EP1196473A1 - Procede d'elaboration de catalyseurs de cyanure metallique utilisant des acides polycarboxyliques - Google Patents

Procede d'elaboration de catalyseurs de cyanure metallique utilisant des acides polycarboxyliques

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Publication number
EP1196473A1
EP1196473A1 EP00945237A EP00945237A EP1196473A1 EP 1196473 A1 EP1196473 A1 EP 1196473A1 EP 00945237 A EP00945237 A EP 00945237A EP 00945237 A EP00945237 A EP 00945237A EP 1196473 A1 EP1196473 A1 EP 1196473A1
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European Patent Office
Prior art keywords
metal
compound
polyacid
solution
metal cyanide
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EP00945237A
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German (de)
English (en)
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Richard M. Wehmeyer
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Dow Chemical Co
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Dow Chemical Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/08—Saturated oxiranes
    • C08G65/10—Saturated oxiranes characterised by the catalysts used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B01J27/26—Cyanides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2663—Metal cyanide catalysts, i.e. DMC's
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt

Definitions

  • This invention relates to metal cyanide complexes. More particularly, it relates to metal cyanide catalysts having specific complexing agents, to heterogeneous metal cyanide catalysts, and to methods for polymerizing alkylene oxides in the presence of a metal cyanide catalyst.
  • Polyethers are prepared in large commercial quantities through the polymerization of alkylene oxides such as propylene oxide and ethylene oxide.
  • the polymerization is usually conducted in the presence of an initiator compound and a catalyst.
  • the initiator compound usually determines the functionality (number of hydroxyl groups per molecule) of the polymer and in some instances imparts some desired functionality.
  • the catalyst is used to provide an economical rate of polymerization.
  • Metal cyanide complexes are becoming increasingly important alkylene oxide polymerization catalysts. These complexes are often referred to as "double metal cyanide" or "DMC" catalysts, and are the subject of a number of patents. Those patents include, for example, U. S. Patent Nos.
  • these metal cyanide complexes provide the benefit of fast polymerization rates and narrow polydispersities. Additionally, they catalysts are associated with the production of polyethers having very low levels of monofunctional unsatu rated compounds.
  • this invention is a process for making a metal cyanide catalyst complex, comprising mixing a first solution of a metal salt in an inert solvent with a second solution of a metal cyanide compound in an inert solvent in the presence of an organic polyacid in proportions such that at least a stoichiometric quantity of the metal salt is provided, based on the amount of the metal cyanide compound and the organic polyacid, under conditions such that the metal salt, metal cyanide salt and organic polyacid react to form an insoluble precipitate.
  • this invention is a process for making a metal cyanide catalyst complex, comprising mixing an organic polyacid compound in the M form, where M is a multivalent metal ion that forms an insoluble precipitate with a metal cyanide [M 1 (CN) r (X)] group, with a solution of a metal cyanide compound in an inert solvent, under conditions such that the metal cyanide compound and M ions on the organic polyacid react to form an insoluble metal cyanide compound bound to the organic polyacid compound.
  • this invention is a process comprising polymerizing an alkylene oxide in the presence of an initiator compound and a polymerization catalyst, wherein the polymerization catalyst is one made in accordance with the first or second aspect of the invention.
  • This invention provides two convenient methods for making the catalyst.
  • a metal salt and a metal cyanide compound both as described below, are reacted in the presence of an organic polyacid compound.
  • the organic polyacid compound is conveniently in the acid, ammonium or alkali metal form (i.e., the counter ion is either hydrogen or an alkali metal ion).
  • an organic polyacid is converted to the M form, and this form of the organic polyacid is reacted with a metal cyanide compound to form the catalyst.
  • the second method is particularly applicable when the organic polyacid is a water insoluble or crosslinked polymeric polyacid.
  • the organic polyacid is a compound or polymer having at least two acid groups, which may be in the salt form.
  • Preferred acid groups are carboxyl (-COOH) and carboxylate (-COOM 4 , where M 4 is alkali metal or ammonium) groups.
  • the acid groups may be bound to aliphatic, cycloaliphatic or aromatic carbon atoms.
  • the organic polyacid contains at least two acid groups per molecule, and may contain any larger number of acid groups per molecule.
  • suitable organic polyacids are:
  • Aliphatic polyacids such as citric acid, tartaric acid and various cycloalkane polycarboxylic acids such as 1 ,2-cyclohexane dicarboxylic acid, 1 ,4- cyclohexanedicarboxylic acid and 1 ,3,5-cyclohexanetricarboxylic acid.
  • Aromatic polyacids such as 1 ,3,5-benzene tricarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid;
  • Chelating agents such as ethylene diamine tetraaccetic acid, nitrilotriacetic acid, and ethylene glycol bis ( ⁇ -aminoethyl ether)-N,N-tetraacetic acid;
  • Water soluble (non-crosslinked) polymeric polyacids such as alginic acid and polymers and copolymers of ethylenically unsaturated acids such as acrylic acid, methacrylic acid, maleic acid, and fumaric acid; carboxylated polystyrene polymers and copolymers, sulfonated polystyrene polymers and copolymers, graft copolymers of poly((meth)acrylic acid) and polyethers such as polyethylene oxide; Water insoluble (crosslinked) polymeric polyacids such as sulfonated or carboxylated crosslinked polystyrene copolymers, crosslinked polymers of ethylenically unsaturated monomers such as acrylic acid, me
  • Phosphonate-containing and sulfonate-containing polyacids such as poly(vinylphosphonic acid) and poly(vinylsulfonic acid).
