WO2016020140A2 - Composés azotés adaptés à une utilisation dans la fabrication de polyuréthanes - Google Patents

Composés azotés adaptés à une utilisation dans la fabrication de polyuréthanes Download PDF

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WO2016020140A2
WO2016020140A2 PCT/EP2015/065836 EP2015065836W WO2016020140A2 WO 2016020140 A2 WO2016020140 A2 WO 2016020140A2 EP 2015065836 W EP2015065836 W EP 2015065836W WO 2016020140 A2 WO2016020140 A2 WO 2016020140A2
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Prior art keywords
formula
weight
nitrogen
containing compound
foam
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PCT/EP2015/065836
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German (de)
English (en)
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WO2016020140A3 (fr
Inventor
Thomas Günther
Michael Fiedel
Martin Glos
Roland Hubel
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Evonik Degussa Gmbh
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Publication of WO2016020140A2 publication Critical patent/WO2016020140A2/fr
Publication of WO2016020140A3 publication Critical patent/WO2016020140A3/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
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/20—Heterocyclic amines; Salts thereof
    • C08G18/2009—Heterocyclic amines; Salts thereof containing one heterocyclic ring
    • C08G18/2018—Heterocyclic amines; Salts thereof containing one heterocyclic ring having one nitrogen atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—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
    • C08G18/4829—Polyethers containing at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—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
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl 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
    • C08G2101/00—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
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid

Definitions

  • the present invention is in the field of nitrogen containing compounds, especially amines, and polyisocyanate polyaddition products, especially polyurethanes. It relates in particular to the use of nitrogen-containing compounds of the formula (I), corresponding to quaternized and / or protonated compounds, for the preparation of polyurethanes, in particular polyurethane foams, compositions containing these compounds and polyurethane systems obtained using the compounds.
  • tertiary amines in the preparation of polyurethanes is known.
  • a variety of structurally different amines is used as catalysts.
  • Polyurethanes are understood here to mean all reaction products starting from isocyanates, in particular from polyisocyanates, and correspondingly isocyanate-reactive molecules. This includes, inter alia, polyisocyanurates, polyureas and allophanate, biuret, uretdione, uretimine or carbodiimide-containing isocyanate or polyisocyanate reaction products. Preference is given to the use of tertiary amines in the preparation of polyisocyanate polyaddition products.
  • Polyurethane systems are z. Polyurethane coatings, polyurethane adhesives, polyurethane sealants, polyurethane elastomers or polyurethane foams, also referred to as polyurethane foams or PU foams.
  • tertiary amines play an important role, since the so-called blowing reaction - water reacts with isocyanate to form carbon dioxide as a propellant gas - and the gel reaction - polyols react with isocyanates to urethanes, resulting in an increase in molecular weight and corresponding gelling leads - must be precisely coordinated so that a high-quality foam can arise.
  • Polyurethane foams are cellular and / or microcellular polyurethane materials and can be broadly divided into closed cell or partially closed cell rigid polyurethane foams and open cell or partially open cell flexible polyurethane foams.
  • Polyurethane rigid foams are predominantly used as insulating materials used for example in refrigerator systems or in the thermal insulation of buildings.
  • Flexible polyurethane foams are used in a large number of industrial and private technical applications, for example for noise insulation, the manufacture of mattresses or the upholstery of furniture.
  • PU foams such as conventional flexible foams based on ether or ester polyol, cold flexible foams, also referred to as cold foams (often referred to as "high resilience” (HR) foams), and rigid foams, and foams their properties
  • HR foams high resilience foams
  • hard foams can be used as a headliner, ester foams for interior lining of the doors and for punched-out sun visors, cold and soft foams for seating systems and mattresses.
  • a concrete object of the present invention was therefore to provide an alternative catalyst for the preparation of polyisocyanate reaction products, preferably polyurethanes, in particular polyurethane foams, which are preferably low odor, resistant to aging and / or free of emissions or possibly with low amine or other emissions, such as Formaldehyde and / or dimethylformamide (DMF), are afflicted.
  • polyisocyanate reaction products preferably polyurethanes, in particular polyurethane foams, which are preferably low odor, resistant to aging and / or free of emissions or possibly with low amine or other emissions, such as Formaldehyde and / or dimethylformamide (DMF), are afflicted.
  • the present invention thus relates to the use of a nitrogen-containing compound, a corresponding quaternized and / or protonated compound in the preparation of polyisocyanate polyaddition products, preferably of polyurethanes, in particular polyurethane foams, wherein the nitrogen-containing compound of formula (I) is sufficient
  • n 1 to 30, in particular 1 to 12, preferably 2 to 6, preferably 2 or 3, particularly preferably 2,
  • a, b are the same or different from each other 0 or a natural number of 1 to 100, in particular 0 to 20, preferably 0 to 12, particularly preferably 0 to 4,
  • R 1, R 2 equal or different from one another, is a linear, branched or cyclic, aliphatic, saturated or unsaturated hydrocarbon radical having 1 to 30 carbon atoms, in particular 2 to 12, preferably 2 to 6, preferably 2 or 3 carbon atoms, particularly preferably 2 carbon atoms is
  • R 3 is H or a linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated, optionally substituted by one or more hetero atoms or interrupted by one or more hetero atoms hydrocarbon radical having 1 to 30 carbon atoms,
  • R 4 , R 5 are identical or different, are H, a linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated, optionally substituted by one or more hetero atoms or interrupted by one or more hetero atoms hydrocarbon radical or R 4 and R 5 to a cycle, preferably to a pyrrolidine residue, a morpholine residue, an imidazole residue or a piperazine residue v
  • R7, Rs, 9 are the same or different from each other H or a linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated, optionally substituted by one or more heteroatoms or by one or more
  • R6 is H or a linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated, optionally substituted by one or more heteroatoms or interrupted by one or more heteroatoms
  • Hydrocarbon radical is,
  • Y is -OH, * NH 2 j , ⁇ ⁇ , or
  • the term "use of at least one nitrogen-containing compound, a corresponding quaternized and / or protonated compound" in the context of this invention here and in the following includes the use of the relevant nitrogen-containing compound as well as the use of the corresponding protonated compounds as well as the use of the corresponding quaternized compounds.
  • the use of corresponding mixtures The inventively used nitrogen-containing compounds of the formula (I) and correspondingly quaternized and / or protonated compounds, and mixtures of The above are suitable as catalysts for the preparation of polyisocyanate reaction products, preferably of polyurethanes, in particular of polyurethane foams and can catalyze both the gel and the blowing reaction in the foaming, and advantageously further isocyanate reactions, as described below.
  • the present invention also enables a reduction or avoidance of the catalysis-related emissions in the production of polyurethane systems, in particular of polyurethane foams.
  • an additional advantage of the invention is that the nitrogen-containing compounds according to the invention used according to the formula (I), corresponding quaternized and / or protonated compounds, and mixtures of the aforementioned, advantageously low emissions, preferably free with respect to typical undesirable emissions of the resulting polyurethane systems, especially polyurethane foams
  • Particularly preferred polyurethane flexible foams are, namely advantageously low emissions with respect to emissions of nitrogen-containing compounds, hereinafter also referred to as amine emissions, advantageously low emissions with respect to emissions of dimethylformamide (DMF), and advantageously low emissions with respect to aldehyde emissions, especially in terms of formaldehyde emissions.
  • "low emission" with respect to amines comprises in particular that the polyurethane system, preferably the polyurethane foam, more preferably the flexible polyurethane foam, particularly preferably the flexible polyurethane hot foam, preferably for the production of mattresses and / or upholstered furniture, an amine emission of> 0 ⁇ g m 3 and ⁇ 40 ⁇ g m 3 , preferably ⁇ 10 ⁇ g m 3 , more preferably ⁇ 5 ⁇ g / m 3 , determined according to the test chamber method based on the DIN standard DIN EN ISO 16000-9: 2008-04, 24 hours after sketch, and / or that the polyurethane system, preferably the polyurethane foam, in particular the flexible polyurethane foam, particularly preferably the Polyurethanaltweichschaum, preferably for the production of polyurethanes for use in the automotive industry, especially in automotive interiors, for example as a headliner, interior lining of doors, punched out Sun visors, steering wheels
  • Low emissions with regard to emissions of dimethylformamide (DMF) in the context of the present invention means in particular that the nitrogen-containing compounds according to the invention of the formula (I), (II), (III) and / or (IV) and / or corresponding polyurethane systems are preferred
  • Polyurethane foams in particular flexible polyurethane foams, more preferably polyurethane hot foams produced using the aforementioned compounds, have a DMF emission of> 0 ppm and ⁇ 5 ppm, preferably ⁇ 1 ppm, more preferably ⁇ 0.1 ppm
  • the invention thus provides, in particular, the provision of flexible polyurethane foams, especially polyurethane hot foams, which are particularly low in emissions with respect to dimethylformamide.
  • “DMF emission” is not a subset of "Armin emission” for the purposes of the present invention.
  • low emissions with regard to emissions of aldehydes, in particular of formaldehyde, mean in particular that the polyurethane system, preferably the polyurethane foam, in particular the flexible polyurethane foam, by the foam manufacturers and the furniture industry in Europe and the USA within the framework of the voluntarily imposed program "CertiPUR" limits for aldehyde emissions, in particular for formaldehyde emissions and / or that the replacement of the conventional catalysts, in particular of amines, especially of tertiary amines, containing one or more N-methyl or N, N-dimethyl groups, according to the prior art by nitrogen compounds to be used according to the invention in the formulation of a corresponding polyurethane system leads to an improvement of the aldehyde, in particular formaldehyde-related emissions.
  • VDA 275 provides a measuring method for the determination of aldehyde, in particular the formaldehyde release by the modified bottle method, wherein as derivatization of aldehydes in addition to the commonly used acetylacetone (via photometric detection) and 2.4 - Dinitrophenylhydrazine (2,4-DNP) (detection by HPLC after external calibration) can be used to determine acetaldehyde and propionaldehyde better in addition to formaldehyde In the context of this invention is based on both process interpretations of this VDA 275 as a preferred method for the determination of aldehyde -, In particular formaldehyde emissions, reference is made.
  • the present invention thus makes it possible to provide polyurethane systems, preferably polyurethane foams, in particular flexible polyurethane foams which, with regard to emissions of nitrogen-containing compounds, also referred to below as amine emissions, are particularly low in emissions, preferably free from such emissions, even if different requirements are met.
  • polyurethane systems preferably polyurethane foams, in particular flexible polyurethane foams which, with regard to emissions of nitrogen-containing compounds, also referred to below as amine emissions, are particularly low in emissions, preferably free from such emissions, even if different requirements are met.
  • the present invention thus makes it possible to provide polyurethane systems, preferably polyurethane foams, in particular flexible polyurethane foams prepared using the aforementioned nitrogen-containing compounds which are particularly low in emissions of dimethylformamide (DMF), preferably emission-free, preferably free of such emissions.
  • the present invention contributes to the provision of polyurethane systems, preferably polyurethane foams, in particular of
  • conventional catalysts especially tertiary amines containing one or more N-methyl - or N, N-dimethyl groups, according to the prior art, can be used.
  • amines or PU systems containing commercially available amines may otherwise contain, for example due to their industrial production formaldehyde as an impurity, for example, were used in the amine in the formaldehyde or methanol as the alkylating agent.
  • the present invention also contributes to the provision of low-odor polyurethane systems, preferably polyurethane foams, in particular flexible polyurethane foams.
  • Low odor here means that the resulting polyurethane system has the lowest possible product odor, especially when using the nitrogen-containing compounds according to the invention as alternative catalysts to catalysts according to the prior art, which is verifiable in particular by olfactory review by a panel of people with an odor.
  • the present invention further contributes to the improvement of the aging behavior, in particular to the heat resistance and / or aging resistance during tempering (heat aging), of polyurethane systems, preferably polyurethane foams, in particular flexible polyurethane foams.
  • aging phenomena are often closely linked to the choice of the catalyst system for preparing the polyurethane systems and generally lead to material fatigue.
  • the nitrogen-containing compounds according to the invention the heat resistance and / or durability of the corresponding polyurethane systems over polyurethane systems which have been prepared with conventional catalysts according to the prior art can be advantageously improved here.
  • this effect can be observed especially in the case of polyurethane foams, preferably soft-block foams, in particular in the sense of a dry heat aging according to the DIN standard DIN EN ISO 2440 / A1: 2009-01, in particular at a temperature of 70, 100, 120, 125 and / or 140 ° C and an aging time of 2, 4, 16, 22, 24, 48, 72 and / or 168 hours, preferably at 2, 24 and / or 168 hours, if in the expansion according to the invention nitrogen-containing compounds according to formula (I) as alternatives are used to structurally related catalysts according to the prior art.
  • the present invention also provides the provision of preferably discoloration minimized polyurethane systems, in particular polyurethane foams, preferably of polyurethanes for use in the automotive industry, especially in automotive interiors, such as headliners, door panels, punched sun visors, steering wheels and / or seating systems, the polyurethane systems prepared by using nitrogen-containing catalysts according to the invention in particular to lower discoloration of plastics, in particular plastic covers, in automotive interiors as such polyurethane systems that can be prepared using conventional catalysts according to the prior art, in particular non-inventive amines.
  • This can be demonstrated, in particular, by means of a PVC discoloration test according to the Volkswagen test specification VW PV 3937, amine emissions according to the indicator method.
  • the present invention allows a broader processing play in the production of polyurethane systems, in particular semi-rigid polyurethane foams (open-cell rigid foams, for example for use as a headliner in automotive interiors).
  • polyurethane systems in particular semi-rigid polyurethane foams (open-cell rigid foams, for example for use as a headliner in automotive interiors).
  • quaternizing reagents for possible quaternization of the compounds of the formula (I), all reagents known as quaternizing reagents can be used.
  • Preferably used as quaternizing alkylating agents such as.
  • dimethyl sulfate, methyl chloride or benzyl chloride preferably methylating agent used in particular dimethyl sulfate.
  • alkylene oxides for example ethylene oxide, propylene oxide or butylene oxide, preferably with subsequent neutralization with inorganic or organic acids.
  • the compounds of formula (I), if quaternized, may be quaternized one or more times.
  • the compounds of formulas (I) are only quaternized.
  • the compounds of the formulas (I) preferably quaternized on a nitrogen atom which is part of a ring, preferably a pyrrolidine ring.
  • the compounds of the formula (I) can be converted by reaction with organic or inorganic acids into the corresponding protonated compounds.
  • These protonated compounds may e.g. be preferred if e.g. a slower polyurethane reaction is to be achieved or when the reaction mixture should have an improved flow behavior in the application.
  • organic acids for example, all of the following organic acids, for example, carboxylic acids having 1 to 36 carbon atoms (aromatic or aliphatic, linear or branched), for example, formic acid, lactic acid, 2-ethylhexanoic acid, salicylic acid and neodecanoic acid, or polymeric acids such as e.g. Polyacrylic or polymethacrylic acids are used.
  • inorganic acids e.g. Phosphorus-based acids, sulfur-based acids or boron-based acids can be used.
  • polyurethane is in particular a product obtainable by reaction of polyisocyanates and polyols or compounds with isocyanate groups. understood reactive groups.
  • PU polyurethane
  • polyurethane foam is understood as meaning foam which is obtained as a reaction product based on polyisocyanates and polyols or compounds with isocyanate-reactive groups.
  • PU foam in the sense of the present invention are understood as meaning both polyurethane foams (PUR foams) and polyisocyanurate foams (PIR foams).
  • Preferred polyurethane foams are flexible polyurethane foams, rigid polyurethane foams and polyurethane integral foams. Particularly preferred herein are conventional flexible polyurethane foams based on ether or ester polyol, high-elastic polyurethane foams (often also referred to as "high resilience” (HR) foams), viscoelastic polyurethane foams, semi-rigid polyurethane foams and rigid polyurethane foams, as well as foams whose properties lie between these classifications and are used in the automotive industry become.
