Polyether Polymerization Process

Abstract

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

Description

[Technical field]

[0001] The present invention relates to a process for polymerizing alkylene oxides to form polyethers. [Background technology]

[0002] Poly(alkylene oxides) are produced in large quantities worldwide by polymerizing one or more alkylene oxides in the presence of a polymerization catalyst. They are important raw materials for producing polyurethanes and are used as surfactants and industrial solvents, among other applications. The primary polymerization catalysts are alkali metal hydroxides or alkoxides and certain metal complexes commonly referred to as double metal cyanide (DMC) catalysts.

[0003] Double metal cyanide catalysts have certain advantages. They do not strongly catalyze the rearrangement of propylene oxide to form propenyl alcohol. Therefore, polyether polyols made using DMC catalysts tend to have a low amount of undesirable monofunctional polymers. In addition, DMC catalyst residues usually do not need to be removed from the product. In this way, the steps of neutralization and catalyst removal that are necessary when using alkali metal catalysts are avoided.

[0004] However, DMC catalysts have certain disadvantages. They exhibit a latency period after exposure to alkylene oxide under polymerization conditions before they are "activated" and rapid polymerization begins. Another important problem is that DMC catalysts function slowly in the presence of high concentrations of hydroxyl groups. For this reason, DMC catalysts are not favored when making low molecular weight products and in semi-batch processes starting from low equivalent weight starters.

[0005] US Patent No. 9,040,657 discloses a method for producing polyether mono-ols or polyols in the presence of a DMC catalyst and magnesium, a Group 3-15 metal, or a Lanthanide series compound, wherein the magnesium, Group 3-15 metal, or Lanthanide series metal is bound to at least one alkoxide, aryloxy, carboxylate, acyl, pyrophosphate, phosphate, thiophosphate, dithiophosphate, phosphate ester, thiophosphate ester, amide, siloxide, hydride, carbamate, or hydrocarbon anion, and the magnesium, Group 3-15 metal, or Lanthanide series metal compound is devoid of halide anions. This technology is highly effective in reducing activation time and improving catalyst performance when exposed to high concentrations of hydroxyl groups. Nevertheless, further improvements are desirable, and in particular, a catalyst system that performs better under stringent polymerization conditions and / or in the polymerization of ethylene oxide would be beneficial. Summary of the Invention

[0006] The present invention is a method for producing a polyether, the method comprising: forming a reaction mixture comprising Ia) a hydroxyl-containing starter, b) at least one alkylene oxide, c) a water-insoluble polymerization catalyst complex comprising 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 phosphate, tartaric acid, malic acid and succinic acid; II. Polymerizing an alkylene oxide onto a hydroxyl-containing starter in the presence of a water-insoluble polymerization catalyst complex and an additive to produce a polyether.

[0007] The presence of the additive has been found to significantly increase the activity of double metal cyanide catalysts, even in the presence of "promoter" compounds such as those described in WO 2012 / 091968. The additive enhances catalyst activation and polymerization rate under conditions of high hydroxyl concentration and / or very low molecular weight starter. Very importantly, the presence of the additive improves catalyst performance in ethylene oxide polymerization. According to the present invention, ethylene oxide can be polymerized even on low molecular weight starters and under conditions of high hydroxyl concentration to produce poly(ethylene oxide) polymers of controlled molecular weight and low polydispersity.

[0008] In the process of the present invention, the polymerization mixture comprises a) a hydroxyl-containing starter, b) at least one alkylene oxide, c) a water-insoluble polymerization catalyst complex comprising at least one double metal cyanide compound, and d) an additive as described herein. The polyether is produced by polymerizing the alkylene oxide onto the hydroxyl-containing starter in the presence of the water-insoluble polymerization catalyst complex and the additive.

[0009] The primary function of the starter compound is to provide molecular weight control and establish the number of hydroxyl groups that the polyether product will have. Hydroxyl-containing starter compounds can contain one or more (preferably two or more) hydroxyl groups and as many as twelve or more hydroxyl groups. For example, starters for producing polyols for use in polyurethane applications typically have 2-8 hydroxyl groups per molecule. In some embodiments, the starter compound will have 2-4 or 2-3 hydroxyl groups. In other embodiments, the starter compound will have 4-8 or 4-6 hydroxyl groups. The starter compound can have at least two hydroxyl groups in the 1,2 or 1,3 positions relative to each other (one of the hydroxyl groups takes the carbon atom to which it is attached as the "1" position). Mixtures of starter compounds can be used.

[0010] The starter compound will have a hydroxyl equivalent weight less than the hydroxyl equivalent weight of the mono-ol or polyol product. It may have a hydroxyl equivalent weight of 30 to 500 g / equivalent or more, as determined by measuring the hydroxyl number according to ASTM D4274-21 and converting the hydroxyl number (mg KOH / g) to equivalent weight using the relationship equivalent weight = 56,100 ÷ hydroxyl number. The equivalent weight may be up to 500, up to 250, up to 125, and / or up to 100 g / equivalent.

[0011] Exemplary starters 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, cyclohexanedimethanol, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol, sucrose, phenol, and polyphenol starters such as bisphenol A or 1,1,1-tris(hydroxyphenyl)ethane, as well as alkoxylates (such as ethoxylates and / or propoxylates) of any of these with a hydroxyl equivalent less than that of the polymerization product. The starter compound can also be water. The starter can be neutralized with or contain a small amount of acid, especially when the starter is prepared in the presence of a base (as is often the case with glycerin). If present, the acid may be present in an amount of about 10 to 100 ppm based on the weight of the starter, as described, for example, in U.S. Patent No. 6,077,978. The acid may be used in somewhat higher amounts, such as 100 to 1000 ppm based on the weight of the starter, as described, for example, in U.S. Patent Application Publication No. 2005 / 0209438. The acid may be added to the starter before or after the starter is combined with the catalyst complex.

[0012] Certain starters may have unique advantages. Triethylene glycol has been found to be a particularly good starter 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 starters for use in combination with the catalyst complexes of the present invention.

