EP1448665A1 - Procede de production d'alcools de polyether - Google Patents

Procede de production d'alcools de polyether

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Publication number
EP1448665A1
EP1448665A1 EP02802999A EP02802999A EP1448665A1 EP 1448665 A1 EP1448665 A1 EP 1448665A1 EP 02802999 A EP02802999 A EP 02802999A EP 02802999 A EP02802999 A EP 02802999A EP 1448665 A1 EP1448665 A1 EP 1448665A1
Authority
EP
European Patent Office
Prior art keywords
alkylene oxides
polyether
amines
compounds
polyether alcohols
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP02802999A
Other languages
German (de)
English (en)
Inventor
Bernd Güttes
Kathrin Harre
Gottfried Knorr
Marita Schuster
Monika Wetterling
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1448665A1 publication Critical patent/EP1448665A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2669—Non-metals or compounds thereof
    • C08G65/2672—Nitrogen or compounds thereof
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular 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
    • 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
    • C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G2110/0025—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
    • 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
    • C08G2290/00—Compositions for creating anti-fogging

Definitions

  • the invention relates to a process for the preparation of polyether alcohols by reacting H-functional starter substances with alkylene oxides.
  • polyether alcohols by reacting H-functional starter substances, in particular alcohols and primary and / or secondary amines with alkylene oxides, is generally known.
  • the reaction of the alkylene oxides with the H-functional starter substances is usually carried out in the presence of catalysts, for example basic or acidic substances or multi-metal cyanide catalysts.
  • catalysts for example basic or acidic substances or multi-metal cyanide catalysts.
  • Potassium hydroxide is usually used as a catalyst, which is separated from the polyether alcohol after the synthesis by purification operations such as neutralization, distillation, and filtration. Only these pure polyether polyols are used for the reaction with di- and / or polyisocyanates to form polyurethanes.
  • aminic substances such as triethylamine or, as described in WO 9825878, of alkanolamines as catalysts is also known.
  • the separation of these substances from the polyether alcohol is usually technically difficult. Traces of these amines used as catalysts, however, frequently interfere with the subsequent conversion of the polyether alcohols into polyurethanes.
  • US Pat. No. 3,346,557 describes a process for the preparation of polyether alcohols in which a mixture of solid alcohols and liquid amines is used as the starting substance.
  • the A in serves both as a solvent for the solid alcohols and as a catalyst for the addition of the alkylene oxides.
  • a prepolymer is produced from the solid alcohol and alkylene oxide in the presence of the amines in a first step, which is reacted with further solid alcohol and further amine with alkylene oxides in a second step.
  • the amine is added to the reaction mixture at the beginning of each stage.
  • US Pat. No. 4,228,310 describes a process for the production of polyether alcohols which are suitable for the production of polyisocyanurate foams.
  • carbamate salts, aminophenols, hexahydrotriazines and tetrahydrooxadiazines are used as catalysts.
  • the catalysts are added once at the beginning of the addition of the alkylene oxides. Since the compounds used as catalysts also act as catalysts act for the formation of isocyanurates, they can remain in the product after the production of the polyether alcohols.
  • the object of the invention was to develop a process for the preparation of polyether alcohols using amine catalysts which proceeds in a high space / time yield and in which side reactions are avoided as far as possible, the catalysts remaining in the polyether alcohol after the reaction and at the use of these polyether alcohols for the production of polyurethanes can act as a catalyst.
  • the object is achieved in that amines are used as catalysts in the production of polyether alcohols by reacting alkylene oxides with H-functional starters, the amines being added at least once before or at the beginning of the addition of the alkylene oxides and in the course of the reaction , the repeated addition of the catalyst at the point of the reaction at which there is a strong course of side reactions, and / or when the alkylene oxides in the polyether chain change.
  • the invention relates to a process for the preparation of polyether alcohols by catalytic addition of alkylene oxides to H-functional starter substances using amines as catalysts, characterized in that the addition of the amines to the reaction mixture before or at the beginning of the addition of the alkylene oxides and in the course of the reaction is carried out at least once more, the catalyst being added again at the point of the reaction at which there is a strong course of side reactions and / or when the alkylene oxides in the polyether chain change.
  • the invention further relates to the polyether alcohols produced by the process according to the invention.
