METHOD FOR PRODUCING A POLYETHER

Abstract

Alkylene oxides polymerize in the presence of a catalyst system that includes a double-metal cyanide catalyst. At least one additive is present. The additive is an alkali metal salt, ammonium or quaternary ammonium salt of a monocarboxylic acid having up to 24 carbon atoms; monobasic potassium phosphate, monobasic ammonium phosphate or quaternary ammonium, dibasic ammonium and quaternary ammonium phosphate, or phosphoric acid.

Description

84367-AR-NP POLYETHER POLYMERIZATION PROCESS The present invention relates to processes for polymerizing alkylene oxides to form polyethers. Poly(alkylene oxides) are produced globally in large quantities by the polymerization of one or more alkylene oxides in the presence of a polymerization catalyst. They are important raw materials for the production of polyurethanes and are used as surfactants and industrial solvents, among other applications. The predominant polymerization catalysts are alkali metal hydroxides or alkoxides and certain metal complexes commonly referred to as double metal cyanide (DMC) catalysts. Double metal cyanide catalysts have certain advantages. They do not strongly catalyze a rearrangement of propylene oxide to form propenyl alcohol. Therefore, polyether polyols made using DMC catalysts tend to have lower amounts of unwanted monofunctional polymers. In addition, DMC catalyst residues usually do not need to be removed from the product. This avoids the catalyst neutralization and extraction steps that are necessary when using alkali metal catalysts. However, DMC catalysts have certain disadvantages. They exhibit a latency period after exposure to an alkylene oxide under polymerization conditions before they "activate" and rapid polymerization begins. Another significant problem is that the DMC catalyst performs poorly in the presence of high concentrations of hydroxyl groups. For this reason, DMC catalysts are disadvantaged when... 2005090 of 33 84367-AR-NP manufacture low molecular weight products and in semi-batch processes that begin with equivalent low weight starters. U.S. Patent No. 9,040,657 describes a method for producing a polyether mono- or polyol in the presence of a DMC catalyst and a lanthanide, Group 3-Group 15 metal, or magnesium compound, wherein the lanthanide, Group 3-Group 15 metal, or magnesium compound is bonded to at least one alkoxide, aryloxy, carboxylate, acyl, pyrophosphate, phosphate, thiophosphate, dithiophosphate, phosphate ester, thiophosphate ester, amide, siloxide, hydride, carbamate, or hydrocarbon anion, the lanthanide, Group 3-Group 15 metal, or magnesium compound lacking halide anions. This technology is highly effective in reducing activation time and improving catalyst performance when exposed to high concentrations of hydroxyl groups.However, further improvements are desirable; in particular, a catalyst system that performs better under rigorous polymerization conditions and / or in the polymerization of ethylene oxide would be beneficial. The present invention is a method for producing a polyether, the method comprising: I. forming a reaction mixture comprising a) an initiator containing hydroxyl, b) at least one alkylene oxide, c) a water-insoluble polymerization catalyst complex including at least one double metal cyanide compound, and d) an additive selected from the group consisting of alkali metal, ammonium, and quaternary ammonium salts of monocarboxylic acids having up to 24 carbon atoms; monobasic alkali metal phosphates, dibasic phosphate of 2005090 of 33 84367-AR-NP sodium, monobasic ammonium phosphate, quaternary monobasic ammonium phosphates, tartaric acid, malic acid and succinic acid, and II. Polymerize the alkylene oxide on the hydroxyl-containing initiator in the presence of the water-insoluble polymerization catalyst complex and the additive to produce the polyether. The presence of the additive has been found to significantly increase the activity of the double-metal cyanide catalyst, even when a "promoter" compound as described in WO 2012 / 091968 is present. The additive improves the activation and polymerization rates of the catalyst under conditions of high hydroxyl concentrations and / or very low molecular weight initiators. Most significantly, the presence of the additive improves the catalyst's performance in ethylene oxide polymerizations. With this invention, ethylene oxide can be polymerized even in low molecular weight initiators and even under conditions of high hydroxyl concentrations to produce controlled molecular weight, low-polydispersity poly(ethylene oxide) polymers. In the process of the invention, a polymerization mixture includes: a) a hydroxyl-containing initiator, b) at least one alkylene oxide, c) a water-insoluble polymerization catalyst complex including at least one double metal cyanide compound, and d) an additive as described herein. A polyether is produced by polymerizing the alkylene oxide on the hydroxyl-containing initiator in the presence of the water-insoluble polymerization catalyst complex and the additive. The main functions of the initiator compound are to provide molecular weight control and establish the number of hydroxyl groups the polyether product will have. A hydroxyl-containing initiator compound can 2005090 of 33 84367-AR-NP may contain one or more (preferably two or more) hydroxyl groups and up to 12 or more hydroxyl groups. For example, initiators for producing polyols for use in polyurethane applications usually have two to eight hydroxyl groups per molecule. In some embodiments, the initiator compound will have two to four or two to three hydroxyl groups. In other embodiments, the initiator compound will have four to eight or four to six hydroxyl groups. The initiator compound may have at least two hydroxyl groups located at positions 1, 2, or 1, 3 relative to each other (taking the carbon atom to which one of the hydroxyl groups is attached as position “1”). Mixtures of initiator compounds may be used. The starting compound will have a lower hydroxyl equivalent weight than the monool or polyol product. It may have a hydroxyl equivalent weight of 30 to 500 g / equivalent or more. The equivalent weight may be up to 500, up to 250, up to 125, and / or up to 100 g / equivalent. Illustrative initiators include, but are not limited to, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, cyclohexane dimethanol, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol, sucrose, phenol, and polyphenolic initiators such as bisphenol A or 1,1,1-tris(hydroxyphenyl)ethane, and alkoxylates (such as ethoxylates and / or propoxylates) of any of these having a hydroxyl equivalent weight less than that of the polymerization product. The initiator compound may also be water. The initiator may be neutralized with or contain a small amount of an acid, particularly if the initiator is prepared in the presence of a base (as is frequently the case with glycerin). If an acid is present, it may be present in an amount of approximately 10 to 100 ppm, based on the