EP1233996A1 - Method for producing polyether alcohols - Google Patents

Method for producing polyether alcohols

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Publication number
EP1233996A1
EP1233996A1 EP00966099A EP00966099A EP1233996A1 EP 1233996 A1 EP1233996 A1 EP 1233996A1 EP 00966099 A EP00966099 A EP 00966099A EP 00966099 A EP00966099 A EP 00966099A EP 1233996 A1 EP1233996 A1 EP 1233996A1
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EP
European Patent Office
Prior art keywords
ppm
basic
alkylene oxides
acidic
catalyst
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EP00966099A
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German (de)
French (fr)
Inventor
Eva Baum
Georg Heinrich Grosch
Kathrin Harre
Jürgen Winkler
Thomas Ostrowski
Gerd Hoeppner
Els Paredis
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BASF SE
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BASF SE
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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

Definitions

  • the invention relates to a process for the preparation of polyether alcohols by catalytic reaction of H-functional compounds with alkylene oxides, using at least one multi-metal cyanide compound as catalyst.
  • Multimetal cyanide catalysts are effective catalysts for the ring-opening polymerization of epoxides to polyetherols.
  • Multimetal cyanide catalysts in epoxy polymerization can be used up to catalyst concentrations below 100 ppm.
  • WO 97 / 23,544 also describes catalyst concentrations of less than or equal to 15 ppm. With multimetal cyanide catalyst concentrations of less than 100 ppm, however, problems very often arise during the polymerization. This can result in a gradual deactivation of the catalyst during the polymerization. In the batch mode, there can be significant fluctuations in the quality of the polyetherols thus produced. Different molecular weight distributions, viscosities and levels of unsaturated constituents can result from batch batch to batch batch.
  • a decrease in the catalyst activity during the polymerization can lead to dangerous conditions in the production plants if the reaction completely falls asleep.
  • the starting materials used for the polymerization such as the OH-functional starters or the alkylene oxides
  • These foreign substances can be both organic compounds, preferably containing heteroatoms, the heteroatoms often belonging to groups Va, such as nitrogen, phosphorus, arsenic, antimony, bismuth, via, such as oxygen, sulfur, selenium, tellurium, or Vlla, such as fluorine, chlorine, Bromine, iodine, belonging to the Periodic Table of the Elements, as well as inorganic compounds, too Atoms from the groups Va, Via and Vlla of the Periodic Table of the Elements can contain. These compounds can react basicly, ie have pH values greater than 7 in water.
  • Such compounds with a basic reaction can be compounds containing amine or phosphine, such as amines, amine-started polyetherols or phosphine catalysts. Remnants of these substances can remain in the production facilities or in tank farms. In particular, it can be critical if a precursor procedure is used in the multimetal cyanide processes, ie polyetherols with molecular weights of 250 to 800 daltons are produced from low molecular weight OH-functional starters by means of basic catalysis. These precursors are often not produced in the reactors designed for multi-metal cyanide catalysis, but in multi-purpose reactors.
  • substances with an acidic character ie with pH values in water less than 7, can also be found in the starting materials.
  • traces of acid from the finish process such as hydrochloric acid or phosphoric acid, from the precursors, which in turn are used as OH-functional starters for DMC catalysis, can occur in the precursor procedure.
  • sulfur-containing compounds can occur if hydrogen sulfide alkoxlylates were previously produced in the plants.
  • Another source of foreign substances can also be the low-molecular starters themselves.
  • glycerol can contain traces of base, as described for example in WO 99/14,258.
  • OH-functional starters but also the alkylene oxides, depending on the manufacturing process, can have impurities.
  • propylene oxide which is produced using the chlorohydrin process, may contain traces of chlorine or chlorine-containing compounds.
  • Fluctuations in the production process are undesirable in the technical production of polyetherols by means of multimetal cyanide catalysis, so that it is necessary to find measures with which these fluctuations can be avoided.
  • the content of the heteroatoms contained in such compounds should preferably be selected from the group nitrogen, phosphorus, arsenic, antimony, sulfur, selenium, tellurium, fluorine, chlorine, bromine and iodine, in each case less than 100 ppm, in order to keep their influence on the multi-metal cyanide catalysts as low as possible.
  • the invention accordingly relates to a process for the preparation of polyether alcohols by catalytic addition of alkylene oxides onto H-functional starter substances, the catalysts used being multimetal cyanide compounds, characterized in that the content of the basic and acidic impurities in the starter substance and / or the Alkylene oxides, which reduce the activity of the catalyst, contain heteroatoms, selected from the group consisting of nitrogen, phosphorus, arsenic, antimony, sulfur, selenium, tellurium, fluorine, chlorine, bromine and iodine, in each case less than 100 ppm.
  • the invention furthermore relates to a process for the preparation of polyether alcohols by catalytic addition of alkylene oxides onto H-functional starter substances, multimetal cyanide compounds being used as catalysts, characterized in that the content of the basic and acidic impurities in the starter substance and / or the heteroatoms containing the alkylene oxides, selected from the group consisting of nitrogen, phosphorus, arsenic, antimony, sulfur, selenium, tellurium, fluorine, chlorine, bromine and iodine, in each case less than 100 ppm and the starter substance and / or the alkylene oxides before the implementation of a treatment with heterogeneous adsorbents.
  • the content of heteroatoms selected from the group consisting of nitrogen, phosphorus, arsenic, antimony, sulfur, selenium, tellurium, fluorine, chlorine, bromine and iodine, which originate from the foreign substances in the starting materials which damage the multimetal cyanide catalysts used, should in each case be less than 100 ppm, preferably less than 50 ppm, particularly preferably less than 25 ppm, particularly preferably less than 10 ppm and especially preferably less than 1 ppm.
  • the upper limits preferred according to the invention for the heteroatoms contained in the individual foreign substances naturally depend on the damaging potency of these foreign substances.
  • the upper limits of the heteroatom content are selected from the group consisting of nitrogen, phosphorus, arsenic, antimony, sulfur, selenium, tellurium, Fluorine, chlorine, bromine and iodine, in foreign substances with a strongly damaging effect in each case less than 25 ppm and preferably less than 10 ppm, particularly preferably 1 ppm.
  • Basic compounds which contain amine, phosphine or sulfide groups have proven to be strong catalyst poisons for multimetal cyanide compounds.
