Polyether Polymerization Process

Abstract

The alkylene oxide is polymerized in the presence of a catalyst system that includes a double metal cyanide catalyst modified with a specific metal or semimetal compound. 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, or Lanthanide series metal compound is devoid of halide anions. This technique is highly effective in reducing activation time and improving catalyst performance when exposed to high concentrations of hydroxyl groups. However, the addition of the second component of the catalyst system to the polymerization reaction requires additional equipment for storage and metering. Because of the small amounts required, it can be difficult to precisely control the addition of the second component.

[0006] WO 2018 / 209069 and WO 2018 / 209075 disclose catalyst compositions made by precipitating a catalyst in the presence of certain metal compounds, which may include gallium, hafnium, indium or aluminum compounds. This avoids the problem of metering small amounts of a second component into the polymerization reaction, while still producing a highly active and robust catalyst complex. Nevertheless, further improvements are desirable, and catalyst systems that perform better under stringent polymerization conditions and / or in the polymerization of ethylene oxide would be beneficial. Summary of the Invention

[0007] The present invention is a process for producing a polyether, the process comprising forming a reaction mixture including a hydroxyl-containing starter, at least one alkylene oxide, a catalyst complex, and an additive, polymerizing the alkylene oxide on the hydroxyl-containing starter to produce a polyether, the catalyst complex being selected from the group consisting of catalyst complexes I and II; The catalyst complex I is a) i) a solvent comprising at least one of water and a liquid aliphatic alcohol dissolved therein; ii) M 2 iii) a cyanometallate compound having a metal cyanometallate group, and iii) a water-insoluble M 1 M forming metal cyanometallates 1 forming a starting solution containing a metal compound, the starting solution comprising 0.01 to 10 moles of iii) M per mole of cyanometallate compound; 1 At least one M different from the metal salt 5 Further containing a metal or semimetal compound, M 5 The metal or semimetal compound is M 5 Compounds of metals or metalloids and anions, M 5 Metal or semimetal is M 5 the metal or metalloid is selected from one or more of magnesium, a metal or metalloid of Groups 3 to 15, or a lanthanide series metal bound to at least one alkoxide, aryloxy, carboxylate, acyl, pyrophosphate, phosphate, thiophosphate, dithiophosphate, phosphate ester, thiophosphate ester, amide, oxide, siloxide, hydride, carbamate, or hydrocarbon anion; 5 forming a metal or metalloid compound lacking a halide anion; b) Cyanometallate compounds and M 1 React with a metal compound to form M 1 forming a water-insoluble catalyst complex comprising a metal cyanometalate; Catalyst complex II corresponds to the formula: M 1 b [M 2 (CN) r (X 1 ) t ] c [M 3 (X 2 )6] d ·nM 4 x A 1 y pM5 w A 2 z During the ceremony, M 1 and M 4 are 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 M 5 represents at least one magnesium, Group 3 to Group 15 metal, or Lanthanide series metal or metalloid ion; 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, A1 represents an anion selected from a halide, nitrate, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, perchlorate, isothiocyanate, alkane sulfonate, arylene sulfonate, or trifluoromethanesulfonate ion; A 2 represents at least one alkoxide, aryloxy, carboxylate, acyl, pyrophosphate, phosphate, thiophosphate, amide, oxide, siloxide, hydride, carbamate, or hydrocarbon anion; b, c and d are each M 1 b [M 2 (CN) r (X 1 ) t ] c [M 3 (X 2 )6] d are numbers such that the group is electrostatically neutral, provided that b and c are each greater than zero; x and y are the metal salts M 4 x A 1 y are electrostatically neutral integers, r is an integer from 4 to 6; t is an integer from 0 to 2; n is a number from 0 to 20; p is 0.002 to 10; w and z are the metal salt M 5 z A 2 z is an electrostatically neutral integer, with the proviso that w is 1 to 4; The additive is selected from the group consisting of alkali metal, ammonium and quaternary ammonium salts of monocarboxylic acids having up to 24 carbon atoms; monobasic potassium phosphates, monobasic and quaternary ammonium phosphates, dibasic and quaternary ammonium phosphates, and phosphoric acid.

[0008] The presence of the additive has been found to significantly increase the activity of double metal cyanide catalysts. 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.

[0009] The polyethers are prepared in accordance with the present invention in a process which includes forming a polymerization mixture which includes a catalyst complex, an alcohol starter compound, an alkylene oxide, and an additive to form a polymerization mixture. The polyethers are produced by polymerizing an alkylene oxide onto a hydroxyl-containing starter in the presence of the catalyst complex and the additive.

[0010] 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.

[0011] 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.

[0012] 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 having a hydroxyl equivalent less than that of the polymerization product. The starter compound can also be water.

[0013] 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.

[0014] 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.

[0015] The components that make up the reaction mixture can be combined in any order.

[0016] 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.

[0017] 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.

[0018] 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.).

[0019] 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).

[0020] The polymerization is preferably carried out under vacuum or under an inert atmosphere such as a nitrogen, helium, or argon atmosphere.

[0021] 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.

[0022] 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 provide and / 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.

[0023] The product obtained from any of the above processes may contain up to 0.5% by weight of unreacted alkylene oxide, small amounts of starter compounds and their low molecular weight alkoxylates, and small amounts of other organic impurities and water, based on the total weight. Volatile impurities should be flashed or stripped from the resulting polyether. The product typically contains catalyst residues and may contain 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.