  • HR high resilience
  • At least one nitrogen-containing compound of the formula (I) is used in the context of the use according to the invention with R 3 selected from the following
  • R io preferably '- /, * m Nh
  • RH, R12, R13 the same or unequal to each other is H or a linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated, optionally substituted by one or more heteroatoms or by one or more
  • Y in particular selected from the following radicals: * OH, * NM 2 j or
  • n and q are particularly preferably used in each case 2,
  • a, b are the same or different 0, 1, 2, 3 or 4
  • ether and amine building blocks if present, can occur cumulatively, alternately, blockwise or disorderly.
  • At least one nitrogen-containing compound of the formula (I), preferably of the formula (II), in particular of the formula (III) is used, wherein
  • Verbindun a Verbindun
  • a further preferred embodiment of the invention corresponds to when at least one nitrogen-containing compound of the formula (I), preferably of the formula (II), in particular of the formula (III) is used, wherein
  • Yet another preferred embodiment of the invention corresponds to when at least one nitrogen-containing compound of the formula (I), preferably of the formula (II), in particular of the formula (III) is used, wherein
  • a, b, n, Ri, R2, R3 as defined above, c, d are identical or different from one another 0 to 6, in particular 0 to 3, preferably 1 or 2, with R14, R15 equal to or not equal to each other, a linear, branched or cyclic, aliphatic, saturated or unsaturated hydrocarbon radical having 2 to 30
  • Carbon atoms in particular 2 to 12, preferably 2 to 6, preferably 2 or 3
  • Carbon atoms more preferably having 2 carbon atoms
  • Ri6 H or a linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated, optionally substituted by one or more heteroatoms or interrupted by one or more heteroatoms Kohlenwasserstoffre 0 carbon atoms, preferably a radical selected from
  • the present invention also includes the use of several different nitrogen-containing compounds of the formulas (I), (II), (III) and / or (IV), for example, with regard to all their objects and preferred embodiments thereof.
  • Preferred synthesis components are in particular amines, polyamines, polyols, preferably diols, in particular glycols, amino alcohols, bischloroalkyl ethers and amino-containing alkyl chlorides.
  • Polyamines which are preferably used are, for example, ethylenediamine (EDA) and higher homologs, such as diethylenetriamine (DETA), triethylenetetramine (TETA) or tris (2-aminoethyl) amine (trene).
  • Amines which are preferably used for amino alcohols or hydroxyl groups can be synthesized, for example, by reaction of ammonia or amines with epoxides (alkoxylation), preferably with ethylene oxide (EO) and / or propylene oxide (PO) and / or by amination of alcohols or polyols, preferably diols , in particular of glycols such as monoethylene glycol (MEG), diethylene glycol (DEG), 1,2-propylene glycol (PG), dipropylene glycol (DPG), with ammonia or amines according to known methods, as described, for example, by Beller et al. in Chem. Asian J. 2007, 2, 403-410, by Milstein et al. in Angew.
  • EO ethylene oxide
  • PO propylene oxide
  • amination of alcohols or polyols preferably diols
  • glycols such as monoethylene glycol (MEG), diethylene glycol (DEG), 1,2-propylene glycol
  • Preferred amino alcohols for the purposes of this invention are, for example, monoethanolamine (MEA), 1- (2-hydroxyethyl) pyrrolidine, diethanolamine (DEOA), triethanolamine, monoisopropanolamine, diisopropanolamine and triisopropanolamine.
  • MEA monoethanolamine
  • DEOA diethanolamine
  • triethanolamine monoisopropanolamine
  • diisopropanolamine diisopropanolamine
  • the amino alcohols described in detail herein are all commercially available.
  • An example of a bischloroalkylamine inter alia, the commercially available bis (2-chloroethyl) amine hydrochloride.
  • Amino group-bearing alkyl chlorides can be obtained, for example, by reacting bischloro-alkyl compounds with one equivalent of an amine, in particular with pyrrolidine (nucleophilic substitution).
  • pyrrolidine groups contained in all compounds can be introduced either at the beginning or at the end, depending on the desired synthesis route.
  • pyrrolidine and / or by reaction of pyrrolidine with alcohols and / or polyols, preferably diols, in particular glycols, for example in a transition metal catalyzed embodiment as described by Jenner et al. in Journal of Organometallic Chemistry, 373 (1989), 343-352.
  • the pyrrolidine function can also be carried out by reacting 1,4-butanediol with primary amines, such as, for example, again by Jenner et al.
  • the amines thus obtained can also be further derivatized, for example in the sense of an alkoxylation, preferably with ethylene oxide (EO) and / or propylene oxide (PO), as already described above.
  • ethylene oxide (EO) and / or propylene oxide (PO) preferably with ethylene oxide (EO) and / or propylene oxide (PO), as already described above.
  • methyl groups can also be added to the molecular structure in the sense of N-methylation.
  • the reductive methylation of primary and secondary amines using formaldehyde and formic acid in the sense of Eschweiler-Clarke methylation is known, which is a special case of the Leuckart-Wallach reaction (R. Leuckart, Ber. 18, 2341 (1885 ), O. Wallach, Ann. 272, 99 (1892)).
  • the N-methyl groups can be introduced into the molecular structure, for example by using monomethyalmin as the N-methyl building block, for example by transition-metal-catalyzed reaction, for example using Raney metals such as Raney metal. Cobalt or Raney nickel, with hydroxyl group-bearing compounds such as diols or aminoalcohols.
  • monomethyalmin as the N-methyl building block
  • transition-metal-catalyzed reaction for example using Raney metals such as Raney metal.
  • Raney metals such as Raney metal.
  • Cobalt or Raney nickel with hydroxyl group-bearing compounds such as diols or aminoalcohols.
  • Such aminations of alcohols with monomethylamine are widely described in the literature, for example in US 5639916 or DE 4230402.
  • a nitrogen-containing compound of the formula (I), preferably a nitrogen-containing compound of the formula (II), (III) or (IV), in particular a nitrogen-containing compound of the formula (III), depending on the quality of the selected process and number of corresponding purification steps in technical quality, hereinafter also referred to as technical product mixture, are present, so for example, have intermediate and / or by-products as minor components and / or other impurities.
  • the use corresponds to at least one nitrogen-containing compound of the formula (I), preferably at least one nitrogen-containing compound of the formula (II), (III) or (IV), in particular a nitrogen-containing compound of the formula (III), as a technical Product mixture is used, in particular containing impurities, intermediates and / or by-products as further ingredients, in particular comprising 1- (3-aminopropyl) pyrrolidine, 1- (2-aminoethyl) pyrrolidine, 1- (2-hydroxyethyl) pyrrolidine, 1 - ( 3-hydroxypropyl) pyrrolidine, 2- (2- (pyrrolidin-1-yl) ethoxy) ethanol, 1, 1 '- (oxybis (ethane-2,1-diyl)) dipyrrolidine, ethylenediamine (EDA), 1, 4- Butanediol, monoethylene glycol (MEG), diethylene glycol (DEG), 1, 2-propylene glycol (PG), dipropylene glycol (D
  • % preferably ⁇ 70% by weight, in particular ⁇ 30% by weight, preferably ⁇ 10% by weight, more preferably ⁇ 5% by weight of a preferred embodiment of this invention.
  • ethylenediamine advantageously in an amount of ⁇ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
  • (j) optionally monoethylene glycol (MEG), advantageously in an amount of ⁇ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
  • (k) optionally diethylene glycol (DEG), advantageously in an amount of ⁇ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
  • DEG diethylene glycol
  • (I) optionally 1, 2-propylene glycol (PG), advantageously in an amount of ⁇ 95 wt .-%, in particular 20-90 wt .-%, preferably 30-80 wt .-%,
  • PG 2-propylene glycol
  • DPG dipropylene glycol
  • (O) optionally triethanolamine advantageously in an amount of ⁇ 95 wt .-%, in particular 20- 90 wt .-%, preferably 30-80 wt .-%, and / or
  • (p) optionally monoethanolamine (MEA), advantageously in an amount of ⁇ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
  • particularly preferred technical product mixtures in the context of the present invention are those compositions in which at least one nitrogen-containing compound of the formula (I), in particular of the formula (II), (III) or (IV), preferably according to the Formula (III), and / or a corresponding quaternized and / or protonated compound is used in combination
  • the compounds of the formula (I), (II), (III) and / or (IV) described above and / or corresponding quaternized and / or protonated compounds are preferably used in the preparation of polyurethane systems according to the invention, preferably for the production of polyurethane coatings, polyurethane adhesives, polyurethane sealants,
  • Polyurethane elastomers or in particular for the production of polyurethane foams used as catalysts can be used in addition to conventional catalysts or as a replacement for conventional catalysts.
  • the compounds of the invention can be used as a replacement for other nitrogen-containing catalysts, hereinafter also referred to as amine catalysts or amines, and depending on the application as a partial or complete replacement of conventional metal-containing catalysts according to the prior art.
  • said nitrogen-containing compound can also be used as a technical product mixture. Suitable technical product mixtures are described in more detail below.
  • polyurethane foams preferably at least one nitrogen-containing compound of the formula (I), preferably at least one nitrogen-containing compound of the formula (II), (III) or (IV), in particular at least one nitrogen-containing compound according to the Formula (III), and / or a corresponding quaternized and / or protonated compound, at least one polyol component and at least one isocyanate component, optionally in the presence of water, physical blowing agents, flame retardants, additional catalysts and / or other additives, with each other.
  • the compounds of the formula (I), (II), (III) and / or (IV) to be used according to the invention and / or a correspondingly quaternized and / or protonated compounds, in total amount, are preferably present in a proportion by mass of from 0.01 to 20 , 0 parts (pphp), preferably 0.01 to 5.00 parts and particularly preferably 0.02 to 3.00 parts based on 100 parts (pphp) of polyol used.
  • a composition which comprises at least one nitrogen-containing compound of the formula (I), preferably at least one nitrogen-containing compound of the formula (II), (III) or (IV), in particular at least one nitrogen-containing compound of the formula (III) and / or a corresponding quaternized and / or protonated compound, and furthermore at least one polyol component, at least one isocyanate component and optionally one or more blowing agents, and this composition is reacted ,
  • said nitrogen-containing compound can also be used as a technical product mixture. Suitable technical product mixtures are described in more detail below.
  • isocyanate components one or more organic polyisocyanates having two or more isocyanate functions are preferably used.
  • the polyol components used are preferably one or more polyols having two or more isocyanate-reactive groups.
  • Isocyanate suitable isocyanates in the context of this invention are all isocyanates containing at least two isocyanate groups.
  • all known aliphatic, cycloaliphatic, arylaliphatic and preferably aromatic polyfunctional isocyanates can be used.
  • Isocyanates are preferably used in a range from 60 to 350 mol%, particularly preferably in a range from 60 to 140 mol%, relative to the sum of the isocyanate-consuming components.
  • alkylene diisocyanates having 4 to 12 carbon atoms in the alkylene radical such as 1,12-dodecane diisocyanate, 2-ethyltetramethylene diisocyanate-1,4-2-methylpentamethylene diisocyanate-1,5, tetramethylene diisocyanate 1,4, and preferably hexamethylene diisocyanate 1,6 (HMDI), cycloaliphatic diisocyanates, such as cyclohexane-1, 3- and 1 -4-diisocyanate and any desired mixtures of these isomers, 1-isocyanato-3,35-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate or IPDI for short), 2,4- and 2,6-hexa-hydrotoluylene diisocyanate and the corresponding isomer mixtures, and preferably aromatic diisocyanates and polyisocyanates, such as, for example
  • the organic di- and polyisocyanates can be used individually or in the form of their mixtures. It is also possible to use isocyanates which have been modified by the incorporation of urethane, uretdione, isocyanurate, allophanate and other groups, so-called modified isocyanates.
  • Particularly suitable organic polyisocyanates and therefore particularly preferably used are various isomers of toluene diisocyanate (2,4- and 2,6-toluene diisocyanate (TDI), in pure form or as isomeric mixtures of different composition), 4,4'-diphenylmethane diisocyanate (MDI), the so-called “crude MDI” or “polymeric MDI” (in addition to the 4,4'- also contains the 2,4'- and 2,2'-isomers of MDI and higher nuclear products) and the dinuclear product referred to as "pure MDI”
  • TDI 2,4- and 2,6-toluene diisocyanate
  • MDI 4,4'-diphenylmethane diisocyanate
  • the so-called "crude MDI” or "polymeric MDI” in addition to the 4,4'- also contains the 2,4'- and 2,2'-isomers of MDI and higher nuclear products
  • pure MDI Examples of
  • Suitable polyol components in the context of the present invention are all organic substances having a plurality of isocyanate-reactive groups, preferably OH groups, and also their preparations.
  • Preferred polyols are all for the production of polyurethane systems, in particular polyurethane foams;
  • the polyols are used with OH numbers in the range of 10 to 1200 mgKOH / g
  • the number average molecular weights are usually by gel permeation chromatography (GPC), in particular with Polypropylene glycol as Refere nesubstanz and tetrahydrofuran (THF) as eluent.
  • GPC gel permeation chromatography
  • Polypropylene glycol as Refere nesubstanz and tetrahydrofuran (THF) as eluent.
  • the OH numbers can be determined in particular according to the DIN standard DIN 53240: 1971-12.
  • Polyether polyols can be prepared by known methods, for example by anionic polymerization of alkylene oxides in the presence of alkali metal hydroxides, Alkylialkoholaten or amines as catalysts and with the addition of at least one starter molecule, preferably containing 2 or 3 reactive hydrogen atoms bonded or by cationic polymerization of alkylene oxides in the presence of Lewis acids such as antimony pentachloride or boron trifluoride etherate or by double metal cyanide catalysis.
  • Suitable alkylene oxides contain 2 to 4 carbon atoms in the alkylene radical.
  • Examples are tetrahydrofuran, 1, 3-propylene oxide, 1, 2 or 2,3-butylene oxide; Preferably, ethylene oxide and 1, 2-propylene oxide are used.
  • the alkylene oxides can be used individually, cumulatively, in blocks, alternately one after another or as mixtures. In particular, compounds having at least 2, preferably 2 to 8 hydroxyl groups or having at least two primary amino groups in the molecule are used as starting molecules.
  • water, 2-, 3- or 4-hydric alcohols such as ethylene glycol, propanediol-1, 2 and -1, 3, diethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, pentaerythritol, castor oil, etc., higher polyfunctional polyols, can be used as starter molecules.
  • sugar compounds such as glucose, sorbitol, mannitol and sucrose, polyhydric phenols, resoles such as oligomeric condensation products of phenol and formaldehyde and Mannich condensates of phenols, formaldehyde and dialkanolamines and melamine, or amines such as aniline, EDA, TDA, MDA and PMDA , more preferably TDA and PMDA.
  • suitable starter molecule depends on the respective field of application of the resulting polyether polyol in polyurethane production (for example, other polyols are used for the production of flexible polyurethane foams than in the production of rigid polyurethane foams).
  • Polyester polyols are based on esters of polybasic aliphatic or aromatic carboxylic acids, preferably having 2 to 12 carbon atoms.
  • aliphatic carboxylic acids are succinic, glutaric, adipic, suberic, azelaic, sebacic, decanedicarboxylic, maleic and fumaric acids.
  • aromatic carboxylic acids are phthalic acid, isophthalic acid, terephthalic acid and the isomeric naphthalenedicarboxylic acids.
  • polyester polyols are obtained by condensation of these polybasic carboxylic acids with polyhydric alcohols, preferably diols or triols having 2 to 12, more preferably having 2 to 6 carbon atoms, preferably trimethylolpropane and glycerol.
