WO2004029131A1 - Procede de production d'alcools de polyether - Google Patents

Procede de production d'alcools de polyether Download PDF

Info

Publication number
WO2004029131A1
WO2004029131A1 PCT/EP2003/010155 EP0310155W WO2004029131A1 WO 2004029131 A1 WO2004029131 A1 WO 2004029131A1 EP 0310155 W EP0310155 W EP 0310155W WO 2004029131 A1 WO2004029131 A1 WO 2004029131A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
propylene oxide
oxide
reactor
polyether
Prior art date
Application number
PCT/EP2003/010155
Other languages
German (de)
English (en)
Inventor
Kathrin Harre
Reinhard Lorenz
Raimund Ruppel
Thomas Ostrowski
Edward Bohres
Gerd HÖPPNER
Andreas Hoppe
Anne-Kathrin Merten
Jürgen Winkler
Original Assignee
Basf Aktiengesellschaft
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 Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to AU2003273863A priority Critical patent/AU2003273863A1/en
Publication of WO2004029131A1 publication Critical patent/WO2004029131A1/fr

Links

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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4866—Polyethers having a low unsaturation value
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B01J27/26—Cyanides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—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
    • C08G65/2612—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 aromatic or arylaliphatic hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2663—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
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

Definitions

  • the invention relates to a process for the preparation of polyether alcohols using multimetal cyanide compounds as catalysts.
  • Polyether alcohols are important feedstocks in the production of polyurethanes. They are usually produced by catalytic addition of lower alkylene oxides, in particular ethylene oxide and / or propylene oxide, to H-functional starters.
  • Soluble basic metal hydroxides or salts are mostly used as catalysts, with potassium hydroxide being of the greatest practical importance.
  • a disadvantage of the use of potassium hydroxide as a catalyst is above all that the production of high molecular weight polyether alcohols leads to the formation of unsaturated by-products which reduce the functionality of the polyether alcohols and are very disadvantageously noticeable in the production of polyurethanes.
  • the polyether alcohols produced using multimetal cyanide compounds are distinguished by a very low content of unsaturated constituents.
  • Another advantage of using multimetal cyanide compounds as catalysts is the significantly increased space-time yield during the addition of the alkylene oxides.
  • polyether alcohols differ in their reactivity from otherwise identical polyether alcohols that were produced with other catalysts. This is very troublesome when processing into foams, since every change of the polyether alcohols involves changes in the process of foam production.
  • WO 00/63270 proposes adding small amounts of salts to the polyether alcohol before the reaction with the isocyanates.
  • WO 01/16209 proposes to control the reactivity of the polyether alcohol by adding a propylene oxide end block.
  • these measures also restrict the use of the polyether alcohols.
  • the object of the invention was to provide polyether alcohols catalyzed with multimetal cyanide compounds which have a low content of very high molecular weight fractions. Furthermore, when dosing propylene oxide at the chain end of the polyether alcohols, only a small proportion of primary hydroxyl groups derived from propylene oxide units should form. Furthermore, products with a narrow molecular weight distribution should also be formed when ethylene oxide is added to the chain end.
  • the amount of primary hydroxyl groups present in the reactor during the reaction of free alkylene oxide, in particular propylene oxide which can be controlled by various parameters, in particular catalyst activity, amount of catalyst and metering rate and the content of very high molecular weight components in the polyether alcohol can be influenced. Furthermore, it was found that in the course of the metering, in particular at the end of the reaction and in the course of the so-called post-reaction phase, the content of high molecular weight components and the content of primary hydroxyl groups increased sharply.
  • very high molecular weight is understood below to mean a molecular weight (M ") of more than 3 times the average molecular weight (M w ) of the polyether alcohol.
  • the post-reaction phase describes the period of time which is necessary after the end of the metering in of the alkylene oxides in order to allow free alkylene oxide still present in the reaction mixture to react.
  • the post-reaction phase is ended when the pressure in the reactor is constant.
  • the amount of free alkylene oxide in the reactor during the reaction is preferably less than or equal to 8 6 particularly preferably 5% by weight, in particular 2% by weight, and particularly preferably 0.5% by weight, in each case based on the total amount of the starting materials and reaction products present in the reactor.
  • starting materials are understood to mean the starting substance and the alkylene oxides.
  • Reaction products mean the reaction products of the starting materials located in the reactor.
  • the invention accordingly relates to a process for the preparation of polyether alcohols by polymerizing alkylene oxides with multimetal cyanide compounds as catalysts, characterized in that, at least when the last 10% by weight of alkylene oxide is metered in, based on the total amount of alkylene oxide, the amount of in the reactor free alkylene oxide present is less than or equal to 8, preferably 6 and in particular 5% by weight, in each case based on the total amount of the starting materials and reaction products in the reactor.