[0013] 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, 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 particular embodiments, the alkylene oxide is 1,2-propylene oxide, or a mixture of at least 40% by weight (preferably at least 80% by weight) of 1,2-propylene oxide and up to 60% by weight (preferably up to 20% by weight) 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 only or predominant alkylene oxide, and that ethylene oxide can be easily polymerized even on a low molecular weight starter. Thus, in some embodiments, the alkylene oxide is ethylene oxide or a mixture of at least 60% or at least 80% by weight ethylene oxide with, correspondingly, up to 40% or up to 20% by weight 1,2-propylene oxide.

[0014] The reaction mixture in some embodiments contains 1 to 25 weight percent hydroxyl groups based on the total weight of the reaction mixture. The reaction mixture may contain, for example, 4.5 to 20 weight percent, 4.5 to 15 weight percent, 4.5 to 12 weight percent, or 4.5 to 10 weight percent hydroxyl groups for at least a portion of the polymerization reaction.

[0015] The reaction mixture in some embodiments contains up to 10% by weight ethylene oxide. The reaction mixture may contain, for example, up to 8%, up to 6%, or up to 5% by weight ethylene oxide at the point in the polymerization when the ethylene oxide content (if any) is at its highest. In some embodiments, the reaction mixture contains at least 2% or at least 3% by weight ethylene oxide for at least a portion of the polymerization reaction.

[0016] The components that make up the reaction mixture can be combined in any order.

[0017] The polymerization is typically carried out at an elevated temperature. The temperature of the polymerization mixture may be, for example, 80 to 220° C. (eg, 120 to 190° C.).

[0018] The polymerization reaction is usually carried out at superatmospheric pressure, but can also be carried out at atmospheric pressure or even subatmospheric pressure.Preferred pressures are gauge pressures of 0 to 10 atmospheres (0 to 1013 kPa), in particular 0 to 6 atmospheres (0 to 608 kPa).

[0019] The polymerization is preferably carried out under vacuum or under an inert atmosphere such as a nitrogen, helium, or argon atmosphere.

[0020] While sufficient water-insoluble polymerization catalyst complex may be used to provide a reasonable polymerization rate, it is generally desirable to use as little catalyst complex as possible consistent with a reasonable polymerization rate, both because it reduces the cost of the catalyst and because it can eliminate the need to remove catalyst residues from the product if the catalyst level is low enough. Using a lower amount of catalyst also reduces the residual metal content of the product. The amount of catalyst complex may be from 1 to 5000 ppm based on the weight of the product. The amount of catalyst complex may 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 weight of the product. When the catalyst complex contains a hexacyanocobaltate compound, the amount of catalyst complex may 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 the product.

[0021] The polymerization reaction can be carried out in any type of reactor suitable for the pressures and temperatures encountered. In a continuous or semi-batch process, the alkylene oxide, additional starter compound and preferably water-insoluble polymerization catalyst complex, promoter (if used) and additives are introduced as the polymerization proceeds. The vessel should therefore have one or more inlets through which those components can be introduced during the reaction. In a continuous process, the reaction vessel should include at least one outlet through which a portion of the partially polymerized reaction mixture can be withdrawn. In a semi-batch operation, the alkylene oxide (and optionally additional starter and catalyst complex) is added during the reaction, but the product is usually not removed until the polymerization is complete. Tubular reactors, loop reactors, and continuous stirred tank reactors (CTSRs) with multiple points for injection of starter materials are all suitable types of vessels for continuous or semi-batch operation. The reactor should be equipped with a means to supply or remove heat so that the temperature of the reaction mixture can be maintained within the required range. Suitable means include various types of jackets for the heating fluid, various types of internal or external heaters, etc. The boil-down step, which is carried out on the continuously withdrawn product, is conveniently carried out within the reactor, thereby preventing significant backmixing from occurring. Plug flow operation in a pipe or tubular reactor is the preferred mode of carrying out such a boil-down step.

[0022] The product obtained from any of the aforementioned processes may contain up to 0.5% by weight of unreacted alkylene oxide, based on the total weight, small amounts of starter compounds and their low molecular weight alkoxylates, as well as small amounts of other organic impurities and water. Volatile impurities should be flashed or stripped 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 may be removed if desired. Water and volatiles can be removed by stripping the polyol.

[0023] Polymerization reactions may be characterized by a "build ratio," defined as the ratio of the number average molecular weight of the product to the number average molecular weight of the starter compound. This build ratio may be as high as 160, but is more typically in the range of 2.5 to about 65, and even more typically in the range of 2.5 to about 50, 2.5 to 35, 2.5 to 11, or 7 to 11.

[0024] The present invention is particularly useful in polymerization processes characterized by one or more of the following: i) the use of a starter having an equivalent weight of at most 125, especially at most 100 or at most 75 g / equivalent; ii) a hydroxyl content of from 4.25 to 20 wt.-%, especially from 4.25 to 15 wt.-%, especially from 4.25 to 12 wt.-% or even from 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 concentration of the catalyst complex sufficient to provide at most 5 ppm cobalt, especially from 0.5 to 2 ppm cobalt, 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 1,2-propylene oxide); and (v) an ethylene oxide concentration of from 2 to 10 wt.-%, 2 to 8 wt.-%, 2 to 6 wt.-%, or 2 to 5 wt.-%, at the point in the polymerization when the ethylene oxide content, if present, is at its highest. Each of these represents severe conditions under which conventional zinc hexacyanometallate catalysts perform poorly.

[0025] In some embodiments, the polymerization step is carried out in the presence of 0.01 mole or less of a carbonate precursor per mole of alkylene oxide to be polymerized. A "carbonate" precursor is a compound that, when polymerized with an alkylene oxide, produces a carbonate (-OC(O)-O-) bond. Examples of carbonate precursors include carbon dioxide, linear carbonates, cyclic carbonates, phosgene, and the like.

