KR20020027473A - Method for preparing metal cyanide catalysts using polycarboxylic acids - Google Patents

Abstract

The present invention relates to metal cyanide catalysts prepared in the presence of organic polyacids. Active alkylene oxide polymerization catalysts having a larger particle size than conventional metal cyanide catalysts are formed, and are therefore more easily separated from polymers produced using the catalyst. Preferred organic polyacids are crosslinked or uncrosslinked polymers containing pendant carboxyl groups or carboxylate groups.

Description

Method for preparing metal cyanide catalysts using polycarboxylic acids

The present invention relates to metal cyanide complexes. More particularly, the present invention relates to a process for polymerizing alkylene oxides in the presence of metal cyanide catalysts, heterogeneous metal cyanide catalysts, and metal cyanide catalysts with specific complexing agents.

Polyethers are prepared in large amounts by conventional polymerization of alkylene oxides such as propylene oxide and ethylene oxide. The polymerization is generally carried out in the presence of an initiator compound and a catalyst. Initiator compounds generally measure the functionality of the polymer (number of hydroxyl groups per molecule) and in some cases impart some desired functionality. Catalysts are used to provide economic polymerization rates.

Metal cyanide complexes are becoming increasingly important alkylene oxide polymerization catalysts. These complexes are often referred to as "metalloid cyanide" or "DMC" catalysts and are the subject of many patent documents. These patent documents include, among others, US Pat. Nos. 3,278,457, 3,278,458, 3,278,459, 3,404,109, 3,427,256, 3,427,334, 3,427,335 and 5,470,813, for example. In some instances, these metal cyanide complexes offer the advantage of high polymerization rates and narrow polydispersities. In addition, these catalysts relate to the preparation of polyethers containing very small amounts of monofunctional unsaturated compounds.

The most common of these metal cyanide complexes, zinc hexacyanocobaltate (along with the appropriate amount of complexing agent and poly (propylene-oxide)), has the advantage of forming active poly (propylene oxide) with very low unsaturation. However, the catalyst is very difficult to remove from the product polyether. Since these difficulties, and catalysts can be used in small amounts, a common practice is to simply release the catalyst in the product. However, this means that the catalyst must be replaced. In addition, the presence of residual catalysts in polyether products has been reported to cause certain performance problems such as poor shelf life. In order to reduce catalyst costs and avoid these problems, it would be desirable to provide a catalyst that can be easily recovered from the product polyether.

In one aspect, the present invention provides a first solution of a metal salt in an inert solvent, the second solution of the metal cyanide compound in an inert solvent in the presence of an organic polyacid, and the metal salt of the metal cyanide compound and an organic polyacid. The preparation of metal cyanide catalyst complexes comprising mixing under conditions such that metal salts, metal cyanide salts and organic polyacids react to form insoluble precipitates in proportions that can be provided in at least stoichiometric amounts based on amounts It is about a method.

In a second aspect, the present invention provides an organic polyacid compound of the M form wherein M is a polyvalent metal ion that forms an insoluble precipitate with a group of metal cyanide [M ¹ (CN) _r (X)]. A metal cyanide catalyst complex comprising mixing with a solution of a metal cyanide compound in an inert solvent under conditions such that the amide compound and M ions on the organic polyacid react to form an insoluble metal cyanide compound bonded to the organic polyacid compound. It relates to a manufacturing method of.

In a third aspect, the invention relates to a process comprising polymerizing an alkylene oxide in the presence of an initiator and a polymerization catalyst which is one of those prepared according to the first or second aspect of the invention.

The present invention provides two convenient methods for preparing the catalyst. In the first method, both the metal salt and metal cyanide compound described below are reacted in the presence of an organic polyacid compound. In this process, the organic polyacid compound is conveniently in acid, ammonium or alkali metal form (ie the counterion is hydrogen or an alkali metal ion). In a second method, the organic polyacid is converted to the M form, which form of the organic polyacid reacts with the metal cyanide compound to form a catalyst. The second method is particularly useful when the organic polyacid is a water insoluble or crosslinked polymeric polyacid.

Organic polyacids are compounds or polymers having two or more acid groups, which may exist in salt form. Preferred acid groups are carboxyl (-COOH) and carboxylate (-COOM ⁴ , where M ⁴ is an alkali metal or ammonium) group. Acid groups may be bonded to aliphatic, cycloaliphatic or aromatic carbon atoms. Organic polyacids contain two or more acid groups per molecule and may contain multiple acid groups per molecule. Suitable organic polyacids are as follows:

Aliphatic polyacids such as citric acid, tartaric acid, and various cycloalkane polycarboxylic acids such as 1,2-cyclohexane dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and 1,3,5-cyclohexanetricarboxylic acid;

Aromatic polyacids such as 1,3,5-benzene tricarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid;

Chelating agents such as ethylene diamine tetraacetic acid, nitrilotriacetic acid and ethylene glycol bis (β-aminoethyl ether) -N, N-tetraacetic acid;

Polymers and copolymers of water-soluble (uncrosslinked) polymeric polyacids such as alginic acid and ethylenically unsaturated acids such as acrylic acid, methacrylic acid, maleic acid and fumaric acid; Carboxylated polystyrene polymers and copolymers, sulfonated polystyrene polymers and copolymers, graft copolymers of poly ((meth) acrylic acid) with polyethers such as polyethylene oxide;

Water insoluble (crosslinked) polymeric polyacids such as sulfonated or carboxylated crosslinked polystyrene copolymers, ethylenically unsaturated monomers such as crosslinked polymers of acrylic acid, methacrylic acid, maleic acid and fumaric acid ;

Phosphonate-containing and sulfonate-containing polyacids such as poly (vinylphosphonic acid) and poly (vinylsulfonic acid).

Thus, in the first method, the metal salt and the metal cyanide compound are each dissolved or dispersed separately in an inert solvent. "Inert" in this context means that the solvent does not react with metal salts, metal cyanide, polycarboxylic acid compounds, complexing agents that may be present, or precipitated catalyst complexes. The solvent may be water or an organic compound such as methanol, acetone and isopropanol. The solvent is one which acts as an initiator to polymerize water or a mixture of methanol and miscible organic compounds, preferably a complexing agent or alkylene oxide to form a polyether. Compounds that are suitable complexing agents and initiators are described in detail below. Most preferred solvents are water or a mixture of water and a complexing agent. Although not preferred, different solvents may be used to form solutions or dispersions of metal salts and solutions or dispersions of metal cyanide compounds. If different solvents are used, they are suitably miscible with each other.

By "metal salt" is meant a salt of the formula M _x A _y or M ³ _x A _y , wherein M and M ³ are each a polyvalent metal that forms an insoluble precipitate with the metal cyanide group M ¹ (CN) _r (X) _t Ions, and A is an anion which forms a water-soluble salt with M ions).