  • the nitrogen, phosphorus or sulfur contents of these compounds present in the starting materials should, according to the invention, be less than 25 ppm, preferably less than 10 ppm and particularly preferably 1 ppm.
  • Slightly weaker catalyst poisons for multimetal cyanide compounds are acidic compounds, in particular those which contain nitrogen, phosphorus, arsenic, antimony, oxygen, sulfur, selenium and / or halogen atoms.
  • the contents of the corresponding heteroatoms in the starting materials should not exceed 100 ppm, preferably 50 ppm, particularly preferably 25 ppm.
  • solids are preferably used to remove undesired foreign substances from the starting materials.
  • neutralizers homogeneously soluble in the starting materials, as described in WO 99/14,258, has the disadvantage that both the foreign substance and the substance added to render it harmless remain in the product. This may have the consequence that they may favor the formation of undesired by-products during the addition of the alkylene oxides or damage plant parts, e.g. in the form of deposits.
  • heterogeneous adsorbents are used, they can simply be separated from the starting materials together with the adsorbed foreign substance. Contamination of the end product with foreign matter or adsorber material can be excluded.
  • Suitable heterogeneous adsorbents can be selected according to the acidic or basic character of the impurities present in the starting compounds.
  • solids with acidic centers pKa value of the centers less than 7 are used to remove foreign substances with a basic character.
  • Such solids with acidic centers used according to the invention include organic ion exchangers and inorganic materials such as layered silicates, aluminosilicates, zeolites and other mixed oxides with acidic centers.
  • organic ion exchangers and inorganic materials such as layered silicates, aluminosilicates, zeolites and other mixed oxides with acidic centers.
  • the acidic ion exchangers depending on the strength of the basic character, either strongly acidic or weakly acidic ion exchangers can be used.
  • organic ion exchangers are described in Ullmanns's Encyclopedy of industrial chemistry, 5 th rev. Ed. (1989) Volume A14, pages 394 to 458.
  • the organic ion exchangers are based on polystyrene, polyacrylic matrices or phenol-formaldehyde or polyalkyl resins.
  • the strongly acidic ion exchangers generally contain sulfonic acid groups, while the weakly acidic ion exchangers have carboxyl groups.
  • solids which have basic centers (pKb value of the centers less than 7).
  • basic organic ion exchangers can include basic organic ion exchangers, basic metal oxides, such as hydrotalcite, doped alkaline earth oxides, carbonates or hydroxides, or basic solids, as described, for example, by
  • groups Ia such as lithium, sodium, potassium, rubidium or cesium, and Ha
  • beryllium, magnesium, calcium, strontium or barium of the periodic table of the elements
  • the strongly basic ion exchangers whose polymer matrix corresponds to that of the acidic ion exchanger, generally have quaternary ammonium groups, while weakly basic ion exchangers have amine residues as basic groups.
  • Adsorbents such as activated carbon, aluminum oxides, silicon oxides, non-functionalized polystyrene-divinylbenzene polymers, etc., which cannot be referred to directly as acidic or basic materials, can also be used.
  • the starting materials can be treated with the heterogeneous adsorbents in various ways.
  • a preferred embodiment for the depletion of the undesirable foreign substances from the starting materials is that the heterogeneous adsorbents are packed as beds and the starting materials to be treated are passed over the adsorbents packed as fixed, moving, moving or floating beds.
  • the various options for designing this method can be found, inter alia, from Konrad Dorfner, "Ion Exchangers", Walter de Gruyter-Verlag, Berlin, 1991, or Ullmanns's Encyclopedy of industrial chemistry, 5 th rev. Ed. (1989) Volume A14, pages 394 to 459.
  • the various adsorbents can either be packed in a bed or arranged in succession in different beds.
  • Another embodiment of the process according to the invention consists in stirring the adsorbents into the starting materials and, after a stirring time of a few minutes to a few hours, separating them from the starting materials by filtration or centrifugation.
  • a special embodiment provides for the separation of the heterogeneous adsorbents not before the alkoxylation, but together with the removal of the multimetal cyanide compound after
  • the adsorbents should be selected so that negative influences of the heterogeneous adsorbent on the multimetal cyanide compound can be excluded.
  • both the OH-functional starters and the alkylene oxides can be treated.
  • a distillation, extraction or extractive distillation is also suitable as a purification stage.
  • the depletion of the basic or acidic impurities from the starting materials is preferably carried out at temperatures between 10 and 120 ° C., the alkylene oxides being treated at temperatures below 25 ° C.
  • the pressures are preferably between 1 bar and 10 bar and are chosen so that the starting material to be treated is in liquid form during depletion.
  • OH-functional starters such as glycerol
  • glycerol have viscosities at room temperature which make the depletion processes according to the invention described above more difficult.
  • methods are preferably used which make it possible to lower the viscosity.
  • the temperature can be increased.
  • the educt to be cleaned can be diluted with an inert, miscible, easily removable and viscosity-reducing liquid.
  • the time of cleaning can be selected according to the different viscosities depending on the degree of alkoxylation.
  • glycerol propoxylates with molecular weights of 400 to 600 daltons have lower viscosities than the starting material glycerol itself.

Abstract

The invention relates to a method for producing polyether alcohols by the catalytic reaction of H functional compounds with alkylene oxides, whereby at least one multi-metal cyanide compound is used as the catalyst. The method is characterised in that the total content of alkaline and acidic impurities contained in the starting material and the alkylene oxides, which reduce the activity of the catalyst, is less than 100 ppm.

Description

Verfahren zur Herstellung von PolyetheralkoholenProcess for the preparation of polyether alcohols
Beschreibungdescription
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von Polyetheralkoholen durch katalytische Umsetzung von H-funktio- nellen Verbindungen mit Alkylenoxiden, unter Verwendung mindestens einer Multi etallcyanidverbindung als Katalysator.The invention relates to a process for the preparation of polyether alcohols by catalytic reaction of H-functional compounds with alkylene oxides, using at least one multi-metal cyanide compound as catalyst.
