EP1516005A1 - Method for the production of polyurethane foam materials - Google Patents

Method for the production of polyurethane foam materials

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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)
French (fr)
Inventor
Dieter Rodewald
Bernd Bruchmann
Horst Binder
Heinz-Dieter Lutter
Ansgar Frericks
Markus Templin
Martin Kreyenschmidt
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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/en
Withdrawn legal-status Critical Current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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Abstract

The invention relates to a method for producing polyurethane foam materials having a density of less than 200 g/l by reacting a) polyisocyanates with b) compounds that comprise at least two hydrogen atoms reactive with isocyanate groups, said polyisocyanates being aromatic diisocyanates or polyisocyanates while the compounds which comprise at least two hydrogen atoms reactive with isocyanate groups contain at least one acrylate polyol.

Description

Verfahren zur Herstellung von Polyurethan-SchaumstoffenProcess for the production of polyurethane foams
Beschreibungdescription
Die Erfindung betrifft ein Verfahren zur Herstellung von Polyurethan-Schaumstoffen, insbesondere Polyurethan-Weich- und Halbhartschaumstoffen durch Umsetzung von Polyisocyanaten mit Verbindungen mit mindestens zwei mit Isocyanatgruppen reaktiven Wasserstoffatomen.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.
Polyurethan-Schaumstoffe sind seit langem bekannt und vielfach in der Literatur beschrieben. Ihre Herstellung erfolgt üblicherweise durch Umsetzung von Isocyanaten mit Verbindungen mit min- destens zwei mit Isocyanatgruppen reaktiven Wasserstoffatomen. Als Isocyanate werden zumeist aromatische Di- und Polyisocyanate verwendet, wobei Isomere des Toluylendiisocyanats (TDI) , Isomere des Diphenylmethandiisocyanats (MDI) sowie Mischungen aus Diphenylmethandiisocyanat und Polymethylen-polyphenylen-poly- isocyanaten (Roh-MDI) die größte technische Bedeutung haben.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. Mostly 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.
Polyurethan-Schaumstoffe sind wie biologische Materialien einem Alterungsprozess unterworfen, der im allgemeinen mit zunehmender Zeit zu einer signifikanten Verschlechterung der Gebrauchseigen- schatten führt. Wesentliche Alterungseinflüsse sind beispielsweise Hydrolyse, Photooxidation und Thermooxidation, die zu Bindungsbrüchen in der Polymerkette führen. Bei Polyurethanwerkstoffen führt speziell die Einwirkung von Feuchtigkeit und erhöhten Temperaturen zur hydrolytischen Spaltung der Urethan- und Harnstoffbindungen. Auch starke Temperaturbelastung ohne zusätzliche verstärkte Feuchtigkeitseinwirkung kann zur Rückspaltung von Urethan- und Harnstoffbindungen führen. Diese Spaltung äußert sich nicht nur in einer signifikanten Verschlechterung der Gebrauchseigenschaften, sondern führt auch zur Bildung von aromatischen Aminen wie Toluylendiamin (TDA) und Diaminodiphenylmethan (MDA) .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. In the case of polyurethane materials, 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).
Die Aminbildung wird von einer Reihe von Parametern beeinflusst. Besonders niedrige Indices führen auch ohne Alterung zu messbaren Gehalten an aromatischem Amin in Polyurethanen. Derart niedrige Indices werden vor allem bei sehr weichen, viskoelastischen Schaumstoffqualitäten verwendet, die gegen Wundliegen oder Wundsitzen, z.B. als Rollstuhlkissen verwendet werden. Ferner führen hohe Temperaturen, besonders in Kombination mit hoher Luft- feuchtigkeit, zur Spaltung der Urethan- und Harnstoffbindungen. Derartige Bedingungen sind für einige spezielle Anwendungsgebiete von PUR-Weichschaumstoffen von Bedeutung. Ein Beispiel für solche Spezialanwendungen stellen Krankenhausmatratzen dar, die einer Heißdampfsterilisierung unterzogen werden. Dabei kann es auch zu einer Verschlechterung der mechanischen Eigenschaften kommen. Aus diesem Grund wird häufig die weniger drastische Heißdampf- desinfektion nach DIN 13 014 (105°C; max. 10 min) durchgeführt. Ein weiteres Beispiel stellen Polstermöbel dar, die im Haushalt mit Heißdampfreinigern gereinigt werden. Abgesehen von diesen Spezialanwendungen ist jedoch beim bestimmungsgemäßen Gebrauch von Produkten aus PUR-Weich- und Halbhartschaumstoffen nicht mit einer Belastung durch aromatische Amine zu rechnen.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.