[0026] The water-insoluble polymerization catalyst complex comprises at least one double metal cyanide compound. This type of polymerization catalyst complex and double metal cyanide compound are generally well known, 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 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) During the ceremony, M1 and M4 each represent a metal ion independently selected from Zn2+, Fe2+, Co2+, Ni2+, Mo4+, Mo6+, Al3+, V4+, V5+, Sr2+, W4+, W6+, Mn2+, Sn2+, Sn4+, Pb2+, Cu2+, La3+, and Cr3+; M2 and M3 each represent a metal ion independently selected from Fe3+, Fe2+, Co3+, Co2+, Cr2+, Cr3+, Mn2+, Mn3+, Ir3+, Ni2+, Rh3+, Ru2+, V4+, V5+, Ni2+, Pd2+, and Pt2+; X1 represents a group other than cyanide that coordinates with the M2 ion; X2 represents a group other than cyanide that coordinates with the M3 ion; A1 represents a halide such as chloride, bromide, iodide, etc.; a nitrate; a sulfate; a carbonate; a cyanide; an oxalate; a thiocyanate; an isocyanate; a perchlorate; an isothiocyanate; an alkane sulfonate such as methane sulfonate; an arylene sulfonate such as p-toluene sulfonate; and a trifluoromethane sulfonate (triflate), b, c, and d are each numbers such that the group M1b[M2(CN)r(X1)t]c[M3(X2)6]d is electrostatically neutral, provided that b and c are each greater than zero; x and y are integers such that the metal salt M4xA1y is electrostatically neutral; r is an integer from 4 to 6; t is an integer from 0 to 2; n is a number from 0 to 20.

[0027] M1 and M4 (if present) are each most preferably zinc. M2 and M3 (if present) are each most preferably iron and cobalt, especially cobalt. r is most preferably 6 and t is most preferably 0. d is most preferably 0 to 1. The molar ratio of the combined M1 and M4 metals to the combined M2 and M3 metals is preferably 0.8:1 to 20:1.

[0028] 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. Small values ​​of p and q do not improve the performance of the catalyst complex. Higher amounts do not improve the performance of the catalyst, and actually tend to reduce the performance.

[0029] In some embodiments, the ratio p:q may be at least 0.025 or at least 0.05, and up to 1.5, up to 1, or up to 0.5.

[0030] The values ​​of p, q and the ratio p:q are conveniently determined using X-ray fluorescence (XRF) techniques.

[0031] The catalyst complex of the above formula can be made in a precipitation process in which a solution containing starting materials including a cyanometallate compound and a starting M1 compound is prepared, the specific starting materials are reacted, and the catalyst complex is precipitated from the starting solution. In general, the methods for producing DMC catalysts are as described in, 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.

[0032] The solvent comprises at least one of water and a liquid aliphatic alcohol. The solvent is one in which the starting cyanometallate compound and the M1 metal compound are soluble.

[0033] The solvent may be, for example, water, n-propanol, iso-propanol, n-butanol, sec-butanol, t-butanol, other alkylene monoalcohols, e.g. having up to 12 carbon atoms, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, or other polyethers having one or more hydroxyl groups and a number average molecular weight, e.g. up to 8000 g / mol, measured by gel permeation chromatography against polystyrene standards. Of these, aliphatic monoalcohols having 3 to 6 carbon atoms, especially t-butanol, are preferred. Particularly preferred are mixtures of water and liquid aliphatic alcohols (especially aliphatic monoalcohols having 3 to 6 carbon atoms, most preferably t-butanol) that are soluble in water in the relative proportions present in the mixture, in a volume ratio of 25:75 to 90:10.

[0034] The M1 metal compound is preferably water-soluble. Typically, it is a salt of M1 metal and one or more anions. Such salts may have the formula M1xA1y, where x, A1 and y are as described above. In an exemplary embodiment, the anion A1 is not any of alkoxide, aryloxy, carboxylate, acyl, pyrophosphate, phosphate, thiophosphate, dithiophosphate, phosphate ester, thiophosphate ester, amide, oxide, siloxide, hydride, carbamate or hydrocarbon anion.

[0035] The M1 metal 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 M1 metal. ZnCl2 is the preferred M1 metal compound.

[0036] The cyanometallate compound comprises the M2(CN)r(X1)t anion, where r, X1, and t are as previously described. r is preferably 6 and t is preferably zero. The M2 metal is one or more of Fe3+, Fe2+, Co3+, Co2+, Cr2+, Cr3+, Mn2+, Mn3+, Ir3+, Ni2+, Rh3+, Ru2+, V4+, V5+, Ni2+, Pd2+, and Pt2+. The M2 metal is preferably Fe3+ or Co3+, with Co3+ being particularly preferred. The cyanometallate compound is preferably an alkali metal or ammonium salt, although the corresponding cyanometallic acid can be used. Potassium hexacyanocobaltate is a particularly preferred cyanometallate compound.

[0037] The cyanometallate compound and the M1 metal compound react to form a catalyst complex containing a water-insoluble M1 metal cyanometallate. This reaction proceeds spontaneously at temperatures near room temperature (23°C) or slightly higher. Therefore, no special reaction conditions are required. The temperature may be, for example, 0-60°C. A preferred temperature is 20-50°C or 25-45°C. It is preferable to continue stirring until precipitation occurs, which is generally indicated by a change in the appearance of the solution. The reaction pressure is not particularly important as long as the solvent does not evaporate. An absolute pressure of 10-10,000 kPa is suitable, and an absolute pressure of 50-250 kPa is entirely suitable. The reaction time may be from 30 minutes to 24 hours or more.

[0038] The precipitated double metal cyanide is preferably treated with a complexing agent, which is incorporated into the catalyst complex. This is conveniently done by washing the precipitated double metal cyanide one or more times with the complexing agent or an aqueous solution of the complexing agent. The complexing agent component may comprise at least one of the following: alcohols, polyethers, polyesters, polycarbonates, glycidyl ethers, glycosides, polyhydric alcohol carboxylates, polyalkylene glycol sorbitan esters, bile acids or salts, carboxylic acid esters or amides thereof, cyclodextrins, organic phosphates, phosphites, phosphonates, phosphonites, phosphinates, phosphinites, ionic surface-active or surfactant compounds, and / or α,β-unsaturated carboxylic acid esters, as previously described with respect to the starting solution. In an exemplary embodiment, the organic complexing agent is one or more of n-propanol, iso-propanol, n-butanol, sec-butanol, t-butanol, other alkylene monoalcohols having up to 12 carbon atoms, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, or other polyethers having one or more hydroxyl groups and a number average molecular weight of, for example, up to 8000 g / mole as measured by gel permeation chromatography against polystyrene standards.

