WO2001090217A1 - Procede de preparation de catalyseurs de cyanure metallique et utilisation correspondante - Google Patents

Procede de preparation de catalyseurs de cyanure metallique et utilisation correspondante Download PDF

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WO2001090217A1
WO2001090217A1 PCT/US2000/018623 US0018623W WO0190217A1 WO 2001090217 A1 WO2001090217 A1 WO 2001090217A1 US 0018623 W US0018623 W US 0018623W WO 0190217 A1 WO0190217 A1 WO 0190217A1
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metal
compound
salt
initiator
dispersion
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PCT/US2000/018623
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English (en)
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Katherine S. Clement
Louis L. Walker
David C. Molzahn
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The Dow Chemical Company
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Priority to AU2000260776A priority Critical patent/AU2000260776A1/en
Publication of WO2001090217A1 publication Critical patent/WO2001090217A1/fr

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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
    • C08G65/26—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
    • 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
    • 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
    • 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

Definitions

  • This invention relates to methods for making metal cyanide catalysts complexes 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. This polymerization reaction 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, including, for example, U.S. Patent Nos. 3,278,457, 3,278,458, 3,278,459, 3,404,109, 3,427,256, 3,427,334, 3,427,335 and 5,470,813, among many others. In some instances, these complexes provide the benefit of fast polymerization rates and narrow polydispersities. Additionally, these catalysts are associated with the production of polyethers having very low levels of monofunctional unsaturated compounds.
  • the catalyst is typically prepared in a multistep process. First, separate solutions of zinc chloride and potassium hexacyanocobaltate are prepared. These solutions are then mixed together, followed immediately by adding a mixture of water and the complexing agent, t-butanol. A catalyst complex precipitates and is recovered and washed multiple times with mixtures of water and t-butanol. This washing process removes unwanted occluded ions, particularly potassium and chlorine, and contributes the complexing agent to the structure of the catalyst complex. Often, a polyether polyol is included in one or more of these washings. Finally, the catalyst complex is dried and ground. It is then mixed with an initiator compound and an alkylene oxide to prepare the desired polyether.
  • this invention is a method for preparing an active metal cyanide catalyst, comprising
  • this invention is a process wherein a dispersion made in accordance with the first aspect is mixed with an alkylene oxide and the resulting mixture subjected to conditions sufficient to polymerize the alkylene oxide to form a poly(alkylene oxide) based on said initiator compound.
  • an aqueous solution or dispersion of a metal compound is mixed with an aqueous solution or dispersion of a metal salt.
  • the metal compound is represented by the general formula B u [M 1 (CN) r (X),] v , in which M ⁇ X, r, t, u and v are as described before.
  • M 1 is preferably Fe* Fe +2 , Co Co +2 , Cr +2 , Cr* Mn +2 , Mn* lr* Ni +2 , Rh* Ru +2 ( V" 4 and V*.
  • those in the plus-three oxidation state are more preferred.
  • Co* and Fe* are even more preferred and Co* 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.
  • w is usually 2 or 3, and is most typically 3. In most cases, r + 1 will equal six.
  • the metal cyanide solution may also contain compounds that have the structure B u [M 2 (X) e ] v , wherein M 2 is a transition metal and u, v and X is 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.
  • B is preferably hydrogen, sodium or potassium and is most preferably hydrogen.
  • Compounds in which B is hydrogen are conveniently formed by passing an aqueous solution of the corresponding alkali metal salt through a cation-exchange resin that is in the hydrogen form.
  • the metal salt is represented by the general formula M x A y .
  • M is preferably a metal ion selected from the group consisting of Zn +2 , Fe +2 , Co +2 , Ni +2 , Mo" 4 , Mo*, Al*, V 44 , V*, Sr +2 , W 4 , W Mn* Sn* Sn 44 , Pb* Cu La* and Cr*.
  • M is more preferably Zn Fe +2 , Co +2 , Ni* La* and Cr*.
  • M is most preferably Z ⁇ +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 4 carboxylate. Chloride ion is especially preferred.
  • the solutions are mixed in proportions such that at least a stoichiometric amount of the metal salt is provided, based on the amount of metal cyanide compound.
  • metal ion (M) is delivered per equivalent of M 1 (CN) r (X) t ion (or combined equivalents of M 1 (CN) r (X) t and M 2 (X) e ions, when M 2 (X) 6 ions are present).
  • M metal ion
  • Agitation is preferably continued for a period after the mixing is completed.
  • the metal cyanide catalyst precipitates and forms a fine dispersion in the aqueous supernatant.
  • the catalyst is represented by the formula M b [M 1 (CN) r (X) t ] o [M 2 (X) 6 ] d , where d is zero or a positive number, b, c and d together reflect an electrostatically neutral complex, and M, M ⁇ M 2 , X, r and t are as defined before.
  • the additional metal salt can be of the form M 3 A , where M 3 is the same or different than M, and A, x and y are as defined before.
  • the metal cyanide catalyst is precipitated in the presence of an organic complexing agent.
  • complexing agent is used herein to refer to a heteroatom-containing organic compound that becomes associated with the metal cyanide catalyst.
  • the nature of the complexing is not fully understood and may be due to a combination of factors.
  • the complexing may be due to the formation of a coordinate bond between a heteroatom of the complexing agent and one or more of the metal ions (M, M 1 , M 2 , M 3 ) of the metal cyanide catalyst.
  • Another explanation of the complexing is that it is due to the complexing agent occupying vacancies within the crystalline structure of the metal cyanide, or that it otherwise is occluded within or bound into the crystalline lattice. However, it is not intended to limit this invention to any particular complexing mechanism.
