EP1516005A1 - Procede de production de mousses de polyurethanne - Google Patents

Procede de production de mousses de polyurethanne

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Publication number
EP1516005A1
EP1516005A1 EP03740193A EP03740193A EP1516005A1 EP 1516005 A1 EP1516005 A1 EP 1516005A1 EP 03740193 A EP03740193 A EP 03740193A EP 03740193 A EP03740193 A EP 03740193A EP 1516005 A1 EP1516005 A1 EP 1516005A1
Authority
EP
European Patent Office
Prior art keywords
acrylate
parts
meth
acrylates
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP03740193A
Other languages
German (de)
English (en)
Inventor
Dieter Rodewald
Bernd Bruchmann
Horst Binder
Heinz-Dieter Lutter
Ansgar Frericks
Markus Templin
Martin Kreyenschmidt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1516005A1 publication Critical patent/EP1516005A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • 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
    • 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
    • C08G2110/0016—Foam properties semi-rigid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/005—< 50kg/m3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

Definitions

  • the invention relates to a process for the production of polyurethane foams, in particular flexible and semi-rigid foams by reaction of polyisocyanates with compounds having at least two hydrogen atoms reactive with isocyanate groups.
  • Polyurethane foams have been known for a long time and have been described many times in the literature. They are usually prepared by reacting isocyanates with compounds having at least two hydrogen atoms reactive with isocyanate groups. Usually aromatic di- and polyisocyanates are used as isocyanates, isomers of tolylene diisocyanate (TDI), isomers of diphenylmethane diisocyanate (MDI) and mixtures of diphenylmethane diisocyanate and polymethylene-polyphenylene-poly-isocyanates (crude MDI) having the greatest technical importance.
  • TDI tolylene diisocyanate
  • MDI diphenylmethane diisocyanate
  • CAde MDI polymethylene-polyphenylene-poly-isocyanates
  • Polyurethane foams like biological materials, are subject to an aging process which generally leads to a significant deterioration in the properties of the product over time.
  • Significant aging influences are, for example, hydrolysis, photooxidation and thermal oxidation, which lead to bond breaks in the polymer chain.
  • the action of moisture and elevated temperatures in particular leads to the hydrolytic cleavage of the urethane and urea bonds.
  • Even high temperature loads without additional increased exposure to moisture can lead to the breakdown of urethane and urea bonds. This cleavage not only manifests itself in a significant deterioration in the properties of use, but also leads to the formation of aromatic amines such as toluenediamine (TDA) and diaminodiphenylmethane (MDA).
  • TDA toluenediamine
  • MDA diaminodiphenylmethane
  • Amine formation is affected by a number of parameters. Particularly low indices lead to measurable levels of aromatic amine in polyurethanes even without aging. Such low indices are mainly used for very soft, viscoelastic foam qualities that are used against bedsores or bedsores, for example as a wheelchair cushion. Furthermore, high temperatures, especially in combination with high air humidity, lead to the cleavage of the urethane and urea bonds. Such conditions are important for some special areas of application of flexible PUR foams.
  • An example of such Special applications are hospital mattresses that are subjected to steam sterilization. This can also lead to a deterioration in the mechanical properties. For this reason, the less drastic hot steam disinfection according to DIN 13 014 (105 ° C; max. 10 min) is often carried out. Another example is upholstered furniture that is cleaned in the home with steam cleaners. Apart from these special applications, however, exposure to aromatic amines is not to be expected when using products made of PUR soft and semi-rigid foams as intended.
  • Another parameter that significantly influences the formation of aromatic amines and / or also the aging resistance to heat or wet-heat conditions is the type and amount of the catalysts used.
  • the catalysts contained in polyurethane systems which are necessary for the urethanization and blowing reaction, also catalyze the re-cleavage reaction to a considerable extent.
  • the presence of catalysts is therefore an essential prerequisite for the cleavage of urethane and urea bonds.
  • the extent of the cleavage depends to a large extent on the activity and type of the catalyst and on whether the catalyst remains in the system or can migrate from the material.
  • tertiary amine catalysts with reactive functional groups such as OH and NH groups accelerate the amine formation in the polyurethane considerably by lowering the activation energy for the cleavage reaction.
