WO2003076488A1 - Procede de production d'alcools de polyether de haute fonctionnalite - Google Patents

Procede de production d'alcools de polyether de haute fonctionnalite Download PDF

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Publication number
WO2003076488A1
WO2003076488A1 PCT/EP2003/002182 EP0302182W WO03076488A1 WO 2003076488 A1 WO2003076488 A1 WO 2003076488A1 EP 0302182 W EP0302182 W EP 0302182W WO 03076488 A1 WO03076488 A1 WO 03076488A1
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WO
WIPO (PCT)
Prior art keywords
alcohols
polyether
production
polyether alcohols
reaction
Prior art date
Application number
PCT/EP2003/002182
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German (de)
English (en)
Inventor
Eva Baum
Raimund Ruppel
Gerlinde Tischer
Kathrin Harre
Edward Bohres
Original Assignee
Basf Aktiengesellschaft
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Filing date
Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to AU2003210406A priority Critical patent/AU2003210406A1/en
Publication of WO2003076488A1 publication Critical patent/WO2003076488A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2663—Metal cyanide catalysts, i.e. DMC's
    • 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
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more polyetherpolyols having at least three hydroxy 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
    • 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
    • C08G18/4887—Polyethers containing carboxylic ester groups derived from carboxylic acids other than acids of higher fatty oils or other than resin acids
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2615—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen the other compounds containing carboxylic acid, ester or anhydride groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
    • 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

