EP1196473A1

EP1196473A1 - Method for preparing metal cyanide catalysts using polycarboxylic acids

Info

Publication number: EP1196473A1
Application number: EP00945237A
Authority: EP
Inventors: Richard M. Wehmeyer
Original assignee: Dow Chemical Co
Current assignee: Dow Chemical Co
Priority date: 1999-07-09
Filing date: 2000-07-07
Publication date: 2002-04-17
Also published as: AR024682A1; JP2003504465A; MXPA02000305A; KR20020027473A; WO2001004180A1; AU5921000A; CN1360608A

Abstract

Metal cyanide catalysts are prepared in the presence of an organic polyacid. Active alkylene oxide polymerization catalysts are formed that have larger particle sizes than conventional metal cyanide catalysts, and thus are more easily separated from a polymer prepared with the catalyst. Preferred organic polyacids are crosslinked or uncrosslinked polymers containing pendant carboxyl or carboxylate groups.

Description

METHOD FOR PREPARING METAL CYANIDE CATALYSTS USING POLYCARBOXYLIC ACIDS

This invention relates to metal cyanide complexes. More particularly, it relates to metal cyanide catalysts having specific complexing agents, to heterogeneous metal cyanide catalysts, and to methods for polymerizing alkylene oxides in the presence of a metal cyanide catalyst.

Polyethers are prepared in large commercial quantities through the polymerization of alkylene oxides such as propylene oxide and ethylene oxide. The polymerization is usually conducted in the presence of an initiator compound and a catalyst. The initiator compound usually determines the functionality (number of hydroxyl groups per molecule) of the polymer and in some instances imparts some desired functionality. The catalyst is used to provide an economical rate of polymerization. Metal cyanide complexes are becoming increasingly important alkylene oxide polymerization catalysts. These complexes are often referred to as "double metal cyanide" or "DMC" catalysts, and are the subject of a number of patents. Those patents include, for example, U. S. Patent 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, among many others. In some instances, these metal cyanide complexes provide the benefit of fast polymerization rates and narrow polydispersities. Additionally, they catalysts are associated with the production of polyethers having very low levels of monofunctional unsatu rated compounds.

The most common of these metal cyanide complexes, zinc hexacyanocobaltate (together with the proper complexing agent and an amount of a polypropylene oxide), has the advantages of being active and of forming polypropylene oxide) having very low unsaturation. However, the catalyst is quite difficult to remove from the product polyether. Because of this difficulty, and because the catalyst can be used in small amounts, the usual practice is to simply leave the catalyst in the product. However, this means that the catalyst must be replaced. In addition, the presence of the residual catalyst in the polyether product has been reported to cause certain performance problems such as poor storage stability. In order to reduce catalyst expense and to avoid these problems, it would be desirable to provide a catalyst that can be recovered easily from the product polyether.

In one aspect, this invention is a process for making a metal cyanide catalyst complex, comprising mixing a first solution of a metal salt in an inert solvent with a second solution of a metal cyanide compound in an inert solvent in the presence of an organic polyacid in proportions such that at least a stoichiometric quantity of the metal salt is provided, based on the amount of the metal cyanide compound and the organic polyacid, under conditions such that the metal salt, metal cyanide salt and organic polyacid react to form an insoluble precipitate.

In a second aspect, this invention is a process for making a metal cyanide catalyst complex, comprising mixing an organic polyacid compound in the M form, where M is a multivalent metal ion that forms an insoluble precipitate with a metal cyanide [M¹(CN)_r(X)] group, with a solution of a metal cyanide compound in an inert solvent, under conditions such that the metal cyanide compound and M ions on the organic polyacid react to form an insoluble metal cyanide compound bound to the organic polyacid compound.

In a third aspect, this invention is a process comprising polymerizing an alkylene oxide in the presence of an initiator compound and a polymerization catalyst, wherein the polymerization catalyst is one made in accordance with the first or second aspect of the invention.

This invention provides two convenient methods for making the catalyst. In the first method, a metal salt and a metal cyanide compound, both as described below, are reacted in the presence of an organic polyacid compound. In this method, the organic polyacid compound is conveniently in the acid, ammonium or alkali metal form (i.e., the counter ion is either hydrogen or an alkali metal ion). In the second method, an organic polyacid is converted to the M form, and this form of the organic polyacid is reacted with a metal cyanide compound to form the catalyst. The second method is particularly applicable when the organic polyacid is a water insoluble or crosslinked polymeric polyacid.

The organic polyacid is a compound or polymer having at least two acid groups, which may be in the salt form. Preferred acid groups are carboxyl (-COOH) and carboxylate (-COOM⁴, where M⁴ is alkali metal or ammonium) groups. The acid groups may be bound to aliphatic, cycloaliphatic or aromatic carbon atoms. The organic polyacid contains at least two acid groups per molecule, and may contain any larger number of acid groups per molecule. Among the suitable organic polyacids are:

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 tetraaccetic acid, nitrilotriacetic acid, and ethylene glycol bis (β-aminoethyl ether)-N,N-tetraacetic acid; Water soluble (non-crosslinked) polymeric polyacids such as alginic acid and polymers and copolymers of 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) and polyethers such as polyethylene oxide; Water insoluble (crosslinked) polymeric polyacids such as sulfonated or carboxylated crosslinked polystyrene copolymers, crosslinked polymers of ethylenically unsaturated monomers such as acrylic acid, methacrylic acid, maleic acid, 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 separately dissolved or dispersed into an inert solvent. In this context "inert" means that the solvent does not react with the metal salt, metal cyanide, polycarboxylic acid compound, any complexing agent that may be present, or the precipitated catalyst complex. The solvent may be water or an organic compound such as methanol, acetone, and isopropanol. The solvent may be a mixture of water or methanol and a miscible organic compound, preferably one that acts as a complexing agent or as an initiator for polymerization alkylene oxides to form a polyether. Compounds that are suitable complexing agents and initiators are described more below. The most preferred solvent is water or a mixture of water and a complexing agent. Although not preferred, different solvents can be used to form the solution or dispersion of the metal salt and the solution or dispersion of the metal cyanide compound. If different solvents are used, they are suitably miscible in each other. By "metal salt", it is meant a salt represented by the general formula M A_y, or

M³ A in which M and M³ are each a multivalent metal ion that forms an insoluble precipitate with a metal cyanide grouping M¹(CN)_r(X)_t and A represents an anion that forms a water-soluble salt with M ion.