  • complexing agents are potentially useful, although catalyst activity may vary according to the selection of a particular complexing agent.
  • 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, octadecanoi, 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-l-propanol, 3-chloro-1-propanol, 3-bromo-1-propanol, 1 ,3-dichloro-2-propanoi, 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-l-propanol, 3-chloro-1-propanol, 3-bromo-1-propanol, 1 ,3-dichloro-2-propanoi, 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-trimethyloi 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 octaethylene 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 or
  • 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 those that contain hydroxyl groups and also function as an initiator compound when the catalyst is used to polymerize an alkylene oxide.
  • the complexing agent is either added to one or both solutions of starting materials before they are mixed, or else is added to them immediately after they are mixed together. Once the starting solutions and complexing agent are mixed, they are agitated for several minutes until the catalyst complex precipitates and a slurry is formed.
  • the starting metal cyanide compound is an alkali metal salt
  • the alkali metal ions will usually be dissolved in the supernatant fluid, a convenient method of removing them is through a solid/liquid separation technique, such as filtration or, more preferably, centrifugation followed by decanting.
  • the precipitate may be washed one or more times with water, more complexing agent, or a mixture of water and complexing agent, but this is not required. There is no need to dry the precipitate at any point in this procedure, it being an advantage of this process that the process steps attendant to drying, especially grinding the dried catalyst, can be eliminated.
  • metal cyanide compound is in the hydrogen form (i.e. B is hydrogen)
  • the metal cyanide compound is in the hydrogen form (i.e. B is hydrogen)
  • the precipitated catalyst complex may be washed with or diluted with additional quantities of the complexing agent, if the complexing agent is different from the initiator compound, but this is usually not preferred. If the complexing agent is an initiator compound, there is no need to perform any such washings.
  • the precipitated catalyst (and optionally the supernatant fluid) is then dispersed into the initiator compound without isolating a dried catalyst.
  • the initiator compound is a material having at least one heteroatom-containing group that will react with an alkylene oxide to form a covalent bond between a carbon atom of the alkylene oxide and the heteroatom, and opening the ring of the alkylene oxide to form a terminal hydroxyl group.
  • Suitable initiator compounds are alcohols, thiols (R-SH compounds) and aliphatic carboxylic acids.
  • the initiator compound may contain as few as one or as many as eight or more such heteroatom-containing groups, depending on the desired nominal functionality of the product polyether.
  • the initiator compound may contain one or more other functional groups that may be desirable in the product polyether, such as alkenyl or alkynyl unsaturation.
  • Suitable initiator compounds include monoalcohols such methanol, ethanol, n- propanol, isopropanol, n-butanol, isobutanol, t-butanol, 1 -t-butoxy-2-propanol, 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-oi, 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-chIoro-1 -propanol, 3-bromo-1- propanol, 1 ,3-dichloro-2-propanol, 1 -chloro-2-methyl-2-propanol as well as nitroalcohols, keto-alcohols, ester-alcohols, cyanoalcohols, and other inertly substituted alcohols.
  • Suitable polyalcohol initiators include ethylene glycol, propylene glycol, glycerine, 1 ,1 ,1-trimethylol propane, 1 ,1 ,1-trimethylol ethane, 1 ,2,3- trihydroxybutane, pentaerythritoi, 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 particular those having an equivalent weight of about 350 or less, more preferably about 125-250, are also useful initiator compounds.
  • the complexing agent is the more volatile of the two, so that any excess complexing agent can be stripped away from the final initiator/catalyst complex dispersion if desired. This is especially important if the complexing agent is an alcohol having an undesirable functionality.
  • At least enough of the dispersion of the metal cyanide catalyst complex is added to the initiator to provide a catalytically effective amount of the catalyst complex in the initiator mixture.
  • the amount of catalyst complex added is generally at least about 50 ppm, based on the combined weight of the initiator plus catalyst complex, preferably at least about 200 ppm, more preferably at least about 1000 ppm.
  • the initiator/catalyst complex mixture as prepared according to the invention will contain from about 0.2 weight percent, more preferably from about 0.5 weight percent, most preferably from about 1 weight percent, to about 50 weight percent, preferably about 25 weight percent, more preferably about 10 weight percent, metal catalyst complex, based on the combined weight of metal catalyst complex (as M b [M 1 (CN) r (X) t ] c [M 2 (X)J d • nM 3 x A y ) and initiator. It is more preferred to form a dispersion that has a higher concentration of the metal catalyst than will be used in the subsequent alkylene oxide polymerization. Such a more concentrated dispersion can be divided and/or diluted with additional initiator when it is used to prepare a polyether.
  • any remaining water is removed. Removal is conveniently performed by stripping the water and other volatiles through the application of heat and/or vacuum. If the complexing agent is a different material than the initiator compound, excess quantities of it can be removed as well.
  • the resulting product is usually a fine dispersion of the metal cyanide catalyst complex in the initiator.
  • the metal cyanide catalyst complex is present in an active form, and no other treatment or preparation is required.
  • the metal-containing cyanide catalyst can be represented by the general formula:
  • M, M 1 , M 2 , M 3 , X, A, b, c, d, r, t, x and y are ail as defined before
  • n is a number indicating the relative number of moles of M 3 x A y
  • M 3 may be the same or different than M.
  • M 3 will be different from M, for example, when a stoichiometric amount of a metal salt M A is used in precipitating the catalyst complex, and the precipitated catalyst is then treated with an additional quantity of an M 3 x A y salt.