[0039] The catalyst complex so produced is conveniently recovered from the starting solution or any washings, dried, and optionally ground or pulverized to reduce the catalyst complex to a powder having, for example, a volume average particle size of 100 μm or less. Drying can be accomplished by application of heat and / or vacuum.

[0040] The additive in some embodiments is or includes an alkali metal, ammonium, or quaternary ammonium salt of a monocarboxylic acid having up to 24 carbon atoms. The monocarboxylic acid can have 1-18 carbon atoms, 1-12 carbon atoms, 1-8 carbon atoms, or 1-2 carbon atoms. The monocarboxylic acid can be aliphatic or straight chain. In other embodiments, the monocarboxylic acid can be aromatic (such as benzoic acid). The alkali metal can be lithium, sodium, potassium, and / or cesium. "Ammonium" refers to the NH4+ ion. The quaternary ammonium ion takes the form NR4+, where each R is independently H or hydrocarbyl, provided that at least one R is hydrocarbyl. Specific examples include lithium formate, sodium formate, potassium formate, cesium formate, or ammonium formate; lithium acetate, sodium acetate, potassium acetate, cesium acetate, or ammonium acetate; lithium benzoate, sodium benzoate, potassium benzoate, cesium benzoate, or ammonium benzoate, and lithium salts, sodium salts, potassium salts, cesium salts, or ammonium salts of linear or branched aliphatic C4 to C18 monocarboxylic acids.

[0041] The additive may be or include one or more of a monobasic alkali metal phosphate, a monobasic ammonium phosphate, and a monobasic quaternary ammonium phosphate, examples of which include lithium dihydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, cesium dihydrogen phosphate, and ammonium dihydrogen phosphate.

[0042] The additive may be or include dibasic sodium phosphate (Na2HPO4).

[0043] The additive may be or include one or more of tartaric acid, malic acid or succinic acid.

[0044] The weight of the additive is, in some embodiments, 1 to 25 times the weight of the catalyst complex. The weight of the additive may be, for example, at least 2 times or at least 3 times the weight of the catalyst complex. The weight of the additive may be up to 15 times, up to 10 times, up to 7.5 times, or up to 5 times the weight of the catalyst complex.

[0045] Stated another way, the additive is conveniently present in the polymerization mixture in an amount of about 50 to 50,000 parts per million (ppm) by weight based on the weight of the product. Preferred lower limits are at least 100 ppm, at least 250 ppm, at least 500 ppm, or at least 1000 ppm. Preferred upper limits are up to 10,000 ppm, up to 5,000 ppm, up to 2500 ppm, or up to 1500 ppm.

[0046] A promoter is optionally present in the reaction mixture. For purposes of the present invention, the promoter is a separate component from the water-insoluble polymerization catalyst complex, which means that for purposes of the present invention, neither the promoter nor the M5 metal or metalloid-containing precursor is present during the precipitation step that forms the double metal cyanide component of the catalyst complex. The promoter can be combined with the other components in any order, and in particular, can be combined with the catalyst complex before being combined with the other components of the polymerization mixture.

[0047] The M5 metal or metalloid compound is a compound of magnesium or any metal or metalloid M5 found in any of Groups 3 to 15 of the 2010 IUPAC Periodic Table of the 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 anion.

[0048] The metal may be, for example, 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 the lanthanide series metals, which include those having atomic numbers from 58 (cerium) to 71 (ruthenium), inclusive.

[0049] Preferred M5 metals and metalloids include yttrium, zirconium, niobium, silicon, titanium, tungsten, cobalt, scandium, vanadium, molybdenum, nickel, zinc and tin. More preferably, hafnium, aluminum, manganese, gallium and indium.

[0050] By "alkoxide" ion is meant a species having the form -OR, where R is an alkyl or substituted alkyl group, and is the conjugate base of an alcohol compound having the form HO-R after removal of the hydroxyl hydrogen. These alcohols may have pKa values ​​ranging from 13 to 25 or more. In some embodiments, the alkoxide ion may contain 1 to 20 (e.g., 1 to 6 and / or 2 to 6) carbon atoms. The alkyl or substituted alkyl groups may be linear, branched, and / or cyclic. Examples of suitable substituents include, for example, additional hydroxyl groups (which may be in the form of alkoxides), ether groups, carbonyl groups, ester groups, urethane groups, carbonate groups, silyl groups, aromatic groups (e.g., phenyl and alkyl-substituted phenyl), and halogens. Examples of such alkoxide ions include methoxide, ethoxide, isopropoxide, n-propoxide, n-butoxide, sec-butoxide, t-butoxide, benzyloxy, and the like. The R group may contain one or more hydroxyl groups and / or one or more ether linkages. The alkoxide ion may correspond to the residue (after removal of one or more hydroxyl group hydrogens) of a starter compound present during polymerization, such as the starter compounds described below. The alkoxide ion may be an alkoxide formed by removing one or more hydroxyl group hydrogens from a polyether monol or polyether polyol, in some embodiments, such alkoxides correspond to the residue after removing one or more hydroxyl group hydrogen atoms, after removing a polyether monol or polyether polyol product resulting from an alkoxylation reaction, or after removing a polyether having a molecular weight intermediate between the molecular weights of the starter compound and the product of the alkoxylation reaction.

[0051] By "aryloxy" anion is meant a species having the form -O-Ar, where Ar is an aromatic or substituted aromatic group, which corresponds to phenolic compounds having the form HO-Ar, after removal of the hydroxyl hydrogen. These phenolic compounds may have a pKa of, for example, from 9 to about 12. Examples of such aryloxy anions include phenoxides and ring-substituted phenoxides, where the ring substituents include, for example, one or more of alkyl, CF3, cyano, COCH3, halogen, hydroxyl, and alkoxyl. The ring substituents, when present, may be in one or more of the ortho, para, and / or meta positions relative 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.