  • the invention furthermore relates to the use of the polyether alcohols according to the invention for the production of polyurethanes.
  • the invention further relates to a process for the production of polyurethanes by reacting
  • At least one polyether alcohol according to the invention is used as compounds having at least two hydrogen atoms b) reactive with isocyanate groups.
  • the addition of catalyst can be adjusted accordingly.
  • the catalyst In order to effectively suppress side reactions, the catalyst must be added before the rate of aldehyde formation exceeds 100 ppm aldehyde / 100 g molecular weight build-up.
  • the amount of aldehydes in the reaction mixture can be routinely easily determined in the industrial production of polyether alcohols.
  • the reaction mixture becomes further Amine catalyst added.
  • Amines which can be used as catalysts in the process according to the invention are aliphatic and / or aromatic amines with primary, secondary or tertiary amino groups. Amines with a ring structure in which the nitrogen atom is incorporated in the ring are also particularly suitable.
  • Preferred ring-shaped amines are piperazine derivatives such as 1,4-dimethylpiperazine, N-hydroxyethylpiperazine, 1,3,5-tris (dimethylaminopropyl) hexahydro-s-triazine, and / or N, N-dimethylcyclohexylamine, dimethylbenzylamine and / or 2,2'-bis (2-ethyl-2-azobicycloether) and / or 1,8-diazabicyclo- (5,4,0) undecen-7 and / or morpholine derivatives such as 4-methyl and / or 4-ethyl morpholine and / or 2,2-dimorpholinethyl ether and / or imidazole derivatives such as 1-methyl- and / or 1, 2-dimethylimidazole and / or N- (3-aminopropyl) imidazole, diazobicyclooctane (sold under the name Dabco® by
  • Those amines which are usually used as catalysts for the production of polyurethanes, in particular imidazoles and / or diazobicyclooctane and its derivatives, are preferably used.
  • the reaction products of the amines mentioned with alkylene oxides, in particular, can also be used as catalysts
  • Ethylene oxide and / or propylene oxide, particularly preferably propylene oxide, can be used. These reaction products preferably have a molar mass in the range between 160 to 500 g / mol.
  • the amines with primary and secondary amino groups or hydroxyl groups used according to the invention not only act as catalysts in the preparation of the polyether alcohols.
  • Alkylene oxides can also attach to their free hydrogen atoms. This means that they also act as starting substances in the method according to the invention. By the addition of alkylene oxides to the free hydrogen atoms of the amino groups in the amines used, these amino groups are converted into tertiary amino groups.
  • amines are used which have at least one tertiary amino group and at least one reactive hydrogen atom in the molecule.
  • the reactive hydrogen atoms can preferably come from primary and / or secondary amino groups and / or hydroxyl groups. Since alkylene oxides also attach to these reactive hydrogen atoms and the polyether chains thus formed carry hydroxyl groups at the chain end, these compounds act as built-in catalysts in the formation of polyurethane.
  • the advantage of the built-in catalysts is that they are built into the polyurethane matrix and therefore cannot diffuse out of the foam. The diffusion out of the polyurethane catalysts used is undesirable since they mostly have a strong odor and high fogging and VOC values. VOC values mean the value for volatile organic components.
  • Examples of compounds with tertiary amino groups and reactive hydrogen atoms are N- (2-hydroxyethylmorpholine), N-3 (aminopropyl) imidazole, dirnethylaminopropylamine, diethylaminoethylamine.
  • the amines used according to the invention are preferably used in the preparation of the polyether alcohols in an amount of 0.01 to 50 g, in particular 0.2 to 2 g, per 100 g of starting substance.
  • polyether alcohols for the production of flexible polyurethane foams and rigid polyurethane foams can be produced by the process according to the invention.
  • alcohols with 2 or 3 hydroxyl groups are mostly used as starting substances.
  • Preferred starter substances are glycerol, trimethylolpropane, ethylene glycol, diethylene glycol, propylene glycol, propylene glycol and any mixtures of at least two of the alcohols mentioned.
  • alkylene oxides mostly ethylene oxide and propylene oxide are used alone or together. When using mixtures of ethylene oxide and propylene oxide, the alkylene oxides can be added individually one after the other in so-called blocks or mixed with one another as so-called statistics.
  • an ethylene oxide block can be added to the end of the polyether chain.
  • the polyether alcohols which are used for the production of flexible polyurethane foams usually have a molecular weight M n in the range between 1000 and 10000, in particular 1000 to 7000 g / mol.
  • polyether alcohols which are used in the production of rigid polyurethane foams, mostly starting substances with at least 4 active hydrogen atoms, preferably at least 4-valent alcohols and / or amines with at least 4 reactive hydrogen atoms are used. Both aliphatic and aromatic amines can be used. Aromatic amines are preferred.
