EP3768746A1 - Verfahren zur herstellung von polyurethanweichschaumstoffen mit hoher rohdichte - Google Patents
Verfahren zur herstellung von polyurethanweichschaumstoffen mit hoher rohdichteInfo
- Publication number
- EP3768746A1 EP3768746A1 EP19711137.0A EP19711137A EP3768746A1 EP 3768746 A1 EP3768746 A1 EP 3768746A1 EP 19711137 A EP19711137 A EP 19711137A EP 3768746 A1 EP3768746 A1 EP 3768746A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- component
- parts
- koh
- weight
- polyols
- 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- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
-
- 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
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/1833—Catalysts containing secondary or tertiary amines or salts thereof having ether, acetal, or orthoester 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/20—Heterocyclic amines; Salts thereof
- C08G18/2009—Heterocyclic amines; Salts thereof containing one heterocyclic ring
- C08G18/2027—Heterocyclic amines; Salts thereof containing one heterocyclic ring having two nitrogen atoms in the ring
-
- 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
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/222—Catalysts containing metal compounds metal compounds not provided for in groups C08G18/225 - C08G18/26
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/302—Water
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
-
- 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
- C08G2110/0041—Foam properties having specified density
- C08G2110/0058—≥50 and <150kg/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
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
Definitions
- the present invention relates to a process for the production of flexible polyurethane foams having a density according to DIN EN ISO 845: 2009-10 of 50.0 to 80.0 kg / m 3 , in particular of high density open-cell polyurethane foams based on polyetherpolyol and tolylene diisocyanate, the resulting polyurethane foams have similar properties to the previously known flexible polyurethane foams but are simpler and more sustainable in their manufacture.
- the first batch is a mixture of 80% by weight of 2,4-tolylene diisocyanate and 20% by weight of 2,6-tolylene diisocyanate obtainable by simple preparation, namely nitration and then reduction to amine and phosgenation.
- the second mixture consists of 67% by weight of 2,4-tolylene diisocyanate and 33% by weight of 2,6-tolylene diisocyanate and, in order to obtain the higher content of 2,6-tolylene diisocyanate, it must be worked up in a cost-intensive and labor-intensive manner.
- tolylene diisocyanate is crystallized out of the mixture in order to increase the proportion of 2,6-toluene diisocyanate.
- the higher content of 2,6-toluene diisocyanate is necessary to increase the content of this compound in the reaction for the flexible polyurethane foams.
- the higher content of 2,6-tolylene diisocyanate is again necessary to obtain the desired open-celledness.
- the object of the present invention was therefore to find a system for the production of flexible foams of high bulk density, in which the use of the reclaimed by crystallization charge of Toluylendiisocyanatgemischs can be reduced or completely avoided.
- the inventors of the present invention have surprisingly found that this is possible through the use of specific carboxylic acid esters of the present invention.
- the object of the present invention is achieved by a process for producing polyurethane foams having a density according to DIN EN ISO 845: 2009-10 of 50.0 to 80.0 kg / m 3 by reacting
- R 1 is an aromatic hydrocarbon radical having at least 5 carbon atoms or is a linear, branched, substituted or unsubstituted aliphatic hydrocarbon radical having at least 2 or in the case of branched at least 3 carbon atoms;
- R 2 is a linear, branched, substituted or unsubstituted aliphatic hydrocarbon radical
- the present invention relates to:
- diisocyanates and / or polyisocyanates which contain 2,4-tolylene diisocyanate and 2,6-
- the preparation being carried out at a ratio of 90 to 120, preferably 100 to 115, particularly preferably 102 to 110,
- R 1 is an aromatic hydrocarbon radical having at least 5 carbon atoms or a linear, branched, substituted or unsubstituted aliphatic radical
- Hydrocarbon radical having at least 2, in the case of branched at least 3, carbon atoms
- R 2 is a linear, branched, substituted or unsubstituted aliphatic
- Hydrocarbon radical is;
- n 1 to 3.
- R 1 is an aromatic hydrocarbon radical having at least 6 carbon atoms or a linear, branched, substituted or unsubstituted aliphatic radical
- Hydrocarbon radical having at least 3, preferably 3 to 10, carbon atoms
- R 2 is a linear, branched, substituted or unsubstituted aliphatic
- Hydrocarbon radical having at least 3, preferably 3 to 16, carbon atoms; and n is 1 to 3; preferably R 1 is an aromatic hydrocarbon radical having 6 carbon atoms or a linear, branched, substituted or unsubstituted aliphatic saturated hydrocarbon radical having at least 3, preferably 3 to 10, carbon atoms;
- the compound is an ester of an optionally substituted C 3-12 monocarboxylic acid which has been esterified with a linear or branched C 3-16 alkylalcohol, especially hexylhexanoate;
- component A has the following composition:
- A2 0 to 60 parts by wt., Preferably 0.1 to 20 wt. Parts of one or more polyether carbonate polyols having a hydroxyl number according to DIN 53240-1: 2013-06 of 20 mg KOH / g to 120 mg KOH / g,
- A3 is from 0 to 60 parts by weight, preferably from 0.1 to 20 parts by weight, based on the sum of the parts by weight of components A1 and A2, of one or more polyether polyols having a hydroxyl number according to DIN 53240-1: 2013- 06 from 20 mg KOH / g to 250 mg KOH / g, and a content of ethylene oxide of at least 60 wt .-%, wherein the polyether polyols A3 are in particular free of carbonate units, A4 from 0 to 40 parts by weight, preferably from 0.1 to 30 parts by weight, based on the sum of the parts by weight of the components A1 and A2, of one or more polymer polyols, PHD polyols and / or PIPA polyols,
- A5 0 to 40 parts by wt., Preferably 0.1 to 25 parts by wt., Based on the sum of the parts by wt.
- polyols which do not fall under the definition of the components A1 to A4, where all parts by weight of the components Al, A2, A3, A4, A5 are normalized such that the sum of parts by weight gives Al + A2 in the composition 100.
- aliphatic tertiary amines a) aliphatic tertiary amines, cycloaliphatic tertiary amines, aliphatic amino, cycloaliphatic amino, aliphatic amidines, cycloaliphatic amidines, urea and derivatives of urea and / or
- B2 optionally adjuvants and additives are used.
- component A comprises:
- polyether polyols having a hydroxyl value according to DIN 53240 of 20 mg KOH / g to 250 mg KOH / g, preferably 40 to 60 mg KOH / g, and a content of ethylene oxide of 0.10 59.0 wt .-%, preferably 1 to 30 wt .-%, more preferably 5 to 15 wt .-% and / or a content of propylene oxide from 40 to 99.9 wt .-%, preferably 70 to 99 wt. %, more preferably 85 to 95% by weight, wherein the polyether polyols are free from carbonate units, and
- component A2 comprises a polyethercarbonate polyol obtainable by copolymerization of carbon dioxide, one or more alkylene oxides, in the presence of one or more H-functional starter molecules, the polyethercarbonate polyol preferably having a C0 2 - Has content of 15 to 25 wt .-%.