  • the metal salt and the metal cyanide compound are each separately dissolved or dispersed into an inert solvent.
  • inert means that the solvent does not react with the metal salt, metal cyanide, polycarboxylic acid compound, any complexing agent that may be present, or the precipitated catalyst complex.
  • the solvent may be water or an organic compound such as methanol, acetone, and isopropanol.
  • the solvent may be a mixture of water or methanol and a miscible organic compound, preferably one that acts as a complexing agent or as an initiator for polymerization alkylene oxides to form a polyether. Compounds that are suitable complexing agents and initiators are described more below.
  • the most preferred solvent is water or a mixture of water and a complexing agent.
  • different solvents can be used to form the solution or dispersion of the metal salt and the solution or dispersion of the metal cyanide compound. If different solvents are used, they are suitably miscible in each other.
  • metal salt it is meant a salt represented by the general formula M A y , or
  • M and M 3 are preferably metal ions selected from the group consisting of Zn +2 , Fe +2 , Co* 2 , Nr 2 , Mo 44 , Mo Al *3 , V *4 , V 6 , Sr *2 , W 4 , W *6 , Mn +2 , Sn +2 , Sn *4 , Pb +2 , Cu +2 , La 43 and Cr .
  • M and M 3 are more preferably Zn +2 , Fe *2 , Co *2 , Nr 2 , La 43 and Cr 43 .
  • M is most preferably Zn +2 .
  • Suitable anions A include halides such as chloride and bromide, nitrate, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, perchlorate, isothiocyanate, an alkanesulfonate such as methanesulfonate, an arylenesulfonate such as p- toluenesulfonate, trifluoromethanesulfonate (triflate) and a C 1-t carboxylate. Chloride ion is especially preferred.
  • the solution of the metal salt usually can be prepared by directly dissolving the metal salt into the inert solvent.
  • the metal cyanide compound is represented by the structure B M 1 (CN) r (X) t ], where M 1 is a transition metal ion, each X independently represents a group other than cyanide that coordinates with an M 1 ion; B represents hydrogen or a metal atom that forms a water soluble salt with the M 1 (CN) r (X), group, w represents the absolute value of the valence of the M 1 (CN) r (X) t grouping; r is from 4 to 6 and t is from 0-2.
  • B is preferably hydrogen or an alkali metal such as lithium, potassium, sodium or cesium.
  • M 1 is preferably Fe *3 , Fe *2 , Co *3 , Co +2 , Cr +2 , Cr *3 , Mn *2 , Mn *3 , Ir *3 , Ni +2 , Rh *3 , Ru +2 ,
  • V *4 and V *5 are more preferred.
  • Co *3 and Fe *3 are even more preferred and Co *3 is most preferred.
  • Preferred groups X include anions such as halide (especially chloride), hydroxide, sulfate, carbonate, oxalate, thiocyanate, isocyanate, isothiocyanate, C ⁇ carboxylate and nitrite (NO 2 ⁇ ), and uncharged species such as CO, H 2 O and NO.
  • Particularly preferred groups X are NO, NO 2 and CO.
  • r is preferably 5 or 6, most preferably 6, t is preferably 0 or 1 , most preferably 0. In most cases, r + 1 will equal six.
  • w is usually 2 or 3, and is most typically 3.
  • the solution may also contain compounds that have the structure B w M (X) 6 , wherein M 2 is a transition metal and B, w and X are as before. M 2 may be the same as or different from M 1 .
  • the X groups in any M 2 (X) ⁇ do not have to be all the same.
  • the solution or dispersion of the metal cyanide compound can be prepared in several ways.
  • the metal cyanide compound is an alkali metal salt, it is conveniently added directly to the inert solvent.
  • the metal cyanide compound is the acid (i.e. H M 1 (CN) r (X) t )
  • a convenient way to prepare the solution or dispersion is to add the corresponding alkali metal salt to the inert solvent, and then use an ion exchange technique to replace the alkali metal ions with hydrogen. This can be done, for example, through the addition of a strong mineral acid such as sulfuric or hydrochloric acid (followed by separation from the salts formed in the reaction), or through treatment with a cation exchange resin in the hydrogen form.
  • the starting solution or dispersion of the metal cyanide compound suitably contains from about 0.1%, preferably from about 1%, more preferably from about 5% to about 30%, preferably to about 25%, more preferably to about 20% of the metal cyanide compound, by weight.
  • the starting solutions or dispersions of the metal salt suitably contains from about 0.1%, preferably from about 5%, more preferably from about 10% to about 70%, preferably to about 50%, more preferably to about 35% of the metal salt, by weight.
  • the solution or dispersion of the metal salt is then mixed with the solution or dispersion of the metal cyanide compound in the presence of the organic polyacid.