  • Examples of at least 4-valent alcohols are sugar alcohols, such as glucose, sorbitol, sucrose, mannitol. Since these compounds are mostly solid, they are usually reacted with the alkylene oxides in a mixture with liquid compounds such as water, glycerol and / or ethylene glycol. In principle, it is also possible in the process according to the invention to use mixtures of the solid compounds mentioned and the amines used according to the invention as the starting substance.
  • Toluene diamine, diphenyl methane diamine and mixtures of diphenyl methane diamine and polyphenylene polymethylene polyamines are mostly used as aromatic amines.
  • As aliphatic amines mostly uses ethylenediamine, diethylenetriamine, dimethylpropylamine or their higher homologues.
  • the reaction of the starting substance with the alkylene oxides is carried out at the pressures customary for this in the range between 0.1 and 1.0 MPa and the customary temperatures in the range between 80 and 140 ° C.
  • the metering of the alkylene oxides is usually followed by a post-reaction phase for the complete reaction of the alkylene oxides.
  • amine catalyst is again added to the reaction mixture at the beginning of the post-reaction phase, preferably immediately after the metering in of the alkylene oxides has ended.
  • the polyether alcohols are usually subjected to a short distillation treatment to remove volatile impurities. If necessary, the polyether alcohol can then be filtered to remove any solid contaminants. It can then be processed into polyurethanes by reaction with polyisocyanates.
  • polyurethanes in particular the polyurethane foams, are produced using the polyether alcohols produced by the process according to the invention by processes known per se by reaction with polyisocyanates, usually in the presence of catalysts, blowing agents, and, if appropriate, chain extenders, crosslinking agents, and auxiliaries and / or additives.
  • Aliphatic and preferably aromatic di- and / or polyisocyanates can be used as polyisocyanates.
  • diisocyanates in particular tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI) are mostly used individually or in a mixture with one another or in a mixture with higher-functionality polyisocyanates.
  • Bifunctional and higher-functional polyisocyanates are preferably used in the production of rigid polyurethane foams.
  • Mixtures of diphenyl methane diisocyanate and polyphenylene polymethylene polyisocyanates, often also referred to as crude MDI, are preferably used.
  • the polyether alcohols according to the invention are used as compounds with at least two hydrogen atoms reactive with isocyanate groups, alone or in a mixture with other compounds with at least two hydrogen atoms reactive with isocyanate groups.
  • the other compounds having at least two H atoms reactive toward isocyanate groups are polyether polyols.
  • polyether polyols These are prepared by known processes, for example by anionic polymerization using alkali hydroxides or alkali alcoholates as catalysts and with the addition of at least one starter molecule which contains 2 to 3 reactive hydrogen atoms, from one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene radical.
  • Suitable alkylene oxides are, for example, tetrahydrofuran, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide and preferably ethylene oxide and 1,2-propylene oxide.
  • the alkylene oxides can be used individually, alternately in succession or as mixtures. Mixtures of 1,2-propylene oxide and ethylene oxide are preferred, the ethylene oxide being used in amounts of 10 to 50% as the ethylene oxide end block, so that over 70% of the resulting polyols have primary OH end groups.
  • Suitable starter molecules are water or di- and trihydric alcohols, such as ethylene glycol, 1,2-propanediol, 2,3 and 1,3, diethylene glycol, dipropylene glycol, 1,4-butanediol, glycerol, trimethylolpropane etc.
  • the polyether polyols preferably polyoxypropylene-polyoxyethylene-polyols, have a functionality of 2 to 3 and molecular weights of 1,000 to 8,000, preferably 2,000 to 7,000.
  • polyetherols are polymer-modified polyether polyols, preferably graft polyether polyols, in particular those based on styrene and / or acrylonitrile, which are prepared by in situ polymerization of acrylonitrile, styrene or preferably mixtures of styrene and acrylonitrile.
  • Polyester polyols are also suitable. These can be prepared, for example, from organic dicarboxylic acids with 2 to 12 carbon atoms, preferably aliphatic dicarboxylic acids with 4 to 6 carbon atoms, polyhydric alcohols, preferably diols, with 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms.
  • dicarboxylic acids Wise consider: succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isdphthalic acid and terephthalic acid.
  • the dicarboxylic acids can be used both individually and in a mixture with one another.
  • dicarboxylic acid derivatives such as, for example, dicarboxylic acid esters of alcohols having 1 to 4 carbon atoms or dicarboxylic acid anhydrides, can also be used.
  • Dicarboxylic acid mixtures of succinic, glutaric and adipic acid and aromatic diacids are preferably used.
  • dihydric and polyhydric alcohols are: ethanediol, diethylene glycol, 1,2- or 1,3-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,1 10-decanediol, glycerol and trimethylolpropane, and also dialcohols which contain aromatic or aliphatic ring systems, such as 1,4-bisdihydroxymethylbenzene or 1,4-bisdihydroxyethylbenzene.