Ein weiterer Parameter, der die Bildung aromatischer Amine und/oder auch die Alterungsbeständigkeit gegenüber Wärme- oder Feucht-Wärme-Bedingungen signifikant beeinflusst, ist die Art und Menge der verwendeten Katalysatoren. Die in Polyurethansystemen enthaltenen, für die Urethanisierungs- und Treibreaktion notwendigen Katalysatoren katalysieren in erheblichem Maß auch die Rückspaltungsreaktion. Die Anwesenheit von Katalysatoren ist somit eine wesentliche Voraussetzung für die Spaltung der Urethan- und Harnstoffbindungen. Darüber hinaus hängt das Ausmaß der Rückspaltung in hohem Maße von der Aktivität und der Art des Katalysators sowie davon ab, ob der Katalysator im System verbleibt oder aus dem Material migrieren kann. Insbesondere tertiäre Aminkatalysatoren mit reaktionsfähigen funktioneilen Gruppen wie OH- und NH -Gruppen beschleunigen die Aminbildung im Polyurethan durch Absenkung der Aktivierungsenergie für die Spaltreaktion erheblich. Die funktionellen Gruppen bewirken den Einbau der Katalysatoren in das entstehende Polyurethan-Netz- werk, und die damit hergestellten Produkte weisen den Vorteil ge- ringerer Geruchs- und Foggingproblematik auf, die Katalysatoren können jedoch nach der Fertigstellung des Polyurethans nicht durch Diffusion entweichen. Dasselbe gilt für Rezepturen mit Polyolen, die mit primären oder sekundären Aminen als Startmoleküle hergestellt wurden und somit katalytisch aktive Zentren besitzen, die im Schaum vorliegen. Derartige Polyole kommen in jüngster Zeit vermehrt zum Einsatz. Bei Schaumstoffen mit Aminkatalysatoren, die keine einbaufähigen funktionellen Gruppen enthalten, entweichen die Amine dagegen in der Regel bereits kurze Zeit nach der Fertigstellung, bzw. bei der Alterung des Schaumes. Bei solchen Schaumstoffen führen z.B. starke hydrolytische Belastungen zu wesentlich geringeren Amingehalten und/oder auch zu einer geringeren Abnahme der Gebrauchseigenschaften während der Alterung.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. In addition, 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. In particular, 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. The same applies to 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. In contrast, in the case of foams with amine catalysts which do not contain functional groups which can be incorporated, the amines generally escape shortly after completion or when the foam ages. With such foams e.g. strong hydrolytic loads to much lower amine contents and / or to a smaller decrease in the properties of use during aging.
Um bei Polyurethanwerkstoffen, vorzugsweise solchen, die mit niedrigen Indices, hergestellt werden oder die besonderen klimatischen Bedingungen ausgesetzt sind, die Freisetzung aromatischer Amine zu vermindern und/oder die Alterungsbeständigkeit gegenüber Wärme- oder Feucht-Wärme-Bedingungen zu verbessern, war es notwendig, Additive zu finden, welche die Migration gebildeter aromatischer Amine aus dem Schaum oder die Bildung aromatischer Amine unter klimatischer Belastung verhindern und/oder die Alterungsbeständigkeit gegenüber Wärmeoder Feucht-Wärme-Bedingungen verbessern.In order to release polyurethane materials, preferably those that are manufactured with low indices or that are exposed to the special climatic conditions To reduce aromatic amines and / or to improve the aging resistance to heat or moist-heat conditions, it was necessary to find additives which prevent the migration of aromatic amines formed from the foam or the formation of aromatic amines under climatic stress and / or improve the aging resistance to heat or wet-heat conditions.
