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WO2018177990A1 - Method for preparing high resilience and soft polyurethane foam - Google Patents

Method for preparing high resilience and soft polyurethane foam Download PDF

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Publication number
WO2018177990A1
WO2018177990A1 PCT/EP2018/057606 EP2018057606W WO2018177990A1 WO 2018177990 A1 WO2018177990 A1 WO 2018177990A1 EP 2018057606 W EP2018057606 W EP 2018057606W WO 2018177990 A1 WO2018177990 A1 WO 2018177990A1
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WIPO (PCT)
Prior art keywords
carbamide
polyurethane foam
component
high resilience
soft polyurethane
Prior art date
Application number
PCT/EP2018/057606
Other languages
French (fr)
Inventor
Jun Zhang
Original Assignee
Covestro Deutschland Ag
Covestro Polymers (China) Co. Ltd.
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Publication date
Application filed by Covestro Deutschland Ag, Covestro Polymers (China) Co. Ltd. filed Critical Covestro Deutschland Ag
Publication of WO2018177990A1 publication Critical patent/WO2018177990A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/227—Catalysts containing metal compounds of antimony, bismuth or arsenic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
    • C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
    • 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
    • C08G18/1841—Catalysts containing secondary or tertiary amines or salts thereof having carbonyl groups which may be linked to one or more nitrogen or oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271—Hydroxyamines
    • C08G18/3275—Hydroxyamines containing two 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
    • C08G18/28—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
    • C08G18/409—Dispersions of polymers of C08G in organic compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6523—Compounds of group C08G18/3225 or C08G18/3271 or polyamines of C08G18/38
    • C08G18/6535—Compounds of group C08G18/3271
    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/0058—≥50 and <150kg/m3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent
    • 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
    • C08G2290/00—Compositions for creating anti-fogging
    • 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
    • C08G2350/00—Acoustic or vibration damping material

Definitions

  • the present invention belongs to polyurethane field. Specifically, it relates to a method for preparing a high resilience and soft polyurethane foam.
  • High resilience and soft polyurethane foam has been widely used in home decoration and automobile filed, such as for manufacturing sofa, mattress, pillow, automobile seat etc., due to its capability of providing superior comfort, support and physical properties.
  • the high resilience and soft polyurethane foam may be produced by continuous foaming process, non-continuous foaming process and moulding process.
  • Organic tertiary amines and organotin are commonly used as catalyst in traditional foaming formulations of high resilience and soft polyurethane foam so as to accelerate foam curing and moulding.
  • Catalysts that are relatively commonly used include tertiary amines such as dimethylaminoethyl ether, triethylenediamine, 2- [[2- [2- (dimethylamino)ethoxyethyl]methylamino]-ethanol, and dimethylethanolamine.
  • tertiary amines such as dimethylaminoethyl ether, triethylenediamine, 2- [[2- [2- (dimethylamino)ethoxyethyl]methylamino]-ethanol, and dimethylethanolamine.
  • Such amines provide many advantages such as high efficiency, high selectivity and easy operation to traditional foaming reactions and thus have been widely used in various applications of the polyurethane field.
  • Organotin such as dibutyltin dilaurate and stannous octoate have some toxicity.
  • the high resilience and soft polyurethane foam is widely used in the areas that come into frequent contact with human body such as sofa, mattress, pillow and automobile seat, which will continuously do harm to human body.
  • it has long been the development direction in polyurethane technical field to reduce release of VOC and irritating odor of polyurethane foam, and use of toxic substance in preparation thereof.
  • the technical problem to be solved by the present invention is to avoid use of toxic substances as far as possible and reduce release of VOC and irritating odor during preparation of high resilience and soft polyurethane foam.
  • a method for preparing a high resilience and soft polyurethane foam comprising the following steps: i) Mixing the following components and stirring to give component A as a uniform mixture:
  • Component B which is one or more polyisocyanates
  • a high resilience and soft polyurethane foam which is obtained by reaction of the following two components A and B:
  • Component A comprising:
  • Component B which is one or more polyisocyanates.
  • a composition in particular for the preparation of a high resilience and soft polyurethane foam, comprising carbamide and an organobismuth compound wherein the weight ratio of carbamide and organobismuth compound is 2 : 1 to less than 12 : 1.
  • the use of the above composition is provided as a catalyst in preparation of a high resilience and soft polyurethane foam.
  • the present invention can avoid use of tertiary amine catalyst and organotin by employing a harmless and environmental combination of carbamide and organobismuth as catalyst, while achieving the same foaming and curing effect, thus producing healthier and more environmental polyurethane foam articles with final mechanical properties satisfying usage requirements.