[0024] 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.

[0025] The present invention is particularly useful in polymerization processes characterized by any 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 where the ethylene oxide content, if present, is at its highest. Each of these represents severe conditions under which conventional zinc hexacyanometallate catalysts perform poorly.

[0026] 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.

[0027] The catalyst complex in some embodiments is made in a precipitation process in which a solution containing starting materials is prepared, the particular starting materials are reacted, and the catalyst complex precipitates from the starting solution. Generally, methods for producing polymerization catalysts such as those described in WO 2018 / 209069 and WO 2018 / 209075 are suitable.

[0028] The solvent comprises at least one of water and a liquid aliphatic alcohol. 1 The solvent is one in which the metal compound can be dissolved. 5 It may or may not be a solvent for the metal or metalloid compound.

[0029] 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.

[0030] The starting solution contains the starting cyanometallate compound and M 1 This is conveniently done by forming separate solutions of the metal compounds and combining them. 5 The metal or semimetallic compound may be present in one or the other of these separate solutions, preferably M 1The cyanometallate compound solution is conveniently added to the metal or metalloid compound solution. Combining the starting solutions should involve mixing. 1 It is generally preferred to mix the cyanometallate compound in a solution of the metal compound by gradually adding the cyanometallate compound solution to the metal compound. 1 It is preferred that the metal compound is always present in excess.

[0031] Cyanometallate Compounds Exceeding M 1 It is preferred to provide a metal compound. In some embodiments, M 1 The molar ratio of metal compound to cyanometallate compound is at least 2:1, preferably at least 3:1, or at least 5:1. This ratio can be, for example, up to 20:1 or up to 15:1.

[0032] The starting solution contains 0.01 to 10 moles of M per mole of cyanometallate compound prior to the reaction. 5 The catalyst complex contains a metal or semi-metal compound. Lower amounts do not improve the performance of the catalyst complex. Higher amounts do not improve the performance of the catalyst and may actually tend to decrease its performance.

[0033] Cyanometallate Compounds and M 1 The metal compounds react to form water-insoluble M 1 A catalytic complex containing a metal cyanometalate is formed. This reaction proceeds spontaneously at temperatures around 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.

[0034] In some cases, M 5Metal or semimetallic compounds may react during the catalyst preparation step. For example, certain M 5 Metal or semimetallic compounds react with water during catalyst preparation to form the corresponding M 5 In some embodiments, M may form a metal oxide. 5 Metal or semimetal compounds or their reaction products (especially M 5 Metal or semi-metal oxide) is M 1 Together with the reaction product of the metal compound and the cyanometallate compound, M 1 b [M 2 (CN) r (X 1 ) t ] c Phase and M 5 Hybrid particles are formed that have both metal or semi-metal oxide phases.

[0035] The precipitated catalyst is preferably treated with a complexing agent. This is conveniently done by washing the precipitated catalyst 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, 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., of up to 8000 g / mole, as measured by gel permeation chromatography against polystyrene standards.

[0036] 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 carried out by application of heat and / or vacuum.

[0037] M 1 The metal compound is preferably water soluble. Typically, M 1 A salt of a metal and one or more anions. Such salts have the formula M 1 x A 1 y where x, A 1 and y are as defined above. 1 Examples of anions include, but are not limited to, halides (such as chloride, bromide, and iodide), nitrates, sulfates, carbonates, cyanides, oxalates, thiocyanates, isocyanates, perchlorates, isothiocyanates, alkanesulfonates (such as methanesulfonate), arylenesulfonates (such as p-toluenesulfonate), and trifluoromethanesulfonates (triflates). 1 is not an alkoxide, aryloxy, carboxylate, acyl, pyrophosphate, phosphate, thiophosphate, dithiophosphate, phosphate ester, thiophosphate ester, amide, oxide, siloxide, hydride, carbamate, or hydrocarbon anion. 1 The metal is 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+ , Sn4+ , Pb 2+ , Cu 2+ , La 3+ and Cr 3+ Zn 2+ is the preferred M 1 ZnCl2 is the preferred M 1 It is a metal compound.

[0038] Cyanometallate compounds are 2 (CN) r (X 1 ) t An anion, wherein r, X 1 , and t are as previously described. r is preferably 6 and t is preferably zero. M 2 The metal is 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+ One or more of the following: M 2 The metal is preferably Fe. 3+ Or Co 3+ and Co 3+ is particularly preferred. The cyanometallate compounds are preferably alkali metal or ammonium salts, although the corresponding cyanometallic acids can be used. Potassium hexacyanocobaltate is a particularly preferred cyanometallate compound.

[0039] M 5 The metal or metalloid compound may be magnesium or a metal or metalloid M in any of groups 3 to 15 of the 2010 IUPAC Periodic Table of the Elements and one or more anions. 5The 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.

[0040] Preferred M 5 Metals and semi-metals include yttrium, zirconium, niobium, silicon, titanium, tungsten, cobalt, scandium, vanadium, molybdenum, nickel, zinc and tin, more preferably hafnium, aluminum, manganese, gallium and indium.

[0041] For example, as described in WO 2020 / 131508, two or more different M 5 Mixtures of metal or metalloid compounds may be present. 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).

