EP4077452A1 - Mousses de polyuréthane à base de polyéther-carbonate-polyols - Google Patents

Mousses de polyuréthane à base de polyéther-carbonate-polyols

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Publication number
EP4077452A1
EP4077452A1 EP20821232.4A EP20821232A EP4077452A1 EP 4077452 A1 EP4077452 A1 EP 4077452A1 EP 20821232 A EP20821232 A EP 20821232A EP 4077452 A1 EP4077452 A1 EP 4077452A1
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European Patent Office
Prior art keywords
unsubstituted
substituted
weight
parts
heteroatoms
Prior art date
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German (de)
English (en)
Inventor
Christos Karafilidis
Matthias LEVEN
Persefoni HILKEN
Veronica-Alina FAERBER
Darius MICHALIK
Antje WEHLAU
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Covestro Intellectual Property GmbH and Co KG
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Covestro Intellectual Property GmbH and Co KG
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Publication of EP4077452A1 publication Critical patent/EP4077452A1/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
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • 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
    • C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
    • C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
    • C08G18/165—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22 covered by C08G18/18 and C08G18/24
    • 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
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
    • 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
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • 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
    • C08G18/485—Polyethers containing oxyethylene units and other oxyalkylene units containing mixed oxyethylene-oxypropylene or oxyethylene-higher oxyalkylene end 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
    • C08G18/70—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
    • C08G2110/005—< 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
    • 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 polyurethane foams, preferably flexible polyurethane foams, by reacting an isocyanate component with an isocyanate-reactive component which comprises at least one polyether carbonate polyol, and wherein the reaction takes place in the presence of a component K, which is described in more detail below becomes.
  • the invention further relates to polyurethane foams produced by the process according to the invention and to their use. In the context of an environmentally friendly orientation of production processes, it is generally desirable to use CCE-based starting materials, for example in the form of polyether carbonate polyols, in relatively large quantities.
  • WO 2016/097729 A1 describes that the use of esters of monobasic or polybasic carboxylic acids, the (first) dissociation of which has a pKa value of 0.5 to 4.0, as additives when foaming polyurethane foams, results in a reduction in the Emission of cyclic propylene carbonate can be observed.
  • the object of the present invention was to provide a process for the production of polyurethane foams which leads to polyurethane foams with reduced emissions of cyclic propylene carbonate.
  • this object was achieved by a process for the production of polyurethane foams by reacting the component A containing a polyol component
  • polyether polyol with a hydroxyl number according to DIN 53240-1 (June 2013) of 20 mg KOH / g to 250 mg KOH / g and an ethylene oxide content of 0 to 60% by weight, with polyether polyol A2 is free of carbonate units,
  • R 1 for a substituted or unsubstituted Cl-C22-alkyl group which may optionally be interrupted by heteroatoms, substituted or unsubstituted Cl-C22-alkenyl group which may optionally be interrupted by heteroatoms, substituted or unsubstituted Cl-C22-alkoxy group which may be interrupted by heteroatoms can be substituted or unsubstituted C6-C18- Aryl group, substituted or unsubstituted C6-C18 aryloxy group, heteroaryl group, thiols, phosphorus compounds, carboxylates, isocyanates, amines, carbamines, amides or carbamides,
  • R 2 can be the same or different and for a substituted or unsubstituted Cl-C22-alkyl group which can optionally be interrupted by heteroatoms, substituted or unsubstituted Cl-C22-alkenyl group which can optionally be interrupted by heteroatoms, substituted or unsubstituted C1-C22- Alkoxy group which can optionally be interrupted by heteroatoms, substituted or unsubstituted C6-C18 aryl group, substituted or unsubstituted C6-C18 aryloxy group,
  • X can be identical or different and represents F, CI, Br or I.
  • the invention preferably relates to a process for producing polyurethane foams, preferably flexible polyurethane foams, by reacting
  • A2 0 to 60 parts by weight, preferably 0 to 40 parts by weight, particularly preferably 0 to 20 parts by weight, of one or more polyether polyols with a hydroxyl number according to DIN 53240-1 (June 2013) of 20 mg KOH / g to 250 mg KOH / g and an ethylene oxide content of 0 to 60% by weight, the polyether polyols A2 being free of carbonate units,
  • A3 0 to 20 parts by weight, based on the sum of the parts by weight of components Al and A2, of one or more polyether polyols with a hydroxyl number according to DIN 53240-1 (June 2013) 20 mg KOH / g to 250 mg KOH / g, and an ethylene oxide content of> 60% by weight, the polyether polyols A3 being free of carbonate units,
  • A4 0 to 40 parts by weight, based on the sum of the parts by weight of components Al and A2, one or more polymer polyols, PHD polyols and / or PIPA polyols,
  • A5 0 to 40 parts by weight, based on the sum of the parts by weight of components Al and A2, polyols that do not fall under the definition of components A1 to A4,
  • B2 optionally auxiliaries and additives C water and / or physical blowing agents, with
  • R 1 for a substituted or unsubstituted Cl-C22-alkyl group which may optionally be interrupted by heteroatoms, substituted or unsubstituted Cl-C22-alkenyl group which may optionally be interrupted by heteroatoms, substituted or unsubstituted Cl-C22-alkoxy group which may be interrupted by heteroatoms substituted or unsubstituted C6-C18 aryl group, substituted or unsubstituted C6-C18 aryloxy group,
  • R 2 can be the same or different and for a substituted or unsubstituted Cl-C22-alkyl group which can optionally be interrupted by heteroatoms, substituted or unsubstituted Cl-C22-alkenyl group which can optionally be interrupted by heteroatoms, substituted or unsubstituted C1-C22- Alkoxy group which can optionally be interrupted by heteroatoms, substituted or unsubstituted C6-C18-aryl group, substituted or unsubstituted C6-C18-aryloxy group,
  • X can be identical or different and represents F, CI, Br or I.
  • the components A1 to A5 each relate to “one or more” of the compounds mentioned. If several compounds of a component are used, the amount given corresponds to the sum of the parts by weight of the compounds.