  • Polyether polycarbonate polyols are polyols containing carbon dioxide bonded as carbonate. Since carbon dioxide is by-produced in large quantities in many processes in the chemical industry, the use of carbon dioxide as a comonomer in alkylene oxide polymerizations is of particular interest from a commercial point of view. A partial replacement of alkylene oxides in polyols by carbon dioxide has the potential that Significantly lower costs for the production of polyols. In addition, the use of CO2 as a comonomer is ecologically very advantageous because this reaction is the conversion of a greenhouse gas to a polymer. The preparation of Polyetherpolycarbonat- polyols by addition of alkylene oxides and carbon dioxide to H-functional starter substances using catalysts has long been known.
  • the first generation represented heterogeneous zinc or aluminum salts, as described for example in US-A 3,900,424 or US-A 3,953,383.
  • mono- and binuclear metal complexes have been used successfully for the copolymerization of CO 2 and alkylene oxides (WO 2010/028362, WO 2009/130470, WO 2013/022932 or WO 201 1/163133).
  • the most important class of catalyst systems for the copolymerization of carbon dioxide and alkylene oxides are the double metal cyanide catalysts, also referred to as DMC catalysts (US-A 4500704, WO 2008/058913).
  • Suitable alkylene oxides and H-functional starter substances are those which are also used for the preparation of carbonate-free polyether polyols - as described above.
  • Natural oil based polyols for the production of polyurethane foams are of increasing interest, and already many, in view of the long-term limited availability of fossil resources, namely oil, coal and gas, and in light of rising crude oil prices
  • polyols with different properties can be obtained, whereby essentially two groups can be distinguished are: a) polyols based on renewable raw materials, which are modified so that they are 100% for the production of Pol yurethanes can be used (WO2004 / 020497, US2006 / 0229375); b) polyols based on renewable raw materials, which due to their workup and properties can replace the petrochemically based polyol only to a certain extent (WO2009 / 058367).
  • basic raw material eg soybean oil, palm oil or castor oil
  • Another class of usable polyols are the so-called Gremanyole (polymer polyols). These are characterized in that they contain solid organic fillers to a solids content of 40% or more in disperse distribution.
  • SAN polyols are highly reactive polyols containing a copolymer based on styrene / acrylonitrile (SAN) dispersed.
  • PHD Polyols are highly reactive polyols which also contain polyurea in dispersed form.
  • PIPA polyols are highly reactive polyols which contain a polyurethane in dispersed form, for example, by in situ reaction of an isocyanate with an alkanolamine in a conventional polyol.
  • the solids content which is preferably between 5 and 40%, based on the polyol, depending on the application, is responsible for an improved cell opening, so that the polyol is in particular controllably foamable with TDI and no shrinkage of the foams occurs.
  • the solid acts as an essential process aid. Another function is to control the hardness via the solids content, because higher solids contribute to a higher hardness of the foam.
  • the formulations containing solids-containing polyols are significantly less intrinsically stable and therefore, in addition to the chemical stabilization by the crosslinking reaction, rather require physical stabilization as well. Depending on the solids content of the polyols, these may be e.g. alone or e.g. be used in admixture with the above unfilled polyols.
  • Another class of employable polyols are those which are obtained as prepolymers by reacting polyol with isocyanate in a molar ratio of 100: 1 to 5: 1, preferably 50: 1 to 10: 1. Such prepolymers are preferably dissolved in polymer, wherein the polyol preferably corresponds to the polyol used to prepare the prepolymers.
  • polystyrene resins are the so-called autocatalytic polyols, in particular autocatalytic polyether polyols.
  • Such polyols are based, for example, on polyether blocks, preferably on ethylene oxide and / or propylene oxide blocks, and also contain catalytically active functional groups, such as nitrogen-containing functional groups, in particular amino groups, preferably tertiary amine functions, urea groups and / or heterocycles containing nitrogen atoms.
  • Suitable polyols are described, for example, in WO0158976A1, WO2005063841 A1, WO0222702A1, WO2006055396A1, WO03029320A1, WO0158976A1, US6924321 B2, US6762274B2, EP2104696B1, WO2004060956A1 or WO2013102053A1 and can be obtained, for example, under the trade names Voractiv TM and / or SpecFlex TM Activ from Dow become.
  • corresponding polyols can be used, as described, for example, in: US 2007/0072951 A1, WO 2007/1 1 1828, US 2007/0238800, US 6359022 or WO 96/12759.
  • Other polyols are known to those skilled in the art and can be found, for example, in EP-A-0380993 or US-A-3346557, to which reference is made in its entirety.
  • di- and / or trifunctional polyether alcohols which have primary hydroxyl groups, preferably over 50%, more preferably over 80%, especially those with an ethylene oxide block on chain end.
  • polyether alcohols described herein in addition to the polyether alcohols described herein preferably further polyether alcohols are used which carry primary hydroxyl groups and based predominantly on ethylene oxide, in particular with a proportion of ethylene oxide blocks of> 70%, preferably> 90%.
  • All polyether alcohols described in the context of this preferred embodiment preferably have a functionality of 2 to 8, more preferably 2 to 5, number average molecular weights in the range of 2500 to 15000, preferably 4500 to 12000 and usually OH numbers in the range of 5 to 80, preferably 20 to 50 mgKOH / g.
  • dihydric and / or trifunctional polyether alcohols which have secondary hydroxyl groups, preferably more than 50%, particularly preferably more than 90%, in particular those with a propylene oxide block or random propylene and ethylene oxide block at the chain end or those based only on propylene oxide blocks.
  • Such polyether alcohols preferably have a functionality of 2 to 8, more preferably 2 to 4, number average molecular weights in the range of 500 to 8000, preferably 800 to 5000, more preferably 2500 to 4500 and usually OH numbers in the range of 10 to 100, preferably 20 to 60 mgKOH / g.
  • polyester alcohols based on diols and / or triols, preferably glycerol and / or trimethylolpropane, and aliphatic carboxylic acids, preferably adipic acid, suberic acid, azelaic acid and / or sebacic acid, are used .
  • Such polyester alcohols preferably have a functionality of 2 to 4, particularly preferably 2 to 3, number average molecular weights in the range from 200 to 4000, preferably 400 to 3000, particularly preferably 600 to 2500 and usually OH numbers in the range of 10 to 1000, preferably 20 500, more preferably 30-300 mgKOH / g.
  • polyester alcohols based on diols and / or triols, preferably monoethylene glycol, and aromatic carboxylic acids, preferably phthalic acid and / or terephthalic acid, are used.
  • Such polyester alcohols preferably have a functionality of 2 to 4, more preferably 2 to 3, number average molecular weights in the range of 200-1500, preferably 300-1200, more preferably 400-1000, and usually OH numbers in the range of 100-500, preferably 150 300, more preferably 180-250 mgKOH / g.
  • two- to eight-functional polyether alcohols which have secondary hydroxyl groups, preferably over 50%, more preferably over 90%, especially those having a propylene oxide block or random Propylene and ethylene oxide block at the chain end or those based only on propylene oxide blocks.
  • Such polyether alcohols preferably have a functionality of 2 to 8, more preferably 3 to 8, number average molecular weights in the range of 500 to 2000, preferably 800 to 1200 and usually OH numbers in the range of 100 to 1200, preferably 120 to 700, particularly preferably 200 to 600 mgKOH / g.
  • inventively preferred foams in addition to the polyols described herein additionally polyether, as described above with larger number average molecular weights and lower OH numbers, and / or additional polyester polyols, as described above based on aromatic carboxylic acids used.
  • polyether as described above with larger number average molecular weights and lower OH numbers
  • polyester polyols as described above based on aromatic carboxylic acids used.
  • mixtures of different, preferably two or three, polyfunctional polyester alcohols are preferably used and / or polyether alcohols used.
  • the polyol combinations used here consist of a low molecular weight "crosslinker” polyol, for example a rigid foam polyol with high functionality (> 3) and / or a conventional high molecular weight block foam or HR polyol and / or a "hypersoft polyether - Polyol with high content of ethylene oxide blocks and with cell-opening properties.
  • crosslinker for example a rigid foam polyol with high functionality (> 3) and / or a conventional high molecular weight block foam or HR polyol and / or a "hypersoft polyether - Polyol with high content of ethylene oxide blocks and with cell-opening properties.
  • a preferred ratio of isocyanate to polyol expressed as the index of the formulation, i. as a stoichiometric ratio of isocyanate groups to isocyanate-reactive groups (eg, OH groups, NH groups) multiplied by 100, is in the range of 10 to 1000, preferably 40 to 350, particularly preferably 70 to 140.
  • An index of 100 stands for a molar ratio of the reactive groups of 1 to 1.
  • additional catalysts are used be individually during the expansion or as with the inventive nitrogen-containing compounds of the formula (I), (II), (III) and / or (IV), and / or corresponding protonated and / or quaternized compounds premixed catalyst combination.
  • additional catalysts in the context of this invention comprises in particular the use of compounds which are different from the nitrogen-containing compounds according to the invention of the formula (I), (II), (III) and / or (IV) and / or corresponding protonated and / or or quaternized compounds, and at the same time capable of catalyzing isocyanate reactions, in particular the reactions mentioned below, and / or in the preparation of polyisocyanate reaction products, in particular in the preparation of polyurethane systems, particularly preferably in the preparation of polyurethane foams Catalysts, co-catalysts or activators are used.
  • premixed catalyst combination comprises in the context of this invention in particular finished mixtures of nitrogen-containing compounds according to the invention of the formula (I), (II), (III) and / or (IV), corresponding protonated and / or quaternized compounds, additional catalysts, and optionally further ingredients or additives such as water, organic solvents, acids for blocking the amines, emulsifiers, surfactants, blowing agents, antioxidants, flame retardants, stabilizers and / or siloxanes, preferably polyether siloxanes, the already exist as such before foaming and during the foaming process need not be added as individual components.
  • Suitable additional catalysts in the context of the present invention are, for example, substances which catalyze one of the abovementioned reactions, in particular the gel reaction (isocyanate-polyol), the blowing reaction (isocyanate-water) and / or the di- or trimerization of the isocyanate.
  • Such catalysts are preferably nitrogen-containing compounds, in particular amines and ammonium salts, and / or metal-containing compounds.
  • Suitable nitrogen-containing compounds as additional catalysts for the purposes of the present invention are all nitrogen-containing compounds according to the prior art, unlike the inventive nitrogen-containing compounds of the formula (I) to (IV), which catalyze one of the above isocyanate reactions and / or Production of polyurethanes, in particular polyurethane foams can be used.
  • nitrogen-containing compounds of the formula (I) in the context of this invention in each case comprises the corresponding protonated and / or quaternized compounds and mixtures of these compounds.
  • nitrogen-containing compounds of the formula (I), (II), (III) and / or (IV) in the context of this invention in each case comprises the corresponding protonated and / or quaternized compounds and mixtures of these compounds nitrogen-containing compound of the formula (I), preferably at least one nitrogen-containing compound of the formula (II), (III) or (IV), in particular at least one nitrogen-containing compound of the formula (III) "in the context of this invention also includes the joint use of such nitrogen-containing compounds, ie, for example, the joint use of nitrogen-containing compounds of the formula (III) and (IV).
  • Suitable additional nitrogen-containing compounds as catalysts for the purposes of the present invention are the amines triethylamine, ⁇ , ⁇ -dimethylcyclohexylamine, N, N-dicyclohexylmethylamine, ⁇ , ⁇ -dimethylaminoethylamine, N, N, N ', N'-tetramethylethylene-1, 2- diamine, N, N, N ', N'-tetramethylpropylene-1,3-diamine, N, N, N', N'-tetramethyl-1,4-butanediamine, N, N, N ', N'- Tetramethyl-1,6-hexanediamine, N, N, N ', N ", N" -pentamethyldiethylenetriamine, ⁇ , ⁇ , ⁇ '-trimethylaminoethylethanolamine, ⁇ , ⁇ -dimethylaminopropylamine, N, N-diethylaminopropylamine, 1
  • Dimethylaminoethyl ether N, N, N'-trimethyl-N '- (2-hydroxyethyl) bis (2-aminoethyl) ether, N, N, N'-trimethyl-N-3'-aminopropyl (bisaminoethyl) ether, tris ( dimethylaminopropyl) - hexahydro-1,3,5-triazine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1, 5-diazabicyclo [4.3.0] non-5-ene, 1, 5, 7 -triazabicyclo [4.4.0] dec-5-ene, N-methyl-1, 5,7-triazabicyclo [4.4.0] dec-5-ene, 1, 4,6-triazabicyclo [3.3.0] oct 4-ene, 1, 1, 3,3-tetramethylguanidine, tert-butyl-1, 1, 3,3-tetramethylguanidine, guanidine
  • Suitable metal-containing compounds as additional catalysts in the context of the present invention are all metal-containing compounds according to the prior art which catalyze one of the abovementioned isocyanate reactions and / or for the preparation of polyurethanes, in particular polyurethane foams in addition to the nitrogen-containing compounds of the formula ( I) to (IV) can be used. They can be selected, for example, from the group of organometallic or organometallic compounds, organometallic or organometallic salts, organic metal salts, inorganic metal salts and from the group of charged or uncharged metal-containing coordination compounds, in particular the metal chelate complexes.
  • organometallic or organometallic compounds for the purposes of this invention, in particular the use of metal-containing compounds which have a direct carbon-metal bond, here as metal organyls (eg tin organyls) or organometallic or organometallic compounds (eg organotin compounds)
  • metal organyls eg tin organyls
  • organometallic or organometallic compounds eg organotin compounds
  • organotin compounds eg organotin compounds
  • organotin compounds eg organotin compounds
  • organotin compounds eg organotin compounds
  • organotin compounds eg organotin compounds
  • organic metal salts includes in particular the use of metal-containing compounds which have no direct carbon-metal bond and at the same time are metal salts in which either the anion or the cation is an organic compound (eg tin (II).
  • organic metal salts encompasses in particular the use of metal-containing compounds or of metal salts in which neither anion nor cation is an organic compound, for example metal chlorides (eg tin (II) chloride). , pure or mixed, ie containing several metals, metal oxides (eg tin oxides) and / or metal silicates or aluminosilicates.
  • coordination compound in the context of this invention in particular comprises the use of metal-containing compounds which are composed of one or more central particles and one or more ligands, wherein the central particles are charged or uncharged metals (eg metal or tin-amine complexes
  • metal chelate complexes encompasses in particular the use of metal-containing coordination compounds which have ligands with at least two coordination or bonding sites to the metal center (eg metal or tin-polyamine or metal or tin-polyether complexes).
  • Suitable metal-containing compounds in particular as defined above, as additional catalysts in the context of the present invention can be selected, for example, from all metal-containing compounds containing lithium, sodium, potassium, magnesium, calcium, scandium, yttrium, titanium, zirconium, vanadium, niobium, chromium , Molybdenum, tungsten, manganese, cobalt, nickel, copper, zinc, mercury, aluminum, gallium, indium, germanium, tin, lead, and / or bismuth, especially sodium, potassium, magnesium, calcium, titanium, zirconium, molybdenum, tungsten , Zinc, aluminum, tin and / or bismuth, particularly preferably tin, bismuth, zinc and / or potassium.
  • Suitable inorganic metal salts in particular as defined above, as additional catalysts in the context of the present invention may for example be selected from the group of salts of inorganic acids such as hydrochloric acid, carbonic acid, sulfuric acid, nitric acid and phosphoric acid and / or other halogen-containing acids.
  • the resulting inorganic metal salts for example metal chlorides, metal sulfates, metal phosphates, preferably metal chlorides such as tin (II) chloride, in the preparation of polyurethane systems, in particular polyurethane foams, usually only in combination with other organometallic salts, organic metal salts or nitrogen-containing catalysts and not as the only catalysts, in pure form or mixed in a solvent used.
  • Suitable charged or uncharged metal-containing coordination compounds in particular the metal chelate complexes, in particular as defined above, as additional catalysts in the context of the present invention can be selected, for example, from the group of mononuclear or polynuclear metal armin, metal polyamine , Metal-polyether, metal-polyester and / or metal-polyamine-polyether complexes.