Multimetallcyanid-Katalysatoren sind effektive Katalysatoren zur ringöffnenden Polymerisation von Epoxiden zu Polyetherolen. Multimetallcyanid-Katalysatoren bei der Epoxidpolymerisation können bis zu Katalysatorkonzentrationen kleiner 100 ppm eingesetzt werden. In WO 97/23,544 werden auch Katalysatorkonzentrationen kleiner gleich 15 ppm beschrieben. Bei Multi- metallcyanid-Katalysatorkonzentrationen kleiner 100 ppm treten jedoch sehr häufig Probleme bei der Polymerisation auf. So kann es während der Polymerisation zu einer schleichenden Deaktivierung des Katalysators kommen. Bei Batchfahrweise kann es zu deutlichen Qualitätsschwankungen der so hergestellten Polyetherole kommen. So können sich von Batchansatz zu Batchansatz unterschiedliche Molgewichtsverteilungen, Viskositäten und Gehalte an ungesättigten Bestandteilen ergeben.Multimetal cyanide catalysts are effective catalysts for the ring-opening polymerization of epoxides to polyetherols. Multimetal cyanide catalysts in epoxy polymerization can be used up to catalyst concentrations below 100 ppm. WO 97 / 23,544 also describes catalyst concentrations of less than or equal to 15 ppm. With multimetal cyanide catalyst concentrations of less than 100 ppm, however, problems very often arise during the polymerization. This can result in a gradual deactivation of the catalyst during the polymerization. In the batch mode, there can be significant fluctuations in the quality of the polyetherols thus produced. Different molecular weight distributions, viscosities and levels of unsaturated constituents can result from batch batch to batch batch.
Ein Nachlassen der Katalysatoraktivität bei der Polymerisation kann bei einem vollständigen Einschlafen der Reaktion zu gefährlichen Zuständen in den Produktionsanlagen führen.A decrease in the catalyst activity during the polymerization can lead to dangerous conditions in the production plants if the reaction completely falls asleep.
Diese Probleme sind für den technischen Einsatz von Multi- metallcyanid-Katalysatoren in diesen kleinen Konzentrationen prohibitiv. Andererseits ist aus Kostengründen ein Polymerisationsprozeß mit deutlich höheren Multimetallcyanid-Katalysator- konzentrationen als 100 ppm wirtschaftlich unattraktiv.These problems are prohibitive for the technical use of multimetal cyanide catalysts in these small concentrations. On the other hand, for reasons of cost, a polymerization process with significantly higher multimetal cyanide catalyst concentrations than 100 ppm is economically unattractive.
Überraschenderweise hat sich gezeigt daß die verwendeten Edukte für die Polymerisation, wie die OH-funktionellen Starter oder die Alkylenoxide, gemäß ihrer jeweiligen Vorgeschichte, d.h. je nach Herstellprozeß, Transport, Lagerung etc., Fremdstoffe im Bereich bis 100 ppm und mehr enthalten können, die Einfluß auf die Aktivität der Multimetallcyanid-Katalysatoren ausüben. Diese Fremdstoffe können sowohl organische, vorzugsweise Heteroatome enthaltende Verbindungen sein, wobei die Heteroatome oft den Gruppen Va, wie Stickstoff, Phosphor, Arsen, Antimon, Bismuth, Via, wie Sauerstoff, Schwefel, Selen, Tellur, oder Vlla, wie Fluor, Chlor, Brom, Iod, des Periodensystems der Elemente angehören, als auch anorganische Verbindungen sein, die ebenfalls Atome aus den Gruppen Va, Via und Vlla des Periodensystems der Elemente enthalten können. Diese Verbindungen können basisch reagieren, d.h in Wasser pH-Werte größer 7 haben. Solche basisch reagierenden Verbindungen können Amin- oder phosphinhaltige Ver- bindungen sein, wie Amine, Amin-gestartete Polyetherole oder Phosphinkatalysatoren. Reste dieser Stoffe können unter anderem in den Produktionsanlagen oder in Tanklagern verbleiben. Insbesondere kann es kritisch sein, wenn bei den Multimetallcyanid- Verfahren eine Vorstufenfahrweise genutzt wird, also aus nieder- molekularen OH-funktionellen Startern mittels basischer Katalyse Polyetherole mit Molekulargewichten von 250 bis 800 Dalton hergestellt werden. Diese Vorstufen werden oft nicht in den für die Multi etallcyanid-Katalyse designierten Reaktoren, sondern in Vielzweck-Reaktoren hergestellt.Surprisingly, it has been found that the starting materials used for the polymerization, such as the OH-functional starters or the alkylene oxides, can contain foreign substances in the range up to 100 ppm and more, depending on their respective history, ie depending on the manufacturing process, transport, storage etc. Influence the activity of the multimetal cyanide catalysts. These foreign substances can be both organic compounds, preferably containing heteroatoms, the heteroatoms often belonging to groups Va, such as nitrogen, phosphorus, arsenic, antimony, bismuth, via, such as oxygen, sulfur, selenium, tellurium, or Vlla, such as fluorine, chlorine, Bromine, iodine, belonging to the Periodic Table of the Elements, as well as inorganic compounds, too Atoms from the groups Va, Via and Vlla of the Periodic Table of the Elements can contain. These compounds can react basicly, ie have pH values greater than 7 in water. Such compounds with a basic reaction can be compounds containing amine or phosphine, such as amines, amine-started polyetherols or phosphine catalysts. Remnants of these substances can remain in the production facilities or in tank farms. In particular, it can be critical if a precursor procedure is used in the multimetal cyanide processes, ie polyetherols with molecular weights of 250 to 800 daltons are produced from low molecular weight OH-functional starters by means of basic catalysis. These precursors are often not produced in the reactors designed for multi-metal cyanide catalysis, but in multi-purpose reactors.
Ferner können sich auch Substanzen mit saurem Charakter, also mit pH-Werten in Wasser kleiner 7, in den Edukten finden. So können insbesondere bei der Vorstufenfahrweise Säurespuren aus dem Finish-Prozeß, wie Salzsäure oder Phosphorsäure, der Vor- stufen, die wiederum als OH-funktionelle Starter für die DMC- Katalyse verwendet werden, auftreten. Ebenso können schwefelhaltige Verbindungen auftreten, wenn in den Anlagen vorher Schwefelwasserstoffalkoxlylate produziert wurden. Eine weitere Quelle für Fremdsubstanzen können unter anderem auch die nieder- molekularen Starter selbst sein. So kann Glycerin je nach Herstellprozeß durchaus Basenspuren enthalten, wie beispielsweise in WO 99/14,258 beschrieben.In addition, substances with an acidic character, ie with pH values in water less than 7, can also be found in the starting materials. For example, traces of acid from the finish process, such as hydrochloric acid or phosphoric acid, from the precursors, which in turn are used as OH-functional starters for DMC catalysis, can occur in the precursor procedure. Likewise, sulfur-containing compounds can occur if hydrogen sulfide alkoxlylates were previously produced in the plants. Another source of foreign substances can also be the low-molecular starters themselves. Depending on the manufacturing process, glycerol can contain traces of base, as described for example in WO 99/14,258.
