CA2385085A1 - Method for producing flexible block foam polyols - Google Patents
Method for producing flexible block foam polyols Download PDFInfo
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- CA2385085A1 CA2385085A1 CA002385085A CA2385085A CA2385085A1 CA 2385085 A1 CA2385085 A1 CA 2385085A1 CA 002385085 A CA002385085 A CA 002385085A CA 2385085 A CA2385085 A CA 2385085A CA 2385085 A1 CA2385085 A1 CA 2385085A1
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- ethylene oxide
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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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
-
- 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
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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
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/005—< 50kg/m3
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to polyether alcohols that are produced by a ring- opening polymerization of ethylene oxide and at least one alkylene oxide wit h at least 3 carbon atoms in the molecule to H-functional starting substances. The inventive method is further characterized in that ethylene oxide or a mixture of ethylene oxide and at least one alkylene oxide with at least 3 carbon atoms in the molecule with an ethylene oxide content of at least 98 % , based on the mixture, is added to the starting substance in an amount of maximally 40 % by weight, based on the weight of the polyether alcohol. At least one alkylene oxide with at least 3 carbon atoms in the molecule or a mixture of ethylene oxide and at least one alkylene oxide with at least 3 carbon atoms in the molecule and an ethylene oxide content of maximally 20 % by weight, based on the mixture, is added.
Description
METHOD FOR PRODUCING FLEXIBLE BLOCK FOAM POLYOLS
The present invention relates to a process for preparing polyether alcohols, to the polyether alcohols prepared by this process and to their use for producing polyurethanes.
Polyether alcohols are used in large quantities for producing polyurethanes. They are usually prepared by catalytic addition of lower alkylene oxides, in particular ethylene oxide and propylene oxide, onto H-functional initiator substances. Catalysts used are usually basic metal hydroxides or salts, with potassium hydraxide having the greatest practical importance.
The alkylene oxides are usually added on as a block or as a random mixture. In the blockwise molecular addition, only one alkylene oxide at a time is added on, while in the random molecular addition, a mixture of alkylene oxides is present in the reaction mixture.
In the industry, ethylene oxide and propylene oxide axe usually used as alkylene oxides, since they are readily available and inexpensive. The reactivity of ethylene oxide is higher than that of propylene oxide, so that the molecular addition of ethylene oxide proceeds at a higher reaction rate. To increase the space-time yield in the preparation of polyether alcohols it would be desirable for the proportion of ethylene oxide in the polyether alcohol to be as high as possible. Provision of polyether alcohols which are intended for use in flexible foams with terminal ethylene oxide blocks is known and customary. The associated increase in the number of primary hydroxyl groups in the polyether alcohols results in an increase in their reactivity in the reaction with polyisocyanates. However, the increase in the ethylene oxide content of the polyether alcohol also results in an increase in the hydrophilicity of the polyether alcohol, which can lead, inter alia, to undesirable gel formation in the polyether alcohols.
Furthermore, in the synthesis of polyether alcohols having long chains, as are used for producing flexible polyurethane foams, increasing chain growth is associated with secondary reactions which lead to defects in the chain structure. These by-products are referred'to as unsaturated constituents and lead to a deterioration in the properties of the resulting polyurethanes.
Many attempts have therefore been made in the past to prepare polyether alcohols having a low content of unsaturated constituents. In particular, the alkoxylation catalysts used have , ~05~/50735 CA 02385085 2002-03-15 been altered in a targeted way in an attempt to achieve this.
Thus, EP-A-268 922 proposes using cesium hydroxide. Although this enables the content of unsaturated constituents to be reduced, cesium hydroxide is expensive and disposing of it is problematical.
Furthermore, the use of multimetal cyanide complexes, usually zinc hexacyanometalates, also known as DMG catalysts, for preparing polyether alcohols having low contents of unsaturated IO constituents is also known. There is a large number of documents in which the preparation of such compounds is described. Thus, DD-A-203 735 and DD-A-203 734 describe the preparation of polyetherols using zinc hexacyanocobaltate.
I5 The preparation of the zinc hexacyanometalates is also known.
These catalysts are usually prepared by reacting solutions of metal salts such as zinc chloride with solutions of alkali metal or alkaline earth metal cyanometalates, e.g. potassium hexacyanocobaltate. A water-miscible, heteroatom-containing 20 component is generally added to the resulting suspension immediately after the precipitation step. This component can also be present initially in one or both starting solutions. This water-miscible, heteroatom-containing component can be, for example, an ether, polyether, alcohol, ketone or a mixture 25 thereof. Such processes are described, for example, in US
3,278,457, US 3,278,458, US 3,278,459, US 3,427,256, US
3,427,334, US 3,404,109.
Polyether alcohols used fox producing flexible slabstock foams 30 generally have a complete propylene oxide inner block which can make up as much as 40% by weight of the total polyol bound directly to the initiator substance and on this propylene oxide inner block have mixed blocks of propylene oxide and ethylene oxide which make up at least 60% by weight of the total polyol 35 and contain at least 2% by weight of ethylene oxide. These polyols are generally prepared using basic catalysts.
WO-A-97/27,236 describes the preparation of a flexible slabstock foam~polyol in which at least one propylene oxide inner block is added on using multimetal cyanides as catalyst. However, this 40 process does not permit a further increase in the ethylene oxide content of the polyether alcohol without the abovementioned disadvantages.
It is an object of the present invention to develop polyether alcohols which have a high ethylene oxide content without there being a significant increase in the hydrophilicity of the product.
We have found that this object is achieved by a polyether alcohol which can be prepared by ring-opening polymerization of ethylene oxide and alkylene oxides having at least 3 carbon atoms, which comprises an inner block of ethylene oxide or a mixture of ethylene oxide and alkylene oxides having at least 3 carbon atoms, and attached to this a block comprising at least one alkylene oxide having at least 3 carbon atoms or a mixture of ethylene oxide and alkylene oxides having at least 3 carbon atoms, preferably propylene oxide, where the mixed blocks preferably contain at least 2% by weight and not more than ZO% by weight of ethylene oxide, based on the mixture.
The present invention accordingly provides polyether alcohols which can be prepared by ring-opening polymerization of ethylene oxide and propylene oxide onto H-functional initiator substances, wherein not more than 40% by weight, based on the weight of the polyether alcohol, of ethylene oxide or a mixture of ethylene oxide and alkylene oxides having at least 3 carbon atoms, where the mixture has an ethylene oxide content of at least 98% by weight, based on the mixture, is added onto the initiator substance and subsequently at least one alkylene oxide having at least 3 carbon atoms or a mixture of ethylene oxide and at least one alkylene oxide having at least 3 carbon atoms, where the mixture has a maximum ethylene oxide content of 20% by weight, based on the mixture, is added on.