- component D comprises at least 50 wt .-%, preferably at least 80 wt .-% 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate.
- component D at most 26.5% by weight of 2,6-tolylene diisocyanate are present, based on the total weight of component D, preferably wherein 22.0 to 26, 5 wt% of 2,6-tolylene diisocyanate based on the total weight of component D, more preferably wherein 20.0 to 23.3 wt% of 2,6-tolylene diisocyanate are contained based on the total weight of the component Component D, most preferably wherein 20.0% by weight of 2,6-tolylene diisocyanate are included, based on the total weight of component D.
- polyurethane foams according to aspect 11 characterized in that it is polyurethane flexible foams, in particular open-cell polyurethane flexible foams.
- polyurethane foams for the manufacture of furniture upholstery, textile inserts, mattresses, automobile seats, headrests, armrests, sponges, foam sheets for use in automotive parts such as headliners, door panels, seat cushions and building components.
- Two-component system for the production of polyurethane foams having a density according to DIN EN ISO 845: 2009-10 of 50.0 to 80.0 kg / m 3 comprising a first component K 1 comprising or consisting of:
- Component A) comprising one or more polyether polyols, in particular having a hydroxyl number according to DIN 53240-1: 2013-06 of 20 mg KOH / g to 250 mg KOH / g, preferably 40 to 60 mg KOH / g, and a content of ethylene oxide of 0.10 to 59.0 wt .-% (component Al), wherein the polyether polyols Al are preferably free of carbonate units,
- R 1 is an aromatic hydrocarbon radical having at least 5 carbon atoms or is a linear, branched, substituted or unsubstituted aliphatic hydrocarbon radical having at least 2 carbon atoms;
- R 2 is a linear, branched, substituted or unsubstituted aliphatic hydrocarbon radical
- n 1 to 3
- diisocyanates and / or polyisocyanates which contain or consist of 2,4-tolylene diisocyanate and tolylene 2,6-diisocyanate,
- the component Kl and the component K2 in a ratio of an isocyanate index of 90 to 120, preferably 100 to 115, more preferably 102 to 110, to each other.
- Another aspect of the invention is a process for the production of polyurethane foams, preferably flexible polyurethane foams, by reacting
- the preparation being carried out at a ratio of 90 to 120, preferably 100 to 115, particularly preferably 102 to 110,
- the components A1 to A5 each refer to "one or more" of said compounds.
- the quantity corresponds to the sum of the parts by weight of the compounds.
- component A contains
- component A is preferably free of component A3 and / or A4.
- component A comprises Al ⁇ 95 to> 65 parts by wt., Preferably ⁇ 90 to> 80 wt.
- A3 ⁇ 20 to> 2 parts by wt., Preferably ⁇ 10 to> 2 wt. Parts, based on the sum of the parts by wt.
- components Al and A2 of one or more polyether polyols having a hydroxyl number according to DIN 53240> 20 mg KOH / g to ⁇ 250 mg KOH / g, and a content of ethylene oxide of> 60 wt .-%, wherein the polyether polyols A3 are in particular free of carbonate units,
- component A is preferably free of component A4.
- component A comprises
- Parts of one or more polyether polyols a hydroxyl number according to D1N 53240 of> 20 mg KOH / g to ⁇ 250 mg KOH / g and an ethylene oxide content of 0.10 to 59.0 wt.%, preferably 1 to 30 wt.%, more preferably 5 to 15 wt .-% and / or a content of propylene oxide from 40 to 99.9 wt .-%, preferably 70 to 99 wt .-%, more preferably 85 to 95 wt -.%, Wherein the polyether polyols Al preferably free of carbonate are and
- A5 ⁇ 40 to> 0 parts by weight, preferably ⁇ 20 to> 0.01 parts by weight, based on the sum of the parts by weight of the components Al and A2, polyols which are not covered by the definition of the components Al to A4 fall, wherein the component A is preferably free from Component A3.
- the specified ranges and preferred ranges of the components A1, A2, A4 and A5 are freely combinable with one another.
- component A consists only of Al.
- the component Al comprises polyether polyols, preferably having a hydroxyl number according to DIN 53240 of> 20 mg KOH / g to ⁇ 250 mg KOH / g, preferably from> 20 to ⁇ 112 mg KOH / g and more preferably> 20 mg KOH / g to ⁇ 80 mg KOH / g.
- the component Al is free of carbonate moieties.
- the preparation of the compounds according to Al can be carried out by catalytic addition of one or more alkylene oxides to H-functional starter compounds.
- alkylene oxides it is possible to use alkylene oxides having 2 to 24 carbon atoms.
- the alkylene oxides having 2 to 24 carbon atoms are, for example, one or more compounds selected from the group consisting of ethylene oxide, propylene oxide, 1-butene oxide, 2,3-butene oxide, 2-methyl-1,2-propene oxide (isobutene oxide), 1- pentenoxide, 2,3-pentenoxide, 2-methyl-l, 2-butene oxide, 3-methyl-1,2-butene oxide, l-hexene oxide, 2,3-hexene oxide, 3,4-hexene oxide, 2-methyl- l, 2-pentenoxide, 4-methyl-l, 2-pentenoxide, 2-ethyl-1, 2-butene oxide, 1-epoxide, 1-octene oxide, 1-nonoxide, 1-decene oxide, 1-undecenoxide, 1-dodecene oxide, 4-methyl-l, 2-pentenoxide, but
- the alkylene oxides used are preferably ethylene oxide and / or propylene oxide and / or 1,2-butylene oxide. Particularly preferred is a Excess of propylene oxide and / or 1, 2-butylene oxide used.
- the alkylene oxides can be fed to the reaction mixture individually, in a mixture or in succession. They may be random or block copolymers. If the alkylene oxides are metered in succession, the products produced (polyether polyols) contain polyether chains with block structures.
- the H-functional starter compounds have functionalities of> 2 to ⁇ 6 and are preferably hydroxy-functional (OH-functional).
- hydroxy-functional starter compounds are propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, 1, 2-butanediol, l, 3-butanediol, 1, 4-butanediol, hexanediol, pentanediol, 3-methyl-l, 5-pentanediol, l, l2-dodecanediol , Glycerol, trimethylolpropane, triethanolamine, pentaerythritol, sorbitol, sucrose, hydroquinone, pyrocatechol, resorcinol, bisphenol F, bisphenol A, 1,3,5-trihydroxybenzene, condensates of formaldehyde and phenol or melamine or urea containing methylol groups. These can also be used in mixture.
