EP4121476A1 - Procédé de production de polyéther carbonate polyols - Google Patents

Procédé de production de polyéther carbonate polyols

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Publication number
EP4121476A1
EP4121476A1 EP21712148.2A EP21712148A EP4121476A1 EP 4121476 A1 EP4121476 A1 EP 4121476A1 EP 21712148 A EP21712148 A EP 21712148A EP 4121476 A1 EP4121476 A1 EP 4121476A1
Authority
EP
European Patent Office
Prior art keywords
reactor
catalyst
alkylene oxide
functional starter
concentration
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP21712148.2A
Other languages
German (de)
English (en)
Inventor
Stefanie Braun
Rolf Bachmann
Burkhard Becker
Dirk Becker
Friedhelm BAER
Pascal BACHMANN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Original Assignee
Covestro Deutschland AG
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Filing date
Publication date
Application filed by Covestro Deutschland AG filed Critical Covestro Deutschland AG
Publication of EP4121476A1 publication Critical patent/EP4121476A1/fr
Withdrawn legal-status Critical Current

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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
    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/32—General preparatory processes using carbon dioxide
    • C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
    • 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
    • C08G65/2603—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 the other compounds containing oxygen
    • 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
    • C08G65/2603—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 the other compounds containing oxygen
    • C08G65/2606—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 the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2609—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 the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
    • 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
    • C08G65/266—Metallic elements not covered by group C08G65/2648 - C08G65/2645, or compounds thereof
    • 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
    • C08G65/2696—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 process or apparatus 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/12—Copolymers
    • 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
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/22—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the initiator used in polymerisation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock

Definitions

  • the present invention relates to a process for the continuous production of polyether carbonate polyols by the addition of alkylene oxide and carbon dioxide in the presence of a DMC catalyst and / or a metal complex catalyst based on the metals cobalt and / or zinc on H-functional starter substance.
  • EP-A 0222453 discloses a process for the production of polycarbonates from alkylene oxides and carbon dioxide using a catalyst system composed of DMC catalyst and a cocatalyst such as zinc sulfate. The polymerization is initiated by bringing part of the alkylene oxide into contact with the catalyst system once. Only then are the remainder of the alkylene oxide and the carbon dioxide metered in simultaneously.
  • the amount specified in EP-A 0222453 for the activation step in Examples 1 to 7 of 60 wt .-% alkylene oxide compound relative to the H-functional starter substance is high and has the disadvantage that this is for Large-scale applications due to the high exothermic nature of the homopolymerization of alkylene oxide compounds represents a certain safety risk.
  • EP 3 164 442 B1 discloses a process for the production of polyether carbonate polyols, characterized in that one or more H-functional starter substances are placed in the reactor and that one or more H-functional starter substances are continuously metered into the reactor during the reaction.
  • EP 3 164442 discloses that with a concentration of free alkylene oxide above 5.0% by weight, stable process control was no longer possible due to strong pressure and temperature fluctuations. A slow increase in the mass flow rate of the alkylene oxide for the addition to H-functional starter substance is not disclosed.
  • WO 2005/047365 A1 discloses a continuous process for the production of polyether polyols by adding alkylene oxide onto H-functional starter substance in the presence of a DMC catalyst. It is disclosed that the metering rates of alkylene oxide, which is maintained for the continuous operation of the reactor, should be reached in a time between 100 to 3000 seconds, so that a smooth reaction is obtained. However, WO 2005/047365 A1 does not disclose a process for producing polyether carbonate polyols.
  • the process according to the invention simultaneously leads to a polyether carbonate polyol with improved selectivity.
  • the concentration s is determined by the previous weight of the catalyst as follows: mQiatalyst) s [in ppm] m ⁇ catalyst) + m ⁇ H- functional starter substance) + m (suspension medium) According to the invention, the concentration of the catalyst used is in the range of 10 y > s>
  • the steady state is the state in the process in which there is an equilibrium between the substances metered into the reactor and the substances withdrawn from the reactor.
  • the catalyst concentration y, the proportion of functional starter substance and the proportion of alkylene oxide in the reaction mixture in step (g) thus remain constant in the reactor during the steady state.
  • the reactor can also be filled with the catalyst first and then a portion of the H-functional starter substance.
  • the catalyst can first be suspended in a partial amount of H-functional starter substance and the suspension can then be filled into the reactor.
  • an H-functional starter substance is placed in the reactor, optionally together with the catalyst, and no suspending agent which does not contain any H-functional groups is placed in the reactor.
  • the catalyst is preferably used in an amount such that the content of catalyst in the resulting reaction product is 10 to 10,000 ppm, particularly preferably 20 to 5000 ppm and most preferably 50 to 500 ppm.
  • inert gas for example argon or nitrogen
  • inert gas is added to the resulting mixture of (a) a partial amount of H-functional starter substance and (b) catalyst at a temperature of 90 to 150 ° C, particularly preferably 100 to 140 ° C, an inert gas / carbon dioxide mixture or carbon dioxide is introduced and at the same time a reduced pressure (absolute) of 10 mbar to 800 mbar, particularly preferably 50 mbar to 200 mbar, is applied.
  • the catalyst can be added in solid form or as a suspension in a suspension medium which does not contain any H-functional groups, in an H-functional starter substance or in a mixture of the above.
  • step (a) in step (a)
  • Reactor lowered to less than 500 mbar, preferably 5 mbar to 100 mbar, where appropriate, an inert gas stream (for example of argon or nitrogen), an inert gas-carbon dioxide stream or a carbon dioxide stream is passed through the reactor, the catalyst for Partial amount of H-functional starter substance is added in step (aI) or immediately thereafter in step (a-II).
  • an inert gas stream for example of argon or nitrogen
  • an inert gas-carbon dioxide stream or a carbon dioxide stream is passed through the reactor, the catalyst for Partial amount of H-functional starter substance is added in step (aI) or immediately thereafter in step (a-II).
