EP4069763A1 - Procédé de production de polyéthercarbonate polyols - Google Patents

Procédé de production de polyéthercarbonate polyols

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Publication number
EP4069763A1
EP4069763A1 EP20812059.2A EP20812059A EP4069763A1 EP 4069763 A1 EP4069763 A1 EP 4069763A1 EP 20812059 A EP20812059 A EP 20812059A EP 4069763 A1 EP4069763 A1 EP 4069763A1
Authority
EP
European Patent Office
Prior art keywords
temperature
alkylene oxide
reactor
functional starter
catalyst
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Withdrawn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
EP20812059.2A
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German (de)
English (en)
Inventor
Stefanie Braun
Joerg Hofmann
Michael Traving
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 Intellectual Property GmbH and Co KG
Original Assignee
Covestro Intellectual Property GmbH and Co KG
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Publication date
Application filed by Covestro Intellectual Property GmbH and Co KG filed Critical Covestro Intellectual Property GmbH and Co KG
Publication of EP4069763A1 publication Critical patent/EP4069763A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/02—Aliphatic polycarbonates
    • C08G64/0208—Aliphatic polycarbonates saturated
    • 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
    • C08G65/2615—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 the other compounds containing carboxylic acid, ester or anhydride 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
    • C08G65/2663—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
    • 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

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 or a metal complex catalyst based on the metals cobalt and / or zinc on H-functional starter substance.
  • EP-A 0 222 453 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 0 222 453 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 initially introduced into the reactor and that one or more H-functional starter substances are continuously metered into the reactor during the reaction.
  • EP 3 164 442 discloses that with a concentration of free alkylene oxide above 5.0% by weight, stable process performance was no longer possible due to strong pressure and temperature fluctuations.
  • step (ß) if necessary 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 can take place in the presence of CO2, and then waiting for the temperature peak ("hotspot") and / or a pressure drop in the reactor that occurs due to the following exothermic chemical reaction, and where step (ß) for activation can also be carried out several times,
  • a suspension of catalyst in suspension medium and / or H-functional starter substance in the reactor to a temperature Ti is set in the range from 100 to 150 ° C, where Ti is at least 10%, based on Ti, above a temperature T2 and T2 is a temperature in the range from 50 to 135 ° C,
  • step (ii) from the beginning of the addition of alkylene oxide in step (g), the temperature Ti set in (i) in the reactor is continuously reduced to temperature T2 and temperature T2 is reached after 50 minutes at the earliest.
  • a partial amount of H-functional starter substance and / or a suspension medium which has no H-functional groups can first be placed in the reactor. If appropriate, the amount of catalyst required for the polyaddition is then added to the reactor. The order in which they are added is not critical.
  • the reactor can also be filled first with the catalyst and then a portion of the H-functional starter substance. Alternatively, 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.
  • step (a) 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 portion 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.
  • an inert gas for example argon or nitrogen
  • 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)
  • step (aI) a subset of the H-functional starter substances and / or suspending agents and presented (a-II) the temperature of the partial amount of H-functional starter substance is brought to 50 to 200 ° C., preferably 80 to 160 ° C., particularly preferably 100 to 140 ° C. and / or the pressure in the reactor 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 being added to the partial amount of H-functional starter substance in step ( aI) or is added immediately afterwards 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 being added to the partial amount of H-functional starter substance in step ( aI) or is added immediately afterwards 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 in the context 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 to 150 ° C and the addition of the alkylene oxide is then interrupted, with the development of heat due to a subsequent exothermic chemical reaction which can lead 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 process step of activation is the period of time from the addition of the partial amount of alkylene oxide, optionally in the presence of CO 2, 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 CO2, 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) being 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 starter substance 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 ß) is also preferred, with (ßl) in a first activation stage the addition of a first portion of alkylene oxide under an inert gas atmosphere or carbon dioxide atmosphere and (ß2) in a second activation stage the addition of a second portion of alkylene oxide takes place under a carbon dioxide atmosphere.
  • the metering of H-functional starter substance, alkylene oxide and optionally also the carbon dioxide into the reactor takes place continuously according to the invention.