- the polyether polyols according to Al have a content of> 0.1 to ⁇ 59.0 wt .-%, preferably from> 1 to ⁇ 30 wt .-%, more preferably> 5 to ⁇ 15 wt .-% of ethylene oxide and / or a content of 40 to 99.9 wt .-%, preferably 70 to 99 wt .-%, more preferably 85 to 95 wt -.% Of propylene oxide.
- the propylene oxide units are terminal.
- Component A2 comprises a polyethercarbonate polyol having a preferred hydroxyl number (OH number) according to DIN 53240-1: 2013-06 of> 20 mg KOH / g to ⁇ 120 mg KOH / g, preferably from> 20 mg KOH / g to ⁇ 100 KOH / g, more preferably from> 25 mg KOH / g to ⁇ 90 mg KOH / g, which can be obtained by copolymerization of carbon dioxide, one or more alkylene oxides, in the presence of one or more H-functional starter molecules, wherein the polyethercarbonate polyol is preferably has a CO2 content of 15 to 25 wt .-%.
- OH number hydroxyl number
- Component A2 preferably comprises a polyethercarbonate polyol which is obtainable by copolymerization of> 2% by weight to ⁇ 30% by weight of carbon dioxide and> 70% by weight to ⁇ 98% by weight of one or more alkylene oxides, in the presence of one or more several H-functional starter molecules having an average functionality of> 1 to ⁇ 6, preferably from> 1 to ⁇ 4, especially preferably from> 2 to ⁇ 3.
- H-functional is understood to mean a starter compound which has active H atoms in relation to alkoxylation.
- the copolymerization of carbon dioxide and one or more alkylene oxides is preferably carried out in the presence of at least one DMC catalyst (double metal cyanide catalyst).
- DMC catalyst double metal cyanide catalyst
- the polyether carbonate polyols used according to the invention also have ether groups between the carbonate groups, which is shown schematically in formula (II).
- R is an organic radical such as alkyl, alkylaryl or aryl, which may also contain heteroatoms such as O, S, Si, etc.
- e and f are an integer number.
- the polyethercarbonate polyol shown in the scheme according to formula (11) is merely to be understood so that blocks having the structure shown can in principle be found in the polyethercarbonate polyol, but the order, number and length of the blocks can vary and not to that shown in formula (11) Polyethercarbonatepolyol is limited. With respect to formula (II), this means that the ratio of e / f is preferably from 2: 1 to 1:20, more preferably from 1.5: 1 to 1:10.
- the proportion of incorporated CO2 ("carbon dioxide-derived units", "CCk content") in a polyethercarbonate polyol can be determined from the evaluation of characteristic signals in the H-NMR spectrum.
- the following example illustrates the determination of the level of carbon dioxide-derived moieties in a C0 2 / propylene oxide polyether carbonate polyol started on l, 8-octanediol.
- the proportion of incorporated CO.sub.2 in a polyethercarbonate polyol and the ratio of propylene carbonate to polyethercarbonate polyol can be determined by 1H-NMR (a suitable device is from Broker, DPX 400, 400 MHz, pulse program zg30, waiting time dl: 10s, 64 scans). Each sample is dissolved in deuterated chloroform.
- N [F (5,1-4,8) -F (4,5)] * 102 + F (4,5) * 102 + F (2,4) * 58 + 0,33 * F (l, 2 - 1.0) * 58 + 0.25 * F (l, 6 - 1.52) * 146 (IV)
- F (4,5) area of resonance at 4.5 ppm for cyclic carbonate (equivalent to one atom of H)
- F (5, 1-4,8) area of resonance at 5, 1-4,8 ppm for polyethercarbonate polyol and a H atom for cyclic carbonate.
- F (1, 6-l, 52) area of resonance at 1.6 to 1.52 ppm for 1.8 octanediol (starter), if any.
- the factor 102 results from the sum of the molar masses of CO2 (molar mass 44 g / mol) and that of propylene oxide (molar mass 58 g / mol), the factor 58 results from the molar mass of propylene oxide and the factor 146 results from the molar mass of the initiator used 1,8-octanediol (if present).
- the indication of the C0 2 content in the polyethercarbonate polyol is normalized to the proportion of the polyethercarbonate polyol molecule formed in the copolymerization and, if appropriate, the activation steps in the presence of CO 2 (ie the proportion of the polyethercarbonate polyol molecule present from the initiator (1, US Pat. 8-octanediol, if any) and from the reaction of the initiator with epoxide resulting added under C0 2 -free conditions was not considered).
- the preparation of polyethercarbonate polyols according to A2 comprises:
- an H-functional initiator compound or a mixture of at least two H-functional starter compounds and optionally water and / or other volatile compounds by increased temperature and / or reduced pressure are removed ("drying"), wherein the DMC catalyst the H-functional initiator compound or the mixture of at least two H-functional starter compounds is added before or after drying,
- step (ß) for the activation of a partial amount (based on the total amount used in the activation and copolymerization of alkylene oxides) of one or more alkylene oxides to the mixture resulting from step (a) is added, wherein this addition of a partial amount of alkylene oxide, optionally in the presence CO2 can be carried out, and in which case the temperature peak occurring due to the following exothermic chemical reaction ("hotspot") and / or a pressure drop in the reactor is respectively awaited, and wherein the step ( ⁇ ) for activating can also take place several times,
- step (g) one or more of the alkylene oxides and carbon dioxide are added to the mixture resulting from step ( ⁇ ), wherein the alkylene oxides used in step ( ⁇ ) may be the same or different from the alkylene oxides used in step (g).
- alkylene oxides (epoxides) having 2 to 24 carbon atoms can be used to prepare the polyethercarbonate polyols A2.
- the alkylene oxides having 2 to 24 carbon atoms are, for example, one or more compounds selected from the group consisting of ethylene oxide, propylene oxide, 1-butene oxide, 2,3-butene oxide, 2-methyl-1,2-propene oxide (isobutene oxide), 1-pentoxide, 2,3-pentene oxide, 2-methyl-1,2-butene oxide, 3-methyl-1,2-butene oxide, 1-hexene oxide, 2,3-hexene oxide, 3,4-hexene oxide, 2-methyl- l, 2-pentenoxide, 4-methyl-l, 2-pentenoxide, 2-ethyl-l, 2-butene oxide, 1-epoxide, 1-octene oxide, 1-nonoxide, 1-decene oxide, 1-undecenoxide, 1-dodecenoxide, 4-methyl-1, 2-pentene oxide, butadiene monoxide, isoprene monoxide, cyclopentene oxide, cyclohexene oxide, cycl
- the proportion of ethylene oxide in the total amount of propylene oxide and ethylene oxide used is> 0 and ⁇ 90 wt .-%, preferably> 0 and ⁇ 50 wt .-% and particularly preferably free of ethylene oxide.