Doch nicht nur die OH-funktionellen Starter, sondern auch die Alkylenoxide können je nach Herstellprozeß Verunreinigungen aufweisen. So kann Propylenoxid, das mittels Chlorhydrin-Verfahren hergestellt wird, Spuren an Chlor oder chlorhaltigen Verbindungen enthalten.However, not only the OH-functional starters, but also the alkylene oxides, depending on the manufacturing process, can have impurities. For example, propylene oxide, which is produced using the chlorohydrin process, may contain traces of chlorine or chlorine-containing compounds.
In der technischen Produktion von Polyetherolen mittels Multimetallcyanid-Katalyse sind Schwankungen im Produktionsprozeß unerwünscht, so daß es nötig ist, Maßnahmen zu finden, mit denen sich diese Schwankungen vermeiden lassen.Fluctuations in the production process are undesirable in the technical production of polyetherols by means of multimetal cyanide catalysis, so that it is necessary to find measures with which these fluctuations can be avoided.
Überraschenderweise wurde gefunden, daß eine gleichbleibende Aktivität der Multimetallcyanid-Katalysatoren gewährleistet und Schwankungen in der Qualität der Polyetherole vermieden werden können, wenn die Gehalte an basischen und/oder sauren Fremdsubstanzen, die die Aktivität der Multimetallcyanid-Katalysatoren beeinträchtigen, aus den OH-funktionellen Startern und den Alkylenoxiden entfernt werden. Vorzugsweise sollte der Gehalt an den in derartigen Verbindungen enthaltenen Heteroatomen, aus- gewählt aus der Gruppe Stickstoff, Phosphor, Arsen, Antimon, Schwefel, Selen, Tellur, Fluor, Chlor, Brom und Iod, jeweils kleiner 100 ppm sein, um ihren Einfluß auf die Multi etallcyanid- Katalysatoren möglichst gering zu halten. Es wurde weiterhin gefunden, daß diese niedrigen Gehalte an Verbindungen, welche die Multimetallcyanid-Katalysatoren schädigen können, in den OH- funktionellen Startern und Alkylenoxiden dadurch erreicht werden können, daß die verwendeten OH-funktionellen Starter und/oder Alkylenoxide vor oder während dem Einsatz in der Multimetall- cyanid-katalysierten Polymerisation mit heterogenen Adsorbentien behandelt werden.It has surprisingly been found that constant activity of the multimetal cyanide catalysts is ensured and fluctuations in the quality of the polyetherols can be avoided if the levels of basic and / or acidic foreign substances which impair the activity of the multimetal cyanide catalysts from the OH-functional starters and the alkylene oxides are removed. The content of the heteroatoms contained in such compounds should preferably be selected from the group nitrogen, phosphorus, arsenic, antimony, sulfur, selenium, tellurium, fluorine, chlorine, bromine and iodine, in each case less than 100 ppm, in order to keep their influence on the multi-metal cyanide catalysts as low as possible. It has also been found that these low levels of compounds which can damage the multimetal cyanide catalysts in the OH-functional starters and alkylene oxides can be achieved by using the OH-functional starters and / or alkylene oxides before or during use in the multimetal cyanide-catalyzed polymerization are treated with heterogeneous adsorbents.
Gegenstand der Erfindung ist demzufolge ein Verfahren zur Herstellung von Polyetheralkoholen durch katalytische Anlagerung von Alkylenoxiden an H-funktionelle Startsubstanzen, wobei als Katalysatoren Multimetallcyanidverbindungen eingesetzt werden, dadurch gekennzeichnet, daß der Gehalt an den in den basischen und sauren Verunreinigungen in der Startsubstanz und/oder den Alkylenoxiden, welche die Aktivität des Katalysators herabsetzen, enthaltenen Heteroatomen, ausgewählt aus der Gruppe Stickstoff, Phosphor, Arsen, Antimon, Schwefel, Selen, Tellur, Fluor, Chlor, Brom und Iod, jeweils kleiner 100 ppm ist.The invention accordingly relates to a process for the preparation of polyether alcohols by catalytic addition of alkylene oxides onto H-functional starter substances, the catalysts used being multimetal cyanide compounds, characterized in that the content of the basic and acidic impurities in the starter substance and / or the Alkylene oxides, which reduce the activity of the catalyst, contain heteroatoms, selected from the group consisting of nitrogen, phosphorus, arsenic, antimony, sulfur, selenium, tellurium, fluorine, chlorine, bromine and iodine, in each case less than 100 ppm.
Gegenstand der Erfindung ist weiterhin ein Verfahren zur Her- Stellung von Polyetheralkoholen durch katalytische Anlagerung von Alkylenoxiden an H-funktionelle Startsubstanzen, wobei als Katalysatoren Multimetallcyanidverbindungen eingesetzt werden, dadurch gekennzeichnet, daß der Gehalt an den in den basischen und sauren Verunreinigungen in der Startsubstanz und/oder den Alkylenoxiden enthaltenen Heteroatomen, ausgewählt aus der Gruppe Stickstoff, Phosphor, Arsen, Antimon, Schwefel, Selen, Tellur, Fluor, Chlor, Brom und Iod, jeweils kleiner 100 ppm ist und die Startsubstanz und/oder die Alkylenoxide vor der Umsetzung einer Behandlung mit heterogenen Adsorbentien unterzogen werden.The invention furthermore relates to a process for the preparation of polyether alcohols by catalytic addition of alkylene oxides onto H-functional starter substances, multimetal cyanide compounds being used as catalysts, characterized in that the content of the basic and acidic impurities in the starter substance and / or the heteroatoms containing the alkylene oxides, selected from the group consisting of nitrogen, phosphorus, arsenic, antimony, sulfur, selenium, tellurium, fluorine, chlorine, bromine and iodine, in each case less than 100 ppm and the starter substance and / or the alkylene oxides before the implementation of a treatment with heterogeneous adsorbents.