  • the functional groups bring about the incorporation of the catalysts into the resulting polyurethane network, and the products produced with them have the advantage of less odor and fogging problems, but the catalysts cannot escape by diffusion after the polyurethane has been finished.
  • formulations with polyols which were produced with primary or secondary amines as starting molecules and thus have catalytically active centers which are present in the foam. Such polyols have been used increasingly recently.
  • ß-unsaturated carboxylic acid derivatives can be used. These compounds are often low molecular weight or contain low molecular weight polymerization stabilizers and can therefore contribute to undesirable emissions from the foam. They can also have a negative effect on the foam structure (coarse cell structure).
  • US 5990232 describes the use of unsaturated carbonyl compounds, in particular carboxylic acids, in the production of polyols by means of DMC catalysts. These unsaturated polyols are used to stabilize polymer polyols.
  • sterically hindered cycloaliphatic monoisocyanates and monothioisocyanates can be used to reduce aromatic amines in polyurethanes.
  • the disadvantages here are the relatively high price of these products and their low vapor pressure, which leads to the fact that unreacted portions migrate out of the foam and pose a health risk due to the occurrence of free isocyanate.
  • the object of the present invention was to provide flexible polyurethane and semi-rigid foams, in particular viscoelastic polyurethane flexible and semi-rigid foams, in which the formation of free aromatic amines, which have good mechanical properties, and / or is significantly reduced even under the conditions of moist storage whose aging resistance to heat or wet-heat conditions is improved.
  • polyurethane foams which were produced with polyols based on modified acrylate or methacrylate monomers, had significantly lower aromatic amine contents after moist heat storage than polyurethane foams, which were based on conventional polyetherols, which had a hydroxyl number and molecular weight polyols based on modified acrylate or methacrylate monomers were comparable. Furthermore, by using these polyols based on acrylate or methacrylate monomers, an improvement in the aging resistance under heat or wet-heat conditions can be achieved.
  • the acrylate polyols used according to the invention bring about Hydrophobization of the foam so that hydrolytic degradation with the release of aromatic amines is at least partially suppressed due to a reduced water absorption of the foam.
  • an initial hydrolysis of the acrylic or methacrylic ester side chains with generation of free acid groups is conceivable under moist and warm conditions. These acid groups can then protonate and deactivate amine catalysts present in the foam. These protonated catalysts can then no longer catalyze the cleavage of the urethane or urea bonds with the release of aromatic amines, which results in lower aromatic amine contents in aged foams and / or lower decreases in mechanical properties after heat or moisture heat aging.
  • the invention accordingly relates to a process for the production of polyurethane foams, preferably polyurethane soft and semi-rigid foams, in particular viscoelastic polyurethane soft and semi-rigid foams, by reacting
  • polyisocyanates a) are aromatic di- and / or polyisocyanates and the compounds containing at least two hydrogen atoms reactive with isocyanate groups b) contain at least one acrylate polyol.
  • Viscoelastic foams are soft and semi-rigid foams with very low rebound elasticity, e.g. ⁇ 50%, in particular ⁇ 40% understood.
  • the invention further relates to polyol mixtures comprising at least one acrylate polyol and at least one further alcohol, preferably an at least difunctional polyether alcohol or a polyester alcohol.
  • Low molecular weight acrylate polyols are preferably used as the acrylate polyols, ie those whose number average molecular weight is at most 12000 g / mol, preferably at most 8000 g / mol, particularly preferably at most 6000 g / mol and at least 400 g / mol.
  • the terms "acrylate polyols” and "polyacrylate polyols” are used synonymously.
  • the acrylate polyols used according to the invention can be prepared by polymerizing hydroxy-functionalized (meth) acrylates, preferably by copolymerizing hydroxy-functionalized (meth) acrylates with non-hydroxyl-functional (meth) acrylates.
  • acrylate monomers mentioned with other aliphatic or aromatic, ethylenically unsaturated monomers such as, for example, ethene, propene, butene, isobutene, diisobutene, acrylonitrile, acrylamide, acrolein, styrene, methylstyrene, divinylbenzene, Maleic anhydride, vinyl esters of carboxylic acids or unsaturated carboxylic acids, such as maleic acid, fumaric acid or crotonic acid or their derivatives.