  • the partial amount of the H-functional starter substance used in (a) can contain component K, preferably in an amount of at least 50 ppm, particularly preferably from 100 to 10,000 ppm.
  • Step (ß) is used to activate the DMC catalyst. This step can optionally be carried out under an inert gas atmosphere, under an atmosphere of an inert gas-carbon dioxide mixture or under a carbon dioxide atmosphere.
  • activation within the meaning of this invention is a step in which a partial amount of alkylene oxide is added to the DMC catalyst suspension at temperatures of 90 ° C to 150 ° C and then the addition of the alkylene oxide is interrupted, with a subsequent exothermic chemical reaction generating heat that leads to a Temperature spike (“hotspot”), and a pressure drop in the reactor is observed due to the conversion of alkylene oxide and possibly CO2.
  • hotspot Temperature spike
  • the activation process step is the period of time from the addition of the partial amount of alkylene oxide, optionally in the presence of CO2, to the DMC catalyst until the development of heat occurs.
  • the partial amount of the alkylene oxide can be added to the DMC catalyst in several individual steps, if appropriate in the presence of CO 2, and the addition of the alkylene oxide can then be interrupted in each case.
  • the process step of activation comprises the time span from the addition of the first partial amount of alkylene oxide, optionally in the presence of CO 2, to the DMC catalyst until the development of heat occurs after the addition of the last partial amount of alkylene oxide.
  • the activation step can be preceded by a step for drying the DMC catalyst and optionally the H-functional starter substance at elevated temperature and / or reduced pressure, optionally with an inert gas being passed through the reaction mixture.
  • the alkylene oxide (and optionally the carbon dioxide) can in principle be metered in in different ways. Dosing can be started from the vacuum or with a pre-selected pre-pressure.
  • the admission pressure is preferably set by introducing an inert gas (such as nitrogen or argon) or carbon dioxide, the
  • Pressure absolute is 5 mbar to 100 bar, preferably 10 mbar to 50 bar and preferably 20 mbar to 50 bar.
  • the amount of alkylene oxide used in the activation in step ( ⁇ ) is 0.1 to 25.0% by weight, preferably 1.0 to 20.0% by weight, particularly preferably 2.0 to 16 , 0% by weight (based on the amount of H functional plate used in step (a)
  • the alkylene oxide can be added in one step or in portions in several partial amounts. After a portion of the alkylene oxide has been added, the addition of the alkylene oxide is preferably interrupted until the evolution of heat occurs and only then is the next portion of alkylene oxide added.
  • a two-stage activation (step ⁇ ) is also preferred, with
  • the H-functional starter substance used in step (g) optionally contains at least 50 ppm of component K, preferably at least 100 ppm.
  • the bi-functional starter substance used in step (g) contains at least 1000 ppm of component K.
  • the total pressure is preferably kept constant during the reaction by adding more carbon dioxide.
  • the metering of the alkylene oxide and / or H-functional starter substance takes place simultaneously or sequentially with the metering of carbon dioxide. It is possible to meter in the alkylene oxide at a constant metering rate or to increase the metering rate gradually or in steps or to add the alkylene oxide in portions.
  • the alkylene oxide is preferably added to the reaction mixture at a constant metering rate.
  • step (g) alkylene oxide is metered in at a mass flow rate Xi and Xi is continuously increased until the mass flow rate X2 required for the steady state in the reactor is reached.
  • the time until reaching the mass flow X2 is at least one hour, the mass flow is preferred after 1.1 hours at the earliest and after 6 hours at the latest, in particular after 1.5 hours at the earliest and after 6 hours at the latest and particularly preferably after two hours at the earliest and at the latest reached after six hours.
  • the alkylene oxides and / or H-functional starter substances can be metered in individually or as a mixture.
  • the metering of the alkylene oxides or the H-functional starter substances can be carried out simultaneously or sequentially via separate meterings (additions) in each case or via one or more meterings, with the alkylene oxides or the H-functional starter substances being metered in individually or as a mixture.
  • An excess of carbon dioxide based on the calculated amount of built-in carbon dioxide in the polyether carbonate polyol is preferably used, since an excess of carbon dioxide is advantageous due to the inertia of carbon dioxide.
  • the amount of carbon dioxide can be determined via the total pressure under the respective reaction conditions. The range from 0.01 to 120 bar, preferably 0.1 to 110 bar, particularly preferably from 1 to 100 bar, has proven to be advantageous as the total pressure (absolute) for the copolymerization for the preparation of the polyether carbonate polyols. It is possible to supply the carbon dioxide continuously or in portions.
  • the amount of carbon dioxide (expressed as pressure) can vary with the addition of the alkylene oxide.
  • step (g)) for the production of the polyether carbonate polyols advantageously takes place at 50 ° C to 150 ° C, preferably at 60 ° C to 145 ° C, particularly preferably at 70 ° C to 140 ° C and very particularly preferably at 90 ° C to 130 ° C is carried out. If temperatures are set below 50 ° C., the reaction is generally very slow. At temperatures above 150 ° C., the amount of undesired by-products increases sharply.
  • alkylene oxide, H-functional starter substance and the catalyst can be metered in via separate or shared metering points.
  • alkylene oxide and H-functional starter substance are fed continuously to the reaction mixture via separate metering points.
  • This addition of H-functional starter substance can take place as a continuous metering into the reactor or in portions.
  • Steps (a), ( ⁇ ) and (g) can be carried out in the same reactor or in each case separately in different reactors.
  • Particularly preferred reactor types are: tubular reactors, stirred tanks and loop reactors.
  • Polyether carbonate polyols can be produced in a stirred tank, the stirred tank being cooled, depending on the embodiment and mode of operation, via the reactor jacket, internal cooling surfaces and / or cooling surfaces located in a pumping circuit.
