WO2018050628A1 - Verfahren zur erniedrigung der aldehydemissionen von polyurethanschaumstoffen - Google Patents

Verfahren zur erniedrigung der aldehydemissionen von polyurethanschaumstoffen Download PDF

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WO2018050628A1
WO2018050628A1 PCT/EP2017/072870 EP2017072870W WO2018050628A1 WO 2018050628 A1 WO2018050628 A1 WO 2018050628A1 EP 2017072870 W EP2017072870 W EP 2017072870W WO 2018050628 A1 WO2018050628 A1 WO 2018050628A1
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parts
weight
butyl
component
phenol
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English (en)
French (fr)
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Stefan Lindner
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Covestro Deutschland AG
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Covestro Deutschland AG
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Application filed by Covestro Deutschland AG filed Critical Covestro Deutschland AG
Priority to EP17768422.2A priority Critical patent/EP3512896B1/de
Priority to JP2019513925A priority patent/JP7034143B2/ja
Priority to CN201780055879.1A priority patent/CN109661415B/zh
Priority to ES17768422T priority patent/ES2887328T3/es
Priority to US16/330,596 priority patent/US11572435B2/en
Priority to CA3035138A priority patent/CA3035138A1/en
Publication of WO2018050628A1 publication Critical patent/WO2018050628A1/de
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4833Polyethers containing oxyethylene units
    • C08G18/4837Polyethers containing oxyethylene units and other oxyalkylene units
    • C08G18/4841Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4804Two or more polyethers of different physical or chemical nature
    • C08G18/4812Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4833Polyethers containing oxyethylene units
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/125Water, e.g. hydrated salts
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/13Phenols; Phenolates
    • C08K5/134Phenols containing ester groups
    • C08K5/1345Carboxylic esters of phenolcarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00Foam properties
    • C08G2110/0083Foam properties prepared using water as the sole blowing agent
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00Foams characterized by the expanding agent
    • C08J2203/10Water or water-releasing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04Polyurethanes
    • C08J2375/08Polyurethanes from polyethers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/019Specific properties of additives the composition being defined by the absence of a certain additive

Definitions

  • the present invention relates to a process for the preparation of low-aldehyde-emitting polyurethanes using high levels of phenolic antioxidants. Furthermore, the present invention relates to the polyurethanes obtainable from this process, as well as the use of such polyurethanes, for example in the interior of automobiles.
  • Polyurethanes are characterized by a variety of uses, for example in the furniture industry as a seat cushion or as a binder for chipboard, as insulating material in the construction industry, as insulating material, such as pipes, hot water tanks or refrigerators and as trim parts, for example in vehicle manufacturing.
  • polyurethanes are frequently used, for example in the automobile outer lining as spoilers, roof elements, spring elements and in the automotive interior trim as roof linings, carpet underfoaming, door linings, steering wheels, shift knobs and seat cushions.
  • the emission values should not exceed 160 ⁇ g / m 3 (VDA 276).
  • VDA 278 the emission of other substances harmful to health or the environment, in particular of substances that can be detected in the emissions test in accordance with VDA 278, should be avoided as far as possible.
  • the present invention therefore provides a process for producing polyurethane foams by reacting component A comprising Al with respect to isocyanates reactive hydrogen atoms containing compounds having an OH number according to DIN 53240 of> 15 to ⁇ 280 mg KOH / g,
  • A2 optionally having isocyanate-reactive hydrogen atoms
  • A4 possibly additives and additives like
  • A5 one or more phenolic antioxidants, except 2,4-dimethyl-6-ocytyl-phenol, 2,6-di-t-butyl-4-methyl-phenol, 2,6-di-t-butyl-4-ethyl phenol, 2,6-di-t-butyl-4-n-butylphenol, 2,2'-methylenebis (4-methyl-6-t-butyl-phenol) and 2,2'-methylenebis (4 ethyl-6-t-butylphenol),
  • component A5 in amounts of> 0.07 parts by weight, preferably> 0.08 parts by weight, particularly preferably> 0.1 parts by weight, based on 100 parts by weight of component AI, is used, and
  • component A in addition to the antioxidant A5 up to 0.01 parts by weight ( ⁇ 0.01 parts by weight), based on 100 parts by weight of component AI, of antioxidants having amino groups may contain.