  • Such complexes can be formed either in situ during foaming and / or foaming, or as isolated complexes, in pure form or mixed in a solvent.
  • Suitable complexing agents, ligands and / or chelating ligands are, for example, acetylacetone, benzoylacetone, trifluoroacetylacetone, ethylacetoacetate, salicylaldehyde, salicyladehydimine and other Schiff bases, cyclopentanone-2-carboxylate, pyrrolidones such as, for example, N-methyl-2-pyrollidone, N- Ethyl-2-pyrrolidone and polyvinylpyrrolidone (various molecular weight distributions), polyethers of different molecular weights, cyclic polyethers such as crown ethers and diamines and polyamines containing primary, secondary and / or tertiary amines into consideration.
  • Suitable metal-containing coordination compounds are, for example, all metal acetylacetonates such as nickel (II) acetylacetonate, zinc (II) acetylacetonate, copper (II) acetylacetonate, molybdenum dioxo-acetylacetonate, all iron acetylacetonates, all cobalt acetylacetonates, all zirconium acetylacetonates , all titanium acetylacetonates, all bismuth acetylacetonates and all tin acetylacetonates.
  • all metal acetylacetonates such as nickel (II) acetylacetonate, zinc (II) acetylacetonate, copper (II) acetylacetonate, molybdenum dioxo-acetylacetonate, all iron acetylacetonates, all cobalt acetylace
  • organometallic salts and organic metal salts in particular as defined above, as additional catalysts in the context of the present invention can be selected, for example, from the group of salts of organic acids.
  • organic acids in the context of this invention includes all organic chemical, ie carbon-containing, compounds which have a functional group which can enter into an equilibrium reaction in the sense of an acid-base reaction with water and other protonatable solvents.
  • Suitable organic acids may for example be selected from the group of carboxylic acids, ie organic compounds which carry one or more carboxy groups ( * - COOH), so-called carboxylates, and / or of alcohols, ie organic compounds one or more hydroxyl groups ( * - OH), so-called alcoholates, and / or of thiols, ie organic compounds which carry one or more thiol groups ( * - SH, also referred to as mercapto groups in higher priority functional group molecules), so-called thiolates (or mercaptides ), and / or Mercaptoessigklastern as a special case of thiols, ie organic compounds which carry one or more mercaptoacetic acid ester groups (* -0-CO-CH2-CH2-SH) wear, so-called mercaptoacetates, and / or of Sulfuric acid esters, ie organic compounds which carry one or more sulfate groups (* -O-SOsH
  • Suitable carboxylic acids in the context of the present invention are, for example, all linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated, optionally with one or more heteroatoms, preferably with hydroxy groups ( * -OH), primary, secondary or tertiary amino groups ( * -NH 2 , * -NHR, * -NR 2 ) or mercapto groups ( * -SH), substituted, or interrupted by one or more heteroatoms mono-, di- or poly-carboxylic acids.
  • carboxylic acids whose carbobyl carbon atom is a hydrogen atom or a linear, branched or cyclic, aliphatic saturated or unsaturated, optionally with one or more heteroatoms, preferably with hydroxy groups ( * -OH), primary, secondary or tertiary amino groups ( * -NH 2, * -NHR, * -NR 2 ) or mercapto groups ( * -SH), substituted, or is interrupted by one or more hetero atoms interrupted hydrocarbon radical.
  • carbobyl carbon atom is a hydrogen atom or a linear, branched or cyclic, aliphatic saturated or unsaturated, optionally with one or more heteroatoms, preferably with hydroxy groups ( * -OH), primary, secondary or tertiary amino groups ( * -NH 2, * -NHR, * -NR 2 ) or mercapto groups ( * -SH), substituted, or is interrupted by one or more hetero atoms interrupted hydrocarbon radical.
  • Particularly suitable in Sense of the present invention are those aliphatic carboxylic acids which in the 2-position, ie on the carbon atom in addition to the carbonyl, disubstituted (tertiary) or trisubstituted (quaternary) carbons, or corresponding hydrocarbon radicals possess.
  • Preferred for the purposes of the present invention are those aliphatic carboxylic acids which have one or two methyl, ethyl, n-propyl, iso-propyl, n-butyl and / or iso-butyl branch (s) in the 2-position.
  • aliphatic carboxylic acids especially monocarboxylic acids, which in addition to the described branching in the 2-position have a saturated or unsaturated, linear or branched alkyl chain and optionally with one or more heteroatoms, preferably with hydroxyl groups ( * -OH) , primary, secondary or tertiary amino groups (* -NH2, * -NHR, * -NR2) or mercapto groups ( * -SH).
  • suitable carboxylic acids can be selected from the group of the neo acids or cooking acids.
  • carboxylic acids such as formic acid, acetic acid, propionic acid, propionic acids, acrylic acid, butyric acid, isobutyric acid, 2,2- Dimethylbutyric acid, valeric acid, isovaleric acid, 2-methylvaleric acid, 2,2-dimethylvaleric acid (isoheptanoic acid), pivalic acid, caproic acid, 2-ethylhexanoic acid (iso-octanoic acid), oleic acid, caprylic acid, pelargonic acid, iso-nonanoic acid, 3,5,5- Trimethylhexanoic acid, 2,5,5-trimethylhexanoic acid, 4,5,5-trimethylhexanoic acid, 2,2,4,4-tetramethylpentanoic acid, 6,6-dimethylhept
  • Suitable alcohols are all linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated, optionally with one or more heteroatoms, preferably with primary, secondary or tertiary amino groups (* -NH 2, * -NHR, * -NR 2) or mercapto Groups ( * -SH), substituted, or by one or more Heteroatoms interrupted monohydric alcohols, dihydric alcohols (diols) and / or polyhydric alcohols (polyols).
  • Suitable for this purpose are, for example, methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, neopentyl alcohol, phenols and / or nonylphenol.
  • Suitable thiols, mercaptoacetic acid esters, sulfuric acid esters, sulfonic acids, phosphoric acid esters (alkyl phosphates), phosphonic acids and / or phosphoric acid esters are, for example, all linear, branched or cyclic, aliphatic or aromatic, saturated or unsaturated, optionally substituted by one or more heteroatoms, or by one or more heteroatoms interrupted organic compounds containing one or more corresponding functional groups, as defined above.
  • Suitable for this purpose are, for example, dialkyl phosphites, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, dodecylbenzylsulfonic acid, taurine, isooctylmercaptoacetate, 2-ethylhexylmercaptoacetate, ethanediol and / or n-laurylmercaptide.
  • organometallic salts and organic metal salts are, for example, organotin, tin, zinc, bismuth and potassium salts, in particular corresponding metal carboxylates, -alcoholates, -thiolates and -Mercaptoacetate such as dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate (DBTDL), dioctyltin dilaurate (DOTDL), dimethyltin, Dibutylzinndineodecanoat, Dioctylzinndineodecanoat, dibutyltin dioleate, dibutyltin-bis-n-laurylmercaptid, dimethyltin-bis-n-laurylmercaptid, monomethyltin tris-2- ethylhexylmercaptoacetate, dimethyltin-bis-2-ethylhexylmercaptoacetate, dimethyltin-bis-2
  • organometallic salts for example of dibutyltin dilaurate.
  • Suitable additional metal-containing catalysts are generally preferably selected so that they have no disturbing intrinsic odor, are toxicologically substantially harmless and that the resulting polyurethane systems, in particular polyurethane foams have as low as possible catalyst-related emissions.
  • additional catalysts In addition to additional amines and metal-containing compounds and ammonium salts can be used as additional catalysts. Suitable examples are ammonium formate and / or ammonium acetate. Suitable additional catalysts are mentioned, for example, in DE 102007046860, EP 1985642, EP 1985644, EP 1977825, US 2008/0234402, EP 0656382 B1 and US 2007/0282026 A1 and the patents cited therein.
  • additional catalysts and / or premixed catalyst combinations are free of dimethylamine-carrying nitrogen-containing compounds.
  • Free of dimethylamine-carrying nitrogen-containing compounds are catalyst combinations in the context of this invention preferably when less than 75% by weight, in particular less than 50% by weight, preferably less than 30% by weight, particularly preferably less than 10% by weight of the catalysts in the catalyst mixture include dimethylamine-bearing, nitrogen-containing compounds.
  • catalyst combinations which contain no, that is to say 0% by weight, dimethylamine-bearing, nitrogen-containing compounds.
  • one or more additional metal-containing catalysts in particular one or more tin, zinc, bismuth and / or potassium compounds, preferably as defined above and described by way of example,
  • one or more stabilizers against oxidative degradation for example antioxidants, preferably as described below,
  • one or more flame retardants preferably as described below, and / or
  • foam stabilizers based on siloxanes and / or polydialkylsiloxane-polyoxyalkylene copolymers, preferably as defined and described below, and / or
  • one or more further additives for example selected from the group of surfactants biocides, dyes, pigments, fillers, antistatic additives, crosslinkers, chain extenders, cell openers, and / or fragrances
  • a composition is prepared, for example in the sense of a predosing of the individual components in the mixing head or as a premixed Catalyst combination, in particular as defined above, containing the aforementioned combination.
  • said nitrogen-containing compound of formula (I), (II), (III) or (IV) can also be used as a technical product mixture. Suitable technical product mixtures are explained in the description.
  • particularly preferred combinations in the context of the present invention are those compositions in which at least one nitrogen-containing compound of formula (I), (II), (III) and / or (IV) and / or a corresponding quaternized and or protonated compound is used in combination with a), with b), with c), with d), with e), with f), with a), b), c), d) e) and f), with a) and b), with a) and c), with a), b) and c), with a), b) and d), with a), b) and e), with a), b) , d) and e), with a), b), d), e) and f), with a), b), e) and f), with a), b), e) and f), with a), c) and d), with a), c) and e), with a), c), d) and e),
  • the compounds according to the invention of the formulas (I), (II), (II) and / or (IV), the corresponding protonated and / or quaternized compounds can be used as pure substance or in admixture, for example with suitable solvents and / or further additives individually during foaming or as a premixed catalyst combination as defined above.
  • Suitable solvents are all suitable according to the prior art substances in question.
  • aprotic-apolar, aprotic-polar and protic solvents can be used.
  • Suitable aprotic-nonpolar solvents can be selected, for example, from the following classes of substance or substance classes containing the following functional groups: aromatic hydrocarbons, aliphatic hydrocarbons (alkanes (paraffins) and olefins), carboxylic acid esters and polyesters, (poly) ethers and / or halogenated hydrocarbons lower Polarity.
  • Suitable aprotic-polar solvents can be selected, for example, from the following classes of substance or substance classes containing the following functional groups: ketones, lactones, lactams, nitriles, carboxamides, sulfoxides and / or sulfones.
  • Suitable protic solvents can be selected, for example, from the following substance classes or substance classes containing the following functional groups: alcohols, polyols, (poly) alkylene glycols, amines, carboxylic acids, in particular fatty acids and / or primary and secondary amides.
  • Preferred solvents are, for example, mineral oils, hexane, pentane, heptane, decane or mixtures of saturated hydrocarbons, such as. B.
  • glycol ethers such as ethylene glycol dimethyl ether (monoglyme), bis (2-methoxyethyl) ether (diglyme), triethylene glycol dimethyl ether (triglyme), tetraethylene glycol dimethyl ether (tetraglyme), polyester and polyether polyols, polyols based on renewable raw materials (NOPs), end-capped polyethers, preferably dialkyl polyethers having as alkyl radicals butyl / methyl, methyl / methyl or butyl / butyl radicals, preferably those obtainable from diol-initiated polyethers, Glycols, glycerol, carboxylic esters, preferably fatty acid esters, for example ethyl acetate and isopropyl myristate, polycarbonates, phthalates, preferably dibutyl phthalate (DBP), dioctyl phthalate (DNOP), dieth
  • DBP dibutyl phthal
  • solvents are compounds that can be processed easily in the foaming and do not adversely affect the properties of the foam.
  • isocyanate-reactive compounds are suitable because they react with the polymer matrix and generate no emissions in the foam.
  • OH-functional compounds such as (poly) alkylene glycols, preferably monoethylene glycol (MEG or EG), diethylene glycol (DEG), triethylene glycol (TEG), 1 -2-propylene glycol (PG), dipropylene glycol (DPG), trimethylene glycol (1,3-propanediol PDO), tetramethylene glycol (butanediol BDO), butyl diglycol (BDG), neopentyl glycol, 2-methyl-1,3-propanediol (Ortegol CXT), 3-methyl-1,5-pentanediol and higher homologs such as polyethylene glycol (PEG) with average molecular weights between 200 and 3000.
  • MEG monoethylene glycol
  • OH-functional compounds are polyethers having average molecular weights of 200 to 4500, in particular 400 to 2000, preferably water, allyl, butyl or nonyl -started polyethers, especially those based on propylene oxide (PO) and / or ethylene oxide blocks (EO).
  • PO propylene oxide
  • EO ethylene oxide blocks
  • the mass ratio is of catalyst or catalyst combination to solvent preferably from 100 to 1 to 1 to 4, preferably from 50 to 1 to 1 to 3 and more preferably from 25 to 1 to 1 to 2.
  • additives it is possible to use all substances known from the prior art which are used in the preparation of polyurethanes, in particular polyurethane foams, such as, for example, blowing agents, preferably water for formation of CO2 and, if necessary, other physical blowing agents, crosslinkers and chain extenders, stabilizers against oxidative degradation (so-called antioxidants), flame retardants, surfactants, biocides, cell-refining additives, cell openers, solid fillers, antistatic additives, nucleating agents, thickeners, dyes, pigments , Color pastes, fragrances, emulsifiers, buffer substances and / or additional catalytically active substances, in particular as defined above.
  • blowing agents preferably water for formation of CO2 and, if necessary, other physical blowing agents, crosslinkers and chain extenders, stabilizers against oxidative degradation (so-called antioxidants), flame retardants, surfactants, biocides, cell-refining additives, cell openers, solid fillers, antistatic
  • polyurethane foams are to be prepared as polyurethane systems, it may be advantageous to use water as blowing agent.
  • suitable physical blowing agents are, for example, liquefied CO2, and volatile liquids, for example hydrocarbons having 3, 4 or 5 carbon atoms, preferably cyclo, iso and n-pentane, hydrofluorocarbons, preferably HFC 245fa, HFC 134a and HFC 365mfc, chlorofluorocarbons, preferred HCFC 141 b, hydrofluoroolefins (HFO) or hydrohaloolefins such as 1234ze, 1233zd (E) or 1336mzz, oxygen-containing compounds such as methyl formate, acetone and dimethoxymethane, or chlorohydrocarbons, preferably dichloromethane and 1,2-dichloroethane.
  • hydrocarbons having 3, 4 or 5 carbon atoms preferably cyclo, iso and n-pentane
  • hydrofluorocarbons preferably HFC 245fa, HFC 134a and HFC 365mfc
  • Crosslinkers and chain extenders are low molecular weight, isocyanate-reactive, polyfunctional compounds. Suitable examples are hydroxyl- or amine-terminated substances such as glycerol, neopentyl glycol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, triethanolamine (TEOA), diethanolamine (DEOA) and trimethylolpropane.
  • TEOA triethanolamine
  • DEOA diethanolamine
  • trimethylolpropane trimethylolpropane.
  • the use concentration is usually between 0.1 and 5 parts, based on 100 parts of polyol, but may vary depending on the formulation thereof. When crude MDI is used in foam molding, this also assumes a crosslinking function.
  • the content of low molecular weight crosslinkers can therefore be correspondingly reduced with increasing amount of crude MDI.
  • Suitable stabilizers against oxidative degradation are preferably all common radical scavengers, peroxide scavengers, UV absorbers, light stabilizers, complexing agents for metal ion impurities (metal deactivators).