weight of the initiator, e.g., as 2005090 of 33 84367-AR-NP is described in U.S. Patent No. 6,077,978. The acid can be used in somewhat larger quantities, such as 100 to 1000 ppm, based on the weight of the initiator, as described in U.S. Patent Publication Application No. 2005-0209438. The acid can be added to the initiator before or after combining the initiator with the catalyst complex. Certain initiators can provide specific advantages. Triethylene glycol has been found to be a particularly good initiator for use in batch and semi-batch processes for producing polyether diols. Tripropylene glycol and dipropylene glycol have also been found to be particularly good initiators for use in conjunction with the catalyst complex of the invention. The alkylene oxide may be, for example, ethylene oxide, 1,2-propylene oxide, 2,3-propylene oxide, 1,2-butane oxide, 2-methyl-1,2-butane oxide, 2,3-butane oxide, tetrahydrofuran, epichlorohydrin, hexane oxide, styrene oxide, divinylbenzene dioxide, a glycidyl ether such as bisphenol A diglycidyl ether, allyl glycidyl ether, another polymerizable oxirane, or a mixture of any two or more of these. In some specific embodiments, the alkylene oxide is 1,2-propylene oxide, or a mixture of at least 40% (preferably at least 80%) by weight of propylene oxide and up to 60% by weight (preferably up to 20%) of ethylene oxide. An important advantage of the present invention is that the catalyst can be activated in the presence of ethylene oxide as the sole or predominant alkylene oxide, and that the ethylene oxide can be readily polymerized even on low molecular weight initiators.Therefore, in some embodiments, the alkylene oxide is either ethylene oxide or a mixture of at least 60% or at least 80% by weight of ethylene oxide, and consequently up to 40% or up to 20% of propylene oxide. 2005090 of 33 84367-AR-NP In some embodiments, the reaction mixture contains from 1 to 25 wt% of hydroxyl groups, based on the total weight of the reaction mixture. The reaction mixture may contain, for example, from 4.5 to 20 wt%, 4.5 to 15 wt%, 4.5 to 12 wt%, or 4.5 to 10 wt% of hydroxyl groups for at least a portion of the polymerization reaction. In some embodiments, the reaction mixture contains up to 10% by weight of ethylene oxide. The reaction mixture may contain, for example, up to 8% by weight, up to 6% by weight, or up to 5% by weight of ethylene oxide at a point in the polymerization where the ethylene oxide content (if any) is at its highest. In some embodiments, the reaction mixture contains, for at least a portion of the polymerization reaction, at least 2% by weight or at least 3% by weight of ethylene oxide. The components that make up the reaction mixture can be combined in any order. Polymerization is typically carried out at an elevated temperature. The temperature of the polymerization mixture can be, for example, from 80 to 220 °C (e.g., from 120 to 190 °C). The polymerization reaction is usually carried out at superatmospheric pressure, but it can be performed at atmospheric or even subatmospheric pressures. A preferred pressure is 0 to 10 atmospheres (101 to 1013 kPa), especially 0 to 6 atmospheres (101 to 608 kPa), gauge pressure. Preferably, polymerization is carried out in a vacuum or in an inert atmosphere such as a nitrogen, helium, or argon atmosphere. Sufficient quantity of the water-insoluble polymerization catalyst complex can be used to provide a reasonable polymerization rate. 2005090 of 33 84367-AR-NP, but it is generally desirable to use the smallest possible amount of catalyst complex consistent with reasonable polymerization rates, as this reduces catalyst costs and, if catalyst levels are low enough, can eliminate the need to remove catalyst residues from the product. Using smaller amounts of catalyst also reduces the residual metal content of the product. The amount of catalyst complex can be from 1 to 5000 ppm based on the product weight. The amount of catalyst complex can be at least 2 ppm, at least 5 ppm, at least 10 ppm, at least 25 ppm, or up to 500 ppm, or up to 200 ppm, or up to 100 ppm, based on the product weight. When the catalyst complex contains a hexacyanocobaltate compound, the amount of catalyst complex can be selected to provide 0.25 to 20, 0.5 to 10, 0.5 to 1, or 0.5 to 2.5 parts by weight of cobalt per million parts by weight of product. The polymerization reaction can be carried out in any type of vessel suitable for the pressures and temperatures encountered. In a continuous or semi-batch process, the alkylene oxide, additional initiator compound, and preferably the water-insoluble polymerization catalyst complex, the promoter (if used), and the additive are introduced as polymerization progresses. Consequently, the vessel must have one or more inlets through which these components can be introduced during the reaction. In a continuous process, the reactor vessel must contain at least one outlet through which a portion of the partially polymerized reaction mixture can be removed. In a semi-batch operation, alkylene oxide (and optionally an additional initiator and catalyst complex) is added during the reaction, but the product is usually not removed until the reaction is complete. 2005090 of 33 84367-AR-NP Polymerization. A tubular reactor with multiple injection points for starting materials, a loop reactor, and a continuous stirred tank reactor (CSTR) are all vessel types suitable for continuous or semi-batch operations. The reactor must be equipped with a means of supplying or removing heat so that the temperature of the reaction mixture can be maintained within the required range. Suitable means include various types of heat transfer fluid covers, various types of internal or external heaters, and the like. A cooking stage is conveniently performed on a product that is continuously drawn into a reactor that prevents significant backmixing. Plug flow operation in a tube or tubular reactor is a preferred way of performing such a cooking stage. The product obtained from any of the above processes may contain up to 0.5% by weight, based on the total weight of unreacted alkylene oxide; small amounts of the starting compound and low molecular weight alkoxylates thereof; and small amounts of other organic impurities and water. Volatile impurities must be evaporated or removed from the resulting polyether. The product typically contains catalyst residues and may contain promoter (if used) and additive residues. It is typical to leave these residues in the product, but they can be extracted if desired. Moisture and volatiles can be removed by polyol extraction. The polymerization reaction can be characterized by the “formation ratio,” which is defined as the ratio of the numerical average molecular weight of the product to that of the starting compound. This formation ratio can be as high as 160, but is more commonly in the range of 2.5 to 2005090 of 33 84367-AR-NP approximately 65 and even more commonly in the range of 2.5 to approximately 50, 2.5 to 35, 2.5 to 11 or 7 to 11. The invention