[0042] M 5The anion of the metal or metalloid compound can be, for example, one or more of alkoxide, aryloxy, carboxylate, acyl, pyrophosphate, phosphate, thiophosphate, dithiophosphate, phosphate ester, thiophosphate ester, amide, oxide, siloxide, hydride, carbamate, and / or hydrocarbon anions. Exemplary embodiments include oxide, hydrocarbyl, oxide and / or alkoxide ions. The anion is not a halide or cyanide anion.

[0043] M 5 The metal or metalloid compound may be insoluble in the solvent or, if soluble, may react during preparation of the catalyst complex to form an insoluble reaction product that becomes part of the catalyst complex. 5 The metal or metalloid also does not reduce the cyanometallate group or M 1 Metal compounds react with cyanometallate compounds to produce M 1 It is preferred not to prevent the formation of metal cyanometalates.

[0044] What is an "alkoxide" ion? -It means a species having the form OR, where R is an alkyl or substituted alkyl group, and is a 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. The alkoxide ion in some embodiments may contain 1 to 20 (e.g., 1 to 6 and / or 2 to 6) carbon atoms. The alkyl or substituted alkyl group may be linear, branched, and / or cyclic. Examples of suitable substituents include, for example, additional hydroxyl groups (which may be in the form of an alkoxide), 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, 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, and in some embodiments such an alkoxide corresponds to the residue after removal of one or more hydroxyl group hydrogen atoms, after removal of a polyether monol or polyether polyol product resulting from an alkoxylation reaction, or after removal of a polyether having a molecular weight intermediate between the molecular weights of the starter compound and the product of the alkoxylation reaction.

[0045] The "aryloxy" anion has the form -It refers to species having O-Ar, where Ar is an aromatic group or substituent, which corresponds to phenolic compounds having the form HO-Ar after removal of the hydroxyl hydrogen. These phenolic compounds may have, for example, a pKa of about 9 to about 12. Examples of such aryloxy anions include phenoxides and ring-substituted phenoxides, where the ring substituents include, for example, 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.

[0046] 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).

[0047] 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.

[0048] 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.

[0049] The "pyrophosphate" anion is P2O7 4- It means an anion.

[0050] 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 R 2 The groups may be taken together to form a ring structure which may be unsaturated and / or contain one or more heteroatoms in the ring (in addition to the amide nitrogen).

[0051] The "oxide" anion is the anion of atomic oxygen, i.e., O 2- means...

[0052] A "siloxide" anion means a silanoate having the formula (R3)3SiO-, where the R3 groups are independently hydrogen or alkyl groups.

[0053] By "hydride" anion is meant the anion of hydrogen, i.e., H-.

[0054] By "carbamate" anion is meant the anion -OOCNH2.

[0055] 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 an alkyl group containing 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.