If a mixture of ethylene oxide and at least one alkylene oxide having at least 3 carbon atoms is added on, the content of ethylene oxide should be at least 0.5% by weight, based on the mixture.
As alkylene oxides having at least 3 carbon atoms in the molecule, preference is given to using propylene oxide, butylene oxide and isobutylene oxide and also any mixtures of at least two of the alkylene oxides mentioned, particularly preferably propylene oxide.
In a preferred embodiment of the present invention, ethylene oxide can be added onto the polyether alcohol at the end of the chain, i.e. after the molecular addition of the alkylene oxides having at least 3 carbon atoms or of the mixture of ethylene oxide and alkylene oxides having at least 3 carbon atoms. The ~~ 005/50735 CA 02385085 2002-03-15 amount of this ethylene oxide added onto the end of the chain is preferably not more than 15% by weight, based on the weight of the polyether alcohol. Such polyether alcohols are preferably used for producing cold-cure polyurethane foams. Polyether alcohols of the present invention without this ethylene oxide end block are preferably used for producing flexible polyurethane foams, in particular flexible slabstock foams.
It has surprisingly been found that the hydrophilicity of the polyether alcohols of the present invention is significantly lower than that of conventional polyether alcohols containing the same amount of ethylene oxide in the polyether chain but having a different distribution of alkylene oxides in the chain.
The present invention further provides a process for preparing the above-described polyether alcohols. The polyether alcohols of the present invention are prepared by ring-opening polymerization of the alkylene oxides ethylene oxide and the alkylene oxides having at least 3 carbon atoms onto H-functional initiator substances in the presence of catalysts.
In a preferred embodiment of the process of the present invention, the molecular addition of the total amount of alkylene oxide is carried out in the presence of basic catalysts. Basic catalysts which can be used are, for example, amines, basic salts, metal oxides and metal hydroxides. Preference is given to using alkali metal and/or alkaline earth metal hydroxides. In industry, potassium hydroxide is usually used.
In a further preferred embodiment of the process of the present invention, multimetal cyanides, frequently also referred to as DMC catalysts, are used as catalyst for the molecular addition of the alkylene oxides. The advantages of using these catalysts are firstly the higher reaction rate in the molecular addition of the alkylene oxides and secondly the fact that the polyether alcohols prepared in this way have a lower content of unsaturated constituents. However, this embodiment has the disadvantage that there can be a delayed start of the reaction at the beginning when using DMC catalysts.
In further preferred embodiments of the process of the present invention, the various sections of the polyether chain are added on using different catalysts. Thus, it is advantageous to add on an ethylene oxide block at the beginning of the chain using basic catalysts and to add on the subsequent block consisting entirely or predominantly of alkylene oxides having at least 3 carbon atoms using DMC catalysts. The ethylene oxide block which may, if desired, be present at the end of the chain can likewise be added on by means of DMC catalysts, but preferably by means of basic catalysts. This procedure has the advantage that the delay which frequently occurs at the start of the reaction when using 5 multimetal cyanide catalysts is avoided. This is balanced by increased costs due to the additional purification step.
When using different catalysts, it may be necessary to purity the polyether alcohol to remove catalyst prior to changing the catalysts. Particularly when changing from basic catalysts to DMC
catalysts, a thorough purification is usually carried out because traces of the basic catalyst, in particular the alkali metal hydroxides customarily used, can poison the DMC catalyst.
The invention further provides polyurethanes which can be produced by reacting polyisocyanates with compounds having at least two hydrogen atoms which are reactive toward isocyanate groups, wherein the polyether alcohols of the present invention are used as compounds having at least two hydrogen atoms which are reactive toward isocyanate groups. The polyether alcohols of the present invention are preferably used for producing flexible polyurethane foams, with the polyether alcohols without a terminal ethylene oxide block being used, in particular, for producing slabstock foams and not-cure molded foams and the polyether alcohols having a terminal ethylene oxide block being used, in particular, for producing cold-cure molded foams.
As initiator substances for preparing the polyetherols of the present invention, use is made of the customary polyfunctional alcohols having from 2 to 8 hydroxyl groups in the molecule. In particular, 2- and/or 3-functional alcohols, for example ethylene glycol, propylene glycol, glycerol or trimethylolpropane, are used for preparing polyether alcohols as are customarily used for producing flexible polyurethane foams.
The polyether alcohols of the present invention preferably have a molecular weight in the range from 1000 to 100,000.
Alkylene oxides used are, as indicated above, ethylene oxide and alkylene oxides having at least 3 carbon atoms, in the abovementioned ratios.
The multimetal cyanides used as catalysts in the process of the present invention usually have the formula (I) MZa[P'IZ(CN)b(A)c~d ' fMlgXn ~ h(H2C?) ~ eL (I).
where M1 is a metal ion selected from the group consisting of Znz+, Fez+, Co3+, Niz+, Mnz+, Coz+, Snz+, Pbz+, Mo4+, Mo6+, A13+, V4+, V5+, Srz+, W4+, W6+, Crz+, Cr3+, Cdz+, _.
M2 is a metal ion selected from the group consisting of Fez+, Fe3+, Coz+, Co3+, Mnz+, Mn3+, V4+, VS+, Crz+, Cr3+, Rh3+, Ruz+, Ir3+
and M1 and Mz are identical or different, A is an anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate and nitrate, X is an anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate and nitrate, L is a water-miscible ligand selected from the group consisting of alcohols, aldehydes, ketones, ethers, polyethers, esters, ureas, amides, nitriles and sulfides, and a, b, c, d, g and n are selected so that the compound is electrically neutral, and a is the coordination number of the ligand, f is a fraction or integer greater than or equal to 0 and h is a fraction or integer greater than or equal to 0.
These compounds are prepared by generally known methods by combining the aqueous solution of a water-soluble metal salt with the aqueous solution of a hexacyanometalate compound, in particular a salt or an acid, and adding a water-soluble ligand thereto during or after the mixing of the solutions.