  • component A contains
  • polyether polyols with a hydroxyl number according to DIN 53240-1 (June 2013) of 20 mg KOH / g to 250 mg KOH / g and a content of Ethylene oxide from 0 to 60% by weight, the polyether polyols A2 being free from carbonate units, component A preferably being free from component A3 and / or A4.
  • component A comprises
  • A2 25 to 35 parts by weight, preferably 28 to 32 parts by weight, of one or more polyether polyols with a hydroxyl number according to DIN 53240-1 (June 2013) of 20 mg KOH / g to 250 mg KOH / g and a content of ethylene oxide from 0 to 60% by weight, the polyether polyols A2 being free of carbonate units,
  • component A comprises
  • A2 0 to 60 parts by weight, preferably 0 to 40 parts by weight, particularly preferably 0 to 20 parts by weight, most preferably 25 to 35 parts by weight of one or more polyether polyols with a hydroxyl number according to DIN 53240-1 ( June 2013) from 20 mg KOH / g to 250 mg KOH / g and an ethylene oxide content of 0 to 60% by weight, the polyether polyols A2 being free of carbonate units,
  • A4 0.01 to 40.00 parts by weight, preferably 0.01 to 20.00 parts by weight, particularly preferably 1.00 to 20.00 parts by weight, most preferably 2.00 to 20.00 parts by weight Parts, based on the sum of the parts by weight of components Al and A2, of one or more polymer polyols, PHD polyols and / or PIPA polyols, A5 0 to 40 parts by weight, based on the sum of the parts by weight of components A1 and A2, polyols which do not come under the definition of components A1 to A4, component A preferably being free from component A3.
  • Component Al comprises a polyether carbonate polyol with a hydroxyl number (OH number) according to DIN 53240-1 (June 2013) of 20 mg KOH / g to 120 mg KOH / g, preferably from 20 mg KOH / g to 100 mg KOH / g, particularly preferably from 25 mg KOH / g to 90 mg KOH / g, which is obtainable by copolymerization of carbon dioxide, one or more alkylene oxides, in the presence of one or more H-functional starter molecules, the polyether carbonate polyol preferably having a C0 2 content of 15 to 25% by weight.
  • OH number hydroxyl number
  • Component Al preferably comprises a polyether carbonate polyol which is obtainable by copolymerizing 2% by weight to 30% by weight carbon dioxide and 70% by weight to 98% by weight of one or more alkylene oxides, in the presence of one or more H-functional groups Starter molecules with an average functionality of 1 to 6, preferably 1 to 4, particularly preferably 2 to 3.
  • H-functional is understood to mean a starter compound which has hydrogen atoms active against 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 preferably also have ether groups between the carbonate groups, which is shown schematically in formula (III).
  • R stands for an organic radical such as alkyl, alkylaryl or aryl, which in each case can also contain heteroatoms such as, for example, O, S, Si, etc.
  • e and f stand for an integer number.
  • the polyether carbonate polyol shown in the scheme according to formula (III) should only be understood in such a way that blocks with the structure shown can in principle be found in the polyether carbonate polyol, but the order, number and length of the blocks can vary and not to that shown in formula (III) Polyether carbonate polyol is limited.
  • the ratio of e / f is preferably from 2: 1 to 1:20, particularly preferably from 1.5: 1 to 1:10.
  • the proportion of built-in CO2 (“units derived from carbon dioxide”; “C0 2 content”) in a polyether carbonate polyol can be determined from the evaluation of characteristic signals in the 'H-NMR spectrum. The following example illustrates the determination of the proportion of units originating from carbon dioxide in a C0 2 / propylene oxide polyether carbonate polyol started on 1,8-octanediol.
  • the proportion of built-in CO2 in a polyether carbonate polyol and the ratio of propylene carbonate to polyether carbonate polyol can be determined by means of 'H-NMR (a suitable device is from Bruker, DPX 400, 400 MEIz; pulse program zg30, waiting time dl: 10s, 64 scans) .
  • the sample is dissolved in each case in deuterated chloroform.
  • Cyclic propylene carbonate (which was formed as a by-product) resonating at 4.5 ppm; Carbonate, resulting from carbon dioxide incorporated in the polyether carbonate polyol with resonances at 5.1 to 4.8 ppm; unreacted propylene oxide (PO) with resonance at 2.4 ppm; Polyether polyol (i.e., with no built-in carbon dioxide) with resonances at 1.2 to 1.0 ppm; that as a starter molecule
  • N [F (5, l-4.8) -F (4.5)] * 102 + F (4.5) * 102 + F (2.4) * 58 + 0.33 * F (l, 2-l, 0) * 58 + 0.25 * F (l, 6-l, 52) * 146
  • F (4.5) area of the resonance at 4.5 ppm for cyclic carbonate (corresponds to one H atom)
  • F (5, 1-4.8) area of the resonance at 5.1 to 4.8 ppm for polyether carbonate polyol and an H-
  • F (1.6-1.52) area of the resonance at 1.6 to 1.52 ppm for 1,8-octanediol (starter), if available.
  • 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 1,8-octanediol starter used (if available).
  • the non-polymer components of the reaction mixture ie cyclic propylene carbonate and any unreacted propylene oxide present
  • the specification of the CCf content in the polyether carbonate polyol is standardized to the proportion of the polyether carbonate polyol molecule that was formed during the copolymerization and, if applicable, the activation steps in the presence of CO2 (i.e. the proportion of the polyether carbonate polyol molecule that was formed from the starter (1.8 -Octanediol, if present) and resulting from the reaction of the starter with epoxide, which was added under CO 2 -free conditions, was not taken into account).