Definitions

  • the invention relates to highly functional polyether alcohols, a process for their preparation and their use, in particular for the production of polyurethanes.
  • Polyurethanes are manufactured in large quantities. They are usually prepared by reacting polyisocyanates with compounds having at least two hydrogen atoms which are reactive with isocyanate groups, in particular polyether alcohols and / or polyester alcohols.
  • Polyester alcohols are usually produced by reacting polyfunctional alcohols with polyfunctional carboxylic acids.
  • Polyether alcohols are usually produced by catalytic addition of alkylene oxides onto H-functional starter substances, in particular alcohols and / or amines.
  • Alkaline substances preferably alkali metal hydroxides, are mostly used as catalysts in industry.
  • Multimetal cyanide catalysts have recently become increasingly important.
  • the advantages of DMC catalysts are, on the one hand, that the addition of the alkylene oxides takes place at a higher reaction rate, and on the other hand, the polyether alcohols produced in this way are characterized by a lower content of unsaturated components in the polyether chain.
  • the DMC catalysts are used particularly advantageously in the production of polyether alcohols with a high molecular weight and low functionality, as are used in particular for the production of flexible polyurethane foams.
  • polyether alcohols with a high functionality in particular those with a functionality of at least 3, in particular 4 and higher, are used.
  • the starter substances used to produce such polyether alcohols are mostly solid. Solid starter substances of this type have hitherto not been able to be satisfactorily reacted with alkylene oxides by means of DMC catalysts.
  • DMC catalysts Another disadvantage of using DMC catalysts is the difficult light-off behavior when starting the reaction. For example, it is very difficult to react low molecular weight alcohols, such as glycerol, with alkylene oxides using DMC catalysts.
  • the low molecular weight alcohols are first reacted with alkylene oxides to form an intermediate product using other catalysts, purified if necessary, and then reacted with further alkylene oxide to give the desired polyether alcohol using DMC catalysts.
  • This procedure is very complex and therefore has an adverse effect on the economy of the process.
  • polyester alcohols are used as starting compounds for the addition of the alkylene oxides in order to avoid the problems which arise from the high viscosity of the polyester alcohols.
  • the structure of the polyetheresterols described in WO 01/27185 is therefore essentially suitable for the production of flexible polyurethane foams.
  • the object of the present invention was to provide polyether alcohols with a functionality of at least 3, which can be prepared by adding alkylene oxides to H-functional starter substances using DMC catalysts.
  • the task was surprisingly achieved in that a polyester alcohol with a functionality of at least 3 is used as the starting substance for the addition of alkylene oxides.
  • the invention accordingly relates to a method for producing polyether alcohols with a functionality greater than 2, in particular at least 3, comprising the steps
  • the invention also relates to polyether alcohols which can be prepared by the process according to the invention and the use of the polyether alcohols according to the invention, in particular for the production of polyurethanes.
  • the invention further relates to a process for producing polyurethanes by reacting
  • the polyether alcohols according to the invention are polyether ester alcohols, since they contain both ether groups and ester groups in their chain.
  • the designation polyether alcohol or polyetherol is retained.
  • polyester alcohols used as starting material for producing the polyether alcohols of the invention may, as indicated above, are prepared by reacting more functional eiler alcohols with multi • * "carboxylic acids.
  • alcohols with 2 to 6 hydroxyl groups preferably aliphatic alcohols with 2 to 8 carbon atoms in the branched or unbranched, are used as polyfunctional alcohols
  • the alkyl chain is used.
  • the polyfunctional alcohols are two to four functional and are selected in particular from the group comprising glycerol, trimethylolpropane, pentaerythritol, sorbitol, ethylene glycol and its homologues, in particular ethylene glycol and / or diethylene glycol, propylene glycol
  • Aliphatic carboxylic acids or hydroxycarboxylic acids with preferably three to six carbon atoms in the branched or unbranched chain can be used as polyfunctional carboxylic acids.
  • aliphatic carboxylic acids examples include adipic acid and succinic acid.
  • Aromatic polycarboxylic acids such as phthalic acid, terephthalic acid, trimesic acid, pyromellitic acid or trimellitic acid can also be used for the process according to the invention.
  • the starting materials for the polyester alcohols produced in step a) are used in such a ratio that the functionality of the resulting polyester alcohols is greater than 2, in particular at least 3. This means that if only two-functional carboxylic acids are used, at least one of the alcohols used must have a functionality of at least 3, and if only two-functional alcohols are used, at least one of the carboxylic acids used must have at least three acid groups or at least two acid groups and at least one hydroxyl group.