[0052] By "carboxylate" anion is meant 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. The aliphatic carboxylic acid may contain a substituent. Examples of such include hydroxyl groups (which may be in the form of alkoxides), 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-octanoate, decanoate, laurate and other alkanoates, as well as halogen-substituted alkanoates, such as 2,2,2-trifluoroacetate, 2-fluoroacetate, 2,2-difluoroacetate, 2-chloroacetate, 2,2,2-trichloroacetate. Examples of aromatic carboxylates include benzoate, alkyl-substituted benzoates, halo-substituted benzoates, 4-cyanobenzoate, 4-trifluoromethylbenzoate, salicylate, 3,5-di-t-butylsalicylate, and subsalicylate. In some embodiments, such carboxylate ions can be the conjugate bases of carboxylic acids having pKa's of 1-6 (e.g., 3-5).

[0053] By "acyl" anion is meant the conjugate base of a compound containing a carbonyl group, including, for example, an aldehyde, ketone, acetylacetonate, carbonate, ester, or similar compound in the enol form. Examples of these are β-diketo compounds such as acetoacetonate and butylacetoacetonate.

[0054] By "phosphate" anion is meant a phosphate anion having the formula -OP(O)(OR1)2, where R1 is alkyl, substituted alkyl, phenyl, or substituted phenyl. By "thiophosphate" anion is meant a thiophosphate anion having the corresponding structure in which one or more of the oxygens are replaced with sulfur. Phosphates and thiophosphates may also be ester anions, such as phosphate esters and thiophosphate esters.

[0055] By "pyrophosphate" anion is meant the P2O74- anion.

[0056] An "amide" anion refers to an ion in which the nitrogen atom carries a negative charge. An amide ion generally takes the form -N(R2)2, where the R2 groups are independently hydrogen, alkyl, aryl, trialkylsilyl, or triarylsilyl. The alkyl groups may be linear, branched, or cyclic. Any of these groups may contain substituents such as ether or hydroxyl. Two R2 groups may together form a ring structure, which may be unsaturated and / or contain one or more heteroatoms in the ring (in addition to the amide nitrogen).

[0057] By "oxide" anion is meant the anion of atomic oxygen, i.e., O2-.

[0058] A "siloxide" anion means a silanoate having the formula (R3)3SiO-, where the R3 groups are independently hydrogen or alkyl groups.

[0059] By "hydride" anion is meant the anion of hydrogen, ie, H-.

[0060] By "carbamate" anion is meant the anion -OOCNH2.

[0061] By "hydrocarbon" anion is meant a hydrocarbyl anion, including aliphatic, alicyclic, and / or aromatic anions, in which the negative charge resides on a carbon atom. The hydrocarbyl anion is typically a conjugate base of a hydrocarbon having a pKa value greater than 30. The hydrocarbyl anion may also contain inert substituents. Of the aromatic hydrocarbyl anions, phenyl and substituted phenyl groups may be used. The aliphatic hydrocarbyl anion may be, for example, an alkyl group, which may contain 1 to 12 (e.g., 2 to 8) carbon atoms. For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, cyclopentadienyl, and t-butyl anions are all useful.

[0062] "Halide" anion means F-, Cl-, Br-, and I-.

[0063] Examples of useful gallium compounds include trialkylgallium compounds such as trimethylgallium, triethylgallium, tributylgallium, tribenzylgallium; gallium oxide; gallium alkoxides such as gallium trimethoxide, gallium triethoxide, gallium triisopropoxide, gallium tri-t-butoxide, gallium tri-sec-butoxide; gallium aryloxides such as gallium phenoxides and gallium phenoxides in which one or more of the phenoxide groups are ring substituted with one or more of alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like; gallium formate, gallium acetate, gallium propionate, gallium 2-ethylhexanoate, gallium benzoate, benzoic acid, and the like. gallium carboxylates, such as gallium benzoate, gallium salicylate, gallium 3,5-di-t-butylsalicylate, in which one or more of the groups are ring-substituted with one or more of alkyl, CF, cyano, COCH, halogen, hydroxyl, alkoxyl, and the like; gallium amides, such as gallium tris(dimethylamide), gallium tris(diethylamide), gallium tris(diphenylamide), gallium tris(di(trimethylsilyl)amide); gallium acetylacetonate; gallium t-butylacetylacetonate; and alkylgallium alkoxides, such as diethylgallium ethoxide, dimethylgallium ethoxide, diethylgallium isopropoxide, and dimethylgallium isopropoxide.

[0064] Examples of useful hafnium compounds include, for example, hafnium alkyls, such as, for example, tetraethylhafnium, tetrabutylhafnium, tetrabenzylhafnium; hafnium oxide; hafnium alkoxides, such as hafnium tetramethoxide, hafnium tetraethoxide, hafnium tetraisopropoxide, hafnium tetra-t-butoxide, hafnium tetra-sec-butoxide; hafnium aryloxides, such as hafnium phenoxide and hafnium phenoxides in which one or more of the phenoxide groups are ring substituted with one or more of alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like; hafnium formate, hafnium acetate, and the like. hafnium carboxylates such as hafnium propionate, hafnium 2-ethylhexanoate, hafnium benzoate, hafnium benzoates where one or more of the benzoic acid groups are ring substituted with one or more of alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like, hafnium salicylate, hafnium 3,5-di-t-butylsalicylate, hafnium amides such as hafnium tetra(dimethylamide), hafnium tetra(diethylamide), hafnium tetra(diphenylamide), hafnium tetra((bistrimethylsilyl)amide), hafnium acetylacetonate, and hafnium t-butylacetylacetonate.

[0065] Examples of useful indium compounds include trialkylindium compounds such as trimethylindium; indium oxide; indium alkoxides such as indium methoxide, indium ethoxide, indium isopropoxide, indium t-butoxide, indium sec-butoxide; indium phenoxides, and indium phenoxides in which one or more of the phenoxide groups are ring substituted with one or more of alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like. indium aryloxides; indium formate, indium acetate, indium propionate, indium 2-ethylhexanoate, indium benzoate, indium carboxylates such as indium benzoates where one or more of the benzoic acid groups are ring substituted with one or more of alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like, indium salicylate, indium 3,5-di-t-butylsalicylate; indium acetylacetonate; and indium t-butyl acetylacetonate.