M and M ³ are 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 . M and M ³ are more preferably Zn ⁺² , Fe ⁺² , Co ⁺² , Ni ⁺² , La ⁺³ and Cr ⁺³ . M is most preferably Zn ⁺² .

Suitable anions A include halides such as chloride and bromide, nitrates, sulfates, carbonates, cyanides, oxalates, thiocyanates, isocyanates, perchlorates, isothiocyanates, alkanesulfonates, for example methanesulfonates, Arylenesulfonates such as p-toluenesulfonate, trifluoromethanesulfonate (triplate) and C _1-4 carboxylates. Chloride ions are particularly preferred.

Solutions of metal salts can generally be prepared by dissolving the metal salts directly in an inert solvent.

The metal cyanide compound is a compound of the formula B _w [M ¹ (CN) _r (X) _t ], wherein M ¹ is a transition metal ion and each X is a group other than cyanide, independently coordinated with M ¹ ion , B is hydrogen or _{^{M 1 (CN) r (X}} ) t metal to form a group of water-soluble salts atom, w is the absolute value of the _{^{M 1 (CN) r (X}} ) t group atoms, r is from 4 to 6 and t is 0 to 2). B is preferably hydrogen or an alkali metal, for example lithium, potassium, sodium or cesium.

M ¹ is 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 or V ⁺⁵ . Among the above, those having an oxidation state of +3 are more preferable. Co ⁺³ and Fe ⁺³ are even more preferred, and Co ⁺³ is most preferred.

Preferred groups X include anions such as halides (especially chloride), hydroxides, sulfates, carbonates, oxalates, thiocyanates, isocyanates, isothiocyanates, C _1-4 carboxylates and nitrites (NO ₂ ^−). ), And uncharged species such as CO, H ₂ O, and NO. Particularly preferred groups X are NO, NO ₂ ^- and CO.

r is preferably 5 or 6, more preferably 6, and t is preferably 0 or 1, most preferably 0. In most cases, r + t is six. w is generally 2 or 3, most typically 3.

Mixtures of two or more metal cyanide compounds may be used. In addition, the solution may also contain a compound of the formula B _w M ² (X) ₆ , wherein M ² is a transition metal and B, w and X are as defined above. M ² may be the same as or different from M ¹ . The X groups in all M ² (X) ₆ need not all be identical.

Solutions or dispersions of metal cyanide compounds can be prepared in a number of ways. If the metal cyanide compound is an alkali metal salt, it is conveniently added directly to an inert solvent. When the metal cyanide compound is an acid (ie, H _w [M ¹ (CN) _r (X) _t ]), a convenient way to prepare a solution or dispersion is to add the corresponding alkali metal salt to an inert solvent and then Ion exchange techniques are used to replace ions with hydrogen, for example by adding strong inorganic acids such as sulfuric acid or hydrochloric acid (after separation from salts formed during the reaction) or by treatment with a cation exchange resin in the form of hydrogen. These methods are described more fully in the US patent entitled "Method for Preparing Metal Cyanide Catalyst / Polyol Initiator Slurries" of the corresponding Weehmeyer, filed identically to this application.

The starting solution or dispersion of the metal cyanide compound suitably contains from about 0.1 to about 30% by weight, preferably from about 1 to about 25% by weight, more preferably from about 5 to about 20% by weight of the metal cyanide compound. . The starting solution or dispersion of the metal salts suitably contains about 0.1 to about 70 weight percent, preferably about 5 to about 50 weight percent, more preferably about 10 to about 35 weight percent metal salt.

The solution or dispersion of the metal salt is then mixed with the solution or dispersion of the metal cyanide compound in the presence of the organic polyacid. The organic polyacid and metal cyanide compound are conveniently mixed before adding the metal salt solution. Alternatively, both starting solution or dispersion can be added together with the organic polyacid. Although not preferred, a third method is to add an organic polyacid immediately after mixing the starting solution or dispersion.

If the organic polyacid is an insoluble polymer, it is preferably swollen in an inert solvent before being combined with the starting solution or dispersion.

The mixing temperature is not critical as long as the starting material remains in solution until mixing is performed. Most suitable are temperatures between about 10 ° C. and the boiling point of the inert solvent, in particular 15-40 ° C. Mixing can be carried out with rapid shaking. Close mixing schemes as described in US Pat. No. 5,470,813 can be used, but this is not necessary.

In precipitating the catalyst, at least enough metal salts are used and, if used, metal cyanide ions (M ¹ (CN) _r (X) _t , with each equivalent of organic polyacid and each equivalent of M ² (X) ₆ ions ) 1 equivalent of metal ion (M) is provided for each equivalent.

In general, more active catalysts have been found to be those prepared using excess metal salts. This excess metal is considered to be present in the catalyst complex as a salt in the form of M _x A _y or M ³ _x A _y , where A is an anion and x and y are numbers that cause the salt to be electrostatically neutral. . Such excess metal salt is, for example, about 3 equivalents or less, preferably about 1.1 to 3 equivalents, more preferably, metal salt per combined equivalent of metal cyanide ions, organic polyacids + certain M ² (X) ₆ ions Can be added to the precipitation step by adding about 1.5 to about 2.5 equivalents.

Another method of adding excess metal salt is performed in a separate step following the precipitation step, as described more fully below.

When the starting solution is mixed, the complex of metal catalyst and organic polyacid is formed as a solid precipitate. While not wishing to be bound by any particular theory, the invention provides that some of the M ions are acid groups and M ¹ (CN) _r (X) _t ions on the organic polyacid (or M ² (X) ₆ ions, if present). Is considered to form an ionic bond. Different acid groups on organic polyacid molecules form ionic bonds to other M ions (in the case of polycarboxylic acids) [M ¹ (CN) _r (X) _t -M ^{+ --} OOC-R-COO ^-- M ⁺ It is also considered to form a "bridge" which can be represented by -M ¹ (CN) _r (X) _t ]. Since M ¹ (CN) _r (X) _t ions are also multivalent, they are ion bonded to additional M ions and also ionic bonds with other M ¹ (CN) _r (X) _t ions and / or other acid groups, etc. Has This allows for formation of relatively large particles of catalyst complex that can be more easily recovered from the polyether polyols. When insoluble organic polyacids are used, this allows the formation of a catalyst complex bonded directly to the particulate substrate.

In a second method of preparing the catalyst, the organic polyacid is first converted to the M form and then contacted with a solution of the metal cyanide compound. The organic polyacid is conveniently converted to the M form by washing one or more times with a metal salt (M _x A _y ) solution until the counterion on the acid group is replaced by M ions. The organic polyacid in the form of M ^{1 is} then contacted with a solution of the metal cyanide compound B _w [M ¹ (CN) _r (X) _t ]. M ¹ (CN) _r (X) _t ions are considered to react with M ions to form a “bridge” between the M ¹ (CN) _r (X) _t group and the organic polyacid molecule. In this method, it is preferable to subsequently treat the catalyst with an additional amount of the metal salt compound M _x A _y or M ³ _x A _y to ensure a more complete reaction of the M ¹ (CN) _r (X) _t group.