Um entstandene aromatische Amine chemisch zu binden, sind eine Reihe von Lösungen bekannt. So können gemäß DE 19919826-A1 θt,ß-ungesättigte Carbonsäurederivate eingesetzt werden. Diese Verbindungen sind häufig niedermolekular oder enthalten niedermolekulare Polymerisationsstabilisatoren und können daher zu unerwünschten Emissionen aus dem Schaumstoff beitragen. Ferner können sie die Schaumstruktur (Grobzelligkeit) negativ beeinflussen. US 5990232 beschreibt die Verwendung ungesättigter CarbonylVerbindungen, insbesondere Carbonsäuren, bei der Polyol- herstellung mittels DMC-Katalysatoren. Diese ungesättigten Poly- ole werden zur Stabilisierung von Polymerpolyolen eingesetzt. Gemäß US 4211847, GB 1565124 und DE-A 2946625 können sterisch gehinderte cycloaliphatische Monoisocyanate und Monothioisocyanate zur Reduktion aromatischer Amine in Polyurethanen verwendet werden. Nachteilig dabei ist der relativ hohe Preis dieser Produkte und ihr geringer Dampfdruck, der dazu führt, dass nicht umgesetzte Anteile aus dem Schaum migrieren und eine Gesundheitsgefahr durch Auftreten freien Isocyanats darstellen.A number of solutions are known for chemically binding aromatic amines formed. According to DE 19919826-A1 θt, 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. According to US 4211847, GB 1565124 and DE-A 2946625, 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.
Aufgabe der vorliegenden Erfindung war es, Polyurethan-Weich- und Halbhartschaumstoffe, insbesondere viskoeleastische Polyurethan- Weich- und Halbhartschaumstoffe bereitzustellen, bei denen auch unter den Bedingungen der Feuchtlagerung die Bildung von freien aromatischen Aminen deutlich reduziert ist, die gute mechanische Eigenschaften aufweisen und/oder deren Alterungsbeständigkeit gegenüber Wärme- oder Feucht-Wärme-Bedingungen verbessert wird.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.
Es wurde überraschenderweise gefunden, dass Polyurethanschaumstoffe, die mit Polyolen auf Basis von modifizierten Acrylat- oder Methacrylatmonomeren hergestellt wurden, nach Feuchtwärmelagerung deutlich niedrigere Gehalte an aromatischen Aminen auf- wiesen als Polyurethanschaumstoffe, die auf herkömmlichen Poly- etherolen basierten, die in Hydroxylzahl und Molekulargewicht den auf modifizierten Acrylat- oder Methacrylatmonomeren basierenden Polyolen vergleichbar waren. Des weiteren kann durch den Einsatz dieser auf Acrylat- oder Methacrylatmonomeren basierenden Polyole eine Verbesserung der Alterungsbeständigkeit gegenüber Wärmeoder Feucht-Wärme-Bedingungen erzielt werden. Möglicherweise bewirken die erfindungsgemäß eingesetzten Acrylatpolyole eine Hydrophobierung des Schaumstoffs, so dass ein hydrolytischer Abbau unter Freisetzung aromatischer Amine aufgrund einer verminderten Wasseraufnahme des Schaums zumindest teilweise unterdrückt wird. Alternativ ist unter feucht-warmen Bedingungen eine anfängliche Hydrolyse der Acryl- oder Methacrylsäureesterseiten- ketten unter Generierung freier Säuregruppen denkbar. Diese Säuregruppen können dann im Schaum vorhandene Aminkatalysatoren protonieren und so deaktivieren. Diese protonierten Katalysatoren können dann im Schaum die Rückspaltung der Urethan- oder Harn- Stoffbindungen unter Freisetzung aromatischer Amine nicht mehr katalysieren, woraus geringere Gehalte an aromatischen Aminen in gealterten Schäumen und/oder geringere Abnahmen der mechanischen Eigenschaften nach Wärme- oder Feuch -Wärmealterung resultieren.Surprisingly, it was found that 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. Possibly 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. Alternatively, 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.