Owing to their high activity, the multimetal cyanide compounds are very well suited to the synthesis of the polyether alcohols of the present invention. The catalyst concentrations used are less than 1~ by weight, preferably less than 0.5~ by weight, particularly preferably less than 1000 ppm, in particular less .~ 0050/50735 CA 02385085 2002-03-15 _ 7 than 500 ppm, very particularly preferably less than 100 ppm, based on the total mass of the polyether polyol prepared. The preparation of the polyether alcohols by means of the multimetal cyanide compounds can be carried out either continuously or batchwise. The synthesis can be carried out in suspension, in a fixed bed, in a moving bed or in a fluidized bed.
As far as the reaction conditions pressure and temperature are concerned, there is no difference in principle between catalysis by means of basic compounds and by means of multimetal cyanide compounds. The molecular addition of the alkylene oxides is carried out at from 50°C to 200°C, preferably from 90°C
to 150°C, and at pressures in the range from 0.001 bar to 100 bar, preferably from 0.001 bar to 20 bar for the molecular addition of alkylene oxides having at least 3 carbon atoms in the molecule and preferably from 1 to 40 bar for the molecular addition of ethylene oxide. Before introducing the alkylene oxides, the reaction vessel is usually made inert by flushing with an inert gas, for example nitrogen.
The molecular addition of the alkylene oxides is usually followed by an after-reaction phase in order to effect complete reaction of the alkylene oxides.
After the reaction, the polyether alcohol farmed is worked up in a customary fashion by firstly removing unreacted alkylene oxide and other volatile constituents from the crude polyether alcohol by stripping or distillation and, if necessary, removing suspended material and/or mechanical contamination by means of filtration.
If the last process step was base-catalyzed, the catalyst has to be removed as usual from the polyether alcohol. Fox this purpose, the basic catalyst is usually neutralized with an acid and the salts formed are removed from the polyether alcohol by means of filtration.
If the last process step has been catalyzed using multimetal cyanide compounds, the catalyst can in principle remain in the polyether alcohol, but it can also be removed if necessary, for example by means of filtration.
The polyether alcohols of the present invention are very well suited to the production of polyurethanes, in particular flexible polyurethane foams. They are very readily compatible with the other constituents of the polyurethane formulations and have, despite their comparatively high content of ethylene oxide units ~~5~/50735 CA 02385085 2002-03-15 in the polyether chain, a low hydrophilicity. Owing to the higher reaction rate of the polymerization of ethylene oxide compared to propylene oxide, the space-time yield in the preparation of the polyether alcohols of the present invention is higher than that in the case of conventional polyether alcohols for the same application areas. A further increase in the space-time yield can be achieved when at least part of the alkylene oxides is added on using multimetal cyanide compounds as catalyst.
The invention is illustrated by the following examples:
Examples 1 and 2 Addition of ethylene oxide onto an initiator substance Example 1 1115 g of glycerol and 32.5 g of a 47% strength aqueous potassium hydroxide solution were placed in a 10 1 reactor. The water was removed at 95-I00°C under a reduced pressure of less than 1 mm of mercury over a period of 1.5 hours. At 110°C and a nitrogen prepressure of 3.5 bar abs., 3980 g of ethylene oxide were metered in over a period of 6 hours. After reaction was complete, a water pump vacuum was applied, 250 g of Ambosol~ magnesium silicate and 50 g of water were subsequently added to remove the catalyst and the polyether alcohol was subsequently filtered and dewatered by means of distillation.
The polyether alcohol formed had the following properties:
hydroxyl number: 394 mg KOH/g, viscosity at 25°C: 240 mPa*s, potassium content: 5 ppm.
Example 2 The procedure of Example 1 was repeated, but 612 g of glycerol, 31.7 g of a 47% strength aqueous potassium hydroxide solution and 4356 g of ethylene oxide were reacted.
The polyether alcohol formed had the following properties:
hydroxyl number: 27.9 mg KOH/g, viscosity at 25 °C: 222 mPa*s, potassium content: 3 ppm.
- 0050/50?35 CA 02385085 2002-03-15 Examples 3 and 4 Preparation of the polyether alcohols The syntheses were carried out in a 10 1 stirred reactor. This was charged with the reaction products from Examples 1 and 2 at 50°C. The contents of the reactor were made inert by evacuating three times and each time filling with nitrogen. Degassing was carried out by evacuation at 105°C and a pressure of less than 1 mbar abs. for 1.5 hours. A double metal cyanide catalyst from the reaction of zinc acetate with hexacyanocobaltic acid and tert-butanol were then added. The reactor was again evacuated three times and each time filled with nitrogen. This was followed by evacuation to a pressure of less than 1 mbar abs. for about half an hour with the temperature being increased to 125°C. At this temperature, a mixture of propylene oxide and ethylene oxide was added. After a further 30 minutes at 125°C, the polyether alcohol formed was freed of volatile constituents under reduced pressure. To remove the catalyst, the polyether alcohol was filtered through a double layer of a Seitz deep filter (K 900).
The amounts of starting materials used and the properties of the polyether alcohols prepared are shown in Table 1.
Result:
All polyether alcohols have an inner block of glycerol and ethylene oxide. In Example 3, this is adjoined by a mixed block of ethylene oxide and propylene oxide, in Example 4 by a block of propylene oxide.
Polyether alcohols which have only a small proportion of unsaturated constituents were obtained. Products having a very low hydroxyl number can also be obtained by the process of the present invention. The polyether alcohols have narrow molecular weight distributions in all cases.
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Examples 5 (comparative example) and 6 Production of foams In Comparative Example 5 and Example 6, the polyol and isocyanate components shown in Table 2 were reacted to produce flexible polyurethane foams. The constituents of the polyol component were intensively mixed. The isocyanate component was then added while stirring and the reaction mixture was poured into an open mold in which it foamed to form the polyurethane foam.
The product properties of the polyurethane foam of the present invention are likewise summarized in Table 2. The testing standards used are shown in Table 3.