  • the composition for the preparation of a high resilience and soft polyurethane foam is substantially free of tertiary amine catalyst and organotin catalysts.
  • a method for preparing a high resilience and soft polyurethane foam comprising the following steps:
  • component A i) Mixing the following components and stirring to give component A as a uniform mixture:
  • Component B which is one or more polyisocyanates
  • al) can be one or more polyols, which are selected from polyether polyols, polymeric polyether polyols, polyurea polyols etc.
  • the polyether polyol has a mass average molecular weight of 500 to 8000 g/mol (Mw), determined by GPC (gel permeation chromatography) with PEG as standard and tetrahydrofurane as solvent, a functionality of 2 to 4 and an ethylene oxide content of 0 to 80 wt.- , preferably a molecular weight of 3500 to 6500 g/mol, a functionality of 3 and an ethylene oxide content of 10 to 80 wt.- .
  • polyether polyol examples that can be mentioned include the VORANOL 4701, VORANOL 4703 and VORANOL CP 1421 manufactured by Dow Chemical Company; Arcol 3553, Arcol polyol 3553, Arcol polyol 1362, Arcol polyol 5613, SBU polyol S240, Hyperlite 1629 and Hyperlite E848 manufactured by Covestro Polymers Company Limited; Caradol SC34-05, Caradol SC28-02, Caradol SC48-08 and Caradol SC56-16 manufactured by the company Shell; and JEFFOL G31-28 Polyol, JEFFOL G31-35 Polyol and JEFFOL G31-43 Polyol manufactured by the company Huntsman.
  • polyether polyol when referred to without defining it with “polymeric”, it is intended to mean the “polyether polyol” defined here, instead of the “polymeric polyether polyol” defined hereinafter, unless expressly stated otherwise.
  • the polymeric polyether polyol is preferably selected from the graft copolyethers in a polymeric dispersion prepared by graft polymerization of acrylonitrile and/or styrene and the like with polyether polyol, having a hydroxyl value of 16 to 35 mg KOH/g, an acrylonitrile and/or styrene content of 5 to 60wt.- and preferably of 25 to 45wt.- , based on the weight of the polymeric polyether polyols.
  • the hydroxyl value is in general determined according to ASTM D4274 throughout this application.
  • polyether polyol mentioned here is that commonly understood by those skilled in the art. Examples that can be mentioned include the VORALUX HL 431, SPECFLEX NC 700, VORANOL NC-701 and VORANOL 3943A manufactured by Dow Chemical Company; Arcol HS-200 and Hyperlite E-850 manufactured by Covestro Polymers Company Limited; and TPOP36-28, TPOP36-42, TPOP36-45 and TPOP93-28 manufactured by No. 3 Petrochemical Factory of Tianjin Petrochemical Corporation, and the like.
  • the polyurea polyol is preferably that prepared by in-situ stepwise polymerization of hydrazine and toluene diisocyanate in a polyether polyol, having a solid content of 10 to 40wt.- .
  • the "polyether polyol” mentioned here is that commonly understood by those skilled in the art.
  • the small molecule chain extender may be selected from those commonly used in preparation of high resilience and soft polyurethane foam, and preferably selected from diethanolamine, glycerol, triethanolamine, ethylene glycol, propylene glycol, butylene glycol, and the like.
  • the small molecule chain extender may be present in an amount of 0.1 to 4.0 pbw and preferably of 0.5 to 2.0 pbw, based on that the weight of the polyols is 100 pbw.
  • the foaming agent may be those commonly used in preparation of high resilience and soft polyurethane foam, such as water, liquid carbon dioxide, dichloromethane, fluorinated hydrocarbons, and the like.
  • Water may be present in an amount of 0.5 to 5 pbw, preferably of 1 to 4 pbw and particularly preferably of 2 to 3.5 pbw and a compound selected from liquid carbon dioxide, dichloromethane and fluorinated hydrocarbons in an amount of 0 to 50 pbw and preferably of 2 to 20 pbw may be used as foaming agent, based on that the weight of the polyols is 100 pbw.
  • the foam stabilizer may be selected from organosilicon surfactants, such as the Niax L- 5333 and Niax L-2100 manufactured by the company Momentive; and TEGOSTAB B 8681, TEGOSTAB B8715 and TEGOSTANB B 8719 manufactured by the company Evonik.
  • the foam stabilizer may be present in an amount of 0.05 to 5 pbw, preferably of 0.1 to 3 pbw, and particularly preferably of 0.4 to 1.5 pbw, based on that the weight of the polyols is 100 pbw.
  • the carbamide may be selected from those carbamide synthesized via experiments, or commercially available urea or carbamide for industrial use with purity of at least 98 wt.-%.