  • phenols which can be used are esters based on 3- (4-hydroxyphenyl) propionic acid, such as triethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], octadecyl-3- (3,5-) di-tert-butyl-4-hydroxyphenyl) propionate, or methylene diphenols such as 4,4'-butylidene-bis (6-tert-butyl-3-methylphenol).
  • esters based on 3- (4-hydroxyphenyl) propionic acid such as triethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], octadecyl-3- (3,5-) di-tert-butyl-4-hydroxyphenyl) propionate, or methylene diphenols such as 4,4'-butylidene-bis (6-tert-butyl-3-methylphenol).
  • 2- (2'-hydroxyphenyl) benzotriazoles for example, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole or 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole are preferred.
  • 2-hydroxybenzophenones for example, 2-hydroxy-4-n-octoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone or 2,4-dihydroxybenzophenone are preferred.
  • benzoates for example, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate or tannins are preferred.
  • Suitable flame retardants in the context of this invention are all substances which, according to the prior art, will be considered suitable for this purpose.
  • Preferred flame retardants are, for example, liquid organic phosphorus compounds such as halogen-free organic phosphates, e.g. Triethyl phosphate (TEP), halogenated phosphates, e.g. Tris (1-chloro-2-propyl) phosphate (TCPP) and tris (2-chloroethyl) phosphate (TCEP) and organic phosphonates, e.g. Dimethylmethanephosphonate (DMMP), dimethylpropanephosphonate (DMPP), or solids such as ammonium polyphosphate (APP) and red phosphorus.
  • halogenated compounds for example halogenated polyols, and solids such as expanded graphite and melamine are suitable as flame retardants.
  • Surfactants which are used in particular in the production of polyurethane foams can, for example, be selected from the group comprising anionic surfactants, cationic surfactants, nonionic surfactants and / or amphoteric surfactants.
  • Also suitable as surfactants according to the invention are polymeric emulsifiers, such as polyalkylpolyoxyalkylpolyacrylates, polyvinylpyrrolidones or polyvinyl acetates.
  • biocides for example, commercially available products can be used, such as chlorophene, benzisothiazoline, hexahydro-1, 3,5-tris (hydroxyethyl-s-triazine), chloromethylisothiazoline, methylisothiazoline or 1,6-dihydroxy-2,5-dioxohexane, the the trade names BIT 10, Nipacide BCP, Acticide MBS, Nipacide BK, Nipacide Cl, Nipacide FC.
  • siloxanes or organomodified siloxanes can be used in their preparation, wherein the substances mentioned in the prior art can be used.
  • such compounds are used, which are particularly suitable for the respective foam types (rigid foams, hot foams, viscoelastic foams, ester foams, cold foams (HR foams), semi-rigid foams).
  • Suitable (organomodified) siloxanes are described, for example, in the following documents: EP 0839852, EP 1544235, DE 102004001408, EP 0839852, WO 2005/1 18668, US 20070072951, DE 2533074, EP 1537159, EP 533202, US Pat. No.
  • foam stabilizers it is possible to use all stabilizers known from the prior art. Preference is given to using foam stabilizers based on polydialkylsiloxane-polyoxyalkylene copolymers, as are generally used in the production of urethane foams. These compounds are preferably constructed such that, for example, a long-chain copolymer of ethylene oxide and propylene oxide is bonded to a polydimethylsiloxane radical. The link between the polydialkylsiloxane and the polyether part can take place via an SiC linkage or a Si-OC bond. Structurally, the or the different polyethers may be terminally or pendantly attached to the polydialkylsiloxane.
  • the alkyl radical or the various alkyl radicals may be aliphatic, cycloaliphatic or aromatic. Very particularly advantageous are methyl groups.
  • the polydialkylsiloxane may be linear or contain branches.
  • Suitable stabilizers, in particular foam stabilizers, are described inter alia in US Pat. No. 2,834,748, US Pat. No. 2,917,480 and US Pat. No. 3,629,308. Suitable stabilizers are available from Evonik Industries AG under the trade name TEGOSTAB ®.
  • Suitable siloxanes which in the inventive use of the nitrogen-containing compounds according to the formula (I), (II), (III) and / or (IV) and / or the corresponding quaternized and / or protonated compounds can be used in the preparation of polyurethane foams, have in particular the following structure:
  • a is independently 0 to 500, preferably 1 to 300 and in particular 2 to 150,
  • b is independently 0 to 60, preferably 1 to 50 and in particular 1 to 30,
  • c is independently 0 to 10, preferably 0 or> 0 to 5,
  • d is independently 0 to 10, preferably 0 or> 0 to 5,
  • R independently of one another at least one radical from the group of linear, cyclic or branched, aliphatic or aromatic, saturated or unsaturated hydrocarbon radicals having 1 to 20 carbon atoms, but preferably one
  • Methyl radical is,
  • R 2 is independently R 1 or R
  • R 1 is different from R and independently of one another an organic radical and / or a
  • Polyether radical, R 1 is preferably a radical selected from the group
  • H is CH 2 - CH 2 - CH 2 O CH 2 C
  • -CH 2 is -CH 2 -CH 2 -O-CH 2 -c (CH 2 OH) 2-CH 2 -CH 3 ,
  • x 0 to 100 preferably> 0, in particular 1 to 50
  • y is 0 to 100, preferably> 0, in particular 1 to 50,
  • z is 0 to 100, preferably> 0, in particular 1 to 10,
  • R ' is independently an optionally substituted, for example, alkyl, aryl or haloalkyl or haloaryl substituted, alkyl or aryl group having 1 to 12 carbon atoms, wherein within a radical R 1 and / or a molecule of formula (V) with each other different substituents R 'may be present, and
  • Halogen-substituted, hydrocarbon radical having 1 to 50, preferably 9 to 45, preferably 13 to 37 carbon atoms,
  • R 4 independently of one another R, R 1 and / or a heteroatom-substituted
  • R 1 , R 2 and R 4 may be functionalized, organic, saturated or unsaturated radical selected from the group of the alkyl, aryl, chloroalkyl, chloroaryl, fluoroalkyl, cyanoalkyl, acryloxyaryl, acryloyloxyalkyl, methacryloxyalkyl, methacryloxypropyl or vinyl radical, with with the proviso that at least one substituent of R 1 , R 2 and R 4 is not equal to R.
  • R 1 , R 2 and R 4 is not equal to R.
  • siloxane chains or polyoxyalkylene chain may be constructed in blocks with each other with any number of blocks and any sequence or a statistical distribution subject.
  • the indices used in the formulas are to be regarded as statistical averages.
  • the preparation of the siloxanes of the formula (V) can be carried out by the known methods, such as, for example, the noble metal-catalyzed hydrosilylation reaction of compounds containing a double bond with corresponding hydrogen siloxanes as described, for example, in EP 1520870.
  • EP 1520870 is hereby incorporated by reference and is considered part of the disclosure of the present invention.
  • z As compounds which have at least one double bond per molecule, z.
  • ⁇ -olefins Vinylpolyoxyalkylene and / or Allylpolyoxyalkylene be used.
  • vinylpolyoxyalkylenes and / or allylpolyoxyalkylenes are used.
  • Particularly preferred Vinylpolyoxyalkylene are z. B.
  • vinylpolyoxyalkylenes having a molecular weight in the range of 100 g / mol to 8,000 g / mol, which may be constructed blockwise or randomly distributed from the monomers propylene oxide, ethylene oxide, butylene oxide and / or styrene oxide and which are both hydroxy-functional and by a methyl ether or a Acetoxy function may be endcapped.
  • Particularly preferred Allylpolyoxyalkylene are z. B.
  • allylpolyoxyalkylenes having a molecular weight in the range of 100 g / mol to 5,000 g / mol, which may be constructed blockwise or randomly distributed from the monomers propylene oxide, ethylene oxide, butylene oxide and / or styrene oxide and both hydroxy-functional as by a methyl ether or a Acetoxy function can be end-capped.
  • Particularly preferred compounds which have at least one double bond per molecule, the ⁇ -olefins mentioned in the examples, allyl alcohol, 1 -hexenol, Vinylpolyoxyalkylene and / or Allylpolyoxyalkylene and Allylglycidylether and vinylcyclohexene oxide used.
  • siloxanes of the formula (V) in which a is independently from 1 to 300, b is independently from 1 to 50, c is independently 0 to 4, d is independently of one another 0 to 4, with the proviso that per molecule of the formula (V), the average number ⁇ d of the T units and the average number ⁇ c of the Q units per molecule is not greater than 20, the average number E a of D units per molecule not greater than 1500 and the average number E b of the R 1 bearing siloxy units per molecule is not greater than 50.
  • V siloxanes of the formula (V) in which a is independently from 1 to 300, b is independently from 1 to 50, c is independently 0 to 4, d is independently of one another 0 to 4, with the proviso that per molecule of the formula (V), the average number ⁇ d of the T units and the average number ⁇ c of the Q units per molecule is not greater than 20, the average number E a of D units per molecule not greater than 1500 and the average number
  • siloxanes of the formula (V) are used in which R 1 independently of one another is an organic radical
  • R ' can independently of one another be different and methyl, ethyl and / or phenyl Represent remnants.
  • a benzyl group the group -C (O) NH-R ', R IV is a linear, cyclic or branched, optionally substituted, for example, halogen-substituted, hydrocarbon radical having 1 to 50, preferably 9 to 45, preferably 13 to 37 carbon atoms.
  • siloxanes of the formula (V) are used in which R 1 is independently an organic radical selected from the group comprising -CH 2 -CH 2 - CH 2 -O- (CH 2 -CH 2 O-) x- (CH 2 -CH (R ') O-) y R "and / or
  • siloxanes of the formula (V) in which the oxalkylene contained in the radical R 1 are used Units are exclusively oxyethylene
  • siloxanes of the formula (V) are used in which R 1 independently of one another is an organic radical selected from the group comprising -CH 2 -CH 2 -CH 2 -O- (CH 2 -CH 2 O-) x- (CH 2 -CH (R ') O-) y R "and / or
  • x is 0 to 100, preferably> 0, in particular 1 to 50
  • y is 0 to 100, preferably> 0, in particular 1 to 50
  • R ' is methyl and R "is independently a hydrogen radical or an alkyl group having 1 to 4 carbon atoms
  • a group C (0) -R "'with R'" alkyl group, a group -CH 2 -O-R ', an alkylaryl group, such as a benzyl group, the group C (0) NH-R ', where the molar proportion of oxyethylene units, based on the total amount of oxyalkylene units is at most 60% of the oxalkylene units, ie x / (x + y) ⁇ 0.6.
  • siloxanes of the formula (V) are used in which, among others, olefins are used in the hydrosilylation, whereby R 1 is at least 10 mol%, preferably at least 20 mol%, more preferably at least 40 mol% of CH 2 -R IV , wherein R IV is a linear or branched hydrocarbon having 9 to 17 carbon atoms.
  • siloxanes of the formula (V) are used in which the terminal, or also alpha and omega mentioned, positions on the siloxane are at least partially functionalized with radicals R 1 .
  • at least 10 mol%, preferably at least 30 mol%, particularly preferably at least 50 mol% of the terminal positions are functionalized with radicals R 1 .
  • siloxanes of the formula (V) are used in which a maximum of 50%, preferably not more than 45%, particularly preferably not more than 40% of the total average molecular weight of the siloxane on the statistical average added molecular weight of all, optionally different, radicals R 1 in the siloxane omitted.
  • siloxanes of the formula (V) are used in which the radical R is methyl and the number of structural elements with the index a in greater number than the structural elements with the Index b, in such a way that the quotient a / b is at least equal to seven, preferably greater than 10, particularly preferably greater than 12.
  • siloxanes of the formula (V) are used in where the oxalkylene units contained in the radical R 1 are exclusively oxyethylene units and the radical R "is not hydrogen.
  • the siloxanes can also be used as part of compositions with various carrier media.
  • suitable carrier media are, for example, glycols, such as, for example, monoethylene glycol (MEG), diethylene glycol (DEG), propylene glycol (PG) or dipropylene glycol (DPG), alkoxylates or oils of synthetic and / or natural origin.
  • the composition for the preparation of polyurethane systems preferably polyurethane foams, as much of the siloxanes of the formula (V) is added that the mass fraction of compounds of formula (V) on the finished polyurethane system, preferably the polyurethane foam from 0.01 to 10 wt. -%, preferably from 0.1 to 3 wt .-% is.
  • the nitrogen-containing compounds according to the invention of the formula (I), (II); (II) and / or (IV), corresponding quaternized and / or protonated compounds are preferably used in the preparation of polyurethane systems, in particular polyurethane foams.
  • a composition is prepared and / or used which comprises at least one nitrogen-containing compound according to the invention of the formula (I), (II), (II) and / or (IV) as defined above , and / or a corresponding quaternized and / or protonated compound, at least one polyol component, optionally at least one isocyanate component and optionally one or more blowing agents, and this composition is reacted.
  • Particular preference is given to using those compositions which have the substances or components described above for use in the production of polyurethanes, in particular polyurethane foams.
  • Another object of the invention is the use of the above-described nitrogen-containing compound of formula (I), (II), (III) and / or (IV), and / or a corresponding quaternized and / or protonated compound, for the production of low-emission Polyurethanes, especially of low-emission polyurethane foam materials, namely advantageously low emissions with respect to emissions of nitrogen-containing compounds, as previously also called amine emissions, advantageously low emissions with respect to emissions of dimethylformamide (DMF), and / or advantageously low emissions with regard to aldehyde emissions, in particular formaldehyde emissions.
  • DMF dimethylformamide
  • aldehyde emissions in particular formaldehyde emissions.
  • Another object of the invention is the use of the above-described nitrogen-containing compound of formula (I), (II), (III) and / or (IV), and / or a corresponding quaternized and / or protonated compound, for the production of low-odor Polyurethanes, preferably of low-odor polyurethane foams, in particular odor-poor polyurethane foams.
  • low odor preferably of low-odor polyurethane foams, in particular odor-poor polyurethane foams.
  • Another object of the invention is the use of the above-described nitrogen-containing compound of formula (I), (II), (III) and / or (IV), and / or a corresponding quaternized and / or protonated compound, for the production of age-resistant Polyurethane systems, in particular polyurethane foams.
  • age-resistant reference is made to the preceding description and the explanations and test methods given there, With regard to preferred embodiments of this subject matter, reference is also made to the preceding description, in particular to the said preferred embodiments.
  • Another object of the invention is the use of the above-described nitrogen-containing compound of the formula (I), (II), (III) and / or (IV), and / or a corresponding quaternized and / or protonated compound, for the production of discoloration-minimized Polyurethane systems, in particular of polyurethane foams, preferably of polyurethanes for use in the automotive industry, in particular in automotive interiors, for example as a headliner, interior linings of doors, punched-out sun visors, steering wheels and / or seating systems.
  • Discoloration-minimized means that the polyurethane systems provided using nitrogen-containing catalysts according to the invention lead in particular to lower discoloration of plastics, in particular plastic covers, in automobile interiors than those polyurethane systems which are produced using conventional catalysts according to the prior art, in particular non-inventive amines, like this for example, by a PVC discoloration test can be shown.
  • PVC discoloration test a PVC discoloration test
  • Another object of the invention is the use of the above-described nitrogen-containing compound of formula (I), (II), (III) and / or (IV), and / or a corresponding quaternized and / or protonated compound, for the preparation of polyurethane systems With broad processing play, in particular of semi-hard polyurethane foams (open-cell rigid foams, in particular for use as headliners in automobile interiors).
  • Broad processing play means that advantageously a larger variation of the use concentration of the nitrogen-containing compounds according to the invention without negatively influencing the desired material properties, for example off-line of the foam or the distribution of the weight-density over the foam block, is possible in comparison to comparable prior art amine catalysts or customarily used for such applications and the explanations and test methods there.