[0056] M 5 Examples of metal or semi-metal compounds include, but are not limited to, the following: a) magnesium alkyls such as diethyl magnesium, dibutyl magnesium, butylethyl magnesium, dibenzyl magnesium; magnesium alkoxides such as magnesium methoxide, magnesium ethoxide, magnesium isopropoxide, magnesium t-butoxide, magnesium sec-butoxide; magnesium aryloxides such as magnesium phenoxide and magnesium phenoxides in which one or more of the phenoxide groups are ring-substituted with alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, etc.; magnesium formate, magnesium acetate, magnesium propionate, etc. magnesium carboxylates such as magnesium benzoate, magnesium 2-ethylhexanoate, magnesium benzoate, magnesium benzoates where one or more of the benzoic acid groups are ring-substituted with 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-butylacetylacetonate; b) scandium alkoxides such as scandium methoxide, scandium ethoxide, scandium isopropoxide, scandium t-butoxide, scandium sec-butoxide; scandium oxide; scandium aryloxides such as scandium phenoxide and scandium phenoxides in which one or more of the phenoxide groups are ring substituted with 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 alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like; scandium salicylate; scandium acetylacetonate and scandium t-butyl acetylacetonate; c) yttrium alkoxides such as yttrium methoxide, yttrium ethoxide, yttrium isopropoxide, yttrium t-butoxide, yttrium sec-butoxide; yttrium oxide; yttrium phenoxide, and yttrium aryloxides such as yttrium phenoxide and yttrium phenoxides in which one or more of the phenoxide groups are ring-substituted with alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like; yttrium formate, yttrium acetate, yttrium propionate, yttrium 2-ethylhexano ... yttrium carboxylates such as yttrium benzoate, yttrium benzoates in which one or more of the benzoic acid groups are ring-substituted with alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, etc., yttrium salicylate, yttrium 3,5-di-t-butylsalicylate, etc.; yttrium amides such as yttrium dimethylamide, yttrium diethylamide, yttrium diphenylamide, yttrium bis(trimethylsilyl)amide, etc.; yttrium acetylacetonate and yttrium t-butylacetylacetonate; d) 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 phenoxides, and hafnium aryloxides, such as hafnium phenoxides in which one or more of the phenoxide groups are ring-substituted with alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like; hafnium formate, hafnium acetate, propionate, etc. Hafnium carboxylates such as hafnium pionate, hafnium 2-ethylhexanoate, hafnium benzoate, hafnium benzoates in which one or more of the benzoic acid groups are ring-substituted with alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, etc., hafnium salicylate, hafnium 3,5-di-t-butylsalicylate, etc.; hafnium amides such as hafnium tetra(dimethylamide), hafnium tetra(diethylamide), hafnium tetra(diphenylamide), hafnium tetra((bistrimethylsilyl)amide); hafnium acetylacetonate and hafnium t-butylacetylacetonate; e) zirconium alkyls such as tetraethylzirconium, tetrabutylzirconium, and tetrabenzylzirconium; zirconium oxide; zirconium alkoxides such as zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetraisopropoxide, zirconium tetra-t-butoxide, and zirconium tetra-sec-butoxide; zirconium aryloxides such as zirconium phenoxide and zirconium phenoxide in which one or more of the phenoxide groups are ring-substituted with alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like; zirconium formate, zirconium acetate, propionate, zirconium carboxylates such as zirconium acid, zirconium 2-ethylhexanoate, zirconium benzoate, zirconium benzoate in which one or more of the benzoic acid groups are ring-substituted with alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, etc., zirconium salicylate, zirconium 3,5-di-t-butylsalicylate, etc.; zirconium amides such as zirconium tetra(dimethylamide), zirconium tetra(diethylamide, zirconium tetra(diphenylamide), zirconium tetra((bistrimethylsilyl)amide); zirconium acetylacetonate and zirconium t-butylacetylacetonate; f) vanadium alkoxides such as vanadium methoxide, vanadium ethoxide, vanadium isopropoxide, vanadium t-butoxide, vanadium sec-butoxide; vanadium oxide; vanadium oxotris(alkoxides) such as vanadium oxotris(methoxide), vanadium oxotris(ethoxide), vanadium oxotris(isopropoxide), vanadium oxotris(t-butoxide), vanadium oxotris(sec-butoxide); vanadium phenoxide, and compounds in which one or more of the phenoxide groups are alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, etc. vanadium aryloxides such as vanadium phenoxides ring-substituted with;vanadium formate, vanadium acetate, vanadium propionate, vanadium 2-ethylhexanoate, vanadium benzoate, vanadium benzoates, vanadium salicylates, vanadium 3,5-di-t-butylsalicylate, etc., where one or more of the benzoic acid groups are ring-substituted with alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, etc.;vanadium carboxylates such as vanadium tris(acetylacetonate) and vanadium tris(t-butylacetylacetonate);vanadium oxobis(acetylacetonate); g) zinc alkyls such as dimethylzinc, diethylzinc, dibutylzinc, dibenzylzinc; alkylzinc alkoxides such as zinc oxide, ethylzinc isopropoxide; zinc alkoxides such as zinc methoxide, zinc ethoxide, zinc isopropoxide, zinc t-butoxide, zinc sec-butoxide; zinc aryloxides such as zinc phenoxide and zinc phenoxides in which one or more of the phenoxide groups are ring-substituted with alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, etc.; zinc formate. zinc carboxylates such as lead, zinc acetate, zinc propionate, zinc 2-ethylhexanoate, zinc benzoate, zinc benzoates where one or more of the benzoic acid groups are ring-substituted with alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, etc., 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; h) trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, tributylaluminum, and tribenzylaluminum; aluminum alkoxides such as aluminum trimethoxide, aluminum triethoxide, aluminum triisopropoxide, aluminum triisopropoxide, aluminum tri-t-butoxide, and aluminum tri-sec-butoxide; aluminum phenoxides; and aluminum aryloxides such as aluminum phenoxides in which one or more of the phenoxide groups are ring-substituted with alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like; aluminum oxide; aluminum formate, aluminum acetate, aluminum propionate, aluminum 2-ethylhexanoate, aluminum benzoate, and aluminum aryloxides in which the benzoic acid group is substituted with an alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, or the like; Aluminum carboxylates, such as aluminum benzoate, aluminum salicylate, and aluminum 3,5-di-t-butylsalicylate, having one or more ring substitutions with alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like; aluminum amides, such as aluminum tris(dimethylamide), aluminum tris(diethylamide), aluminum tris(diphenylamide), and aluminum tris(di(trimethylsilyl)amide); aluminum acetylacetonate; aluminum t-butyl acetylacetonate, and alkyl aluminum oxides and alkoxides, such as diethylaluminum ethoxide, dimethylaluminum ethoxide, diethylaluminum isopropoxide, dimethylaluminum isopropoxide, methylaluminoxane, and tetraethyldialuminoxane; i) trialkylgallium