  • Ethanediol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol are preferably used.
  • Polyester polyols from lactones, for example e-caprolactone or hydroxycarboxylic acids, for example w-hydroxycaproic acid, can also be used.
  • Mixing systems which contain both polyesterols and polyetherols can also be used.
  • mixtures of at least two hydrogen atoms reactive with isocyanate groups from mixtures of conventional polyols and polyether alcohols with tertiary amino groups described above which are obtained by reacting amines selected from the group described above containing piperazine derivatives such as 1,4-dimethylpiperazine, N-hydroxyethylpiperazine,
  • 1,3,5-tris (dimethylaminopropyl) hexahydro-s-triazine, and / or N, N-dimethylcyclohexylamine, dimethylbenzylamine and / or 2,2'-bis (2-ethyl-2-azobicycloether) and / or 1, 8-diazabicyclo- (5, 4, 0) - undecene-7 and / or morpholine derivatives such as 4-methyl and / or 4-ethylmorpholine and / or 2,2-dimorpholinethyl ether and / or
  • Imidazole derivatives such as 1-methyl- and / or 1,2-dimethylimidazole and / or N- (3-aminopropyl) imidazole, diazobicyclooctane, triethylamine, dimethylaminopropylamine, diethylaminoethylamine or any mixtures of at least two of the amines mentioned with alkylene oxides were used .
  • the amines are reacted with alkylene oxides without the presence of further starting substances, and the polyether alcohols thus obtained are mixed with other polyether alcohols before the reaction with the polyisocyanates.
  • So-called chain extenders and / or crosslinkers are also often used to produce the polyurethanes. Chain extenders and crosslinking agents are usually two or more functional alcohols or amines with molecular weights in the range between 60 and 400 g / mol.
  • blowing agent Water which reacts with the isocyanate groups with the elimination of carbon dioxide and / or compounds which are inert to the starting compounds of the polyurethane reaction and which evaporate as a result of the heat of reaction during the formation of polyurethane, so-called physical blowing agents, can preferably be used as blowing agent.
  • physical blowing agents are aliphatic hydrocarbons with 3 to 8 carbon atoms, in particular pentanes, halogenated hydrocarbons, or acetals.
  • gases dissolved under pressure in the starting compounds for example carbon dioxide, nitrogen or noble gases as blowing agents.
  • the amines used as catalysts for the production of the polyether alcohols also act as catalysts for the production of polyurethane.
  • additional catalysts can also be used for the production of polyurethane, in particular compounds with tertiary amino groups and / or organic metal compounds, in particular tin compounds.
  • the above-mentioned reaction products of the amines used as catalysts for the preparation of the polyether alcohols with alkylene oxides, in particular ethylene oxide and / or propylene oxide, particularly preferably propylene oxide, with a molar mass in the range between 160 to 400 g / mol can also be used as catalysts.
  • Stabilizers flame retardants and / or pigments, for example, are used as auxiliaries and / or additives.
  • the polyurethanes can be produced by known processes, for example by the one-shot or the prepolymer process, and the foams can be produced by the block foam technique or the molded foam technique.
  • the method according to the invention has several advantages. Since the same aminic for the successive polyaddition reactions for polyether alcohol and polyurethane production Catalysts can be used, it is possible to do without the complex cleaning operations after the production of the polyether alcohols.
  • the targeted addition of the catalysts at monomer change points or at reaction points before the increased by-product formation increases the space / time yield in the production of the polyether alcohols and suppresses the formation of by-products.
  • the polyurethanes produced using the polyether alcohols produced by the process according to the invention are less prone to fogging and are largely odorless. This is due on the one hand to the significantly reduced amount of by-products and on the other hand to the fixation of the catalyst in the polyurethane structure.
  • the foam produced in this way had a density of 29 g / l when foamed freely in the foam cup.
  • the compressive strength of a foam produced with these starting materials in a closed mold with a 10% compression was 0.14 N / mm 2 .
  • Example 4 The procedure was as in Example 4, but instead of the polyether alcohol from Example 3, 82.95 parts by weight of a polyether alcohol based on glycerol, propylene oxide and ethylene oxide with a hydroxyl number of 28 mgKOH / g and an additional 0.35 part by weight of amine catalyst dimethylpropyl diamine were used.
  • Example 6 The procedure was as in Example 6, but instead of 83.3 parts by weight, 82.95 parts by weight of the polyether alcohol based on glycerol, propylene oxide and ethylene oxide with a hydroxyl number of 28 mgKOH / g, 0.5 part by weight of glycerol, 5 parts by weight of amine catalyst Dabco® 2025 from Air Products, no polyether alcohol based on dimethylpropyl diamine and Propylene oxide and 0.35 parts by weight of dimethylpropyldiamine.
  • VOC volatile organic chemicals
  • FOG is a measure of condensable emissions from the foam.