Table 2:
Production and properties of flexible slabstock foams Example Example (C) Polyol component Hydroxyl Amount [g] Amount number [g]
[mgKOI-i/g]
Polyol A 48 1000 Polyol from Example 4 48 1000 Water 6233 38 38 Amine catalyst N 201 560 1,9 1.9 Amine catalyst N 206 426 0.6 0.6 Tin catalyst K 29 0 2.3 2.5 Total 1053 1053.0 Isocyanate component NCO [%] Amount [g) Amount [g) TDI80/20 48.3 488.0 488.0 Index 110 110 Test data Unit Cream time [s] 15 10 Fiber time [s] 90 80 Rise time [s] 90 85 Rise height [mm] 275 265 Rise height after 5 min [mmJ 270 260 Air permeability [mmWsJ 10 10 Foam density [kg/m3J 25,3 26.4 Compressive strength at [kPaJ 4.7 4.1 40% com-pression Tensile strength [kPaJ 79,I 88 Elongation [%J 12I I46 l0 Compressive set at 50% [%J 2.4 2.4 compres-sion Polyol A: Glycerol-initiated polyether alcohol having an inner block of 30 parts by weight of propylene oxide and an adjoining mixed block of 57 parts by weight of propylene oxide and 10 parts by weight of ethylene oxide.
Table 3: Testing standards ----.---Test method Standard Foarn density DIN 53420 Tensile test (tensile strength,DIN 53571 elongation) Compressive set DIN 53572 Rebound resilience DIN 53573 Indentation hardness DIN 53576 Compressive strength DIN 53577
The present invention relates to a process for preparing polyether alcohols, to the polyether alcohols prepared by this process and to their use for producing polyurethanes.
Polyether alcohols are used in large quantities for producing polyurethanes. They are usually prepared by catalytic addition of lower alkylene oxides, in particular ethylene oxide and propylene oxide, onto H-functional initiator substances. Catalysts used are usually basic metal hydroxides or salts, with potassium hydraxide having the greatest practical importance.
The alkylene oxides are usually added on as a block or as a random mixture. In the blockwise molecular addition, only one alkylene oxide at a time is added on, while in the random molecular addition, a mixture of alkylene oxides is present in the reaction mixture.
In the industry, ethylene oxide and propylene oxide axe usually used as alkylene oxides, since they are readily available and inexpensive. The reactivity of ethylene oxide is higher than that of propylene oxide, so that the molecular addition of ethylene oxide proceeds at a higher reaction rate. To increase the space-time yield in the preparation of polyether alcohols it would be desirable for the proportion of ethylene oxide in the polyether alcohol to be as high as possible. Provision of polyether alcohols which are intended for use in flexible foams with terminal ethylene oxide blocks is known and customary. The associated increase in the number of primary hydroxyl groups in the polyether alcohols results in an increase in their reactivity in the reaction with polyisocyanates. However, the increase in the ethylene oxide content of the polyether alcohol also results in an increase in the hydrophilicity of the polyether alcohol, which can lead, inter alia, to undesirable gel formation in the polyether alcohols.
Furthermore, in the synthesis of polyether alcohols having long chains, as are used for producing flexible polyurethane foams, increasing chain growth is associated with secondary reactions which lead to defects in the chain structure. These by-products are referred'to as unsaturated constituents and lead to a deterioration in the properties of the resulting polyurethanes.
Many attempts have therefore been made in the past to prepare polyether alcohols having a low content of unsaturated constituents. In particular, the alkoxylation catalysts used have , ~05~/50735 CA 02385085 2002-03-15 been altered in a targeted way in an attempt to achieve this.
Thus, EP-A-268 922 proposes using cesium hydroxide. Although this enables the content of unsaturated constituents to be reduced, cesium hydroxide is expensive and disposing of it is problematical.
Furthermore, the use of multimetal cyanide complexes, usually zinc hexacyanometalates, also known as DMG catalysts, for preparing polyether alcohols having low contents of unsaturated IO constituents is also known. There is a large number of documents in which the preparation of such compounds is described. Thus, DD-A-203 735 and DD-A-203 734 describe the preparation of polyetherols using zinc hexacyanocobaltate.
I5 The preparation of the zinc hexacyanometalates is also known.
These catalysts are usually prepared by reacting solutions of metal salts such as zinc chloride with solutions of alkali metal or alkaline earth metal cyanometalates, e.g. potassium hexacyanocobaltate. A water-miscible, heteroatom-containing 20 component is generally added to the resulting suspension immediately after the precipitation step. This component can also be present initially in one or both starting solutions. This water-miscible, heteroatom-containing component can be, for example, an ether, polyether, alcohol, ketone or a mixture 25 thereof. Such processes are described, for example, in US
3,278,457, US 3,278,458, US 3,278,459, US 3,427,256, US
3,427,334, US 3,404,109.
Polyether alcohols used fox producing flexible slabstock foams 30 generally have a complete propylene oxide inner block which can make up as much as 40% by weight of the total polyol bound directly to the initiator substance and on this propylene oxide inner block have mixed blocks of propylene oxide and ethylene oxide which make up at least 60% by weight of the total polyol 35 and contain at least 2% by weight of ethylene oxide. These polyols are generally prepared using basic catalysts.
WO-A-97/27,236 describes the preparation of a flexible slabstock foam~polyol in which at least one propylene oxide inner block is added on using multimetal cyanides as catalyst. However, this 40 process does not permit a further increase in the ethylene oxide content of the polyether alcohol without the abovementioned disadvantages.
It is an object of the present invention to develop polyether alcohols which have a high ethylene oxide content without there being a significant increase in the hydrophilicity of the product.
We have found that this object is achieved by a polyether alcohol which can be prepared by ring-opening polymerization of ethylene oxide and alkylene oxides having at least 3 carbon atoms, which comprises an inner block of ethylene oxide or a mixture of ethylene oxide and alkylene oxides having at least 3 carbon atoms, and attached to this a block comprising at least one alkylene oxide having at least 3 carbon atoms or a mixture of ethylene oxide and alkylene oxides having at least 3 carbon atoms, preferably propylene oxide, where the mixed blocks preferably contain at least 2% by weight and not more than ZO% by weight of ethylene oxide, based on the mixture.
The present invention accordingly provides polyether alcohols which can be prepared by ring-opening polymerization of ethylene oxide and propylene oxide onto H-functional initiator substances, wherein not more than 40% by weight, based on the weight of the polyether alcohol, of ethylene oxide or a mixture of ethylene oxide and alkylene oxides having at least 3 carbon atoms, where the mixture has an ethylene oxide content of at least 98% by weight, based on the mixture, is added onto the initiator substance and subsequently at least one alkylene oxide having at least 3 carbon atoms or a mixture of ethylene oxide and at least one alkylene oxide having at least 3 carbon atoms, where the mixture has a maximum ethylene oxide content of 20% by weight, based on the mixture, is added on.
If a mixture of ethylene oxide and at least one alkylene oxide having at least 3 carbon atoms is added on, the content of ethylene oxide should be at least 0.5% by weight, based on the mixture.