compounds such as trimethylgallium, triethylgallium, tributylgallium, tribenzylgallium, etc.; gallium oxide; gallium alkoxides such as gallium trimethoxide, gallium triethoxide, gallium triisopropoxide, gallium tri-t-butoxide, gallium tri-sec-butoxide, etc.; gallium aryloxides such as gallium phenoxide and gallium phenoxide in which one or more of the phenoxide groups are ring-substituted with alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, etc.; gallium formate, gallium acetate, gallium propionate, gallium 2-ethylhexanoate, gallium benzoate, benzoic acid groups, etc. gallium carboxylates, such as gallium benzoate, gallium salicylate, and gallium 3,5-di-t-butylsalicylate, in which one or more of the above are ring-substituted with alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like; gallium amides, such as gallium tris(dimethylamide), gallium tris(diethylamide), gallium tris(diphenylamide), and gallium tris(di(trimethylsilyl)amide); gallium acetylacetonate; gallium t-butylacetylacetonate; and alkylgallium alkoxides, such as diethylgallium ethoxide, dimethylgallium ethoxide, diethylgallium isopropoxide, and dimethylgallium isopropoxide; j) trialkylindium compounds such as trimethylindium; indium oxide; indium alkoxides such as indium methoxide, indium ethoxide, indium isopropoxide, indium t-butoxide, indium sec-butoxide; indium aryloxides such as indium phenoxide and indium phenoxides in which one or more of the phenoxide groups are ring substituted with alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like; indium carboxylates such as indium formate, indium acetate, indium propionate, indium 2-ethylhexanoate, indium benzoate, indium benzoate in which one or more of the benzoic acid groups are ring substituted with alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like, indium salicylate, indium 3,5-di-t-butylsalicylate; indium acetylacetonate; and indium t-butylacetylacetonate; k) 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 aryloxy compounds such as stannous phenoxide and stannous phenoxide in which one or more of the phenoxide groups are ring-substituted with alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, 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 benzoic acid groups are ring substituted with alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, etc., stannous salicylate, stannous 3,5-di-t-butyl salicylate; stannous acetylacetonate; and stannous t-butyl acetylacetonate; l) manganese phosphates; manganese pyrophosphates, manganese oxides; manganese alkoxides such as manganese methoxide, manganese ethoxide, manganese isopropoxide, manganese t-butoxide, manganese sec-butoxide; manganese aryloxides such as manganese phenoxides and manganese phenoxides in which one or more of the phenoxide groups are ring substituted with alkyl, CF3, cyano, COCH3, halogens, hydroxyl, alkoxyl, and the like; manganese carboxylates such as manganese formate, manganese acetate, manganese propionate, manganese 2-ethylhexanoate, manganese benzoate, manganese benzoate in which one or more of the benzoic acid groups are ring substituted with alkyl, CF3, cyano, COCH3, halogens, hydroxyl, alkoxyl, and the like, manganese salicylate, manganese 3,5-di-t-butylsalicylate; manganese acetylacetonates; and manganese t-butyl acetylacetonate; m) molybdenum compounds, including 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 aryloxides, such as molybdenum phenoxides and molybdenum phenoxides in which one or more of the phenoxide groups are ring substituted with alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like. oxides; molybdenum formates, acetates, propionates, molybdenum 2-ethylhexanoates, benzoates, molybdenum carboxylates such as molybdenum benzoates, molybdenum salicylates, and molybdenum 3,5-di-t-butylsalicylate, in which one or more of the benzoic acid groups are ring-substituted with alkyl, CF3, cyano, COCH3, halogens, hydroxyl, alkoxyl, and the like; molybdenum acetylacetonates; and molybdenum t-butyl acetylacetonates; in each case, Mo(IV) or (MoVI) compounds; m) Cobalt(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 phenoxide and cobalt phenoxide where one or more of the phenoxide groups are ring substituted with alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, etc.; cobalt formate; cobalt carboxylates such as cobalt carboxylate, 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 alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, etc., cobalt salicylate, cobalt 3,5-di-t-butylsalicylate, etc.; cobalt acetylacetonate; and the Co(II) and / or Co(III) compound, cobalt t-butyl acetylacetonate, in each case; o) tungsten compounds such as tungsten phosphate; tungsten pyrophosphate, tungsten oxide; tungsten alkoxides such as tungsten methoxide, tungsten ethoxide, tungsten isopropoxide, tungsten t-butoxide, tungsten sec-butoxide; tungsten aryl compounds such as tungsten phenoxide and tungsten phenoxides in which one or more of the phenoxide groups are ring substituted with alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like. tungsten formate, tungsten acetate, tungsten propionate, tungsten 2-ethylhexanoate, tungsten benzoate, tungsten benzoates in which one or more of the benzoic acid groups are ring-substituted with alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, etc., tungsten salicylate, tungsten 3,5-di-t-butylsalicylate, etc.; tungsten acetylacetonate; and tungsten t-butyl acetylacetonate; p) 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 phenoxide and iron phenoxides in which one or more of the phenoxide groups are ring-substituted with alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, etc.; iron carboxylates such as iron formate, iron acetate, iron propionate, iron 2-ethylhexanoate, iron benzoate, iron benzoate in which one or more of the benzoic acid groups are ring-substituted with alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, etc., iron salicylate, iron 3,5-di-t-butylsalicylate; iron acetylacetonate; and in each case iron(II) and / or Fe(III) compound iron t-butylacetylacetonate; q) titanium compounds such as titanium phosphate; titanium pyrophosphate, titanium oxide; titanium alkoxides such as titanium methoxide, titanium ethoxide, titanium isopropoxide, titanium t-butoxide, titanium sec-butoxide; titanium aryloxides such as titanium phenoxide and titanium phenoxides in which one or more of the phenoxide groups are ring-substituted with alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like; titanium carboxylates such as titanium formate, titanium acetate, titanium propionate, titanium 2-ethylhexanoate, titanium benzoate, titanium benzoate in which one or more of the benzoic acid groups are ring-substituted with alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like, titanium salicylate, titanium 3,5-di-t-butylsalicylate; titanium acetylacetonate; and titanium t-butyl acetylacetonate; and r) Silicon compounds such as silicon oxides and silicon alkoxides such as silicon methoxide, silicon tetraethoxide, silicon tetraisopropoxide, silicon tetra-t-butoxide, silicon tetra sec-butoxide, and the like; silicon aryloxides such as silicon tetraphenoxide and silicon tetraphenoxide in which one or more of the phenoxide groups are ring substituted with alkyl, CF3, cyano, COCH3, halogen, hydroxyl, alkoxyl, and the like.