  • desired material properties for example off-line of the foam or the distribution of the weight-density over the foam block
  • the invention furthermore relates to a composition comprising at least one polyol component, the composition comprising at least one nitrogen-containing compound of the formula (I), (II), (III) and / or (IV) as defined and described above, and / or the corresponding quaternized compounds and / or protonated compounds, wherein the composition preferably has at least one isocyanate component, and wherein the nitrogen-containing compound of formula (I), (II), (III) and / or (IV) preferably as a technical product mixture, as described above, included is
  • composition preferably comprises additional amine catalysts other than formula (I), (II), (III) and / or (IV).
  • the molar ratio of the total amount of the nitrogen-containing catalysts comprising the nitrogen-containing compounds of the formula (I), (II), (III) and / or (IV) to the total amount of the isocyanate-reactive groups of the polyol component is preferably from 4 ⁇ 10 "4 to 1 to 0.2 to 1. It is preferred that the nitrogen-containing compounds of the formula (I), (II), (III) and / or (IV), corresponding quaternized and / or protonated compounds, in total in a proportion by mass of 0.01 to 20.0 parts (pphp), preferably 0.01 to 5.00 parts and more preferably 0.02 to 3.00 parts based on 100 parts (pphp) of polyol component are used.
  • composition of the invention may additionally comprise one or more propellants as described above.
  • the composition of the invention may comprise further additives / auxiliaries or additives which are used in the preparation of polyurethane systems, preferably polyurethane foams.
  • auxiliaries / additives / additives such as foam stabilizers or flame retardants, has been described above in the preparation of the polyurethane systems, in particular the polyurethane foams.
  • foam stabilizers or flame retardants has been described above in the preparation of the polyurethane systems, in particular the polyurethane foams.
  • the processing of the compositions according to the invention into polyurethane systems, in particular polyurethane foams can be carried out by all methods familiar to the person skilled in the art, for example by hand mixing or preferably by means of foaming machines, in particular low-pressure or high-pressure foaming machines. In this case, discontinuous processes, for example for the production of molded foams, refrigerators, automobile seats, and panels, or continuous processes, for example in insulation boards, metal composite
  • compositions used according to the invention can be used for the CC> 2 technology.
  • the use in low-pressure and high-pressure machines is possible, wherein the compositions can be metered either directly into the mixing chamber or even before the mixing chamber of one of the then passing into the mixing chamber components are admixed. The admixture can also be done in the raw material tank.
  • Another object of the present invention is a composition suitable for use in the production of polyurethanes, in particular of polyurethane foams containing
  • ethylenediamine advantageously in an amount of ⁇ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
  • (j) optionally monoethylene glycol (MEG), advantageously in an amount of ⁇ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
  • (k) optionally diethylene glycol (DEG), advantageously in an amount of ⁇ 95% by weight, in particular 20-90% by weight, preferably 30-80% by weight,
  • DEG diethylene glycol
  • (I) optionally 1, 2-propylene glycol (PG), advantageously in an amount of ⁇ 95 wt .-%, in particular 20-90 wt .-%, preferably 30-80 wt .-%,
  • PG 2-propylene glycol
  • DPG dipropylene glycol
  • (q) optionally trimethylene glycol, butyl diglycol, neopentyl glycol, 2-methyl-1,3-propanediol, N, N-dimethylcyclohexylamine, ⁇ , ⁇ -dimethylaminopropylamine, triethylenediamine, 2,2,4-trimethyl-2-silamorpholine, N-ethyl- 2,2-dimethyl-2-silamorpholine, N- (2-aminoethyl) morpholine, N- (2-hydroxyethyl) morpholine, N, N-dimethylaminoethanol, ⁇ , ⁇ -diethylaminoethanol, bis (2-dimethylaminoethyl ether), ⁇ , ⁇ Dimethylaminoethoxyethanol, N, N, N'-trimethyl-N '- (2-hydroxyethyl) bis (2-aminoethyl) ether, tris (dimethylaminopropyl)
  • compositions are those compositions in which at least one nitrogen-containing compound of the formula (I), preferably at least one nitrogen-containing compound of the formula (II), (III) or (IV), in particular at least one nitrogen-containing compound of the formula (III) and / or a corresponding quaternized and / or protonated compound is used in combination:
  • a further subject of the present invention is therefore a polyurethane system obtainable by a use as described above.
  • polyurethane systems are preferably polyurethane foams, preferably rigid polyurethane foams, flexible polyurethane foams, viscoelastic foams, highly elastic foams, so-called high resilience foams (HR), semi-rigid polyurethane foams, thermoformable polyurethane foams or integral foams.
  • polyisocyanurates and polyureas are expressly included.
  • the polyurethane system according to the invention is preferably characterized in that it is a rigid polyurethane foam, a flexible polyurethane foam, a viscoelastic foam, a high resilience (HR) foam, a semi-rigid polyurethane foam, a thermoformable polyurethane foam or an integral foam, wherein it preferably has a mass fraction nitrogen-containing compounds of the formula (I), (II), (III) and / or (IV), and / or the corresponding quaternized and / or protonated compounds or of the radicals obtained by reacting these on the finished polyurethane foam of 0.005 to 10 wt. -%, preferably from 0.05 to 3 wt .-%, particularly preferably 0.1 to 1 wt .-%, having.
  • the polyurethane foams according to the invention or produced according to the invention are open-celled polyurethane foams, in particular flexible foams, particularly preferably hot-melt foams.
  • the air permeability of the foam can be determined by a dynamic pressure measurement on the foam. The dynamic pressure measurement can be carried out in accordance with EN 29053. If the measured back pressure is given in mm water column, then open-cell polyurethane foams, in particular flexible polyurethane foams, have a back pressure of less than 100 mm, preferably ⁇ 50 mm, determined in accordance with the measuring method described in the examples.
  • a preferred composition for the production of polyurethane or polyisocyanurate foam in the context of the present invention has a density (RG) of preferably 5 to 800, in particular 5 to 300, preferably 5 to 150, particularly preferably from 10 to 90 kg / m 3 and in particular has the following composition:
  • Tin catalyst 0 to 5, preferably 0.001 to 2
  • Another object of the invention is the use of polyurethane systems, in particular of polyurethane foams, as described above, as refrigerator insulation, insulation board, sandwich element, pipe insulation, spray foam, 1 - & 1, 5-component canned foam, wood imitation, model foam, floral foam, packaging foam, mattress , Furniture upholstery, foam molded furniture, pillows, rebonded foam, sponge foam, automotive upholstery, headrest, instrument panel, automotive interior trim, automotive headliner, sound absorbing material, steering wheel, shoe sole, carpet back foam, filter foam, caulking foam, sealant and adhesive, or for making such products ,
  • Synthesis Example 1 was prepared. The autoclave previously purged with nitrogen was then heated over the jacket with a thermo-oil to 110 ° C., whereby a pressure increase could be observed. The reaction temperature was then maintained under stirring for 8 hours. After the reaction time was allowed to cool to room temperature, the pressure vessel was depressurized and purged with nitrogen. The solvent was removed several hours on a rotary evaporator at a bath temperature of 50 ° C in a membrane pump vacuum. The reaction mixture was then analyzed by gas chromatography, with no reactant found. Subsequently, distilled off in a sharp oil pump vacuum to remove other volatile components. The GPC and NMR spectroscopic analysis confirmed the addition of two equivalents of ethylene oxide to the desired compound of formula (IIIa).
  • Triphenylphosphine 99% Sigma-Aldrich
  • the autoclave was sealed, rendered inert with nitrogen, and the jacket was heated to 190 ° C. with a thermo-oil, whereby a pressure increase could be observed.
  • the reaction temperature was then maintained under stirring for 9 hours. After the reaction time was allowed to cool to room temperature and the reaction mixture analyzed by gas chromatography.
  • the GC and GC / MS analysis showed not only unreacted 2- (2- (pyrrolidin-1-yl) ethoxy) ethanol but also 38% of the desired product, but also significant amounts of by-products from the intermolecular reaction of the 2 methylamino-ethanol of.
  • Triphenylphosphine 99% 603-35-0 Sigma-Aldrich
  • the autoclave was sealed, rendered inert with nitrogen and the jacket heated to 130 ° C. with a thermo-oil. The reaction temperature was then maintained under stirring for 8 hours. After the reaction time was allowed to cool to room temperature, the Autociav relaxed and purged with nitrogen. The reaction mixture was freed from the solvent and volatile constituents on a rotary evaporator and the residue was analyzed by gas chromatography.
  • Triphenylphosphine 99% 603-35-0 Sigma-Aldrich
  • the autoclave was sealed, rendered inert with nitrogen and the jacket was heated to 140 ° C. with a thermo-oil. The reaction temperature was then maintained under stirring for 8 hours. After the reaction time was allowed to cool to room temperature, the autoclave is expanded and purged with nitrogen.
  • the crude reaction mixture was treated with ethanol and a little filter aid (Celite ®) provided, filtered through a fluted filter and the solvent was then removed on a rotary evaporator. The residue was then subjected to a fractional precision distillation, wherein unreacted educts were distilled off in an oil pump vacuum.
  • Triphenylphosphine 99% 603-35-0 Sigma-Aldrich
  • the Autociav was sealed, rendered inert with nitrogen and the jacket heated to 140 ° C with a thermo-oil. The reaction temperature was then maintained under stirring for 8 hours. After the reaction time was allowed to cool to room temperature, the Autociav relaxed and purged with nitrogen.
  • the crude reaction mixture was treated with ethanol and a little filter aid (Celite ®) provided, filtered through a fluted filter and the solvent was then removed on a rotary evaporator. The residue was then subjected to a fractional precision distillation, wherein unreacted educts were distilled off in an oil pump vacuum.
  • Example 1 Production of rigid polyurethane foams, for example for use in the isolation of refrigerated cabinets
  • Table 1 Formulation 1 for rigid foam applications.
  • Polyol 1 sorbitol / glycerol-based polyether polyol having an OH number of 471 mgKOH / g.
  • the foaming was carried out by hand mixing.
  • the formulations as indicated in Table 1 were used with various nitrogenous catalysts (amines).
  • polyol 1, conventional or inventive nitrogen-containing catalyst (amine), water, foam stabilizer and blowing agent were weighed into a beaker and mixed with a paddle stirrer of 6 cm diameter for 30 seconds at 1000 rev / min. By reweighing, the quantity of blowing agent which was vaporized during the mixing process was determined and supplemented again.
  • MDI isocyanate
  • the reaction mixture was stirred with the described stirrer at 3000 rpm for 5 s and immediately transferred to a box lined with paper (27 cm x 14 cm base and 14 cm height).
  • the following characteristic parameters were determined: cream time, gel time (thread cessation time), rise time and tack-free time.
  • the nitrogen-containing compounds of the formula (III) according to the invention show a moderate to good catalytic activity in the hard foam.
  • the performance of the nitrogen-containing compounds of the formula (III) in this amount is partially comparable to DMEE, in which case in particular the nitrogen-containing compound of the formula (IIIb) has a slight improvement in activity.
  • Density (RG): The determination is carried out by measuring the core density as described in ASTM D 3574-1.1 under test A. The density is given in kg / m 3 .
  • Porosity The air permeability of the foam was determined by a dynamic pressure measurement on the foam. The measured dynamic pressure is given in mm water column, whereby lower dynamic pressure values characterize a more open foam. The values were measured in the range of 0 to 300 mm.
  • the measurement of the dynamic pressure was carried out by means of an apparatus comprising a nitrogen source, reducing valve with pressure gauge, flow control screw, wash bottle,
  • the support nozzle has an edge length of 100 ⁇ 100 mm, a weight of 800 g, a clear width of the outlet opening of 5 mm, a clear width of the lower support ring of 20 mm and an outer diameter of the lower support ring of 30 mm.
  • the measurement is carried out by setting the nitrogen admission pressure by reducing valve to 1 bar and adjusting the flow rate to 480 l / h.
  • the amount of water is adjusted in the scaled glass tube so that no pressure difference is built up and readable.
  • the support nozzle is placed edge-matching at the corners of the specimen and placed once at the (estimated) center of the specimen (each on the side with the largest surface). It is read when a constant dynamic pressure has set.
  • the evaluation is carried out by averaging over the five obtained measured values.
  • the measurement values are given in kilopascals (kPa).
  • VOC and Fog value Measurement of foam emissions (VOC and Fog value) in accordance with the test specification VDA 278 in the version of October 201 1:
  • the method is used to detect non-metallic material emissions that are used in automotive moldings.
  • the emission of volatile organic compounds (VOC value, 30 minutes at 90 ° C) and the proportion Condensable substances (Fog value, 60 minutes at 120 ° C), in particular the catalysis emissions, emissions of the individual components of inventive catalyst combinations or their Zer- or reaction products was determined following the test specification VDA 278 in the version of October 201 1 , In the following, the implementation of the corresponding thermal desorption with subsequent gas chromatography / mass spectrometry coupling (GC / MS) is described.
  • Thermodesorption was performed with a thermal desorber "TDS2" with sample changer from Gerstel, Mülheim, in combination with an Agilent 7890/5975 GC / MSD system.
  • Table 4 Measurement parameters gas chromatography / mass spectrometry for the analysis run.
  • Tenax® TA is a porous polymer resin based on 2,6-diphenylene oxide, available from, for example, Scientific Instrument Services, 1027 Old York Rd., Ringoes, NJ 08551.
  • Sample preparation for VOC measurement 15 mg Foams were placed in three subsamples in a thermal desorption tube. It was ensured that the foam is not compressed.
  • Table 6 Measurement parameters gas chromatography / mass spectrometry for the fog Analytical run.
  • PK test chamber test
  • Thermodesorption was performed with a thermal desorber "TDS2" with a sample changer from Gerstel, Mülheim, in conjunction with an Agilent 7890/5975 GC / MSD system.
  • Table 8 Measurement parameters gas chromatography / mass spectrometry for PK measurement.
  • Table 9 Formulation 2 for soft block foam applications.
  • Polyol 1 Glycerol-based polyether polyol having an OH number of 48 mgKOH / g.
  • COSMOS ® 29 available from Evonik Industries: tin (II) salt of 2-ethylhexanoic acid.
  • Toluylene diisocyanate T 80 (80% 2,4-isomer, 20% 2,6-isomer) from Bayer, 3 mPa.s, 48% NCO, functionality 2.
  • the foaming was carried out by hand mixing. Those given in formulations as shown in Table 9 were used with various nitrogenous catalysts (amines).
  • amines polyol, conventional or inventive nitrogen-containing catalyst (amine), tin catalyst, water and foam stabilizer were weighed into a beaker and mixed for 60 seconds at 1000 rev / min.
  • TDI isocyanate
  • the reaction mixture was stirred for 7 s at 2500 rpm and immediately transferred to a box lined with paper (27 cm x 27 cm base and 27 cm height).
  • the compounds of the formula (III) have a moderate to good catalytic activity in the hot flexible foam.
  • the chosen formulation it was possible with all compounds of the formula (III) to produce sufficient open-cell flexible foams. Only with the compound of the formula (IIIa), the air permeability of the foam block was slightly reduced.
  • the activity and selectivity of the nitrogen-containing compounds have (IIIa), according to the formula (IIIb) and (IIIc) a performance similar TEGOAMIN ® DMEA, with particular compound according to the formula (IIIb) opposite TEGOAMIN ® DMEA a slightly increased blowing selectivity having.
  • Table 1 1 Formulation 3, foam emissions in soft block foam applications. Formulation 3 parts by mass (pphp)
  • Polyol 1 Low-emission glycerol-based polyether polyol having an OH number of 56 mgKOH / g.
  • COSMOS ® EF available from Evonik Industries: tin (II) salt of ricinoleic acid.
  • Toluylene diisocyanate T 80 (80% 2,4-isomer, 20% 2,6-isomer) from Bayer, 3 mPa.s, 48% NCO, functionality 2.
  • the foaming was carried out by hand mixing.