  • the organic polyacid and the metal cyanide compound are conveniently mixed before the metal salt solution is added. Alternately, both starting solutions or dispersions may be added simultaneously with the organic polyacid. A third but less preferred way is to mix the starting solutions or dispersions, followed immediately by adding the organic polyacid.
  • the organic polyacid is an insoluble polymer, it is preferably swollen in the inert solvent before being combined with the starting solutions or dispersions.
  • the temperature of mixing is not critical, provided that the starting materials remain in solution until the mixing is performed. Temperatures of about 10°C to about the boiling point of the inert solvent, particularly 15-40°C, are most suitable.
  • the mixing can be done with rapid agitation. Intimate mixing techniques as are described in U. S. Patent No. 5,470,813 can be used, but are not necessary.
  • At least enough metal salt is used to provide one equivalent of metal ion (M) for each equivalent of metal cyanide ion (M ⁇ CNJ X),), plus each equivalent of organic polyacid and each equivalent of M 2 (X) 6 ion, if used.
  • more active catalysts are those prepared using an excess of the metal salt.
  • This excess metal is believed to exist in the catalyst complex as a salt in the form M x A y , or M 3 x A y , where A is an anion and x and y are numbers that cause the salt to be electrostatically neutral.
  • This excess metal salt can be added in the precipitation step, such as by adding up to about three equivalents of metal salt, preferably from about 1.1 to about 3, more preferably about 1.5 to about 2.5 equivalents of metal salt, per combined equivalents of metal cyanide ion, organic polyacid plus any M 2 (X) 6 ions.
  • the organic polyacid is first converted to the M form, and then contacted with a solution of the metal cyanide compound.
  • the organic polyacid is conveniently converted to the M form by washing it one or more times with a metal salt (M x A y ) solution until the counterions on the acid groups have been replaced with the M ion.
  • the organic polyacid in the M 1 form is then contacted with a solution of the metal cyanide compound B M 1 (CN) r (X)J.
  • the M 1 (CN) r (X),ions react with the M ion, which is believed to form a "bridge" between the M 1 (CN) r (X) t group and the organic polyacid molecule.
  • the reaction sequence can be performed two or more times in succession, if desired.
  • the metal salt solution or the metal cyanide compound solution can be divided into portions and added step-wise.
  • the catalyst may be complexed with an organic complexing agent, although the complexing agent is optional.
  • a great number of complexing agents are potentially useful, although catalyst activity may vary according to the selection of a particular complexing agent. Examples of such complexing agents include alcohols, aldehydes, ketones, ethers, amides, nitriles, and sulfides.
  • Suitable alcohols include monoalcohols and polyalcohols.
  • Suitable monoalcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, octanol, octadecanol, 3-butyn-1-ol, 3-butene-1-ol, propargyl alcohol, 2-methyl-2-propanol, 2-methyl-3-butyn-2-ol, 2-methyl-3-butene-2-ol, 3-butyn- 1-ol, 3-butene-1-ol, and 1 -t-butoxy-2-propanol.
  • Suitable monoalcohols also include halogenated alcohols such as 2-chloroethanol, 2-bromoethanol, 2-chloro-1-propanol, 3-chloro-1-propanol, 3-bromo-1-propanol, 1 ,3-dichloro-2-propanol, 1 -chloro-2-methyl- 2-propanol as well as nitroalcohols, keto-alcohols, ester-alcohols, cyanoalcohols, and other inertly substituted alcohols.
  • halogenated alcohols such as 2-chloroethanol, 2-bromoethanol, 2-chloro-1-propanol, 3-chloro-1-propanol, 3-bromo-1-propanol, 1 ,3-dichloro-2-propanol, 1 -chloro-2-methyl- 2-propanol as well as nitroalcohols, keto-alcohols, ester-alcohols, cyanoalcohol
  • Suitable polyalcohols include ethylene glycol, propylene glycol, glycerine, 1 ,1 ,1-trimethylol propane, 1 ,1 ,1-trimethylol ethane, 1 ,2,3-trihydroxybutane, penta- erythritol, xylitol, arabitol, mannitol, 2,5-dimethyl-3-hexyn-2,5-diol, 2,4,7,9-tetramethyl- 5-decyne-4,7-diol, sucrose, sorbitol, alkyl glucosides such as methyl glucoside and ethyl glucoside.
  • Low molecular weight polyether polyols particular those having an equivalent weight of about 350 or less, more preferably about 125-250, are also useful complexing agents.
  • Suitable aldehydes include formaldehyde, acetaldehyde, butyraldehyde, valeric aldehyde, glyoxal, benzaldehyde, and toluic aldehyde.
  • Suitable ketones include acetone, methyl ethyl ketone, 3-pentanone, and 2-hexanone.
  • Suitable ethers include cyclic ethers such as dioxane, trioxymethylene and paraformaldehyde as well as acyclic ethers such as diethyl ether, 1-ethoxy pentane, bis(betachloro ethyl) ether, methyl propyl ether, diethoxy methane, dialkyl ethers of alkylene or polyalkylene glycols (such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and octaethyle ⁇ e glycol dimethyl ether).