  • the carbamide may be present in an amount of 0.05 to 5 pbw, preferably of 0.1 to 4 pbw, and particularly preferably of 0.3 to 2 pbw, based on that the weight of the polyols is 100 pbw.
  • the organobismuth compound may be a bismuth-containing organic metal salt with a bismuth content of 5wt. to 40wt. .
  • the organobismuth compound that can be used in the present invention include, for example, bismuth 2-ethylhexanoate, bismuth laurate, bismuth neodecanoate, bismuth naphthenate, and the like, such as the Bicat 8118, Bicat 8108, Bicat 8124, Bicat 8106 and Bicat 8210 etc. available from the Shepherd Chemical Company, US.
  • the organobismuth compound may be present in an amount of 0.01 to 0.5 pbw, preferably of 0.05 to 0.3 pbw, and particularly preferably of 0.08 to 0.25 pbw, based on that the weight of the polyols is 100 pbw.
  • the weight ratio of carbamide and the organobismuth compound may in particular range from 2 : 1 to 10 : 1, preferably 3 : 1 to 10 : 1, particularly preferably 4 : 1 to 8 : 1.
  • the polyisocyanate in the component B may be selected from those commonly used in preparation of high resilience and soft polyurethane foam, and more preferably those easily obtained in industry, such as polyphenyl polymethylene polyisocyanates ("MDI"), for example prepared by aniline-formaldehyde condensation followed by phosgenation, and polyisocyanates with carbodiimide group, urethane group, allophanate group, isocyanurate group, urea group or biuret group (“modified polyisocyanates”), in particular from modified polyisocyanates derived from 2,4- and/or 2,6-toluene diisocyanates or 4,4'- and/or 2,4'-diphenylmethane diisocyanates, 2,4- and 2,6-toluene diisocyanates and mixtures thereof.
  • MDI polyphenyl polymethylene polyisocyanates
  • modified polyisocyanates in particular from modified polyisocyanates derived from 2,4- and/or 2,
  • the polyisocyanate may be present in an amount of 20 to 90 pbw, preferably of 30 to 60 pbw, and particularly preferably of 40 to 55 pbw, based on that the weight of the polyols is 100 pbw.
  • the mixing device may be either high pressure or low pressure mixing device, and a high pressure mixing device is preferred.
  • the ambient temperature may commonly be controlled at 10 to 35°C, preferably at 15 to 30°C, and particularly preferably at 20 to 25°C.
  • the catalyst system preferably provides reactivity to the foam such that the rise time of the foam is in the range of 60s to 240s. No undesirable phenomena such as collapse, cracking or shrinkage should occur.
  • a high resilience and soft polyurethane foam which is obtained by reaction of the following two components A and B:
  • Component A comprising:
  • Component B which is one or more polyisocyanates.
  • a composition comprising carbamide and an organobismuth compound wherein the weight ratio of carbamide and organobismuth compound is 2 : 1 to less than 12 : 1.
  • the composition may be used as a catalyst system for preparing a high resilience and soft polyurethane foam.
  • the organobismuth is preferably a bismuth-containing organic metal salt with a bismuth content of 5 wt.% to 40wt.%.
  • the organobismuth compound to be used in the present invention may include bismuth 2-ethylhexanoate, bismuth laurate, bismuth neodecanoate, bismuth naphthenate and the like, such as the Bicat 8118, Bicat 8108, Bicat 8124, Bicat 8106 and Bicat 8210 etc. available from the Shepherd Chemical Company, US.
  • the weight ratio of carbamide and the organobismuth compound may in particular range from 2 : 1 to 10 : 1, preferably 3 : 1 to 10 : 1, particularly preferably 4 : 1 to 8 : 1. According to a fifth aspect of the present invention, there is provided the use of the above composition as a catalyst system in preparation of a high resilience and soft polyurethane foam.
  • Foam hardness is measured in accordance with HG/T2489.
  • Polyol 1 polyether polyol, mass average molecular weight: 6000 g/ mol determined by GPC with PEG as standard and tetrahydrofurane as solvent, hydroxyl value: 28mg KOH/g, purchased as Arcol 1362 from Covestro Polymers Company Limited.
  • Polyol 2 polyurea polyol, hydroxyl value: 28mg KOH/g, solid content: 20 wt.-%, Functionality: 2 to 3, purchased as Multranol 9151 from Covestro Polymers Company Limited.
  • Polyol 3 polyether polyol, average molecular weight: Mw of 4500g/mol, determined by GPC with PEG as standard and tetrahydrofurane as solvent, hydroxyl value: 37mg KOH/g, purchased as SBU polyol S240 from Covestro Polymers Company Limited.
  • Niax L-5333 organosilicon surfactant, purchased as the company Momentive.