  • the production of polyether carbonate polyols according to Al includes:
  • an H-functional starter compound or a mixture of at least two H-functional starter compounds and optionally water and / or other volatile compounds are removed by increased temperature and / or reduced pressure ("drying"), the DMC catalyst the H-functional starter compound or the mixture of at least two H-functional starter compounds is added before or after drying,
  • step (ß) for activation a partial amount (based on the total amount of the amount of alkylene oxides used in the activation and copolymerization) of one or more alkylene oxides is added to the mixture resulting from step (a), this addition of a partial amount of alkylene oxide optionally in the presence of CO2 can take place, and then waiting for the temperature peak ("hotspot") and / or a pressure drop in the reactor that occurs due to the following exothermic chemical reaction, and step ( ⁇ ) for activation can also be carried out several times, (g) one or more of the alkylene oxides and carbon dioxide are added to the mixture resulting from step ( ⁇ ), it being possible for the alkylene oxides used in step ( ⁇ ) to be the same or different from the alkylene oxides used in step (g).
  • Al alkylene oxides (epoxides) having 2 to 24 carbon atoms can be used to produce the polyether carbonate polyols.
  • the alkylene oxides with 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-pentene oxide, 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- 1,2-pentene oxide, 4-methyl-1,2-pentene oxide, 2-ethyl-1,2-butene oxide, 1-heptene oxide, 1-octene oxide, 1-nonene oxide, 1-decene oxide, 1-undecene oxide, 1-dodecene oxide, 4-methyl-1,2-pentene oxide
  • epoxy-functional alkoxysilanes such as 3 -glycidyloxypropyltrimethoxysilane, 3 -glycidyioxypropyltriethoxysilane, 3 -
  • alkylene oxides used are preferably ethylene oxide and / or propylene oxide and / or 1,2-butylene oxide, particularly preferably propylene oxide.
  • the proportion of ethylene oxide in the total amount of propylene oxide and ethylene oxide used is 0 to 90% by weight, preferably 0 to 50% by weight and particularly preferably free of ethylene oxide.
  • H-functional starter compounds Compounds with H atoms active for the alkoxylation can be used as suitable H-functional starter compounds.
  • Groups with active H atoms which are active for the alkoxylation are, for example, -OH, -NH 2 (primary amines), -NH- (secondary amines), -SH and -CO2H, preference is given to -OH and -NH 2 , particularly preferred is - OH.
  • the H-functional starter compound is, for example, one or more compounds selected from the group consisting of water, monohydric or polyhydric alcohols, polyhydric amines, polyhydric thiols, amino alcohols, thioalcohols, hydroxyesters, polyether polyols, polyester polyols, polyester ether polyols, polyether carbonate polyols, polycarbonate polyols, polycarbonates, polyethyleneimines , polyetheramines (z. B. so-called Jeffamine ® from Huntsman, such as. for example, D-230, D-400, D-2000, T-403, T-3000, T-5000 or corresponding BASF products such. B.
  • the C1-C24 alkyl fatty acid esters which on average contain at least 2 OH groups per molecule, are commercial products such as Lupranol Balance ® (BASF AG), Merginol ® types (Hobum Oleochemicals GmbH), Sovermol ® types (from Cognis GmbH & Co. KG) and Soyol ® TM types (from USSC Co.).
  • BASF AG BASF AG
  • Merginol ® types Hobum Oleochemicals GmbH
  • Sovermol ® types from Cognis GmbH & Co. KG
  • Soyol ® TM types from USSC Co.
  • Alcohols, amines, thiols and carboxylic acids can be used as monofunctional starter compounds.
  • the following can be used as monofunctional alcohols: 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, propagyl alcohol, 2-methyl-2-propanol, lt-butoxy-2-propanok, 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-hydroxy
  • Possible monofunctional amines are: butylamine, t-butylamine, pentylamine, hexylamine, aniline, aziridine, pyrrolidine, piperidine, morpholine.
  • monofunctional carboxylic acids 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.
  • Polyhydric alcohols suitable as H-functional starter compounds are, for example, dihydric alcohols (such as, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-butenediol, 1,4-butynediol, neopentyl glycol, 1 , 5-pentanediol, methylpentanediols (such as 3-methyl-1,5-pentanediol), 1,6-hexanediol; 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, bis (hydroxymethyl) - cyclohexane (such as 1,4-bis (hydroxymethyl) cyclohexane), triethylene glycol, tetraethylene glycol,
  • polyethylene glycols dipropylene glycol, tripropylene glycol, polypropylene glycols, dibutylene glycol and polybutylene glycols
  • trihydric alcohols such as trimethylolpropane, glycerin, trishydroxyethyl isocyanurate, castor oil
  • tetravalent alcohols such as pentaerythritol
  • Polyalcohols such as, for example, sorbitol, hexitol, sucrose, starch, starch hydrolysates, cellulose, cellulose hydrolysates, hydroxy-functionalized fats and oils, in particular castor oil
  • trihydric alcohols such as trimethylolpropane, glycerol, trishydroxyethyl isocyanurate and castor oil can also be used.
  • the H-functional starter compounds can also be selected from the class of polyether polyols, in particular those with a molecular weight M n in the range from 100 to 4,000 g / mol, preferably 250 to 2000 g / mol. Preference is given to polyether polyols which are built up from repeating ethylene oxide and propylene oxide units, preferably with a proportion of 35 to 100% propylene oxide units, particularly preferably with a proportion of 50 to 100% propylene oxide units. These can be random copolymers, gradient copolymers, alternating or block copolymers of ethylene oxide and propylene oxide.
  • Suitable polyether polyols made up of repeating propylene oxide and / or ethylene oxide units are, for example Desmophen ® -, Acclaim ® -, Arcol ® -, Baycoll ® -, Bayfill ® -, Bayflex ® - Baygal ® -, PET ® - and polyether polyols the Covestro Germany AG (such.
  • 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 YPPU ® 0789, Baygal ® K55, PET 1 '1004, polyether ® S180).
  • suitable homo- polyethylene oxides are, for example Pluriol ® E brands from BASF SE
  • suitable homo- polypropylene oxides are, for example Pluriol ® P brands from BASF SE
  • suitable mixed copolymers of ethylene oxide and propylene oxide such as the Pluronic ® PE or PLURIOL ® RPE - trademarks of BASF SE.