In either of the two methods above, the reaction sequence may optionally be carried out two or more times in succession. Similarly, the metal salt solution or metal cyanide compound solution can be dispensed in portions or added slowly.

Although the complexing agent is an optional component, the catalyst can be complexed with an organic complexing agent. While catalytic activity may vary depending on the choice of particular complexing agent, many complexing agents are potentially useful. Examples of such complexing agents include alcohols, aldehydes, ketones, ethers, amides, nitriles and sulfides.

Suitable alcohols include monoalcohols and polyalcohols. Suitable monoalcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, octanol, octadecanol, 3-butyn-1-ol, 3-butene-1-ol, propargyl Alcohols, 2-methyl-2-propanol, 2-methyl-3-butyn-2-ol, 2-methyl-3-buten-2-ol, 3-butyn-1-ol, 3-buten-1-ol and Class 1-3 butoxy-2-propanol. Suitable monoalcohols also include halogenated alcohols, for example 2-chloroethanol, 2-bromoethanol, 2-chloro-1-propanol, 3-chloro-1-propanol, 3-bromo-1-propanol, 1,3 Dichloro-2-propanol, 1-chloro-2-methyl-2-propanol and nitroalcohols, keto-alcohols, ester-alcohols, cyanoalcohols and other inert substituted alcohols.

Suitable polyalcohols include ethylene glycol, propylene glycol, glycerin, 1,1,1-trimethylol propane, 1,1,1-trimethylol ethane, 1,2,3-trihydroxybutane, pentaerythritol, xylitol , Arabitol, mannitol, 2,5-dimethyl-3-hexine-2,5-diol, 2,4,7,9-tetramethyl-5-decine-4,7-diol, sucrose, sorbitol, alkyl glucoside Such as methyl glucoside and ethyl glucoside. Low molecular weight polyether polyols, especially those having an equivalent weight of about 350 or less, more preferably about 125 to 250, are also useful complexing agents.

Examples of suitable aldehydes include formaldehyde, acetaldehyde, butyraldehyde, valeric acid aldehyde, glyoxal, benzaldehyde and toluic acid aldehyde. Suitable ketones include acetone, methyl ethyl ketone, 3-pentanone and 2-hexanone.

Suitable ethers include cyclic ethers such as dioxane, trioxymethylene and paraformaldehyde, as well as acyclic ethers such as diethyl ether, 1-ethoxy pentane, bis (betachloroethyl) ether, methyl propyl Dialkyl ethers of ethers, diethoxy methane, alkylene or polyalkylene glycols such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and octaethylene glycol dimethyl ether.

Amides such as formamide, acetamide, propionamide, butyramide and valericamide are useful complexing agents. Esters such as amyl formate, ethyl formate, hexyl formate, propyl formate, ethyl acetate, methyl acetate and triethylene glycol diacetate can also be used. Suitable nitriles include acetonitrile and propionnitrile. Suitable sulfides include dimethyl sulfide, diethyl sulfide, dibutyl sulfide and diamyl sulfide.

Compounds having S═O groups such as dimethyl sulfoxide and sulfolane are also useful complexing agents.

Preferred complexing agents are tert-butanol, tert-butoxy-2-propanol, polyether polyols having an equivalent weight of about 75 to 350 and dialkyl ethers of alkylene and polyalkylene glycols. Particularly preferred complexing agents are tert-butanol, tert-butoxy-2-propanol, polyether polyols having an equivalent weight of 125 to 250 and dimethyl ether of mono-, di- or triethylene glycol. Tertiary butanol and glim (1,2-dimethoxy ethane) are most preferred.

In one method of treatment, the complexing agent, either pure or as an aqueous solution, is added before the catalyst complex is precipitated, usually by adding the complexing agent immediately after mixing the starting solution or dispersion. If desired, the complexing agent may be mixed in one or both of the starting solution or dispersion. After adding this starting amount of the complexing agent, the mixture is generally stirred for several minutes to allow the catalyst complex to form and precipitate.

If desired, the catalyst complex may then be subjected to one or more subsequent treatments using complexing agents. A common and fully suitable practice is to isolate the precipitated catalyst, for example by filtration or centrifugation, and then treat it several times with a mixture of complexing agent and water (and optionally a polyether polyol). It is more preferable to increase the concentration of the complexing agent in each successive treatment, and it is particularly preferable to carry out the final treatment using a pure complexing agent or a mixture of complexing agent and polyether polyol. Each of these treatments is conveniently carried out by reslurried in the liquid while shaking the catalyst complex for several minutes and then filtering.

In addition, when an alkali metal salt is used as the starting solution, it is highly desirable to wash out the precipitated catalyst complex to remove residual alkali metal ions. The washing step is preferably carried out using water or a mixture of water and a complexing agent. In the latter case, washing and treatment with complexing agents are carried out simultaneously. The washing preferably continues at least essentially until all unnecessary ions, in particular alkali metal and halide ions, are removed from the complex.

It may be desirable to provide additional amounts of metal salts (M _x A _y or M ³ _x A _y ) to the wash or complexing agent treatment solution. As mentioned above, good catalytic activity often occurs when excess metal salts are present in the catalyst complex. Such excess metal salts may be added after the precipitation step by including additional amounts of metal salts in one or more washing or treating solutions. As mentioned above, the total amount of metal salts is advantageously about 3 equivalents or less, preferably about 1.1 to about 3 equivalents, more preferably metal cyanide ions, organopolyacid plus M ² (X) ₆ ions Preferably from about 1.5 to about 2.5 equivalents. If desired, other salts M ³ _x A _y may be used instead of those used in the precipitation step. In particular, although M and M ³ are preferably the same, M and M ³ may be different metals.

If a polyether polyol is used in the catalyst complex, it may be added with the starting amount of the complexing agent or in one or more subsequent washing steps of the complex.

In another method of treatment, the catalyst complex is precipitated from the starting solution and washed with water to remove unwanted ions. The precipitate is then combined with a small amount of solution containing water and a complexing agent. If desired, the solution may contain additional M _x A _y or M ³ _x A _y salts as described above. This amount of added solution is preferably an amount that can be absorbed by the precipitate. Typical amounts of the solution are about 0.5 to about 2 ml, preferably about 0.8 to about 1.5 ml, more preferably about 1 to about 1.5 ml, per gram of precipitate isolated. The complexing agent is advantageously present with water in a weight ratio of about 90:10 to about 10:90, preferably about 70:30 to about 30:70. If desired, polyether polyols may be included in the solution. The resulting catalyst complex may be used without further treatment to dryness or may be subjected to further washing steps using water as described above, but without carrying out additional washing steps using complexing agents or polyether polyols. It is preferable not to.