Gegenstand der Erfindung ist demzufolge ein Verfahren zur Herstellung von Polyurethan-Schaumstoffen, vorzugsweise Polyurethan- Weich- und Halbhartschaumstoffen, insbesondere viskoelastischen Polyurethan-Weich- und Halbhartschaumstoffen, durch Umsetzung vonThe 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
a) Polyisocyanaten mita) with polyisocyanates
b) Verbindungen mit mindestens zwei mit Isocyanatgruppen reaktiven Wasserstoffatomen,b) compounds with at least two hydrogen atoms reactive with isocyanate groups,
wobei die Polyisocyanate a) aromatische Di- und/oder Polyisocyanate sind und die Verbindungen mit mindestens zwei mit Isocyanatgruppen reaktiven Wasserstoffatomen b) mindestens ein Acrylatpolyol enthalten.wherein the 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.
Unter viskoelastischen Schaumstoffen werden Weich- und Halbhartschaumstoffe mit sehr geringer Rückprallelastizität, z.B. < 50 %, insbesondere < 40 % verstanden.Viscoelastic foams are soft and semi-rigid foams with very low rebound elasticity, e.g. <50%, in particular <40% understood.
Gegenstand der Erfindung sind weiterhin Polyolmischungen, enthaltend mindestens ein Acrylatpolyol und mindestens einen weiteren Alkohol, vorzugsweise einen mindestens difunktionellen Polyetheralkohol oder einen Polyesteralkohol.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.
Als Acrylatpolyole werden vorzugsweise niedermolekulare Acrylat- polyole eingesetzt, das heißt solche, deren zahlenmittleres Molekulargewicht maximal 12000 g/mol, vorzugsweise maximal 8000 g/mol, besonders bevorzugt maximal 6000 g/mol und minimal 400 g/mol beträgt. Im folgenden werden die Bezeichnungen "Acrylatpolyole" und "Polyacrylatpolyole" synonym verwendet. Die erfindungsgemäß verwendeten Acrylatpolyole können durch Polymerisation von hydroxyfunktionalisierten (Meth)acrylaten, bevorzugt durch Copolymerisation von hydroxyfunktionalisierten (Meth)acrylaten mit nicht hydroxylfunktionellen (Meth)acrylaten hergestellt werden. Weiterhin können sie auch durch Copolymerisation der genannten Acrylat-Monomeren mit anderen ali- phatischen oder aromatischen, ethylenisch ungesättigten Monomeren, wie zum Beispiel Ethen, Propen, Buten, Isobuten, Diiso- buten, Acrylnitril, Acrylamid, Acrolein, Styrol, Methylstyrol , Divinylbenzol, Maleinsäureanhydrid, Vinylester von Carbonsäuren oder ungesättigten Carbonsäuren, wie zum Beispiel Maleinsäure, Fumarsäure oder Crotonsäure oder deren Derivaten, hergestellt werden.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. In the following, 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. Furthermore, they can also be obtained by copolymerization of the 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.
Derartige Copolymerisationen können in kontinuierlich oder diskontinuierlich betriebenen Reaktoren, beispielsweise Kesseln, Ringspaltreaktoren, Taylorreaktoren, Extrudern oder Rohrreaktoren, durchgeführt werden.Such copolymerizations can be carried out in reactors operated continuously or batchwise, for example boilers, annular gap reactors, Taylor reactors, extruders or tubular reactors.