  • the term "continuously" used here can be defined as the mode of adding a reactant in such a way that a concentration of the reactant effective for the copolymerization is maintained, i.e., for example, the metering can be carried out at a constant metering rate, with a varying metering rate or in portions.
  • the H-functional starter substance used in step (g) optionally contains at least 50 ppm of component K, preferably at least 100 ppm. In an alternative embodiment, the H-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 or decrease the metering rate gradually or stepwise or to add the alkylene oxide in portions.
  • the alkylene oxide is preferably added to the reaction mixture at a constant metering rate.
  • the alkylene oxides and / or H-functional starter substances can be metered in individually or as a mixture.
  • the alkylene oxides or the H-functional starter substances can be metered in simultaneously or sequentially via separate meterings (additions) in each case or via one or more meterings, 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 add the carbon dioxide continuously or in portions.
  • the amount of carbon dioxide (expressed as pressure) can vary with the addition of the alkylene oxide. CO2 can also be added to the reactor as a solid and then, under the selected reaction conditions, change into the gaseous, dissolved, liquid and / or supercritical state.
  • a preferred embodiment of the method according to the invention is characterized, inter alia, in that the total amount of H-functional starter substance is added in step (g). This addition can take place at a constant metering rate, with a varying metering rate or in portions.
  • the copolymerization (step (g)) for producing the polyether carbonate polyols is preferably carried out at 60 to 130 ° C, particularly preferably at 70 to 125 ° C and very particularly preferably at 90 to 120 ° C . 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.
  • the metering of the alkylene oxide, H-functional starter substance and the catalyst can take place via separate or common metering points.
  • alkylene oxide and H-functional starter substance are continuously fed 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 bi-functional starter substances.
  • the invention also preferably relates to a process in which, in step (g), egg-functional starter substance containing at least 50 ppm of component K, alkylene oxide 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). But 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 deviate from the present method to incrementally add a catalyst or reactants such that the concentration of the added materials drops to essentially zero for some time before the next incremental addition. It is preferred, however, that the catalyst concentration be maintained at substantially the same concentration during the major part of the course of the continuous reaction and that initiator be present during the major part of the copolymerization process.
  • Incremental addition of catalyst and / or reactant which does not substantially affect the nature of the product is in the j enigen sense in which the term is used here, but "continuous". For example, it is feasible to provide a recycle loop in which some of the reacting mixture is returned to a previous point in the process, thereby smoothing out discontinuities caused by incremental additions.
  • a suspension of catalyst in suspending agent and / or H-functional starter substance is set in the reactor to a temperature Ti in the range from 100 to 150 ° C , where Ti is at least 10%, based on T 2 , above a temperature T 2 and T 2 is a temperature in the range from 50 to 135 ° C,
  • the temperature Ti set in (i) in the reactor is continuously reduced to temperature T 2 and temperature T 2 is reached after 50 minutes at the earliest.
  • the temperature Ti is set in the range from 100 to 150 ° C., preferably from 110 to 150 ° C., particularly preferably from 120 to 140 ° C., and is at least 10%, preferably at least 15%, particularly preferably at least 20%, in each case based on T2, above the temperature T2.
  • the temperature T2 is the temperature of the continuous process in the steady state, ie with constant mass flows of the starting materials and constant filling level of the reactor. From the beginning of the addition of the alkylene oxide, the temperature Ti is continuously reduced until the temperature T2 is reached.
  • the temperature T2 is in the range from 50 to 135.degree. C., preferably from 60 to 130.degree. C., particularly preferably from 70 to 125.degree. C., particularly preferably from 90 to 120.degree.
  • the temperature can be reduced linearly or in several stages in such a way that the temperature T 2 is reached at the earliest after 50 minutes, preferably 100 minutes, particularly preferably 120 minutes.
  • the method according to the invention can be used when starting up a process for the continuous production of polyether carbonate polyols for the first time, and when starting up such a process again. For the purposes of this invention, restarting means that a continuous process for the production of polyether carbonate polyols has been stopped and started up again without removing the entire reaction mixture.
  • the restart takes place preferably after a standstill of 24 hours or less, particularly preferably after a standstill of 12 hours or less, particularly preferably after a standstill of 4 hours or less, after the continuous process for the production of polyether carbonate polyols has been stopped.