The precipitated and treated catalyst complex is conveniently dried at moderately elevated temperatures (eg, about 50-60 ° C.) under vacuum, to remove excess water and volatile organics. Preferably, the catalyst complex is dried until it reaches a certain weight. However, the drying step may be omitted in some cases.

The resulting product is a complex of insoluble metal cyanide complexed with an excess metal salt to complex with an organic polyacid compound. The catalyst complex tends to have a relatively large particle size even when the organic polyacid is, for example, low molecular weight species such as citric acid and 1,3,5-benzene tricarboxylic acid. If the organic polyacid is a polymeric, in particular a water insoluble polymer, the catalyst can be easily filtered and in the form of beads or particles having a predetermined particle size. Metal-containing cyanide catalysts are represented by the formula M _b [M ¹ (CN) _r (X) _t ] _c [M ² (X) ₆ ] _d nM ³ _x A _y , where M, M ¹ , M ² , M ³ , X, A, b, c, d, n, r, t, x and y are all as defined above).

Of particular interest are the following catalysts:

Zinc hexacyanocobaltate.nZnCl ₂ ;

Zn [Co (CN) ₅ NO] .nZnCl ₂ ;

_{Zn s [Co (CN) 6} ] o [Fe (CN) 5 NO] p · zL · nZnCl 2 (o , and p is a positive number, s is 1.5o + p);

Zn _s [Co (CN) ₆ ] _o [Co (NO ₂ ) ₆ ] _p [Fe (CN) ₅ NO] _q nZnCl ₂ (o, p and q are positive numbers, s is 1.5 (o + p) ) + q);

Zinc hexacyanocobaltate.nLaCl ₃ ;

Zn [Co (CN) ₅ NO] nLaCl ₃ ;

Zn _s [Co (CN) ₆ ] _o [Fe (CN) ₅ NO] _p nLaCl ₃ (o and p are positive numbers, s is 1.5o + p);

Zn _s [Co (CN) ₆ ] _o [Co (NO ₂ ) ₆ ] _p [Fe (CN) ₅ NO] _q nLaCl ₃ (o, p and q are positive numbers, s is 1.5 (o + p) ) + q);

Zinc hexacyanocobaltate.nCrCl ₃ ;

Zn [Co (CN) ₅ NO] nCrCl ₃ ;

Zn _s [Co (CN) ₆ ] _o [Fe (CN) ₅ NO] _p nCrCl ₃ (o and p are positive numbers, s is 1.5o + p);

Zn _s [Co (CN) ₆ ] _o [Co (NO ₂ ) ₆ ] _p [Fe (CN) ₅ NO] _q nCrCl ₃ (o, p and q are positive numbers, s is 1.5 (o + p) ) + q);

Magnesium hexacyanocobaltate.nZnCl ₂ ;

Mg [Co (CN) ₅ NO] nZnCl ₂ ;

_{Mg s [Co (CN) 6} ] o [Fe (CN) 5 NO] p · nZnCl 2 ( and o and p are positive numbers, s is 1.5o + p);

Mg _s [Co (CN) ₆ ] _o [Co (NO ₂ ) ₆ ] _p [Fe (CN) ₅ NO] _q nZnCl ₂ (o, p and q are positive numbers, s is 1.5 (o + p) ) + q);

Magnesium hexacyanocobaltate.nLaCl ₃ ;

Mg [Co (CN) ₅ NO] nLaCl ₃ ;

Mg _s [Co (CN) ₆ ] _o [Fe (CN) ₅ NO] _p nLaCl ₃ (o and p are positive numbers, s is 1.5o + p);

Mg _s [Co (CN) ₆ ] _o [Co (NO ₂ ) ₆ ] _p [Fe (CN) ₅ NO] _q nLaCl ₃ (o, p and q are positive numbers, s is 1.5 (o + p) ) + q);

Magnesium hexacyanocobaltate-nCrCl ₃ ;

Mg [Co (CN) ₅ NO] nCrCl ₃ ;

Mg _s [Co (CN) ₆ ] _o [Fe (CN) ₅ NO] _p nCrCl ₃ (o and p are positive numbers, s is 1.5o + p);

Mg _s [Co (CN) ₆ ] _o [Co (NO ₂ ) ₆ ] _p [Fe (CN) ₅ NO] _q nCrCl ₃ (o, p and q are positive numbers, s is 1.5 (o + p) ) + q) and

Various complexes as described in column 3 of US Pat. No. 3,404,109.

In all cases, the catalyst is complexed with organic polyacids and, optionally, one or more other complexing agents and / or water.

The catalyst complex of the present invention is used to polymerize alkylene oxides to produce polyethers. In general, the process involves mixing a catalytically effective amount of catalyst and alkylene oxide under polymerization conditions and continuing to polymerize until the alkylene oxide feed is essentially depleted. The catalyst concentration is selected to polymerize the alkylene oxide at the desired rate or within the desired time. Ignoring the polymer or, if not present in amount of alkylene oxide and, a catalyst initiator, and a combined weight of comonomers 100 manbudang metal cyanide catalyst (binding number and a complexing agent (s) as described above and M _b [M ¹ (CN) _r (X) _t ] _{c. n} M ³ _x A _y ), sufficient to provide about 5 to about 10,000 parts by weight. More preferred catalyst amounts are about 50 ppm, in particular about 100 ppm to about 5000 ppm, more preferably about 1000 ppm on the same basis.

In order to prepare high molecular weight polyfunctional polyethers, it is not necessary to include the initiator compound. However, in order to control the molecular weight and provide the desired functionality (number of hydroxyl groups per molecule) or the desired terminal functional groups, the initiator compounds described above are preferably mixed with the catalyst complex at the beginning of the reaction. Suitable initiator compounds include monoalcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, octanol, octadecanol, 3-butyn-1-ol, 3-butene- 1-ol, propargyl alcohol, 2-methyl-2-propanol, 2-methyl-3-butyn-2-ol, 2-methyl-3-buten-2-ol, 3-butyn-1-ol and 3- Butene-1-ol. Suitable monoalcohol initiator compounds include halogenated alcohols such as 2-chloroethanol, 2-bromoethanol, 2-chloro-1-propanol, 3-chloro-1-propanol, 3-bromo-1-propanol, 1, 3-dichloro-2-propanol, 1-chloro-2-methyl-2-propanol, as well as nitroalcohols, keto-alcohols, ester-alcohols, cyanoalcohols and other inert substituted alcohols. Suitable polyalcohol initiators include ethylene glycol, propylene glycol, glycerin, 1,1,1-trimethylol propane, 1,1,1-trimethylol ethane, 1,2,3-trihydroxybutane, pentaerythritol, xyl Tol, arabitol, mannitol, 2,5-dimethyl-3-hexine-2,5-diol, 2,4,7,9-tetramethyl-5-decine-4,7-diol, sucrose, sorbitol, alkyl Glucosides such as methyl glucoside and ethyl glucoside. Low molecular weight polyether polyols, especially those having an equivalent weight of about 350 or less, more preferably about 125 to 250, are also useful initiator compounds.