  • cyclic ethers such as dioxane, trioxymethylene and paraformaldehyde as well as acyclic ethers such as diethyl ether, 1-ethoxy pentane, bis(betachloro ethyl) ether, methyl propyl ether, diethoxy methane, dialkyl ethers of alkylene
  • Amides such as formamide, acetamide, propionamide, butyramide and valeramide are useful complexing agents.
  • Esters such as amyl formate, ethyl formate, hexyl formate, propyl formate, ethyl acetate, methyl acetate, and triethylene glycol diacetate can be used as well.
  • Suitable nitriles include acetonitrile, and proprionitrile.
  • Suitable sulfides include dimethyl sulfide, diethyl sulfide, dibutyl sulfide, and diamyl sulfide.
  • Preferred complexing agents are t-butanol, 1-t-butoxy-2-propanol, polyether polyols having an equivalent weight of about 75-350 and dialkyl ethers of alkylene and polyalkylene glycols.
  • Especially preferred complexing agents are t-butanol, 1 -t-butoxy- 2-propanol, polyether polyols having an equivalent weight of 125-250 and a dimethyl ether of mono-, di- or triethylene glycol.
  • t-Butanol and glyme (1 ,2-dimethoxy ethane) are most preferred.
  • the complexing agent is added before significant precipitation of the catalyst complex occurs, generally by adding the complexing agent immediately after mixing the starting solutions or dispersions. If desired, the complexing agent can be mixed into either one or both of the starting solutions or dispersions. After adding this initial amount of complexing agent, the mixture is generally stirred for several minutes to allow the catalyst complex to form and precipitate.
  • the catalyst complex may then be subjected to one or more subsequent treatments with complexing agent.
  • a common and entirely suitable practice is to isolate the precipitated catalyst, such as by filtering or centrifuging, and then treating it one or more times with a mixture of the complexing agent and water (and optionally polyether polyol). It is more preferred to increase the concentration of complexing agent in each successive treatment, and especially preferred to perform a final treatment with neat complexing agent or a mixture of complexing agent and polyether polyol. Each of these treatments is conveniently done by re-slurrying the catalyst complex in the liquid with agitation for several minutes and filtering.
  • alkali metal salts are used in the starting solutions, it is highly preferred to wash the precipitated catalyst complex to remove residual alkali metal ions.
  • the washing step is preferably done with water or a mixture of water and complexing agent. In the latter case, washing and treatment with complexing agent is done simultaneously. Washing is preferably continued at least until essentially all unwanted ions, particularly alkali metal and halide ions, are removed from the complex.
  • the metal salt (M x A y or M 3 x A ) in the washing or complexing agent treating solutions. As mentioned before, better catalyst activity is often seen when an excess of the metal salt is present in the catalyst complex. This excess metal salt can be added after the precipitation step by including additional quantities of the metal salt in one or more of the washing or treating solutions. As stated before, the total amount of metal salt is advantageously up to about three equivalents of metal salt, preferably from about 1.1 to about 3, more preferably about 1.5 to about 2.5 equivalents of metal salt, per combined equivalents of metal cyanide ion, organic polyacid plus any M (X) 6 ions. If desired, another salt, M 3 x A can be used instead of that used in the precipitation step.
  • M and M 3 may be different metals, although it is preferred that M and M 3 are the same.
  • a polyether polyol when used in the catalyst complex, it can be added with the initial amount of complexing agent, or in one or more subsequent washings of the complex.
  • the catalyst complex is precipitated from the starting solutions, and washed with water to remove unwanted ions.
  • the precipitate is then combined with a small amount of a solution containing water and complexing agent.
  • the solution may contain additional M x A y or M 3 x A y salt, as discussed before.
  • the amount of this added solution is preferably an amount that can be absorbed by the precipitate.
  • a typical amount of solution to be used is from about 0.5 to about 2, preferably about 0.8 to about 1.5, more preferably about 1 to about 1.5 milliliters of solution per gram of isolated precipitate.
  • the complexing agent is advantageously present in a weight ratio of about 90:10 to about 10:90, preferably about 70:30 to about 30:70, with the water.
  • a polyether polyol can be included in the solution.
  • the resulting catalyst complex can be dried and used without further treatment, or may be subjected to additional washings with water as before, although it is preferred not to perform additional washings with complexing agent or polyether polyol.
  • the precipitated and treated catalyst complex is conveniently dried, preferably under vacuum and moderately elevated temperatures (such as from about 50-60°C), to remove excess water and volatile organics. Drying is preferably done until the catalyst complex reaches a constant weight. However, the drying step can be omitted if desired.
  • the resulting product is a complex of an insoluble metal cyanide associated with excess metal salt and complexed with the organic polyacid compound.
  • the catalyst complex tends to have a relatively large particle size, even when the organic polyacid is a low molecular weight species such as, for example, citric acid, and 1,3,5- benzene tricarboxylic acid.
  • the organic polyacid is polymeric, particularly a water-insoluble polymer
  • the catalyst is in the form of bead or particles that are easily filterable and have a predetermined particle size.
  • the metal-containing cyanide catalyst can be represented by the general formula: wherein M, M 1 , M 2 , M 3 , X, A, b, c, d, n, r, t, x and y are all as defined before.