  • the present invention also provides a process as described above, wherein i) component A contains no antioxidants in addition to the antioxidant A5, the
  • component A contains no other antioxidants in addition to the antioxidant A5.
  • aminic antioxidants leads to high levels in the emissions test according to VDA 278.
  • the emission of amines should be avoided for environmental and health reasons, or at least kept as low as possible.
  • the present invention particularly relates to a process for the preparation of polyurethane foams by reacting component A comprising
  • Parts by weight of components AI to A4) are reactive toward isocyanates
  • A2 0 to 10 parts by wt., Preferably 0.1 to 2 parts by wt. (Based on the sum of the parts by wt. Of components AI to A4) against isocyanates of reactive hydrogen atoms containing compounds having an OH number according to DIN 53240 of > 280 to
  • A3 0.5 to 25 parts by wt., Preferably 2 to 5 parts by wt. (Based on the sum of the parts by wt. Of components AI to A4) of water and / or physical blowing agents,
  • auxiliaries and additives such as
  • component A in addition to the antioxidant A5 up to 0.01 parts by weight ( ⁇ 0.01 parts by weight), based on 100 parts by weight of component AI, of antioxidants having amino groups may contain, and
  • the preparation is carried out at a ratio of 50 to 250, preferably 70 to 130, particularly preferably 75 to 115, and
  • component A contains no other antioxidants in addition to the antioxidant A5.
  • Another object of the invention is the use of phenolic antioxidants, except 2,4-dimethyl-6-ocytyl-phenol, 2,6-di-t-butyl-4-methyl-phenol, 2,6-di-t-butyl 4-ethylphenol, 2,6-di-t-butyl-4-n-butylphenol, 2,2'-methylenebis (4-methyl-6-t-butyl-phenol) and 2,2'-di-tert-butylphenol; Methylenebis- (4-ethyl-6-t-butyl-phenol), in processes for the preparation of polyurethanes, preferably polyurethane foams for lowering the aldehyde emission of the resulting polyurethanes, or polyurethane foams, characterized in that the phenolic antioxidants in amounts of> 0.07 Parts by weight, preferably> 0.08 parts by weight, more preferably> 0.1 parts by weight, based on 100 parts
  • the present invention also relates to the use as described above, wherein i) in addition to the phenolic antioxidants no antioxidants are included, the
  • isocyanate-based foams in addition to the phenolic antioxidants no other antioxidants are included.
  • the preparation of isocyanate-based foams is known per se and, for example, in DE-A 1 694 142, DE-A 1 694 215 and DE-A 1 720 768 and in the Kunststoff-Handbuch Volume VII, Polyurethanes, published by Vieweg and Höchtlein, Carl Hanser Verlag Kunststoff 1966, and in the new edition of this book, edited by G. Oertel, Carl Hanser Verlag Kunststoff, Vienna 1993 described.
  • foams having urethane and / or uretdione and / or urea and / or carbodiimide groups.
  • the use according to the invention is preferably carried out in the production of polyurethane and polyisocyanurate foams.
  • the moldings preferably have a density between 15 and 120 kg / m 3 , more preferably between 30 and 90 kg / m 3 .
  • Starting components according to component AI are compounds having at least two isocyanate-reactive hydrogen atoms having an OH number according to DIN 53240 of> 15 to ⁇ 280 mg KOH / g.
  • PHD polyols and PIPA polyols in component AI can be used.
  • Polymer polyols are polyols which contain portions of free-radical-polymerization-capable monomers such as styrene or acrylonitrile in a base polyol-produced solid polymer.
  • PHD (polyurea dipserion) polyols are prepared by in situ polymerization of an isocyanate or an isocyanate mixture with a diamine and / or hydrazine in a polyol, preferably a polyether polyol.
  • the PHD dispersion is prepared by reacting an isocyanate mixture of 75 to 85 wt .-% 2,4-tolylene diisocyanate (2,4-TDI) and 15 to 25 wt .-% 2,6-tolylene diisocyanate (2.6 -TDI) with a diamine and / or hydrazine in a polyether polyol, preferably a polyether polyol prepared by alkoxylation of a trifunctional initiator (such as glycerol and / or trimethylolpropane).