Bevorzugt werden Reaktionsbedingungen gewählt, die zu Polymeren mit einem geringen Gehalt an Verunreinigungen führen. So wird bei der Herstellung der erfindungsgemäß verwendeten Acrylatpolyole vorzugsweise ohne die Verwendung von Polymerisationsreglern gearbeitet .Reaction conditions are preferably chosen which lead to polymers with a low content of impurities. For example, the production of the acrylate polyols used according to the invention is preferably carried out without the use of polymerization regulators.
Vorzugsweise wird bei der Herstellung der erfindungsgemäß verwendeten Acrylatpolyole bei Temperaturen oberhalb 160°C in Abwesenheit von Polymerisationsreglern und mit möglichst geringen Initiatorkonzentrationen polymerisiert . Die Prozessführung wird vorzugsweise so gewählt, dass am Ende der Umsetzung Acrylatpolyole mit mittleren Molmassen (Mn) von maximal etwa 12000 g/mol vorliegen.In the production of the acrylate polyols used according to the invention, 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.
Bevorzugt geeignet sind Homopolymerisate aus Hydroxyalkyl (meth) - acrylaten oder Copolymerisate aus Hydroxyalkyl (meth) acrylaten mit nicht hydroxylfunktionellen (meth)acrylischen Monomeren. Insbesondere werden bei der Herstellung der erfindungsgemäß verwendeten Acrylatpolyole halogenfreie Monomere eingesetzt.Homopolymers of hydroxyalkyl (meth) acrylates or copolymers of hydroxyalkyl (meth) acrylates with non-hydroxyl-functional (meth) acrylic monomers are particularly suitable. In particular, halogen-free monomers are used in the production of the acrylate polyols used according to the invention.
Die erfindungsgemäß verwendeten Acrylatpolyole werden insbesondere hergestellt durch Polymerisation von Ci-bis Cβ-Hydroxy- alkyl (meth) acrylaten, wie z.B. Hydroxyethyl (meth) acrylat , Hydroxypropyl (meth) acrylat, Hydroxybutyl (meth) acrylat .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.
Als acrylische Monomere ohne OH-Gruppen, die gegebenenfalls als Comonomere eingesetzt werden können, kommen insbesondere aliphatische, olefinische Doppelbindungen enthaltende Monomere unterschiedlichster chemischer Struktur in Betracht, wie beispielsweise Alkene mit 2 bis 6 Kohlenstoffatomen, wie Ethen, Propen, Buten, Isobuten, oder Acrylnitril, Acrylamid, Acrolein, Maleinsäureanhydrid, Vinylester von Carbonsäuren oder ungesättigten Carbonsäuren, wie zum Beispiel Maleinsäure, Fumar- säure oder Crotonsäure oder deren Derivate, und besonders bevorzugt Alkyl (meth)acrylate mit Ci- bis Cio-Alkylgruppen, beispielsweise n-Hexyl (meth) acrylat, Cyclohexyl (meth) acrylat, n-Butyl-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) acrylat, Propyl (meth) acrylat, Ethyl (meth) -acrylat , Methyl- (meth) acrylat, Ethylhexyl (meth) acrylat und/oder Hexandioldi-(eth) acrylate, propyl (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, ethylhexyl (meth) acrylate and / or hexanediol di
( eth) acrylat . Die genannten Monomere können einzeln oder in beliebigen Mischungen untereinander eingesetzt werden.(eth) acrylate. The monomers mentioned can be used individually or in any mixtures with one another.