  • M, M 1 , M 2 , M 3 , X, A, b, c, d, n, r, t, x and y are all as defined before.
  • the catalysts of particular interest are: Zinc hexacyanocobaltate • nZnCI 2 ; Zn[Co(CN) 5 NO]» nZnCI 2 ;
  • the catalyst is complexed with an organic polyacid compound, and optionally at least one other complexing agent and or water.
  • the catalyst complex of the invention is used to polymerize alkylene oxides to make polyethers.
  • the process includes mixing a catalytically effective amount of the catalyst with an alkylene oxide under polymerization conditions, and allowing the polymerization to proceed until the supply of alkylene oxide is essentially exhausted.
  • the concentration of the catalyst is selected to polymerize the alkylene oxide at a desired rate or within a desired period of time.
  • An amount of polymer or supported catalyst as described above sufficient to provide from about 5 to about
  • metal cyanide catalyst (calculated as M b [M 1 (CN) r (X)J c • nM x A yl ignoring associated water and complexing agent(s)) per million parts combined weight of alkylene oxide, and initiator and comonomers, if present. More preferred catalyst levels are from about 50, especially from about 100, to about 5000, more preferably about 1000 ppm, on the same basis.
  • an initiator compound it is not necessary to include an initiator compound. However, to control molecular weight, impart a desired functionality (number of hydroxyl groups/molecule) or a desired terminal functional group, an initiator compound as described before is preferably mixed with the catalyst complex at the beginning of the reaction.
  • Suitable initiator compounds include monoalcohols such methanol, ethanol, n-propanol, isopropanol, n- butanol, isobutanol, t-butanol, octanol, octadecanol, 3-butyn-1-ol, 3-butene-1-ol, propargyl alcohol, 2-methyl-2-propanol, 2-methyl-3-butyn-2-ol, 2-methyl-3-butene-2-ol, 3-butyn-1-ol, and 3-butene-1 -ol.
  • the suitable monoalcohol initiator compounds include halogenated alcohols such as 2-chloroethanol, 2-bromoethanol, 2-chloro-1-propanol, 3-chloro-1-propanol, 3-bromo-l-propanol, 1 ,3-dichloro-2-propanol, 1 -chloro-2-methyl- 2-propanol as well as nitroalcohols, keto-alcohols, ester-alcohols, cyanoalcohols, and other inertly substituted alcohols.
  • halogenated alcohols such as 2-chloroethanol, 2-bromoethanol, 2-chloro-1-propanol, 3-chloro-1-propanol, 3-bromo-l-propanol, 1 ,3-dichloro-2-propanol, 1 -chloro-2-methyl- 2-propanol as well as nitroalcohols, keto-alcohols, ester-alcohols, cyano
  • Suitable polyalcohol initiators include ethylene glycol, propylene glycol, glycerine, 1 ,1 ,1-trimethylol propane, 1 ,1 ,1-trimethylol ethane, 1 ,2,3-trihydroxybutane, pentaerythritol, xylitol, arabitol, mannitol, 2,5-dimethyl-3-hexyn- 2,5-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, sucrose, sorbitol, alkyl glucosides such a methyl glucoside and ethyl glucoside.
  • Low molecular weight polyether polyols particularly those having an equivalent weight of about 350 or less, more preferably about 125-250, are also useful initiator compounds.
  • Various alkylene oxides can be polymerized sequentially to make block copolymers. More preferably, the alkylene oxide is propylene oxide or a mixture of propylene oxide and ethylene oxide and/or butylene oxide.
  • monomers that will copolymerize with the alkylene oxide in the presence of the catalyst complex can be used to prepare modified polyether polyols.
  • Such comonomers include oxetanes as described in U. S. Patent Nos. 3,278,457 and 3,404,109, and anhydrides as described in U. S. Patent Nos. 5,145,883 and 3,538,043, which yield polyethers and polyester or polyetherester polyols, respectively.
  • Hydroxyalkanoates such as lactic acid, 3-hydroxybutyrate, 3-hydroxyvalerate (and their dimers), lactones and carbon dioxide are examples of other suitable monomers that can be polymerized with the catalyst of the invention.
  • the polymerization reaction typically proceeds well at temperatures from about 25 to about 150°C or higher, preferably from about 80-130°C.
  • a convenient polymerization technique involves mixing the catalyst complex and initiator and pressurizing the reactor with the alkylene oxide. After a short induction period, polymerization proceeds, as indicated by a loss of pressure in the reactor. Once the polymerization has begun, additional alkylene oxide is conveniently fed to the reactor on demand, until enough alkylene oxide has been added to produce a polymer of the desired equivalent weight.
  • Another convenient polymerization technique is a continuous method.
  • an activated initiator/catalyst mixture is continuously fed into a continuous reactor such as a continuously stirred tank reactor (CSTR) or a tubular reactor.
  • a feed of alkylene oxide is introduced into the reactor and the product continuously removed.
  • catalyst removal by liquid-solid separation techniques is easier.
  • the catalyst may be recycled if desired.