  • Bicat- 1 Bicat 8118 from the Shepherd Chemical Company, US, bismuth content: 16 wt.%.
  • Bicat-2 Bicat 8108 from the Shepherd Chemical Company, US, bismuth content: 20 wt.%.
  • DEOA diethanolamine chain extender
  • ISO 1 polyisocyanate, modified MDI with NCO content of 32%, purchased as Desmodur 3133 from Covestro Polymers Company Limited.
  • PENDRAULIK stirrer purchased from the company PENDRAULIK was used as a mixing device, with a rotation speed of 1000 rpm ⁇ 2500 rpm and a stirring time of less than 10 min.
  • the mixture component A and component B polyisocyanates were mixed and reacted with a two-component or multi-component polyurethane mixing device.
  • the mixing device used was a high pressure mixing device.
  • Example 1 was a comparative example using no organobismuth compound. Table 1 Raw materialsused and foaming process

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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)
  • Dispersion Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The present invention relates to a method for preparing a high resilience and soft polyurethane foam, comprising the following steps: i) mixing the following components and stirring to give component A as a uniform mixture: al) one or more polyols; a2) one or more small molecule chain extenders with a molecular weight smaller than 200 g/mol; a3) one or more blowing agents; a4) one or more foam stabilizers; a5) carbamide; a6) an organobismuth; wherein the weight ratio of carbamide and organobismuth compound is 2 : 1 to less than 12 : 1; ii) mixing the following component B with the component A to give a reaction mixture: component B, which is one or more polyisocyanates; and iii) reacting the reaction mixture to obtain the high resilience and soft polyurethane foam. The present invention can avoid use of tertiary amine catalyst and organotin by employing a harmless and environmental combination of carbamide and organobismuth as catalyst, while achieving the same foaming and curing effect, thus producing healthier and more environmental polyurethane foam articles with final mechanical properties satisfying usage requirements.

Description

Method for Preparing High resilience and soft polyurethane foam
Technical Field
The present invention belongs to polyurethane field. Specifically, it relates to a method for preparing a high resilience and soft polyurethane foam. Background Art
High resilience and soft polyurethane foam has been widely used in home decoration and automobile filed, such as for manufacturing sofa, mattress, pillow, automobile seat etc., due to its capability of providing superior comfort, support and physical properties. In industry, the high resilience and soft polyurethane foam may be produced by continuous foaming process, non-continuous foaming process and moulding process.
Organic tertiary amines and organotin are commonly used as catalyst in traditional foaming formulations of high resilience and soft polyurethane foam so as to accelerate foam curing and moulding. Catalysts that are relatively commonly used include tertiary amines such as dimethylaminoethyl ether, triethylenediamine, 2- [[2- [2- (dimethylamino)ethoxyethyl]methylamino]-ethanol, and dimethylethanolamine. Such amines provide many advantages such as high efficiency, high selectivity and easy operation to traditional foaming reactions and thus have been widely used in various applications of the polyurethane field. However, they have some volatility and irritating odor, which will do harm to human body and is one of the main components that contribute to VOC. Organotin such as dibutyltin dilaurate and stannous octoate have some toxicity. The high resilience and soft polyurethane foam is widely used in the areas that come into frequent contact with human body such as sofa, mattress, pillow and automobile seat, which will continuously do harm to human body. Thus, it has long been the development direction in polyurethane technical field to reduce release of VOC and irritating odor of polyurethane foam, and use of toxic substance in preparation thereof. Without the use of the tertiary amine and organotin catalysts during the traditional foaming processes, poor foaming phenomena such as slow foaming, collapse, cracking, poor surface curing and mechanical properties, defects in foam and poor moulding will be occurred, which will lead to incapability of production and application.
Therefore, there remains a need for developing a new method for preparing a high resilience and soft polyurethane foam, which is capable of avoiding use of toxic substances and reducing release of VOC and irritating odor.
Summary of the Invention
The technical problem to be solved by the present invention is to avoid use of toxic substances as far as possible and reduce release of VOC and irritating odor during preparation of high resilience and soft polyurethane foam.
The above technical problem is solved by the following technical solutions. According to a first aspect of the present invention, there provides a method for preparing a high resilience and soft polyurethane foam, comprising the following steps: i) Mixing the following components and stirring to give component A as a uniform mixture:
al) one or more polyols;
a2) one or more small molecule chain extenders with a molecular weight smaller than 200 g/mol;
a3) one or more blowing agents;
a4) one or more foam stabilizers;
a5) carbamide;
a6) an organobismuth compound;
wherein the weight ratio of carbamide and organobismuth compound is 2 : 1 to less than 12 : 1,
ii) Mixing the following component B with the component A to give a reaction mixture:
Component B, which is one or more polyisocyanates; and
iii) Reacting the reaction mixture to obtain the high resilience and soft polyurethane foam. According to a second aspect of the present invention, there provides the high resilience and soft polyurethane foam obtained by the above method.