- H-functional starter compound compounds with active for the alkoxylation H atoms can be used.
- alkoxylation active groups having active H atoms are, for example, -OH, -NH 2 (primary amines), -NH- (secondary amines), -SH and -CO 2 H, preferred are -OH and -NH 2, more preferably -OH.
- H-functional starter compound for example, one or more compounds selected from the group consisting of water, monohydric or polyhydric alcohols, polyhydric amines, polyhydric thiols, amino alcohols, thio alcohols, hydroxy esters, polyether polyols, polyester polyols, polyester ether, polyether carbonate, polycarbonate, polycarbonates, polyethyleneimines Polyetheramines (eg so-called Jeffamine® from Huntsman, such as eg D-230, D-400, D-2000, T-403, T-3000, T-5000 or corresponding products of BASF, such as e.g.
- polytetrahydrofurans eg, BASF's PolyTHF®, such as PolyTHF® 250, 650S, 1000, 1000S, 1400, 1800, 2000
- Polytetrahydrofuranamine BASF product polytetrahydr
- the C1-C24 alkyl fatty acid esters which contain on average at least 2 OH groups per molecule are commercial products such as Lupranol Balance® (BASF AG), Merginol® types (Hobum Oleochemicals GmbH), Sovermol® types (Cognis Germany GmbH & Co. KG) and Soyol®TM types (USSC Co.).
- Alcohols, amines, thiols and carboxylic acids can be used as monofunctional starter compounds.
- monofunctional alcohols can be used: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 3-buten-1-ol, 3-butyn-1-ol, 2-methyl 3-buten-2-ol, 2-methyl-3-butyn-2-ol, propargyl alcohol, 2-methyl-2-propanol, lt-butoxy-2-propanol., 1-pentanol, 2-pentanol, 3 Pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 4-octanol, phenol, 2-hydroxybiphenyl, 3 Hydroxybi
- Suitable monofunctional amines are: butylamine, t-butylamine, pentylamine, hexylamine, aniline, aziridine, pyrrolidine, piperidine, morpholine.
- monofunctional thiols can be used: ethanethiol, 1-propanethiol, 2-propanethiol, 1-butanethiol, 3-methyl-1-butanethiol, 2-butene-1-thiol, thiophenol.
- monofunctional carboxylic acids may be mentioned: formic acid, acetic acid, propionic acid, butyric acid, fatty acids such as stearic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, acrylic acid.
- suitable polyhydric alcohols are, for example, dihydric alcohols (such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, l, 3-propanediol, 1, 4-butanediol, 1, 4-butenediol, 1, 4-butynediol, neopentyl glycol, l , 5-pentanediol, methylpentanediols (such as, for example, 3-methyl-1,5-pentanediol), 1,6-hexanediol, 1,8-octanediol, 1, 10-decanediol, 1, 12-dodecanediol, bis-
- dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, l, 3-propanediol, 1, 4-butanediol, 1, 4-butenediol, 1, 4-but
- Triethylene glycol tetraethylene glycol, polyethylene glycols, dipropylene glycol, tripropylene glycol, polypropylene glycols, dibutylene glycol and polybutylene glycols); trihydric alcohols (such as, for example, trimethylolpropane, glycerol, trishydroxyethyl isocyanurate,
- Castor oil Castor oil); tetrahydric alcohols (such as pentaerythritol); Polyalcohols (such as sorbitol, hexitol, sucrose, starch, starch hydrolysates, cellulose, cellulose hydrolysates, hydroxy-functionalized fats and oils, in particular castor oil), and all modification products of these aforementioned alcohols with different amounts of e-caprolactone.
- H-functional initiators it is also possible to use trihydric alcohols, for example trimethylolpropane, glycerol, trishydroxyethyl isocyanurate and castor oil.
- the H-functional starter compounds may also be selected from the class of polyether polyols, in particular those having a molecular weight Mn in the range of 100 to 4000 g / mol, preferably 250 to 2000 g / mol. Preference is given to polyether polyols which are composed of repeating ethylene oxide and propylene oxide units, preferably with a proportion of 35 to 100% propylene oxide units, more preferably with a proportion of 50 to 100% propylene oxide units. These may be random copolymers, gradient copolymers, alternating or block copolymers of ethylene oxide and propylene oxide.
- Suitable polyether polyols composed of repeating propylene oxide and / or ethylene oxide units are, for example, the Desmophen®, Acclaim®, Arcol®, Baycoll®, Bayfill®, Bayflex® Baygal®, PET® and polyether polyols Covestro GmbH AG (such as Desmophen® 3600Z, Desmophen® 1900U, Acclaim® Polyol 2200, Acclaim® Polyol 40001, Arcol® Polyol 1004, Arcol® Polyol 1010, Arcol® Polyol 1030, Arcol® Polyol 1070, Baycoll® BD 1110, Bayfill® VPPU 0789, Baygal® K55, PET® 1004, Desmophen® 50RE40).
- Desmophen®, Acclaim®, Arcol®, Baycoll®, Bayfill®, Bayflex® Baygal®, PET® and polyether polyols Covestro GmbH AG such as Desmophen® 3600Z, Desmophen® 1900U, Acclaim® Polyo
- suitable homo-polyethylene oxides are, for example, the Pluriol® E grades from BASF SE
- suitable homopolypropylene oxides are, for example, the Pluriol® P grades from BASF SE
- suitable mixed copolymers of ethylene oxide and propylene oxide are, for example, Pluronic® PE or Pluriol® RPE - Trademarks of BASF SE.
- the H-functional starter compounds may also be selected from the class of substances of the polyesterpolyols, in particular those having a molecular weight Mn in the range from 200 to 4500 g / mol, preferably from 400 to 2500 g / mol.
- Polyester polyols used are at least difunctional polyesters. Polyester polyols preferably consist of alternating acid and alcohol units. As acid components z. Succinic, maleic, maleic, adipic, phthalic, phthalic, isophthalic, terephthalic, tetrahydrophthalic,
- polyester polyethers are obtained which can likewise serve as starter compounds for the preparation of the polyether carbonate polyols. If polyether polyols are used to prepare the polyester ether polyols, polyether polyols having a number average molecular weight Mn of 150 to 2000 g / mol are preferred.
- polycarbonate polyols such as polycarbonate diols
- polycarbonate polyols can be used, in particular those having a molecular weight Mn in the range of 150 to 4500 g / mol, preferably 500 to 2500, for example by reacting phosgene, dimethyl carbonate, diethyl carbonate or diphenyl carbonate and di- and / or polyfunctional alcohols or polyester polyols or polyether polyols.