  • the catalyst of this invention is especially useful in making propylene oxide homopolymers and random copolymers of propylene oxide and up to about 15 weight percent ethylene oxide (based on all monomers).
  • the polymers of particular interest have a hydroxyl equivalent weight of from about 800, preferably from about 1000, to about 5000, preferably about 4000, more preferably to about 2500, and unsaturation of no more than 0.02 meq/g, preferably no more than about 0.01 meq/g.
  • the product polymer may have various uses, depending on its molecular weight, equivalent weight, functionality and the presence of any functional groups.
  • Polyether polyols so made are useful as raw materials for making polyurethanes. Polyethers can also be used as surfactants, hydraulic fluids, as raw materials for making surfactants and as starting materials for making aminated polyethers, among other uses.
  • a solution of potassium hydroxide in water (0.053 moles KOH in 50 mL water is added to solid 1,3,5-benzene tricarboxylic acid (BTA) (3.71 g, 0.177 mmol), and diluted to a volume of 300 mL with additional water.
  • BTA 1,3,5-benzene tricarboxylic acid
  • An additional 0.26 g of solid 85% KOH and a small quantity of potassium bicarbonate are added to form a clear, colorless solution.
  • Solid K 3 Co(CN) 6 (4.0 g, 0.012 mol) is added with stirring.
  • a solution of 19.35 g (0.142 mol) zinc chloride in 40 mL of water is added with continued stirring.
  • a white flocculent forms as the zinc chloride solution is added.
  • a solution of 50 mL water and 50 mL of t-butanol is immediately added. The mixture is stirred for 10 minutes and filtered through Whatman® #41 filter paper. The filtered solid is reslurried in a solution of zinc chloride (6.45 g, 0.047 mol) in 140 mL t-butanol and 60 mL water, stirred 10 minutes and filtered again. The filtered solids are then reslurried in 200 mL t-butanol, stirred 10 minutes, filtered and dried in a vacuum oven overnight at 50°C. The mass of the final product is 10.16 g.
  • Supported Catalyst A is evaluated by adding 0.12 g of a 700 MW polypropylene oxide) triol, 0.58 g propylene oxide and 0.03 g of Catalyst Complex A in a sealed vial, and heating at 90°C for 18 hours. Within a couple of hours, a thick, barely stirrable mixture of polypropylene glycol) appears in the vial. After 18 hours, essentially quantitative conversion of the propylene oxide occurs. Gel permeation chromatography confirms the presence of a polypropylene glycol) with no peak corresponding to the 700 MW initiator. The same results are seen when the experiment is repeated using only 0.006 g of Catalyst Complex A.
  • Catalyst B is evaluated in the same manner. At a catalyst loading of 0.006 g, 99% of the propylene oxide is converted to polymer within 18 hours. Gel permeation chromatography confirms the presence of a poly(propylene glycol) with no peak corresponding to the 700 MW initiator.
  • lightly crosslinked poly(acrylic acid) potassium salt beads (Aldrich catalog #43,532-5) is prepared. The beads swell when added to the water. To the mixture is added a solution of 4.0 g (0.036 eq.) K 3 Co(CN) e in 100 mL of water. This causes the swollen beads to shrink somewhat. With mixing, a solution of 19.35 g (0.284 eq.) zinc chloride in 50 mL water is added to the bead mixture over about 1 minute. A white precipitate forms immediately. As soon as the zinc chloride addition is complete, 100 mL t-butanol is added. The resulting mixture is stirred for 10 minutes, then filtered through Whatman® #4 filter paper.
  • the filtrate is clear and colorless.
  • the collected solids are reslurried in a solution of 6.45 g (0.094 eq.) zinc chloride in 140 mL t-butanol and 60 mL water, stirred for 10 minutes and filtered again. The filtrate is again clear and colorless.
  • Supported Catalyst C is evaluated in the same manner as described in Example 1. At both 0.3 g and 0.006 g loadings of the catalyst complex, a thick, barely stirrable mixture of polypropylene glycol) appears in the vial within a couple of hours. After 18 hours, essentially quantitative conversion of the propylene oxide occurs at each catalyst loading. In each case, gel permeation chromatography confirms the presence of a polypropylene glycol) with no peak corresponding to the 700 MW initiator.
  • Catalyst D is evaluated in the same manner as described in Example 1. At a catalyst loading of 0.006 g, essentially quantitative conversion of the propylene oxide occurs in 18 hours. Gel permeation chromatography confirms the presence of a polypropylene glycol) with no peak corresponding to the 700 MW initiator.
  • a mixture of 50 mL water and 5 g of a 45% solution of poly(acrylic acid) sodium salt in water (Aldrich catalog #41 ,601-0, about 0.053 mol Na * ) is prepared.
  • a solution of 4.0 g (0.036 eq.) K 3 Co(CN) ⁇ in 70 mL of water is added to the mixture.
  • a solution of 19.35 g (0.142 mol) zinc chloride in 40 mL water is added over about 1 minute.
  • a white precipitate forms immediately.
  • a mixture of 50 mL t-butanol and 50 mL water is added, and the mixture is stirred for 10 minutes and filtered through Whatman® #4 filter paper.