  • polyester alcohols which have been prepared using carboxylic acids having at least one carboxylic acid group and at least one hydroxyl group in the molecule, so-called hydroxycarboxylic acids, and polyfunctional alcohols are particularly suitable for the process according to the invention.
  • Such polyester alcohols have an optimum viscosity for the subsequent addition of alkylene oxides.
  • the functionality of the polyester alcohols can be set to greater than 2, preferably between 3 and 8, and in particular between 3 and 6, by the choice of the starting materials, without an undesirable increase in viscosity or other disadvantages during processing.
  • hydroxycarboxylic acids are used as polyfunctional carboxylic acids in step a). 5
  • the hydroxycarboxylic acids which are particularly suitable for the process according to the invention can be aromatic or preferably aliphatic.
  • the aliphatic hydroxycarboxylic acids can be straight-chain or branched and preferably have 2 to 10 10 carbon atoms in the branched or unbranched alkyl chain.
  • hydroxycarboxylic acids examples include lactic acid, glycolic acid, glyceric acid and the so-called fruit acids, such as 15 e.g. Tartaric acid, malic acid and citric acid.
  • Step a) is preferably designed such that five, preferably one to three, in particular one to two, molecules of alcohol are available per acid group of the carboxylic acid used.
  • the ratio of acid to alcohol in the starting mixture depends on the desired functionality and thus the viscosity of the end product from step a).
  • a functionality of 3 to 6 is preferred.
  • the end product from step a) should accordingly have a functionality of 3 to 6.
  • the structure of the ester resulting from step a) is selected such that the ester molecule contains on average no more than two molecules of carboxylic acid and the conversion is only driven to the extent that the viscosity of the process product from step a) Do not exceed 10,000 Pas at 25 ° C.
  • reaction in process step a) can take place under the conditions customary for the production of polyester alcohols, 5 as described, for example, in the plastics manual, volume 7 "Polyurethane", edited by Günter Oertel, Carl-Hanser-Verlag Kunststoff Vienna 1993, page 70 and 71, are described.
  • the reaction takes place at a temperature in the range between 125 and 220 ° C. and, at least in the last part of the reaction, under vacuum, optionally in the presence of acids, Lewis acids and metal salts, in particular esterification catalysts containing titanium and / or tin , for example n-butyl titanate, tin-II octoate or tin dilaurate.
  • the distillation of the water of reaction is preferably carried out until the reaction mixture has an acid number of ⁇ 10 mg KOH / g, particularly preferably ⁇ 5 mg KOH / g and in particular ⁇ 3 mg KOH / g.
  • the reaction can be carried out under an inert gas, such as nitrogen or argon, in order to prevent product discoloration from oxidation products.
  • the intermediate product from process step a) is preferably prepared without a catalyst and the reaction is terminated at 25 ° C. when the acid number is less than 3 mg KOH / g and the viscosity is less than 10,000 mPas. Another refurbishment, e.g. a possible deactivation of the catalyst used is not necessary. If necessary, the intermediate product is dried by conventional methods at 120 ° C. and pressures ⁇ 100 mbar.
  • the amount of DMC catalyst used depends on its catalytic activity. As a rule, 100 to 500 ppm of catalyst, based in each case on the mass of the end product to be expected, are used.
  • polyether alcohols according to the invention are prepared in step b) of the process according to the invention, as explained above, by addition of alkylene oxides onto the polyester alcohols from step a) using multimetal cyanide catalysts.
  • alkylene oxides which can be used are ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide-1,2 and any mixtures thereof.
  • Ethylene oxide, propylene oxide and mixtures thereof are preferably used.
  • the alkylene oxides can be added individually in the form of blocks and, if more than two different alkylene oxides are used, in any mixing ratio as mixing blocks. In addition, the mixing ratio of the alkylene oxides can be varied both batchwise and continuously during the synthesis.
  • the multimetal cyanide catalysts used are generally those of the general formula (I)
  • M 1 is a metal ion selected from the group comprising Zn 2+ , Fe 2+ , Co 3+ , Ni 2+ , Mn + , Co 2+ , Sn 2+ , Pb 2+ , Mo 4+ , Mo 6+ , Al 3+ , V 4+ , V 5+ , Sr 2+ , W 4+ , W 6+ , Cr 2+ , Cr 3+ , Cd 2+ ,
  • M 2 is a metal ion selected from the group containing Fe 2+ ,
  • A is an anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate or nitrate,
  • X is an anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate or nitrate,
  • L is a water-miscible ligand selected from the group consisting of alcohols, aldehydes, ketones, ethers, polyethers, esters, ureas, amides, nitriles and sulfides,
  • a, b, c, d, g and n are selected so that the connection is electrically neutral
  • e is the coordination number of the ligand, or zero
  • h is a fractional or whole number greater than or equal to 0.