[0066] Examples of useful aluminum compounds include trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, tributylaluminum, tribenzylaluminum, and the like; aluminum alkoxides such as aluminum trimethoxide, aluminum triethoxide, aluminum triisopropoxide, aluminum triisopropoxide, aluminum tri-t-butoxide, aluminum tri-sec-butoxide, and the like; aluminum aryloxides such as aluminum phenoxides and aluminum phenoxides in which one or more of the phenoxide groups are ring-substituted with one or more of alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like; aluminum oxide; aluminum formate, aluminum acetate, aluminum propionate, aluminum 2-ethylhexanoate, aluminum benzoate, and the like. wherein one or more of the following are ring-substituted with one or more of alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like; aluminum amides such as aluminum tris(dimethylamide), aluminum tris(diethylamide), aluminum tris(diphenylamide), aluminum tris(di(trimethylsilyl)amide), aluminum acetylacetonate, aluminum t-butylacetylacetonate, and alkyl aluminum oxides such as diethylaluminum ethoxide, dimethylaluminum ethoxide, diethylaluminum isopropoxide, dimethylaluminum isopropoxide, methylaluminoxane, tetraethyldialuminoxane, and alkoxides.

[0067] Examples of useful magnesium compounds include alkyl magnesium compounds such as diethyl magnesium, dibutyl magnesium, butylethyl magnesium, dibenzyl magnesium, and the like; magnesium alkoxides such as magnesium methoxide, magnesium ethoxide, magnesium isopropoxide, magnesium t-butoxide, magnesium sec-butoxide, and the like; magnesium aryloxides such as magnesium phenoxide and magnesium phenoxides in which one or more of the phenoxide groups are ring substituted with one or more of alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like; magnesium formate, magnesium acetate, magnesium propionate, magnesium alkoxide, magnesium alkoxide, magnesium alkoxide, magnesium methoxide, magnesium eth ... Magnesium carboxylates such as magnesium pionate, magnesium 2-ethylhexanoate, magnesium benzoate, magnesium benzoates where one or more of the benzoic acid groups are ring substituted with one or more of alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, etc., magnesium salicylate, magnesium 3,5-di-t-butylsalicylate; magnesium amides such as magnesium dimethylamide, magnesium diethylamide, magnesium diphenylamide, magnesium bis(trimethylsilyl)amide; magnesium oxide, magnesium acetylacetonate, and magnesium t-butyl acetylacetonate.

[0068] Examples of useful manganese compounds include Mn(II) and / or Mn(III) and / or Mn(IV) compounds, including manganese phosphates; manganese pyrophosphates; manganese oxides; manganese alkoxides, such as manganese methoxide, manganese ethoxide, manganese isopropoxide, manganese t-butoxide, manganese sec-butoxide; manganese phenoxides, and manganese compounds in which one or more of the phenoxide groups are ring substituted with one or more of alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like. manganese aryloxides, such as manganese phenoxide; manganese carboxylates, such as manganese formate, manganese acetate, manganese propionate, manganese 2-ethylhexanoate, manganese benzoate, manganese benzoates in which one or more of the benzoic acid groups are ring substituted with one or more of alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like, manganese salicylate, manganese 3,5-di-t-butylsalicylate; manganese acetylacetonate; and manganese t-butyl acetylacetonate.

[0069] Examples of useful scandium compounds include scandium alkoxides, such as scandium methoxide, scandium ethoxide, scandium isopropoxide, scandium t-butoxide, and scandium sec-butoxide; scandium oxide; scandium aryloxides, such as scandium phenoxides and scandium phenoxides in which one or more of the phenoxide groups are ring substituted with one or more of alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like; scandium carboxylates, such as scandium formate, scandium acetate, scandium propionate, scandium 2-ethylhexanoate, scandium benzoate, and scandium benzoate in which one or more of the benzoic acid groups are ring substituted with one or more of alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like; scandium salicylate; scandium acetylacetonate, and scandium t-butyl acetylacetonate.

[0070] 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, molybdenum t-butoxide, molybdenum sec-butoxide; molybdenum phenoxides, and compounds in which one or more of the phenoxide groups are ring substituted with one or more of alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like. molybdenum aryloxides such as molybdenum phenoxides in which one or more of the benzoic acid groups are ring substituted with one or more of the following: molybdenum formate, molybdenum acetate, molybdenum propionate, molybdenum 2-ethylhexanoate, molybdenum benzoate, molybdenum carboxylates such as molybdenum benzoates, molybdenum salicylates, and molybdenum 3,5-di-t-butylsalicylate, where one or more of the benzoic acid groups are ring substituted with one or more of alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like; and molybdenum acetylacetonates.

[0071] 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; cobalt aryloxides such as cobalt phenoxides and cobalt phenoxides in which one or more of the phenoxide groups are ring substituted with one or more of alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like. cobalt carboxylates such as cobalt formate, cobalt acetate, cobalt propionate, cobalt 2-ethylhexanoate, cobalt benzoate, cobalt benzoates in which one or more of the benzoic acid groups are ring-substituted with one or more of alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, etc., cobalt salicylate, cobalt 3,5-di-t-butylsalicylate; cobalt acetylacetonate; and cobalt t-butylacetylacetonate, which in each case is a Co(II) and / or Co(III) compound.

[0072] Examples of useful tungsten compounds include tungsten phosphates; tungsten pyrophosphates, tungsten oxides; tungsten alkoxides, such as tungsten methoxide, tungsten ethoxide, tungsten isopropoxide, tungsten t-butoxide, tungsten sec-butoxide; tungsten aryl compounds, such as tungsten phenoxides and tungsten phenoxides in which one or more of the phenoxide groups are ring substituted with one or more of alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like. tungsten carboxylates such as tungsten formate, tungsten acetate, tungsten propionate, tungsten 2-ethylhexanoate, tungsten benzoate, tungsten benzoates where one or more of the benzoic acid groups are ring substituted with one or more of alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like, tungsten salicylate, tungsten acetylacetonate, and tungsten t-butyl acetylacetonate.