M and M³ are preferably metal ions selected from the group consisting of Zn⁺², Fe⁺², Co*², Nr², Mo⁴⁴, Mo Al^*3, V^*4, V⁶, Sr^*2, W⁴, W^*6, Mn⁺², Sn⁺², Sn^*4, Pb⁺², Cu⁺², La⁴³ and Cr . M and M³ are more preferably Zn⁺², Fe^*2, Co^*2, Nr², La⁴³ and Cr⁴³. M is most preferably Zn⁺².

Suitable anions A include halides such as chloride and bromide, nitrate, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, perchlorate, isothiocyanate, an alkanesulfonate such as methanesulfonate, an arylenesulfonate such as p- toluenesulfonate, trifluoromethanesulfonate (triflate) and a C_1-t carboxylate. Chloride ion is especially preferred.

The solution of the metal salt usually can be prepared by directly dissolving the metal salt into the inert solvent.

The metal cyanide compound is represented by the structure B M¹(CN)_r(X)_t], where M¹ is a transition metal ion, each X independently represents a group other than cyanide that coordinates with an M¹ ion; B represents hydrogen or a metal atom that forms a water soluble salt with the M¹(CN)_r(X), group, w represents the absolute value of the valence of the M¹(CN)_r(X)_t grouping; r is from 4 to 6 and t is from 0-2. B is preferably hydrogen or an alkali metal such as lithium, potassium, sodium or cesium. M¹ 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 and V^*5. Among the foregoing, those in the plus-three oxidation state are more preferred. Co^*3 and Fe^*3 are even more preferred and Co^*3 is most preferred.

Preferred groups X include anions such as halide (especially chloride), hydroxide, sulfate, carbonate, oxalate, thiocyanate, isocyanate, isothiocyanate, C^ carboxylate and nitrite (NO₂ ^~), and uncharged species such as CO, H₂O and NO. Particularly preferred groups X are NO, NO₂ and CO. r is preferably 5 or 6, most preferably 6, t is preferably 0 or 1 , most preferably 0. In most cases, r + 1 will equal six. w is usually 2 or 3, and is most typically 3.

Mixtures of two or more metal cyanide compounds can be used. In addition, the solution may also contain compounds that have the structure B_wM (X)₆, wherein M² is a transition metal and B, w and X are as before. M² may be the same as or different from M¹. The X groups in any M²(X)_β do not have to be all the same.

The solution or dispersion of the metal cyanide compound can be prepared in several ways. When the metal cyanide compound is an alkali metal salt, it is conveniently added directly to the inert solvent. When the metal cyanide compound is the acid (i.e. H M¹(CN)_r(X)_t), a convenient way to prepare the solution or dispersion is to add the corresponding alkali metal salt to the inert solvent, and then use an ion exchange technique to replace the alkali metal ions with hydrogen. This can be done, for example, through the addition of a strong mineral acid such as sulfuric or hydrochloric acid (followed by separation from the salts formed in the reaction), or through treatment with a cation exchange resin in the hydrogen form. These methods are described more fully in corresponding U. S. application of Wehmeyer entitled Method for Preparing Metal Cyanide Catalyst/Polyol Initiator Slurries, filed on even date herewith.

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

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 the metal cyanide compound are conveniently mixed before the metal salt solution is added. Alternately, both starting solutions or dispersions may be added simultaneously with the organic polyacid. A third but less preferred way is to mix the starting solutions or dispersions, followed immediately by adding the organic polyacid.

If the organic polyacid is an insoluble polymer, it is preferably swollen in the inert solvent before being combined with the starting solutions or dispersions. The temperature of mixing is not critical, provided that the starting materials remain in solution until the mixing is performed. Temperatures of about 10°C to about the boiling point of the inert solvent, particularly 15-40°C, are most suitable. The mixing can be done with rapid agitation. Intimate mixing techniques as are described in U. S. Patent No. 5,470,813 can be used, but are not necessary. In precipitating the catalyst, at least enough metal salt is used to provide one equivalent of metal ion (M) for each equivalent of metal cyanide ion (M^CNJ X),), plus each equivalent of organic polyacid and each equivalent of M²(X)₆ ion, if used.

It has been found that in general, more active catalysts are those prepared using an excess of the metal salt. This excess metal is believed to exist in the catalyst complex as a salt in the form M_xA_y, or M³ _xA_y, where A is an anion and x and y are numbers that cause the salt to be electrostatically neutral. This excess metal salt can be added in the precipitation step, such as by adding up to about three equivalents of metal salt, preferably from about 1.1 to about 3, more preferably about 1.5 to about 2.5 equivalents of metal salt, per combined equivalents of metal cyanide ion, organic polyacid plus any M²(X)₆ ions.

An alternate way to add the excess metal salt is to do so in a separate step following the precipitation step, as described more fully below.

When the starting solutions are mixed, a complex of the metal catalyst and the organic polyacid forms as a solid precipitate. Although this invention is not bound by any theory, it is believed that some of the M ions form ionic bonds to an acid group on the organic polyacid and to a M¹(CN)_r(X), ion (or an M²(X) on, if present). It is further believed that another acid group on the organic polyacid molecule forms an ionic bond to another M ion, thereby forming a "bridge" that can be represented as (in the case of a polycarboxylic acid) [M¹(CN)_r(X)_t-M^*- OOC-R-COO -M^*-M¹(CN)_r(X)_t]. As the M¹(CN)_r(X)_t ion is also multivalent, it will be ionically bonded to additional M ions, which in turn will have ionic bonds with yet other M¹(CN)_r(X)_t ions and/or other acid groups, and so forth. This permits the formation of relatively large particles of the catalyst complex, which can be more easily recovered from a polyether polyol. When an insoluble organic polyacid is used, this permits the formation of a catalyst complex bound directly to a paniculate substrate. In a second method of making 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 it one or more times with a metal salt (M_xA_y) solution until the counterions on the acid groups have been replaced with the M ion. The organic polyacid in the M¹ form is then contacted with a solution of the metal cyanide compound B M¹(CN)_r(X)J. The M¹(CN)_r(X),ions react with the M ion, which is believed to form a "bridge" between the M¹(CN)_r(X)_t group and the organic polyacid molecule. In this method, it is preferred to subsequently treat the catalyst with an additional quantity of metal salt compound, either M_xA_y or M³ _xA_y, to ensure a more complete reaction of the M^CNJ^X), groups. In either of the two methods described above, the reaction sequence can be performed two or more times in succession, if desired. Similarly, the metal salt solution or the metal cyanide compound solution can be divided into portions and added step-wise.