  • 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
  • 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.
  • the number average molar mass M n (also: molecular weight) is determined in the context of this invention by gel permeation chromatography according to DIN 55672-1 (March 2007).
  • Groups with active H atoms which are active for the alkoxylation are, for example, -OH, -NH 2 (primary amines), -NH- (secondary amines), -SH and -CO2H, preference is given to -OH and -NH 2 , particularly preferred is - OH.
  • 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, polyethylene imines, polyether amines , Polytetrahydrofurans (e.g.
  • PolyTHF ® from BASF polytetrahydrofuranams, 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 Ci-C 24 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 ® grades (Messrs. Cognis Germany GmbH & Co. KG) and Soyol ® TM types (Fa. USSC Co.). Alcohols, amines, thiols and carboxylic acids can be used as monofunctional starter substances.
  • BASF AG Lupranol Balance ®
  • Merginol ® types Hobum Oleochemicals GmbH
  • Sovermol ® grades Messrs. Cognis Germany GmbH & Co. KG
  • Soyol ® TM types Fa. USSC Co.
  • 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
  • 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. Preference is given to 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 production 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 H-functional starter substance.
  • polyether carbonate polyols which can be obtained by the process according to the invention described here are used.
  • These polyether carbonate polyols used as egg-functional starter substances are prepared beforehand in a separate reaction step for this purpose.
  • the H-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 in step (a) is selected 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 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.
  • 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 are suitable as component K: phosphoric acid triethyl 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 dibutyl ester,
  • Phosphoric acid monobutyl ester Phosphoric acid monobutyl ester, phosphoric acid trioctyl ester, phosphoric acid tris (2-ethylhexyl) ester, phosphoric acid ns- (2-butoxyethyl) ester, phosphoric acid diphenyl ester, phosphoric acid dicresyl ester, fructose-1, 6-bisphosphate, glucose-1-phosphate, phosphoric acid bis (dimethyl amide) chloride, phosphoric acid bis (4-nitrophenyl) ester, phosphoric acid cyclopropylmethyl diethyl ester,
  • 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 triesters of phosphorous acid and alcohols with 1 to 30 Carbon atoms.
  • 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.
  • esters of phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, phosphonous acid or phosphinous acid which are suitable as component K are generally obtained by reaction of phosphoric acid, pyrophosphoric acid, polyphosphoric acids, phosphonic acid, alkylphosphonic acids, arylphosphonic acids, alkoxycarbonylalkylphosphonic acids, alkoxycarbonylphosphonic acids, alkylphosphonic acids, alkyliphosphonic acids, cyanophosphonic acids, alkoxycarbonylphosphonic acids, alkylphosphonic acids, alkoxycarbonylphosphonic acids, alkylphosphonic acids.
  • Phosphonous acid, 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, tetradecanol, pentadecanol , Hexadecanol, heptadecanol, octadecanol, nonadecanol, methoxymethanol, ethoxymethanol, propoxymethanol, butoxymethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, phenol, ethyl hydroxyacetate, propyl hydroxyacetate, hydroxypropionic acid, etc.
  • hyl ester propyl hydroxypropionate, 1,2-ethanediol, 1,2-propanediol, 1,2,3-trihydroxypropane, 1,1,1-trimethylolpropane or pentaerythritol.
  • 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.
  • phosphorus (V) sulfide phosphorus tribromide
  • phosphorus trichloride phosphorus triiodide
  • 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 as examples at this point: 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- Methyl pyrrolidone.
  • cyclic propylene carbonate or cPC 1,3-dioxolan-2-one
  • cEC 1,3-dioxolan-2-one
  • acetone methyl ethyl ketone
  • acetonitrile nitromethane
  • dimethyl sulfoxide dimethyl sulfoxide
  • sulfolane dimethylformamide
  • the group of non-polar and weakly polar aprotic solvents includes, 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
  • Preferred suspending agents which have no H-functional groups are 4-methyl-2-oxo-1,3-dioxolane, 1,3-dioxolan-2-one, toluene, xylene, ethylbenzene, chlorobenzene and dichlorobenzene and mixtures of two or more several of these suspension agents are used, 4-methyl-2-oxo-1,3-dioxolane and 1,3-dioxolan-2-one or a mixture of 4-methyl-2-oxo-1,3-dioxolane and 1 is particularly preferred , 3-dioxolan-2-one.