  • the resulting reaction mixture is continuously withdrawn from the reactor, particular attention must be paid to the metering rate of the alkylene oxide. It is to be set in such a way that the alkylene oxides react sufficiently quickly despite the inhibiting effect of the carbon dioxide.
  • the concentration of free alkylene oxides in the reaction mixture during the activation step (step ⁇ ) is preferably> 0 to 100% by weight, particularly preferably> 0 to 50% by weight, most preferably> 0 to 20% by weight (in each case based on the weight of the reaction mixture).
  • the free alkylene oxide concentration in the reaction mixture during the addition (step g) is preferably 1.5 to 5.0% by weight, particularly preferably 1.5 to 4.5% by weight, particularly preferably 2.0 to 4.0 % By weight (in each case based on the weight of the reaction mixture).
  • the polyether carbonate polyols are produced in a continuous process which comprises both continuous copolymerization and continuous addition of the one or more H-functional starter substances.
  • the invention also preferably relates to a process, wherein in step (g) one or more H-functional starter substances containing at least 50 ppm of component K, one or more Alkylene oxides and catalyst in the presence of carbon dioxide (“copolymerization”) are continuously metered into the reactor and the resulting reaction mixture (containing the reaction product) is continuously removed from the reactor.
  • the catalyst, suspended in H-functional starter substance, is preferably added continuously in step (g).
  • step (g) the catalyst is preferably added suspended in the H-functional starter substance, the amount preferably being selected so that the content of catalyst in the resulting reaction product is 10 to 10,000 ppm, particularly preferably 20 to 5000 ppm and most preferably 50 to Is 500 ppm.
  • Steps (a) and / or ( ⁇ ) are preferably carried out in a first reactor, and the resulting reaction mixture is then transferred to a second reactor for the copolymerization according to step (g). However, it is also possible to carry out steps (a), ( ⁇ ) and (g) in one reactor.
  • the process of the present invention can be used to produce large quantities of the polyether carbonate polyol product, initially with a DMC activated according to steps (a) and ( ⁇ ) in a subset of the H-functional starter substances and / or in suspending agents -Catalyst is used, and during the copolymerization (g) the DMC catalyst is added without prior activation.
  • continuous can be defined as a mode of adding a relevant catalyst or reactant such that a substantially continuous effective concentration of the catalyst or reactants is maintained.
  • the catalyst supply and the supply of the reactants can be carried out in a truly continuous manner or in relatively closely spaced increments.
  • a continuous addition of starter can be genuinely continuous or take place in increments. It would not be affected by the present proceedings differ, to add a catalyst or reactants incrementally in such a way that the concentration of the added materials falls substantially to zero for some time before the next incremental addition.
  • the catalyst concentration be maintained at substantially the same concentration during the major part of the course of the continuous reaction and that initiator substance be present during the major part of the copolymerization process.
  • the process can be stopped in step (g) and restarted with the same reaction mixture after a standstill of 24 hours or less.
  • Step (a) according to the invention does not have to be carried out again and the process can be continued with the previously set catalyst concentration for the steady state y.
  • alkylene oxides (epoxides) with 2-24 carbon atoms can be used for the process.
  • the alkylene oxides with 2-24 carbon atoms are, for example, one or more compounds selected from the group consisting of ethylene oxide, propylene oxide, 1-butene oxide, 2,3-butene oxide, 2-methyl-1,2-propene oxide (isobutene oxide), 1-pentene oxide, 2,3-pentene oxide, 2-methyl-1,2-butene oxide, 3-methyl-1,2-butene oxide, 1-hexene oxide, 2,3-hexene oxide, 3,4-hexene oxide, 2-methyl 1,2-pentene oxide, 4-methyl-1,2-pentene oxide, 2-ethyl-1,2-butene oxide, 1-heptene oxide, 1-octene oxide, 1-nonene oxide, 1-decene oxide, 1-undecene oxide, 1-dodecene oxide, 4-methyl-1,2-pentene oxide, butadiene monoxide, isopre
  • alkylene oxide used is preferably ethylene oxide and / or propylene oxide, in particular propylene oxide.
  • a mixture of alkylene oxides can also be used as the alkylene oxide.
  • Suitable H-functional starter substances which can be used are compounds with H atoms active for the alkoxylation, which have a molar mass from 18 to 4500 g / mol, preferably from 62 to 500 g / mol and particularly preferably from 62 to 182 have g / mol.
  • Groups with active H atoms which are active for the alkoxylation are, for example, -OH, -NH2 (primary amines), -NH- (secondary amines), -SH and -CO2H, -OH and -NH2 are preferred, -OH is particularly preferred.
  • one or more compounds are selected from the group consisting of monohydric or polyhydric alcohols, polyhydric amines, polyhydric thiols, amino alcohols, thioalcohols, hydroxyesters, polyether polyols, polyester polyols, polyester ether polyols, polyether carbonate polyols, polycarbonate polyols, polycarbonates, polyethylenimines, polyethylenimines , Polytetrahydrofuran (e.g.
  • PolyTHF ® from BASF polytetrahydrofuran amines, polyether thiols, polyacrylate polyols, castor oil, the mono- or diglyceride of ricinoleic acid, monoglycerides of fatty acids, chemically modified mono-, di- and / or triglycerides of fatty acids, and C1- C24 alkyl fatty acid esters containing on average at least 2 OH groups per molecule are used.
  • the C1-C24 alkyl fatty acid esters which contain on average at least 2 OH groups per molecule, are commercial products such as Lupranol Balance ® (BASF AG), Merginol ® types (Hobum Oleochemicals GmbH), Sovermol ® types (from Cognis GmbH & Co. KG) and Soyol ® TM types (from USSC Co.).