Among the alkylene oxides that can be polymerized with the catalyst complex of the present invention are ethylene oxide, propylene oxide, 1,2-butylene oxide, styrene oxide and mixtures thereof. Various alkylene oxides can be polymerized 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. Particular preference is given to propylene oxide alone or to a mixture of at least about 75% by weight of propylene oxide and up to about 25% by weight of ethylene oxide.

In addition, monomers copolymerized with alkylene oxides in the presence of catalyst complexes can be used to prepare modified polyether polyols. Such comonomers include the oxetanes described in US Pat. Nos. 3,278,457 and 3,404,109, and the anhydrides described in US Pat. Nos. 5,145,883 and 3,538,043, which are polyethers and polyesters or polyetheresters, respectively. Obtain a polyol. Hydroxyalkanoates such as lactic acid, 3-hydroxybutyrate, 3-hydroxyvalerate (and dimers thereof), lactones and carbon dioxide are examples of other suitable monomers that can be copolymerized with the catalyst of the present invention. .

The polymerization reaction usually proceeds well at temperatures of about 25 to about 150 ° C. or higher, preferably about 80 to 130 ° C. Convenient polymerization techniques include mixing the catalyst complex and the initiator and pressing the reactor with alkylene oxide. After a short induction period, the polymerization proceeds as indicated by the pressure loss in the reactor. Once the polymerization is initiated, additional alkylene oxide is conveniently fed to the reactor until sufficient alkylene oxide is added as necessary to produce the desired equivalent polymer.

Another convenient polymerization technique is the continuous process. In this continuous process, the activation initiator / catalyst mixture is continuously fed to a continuous reactor such as a continuous stirred tank reactor (CSTR) or tubular reactor. The alkylene oxide feed is introduced into the reactor and the product is separated off continuously.

Since the particle size of the catalyst complex is somewhat larger than conventional unsupported metal cyanide catalysts, catalyst separation by liquid-solid separation techniques is easier. The catalyst can be recycled as the case may be.

The catalyst of the present invention is particularly useful for preparing propylene oxide homopolymers and random copolymers of propylene oxide with up to about 15% by weight of ethylene oxide (based on all monomers). The hydroxyl equivalent of the polymer of particular interest is about 800, preferably about 1000 to about 5000, preferably about 4000, more preferably about 2500, and an unsaturation of 0.02 meq / g or less, preferably about It is 0.01 meq / g or less.

The resulting polymer may have a variety of uses depending on its molecular weight, equivalent weight, functionality and the presence of functional groups. The polyether polyols thus prepared are useful as raw materials for producing polyurethanes. Polyethers can also be used as surfactants, working fluids, as raw materials for the preparation of 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 thereof. All parts and percentages are by weight unless otherwise specified.

Example 1

A. Preparation of Catalyst Complex A

Solid 1,3,5-benzene tricarboxylic acid (BTA) (5.0 g, 0.0714eq.) Is added to 400 ml of water with stirring. Solid K ₃ Co (CN) ₆ (4.0 g, 0.036 eq.) Is added. A white slurry of BTA dispersed in a colorless solution is obtained. The slurry is stirred for 10 minutes. A solution of 12.38 g (0.1128 eq., 5% excess) of zinc acetate dihydrate in 100 ml of water and 100 ml of tert-butanol is then added for 30 minutes with continuous stirring. When a zinc acetate solution is added, white agglomerates are formed and the mixture is concentrated during residual stirring. After all zinc acetate solution is added, the mixture is stirred for 10 minutes and filtered through Whatman ^R # 41 filter paper. Filtration proceeds quickly to give a slightly cloudy filtrate.

The collected solid is reslurried in a solution of 6.45 g (0.094 eq.) Of zinc chloride in 140 ml of tert-butanol and 60 ml of water. After stirring for 10 minutes, it is filtered again. During this time the solid is reslurried once more in 200 ml tert-butanol, stirred for 10 minutes and filtered. The collected solids are then dried overnight at 50 ° C. in a vacuum oven. The final mass of dried solids is 10.04 g.

B. Preparation of Catalyst Complex B

A solution of potassium hydroxide in water (0.005 mol KOH in 50 ml of water) is added to solid 1,3,5-benzene tricarboxylic acid (BTA) (3.71 g, 0.177 mmol) and diluted to 300 ml with additional water. Additional 0.26 g of solid 85% KOH and a small amount of potassium bicarbonate are added to form a clear colorless solution. Solid K ₃ Co (CN) ₆ (4.0 g, 0.012 mol) is added with stirring. Then a solution of 19.35 g (0.142 mol) of zinc chloride in 40 ml of water is added with constant stirring. When a zinc chloride solution is added, a white coagulum is formed. A solution of 50 ml of water and 50 ml of tert-butanol is added immediately. The mixture is stirred for 10 minutes and filtered through Whatman ^R # 41 filter paper. The filtered solid is reslurried in zinc chloride solution (6.45 g, 0.047 mol) in 140 ml tert-butanol and 60 ml water, stirred for 10 minutes and filtered again. The filtered solid is then reslurried in 200 ml tert-butanol, stirred for 10 minutes, filtered and dried in a vacuum oven at 50 ° C. The mass of the final product is 10.16 g.

C. Propylene Oxide Polymerization Using Supported Catalysts A and B

0.12 g of 700 MW poly (propylene oxide) triol, 0.58 g of propylene oxide and 0.03 g of catalyst complex A were added to a sealed bottle and heated at 90 ° C. for 18 hours to evaluate supported catalyst A. Within 2 hours, a rich mixture of nearly stirrable poly (propylene glycol) appears in the bottle. After 18 hours, essentially quantitative conversion of propylene oxide occurs. Gel permeation chromatography confirms the presence of poly (propylene glycol) without peaks corresponding to 700MW initiators. The same result is obtained when the experiment is repeated using only 0.006 g of catalyst complex A.

Supported catalyst B is evaluated in the same manner. At a catalyst loading of 0.006 g, 99% of propylene oxide is converted to the polymer within 18 hours. Gel permeation chromatography confirms the presence of poly (propylene glycol) without peaks corresponding to 700MW initiators.

Example 2

A. Preparation of Catalyst Complex C

(Less than 99% of 1000μ), 600ml water, and a few small crosslinked poly (acrylic acid) potassium salt beads (Aldrich catalog # 43,532-5) 5g ^- prepare a mixture (about -COO 0.0454eq.). The beads swell when added to water. To the mixture is added a solution of 4.0 g (0.036 eq.) K ₃ Co (CN) _{6 in} 100 ml of water. This somewhat shrinks the swollen beads.