According to a third aspect of the present invention, there provides a high resilience and soft polyurethane foam, which is obtained by reaction of the following two components A and B:
Component A, comprising:
al) one or more polyols;
a2) one or more small molecule chain extenders with a molecular weight smaller than 200 g/mol;
a3) one or more blowing agents;
a4) one or more foam stabilizers;
a5) carbamide;
a6) an organobismuth compound;
wherein the weight ratio of carbamide and organobismuth compound is 2 : 1 to less than 12 : 1,
Component B, which is one or more polyisocyanates.
According to a fourth aspect of the present invention, a composition is provided, in particular for the preparation of a high resilience and soft polyurethane foam, comprising carbamide and an organobismuth compound wherein the weight ratio of carbamide and organobismuth compound is 2 : 1 to less than 12 : 1.
According to a fifth aspect of the present invention, the use of the above composition is provided as a catalyst in preparation of a high resilience and soft polyurethane foam.
The present invention can avoid use of tertiary amine catalyst and organotin by employing a harmless and environmental combination of carbamide and organobismuth as catalyst, while achieving the same foaming and curing effect, thus producing healthier and more environmental polyurethane foam articles with final mechanical properties satisfying usage requirements. Hence, according to a preferred embodiment of the invention, the composition for the preparation of a high resilience and soft polyurethane foam is substantially free of tertiary amine catalyst and organotin catalysts. Detailed Description of the Invention
The embodiments for carrying out the invention are described hereinafter. According to a first aspect of the present invention, there provides a method for preparing a high resilience and soft polyurethane foam, comprising the following steps:
i) Mixing the following components and stirring to give component A as a uniform mixture:
al) one or more polyols;
a2) one or more small molecule chain extenders with a molecular weight smaller than 200 g/mol;
a3) one or more blowing agents;
a4) one or more foam stabilizers;
a5) carbamide;
a6) an organobismuth compound;
wherein the weight ratio of carbamide and organobismuth compound is 2 : 1 to less than 12 : 1,
ii) Mixing the following component B with the component A to give a reaction mixture:
Component B, which is one or more polyisocyanates; and
iii) Reacting the reaction mixture to obtain the high resilience and soft polyurethane foam. al) can be one or more polyols, which are selected from polyether polyols, polymeric polyether polyols, polyurea polyols etc. Preferably, the polyether polyol has a mass average molecular weight of 500 to 8000 g/mol (Mw), determined by GPC (gel permeation chromatography) with PEG as standard and tetrahydrofurane as solvent, a functionality of 2 to 4 and an ethylene oxide content of 0 to 80 wt.- , preferably a molecular weight of 3500 to 6500 g/mol, a functionality of 3 and an ethylene oxide content of 10 to 80 wt.- .
As the polyether polyol, examples that can be mentioned include the VORANOL 4701, VORANOL 4703 and VORANOL CP 1421 manufactured by Dow Chemical Company; Arcol 3553, Arcol polyol 3553, Arcol polyol 1362, Arcol polyol 5613, SBU polyol S240, Hyperlite 1629 and Hyperlite E848 manufactured by Covestro Polymers Company Limited; Caradol SC34-05, Caradol SC28-02, Caradol SC48-08 and Caradol SC56-16 manufactured by the company Shell; and JEFFOL G31-28 Polyol, JEFFOL G31-35 Polyol and JEFFOL G31-43 Polyol manufactured by the company Huntsman. In the present application, when "polyether polyol" is referred to without defining it with "polymeric", it is intended to mean the "polyether polyol" defined here, instead of the "polymeric polyether polyol" defined hereinafter, unless expressly stated otherwise.
The polymeric polyether polyol is preferably selected from the graft copolyethers in a polymeric dispersion prepared by graft polymerization of acrylonitrile and/or styrene and the like with polyether polyol, having a hydroxyl value of 16 to 35 mg KOH/g, an acrylonitrile and/or styrene content of 5 to 60wt.- and preferably of 25 to 45wt.- , based on the weight of the polymeric polyether polyols.
The hydroxyl value is in general determined according to ASTM D4274 throughout this application.