Der Gehalt an Heteroatomen, ausgewählt aus der Gruppe Stickstoff, Phosphor, Arsen, Antimon, Schwefel, Selen, Tellur, Fluor, Chlor, Brom und Iod, welche aus den die eingesetzten Multimetallcyanid- Katalysatoren schädigenden Fremdstoffen in den Edukten stammen, sollte jeweils kleiner 100 ppm, bevorzugt kleiner 50 ppm, besonders bevorzugt kleiner 25 ppm, insbesondere bevorzugt kleiner 10 ppm und speziell bevorzugt kleiner 1 ppm sein. Dabei hängen die erfindungsgemäß bevorzugten Obergrenzen für die in den einzelnen Fremdstoffen enthaltenen Heteroatome natürlich von der schädigenden Potenz dieser Fremdstoffe ab. So sind die Obergrenzen der Gehalte an Heteroatomen, ausgewählt aus der Gruppe Stickstoff, Phosphor, Arsen, Antimon, Schwefel, Selen, Tellur, Fluor, Chlor, Brom und Iod, in Fremdstoffen mit einer stark schädigenden Wirkung jeweils kleiner 25 ppm und bevorzugt kleiner 10 ppm, insbesondere bevorzugt 1 ppm.The content of heteroatoms, selected from the group consisting of nitrogen, phosphorus, arsenic, antimony, sulfur, selenium, tellurium, fluorine, chlorine, bromine and iodine, which originate from the foreign substances in the starting materials which damage the multimetal cyanide catalysts used, should in each case be less than 100 ppm, preferably less than 50 ppm, particularly preferably less than 25 ppm, particularly preferably less than 10 ppm and especially preferably less than 1 ppm. The upper limits preferred according to the invention for the heteroatoms contained in the individual foreign substances naturally depend on the damaging potency of these foreign substances. The upper limits of the heteroatom content are selected from the group consisting of nitrogen, phosphorus, arsenic, antimony, sulfur, selenium, tellurium, Fluorine, chlorine, bromine and iodine, in foreign substances with a strongly damaging effect in each case less than 25 ppm and preferably less than 10 ppm, particularly preferably 1 ppm.
Als starke Katalysatorgifte für Multimetallcyanidverbindungen erweisen sich unter anderem basische Verbindungen, die Amin-, Phosphin- oder Sulfidgruppen enthalten. Die in den Edukten vorhandenen Stickstoff-, Phosphor- oder Schwefelgehalte aus diesen Verbindungen sollten erfindungsgemäß kleiner 25 ppm, bevorzugt kleiner 10 ppm und insbesondere bevorzugt 1 ppm betragen. Geringfügig schwächere Katalysatorgifte für Multimetallcyanidverbindungen sind saure Verbindungen, insbesondere solche, welche Stickstoff, Phosphor, Arsen, Antimon, Sauerstoff, Schwefel, Selen und/oder Halogenatome enthalten. Hier sollten die Gehalte an den entsprechenden Heteroatomen in den Edukten erfindungsgemäß jeweils 100 ppm, bevorzugt 50 ppm, insbesondere bevorzugt 25 ppm, nicht übersteigen.Basic compounds which contain amine, phosphine or sulfide groups have proven to be strong catalyst poisons for multimetal cyanide compounds. The nitrogen, phosphorus or sulfur contents of these compounds present in the starting materials should, according to the invention, be less than 25 ppm, preferably less than 10 ppm and particularly preferably 1 ppm. Slightly weaker catalyst poisons for multimetal cyanide compounds are acidic compounds, in particular those which contain nitrogen, phosphorus, arsenic, antimony, oxygen, sulfur, selenium and / or halogen atoms. According to the invention, the contents of the corresponding heteroatoms in the starting materials should not exceed 100 ppm, preferably 50 ppm, particularly preferably 25 ppm.
Gemäß der Lehre dieser Erfindung werden zur Entfernung von unerwünschten Fremdstoffen aus den Edukten bevorzugt Feststoffe benutzt. Die Verwendung von homogen in den Edukten löslichen "Neutralisatoren", wie in WO 99/14,258 beschrieben, hat den Nachteil, daß sowohl der Fremdstoff als auch die zur Unschädlichmachung zugesetzte Substanz im Produkt verbleiben. Dies kann zur Folge haben, daß sie unter Umständen die Bildung von unerwünschten Nebenprodukten bei der Anlagerung der Alkylenoxide begünstigen oder Anlagenteile schädigen, z.B. in Form von Ablagerungen.According to the teaching of this invention, solids are preferably used to remove undesired foreign substances from the starting materials. The use of "neutralizers" homogeneously soluble in the starting materials, as described in WO 99/14,258, has the disadvantage that both the foreign substance and the substance added to render it harmless remain in the product. This may have the consequence that they may favor the formation of undesired by-products during the addition of the alkylene oxides or damage plant parts, e.g. in the form of deposits.
Verwendet man dagegen heterogene Adsorbentien, so können diese zusammen mit dem adsorbierten Fremdstoff von den Edukten einfach abgetrennt werden. Kontaminationen des Endprodukts mit Fremdstoff oder Adsorbermaterial lassen sich damit ausschließen.If, on the other hand, heterogeneous adsorbents are used, they can simply be separated from the starting materials together with the adsorbed foreign substance. Contamination of the end product with foreign matter or adsorber material can be excluded.
Geeignete heterogene Adsorbentien können jeweils entsprechend dein saurem oder basischen Charakter der in den Ausgangsverbindungen vorhandenen Verunreinigungen ausgewählt werden. Zur Entfernung von Fremdstoffen mit basischem Charakter werden erfindungsgemäß Feststoffe mit sauren Zentren (pKs-Wert der Zentren kleiner 7) verwendet. Solche erfindungsgemäß verwendeten Feststoffe mit sauren Zentren sind unter anderem organische Ionenaustauscher sowie anorganische Materialien, wie Schichtsilikate, Alumo- silikate, Zeolithe sowie andere Mischoxide mit sauren Zentren. Bei den sauren Ionenaustauschern können je nach Stärke des basischen Charakters, entweder stark saure oder schwach saure Ionenaustauscher, verwendet werden. Die verschiedenen Arten von organischen Ionenaustauschern sind in Ullmanns's Encyclopedy of industrial chemistry, 5th rev. Ed. (1989) Band A14, Seite 394 bis 458, beschrieben. Die organischen Ionentauscher basieren auf Polystyrol-, Polyacrylmatrices oder Phenol-Formaldehyd- oder Polyalkyla inharzen. Die stark sauren Ionenaustauscher enthalten in der Regel Sulfonsäuregruppen, während die schwach sauren Ionenaustauscher Carboxylgruppen besitzen.Suitable heterogeneous adsorbents can be selected according to the acidic or basic character of the impurities present in the starting compounds. According to the invention, solids with acidic centers (pKa value of the centers less than 7) are used to remove foreign substances with a basic character. Such solids with acidic centers used according to the invention include organic ion exchangers and inorganic materials such as layered silicates, aluminosilicates, zeolites and other mixed oxides with acidic centers. With the acidic ion exchangers, depending on the strength of the basic character, either strongly acidic or weakly acidic ion exchangers can be used. The different types of organic ion exchangers are described in Ullmanns's Encyclopedy of industrial chemistry, 5 th rev. Ed. (1989) Volume A14, pages 394 to 458. The organic ion exchangers are based on polystyrene, polyacrylic matrices or phenol-formaldehyde or polyalkyl resins. The strongly acidic ion exchangers generally contain sulfonic acid groups, while the weakly acidic ion exchangers have carboxyl groups.