  • BASF AG BASF AG
  • Merginol ® types Hobum Oleochemicals GmbH
  • Sovermol ® types from Cognis GmbH & Co. KG
  • Soyol ® TM types from USSC Co.
  • Alcohols, amines, thiols and carboxylic acids can be used as monofunctional starter substances.
  • the following can be used as monofunctional alcohols: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 3-buten-1-ol, 3-butyn-1-ol, 2-methyl -3-buten-2-ol, 2-methyl-3-butyn-2-ol, propagyl alcohol, 2-methyl-2-propanol, 1-tert-butoxy-2-propanol, 1-pentanol, 2-pentanol, 3 -Pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 4-octanol, phenol, 2-hydroxybiphenyl
  • Possible monofunctional amines are: butylamine, tert-butylamine, pentylamine, hexylamine, aniline, aziridine, pyrrolidine, piperidine, morpholine.
  • Monofunctional carboxylic acids are: formic acid, acetic acid, propionic acid, butyric acid, fatty acids such as stearic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, acrylic acid.
  • Polyhydric alcohols suitable as H-functional starter substance are, for example, dihydric alcohols (such as, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-butenediol, 1,4-butynediol, neopentyl glycol, 1,5-pentanediol, methylpentanediols (such as 3-methyl-1,5-pentanediol), 1,6 -Hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, bis (hydroxymethyl) cyclohexanes (such as 1,4-bis (hydroxymethyl) cyclohexane), triethylene glycol, tetraethylene glycol, polyethylene glycols, dipropylene glycol , Tri
  • the H-functional starter substance can also be selected from the class of polyether polyols which have a molecular weight M n in the range from 18 to 4500 g / mol and a functionality of 2 to 3. The molecular weight is determined according to the hydroxyl number
  • polyether polyols which are built up from repeating ethylene oxide and propylene oxide units, preferably with a proportion of 35 to 100% propylene oxide units, particularly preferably with a proportion of 50 to 100% propylene oxide units.
  • These can be random copolymers, gradient copolymers, alternating or block copolymers of ethylene oxide and propylene oxide.
  • the H-functional starter substance can also be selected from the substance class of polyester polyols. At least difunctional polyesters are used as polyester polyols. Polyester polyols preferably consist of alternating acid and alcohol units.
  • acid components for. B. succinic acid, maleic acid, maleic anhydride, adipic acid, phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride or mixtures of the acids and / or anhydrides mentioned.
  • As alcohol components for. B.
  • ethanediol 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4-bis (hydroxymethyl) cyclohexane, diethylene glycol, Dipropylene glycol, trimethylolpropane, glycerol, pentaerythritol or mixtures of the alcohols mentioned are used. If dihydric or polyhydric polyether polyols are used as the alcohol component, polyester ether polyols are obtained which can also serve as starter substances for the preparation of the polyether carbonate polyols.
  • polycarbonate diols can be used as H-functional starter substance, which, for example, by reaction of phosgene, dimethyl carbonate, diethyl carbonate or Diphenyl carbonate and difunctional alcohols or polyester polyols or polyether polyols are produced.
  • polycarbonates can be found e.g. B. in EP-A 1359177.
  • polyether carbonate polyols can be used as functional starter substances.
  • polyether carbonate polyols which can be obtained by the process according to the invention described here are used.
  • These polyether carbonate polyols used as functional starter substances are prepared beforehand in a separate reaction step for this purpose.
  • the egg-functional starter substance generally has a functionality (i.e. number of H atoms active for the polymerization per molecule) of 1 to 8, preferably 2 or 3.
  • the H-functional starter substance is used either individually or as a mixture of at least two H-functional starter substances.
  • the H-functional starter substance is particularly preferably at least one compound selected from the group consisting of ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2 -Methylpropane-1,3-diol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, diethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, polyether carbonate polyols with a molecular weight M n in the range from 150 to 8000 g / mol with a functionality of 2 to 3 and polyether polyols with a molecular weight M n in the range from 150 to 8000 g / mol and a functionality of 2 to 3.
  • the subset of H-functional starter substance is selected in step (a) from at least one compound from the group consisting of polyether carbonate polyols with a molecular weight M n in the range from 150 to 8000 g / mol with a functionality of 2 to 3 and polyether polyols with a molecular weight M n in the range from 150 to 8000 g / mol and a functionality of 2 to 3.
  • the H-functional starter substance in step (g) is selected from at least one compound from the group consisting of ethylene glycol, Propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2-methylpropane-1,3-diol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, Diethylene glycol, dipropylene glycol, glycerine, trimethylol propane, pentaerythritol and sorbitol.
  • the polyether carbonate polyols are produced by the catalytic addition of carbon dioxide and alkylene oxide onto H-functional starter substances.
  • H-functional is understood to mean the number of H atoms active for the alkoxylation per molecule of the starter substance.
  • the H-functional starter substance which is continuously metered into the reactor during the reaction, can contain component K.
  • Component K Compounds suitable as component K are characterized in that they contain at least one phosphorus-oxygen bond.
  • suitable components K are phosphoric acid and phosphoric acid salts, phosphoric acid halides, phosphoric acid amides, phosphoric acid esters and salts of the mono- and diesters of phosphoric acid.
  • esters mentioned above and below under component K are understood to mean the alkyl esters, aryl esters and / or alkaryl ester derivatives.
  • Suitable phosphoric acid esters are, for example, mono-, di- or triesters of phosphoric acid, mono-, di-, tri- or tetraesters of pyrophosphoric acid and mono-, di-, tri-, tetra- or polyesters of polyphosphoric acid and alcohols at 1 to 30 ° C Atoms.