  • the formulations given in Table 1 1 were used with various nitrogenous catalysts (amines).
  • amines nitrogenous catalysts
  • low-emission polyol, conventional or inventive nitrogen-containing catalyst (amine), low-emission tin catalyst, water and foam stabilizer were weighed into a beaker and mixed for 60 seconds at 1000 rev / min.
  • the reaction mixture was stirred for 7 s at 2500 rpm and immediately transferred to a box lined with paper (27 cm x 27 cm base and 27 cm height) and the resulting foam after blowing off with polyethylene film hermetically sealed.
  • PKges total emission
  • ⁇ TM amine emissions of all volatile organic compounds in the test chamber test.
  • Table 12 shows that the slabstock foams obtained using the nitrogen-containing compounds according to formula (III), have lower amine emissions as described above after the sketchhunttest, when using conventional catalysts such as TEGOAMIN ® BDE or TEGOAMIN ® 33 .
  • formulation ZF-10 at most a low amine emissions were even how to TEGOAMIN ® DMEA and Jeffcat® also m 3 can be obtained, in most cases, the resulting foams were even free of such emissions ⁇ 10 g /.
  • the amine emissions in accordance with the VDA 278, as described above, a partial reduction of the amine emissions with appropriate catalyst-exchange TEGOAMIN ® BDE or TEGOAMIN ® 33 was observed.
  • Polyol 1 sorbitol / glycerol-based polyether polyol having an OH number of 32 mgKOH / g.
  • Polyol 2 Glycerol-based polyether polyol containing 43% solids (SAN) with an OH number of 20 mgKOH / g.
  • Table 14 again shows that the compounds of the formula (III) have, in part, a high catalytic activity in the cold foam.
  • the catalysts are as partially balanced catalysts with slight preference for the blowing reaction (for example, the nitrogen-containing compounds of the formula (IIIa), (Never)) or as catalysts which preferentially catalyze the blowing reaction (for example the nitrogen-containing compounds) of the formula (IIIb) to divide.
  • the use amount of the nitrogen-containing compound ranges according to the formula (IIIa) and (IIIc) is not sufficient to obtain a stable foam.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne l'utilisation de composés azotés représentés par la formule (I) et/ou d'un composé quaternisé et/ou protoné correspondant pour la fabrication de polyuréthanes, des compositions contenant ces composés et des système de polyuréthane obtenus par utilisation de ces composés.
PCT/EP2015/065836 2014-08-05 2015-07-10 Composés azotés adaptés à une utilisation dans la fabrication de polyuréthanes WO2016020140A2 (fr)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10870723B2 (en) 2015-07-07 2020-12-22 Evonik Operations Gmbh Production of polyurethane foam
US11021608B2 (en) 2018-02-08 2021-06-01 Evonik Operations Gmbh Aqueous polyorganosiloxane hybrid resin dispersion
US11236204B2 (en) 2019-05-28 2022-02-01 Evonik Operations Gmbh Production of SiOC-bonded polyether siloxanes
US11377523B2 (en) 2019-05-28 2022-07-05 Evonik Operations Gmbh Process for producing non-cyclic alkoxy-functional polysiloxanes
EP3999232A4 (fr) * 2019-07-18 2023-06-07 Huntsman Petrochemical LLC Catalyseurs de pyrrolidine bloqués par un acide pour mousse de polyuréthane
US11851583B2 (en) 2016-07-19 2023-12-26 Evonik Operations Gmbh Process for producing porous polyurethane coatings using polyol ester additives

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE202018101701U1 (de) * 2018-03-27 2019-07-02 Illinois Tool Works Inc. Innenraumkomponente eines Fahrzeugs

Citations (67)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE701825C (de) 1938-03-29 1941-01-24 I G Farbenindustrie Akt Ges Verfahren zur Herstellung von Pyrrolen und hydrierten Pyrrolen
US2834748A (en) 1954-03-22 1958-05-13 Union Carbide Corp Siloxane-oxyalkylene block copolymers
US2917480A (en) 1954-06-10 1959-12-15 Union Carbide Corp Siloxane oxyalkylene block copolymers
US3346557A (en) 1965-06-04 1967-10-10 Wyandotte Chemicals Corp Process for oxyalkylating solid polyols
US3629308A (en) 1966-07-25 1971-12-21 Union Carbide Corp Siloxane-oxyalkylene block copolymers
US3900424A (en) 1972-07-21 1975-08-19 Nippon Oil Seal Ind Co Ltd Catalyst for copolymerizing epoxy compounds with carbon dioxide
US3933695A (en) 1972-12-29 1976-01-20 Union Carbide Corporation Hydroxyalkenylsiloxane rigid poly urethane foam stabilizers
DE2533074A1 (de) 1974-08-30 1976-03-11 Goldschmidt Ag Th Verfahren zur herstellung von hochelastischen polyurethanweichschaeumen
US3953383A (en) 1972-07-21 1976-04-27 Nippon Oil Seal Industry Co., Ltd. Catalytic process for copolymerizing epoxy compounds with carbon dioxide
US4147847A (en) 1973-11-14 1979-04-03 Dow Corning Corporation Method of preparing flexible flame retardant polyether based one-shot polyurethane foams and compositions therefore
US4500704A (en) 1983-08-15 1985-02-19 The Dow Chemical Company Carbon dioxide oxirane copolymers prepared using double metal cyanide complexes
US4855379A (en) 1988-03-08 1989-08-08 Union Carbide Corporation Silicone surfactants containing cyclic siloxane pendants
EP0380993A2 (fr) 1989-02-02 1990-08-08 Bayer Ag Procédé de fabrication de mousses souples de polyuréthane élastiques et à cellules ouvertes
EP0493836A1 (fr) 1990-12-31 1992-07-08 OSi Specialties, Inc. Tensio-actifs pour la fabrication de mousses de polyuréthane
EP0533202A1 (fr) 1991-09-20 1993-03-24 Union Carbide Chemicals & Plastics Technology Corporation Utilisation d'agents tensio-actifs masqués pour la production de mousses rigides de polyuréthane, gonflées par des hydrochlorofluorocarbones
DE4229402A1 (de) 1992-09-03 1994-03-10 Goldschmidt Ag Th Polysiloxan-Polyoxyalkylen-Blockmischpolymerisat mit unterschiedlichen Polyoxyalkylenblöcken im durchschnittlichen Molekül
DE4230402A1 (de) 1992-09-11 1994-03-17 Basf Ag Verfahren zur Herstellung von sekundären Aminen
DE4239054A1 (de) 1992-11-20 1994-05-26 Goldschmidt Ag Th Polysiloxan-Polyoxyalkylen-Blockmischpolymerisat mit unterschiedlichen Polyoxyalkylenblöcken im durchschnittlichen Molekül
WO1996012759A2 (fr) 1994-10-20 1996-05-02 The Dow Chemical Company Procede de preparation de mousse de polyurethane en presence d'un hydrocarbure servant d'agent gonflant
US5639916A (en) 1995-11-29 1997-06-17 Air Products And Chemicals, Inc. Amination of allylic alcohols
EP0780414A2 (fr) 1995-12-22 1997-06-25 Air Products And Chemicals, Inc. Méthode pour la préparation de mousses de polyuréthane flexibles
EP0839852A2 (fr) 1996-10-31 1998-05-06 OSi Specialties, Inc. Hydrosilylation dans un milieu d'huile végétale naturelle à point d'ébullition élevée
EP0656382B1 (fr) 1993-12-03 1998-08-26 Nisshinbo Industries, Inc. Procédé de préparation de mousses modifiées de polyisocyanurate
EP0867465A1 (fr) 1997-03-29 1998-09-30 Th. Goldschmidt AG Utilisation de copolymères séquencés ayant de séquences de siloxanes liés pour la préparation de mousses de polyréthane
WO2000058383A1 (fr) 1999-03-31 2000-10-05 Oxid L.P. Polyols de polyesters aromatiques produits a partir d'une huile naturelle
WO2001058976A1 (fr) 2000-02-10 2001-08-16 Dow Global Technologies Inc. Polymeres polyurethanes a faible taux d'emission fabriques avec des polyols autocatalytiques
EP1161474A1 (fr) 1999-02-13 2001-12-12 Bayer Ag Mousses rigides de polyurethane a petits alveoles, entrainables par l'eau
US6359022B1 (en) 1997-10-10 2002-03-19 Stepan Company Pentane compatible polyester polyols
WO2002022702A1 (fr) 2000-09-13 2002-03-21 Dow Global Technologies Inc. Polyols presentant des caracteristiques autocatalytiques et produits de polyurethane fabriques a partir de ceux-ci
US20020103091A1 (en) 2001-01-29 2002-08-01 Kodali Dharma R. Reactive oil compositions and uses thereof
WO2003029320A1 (fr) 2001-10-01 2003-04-10 Dow Global Technologies Inc. Polyols autocatalytiques presentant des caracteristiques de gelification, et produits en polyurethane obtenus a partir desdits polyols
WO2004020497A1 (fr) 2002-08-28 2004-03-11 Basf Aktiengesellschaft Procede de preparation de materiaux expanses souples polyurethane a emissions faibles
US6762274B2 (en) 2000-02-10 2004-07-13 Dow Global Technologies Inc. Low emission polyurethane polymers made with autocatalytic polyols
WO2004060956A1 (fr) 2002-12-17 2004-07-22 Dow Global Technologies Inc. Polymeres autocatalytiques amine-epoxy et produits de polyurethanne fabriques a partir de ces polymeres
WO2004096882A1 (fr) 2003-04-25 2004-11-11 Dow Global Technologies, Inc. Huile vegetale a base de polyols et polyurethannes conçus a partir de celle-ci
EP1520870A1 (fr) 2003-10-04 2005-04-06 Goldschmidt GmbH Procédé pour préparation des combinaisons organiques de silicium
WO2005033167A2 (fr) 2003-09-30 2005-04-14 Cargill Incorporated Polyurethane expanse souple prepare a l'aide de polyols a base d'huiles vegetales modifiees
EP1544235A1 (fr) 2003-12-15 2005-06-22 Air Products And Chemicals, Inc. Tensioactifs aux silicones utilisés dans des mousses de polyuréthanne rigides obtenues avec des agents gonflants du type hydrocarbures
WO2005063841A1 (fr) 2003-12-23 2005-07-14 Dow Global Technologies Inc. Procede de production de produits en polyurethanne au moyen de polyols de polyether autocatalytiques a coiffe amine tertiaire
DE102004001408A1 (de) 2004-01-09 2005-07-28 Goldschmidt Ag Verwendung blockweise aufgebauter Polyethersiloxane als Stabilisatoren in Polyurethanschäumen
US6924321B2 (en) 2001-08-16 2005-08-02 Dow Global Technologies Inc. Polyols with autocatalytic characteristics and polyurethane products made therefrom
WO2005085310A2 (fr) 2004-03-08 2005-09-15 Rathor Ag Prépolymères de polyuréthanne à stabilité de phase
WO2005118668A1 (fr) 2004-05-25 2005-12-15 General Electric Company Procede de preparation de mousses de polyurethane ayant des emissions en composes organiques volatils reduites
WO2006055396A1 (fr) 2004-11-17 2006-05-26 Dow Global Technologies, Inc. Polyols autocatalytiques a base d'amine bloques par un acide et mousses de polyurethanne produites a partir desdits polyols
WO2006094227A2 (fr) 2005-03-03 2006-09-08 South Dakota Soybean Processors, Llc Nouveaux polyols issus d'une huile vegetale au moyen d'un procede d'oxydation
US20060229375A1 (en) 2005-04-06 2006-10-12 Yu-Ling Hsiao Polyurethane foams made with alkoxylated vegetable oil hydroxylate
EP1712578A1 (fr) 2005-04-13 2006-10-18 Bayer MaterialScience LLC Mousses de polyuréthane à base d'huile végétale hydroxylée, de polyol polymère et d'alcool aliphatique polyhydroxy
WO2006116456A1 (fr) 2005-04-25 2006-11-02 Cargill, Incorporated Mousses de polyurethane comprenant des polyols oligomeriques
US20060293400A1 (en) 2003-04-25 2006-12-28 Wiltz Jr Eugene P Dow global technologies inc
US20070072951A1 (en) 2005-09-27 2007-03-29 Bender Jared D Silanol-functionalized compounds for the preparation of polyurethane foams
WO2007111828A2 (fr) 2006-03-23 2007-10-04 Dow Global Technologies Inc. Mousse de polyurethane de basse densite a base d'huile naturelle sans additif de stabilisation de cellules a base de silicone
US20070238800A1 (en) 2006-04-11 2007-10-11 Bayer Materialscience Llc Storage stable isocyanate-reactive component containing vegetable oil-based polyol
US20070282026A1 (en) 2003-07-24 2007-12-06 Huntsman Petrochemical Corporation Low-Odor Catalyst for Isocyanate-Derived Foams and Elastomers
WO2008058913A1 (fr) 2006-11-15 2008-05-22 Basf Se Procédé de fabrication de mousses souples en polyuréthanne
US20080234402A1 (en) 2005-09-01 2008-09-25 Basf Se Polyisocyanurate Rigid Foam and Method for the Production Thereof
EP1977825A1 (fr) 2006-07-13 2008-10-08 Air Products and Chemicals, Inc. N,N,N'-triméthyl-bis-(aminoéthyl) éther et ses dérivés en tant que catalyseurs pour polyuréthanes
EP1985644A1 (fr) 2007-04-26 2008-10-29 Air Products and Chemicals, Inc. Composition de polyamine
EP1985642A1 (fr) 2007-04-25 2008-10-29 Air Products and Chemicals, Inc. Additifs pour améliorer le durcissement de surface et la stabilité dimensionnelle de mousses de polyuréthane
EP2042534A1 (fr) 2007-09-28 2009-04-01 Evonik Goldschmidt GmbH Catalyseur par amine adapté à la fabrication de mousses de polyuréthane flexibles pauvres en émissions et résistant à la recatalyse
WO2009058367A1 (fr) 2007-11-01 2009-05-07 Cargill, Incorporated Polyols de polyester dérivés d'huile naturelle et polyuréthanes obtenus à partir de ceux-ci
WO2009130470A1 (fr) 2008-04-25 2009-10-29 Imperial Innovations Limited Complexes catalytiques bimétalliques pour la copolymérisation de dioxyde de carbone et d’un époxyde
WO2010028362A1 (fr) 2008-09-08 2010-03-11 Novomer, Inc. Compositions de polycarbonate-polyol et procédés
WO2011163133A1 (fr) 2010-06-20 2011-12-29 Novomer, Inc. Polycarbonates aliphatiques
EP1945222B1 (fr) 2005-11-02 2012-12-26 Bayer Pharma Aktiengesellschaft Derives pyrrolo[2,1-f] [1,2,4] triazin-4-ylamines comme inhibiteurs de la igf-1r kinase pour le traitement des cancers et d'autres maladies hyperproliferatives
WO2013022932A1 (fr) 2011-08-08 2013-02-14 Novomer, Inc. Catalyseurs et procédés de synthèse de polymères
WO2013102053A1 (fr) 2011-12-29 2013-07-04 Dow Global Technologies Llc Polyéther polyols d'amine et compositions de mousse polyuréthane fabriquée à partir de composés amine cycliques