Zur Entfernung von Fremdstoffen mit saurem Charakter werden entsprechend Feststoffe verwendet, die basische Zentren (pKb- Wert der Zentren kleiner 7) besitzen. Dies können unter anderem basische organische Ionenaustauscher, basische Metalloxide, wie Hydrotalcit, dotierte Erdalkalioxide, -carbonate oder -hydroxide, oder basisch gestellte Festkörper, wie sie zum Beispiel durchTo remove foreign substances with an acidic character, solids are used which have basic centers (pKb value of the centers less than 7). These can include basic organic ion exchangers, basic metal oxides, such as hydrotalcite, doped alkaline earth oxides, carbonates or hydroxides, or basic solids, as described, for example, by
Imprägnierung oder Tränkung und anschließender Trocknung und/oder Kalzinierung von metalloxidhaltigen Festkörpern mit Metallsalzen der Gruppen Ia, wie Lithium, Natrium, Kalium, Rubidium oder Cäsium, und Ha, wie Beryllium, Magnesium, Calcium, Strontium oder Barium, des Periodensystems der Elemente erhalten werden können. Je nach saurem Charakter des Fremdstoffes kann bei den basischen organischen Ionenaustauschern ebenfalls zwischen stark und schwach basischen Ionenaustauschern gewählt werden. Die stark basischen Ionenaustauscher, deren Polymermatrix der der sauren Ionenaustauscher entspricht, besitzen in der Regel quarternäre Ammoniumgruppen, während schwach basische Ionenaustauscher Amin- reste als basische Gruppen aufweisen.Impregnation or impregnation and subsequent drying and / or calcination of metal oxide-containing solids with metal salts of groups Ia, such as lithium, sodium, potassium, rubidium or cesium, and Ha, such as beryllium, magnesium, calcium, strontium or barium, of the periodic table of the elements can be obtained can. Depending on the acidic character of the foreign substance, it is also possible to choose between strong and weakly basic ion exchangers for the basic organic ion exchangers. The strongly basic ion exchangers, whose polymer matrix corresponds to that of the acidic ion exchanger, generally have quaternary ammonium groups, while weakly basic ion exchangers have amine residues as basic groups.
Ferner können auch Adsorbentien, wie Aktivkohle, Aluminiumoxide, Siliziumoxide, nicht funktionalisierte Polystyrol-Divinyl- benzol-Polymere, etc, die nicht direkt als saure oder basische Materialien bezeichnet werden können, verwendet werden.Adsorbents, such as activated carbon, aluminum oxides, silicon oxides, non-functionalized polystyrene-divinylbenzene polymers, etc., which cannot be referred to directly as acidic or basic materials, can also be used.
Bei all diesen heterogenen Adsorbentien ist darauf zu achten, daß diese ihrerseits die mit ihnen behandelten Edukte nicht selbst mit Multimetallcyanid-schädigenden Substanzen kontaminieren.With all these heterogeneous adsorbents, care must be taken that they in turn do not themselves contaminate the educts treated with them with substances which damage multimetal cyanide.
Die Behandlung der Edukte mit den heterogenen Adsorbentien kann erfindungsgemäß auf verschiedene Arten erfolgen. Eine bevorzugte Ausführungsform zur Abreicherung der unerwünschten Fremdstoffe aus den Edukten besteht darin, daß die heterogenen Adsorbentien als Betten gepackt werden und die zu behandelnden Edukte über die als Fest-, Wander-, Fließ- oder Schwebebett gepackten Adsorbentien geleitet werden. Die verschiedenen Möglichkeiten zur Ausgestaltung dieses Verfahrens können unter anderem aus Konrad Dorfner, "Ion Exchangers", Walter de Gruyter-Verlag, Berlin, 1991, oder Ullmanns's Encyclopedy of industrial chemistry, 5th rev. Ed. (1989) Band A14, Seite 394 bis 459, entnommen werden.According to the invention, the starting materials can be treated with the heterogeneous adsorbents in various ways. A preferred embodiment for the depletion of the undesirable foreign substances from the starting materials is that the heterogeneous adsorbents are packed as beds and the starting materials to be treated are passed over the adsorbents packed as fixed, moving, moving or floating beds. The various options for designing this method can be found, inter alia, from Konrad Dorfner, "Ion Exchangers", Walter de Gruyter-Verlag, Berlin, 1991, or Ullmanns's Encyclopedy of industrial chemistry, 5 th rev. Ed. (1989) Volume A14, pages 394 to 459.
Zur Abreicherung sowohl der sauren als auch der basischen Fremd- stoffe können die verschiedenen Adsorbentien entweder in ein Bett gepackt oder in verschiedene Betten gepackt nacheinander angeordnet sein.To deplete both the acidic and the basic foreign substances, the various adsorbents can either be packed in a bed or arranged in succession in different beds.