  • the invention further relates to polyether alcohols which can be prepared by the process according to the invention and have a functionality of 2 to 8, in particular those with a functionality of 2 to 3 and a hydroxyl number in the range between 20 and 150 mgKOH / g and contain high molecular weight compounds of less than 2% by weight .-%, preferably less than 1 wt .-%, each based on the weight of the polyether alcohol.
  • the invention furthermore relates to polyether alcohols which can be prepared by the process according to the invention, in particular those having an end block of propylene oxide units and containing primary hydroxyl groups derived from propylene oxide units of a maximum of 10%, preferably a maximum of 8% and in particular a maximum of 6%, preferably 5 %, particularly preferably 4%, particularly preferably 3%, and preferably 2%, in each case based on the total number of hydroxyl groups of the polyether alcohol.
  • the polyether alcohols produced by the process according to the invention preferably have a content of very high molecular weight of at most 5% by weight, particularly preferably 4% by weight, particularly preferably 3% by weight, particularly preferably 2% by weight, and particularly preferably 1 wt .-%, each based on the polyether alcohol.
  • the invention further relates to a process for the preparation of polyurethanes by reacting polyisocyanates with compounds having at least two hydrogen atoms reactive with isocyanate groups, characterized in that polyether alcohols which can be prepared by the process according to the invention are used as compounds having at least two hydrogen atoms reactive with isocyanate groups.
  • the amount of free alkylene oxide present in the reactor can be influenced by various parameters, but especially, as stated, by catalyst activity, amount of catalyst and metering rate.
  • the metering is carried out in such a way that the propylene oxide reacts immediately after the metering and thus there is practically no free alkylene oxide in the reactor.
  • the pressure in the reactor can be maintained with inert gases, preferably nitrogen.
  • the amount of free alkylene oxide in the reactor can be measured by different methods.
  • calorimetric determinations for example heat balancing or heat flow calorimetry.
  • the pressure drop after the end of the alkylene oxide metering can also be used as an indirect measure of the amount of free alkylene oxide in the reactor. The higher this is, the greater the amount of free alkylene oxide.
  • the pressure drop is measured using the normal pressure measurement of the reactor.
  • the amount of free alkylene oxide also depends on other boundary conditions, for example the level of the reactor and the solubility of the alkylene oxide in the liquid phase, only a relatively rough estimate is possible here.
  • Another indirect measure of the amount of free alkylene oxide is the duration of the after-reaction to constant pressure or a low value of free alkylene oxide, preferably. 0.2% by weight, based on the total amount of the reactants and reaction products in the reactor.
  • the amount of free alkylene oxide is less than or equal to 8, preferably less than or equal to 5% by weight, particularly preferably less than or equal to 3% by weight, in particular less than or equal to 2 wt .-%, based in each case on the total amount of the reactants and reaction products in the reactor.
  • the pressure drop between the completion of the metering and the completion of the after-reaction phase should be less than or equal to 10, preferably 5, particularly preferably 2 bar, 1 bar and in particular 0.5 bar, and particularly preferably 0.2 bar.
  • the post-reaction time should be less than 60, 40 minutes, preferably less than 20, preferably less than 10, preferably less than 5, and in particular less than 2 minutes.
  • the amount of free alkylene oxide can be in the range according to the invention during the entire metering time. In this case, there is a particularly marked reduction in the high molecular weight content.
  • the metering is only towards the end of the supply of the alkylene oxides, especially during the metering of the last 10% by weight of the alkylene oxide is such that the amount of free propylene oxide is less than or equal to 8% by weight, based on the total amount of the starting materials and reaction products in the reactor.
  • the concentration of the alkylene oxides in the reactor is usually not uniform over the entire volume. In general, the concentration of the alkylene oxides in the area of the metering point is higher than in areas of the reactor which are further away from the metering point. As long as the total concentration of the alkylene oxides, averaged over the entire reactor, is in the range according to the invention, these concentration differences are irrelevant.
  • Propylene oxide and ethylene oxide are preferably used as alkylene oxides.
  • the production process according to the invention regardless of the type of alkylene oxides used, leads to a significant reduction in the high molecular weight proportions in the polyether alcohol.
  • the process according to the invention makes it possible to adjust the content of primary hydroxyl groups in the polyether alcohol and thus the reactivity of the polyether alcohols. Since the formation of primary hydroxyl groups from propylene oxide is suppressed, the amount of ten ethylene oxide, which forms only primary hydroxyl groups, the
  • Amount of primary hydroxyl groups can be set specifically.
  • the process according to the invention can be used to produce polyether alcohols, the chain of which only contains propylene oxide or the end of which is pure propylene oxide.