[0073] 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, iron t-butoxide, iron sec-butoxide; iron aryloxides, such as iron phenoxides and iron phenoxides in which one or more of the phenoxide groups are ring-substituted with one or more of alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like; iron formate. , iron acetate, iron propionate, iron 2-ethylhexanoate, iron benzoate, iron carboxylates such as iron benzoates where one or more of the benzoic acid groups are ring-substituted with one or more of alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, etc., iron salicylate, iron 3,5-di-t-butylsalicylate; iron acetylacetonate; and iron t-butyl acetylacetonate, which in each case is an Fe(II) and / or Fe(III) compound.

[0074] Examples of useful vanadium compounds include vanadium alkoxides, such as vanadium methoxide, vanadium ethoxide, vanadium isopropoxide, vanadium t-butoxide, and vanadium sec-butoxide; vanadium oxide; vanadium oxotris(alkoxides), such as vanadium oxotris(methoxide), vanadium oxotris(ethoxide), vanadium oxotris(isopropoxide), vanadium oxotris(t-butoxide), and vanadium oxotris(sec-butoxide); vanadium phenoxides, and compounds in which one or more of the phenoxide groups are alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like. vanadium aryloxides such as vanadium phenoxides ring-substituted with one or more of the following: vanadium formate, vanadium acetate, vanadium propionate, vanadium 2-ethylhexanoate, vanadium benzoate, vanadium carboxylates such as vanadium benzoate, vanadium salicylate, and vanadium 3,5-di-t-butylsalicylate where one or more of the benzoic acid groups are ring-substituted with one or more of the following: alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like; vanadium tris(acetylacetonate) and vanadium tris(t-butylacetylacetonate); and vanadium oxobis(acetylacetonate).

[0075] 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; stannous aliphatic compounds, such as stannous phenoxide, and stannous phenoxides in which one or more of the phenoxide groups are ring-substituted with one or more of alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like. stannous oxides; stannous formate, stannous acetate, stannous propionate, stannous 2-ethylhexanoate, stannous benzoate, stannous carboxylates such as stannous benzoates where one or more of the benzoic acid groups are ring-substituted with one or more of alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like, stannous salicylate, stannous 3,5-di-t-butylsalicylate; stannous acetylacetonate; and stannous t-butyl acetylacetonate.

[0076] Examples of useful zinc compounds include zinc alkyls such as dimethylzinc, diethylzinc, dibutylzinc, dibenzylzinc, etc.; zinc oxide, alkylzinc alkoxides such as ethylzinc isopropoxide, etc.; zinc alkoxides such as zinc methoxide, zinc ethoxide, zinc isopropoxide, zinc t-butoxide, zinc sec-butoxide, etc.; zinc phenoxides, and zinc aryloxys such as zinc phenoxides where one or more of the phenoxide groups are ring substituted with one or more of alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, etc. zinc carboxylates such as zinc formate, zinc acetate, zinc propionate, zinc 2-ethylhexanoate, zinc benzoate, zinc benzoates in which one or more of the benzoic acid groups are ring-substituted with one or more of alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like, zinc salicylate, zinc 3,5-di-t-butylsalicylate; zinc amides such as zinc dimethylamide, zinc diethylamide, zinc diphenylamide, zinc (bistrimethylsilyl)amide; zinc acetylacetonate and zinc t-butylacetylacetonate.

[0077] 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, titanium tetraphenoxide in which one or more of the phenoxide groups are independently ring substituted with one or more of alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like.

[0078] 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 tetra-t-butoxide, silicon tetra-sec-butoxide, silicon tetraphenoxide, silicon tetraphenoxide in which one or more of the phenoxide groups are independently ring substituted with one or more of alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like.

[0079] The promoter is preferably a M provided by a double metal cyanide catalyst. 2 +M 3 At least 0.001 or at least 0.0025 moles of M per mole of metal 5 The promoter is present in an amount to provide a metal or metalloid. 2 +M 3 M up to 50, up to 10, up to 5, up to 1.5, up to 0.25 or up to 0.125 moles per mole of metal 5 It may be present in an amount to provide a metal or metalloid.

[0080] For example, as described in WO 2020 / 131508, two or more different M 5There may be promoter mixtures of metal or metalloid compounds. In such mixtures, M 5 At least one of the metals or semimetals is gallium, indium, hafnium or titanium (particularly gallium or hafnium) and at least one other M 5 Preferably the metal or semi-metal is aluminium, silicon or titanium (especially aluminium).

[0081] In certain embodiments, the facilitator is generally 5 As in the case of metal or semi-metal oxides, they are present in the form of discrete particles. Such particles have a size of at least 1 m as measured using gas sorption techniques. 2 The surface area of ​​such promoter particles may be at least 10 m 2 / g, or at least 100m 2 / g, for example up to 300m 3 / g or more. Their volume average particle size can be 100 μm or less, 25 μm or less, 1 μm or less, or 500 nm or less. Such physical mixtures can be made, for example, by forming solid particles of the double metal cyanide catalyst (or a catalyst complex containing the double metal cyanide) and combining them with 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 the precipitated double metal cyanide one or more times with water and / or ligand before final drying. The promoter particles can be combined with the zinc hexacyanocobaltate during any such washing step.

[0082] Polyethers made according to the invention can include monoalcohols, such as those useful for surfactants, and industrial solvent or lubricant applications, and polyols, such as useful raw materials for producing polymers such as polyurethanes for molded foams, slabstock foams, high resilience foams, viscoelastic foams, rigid foams, adhesives, sealants, coatings, elastomers, composites, and the like.

[0083] The following examples are provided to illustrate exemplary embodiments and are not intended to limit the scope thereof. All parts and percentages are by weight unless otherwise indicated.

[0084] Examples 1 to 12 and Comparative Samples A to F Ethylene oxide polymerization is carried out using a 48-well Symyx Technologies Parallel Pressure Reactor (Parallel Pressure Reactor, PPR). Each of the wells is equipped with an individually weighed glass insert with an internal working liquid volume of approximately 5 mL. 3 mL of a mixture of 98.5% 625 weight average molecular weight poly(ethylene oxide) triol and 1.5% glycerol is added to each well along with 265 parts per million (ppm, based on the expected mass of the product) zinc hexacyanocobaltate catalyst complex (Arcol® 3 Catalyst from Covestro), 265 ppm aluminum oxide (Catalox® BA from Sasol North America), and 1335 ppm additives as shown in Table 1. The wells are pressurized with 70 psig (483 kPa) 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). The internal pressure is monitored over time as an indication of the progress of the ethylene oxide polymerization reaction. The time required for the pressure to decrease to 90 psig (621 kPa) and then to 80 psig (552 kPa) is recorded. A shorter time indicates greater catalytic activity. The results are shown in Table 1.