  • the following compounds, for example, are suitable as component K: phosphoric acid triethyl ester,
  • Phosphoric acid diethyl ester Phosphoric acid diethyl ester, phosphoric acid monoethyl ester, phosphoric acid tripropyl ester, phosphoric acid dipropyl ester, phosphoric acid monopropyl ester, phosphoric acid tributyl ester,
  • Phosphoric acid diphenyl ester Phosphoric acid diphenyl ester, phosphoric acid dicresyl ester, fructose 1,6-bisphosphate, glucose 1-phosphate, phosphoric acid bis (dimethylamide) chloride, phosphoric acid bis (4-nitrophenyl) ester, phosphoric acid cyclopropylmethyl diethyl ester, phosphoric acid dibenzyl ester, phosphoric acid diethyl 3-butenyl ester, phosphoric acid dihexadecyl ester, phosphoric acid diisopropyl ester chloride, phosphoric acid diphenyl ester, phosphoric acid diphenyl ester chloride, phosphoric acid 2-hydroxyethyl methacrylate ester, phosphoric acid mono- (4-chlorophenyl ester) dichloride,
  • Phosphoric acid mono- (4-nitrophenyl ester) dichloride Phosphoric acid mono- (4-nitrophenyl ester) dichloride, phosphoric acid monophenyl ester dichloride, phosphoric acid tridecyl ester, phosphoric acid tricresyl ester, phosphoric acid trimethyl ester,
  • Phosphoric acid triphenyl ester Phosphoric acid triphenyl ester, phosphoric acid tripyrolidide, phosphorus sulfochloride, phosphoric acid dichloride dimethylamide, phosphoric acid dichloride methyl ester, phosphoryl bromide,
  • Phosphoryl chloride phosphorylquinoline chloride calcium salt and O-phosphorylethanolamine, alkali and ammonium dihydrogen phosphates, alkali, alkaline earth and ammonium hydrogen phosphates, alkali, alkaline earth and ammonium phosphates.
  • Phosphoric acid esters are also understood to mean the products obtainable by propoxylation of phosphoric acid (for example available as Exolit® OP 560).
  • component K Also suitable as component K are phosphonic acid and phosphorous acid and mono- and diesters of phosphonic acid and mono-, di- and triesters of phosphorous acid and their salts, halides and amides.
  • Suitable phosphonic acid esters are, for example, mono- or diesters of phosphonic acid, alkylphosphonic acids, arylphosphonic acids, alkoxycarbonylalkylphosphonic acids, alkoxycarbonylphosphonic acids, cyanoalkylphosphonic acids and cyanophosphonic acids or mono-, di-, tri- or tetraesters of alkyldiphosphonic acids and alcohols having 1 to 30 carbon atoms.
  • Suitable phosphorous acid esters are, for example, mono-, di- or tri-esters of phosphorous acid and alcohols with 1 to 30 carbon atoms.
  • Phosphorous acid dibutyl ester Phosphorous acid dibutyl ester, phosphorous acid (diethylamide) dibenzyl ester, phosphorous acid (diethylamide) di-tert-butyl ester, phosphorous acid diethyl ester, phosphorous acid
  • Phosphorous acid (o-phenylene ester) chloride phosphorous acid tributyl ester, phosphorous acid triethyl ester, phosphorous acid triisopropyl ester, phosphorous acid triphenyl ester, phosphorous acid tris (tert-butyl-dimethylsilyl) ester, phosphorous acid (tris-l, l, 1,3,3,3-hexafluoro-2-propyl) ester, phosphorous acid tris (trimethylsilyl) ester, phosphorous acid dibenzyl ester.
  • Phosphorous acid esters are also understood to mean the products obtainable by propoxylation of phosphorous acid (for example available as Exolit® OP 550).
  • Phosphinic acid, phosphonous acid and phosphinous acid and their esters are also suitable as component K.
  • Suitable phosphinic esters are, for example, esters of phosphinic acid, alkylphosphinic acids, dialkylphosphinic acids or arylphosphinic acids and alcohols having 1 to 30 carbon atoms.
  • Suitable phosphonous esters are, for example, mono- and diesters of phosphonous acid or arylphosphonous acid and alcohols having 1 to 30 carbon atoms. This includes, for example, diphenylphosphinic acid or 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
  • the suitable as component K esters of phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, phosphonous or phosphinous be, usually by reaction of phosphoric acid, pyrophosphoric acid, polyphosphoric acids, phosphonic acid, alkyl phosphonic acids, aryl phosphonic acids, Alkoxycarbonylalkylphosphonklaren, Alkoxycarbonylphosphonklaren, Cyanalkylphosphonklaren, Cyanphosphonklare, alkyldiphosphonic acids, phosphonous Phosphorous acid, phosphinic acid, phosphinous acid or their halogen derivatives or phosphorus oxides with hydroxy compounds with 1 to 30 carbon atoms such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, dodecanol, tridecanol, tetrade
  • Phosphine oxides suitable as component K contain one or more alkyl, aryl or aralkyl groups with 1-30 carbon atoms which are bonded to the phosphorus.
  • Suitable phosphine oxides are, for example, trimethylphosphine oxide, tri (n-butyl) phosphine oxide, tri (n-octyl) phosphine oxide, triphenylphosphine oxide, methyldibenzylphosphine oxide and mixtures thereof.
  • compounds of phosphorus which can form one or more P-O bond (s) through reaction with OH-functional compounds (such as, for example, water or alcohols) are suitable as component K.
  • OH-functional compounds such as, for example, water or alcohols
  • such compounds of phosphorus are phosphorus (V) sulfide, phosphorus tribromide, phosphorus trichloride and phosphorus triiodide. Any mixtures of the aforementioned compounds can also be used as component K.
  • Phosphoric acid is particularly preferred as component K.
  • the suspending agent used does not contain any H-functional groups. All polar-aprotic, weakly polar-aprotic and non-polar-aprotic solvents, which in each case do not contain any H-functional groups, are suitable as suspending agents which do not contain any H-functional groups. A mixture of two or more of these suspending agents can also be used as the suspending agent which has no H-functional groups.