  • the catalysts of particular interest are:
  • 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 catalysfinitiator dispersion 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 catalyst sufficient to provide from about 5 to about 10,000 parts by weight metal cyanide catalyst (calculated as M b [M i (CN) r (X),] o [M 2 (X) e ] d • nM 3 x A y , exclusive of any associated water and initiator) per million parts combined weight of alkylene oxide, and initiator and comonomers, if present. More preferred catalyst levels are from about 20, especially from about 30, to about 5000, more preferably to about 1000 ppm, even more preferably to about 100 ppm, on the same basis.
  • 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 more, preferably from about 80-130°C.
  • a convenient polymerization technique involves charging the catalyst dispersion to a reactor and pressurizing the reactor with the alkylene oxide. Polymerization proceeds after a short induction period 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.
  • the activated catalyst/initiator dispersion is continuously fed into a continuous reactor such as a continuously stirred tank reactor (CSTR) or a tubular reactor.
  • CSTR continuously stirred tank reactor
  • a feed of alkylene oxide is introduced into the reactor and the product continuously removed.
  • the catalyst of this invention is especially useful in making propylene oxide homopolymers and random copolymers of propylene oxide and up to about 15 weight percent ethylene oxide (based on all monomers).
  • the polymers of particular interest have a hydroxyl equivalent weight of from about 800, preferably from about 1000, to about 5000, preferably about 4000, more preferably to about 2500, and unsaturation of no more than 0.02 meq/g, preferably no more than about 0.01 meq/g.
  • the product polymer may have various uses, depending on its molecular weight, equivalent weight, functionality and the presence of any functional groups.
  • Polyether polyols so made are useful as raw materials for making polyurethanes.
  • Polyethers can also be used as surfactants, hydraulic fluids, as raw materials for making surfactants and as starting materials for making aminated polyethers, among other uses.
  • the following examples are provided to illustrate the invention, but are not intended to limit its scope. All parts and percentages are by weight unless otherwise indicated. Catalyst loadings are based on weight of Zn 3 [Co(CN)J 2 • nZnCI 2 , calculated from the starting materials and ignoring any associated water and initiator.
  • Zinc chloride (3.4 parts by weight ) is dissolved in 10.2 parts water to form a solution. To this are added 50 parts of a 700 molecular weight, nominally trifunctional poly(propylene oxide). A second solution is prepared from 4 parts potassium hexacyanocobaltate and 10 parts water. The potassium hexacyano-cobaltate solution is added to the zinc chloride solution, with stirring, over a period of about one minute. A precipitate forms. Additional water (about 40 parts) is added, the resulting slurry is centrifuged and the supernatant fluid decanted. The wet solids are resuspended in about 100 parts water, stirred, centrifuged and decanted a total of four times to remove potassium ions. The resulting wet, washed precipitate is then blended with about 50 parts of the polypropylene oxide) described above to form a catalyst/initiator mixture.
  • the catalyst/initiator mixture is dried at 80°C under vacuum to remove residual water.
  • the resulting catalyst initiator mixture contains about 92 mg/g of Zn 3 [Co(CN) e ] 2 • ZnCI 2 .
  • a portion (0.6) parts of the catalyst/initiator mixture is mixed with 10.24 more parts of the same polypropylene oxide) to provide a mixture containing about 5277 ppm catalyst.
  • This mixture is charged to a pressure reactor, which is then purged with nitrogen and heated to 110°C.
  • Propylene oxide is added to the reactor at a rate of about 0.4 parts/minute.
  • the pressure inside the reactor increases to about 20-25 psig, after which it remains constant until ail propylene oxide is fed.
  • About 29 parts of propylene oxide are fed over 70 minutes.
  • a cloudy, water-white polypropylene oxide) having a molecular weight of about 2100 is obtained.
  • Another portion (0.128 parts) of the catalyst/initiator mixture is mixed with 16.8 parts of the same polypropylene oxide) to provide a mixture containing about 698 ppm catalyst.
  • This is reacted with propylene oxide as before, with a slightly lower propylene oxide feed rate.
  • the reactor becomes pressurized to about 40 psig before polymerization begins, followed by a slow reaction for about 5 minutes. Thereafter, the reaction rate is limited by the rate at which the propylene oxide is fed. About 21 parts of propylene oxide are fed over 60 minutes.
  • the resulting polyol has a molecular weight of about 1700. It is a slightly cloudy, water-white liquid.
  • Example 2 Potassium hexacyanocobaltate (8 parts) is dissolved in about 210 parts deionized water and then mixed with about 50 parts t-butanol. The resulting solution is added to a mixer, and a solution of 25 parts zinc chloride in 40 parts water is added dropwise over about 15 minutes with continued stirring. A slurry forms, which is centrifuged for 30 minutes at 3200 rpm. The supernatant liquid is decanted. The wet solids are dispersed into 175 parts t-butanol and then mixed into 265 parts of a 450 molecular weight, nominally trifunctional polypropylene oxide) initiator compound.
  • the resulting catalyst/initiator dispersion is then stripped by rotary evaporation to remove water and excess t-butanol, yielding 274.7 parts of a liquid containing 2186 ppm residual water.
  • the concentration of catalyst in the dispersion is 3.26 wt-%.
  • the dispersion has the appearance of a milky liquid with no solids being discernible with the naked eye. When examined microscopically, the catalyst particles are uniform and have the appearance of broken glass.
  • a portion of the dispersion (0.086 parts) is charged to a dried Wheaton vial fitted with a stir bar.
  • the vial is sealed with a septum cap and purged with nitrogen.
  • About 0.5 g of propylene oxide are added by syringe, and the septum cap replaced with a solid cap under nitrogen.
  • the vial is then heated to 90°C for 4 hours.
  • a slightly purplish polyol having a molecular weight of 2950 is obtained.