- polycarbonate polyols are found, for. As in EP-A 1359177.
- Desmophen® C-types of Covestro Germany AG can be used, such as. Desmophen® C 1100 or Desmophen® C 2200.
- polyethercarbonate polyols can be used as H-functional starter compounds.
- polyether carbonate polyols prepared by the method described above are used.
- These polyether carbonate polyols used as H-functional starter compounds are prepared beforehand in a separate reaction step for this purpose.
- Preferred H-functional starter compounds are alcohols of the general formula (VI)
- alcohols according to formula (VI) are ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol and 1,12-dodecanediol.
- H-functional starter compounds are neopentyl glycol, trimethylolpropane, glycerol, pentaerythritol, reaction products of the alcohols of the formula (II) with e-caprolactone, for example reaction products of trimethylolpropane with e-caprolactone, reaction products of glycerol with e-caprolactone, and reaction products of pentaerythritol with e-caprolactone.
- Preference is furthermore given to using water, diethylene glycol, dipropylene glycol, castor oil, sorbitol and polyether polyols composed of repeating polyalkylene oxide units as H-functional starting compounds.
- the H-functional starter compounds are particularly preferably one or more compounds selected from the group consisting of ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,1-pentanediol, 2-methylpropane-1, 3-diol, neopentyl glycol, l, 6-hexanediol, diethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, di- and trifunctional polyether polyols, wherein the polyether polyol from a di- or tri-H-functional starter substance and propylene oxide or a di- or tri-H-functional starter substance, propylene oxide and ethylene oxide is constructed.
- the polyether polyols preferably have a number average molecular weight Mn in the range of 62 to 4500 g / mol and in particular a number average molecular weight Mn in the range of 62 to 3000 g / mol, very particularly preferably a molecular weight of 62 to 1500 g / mol.
- the polyether polyols preferably have a functionality of> 2 to ⁇ 3.
- the polyethercarbonate polyol A2 is obtainable by addition of carbon dioxide and alkylene oxides to H-functional starter compounds using multimetal cyanide (DMC) catalysts.
- DMC multimetal cyanide
- the preparation of polyethercarbonate polyols by addition of alkylene oxides and CO.sub.2 to H-functional starter compounds using DMC catalysts is known, for example, from EP-A 0222453, WO-A 2008/013731 and EP-A 2115032.
- DMC catalysts are known, in principle, from the prior art for the homopolymerization of epoxides (see, for example, US-A 3 404 109, US-A 3 829 505, US-A 3 941 849 and US-A 5 158 922). DMC catalysts, e.g. in US Pat. No.
- a typical example are the highly active DMC catalysts described in EP-A 700 949 which, in addition to a double metal cyanide compound (eg zinc hexacyanocobaltate (III)) and an organic complex ligand (eg tert-butanol), also have a polyether with a number average molecular weight Mn greater than 500 g / mol.
- a double metal cyanide compound eg zinc hexacyanocobaltate (III)
- an organic complex ligand eg tert-butanol
- the DMC catalyst is usually used in an amount of ⁇ 1% by weight, preferably in an amount of ⁇ 0.5% by weight, more preferably in an amount of ⁇ 500 ppm and in particular in an amount of ⁇ 300 ppm, each based on the weight of the polyether carbonate used.
- the polyethercarbonate polyol A2 has a content of carbonate groups ("units derived from carbon dioxide"), calculated as CO 2, of> 2.0 and ⁇ 30.0 wt.%, Preferably of> 5.0 and ⁇ 28.0 wt .-% and particularly preferably of> 10.0 and ⁇ 25.0 wt .-% to.
- the polyether carbonate polyols or polyols A2 have a hydroxyl number of> 20 mg KOH / g to ⁇ 250 mg KOH / g and are obtainable by copolymerization from> 2.0% by weight to ⁇ 30.0 Wt .-% carbon dioxide and> 70 wt .-% to ⁇ 98 wt .-% of propylene oxide in the presence of a hydroxy-functional starter molecule, such as trimethylolpropane and / or glycerol and / or propylene glycol and / or sorbitol.
- the hydroxyl number can be determined according to DIN 53240.
- a polyethercarbonate polyol A2 comprising blocks of the formula (II) where the ratio e / f is from 2: 1 to 1:20.
- Component A3 comprises polyether polyols having a hydroxyl number according to DIN 53240> 20 mg KOH / g to ⁇ 250 mg KOH / g, preferably from> 20 to ⁇ 112 mg KOH / g and more preferably> 20 mg KOH / g to ⁇ 80 mg KOH /G.
- the preparation of the component A3 is in principle analogous to that of the component Al, but a content of ethylene oxide in the polyether polyol of> 60 wt .-%, preferably> 65% by weight is set.
- alkylene oxides and H-functional starter compounds are the same in question, as described for component Al.
- H-functional starter compounds preference is given to those which have a functionality of> 3 to ⁇ 6, more preferably of 3, so that polyether triols arise.
- Preferred starter compounds having a functionality of 3 are glycerol and / or trimethylolpropane, particularly preferred is glycerol.
- the component A3 is a glycerol-started trifunctional polyether having an ethylene oxide content of 68 to 73 wt .-% and an OH number of 35 to 40 mg KOH / g.
- Component A4 includes polymer polyols, PHD polyols, and PIPA polyols.
- Polymer polyols are polyols which contain portions of free radical polymerization monomers such as styrene or acrylonitrile in a base polyol, e.g. a polyether polyol and / or Polyethercabonatpolyol, produced solid polymers.
- PHD (polyurea dispersion) polyols are prepared, for example, by in situ polymerization of an isocyanate or an isocyanate mixture with a diamine and / or hydrazine in a polyol, preferably a polyether polyol.
- the PHD dispersion is preferably prepared by reacting an isocyanate mixture used from a mixture of 75 to 85% by weight of 2,4-tolylene diisocyanate (2,4-TDI) and 15 to 25% by weight of 2,6-tolylene diisocyanate (2,6-TDI) with a diamine and / or hydrazine in a polyether polyol, preferably a polyether polyol and / or polyether carbonate polyol, prepared by alkoxylation of a trifunctional initiator (such as glycerol and / or trimethylolpropane) in the case of the polyethercarbonate polyol in the presence of carbon dioxide , Methods of making PHD dispersions are described, for example, in US 4,089,835 and US 4,260,530.
- the PIPA polyols are polyisocyanate polyaddition with alkanolamine-modified, preferably triethanolamine-modified polyether polyols and / or polyether carbonate polyols, wherein the polyether (carbonate) polyol has a functionality of 2.5 to 4 and a hydroxyl number of> 3 mg KOH / g to ⁇ 112 mg KOH / g (molecular weight 500 to 18,000).