The "polyether polyol" mentioned here is that commonly understood by those skilled in the art. Examples that can be mentioned include the VORALUX HL 431, SPECFLEX NC 700, VORANOL NC-701 and VORANOL 3943A manufactured by Dow Chemical Company; Arcol HS-200 and Hyperlite E-850 manufactured by Covestro Polymers Company Limited; and TPOP36-28, TPOP36-42, TPOP36-45 and TPOP93-28 manufactured by No. 3 Petrochemical Factory of Tianjin Petrochemical Corporation, and the like. The polyurea polyol is preferably that prepared by in-situ stepwise polymerization of hydrazine and toluene diisocyanate in a polyether polyol, having a solid content of 10 to 40wt.- . The "polyether polyol" mentioned here is that commonly understood by those skilled in the art. The small molecule chain extender may be selected from those commonly used in preparation of high resilience and soft polyurethane foam, and preferably selected from diethanolamine, glycerol, triethanolamine, ethylene glycol, propylene glycol, butylene glycol, and the like. The small molecule chain extender may be present in an amount of 0.1 to 4.0 pbw and preferably of 0.5 to 2.0 pbw, based on that the weight of the polyols is 100 pbw.
The foaming agent may be those commonly used in preparation of high resilience and soft polyurethane foam, such as water, liquid carbon dioxide, dichloromethane, fluorinated hydrocarbons, and the like.
Water may be present in an amount of 0.5 to 5 pbw, preferably of 1 to 4 pbw and particularly preferably of 2 to 3.5 pbw and a compound selected from liquid carbon dioxide, dichloromethane and fluorinated hydrocarbons in an amount of 0 to 50 pbw and preferably of 2 to 20 pbw may be used as foaming agent, based on that the weight of the polyols is 100 pbw.
The foam stabilizer may be selected from organosilicon surfactants, such as the Niax L- 5333 and Niax L-2100 manufactured by the company Momentive; and TEGOSTAB B 8681, TEGOSTAB B8715 and TEGOSTANB B 8719 manufactured by the company Evonik.
The foam stabilizer may be present in an amount of 0.05 to 5 pbw, preferably of 0.1 to 3 pbw, and particularly preferably of 0.4 to 1.5 pbw, based on that the weight of the polyols is 100 pbw.
The carbamide may be selected from those carbamide synthesized via experiments, or commercially available urea or carbamide for industrial use with purity of at least 98 wt.-%.
The carbamide may be present in an amount of 0.05 to 5 pbw, preferably of 0.1 to 4 pbw, and particularly preferably of 0.3 to 2 pbw, based on that the weight of the polyols is 100 pbw.
The organobismuth compound may be a bismuth-containing organic metal salt with a bismuth content of 5wt. to 40wt. . The organobismuth compound that can be used in the present invention include, for example, bismuth 2-ethylhexanoate, bismuth laurate, bismuth neodecanoate, bismuth naphthenate, and the like, such as the Bicat 8118, Bicat 8108, Bicat 8124, Bicat 8106 and Bicat 8210 etc. available from the Shepherd Chemical Company, US.
The organobismuth compound may be present in an amount of 0.01 to 0.5 pbw, preferably of 0.05 to 0.3 pbw, and particularly preferably of 0.08 to 0.25 pbw, based on that the weight of the polyols is 100 pbw. The weight ratio of carbamide and the organobismuth compound may in particular range from 2 : 1 to 10 : 1, preferably 3 : 1 to 10 : 1, particularly preferably 4 : 1 to 8 : 1.
There is no special limitation on the mixing device and conditions employed to mix components so as to obtain the component A, and a low-speed mixer may be used.
The polyisocyanate in the component B may be selected from those commonly used in preparation of high resilience and soft polyurethane foam, and more preferably those easily obtained in industry, such as polyphenyl polymethylene polyisocyanates ("MDI"), for example prepared by aniline-formaldehyde condensation followed by phosgenation, and polyisocyanates with carbodiimide group, urethane group, allophanate group, isocyanurate group, urea group or biuret group ("modified polyisocyanates"), in particular from modified polyisocyanates derived from 2,4- and/or 2,6-toluene diisocyanates or 4,4'- and/or 2,4'-diphenylmethane diisocyanates, 2,4- and 2,6-toluene diisocyanates and mixtures thereof.
The polyisocyanate may be present in an amount of 20 to 90 pbw, preferably of 30 to 60 pbw, and particularly preferably of 40 to 55 pbw, based on that the weight of the polyols is 100 pbw. There is no special limitation on the mixing device and conditions employed to mix component A and component B. The mixing device may be either high pressure or low pressure mixing device, and a high pressure mixing device is preferred. The ambient temperature may commonly be controlled at 10 to 35°C, preferably at 15 to 30°C, and particularly preferably at 20 to 25°C.
In order to prepare the high resilience and soft polyurethane foam, it is usually desirable that during foaming process, the catalyst system preferably provides reactivity to the foam such that the rise time of the foam is in the range of 60s to 240s. No undesirable phenomena such as collapse, cracking or shrinkage should occur.