While mixing, a solution of 19.35 g (0.284 eq.) Of zinc chloride in 50 ml of water is added to the bead mixture for about 1 minute. Immediately a white precipitate forms. Immediately after the addition of zinc chloride, 100 ml of tert-butanol is added. The resulting mixture is stirred for 10 minutes and then filtered through Whatman ^R # 4 filter paper. The filtrate is transparent and colorless. The collected solid is reslurried in a solution of 6.45 g (0.094 eq.) Zinc chloride in 140 ml tert-butanol and 60 ml water, stirred for 10 minutes and filtered again. The filtrate is again transparent and colorless.

The solid is reslurried again in 200 ml of tert-butanol, stirred for 10 minutes and filtered as described above. A white powdery filtrate is obtained, which is dried overnight in a vacuum oven (30 mmHg, 50 ° C.). The mass of dried catalyst complex is 8.85 g.

B. Propylene Oxide Polymerization Using Supported Catalyst C

Supported catalyst C is evaluated in the same manner as described in Example 1. At two loadings of 0.3 g and 0.006 g of the catalyst complex, a mixture of poly (propylene glycol), which is rich and hardly agitable, appears in the bottle within 2 hours. After 18 hours, essentially quantitative conversion of propylene oxide occurs at each catalyst load. In each case, gel permeation chromatography confirms the presence of poly (propylene glycol) without peaks corresponding to 700MW initiators.

Example 3

A. Preparation of Supported Catalyst D

A mixture of 50 ml of water and 5 g of a 45% solution of poly (acrylic acid) sodium salt in water (Aldrich catalog # 41,601-0, about 0.053 mol Na ⁺ ) is prepared. To this mixture is added a solution of 4.0 g (0.036 eq.) Of K ₃ Co (CN) _{6 in} 100 ml of water. While mixing, a solution of 17.1 g (0.045 mol) of zinc salicylate trihydrate in 600 ml of water is added for about 1 minute. Immediately a white precipitate forms. The mixture is stirred for 5 minutes and a solution of 6.8 g of zinc chloride in 20 ml of water is added. After further stirring for 10 minutes, the resulting mixture is filtered through Whatman ^R # 4 filter paper. The collected solid is reslurried in a solution of 6.8 g of zinc chloride in 300 ml of water, stirred for 10 minutes and filtered again. A white filtrate is obtained, which is dried in a vacuum oven (30 mmHg, 50 ° C.) for 1 to 1/2 days. The mass of dried catalyst complex is 6.77 g.

B. Propylene Oxide Polymerization Using Supported Catalyst D

Supported catalyst D is evaluated in the same manner as described in Example 1. At a loading of 0.006 g of catalyst, essentially quantitative conversion of propylene oxide occurs within 18 hours. Gel permeation chromatography confirms the presence of poly (propylene glycol) without peaks corresponding to 700MW initiators.

Example 4

A. Preparation of Supported Catalyst E

A mixture of 50 ml of water and 5 g of a 45% solution of poly (acrylic acid) sodium salt in water (Aldrich catalog # 41,601-0, about 0.053 mol Na ⁺ ) is prepared. To this mixture is added a solution of 4.0 g (0.036 eq.) Of K ₃ Co (CN) _{6 in} 70 ml of water. While mixing, a solution of 19.35 g (0.142 mol) of zinc chloride in 40 ml of water is added for about 1 minute. Immediately a white precipitate forms. A mixture of 50 ml tert-butanol and 50 ml water is added and the mixture is stirred for 10 minutes and then filtered through Whatman ^R # 4 filter paper. The collected solid is reslurried in a solution of 6.45 g of zinc chloride in 140 ml of tert-butanol and 60 ml of water, stirred for 10 minutes and filtered again. The collected solid is then reslurried in 200 ml of tert-butanol, stirred as described above and filtered again. A white filtrate is obtained, which is dried overnight in a vacuum oven (30 mmHg, 50 ° C.). The mass of dried catalyst complex is 9.26 g.

B. Propylene Oxide Polymerization Using Supported Catalyst E

Supported catalyst E is evaluated in the same manner as described in Example 1. At a loading of 0.006 g of catalyst, essentially quantitative conversion of propylene oxide occurs within 18 hours. Gel permeation chromatography confirms the presence of poly (propylene glycol) without peaks corresponding to 700MW initiators.

Example 5

A. Preparation of Supported Catalyst F

Prepare a mixture of 600 ml of water and 1 g of small (99% less than 1000 μ) slightly crosslinked poly (acrylic acid) potassium salt beads (Aldrich catalog # 43,636-4, about 0.0106 mol Na ⁺ ). If swelling. (1) a solution of 1.0 g (0.003 mol) of K ₃ Co (CN) _{6 in} 25 ml of water and (2) 1.34 g (0.01 mol) of zinc chloride in 15 ml of water and 10 ml of tertiary butanol for 15-20 minutes to the mixture. The solution is added simultaneously. Immediately a white precipitate forms. The resulting mixture is stirred for 10 minutes and then filtered through Whatman ^R # 41 filter paper. The collected solid is reslurried in a solution of 1.34 g of zinc chloride in 150 ml of tert-butanol and 150 ml of water, stirred for 10 minutes and filtered again. The collected solids are reslurried again in 300 ml of tert-butanol, stirred for 10 minutes and filtered as described above. A white powdery filtrate is obtained, which is dried overnight in a vacuum oven (30 mmHg, 50 ° C.). The mass of dried catalyst complex is 2.13 g.

B. Propylene Oxide Polymerization Using Supported Catalyst F

Supported catalyst F is evaluated in the same manner as described in Example 1. At a loading of 0.006 g of catalyst complex, essentially quantitative conversion of propylene oxide occurs within 18 hours. In each case, gel permeation chromatography confirms the presence of poly (propylene glycol) without peaks corresponding to 700MW initiators.

Example 6

A. Preparation of Supported Catalyst G

₅ g of poly (acrylic acid, sodium salt) -graft-poly (ethylene oxide) polymer slightly crosslinked to a solution of 4.0 g (0.012 mol) of K ₃ Co (CN) _{6 in} 800 ml of water (Aldrich catalog # 43,278-4) Add. While mixing, a solution of 19.35 g (0.284 eq.) Of zinc chloride in 50 ml of water is added for about 1 minute. Immediately a white precipitate forms. Immediately after the addition of zinc chloride, 100 ml of tert-butanol is added. The resulting mixture is stirred for 10 minutes and then filtered through Whatman ^R # 4 filter paper. The filtrate is transparent and colorless. The collected solid is reslurried in a solution of 6.45 g (0.094 eq.) Zinc chloride in 140 ml tert-butanol and 60 ml water, stirred for 10 minutes and filtered again. The solid is reslurried again in 200 ml of tert-butanol, stirred for 10 minutes and filtered as described above. A white powdery filtrate is obtained, which is dried overnight in a vacuum oven (30 mmHg, 50 ° C.). The mass of dried catalyst complex is 8.45 g.