  • These compounds are prepared by generally known processes, for example described in EP 862 947, 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 if necessary, during or after the combination gives a water-soluble ligand.
  • the polyester alcohols are first mixed with the DMC catalyst and the alkylene oxide or the mixture of the alkylene oxides is metered into this mixture.
  • solvents such as, for example, toluene, xylene, tetrahydrofuran, acetone, 2-methylpentanone, cyclohexanone, are optionally added to the reaction mixture.
  • reaction of the reaction products from process step a) starts with the alkylene oxides in the presence of the multimetal cyanide catalysts without problems and without the occurrence of an induction period.
  • the reaction proceeds even at higher molecular weights without an undesirable increase in viscosity.
  • the reaction of the polyester alcohols with the alkylene oxides preferably takes place at pressures in the range from 1 to 20, in particular between 2 and 10 bar and temperatures in the range from 60 to
  • the production is also preferably carried out under a protective gas atmosphere, in particular under a nitrogen and / or argon atmosphere.
  • a post-reaction phase usually follows in order to achieve complete conversion of the alkylene oxides.
  • the polyether esterols are then worked up. Secondary compounds, such as unreacted monomers or volatile compounds, can be removed by various methods known to the person skilled in the art, for example by distillation, working up using a thin-film evaporator, nitrogen and / or steam stripping.
  • suspended matter and solids can be removed from the reaction mixture by various methods known to the person skilled in the art, such as, for example, centrifugation or filtration.
  • the catalyst can also remain in the end product.
  • the polyether alcohols according to the invention preferably have an average functionality of greater than 2, particularly preferably at least 3, in particular in the range from 3 to 5, a hydroxyl number in the range between 5 and 600, preferably between 30 and 400 mg KOH / g and a viscosity in the range between 50 and 5000 mPas, determined according to DIN 53015 at 25 ° C.
  • the polyether alcohols according to the invention can preferably be used for the production of polyurethanes.
  • the polyurethanes are produced by processes known per se by reacting the polyols with polyisocyanates. Depending on the desired properties of the polyurethanes, it is possible to use the polyether alcohols according to the invention alone or together with other compounds having at least two hydrogen atoms reactive with isocyanate groups.
  • Compounds with at least two hydrogen atoms which are reactive with isocyanate groups and which can be used together with the polyether alcohols according to the invention with polyisocyanates include, in particular, the polyether alcohols, polyester alcohols, and, if appropriate, bifunctional or polyfunctional alcohols and amines with a molecular weight M n in the range between 62 and 1000 g / mol, so-called chain extenders and crosslinkers. Furthermore, catalysts, blowing agents and the usual auxiliaries and / or additives can be used.
  • the customary and known aliphatic and in particular aromatic polyisocyanates can be used as polyisocyanates.
  • polyether ester alcohols produced by the process according to the invention can be used, for example, to produce polyurethane foams, casting compounds or coatings or as
  • Crosslinkers are used.
  • the products with high functionality preferably with a functionality greater than 3, are used in particular for the production of rigid polyurethane foams.
  • Products with a functionality in the range between 2 and 3 are preferably used for the production of flexible polyurethane foams and elastomers. It is thus surprisingly possible to use a simple process by means of DMC catalysis to also provide polyether alcohols with a high functionality, such as can be used for the production of rigid polyurethane foams.
  • polyether alcohols produced in particular by the process according to the invention can be used, in which hydroxycarboxylic acids are used in step a), since the intermediates from step a) then have a low viscosity even with high functionality and are therefore easily reacted with alkylene oxides in step b) can.
  • the polyether ester alcohols produced by the process according to the invention are very easy to handle, are compatible both with polyetherols and with polyesterols and can therefore also be used for applications which were previously closed for polyester alcohols and also for polyether alcohols produced by means of DMC catalysts.
  • Polyol B polyether alcohol according to Example 8 Polyol C sucrose-glycerol propoxylate, molecular weight 630 g / mol, functionality 4
  • Polyol D polypropylene glycol, molecular weight 1000 g / mol (BASF Aktiengesellschaft)
  • DMCHA Dimethylcyclohexylamine (BASF Aktiengesellschaft)
  • R141b 1, 1-dichloro-l-fluoro-ethane Lupranat® M20A: 4, 4 ⁇ -diphenylmethane diisocyanate (BASF Aktiengesellschaft)
  • the homogeneity of the polyol component in Examples 10 and 11 was very good and there was no phase separation.
  • polyether ester alcohols according to the invention polyols A and B, a phase-stable polyol component could be produced with the polyols C and D and the additives. After sales of these polyol mixtures with isocyanate, homogeneous, fine-celled rigid foams were formed without streaking and cracking.