  • Such polyether alcohols can be used in particular for the production of flexible block foams.
  • a mixture of ethylene oxide and propylene oxide is added at the beginning of the chain or after addition of a pure ethylene oxide or propylene oxide block.
  • a pure propylene oxide block then preferably follows at the chain end. This preferably has a length of 2 to 50% by weight, preferably 5 to 20% by weight and in particular 5 to 15% by weight, in each case based on the total weight of the polyether alcohol.
  • the content of primary hydroxyl groups from ethylene oxide and propylene oxide and secondary hydroxyl groups was determined in the context of the invention by derivatization of the
  • the primary hydroxyl groups from ethylene oxide, the primary hydroxyl groups from propylene oxide and the secondary hydroxyl groups have different peaks.
  • propylene oxide, ethylene oxide or mixtures of ethylene oxide and propylene oxide is formed at the beginning of the chain and a block is formed at the end of the chain
  • the end block made of ethylene oxide preferably has a content of 5 to 50% by weight, in particular 5 to 20% by weight, in each case based on the weight of the polyether alcohol.
  • polyether alcohols have a very narrow molecular weight distribution.
  • Such polyether alcohols are used in particular for the production of flexible molded foams.
  • the mixing ratio of the alkylene oxides can be kept constant during the entire metering time or can be varied both batchwise and continuously during metering, as described in WO 01/44347.
  • the polyether alcohols are prepared by a known method of adding alkylene oxides to H-functional starter substances using multimetal cyanide compounds as catalysts.
  • Alcohols with functionalities in the range between 2 and 8, preferably 2 to 3, are usually used as H-functional starter substances.
  • these are glycols, such as ethylene glycol or propylene glycol, 1,4-butanediol, glycerol or trimethylolpropane. Since low molecular weight alcohols often show a delayed reaction start when reacting with alkylene oxides using multimetal cyanide compounds as catalysts, it is customary to use propoxylates of the alcohols mentioned with a molecular weight in the range between 400 and 1000 as starting substances as starting substances.
  • polymers can be prepared, for example, by conventional addition of the propylene oxide with basic catalysts, the basic catalyst having to be removed thoroughly after the end of the addition, since it deactivates the multimetal cyanide compounds. It is also possible to prepare these polymers using heterogeneous catalysts, as described, for example, in WO 99/44739. Another possibility is to prepare a prepolymer by simultaneously metering in a low molecular weight alcohol and an alkylene oxide, as described in DD-A-203 734.
  • the starting substance is introduced and, if necessary, water and other volatile compounds are removed. This is usually done by distillation, preferably under vacuum.
  • the catalyst may already be present in the starting substance, but it is also possible to add the catalyst only after the starting substance has been treated. In the latter variant, the catalyst is subjected to less thermal stress. As described in WO 98/52689, the stripping can also be carried out in the presence of inert gas.
  • An advantageous embodiment of the method according to the invention consists, at least during part of the
  • part of the starter substance can be initially charged with the catalyst and, after the reaction has started, further starters and alkylene oxide can be fed in continuously up to the desired chain length of the polyether alcohol 5. It is also possible to meter in starters continuously only at the beginning of the addition of the alkylene oxides and then, as usual, to meter in only alkylene oxides up to the desired chain length of the polyether alcohol.
  • the alkylene oxides are then metered in, the addition being carried out in the manner described above.
  • the alkylene oxides are usually added at pressures in the range from 0.01 bar and 20 bar and temperatures in the range from 50 to 200 ° C., preferably 90 to
  • inert gas for example nitrogen
  • an after-reaction follows in order to obtain a
  • the process according to the invention it is advantageous for the process according to the invention to meter the alkylene oxides, in particular the propylene oxide, as slowly as possible in order not to exceed the amount of free propylene oxide in the reactor according to the invention: the amount metered in in each case depends on the amount of the free one Alkylene oxide in the reactor, which, as stated above, can be monitored continuously.
  • the multimetal cyanide compounds used as catalysts for the process according to the invention mostly have the general formula (I)
  • M 1 is a metal ion selected from the group containing Zn2 +,
  • M 2 is a metal ion selected from the group containing Fe2 +,
  • A is an anion selected from the group containing halide
  • X is an anion selected from the group containing halide
  • L is a water-miscible ligand, selected from the group consisting of alcohols, aldehydes, ketones, ethers, polyether esters, ureas, amides, nitriles, and sulfides,
  • a, b, c, d, g and n are selected so that the electro-neutrality of the connection is ensured, where c can be zero, and
  • h is a fractional or whole number greater than or equal to 0.
  • the catalyst is usually obtained in an amount of less than 1% by weight, preferably in an amount of less than 0.5% by weight, particularly preferably in an amount of less than 1000 ppm and in particular in an amount of less than 500 ppm on the weight of the polyether alcohol used.
  • the catalyst is also possible to use 100 ppm, 50 ppm or less.