As alkylene oxides having at least 3 carbon atoms in the molecule, preference is given to using propylene oxide, butylene oxide and isobutylene oxide and also any mixtures of at least two of the alkylene oxides mentioned, particularly preferably propylene oxide.
In a preferred embodiment of the present invention, ethylene oxide can be added onto the polyether alcohol at the end of the chain, i.e. after the molecular addition of the alkylene oxides having at least 3 carbon atoms or of the mixture of ethylene oxide and alkylene oxides having at least 3 carbon atoms. The ~~ 005/50735 CA 02385085 2002-03-15 amount of this ethylene oxide added onto the end of the chain is preferably not more than 15% by weight, based on the weight of the polyether alcohol. Such polyether alcohols are preferably used for producing cold-cure polyurethane foams. Polyether alcohols of the present invention without this ethylene oxide end block are preferably used for producing flexible polyurethane foams, in particular flexible slabstock foams.
It has surprisingly been found that the hydrophilicity of the polyether alcohols of the present invention is significantly lower than that of conventional polyether alcohols containing the same amount of ethylene oxide in the polyether chain but having a different distribution of alkylene oxides in the chain.
The present invention further provides a process for preparing the above-described polyether alcohols. The polyether alcohols of the present invention are prepared by ring-opening polymerization of the alkylene oxides ethylene oxide and the alkylene oxides having at least 3 carbon atoms onto H-functional initiator substances in the presence of catalysts.
In a preferred embodiment of the process of the present invention, the molecular addition of the total amount of alkylene oxide is carried out in the presence of basic catalysts. Basic catalysts which can be used are, for example, amines, basic salts, metal oxides and metal hydroxides. Preference is given to using alkali metal and/or alkaline earth metal hydroxides. In industry, potassium hydroxide is usually used.
In a further preferred embodiment of the process of the present invention, multimetal cyanides, frequently also referred to as DMC catalysts, are used as catalyst for the molecular addition of the alkylene oxides. The advantages of using these catalysts are firstly the higher reaction rate in the molecular addition of the alkylene oxides and secondly the fact that the polyether alcohols prepared in this way have a lower content of unsaturated constituents. However, this embodiment has the disadvantage that there can be a delayed start of the reaction at the beginning when using DMC catalysts.
In further preferred embodiments of the process of the present invention, the various sections of the polyether chain are added on using different catalysts. Thus, it is advantageous to add on an ethylene oxide block at the beginning of the chain using basic catalysts and to add on the subsequent block consisting entirely or predominantly of alkylene oxides having at least 3 carbon atoms using DMC catalysts. The ethylene oxide block which may, if desired, be present at the end of the chain can likewise be added on by means of DMC catalysts, but preferably by means of basic catalysts. This procedure has the advantage that the delay which frequently occurs at the start of the reaction when using 5 multimetal cyanide catalysts is avoided. This is balanced by increased costs due to the additional purification step.
When using different catalysts, it may be necessary to purity the polyether alcohol to remove catalyst prior to changing the catalysts. Particularly when changing from basic catalysts to DMC
catalysts, a thorough purification is usually carried out because traces of the basic catalyst, in particular the alkali metal hydroxides customarily used, can poison the DMC catalyst.
The invention further provides polyurethanes which can be produced by reacting polyisocyanates with compounds having at least two hydrogen atoms which are reactive toward isocyanate groups, wherein the polyether alcohols of the present invention are used as compounds having at least two hydrogen atoms which are reactive toward isocyanate groups. The polyether alcohols of the present invention are preferably used for producing flexible polyurethane foams, with the polyether alcohols without a terminal ethylene oxide block being used, in particular, for producing slabstock foams and not-cure molded foams and the polyether alcohols having a terminal ethylene oxide block being used, in particular, for producing cold-cure molded foams.
As initiator substances for preparing the polyetherols of the present invention, use is made of the customary polyfunctional alcohols having from 2 to 8 hydroxyl groups in the molecule. In particular, 2- and/or 3-functional alcohols, for example ethylene glycol, propylene glycol, glycerol or trimethylolpropane, are used for preparing polyether alcohols as are customarily used for producing flexible polyurethane foams.
The polyether alcohols of the present invention preferably have a molecular weight in the range from 1000 to 100,000.
Alkylene oxides used are, as indicated above, ethylene oxide and alkylene oxides having at least 3 carbon atoms, in the abovementioned ratios.
The multimetal cyanides used as catalysts in the process of the present invention usually have the formula (I) MZa[P'IZ(CN)b(A)c~d ' fMlgXn ~ h(H2C?) ~ eL (I).
where M1 is a metal ion selected from the group consisting of Znz+, Fez+, Co3+, Niz+, Mnz+, Coz+, Snz+, Pbz+, Mo4+, Mo6+, A13+, V4+, V5+, Srz+, W4+, W6+, Crz+, Cr3+, Cdz+, _.
M2 is a metal ion selected from the group consisting of Fez+, Fe3+, Coz+, Co3+, Mnz+, Mn3+, V4+, VS+, Crz+, Cr3+, Rh3+, Ruz+, Ir3+
and M1 and Mz are identical or different, A is an anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate and nitrate, X is an anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate and nitrate, L is a water-miscible ligand selected from the group consisting of alcohols, aldehydes, ketones, ethers, polyethers, esters, ureas, amides, nitriles and sulfides, and a, b, c, d, g and n are selected so that the compound is electrically neutral, and a is the coordination number of the ligand, f is a fraction or integer greater than or equal to 0 and h is a fraction or integer greater than or equal to 0.
These compounds are prepared by generally known methods by combining the aqueous solution of a water-soluble metal salt with the aqueous solution of a hexacyanometalate compound, in particular a salt or an acid, and adding a water-soluble ligand thereto during or after the mixing of the solutions.
Owing to their high activity, the multimetal cyanide compounds are very well suited to the synthesis of the polyether alcohols of the present invention. The catalyst concentrations used are less than 1~ by weight, preferably less than 0.5~ by weight, particularly preferably less than 1000 ppm, in particular less .~ 0050/50735 CA 02385085 2002-03-15 _ 7 than 500 ppm, very particularly preferably less than 100 ppm, based on the total mass of the polyether polyol prepared. The preparation of the polyether alcohols by means of the multimetal cyanide compounds can be carried out either continuously or batchwise. The synthesis can be carried out in suspension, in a fixed bed, in a moving bed or in a fluidized bed.