The catalyst may be complexed with an organic complexing agent, although the complexing agent is optional. A great number of complexing agents are potentially useful, although catalyst activity may vary according to the selection of a particular complexing agent. 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, t-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-butene-2-ol, 3-butyn- 1-ol, 3-butene-1-ol, and 1 -t-butoxy-2-propanol. Suitable monoalcohols also 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 inertly substituted alcohols.

Suitable polyalcohols include ethylene glycol, propylene glycol, glycerine, 1 ,1 ,1-trimethylol propane, 1 ,1 ,1-trimethylol ethane, 1 ,2,3-trihydroxybutane, penta- erythritol, xylitol, arabitol, mannitol, 2,5-dimethyl-3-hexyn-2,5-diol, 2,4,7,9-tetramethyl- 5-decyne-4,7-diol, sucrose, sorbitol, alkyl glucosides such as methyl glucoside and ethyl glucoside. Low molecular weight polyether polyols, particular those having an equivalent weight of about 350 or less, more preferably about 125-250, are also useful complexing agents.

Suitable aldehydes include formaldehyde, acetaldehyde, butyraldehyde, valeric aldehyde, glyoxal, benzaldehyde, and toluic 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(betachloro ethyl) ether, methyl propyl ether, diethoxy methane, dialkyl ethers of alkylene or polyalkylene glycols (such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and octaethyleπe glycol dimethyl ether).

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

Compounds having an S=O group, such as dimethyl sulfoxide and sulfolane, are also useful complexing agents.

Preferred complexing agents are t-butanol, 1-t-butoxy-2-propanol, polyether polyols having an equivalent weight of about 75-350 and dialkyl ethers of alkylene and polyalkylene glycols. Especially preferred complexing agents are t-butanol, 1 -t-butoxy- 2-propanol, polyether polyols having an equivalent weight of 125-250 and a dimethyl ether of mono-, di- or triethylene glycol. t-Butanol and glyme (1 ,2-dimethoxy ethane) are most preferred. In one treating method, the complexing agent, either neat or as an aqueous solution, is added before significant precipitation of the catalyst complex occurs, generally by adding the complexing agent immediately after mixing the starting solutions or dispersions. If desired, the complexing agent can be mixed into either one or both of the starting solutions or dispersions. After adding this initial amount of 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 with complexing agent. A common and entirely suitable practice is to isolate the precipitated catalyst, such as by filtering or centrifuging, and then treating it one or more times with a mixture of the complexing agent and water (and optionally polyether polyol). It is more preferred to increase the concentration of complexing agent in each successive treatment, and especially preferred to perform a final treatment with neat complexing agent or a mixture of complexing agent and polyether polyol. Each of these treatments is conveniently done by re-slurrying the catalyst complex in the liquid with agitation for several minutes and filtering.

In addition, if alkali metal salts are used in the starting solutions, it is highly preferred to wash the precipitated catalyst complex to remove residual alkali metal ions. The washing step is preferably done with water or a mixture of water and complexing agent. In the latter case, washing and treatment with complexing agent is done simultaneously. Washing is preferably continued at least until essentially all unwanted ions, particularly alkali metal and halide ions, are removed from the complex.

It may be desirable to provide additional amounts of the metal salt (M_xA_y or M³ _xA ) in the washing or complexing agent treating solutions. As mentioned before, better catalyst activity is often seen when an excess of the metal salt is present in the catalyst complex. This excess metal salt can be added after the precipitation step by including additional quantities of the metal salt in one or more of the washing or treating solutions. As stated before, the total amount of metal salt is advantageously up to about three equivalents of metal salt, preferably from about 1.1 to about 3, more preferably about 1.5 to about 2.5 equivalents of metal salt, per combined equivalents of metal cyanide ion, organic polyacid plus any M (X)₆ ions. If desired, another salt, M³ _xA can be used instead of that used in the precipitation step. In particular, M and M³ may be different metals, although it is preferred that M and M³ are the same. When a polyether polyol is used in the catalyst complex, it can be added with the initial amount of complexing agent, or in one or more subsequent washings of the complex.

In another treating method, the catalyst complex is precipitated from the starting solutions, and washed with water to remove unwanted ions. The precipitate is then combined with a small amount of a solution containing water and complexing agent. If desired, the solution may contain additional M_xA_y or M³ _xA_y salt, as discussed before. The amount of this added solution is preferably an amount that can be absorbed by the precipitate. A typical amount of solution to be used is from about 0.5 to about 2, preferably about 0.8 to about 1.5, more preferably about 1 to about 1.5 milliliters of solution per gram of isolated precipitate. The complexing agent is advantageously present in a weight ratio of about 90:10 to about 10:90, preferably about 70:30 to about 30:70, with the water. If desired, a polyether polyol can be included in the solution. The resulting catalyst complex can be dried and used without further treatment, or may be subjected to additional washings with water as before, although it is preferred not to perform additional washings with complexing agent or polyether polyol.

The precipitated and treated catalyst complex is conveniently dried, preferably under vacuum and moderately elevated temperatures (such as from about 50-60°C), to remove excess water and volatile organics. Drying is preferably done until the catalyst complex reaches a constant weight. However, the drying step can be omitted if desired.