  • polar aprotic solvents may be mentioned here as examples: 4-methyl-2-oxo-1,3-dioxolane (hereinafter also referred to as cyclic propylene carbonate or cPC), 1,3-dioxolan-2-one (hereinafter also called cyclic ethylene carbonate or cEC), acetone, methyl ethyl ketone, acetonitrile, nitromethane, dimethyl sulfoxide, sulfolane, dimethylformamide, dimethylacetamide and N-methylpyrrolidone.
  • cyclic propylene carbonate or cPC 1,3-dioxolan-2-one
  • cEC 1,3-dioxolan-2-one
  • acetone methyl ethyl ketone
  • acetonitrile acetone
  • nitromethane dimethyl sulfoxide
  • sulfolane dimethylformamide
  • dimethylacetamide dimethylacetamide
  • Non-polar and weakly polar Aprotic solvents include, for example, ethers such as dioxane, diethyl ether, methyl tert-butyl ether and tetrahydrofuran, esters such as ethyl acetate and butyl acetate, hydrocarbons such as pentane, n-hexane, benzene and alkylated benzene derivatives (e.g. toluene, xylene, ethylbenzene) and chlorinated hydrocarbons such as chloroform, chlorobenzene, dichlorobenzene and carbon tetrachloride.
  • ethers such as dioxane, diethyl ether, methyl tert-butyl ether and tetrahydrofuran
  • esters such as ethyl acetate and butyl acetate
  • hydrocarbons such as pentane, n-hexane, benzene
  • DMC catalysts for use in the homopolymerization of alkylene oxides are known in principle from the prior art (see, for example, US-A 3 404 109, US-A 3 829 505, US-A 3 941 849 and US-A 5 158 922) .
  • DMC catalysts which are described, for example, in US Pat. No. 5,470,813, EP-A 700 949, EP-A 743 093, EP-A 761 708, WO 97/40086, WO 98/16310 and WO 00/47649 have a very high activity and enable the production of polyether carbonate polyols with very low catalyst concentrations, so that the catalyst can generally be separated off from the finished product is no longer required.
  • a typical example are the highly active DMC catalysts described in EP-A 700 949 which, in addition to a double metal cyanide compound (eg zinc hexacyanocobaltate (III)) and an organic complex ligand (eg tert-butanol), also contain a polyether with a number average molecular weight greater than 500 g / mol.
  • the DMC catalysts are preferably obtained by
  • an aqueous solution of a metal salt is reacted with the aqueous solution of a metal cyanide salt in the presence of one or more organic complex ligands, e.g. an ether or alcohol,
  • step (D) the solid obtained, optionally after pulverization, is dried at temperatures of generally 20-120 ° C. and at pressures of generally 0.1 mbar to normal pressure (1013 mbar), and in the first step or immediately after the filling of the double metal cyanide compound (step (B)) one or more organic complex ligands, preferably in excess (based on the double metal cyanide compound) and optionally further complex-forming components are added.
  • the double metal cyanide compounds contained in the DMC catalysts are the reaction products of water-soluble metal salts and water-soluble metal cyanide salts.
  • an aqueous solution of zinc chloride (preferably in excess based on the metal cyanide salt such as potassium hexacyanocobaltate) and potassium hexacyanocobaltate are mixed and then dimethoxyethane (glyme) or tert-butanol (preferably in excess based on zinc hexacyanocobaltate) are added to the suspension formed.
  • Metal salts suitable for preparing the double metal cyanide compounds preferably have the general formula (II),
  • M is selected from the metal cations Zn 2+ , Fe 2+ , Ni 2+ , Mn 2+ , Co 2+ , Sr 2 . Sn 2+ , Pb 2+ and, Cu 2+ , M is preferably Zn 2+ , Fe 2+ , Co 2+ or Ni 2+ ,
  • M is selected from the metal cations Fe 3+ , Al 3+ , Co 3+ and Cr '.
  • M is selected from the metal cations Mo 6+ and W 6+
  • suitable metal salts are zinc chloride, zinc bromide, zinc iodide, zinc acetate, zinc acetylacetonate, zinc benzoate, zinc nitrate, iron (II) sulfate, iron (II) bromide, iron (II) chloride, iron (III) chloride, cobalt (II) chloride, cobalt ( II) thiocyanate, nickel (II) chloride and nickel (II) nitrate. Mixtures of different metal salts can also be used.
  • Metal cyanide salts suitable for preparing the double metal cyanide compounds preferably have the general formula (VI)
  • M ' is selected from one or more metal cations from the group consisting of Fe (II), Fe (III), Co (II), Co (III), Cr (II), Cr (III), Mn (II), Mn ( III), Ir (III), Ni (II), Rh (III), Ru (II), V (IV) and V (V), M 'is preferably one or more metal cations from the group consisting of Co (II), Co (III), Fe (II), Fe (III), Cr (III), Ir (III) and Ni (II),
  • Y is selected from one or more metal cations from the group consisting of alkali metal (ie Li + , Na + , K + , Rb> nd alkaline earth metal (ie Be 2+ , Mg 2+ , Ca 2+ , Sr 2. Ba 2+ ),
  • A is selected from one or more anions from the group consisting of halides (ie fluoride, chloride, bromide, iodide), hydroxide, sulfate, carbonate, cyanate, thiocyanate, isocyanate, isothiocyanate, carboxylate, azide, oxalate or nitrate and a, b and c are integer numbers, the values for a, b and c being chosen so that the electrical neutrality of the metal cyanide salt is given; a is preferably 1, 2, 3 or 4; b is preferably 4, 5 or 6; c preferably has the value 0.