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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)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un procédé permettant de produire des alcools de polyéther par fixation par addition catalytique d'oxydes d'alkylène sur des substances de départ à l'aide d'amines comme catalyseurs. Ledit procédé se caractérise en ce que l'adjonction des amines au mélange de réaction intervient avant ou au début du processus d'addition des oxydes d'alkylène, ainsi qu'au moins une fois encore au cours de la réaction. L'adjonction réitérée du catalyseur intervient au point de réaction auquel se produit une succession marquée de réactions secondaires, et/ou lors du changement d'oxydes d'alkylène dans la chaîne polyéther.
EP02802999A 2001-11-15 2002-11-08 Procede de production d'alcools de polyether Withdrawn EP1448665A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10156014A DE10156014A1 (de) 2001-11-15 2001-11-15 Verfahren zur Herstellung von Polyetheralkoholen
DE10156014 2001-11-15
PCT/EP2002/012493 WO2003042281A1 (fr) 2001-11-15 2002-11-08 Procede de production d'alcools de polyether

Publications (1)

Publication Number Publication Date
EP1448665A1 true EP1448665A1 (fr) 2004-08-25

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EP02802999A Withdrawn EP1448665A1 (fr) 2001-11-15 2002-11-08 Procede de production d'alcools de polyether

Country Status (4)

Country Link
US (1) US20050004403A1 (fr)
EP (1) EP1448665A1 (fr)
DE (1) DE10156014A1 (fr)
WO (1) WO2003042281A1 (fr)

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US20070203319A1 (en) * 2006-02-27 2007-08-30 Dexheimer Edward M Process of forming a polyol
US20070199976A1 (en) * 2006-02-27 2007-08-30 Mao-Yao Huang Process of forming a polyol
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