  • a trifunctional initiator such as glycerol and / or trimethylolpropane
  • the PIPA polyols are polyisocyanate polyaddition with alkanolamine-modified polyether polyols, the polyether polyol having a functionality of 2.5 to 4 and a hydroxyl number of> 3 mg KOH / g to ⁇ 112 mg KOH / g (molecular weight 500 to 18000).
  • PIPA polyols are described in detail in GB 2 072 204 A, DE 31 03 757 A1 and US Pat. No. 4,374,209.
  • hydroxyl-containing polyether having an OH number according to DIN 53240 of> 20 to ⁇ 50 mg KOH / g are used, wherein the OH groups to> 80 mol% of primary OH groups consist (determination by means of ⁇ - ⁇ (eg Bruker DPX 400, deuterochloroform)).
  • the OH number is particularly preferably from> 25 to ⁇ 40 mg KOH / g, very particularly preferably from> 25 to ⁇ 35 mg KOH / g.
  • component A2 compounds having at least two isocyanate-reactive hydrogen atoms and an OH number according to DIN 53240 of> 280 to ⁇ 4000 mg KOH / g, preferably> 400 to ⁇ 3000 mg KOH / g, more preferably> 1000 to ⁇ 2000 mg KOH / g used.
  • These are to be understood as meaning hydroxyl-containing and / or amino-containing and / or thiol-containing and / or carboxyl-containing compounds, preferably hydroxyl-containing and / or amino-containing compounds which serve as chain extenders or crosslinkers.
  • These compounds generally have from 2 to 8, preferably from 2 to 4, isocyanate-reactive hydrogen atoms.
  • component A2 ethanolamine, diethanolamine, triethanolamine, sorbitol and / or glycerol can be used as component A2. Further examples of compounds according to component A2 are described in EP-A 0 007 502, pages 16-17.
  • Component A3 is described in EP-A 0 007 502, pages 16-17.
  • component A3 water and / or physical blowing agents are used.
  • physical blowing agents for example, carbon dioxide and / or volatile organic substances are used as blowing agents.
  • auxiliary agents and additives are optionally used, such as
  • surfactants such as emulsifiers and foam stabilizers insbesodere those with low emissivity such as products of Tegostab ® LF2-
  • reaction retarders eg acidic substances such as hydrochloric acid or organic acid halides
  • cell regulators such as paraffins or fatty alcohols or dimethylpolysiloxanes
  • pigments such as TCPP
  • flame retardants such as TCPP
  • plasticizers such as fungistatic and bacteriostatic substances
  • fillers such as barium sulfate, kieselguhr, soot or whiting
  • release agents such as reaction retarders (eg acidic substances such as hydrochloric acid or organic acid halides), cell regulators (such as paraffins or fatty alcohols or dimethylpolysiloxanes), pigments, dyes, flame retardants (such as TCPP), stabilizers against aging and weathering, plasticizers, fungistatic and bacteriostatic substances, fillers (such as barium sulfate, kieselguhr, soot or whiting) and release agents.
  • reaction retarders eg acidic substances such as hydrochloric acid
  • auxiliaries and additives are described, for example, in EP-A 0 000 389, pages 18-21. Further examples of auxiliaries and additives which may optionally be used according to the invention and details of the use and mode of action of these auxiliaries and additives are published in the Kunststoff-Handbuch, Volume VII, by G. Oertel, Carl Hanser Verlag, Kunststoff, 3rd edition, 1993 , eg on pages 104-127.
  • Suitable catalysts are aliphatic tertiary amines (for example triethylamine, tetramethylbutanediamine), cycloaliphatic tertiary amines (for example 1,4-diaza (2,2,2) bicyclooctane), aliphatic aminoethers (for example dimethylaminoethyl ether and N, N, N-trimethyl-N- hydroxyethyl bisaminoethyl ethers), cycloaliphatic amino ethers (for example N-ethylmorpholine), aliphatic amidines, cycloaliphatic amidines, urea, derivatives of urea (such as, for example, aminoalkyl ureas, see, for example, EP-A 0 176 013, in particular (3-dimethylaminopropylamine) urea), and tin catalysts (such as dibutyltin oxide, dibutyltin dilaurate, tin
  • ß ß
  • ß ß
  • amines and amino ethers which each contain a functional group which reacts chemically with the isocyanate.