is particularly useful in polymerization processes characterized by one or more of the following: i) the use of an initiator having an equivalent weight of up to 125, especially up to 100 or up to 75 g / equivalent;(ii) a hydroxyl content of 4.25 to 20 wt%, especially 4.25 to 15 wt%, 4.25 to 12 wt%, or 4.25 to 10 wt%, based on the total weight of the reaction mixture, during at least a portion of the polymerization process; (iii) a catalyst complex concentration sufficient to provide at most 5 ppm of cobalt, especially 0.5 to 2 ppm, based on the weight of the product; (iv) the alkylene oxide is ethylene oxide or a mixture of alkylene oxides containing at least 60 wt% or at least 80 wt% ethylene oxide (the remainder being preferably propylene oxide); and (v) an ethylene oxide concentration of 2 to 10 wt%, 2 to 8 wt%, 2 to 6 wt%, or 2 to 5 wt% at a point in the polymerization where the content The concentration of ethylene oxide (if present) is at its highest point. Each of these represents a serious condition in which the conventional zinc hexacyanometalate catalyst performs poorly. In some embodiments, the polymerization step is carried out in the presence of no more than 0.01 mol of a carbonate precursor per mole of alkylene oxide being polymerized. A carbonate precursor is a compound that gives rise to carbonate linkages (-OC(O)-O-) when polymerized with an alkylene oxide. Examples of carbonate precursors include carbon dioxide, linear carbonates, cyclic carbonates, phosgene, and the like. The water-insoluble polymerization catalyst complex includes at least one double metal cyanide compound. The catalyst complexes of 2005090 of 33 84367-AR-NP polymerization of this type, and double metal cyanide compounds are known and generally include, for example, those described in 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 embodiments, the double metal cyanide compound is represented by the formula: M1b[M2(CN)r(X1)t]c[M3(X2)6]d · nM4xA1y (I) where: M1 and M4 each represent an independently selected metal ion from Zn2+, Fe2+, Co+2+, Ni2+, Mo4+, Mo6+, Al3+, V4+, V5+, Sr2+, W4+, W6+, Mn2+, Sn2+, Sn4+, Pb2+, Cu2+, La3+ and Cr3+; M2 and M3 each represent an independently selected metal ion from Fe3+, Fe2+, Co3+, Co2+, Cr2+, Cr3+, Mn2+, Mn3+, Ir3+, Ni2+, Rh3+, Ru2+, V4+, V5+, Ni2+, Pd2+ and Pt2+; X1 represents a different cyanide group that coordinates with the M2 ion; X2 represents a different cyanide group that coordinates with the M3 ion; A1 represents a halide such as chloride, bromide, and iodide; nitrate; sulfate; carbonate; cyanide; oxalate; thiocyanate; isocyanate; perchlorate; isothiocyanate; an alkanesulfonate such as methanesulfonate; an arylesulfonate such as p-toluensulfonate; and trifluoromethanesulfonate (triflate); b, c, and d are each numbers such that the group M1b[M2(CN)r(X1)t]c[M3(X2)6]d reflects an electrostatically neutral, provided that each of b and c are greater than zero; 2005090 of 33 84367-AR-NP xey are integers so that the metallic salt M4xA1y is electrostatically neutral; r is an integer from 4 to 6; t is an integer from 0 to 2; yn is a number from 0 to 20; M1 and M4 (if present) each of them is with the highest preference zinc. M2 and M3 (if present) are each of them with maximum preference iron and cobalt, especially cobalt. r has maximum preference 6 and t has maximum preference zero. d has maximum preference 0 to 1. The molar ratio of metallic M1 and metallic M4 combined with metallic M2 and M3 combined is preferably from 0.8:1 to 20:1. In some embodiments, p can be at least 0.001, at least 0.0025, and can be up to 10, up to 5, up to 1.5, up to 0.25, or up to 0.125. In some embodiments, q can be at least 0.002, at least 0.01, at least 0.025, or at least 0.05, and can be up to 10, up to 2, up to 1.25, or up to 0.5. Smaller values ​​of pyq do not lead to any improvement in the performance of the catalyst complex. Larger amounts not only fail to improve catalyst performance but actually tend to decrease it. In some modalities, the p-q ratio can be at least 0.025 or at least 0.05 and up to 1.5, up to 1 or up to 0.5. The values ​​of p, qy and the p:q ratio are conveniently determined using X-ray fluorescence (XRF) methods. The catalyst complexes of the above formula can be prepared in a precipitation process in which a solution containing the starting materials, which include a cyanometalate compound and a starting compound M1, is 2005090 of 33 84367-AR-NP prepares, some of the starting materials react and the catalyst complex precipitates from the starting solution. In general, methods for producing DMC catalysts as described, e.g., in U.S. patents 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. The solvent includes at least one water and one liquid aliphatic alcohol. The solvent is one in which the starting cyanometalate compound and the metallic compound M1 are soluble. The solvent can be, for example, water, n-propanol, isopropanol, n-butanol, sec-butanol, t-butanol, another alkylene monoalcohol having up to, for example, 12 carbon atoms, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, or another polyether having one or more hydroxyl groups and a molecular weight up to, for example, 8000 g / mol. Among these, aliphatic monoalcohols having 3 to 6 carbon atoms are preferred, especially t-butanol. A mixture of water and a liquid aliphatic alcohol that is soluble in water in the relative proportions present in the mixture is especially preferred (especially an aliphatic monoalcohol having 3 to 6 carbon atoms and with maximum preference t-butanol), in a volume ratio of 25:75 to 90:10. The metallic compound M1 is preferentially soluble in water. It is typically a salt of a metallic M1 and one or more anions. Such a salt may have the formula M1xA1y, where x, A1e, and y are as described above. In illustrative forms, the A1 anion is none of the alkoxide, aryloxy, carboxylate, acyl, pyrophosphate, phosphate, thiophosphate, dithiophosphate, phosphate ester, thiophosphate ester, amide, oxide, siloxide, hydride, carbamate, or hydrocarbon anion. 2005090 of 33 84367-AR-NP The metallic M1 is one or more of Zn2+, Fe2+, Co+2+, Ni2+, Mo4+, Mo6+, Al+3+, V4+, V5+, Sr2+, W4+, W6+, Mn2+, Sn2+, Sn4+, Pb2+, Cu2+, La3+, and Cr3+. Zn2+ is the preferred metallic M1. ZnCl2 is a preferred metallic compound. The cyanometalate compound includes an M₂(CN)ₙ(X₁)ᵗ anion, where r, X₁, and t are as described above. r is preferably 6 and t is preferably zero. The metallic M₂ is one or more of Fe³⁺, Fe²⁺, Co³⁺, Cr²⁺, Mn²⁺, Ir³⁺, Ni²⁺, Rh³⁺, Ru²⁺, V⁴⁺, V⁵⁺, Ni²⁺, Pd²⁺, and Pt²⁺. The metallic M₂ is preferably Fe³⁺ or Co³⁺, with Co³⁺ being especially preferred. The cyanometalate compound is preferably an ammonium or alkali metal salt, although the corresponding cyanometalytic acid may be used. Potassium hexacyanocobaltate is a particularly preferred cyanometalate compound. The cyanometalate compound and the metallic compound M1 react to form a catalyst complex that includes a water-insoluble cyanometalate of the metallic M1. This reaction proceeds spontaneously at temperatures around room temperature (23 °C) or slightly elevated. Therefore, no special reaction conditions are required. The temperature can be, for example, from 0 to 60 °C. A preferred temperature is 20 to 50 °C or 25 to 45 °C. Stirring is preferred until precipitation occurs, which is generally indicated by a change in the appearance of the solution. The reaction pressure is not particularly critical, provided the solvent does not evaporate. A pressure of 10 to 10,000 kPa is suitable, with a pressure of 50 to 250 kPa being perfectly adequate. The reaction time can be from 30 minutes to 24 hours or more. It is preferable to treat the precipitated double-metal cyanide with a complexing agent, which is incorporated into the catalyst complex. This is conveniently accomplished by washing the precipitated double-metal cyanide one or more times. 