  • halides ie fluoride, chloride, bromide, iodide
  • hydroxide sulfate
  • carbonate cyanate
  • thiocyanate isocyanate
  • isothiocyanate carboxylate
  • azide oxalate or nitrate
  • a, b and c are integer numbers, the values
  • suitable metal cyanide salts are sodium hexacyanocobaltate (III), potassium hexacyanocobaltate (III), potassium hexacyanoferrate (II), potassium hexacyanoferrate (III), calcium hexacyanocobaltate (III) and lithium hexacyanocobaltate (III).
  • Preferred double metal cyanide compounds contained in the DMC catalysts are compounds of the general formula (VII)
  • M x [M ' x , (CN) y ] z (VII) wherein M is as defined in formula (II) to (V) and M' is as defined in formula (VI), and x, x ', y and z are whole numbers and chosen so that the electron neutrality of the double metal cyanide compound is given.
  • Suitable double metal cyanide compounds are zinc hexacyanocobaltate (III), zinc hexacyanoiridate (III), zinc hexacyanoferrate (III) and cobalt (II) hexacyanocobaltate (III). Further examples of suitable double metal cyanide compounds can be found, for example, in US Pat. No. 5,158,922 (column 8, lines 29-66). Zinc hexacyanocobaltate (III) is particularly preferably used.
  • organic complex ligands added in the preparation of the DMC catalysts are described, for example, in US Pat. No. 5,158,922 (see in particular column 6, lines 9 to 65), US Pat. No. 3,404,109, US Pat. No. 3,829,505, US Pat 941 849, EP-A 700 949, EP-A 761 708, JP 4 145 123, US-A 5 470 813, EP-A 743 093 and WO-A 97/40086).
  • water-soluble, organic compounds with heteroatoms, such as oxygen, nitrogen, phosphorus or sulfur which can form complexes with the double metal cyanide compound, are used as organic complex ligands.
  • Preferred organic complex ligands are alcohols, aldehydes, ketones, ethers, esters, amides, ureas, nitriles, sulfides and mixtures thereof.
  • Particularly preferred organic complex ligands are aliphatic ethers (such as dimethoxyethane), water-soluble aliphatic alcohols (such as ethanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, 2-methyl-3-buten-2-ol and 2-methyl-3-butyn-2-ol), compounds which contain both aliphatic or cycloaliphatic ether groups and aliphatic hydroxyl groups (such as, for example, ethylene glycol mono-tert-butyl ether, diethylene glycol mono-tert-butyl ether, tripropylene glycol mono methyl ether and 3-methyl-3-oxetane-methanol).
  • Highly preferred organic complex ligands are selected from one or more compounds from the group consisting of dimethoxyethane, tert-butanol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, ethylene glycol mono-tert . butyl ether and 3-methyl-3-oxetane-methanol.
  • Polyvinyl alcohol poly-N-vinylpyrrolidone, poly (N-vinylpyrrolidone-co-acrylic acid),
  • the metal salt e.g. zinc chloride
  • the metal cyanide salt i.e. at least a molar ratio of metal salt to metal cyanide salt of 2.25 to 1.00
  • the metal cyanide salt e.g. potassium hexacyanocobaltate
  • the organic complex ligand e.g. tert -butanol
  • the organic complex ligand can be present in the aqueous solution of the metal salt and / or the metal cyanide salt, or it is added directly to the suspension obtained after precipitation of the double metal cyanide compound. It has proven advantageous to mix the aqueous solutions of the metal salt and the metal cyanide salt and the organic complex ligand with vigorous stirring.
  • the suspension formed in the first step is then treated with a further complex-forming component.
  • the complex-forming component is preferably used in a mixture with water and organic complex ligands.
  • a preferred method for carrying out the first step i.e. the preparation of the suspension
  • step (B) the solid (i.e. the precursor of the catalyst) is isolated from the suspension by known techniques, such as centrifugation or filtration.
  • the isolated solid is then washed in a third step (step (C)) with an aqueous solution of the organic complex ligand (for example by resuspension and subsequent renewed isolation by filtration or centrifugation).
  • an aqueous solution of the organic complex ligand for example by resuspension and subsequent renewed isolation by filtration or centrifugation.
  • water-soluble by-products such as potassium chloride can be obtained from the Catalyst to be removed.
  • the amount of the organic complex ligand in the aqueous washing solution is preferably between 40 and 80% by weight, based on the total solution.
  • aqueous washing solution preferably in the range between 0.5 and 5% by weight, based on the total solution. It is also advantageous to wash the isolated solid more than once.
  • a first washing step (C-l) it is preferred to wash with an aqueous solution of the organic complex ligand (e.g. by resuspension and subsequent renewed isolation by filtration or centrifugation) in order to remove, for example, water-soluble by-products such as potassium chloride from the catalyst.
  • the amount of the organic complex ligand in the aqueous washing solution is particularly preferably between 40 and 80% by weight, based on the total solution of the first washing step.
  • the first washing step is repeated once or several times, preferably once to three times, or preferably a non-aqueous solution, such as a mixture or solution of organic complexing ligands and other complexing components (preferably in the range between 0.5 and 5% by weight, based on the total amount of the washing solution of step (C-2)), is used as washing solution and the solid is thus washed once or several times, preferably once to three times.
  • a non-aqueous solution such as a mixture or solution of organic complexing ligands and other complexing components (preferably in the range between 0.5 and 5% by weight, based on the total amount of the washing solution of step (C-2)
  • the isolated and optionally washed solid is then, optionally after pulverization, dried at temperatures of generally 20-100 ° C. and at pressures of generally 0.1 mbar to normal pressure (1013 mbar).
  • DMC catalysts based on zinc hexacyanocobaltate (Zn3 [Co (CN) e] 2) other metal complex catalysts based on the metals zinc known to those skilled in the art from the prior art for the copolymerization of epoxides and carbon dioxide can be used for the process according to the invention and / or cobalt can be used.