  • the collected solids are reslurried in a solution of 6.45 g zinc chloride in 140 mL t-butanol and 60 mL water, stirred for 10 minutes and filtered again.
  • the collected solids are then reslurried in 200 mL t-butanol, stirred as before and filtered again.
  • a white filtrate is obtained, which is dried overnight in a vacuum oven (30 mm Hg, 50°C).
  • the mass of the dried catalyst complex is 9.26 g.
  • Example 1 At a catalyst loading of 0.006 g, essentially quantitative conversion of the propylene oxide occurs in 18 hours. Gel permeation chromatography confirms the presence of a polypropylene glycol) with no peak corresponding to the 700 MW initiator.
  • a mixture of 600 mL water and 1 g of small (99% ⁇ 1000 microns) lightly crosslinked poly(acrylic acid) potassium salt beads (Aldrich catalog #43,636-4, about 0.0106 mol Na * ) is prepared. The beads swell when added to the water. To the mixture are simultaneously added, over 15-20 minutes, (1) a solution of 1.0 g (0.003 mol) K 3 Co(CN) ⁇ in 25 mL of water and (2) a solution of 1.34 g (0.01 mol) zinc chloride in 15 mL water and 10 mL t-butanol. A white precipitate forms immediately. The resulting mixture is stirred for 10 minutes, then filtered through Whatman® #41 filter paper.
  • the collected solids are reslurried in a solution of 1.34 g zinc chloride in 150 mL t-butanol and 150 mL water, stirred for 10 minutes and filtered again.
  • the solids are again reslurried in 300 mL t-butanol, stirred for 10 minutes and filtered as before.
  • a white, powdery filtrate is obtained, which is dried overnight in a vacuum oven (30 mm Hg, 50°C).
  • the mass of the dried catalyst complex is 2.13 g.
  • Supported Catalyst F is evaluated in the same manner as described in Example 1. At a loading of 0.006 g of the catalyst complex, essentially quantitative conversion of the propylene oxide occurs in 18 hours. In each case, gel permeation chromatography confirms the presence of a polypropylene glycol) with no peak corresponding to the 700 MW initiator.
  • the collected solids are reslurried in a solution of 6.45 g (0.094 eq.) zinc chloride in 140 mL t-butanol and 60 mL water, stirred for 10 minutes and filtered again.
  • the solids are again reslurried in 200 mL t-butanol, stirred for 10 minutes and filtered as before.
  • a white, powdery filtrate is obtained, which is dried overnight in a vacuum over (30 mm Hg, 50°C).
  • the mass of the dried catalyst complex is 8.45 g.
  • Example 1 At a loading of 0.006 g of the catalyst complex, essentially quantitative conversion of the propylene oxide occurs in 18 hours. In each case, gel permeation chromatography confirms the presence of a polypropylene glycol) with no peak corresponding to the 700 MW initiator.
  • Haas, hydrogen form, approximately 216 meq. acid groups are slurried in water. A 20% by weight solution of sodium carbonate in water is added, and the mixture stirred until bubble formation ceased. The resin is then washed with 200 mL of a 1% aqueous NaOH solution to convert the resin to the Na * form. The resin is then washed three times with about 200 mL of water each time.
  • One-third of the resulting resin beads is added to 500 mL water.
  • a solution of 20 g (0.147 mol) zinc chloride in 40 mL water is added and the resulting slurry allowed to stand for several minutes before it is filtered.
  • the resin is washed with a solution of 10 g (0.073 mol) zinc chloride in 50 mL water and washed again with 200 mL water.
  • the resin is then slurried in 100 mL water and to the slurry is added a solution of 13.29 g (0.04 mol) K 3 Co(CN) 6 in 200 mL water.
  • the slurry is stirred occasionally for about an hour, then left to stand ovemight, and filtered.
  • the resin is again washed with 400 mL of water, then with a solution of 10 g zinc chloride in 100 mL of t-butanol and 100 mL of water.
  • the resin is then washed with a mixture of 70 mL t-butanol and 30 mL water, and again with 100 mL t-butanol.
  • the resulting beads are dried ovemight at 50°C in a vacuum oven.
  • the mass of the dried catalyst complex is 7.68 g.
  • Catalyst H is evaluated in the same manner as described in Example 1. At both 0.3 g and 0.006 g catalyst loadings, essentially quantitative conversion of the propylene oxide occurs within 18 hours. Gel permeation chromatography confirms the presence of a polypropylene glycol) with no . peak corresponding to the 700 MW initiator.
  • a weakly acid ion exchange resin (Amberlite® CC-50, from Rohm & Haas, hydrogen form, approximately 216 meq. acid groups) are washed with water several times and then slurried in a solution of 11 g (50 mmol) zinc acetate dihydrate in 83.3 mL water and 16.7 mL t-butanol. The resin is then washed three times with about 100 mL of water each time, and then slurried in a solution of 6 g (18 mmol) K 3 Co(CN) 6 in 100 mL water and 50 mL t-butanol. This is followed with three washes with 100 mL water. This sequence of washings is repeated three times.