2005090 of 33 84367-AR-NP with a complexing agent or a solution of the complexing agent in water. The complexing agent component may include at least one of an alcohol as described above with respect to the starting solution, a polyether, a polyester, a polycarbonate, a glycidyl ether, a glucoside, a polyhydric alcohol carboxylate, a polyalkylene glycol sorbitan ester, a bile acid or salt, a carboxylic acid ester or amide thereof, cyclodextrin, an organic phosphate, a phosphite, a phosphonate, a phosphonite, a phosphinate, a phosphinite, an ionic surface or interface active compound, and / or an α,β-unsaturated carboxylic acid ester.In illustrative embodiments, the organic complexing agent is one or more of n-propanol, iso-propanol, n-butanol, sec-butanol, t-butanol, another alkylene monoalcohol having up to 12 carbon atoms, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, or another polyether having one or more hydroxyl groups and a molecular weight up to, for example, 8000 g / mol. The catalyst complex thus prepared is conveniently recovered from the match solution or any washing liquid, dried, and, if desired, ground or milled to reduce the catalyst complex to a powder having a volume-average particle size of, for example, 100 µm or smaller. Drying can be carried out by heating and / or applying a vacuum. In some embodiments, the additive is or includes an alkali metal, ammonium, or quaternary ammonium salt of a monocarboxylic acid having up to 24 carbon atoms. The monocarboxylic acid may have 1 to 18 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 2 carbon atoms. The monocarboxylic acid may be aliphatic and linear; in other embodiments, the monocarboxylic acid may be aromatic (such as benzoic acid). The alkali metal may be lithium, sodium, potassium, and / or cesium. For “ammonium” 2005090 of 33 84367-AR-NP is understood to be an NH4+ ion. A quaternary ammonium ion takes the form NR4+, where each R is independently H or hydrocarbyl, provided that at least one R is a hydrocarbyl. Specific examples include lithium, sodium, potassium, cesium, or ammonium formate; lithium, sodium, potassium, cesium, or ammonium acetate; lithium, sodium, potassium, cesium, or ammonium benzoate; and lithium, sodium, potassium, cesium, or ammonium salts of a linear or branched aliphatic C4-C18 monocarboxylic acid. The additive may be or include one or more of a monobasic alkali metal phosphate, monobasic ammonium phosphate, and quaternary monobasic ammonium phosphate. Examples of these include lithium dihydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, cesium dihydrogen phosphate, and ammonium dihydrogen phosphate. The additive may be or include sodium dibasic phosphate (Na2HPO4). The additive may be or include one or more of tartaric acid, malic acid, or succinic acid. In some formulations, the weight of the additive is 1 to 25 times that of the catalyst complex. For example, the additive weight may be at least 2 or at least 3 times the weight of the catalyst complex. The additive weight may be up to 15, 10, 7.5, or 5 times the weight of the catalyst complex. Alternatively, the additive is conveniently present in the polymerization mixture in an amount of approximately 50 to 50,000 parts per million by weight (ppm), based on the weight of the product. A preferred lower amount is at least 100 ppm, at least 250 ppm, at least 500 ppm, or at least 1,000 ppm. A preferred upper amount is up to 10,000 ppm, up to 5,000 ppm, up to 2,500 ppm, or up to 1,500 ppm. 2005090 of 33 84367-AR-NP A promoter is optionally present in the reaction mixture. For the purposes of this invention, the promoter is a separate component of the water-insoluble polymerization catalyst complex. This means that neither the promoter nor a metallic or semi-metallic precursor M5 is present during a precipitation step that forms the double-metal cyanide component of the catalyst complex. The promoter can be combined with the other ingredients in any order, and in particular, it can be combined with the catalyst complex before being combined with the other components of the polymerization mixture. A metallic or semi-metallic M5 compound is a magnesium compound or a metallic or semi-metallic M5 that is part of any of Groups 3 to 15 inclusive of the 2010 IUPAC periodic table of elements, and one or more anions selected from the group consisting of alkoxide, aryloxy, carboxylate, acyl, pyrophosphate, phosphate, thiophosphate, dithiophosphate, phosphate ester, thiophosphate ester, amide, oxide, siloxide, hydride, carbamate, halide, or hydrocarbon anions. The metal may be, e.g., scandium, yttrium, lanthanum, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, titanium, silicon, palladium, platinum, copper, silver, gold, zinc, cadmium, mercury, aluminum, gallium, indium, tellurium, tin, lead, bismuth, and lanthanide series metals which include those having atomic numbers from 58 (cerium) to 71 (lutetium), inclusive. The preferred M5 metallic and semi-metallic elements include yttrium, zirconium, niobium, silicon, titanium, tungsten, cobalt, scandium, vanadium, molybdenum, nickel, zinc, and tin. Hafnium, aluminum, manganese, gallium, and indium are preferred even more. An “alkoxide” ion is understood to be a species that has the form -O—R, where R is an alkyl group or substituted alkyl group, and which is the conjugate base, after 2005090 of 33 84367-AR-NP involves removing a hydroxyl hydrogen from an alcohol compound of the form HO-R. These alcohols can have pKa values ​​in the range of 13 to 25 or higher. The alkoxide ion in some embodiments can contain from 1 to 20 (e.g., 1 to 6 and / or 2 to 6) carbon atoms. The alkyl or substituted alkyl group can be linear, branched, and / or cyclic. Examples of suitable substituents include, for example, additional hydroxyl groups (which may be in the alkoxide form), ether groups, carbonyl groups, ester groups, urethane groups, carbonate groups, silyl groups, aromatic groups such as phenyl and alkyl-substituted phenyl, and halogens. Examples of such alkoxide ions include methoxide, ethoxide, isopropoxide, n-propoxide, n-butoxide, sec-butoxide, t-butoxide, and benzyloxy. The R group may contain one or