly short induction period in the polymerization of propylene oxide.

─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Lacock, David E.             Ontario, Canada N7 Tea 6             N6, Sarnia, Branch Street               335 F-term (reference) 4J005 AA04 BB02

Claims (16)

[Claims] 1. A metal cyanide catalyst complexed with an organic sulfone compound or an organic sulfoxide compound. _2. Complexed with an organic sulfone represented by the general structure R ⁵ —S (O) ₂ —R ⁵ , wherein each R ⁵ is independently unsubstituted or substituted. Inertly substituted, alkyl, cycloalkyl, aryl, or together with the other R ⁵ forms part of a ring structure containing a sulfur atom of the sulfone group. The catalyst according to claim 1. 3. The metal cyanide catalyst is represented by the following general structure: M _b [M ¹ (CN) _r (X) _t ] _c [M ² (X) ₆ ] _d · zL · aH ₂ O · nM ³ _x A _{y In the} above formula, M is a metal ion that forms an insoluble precipitate with the above M ¹ (CN) _r (X) _t group having at least one water-soluble salt, and M ¹ and M ² are , X, which may be the same or different, and each X independently represents a group other than cyanide, which coordinates with the M ¹ ion or the M ² ion, and M ³ _x A _y Represents a water-soluble salt of the metal ion M ³ and the anion A, where M ³ is M
Same as or different from, L represents an organic sulfone compound, b and c are positive numbers together with d, resulting in an electrostatically neutral complex, and d is zero. Or a positive number, x and y are numbers that result in an electrostatically neutral salt, r is 4-6, t is 0-2, and z, a, and n are The catalyst according to claim 2, wherein each is a positive number indicating a relative amount of the organic sulfone compound, water, and M ³ _x A _y . 4. The catalyst according to claim 2, wherein each R ⁵ is an alkyl group having 1 to 4 carbon atoms. 5. The catalyst according to claim 2, wherein each of the R ⁵ groups together form a 5- to 8-membered ring with the sulfur atom of the sulfone group. 6. M and M ³ are zinc ions, M ¹ is a cobalt ion, t is zero, A is a chloride ion, x is 1 and y is 2, The catalyst according to claim 3. 7. M and M ³ are zinc ions, M ¹ (CN) _r (X) _t is a mixture of hexacyanocobaltate ion and nitroferricyanide ion, d is zero, and A Is a chloride ion, x is 1 and y is 2; 8. A complex with an organic sulfoxide represented by the general structure R ⁵ —S (O) —R ⁵ , wherein each R ⁵ is independently unsubstituted or substituted. Actively substituted, an alkyl group, a cycloalkyl group, an aryl group, or together with R ^{5 on the} other side, forms part of a ring structure containing a sulfur atom of the sulfoxide group, The catalyst according to claim 1. 9. The metal cyanide catalyst is represented by the following general structure: M _b [M ¹ (CN) _r (X) _t ] _c [M ² (X) ₆ ] _d · zL · aH ₂ O · nM ³ _x A _{y In the} above formula, M is a metal ion that forms an insoluble precipitate with the above M ¹ (CN) _r (X) _t group having at least one water-soluble salt, and M ¹ and M ² are , X, which may be the same or different, and each X independently represents a group other than cyanide, which coordinates with the M ¹ ion or the M ² ion, and M ³ _x A _y Represents a water-soluble salt of the metal ion M ³ and the anion A, where M ³ is M
Same as or different from, L represents an organic sulfone compound, b and c are positive numbers together with d, resulting in an electrostatically neutral complex, and d is zero. Or a positive number, x and y are numbers that result in an electrostatically neutral salt, r is 4-6, t is 0-2, and z, a, and n are The catalyst according to claim 8, wherein each is a positive number indicating the relative amounts of the organic sulfoxide compound, water, and M ³ _x A _y . 10. The catalyst according to claim 9, wherein each R ⁵ is an alkyl group having 1 to 4 carbon atoms. 11. The catalyst according to claim 9, wherein each R ⁵ group together forms a 5- to 8-membered ring with the sulfur atom of the sulfone group. 12. M and M ³ are zinc ions, M ¹ is a cobalt ion, t is zero, A is a chloride ion, x is 1 and y is 2, The catalyst according to claim 9. 13. M and M ³ are zinc ions, M ¹ (CN) _r (X) _t is a mixture of hexacyanocobaltate ion and nitroferricyanide ion, and d
Is zero, A is chloride, x is 1, and y is 2,
The catalyst according to claim 9. 14. A method for polymerizing an epoxide compound in the presence of a catalyst and an initiator compound, wherein the catalyst is a metal cyanide catalyst complexed with an organic sulfone compound or an organic sulfoxide compound. 15. The method of claim 14, wherein the epoxide compound is a mixture of propylene oxide or propyne oxide and ethylene oxide. 16. The product has a hydroxyl equivalent weight of at least 1000 and 0.02.
16. The method of claim 15, which is a polyether polyol having an unsaturation content of less than meq / g.