  • the reaction can be carried out continuously or preferably batchwise. After the reaction has ended, the unreacted monomers and volatile compounds can be removed from the reaction mixture, usually by means of distillation. Usually, the polyether alcohols are added with customary antioxidants and / or stabilizers after their production.
  • the catalyst can remain in the polyether alcohol since it does not interfere with the further processing of the polyether alcohols to give polyurethanes.
  • the polyether alcohols produced by the process according to the invention are mostly used for the production of polyurethanes.
  • Preferred areas of application are the production of elastomers, for example thermoplastic elastomers, and the production of polyurethane foams, in particular rigid polyurethane foams and flexible polyurethane foams.
  • the flexible polyurethane foams can be molded foams and preferably block foams, also referred to as slabstock foams. With these foam Substances are particularly dependent on well-coordinated reactivity. While a reactivity that is too low can usually be compensated for in the formulation, this is difficult with a reactivity that is too high, such as is caused by an excessively high content of primary hydroxyl groups. If the reactivity is too high, the foams will shrink undesirably.
  • a low reactivity of the polyether alcohols is also desirable in the production of rigid polyurethane foams. This is intended to ensure that when cavities are foamed, for example in the case of cooling devices or ro-jackets, the liquid reaction mixture reaches the entire area to be foamed, as long as the reaction mixture is still flowable.
  • the polyether alcohols suitable for the production of flexible polyurethane foams preferably have a functionality of 2 to 3, a hydroxyl number in the range between 20 and 150, preferably 30 to 70 mgKOH / g and are preferably composed of propylene oxide, optionally mixtures of propylene oxide and ethylene oxide.
  • those polyether alcohols which contain ethylene oxide in the interior of the polyether chain, as a pure block or preferably in a mixture with propylene oxide, and at the chain end a pure block of propylene oxide.
  • such polyether alcohols can also be used as starting substances for the production of high molecular weight polyether alcohols.
  • the polyether alcohols suitable for the production of rigid polyurethane foams mostly have a functionality in the range between 3 and 8 and a hydroxyl number in the range between 150 and 800 mgKOH / g.
  • polyether alcohols with low molecular weights in particular those with a functionality in the range between 2 and 8, preferably 2 and 4, particularly preferably 2 and 3 and a hydroxyl number in the range between 150 and 500 mgKOH / g, manufactured.
  • the addition is carried out in such a way that, in addition to the continuous metering of the alkylene oxides, there is also a continuous metering of at least part of the starting substance.
  • the products produced according to this embodiment of the method according to the invention are distinguished by a particularly narrow molecular weight distribution.
  • very high molecular weight also means a molecular weight (M w ) of more than 3 times the average molecular weight (M- of the polyether alcohol).
  • Such low molecular weight products can be used, for example, for the production of rigid polyurethane foams or as starting substances for the production of high molecular weight polyether alcohols by further addition of alkylene oxides, in particular using DMC catalysts.
  • the process according to the invention has the advantage that it can be carried out in any plant for the production of polyether alcohols without additional effort.
  • the resulting polyether alcohols are characterized by a low content of primary hydroxyl groups, which are derived from propylene oxide, and a low content of fractions with a very high molecular weight.
  • the polyether alcohols produced by the process according to the invention also contain less volatile components than polyether alcohols produced by conventional processes.
  • the volatile constituents are very undesirable as odor carriers in polyether alcohols, since a strong smell of the polyurethanes produced from the polyether alcohols is perceived as a poor quality.
  • the polyether alcohols produced by the process according to the invention are mostly used for the production of polyurethanes by reaction with polyisocyanates, usually in the presence of catalysts and, in the case of the production of polyurethane foams, in the presence of blowing agents. Further possible uses of the polyether alcohols produced by the process according to the invention are surfactants and carrier oils.
  • isocyanates with two or more isocyanate groups in the molecule can be used as polyisocyanates.
  • Both aliphatic isocyanates such as hexamethylene diisocyanate (HDI) or isophorone diisocyanate (IPDI), or preferably aromatic isocyanates, such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) or mixtures of diphenylmethane diisocyanate and Polymethylene polyphenylene polyisocyanates (raw MDI) can be used.
  • TDI tolylene diisocyanate
  • MDI diphenylmethane diisocyanate
  • MDI diphenylmethane diisocyanate
  • raw MDI Polymethylene polyphenylene polyisocyanates
  • isocyanates which, through the incorporation of uretane, uretdione, isocyanurate, allophanate,
  • TDI is used in particular for the production of flexible flexible foams, while MDI and its higher homologues are preferably used in the production of molded foams.
  • Raw MDI is mostly used in the production of rigid foams.
  • polyether polyols In a mixture with the polyether alcohols produced by the process according to the invention, further compounds having at least two hydrogen atoms reactive with isocyanate groups, preferably polyols, can be used.