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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)
  • Toxicology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne un procédé de production d'alcools de polyéther comprenant une fonctionnalité supérieure à 2. Ce procédé consiste a) à produire un alcool de polyester ayant une fonctionnalité supérieure à 2, notamment de 3 minimum, en faisant réagir au moins un alcool multifonctionnel avec au moins un acide carboxylique multifonctionnel ; b) à faire réagir cet alcool de polyester avec des oxydes d'alkylène à l'aide d'au moins un catalyseur DMC.
PCT/EP2003/002182 2002-03-08 2003-03-04 Procede de production d'alcools de polyether de haute fonctionnalite WO2003076488A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003210406A AU2003210406A1 (en) 2002-03-08 2003-03-04 Method for the production of highly functional polyether alcohols

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10210125.6 2002-03-08
DE10210125A DE10210125A1 (de) 2002-03-08 2002-03-08 Verfahren zur Herstellung von hochfunktionellen Polyetheralkoholen

Publications (1)

Publication Number Publication Date
WO2003076488A1 true WO2003076488A1 (fr) 2003-09-18

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DE (1) DE10210125A1 (fr)
WO (1) WO2003076488A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004072148A1 (fr) * 2003-02-11 2004-08-26 Basf Corporation Procede destine a extraire et regenerer un catalyseur de cyanure metallique double (dmc) a partir d'un polyol polymere
EP1702941A1 (fr) * 2005-03-19 2006-09-20 Bayer MaterialScience AG Poly(etherester)polyols et leur procede de production
WO2008055952A1 (fr) 2006-11-09 2008-05-15 Basf Se Procédé de production de dispersions de polyol
US9234066B2 (en) 2008-05-13 2016-01-12 Basf Se Process for preparing polyol dispersions
CN107857871A (zh) * 2017-11-13 2018-03-30 常州大学 一种苹果酸多元醇的制备方法及其在聚氨酯泡沫中的应用

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3352829A (en) * 1964-02-12 1967-11-14 Bayer Ag Polyurethane forming compositions containing sulfurous acid esters as retarding agents
US3678009A (en) * 1968-12-17 1972-07-18 Ciba Geigy Ag Thermocurable crystalline polyurethanes based on branched polyesters
US3849515A (en) * 1972-03-07 1974-11-19 Bayer Ag Process for the preparation of polyether/polyester block copolymers
JPH0741538A (ja) * 1993-07-31 1995-02-10 Nippon Polyurethane Ind Co Ltd 加水分解性ポリウレタンフォーム
EP0821019A1 (fr) * 1996-07-26 1998-01-28 Basf Aktiengesellschaft Procédé de préparation de mousses rigides de polyuréthane
WO2001027185A2 (fr) * 1999-10-12 2001-04-19 Basf Aktiengesellschaft Copolymeres blocs de polyester-polyether
DE10001779A1 (de) * 2000-01-18 2001-07-19 Basf Ag Verfahren zur Herstellung von Polyetheralkoholen

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DE3613875A1 (de) * 1986-04-24 1987-10-29 Basf Ag Verfahren zur herstellung von polyester-polyolen

Patent Citations (7)

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Publication number Priority date Publication date Assignee Title
US3352829A (en) * 1964-02-12 1967-11-14 Bayer Ag Polyurethane forming compositions containing sulfurous acid esters as retarding agents
US3678009A (en) * 1968-12-17 1972-07-18 Ciba Geigy Ag Thermocurable crystalline polyurethanes based on branched polyesters
US3849515A (en) * 1972-03-07 1974-11-19 Bayer Ag Process for the preparation of polyether/polyester block copolymers
JPH0741538A (ja) * 1993-07-31 1995-02-10 Nippon Polyurethane Ind Co Ltd 加水分解性ポリウレタンフォーム
EP0821019A1 (fr) * 1996-07-26 1998-01-28 Basf Aktiengesellschaft Procédé de préparation de mousses rigides de polyuréthane
WO2001027185A2 (fr) * 1999-10-12 2001-04-19 Basf Aktiengesellschaft Copolymeres blocs de polyester-polyether
DE10001779A1 (de) * 2000-01-18 2001-07-19 Basf Ag Verfahren zur Herstellung von Polyetheralkoholen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 1995, no. 05 30 June 1995 (1995-06-30) *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004072148A1 (fr) * 2003-02-11 2004-08-26 Basf Corporation Procede destine a extraire et regenerer un catalyseur de cyanure metallique double (dmc) a partir d'un polyol polymere
EP1702941A1 (fr) * 2005-03-19 2006-09-20 Bayer MaterialScience AG Poly(etherester)polyols et leur procede de production
US7687599B2 (en) 2005-03-19 2010-03-30 Bayer Materialscience Ag Poly(ether-ester) polyols and processes for their production
US7893189B2 (en) 2005-03-19 2011-02-22 Bayer Materialscience Ag Poly(ether-ester) polyols and processes for their production
WO2008055952A1 (fr) 2006-11-09 2008-05-15 Basf Se Procédé de production de dispersions de polyol
US8344061B2 (en) 2006-11-09 2013-01-01 Basf Aktiengesellschaft Process for producing polyol dispersions
US9080047B2 (en) 2006-11-09 2015-07-14 Basf Aktiengesellschaft Process for producing polyol dispersions
US9234066B2 (en) 2008-05-13 2016-01-12 Basf Se Process for preparing polyol dispersions
CN107857871A (zh) * 2017-11-13 2018-03-30 常州大学 一种苹果酸多元醇的制备方法及其在聚氨酯泡沫中的应用

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AU2003210406A1 (en) 2003-09-22
DE10210125A1 (de) 2003-09-25

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