- the polyether polyol is "EO capped", i. the polyether polyol has terminal ethylene oxide groups.
- PIPA polyols are described in detail in GB 2 072 204 A, DE 31 03 757 A1 and US 4,374,209 A.
- component A5 As component A5, it is possible to use all polyhydroxy compounds known to the person skilled in the art which do not fall under the definition of the components A1 to A4, and preferably have an average OH functionality of> 1.5.
- diols eg 1, 2-ethanediol, 1,3- or 1,2-propanediol, 1,4-butanediol
- triols eg glycerol, trimethylolpropane
- tetraoie eg pentaerythritol
- polyesterpolyols polythioetherpolyols or polyacrylatepolyols
- polyether polyols or polycarbonate polyols which do not fall under the definition of the components A1 to A4.
- It can e.g. Also be used ethylenediamine and triethanolamine started polyethers.
- catalysts according to the component B 1 are preferably
- aliphatic tertiary amines for example trimethylamine, tetramethylbutanediamine,
- tin (II) salts of carboxylic acids are used, the respective underlying carboxylic acid having from 2 to 24 carbon atoms.
- tin (II) salts of carboxylic acids one or more compounds selected from the group consisting of tin (II) salt of 2-ethylhexanoic acid (ie, stannous (2-ethylhexanoate) or stannous octoate), stannous (II ) Salt of 2-butyloctanoic acid, stannous salt of 2-hexyldecanoic acid, stannous salt of neodecanoic acid, stannous salt of isononanoic acid, tin (II) salt of oleic acid, stannous (II ) Salt of ricinoleic acid and tin (II) laurate used.
- x is an integer from 8 to 24, preferably 10 to 20, particularly preferably from 12 to 18.
- Particularly preferred in formula (IX) is the alkyl chain C X H 2X + I of the carboxylate is a branched carbon chain, ie C X H 2X + I is an iso-alkyl group.
- tin (II) salts of carboxylic acids are one or more compounds selected from the group consisting of stannous salt of 2-butyloctanoic acid, i. Tin (II) - (2-butyloctoate), stannous (II) salt of ricinoleic acid, i. Tin (II) ricinoleate and stannous salt of 2-hexyl decanoic acid, i. Tin (II) - (2-hexyldecanoate) used.
- Component Bl.l comprises urea and derivatives of urea.
- derivatives of urea mention may be made, for example, of aminoalkyl ureas, e.g. (3-Dimethylaminopropylamine) - urea and l, 3-bis [3- (dimethylamino) propyl] urea. It is also possible to use mixtures of urea and urea derivatives. Preference is given to using exclusively urea in component B1.1.
- the component Bl.l is used in amounts of> 0.05 to ⁇ 1.5 parts by weight, preferably from> 0.1 to ⁇ 0.5 parts by weight, particularly preferably from> 0.25 to ⁇ 0, 35 parts by weight, based on the sum of the parts by weight of components Al to A2 used.
- Component Bl.2 is used in amounts of> 0.03 to ⁇ 1.5 parts by weight, preferably> 0.03 to ⁇ 0.5 parts by weight, more preferably from> 0.1 to ⁇ 0.3 Parts by weight, very particularly preferably from> 0.2 to ⁇ 0.3 parts by weight, based on the sum of the parts by weight of the components Al to A2 used.
- component Bl.2 The content of amine catalysts in component Bl.2 is preferably at most 50% by weight, based on component B1.1, more preferably at most 25% by weight, based on component B1.1. Most preferably, component Bl.2 is free from amine catalysts.
- catalysts of component Bl.2 for example, the tin (II) salts of carboxylic acids described above can be used.
- aminic catalysts may be mentioned: aliphatic tertiary amines (for example trimethylamine, tetramethylbutanediamine, 3-dimethylaminopropylamine, N, N-bis (3-dimethylaminopropyl) -N-isopropanolamine), cycloaliphatic tertiary amines (for example 1, 4-diaza (2,2,2) bicyclooctane), aliphatic amino ethers (e.g., bis-dimethylaminoethyl ether, 2- (2-dimethylaminoethoxy) ethanol, and N, N, N-trimethyl-N-hydroxyethyl-bisaminoethyl ether), cycloaliphatic aminoethers (e.g., N-ethylmorpholine ), aliphatic amidines and cycloaliphatic amidines.
- aliphatic tertiary amines for example trimethylamine, tetra
- the "amine catalysts" mentioned in Bl.2 do not include urea or its derivatives.
- a non-alkaline medium can preferably be achieved by using urea and / or derivatives of urea as catalysts according to component B1, and no amine catalysts are used.
- auxiliaries and additives can be used, such as
- a) surface-active additives such as emulsifiers and foam stabilizers, in particular those with low emission, such as products of the Tegostab® series
- additives such as reaction retarders (eg acidic substances such as hydrochloric acid or organic acid halides), cell regulators (such as paraffins or fatty alcohols or dimethylpolysiloxanes), Pigments, dyes, flame retardants (other than component K3, such as ammonium polyphosphate), other stabilizers against aging and weathering, antioxidants, plasticizers, fungistatic and bacteriostatic substances, fillers (such as barium sulfate, kieselguhr, carbon black or whiting) and release agents.
- reaction retarders eg acidic substances such as hydrochloric acid or organic acid halides
- cell regulators such as paraffins or fatty alcohols or dimethylpolysiloxanes
- Pigments such as paraffins or fatty alcohols or dimethylpolysiloxanes
- Pigments such
- auxiliaries and additives are described, for example, in EP-A 0 000 389, pages 18 to 21. Further examples of auxiliaries and additives which may be used according to the invention and details of the use and mode of action of these auxiliaries and additives are published in the Kunststoff-Handbuch, Volume VII, edited by G. Oertel, Carl Hanser Verlag, Kunststoff, 3rd edition, 1993 , eg on pages 104-127. Component C
- component C water and / or physical blowing agents are used.
- physical blowing agents for example, carbon dioxide and / or volatile organic substances are used as blowing agents.
- water is used as component C.
- the di- and / or polyisocyanates of the present invention contain or consist of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate. These are, for example, those polyisocyanates as described in EP-A 0 007 502, pages 7-8.
- polyisocyanates for example 2,4- and 2,6-toluene diisocyanate, and any desired mixtures of these with isomers (“TDI”) are preferred; Polyphenylpolymethylenpolyisocyanate as prepared by aniline-formaldehyde condensation and subsequent phosgenation ("crude MDI”) and carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret polyisocyanates (“modified polyisocyanates”), especially those modified polyisocyanates, which differs from Derive 2,4- and / or 2,6-toluene diisocyanate or from 4,4'- and / or 2,4'-diphenylmethane diisocyanate.