The resulting product is a complex of an insoluble metal cyanide associated with excess metal salt and complexed with the organic polyacid compound. The catalyst complex tends to have a relatively large particle size, even when the organic polyacid is a low molecular weight species such as, for example, citric acid, and 1,3,5- benzene tricarboxylic acid. When the organic polyacid is polymeric, particularly a water-insoluble polymer, the catalyst is in the form of bead or particles that are easily filterable and have a predetermined particle size. The metal-containing cyanide catalyst can be represented by the general formula: wherein M, M¹, M², M³, X, A, b, c, d, n, r, t, x and y are all as defined before. Among the catalysts of particular interest are: Zinc hexacyanocobaltate • nZnCI₂; Zn[Co(CN)₅NO]» nZnCI₂;

Zn_s[Co(CN)J_β[Fe(CN)₅NO]_p ^» zL • nZnCI. (o, p = positive numbers, s=1.5o + p); Zn,[Co(CN)J_β[Co(NO₂)_β]_p[Fe(CN)₅NO]_<ι • nZnCI₂ (o, p, q = positive numbers, s=1.5(o+p)+q); Zinc hexacyanocobaltate • nLaCI₃;

Zn[Co(CN)₅NO] • nLaCI₃;

Zn[Co(CN)₆] Fe(CN)₅NO]_p ^» nLaCI₃ (o, p = positive numbers, s=1.5o + p);

Zn,[Co(CN)J_β[Co(N0₂)J_p[Fe(CN)₅NO]_q ^• nLaCI₃ (o, p, q = positive numbers, s=1.5(o+p)+q);

Zinc hexacyanocobaltate • nCrCI₃;

Zn[Co(CN)₅NO]^« nCrCI₃;

Zn_s[Co(CN)₆]_o[Fe(CN)₅NO]_p ^» nCrCI₃ (o, p = positive numbers, s=1.5o + p);

Zn.[Co(CN)J_β[Co(NO_a)J_p[Fe(CN)_βNO]_q ^• nCrCI₃ (o, p, q = positive numbers, s=1.5(o+p)+q);

Magnesium hexacyanocobaltate ^»nZnCI₂;

Mg[Co(CN)₅NO] • nZnCI₂;

Mg,[Co(CN)J_β[Fe(CN)_βNO]_p- nZnCI₂ (o, p = positive numbers,s=1.5o + p);

Mg_s[Co(CN) Co(NO₂)₆]_p[Fe(CN)₅NO]_q ^• nZnCI₂ (o, p, q = positive numbers, s=1.5(o+p)+q);

Magnesium hexacyanocobaltate • nLaCI₃;

Mg[Co(CN)₅NO]^» nLaCI₃;

Mg_s[Co(CN)J Fe(CN)₅NO]_p ^» nLaCI₃ (o, p = positive numbers, s=1.5o + p);

Mg_s[Co(CN)J_o[Co(NO₂)J_p[Fe(CN)₅NO]_q • nLaCI₃ (o, p, q = positive numbers, s=1.5(o+p)+q);

Magnesium hexacyanocobaltate • nCrCI₃;

Mg[Co(CN)₅NO] • nCrCI₃;

Mg Co(CN)J_o[Fe(CN)₅NO]_p ^» nCrCI₃ (o, p = positive numbers, s=1.5o + p);

Mg_s[Co(CN)J_o[Co(NO₂)J_p[Fe(CN)_sNO]_q • nCrCI₃ (o, p, q = positive numbers, s=1.5(o+p)+q); as well as the various complexes such as are described at column 3 of U. S. Patent

No. 3,404,109. In all cases, the catalyst is complexed with an organic polyacid compound, and optionally at least one other complexing agent and or water.

The catalyst complex of the invention is used to polymerize alkylene oxides to make polyethers. In general, the process includes mixing a catalytically effective amount of the catalyst with an alkylene oxide under polymerization conditions, and allowing the polymerization to proceed until the supply of alkylene oxide is essentially exhausted. The concentration of the catalyst is selected to polymerize the alkylene oxide at a desired rate or within a desired period of time. An amount of polymer or supported catalyst as described above sufficient to provide from about 5 to about

10,000 parts by weight metal cyanide catalyst (calculated as M_b[M¹(CN)_r(X)J_c • nM _xA_yl ignoring associated water and complexing agent(s)) per million parts combined weight of alkylene oxide, and initiator and comonomers, if present. More preferred catalyst levels are from about 50, especially from about 100, to about 5000, more preferably about 1000 ppm, on the same basis. For making high molecular weight monofunctional polyethers, it is not necessary to include an initiator compound. However, to control molecular weight, impart a desired functionality (number of hydroxyl groups/molecule) or a desired terminal functional group, an initiator compound as described before is preferably mixed with the catalyst complex at the beginning of the reaction. Suitable initiator compounds include monoalcohols such methanol, ethanol, n-propanol, isopropanol, n- butanol, isobutanol, t-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-butene-2-ol, 3-butyn-1-ol, and 3-butene-1 -ol. The suitable monoalcohol initiator compounds include halogenated alcohols such as 2-chloroethanol, 2-bromoethanol, 2-chloro-1-propanol, 3-chloro-1-propanol, 3-bromo-l-propanol, 1 ,3-dichloro-2-propanol, 1 -chloro-2-methyl- 2-propanol as well as nitroalcohols, keto-alcohols, ester-alcohols, cyanoalcohols, and other inertly substituted alcohols. Suitable polyalcohol initiators include ethylene glycol, propylene glycol, glycerine, 1 ,1 ,1-trimethylol propane, 1 ,1 ,1-trimethylol ethane, 1 ,2,3-trihydroxybutane, pentaerythritol, xylitol, arabitol, mannitol, 2,5-dimethyl-3-hexyn- 2,5-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, sucrose, sorbitol, alkyl glucosides such a methyl glucoside and ethyl glucoside. Low molecular weight polyether polyols, particularly those having an equivalent weight of about 350 or less, more preferably about 125-250, are also useful initiator compounds.