more hydroxyl groups and / or may contain one or more ether linkages.An alkoxide ion may correspond to the residue (after the removal of one or more hydroxyl hydrogens) of a starting compound present in the polymerization, such as the starting compounds described below. The alkoxide ion may be an alkoxide formed by the removal of one or more hydroxyl hydrogens from a polyether mono-ol or polyether polyol; such an alkoxide, in some embodiments, corresponds to a residue, after the removal of one or more hydroxyl hydrogen atoms, from the polyether mono-ol or polyol product obtained from the alkoxylation reaction, or from a polyether having a molecular weight intermediate to that of the starting compound and the alkoxylation reaction product. An aryloxy anion is understood to be a species having the form -O—Ar, where Ar is an aromatic or substituted aromatic group, and which corresponds, after the removal of a hydroxyl hydrogen, to a phenolic compound having the form HO-Ar. These phenolic compounds can have a pKa of, for example, 9 to approximately 12. Examples of such aryloxy anions include phenoxide and 2005090 of 33 84367-AR-NP ring-substituted phenoxides, wherein the ring substituents include, e.g., one or more alkyl, CF3, cyano, COCH3, halogen, hydroxyl, and alkoxy groups. The ring substituent(s), if present, may be in one or more of the ortho, para, and / or meta positions with respect to the phenolic group. Phenoxide anions also include the conjugate bases of polyphenolic compounds such as bisphenol A, bisphenol F, and various other bisphenols, 1,1,1-tris(hydroxyphenyl)ethane, and fused-ring aromatics such as 1-naphthol. The term “carboxylate” anion refers to a carboxylate containing 1 to 24 (e.g., 2 to 18 and / or 2 to 12) carbon atoms. The carboxylate may be aliphatic or aromatic. An aliphatic carboxylic acid may contain substituent groups. Examples of such groups include hydroxyl groups (which may be in the alkoxide form), ether groups, carbonyl groups, ester groups, urethane groups, carbonate groups, silyl groups, aromatic groups such as phenyl and alkyl-substituted phenyl, and halogens. Examples of aliphatic carboxylate anions include formate, acetate, propionate, butyrate, 2-ethylhexanoate, n-octoate, decanoate, laurate, and other halogen-substituted alkanoates and alkanoates such as 2,2,2-trifluoroacetate, 2-fluoroacetate, 2,2-difluoroacetate, 2-chloroacetate, and 2,2,2-trichloroacetate.Examples of aromatic carboxylates include benzoate, alkyl-substituted benzoate, halo-substituted benzoate, 4-cyanobenzoate, 4-trifluoromethylbenzoate, salicylate, 3,5-di-t-butylsalicylate, and subsalicylate. In some embodiments, this carboxylate ion can be the conjugate base of a carboxylic acid having a pKa of 1 to 6 (e.g., 3 to 5). An acyl anion is understood to be a conjugate base of a compound containing a carbonyl group, including, for example, an aldehyde, ketone, acetylacetonate, carbonate, ester, or similar compound that has an enol form. Examples of these are β-diketes, such as acetoacetonate and butylacetoacetonate. 2005090 of 33 84367-AR-NP The term “phosphate” anion means a phosphate anion having the formula -OP(O)(OR1)2, where R1 is alkyl, substituted alkyl, phenyl, or substituted phenyl. The term “thiophosphate” anion means thiophosphate anions having the corresponding structure in which one or more of the oxygens are replaced by sulfur. Phosphate and thiophosphates may be ester anions, such as phosphate ester and thiophosphate ester. The anion “pyrophosphate” is understood to be the P2O74- anion. An amide anion is defined as an ion in which a nitrogen atom carries a negative charge. The amide ion typically takes the form -N(R2)2, where R2 is either hydrogen, alkyl, aryl, trialkylsilyl, or triarylsilyl. The alkyl groups can be linear, branched, or cyclic. Any of these groups may contain substituents such as ether or hydroxyl. The two R2 groups can form a ring structure, which may be unsaturated and / or contain one or more heteroatoms (in addition to the amide nitrogen). The term “oxide” anion refers to the anion of atomic oxygen, that is, O2-. The term “siloxide” anion refers to silanoates having the formula (R3)3SiO-, where the R3 groups are independently a hydrogen or alkyl group. The “hydride” anion is understood to be the hydrogen anion, i.e., H₂. The “carbamate” anion is understood to be the -OOCNH₂ anion. The term “hydrocarbon” anion refers to hydrocarbyl anions, which include aliphatic, cycloaliphatic, and / or aromatic anions where the negative charge resides on a carbon atom. Hydrocarbyl anions are conjugate bases of hydrocarbons that typically have pKa values ​​greater than 30. Hydrocarbyl anions may also contain inert substituents. Among aromatic hydrocarbyl anions, phenyl groups and substituted phenyl groups may be used. Aliphatic hydrocarbyl anions 2005090 of 33 84367-AR-NP can be alkyl groups that can contain, for example, 1 to 12 (e.g., 2 to 8) carbon atoms. For example, all methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, cyclopentadienyl, and t-butyl anions are useful. The anion “halide” is understood to be F-, Cl-, Br- and I-. Examples of useful gallium compounds include trialkylgallium compounds such as trimethylgallium, triethylgallium, tributylgallium, tribenylgallium and the like; gallium oxide; gallium alkoxides such as gallium trimethoxide, gallium triethoxide, gallium triisopropoxide, gallium tri-t-butoxide, gallium tri-sec-butoxide and the like; gallium aryloxides such as gallium phenoxide and gallium phenoxides in which one or more of the phenoxide groups are substituted on the ring with one or more alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy groups and the like; gallium carboxylates such as gallium formate, gallium acetate, gallium propionate, gallium 2-ethylhexanoate, gallium benzoate, gallium benzoates wherein one or more of the benzoate groups are substituted on the ring with one or more alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy and the like, gallium salicylate, 3,5-di-t-butyl gallium salicylate;Gallium amides such as gallium tris(dimethylamide), gallium tris(diethylamide), gallium tris(diphenylamide), gallium tris(di(trimethylsilyl)amide) and the like; gallium acetylacetonate; gallium t-butylacetylacetonate; and alkylgallium alkoxides such as diethylgallium ethoxide, dimethylgallium ethoxide, diethylgallium isopropoxide and dimethylgallium isopropoxide. Examples of useful hafnium compounds include hafnium alkyls such as tetraethylhafnium, tetrabutylhafnium, tetrabenzylhafnium, and the like; hafnium oxide; hafnium alkoxides such as hafnium tetramethoxide, hafnium tetraethoxide, hafnium tetraisopropoxide, hafnium tetra-tert-butoxide, hafnium tetra-sec-butoxide, and the like; and gallium aryloxides such as hafnium phenoxide and hafnium phenoxides. 