  • a weakly acid ion exchange resin (Amberlite® CC-50, from Rohm & Haas, hydrogen form, approximately 216 meq. acid groups) are washed with water several times and then slurried in a solution of 11 g (50
  • the beads are then given a final rinse with a solution of 6.81 g (50 mmol) zinc chloride in 50 mL water and 50 mL t-butanol, and slurried in 100 mL t-butanol and drained.
  • the beads are then dried ovemight at 50°C in a vacuum oven.
  • the mass of the dried catalyst complex is 22.1 g.
  • Supported Catalyst I is evaluated in the same manner as described in Example 1. At a loading of 0.006 g of the catalyst complex, 84% conversion of the propylene oxide occurs in 18 hours. Gel permeation chromatography confirms the presence of a polypropylene glycol) with no peak corresponding to the 700 MW initiator.
  • the filtered solid is reslurried in a solution of zinc chloride (6.45 g, 0.047 mol) in 250 mL water, stirred 10 minutes and filtered again.
  • the filtered solids are dried in a vacuum oven overnight at 50°C.
  • the mass of the final product is 6.26 g.
  • Example 1 At both 0.3 g and 0.006 g catalyst loadings, essentially quantitative conversion of the propylene oxide occurs within 18 hours. Gel permeation chromatography confirms the presence of a polypropylene glycol) with no peak corresponding to the 700 MW initiator.
  • the collected solids are reslurried in a solution of 6.45 g zinc chloride in 140 mL t-butanol and 60 mL water, stirred for 10 minutes and filtered again.
  • the collected solids are then reslurried in 200 mL t-butanol, stirred as before and filtered again.
  • a white filtrate is obtained, which is dried overnight in a vacuum oven (30 mm Hg, 50°C).
  • the mass of the dried catalyst complex is 8.36
  • Example 11 Supported Catalyst K is evaluated in the same manner as described in Example 1. At a catalyst loading of 0.006 g, essentially quantitative conversion of the propylene oxide occurs in 18 hours. Similar results are obtained at a catalyst loading of 0.03 g. Gel permeation chromatography confirms the presence of a poly(propylene glycol) with no peak corresponding to the 700 MW initiator.
  • Example 11
  • the filtered solid is reslurried in a solution of zinc chloride (6.45 g, 0.047 mol) in 140 mL t-butanol and 60 mL water, stirred 10 minutes and filtered again.
  • the filtered solids are dried in a vacuum oven overnight at 50°C.
  • the mass of the final product is 10.25 g.
  • Catalyst L is evaluated in the same manner as described in Example 1. At a catalyst loading of 0.006 g, essentially quantitative conversion of the propylene oxide occurs within 18 hours. Gel permeation chromatography confirms the presence of a polypropylene glycol) with no peak corresponding to the 700 MW initiator. Similar results are seen when the catalyst loading is increased to about 0.03 9-

Abstract

L'invention concerne l'élaboration de catalyseurs de cyanure métallique en présence d'un polyacide organique. On forme des catalyseurs actifs de polymérisation d'oxyde d'alkylène qui présentent des tailles de particules supérieures à celles de catalyseurs de cyanure métallique classiques, et qui, de ce fait, peuvent être séparés plus facilement d'un polymère préparé à l'aide du catalyseur. Les polyacides organiques préférés sont des polymères réticulés ou non réticulés contenant des groupes libres carboxyle ou carboxylate.
EP00945237A 1999-07-09 2000-07-07 Procede d'elaboration de catalyseurs de cyanure metallique utilisant des acides polycarboxyliques Withdrawn EP1196473A1 (fr)

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US6696383B1 (en) 2002-09-20 2004-02-24 Bayer Polymers Llc Double-metal cyanide catalysts which can be used to prepare polyols and the processes related thereto
US6806348B2 (en) * 2003-02-11 2004-10-19 Basf Corporation Process for removing and regenerating a double metal cyanide (DMC) catalyst from a polymer polyol
DE102005011581A1 (de) * 2005-03-10 2006-09-14 Basf Ag Verfahren zur Herstellung von DMC-Katalysatoren
DE102005057895A1 (de) * 2005-12-02 2007-06-06 Basf Ag Verfahren zur Herstellung von Multimetallcyanidverbindungen
WO2011160296A1 (fr) 2010-06-23 2011-12-29 Basf Se Catalyseur de type cyanure métallique double modifié
PL2748226T3 (pl) 2011-08-25 2016-02-29 Dow Global Technologies Llc Sposób wytwarzania polieteroalkoholi zawierających jednostki oksyetylenowe przez polimeryzację węglanu etylenu w obecności katalizatorów dimetalocyjankowych
US9562134B2 (en) 2013-03-12 2017-02-07 Covestro Llc Catalyst for the production of polyols having lower amounts of high molecular weight tail
US9790395B2 (en) 2013-12-26 2017-10-17 Itaconix Corporation Soluble aqueous compositions of zinc salts of selected polyitaconic acid polymers
US9284446B2 (en) * 2013-12-26 2016-03-15 Itaconix Corporation Soluble aqueous compositions of zinc salts of selected polyitaconic acid polymers
KR101466803B1 (ko) 2014-02-14 2014-11-28 부산대학교 산학협력단 이중금속시안염 촉매 및 이를 제조하는 방법
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