[0057] The catalyst complexes in some embodiments of the present invention (including those prepared by the processes described above) correspond to the formula: M 1 b [M 2 (CN) r (X 1 ) t ] c [M 3 (X 2 )6] d ·nM 4 x A 1 y pM 5 w A 2 z where the variables are as previously described. 1 and M 4 Each of M is most preferably zinc. 2 and M 3 are most preferably iron and cobalt, respectively, especially cobalt. 5 and A 2 is preferably M 5 As described above for the metal or metalloid compound. r is most preferably 6, t is most preferably zero, and d is most preferably 0 to 1. The combined M 1 and M 4 Metal vs. Combined M 2 and M 3 The molar ratio of metals is preferably 0.8:1 to 20:1. 5 Metal or semimetal pair combined M 2 and M 3The molar ratio of the metals can be, for example, 0.002:50 or 0.0025:10, as determined by X-ray fluorescence (XRF) techniques. It is noted that the ratio of metals in the catalyst complex can be substantially different from the ratio used in the catalyst preparation process.

[0058] The formulas in the above process do not necessarily represent the M of any particular crystal form or catalyst complex. 1 b [M 2 (CN) r (X 1 ) t ] c [M 3 (X 2 )6] d , M 4 x A 1 y and M 5 w A 2 z It is not intended to imply any other spatial or chemical relationships between the components. Scanning transmission electron microscopy analysis of certain catalyst complexes has demonstrated that in at least some of such embodiments, the catalyst complexes are 1 b [M 2 (CN) r (X 1 t ] c Phase and M 5 Metal or semi-metal oxides (i.e., M 5 w O z It was revealed that the particles contained hybrid particles that had both the M 4 x A 1 y Phase, if present, is M 1 b [M 2 (CN) r (X 1 ) t ] c In addition to such hybrid particles, the catalyst complex may be at least partially present on the particles of the M 1 b [M2 (CN) r (X 1 ) t ] c Phase particles or M 1 b [M 2 (CN) r (X 1 ) t ] c [M 3 (X 2 )6] d ·nM 4 x A 1 y It may contain particles of only the M phase. 5 Part of the metal or semimetal is M 1 b [M 2 (CN) r (X 1 ) t ] c Phase or M 1 b [M 2 (CN) r (X 1 ) t ] c [M 3 (X 2 )6] d ·nM 4 x A 1 y It can be incorporated into the phase.

[0059] The additive is selected from the group consisting of alkali metal, ammonium and quaternary ammonium salts of monocarboxylic acids having up to 24 carbon atoms; monobasic potassium phosphate, monobasic ammonium phosphate, monobasic quaternary ammonium phosphate, dibasic ammonium phosphate and quaternary ammonium phosphate, and phosphoric acid.

[0060] In some embodiments, the additive is or includes alkali metal, ammonium, and quaternary ammonium salts of monocarboxylic acids having up to 24 carbon atoms. The monocarboxylic acids can have 1-18 carbon atoms, 1-12 carbon atoms, 1-8 carbon atoms, or 1-2 carbon atoms. The monocarboxylic acids can be aliphatic or straight chain. In other embodiments, the monocarboxylic acids can be aromatic (such as benzoic acid). The alkali metal can be lithium, sodium, potassium, and / or cesium. "Ammonium" refers to NH4 + The quaternary ammonium ion is NR 4+ where each R is independently H or hydrocarbyl, provided that at least one R is 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 the lithium, sodium, potassium, cesium or ammonium salts of linear or branched aliphatic C4 to C18 monocarboxylic acids.

[0061] The additive may be or include one or more of monobasic potassium phosphate, monobasic ammonium phosphate, and monobasic quaternary ammonium phosphate.

[0062] The additive is dibasic ammonium phosphate ((NH4 + )2HPO4), and structure (NR4 + ) 2HPO4, where R is as defined above.

[0063] The weight of the additive is, in some embodiments, 1 to 25 times the weight of the catalyst complex, except in the case of phosphoric acid. 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.

[0064] The additives, except for phosphoric acid, are 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.

[0065] Phosphoric acid, if present, is conveniently present in an amount of 0.01 to 1000 ppm based on the aforementioned criteria. A preferred lower limit is at least 0.5 ppm, or at least 1 ppm. A preferred upper limit is up to 100 ppm, up to 50 ppm, or up to 25 ppm. Increasing the concentration of phosphoric acid beyond about 25 ppm may lead to a decrease in performance. Phosphoric acid, if used, may be present in an amount of 0.001 to 0.2 times the weight of the catalyst complex.

[0066] 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.

[0067] 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.