2005090 of 33 84367-AR-NP wherein one or more of the phenoxide groups are substituted on the ring with one or more alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy and the like; hafnium carboxylates such as hafnium formate, hafnium acetate, hafnium propionate, hafnium 2-ethylhexanoate, hafnium benzoate, hafnium benzoates wherein one or more of the benzoate groups are substituted on the ring with one or more alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy and the like, hafnium salicylate, 3,5-di-t-butyl hafnium salicylate; hafnium amides such as hafnium tetra(dimethylamide), hafnium tetra(diethylamide), hafnium tetra(diphenylamide), hafnium tetra(bistrimethylsilyl)amide; hafnium acetylacetonate and hafnium t-butylacetylacetonate. Examples of useful indium compounds include indium trialkyl compounds such as indium trimethyl; indium oxide; indium alkoxides such as indium methoxide, indium ethoxide, indium isopropoxide, indium t-butoxide, indium sec-butoxide and the like; indium aryloxides such as indium phenoxide and indium phenoxides in which one or more of the phenoxide groups are substituted on the ring with one or more alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy and the like; indium carboxylates such as indium formate, indium acetate, indium propionate, indium 2-ethylhexanoate, indium benzoate, indium benzoates in which one or more of the benzoate groups are substituted on the ring with one or more alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy and the like, indium salicylate, indium 3,5-di-t-butyl salicylate; indium acetylacetonate; and indium t-butylacetylacetonate. Examples of useful aluminum compounds include trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, tributylaluminum, tribencillaluminum, and the like; aluminum alkoxides such as aluminum trimethoxide, aluminum triethoxide, aluminum triisopropoxide, aluminum tri-t-butoxide, aluminum tri-sec-butoxide, and the like; and aluminum aryloxides such as phenoxide. 2005090 of 33 84367-AR-NP of aluminum and aluminum phenoxides in which one or more of the phenoxide groups are substituted on the ring with one or more alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy and the like; aluminum oxide; aluminum carboxylates such as aluminum formate, aluminum acetate, aluminum propionate, aluminum 2-ethylhexanoate, aluminum benzoate, aluminum benzoates in which one or more of the benzoate groups are substituted on the ring with one or more alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy and the like, aluminum salicylate, 3,5-di-t-butyl aluminum salicylate; aluminum amides such as aluminum tris(dimethylamide), aluminum tris(diethylamide), aluminum tris(diphenylamide), aluminum tris(di(trimethylsilyl)amide) and the like; aluminum acetylacetonate; t-butylacetylacetonate;and alkylaluminum oxides and alkoxides such as diethylaluminum ethoxide, dimethylaluminum ethoxide, diethylaluminum isopropoxide, dimethylaluminum isopropoxide, methylaluminoxane, tetraethyldialuminoxane and the like.; Examples of useful magnesium compounds include magnesium alkyls such as diethyl magnesium, dibutyl magnesium, butylethyl magnesium, dibenzyl magnesium and the like; magnesium alkoxides such as magnesium methoxide, magnesium ethoxide, magnesium isopropoxide, t-magnesium butoxide, sec-magnesium butoxide and the like; magnesium aryloxides such as magnesium phenoxide and magnesium phenoxides in which one or more of the phenoxide groups are substituted on the ring with one or more alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy and the like; magnesium carboxylates such as magnesium formate, magnesium acetate, magnesium propionate, magnesium 2-ethylhexanoate, magnesium benzoate, magnesium benzoates in which one or more of the benzoate groups are substituted on the ring with one or more alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy and the like, magnesium salicylate, 3,5-di-t magnesium salicylate 2005090 of 33 84367-AR-NP butyl; magnesium amides such as magnesium dimethylamide, magnesium diethylamide, magnesium diphenylamide, magnesium bis(trimethylsilyl)amide and the like; magnesium oxide, magnesium acetylacetonate and magnesium t-butylacetylacetonate Examples of useful manganese compounds include Mn(II) and / or Mn(III) and / or Mn(IV) compounds including manganese phosphate; pyrophosphate, manganese oxide; manganese alkoxides such as manganese methoxide, manganese ethoxide, manganese isopropoxide, t-manganese butoxide, manganese sec-butoxide and the like; manganese aryloxides such as manganese phenoxide and manganese phenoxides in which one or more of the phenoxide groups are substituted on the ring with one or more of alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy and the like; manganese carboxylates such as manganese formate, manganese acetate, manganese propionate, manganese 2-ethylhexanoate, manganese benzoate, manganese benzoates wherein one or more of the benzoate groups are substituted on the ring with one or more alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy and the like, manganese salicylate, 3,5-di-t-butyl manganese salicylate;manganese acetylacetonate; and t-butylacetylacetonate manganese.; Examples of useful scandium compounds include scandium alkoxides such as scandium methoxide, scandium ethoxide, scandium isopropoxide, scandium t-butoxide, scandium sec-butoxide, and the like; scandium oxide; scandium aryloxides such as scandium phenoxide and scandium phenoxides in which one or more of the phenoxide groups are substituted on the ring with one or more alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy, and the like; scandium carboxylates such as scandium formate, scandium acetate, scandium propionate, scandium 2-ethylhexanoate, scandium benzoate, and scandium benzoates 2005090 of 33 84367-AR-NP wherein one or more of the benzoate groups are substituted on the ring with one or more alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy and the like; scandium salicylate; scandium acetylacetonate and t-butylacetylacetonate. Examples of useful molybdenum compounds include Mo(IV) and / or Mo(VI) compounds such as molybdenum phosphate; molybdenum pyrophosphate, molybdenum oxide; molybdenum alkoxides such as molybdenum methoxide, molybdenum ethoxide, molybdenum isopropoxide, t-molybdenum butoxide, molybdenum sec-molybdenum butoxide and the like; molybdenum aryloxides such as molybdenum phenoxide and molybdenum phenoxides in which one or more of the phenoxide groups are substituted on the ring with one or more alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy and the like; molybdenum carboxylates such as molybdenum formate, molybdenum acetate, molybdenum propionate, molybdenum 2-ethylhexanoate, molybdenum benzoate, molybdenum benzoates wherein one or more of the benzoate groups are substituted on the ring with one or more alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy and the like, molybdenum salicylate, 3,5-di-t-butyl molybdenum salicylate;molybdenum acetylacetonate.; Examples of useful cobalt compounds include Co(II) and / or Co(III) compounds such as cobalt phosphate; cobalt pyrophosphate, cobalt oxide; cobalt alkoxides such as cobalt methoxide, cobalt ethoxide, cobalt isopropoxide, cobalt t-butoxide, cobalt sec-butoxide and the like; cobalt