  • step (g) 2% by weight to 20% by weight of the suspending agent, based on the sum of the components metered in in step (g), can be added in step (g).
  • DMC catalysts for use in the elomopolymerization of alkylene oxides are known in principle from the prior art (see e.g. US-A 3404 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 700949 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 contained than 500 g / mol.
  • a double metal cyanide compound eg zinc hexacyanocobaltate (III)
  • an organic complex ligand eg tert-butanol
  • 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, being dried at temperatures of generally 20-120 ° C. and at pressures of generally 0.1 mbar to normal pressure (1013 mbar), and wherein in the first step or immediately after the precipitation of the double metal cyanide compound (step (B)) one or more organic complexing ligands, preferably in excess (based on the double metal cyanide compound) and optionally further complexing 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
  • potassium hexacyanocobaltate preferably in excess based on the metal cyanide salt such as potassium hexacyanocobaltate
  • dimethoxyethane glyme
  • tert-butanol preferably in excess based on zinc hexacyanocobaltate
  • 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. 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 4+ , V 4+ and W 4+
  • 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 of the group consisting of alkali metal (i.e. Li + , Na + , K + , Rb + ) and alkaline earth metal (i.e. Be 2+ , Mg 2+ , Ca 2+ , Sr 24 , 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 of their a, b and c being selected in such a way that the metal cyanide salt is electronically neutral; 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
  • 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 during 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.
  • 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 the double metal cyanide compound has been filled. 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 removed from the catalyst.
  • 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.
  • 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).
  • Zinc and / or cobalt can be used. This includes in particular what are known as zinc glutarate catalysts (described, for example, in MH Chisholm et al., Macromolecules 2002, 35, 6494), so-called zinc diiminate catalysts (described, for example, in SD Allen, J. Am. Chem. Soc.
  • cobalt-salen catalysts described, for example, in US 7,304,172 B2, US 2012/0165549 A1
  • bimetallic zinc complexes with macrocyclic ligands described, for example, in MR Kember et ah, Angew. Chem., Int . Ed., 2009, 48, 931).
  • a DMC catalyst is preferably used for the process.
  • the 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 a DMC catalyst or a metal complex catalyst based on the metals cobalt and / or zinc on H-functional starter substance, wherein
  • a partial amount of H-functional starter substance and / or a suspending agent which does not contain any H-functional groups is placed in a reactor, optionally together with a DMC catalyst or a metal complex catalyst based on the metals zinc and / or cobalt,
  • step (ß) if necessary 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 can take place in the presence of CO2, and then waiting for the temperature peak ("hotspot") and / or a pressure drop in the reactor that occurs due to the following exothermic chemical reaction, and where step (ß) for activation can also be carried out several times,
  • a suspension of catalyst in suspending agent and / or H-functional starter substance is set in the reactor to a temperature Ti in the range from 100 to 150.degree where Ti is at least 10%, based on T 2 , above a temperature T 2 and T 2 is a temperature in the range from 50 to 135 ° C,
  • the temperature Ti set in (i) in the reactor is continuously reduced to temperature T 2 and temperature T 2 is reached after 50 minutes at the earliest.
  • the invention relates to a method according to the first embodiment, characterized in that the temperature T 2 is 60 to 130 ° C.
  • the invention relates to a method according to the second embodiment, characterized in that the temperature Ti is set in the range from 110 to 150 ° C.
  • the invention relates to a method according to one of embodiments 1 to 3, characterized in that the temperature Ti is at least 15%, based on T 2 , above the temperature T 2 .
  • the invention relates to a method according to one of the
  • Embodiments 1 to 3 characterized in that in (ii) the temperature T2 is reached after 100 minutes at the earliest.
  • the invention relates to a method according to one of the
  • Embodiments 1 to 5 characterized in that the concentration of free alkylene oxide in the reactor during the addition of alkylene oxide is 1.5 to 5.0% by weight, based on the reaction mixture in the reactor.
  • the invention relates to a method according to one of the
  • Embodiments 1 to 6 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 the
  • Embodiments 1 to 7 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) through reaction with OH functional compounds.