[0085] [Table 1] * This is not an embodiment of the present invention.

[0086] Comparative sample A represents the baseline case. The catalyst complex itself is unable to initiate polymerization under these very stringent conditions (high concentration of hydroxyl groups + ethylene oxide selection). Examples 1-12 show that active polymerization occurs when alkali metal carboxylates (Examples 1-6 and 12), monobasic potassium phosphate, ammonium dihydrogen phosphate or lithium dihydrogen phosphate (Examples 7-9), tartaric acid (Example 11) or dibasic sodium phosphate (Example 12) are additionally present in the reaction mixture. The time for the reactor pressure to drop to 90 psig (621 kPa) is reduced by more than 9 times in each case.

[0087] Comparative samples B-F show poorer effectiveness of various other additives. Triflate salts (compound B) provide some benefit but are much less effective than the additives of the present invention. Dibasic potassium phosphate, carbonate salts and alkaline earth carboxylate salts (compounds C, D, E and F) provide little benefit.

[0088] Examples 13 to 23 and Comparative Samples G to K Ethylene oxide polymerization is carried out in the same manner as in the previous series of examples, substituting an equal concentration of aluminum tri(sec-butoxide) for aluminum oxide. The additives and results are as shown in Table 2.

[0089] [Table 2] * This is not an embodiment of the present invention.

[0090] Alkali metal carboxylates (Examples 13-18 and 21), monobasic phosphates (Examples 19 and 20), tartaric acid and disodium hydrogen phosphate (Examples 22, 23) all dramatically increase the rate of polymerization. Triflate salts, K2HPO4, carbonate salts and LiH2PO4 have little, if any, beneficial effect.

Claims

1. 1. A method for producing a polyether, comprising: I. forming a reaction mixture comprising: a) a hydroxyl-containing starter, b) at least one alkylene oxide, c) a water-insoluble polymerization catalyst complex comprising 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 phosphate, tartaric acid, malic acid, and succinic acid; II. polymerizing said alkylene oxide onto said hydroxyl-containing starter in the presence of said water-insoluble polymerization catalyst complex and said additive to produce said polyether.

2. The double metal cyanide compound is represented by the following formula: M １ ｂ [M ２ (CN) ｒ (X １ ) ｔ ] ｃ [M ３ (X ２ ) ６ ] ｄ ・nM ４ ｘ A １ ｙ (I) During the ceremony, M １ and M ４ are respectively Zn ２＋ , Fe ２＋ , Co ＋２＋ , Ni ２＋ , Mo ４＋ , Mo ６＋ , Al ＋３＋ , V ４＋ , V ５＋ , Sr ２＋ , W ４＋ , W ６＋ , Mn ２＋ , Sn ２＋ , Sn ４＋ , Pb ２＋ , Cu ２＋ , La ３＋ , and Cr ３＋ represents a metal ion independently selected from M ２ and M ３ are respectively 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＋ , V ５＋ , Ni ２＋ , Pd ２＋ , and Pt ２＋ represents a metal ion independently selected from X １ But M ２ represents a group other than cyanide that coordinates with an ion, X ２ But M ３ represents a group other than cyanide that coordinates with an ion, A １ is a halide, nitrate, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, perchlorate, isothiocyanate, alkane sulfonate, arylene sulfonate, trifluoromethane sulfonate, or C １－４ represents a carboxylate, b, c, and d are each values ​​reflecting an electrostatically neutral complex, provided that b and c are each greater than zero; x and y are metal salts M ４ ｘ A １ ｙ is an integer that balances the charge in r is an integer from 4 to 6, t is an integer from 0 to 2, 2. The method of claim 1, wherein n is a number from 0 to 20.

3. The reaction mixture further comprises, as a component other than the water-insoluble polymerization catalyst complex, e) at least one M ５ Further comprising a metal or semimetal compound, ５ The metal or metalloid is magnesium or a metal or metalloid M included in any of Groups 3 to 15 of the 2010 IUPAC Periodic Table of the Elements. ５ and M ５ 10. The process of claim 1, wherein the metal or metalloid is bound to at least one alkoxide, aryloxy, carboxylate, acyl, pyrophosphate, phosphate, thiophosphate, dithiophosphate, phosphate ester, thiophosphate ester, amide, oxide, siloxide, hydride, carbamate, halide, or hydrocarbon anion.

4. Component e) is M provided by the double metal cyanide catalyst ２ and M ３ 0.0025 to 50 moles of M per total mole of metal ５ The method of claim 3 wherein the metal is present in an amount providing

5. Said M ５ 4. The method of claim 3, wherein the metal or metalloid is selected from the group consisting of aluminum, gallium, and hafnium.

6. 10. The method of claim 1, wherein the additive is present in an amount of 1 to 10 times the weight of the catalyst complex.

7. The additive is an alkali metal carboxylate, NH ４ H ２ P.O. ４ , monobasic alkali metal phosphate and Na ２ HPO ４ 10. The method of claim 1, wherein the compound is one or more compounds selected from the group consisting of:

8. The method of claim 1 wherein the alkylene oxide is ethylene oxide.

9. 10. The method of claim 1, wherein the catalyst complex and starter are charged to a reaction vessel, the catalyst complex is activated, and then at least a portion of the alkylene oxide is added to the reaction vessel containing the activated catalyst complex and starter under polymerization conditions without removing product until all of the alkylene oxide has been added; or a continuous process wherein the catalyst complex, starter, and alkylene oxide are continuously fed to a reaction vessel under polymerization conditions and product is continuously removed from the reaction vessel.

10. 10. The method of any one of claims 1 to 9, wherein the reaction mixture during at least a portion of step II has a hydroxyl content of 4.25 to 15 wt. %, based on the total weight of the reaction mixture.