aryloxides such as cobalt phenoxide and cobalt phenoxides in which one or more of the phenoxide groups are substituted on the ring with one or more alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy and the like; cobalt carboxylates such as cobalt formate, cobalt acetate, cobalt propionate, cobalt 2-ethylhexanoate, cobalt benzoate, cobalt benzoates in which 2005090 of 33 84367-AR-NP one or more of the benzoate groups are substituted on the ring with one or more of alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy and the like, cobalt salicylate, 3,5-di-t-butyl cobalt salicylate; cobalt acetylacetonate; and cobalt t-butylacetylacetonate, which in each case is a Co(II) and / or Co(III) compound. Examples of useful tungsten compounds include tungsten phosphate; tungsten pyrophosphate, tungsten oxide, tungsten alkoxides such as tungsten methoxide, tungsten ethoxide, tungsten isopropoxide, t-tungsten butoxide, sec-tungsten butoxide and the like; tungsten aryloxides such as tungsten phenoxide and tungsten phenoxides in which one or more of the phenoxide groups are substituted on the ring with one or more of alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy and the like; tungsten carboxylates such as tungsten formate, tungsten acetate, tungsten propionate, tungsten 2-ethylhexanoate, tungsten benzoate, tungsten benzoates in which one or more of the benzoate groups are substituted on the ring with one or more alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy and the like, tungsten salicylate, 3,5-di-t-butyl tungsten salicylate; tungsten acetylacetonate;and tungsten t-butylacetylacetonate.; Examples of useful iron compounds include iron(II) and / or iron(III) compounds, such as iron phosphate; iron pyrophosphate; iron oxide; iron alkoxides such as iron methoxide, iron ethoxide, iron isopropoxide, t-iron butoxide, sec-iron butoxide, and the like; iron aryloxides such as iron phenoxide and iron phenoxides in which one or more of the phenoxide groups are substituted on the ring with one or more alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy, and the like; iron carboxylates such as iron formate, iron acetate, iron propionate, 2 2005090 of 33 84367-AR-NP iron ethylhexanoate, iron benzoate, iron benzoates wherein one or more of the benzoate groups are substituted on the ring with one or more alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy and the like, iron salicylate, iron 3,5-di-t-butyl salicylate; iron acetylacetonate; and iron t-butylacetylacetonate, which in each case is an Fe(II) and / or Fe(III) compound. Examples of useful vanadium compounds include vanadium alkoxides, such as vanadium methoxide, vanadium ethoxide, vanadium isopropoxide, vanadium t-butoxide, vanadium sec-butoxide, and the like; vanadium oxide; vanadium oxotris(alkoxides), such as vanadium oxotris(methoxide), vanadium oxotris(ethoxide), vanadium oxotris(isopropoxide), vanadium oxotris(t-butoxide), vanadium oxotris(sec-butoxide), and the like; vanadium aryloxides, such as vanadium phenoxide and vanadium phenoxides in which one or more of the phenoxide groups are substituted on the ring with one or more alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy, and the like;vanadium carboxylates such as vanadium formate, vanadium acetate, vanadium propionate, vanadium 2-ethylhexanoate, vanadium benzoate, vanadium benzoates in which one or more of the benzoate groups are substituted on the ring with one or more alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy and the like, vanadium salicylate, 3,5-di-t-butyl vanadium salicylate; vanadium tris(acetylacetonate) and vanadium tris(t-butylacetylacetonate); vanadium oxo bis(acetylacetonate). Examples of useful tin compounds include stannous phosphate; stannous pyrophosphate; stannous oxide; stannic oxide; stannous alkoxides such as stannous methoxide, stannous ethoxide, stannous isopropoxide, stannous t-butoxide, stannous sec-butoxide and the like; tin aryloxides such as stannous phenoxide and stannous phenoxides in which one or more of the groups 2005090 of 33 84367-AR-NP phenoxides are substituted on the ring with one or more alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy and the like; stannous carboxylates such as stannous formate, stannous acetate, stannous propionate, stannous 2-ethylhexanoate, stannous benzoate, stannous benzoates in which one or more of the benzoate groups are substituted on the ring with one or more alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy and the like, stannous salicylate, 3,5-di-t-butyl stannous salicylate; stannous acetylacetonate; and stannous t-butylacetylacetonate. Examples of useful zinc compounds include zinc alkyls such as dimethyl zinc, diethyl zinc, dibutyl zinc, dibenzyl zinc and the like; zinc oxide; alkyl zinc alkoxides such as ethyl zinc isopropoxide; zinc alkoxides such as zinc methoxide, zinc ethoxide, zinc isopropoxide, t-zinc butoxide, sec-zinc butoxide and the like; zinc aryloxides such as zinc phenoxide and zinc phenoxides in which one or more of the phenoxide groups are substituted on the ring with one or more alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy and the like; zinc carboxylates such as zinc formate, zinc acetate, zinc propionate, zinc 2-ethylhexanoate, zinc benzoate, zinc benzoates wherein one or more of the benzoate groups are substituted on the ring with one or more alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy and the like, zinc salicylate, 3,5-di-t-butyl zinc salicylate;zinc amides such as zinc dimethylamide, zinc diethylamide, zinc diphenylamide, zinc (bistrimethylsilyl)amide; zinc acetylacetonate and zinc t-butylacetylacetonate.; Examples of useful titanium compounds include titanium dioxide and titanium alkoxides having the structure Ti(OR)4 where R is alkyl or phenyl (which may be substituted), such as titanium tetraethoxide, titanium tetraisopropoxide, titanium tetra-t-butoxide, titanium tetra-sec-butoxide, titanium tetraphenoxide 2005090 of 33 84367-AR-NP titanium, titanium tetraphenoxides wherein one or more of the phenoxide groups are independently substituted on the ring with one or more alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy and the like. Examples of useful silicon compounds include silica and silicon alkoxides having the structure Si(OR)4 where R is alkyl or phenyl (which may be substituted), such as silicon tetraethoxide, silicon tetraisopropoxide, silicon tetrath-butoxide, silicon tetra-sec-butoxide, silicon tetraphenoxide, silicon tetraphenoxides in which one or more of the phenoxide groups are independently substituted on the ring with one or more alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxy, and the like. The promoter is preferably present in an amount that provides at least 0.001 or at least 0.0025 moles of metallic or semi-metallic M5 per mole of metallic M2 plus M3 provided by the double metal cyanide catalyst. The promoter may be present in an amount that provides up to 50, up to 10, up to 5, up to 1.5, up to 0.25, or up to 0.125 moles of