According to a second aspect of the present invention, there is provided a high resilience and soft polyurethane foam obtained by the above method.
According to a third aspect of the present invention, there is provided a high resilience and soft polyurethane foam, which is obtained by reaction of the following two components A and B:
Component A, comprising:
al) one or more polyols;
a2) one or more small molecule chain extenders with a molecular weight smaller than 200 g/mol;
a3) one or more blowing agents;
a4) one or more foam stabilizers;
a5) carbamide;
a6) an organobismuth;
wherein the weight ratio of carbamide and organobismuth compound is 2 : 1 to less than 12 : 1,
Component B, which is one or more polyisocyanates.
The types and amounts of the above components are the same as those described for the method for preparing the high resilience and soft polyurethane foam.
According to a fourth aspect of the present invention, a composition is provided, comprising carbamide and an organobismuth compound wherein the weight ratio of carbamide and organobismuth compound is 2 : 1 to less than 12 : 1. The composition may be used as a catalyst system for preparing a high resilience and soft polyurethane foam.
The organobismuth is preferably a bismuth-containing organic metal salt with a bismuth content of 5 wt.% to 40wt.%.
The organobismuth compound to be used in the present invention may include bismuth 2-ethylhexanoate, bismuth laurate, bismuth neodecanoate, bismuth naphthenate and the like, such as the Bicat 8118, Bicat 8108, Bicat 8124, Bicat 8106 and Bicat 8210 etc. available from the Shepherd Chemical Company, US.
The weight ratio of carbamide and the organobismuth compound may in particular range from 2 : 1 to 10 : 1, preferably 3 : 1 to 10 : 1, particularly preferably 4 : 1 to 8 : 1. According to a fifth aspect of the present invention, there is provided the use of the above composition as a catalyst system in preparation of a high resilience and soft polyurethane foam.
Unless defined otherwise, all the technical and scientific terms used herein have the same meanings as those commonly understood by those skilled in the art to which the present invention pertains. In the case that the definition of a term in the specification conflicts with that commonly understood by those skilled in the art to which the present invention pertains, the definition described herein controls. The present invention is illustrated through examples hereinafter. However, it is to be understood that the scope of the present invention is not limited to those examples.
Examples
The following test methods are employed in the following examples:
Rise time of foam is measured with the following equipments: a square wooden box of 20cm*20cm* 15cm in size, a PENDRAULIK stirrer and a stopwatch. Component B is poured into component A proportionally, the stirrer and the stopwatch are started at the same time. Foam rising is observed and the time at which the foam rises to the highest point is recorded as the rise time of the foam. Foam density is measured in accordance with ASTM D3574.
Foam hardness is measured in accordance with HG/T2489.
The following raw materials are used in the present examples:
Polyol 1 : polyether polyol, mass average molecular weight: 6000 g/ mol determined by GPC with PEG as standard and tetrahydrofurane as solvent, hydroxyl value: 28mg KOH/g, purchased as Arcol 1362 from Covestro Polymers Company Limited.
Polyol 2: polyurea polyol, hydroxyl value: 28mg KOH/g, solid content: 20 wt.-%, Functionality: 2 to 3, purchased as Multranol 9151 from Covestro Polymers Company Limited.
Polyol 3: polyether polyol, average molecular weight: Mw of 4500g/mol, determined by GPC with PEG as standard and tetrahydrofurane as solvent, hydroxyl value: 37mg KOH/g, purchased as SBU polyol S240 from Covestro Polymers Company Limited.
Niax L-5333: organosilicon surfactant, purchased as the company Momentive. Bicat- 1 : Bicat 8118 from the Shepherd Chemical Company, US, bismuth content: 16 wt.%.
Bicat-2: Bicat 8108 from the Shepherd Chemical Company, US, bismuth content: 20 wt.%.
DEOA: diethanolamine chain extender.
Urea: carbamide purity: 99 wt.%.
ISO 1 : polyisocyanate, modified MDI with NCO content of 32%, purchased as Desmodur 3133 from Covestro Polymers Company Limited.
Examples 1-8: Preparation of high resilience and soft polyure thane foam
The polyol, chain extender, foaming agent, foam stabilizer, carbamide and organobismuth were mixed uniformly with a stirrer in accordance with the quantities described in Table 1, to give component A as a mixture. PENDRAULIK stirrer purchased from the company PENDRAULIK was used as a mixing device, with a rotation speed of 1000 rpm~2500 rpm and a stirring time of less than 10 min.
The mixture component A and component B polyisocyanates were mixed and reacted with a two-component or multi-component polyurethane mixing device. The mixing device used was a high pressure mixing device.