  • cobalt-salen catalysts described, for example, in US Pat. No. 7,304,172 B2, US 2012/0165549 A1
  • bimetallic zinc complexes with macrocyclic ligands described, for example, in MR Kember et al., Angew. Chem., Int. Ed., 2009, 48, 931).
  • a DMC catalyst is preferably used for the process.
  • the invention relates to a process for starting up the reactor for the continuous production process of polyether carbonate polyols by the addition of alkylene oxide and carbon dioxide in the presence of a DMC catalyst and / or a Metal complex catalyst based on the metals cobalt and / or zinc on H-functional starter substance, with
  • the invention relates to a method according to the first embodiment, characterized in that the concentration s is in the range of 5 y> s> 1.5 y.
  • the invention relates to a method according to the first embodiment, characterized in that the concentration s is in the range of 2.5 y> s> 1.8 y.
  • the invention relates to a method according to one of the embodiments 1 to 3, characterized in that the mass flow X is reached after two hours at the earliest and after six hours at the latest.
  • the invention relates to a method according to one of embodiments 1 to 4, characterized in that the concentration of free alkylene oxide in the reactor during the addition of alkylene oxide in step (g) after the mass flow X has been reached between 1.5 and 5 , 0 wt .-% and during the increase in the mass flow Xi, the concentration of free alkylene oxide is ⁇ 5%.
  • the invention relates to a method according to one of embodiments 1 to 5, characterized in that the alkylene oxide is selected from at least one compound from the group consisting of ethylene oxide and propylene oxide.
  • the invention relates to a method according to one of embodiments 1 to 6, characterized in that
  • one or more H-functional starter substance (s) containing at least 50 ppm component K are continuously metered into the reactor during the reaction, component K being selected from at least one compound containing a phosphorus-oxygen bond or one Compound of phosphorus, which can form one or more PO bond (s) by reacting with OH-functional compounds.
  • the invention relates to a method according to one of embodiments 1 to 7, characterized in that the H-functional starter substance is selected from at least one compound from the group consisting of ethylene glycol,
  • the invention relates to a method according to one of embodiments 1 to 7, characterized in that the H-functional starter substance is selected from at least one compound from the group consisting of ethylene glycol,
  • Propylene glycol 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2-methylpropane-1,3-diol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, Diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane and pentaerythritol.
  • the invention relates to a method according to one of embodiments 1 to 9, characterized in that the continuous process is restarted after a standstill of 24 hours or less.
  • the invention relates to a method according to one of embodiments 1 to 10, characterized in that, if DMC catalyst is used in step (a) after step (a) and before step (g), a step ( ⁇ ) is carried out, where (ß) To activate a DMC catalyst, a partial amount (based on the total amount of the amount of alkylene oxide used in the activation and copolymerization) of alkylene oxide is added to the mixture resulting from step (a), this addition of a partial amount of alkylene oxide optionally in The presence of CO2 can occur, and then the exothermic chemical reaction occurring due to the following
  • step ( ⁇ ) for activating a DMC catalyst can also be carried out several times.
  • Catalyst starter mixture 1 DMC catalyst suspended in monopropylene glycol.
  • Starter mixture 2 glycerol containing 170ppm H3PO4 (85%)
  • Example 1 not according to the invention
  • the reaction mixture was continuously withdrawn from the reactor via the bottom outlet. The aim was to remove a total of 670 kg / h after 2 hours. To complete the reaction, the reaction mixture was from the
  • Starter mixture 2 is metered mixed into the reactor.
  • the CCE metering was pressure-regulated.
  • the reaction mixture was continuously withdrawn from the reactor via the bottom outlet. The aim was to remove a total of 670 kg / h after 2 hours.
  • reaction mixture was conveyed from the bottom outlet via an adiabatically temperature-controlled tubular reactor.
  • free PO concentration measured by means of the MIR probe in the stirred reactor always remained below 5% by weight.

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Abstract

L'invention concerne un procédé de démarrage d'un réacteur pour le procédé de production continue de polyéther carbonate polyols par addition d'oxyde d'alkylène et de dioxyde de carbone en présence d'un catalyseur DMC et/ou d'un catalyseur complexe métallique à base des métaux cobalt et/ou zinc à une substance de départ à fonctionnalité H, procédé dans lequel : (α) une partie de la substance de départ à fonctionnalité H et/ou un milieu de suspension qui a des groupes à fonctionnalité H sont mélangés dans un réacteur avec un catalyseur DMC et/ou un catalyseur complexe métallique à base des métaux zinc et/ou cobalt, le catalyseur DMC et/ou le catalyseur complexe métallique ayant une concentration s dans le mélange ; et (γ), après l'étape (α), la substance de départ à fonctionnalité H, l'oxyde d'alkylène et le catalyseur DMC et/ou le catalyseur complexe métallique à base des métaux zinc et/ou cobalt sont introduits en continu dans le réacteur au cours de l'opération d'addition, et le mélange réactionnel obtenu est soutiré du réacteur, et on atteint un état permanent, caractérisé en ce que, dans l'étape (α), la concentration s du catalyseur utilisé, par rapport au mélange résultant de l'étape (α), est comprise dans la plage 10 y ≥ s ≥ 1,1 y, y étant la concentration du catalyseur, par rapport au mélange réactionnel de l'étape (γ), de l'état permanent de l'étape (γ), et en ce que dans l'étape (γ), un oxyde d'alkylène est amené à un débit massique X1, et X1 étant augmenté en continu jusqu'à ce que le débit massique X2, qui est nécessaire pour l'état permanent dans le réacteur, soit atteint, et le temps jusqu'à ce que soit atteinte X2 est d'au moins une heure.
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WO2021185710A1 (fr) 2021-09-23
US20230069332A1 (en) 2023-03-02
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