EP1233996A1 - Verfahren zur herstellung von polyetheralkoholen - Google Patents

Verfahren zur herstellung von polyetheralkoholen

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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
Authority
EP
European Patent Office
Prior art keywords
ppm
basic
alkylene oxides
acidic
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Withdrawn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
EP00966099A
Other languages
German (de)
English (en)
French (fr)
Inventor
Eva Baum
Georg Heinrich Grosch
Kathrin Harre
Jürgen Winkler
Thomas Ostrowski
Gerd Hoeppner
Els Paredis
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.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1233996A1 publication Critical patent/EP1233996A1/de
Withdrawn legal-status Critical Current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
    • C08G65/2642—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.

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Toxicology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyethers (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP00966099A 1999-10-12 2000-10-02 Verfahren zur herstellung von polyetheralkoholen Withdrawn EP1233996A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19949092A DE19949092A1 (de) 1999-10-12 1999-10-12 Verfahren zur Herstellung von Polyetheralkoholen
DE19949092 1999-10-12
PCT/EP2000/009629 WO2001027186A1 (de) 1999-10-12 2000-10-02 Verfahren zur herstellung von polyetheralkoholen

Publications (1)

Publication Number Publication Date
EP1233996A1 true EP1233996A1 (de) 2002-08-28

Family

ID=7925330

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00966099A Withdrawn EP1233996A1 (de) 1999-10-12 2000-10-02 Verfahren zur herstellung von polyetheralkoholen

Country Status (12)

Country Link
EP (1) EP1233996A1 (cs)
JP (1) JP2003511533A (cs)
CN (1) CN1378571A (cs)
AR (1) AR025992A1 (cs)
AU (1) AU7661000A (cs)
BR (1) BR0014701A (cs)
CA (1) CA2387155A1 (cs)
CZ (1) CZ20021287A3 (cs)
DE (1) DE19949092A1 (cs)
HU (1) HUP0203083A2 (cs)
PL (1) PL355605A1 (cs)
WO (1) WO2001027186A1 (cs)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE334992T1 (de) 2001-04-30 2006-08-15 Univ Michigan Isoretikuläre organometallische grundstrukturen, verfahren zu deren bildung und systematische entwicklung von deren porengrösse und funktionalität, mit anwendung für die gasspeicherung
US20030078311A1 (en) 2001-10-19 2003-04-24 Ulrich Muller Process for the alkoxylation of organic compounds in the presence of novel framework materials
US6806348B2 (en) * 2003-02-11 2004-10-19 Basf Corporation Process for removing and regenerating a double metal cyanide (DMC) catalyst from a polymer polyol
EP1633760B1 (en) 2003-05-09 2010-05-05 The Regents of The University of Michigan MOFs with a high surface area and methods for producing them
DE10324998A1 (de) * 2003-06-03 2004-12-23 Basf Ag Herstellung von Polyetheralkoholen unter Verwendung der DMC-Katalyse
DE102004013408A1 (de) * 2004-03-18 2005-10-06 Basf Ag Polyetheralkohole und Verfahren zur Herstellung von Polyetheralkoholen zur Polyurethansynthese
US7300993B2 (en) * 2004-06-03 2007-11-27 Shell Oil Company Process for the preparation of polyether polyols
KR101227824B1 (ko) 2004-10-22 2013-01-30 더 리젠츠 오브 더 유니버시티 오브 미시간 공유 결합 유기물의 골격구조들 및 폴리헤드라
CN101151091B (zh) 2005-04-07 2010-06-23 密歇根大学董事会 具有敞开的金属部位的微孔金属有机构架中的气体高吸附
US7799120B2 (en) 2005-09-26 2010-09-21 The Regents Of The University Of Michigan Metal-organic frameworks with exceptionally high capacity for storage of carbon dioxide at room-temperature
PL1988996T3 (pl) 2006-02-28 2018-01-31 Univ Michigan Regents Otrzymywanie szkieletów zeolitu z grupami funkcyjnymi
JP7719411B1 (ja) * 2024-07-12 2025-08-06 Ａｇｃ株式会社 ポリエーテル化合物の製造方法
EP4737503A1 (en) * 2024-07-12 2026-05-06 Agc Inc. Method for producing polyether compound, method for producing polyether compound having reactive silicon group, method for producing polyether compound having urethane bond, and method for producing polyether compound having polymerizable unsaturated group

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69306607D1 (de) * 1992-02-20 1997-01-30 Arco Chem Tech Reinigung von niedrigem Alkylenoxyd
US5235075A (en) * 1992-12-10 1993-08-10 The Dow Chemical Company Purification of propylene oxide
US6077978A (en) * 1997-09-17 2000-06-20 Arco Chemical Technology L.P. Direct polyoxyalkylation of glycerine with double metal cyanide catalysis
CA2367867A1 (en) * 1999-03-16 2000-09-21 Shell Internationale Research Maatschappij B.V. Process for the purification of propylene oxide

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0127186A1 *

Also Published As

Publication number Publication date
BR0014701A (pt) 2002-06-18
PL355605A1 (en) 2004-05-04
HUP0203083A2 (en) 2002-12-28
AR025992A1 (es) 2002-12-26
CN1378571A (zh) 2002-11-06
CA2387155A1 (en) 2001-04-19
CZ20021287A3 (cs) 2002-07-17
WO2001027186A1 (de) 2001-04-19
DE19949092A1 (de) 2001-04-19
JP2003511533A (ja) 2003-03-25
AU7661000A (en) 2001-04-23

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