As far as the reaction conditions pressure and temperature are concerned, there is no difference in principle between catalysis by means of basic compounds and by means of multimetal cyanide compounds. The molecular addition of the alkylene oxides is carried out at from 50°C to 200°C, preferably from 90°C
to 150°C, and at pressures in the range from 0.001 bar to 100 bar, preferably from 0.001 bar to 20 bar for the molecular addition of alkylene oxides having at least 3 carbon atoms in the molecule and preferably from 1 to 40 bar for the molecular addition of ethylene oxide. Before introducing the alkylene oxides, the reaction vessel is usually made inert by flushing with an inert gas, for example nitrogen.
The molecular addition of the alkylene oxides is usually followed by an after-reaction phase in order to effect complete reaction of the alkylene oxides.
After the reaction, the polyether alcohol farmed is worked up in a customary fashion by firstly removing unreacted alkylene oxide and other volatile constituents from the crude polyether alcohol by stripping or distillation and, if necessary, removing suspended material and/or mechanical contamination by means of filtration.
If the last process step was base-catalyzed, the catalyst has to be removed as usual from the polyether alcohol. Fox this purpose, the basic catalyst is usually neutralized with an acid and the salts formed are removed from the polyether alcohol by means of filtration.
If the last process step has been catalyzed using multimetal cyanide compounds, the catalyst can in principle remain in the polyether alcohol, but it can also be removed if necessary, for example by means of filtration.
The polyether alcohols of the present invention are very well suited to the production of polyurethanes, in particular flexible polyurethane foams. They are very readily compatible with the other constituents of the polyurethane formulations and have, despite their comparatively high content of ethylene oxide units ~~5~/50735 CA 02385085 2002-03-15 in the polyether chain, a low hydrophilicity. Owing to the higher reaction rate of the polymerization of ethylene oxide compared to propylene oxide, the space-time yield in the preparation of the polyether alcohols of the present invention is higher than that in the case of conventional polyether alcohols for the same application areas. A further increase in the space-time yield can be achieved when at least part of the alkylene oxides is added on using multimetal cyanide compounds as catalyst.
The invention is illustrated by the following examples:
Examples 1 and 2 Addition of ethylene oxide onto an initiator substance Example 1 1115 g of glycerol and 32.5 g of a 47% strength aqueous potassium hydroxide solution were placed in a 10 1 reactor. The water was removed at 95-I00°C under a reduced pressure of less than 1 mm of mercury over a period of 1.5 hours. At 110°C and a nitrogen prepressure of 3.5 bar abs., 3980 g of ethylene oxide were metered in over a period of 6 hours. After reaction was complete, a water pump vacuum was applied, 250 g of Ambosol~ magnesium silicate and 50 g of water were subsequently added to remove the catalyst and the polyether alcohol was subsequently filtered and dewatered by means of distillation.
The polyether alcohol formed had the following properties:
hydroxyl number: 394 mg KOH/g, viscosity at 25°C: 240 mPa*s, potassium content: 5 ppm.
Example 2 The procedure of Example 1 was repeated, but 612 g of glycerol, 31.7 g of a 47% strength aqueous potassium hydroxide solution and 4356 g of ethylene oxide were reacted.
The polyether alcohol formed had the following properties:
hydroxyl number: 27.9 mg KOH/g, viscosity at 25 °C: 222 mPa*s, potassium content: 3 ppm.
- 0050/50?35 CA 02385085 2002-03-15 Examples 3 and 4 Preparation of the polyether alcohols The syntheses were carried out in a 10 1 stirred reactor. This was charged with the reaction products from Examples 1 and 2 at 50°C. The contents of the reactor were made inert by evacuating three times and each time filling with nitrogen. Degassing was carried out by evacuation at 105°C and a pressure of less than 1 mbar abs. for 1.5 hours. A double metal cyanide catalyst from the reaction of zinc acetate with hexacyanocobaltic acid and tert-butanol were then added. The reactor was again evacuated three times and each time filled with nitrogen. This was followed by evacuation to a pressure of less than 1 mbar abs. for about half an hour with the temperature being increased to 125°C. At this temperature, a mixture of propylene oxide and ethylene oxide was added. After a further 30 minutes at 125°C, the polyether alcohol formed was freed of volatile constituents under reduced pressure. To remove the catalyst, the polyether alcohol was filtered through a double layer of a Seitz deep filter (K 900).
The amounts of starting materials used and the properties of the polyether alcohols prepared are shown in Table 1.
Result:
All polyether alcohols have an inner block of glycerol and ethylene oxide. In Example 3, this is adjoined by a mixed block of ethylene oxide and propylene oxide, in Example 4 by a block of propylene oxide.
Polyether alcohols which have only a small proportion of unsaturated constituents were obtained. Products having a very low hydroxyl number can also be obtained by the process of the present invention. The polyether alcohols have narrow molecular weight distributions in all cases.
~~5~/50735 CA 02385085 2002-03-15 l~
'd +i N C
~ GS
ro ~
H +~ __ --~ .1 o 00 O
~ +.~ o w ro o 0 m tr fp O O
G
E
~ U o 0 ~
M a o~O
tT O o '~', M M
'b n o~
O _ n a S1 C G~ G7OD
ro ,'~ N N
.--.
N
p, ro ro N
~ U
O
U N N u1 r1 r1 N N
~f1 ',~ n n N
~
'' ,'i \
xNx ro a ~ M
x a~ a~
a a~
O ,C n ~
~
.u o x o~
a~ w o ~
.r N
N 'O
ri ,-1 >, x Ga aoo~
o cd o ao0 1-I N O~
G) ~
'd Q1 d'f7 G~
~
i~
b N
r1 -~N
ro ,~,~ .~'1 ...
ro ~
f!1 V .-, N N
W 1.1 O d ;.1 M
~i-~ .~.!
~ ~ n .F, O r1 C1Ov ~
W
tr~ CL o C
H
rd .
GL
r, o ro W o w x O W W -iN
W
r1 (17 N G
ro M C
,. X050/50735 CA 02385085 2002-03-15 - 1 ~.
Examples 5 (comparative example) and 6 Production of foams In Comparative Example 5 and Example 6, the polyol and isocyanate components shown in Table 2 were reacted to produce flexible polyurethane foams. The constituents of the polyol component were intensively mixed. The isocyanate component was then added while stirring and the reaction mixture was poured into an open mold in which it foamed to form the polyurethane foam.