  • ethylenically unsaturated monomers such as, for example, ethene, propene, butene, isobutene, diisobutene, acrylonitrile, acrylamide, acrolein, styrene, methylstyrene, divinylbenzene, Maleic anhydride, vinyl esters of carboxylic acids or unsaturated carboxylic acids, such as maleic
  • Such copolymerizations can be carried out in reactors operated continuously or batchwise, for example boilers, annular gap reactors, Taylor reactors, extruders or tubular reactors.
  • Reaction conditions are preferably chosen which lead to polymers with a low content of impurities.
  • the production of the acrylate polyols used according to the invention is preferably carried out without the use of polymerization regulators.
  • the polymerization is preferably carried out at temperatures above 160 ° C. in the absence of polymerization regulators and with the lowest possible initiator concentrations.
  • the process control is preferably chosen so that at the end of the reaction there are acrylate polyols with average molecular weights (Mn) of at most about 12000 g / mol.
  • Homopolymers of hydroxyalkyl (meth) acrylates or copolymers of hydroxyalkyl (meth) acrylates with non-hydroxyl-functional (meth) acrylic monomers are particularly suitable.
  • halogen-free monomers are used in the production of the acrylate polyols used according to the invention.
  • the acrylate polyols used in accordance with the invention are in particular produced by polymerizing C 1 -C 6 -hydroxyalkyl (meth) acrylates, such as e.g. Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate.
  • C 1 -C 6 -hydroxyalkyl (meth) acrylates such as e.g. Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate.
  • Acrylic monomers without OH groups which can optionally be used as comonomers, are, in particular, monomers containing aliphatic olefinic double bonds
  • a wide variety of chemical structures such as alkenes with 2 to 6 carbon atoms, such as ethene, propene, butene, isobutene, or acrylonitrile, acrylamide, acrolein, maleic anhydride, vinyl esters of carboxylic acids or unsaturated carboxylic acids, such as maleic acid, fumaric acid or crotonic acid or their derivatives, and particularly preferably alkyl (meth) acrylates with Ci to Cio-alkyl groups, for example n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-butyl
  • (eth) acrylate (eth) acrylate.
  • the monomers mentioned can be used individually or in any mixtures with one another.
  • the acrylate polyols used according to the invention are preferably prepared by copolymerization of C 1 -C 4 -hydroxyalkyl (meth) acrylates with the non-OH-functional (meth) acrylic monomers described above, the combination of different hydroxyalkyl (meth) acrylates with the non- functional (meth) acrylates is possible.
  • the monomers containing OH groups are preferably used in concentrations of 2 to 98 mol%, particularly preferably 5 to 95 mol%, based on the monomers used.
  • the acrylate polyols are prepared by copolymerizing C 1 -C 8 -hydroxyalkyl (meth) acrylates with alkyl (meth) acrylates with C 1 -C 10 -alkyl groups.
  • the number-average molar masses (Mn) of the acrylate polyols used according to the invention are particularly preferably between
  • the acrylate polyols are too viscous or solid and are therefore difficult to process in polyurethane systems.
  • the polyacrylate alcohols are preferably present in an amount of 0.1 to 100, preferably 0.5 to 50 and particularly preferably 1 to 30 parts by weight, based on 100 parts by weight of the compounds having at least two hydrogen atoms reactive with isocyanate groups b) , used.
  • polyester alcohols and preferably polyether alcohols with a medium one come as a compound with at least two active hydrogen atoms b) which can be used together with the acrylate polyols used according to the invention
  • Functionality from 2 to 8, in particular from 2 to 6, preferably from 2 to 4 and an average molecular weight in the range from 400 to 10000 g / mol, preferably 1000 to 8000 g / mol, into consideration.
  • the polyether alcohols can be prepared by known processes, usually by catalytic addition of alkylene oxides, in particular ethylene oxide and / or propylene oxide, onto H-functional starter substances, or by condensation of tetrahydrofuran.
  • Polyfunctional alcohols and / or amines are used in particular as H-functional starters.
  • Water, dihydric alcohols, for example ethylene glycol, propylene glycol, or butanediols, trihydric alcohols, for example glycerol or trimethylolpropane, and higher alcohols, such as pentaerythritol, sugar alcohols, for example sucrose, glucose or sorbitol, are preferably used.
  • Amines used with preference are aliphatic amines having up to 10 carbon atoms, for example ethylenediamine, diethylenetriamine, propylenediamine, and also amino alcohols, such as ethanolamine, diethanolamine or triethanolamine.