  • polyols the polyether polyols and the polyester polyols have the greatest technical importance.
  • the polyether polyols used for the production of polyurethanes are mostly produced by base-catalyzed addition of alkylene oxides, in particular ethylene oxide and / or propylene oxide, onto H-functional starter substances.
  • Polyester polyols are mostly produced by esterification of polyfunctional carboxylic acids with polyfunctional alcohols.
  • the compounds with at least two groups reactive with isocyanate groups also include the chain extenders and / or crosslinking agents, which can optionally also be used. These are at least two-functional amines and / or alcohols with molecular weights in the range from 60 to 400.
  • the blowing agent used is mostly water and, at the reaction temperature of the urethane reaction, gaseous compounds which are inert to the starting materials of the polyurethanes, so-called physically acting blowing agents, and mixtures thereof.
  • Hydrocarbons with 2 to 6 carbon atoms, halogenated hydrocarbons with 2 to 6 carbon atoms, ketones, acetals, ethers, inert gases such as carbon dioxide or noble gases are used as physical blowing agents.
  • Amine compounds and / or metal compounds are preferably used as catalysts.
  • known tertiary amines and / or with organic metal compounds are used as catalysts.
  • the catalysts can be used individually or in the form of mixtures. Auxiliaries and / or additives are, for example
  • the polyurethanes can be produced by the so-called one-shot process or by the prepolymer process.
  • the flexible polyurethane foams can be block foams as well as molded foams.
  • the synthesis was carried out in a cleaned and dried 25-1 stirred autoclave.
  • the amounts of prepolymer given in Table 1 were added to the stirred tank and 50 ppm of a multimetal cyanide compound, prepared from zinc acetate and hexacyanocobaltoic acid in the presence of a surface-active agent, were added.
  • the contents of the kettle were rendered inert with nitrogen and treated in vacuo for a total of 1 hour at 120 ° C.
  • the indicated amounts of alkylene oxides were metered in at 120 ° C. using the metering rates given in the table. After the metering had ended, stirring was continued until the pressure was constant and then the reaction mixture was degassed at 105 ° C. and 10 mbar. Samples were taken from the reactor using gas-tight locks.
  • the respective free propylene oxide content was determined by heat balancing.
  • the characteristic values of the resulting polyether alcohols can also be found in the table.
  • the characteristic values were determined using the following methods:
  • the viscosity given in the examples was measured analogously to DIN 53 015.
  • the OH number was determined in accordance with DIN 51 562.
  • the content of primary hydroxyl groups from ethylene oxide and propylene oxide was determined by derivatizing the hydroxyl groups of the polyether alcohol with trichloroacetyl isocyanate and subsequent measurement using a BRUKER DPX 250 NMR spectrometer with a 5 mm z-shielded inverted probe head.
  • the primary hydroxyl groups from ethylene oxide, the primary hydroxyl groups from propylene oxide and the secondary hydroxyl groups have different peaks.
  • the percentage of volatile constituents was determined by means of gas chromatography.
  • the proportion of high molecular weight components was determined by GPC.
  • a device system consisting of a liquid chromatograph HP 1090 with an RI detector HP 1047A, an autosampler HP 79847 A and an evaluation unit is used for this.
  • the separation is carried out on 3 PL-gel columns (2 x 3 ⁇ m Mixed E, 1 x 5 ⁇ 50 ⁇ ).
  • Tetrahydrofuran is used as the eluent.
  • the high molecular weight fraction is defined as greater than 3 x M (w).
  • the elution volume is determined from the molar mass calibration, which corresponds to 3 x M (w).
  • a PEG standard with a molecular weight of 6000 g / mol was measured in various concentrations.
  • the function concentration f (area) was used to evaluate the high molecular weight fraction.
  • the resulting soft foam block was crack-free and open-celled and had a good foam structure.
  • polystyrene resin BASF Aktiengesellschaft, 0.4 parts by weight of diet anolamine and 2 parts by weight of water were combined to form a polyol component.
  • This polyol component was made with a prepolymer containing NCO groups and based on MDI with an NCO content of 27% by weight.
  • the polyol component tended to phase separate and had to be stirred intensively before the reaction.
  • the resulting foam showed inhomogeneities and hardening.
  • the loss factor according to ISO 7626 was strong and was below 0.2.
  • the polyol component was phase stable.
  • the resulting foam had a uniform foam structure and a density of 55 kg / m 3 .
  • the loss factor according to ISO 7626 was 0.52.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Toxicology (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyethers (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un procédé pour produire des alcools de polyéther par polymérisation catalytique d'oxydes d'alkylène. L'invention est caractérisée en ce que l'oxyde d'alkylène contient de l'oxyde de propylène, au moins un composé de cyanure polymétallique sert de catalyseur, la teneur en oxyde d'alkylène libre se trouvant dans le réacteur est inférieure ou égale à 8 % en poids relativement à la quantité totale des produits de départ et des produits de la réaction contenus dans le réacteur.
PCT/EP2003/010155 2002-09-23 2003-09-12 Procede de production d'alcools de polyether WO2004029131A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003273863A AU2003273863A1 (en) 2002-09-23 2003-09-12 Method for producing polyether alcohols