The product properties of the polyurethane foam of the present invention are likewise summarized in Table 2. The testing standards used are shown in Table 3.
Table 2:
Production and properties of flexible slabstock foams Example Example (C) Polyol component Hydroxyl Amount [g] Amount number [g]
[mgKOI-i/g]
Polyol A 48 1000 Polyol from Example 4 48 1000 Water 6233 38 38 Amine catalyst N 201 560 1,9 1.9 Amine catalyst N 206 426 0.6 0.6 Tin catalyst K 29 0 2.3 2.5 Total 1053 1053.0 Isocyanate component NCO [%] Amount [g) Amount [g) TDI80/20 48.3 488.0 488.0 Index 110 110 Test data Unit Cream time [s] 15 10 Fiber time [s] 90 80 Rise time [s] 90 85 Rise height [mm] 275 265 Rise height after 5 min [mmJ 270 260 Air permeability [mmWsJ 10 10 Foam density [kg/m3J 25,3 26.4 Compressive strength at [kPaJ 4.7 4.1 40% com-pression Tensile strength [kPaJ 79,I 88 Elongation [%J 12I I46 l0 Compressive set at 50% [%J 2.4 2.4 compres-sion Polyol A: Glycerol-initiated polyether alcohol having an inner block of 30 parts by weight of propylene oxide and an adjoining mixed block of 57 parts by weight of propylene oxide and 10 parts by weight of ethylene oxide.
Table 3: Testing standards ----.---Test method Standard Foarn density DIN 53420 Tensile test (tensile strength,DIN 53571 elongation) Compressive set DIN 53572 Rebound resilience DIN 53573 Indentation hardness DIN 53576 Compressive strength DIN 53577
Claims (9)
1. A polyether alcohol which can be prepared by ring-opening polymerization of ethylene oxide and at least one alkylene oxide having at least three carbon atoms in the molecule onto H-functional initiator substances, wherein ethylene oxide or a mixture of ethylene oxide and at least one alkylene oxide having at least three carbon atoms in the molecule, where the mixture has an ethylene oxide content of at least 98% by weight, based on the mixture, is added, in each case in an amount of not more than 40% by weight, based on the weight of the polyether alcohol, onto the initiator substance and subsequently at least one alkylene oxide having at least three carbon atoms in the molecule or a mixture of ethylene oxide and at least one alkylene oxide having at least three carbon atoms in the molecule, where the mixture has a maximum ethylene oxide content of 20% by weight, based on the mixture, is added on, and at least one multimetal cyanide compound is used as catalyst.
2. A polyether alcohol as claimed in claim 1, wherein propylene oxide, butylene oxide, isobutylene oxide or any mixtures of at least two of the alkylene oxides mentioned are used as alkylene oxides having at least three carbon atoms in the molecule.
3. A polyether alcohol as claimed in claim 1, wherein propylene oxide is used as alkylene oxide having at least three carbon atoms in the molecule.
4. A polyether alcohol as claimed in claim 1, wherein ethylene oxide is added on at the end of the chain.
5. A polyether alcohol as claimed in claim 4, wherein a maximum of 15% by weight of ethylene oxide, based on the weight of the polyether alcohol, is added on at the end of the chain.
6. A process for preparing polyether alcohols by ring-opening polymerization of ethylene oxide and at least one alkylene oxide having at least three carbon atoms in the molecule onto H-functional initiator substances, which comprises adding ethylene oxide or a mixture of ethylene oxide and at least one alkylene oxide having at least three carbon atoms in the molecule, where the mixture has an ethylene oxide content of at least 98% by weight, based on the mixture, in each case in an amount of not more than 40% by weight, based on the weight of the polyether alcohol, onto the initiator substance and subsequently adding on at least one alkylene oxide having at least 3 carbon atoms in the molecule or a mixture of ethylene oxide and at least one alkylene oxide having at least 3 carbon atoms in the molecule, where the mixture has a maximum ethylene oxide content of 20% by weight, based on the mixture, and at least one multimetal cyanide compound is used as catalyst.
7. A process as claimed in claim 6, wherein at least one basic compound is used as catalyst for the addition of the ethylene oxide or of the mixture of ethylene oxide and at least one alkylene oxide having at least 3 carbon atoms in the molecule, where the mixture has an ethylene oxide content of at least 98% by weight, based on the mixture, onto the initiator substance, and at least one multimetal cyanide compound is used as catalyst for adding on the alkylene oxide or oxides having at least 3 carbon atoms in the molecule or the mixture of ethylene oxide and at least one alkylene oxide having at least 3 carbon atoms in the molecule, where the mixture has a maximum ethylene oxide content of 20~ by weight, based on the mixture.
8. A process for preparing polyether alcohols as claimed in claim 4, wherein at least one basic compound is used as catalyst for the addition of the ethylene oxide or of the mixture of ethylene oxide and at least one alkylene oxide having at least 3 carbon atoms in the molecule, where the mixture has an ethylene oxide content of at least 98% by weight, based on the mixture, onto the initiator substance and at least one multimetal cyanide compound is used as catalyst for adding on the alkylene oxide or oxides having at least 3 carbon atoms in the molecule or the mixture of ethylene oxide and at least one alkylene oxide having at least 3 carbon atoms in the molecule, where the mixture has a maximum ethylene oxide content of 20% by weight, based on the mixture, and at least one basic compound is used as catalyst for adding on the ethylene oxide at the end of the chain.