  • the functional group is a hydroxyl group, a primary or secondary amino group.
  • catalysts are: (3-dimethylaminopropylamine) urea, 2- (2-dimethylaminoethoxy) ethanol, N, N-bis (3-dimethyl-aminopropyl) -N-isopropanolamine, N, N, N-trimethyl N-hydroxyethyl bisaminoethyl ether and 3-Dimethy laminopropy 1 amine.
  • no tin catalysts are used.
  • component A5 comprises a phenolic antioxidant.
  • Phenolic antioxidants are, for example, tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane, ⁇ , ⁇ '-1,6-hexamethylene-bis-3- (3,5-di-t-butyl 4-hydroxyphenyl) propionamide, alkyl-3- (3,5-di-t-butyl-4-hydroxyphenylpropionate) where alkyl is a carbon radical having> 1 C atom, preferably> 6 C atoms, particularly preferably> 8 C Atoms, very particularly preferably> 9 C atoms (for example octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenylpropionate)), ethylene- (bisoxyethylene) bis- (3, (5-t -butylhydroxy-4-tolyl) -propionate 4,4'-Butylidenbis-
  • Compounds used with a molecular weight of> 380 g / mol, more preferably> 400 g / mol, very particularly preferably> 500 g / mol, are preferably used as component A5.
  • component A5 preference is given to using compounds having> 25 C atoms, particularly preferably> 26 C atoms, very particularly preferably> 30 C atoms.
  • the amount of component A5 used, based on 100 parts by weight of component AI, is> 0.07 parts by weight, preferably> 0.08 parts by weight, more preferably> 0.1 parts by weight.
  • the maximum usage of component A5 is preferably ⁇ 0.4, more preferably ⁇ 0.3 and very particularly preferably 0.25 parts by weight, based on 100 parts by weight of component AI.
  • component A contains, in addition to the antioxidant A5,> 0.05 to ⁇ 4.0, preferably> 0.1 to ⁇ 1.0, particularly preferably> 0.2 to ⁇ 0.4 part by weight of tris-dipropylene glycol phosphite, based on 100 parts by weight of component AI.
  • component B aliphatic, cycloaliphatic, aliphatic, aromatic and heterocyclic polyisocyanates are used, as they are e.g. by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, for example those of the formula (V)
  • n 2 - 4, preferably 2 -3,
  • Q is an aliphatic hydrocarbon radical having 2 to 18, preferably 6 to 10 C atoms, a cycloaliphatic hydrocarbon radical having 4 to 15, preferably 6 to 13 C atoms or an aliphatic hydrocarbon radical having 8 to 15, preferably 8 to 13, C atoms.
  • polyisocyanates as described in EP-A 0 007 502, pages 7-8.
  • the technically readily available polyisocyanates for example the tolylene 2,4- and 2,6-diisocyanate, and any desired mixtures of these isomers (“TDI”) are particularly preferred; polyphenylpolymethylene polyisocyanates, as prepared by aniline-formaldehyde condensation and subsequent phosgenation are ("crude MDI") and carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret polyisocanates ("modified polyisocyanates” or "prepolymers”), in particular those modified polyisocyanates derived from 2,4- and / or 2,6 - Derive tolylene diisocyanate or from 4,4'- and / or 2,4'- and / or 2,2'-diphenylmethane diisocyanate.
  • component B at least one compound selected from the group consisting of 2,4- and 2,6-toluene diisocyanate, 4,4'- and 2,4'- and 2,2'-diphenylmethane diisocyanate and Polyphenylpolymethylenpolyisocyanat ("multi-core MDI "), more preferably at least one compound selected from the group consisting of 4,4'- and 2,4'- and 2,2'-diphenylmethane diisocyanate and polyphenylpolymethylene polyisocyanate (“multi-core MDI”) are used.
  • multi-core MDI polyphenylpolymethylene polyisocyanate
  • the mixtures of diphenylmethane diisocyanate and polyphenylene polymethylene polyisocyanate have a preferred monomer content of between 50 and 100% by weight, preferably between 60 and 95% by weight, particularly preferably between 75 and 90% by weight.
  • the NCO content of the polyisocyanate used should preferably be above 25% by weight, preferably above 30% by weight, particularly preferably above 31.4% by weight.