  • the invention relates to a method according to one of the
  • Embodiments 1 to 8 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 the
  • Embodiments 1 to 8 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 the embodiments 1 to 10, characterized in that the continuous process is restarted after a standstill of 24 hours or less.
  • the catalyst / starter mixture used in the examples consists of a suspension of 6.9 g of DMC catalyst (prepared according to Example 6 of WO-A 01/80994) in 1000 g of a starter mixture of monopropylene glycol / glycerol, the starter mixture having 170 ppm of H 3 Contains PO 4 (85%).
  • a product mixture of 30 liters and a CO2 atmosphere was contained in a nitrogen-flushed 60L pressure reactor with gas metering device (gas inlet pipe) and product discharge pipe (reaction volume Vr 27.4 dm 3) after production was interrupted.
  • the reactor was heated to 123 ° C. to restart.
  • the reactor with CO2 reached a pressure of 64 barg at this temperature.
  • 500 g of propylene oxide (PO) were metered into the reactor at 123 ° C. (Ti) with stirring over the course of 2 minutes.
  • the start of the reaction became noticeable through a temperature peak (“hotspot”) and a decrease in pressure and a change in the measured free PO concentration.
  • This propylene oxide addition was repeated a second time.
  • a product mixture of 40 liters and a CO2 atmosphere was contained in a nitrogen-flushed 60L pressure reactor with gas metering device (gas inlet pipe) and product discharge pipe (reaction volume Vr 27.4 dm 3) after production was interrupted.
  • the reactor was held at 107 ° C. during the interruption.
  • the reactor with CO2 remained at this temperature at a pressure of 64 barg.
  • propylene oxide was metered in at 7.2 kg / h and the catalyst / starter mixture at 0.27 kg / h.
  • the reactor could not be operated stably, the free PO concentration fluctuated strongly, accompanied by temperature and pressure fluctuations.
  • the CCh dosage was added under pressure control in the mass flow and therefore also fluctuated.

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Abstract

La présente invention concerne un procédé de production continue de polyéthercarbonate polyols par l'ajout d'oxyde d'alkylène et de dioxyde de carbone en présence d'un catalyseur du type DMC ou d'un catalyseur du type complexe métallique à base des métaux cobalt et/ou zinc, sur uns substance de départ à fonction H, (α) éventuellement une sous-quantité de la substance de départ à fonction H et/ou un milieu de suspension ne comprenant aucun groupe à fonction H étant initialement introduits dans un réacteur éventuellement en même temps que le catalyseur du type DMC ou qu'un catalyseur du type complexe métallique basé sur les métaux zinc et/ou cobalt, (ß) éventuellement, afin d'activer le catalyseur du type DMC, une sous-quantité (par rapport à la quantité totale de la quantité d'oxyde d'alkylène utilisée pour l'activation et la copolymérisation) d'oxyde d'alkylène étant ajoutée au mélange résultant de l'étape (α), cet ajout d'une sous-quantité d'oxyde d'alkylène pouvant éventuellement être réalisé en présence de CO2, le pic de température résultant de la réaction chimique exothermique ultérieure (point chaud) et/ou une chute de pression dans le réacteur étant ensuite attendus dans chaque cas et l'étape d'activation (ß) pouvant également être réalisée plusieurs fois, (γ) la substance de départ à fonction H, l'oxyde d'alkylène et le catalyseur étant dosés en continu dans la réaction durant l'ajout et le mélange réactionnel résultant étant évacué en continu du réacteur, caractérisé en ce que, (i) avant l'étape (γ) et après les éventuelles étapes (α) et/ou (ß), une suspension de catalyseur dans le milieu de suspension et/ou la substance de départ à fonction H dans le réacteur est ajustée à une température T1 allant de 100 °C à 150 °C, T1 étant au moins supérieure de 10 % à une température T2 et T2 étant une température allant de 50 °C à 135 °C, (ii) à partir du début de l'ajout de l'oxyde d'alkylène à l'étape (γ), la température T1 dans le réacteur ajustée en (i) étant abaissée en continu jusqu'à la température T2 et la température T2 étant atteinte au mieux après 50 minutes.
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