9. A polyurethane which can be produced by reacting polyisocyanates with compounds having at least two hydrogen atoms which are reactive toward isocyanate groups, wherein a polyether alcohol as claimed in any of claims 1 to 5 is used as compound having at least two hydrogen atoms which are reactive toward isocyanate groups.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19944762.4 | 1999-09-17 | ||
| DE19944762A DE19944762A1 (en) | 1999-09-17 | 1999-09-17 | Process for the production of flexible flexible foam polyols |
| PCT/EP2000/008640 WO2001021682A1 (en) | 1999-09-17 | 2000-09-05 | Method for producing flexible block foam polyols |
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|---|---|
| CA2385085A1 true CA2385085A1 (en) | 2001-03-29 |
Family
ID=7922469
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002385085A Abandoned CA2385085A1 (en) | 1999-09-17 | 2000-09-05 | Method for producing flexible block foam polyols |
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| Country | Link |
|---|---|
| EP (1) | EP1230289B1 (en) |
| JP (1) | JP2003510384A (en) |
| CN (1) | CN1180003C (en) |
| AR (1) | AR025579A1 (en) |
| AT (1) | ATE284427T1 (en) |
| AU (1) | AU7514400A (en) |
| BR (1) | BR0014055A (en) |
| CA (1) | CA2385085A1 (en) |
| CZ (1) | CZ2002838A3 (en) |
| DE (2) | DE19944762A1 (en) |
| ES (1) | ES2233443T3 (en) |
| HU (1) | HUP0202600A3 (en) |
| MX (1) | MXPA02002471A (en) |
| PL (1) | PL203194B1 (en) |
| PT (1) | PT1230289E (en) |
| RU (1) | RU2257394C2 (en) |
| WO (1) | WO2001021682A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012027113A1 (en) | 2010-08-24 | 2012-03-01 | Dow Global Technologies Llc | Ethylene oxide/propylene oxide polyether polyols and polyurethanes made therefrom |
| US9284401B2 (en) | 2006-11-13 | 2016-03-15 | Bayer Materialscience Llc | Process for the preparation of polyether-ester polyols |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100509902C (en) | 2003-09-19 | 2009-07-08 | 旭硝子株式会社 | Flexible polyurethane foam and preparation process thereof |
| ZA200709673B (en) * | 2006-11-13 | 2009-09-30 | Bayer Materialscience Ag | Process for the preparation of polyether-ester polyols |
| EP2225307B1 (en) * | 2007-12-19 | 2012-11-21 | Basf Se | Method for producing polyether alcohols |
| WO2017001543A1 (en) * | 2015-07-02 | 2017-01-05 | Shell Internationale Research Maatschappij B.V. | Improvements relating to polyurethanes |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4008189A (en) * | 1974-06-03 | 1977-02-15 | Olin Corporation | Hydrophilic polyurethane foam |
| US4487854A (en) * | 1983-12-27 | 1984-12-11 | Basf Wyandotte Corporation | Polyoxyalkylene polyether polyols and polyurethane foams prepared therefrom |
| DE3531212A1 (en) * | 1985-08-31 | 1987-03-05 | Henkel Kgaa | ALKYLENE OXIDE BLOCK POLYMERS TO BE USED AS A DEFOAMER |
| US5122548A (en) * | 1990-03-23 | 1992-06-16 | The Dow Chemical Company | Elastomeric polyisocyanate-based polymers from polyoxyalkylene polyols containing internal polyoxyethylene blocks |
| JPH07128793A (en) * | 1993-11-05 | 1995-05-19 | Konica Corp | Fine solid particle dispersion of dye and silver halide photographic sensitive material containing the same |
| US5563221A (en) * | 1995-06-21 | 1996-10-08 | Arco Chemical Technology, L.P. | Process for making ethylene oxide-capped polyols from double metal cyanide-catalyzed polyols |
-
1999
- 1999-09-17 DE DE19944762A patent/DE19944762A1/en not_active Withdrawn
-
2000
- 2000-09-05 EP EP00964106A patent/EP1230289B1/en not_active Revoked
- 2000-09-05 CN CNB008129800A patent/CN1180003C/en not_active Expired - Fee Related
- 2000-09-05 MX MXPA02002471A patent/MXPA02002471A/en active IP Right Grant
- 2000-09-05 DE DE2000508921 patent/DE50008921D1/en not_active Revoked
- 2000-09-05 PT PT00964106T patent/PT1230289E/en unknown
- 2000-09-05 HU HU0202600A patent/HUP0202600A3/en unknown
- 2000-09-05 RU RU2002110293/04A patent/RU2257394C2/en not_active IP Right Cessation
- 2000-09-05 JP JP2001525253A patent/JP2003510384A/en not_active Withdrawn
- 2000-09-05 WO PCT/EP2000/008640 patent/WO2001021682A1/en not_active Application Discontinuation
- 2000-09-05 ES ES00964106T patent/ES2233443T3/en not_active Expired - Lifetime
- 2000-09-05 PL PL354042A patent/PL203194B1/en not_active IP Right Cessation
- 2000-09-05 BR BR0014055-4A patent/BR0014055A/en not_active Application Discontinuation
- 2000-09-05 AT AT00964106T patent/ATE284427T1/en not_active IP Right Cessation
- 2000-09-05 CZ CZ2002838A patent/CZ2002838A3/en unknown
- 2000-09-05 AU AU75144/00A patent/AU7514400A/en not_active Abandoned
- 2000-09-05 CA CA002385085A patent/CA2385085A1/en not_active Abandoned
- 2000-09-07 AR ARP000104663A patent/AR025579A1/en unknown
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9284401B2 (en) | 2006-11-13 | 2016-03-15 | Bayer Materialscience Llc | Process for the preparation of polyether-ester polyols |
| WO2012027113A1 (en) | 2010-08-24 | 2012-03-01 | Dow Global Technologies Llc | Ethylene oxide/propylene oxide polyether polyols and polyurethanes made therefrom |
| US9156936B2 (en) | 2010-08-24 | 2015-10-13 | Dow Global Technologies Llc | Ethylene oxide/propylene oxide polyether polyols and polyurethanes made therefrom |
| US9725559B2 (en) | 2010-08-24 | 2017-08-08 | Dow Global Technologies Llc | Ethylene oxide/propylene oxide polyether polyols and polyurethanes made therefrom |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2003510384A (en) | 2003-03-18 |
| EP1230289B1 (en) | 2004-12-08 |
| AU7514400A (en) | 2001-04-24 |
| HUP0202600A3 (en) | 2004-05-28 |
| DE19944762A1 (en) | 2001-03-22 |
| ES2233443T3 (en) | 2005-06-16 |
| PT1230289E (en) | 2005-04-29 |
| RU2257394C2 (en) | 2005-07-27 |
| DE50008921D1 (en) | 2005-01-13 |
| BR0014055A (en) | 2002-05-21 |
| CZ2002838A3 (en) | 2002-08-14 |
| WO2001021682A1 (en) | 2001-03-29 |
| ATE284427T1 (en) | 2004-12-15 |
| HUP0202600A2 (en) | 2002-12-28 |
| CN1374977A (en) | 2002-10-16 |
| PL354042A1 (en) | 2003-12-15 |
| CN1180003C (en) | 2004-12-15 |
| PL203194B1 (en) | 2009-09-30 |
| AR025579A1 (en) | 2002-12-04 |
| MXPA02002471A (en) | 2002-07-30 |
| EP1230289A1 (en) | 2002-08-14 |
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