Example 1 was a comparative example using no organobismuth compound. Table 1 Raw materialsused and foaming process
Figure imgf000012_0001
It can be seen from the above table that a normal effect on catalyzing foaming can be achieved by the combination of carbamide and the organobismuth compound. A rising time of 105 to 190 s was achieved and the articles were molded without considerable shrinkage. Therefore, a certain processing window was satisfied, operability was achieved, while the foam articles produced by the reaction possess ideal foam density and foam hardness, thereby being practical.
Although the present invention has been described above regarding the purpose of the present invention, it is to be understood that such a detailed description is merely illustrative. In addition to those that can be defined by claims, various modifications may be made by those skilled in the art without departing from the spirit and scope of the present invention.

Claims

Claims
1. A method for preparing a high resilience and soft polyurethane foam, wherein, comprising the following steps:
i) Mixing the following components and stirring to give component A as a uniform mixture:
al) one or more polyols;
a2) one or more small molecule chain extenders with a molecular weight smaller than 200 g/mol;
a3) one or more blowing agents;
a4) one or more foam stabilizers;
a5) carbamide;
a6) an organobismuth compound;
wherein the weight ratio of carbamide and organobismuth compound is 2 : 1 to less than 12 : 1 ;
ii) Mixing the following component B with the component A to give a reaction mixture:
Component B, which is one or more polyisocyanates; and
iii) Reacting the reaction mixture to obtain the high resilience and soft polyurethane foam.
2. The method according to Claim 1, characterized in that the al) one or more polyols are selected from polyether polyols, polymeric polyether polyols and polyurea polyols.
3. The method according to Claim 2, characterized in that the polyether polyol has a mass average molecular weight Mw of 500 to 8000 g/mol, determined by GPC with PEG as standard and tetrahydrofurane as solvent, a functionality of 2 to 4 and/or an ethylene oxide content of 0-80 wt.-%, based on the weight of the polyether polyol.
4. The method according to Claim 2 or 3, characterized in that the polymeric polyether polyol is selected from the graft copolyethers in polymeric dispersion prepared by graft polymerization of acrylonitrile and/or styrene with polyether polyol, having a hydroxyl value of 16 to 35 mg KOH/g according to ASTM D4274, an acrylonitrile and/or styrene content of 5 to 60 wt. , based on the weight of the polymeric polyether polyols.
5. The method according to any of Claims 2 to 4, characterized in that the polyurea polyol is selected from the polyurea polyols prepared by in-situ stepwise polymerization of hydrazine and toluene diisocyanate in the polyether polyol, having a solid content of 10 to 40wt.%.
6. The method according to any of the preceding Claims, characterized in that the small molecule chain extender is selected from diethanolamine, glycerol, triethanolamine, ethylene glycol, propylene glycol and butylene glycol.
7. The method according to any of the preceding Claims, characterized in that the foaming agent is selected from water, liquid carbon dioxide, dichloromethane and fluorinated hydrocarbons.
8. The method according to any of the preceding Claims, characterized in that the organobismuth compound is a bismuth-containing organic metal salt with a bismuth content of 5wt.% to 40wt.%.
9. The method according to any of the preceding Claims, characterized in that the weight ratio of carbamide and organobismuth compound is 2 : 1 to 10 : 1, preferably 3 :
1 to 10 : 1 , particularly preferably 4 : 1 to 8 : 1.
10. The method according to any of the preceding Claims, characterized in that the polyisocyanate in the component B is selected from polyphenyl polymethylene polyisocyanates and polyisocyanates with carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups, in particular from modified polyisocyanates derived from 2,4- and/or 2,6-toluene diisocyanates or 4,4'- and/or 2,4'-diphenylmethane diisocyanates, 2,4- and 2,6- toluene diisocyanates and mixtures thereof.
1 1. A high resilience and soft polyurethane foam obtained by a method according to any one of Claims 1 to 10.
12. A composition for the production of a high resilience and soft polyurethane foam, characterized in that it comprises carbamide and an organobismuth compound and wherein the weight ratio of carbamide and organobismuth compound is 2 : 1 to less than 12 : 1.
13. The composition according to Claim 12, characterized in that the organobismuth compound is a bismuth-containing organic metal salt with a bismuth content of 5 wt.% to 40wt.%.
14. The composition according to Claim 12 or 13, characterized in that the weight ratio of carbamide and organobismuth compound is 2 : 1 to 10 : 1, preferably 3 : 1 to 10 : 1 , particularly preferably 4 : 1 to 8 : 1.
15. Use of a composition according to any one of Claims 12 to 14 as a catalyst system in preparation of a high resilience and soft polyurethane foam.
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