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

In addition, monomers that will copolymerize with the alkylene oxide in the presence of the catalyst complex can be used to prepare modified polyether polyols. Such comonomers include oxetanes as described in U. S. Patent Nos. 3,278,457 and 3,404,109, and anhydrides as described in U. S. Patent Nos. 5,145,883 and 3,538,043, which yield polyethers and polyester or polyetherester polyols, respectively. Hydroxyalkanoates such as lactic acid, 3-hydroxybutyrate, 3-hydroxyvalerate (and their dimers), lactones and carbon dioxide are examples of other suitable monomers that can be polymerized with the catalyst of the invention.

The polymerization reaction typically proceeds well at temperatures from about 25 to about 150°C or higher, preferably from about 80-130°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, polymerization proceeds, as indicated by a loss of pressure in the reactor. Once the polymerization has begun, additional alkylene oxide is conveniently fed to the reactor on demand, until enough alkylene oxide has been added to produce a polymer of the desired equivalent weight.

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

Because the particle size of the catalyst complex is somewhat larger than conventional unsupported metal cyanide catalysts, catalyst removal by liquid-solid separation techniques is easier. The catalyst may be recycled if desired.

The catalyst of this invention is especially useful in making propylene oxide homopolymers and random copolymers of propylene oxide and up to about 15 weight percent ethylene oxide (based on all monomers). The polymers of particular interest have a hydroxyl equivalent weight of from about 800, preferably from about 1000, to about 5000, preferably about 4000, more preferably to about 2500, and unsaturation of no more than 0.02 meq/g, preferably no more than about 0.01 meq/g. The product polymer may have various uses, depending on its molecular weight, equivalent weight, functionality and the presence of any functional groups. Polyether polyols so made are useful as raw materials for making polyurethanes. Polyethers can also be used as surfactants, hydraulic fluids, as raw materials for making surfactants and as starting materials for making aminated polyethers, among other uses.

The following examples are provided to illustrate the invention, but are not intended to limit its scope. All parts and percentages are by weight unless otherwise indicated.

Example 1

A. Preparation of catalyst complex A Solid 1 ,3,5-benzene tricarboxylic acid (BTA) (5.0 g, 0.0714 eq.) is added to 400 mL water with stirring. Solid K₃Co(CN)₆ (4.0 g, 0.036 eq.) is added. A white slurry of dispersed BTA in a colorless solution is obtained. The slurry is stirred for 10 minutes. Then, a solution of 12.38 g (0.1128 eq., a 5% excess) zinc acetate dihydrate in 100 mL of water and 100 mL of t-butanol is added over 30 minutes with continued stirring. A white flocculent forms as the zinc acetate solution is added, and the mixture becomes thick while remaining stirrable. After all the zinc acetate solution is added, the mixture is stirred for 10 minutes and filtered through Whatman® #41 filter paper. Filtration proceeds rapidly, yielding a slightly hazy filtrate. The collected solids are reslurried in a solution of 6.45 g (0.094 eq.) zinc chloride in 140 mL t-butanol and 60 mL water. After stirring for 10 minutes, it is again filtered. The solids are once again reslurried, this time in 200 mL t-butanol, stirred 10 minutes and filtered. The collected solids are then dried overnight in a vacuum oven at 50°C. The final mass of the dried solids is 10.04 g. B. Preparation of catalyst complex B

A solution of potassium hydroxide in water (0.053 moles KOH in 50 mL water is added to solid 1,3,5-benzene tricarboxylic acid (BTA) (3.71 g, 0.177 mmol), and diluted to a volume of 300 mL with additional water. An additional 0.26 g of solid 85% KOH and a small quantity of potassium bicarbonate are added to form a clear, colorless solution. Solid K₃Co(CN)₆ (4.0 g, 0.012 mol) is added with stirring. Then, a solution of 19.35 g (0.142 mol) zinc chloride in 40 mL of water is added with continued stirring. A white flocculent forms as the zinc chloride solution is added. A solution of 50 mL water and 50 mL of t-butanol is immediately added. The mixture is stirred for 10 minutes and filtered through Whatman® #41 filter paper. The filtered solid is reslurried in a solution of zinc chloride (6.45 g, 0.047 mol) in 140 mL t-butanol and 60 mL water, stirred 10 minutes and filtered again. The filtered solids are then reslurried in 200 mL t-butanol, stirred 10 minutes, filtered and dried in a vacuum oven overnight at 50°C. The mass of the final product is 10.16 g.

C. Propylene oxide polymerizations with Supported Catalysts A and B

Supported Catalyst A is evaluated by adding 0.12 g of a 700 MW polypropylene oxide) triol, 0.58 g propylene oxide and 0.03 g of Catalyst Complex A in a sealed vial, and heating at 90°C for 18 hours. Within a couple of hours, a thick, barely stirrable mixture of polypropylene glycol) appears in the vial. After 18 hours, essentially quantitative conversion of the propylene oxide occurs. Gel permeation chromatography confirms the presence of a polypropylene glycol) with no peak corresponding to the 700 MW initiator. The same results are seen 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 the propylene oxide is converted to polymer within 18 hours. Gel permeation chromatography confirms the presence of a poly(propylene glycol) with no peak corresponding to the 700 MW initiator.

Example 2

A. Preparation of Catalyst Complex C A mixture of 600 mL water and 5 g (about 0.0454 eq. -COO^") of small (99%

<1000 microns) lightly crosslinked poly(acrylic acid) potassium salt beads (Aldrich catalog #43,532-5) is prepared. The beads swell when added to the water. To the mixture is added a solution of 4.0 g (0.036 eq.) K₃Co(CN)_e in 100 mL of water. This causes the swollen beads to shrink somewhat. With mixing, a solution of 19.35 g (0.284 eq.) zinc chloride in 50 mL water is added to the bead mixture over about 1 minute. A white precipitate forms immediately. As soon as the zinc chloride addition is complete, 100 mL t-butanol is added. The resulting mixture is stirred for 10 minutes, then filtered through Whatman® #4 filter paper. The filtrate is clear and colorless. The collected solids are reslurried in a solution of 6.45 g (0.094 eq.) zinc chloride in 140 mL t-butanol and 60 mL water, stirred for 10 minutes and filtered again. The filtrate is again clear and colorless.