Eine weitere Ausführungsform des erfindungsgemäßen Verfahrens be- steht darin, die Adsorbentien in die Edukte einzurühren und nach einer Rührzeit von wenigen Minuten bis einigen Stunden durch Filtration oder Zentrifugation von den Edukten abzutrennen. Eine spezielle Ausführungsform sieht vor, die Abtrennung der heterogenen Adsorbentien nicht vor der Alkoxylierung, sondern zusammen mit der Abtrennung der Multimetallcyanidverbindung nach derAnother embodiment of the process according to the invention consists in stirring the adsorbents into the starting materials and, after a stirring time of a few minutes to a few hours, separating them from the starting materials by filtration or centrifugation. A special embodiment provides for the separation of the heterogeneous adsorbents not before the alkoxylation, but together with the removal of the multimetal cyanide compound after
Alkoxylierung durchzuführen. Bei dieser speziellen Ausführungsform sollten jedoch die Adsorbentien so gewählt sein, daß negative Einflüsse des heterogenen Adsorbens auf die Multimetallcyanidverbindung ausgeschlossen werden können.Perform alkoxylation. In this special embodiment, however, the adsorbents should be selected so that negative influences of the heterogeneous adsorbent on the multimetal cyanide compound can be excluded.
Gemäß dem oben beschriebenen erfindungsgemäßen Verfahren können sowohl die OH-funktionellen Starter als auch die Alkylenoxide behandelt werden. Für die oft leichterflüchtigen Alkylenoxide bietet sich als Reinigungsstufe aber auch eine Destillation, Extraktion oder Extraktivdestillation an.According to the inventive method described above, both the OH-functional starters and the alkylene oxides can be treated. For the often more volatile alkylene oxides, a distillation, extraction or extractive distillation is also suitable as a purification stage.
Die Abreicherung der basischen oder sauren Verunreinigungen aus den Edukten wird vorzugsweise bei Temperaturen zwischen 10 und 120°C durchgeführt, wobei die Behandlung der Alkylenoxide bei Temperaturen kleiner 25°C erfolgt. Die Drücke liegen vorzugsweise zwischen 1 bar und 10 bar und werden so gewählt, daß das zu behandelnde Edukt während der Abreicherung flüssig vorliegt.The depletion of the basic or acidic impurities from the starting materials is preferably carried out at temperatures between 10 and 120 ° C., the alkylene oxides being treated at temperatures below 25 ° C. The pressures are preferably between 1 bar and 10 bar and are chosen so that the starting material to be treated is in liquid form during depletion.
Verschiedene OH-funktioneile Starter, wie zum Beispiel Glycerin, besitzen bei Raumtemperatur Viskositäten, welche die oben beschriebenen erfindungsgemäßen Abreicherungsverfahren erschweren. In solchen Fällen werden vorzugsweise Methoden angewendet, die eine Absenkung der Viskosität ermöglichen.Various OH-functional starters, such as glycerol, have viscosities at room temperature which make the depletion processes according to the invention described above more difficult. In such cases, methods are preferably used which make it possible to lower the viscosity.
So kann zum Beispiel die Temperatur erhöht werden. Das zu reinigende Edukt kann mit einer inerten, mit ihm mischbaren, gut wieder entfernbaren und die Viskosität senkenden Flüssigkeit verdünnt werden.For example, the temperature can be increased. The educt to be cleaned can be diluted with an inert, miscible, easily removable and viscosity-reducing liquid.
Verwendet man eine Fahrweise, wie sie in WO 97/29,146 beschrieben wird, bei der zu einem vorgelegten Starter ein Starter/Alkylen- oxid-Gemisch zugefahren wird, so wird der vorgelegte Starter nach einem der bereits beschriebenen Verfahren gereinigt. Zur Reinigung des Starters im Alkylenoxid, der sich vom vorgelegten Starter in der Regel unterscheidet, kann man den Gesamtstrom aus Alkylenoxid und Starter mit ein oder mehreren heterogenen Adsorbentien behandeln. Vorteilhaft dabei ist die zeitgleiche Aufreinigung von Starter und Alkylenoxid sowie die Verringerung der Viskosität des Starters.If a procedure is used, as described in WO 97 / 29,146, in which a starter / alkylene oxide mixture is added to a starter, the starter is followed cleaned one of the methods already described. To clean the starter in the alkylene oxide, which generally differs from the starter presented, the total stream of alkylene oxide and starter can be treated with one or more heterogeneous adsorbents. The advantage here is the simultaneous purification of the starter and alkylene oxide and the reduction in the viscosity of the starter.
Ferner kann der Zeitpunkt der Reinigung entsprechend der ver- schiedenen vom Alkoxylierungsgrad abhängigen Viskositäten gewählt werden. So besitzen Glycerinpropoxylate mit Molgewichten von 400 bis 600 Dalton geringere Viskositäten als das Edukt Glycerin selbst. Es kann also sinnvoll sein, anstatt Glycerin die als Starter für die Multimetallcyanid-Katalyse verwendeten Glycerin- propoxylate zu reinigen.Furthermore, the time of cleaning can be selected according to the different viscosities depending on the degree of alkoxylation. For example, glycerol propoxylates with molecular weights of 400 to 600 daltons have lower viscosities than the starting material glycerol itself. Instead of glycerol, it can be useful to clean the glycerol propoxylates used as starters for multimetal cyanide catalysis.
Die Erfindung soll an den nachstehenden Beispielen näher erläutert werden.The invention is illustrated by the examples below.
Beispiel 1example 1
In einem Kolben wurden 3000 g Polypropylenglykol mit einer Molmasse von 400g/mol mit 2,5 Gewichtsprozent Ionenaustauscher des Typs Amberlite® UP252 5 Stunden lang bei Raumtemperatur gerührt. Danach wurde der Ionenaustauscher durch Filtration entfernt. Vor und nach der Behandlung mit Amberlite wurden folgende Kennwerte des Polypropylenglykols ermittelt:In a flask, 3000 g polypropylene glycol were stirred with a molar mass of 400g / mol 2.5 percent by weight of ion exchanger of the type Amberlite ® UP252 for 5 hours at room temperature. The ion exchanger was then removed by filtration. The following characteristics of the polypropylene glycol were determined before and after the treatment with Amberlite:
unbehandelt nach Behandlung Säurezahl, mgKOH/g 0,013 0,061untreated after treatment acid number, mgKOH / g 0.013 0.061
PH-Wert 7,1 5,4PH 7.1 5.4
Alkalität, ppm 3,0 nicht nachweisbarAlkalinity, ppm 3.0 undetectable
Kalium, ppm 0,6 < 0,5Potassium, ppm 0.6 <0.5
Natrium, ppm 2,3 1,4 Stickstoff, ppm 6 3Sodium, ppm 2.3 1.4 nitrogen, ppm 6 3
Chlor, ppm 1 1Chlorine, ppm 1 1
Je 128 g des unbehandelten und des behandelten Polypropylenglykols wurden mit 50 ppm eines Multimetallcyanid-Katalysators (Zinkhexacyanocobaltat) in einen Autoklaven eingefüllt, 2 Stunden lang bei 3 mbar Vakuum entwässert und anschließend mit 72 g Propylenoxid bei 130°C umgesetzt.128 g each of the untreated and the treated polypropylene glycol were introduced into an autoclave with 50 ppm of a multimetal cyanide catalyst (zinc hexacyanocobaltate), dehydrated for 2 hours at 3 mbar vacuum and then reacted with 72 g of propylene oxide at 130 ° C.