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10244283A DE10244283A1 (de) 2002-09-23 2002-09-23 Verfahren zur Herstellung von Polyetheralkoholen
DE10244283.5 2002-09-23

Publications (1)

Publication Number Publication Date
WO2004029131A1 true WO2004029131A1 (fr) 2004-04-08

Family

ID=31969450

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2003/010155 WO2004029131A1 (fr) 2002-09-23 2003-09-12 Procede de production d'alcools de polyether

Country Status (3)

Country Link
AU (1) AU2003273863A1 (fr)
DE (1) DE10244283A1 (fr)
WO (1) WO2004029131A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1818353A1 (fr) * 2006-02-14 2007-08-15 Clariant International Ltd. Huiles à base de lubrifiant polyalkylène-glycol dotées d'une répartition précise de la masse moléculaire
EP2115032B2 (fr) † 2007-01-30 2014-10-22 Basf Se Procédé de production de polyéthercarbonate polyols
WO2017032768A1 (fr) * 2015-08-26 2017-03-02 Covestro Deutschland Ag Procédé de production de polyalkylène polyols à poids moléculaire élevé
CN111183169A (zh) * 2017-11-06 2020-05-19 国际壳牌研究有限公司 用于制备具有高环氧乙烷含量的聚醚多元醇的方法
RU2793131C2 (ru) * 2017-11-06 2023-03-29 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Способ получения простого полиэфирполиола с высоким содержанием этиленоксида