The solids are again reslurried in 200 mL t-butanol, stirred for 10 minutes and filtered as before. A white, powdery filtrate is obtained, which is dried overnight in a vacuum over (30 mm Hg, 50°C). The mass of the dried catalyst complex is 8.85 g.

B. Propylene oxide polymerizations with Supported Catalyst C

Supported Catalyst C is evaluated in the same manner as described in Example 1. At both 0.3 g and 0.006 g loadings of the catalyst complex, a thick, barely stirrable mixture of polypropylene glycol) appears in the vial within a couple of hours. After 18 hours, essentially quantitative conversion of the propylene oxide occurs at each catalyst loading. In each case, gel permeation chromatography confirms the presence of a polypropylene glycol) with no peak corresponding to the 700 MW initiator.

Example 3

A. Preparation of Supported Catalyst D A mixture of 50 mL 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 the mixture is added a solution of 4.0 g (0.036 eq.) K₃Co(CN)₆ in 100 mL of water. With mixing, a solution of 17.1 g (0.045 mol) zinc salicyclate trihydrate in 600 mL water is added over about 1 minute. A white precipitate forms immediately. The mixture is stirred for 5 minutes, and a solution of 6.8 g zinc chloride in 20 mL water is added. After stirring another 10 minutes, the resulting mixture is filtered through Whatman® #4 filter paper. The collected solids are reslurried in a solution of 6.8 g zinc chloride in 300 mL water, stirred for 10 minutes and filtered again. A white filtrate is obtained, which is dried in a vacuum oven (30 mm Hg, 50°C) for 1-1/2 days. The mass of the dried catalyst complex is 6.77 g.

B. Propylene oxide polymerizations with Supported Catalyst D

Supported Catalyst D is evaluated in the same manner as described in Example 1. At a catalyst loading of 0.006 g, essentially quantitative conversion of the propylene oxide occurs in 18 hours. Gel permeation chromatography confirms the presence of a polypropylene glycol) with no peak corresponding to the 700 MW initiator.

Example 4

A. Preparation of Supported Catalyst E

A mixture of 50 mL 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 the mixture is added a solution of 4.0 g (0.036 eq.) K₃Co(CN)_β in 70 mL of water. With mixing, a solution of 19.35 g (0.142 mol) zinc chloride in 40 mL water is added over about 1 minute. A white precipitate forms immediately. A mixture of 50 mL t-butanol and 50 mL water is added, and the mixture is stirred for 10 minutes and filtered through Whatman® #4 filter paper. The collected solids are reslurried in a solution of 6.45 g zinc chloride in 140 mL t-butanol and 60 mL water, stirred for 10 minutes and filtered again. The collected solids are then reslurried in 200 mL t-butanol, stirred as before and filtered again. A white filtrate is obtained, which is dried overnight in a vacuum oven (30 mm Hg, 50°C). The mass of the dried catalyst complex is 9.26 g.

B. Propylene oxide polymerizations with Supported Catalyst E Supported Catalyst E is evaluated in the same manner as described in

Example 1. At a catalyst loading of 0.006 g, essentially quantitative conversion of the propylene oxide occurs in 18 hours. Gel permeation chromatography confirms the presence of a polypropylene glycol) with no peak corresponding to the 700 MW initiator.

Example 5

A. Preparation of Supported Catalyst F

A mixture of 600 mL water and 1 g of small (99% <1000 microns) lightly crosslinked poly(acrylic acid) potassium salt beads (Aldrich catalog #43,636-4, about 0.0106 mol Na^*) is prepared. The beads swell when added to the water. To the mixture are simultaneously added, over 15-20 minutes, (1) a solution of 1.0 g (0.003 mol) K₃Co(CN)_β in 25 mL of water and (2) a solution of 1.34 g (0.01 mol) zinc chloride in 15 mL water and 10 mL t-butanol. A white precipitate forms immediately. The resulting mixture is stirred for 10 minutes, then filtered through Whatman® #41 filter paper. The collected solids are reslurried in a solution of 1.34 g zinc chloride in 150 mL t-butanol and 150 mL water, stirred for 10 minutes and filtered again. The solids are again reslurried in 300 mL t-butanol, stirred for 10 minutes and filtered as before. A white, powdery filtrate is obtained, which is dried overnight in a vacuum oven (30 mm Hg, 50°C). The mass of the dried catalyst complex is 2.13 g.

B. Propylene oxide polymerizations with 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 the catalyst complex, essentially quantitative conversion of the propylene oxide occurs in 18 hours. In each case, gel permeation chromatography confirms the presence of a polypropylene glycol) with no peak corresponding to the 700 MW initiator.

Example 6

A. Preparation of Supported Catalyst G

To a solution of 4.0 g (0.012 mol) K₃Co(CN)₆ in 800 mL of water are added 5 g of a lightly crosslinked poly(acrylic acid, sodium salt)-oτaft-poly(ethylene oxide) polymer (Aldrich catalog #43,278-4). With mixing, a solution of 19.35 g (0.284 eq.) zinc chloride in 50 mL water is added over about 1 minute. A white precipitate forms immediately. As soon as the zinc chloride addition is complete, 100 mL t-butanol is added. The resulting mixture is stirred for 10 minutes, then filtered through Whatman® #4 filter paper. The filtrate is clear and coloriess. The collected solids are reslurried in a solution of 6.45 g (0.094 eq.) zinc chloride in 140 mL t-butanol and 60 mL water, stirred for 10 minutes and filtered again. The solids are again reslurried in 200 mL t-butanol, stirred for 10 minutes and filtered as before. A white, powdery filtrate is obtained, which is dried overnight in a vacuum over (30 mm Hg, 50°C). The mass of the dried catalyst complex is 8.45 g.

B. Propylene oxide polymerizations 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 the catalyst complex, essentially quantitative conversion of the propylene oxide occurs in 18 hours. In each case, gel permeation chromatography confirms the presence of a polypropylene glycol) with no peak corresponding to the 700 MW initiator.