Beim unbehandelten Polypropylenglykol hatte nach 4 Stunden noch keine Reaktion eingesetzt. Der Versuch wurde abgebrochen. Die Reaktion sprang bei dem mit Amberlite behandelten Polypropylenglykol nach 8 Minuten an und ein Druckanstieg von 7 auf 13,8 bar wurde registriert. Der volle Austrag von 200 g zeugte von einer 100%igen Umsatz des Polypropylenglykols .In the case of the untreated polypropylene glycol, no reaction had started after 4 hours. The attempt was canceled. The reaction started with the amberlite-treated polypropylene glycol after 8 minutes and a pressure increase from 7 to 13.8 bar was registered. The full discharge of 200 g testified a 100% conversion of the polypropylene glycol.
Beispiel 2Example 2
In einem Kolben wurden 3000 g Polyetheralkohol aus Glycerin und Propylenoxid mit einer Molmasse von 420 g/mol mit 2,5 Gewichts- prozent Ionenaustauscher des Typs Amberlite® UP252 5 Stunden lang 50°C gerührt. Nach der Filtration des Ionenaustauschers wurden folgende Kennwerte des Polyols ermittelt:In a flask, 3000 g of glycerin and propylene oxide polyether alcohol having a molecular weight of 420 g / mol with 2.5 weight percent ion exchange of the type Amberlite ® UP252 5 hours 50 ° C stirred. After filtering the ion exchanger, the following characteristic values of the polyol were determined:
unbehandelt nach Behandlung Säurezahl, mgKOH/g 0,010 0,257untreated after treatment acid number, mgKOH / g 0.010 0.257
PH-Wert 7,9 5,2PH 7.9 5.2
Alkalität, ppm 18,6 nicht nachweisbarAlkalinity, ppm 18.6 undetectable
Kalium, ppm 1,6 < 0,5Potassium, ppm 1.6 <0.5
Natrium 2,5 <0,5 Stickstoff, ppm 6 <1Sodium 2.5 <0.5 nitrogen, ppm 6 <1
Chlor, ppm 2 <1Chlorine, ppm 2 <1
Je 128 g des unbehandelten und des behandelten o.a. Polyetherols wurden mit 100 ppm eines Multimetallcyanid-Katalysators aus Bei- spiel 1 in einen Autoklaven eingefüllt, 2 Stunden lang bei 3 mbar Vakuum entwässert und anschließend mit 72 g Propylenoxid bei 130°C umgesetzt. Die Aktivitätstest ergab folgende Ergebnisse:128 g each of the untreated and the treated o.a. Polyetherols were introduced into an autoclave with 100 ppm of a multimetal cyanide catalyst from example 1, dewatered at 3 mbar vacuum for 2 hours and then reacted with 72 g of propylene oxide at 130 ° C. The activity test gave the following results:
ohne Behandlung nach Behandlungwithout treatment after treatment
Anspringzeit, min 40 5Starting time, min 40 5
Druckmaximum, bar 7,1 11,5Maximum pressure, bar 7.1 11.5
Austrag, g 167 200 Discharge, g 167 200

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von Polyetheralkoholen durch katalytische Umsetzung von H-funktionellen Verbindungen mit Alkylenoxiden, wobei als Katalysator mindestens eine Multi- metallcyanidverbindung eingesetzt wird, dadurch gekennzeichnet, daß der Gehalt an den in den basischen und sauren Verunreinigungen in der Startsubstanz und/oder den Alkylen- oxiden, welche die Aktivität des Katalysators herabsetzen, enthaltenen Heteroatomen, ausgewählt aus der Gruppe Stickstoff, Phosphor, Arsen, Antimon, Schwefel, Selen, Tellur, Fluor, Chlor, Brom und Iod, jeweils kleiner 100 ppm ist.1. Process for the preparation of polyether alcohols by catalytic reaction of H-functional compounds with alkylene oxides, at least one multimetal cyanide compound being used as the catalyst, characterized in that the content of the basic and acidic impurities in the starting substance and / or the Alkylene oxides, which reduce the activity of the catalyst, contain heteroatoms, selected from the group consisting of nitrogen, phosphorus, arsenic, antimony, sulfur, selenium, tellurium, fluorine, chlorine, bromine and iodine, in each case less than 100 ppm.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die H-funktionellen Verbindungen und/oder die Alkylenoxide zur Abreicherung der basischen und sauren Verunreinigungen vor der Umsetzung einer Behandlung mit heterogenen Adsorbentien unterzogen werden.2. The method according to claim 1, characterized in that the H-functional compounds and / or the alkylene oxides for depletion of the basic and acidic impurities are subjected to a treatment with heterogeneous adsorbents before the reaction.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als heterogene Adsorbentien Feststoffe mit basischen oder sauren Zentren eingesetzt werden.3. The method according to claim 1, characterized in that solids with basic or acidic centers are used as heterogeneous adsorbents.
4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als heterogene Adsorbentien organische Ionenaustauscher eingesetzt werden.4. The method according to claim 1, characterized in that organic ion exchangers are used as heterogeneous adsorbents.
5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als heterogene Adsorbentien Schichtsilikate, Alumosilikate, Zeolithe und/oder andere Mischoxide mit basischen oder sauren Zentren eingesetzt werden.5. The method according to claim 1, characterized in that sheet silicates, aluminosilicates, zeolites and / or other mixed oxides with basic or acidic centers are used as heterogeneous adsorbents.
6. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Startsubstanz und die Alkylenoxide vor der Behandlung mit heterogenen Adsorbentien vermischt werden.6. The method according to claim 1, characterized in that the starting substance and the alkylene oxides are mixed with heterogeneous adsorbents before the treatment.
7. Polyetheralkohole, herstellbar nach einem der Ansprüche 1 bis 6. 7. polyether alcohols, producible according to one of claims 1 to 6.
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