[0068] Catalyst preparation procedure: A mixture of zinc chloride (32.00 g, 234.8 mmol), tert-butyl alcohol (40 mL), and deionized water (40 mL) is heated to 40 °C in a round-bottom flask. Aluminum tri-sec-butoxide (1.66 g, 6.72 mmol) and aqueous HCl (86 μL, 0.001 M) are then added and the mixture is stirred for 10 min. A solution of potassium hexacyanocobaltate (6.91, 20.8 mmol) in water (80 mL) is added dropwise over 2.5 h. The mixture is then further diluted with 40 mL of 50 / 50 v / v deionized water / tert-butyl alcohol and heated under reflux for approximately 20 h until a white gel is formed. The gel is dispersed in water (80 mL) and tert-butyl alcohol (80 mL) and then centrifuged (5000 rpm) for 15 min. The solvent is decanted and the gel is redispersed in a mixture of water (80 mL) and tert-butyl alcohol (80 mL). The dispersion is heated to 55° C. for 35 min and then centrifuged again. The gel is washed four times following the same procedure and then once more with 200 mL of tert-butyl alcohol. The gel is then dried under vacuum in a vacuum oven at 60° C. overnight. The dry solid so obtained is transferred to a nitrogen-filled glove box and crushed to produce the catalyst as a white powder (8.32 g). The powder catalyst has a particle size distribution d 50 <20 μm. The catalyst contains 50.2% by weight zinc, 22.2% by weight cobalt and 1.7% by weight aluminium.

[0069] Examples 1 to 9 and Comparative Samples A to G 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% glycerin is added to each well along with 265 parts by weight of catalyst (based on the expected mass of the product) and additives shown in Table 1. This mixture contains approximately 9% by weight of hydroxyl groups. 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). At this point, the reaction mixture contains approximately 8% by weight of hydroxyl groups and approximately 8% by weight of ethylene oxide. The internal pressure is monitored over time as an indication of the progress of the ethylene oxide polymerization reaction. The ethylene oxide concentration decreases as the polymerization proceeds, when a drop in the internal reactor pressure is observed. The time required for the pressure to drop to 90 psig (621 kPa) and then to 80 psig (552 kPa) is recorded. A shorter time indicates greater catalyst activity. The results are shown in Table 1.

[0070] [Table 1] * This is not an embodiment of the present invention.

[0071] 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 1-9 show that active polymerization occurs when an alkali metal carboxylate (Examples 1-6 and 9), monobasic potassium phosphate or ammonium dihydrogen phosphate is 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.

[0072] Comparative Samples B-G show the poorer effectiveness of various other additives. An alkaline earth carboxylate salt (calcium formate, Comparative Sample B) cuts the time to 90 psig (621 kPa) by nearly half, but does not cut the time to 80 psig (552 kPa). The same is true for dibasic potassium phosphate (Comparative D) and carbonate salts (Comparative E and F). A triflate salt (Comparative C) offers some benefit, but is much less effective than the additives of the present invention. Lithium dihydrogen phosphate (Comparative G) offers no benefit at all.

[0073] Examples 10 to 16 and Comparative Samples H to K 397.2 grams of a solution of 0.7 wt% glycerol in 625 weight average molecular weight poly(ethylene oxide) triol and enough catalyst to provide 250 parts per million by weight based on the expected mass of the product are added to a 500 mL Parker / AutoClave reactor at room temperature. The reactor is sparged with dry nitrogen overnight and then heated to 130°C with continuous sparging for 1.5 hours. The reactor is then heated to 160°C while sparging with nitrogen and then pressurized to 7.5 psig (51.7 kPa) with dry nitrogen. The reaction mixture at this point contains 8-9 wt% hydroxyl groups. 16.2 g of ethylene oxide are then added to the reactor at a rate of 2 g / min at the same temperature. This raises the pressure in the reactor to about 35 psig (241.3 kPa). At the end of the ethylene oxide addition (assuming no polymerization), the reaction mixture contains about 4 wt% ethylene oxide and about 8 wt% hydroxyl groups. The pressure in the reactor is monitored until it drops to 10 psig (68.9 kPa). Note that the reaction conditions at this point are less severe than those in the previous examples due to the lower glycerin concentration and the lower ethylene oxide concentration. The reactor is then depressurized and cooled to about 60° C. under continuous dry nitrogen sparge. An additional 2.8 g of glycerin and the additives shown in Table 2 are then added. The reactor is then returned to the same continuous sparging and warming procedure. Once a temperature of 160° C. is reached, an additional 16.2 g of ethylene oxide is added to the reactor. The drop in pressure in the reactor is continuously monitored until a constant pressure is achieved, indicating consumption of all the ethylene oxide. The time at which a constant reactor pressure is achieved is recorded as an indicator of catalyst performance. The reactor is then sparged with dry nitrogen for 10 minutes, cooled to about 60° C., and the product is collected. The final batch size is approximately 430 grams in each case.

[0074] [Table 2] * This is not an embodiment of the present invention.

[0075] These examples demonstrate the effect of the additives of the present invention on the polymerization rate obtained with an aluminum modified preactivated double metal cyanide catalyst complex. The presence of potassium acetate reduces the polymerization time by about 2-fold (at the 100 ppm level) to about 14-fold (at the 100 ppm level). Phosphoric acid is effective at very low levels, especially as shown by Examples 13-15. At a phosphoric acid concentration of 125 ppm, less benefit is seen than at 12.5 ppm and 1.25 ppm. Acetic acid does not provide any benefit over the wide range of concentrations evaluated.

[0076] Examples 17 to 20 and Comparative Samples L and M 12.2 g of monopropylene glycol containing phosphoric acid (amounts shown in Table 3 below) and 50 parts per million by weight of catalyst were added to a 12 liter reactor along with 2440 g of 400 weight average molecular weight poly(propylene oxide) diol. The reactor contents were heated to 160° C. under nitrogen. 128 g of propylene oxide was fed to the reactor. The reactor was maintained at 160° C. The pressure was monitored until a rapid pressure drop and exotherm was observed, indicating the catalyst was activated. The peak reactor pressure during this activation step was recorded.