Example 7

A. Preparation of Supported Catalyst H 15 g of a weakly acid ion exchange resin (Amberiite® CG-50, from Rohm &

Haas, hydrogen form, approximately 216 meq. acid groups) are slurried in water. A 20% by weight solution of sodium carbonate in water is added, and the mixture stirred until bubble formation ceased. The resin is then washed with 200 mL of a 1% aqueous NaOH solution to convert the resin to the Na^* form. The resin is then washed three times with about 200 mL of water each time.

One-third of the resulting resin beads is added to 500 mL water. A solution of 20 g (0.147 mol) zinc chloride in 40 mL water is added and the resulting slurry allowed to stand for several minutes before it is filtered. The resin is washed with a solution of 10 g (0.073 mol) zinc chloride in 50 mL water and washed again with 200 mL water. The resin is then slurried in 100 mL water and to the slurry is added a solution of 13.29 g (0.04 mol) K₃Co(CN)₆ in 200 mL water. The slurry is stirred occasionally for about an hour, then left to stand ovemight, and filtered. The resin is again washed with 400 mL of water, then with a solution of 10 g zinc chloride in 100 mL of t-butanol and 100 mL of water. The resin is then washed with a mixture of 70 mL t-butanol and 30 mL water, and again with 100 mL t-butanol. The resulting beads are dried ovemight at 50°C in a vacuum oven. The mass of the dried catalyst complex is 7.68 g.

B. Propylene oxide polymerizations with Supported Catalyst H

Supported Catalyst H is evaluated in the same manner as described in Example 1. At both 0.3 g and 0.006 g catalyst loadings, essentially quantitative conversion of the propylene oxide occurs within 18 hours. Gel permeation chromatography confirms the presence of a polypropylene glycol) with no . peak corresponding to the 700 MW initiator.

Example 8 A. Preparation of Supported Catalyst I

15 g of a weakly acid ion exchange resin (Amberlite® CC-50, from Rohm & Haas, hydrogen form, approximately 216 meq. acid groups) are washed with water several times and then slurried in a solution of 11 g (50 mmol) zinc acetate dihydrate in 83.3 mL water and 16.7 mL t-butanol. 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) K₃Co(CN)₆ in 100 mL water and 50 mL t-butanol. This is followed with three washes with 100 mL water. This sequence of washings is repeated three times.

The beads are then given a final rinse with a solution of 6.81 g (50 mmol) zinc chloride in 50 mL water and 50 mL t-butanol, and slurried in 100 mL t-butanol and drained. The beads are then dried ovemight at 50°C in a vacuum oven. The mass of the dried catalyst complex is 22.1 g.

B. Propylene oxide polymerizations with Supported Catalyst I

Supported Catalyst I is evaluated in the same manner as described in Example 1. At a loading of 0.006 g of the catalyst complex, 84% conversion of the propylene oxide occurs in 18 hours. Gel permeation chromatography confirms the presence of a polypropylene glycol) with no peak corresponding to the 700 MW initiator.

In a similar reaction, except with a catalyst loading of 0.03 g loading of the catalyst complex, 100% conversion of the propylene oxide occurs in 18 hours. The polymer is removed from the beads, and the beads are washed several times with methanol and dried ovemight at 50°C / 30 inches Hg vacuum. The beads are then reused at the same concentration, and 100% conversion of propylene oxide is seen. Second and third recycles are performed in the same manner, with propylene oxide conversions of 77% and 20% respectively.

Example 9

A. Preparation of Supported Catalyst J

11.11 g of a 45% solution of water-soluble polyfacrylic acid), sodium salt (Aldrich catalog # 41,601-0, about 0.53 mol Na^*) is diluted to 400 mL with water. To this solution are added solid K₃Co(CN)₆ (4.0 g, 0.012 mol) and solid potassium antimonyl tartrate trihydrate (4 g, 0.006 mol), to form a hazy solution. Then, a solution of 22.61 g (0.166 mol) zinc chloride in 50 mL of water is added with continued stirring. A white precipitate forms as the zinc chloride solution is added. The mixture is stirred for 10 minutes and filtered through Whatman® #41 filter paper. The filtered solid is reslurried in a solution of zinc chloride (6.45 g, 0.047 mol) in 250 mL water, stirred 10 minutes and filtered again. The filtered solids are dried in a vacuum oven overnight at 50°C. The mass of the final product is 6.26 g.

B. Propylene oxide polymerizations with Supported Catalyst J Supported Catalyst J is evaluated in the same manner as described in

Example 1. At both 0.3 g and 0.006 g catalyst loadings, essentially quantitative conversion of the propylene oxide occurs within 18 hours. Gel permeation chromatography confirms the presence of a polypropylene glycol) with no peak corresponding to the 700 MW initiator.

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 water, with stirring. To this is added a solution of 4.0 g (0.012 mol) K₃Co(CN)₆ in 100 mL water. Then, a solution of 11.72 g (0.86 mol) zinc chloride in 50 mL water is added, with stirring, over 10 minutes. A white precipitate forms immediately. 100 mL t-butanol are added, and the mixture is stirred for 10 minutes and filtered through Whatman® #41 filter paper. The collected solids are reslurried in a solution of 6.45 g zinc chloride in 140 mL t-butanol and 60 mL water, stirred for 10 minutes and filtered again. The collected solids are then reslurried in 200 mL t-butanol, stirred as before and filtered again. A white filtrate is obtained, which is dried overnight in a vacuum oven (30 mm Hg, 50°C). The mass of the dried catalyst complex is 8.36

9-

B. Propylene oxide polymerizations with Supported Catalyst K

Supported Catalyst K is evaluated in the same manner as described in Example 1. At a catalyst loading of 0.006 g, essentially quantitative conversion of the propylene oxide occurs in 18 hours. Similar results are obtained at a catalyst loading of 0.03 g. Gel permeation chromatography confirms the presence of a poly(propylene glycol) with no peak corresponding to the 700 MW initiator. Example 11

A. Preparation of Supported Catalyst L

16.7 g of 30% aqueous solution of poly(styrene-alt-maleic acid), sodium salt (Aldrich 43,529-5, about 0.38 mol Na^*) is diluted to 200 mL with water. Solid K₃Co(CN)₆ (4.0 g, 0.012 mol) is added and dissolved. Into this solution is stirred a solution of 15.24 g (0.112 mol) zinc chloride in 100 mL of water and 100 mL t-butanol. A white precipitate forms as the zinc chloride solution is added. The mixture is stirred for 10 minutes and filtered through Whatman® #41 filter paper. The filtered solid is reslurried in a solution of zinc chloride (6.45 g, 0.047 mol) in 140 mL t-butanol and 60 mL water, stirred 10 minutes and filtered again. The filtered solids are dried in a vacuum oven overnight at 50°C. The mass of the final product is 10.25 g.