  • alkylene oxides preference is given to using ethylene oxide and / or propylene oxide, with an ethylene oxide block often being added to the chain end in the case of polyether alcohols which are used for the production of flexible polyurethane foams.
  • basic compounds are used as catalysts in the addition of the alkylene oxides, with potassium hydroxide having the greatest technical importance here. If the content of unsaturated constituents in the polyether alcohols is to be low, multimetal cyanide compounds, so-called DMC catalysts, can also be used as catalysts.
  • two- and / or three-functional polyether alcohols are used to produce viscoelastic flexible foams and integral foams.
  • the compounds with at least two active hydrogen atoms also include the chain extenders and crosslinking agents, which can optionally be used.
  • Chain extenders and crosslinking agents used are preferably 2- and 3-functional alcohols with molecular weights below 400 g / mol, in particular in the range from 60 to 150 g / mol. applies. Examples are ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, glycerol or trimethylolpropane.
  • Diamines can also be used as crosslinking agents. If chain extenders and crosslinking agents are used, their amount is preferably up to 5% by weight, based on the weight of the compounds having at least two active hydrogen atoms.
  • aromatic di- and polyisocyanates can be used individually or in any mixtures with one another as polyisocyanates.
  • aromatic di- or polyisocyanates are 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 4 , 4'-diphenylmethane diisocyanate (4,4'-MDI), polyphenylpolymethylene polyisocyanates, such as those produced by the condensation of aniline and formaldehyde and subsequent phosgenation (polymer MDI), p-phenylene diisocyanate, toluidine diisocyanate, xylylene diisocyanate or 1, 5 -Naphthylene diisocyanate (NDI).
  • polymer MDI polymer MDI
  • p-phenylene diisocyanate toluidine diisocyan
  • Oligo- or polyisocyanates are preferably used together with or instead of these monomeric isocyanates or their mixtures.
  • These oligo- or polyisocyanates can be obtained from the di- or polyisocyanates mentioned or their mixtures and, if appropriate, mono- or polyalcohols by linking using urethane, allophanate, urea, biuret, uretdione, amide, isocyanurate, carbodiimide - Build uretone imine, oxadiazinetrione or iminooxadiazinedione structures.
  • Polymers containing TET or MDI and optionally mono- or poly-alcohols are preferably used here, which contain urethane, allophanate, carbodiimide, uretonimine, biuret or isocyanurate groups.
  • the customary and known polyurethane formation catalysts are used as catalysts for the production of the polyurethane foams according to the invention, for example organic tin compounds, such as tin diacetate, tin dioctoate, dibutyltin dilaurate, and / or strongly basic amines such as diazabicyclooctane, diazabicyclononane, diazabicyclethyldiamine, triethylaminodiamine, triethylamine, triethylamine Tetramethyldiaminoethyl ether, imidazoles or preferably triethylenediamine or bis (N, N-dimethylamino ethyDether.
  • organic tin compounds such as tin diacetate, tin dioctoate, dibutyltin dilaurate, and / or strongly basic amines such as diazabicyclooctane, diazabicyclononane, di
  • Carboxylic acid salts such as, for example, potassium acetate, cesium acetate or tetraalkylammonium salts of carboxylic acids, are also used.
  • built-in catalysts have been increasingly used which contain functional groups such as hydroxyl, primary or secondary amino or other groups which can react with isocyanates. These catalysts are covalently incorporated into the polyurethane matrix and cannot emit from the foam, which contributes to the lower odor and generally lower emissions, as is currently required by the market.
  • Examples of such preferred, insertable catalysts are 3-aminopropylimidazole, N, N, '-trimethyl-N-hydroxyethylbisaminoethyl ether, 6-dimethylamino-1-hexanol, N- (2-hydroxypropyl) imidazole, bis (dimethylamino-propyl) amine or 2- (2- (N, N-dimethylamino) ethoxy) ethanol or, for example, the commercially available catalysts Dabco NE 200, Dabco NE 1060.
  • the catalysts are preferably used in an amount of 0.01 to 10% by weight, preferably 0 , 05 to 5 wt .-%, used.
  • Water which reacts with the isocyanate groups to release carbon dioxide is preferably used as the blowing agent for the production of the polyurethane foams.