  • the H-functional starter compounds can also be selected from the substance class of polyester polyols, in particular those with a molecular weight M n in the range from 200 to 4500 g / mol, preferably from 400 to 2500 g / mol. At least difunctional polyesters are used as polyester polyols. Polyester polyols preferably consist of alternating acid and alcohol units.
  • acid components for. B. succinic acid, maleic acid, maleic anhydride, adipic acid, phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride,
  • Hexahydrophthalic anhydride or mixtures of the acids and / or anhydrides mentioned are used.
  • alcohol components for. B. ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4-bis (hydroxymethyl) cyclohexane, diethylene glycol, Dipropylene glycol, trimethylolpropane, glycerol, pentaerythritol or mixtures of the alcohols mentioned are used.
  • polyester ether polyols are obtained which can also serve as starter compounds for the preparation of the polyether carbonate polyols. If polyether polyols are used to produce the polyester ether polyols, polyether polyols with a number average molecular weight M n of 150 to 2000 g / mol are preferred.
  • polycarbonate polyols can be used as H-functional starter compounds, in particular those with a molecular weight M n in the range from 150 to 4500 g / mol, preferably 500 to 2500, which are produced, for example, by reaction of phosgene, dimethyl carbonate, diethyl carbonate or Diphenyl carbonate and di- and / or polyfunctional alcohols or polyester polyols or Polyether polyols are produced.
  • polycarbonate polyols can be found e.g. As in EP-A 1,359,177th example, the Covestro Germany AG are used as polycarbonate, the Desmophen ® C-types such. B.
  • polyether carbonate polyols can be used as H-functional starter compounds.
  • polyether carbonate polyols which are prepared by the process 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 (VII),
  • 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 according to formula (VI) with e-caprolactone, for example reaction products of trimethylolpropane with e-caprolactone, reaction products of glycerol with e-caprolactone and reaction products of pentaerythritol e-caprolactone.
  • water, diethylene glycol, dipropylene glycol, castor oil, sorbitol and polyether polyols, built up from repeating polyalkylene oxide units are preferably used as H-functional starter 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, 1,5-pentanediol, 2-methylpropane-1,3-diol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, di- and trifunctional polyether polyols, the polyether polyol being made from a di- or tri-H functional starter compound and propylene oxide or a di- or tri-H functional starter compound, propylene oxide and ethylene oxide is built up.
  • the polyether polyols preferably have a number average molecular weight M n in the range from 62 to 4500 g / mol and in particular a number average molecular weight M n in the range from 62 to 3000 g / mol, very particularly preferably a molecular weight from 62 to 1500 g / mol.
  • the polyether polyols preferably have a functionality of 2 to 3.
  • the polyether carbonate polyol Al can be obtained by adding carbon dioxide and alkylene oxides onto H-functional starter compounds using multimetal cyanide catalysts (DMC catalysts).
  • DMC catalysts multimetal cyanide catalysts
  • the production of polyether carbonate polyols by adding alkylene oxides and C0 2 onto 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 Pat. No. 3,404,109, US Pat. No. 3,829,505, US Pat. No. 3,941,849 and US Pat. No. 5,158 922).
  • DMC catalysts which are described, for example, in US-A 5 470 813, EP-A 700 949, EP-A 743 093, EP-A 761 708, WO-A 97/40086, WO-A 98/16310 and WO-A 00 / 47649 are described, have a very high activity in the homopolymerization of epoxides and enable the production of polyether polyols and / or polyether carbonate polyols with very low catalyst concentrations (25 ppm or less).
  • a typical example are the highly active DMC catalysts described in EP-A 700 949 which, in addition to a double metal cyanide compound (e.g.
  • the DMC catalyst is usually used in an amount of ⁇ 1% by weight, preferably in an amount of ⁇ 0.5% by weight, particularly preferably in an amount of ⁇ 500 ppm and in particular in an amount of ⁇ 300 ppm, in each case based on the weight of the polyether carbonate polyol used.
  • the polyether carbonate polyol Al has a carbonate group content (“units derived from carbon dioxide”), calculated as CO2, of 2.0 and 30.0% by weight, preferably 5.0 and 28.0% by weight .-% and particularly preferably from 10.0 and 25.0% by weight.
  • a carbonate group content (“units derived from carbon dioxide”), calculated as CO2, of 2.0 and 30.0% by weight, preferably 5.0 and 28.0% by weight .-% and particularly preferably from 10.0 and 25.0% by weight.
  • the polyether carbonate polyol or polyols according to A1 have a hydroxyl number of 20 mg KOH / g to 250 mg KOH / g and are obtainable by copolymerization of 2.0% by weight to 30.0% by weight Carbon dioxide and 70% by weight to 98% by weight 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 53240-1 (June 2013).
  • a polyether carbonate polyol Al is used, containing blocks of the formula (III) where the ratio e / f is from 2: 1 to 1:20. In a further embodiment of the invention, 100 parts by weight of component Al are used.
  • Component A2 comprises polyether polyols with a hydroxyl number according to DIN 53240-1 (June 2013) of 20 mg KOH / g to 250 mg KOH / g, preferably 20 to 112 mg KOH / g and particularly preferably 20 mg KOH / g to 80 mg KOH / g and is free of carbonate units.
  • the compounds according to A2 can be prepared by catalytic addition of one or more alkylene oxides onto H-functional starter compounds. Alkylene oxides having 2 to 24 carbon atoms can be used as alkylene oxides (epoxides).
  • the alkylene oxides with 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-pentene oxide,
  • the alkylene oxides used are preferably ethylene oxide and / or propylene oxide and / or 1,2-butylene oxide. An excess of propylene oxide and / or 1,2-butylene oxide is particularly preferably used.
  • the alkylene oxides can be fed to the reaction mixture individually, as a mixture or in succession. They can be random or block copolymers. If the alkylene oxides are metered in one after the other, the products produced (polyether polyols) contain polyether chains with block structures.
  • the H-functional starter compounds have functionalities from 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, 1,3-butanediol, 1,4-butanediol, hexanediol, pentanediol, 3-methyl-1,5-pentanediol, 1,12-dodecanediol , Glycerol, trimethylolpropane, triethanolamine, pentaerythritol, sorbitol, sucrose, hydroquinone, pyrocatechol, resorcinol, bisphenol F, bisphenol A, 1,3,5-trihydroxybenzene, methylol group-containing condensates of formaldehyde and phenol or melamine or urea. These can also be used in a mixture.
  • the polyether polyols according to A2 have a content of from 0 to 60% by weight, preferably from 0 to 40% by weight, particularly preferably from 0 to 25% by weight, of ethylene oxide.
  • Component A3 comprises polyether polyols with a hydroxyl number according to DIN 53240-1 (June 2013) 20 mg KOH / g to 250 mg KOH / g, preferably from 20 to 112 mg KOH / g and particularly preferably 20 mg KOH / g to 80 mg KOH /G.
  • component A3 is produced in the same way as component A2, but with an ethylene oxide content of> 60% by weight, preferably> 65% by weight, in the polyether polyol.
  • Suitable alkylene oxides and H-functional starter compounds are the same as those described for component A2.
  • preferred H-functional starter compounds are those which have a functionality of 3 to 6, particularly preferably 3, so that polyether triols are formed.
  • Preferred H-functional starter compounds with a functionality of 3 are glycerol and / or trimethylolpropane, glycerol is particularly preferred.
  • component A3 is a glycerol-started trifunctional polyether with an ethylene oxide content of 68 to 73% by weight and an OH number of 35 to 40 mg KOH / g.
  • Component A4 comprises polymer polyols, PHD polyols and PIPA polyols.
  • Polymer polyols are polyols which contain proportions of monomers suitable for free radical polymerization, such as styrene or acrylonitrile, in a base polyol, such as, for example, a polyether polyol and / or polyether carbonate polyol.
  • PHD (polyurea dispersion) polyols are produced, 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, produced by alkoxylation of a bifunctional starter (such as glycerol and / or trimethylolpropane), in the case of the polyether carbonate polyol in the presence of carbon dioxide .
  • a bifunctional starter such as glycerol and / or trimethylolpropane
  • the PIPA polyols are polyether polyols and / or polyether carbonate polyols modified by polyisocyanate polyaddition with alkanolamines, preferably triethanolamine-modified, the polyether (carbonate) polyol having a functionality of 2.5 to 4.0 and a hydroxyl number of 3 mg KOH / g to 112 mg KOH / g (molecular weight 500 to 18000 g / mol).
  • the polyether polyol is preferably “EO-capped”, ie the polyether polyol has terminal ethylene oxide groups.
  • PIPA polyols are described in detail in GB 2072204 A, DE 31 03 757 A1 and US 4,374,209 A.
  • This can include, for example, low molecular weight diols (eg 1,2-ethanediol, 1,3- or 1,2-propanediol, 1,4-butanediol), triols (eg glycerol, trimethylolpropane) and tetraolics (eg pentaerythritol), polyester polyols not containing any of Malonic acid-derived structural units, polythioether polyols or polyacrylate polyols, and polyether polyols or polycarbonate polyols which do not fall under the definition of components A1 to A4.
  • ethylenediamine and triethanolamine-started polyethers can also be used. These compounds are not among the compounds according to the definition of component B2.
  • the catalysts according to component B 1 are preferably a) aliphatic tertiary amines (for example trimethylamine, tetramethylbutanediamine, 3-
  • the tin (II) salts of carboxylic acids are used, the respective underlying carboxylic acid having from 2 to 24 carbon atoms.
  • one or more compounds are selected as tin (II) salts of carboxylic acids from the group consisting of tin (II) salt of 2-ethylhexanoic acid (i.e.
  • the alkyl chain C x FF x + i of the carboxylate is particularly preferably a branched carbon chain, ie C x FF x + i is an / vo-alkyl group.
  • tin (II) salts of carboxylic acids are one or more compounds selected from the group consisting of tin (II) salt of 2-butyloctanoic acid, ie tin (II) - (2-butyloctoate), tin (II) - Salt of ricinoleic acid, ie tin (II) ricinoleate and tin (II) salt of 2-hexyldecanoic acid, ie tin (II) - (2-hexyldecanoate) are used.
  • Components A1 and A2 catalysts other than those of component B1.2, the content of amine catalysts in component B1.2 being a maximum of 50% by weight based on component B1, are used.
  • Component Bl.l includes urea and derivatives of urea.
  • derivatives of urea include: aminoalkyl ureas, such as (3-dimethylaminopropylamine) urea and 1,3-bis [3- (dimethylamino) propyl] urea. Mixtures of urea and urea derivatives can also be used. Only urea is preferably used in component B 1.1.
  • the component Bl.l is used in amounts of 0.05 to 1.50 parts by weight, preferably from 0.10 to 0.50 parts by weight, particularly preferably from 0.25 to 0.35 parts by weight, based on the sum of the parts by weight of the components A1 to A2.
  • the component Bl.2 is used in amounts of 0.03 to 1.50 parts by weight, preferably 0.03 to 0.50 parts by weight, particularly preferably from 0.10 to 0.30 parts by weight, whole particularly preferably from 0.20 to 0.30 parts by weight, based on the sum of the parts by weight of components A1 to A2.
  • the content of aminic catalysts in component B1.2 is preferably a maximum of 50% by weight based on component Bl.l, particularly preferably a maximum of 25% by weight based on component Bl.l.
  • Component Bl.2 is very particularly preferably free from amine catalysts.
  • tin (II) salts of carboxylic acids for example, can be used as catalysts of component Bl.2.
  • Amine catalysts which may be used in small amounts (see above) include: 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.
  • N-ethylmorpholine aliphatic amidines and cycloaliphatic amidines.
  • the “amine catalysts” mentioned in sheet 2 do not include urea or its derivatives.
  • the invention therefore also provides a process for producing polyurethane foams by reacting component A containing a polyol component
  • polyether polyol with a hydroxyl number according to DIN 53240-1 (June 2013) of 20 mg KOH / g to 250 mg KOH / g and an ethylene oxide content of 0 to 60% by weight, with polyether polyol A2 is free of carbonate units, in a non-alkaline medium with C water and / or physical blowing agents and
  • R 1 for a substituted or unsubstituted Cl-C22-alkyl group which may optionally be interrupted by heteroatoms, substituted or unsubstituted Cl-C22-alkenyl group which may optionally be interrupted by heteroatoms, substituted or unsubstituted Cl-C22-alkoxy group which may be interrupted by heteroatoms substituted or unsubstituted C6-C18 aryl group, substituted or unsubstituted C6-C18 aryloxy group,
  • the non-alkaline medium can preferably be achieved in that urea and / or derivatives of urea are used as catalysts according to component B 1, and no amine catalysts are used.
  • a preferred subject of the invention is therefore a method for producing polyurethane foams, characterized in that A contains a polyol component
  • R 1 for a substituted or unsubstituted Cl-C22-alkyl group which may optionally be interrupted by heteroatoms, substituted or unsubstituted Cl-C22-alkenyl group which may optionally be interrupted by heteroatoms, substituted or unsubstituted Cl-C22-alkoxy group which may be interrupted by heteroatoms substituted or unsubstituted C6-C18 aryl group, substituted or unsubstituted C6-C18 aryloxy group,
  • R 2 can be the same or different and for a substituted or unsubstituted Cl-C22-alkyl group which can optionally be interrupted by heteroatoms, substituted or unsubstituted Cl-C22-alkenyl group which can optionally be interrupted by heteroatoms, substituted or unsubstituted C1-C22- Alkoxy group which can optionally be interrupted by heteroatoms, substituted or unsubstituted C6-C18 aryl group, substituted or unsubstituted C6-C18 aryloxy group,
  • X can be identical or different and represents F, CI, Br or I.
  • component B2 such as a) surface-active additives such as emulsifiers and foam stabilizers, especially those with low emissions such as products from the Tegostab® LF2 series b) additives such as reaction retarders (e.g. acidic substances such as hydrochloric acid or organic acid halides) Cell regulators (such as paraffins or fatty alcohols or dimethylpoly siloxanes), pigments, dyes, flame retardants, other stabilizers against aging and weathering influences, antioxidants, plasticizers, chelngistatic and bacteriostatic substances, fillers (such as barium sulfate, kieselguhr, soot or whiting chalk) and release agents.
  • reaction retarders e.g. acidic substances such as hydrochloric acid or organic acid halides
  • Cell regulators such as paraffins or fatty alcohols or dimethylpoly siloxanes
  • pigments such as paraffins or fatty alcohols or dimethylpoly siloxanes
  • pigments such as par
  • auxiliaries and additives which may also be used, are described, for example, in EP-A 0000389, pages 18-21.
  • component C water and / or physical blowing agents are used. Carbon dioxide and / or volatile organic substances, for example, are used as the physical blowing agent. Water is preferably used as component C.
  • Suitable di- and / or polyisocyanates are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates, for example those of the formula (IX)
  • Q is an aliphatic hydrocarbon radical with 2-18, preferably 6-10, a cycloaliphatic hydrocarbon radical with 4-15, preferably 6-13 carbon atoms, or an araliphatic hydrocarbon radical with 8-15, preferably 8-13 carbon atoms.
  • polyisocyanates such as those described in EP-A 0007502, pages 7-8.
  • the technically easily accessible polyisocyanates for example 2,4- and 2,6-tolylene diisocyanate, and any mixtures of these isomers (“TDI”) are preferred;
  • Polyphenylpolymethylene polyisocyanates such as are produced by aniline-formaldehyde condensation and subsequent phosgenation (“crude MDI”) and modified polyisocyanates containing carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups
  • modified Polyisocyanates especially those modified polyisocyanates which are derived from 2,4- and / or 2,6-tolylene diisocyanate or from 4,4'- and / or 2,4'-diphenylmethane diisocyanate.
  • the polyisocyanate used is preferably one or more Compounds selected from the group consisting of 2,4- and 2,6-tolylene diisocyanate, 4,4'- and 2,4'- and 2,2'-diphenylmethane diisocyanate and polyphenylpolymethylene polyisocyanate (“multi-core MDI”) are used 2,4- and / or 2,6-tolylene diisocyanate used.
  • the isocyanate component B comprises a tolylene diisocyanate isomer mixture of 55 to 90% by weight of 2,4- and 10 to 45% by weight of 2,6-TDI.
  • the isocyanate component D comprises 100% by weight of 2,4-tolylene diisocyanate.
  • the index is 90 to 120.
  • the index is preferably in a range from 100 to 115, particularly preferably 102 to 110.
  • the index indicates the percentage ratio of the isocyanate amount actually used to the stoichiometric, ie for the conversion of the OH equivalents calculated amount of isocyanate groups (NCO) amount.
  • R 1 for a substituted or unsubstituted Cl-C22-alkyl group which can optionally be interrupted by heteroatoms, substituted or unsubstituted C1-C22-alkenyl group which can optionally be interrupted by heteroatoms, substituted or unsubstituted Cl-C22-alkoxy group which can optionally be interrupted by heteroatoms substituted or unsubstituted C6-C18 aryl group, substituted or unsubstituted C6-C18 aryloxy group, heteroaryl group, thiols, phosphorus compounds, carboxylates, isocyanates, amines, carbamines, amides or carbamides,
  • R 2 can be the same or different and for a substituted or unsubstituted C1-C22- alkyl group which can optionally be interrupted by heteroatoms, substituted or unsubstituted Cl-C22-alkenyl group which can optionally be interrupted by heteroatoms, substituted or unsubstituted Cl-C22- Alkoxy group which can optionally be interrupted by heteroatoms, substituted or unsubstituted C6-C18 aryl group, substituted or unsubstituted C6-C18 aryloxy group,
  • X can be identical or different and stands for F, CI, Br or I, is used.
  • Compounds according to formula (II) are for example:
  • Halogen-containing compounds such as chlorine (trimethyl) silane, chlorine (triethyl) silane, chlorine (triisopropyl) silane, chlorine (triethoxy) silane, dichlorodiphenylsilane, dichlorodibutylsilane, difluorodiethoxysilane, (chloromethyl) diethoxymethylsilane, (chloroxymethylsilane, (chloroxymethylsilane) chloroethyl) ester of silicic acid, bis (2-chloroethoxy) dimethylsilane, (2- chloroethyl) diethoxymethylsilane, (bromomethyl) dimethoxymethylsilane, tetrakis (2-fluoroethyl)
  • Alkenyl groups which can optionally be interrupted by heteroatoms and / or substituted or unsubstituted C1-C22-alkoxy groups which can optionally be interrupted by heteroatoms, such as, for example, tetramethylsilane, methyltrimethoxysilane, vinyltrimethoxy silane, triethoxyvinylsilane, tetraethyl orthosilane, tetraethyl orthosilicate, tetraethyl orthosilicate, tetramethyl orthosilicate, tetramethyl orthosilicate, tetramethyl orthosilicate, tetraethyl ortho-methyl orthosilicate, tetramethyl ortho-thoxyl orthosilicate, tetramethyl orthoxyl orthosilicate, tetramethyl orthoxyl orthosilicate, tetramethyl orthoxyl orthosilicate, tetramethyl orthoxyl orthosilicate, tetramethyl
  • Silicic acid tetrahexyl ester of silicic acid, tetrapentyl ester of silicic acid, tetrakis (l-methylpropyl) ester of silicic acid, tetra-2-propen-l-yl ester of silicic acid, Diethoxydipropylsilane, dimethyldipropoxysilane, dimethoxymethylpropylsilane,
  • Benzene diphenylbis (2-propenyloxy) silane, methyl triphenyl ester of silicic acid, diethoxydi-1-naphthalenylsilane, 2,2-diphenyl-1,3-dioxa-2-silacyclohexane,, 1- (dimethoxymethylsilyl) -4-methyl-benzene , 2,2-diphenyl-l, 3,2-benzodioxasilole, 12,12-diphenyl-2,5,8, l 1,13, 16,19, 22-octaoxa-12-silatricosane, 9,9-diethoxy- 9H-9-silafluorene, triethyl p-tolyl ester of silicic acid, 4,4'- (diethoxysilylene) di-benzyl alcohol, bis (isopropenyloxy) diphenylsilane, 1,2-bis (triethoxysilyl) -
  • Benzene amine, 2- (trimethoxysilyl) benzine and l-isocyanato-4- (trimethoxysilyl) benzene Compounds containing thiols such as 3- (dimethoxymethylsilyl) -l-propanethiol, 1- (diethoxymethylsilyl) -methanethiol, 1 - (dimethoxymethylsilyl) -methanethiol, 2-
  • At least one compound from the group consisting of tetramethylorthosilicate, tetraethylorthosilicate, tetrapropylorthosilicate, dichlorodiphenylsilane, 3-glycidyloxypropyltriethoxy silane, 3-glycidyloxypropyltrimethoxysilane, 3 - is preferred as component K
  • Aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane are used.
  • R 1 represents a substituted or unsubstituted Cl-C12-alkyl group which can optionally be interrupted by heteroatoms, substituted or unsubstituted Cl- C12-alkenyl group which can optionally be interrupted by heteroatoms, substituted or unsubstituted Cl-C12-alkoxy group which can optionally be interrupted by heteroatoms, substituted or unsubstituted C6-C18 aryl group, substituted or unsubstituted C6-C18 aryloxy group, heteroaryl group, thiols, phosphorus groups , Carboxylates, isocyanates, amines, carbamines, amides or carbamides.
  • R2 can be identical or different and iur a substituted or unsubstituted C1 -02-alkyl group which can optionally be interrupted by heteroatoms, substituted or unsubstituted C1-C12-alkenyl group which can optionally be interrupted by heteroatoms, substituted or unsubstituted Cl-C12-alkoxy group which can optionally be interrupted by heteroatoms, substituted or unsubstituted C6-C18-aryl group, substituted or unsubstituted C6-C18-aiyloxy group, particularly preferably the same or different and for a substituted or unsubstituted Cl-C12-alkoxy group may optionally be interrupted by heteroatoms, substituted or unsubstituted C6-C18-aryl group, substituted or unsubstituted C6-C18-aryloxy group.
  • X preferably stands for F or CI, particularly preferably for CI.
  • R 1 for a substituted or unsubstituted Cl-C12-alkyl group which can optionally be interrupted by heteroatoms, substituted or unsubstituted Cl-C12-alkoxy group which can optionally be interrupted by heteroatoms, substituted or unsubstituted C6-C12-aryl group, substituted or unsubstituted C6 -C12-aryloxy group, heteroaryl group, thiols, isocyanates, amines or amides,
  • R 2 are the same and represent a substituted or unsubstituted Cl-C12-alkoxy group, a substituted or unsubstituted C6-C12-aryl group or a substituted or unsubstituted C6-C12-aryloxy group,
  • X is the same and stands for F or CI.
  • the reaction components are reacted by the one-step process known per se, often using mechanical equipment, for example those described in EP-A 355,000.
  • the polyurethane foams are preferably in the form of flexible polyurethane foams and can be produced as molded or as block foams, preferably as block foams.
  • the invention therefore relates to a process for producing the polyurethane foams, the polyurethane foams produced by this process, the flexible polyurethane block foams or flexible polyurethane molded foams produced by these processes, the use of the flexible polyurethane foams for the production of molded parts and the molded parts themselves.
  • polyurethane foams obtainable according to the invention, preferably flexible polyurethane foams, are used, for example, in the following ways: furniture upholstery, textile inserts, mattresses, automobile seats, headrests, armrests, sponges, foam sheets for use in automobile parts such as headliners, door side panels, seat covers and components.
  • the flexible foams according to the invention have a bulk density according to DIN EN ISO 3386-1-98 in the range from 16 to 60 kg / m 3 , preferably 20 to 50 kg / m 3 .
  • the cPC content was quantified by means of 'H-NMR spectroscopy (Bruker, DPX 400, 400 MHz): about 24 hours after the flexible polyurethane foams had been produced, a sample of 1.2-1.5 g of the polyurethane was obtained - Soft foam extracted at 60 ° C for 7.5 hours in acetone by Soxhlet. The extract was concentrated under reduced pressure and taken up in deuterated chloroform with dimethyl terephthalate or 1,2,4-trichlorobenzene as an internal standard. The cPC content was then quantified by H-N R by comparing it with the internal standard.
  • Al-1 polyether carbonate polyol, functionality 2.8, OH number 56 mg KOH / g, 24% by weight
  • A2-1 Polyether polyol, functionality 2.9, OH number 48 mg KOH / g, manufactured by
  • Niax Catalyst A1 bis [2- (N, N‘-dimethylammo) ethyl] -based (from Momentive
  • Bl-2 Desmorapid SO, tin catalyst (Covestro AG)
  • D-l Desmodur T 80, mixture of 2,4‘-toluene diisocyanate and 2,6‘-
  • K-6 3 -Glycidyloxypropyltrimethoxy silane
  • K-7 3-aminopropyltrimethoxysilane
  • Fyrol-PNX oligomeric alkyl phosphate (ICL-IP) Production of flexible laboratory foams:
  • the flexible polyurethane foams described in Table 1 were produced in a batch process.
  • the components were mixed using a Pendraulik LM 34 laboratory mixer.
  • the components Al-1 and A2-1 (125 g in total) were weighed into a 500 mL paper cup together with the components B 1-1, B2-1 and C-l and premixed for 10 seconds using a high-speed stirrer.
  • Component B1 -2 was then added and the mixture was mixed for 10 seconds at the same stirring speed.
  • Component D-1 was finally added to this mixture, mixed for 7 seconds and the mixture transferred into a prepared paper box with a floor plan of 20 cm ⁇ 20 cm ⁇ 15 cm.
  • the height of the flexible polyurethane foam blocks was approx. 14-15 cm.
  • the finished flexible polyurethane foam was stored in the paper box for about 20-24 hours before it was sawed into test specimens for testing.
  • the compressive strength and the bulk density of the flexible polyurethane foams were determined in accordance with DIN EN ISO 3386-1-98.
  • Comparative Example 1 contains an additive which already reduces the emission of cyclic propylene carbonate (Fyrol PNX).
  • a component K according to the invention ie a compound according to formula (II)
  • results in lower values for cyclic propylene carbonate in the emission determination (Examples 3 to 6) compared to Comparative Examples 1, 2 and 7 to 10.
  • the addition of a A compound based on formula (II), where R is partially replaced by a hydroxyl group leads to a significant increase in cyclic propylene carbonate in the flexible polyurethane foam (Comparative Examples 7-10).

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  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un procédé de production de mousses de polyuréthane par réaction des constituants suivants : A des constituants de type polyol, contenant A1 40 à 100 parties en poids de polyéther-carbonate-polyol présentant un indice d'hydroxyle selon la norme DIN 53240-1 (juin 2013) de 20 de mg KOH/g à 120 mg de KOH/g, A2 0 à 60 parties en poids de polyéther-polyol présentant un indice d'hydroxyle selon la norme DIN 53240-1 (juin 2013) de 20 mg de KOH/g à 250 mg de KOH/g et une teneur en oxyde d'éthylène de 0 à 60 % en poids, le polyéther-polyol A2 étant exempt de motifs de carbonate ; B B1 un catalyseur et B2 éventuellement des substances auxiliaires et supplémentaires ; C de l'eau et/ou des agents gonflants physiques, avec D des diisocyanates et/ou des polyisocyanates, la production ayant lieu à une valeur caractéristique de 90 à 120. Le procédé est caractérisé en ce que la production a lieu en présence de 0,01 à 10,00 parties en poids d'un constituant K, par rapport à la totalité des parties en poids du constituant A1 + A2 = 100 parties en poids, et le constituant K est un composé selon la formule (II), R1 représentant un groupe C1-C22-alkyle substitué ou non substitué, qui peut éventuellement être interrompu par des hétéroatomes, un groupe C1-C22-alcényle substitué ou non substitué, qui peut éventuellement être interrompu par des hétéroatomes, un groupe C1-C22-alcoxy substitué ou non substitué, qui peut éventuellement être interrompu par des hétéroatomes, un groupe C6-C18-aryle substitué ou non substitué, un groupe C6-C18-aryloxy substitué ou non substitué, un groupe hétéroaryle, des thiols, des composés phosphorés, des carboxylates, des isocyanates, des amines, des carbamines, des amides ou des carbamides, R2, pouvant être identique ou différent, représentant un groupe C1-C22-alkyle substitué ou non substitué, qui peut éventuellement être interrompu par des hétéroatomes, un groupe C1-C22-alcényle substitué ou non substitué, qui peut éventuellement être interrompu par des hétéroatomes, un groupe C1-C22-alcoxy substitué ou non substitué, qui peut éventuellement être interrompu par des hétéroatomes, un groupe C6-C18-aryle substitué ou non substitué, un groupe C6-C18-aryloxy substitué ou non substitué et X, pouvant être identique ou différent, représentant F, Cl, Br ou I.
EP20821232.4A 2019-12-18 2020-12-14 Mousses de polyuréthane à base de polyéther-carbonate-polyols Withdrawn EP4077452A1 (fr)

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EP19217604.8A EP3838964A1 (fr) 2019-12-18 2019-12-18 Mousses de polyuréthane à base de polyéther carbonates polyoles
PCT/EP2020/085932 WO2021122431A1 (fr) 2019-12-18 2020-12-14 Mousses de polyuréthane à base de polyéther-carbonate-polyols

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EP20821232.4A Withdrawn EP4077452A1 (fr) 2019-12-18 2020-12-14 Mousses de polyuréthane à base de polyéther-carbonate-polyols

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