B. Propylene Oxide Polymerization with Supported Catalyst G

Supported catalyst G is evaluated in the same manner as described in Example 1. At a loading of 0.006 g of catalyst complex, essentially quantitative conversion of propylene oxide occurs within 18 hours. In each case, gel permeation chromatography confirmed the presence of poly (propylene glycol) without peaks corresponding to 700MW initiators.

Example 7

A. Preparation of Supported Catalyst H

15 g of weak acid ion exchange resin (Amberlite ^R CG-50, manufactured by Rohm & Haas, hydrogen form, about 216 meq. Acid group) is slurried in water. 20% by weight of a solution of sodium carbonate in water is added and the mixture is stirred until bubble formation stops. The resin is then washed with 200 ml of a 1% NaOH aqueous solution to convert the resin to Na ⁺ form. The resin is then washed three times with about 200 ml of water each time.

One third of the resulting resin beads are added to 500 ml of water. A solution of 20 g (0.147 mol) of zinc chloride in 40 ml of water is added and the resulting slurry is allowed to stand for several minutes before filtration. The resin is washed with a solution of 10 g (0.073 mol) of zinc chloride in 50 ml of water and again with 200 ml of water. The resin is then slurried in 100 ml of water and a solution of 13.29 g (0.04 mol) of K ₃ Co (CN) _{6 in} 200 ml of water is added to the slurry. The slurry is occasionally stirred for about 1 hour, then left overnight and filtered. The resin is washed again with 400 ml of water and then with a solution of 10 ml of zinc chloride in 100 ml of tert-butanol and 100 ml of water. The resin is then washed with a mixture of 70 ml tert-butanol and 30 ml water and again with 100 ml tert-butanol. The resulting beads are dried overnight at 50 ° C. in a vacuum oven. The mass of dried catalyst complex is 7.68 g.

B. Propylene Oxide Polymerization Using Supported Catalyst H

Supported catalyst H is evaluated in the same manner as described in Example 1. At two loadings of 0.3 g and 0.006 g of catalyst, essentially quantitative conversion of propylene oxide occurs within 18 hours. Gel permeation chromatography confirms the presence of poly (propylene glycol) without peaks corresponding to 700MW initiators.

Example 8

A. Preparation of Supported Catalyst I

15 g of weak acid ion exchange resin (Amberlite ^R CG-50, manufactured by Rohm and Haas, hydrogen form, about 216 meq. Acid group) was washed several times with water, followed by 11 g of zinc acetate dihydrate in 83.3 ml of water and 16.7 ml of tert-butanol. Slurry to a solution of (50 mmol). The resin is then washed three times with about 100 ml of water each time and then slurried in a solution of ₆ g (18 mmol) of K ₃ Co (CN) _{6 in} 100 ml of water and 50 ml of tert-butanol. It is washed three times with 100 ml of water.

The beads are then finally washed with a solution of 6.81 g (50 mmol) zinc chloride in 50 ml of water and 50 ml of tert-butanol, slurried in 100 ml of tert-butanol and discharged. The beads are then dried overnight at 50 ° C. in a vacuum oven. The mass of dried catalyst complex is 22.1 g.

B. Propylene Oxide Polymerization Using Supported Catalyst I

Supported catalyst I is evaluated in the same manner as described in Example 1. At a load of 0.006 g of catalyst complex, 84% of propylene oxide is converted within 18 hours. Gel permeation chromatography confirms the presence of poly (propylene glycol) without peaks corresponding to 700MW initiators.

Aside from using a catalyst loading of 0.03 g of catalyst complex, a similar reaction results in 100% conversion of propylene oxide within 18 hours. The polymer is separated from the beads, the beads are washed several times with methanol and dried overnight at 50 ° C./30 mm Hg vacuum. The beads are then reused at the same concentration, resulting in 100% conversion of propylene oxide. If the second and third recycles are carried out in the same way, the propylene oxide conversion is 77% and 20%, respectively.

Example 9

A. Preparation of Supported Catalyst J

11.11 g of a 45% solution of water-soluble poly (acrylic acid), sodium salt (Aldrich catalog # 41,601-0, about 0.53 mol Na ⁺ ) are diluted to 400 ml with water. To this solution was added solid K ₃ Co (CN) ₆ (4.0 g, 0.012 mol) and solid potassium antimonyl tartrate trihydrate (4 g, 0.006 mol) to form a turbid solution. Then a solution of 22.61 g (0.166 mol) of zinc chloride in 50 ml of water is added with constant stirring. A white precipitate forms when the zinc chloride solution is added. The mixture is stirred for 10 minutes and then filtered through Whatman ^R # 41 filter paper. The filtered solid is reslurried in a solution of zinc chloride (6.45 g, 0.047 mol) in 250 ml of water, stirred for 10 minutes and filtered again. The filtered solid is dried in a vacuum oven at 50 ° C. overnight. The mass of the final product is 6.26 g.

B. Propylene Oxide Polymerization Using Supported Catalyst J

Supported catalyst J is evaluated in the same manner as described in Example 1. At two loadings of 0.3 g and 0.006 g of catalyst, essentially quantitative conversion of propylene oxide occurs within 18 hours. Gel permeation chromatography confirms the presence of poly (propylene glycol) without peaks corresponding to 700MW initiators.

Example 10

A. Preparation of Supported Catalyst K

5 g of alginic acid, sodium salt (Aldrich catalog # 18,094-7, 0.025 mol Na ⁺ ) is added to 400 ml of water with stirring. To this was added a solution of 4.0 g (0.012 mol) of K ₃ Co (CN) _{6 in} 100 ml of water. A solution of 11.72 g (0.86 mol) of zinc chloride in 50 ml of water is then added with stirring for 10 minutes. Immediately a white precipitate forms. 100 ml of tert-butanol are added and the mixture is stirred for 10 minutes and then filtered through Whatman ^R # 41 filter paper. The collected solid is reslurried in a solution of 6.45 g of zinc chloride in 140 ml of tert-butanol and 60 ml of water, stirred for 10 minutes and filtered again. The recovered solid is then reslurried in 250 ml of tert-butanol, stirred as described above and filtered again. A white filtrate is obtained, which is dried overnight in a vacuum oven (30 mmHg, 50 ° C.). The mass of dried catalyst complex is 8.36 g.

B. Propylene Oxide Polymerization Using Supported Catalyst K

Supported catalyst K is evaluated in the same manner as described in Example 1. At a loading of 0.006 g of catalyst, essentially quantitative conversion of propylene oxide occurs within 18 hours. Similar results are obtained with a loading of 0.03 g of catalyst. Gel permeation chromatography confirms the presence of poly (propylene glycol) without peaks corresponding to 700MW initiators.