  • Physically active blowing agents for example carbon dioxide, hydrocarbons, such as n-, iso- or cyclopentane, cyclohexane or halogenated hydrocarbons, such as tetrafluoroethane, pentafluoropropane, heptafluoropropane, pentafluorobutane, hexafluorobutane or dichloromonofluoroethane, can also be used together with or instead of water.
  • the amount of the physical blowing agent is preferably in the range between 1 to 15% by weight, in particular 1 to 10% by weight, the amount of water is preferably in the range between 0.5 to 10% by weight, in particular 1 to 5 wt .-%.
  • Auxiliaries and / or additives used are, for example, surface-active substances, foam stabilizers, cell regulators, external and internal release agents, fillers, flame retardants, pigments, hydrolysis protection agents and fungistatic and bacteriostatic substances.
  • polyurethane foams In the technical production of polyurethane foams, it is customary to combine the compounds with at least two active hydrogen atoms b) and the further starting materials and auxiliaries and / or additives to form a so-called polyol component before the reaction. Further information on the starting materials used can be found, for example, in the Plastics Handbook, Volume 7, Polyurethane, edited by Günter Oertel, Carl-Hanser-Verlag, Kunststoff, 3rd edition 1993.
  • the organic polyisocyanates a) are reacted with the compounds having at least two active hydrogen atoms b) and the blowing agents, catalysts and auxiliaries and / or additives (polyol component) mentioned, the acrylate polyols used according to the invention preferably being the Polyol component are added.
  • isocyanate and polyol components are brought together in such an amount that the equivalence ratio of isocyanate groups to the sum of the active hydrogen atoms, also referred to as index, is 0.6 to 1.4, preferably 0.7 to 1.2 ,
  • index the equivalence ratio of isocyanate groups to the sum of the active hydrogen atoms
  • very soft foams with viscoelastic properties are preferably produced with an index in the range between 0.45 to 1.0, preferably 0.55 to 0.95, particularly preferably 0.6 to 0.9.
  • the polyurethane foams are preferably produced using the one-shot process, for example using high-pressure or low-pressure technology.
  • the foams can be produced in open or closed metallic molds or by continuously applying the reaction mixture to belt lines to produce foam blocks.
  • a polyol and an isocyanate component are produced and foamed.
  • the components are preferably mixed at a temperature in the range between 15 to 120.degree. C., preferably 20 to 80.degree. C. and brought into the mold or onto the belt mill.
  • the temperature in the mold is usually in the range between 15 and 120 ° C, preferably between 30 and 80 ° C.
  • the acrylate polyols used according to the invention allow the production of elastic and viscoelastic soft and semi-rigid foams with densities below 200 g / 1 and excellent mechanical properties, for example very good elongation, tensile strength and hardness. Surprisingly, the resilience of the poly- urethane foams are reduced so that the desired viscoelastic properties are further enhanced.
  • Table 1 shows polyacrylate polyols which can be used to produce the foams according to the invention.
  • the foams produced were subjected to a moist heat storage.
  • sample cubes with an edge length of 3 cm were stored at 90% relative humidity and 90 ° C for 72 hours in a climatic cabinet.
  • the subsequent extraction of the aromatic amines formed was carried out using a method developed by Prof. Skarping, University of Lund.
  • the MDA content of the combined extracts was then determined by means of capillary electrophoresis with UV detection (device type: Biofocus 3000, measurement of the peak areas and comparison with imidazole as internal standard).
  • the detection limit of the capillary electrophoresis determination is 1 ppm.
  • the MDA contents given in the examples correspond to the absolute contents of the MDA formed in the PUR foam.
  • Molded flexible foams Reduction in the content of aromatic amines after moist heat storage:
  • the resulting foam contained no detectable amounts of MDA when aged and 32 ppm of 4.4 ⁇ -MDA and 78 ppm of 2,4 , -MDA after aging under moist heat.
  • Example 2 The procedure was as in Example 1, with the difference that instead of Lupranol® 2090, 97 parts by weight of the acrylate polyol 1 from Table 1 were used in the polyol component. Foaming also took place with an index of 0.9.
  • the resulting foam contained no detectable amounts of MDA when aged and 6 ppm of 4.4 -MDA and 20 ppm of 2.4 V -MDA after aging under humid and warm conditions. It was shown that the MDA content of the aged foam could be significantly reduced by using the acrylate polyol according to the invention.