[0077] Then, 4267 g of propylene oxide and 982 g of catalyst- and phosphoric acid-containing monopropylene glycol are simultaneously fed to the reactor while maintaining a constant reactor temperature. The propylene oxide and monopropylene glycol feeds are increased over the time periods shown in Table 3 until the final feed rates shown in Table 3 are achieved. The pressure is monitored as before and the peak pressure during this polymerization step is recorded. At the end of these feeds, the monopropylene glycol feed is stopped and another 160 g of propylene oxide is fed to the reactor at the same final feed rate.

[0078] [Table 3] 1By weight in monopropylene glycol. PO is propylene oxide. MPG is monopropylene glycol.

Claims

1. 1. A process for producing a polyether, the process comprising forming a reaction mixture comprising a hydroxyl-containing starter, at least one alkylene oxide, a catalyst complex, and an additive; polymerizing the alkylene oxide on the hydroxyl-containing starter to produce the polyether; and wherein the catalyst complex is selected from the group consisting of catalyst complexes I and II. Catalyst complex I is a) i) a solvent comprising at least one of water and a liquid aliphatic alcohol dissolved therein; ii) M ２ a cyanometallate compound having a metal cyanometallate group, and iii) a water-insoluble M １ M forming a metal cyanometallate １ forming a starting solution containing a metal compound, said starting solution comprising 0.01 to 10 moles of iii) said M per mole of cyanometallate compound; １ At least one M different from the metal salt ５ Further containing a metal or semimetal compound, ５ The metal or semimetal compound is M ５ a metal or semimetal compound and an anion, ５ The metal or semimetal is the M ５ the metal or metalloid is selected from one or more of magnesium, a Group 3 to 15 metal or metalloid, or a lanthanide series metal bound to at least one alkoxide, aryloxy, carboxylate, acyl, pyrophosphate, phosphate, thiophosphate, dithiophosphate, phosphate ester, thiophosphate ester, amide, oxide, siloxide, hydride, carbamate, or hydrocarbon anion; ５ forming a metal or metalloid compound lacking a halide anion; b) The cyanometallate compound and M １ reacting with a metal compound to form M １ forming a water-insoluble catalyst complex comprising a metal cyanometalate; Catalyst complex II corresponds to the formula: M １ ｂ [M ２ (CN) ｒ (X １ ) ｔ ] ｃ [M ３ (X ２ ) ６ ] ｄ ・nM ４ ｘ A １ ｙ ・pM ５ ｗ A ２ ｚ 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 M ５ represents at least one magnesium, Group 3 to Group 15 metal, or Lanthanide series metal or metalloid ion; 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 represents an anion selected from halide, nitrate, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, perchlorate, isothiocyanate, alkanesulfonate, arylenesulfonate, and trifluoromethanesulfonate; A ２ represents at least one alkoxide, aryloxy, carboxylate, acyl, pyrophosphate, phosphate, thiophosphate, amide, oxide, siloxide, hydride, carbamate, or hydrocarbon anion; b, c and d are each M １ ｂ [M ２ (CN) ｒ (X １ ) ｔ ] ｃ [M ３ (X ２ ) ６ ] ｄ numbers such that the group is electrostatically neutral, provided that b and c are each greater than zero; x and y are the metal salt M ４ ｘ A １ ｙ is an integer such that 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, p is 0.002 to 10; w and z are the metal salt M ５ ｚ A ２ ｚ is an electrostatically neutral integer, with w being 1 to 4; The method of claim 1, wherein the additive is selected from the group consisting of alkali metal, ammonium, and quaternary ammonium salts of monocarboxylic acids having up to 24 carbon atoms; monobasic potassium phosphate, monobasic and quaternary ammonium phosphate, dibasic and quaternary ammonium phosphate, and phosphoric acid.

2. Said M ５ 10. The process of claim 1, wherein the metal or metalloid is one or more of aluminum, hafnium, indium, manganese, or gallium.

3. M5 Metal or semimetal vs. M ２ and M ３ 10. The process of claim 1, wherein the total molar ratio of metals is 0.0025 to 50.

4. M １ 2. The process of claim 1, wherein is zinc and the cyanometallate compound is a hexacyanocobaltate compound.

5. 10. The process of claim 1, wherein the additive is selected from the group consisting of alkali metal, ammonium, and quaternary ammonium salts of monocarboxylic acids having up to 24 carbon atoms; monobasic potassium phosphate, monobasic and quaternary ammonium phosphate, and dibasic and quaternary ammonium phosphate, and the additive is present in an amount of 1 to 10 times the weight of the catalyst complex.

6. 2. The process of claim 1, wherein the additive is phosphoric acid, and the amount of phosphoric acid is 0.001 to 0.2 times the weight of the catalyst complex.

7. 2. The process of claim 1, wherein the alkylene oxide is ethylene oxide.

8. 10. The process 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 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.

9. 2. The process according to claim 1, wherein the reaction mixture has, during at least a portion of step II, a hydroxyl content of 4.25 to 20 wt. %, in particular 4.25 to 15 wt. %, based on the total weight of the reaction mixture.

10. The process of any one of claims 1 to 9, wherein the hydroxyl-containing starter has an equivalent weight of up to 75.