EP2104696B1 (fr) 2006-12-21 2013-09-11 Dow Global Technologies LLC Catalyse de polyuréthane à partir de la combinaison de polyol autocatalytique et d'urée

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE841917C (de) 1949-12-07 1952-06-19 Geigy Ag J R Verfahren zur Herstellung von Bis-tert.-aminoalkoxyalkanen und ihren quaternaeren Ammoniumhalogeniden
JPH08259655A (ja) * 1995-01-25 1996-10-08 Tosoh Corp ポリウレタン製造用アミン触媒及びそれを用いたポリウレタンの製造方法
DE19742720A1 (de) * 1997-09-26 1999-04-01 Performance Chemicals Handels Bis(alkylamino)alkylether-Verbindungen und ihre Verwendung
DE10331137B4 (de) 2003-07-09 2008-04-30 Carl Zeiss Nts Gmbh Detektorsystem für ein Rasterelektronenmikroskop und Rasterelektronenmikroskop mit einem entsprechenden Detektorsystem

Patent Citations (70)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE701825C (de) 1938-03-29 1941-01-24 I G Farbenindustrie Akt Ges Verfahren zur Herstellung von Pyrrolen und hydrierten Pyrrolen
US2834748A (en) 1954-03-22 1958-05-13 Union Carbide Corp Siloxane-oxyalkylene block copolymers
US2917480A (en) 1954-06-10 1959-12-15 Union Carbide Corp Siloxane oxyalkylene block copolymers
US3346557A (en) 1965-06-04 1967-10-10 Wyandotte Chemicals Corp Process for oxyalkylating solid polyols
US3629308A (en) 1966-07-25 1971-12-21 Union Carbide Corp Siloxane-oxyalkylene block copolymers
US3900424A (en) 1972-07-21 1975-08-19 Nippon Oil Seal Ind Co Ltd Catalyst for copolymerizing epoxy compounds with carbon dioxide
US3953383A (en) 1972-07-21 1976-04-27 Nippon Oil Seal Industry Co., Ltd. Catalytic process for copolymerizing epoxy compounds with carbon dioxide
US3933695A (en) 1972-12-29 1976-01-20 Union Carbide Corporation Hydroxyalkenylsiloxane rigid poly urethane foam stabilizers
US4147847A (en) 1973-11-14 1979-04-03 Dow Corning Corporation Method of preparing flexible flame retardant polyether based one-shot polyurethane foams and compositions therefore
DE2533074A1 (de) 1974-08-30 1976-03-11 Goldschmidt Ag Th Verfahren zur herstellung von hochelastischen polyurethanweichschaeumen
US4500704A (en) 1983-08-15 1985-02-19 The Dow Chemical Company Carbon dioxide oxirane copolymers prepared using double metal cyanide complexes
US4855379A (en) 1988-03-08 1989-08-08 Union Carbide Corporation Silicone surfactants containing cyclic siloxane pendants
EP0380993A2 (fr) 1989-02-02 1990-08-08 Bayer Ag Procédé de fabrication de mousses souples de polyuréthane élastiques et à cellules ouvertes
EP0493836A1 (fr) 1990-12-31 1992-07-08 OSi Specialties, Inc. Tensio-actifs pour la fabrication de mousses de polyuréthane
EP0533202A1 (fr) 1991-09-20 1993-03-24 Union Carbide Chemicals & Plastics Technology Corporation Utilisation d'agents tensio-actifs masqués pour la production de mousses rigides de polyuréthane, gonflées par des hydrochlorofluorocarbones
DE4229402A1 (de) 1992-09-03 1994-03-10 Goldschmidt Ag Th Polysiloxan-Polyoxyalkylen-Blockmischpolymerisat mit unterschiedlichen Polyoxyalkylenblöcken im durchschnittlichen Molekül
DE4230402A1 (de) 1992-09-11 1994-03-17 Basf Ag Verfahren zur Herstellung von sekundären Aminen
DE4239054A1 (de) 1992-11-20 1994-05-26 Goldschmidt Ag Th Polysiloxan-Polyoxyalkylen-Blockmischpolymerisat mit unterschiedlichen Polyoxyalkylenblöcken im durchschnittlichen Molekül
EP0656382B1 (fr) 1993-12-03 1998-08-26 Nisshinbo Industries, Inc. Procédé de préparation de mousses modifiées de polyisocyanurate
WO1996012759A2 (fr) 1994-10-20 1996-05-02 The Dow Chemical Company Procede de preparation de mousse de polyurethane en presence d'un hydrocarbure servant d'agent gonflant
US5639916A (en) 1995-11-29 1997-06-17 Air Products And Chemicals, Inc. Amination of allylic alcohols
EP0780414A2 (fr) 1995-12-22 1997-06-25 Air Products And Chemicals, Inc. Méthode pour la préparation de mousses de polyuréthane flexibles
EP0839852A2 (fr) 1996-10-31 1998-05-06 OSi Specialties, Inc. Hydrosilylation dans un milieu d'huile végétale naturelle à point d'ébullition élevée
EP0867465A1 (fr) 1997-03-29 1998-09-30 Th. Goldschmidt AG Utilisation de copolymères séquencés ayant de séquences de siloxanes liés pour la préparation de mousses de polyréthane
US6359022B1 (en) 1997-10-10 2002-03-19 Stepan Company Pentane compatible polyester polyols
EP1161474A1 (fr) 1999-02-13 2001-12-12 Bayer Ag Mousses rigides de polyurethane a petits alveoles, entrainables par l'eau
WO2000058383A1 (fr) 1999-03-31 2000-10-05 Oxid L.P. Polyols de polyesters aromatiques produits a partir d'une huile naturelle
WO2001058976A1 (fr) 2000-02-10 2001-08-16 Dow Global Technologies Inc. Polymeres polyurethanes a faible taux d'emission fabriques avec des polyols autocatalytiques
US6762274B2 (en) 2000-02-10 2004-07-13 Dow Global Technologies Inc. Low emission polyurethane polymers made with autocatalytic polyols
WO2002022702A1 (fr) 2000-09-13 2002-03-21 Dow Global Technologies Inc. Polyols presentant des caracteristiques autocatalytiques et produits de polyurethane fabriques a partir de ceux-ci
US20020103091A1 (en) 2001-01-29 2002-08-01 Kodali Dharma R. Reactive oil compositions and uses thereof
US6924321B2 (en) 2001-08-16 2005-08-02 Dow Global Technologies Inc. Polyols with autocatalytic characteristics and polyurethane products made therefrom
WO2003029320A1 (fr) 2001-10-01 2003-04-10 Dow Global Technologies Inc. Polyols autocatalytiques presentant des caracteristiques de gelification, et produits en polyurethane obtenus a partir desdits polyols
WO2004020497A1 (fr) 2002-08-28 2004-03-11 Basf Aktiengesellschaft Procede de preparation de materiaux expanses souples polyurethane a emissions faibles
EP1537159A1 (fr) 2002-08-28 2005-06-08 Basf Aktiengesellschaft Procede de preparation de materiaux expanses souples polyurethane a emissions faibles
WO2004060956A1 (fr) 2002-12-17 2004-07-22 Dow Global Technologies Inc. Polymeres autocatalytiques amine-epoxy et produits de polyurethanne fabriques a partir de ces polymeres
WO2004096882A1 (fr) 2003-04-25 2004-11-11 Dow Global Technologies, Inc. Huile vegetale a base de polyols et polyurethannes conçus a partir de celle-ci
US20060293400A1 (en) 2003-04-25 2006-12-28 Wiltz Jr Eugene P Dow global technologies inc
US20070282026A1 (en) 2003-07-24 2007-12-06 Huntsman Petrochemical Corporation Low-Odor Catalyst for Isocyanate-Derived Foams and Elastomers
EP1678232A2 (fr) 2003-09-30 2006-07-12 Cargill, Incorporated Polyurethane expanse souple prepare a l'aide de polyols a base d'huiles vegetales modifiees
WO2005033167A2 (fr) 2003-09-30 2005-04-14 Cargill Incorporated Polyurethane expanse souple prepare a l'aide de polyols a base d'huiles vegetales modifiees
EP1520870A1 (fr) 2003-10-04 2005-04-06 Goldschmidt GmbH Procédé pour préparation des combinaisons organiques de silicium
EP1544235A1 (fr) 2003-12-15 2005-06-22 Air Products And Chemicals, Inc. Tensioactifs aux silicones utilisés dans des mousses de polyuréthanne rigides obtenues avec des agents gonflants du type hydrocarbures
WO2005063841A1 (fr) 2003-12-23 2005-07-14 Dow Global Technologies Inc. Procede de production de produits en polyurethanne au moyen de polyols de polyether autocatalytiques a coiffe amine tertiaire
DE102004001408A1 (de) 2004-01-09 2005-07-28 Goldschmidt Ag Verwendung blockweise aufgebauter Polyethersiloxane als Stabilisatoren in Polyurethanschäumen
WO2005085310A2 (fr) 2004-03-08 2005-09-15 Rathor Ag Prépolymères de polyuréthanne à stabilité de phase
WO2005118668A1 (fr) 2004-05-25 2005-12-15 General Electric Company Procede de preparation de mousses de polyurethane ayant des emissions en composes organiques volatils reduites
WO2006055396A1 (fr) 2004-11-17 2006-05-26 Dow Global Technologies, Inc. Polyols autocatalytiques a base d'amine bloques par un acide et mousses de polyurethanne produites a partir desdits polyols
WO2006094227A2 (fr) 2005-03-03 2006-09-08 South Dakota Soybean Processors, Llc Nouveaux polyols issus d'une huile vegetale au moyen d'un procede d'oxydation
US20060229375A1 (en) 2005-04-06 2006-10-12 Yu-Ling Hsiao Polyurethane foams made with alkoxylated vegetable oil hydroxylate
EP1712578A1 (fr) 2005-04-13 2006-10-18 Bayer MaterialScience LLC Mousses de polyuréthane à base d'huile végétale hydroxylée, de polyol polymère et d'alcool aliphatique polyhydroxy
WO2006116456A1 (fr) 2005-04-25 2006-11-02 Cargill, Incorporated Mousses de polyurethane comprenant des polyols oligomeriques
US20080234402A1 (en) 2005-09-01 2008-09-25 Basf Se Polyisocyanurate Rigid Foam and Method for the Production Thereof
US20070072951A1 (en) 2005-09-27 2007-03-29 Bender Jared D Silanol-functionalized compounds for the preparation of polyurethane foams
EP1945222B1 (fr) 2005-11-02 2012-12-26 Bayer Pharma Aktiengesellschaft Derives pyrrolo[2,1-f] [1,2,4] triazin-4-ylamines comme inhibiteurs de la igf-1r kinase pour le traitement des cancers et d'autres maladies hyperproliferatives
WO2007111828A2 (fr) 2006-03-23 2007-10-04 Dow Global Technologies Inc. Mousse de polyurethane de basse densite a base d'huile naturelle sans additif de stabilisation de cellules a base de silicone
US20070238800A1 (en) 2006-04-11 2007-10-11 Bayer Materialscience Llc Storage stable isocyanate-reactive component containing vegetable oil-based polyol
EP1977825A1 (fr) 2006-07-13 2008-10-08 Air Products and Chemicals, Inc. N,N,N'-triméthyl-bis-(aminoéthyl) éther et ses dérivés en tant que catalyseurs pour polyuréthanes
WO2008058913A1 (fr) 2006-11-15 2008-05-22 Basf Se Procédé de fabrication de mousses souples en polyuréthanne
EP2104696B1 (fr) 2006-12-21 2013-09-11 Dow Global Technologies LLC Catalyse de polyuréthane à partir de la combinaison de polyol autocatalytique et d'urée
EP1985642A1 (fr) 2007-04-25 2008-10-29 Air Products and Chemicals, Inc. Additifs pour améliorer le durcissement de surface et la stabilité dimensionnelle de mousses de polyuréthane
EP1985644A1 (fr) 2007-04-26 2008-10-29 Air Products and Chemicals, Inc. Composition de polyamine
EP2042534A1 (fr) 2007-09-28 2009-04-01 Evonik Goldschmidt GmbH Catalyseur par amine adapté à la fabrication de mousses de polyuréthane flexibles pauvres en émissions et résistant à la recatalyse
DE102007046860A1 (de) 2007-09-28 2009-04-09 Evonik Goldschmidt Gmbh Aminkatalysatoren geeignet zur Herstellung emissionsarmer, rekatalysestabiler Polyurethanweichschaumstoffe
WO2009058367A1 (fr) 2007-11-01 2009-05-07 Cargill, Incorporated Polyols de polyester dérivés d'huile naturelle et polyuréthanes obtenus à partir de ceux-ci
WO2009130470A1 (fr) 2008-04-25 2009-10-29 Imperial Innovations Limited Complexes catalytiques bimétalliques pour la copolymérisation de dioxyde de carbone et d’un époxyde
WO2010028362A1 (fr) 2008-09-08 2010-03-11 Novomer, Inc. Compositions de polycarbonate-polyol et procédés
WO2011163133A1 (fr) 2010-06-20 2011-12-29 Novomer, Inc. Polycarbonates aliphatiques
WO2013022932A1 (fr) 2011-08-08 2013-02-14 Novomer, Inc. Catalyseurs et procédés de synthèse de polymères
WO2013102053A1 (fr) 2011-12-29 2013-07-04 Dow Global Technologies Llc Polyéther polyols d'amine et compositions de mousse polyuréthane fabriquée à partir de composés amine cycliques

Non-Patent Citations (21)

* Cited by examiner, † Cited by third party
Title
"KUNSTSTOFFHANDBUCH", 1983
"KUNSTSTOFFHANDBUCH", 1993
"Kunststoffhandbuch", vol. 7, 1966, CARL-HANSER-VERLAG
"Ullmann's Encylopedia of Industrial Chemistry", vol. 2, 2012, WILEY-VCH, article "Amines, Aliphatic", pages: 647 - 698
AITKEN ET AL., TETRAHEDRON, vol. 58, no. 29, 2002, pages 5933 - 5940
BELLER ET AL., CHEM. ASIAN J., vol. 2, 2007, pages 403 - 410
BÖRNER ET AL., CHEMCATCHEM, vol. 2, 2010, pages 640 - 643
E. FARKAS; C. J. SUNMAN, J. ORG. CHEM., vol. 50, 1985, pages 1110
G. JENNER ET AL., JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 373, 1989, pages 343 - 352
H. T. CLARKE ET AL., J. AM. CHEM. SOC., vol. 55, 1933, pages 4571
J. CASANOVA; P. DEVI, SYNTH. COMMUN., vol. 23, 1993, pages 245
JENNER ET AL., JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 373, 1989, pages 343 - 352
MILSTEIN ET AL., ANGEW. CHEM., vol. 120, 2008, pages 8789 - 8792
MOFFETT ET AL., JOURNAL OF ORGANIC CHEMISTRY, vol. 14, 1949, pages 862 - 866
O. WALLACH, ANN., vol. 272, 1892, pages 99
ORG. SYNTH. COLL., vol. IV, 1963, pages 834FF
R. LEUCKART, BER., vol. 18, pages 2341
REPPE ET AL., JUSTUS LIEBIGS ANNALEN DER CHEMIE, vol. 596, 1955, pages 1149
TIJSKENS ET AL., JOURNAL OF ORGANIC CHEMISTRY, vol. 60, no. 26, 1995, pages 8371 - 8374
W. ESCHWEILER, BER., vol. 38, 1905, pages 880
WATSON; WILLIAMS, SCIENCE, vol. 329, 2010, pages 635 - 636

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10870723B2 (en) 2015-07-07 2020-12-22 Evonik Operations Gmbh Production of polyurethane foam
US11851583B2 (en) 2016-07-19 2023-12-26 Evonik Operations Gmbh Process for producing porous polyurethane coatings using polyol ester additives
US11021608B2 (en) 2018-02-08 2021-06-01 Evonik Operations Gmbh Aqueous polyorganosiloxane hybrid resin dispersion
US11236204B2 (en) 2019-05-28 2022-02-01 Evonik Operations Gmbh Production of SiOC-bonded polyether siloxanes
US11377523B2 (en) 2019-05-28 2022-07-05 Evonik Operations Gmbh Process for producing non-cyclic alkoxy-functional polysiloxanes
EP3999232A4 (fr) * 2019-07-18 2023-06-07 Huntsman Petrochemical LLC Catalyseurs de pyrrolidine bloqués par un acide pour mousse de polyuréthane

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