  • the MDI used should have a content of 2,4'-diphenylmethane diisocyanate of at least 3% by weight, preferably at least 15% by weight.
  • reaction components are reacted according to the conventional one-step process, the prepolymer process or the semi-prepolymer process, often using mechanical equipment, e.g. those described in EP-A 355 000. Details of processing means which are also contemplated by this invention are described in the Kunststoff-Handbuch, Volume VII, edited by Vieweg and Hochtlen, Carl-Hanser-Verlag, Kunststoff 1993, e.g. on pages 139 to 265.
  • the polyurethane foams can be produced as molded or also as block foams. Preferably, they are produced as molded foams.
  • the molded foams can be produced in hot or cold foam behavior, preferred is the cold foam process
  • the invention therefore relates to a process for the preparation of the polyurethane foams, the polyurethane foams produced by this process and their use for the production of moldings and the moldings themselves.
  • the polyurethane foams obtainable according to the invention are used, for example, in furniture upholstery, textile inserts, mattresses, automobile seats, headrests, armrests, sponges and construction elements, as well as seat and armature coverings, and have characteristic numbers of 50 to 250, preferably 70 to 130, particularly preferably 75 to 115 on.
  • the index indicates the percentage ratio of the actual amount of isocyanate used to the stoichiometric, ie calculated isocyanate groups (NCO) amount:
  • Ratio [(amount of isocyanate used): (calculated amount of isocyanate)] ⁇ 100 (VI)
  • the starting materials listed in the examples of the following table are reacted with each other.
  • the reaction mixture is introduced into a metal mold heated to 60 ° C. and previously coated with a release agent (PURA E1429H NV (Chem-Trend)) and the mold is then closed.
  • the amount used is determined according to the desired density and
  • Shapes volume used It was worked with 9.7 liters of mold.
  • the density of the molded parts is 50 kg / m 3 .
  • the mold parts were removed from the mold after 4 minutes and pressed.
  • the moldings were sealed in aluminum composite foil after 4 hours and then sent for emission testing.
  • Polyol A Glycerol started polyol with an OH number according to DIN 53240 of 27 mg KOH / g. KOH catalyzed the glycerin was first propoxylated (85%) and danack ethoxylated (15%). The product contains 85 mol% of primary OH groups (determined by means of H-NMR (Bruker DPX 400, deuterochloroform).
  • Polyol B EO-rich polyol: Desmophen 41WB01; Product of Covestro
  • Irganox 1076 product of BASF; Octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate
  • Niax color stabilizer CS-22LF Product of Momentive. Chemical characterization: tris dipropylene glycol phosphite
  • Dabco NE 300 product of Air Products
  • Diphenylmethane diisocyanate is about 19% by weight.
  • the NCO content is 32.6% by weight.
  • VDA 276 determination of organic components of the emissions from automotive interior in a test chamber 3, test standard of the association of the automotive industry. Conditioning phase 1.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
PCT/EP2017/072870 2016-09-13 2017-09-12 Verfahren zur erniedrigung der aldehydemissionen von polyurethanschaumstoffen Ceased WO2018050628A1 (de)

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EP17768422.2A EP3512896B1 (de) 2016-09-13 2017-09-12 Verfahren zur erniedrigung der aldehydemissionen von polyurethanschaumstoffen
JP2019513925A JP7034143B2 (ja) 2016-09-13 2017-09-12 ポリウレタンフォームのアルデヒド放出を軽減する方法
CN201780055879.1A CN109661415B (zh) 2016-09-13 2017-09-12 降低聚氨酯泡沫的醛排放的方法
ES17768422T ES2887328T3 (es) 2016-09-13 2017-09-12 Procedimiento para reducir las emisiones de aldehídos de las espumas de poliuretano
US16/330,596 US11572435B2 (en) 2016-09-13 2017-09-12 Method for reducing the aldehyde emissions of polyurethane foams
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EP3720893B1 (en) 2017-12-08 2021-06-23 Shell Internationale Research Maatschappij B.V. Antioxidant for low-density polyurethane foam

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EP3293218A1 (de) 2018-03-14
CN109661415A (zh) 2019-04-19
EP3512896A1 (de) 2019-07-24
US20210292467A1 (en) 2021-09-23
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