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Abstract

On prépare des dispersions de catalyseur de cyanure métallique dans des composés d'initiateurs en précipitant le catalyseur au cours d'une phase aqueuse, en mélangeant le coulis résultant avec l'initiateur et en éliminant l'eau et les autres volatiles. A l'aide de ce procédé, on prépare un catalyseur de polymérisation d'alkylène-oxyde actif et on simplifie grandement le procédé de préparation. En outre, il n'est pas nécessaire d'utiliser un agent complexant organique séparé dans la préparation.
PCT/US2000/018623 2000-05-19 2000-07-07 Procede de preparation de catalyseurs de cyanure metallique et utilisation correspondante WO2001090217A1 (fr)

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WO2023114343A1 (fr) 2021-12-16 2023-06-22 Dow Global Technologies Llc Nouveaux tensioactifs non ioniques et leurs procédés de fabrication

Citations (3)

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EP0654302A1 (fr) * 1993-11-23 1995-05-24 ARCO Chemical Technology, L.P. Catalyseur amélioré à base de complexe de cyanure métallique double
US5639705A (en) * 1996-01-19 1997-06-17 Arco Chemical Technology, L.P. Double metal cyanide catalysts and methods for making them
US5900384A (en) * 1996-07-18 1999-05-04 Arco Chemical Technology L.P. Double metal cyanide catalysts

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
EP0654302A1 (fr) * 1993-11-23 1995-05-24 ARCO Chemical Technology, L.P. Catalyseur amélioré à base de complexe de cyanure métallique double
US5639705A (en) * 1996-01-19 1997-06-17 Arco Chemical Technology, L.P. Double metal cyanide catalysts and methods for making them
US5900384A (en) * 1996-07-18 1999-05-04 Arco Chemical Technology L.P. Double metal cyanide catalysts

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023114343A1 (fr) 2021-12-16 2023-06-22 Dow Global Technologies Llc Nouveaux tensioactifs non ioniques et leurs procédés de fabrication

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