  • a flexible molded polyurethane foam was produced by mixing 750 g of a polyol component as in Comparative Example 1, but using 0.8 parts by weight of 3-aminopropylimidazole instead of triethylenediamine and 0.14 parts by weight of 0.1 8 parts by weight.
  • the resulting foam contained no detectable amounts of MDA without aging and after wet heat aging 397 ppm 4, 4 * -MDA and 687 ppm 2, 4 '-MDA.
  • the resulting foam contained no detectable amounts of MDA when aged and 58 ppm 4, 4 * MDA and 127 ppm 2, 4'-MDA after aging under moist heat.
  • the MDA content of the aged foam could thus be significantly reduced by using the acrylate polyol according to the invention.
  • Block flexible foams Reduction in the content of aromatic amines after moist heat storage:
  • the resulting foam contained no detectable amounts of TDA when aged and 33 ppm of 2,4-TDA and 9 ppm of 2,6-TDA after aging under moist heat.
  • Example 5 The procedure was as in Example 5, with the difference that 50 parts of Lupranol 2080 and 50 parts of acrylate polyol 3 (Table 1) were used in the polyol component. Foaming also took place at an index of 1.1.
  • the resulting foam contained no detectable amounts of TDA when aged and 20 ppm of 2,4-TDA and 7 ppm of 2,6-TDA after aging under moist heat.
  • the TDA content of the aged foam could thus be significantly reduced by using the acrylate polyol according to the invention.
  • Example 5 The procedure was as in Example 5, with the difference that only 1.7 parts of Lupranol 2080 and 98.3 parts of acrylate polyol 3 (Table 1) were used in the polyol component. Foaming also took place at an index of 1.1.
  • the resulting foam contained no detectable amounts of TDA when aged and 11 ppm of 2,4-TDA and 4 ppm of 2,6-TDA after aging under moist heat.
  • the TDA content of the aged foam could thus be significantly reduced by using the acrylate polyol according to the invention.
  • Example 5 The procedure was as in Example 5, with the difference that 70 parts of Lupranol 2080 and 30 parts of acrylate polyol 6 (Table 1) were used in the polyol component. Foaming also took place at an index of 1.1.
  • the resulting foam contained no detectable amounts of TDA when aged and 13 ppm of 2,4-TDA and 3 ppm of 2,6-TDA after aging under moist heat.
  • the TDA content of the aged foam could thus be significantly reduced by using the acrylate polyol according to the invention.
  • Example 5 The procedure was as in Example 5, with the difference that 30 parts of Lupranol 2080 and 70 parts of acrylate polyol 6 (Table 1) were used in the polyol component. Foaming also took place at an index of 1.1.
  • the resulting foam contained no detectable amounts of TDA when aged and 10 ppm of 2,4-TDA and 3 ppm of 2,6-TDA after aging under moist heat.
  • the TDA content of the aged foam could thus be significantly reduced by using the acrylate polyol according to the invention.
  • Example 5 The procedure was as in Example 5, with the difference that only 1.7 parts of Lupranol 2080 and 98.3 parts of acrylate polyol 6 (Table 1) were used in the polyol component. Foaming also took place at an index of 1.1.
  • the resulting foam contained no detectable amounts of TDA when aged and 9 ppm of 2,4-TDA and 3 ppm of 2,6-TDA after aging under moist heat.
  • the TDA content of the aged foam could thus be significantly reduced by using the acrylate polyol according to the invention.
  • Example 12 (According to the Invention) The procedure was as in Example 11, with the difference that 5 parts of the acrylate polyol 2 from Table 1 and 95 parts of Lupranol 2080 were used in the polyol component. Foaming also took place at an index of 1.15 5
  • Example 11 The procedure was as in Example 11, with the difference that 20 parts of the acrylate polyol 2 from Table 1 and 80 parts of Lupranol 2080 were used in the polyol component. Foaming also took place at an index of 1.15.
  • Semi-rigid foams improvement of aging resistance
  • a polyol component consisting of 92 parts by wt Lupranol ® parts by Polyol PP50 (Perstorp AB), 2 parts by weight were 2090 (Elastogran GmbH), 8 wt of an amine initiated polyoxypropylene diol, hydroxyl number:. 250, 2.81 wt. parts by water, 0.26 wt. parts by Jeffcat ZF10 ® (Huntsman
  • the percentage decrease in tensile strength or elongation after heat storage (7 days at 140 ° C.) was 18% and 14%, respectively.