- TDI 2,4- and 2,6-toluene diisocyanate
- CADI Polyphenylpolymethylenpolyisocyanate as prepared by aniline-formaldehyde condensation and subsequent phos
- a mixture of 2,4- and 2,6-toluene diisocyanate with 4,4'- and / or 2,4'- and / or 2,2'-diphenylmethane diisocyanate and polyphenylpolymethylene polyisocyanate (“multi-core MDI") is used.
- multi-core MDI polyphenylpolymethylene polyisocyanate
- the isocyanate component D comprises 100% of 2,4-tolylene diisocyanate.
- the characteristic number in the process according to the invention is> 90 to ⁇ 120.
- the code is preferably in a range of> 100 to ⁇ 115, more preferably> 102 to ⁇ 110.
- the index (index) indicates the percentage ratio of the isocyanate actually used. Amount to stoichiometric, ie for the implementation of OH equivalents calculated amount of isocyanate groups (NCO) amount.
- Ratio (isocyanate amount used): (calculated amount of isocyanate) ⁇ 100 (VIII)
- the components are used as follows: Component Al in 70 to 100 wt .-%, in particular 90 wt .-% or 100 wt .-%; and / or component A2 or A3 in 0 to 30 wt .-%, in particular 10 wt .-% or 0 wt .-%, wherein the sum of the components Al and A2 or A3 is 100 wt .-%; and or
- Component Bl in 0.02 to 0.8% by weight, preferably 0.06 to 0.25% by weight, particularly preferably 0.22% by weight, based on 100% by weight of Al; and or
- Component B2 in 0.1 to 6 wt .-%, preferably 0.2 to 1.2 wt .-%, particularly preferably 1.3 wt .-%, based on 100 wt .-% of Al; and or
- Component C in 0.8 to 3.0 wt .-%, preferably 1.9 wt .-%, based on 100 wt .-% of Al; and or
- Component E in 2.0 wt .-% to 12 wt%, preferably 2, 0 to 8.0 wt .-%, based on 100 wt .-% of Al.
- reaction components are preferably reacted according to the conventional one-step process, often using machinery, e.g. those described in EP-A 355 000. Details of processing equipment which may also be used according to the invention are given in the Plastics Handbook, Volume VII, by Vieweg and
- the polyurethane foams are preferably in the form of flexible polyurethane foams and can be produced as molded or also as slab foams, preferably as slab foams.
- the invention therefore relates to a process for the preparation of the polyurethane foams, the polyurethane foams produced by these processes, the polyurethane foam foams produced by these processes or
- polyurethane foams obtainable according to the invention preferably
- Flexible polyurethane foams find the following application:
- Component A is a compound having Component A:
- Al-1 ARCOL POLYOL 1108 propylene oxide / ethylene oxide based polyol; prepared by DMC catalysis; Starter: glycerin; OH number: 48 mg KOH / g
- Component B is a compound having Component B:
- Bl-l bis [2-dimethylamino) ethyl] ether (70 wt .-%) (wt .-% in dipropylene glycol 30) (Niax ® Catalyst Al, Momentive Performance Chemicals, Leverkusen, Germany).
- Component C water
- D-l mixture of 2,4- and 2,6-TDI in the weight ratio 80:20 and with an NCO
- E-2 Tris (2-ethylhexyl) O-acetyl citrate, commercially available as Citrofol AHII
- E-3 bis (2-ethylhexyl) adipate, commercially available as Oxsoft DOA
- E-4 acetyltributyl citrate commercially available as Citrofol BII
- E-6 trioctyldodecyl citrate, commercially available as Siltech CE-2000 from Siltech
- the starting components are processed in a one-stage process by means of block foaming.
- the density was determined according to DIN EN ISO 845: 2009-10.
- the compression hardness (CLD 40%) was determined according to DIN EN ISO 845: 2009-10
- the tensile strength and the elongation at break were determined according to
- the compression set (DVR 90%) was determined according to DIN EN ISO 1856: 2008-01 at 90% deformation.
- the compression set (DVR 50%) was determined according to DIN EN ISO 1856: 2008-01 (22 h, 70 ° C) at 50% deformation.
Landscapes
- 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
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP18163429 | 2018-03-22 | ||
PCT/EP2019/057113 WO2019180156A1 (de) | 2018-03-22 | 2019-03-21 | Verfahren zur herstellung von polyurethanweichschaumstoffen mit hoher rohdichte |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3768746A1 true EP3768746A1 (de) | 2021-01-27 |
Family
ID=61763811
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19711137.0A Withdrawn EP3768746A1 (de) | 2018-03-22 | 2019-03-21 | Verfahren zur herstellung von polyurethanweichschaumstoffen mit hoher rohdichte |
Country Status (4)
Country | Link |
---|---|
US (1) | US20210002412A1 (de) |
EP (1) | EP3768746A1 (de) |
CN (1) | CN111954689A (de) |
WO (1) | WO2019180156A1 (de) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116239747A (zh) * | 2021-12-08 | 2023-06-09 | 长华化学科技股份有限公司 | 快速熟化的聚氨酯泡沫及其制备方法与应用 |
CN117186344B (zh) * | 2023-11-08 | 2024-03-08 | 山东一诺威聚氨酯股份有限公司 | 生物基环保透气鞋垫及其制备方法 |
Family Cites Families (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1063525A (en) | 1963-02-14 | 1967-03-30 | Gen Tire & Rubber Co | Organic cyclic oxide polymers, their preparation and tires prepared therefrom |
US3829505A (en) | 1970-02-24 | 1974-08-13 | Gen Tire & Rubber Co | Polyethers and method for making the same |
US3941849A (en) | 1972-07-07 | 1976-03-02 | The General Tire & Rubber Company | Polyethers and method for making the same |
US4089835A (en) | 1975-03-27 | 1978-05-16 | Bayer Aktiengesellschaft | Stable polyurethane dispersions and process for production thereof |
DE2639254A1 (de) | 1976-09-01 | 1978-03-02 | Bayer Ag | Verfahren zur herstellung von stabilen dispersionen |
DE2732292A1 (de) | 1977-07-16 | 1979-02-01 | Bayer Ag | Verfahren zur herstellung von polyurethankunststoffen |
DE2832253A1 (de) | 1978-07-22 | 1980-01-31 | Bayer Ag | Verfahren zur herstellung von formschaumstoffen |
GB2072204B (en) | 1980-02-14 | 1983-12-07 | Rowlands J P | Polymer-modified polyols useful in polyurethane manufacture |