metallic M5 per mole of metallic M2 plus M3 provided by the double metal cyanide catalyst. Promoting mixtures of compounds of two or more different metallic or semi-metallic M5s may be present, as described, for example, in WO 2020 / 131508. In such mixtures, it is preferred that at least one of the metallic or semi-metallic M5s be gallium, indium, hafnium or titanium (especially gallium or hafnium), and at least one other metallic or semi-metallic M5 be aluminum, silicon or titanium (especially aluminum). In certain embodiments, the promoter is present in the form of distinct particles, as is generally the case when the promoter is a metallic or semi-metallic M5 oxide. Such particles can have a surface area of 2005090 of 33 84367-AR-NP at least 1 m² / g as measured using gas sorption methods. The surface area of ​​such promoter particles can be at least 10 m² / g to at least 100 m² / g, and can be up to, for example, 300 m³ / g or more. Their volume-average particle size can be 100 pm or smaller, 25 pm or smaller, 1 pm or smaller, or 500 nm or smaller. Such physical mixtures can be prepared, for example, by forming solid particles of the double-metal cyanide catalyst (or catalyst complex containing the double-metal cyanide) and combining them with the promoter particles. This can be done at any stage of the catalyst complex preparation process after the double-metal cyanide has been precipitated. For example, it is common to wash a precipitated double-metal cyanide with water and / or a ligand one or more times before final drying.Promoter particles can be combined with zinc hexacyanocobaltate during any washing stage. Polyethers manufactured according to the invention may include monoalcohols such as those useful for surfactant and industrial solvent or lubricant applications, and polyols such as raw materials useful for producing polymers such as polyurethanes such as molded foams, flexible block foams, high elasticity foams, viscoelastic foams, rigid foams, adhesives, sealants, coatings, elastomers, composites, etc. The following examples are provided to illustrate the illustrative modalities and are not intended to limit their scope. All parts and percentages are by weight unless otherwise stated. 2005090 of 33 84367-AR-NP Examples 1-12 and comparative AF samples Ethylene oxide polymerizations are performed using a Symyx Technologies 48-well parallel pressure reactor (PPR). Each well is equipped with an individually weighted glass insert that has an internal working fluid volume of approximately 5 mL. Three milliliters of a mixture of 98.5% of a weight average molecular weight poly(ethylene oxide) triol of 625 are added, along with 1.5% glycerol, 265 parts per million by weight (ppm, based on expected product mass) of a zinc hexacyanocobaltate catalyst complex (Covestro's Arcol® 3 catalyst), 265 ppm of aluminum oxide (Sasol North America's Catalox® BA), and 1335 ppm of an additive as indicated in Table 1. The wells are pressurized with 70 psig (483 kPa) of dry nitrogen at 160 °C. 0.3 mL of ethylene oxide is injected into each well, raising the internal pressure of each well to 140–160 psig (966–1103 kPa).Internal pressure is monitored over time as an indication of the progress of the ethylene oxide polymerization reaction. The times required for the pressure to decrease to 90 psig (621 kPa) and then to 80 psig (552 kPa) are recorded. Shorter times indicate greater catalytic activity. The results are shown in Table 1. Table 1 Additive Designation / Time at 90 psig (621 kPa), min. Time at 80 psig (552 kPa), min A* None >180 >180 1 Sodium Acetate 3.5 5.7 2 Potassium Acetate 3.8 5.9 3 Calcium Acetate 5.4 9.0 4 Sodium Formate 8.3 14.4 2005090 of 33 84367-AR-NP 5 K benzoate 6.8 12.25 6 Na laurate 14.7 26.05 7 Monobasic potassium phosphate 4.4 8 8 NH4H2PO4 4.9 7.3 9 UH2PO4 8.0 12.5 10 Na2HPO4 8.0 12.5 11 Tartaric acid 15.9 37.5 12* Na stearate 20.1 35.0 B* Na triflate 40.8 64.4 C* K2HPO4 117. 7 136.4 D* NaHCO3 84.4 126.8 E* Na2CO3 74.1 116.9 F* Ca formate 98.2 >180 * It is not an example of the invention. Comparative sample A represents an initial case. The catalyst complex alone cannot initiate polymerization under these very stringent conditions (high concentration of hydroxyl groups plus the selection of ethylene oxide). Examples 1-9 show that active polymerization occurs when alkali metal carboxylates (e.g., 1-6 and 9), monobasic potassium phosphate, or ammonium dihydrogen phosphate are additionally present in the reaction mixture. The time for the reactor pressure to decrease to 90 psig is reduced by a factor of 9 or more. The comparative samples BF show the poorest effect of several other additives. The triflate salt (comp. C) provides some benefit, but is much less effective than the additives of the invention. The carbonate salts and the alkaline earth carboxylate salt (comp. D, E, and F) provide almost no benefit. Examples 13-23 and comparative samples GK Polymerizations of ethylene oxide are carried out in the same way as in the previous set of examples, replacing aluminum oxide with a 2005090 of 33 84367-AR-NP equivalent concentration of aluminum tri(sec-butoxide). The additive and the results are as indicated in Table 2. Table 2 Designation Additive / Time at 90 psig (621 kPa), min. Time at 80 psig (552 kPa), min. A* None >180 >180 13 Na acetate 4.4 6.55 14 K acetate Not realized 1.8 15 Cs acetate 5.0 8.1 16 Na formate 6.15 9.6 17 K benzoate 9.2 16.4 18 Na laurate 14.2 26.6 19 KH2PO4 13.0 20.1 20 NH4H2PO4 8.5 180 21 Na stearate 19.8 35.0 22 Tartaric acid 6.3 13.3 23 Na2HPO4 4.2 8.3 G* Na triflate 46.0 78.7 H* K2HPO4 106.9 134.5 I* NaHCOa 86.8 125.4 J* Na2CO3 159.7 >180 K* UH2PO4 86.6 >180 * It is not an example of the invention. Alkali metal carboxylates (e.g., 13-18 and 21), monobasic phosphates (examples 19 and 20), disodium hydrogen phosphate, and tartaric acid dramatically increase the polymerization rate. Triflate salts, K₂HPO₄, carbonate salts, and LiH₂PO₄ provide little or no beneficial effect. 2005090 of 33 Alejandra Aoun - 27184140328 Digitally signed by PORTALTRAMITES - INPI Date: 2022.10.19 19:16:22 -03:00 Reason: Digitally Signed by the INPI Location: Buenos Aires, Argentina 2005090

Claims

1. A method for producing a polyether, said method characterized in that it comprises: I. forming a reaction mixture comprising a) a hydroxyl-containing initiator, b) at least one alkylene oxide, c) a water-insoluble polymerization catalyst complex including at least one double metal cyanide compound, and d) an additive selected from the group consisting of alkali metal, ammonium, and quaternary ammonium salts of monocarboxylic acids having up to 24 carbon atoms; monobasic alkali metal phosphates, dibasic sodium phosphate, monobasic ammonium phosphate, monobasic quaternary ammonium phosphates, tartaric acid, malic acid, and succinic acid; and II. polymerizing the alkylene oxide on the hydroxyl-containing initiator in the presence of the water-insoluble polymerization catalyst complex and the additive to produce the polyether. Nine claims follow.