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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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un procédé de production de mousses de polyuréthanne présentant une densité inférieure à 200 g/l, consistant à faire réagir a) des polyisocyanates avec b) des composés comprenant au moins deux atomes d'hydrogène réagissant avec des groupes isocyanate, les polyisocyanates a) étant des diisocyanates ou polyisocyanates aromatiques et les composés b) contenant au moins un polyol acrylique.
EP03740193A 2002-06-13 2003-06-06 Procede de production de mousses de polyurethanne Withdrawn EP1516005A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10226414A DE10226414A1 (de) 2002-06-13 2002-06-13 Verfahren zur Herstellung von Polyurethan-Schaumstoffen
DE10226414 2002-06-13
PCT/EP2003/005935 WO2003106528A1 (fr) 2002-06-13 2003-06-06 Procede de production de mousses de polyurethanne

Publications (1)

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EP1516005A1 true EP1516005A1 (fr) 2005-03-23

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US (1) US20050176838A1 (fr)
EP (1) EP1516005A1 (fr)
JP (1) JP2005534731A (fr)
KR (1) KR20050008814A (fr)
CN (1) CN1313508C (fr)
AU (1) AU2003276909A1 (fr)
CA (1) CA2488636A1 (fr)
DE (1) DE10226414A1 (fr)
WO (1) WO2003106528A1 (fr)

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JP4574278B2 (ja) * 2004-08-09 2010-11-04 株式会社イノアックコーポレーション 軟質ポリウレタンフォームの製造方法
JP4887622B2 (ja) * 2004-12-17 2012-02-29 セントラル硝子株式会社 防曇性物品及びその製造法、並びに防曇性被膜形成用塗布剤
JP5973130B2 (ja) * 2007-09-14 2016-08-23 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ フロアカバリング用の無機物を含む上層を製造する方法
US8153743B2 (en) * 2008-07-31 2012-04-10 Closure Medical Corporation Controlled exotherm of cyanoacrylate formulations
CN101412798B (zh) 2008-11-21 2011-08-10 优洁（亚洲）有限公司 软质聚氨酯低回弹泡沫及其制备方法
JP6125451B2 (ja) * 2013-03-28 2017-05-10 三洋化成工業株式会社 軟質ポリウレタンフォームの製造方法
JP6270420B2 (ja) * 2013-11-08 2018-01-31 コベストロ、ドイチュラント、アクチエンゲゼルシャフトＣｏｖｅｓｔｒｏ Ｄｅｕｔｓｃｈｌａｎｄ Ａｇ インテグラルスキンフォームの製造方法
US9204742B2 (en) * 2013-12-31 2015-12-08 Tempur-Pedic Management, Llc Cover assemblies for mattresses
EP3330307A1 (fr) * 2016-12-05 2018-06-06 Covestro Deutschland AG Utilisation d'esters d'acide acrylique et amides pour élimination des émissions de mousse de polyuréthane
EP3330308A1 (fr) * 2016-12-05 2018-06-06 Covestro Deutschland AG Procédé de fabrication de mousses souples en polyuréthane à base de tdi comprenant des anhydrides d'acide organiques et/ou des chlorures d'acides organiques
WO2019219503A1 (fr) * 2018-05-14 2019-11-21 Huntsman International Llc (méth)acrylates à faible viscosité en tant qu'additifs réactifs dans des compositions réactives pour la fabrication de mousses rigides comprenant du polyuréthane/polyisocyanurate
CN109265616A (zh) * 2018-08-01 2019-01-25 湖南辰砾新材料有限公司 一种保温泡沫材料及其制备方法
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Also Published As

Publication number Publication date
CN1659203A (zh) 2005-08-24
WO2003106528A1 (fr) 2003-12-24
DE10226414A1 (de) 2003-12-24
AU2003276909A1 (en) 2003-12-31
JP2005534731A (ja) 2005-11-17
US20050176838A1 (en) 2005-08-11
KR20050008814A (ko) 2005-01-21
CN1313508C (zh) 2007-05-02
CA2488636A1 (fr) 2003-12-24

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