Example 11

A. Preparation of Supported Catalyst L

16.7 g of a 30% aqueous solution of poly (styrene-alt-maleic acid), sodium salt (Aldrich catalog # 43,529-5, about 0.38 mol Na ⁺ ) are diluted to 200 ml with water. Solid K ₃ Co (CN) ₆ (4.0 g, 0.012 mol) is added to dissolve. In this solution, a solution of 15.24 g (0.112 mol) of zinc chloride in 100 ml of water and 100 ml of tert-butanol is stirred. A white precipitate forms when the zinc chloride solution is added. The mixture is stirred for 10 minutes and then filtered through Whatman ^R # 41 filter paper. The filtered solid was reslurried in a solution of zinc chloride (6.45 g, 0.047 mol) in 140 ml tert-butanol and 60 ml water, stirred for 10 minutes and filtered again. The filtered solid is dried in a vacuum oven at 50 ° C. overnight. The mass of the final product is 10.25 g.

B. Propylene Oxide Polymerization Using Supported Catalyst L

The supported catalyst L is evaluated in the same manner as described in Example 1. At a loading of 0.006 g of catalyst, essentially quantitative conversion of propylene oxide occurs within 18 hours. Gel permeation chromatography confirms the presence of poly (propylene glycol) without peaks corresponding to 700MW initiators. Similar results are seen when increasing the catalyst loading to about 0.03 g.

Claims (18)

At least a stoichiometric amount of the first solution of the metal salt in the inert solvent in the presence of an organic polyacid and the second solution of the metal cyanide compound in the inert solvent and the metal salt based on the amount of the metal cyanide compound and the organic polyacid A method of making a metal cyanide catalyst complex, comprising mixing under conditions such that metal salts, metal cyanide salts and organic polyacids react to form insoluble precipitates in proportions that can be provided in a theoretical amount. The method of claim 1 wherein the organic polyacid contains at least two carboxyl or carboxylate groups per molecule. The metal salt of claim 2, wherein the metal salt is a salt of formula M _x A _y , wherein M is Zn ⁺² , Fe ⁺² , Co ⁺² , Ni ⁺² , La ⁺³ or Cr ⁺³ , and A is chloride, Bromide, nitrate, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, perchlorate, isothiocyanate, methanesulfonate, p-toluenesulfonate, trifluoromethanesulfonate or C _1-4 carboxyl Rate). The compound of claim 3, wherein the metal cyanide compound is a compound of Formula B _w [M ¹ (CN) _r (X) _t ] wherein M ¹ is Co ⁺³ or Fe ^+3, and each X is independently M ¹ Is a group other than cyanide coordinated with ions, B is a metal atom which forms a water-soluble salt with hydrogen or M ¹ (CN) _r (X) _t group, and w is a group of M ¹ (CN) _r (X) _t group Absolute value of the valence, r is 4 to 6 and t is 0 to 2). The method of claim 4 wherein the organic polyacid is a water soluble polymeric polyacid. The method of claim 5 wherein the water soluble polymeric polyacid is a polymer or copolymer of ethylenically unsaturated acids, carboxylated polystyrene polymers or copolymers, sulfonated polystyrene polymers or copolymers, or grafts of poly ((meth) acrylic acid) and polyethers. The method is a copolymer. The method of claim 4 wherein the organic polyacid is a water insoluble polymeric polyacid. 8. The method of claim 7, wherein the water insoluble polymeric polyacid is a sulfonated or carboxylated crosslinked polystyrene copolymer or a crosslinked polymer of ethylenically unsaturated acids. The method of claim 1 wherein a solution of the metal cyanide compound is mixed with the organic polyacid and added to the mixture resulting in a solution of the metal salt. The compound of claim 3, wherein the solution of the metal cyanide compound is a compound of formula B _w M ² (X) ₆ , wherein B, w and X are as defined in claim 3, and M ² is the same as or different from M ^1. And a metal salt is provided in at least stoichiometric amounts based on the amount of the metal cyanide compound, the compound of formula B _w M ² (X) ₆ , and the organic polyacid. . The organic polyacid compound of the M form, wherein M is a polyvalent metal ion that forms an insoluble precipitate with the metal cyanide group, is a solution of the metal cyanide compound and the metal cyanide compound and the M ion in the organic polyacid Reacting to form an insoluble metal cyanide compound bonded to an organic polyacid compound, wherein the metal cyanide catalyst complex is mixed. The method according to claim 11, wherein the M ion is Zn ⁺² , Fe ⁺² , Co ⁺² , Ni ⁺² , La ⁺³ or Cr ⁺³ , and the metal cyanide compound is represented by the formula B _w [M ¹ (CN) _r ( X) a compound of _t ] wherein M ¹ is Co ⁺³ or Fe ⁺³ , X is each independently a group other than cyanide coordinated with M ¹ ion, and B is hydrogen or M ¹ (CN) _r ( X) a metal atom which forms a water-soluble salt with _t group, w is the absolute value of the valence of M ¹ (CN) _r (X) _t group, r is 4 to 6, t is 0 to 2) . The method of claim 12, wherein the organic polyacid is a water soluble polymeric polyacid. The method of claim 13 wherein the water soluble polymeric polyacid is a polymer or copolymer of ethylenically unsaturated acids, carboxylated polystyrene polymers or copolymers, sulfonated polystyrene polymers or copolymers, or grafts of poly ((meth) acrylic acid) and polyethers. The method is a copolymer. The method of claim 12, wherein the organic polyacid is a water insoluble polymeric polyacid. The method of claim 15 wherein the water insoluble polymeric polyacid is a sulfonated or carboxylated crosslinked polystyrene copolymer or a crosslinked polymer of ethylenically unsaturated monomers. The compound of claim 11, wherein the solution of the metal cyanide compound is a compound of formula B _w M ² (X) ₆ , wherein B, w and X are as defined in claim 11, and M ² is the same as or different from M ^1. And a metal salt is provided in at least stoichiometric amounts based on the amount of the metal cyanide compound, the compound of formula B _w M ² (X) ₆ , and the organic polyacid. . And polymerizing the alkylene oxide in the presence of an initiator compound and a polymerization catalyst of the formula: wherein the metal cyanide catalyst is complexed with the organic polyacid compound. ^{_{M b [M 1 (CN)}} r (X) t] c [M 2 (X) 6] d · nM 3 x A y In the above formula, M is an insoluble precipitate with the M ¹ (CN) _r (X) _t group and is a metal ion with at least one water soluble salt, M ¹ and M ² are transition metal ions, which may be the same or different, Each X is independently a group other than cyanide coordinated with M ¹ or M ² ions, M ³ _x A _y is a water soluble salt of metal ion M ³ and anion A, where M ³ is the same as or different from M, b and c, together with d, are a positive number reflecting an electrostatically neutral complex, d is zero or a positive number, x and y are numbers that reflect electrostatically neutral salts, r is 4 to 6, t is from 0 to 2, n is a positive number indicating the relative amount of M ³ _x A _y .