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004028769A1 (de) * 2004-06-16 2005-12-29 Basf Ag Verfahren zur Herstellung von Polyetheralkoholen und Polyurethanen
EP3098251A1 (fr) * 2015-05-26 2016-11-30 Covestro Deutschland AG Utilisation d'alcools, comprenant au moins deux groupes uréthane, destinés à la production de polyols de polyéther

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6083420A (en) * 1997-02-25 2000-07-04 Bayer Antwerp N.V. Method for decreasing the propensity for phase-out of the high molecular weight component of double metal cyanide-catalyzed high secondary hydroxyl polyoxypropylene polyols
WO2001016209A1 (fr) * 1999-08-31 2001-03-08 Basf Aktiengesellschaft Alcools de polyether

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6083420A (en) * 1997-02-25 2000-07-04 Bayer Antwerp N.V. Method for decreasing the propensity for phase-out of the high molecular weight component of double metal cyanide-catalyzed high secondary hydroxyl polyoxypropylene polyols
WO2001016209A1 (fr) * 1999-08-31 2001-03-08 Basf Aktiengesellschaft Alcools de polyether

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1818353A1 (fr) * 2006-02-14 2007-08-15 Clariant International Ltd. Huiles à base de lubrifiant polyalkylène-glycol dotées d'une répartition précise de la masse moléculaire
EP2115032B2 (fr) † 2007-01-30 2014-10-22 Basf Se Procédé de production de polyéthercarbonate polyols
WO2017032768A1 (fr) * 2015-08-26 2017-03-02 Covestro Deutschland Ag Procédé de production de polyalkylène polyols à poids moléculaire élevé
US10457775B2 (en) 2015-08-26 2019-10-29 Covestro Deutschland Ag Method for producing high molecular weight polyoxyalkylene polyols
CN111183169A (zh) * 2017-11-06 2020-05-19 国际壳牌研究有限公司 用于制备具有高环氧乙烷含量的聚醚多元醇的方法
RU2793131C2 (ru) * 2017-11-06 2023-03-29 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Способ получения простого полиэфирполиола с высоким содержанием этиленоксида
CN111183169B (zh) * 2017-11-06 2023-07-04 国际壳牌研究有限公司 用于制备具有高环氧乙烷含量的聚醚多元醇的方法

Also Published As

Publication number Publication date
DE10244283A1 (de) 2004-04-01
AU2003273863A1 (en) 2004-04-19

Similar Documents

Publication Publication Date Title
EP1797129B1 (fr) Procede pour produire des mousses souples de polyurethane
EP1799735B1 (fr) Procede pour produire des mousses souples de polyurethane
EP1240236B1 (fr) Procede de production de polyether-alcools
EP1685179A1 (fr) Procede de production d'alcools de polyether
EP1208132B1 (fr) Alcools de polyether
WO2003042281A1 (fr) Procede de production d'alcools de polyether
WO2001053381A1 (fr) Procede pour la production d'alcools de polyether
WO2004096746A1 (fr) Composes initiaux destines a la production de polyurethanes
WO2004029131A1 (fr) Procede de production d'alcools de polyether
EP1516007B1 (fr) Procede de production de polyether-alcools
EP1230289B1 (fr) Procede de preparation de polyols a mousse souple en bloc
EP1175454B1 (fr) Procede de preparation de polyurethanes
EP1240235B1 (fr) Procede de fabrication de polyether polyols
WO2005014685A1 (fr) Procede pour produire des polyether-alcools
WO2003014190A1 (fr) Procede de production de mousses souples de polyurethanne
DE10210125A1 (de) Verfahren zur Herstellung von hochfunktionellen Polyetheralkoholen
DE4122872A1 (de) Formschaumstoffe
DE19700944A1 (de) Polyetherpolyolgemisch sowie Verfahren zu seiner Herstellung
DE19908613A1 (de) Verfahren zur Herstellung von Polyetherpolyol-Vorpolymeren sowie Polyetherpolyolen für ein breites Einsatzspektrum

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP