EP3774981A1 - Mousses de polyuréthane à base de polyéthercarbonate polyols - Google Patents

Mousses de polyuréthane à base de polyéthercarbonate polyols

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Publication number
EP3774981A1
EP3774981A1 EP19714227.6A EP19714227A EP3774981A1 EP 3774981 A1 EP3774981 A1 EP 3774981A1 EP 19714227 A EP19714227 A EP 19714227A EP 3774981 A1 EP3774981 A1 EP 3774981A1
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EP
European Patent Office
Prior art keywords
parts
weight
component
koh
components
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.)
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Application number
EP19714227.6A
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German (de)
English (en)
Inventor
Persefoni HILKEN
Stefan Lindner
Jörg Hofmann
Klaus Lorenz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Intellectual Property GmbH and Co KG
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Covestro Intellectual Property GmbH and Co KG
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Publication of EP3774981A1 publication Critical patent/EP3774981A1/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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/14—Manufacture of cellular products
    • 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
    • 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
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
    • C08G18/3882—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having phosphorus bound to oxygen only
    • C08G18/3885—Phosphate compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—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
    • C08G18/28—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
    • 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
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5075—Polyethers having heteroatoms other than oxygen having phosphorus
    • C08G18/5081—Polyethers having heteroatoms other than oxygen having phosphorus having phosphorus bound to oxygen only
    • C08G18/5084—Phosphate compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/125—Water, e.g. hydrated salts
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—Polyurethanes from polyethers

Definitions

  • the present invention relates to a process for the preparation of polyurethane foams, preferably of flexible polyurethane foams, by reaction of an isocyanate component with an isocyanate-reactive component comprising at least one polyethercarbonate polyol, and wherein the reaction takes place in the presence of a component K, which will be described in more detail below becomes.
  • the invention further relates to polyurethane foams produced by the process according to the invention and 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 amounts.
  • polyurethane foams based on polyether carbonate polyols and isocyanates is known (eg WO 2012/130760 A1, EP-A 0 222 453). It has been found that when using polyethercarbonate polyols for the production of Polyurethane foams containing the resulting products cyclic propylene carbonate, which can be detected for example by emission measurements on the flexible polyurethane foam.
  • the object of the present invention was to provide a process for producing polyurethane foams which results in polyurethane foams having a reduced emission of cyclic propylene carbonate.
  • Polyethercarbonatepolyol having a hydroxyl number according to DIN 53240-1 (June 2013) of 20 mg KOH / g to 120 mg KOH / g
  • Polyether polyol having 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 wt .-%, wherein polyether polyol A2 is free from carbonate units,
  • component K contains a reaction product of alkoxylated phosphoric acid with 1, 3-dicarbonyl compound or carboxylic anhydride and was optionally alkoxylated in at least one subsequent step,
  • the preferred subject matter of the invention is a process for the production of polyurethane foams, preferably flexible polyurethane foams, by reacting Al 40 to 100 parts by wt., Preferably 60 to 100 parts by wt., Particularly preferably 80 to 100 parts by wt. Of one or more polyether carbonate polyols having a hydroxyl number according to DIN 53240-1 (June 2013) of 20 mg KOH / g 120 mg KOH / g,
  • A2 0 to 60 parts by wt., Preferably 0 to 40 parts by wt., Particularly preferably 0 to 20 wt. Parts of one or more polyether polyols having a hydroxyl number according to DIN 53240-1 (June 2013) of 20 mg KOH / g 250 mg KOH / g and a content of ethylene oxide of 0 to 60 wt .-%, wherein the polyether polyols A2 are free of carbonate units,
  • A3 0 to 20 parts by weight, based on the sum of the parts by weight of the components Al and A2, of one or more polyether polyols having a hydroxyl number according to DIN 53240-1 (June 2013) 20 mg KOH / g to 250 mg KOH / g, and a content of ethylene oxide of> 60 wt .-%, wherein the polyether polyols A3 are free of carbonate units,
  • A4 0 to 40 parts by weight, based on the sum of the parts by weight of the 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 the components Al and A2, of polyols which do not fall under the definition of the components A1 to A4,
  • B2 optionally auxiliaries and additives
  • the components A1 to A5 each refer to “one or more" of said
  • component A contains
  • Polyethercarbonatpolyole having a hydroxyl number according to DIN 53240-1 (June 2013) of 20 mg KOH / g to 120 mg KOH / g and preferably a C0 2 content of 15 to 25 wt .-%, and
  • A2 25 to 35 parts by weight, most preferably 28 to 32 parts by weight of one or more polyether polyols having 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 wt .-%, wherein the polyether polyols A2 are free of carbonate units,
  • component A is preferably free of component A3 and / or A4.
  • component A comprises
  • Polyethercarbonatepolyole having a hydroxyl number according to DIN 53240-1 (June 2013) of 20 mg KOH / g to 120 mg KOH / g and preferably a C0 2 content of 15 to 25 wt .-%, and
  • Polyether polyols having 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 of 0 to 60 wt .-%, wherein the polyether polyols A2 are free from carbonate units,
  • component A is preferably free of component A4.
  • component A comprises
  • Al 40 to 100 parts by wt. Preferably 60 to 100 parts by wt., Particularly preferably 80 to 100 parts by wt., Most preferably 65 to 75 wt.
  • Parts of one or more polyether carbonate polyols having a hydroxyl number according to DIN 53240-1 From 20 mg KOH / g to 120 mg KOH / g and preferably a C0 2 content of 15 to 25% by weight, and
  • A2 0 to 60 parts by wt., Preferably 0 to 40 parts by wt., Particularly preferably 0 to 20 wt. Parts, most preferably 25 to 35 wt. Parts of one or more polyether polyols having a hydroxyl number according to DIN 53240-1 ( 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 from carbonate units,
  • A4 0.01 to 40.00 parts by weight, preferably 0.01 to 20.00 parts by weight, more 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 the components A1 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 the components Al and A2, polyols which do not fall under the definition of the components A1 to A4, wherein the component A is preferably free of component A3.
  • the specified ranges and preferred ranges of the components A1, A2, A4 and A5 are freely combinable with one another.
  • the component Al comprises a polyethercarbonate polyol having 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, wherein the polyethercarbonate polyol preferably has a C0 2 content of 15 to 25% by weight.
  • OH number hydroxyl number
  • Component Al 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 H-functional agents Starter molecules having an average functionality of from 1 to 6, preferably from 1 to 4, particularly preferably from 2 to 3. "H-functional" in the context of the invention is understood to mean a starter compound which has active hydrogen atoms toward 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 polyether carbonate polyol shown in the scheme according to formula (II) 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 catches of the blocks can vary and not to that shown in formula (II) 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", "CCE content") in a polyethercarbonate polyol can be determined from the evaluation of characteristic signals in the 11-NMR spectrum.
  • the following example illustrates the determination of the proportion of carbon dioxide derived units in a CCE / propylene oxide polyether carbonate polyol started on 1,8-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 means of I 1-NMR (a suitable device is from Bruker, DPX 400, 400 MHz, pulse program zg30, waiting time dl: 10 s, 64 scans) , Each sample is dissolved in deuterated chloroform.
  • I 1-NMR a suitable device is from Bruker, DPX 400, 400 MHz, pulse program zg30, waiting time dl: 10 s, 64 scans
  • Cyclic propylene carbonate (which was by-produced) with resonance at 4.5 ppm; Carbonate resulting from carbon dioxide incorporated in the polyethercarbonate polyol having resonances at 5.1 to 4.8 ppm; unreacted propylene oxide (PO) with resonance at 2.4 ppm; Polyether polyol (i.e., without incorporated carbon dioxide) having resonances at 1.2 to 1.0 ppm; the 1,8-octanediol incorporated as a starter molecule (if present) with a resonance at 1.6 to 1.52 ppm.
  • F (5, 1-4,8) area of resonance at 5.1 to 4.8 ppm for polyether carbonate polyol and one H atom for cyclic carbonate.
  • F (1, 6-1.52) 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 weight in part (in% by weight) of cyclic carbonate (CC ') in the reaction mixture was calculated according to formula (V),
  • the composition based on the polymer portion consisting of polyether polyol, which was built up from starter and propylene oxide during the CCE-free activation steps, and polyether carbonate polyol, composed of starter, propylene oxide and carbon dioxide during the in the presence of CO2 activation steps and during copolymerization
  • the non-polymer constituents of the reaction mixture ie, cyclic propylene carbonate and any unreacted propylene oxide present
  • the indication of the CCF 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 which is released from the initiator (1.8 -Octandiol, if any) as well as from the reaction of the initiator with epoxide resulting added under CCE-free conditions was not taken into account here).
  • polyethercarbonate polyols according to Al comprises:
  • Starter compounds are 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 waited for, and wherein the activation step ( ⁇ ) can also be repeated several times, (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).
  • Al alkylene oxides epoxides
  • 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-butene oxide 1-hexene oxide, 2,3-hexene oxide, 3,4-hexene oxide, 2-methyl-l, 2-pentenoxide, 4-methyl-
  • 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 wt .-%, preferably 0 to 50 wt .-% and particularly preferably free of ethylene oxide.
  • alkoxylation active groups with active H atoms are, for example -OH, -NH2 (primary amines), -NH- (secondary amines), -SH and - CO2H, preferred are -OH and -NH2, more preferably -OH.
  • H-functional initiator 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 (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 products from the BASF such. B.
  • 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-l-ol, 3-butyn-l-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- Hydroxy
  • 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-l-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.
  • 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) - cyclohexanes (such as, for example, 1,4-bis (hydroxymethyl) cyclohexane), triethylene glycol, tetraethylene glycol, polyethylene glycols, diprop
  • the H-functional starter compounds may also be selected from the class of polyether polyols, in particular those having a molecular weight M n 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% of propylene oxide units, particularly 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 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 1030 Arcol polyol ® 1070
  • Baycoll ® BD 1110 Bayfill VPPU ® 0789, Baygal ® K55, PET ® 1004 polyether ® S180 ).
  • suitable homo- polyethylene oxides are the BASF SE example Pluriol ® E-marks 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 Brands of BASF SE.
  • the H-functional starter compounds can also be selected from the substance class of the polyesterpolyols, in particular those having a molecular weight M n 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, tetrahydrophthalic,
  • alcohol components z. 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.
  • 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 M n of 150 to 2000 g / mol are preferred.
  • polycarbonate polyols such as, for example, polycarbonate diols
  • H-functional starter compounds in particular those having a molecular weight M n in the range from 150 to 4500 g / mol, preferably 500 to 2500, 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 are found, for. As in EP-A 1359177.
  • Desmophen ® C types of Covestro Germany AG are used, such.
  • 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 (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 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, 1,5-pentanediol, 2-methylpropane-l, 3-diol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, di- and trifunctional polyether polyols, wherein the polyether polyol from a di- or tri-H-functional starter compound and propylene oxide or a di- or tri-H-functional initiator compound, propylene oxide and ethylene oxide is constructed.
  • the polyether polyols preferably have a number average molecular weight M n in the range of 62 to 4500 g / mol and in particular a number average molecular weight M n in the range of 62 to 3000 g / mol, very particularly preferably a molecular weight of 62 to 1500 g / mol.
  • the polyether polyols have a functionality of 2 to 3.
  • the polyethercarbonate polyol Al is obtainable by addition of carbon dioxide and alkylene oxides onto 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 which are described, for example, in US Pat. No. 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 No.
  • 4,676,449 have very high activity in the homopolymerization of epoxides and allow the preparation of polyether polyols and / or polyether carbonate polyols at very low catalyst levels (25 ppm or less).
  • a typical example is 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 t-butanol), also have a polyether with a number average molecular weight M n greater than 500 g / mol.
  • a double metal cyanide compound eg zinc hexacyanocobaltate (III)
  • an organic complex ligand eg t-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 Al has a content of carbonate groups ("carbon dioxide-derived units"), calculated as CO2, of 2.0 and 30.0 wt.%, Preferably of 5.0 and 28.0 wt .-% and more preferably from 10.0 and
  • the polyether carbonate polyols or polyols have a hydroxyl number of from 20 mg KOH / g to 250 mg KOH / g and are obtainable by copolymerization from 2.0% by weight to 30.0% by weight.
  • 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 (II) wherein the ratio e / f of 2: 1 to 1: 20.
  • component Al is used to 100 parts by weight.
  • Component A2 comprises polyether polyols having a hydroxyl number according to DIN 53240-1 (June 2013) 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 and is free of carbonate units.
  • the Preparation of the compounds according to A2 can be carried out by catalytic addition of one or more alkylene oxides to H-functional starter compounds.
  • alkylene oxides As alkylene oxides (epoxides) 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-butenoxide, 3-methyl-1,2-butenoxide, 1-hexenoxid, 2,3-hexenoxid, 3,4-hexenoxid, 2-methyl- l, 2-pentene oxide, 4-methyl-l, 2-pentene oxide, 2-ethyl-1,2-butene oxide, 1-heptene oxide, 1-octene oxide, 1-nonoxide, 1-decene oxide, 1-undecene oxide, 1-dodecene oxide, 4-methyl-l, 2-penten
  • the alkylene oxides used are preferably ethylene oxide and / or propylene oxide and / or 1,2-butylene oxide. Particular preference is given to using an excess of propylene oxide and / or 1,2-butylene oxide.
  • 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 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-l, 5-pentanediol, 1,12-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 starting compound used is
  • the polyether polyols according to A2 have a content of 0 to 60 wt .-%, preferably from 0 to 40 wt .-%, particularly preferably 0 to 25 wt .-% of ethylene oxide.
  • Component A3 comprises polyether polyols having 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 more preferably 20 mg KOH / g to 80 mg KOH /G.
  • component A3 is in principle analogous to that of component A2, but with a content of ethylene oxide in the polyether polyol of> 60 wt .-%, preferably> 65 wt .-% is set.
  • Suitable alkylene oxides and H-functional starter compounds are the same as described for component A2.
  • 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 are formed.
  • Preferred H-functional starter compounds having a functionality of 3 are glycerol and / or trimethylolpropane, more preferably glycerin.
  • the component A3 is a glycerol-initiated bifunctional 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 dipserion) polyols are prepared 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 prepared by reacting an isocyanate mixture used from a mixture of 75 to 85 wt .-% 2,4-tolylene diisocyanate (2,4-TDI) and 15 to 25 wt .-% of 2,6-toluene 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 alkoxylating a bifunctional initiator (such as glycerol and / or trimethylolpropane) in the case of the polyethercarbonate polyol in the presence of carbon dioxide ,
  • a bifunctional initiator such as glycerol and / or trimethylolpropane
  • the PfPA 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 4.0 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 "EO capped", ie, 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 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 Polyacrylate polyols, as well as polyether polyols or polycarbonate polyols, which do not fall under the definition of the components A1 to A4 be.
  • polyether polyols or polycarbonate polyols which do not fall under the definition of the components A1 to A4 be.
  • 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), tin (II ) Salt of 2-butyloctanoic acid, tin (II) salt of 2-hexyldecanoic acid, stannous salt of neodecanoic acid, stannous salt of isononanoic acid, stannous salt of oleic acid, tin (II ) - salt of ricinoleic acid and tin (II) laurate used.
  • At least one tin (II) salt of the formula (VII) used, wherein x is an integer from 8 to 24, preferably 10 to 20, more preferably from 12 to 18 means.
  • the alkyl chain C x H 2x + i of the carboxylate is particularly preferably a branched carbon chain, ie C x H 2x + i is an isoalkyl 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, 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.
  • Components Al and A2 catalysts other than those of component B1.2, wherein the content of amine catalysts in component Bl.2 may be at most 50% by weight, based on component B1,
  • Component Bl.l comprises urea and derivatives of urea.
  • derivatives of urea include: aminoalkyl ureas, e.g. (3-dimethylaminopropylamine) urea and 1,3-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 from 0.05 to 1.50 parts by weight, preferably from 0.10 to 0.50 parts by weight, more 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.
  • the component Bl.2 is in amounts of from 0.03 to 1.50 parts by weight, preferably from 0.03 to 0.50 parts by weight, particularly preferably from 0.10 to 0.30 parts by weight, completely particularly preferably from 0.20 to 0.30 parts by weight, based on the sum of the parts by weight of the components Al to A2 used.
  • component B1.2 The content of amine catalysts in component B1.2 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 B1.2 is free of amine catalysts.
  • catalysts of component Bl.2 e.g. the tin (II) salts of carboxylic acids described above are 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 (for example, bis-dimethylaminoethyl ether, 2- (2-dimethylaminoethoxy) ethanol and N, N, N-trimethyl-N-hydroxyethyl-bisaminoethyl ether), cycloaliphatic amino ethers
  • aliphatic tertiary amines for example trimethylamine, tetramethylbutanediamine, 3-dimethylaminopropylamine, N, N-bis (3-dimethylaminopropyl)
  • N-ethylmorpholine N-ethylmorpholine
  • aliphatic amidines N-ethylmorpholine
  • cycloaliphatic amidines N-ethylmorpholine
  • the "amine catalysts" mentioned in Bl.2 do not include urea or its derivatives.
  • the invention therefore also provides a process for the production of polyurethane foams by reacting the components
  • Polyether polyol having 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 wt .-%, wherein polyether polyol A2 is free from carbonate units,
  • the non-alkaline medium may preferably be achieved by using urea and / or derivatives of urea as catalysts in accordance with component Bl, and using no amine catalysts.
  • a preferred subject of the invention is a process for the production of polyurethane foams, characterized in that
  • Polyether polyol having 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 wt .-%, wherein polyether polyol A2 is free from carbonate units,
  • auxiliaries and additives are 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® LF2 series b) 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 stabilizers against aging and weathering, antioxidants, plasticizers, fungistatic and bacteriostatic substances, fillers (such as barium sulfate, diatomaceous earth, soot 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, dyes, flame retardants, other stabilizers against aging and weathering antioxidant
  • 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 optionally be used according to the invention and details of the use and mode of action of these auxiliaries and additives are described in the Kunststoff-Handbuch, Volume VII, edited by G. Oertel, Carl-Hanser-Verlag, Kunststoff, 3rd edition, 1993 , eg on pages 104-127.
  • 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.
  • Suitable di- and / or polyisocyanates are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates, e.g. by W. Siefken in Justus Fiebig's Annalen der Chemie, 562, pages 75-136, for example those of the formula
  • Q is an aliphatic hydrocarbon radical having 2 to 18, preferably 6 to 10 C atoms, a cycloaliphatic hydrocarbon radical having 4 to 15, preferably 6 to 13 C atoms or an araliphatic hydrocarbon radical having 8 to 15, preferably 8 to 13, C atoms.
  • 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 isomers (“TDI”) are preferred;
  • Polyphenyl polymethylene polyisocyanates, as represented by aniline Formaldehyde condensation and subsequent phosgenation are prepared ("crude MDI") and carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret polyisocyanates (“modified polyisocyanates”), especially those modified polyisocyanates derived from 2,4- and / or Derive 2,6-toluene diisocyanate or from 4,4'- and / or 2,4'-diphenylmethane diisocyanate.
  • TDI 2,4- and 2,6-toluene diisocyanate, and any desired mixtures of these isomers
  • 2,4- and / or 2,6-toluene diisocyanate Particular preference is given to using 2,4- and / or 2,6-toluene diisocyanate.
  • the isocyanate component B comprises a toluylene 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 in a range of 100 to 115, particularly preferably 102 to 110.
  • the index indicates the percentage ratio of the actual amount of isocyanate used to the stoichiometric, i. for the implementation of OH equivalents calculated amount of isocyanate groups (NCO) amount.
  • Component K according to the invention is a reaction product of an alkoxylated phosphoric acid with 1,3-dicarbonyl compound or carboxylic anhydride.
  • Alkoxylated phosphoric acids are reaction products of phosphoric acid with the alkylene oxides described for component Al.
  • the alkylene oxide preference is given to using ethylene oxide, propylene oxide or a mixture of ethylene oxide and propylene oxide, particularly preferably ethylene oxide.
  • Alkoxylated phosphoric acid is preferably obtained by direct reaction of phosphoric acid with alkylene oxides without addition of a catalyst, it being possible to use the phosphoric acid in pure form or as an aqueous solution (for example in the form of an 85% strength by weight solution).
  • 1,3-dicarbonyl compound carboxylic acids having at least two 1,3-position carbonyls such as malonic acid or acetoacetic acid, esters of carboxylic acids having at least two 1,3-position carbonyl groups such as methyl malonate, ethyl malonate or acetoacetate, amides having at least two carbonyl groups in the 1,3-position such as acetoacetamide, are used.
  • 1,3-dicarbonyl ester used of carboxylic acids having at least two carbonyl groups in the 1,3-position esters of malonic acid and / or acetoacetic acid are particularly preferably used.
  • phthalic anhydride 1,2,3,6-tetrahydro-phthalic anhydride, dodecenylsuccinic anhydride, citric anhydride or glutaric anhydride can be used as the carboxylic anhydride, preferably maleic anhydride and / or phthalic anhydride being used.
  • the component K can optionally be reacted in one or more steps with further alkylene oxide.
  • the subsequent alkoxylation can take place, for example, at a temperature of at least 40 ° C., preferably at 40 to 140 ° C. and more preferably at 60 to 100 ° C.
  • component K subsequently becomes
  • Component K preferably has a hydroxyl number of 10 mg KOH / g to 320 mg KOH / g, more preferably from 50 mg KOH / g to 300 mg KOH / g, particularly preferably from 170 mg KOH / g to 300 mg KOH / g, on.
  • reaction components are reacted according to the conventional one-step process, often using machinery, e.g. those described in EP-A 355 000. Details of processing means which are also contemplated by this invention are described in the Kunststoff-Handbuch, Volume VII, edited by Vieweg and Hochtlen, Carl-Hanser-Verlag, Kunststoff 1993, e.g. on pages 139 to 265.
  • 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 soft block foams or flexible polyurethane foams produced by these processes, the use of the flexible polyurethane foams for the production of molded parts and the molded parts themselves.
  • the polyurethane foams obtainable according to the invention are used, for example, for the following applications: furniture upholstery, textile inserts, mattresses, automobile seats, headrests, armrests, sponges, foamed films for use in automotive parts such as headliners, door paneling, seat covers and building components.
  • the flexible foams according to the invention have a density in accordance with DIN EN ISO 3386-1-98 in the range of 16 to 60 kg / m 3 , preferably 20 to 50 kg / m 3 .
  • the invention relates to a process for producing polyurethane foams by reacting the components
  • Polyether polyol having 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 wt .-%, wherein polyether polyol A2 is free from carbonate units,
  • component K contains a reaction product of alkoxylated phosphoric acid with 1, 3-dicarbonyl compound or carboxylic anhydride and was optionally alkoxylated in at least one subsequent step,
  • the invention relates to a method according to the first embodiment, characterized in that component A has the following composition:
  • Polyether polyol having 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 wt .-%, wherein polyether polyol A2 is free from carbonate units,
  • A3 0 to 20 parts by wt., Based on the sum of the parts by wt.
  • polyether polyol having a hydroxyl number according to DIN 53240-1 (June 2013) 20 mg KOH / g to 250 mg KOH / g, and a content of ethylene oxide of> 60% by weight, where polyether polyol A3 is free from carbonate units, A4 0 to 40 parts by weight, based on the sum of the parts by weight of the components Al and A2, polymer polyol, PHD polyol and / or PIPA polyol,
  • the invention relates to a method according to the first or second embodiment, characterized in that component A is free of components A3 and / or A4.
  • the invention relates to a method according to one of the embodiments 1 to 3, characterized in that component A comprises:
  • Polyethercarbonatepolyol having a hydroxyl value according to DIN 53240-1 (June 2013) of 20 mg KOH / g to 120 mg KOH / g, and
  • polyether polyol having 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 wt .-%, wherein polyether polyol A2 is free of carbonate units.
  • the invention relates to a process according to any one of embodiments 1 to 4, characterized in that component Al comprises a polyethercarbonate polyol which is obtainable by copolymerization of carbon dioxide and alkylene oxide in the presence of H-functional starter molecules, wherein the polyethercarbonate polyol preferably has a CCE- Has content of 15 to 25 wt .-%.
  • the invention relates to a method according to one of the embodiments 1 to 5, characterized in that as component B
  • Bl catalyst selected from one or more of the following compounds
  • 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 auxiliaries and additives
  • the invention relates to a method according to one of the embodiments 1 to 5, characterized in that as component B
  • B2 optionally auxiliaries and additives
  • component Bl Bl.l 0.05 to 1.50 parts by weight, based on the sum of the parts by weight of the components Al and A2, urea and / or derivatives of urea and
  • Bl.2 0.03 to 1.50 parts by weight, based on the sum of the parts by weight of the components Al and A2, catalyst other than that of the component B1.2, wherein the content of amine catalyst in the component Bl .2 may be at most 50% by weight, based on component B 1,
  • the invention relates to a method according to one of
  • the invention relates to a method according to one of
  • Embodiments 1 to 8 characterized in that the component K a
  • the invention relates to a method according to one of
  • Embodiments 1 to 9 characterized in that the alkoxylated phosphoric acid is an ethoxylated phosphoric acid.
  • the invention relates to a method according to one of
  • the invention relates to a method according to one of the embodiments 1 to 11, characterized in that the component K was then alkoxylated by
  • the invention relates to polyurethane foams obtainable by a process according to any one of embodiments 1 to 12.
  • the invention relates to polyurethane foams according to the thirteenth embodiment, which are polyurethane flexible foams.
  • the invention relates to the use of the polyurethane foams according to the thirteenth or fourteenth embodiment for the production of furniture upholstery, textile inserts, mattresses, automobile seats, headrests, Armrests, sponges, foam sheets for use in automotive parts such as headliners, door panels, seat pads and structural members.
  • the invention relates to a process according to one of the embodiments 1 to 8, characterized in that the component K is a reaction product of alkoxylated phosphoric acid with 1,3-dicarbonyl compounds or a reaction product of alkoxylated phosphoric acid with carboxylic acid anhydrides and a subsequent step for alkoxylation ,
  • the invention relates to a process according to one of embodiments 1 to 12, characterized in that component K has a hydroxyl number of 10 mg KOH / g to 320 mg KOH / g, more preferably from 50 mg KOH / g to 300 mg KOH / g, especially preferably from 170 mg KOH / g to 300 mg KOH / g.
  • the quantification of the cPC content was carried out by means of I 1-NMR spectroscopy (Bruker, DPX 400, 400 MHz): About 24 h after preparation of the flexible polyurethane foams, 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 internal standard. Subsequently, the cPC content was quantified by I 1-NMR by comparison with the internal standard.
  • Al-1 polyethercarbonate polyol, functionality 2.8, OH number 54 mg KOH / g, 14% by weight
  • Bl -2 Desmorapid SO, tin catalyst (Covestro AG)
  • D-1 Desmodur T 80, mixture of 2,4'-tolylene diisocyanate and 2,6'-
  • the product obtained has an OH number of 327 mg KOH / g and an acid number of 0.0 mg KOH / g.
  • the product obtained has an OH number of 332 mg KOH / g and an acid number of 72 mg KOH / g.
  • the product obtained has an OH number of 258 mg KOH / g and an acid number of 28.5 mg KOH / g.
  • the product obtained has an OH number of 239 mg KOH / g and an acid number of 25.6 mg KOH / g.
  • the product obtained has an acid number of 34 mg KOH / g.
  • step (1) In a 2 liter laboratory autoclave 311.3 g of the intermediate product were placed under a nitrogen atmosphere and then heated to 60 ° C. The pressure was then adjusted to 2.7 bar (absolute) by means of nitrogen. Then at 60 ° C and stirring (800 rev / min) 141.1 g of ethylene oxide over a period of 1.6 hours in the headspace of Autoclaved (step (1)). After a post-reaction time of 5 hours at 60 ° C, volatile fractions were removed at 60 ° C under vacuum (50 mbar) over a period of 30 minutes (step (2)). After cooling to room temperature, 0.288 g of IRGANOX® 1076 was added.
  • the product obtained has an OH number of 210 mg KOH / g and an acid number of 0.7 mg KOH / g.
  • step (1) In a 2 liter laboratory autoclave 399.0 g of the intermediate product were placed under a nitrogen atmosphere and then heated to 60 ° C. The pressure was then adjusted to 2.8 bar (absolute) by means of nitrogen. Then, at 60 ° C. and stirring (800 rpm), 171.0 g of ethylene oxide were metered into the headspace of the autoclave over a period of 1.8 hours (step (1)). After a post-reaction time of 5 hours at 60 ° C, volatile fractions were removed at 60 ° C under vacuum (30 mbar) over a period of 30 minutes (step (2)). After cooling to room temperature, 0.298 g of IRGANOX® 1076 was added. The product obtained has an OH number of 197 mg KOH / g and an acid number of 0.5 mg KOH / g.
  • the flexible polyurethane foams described in Table 1 were prepared in a batch process. The components were mixed by means of a Pendraulik laboratory mixer type LM 34.
  • Component Al-1 (125 g) was weighed in a 500 mL paper cup together with components Bl-1, B2-1 and C-1 and premixed with a high-speed stirrer for 10 seconds. This was followed by the addition of the component Bl -2 and a mixing of 10 seconds at the same stirring speed. Finally, component D-1 was added to this mixture, mixed for 7 seconds, and the mixture was transferred to a prepared 20 cm x 20 cm x 15 cm paper box.
  • the height of the flexible polyurethane foam blocks was about 14-15 cm.
  • the finished flexible polyurethane foam was stored in the paper box for about 20-24 hours before this Test was sawn into test specimens.
  • the compression hardness and the bulk density of the flexible polyurethane foams was determined in accordance with DIN EN ISO 3386-1-98.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un procédé de production de polyéthercarbonate polyols par réaction des composants - A) composant polyol, contenant : A1 entre 40 et 100 parties en poids de polyéthercarbonate polyol ayant un indice d'hydroxyle selon DIN 53240-1 (juin 2013) compris entre 20 et 120 mg KOH/g; A2 entre 0 et 60 parties en poids de polyol de polyéther ayant un indice d'hydroxyle selon DIN 53240-1 (juin 2013) compris entre 20 et 250 mg KOH/g et une teneur en oxyde d'éthylène comprise entre 0 et 60% en poids, le polyol de polyéther A2 étant exempt de fractions carbonate, - B) B1 catalyseur, et B2 éventuellement des auxiliaires et des additifs, C) de l'eau et/ou des agents porogènes physiques, avec - D) des di- et/ou polyisocyanates, la fabrication s'effectuant, à un indice compris entre 90 et 120, en présence d'un composant K. L'invention se caractérise en ce que le composant K contient un produit de réaction d'acide phosphonique alcoxylé comportant un composé 1,3-dicarbonyle ou de l'anhydride d'acide carboxylique et en ce qu'il a éventuellement été alcoxylé dans au moins une étape subséquente, et en ce que le composant K est utilisé dans une quantité comprise entre 0,05 et 10,00 parties en poids, rapporté à la somme des parties en poids des composants A1 + A2 = 100 parties en poids.
EP19714227.6A 2018-04-06 2019-04-04 Mousses de polyuréthane à base de polyéthercarbonate polyols Withdrawn EP3774981A1 (fr)

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PCT/EP2019/058522 WO2019193101A1 (fr) 2018-04-06 2019-04-04 Mousses de polyuréthane à base de polyéthercarbonate polyols

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US20210070916A1 (en) 2021-03-11

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