CA1182600A (en) | 1980-02-14 | 1985-02-12 | Jeffrey P. Rowlands | Polymer-modified polyols useful in polyurethane manufacture |
US4374209A (en) | 1980-10-01 | 1983-02-15 | Interchem International S.A. | Polymer-modified polyols useful in polyurethane manufacture |
DE3435070A1 (de) | 1984-09-25 | 1986-04-03 | Bayer Ag, 5090 Leverkusen | Verfahren zur herstellung von gegebenenfalls geschaeumten polyurethanen, die mit einem anderen werkstoff verbunden oder konfektioniert worden sind |
GB8528071D0 (en) | 1985-11-14 | 1985-12-18 | Shell Int Research | Polycarbonates |
US4722946A (en) * | 1986-07-03 | 1988-02-02 | Polymer Dynamics (Delaware), Ltd. | Energy-attenuating polyurethanes |
JPH0284421A (ja) * | 1988-06-04 | 1990-03-26 | Achilles Corp | 衝撃吸収性ポリウレタンフォーム及びその製造方法 |
DE3827595A1 (de) | 1988-08-13 | 1990-02-22 | Bayer Ag | Verfahren zur herstellung von urethangruppen ausweisenden polyharnstoff-elastomeren |
US5158922A (en) | 1992-02-04 | 1992-10-27 | Arco Chemical Technology, L.P. | Process for preparing metal cyanide complex catalyst |
US5712216A (en) | 1995-05-15 | 1998-01-27 | Arco Chemical Technology, L.P. | Highly active double metal cyanide complex catalysts |
US5470813A (en) | 1993-11-23 | 1995-11-28 | Arco Chemical Technology, L.P. | Double metal cyanide complex catalysts |
US5482908A (en) | 1994-09-08 | 1996-01-09 | Arco Chemical Technology, L.P. | Highly active double metal cyanide catalysts |
US5545601A (en) | 1995-08-22 | 1996-08-13 | Arco Chemical Technology, L.P. | Polyether-containing double metal cyanide catalysts |
US5627120A (en) | 1996-04-19 | 1997-05-06 | Arco Chemical Technology, L.P. | Highly active double metal cyanide catalysts |
US5714428A (en) | 1996-10-16 | 1998-02-03 | Arco Chemical Technology, L.P. | Double metal cyanide catalysts containing functionalized polymers |
DE19905611A1 (de) | 1999-02-11 | 2000-08-17 | Bayer Ag | Doppelmetallcyanid-Katalysatoren für die Herstellung von Polyetherpolyolen |
DE10219028A1 (de) | 2002-04-29 | 2003-11-06 | Bayer Ag | Herstellung und Verwendung von hochmolekularen aliphatischen Polycarbonaten |
US7977501B2 (en) | 2006-07-24 | 2011-07-12 | Bayer Materialscience Llc | Polyether carbonate polyols made via double metal cyanide (DMC) catalysis |
DE502008002134D1 (de) | 2007-01-30 | 2011-02-10 | Basf Se | Verfahren zur herstellung von polyethercarbonatpolyolen |
JPWO2013161931A1 (ja) * | 2012-04-26 | 2015-12-24 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | ポリウレタン発泡組成物および軟質ポリウレタンフォームの製造方法 |
EP3077437A1 (de) * | 2013-11-27 | 2016-10-12 | Covestro Deutschland AG | Mischungen von polyethercarbonatpolyolen und polyetherpolyolen zur herstellung von polyurethanweichschaumstoffen |
US10975211B2 (en) * | 2016-03-29 | 2021-04-13 | Dow Global Technologies Llc | Semi-rigid polyurethane foam and process to make |
-
2019
- 2019-03-21 WO PCT/EP2019/057113 patent/WO2019180156A1/de active Application Filing
- 2019-03-21 CN CN201980021106.0A patent/CN111954689A/zh active Pending
- 2019-03-21 EP EP19711137.0A patent/EP3768746A1/de not_active Withdrawn
- 2019-03-21 US US16/980,891 patent/US20210002412A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
CN111954689A (zh) | 2020-11-17 |
US20210002412A1 (en) | 2021-01-07 |
WO2019180156A1 (de) | 2019-09-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2691434B1 (de) | Verfahren zur herstellung von polyurethan-weichschaumstoffen | |
EP3433298B1 (de) | Flammgeschützte etherweichschaumstoffe | |
WO2015078801A1 (de) | Mischungen von polyethercarbonatpolyolen und polyetherpolyolen zur herstellung von polyurethanweichschaumstoffen | |
EP3387035B1 (de) | Polyurethanschaumstoffe basierend auf polyethercarbonatpolyolen | |
WO2012163944A1 (de) | Verfahren zur herstellung von polyetherpolyolen | |
EP3377553A1 (de) | Polyurethanschaumstoffe basierend auf polyethercarbonatpolyolen | |
EP3288994B1 (de) | Mischungen von polyethercarbonatpolyolen und polyetherpolyolen zur herstellung von polyurethanweichschaumstoffen | |
EP3774981A1 (de) | Polyurethanschaumstoffe basierend auf polyethercarbonatpolyolen | |
EP3262099A1 (de) | Viskoelastische polyurethanweichschaumstoffe basierend auf polyethercarbonatpolyolen | |
EP3178858A1 (de) | Polyurethanschaumstoffe basierend auf polyethercarbonatpolyolen | |
EP3762442B1 (de) | Polyurethanschaumstoffe basierend auf polyethercarbonatpolyolen | |
EP3762441B1 (de) | Polyurethanschaumstoffe basierend auf polyethercarbonatpolyolen | |
EP3768744A1 (de) | Verfahren zur herstellung von polyurethanweichschaumstoffen | |
EP3630859B1 (de) | Polyurethanschaumstoffe basierend auf polyethercarbonatpolyolen | |
EP2730598A1 (de) | Verfahren zur Herstellung von Polyurethanweichschaumstoffen | |
WO2019180156A1 (de) | Verfahren zur herstellung von polyurethanweichschaumstoffen mit hoher rohdichte | |
WO2018114830A1 (de) | Verwendung von physikalischen treibmitteln zur erzeugung von polyethercarbonatpolyol-basierten polyurethanschaumstoffen mit reduzierter emission von cyclischem propylencarbonat | |
WO2021204590A1 (de) | Polyurethanschaumstoffe basierend auf polyethercarbonatpolyolen | |
WO2022258503A1 (de) | Einsatz von bismut-katalysatoren zur verringerung von cyclischem propylencarbonat bei der herstellung von weichschaumstoffen basierend auf polyethercarbonatpolyolen | |
EP4194476A1 (de) | Polyurethanschaumstoffe basierend auf polyethercarbonatpolyolen | |
WO2023144057A1 (de) | Polyurethan-weichschaumstoffe basierend auf aliphatischen oligomeren polyisocyanaten und monohydroxyfunktionellen verbindungen |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: UNKNOWN |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20201022 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20221013 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 20230224 |