B. Propylene oxide polymerizations with Supported Catalyst L

Supported Catalyst L is evaluated in the same manner as described in Example 1. At a catalyst loading of 0.006 g, essentially quantitative conversion of the propylene oxide occurs within 18 hours. Gel permeation chromatography confirms the presence of a polypropylene glycol) with no peak corresponding to the 700 MW initiator. Similar results are seen when the catalyst loading is increased to about 0.03 9-

Claims

CLAIMS:

1. A process for making a metal cyanide catalyst complex, comprising mixing a first solution of a metal salt in an inert solvent with a second solution of a metal ϊ cyanide compound in an inert solvent in the presence of an organic polyacid in proportions such that at least a stoichiometric quantity of the metal salt is provided, based on the amount of the metal cyanide compound and the organic polyacid, under conditions such that the metal salt, metal cyanide salt and organic polyacid react to form an insoluble precipitate.

2. The process of claim 1 wherein the organic polyacid contains at least two carboxyl or carboxylate groups per molecule.

3. The process of claim 2 wherein the metal salt is a salt represented by the general formula M A_y, in which 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, trifluoromethane sulfonate or a C,_, carboxylate

4. The process of claim 3 wherein the metal cyanide compound is represented by the structure B_w[M¹(CN)_r(X)J, where M¹ is Co^*3 or Fe^*3, each X independently represents a group other than cyanide that coordinates with an M¹ ion; B represents hydrogen or a metal atom that forms a water soluble salt with the M¹(CN)_r(X), group, w represents the absolute value of the valence of the M¹(CN)_r(X)_t grouping; r is from 4 to 6 and t is from 0-2.

5. The process of claim 4 wherein the organic polyacid is a water soluble polymeric polyacid.

6. The process of claim 5 wherein said water soluble polymeric polyacid is a polymer or copolymer of an ethylenically unsaturated acid, a carboxylated polystyrene polymer or copolymer, a sulfonated polystyrene polymer copolymer, or a graft copolymer of poly((meth)acrylic acid) and a polyether.

7. The process of claim 4 wherein said organic polyacid is a water insoluble polymeric polyacid.

8. The process of claim 7 wherein said water insoluble polymeric polyacid is a sulfonated or carboxylated crosslinked polystyrene copolymer or a crosslinked polymer of an ethylenically unsaturated acid.

9. The process of claim 1 , wherein said solution of a metal cyanide compound is mixed with the organic polyacid, and the solution of a metal salt is added to the resulting mixture.

10. The process of claim 3, wherein said solution of a metal cyanide compound further contains a compound of the formula B_wM²(X)₆, wherein B, w and X are as defined in claim 3 and M² is a transition metal that may be the same or different that M\ at least a stoichiometric quantity of the metal salt is provided, based on the amount of the metal cyanide compound, the B_wM²(X)₆ compound and the organic polyacid.

11. A process for making a metal cyanide catalyst complex, comprising mixing an organic polyacid compound in the M form, where M is a multivalent metal ion that forms an insoluble precipitate with a metal cyanide group, with a solution of a metal cyanide compound in an inert solvent, under conditions such that the metal cyanide compound and M ions on the organic polyacid react to form an insoluble metal cyanide compound bound to the organic polyacid compound.

12. The process of 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 structure B M¹(CN)_r(X)J, where M¹ is Co^*3 or Fe^*3, each X independently represents a group other than cyanide that coordinates with an M¹ ion; B represents hydrogen or a metal atom that forms a water soluble salt with the M¹(CN)_r(X)_t group, w represents the absolute value of the valence of the M¹(CN)_r(X), grouping; r is from 4 to 6 and t is from 0-2.

13. The process of claim 12 wherein the organic polyacid is a water soluble polymeric polyacid.

14. The process of claim 13 wherein said water soluble polymeric polyacid is a polymer or copolymer of an ethylenically unsaturated acid, a carboxylated polystyrene polymer or copolymer, a sulfonated polystyrene polymer copolymer, or a graft copolymer of poly((meth)acrylic acid) and a polyether.

15. The process of claim 12 wherein said organic polyacid is a water insoluble polymeric polyacid.

16. The process of claim 15 wherein said water insoluble polymeric polyacid is a sulfonated or carboxylated crosslinked polystyrene copolymer or a crosslinked polymer of an ethylenically unsaturated monomer.

17. The process of claim 11 wherein said solution of a metal cyanide compound further contains a compound of the formula B_κM²(X)₆, wherein B, w and X are as defined in claim 11 and M² is a transition metal that may be the same or different that M¹, at least a stoichiometric quantity of the metal salt is provided, based on the amount of the metal cyanide compound, the B_wM²(X)₆ compound and the organic polyacid.

18. A process comprising polymerizing an alkylene oxide in the presence of an initiator compound and a polymerization catalyst, wherein the polymerization catalyst is represented by the general formula: wherein M is a metal ion that forms an insoluble precipitate with the M¹(CN)_r(X)_t group and which has at least one water soluble salt;

M¹ and M² are transition metal ions that may be the same or different; each X independently represents a group other than cyanide that coordinates with an

M¹ or M² ion;

M³ _xA_y represents a water-soluble salt of metal ion M³ and anion A, wherein M³ is the same as or different than M; b and c are positive numbers that, together with d, reflect an electrostatically neutral complex; d is zero or a positive number; x and y are numbers that reflect an electrostatically neutral salt; r is from 4 to 6; t is from 0 to 2; and n is a positive number indicating the relative quantity of M³ _xA_y, and said metal cyanide catalyst is complexed with an organic polyacid compound.