Die erfindungsgemäß verwendeten Acrylatpolyole werden vorzugs- weise durch Copolymerisation von Ci-bis Cs-Hydroxyalkyl (meth) - acrylaten mit den oben beschriebenen nicht OH-funktionellen (meth)acrylischen Monomeren hergestellt, wobei die Kombination unterschiedlicher Hydroxyalkyl (meth) acrylate mit den nicht- funktionellen (Meth) acrylaten beliebig möglich ist. Vorzugsweise werden die OH-Gruppen enthaltenden Monomere in Konzentrationen von 2 bis 98 mol-%, besonders bevorzugt von 5 bis 95 mol-%, bezogen auf die eingesetzten Monomere, eingesetzt.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.
In einer besonders vorteilhaften Ausführungsform der Erfindung werden die Acrylatpolyole durch Copolymerisation von Cι~ bis C8- Hydroxyalkyl (meth) acrylaten mit Alkyl (meth) acrylaten mit Ci- bis Cio-Alkylgruppen hergestellt .In a particularly advantageous embodiment of the invention, 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.
Die zahlenmittleren Molmassen (Mn) der erfindungsgemäß ver- wendeten Acrylatpolyole liegen besonders bevorzugt zwischenThe number-average molar masses (Mn) of the acrylate polyols used according to the invention are particularly preferably between
1000 und 6000 g/mol, die mittleren OH-Funktionalitäten zwischen 1,8 und 20 und die OH-Zahlen zwischen 15 und 500 mg KOH/g. Bei höheren Molekulargewichten und besonders bei höheren OH- Funktionalitäten sind die Acrylatpolyole zu hochviskos oder fest und lassen sich daher nur schwer in Polyurethansystemen verarbeiten.1000 and 6000 g / mol, the average OH functionalities between 1.8 and 20 and the OH numbers between 15 and 500 mg KOH / g. With higher molecular weights and especially with higher OH functionalities, the acrylate polyols are too viscous or solid and are therefore difficult to process in polyurethane systems.
Die Polyacrylatalkohole werden vorzugsweise in einer Menge von 0,1 bis 100, vorzugsweise 0,5 bis 50 und besonders bevorzugt von 1 bis 30 Gew. -Teilen, bezogen auf 100 Gew. -Teile der Verbindungen mit mindestens zwei mit Isocyanatgruppen reaktiven Wasserstoffatomen b) , eingesetzt.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.
Als Verbindung mit mindestens zwei aktiven Wasserstoffatomen b) , die zusammen mit den erfindungsgemäß verwendeten Acrylatpoly- olen eingesetzt werden können, kommen insbesondere Polyesteralkohole und vorzugsweise Polyetheralkohole mit einer mittleren Funktionalität von 2 bis 8, insbesondere von 2 bis 6, vorzugsweise von 2 bis 4 und einem mittleren Molekulargewicht im Bereich von 400 bis 10000 g/mol, vorzugsweise 1000 bis 8000 g/mol, in Betracht .In particular, 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.
Die Polyetheralkohole können nach bekannten Verfahren, zumeist durch katalytische Anlagerung von Alkylenoxiden, insbesondere Ethylenoxid und/oder Propylenoxid, an H-funktionelle Startsubstanzen, oder durch Kondensation von Tetrahydrofuran, her- gestellt werden. Als H-funktionelle Startsubstanzen kommen insbesondere mehrfunktioneile Alkohole und/oder Amine zum Einsatz. Bevorzugt eingesetzt werden Wasser, zweiwertige Alkohole, beispielsweise Ethylenglykol , Propylenglykol , oder Butandiole, dreiwertige Alkohole, beispielsweise Glycerin oder Trimethylol- propan, sowie höherwertige Alkohole, wie Pentaerythrit, Zuckeralkohole, beispielsweise Saccharose, Glucose oder Sorbit. Bevorzugt eingesetzte Amine sind aliphatische Amine mit bis zu 10 Kohlenstoffatomen, beispielsweise Ethylendiamin, Diethylen- triamin, Propylendiamin, sowie Aminoalkohole, wie Ethanolamin, Diethanolamin oder Triethanolamin. Als Alkylenoxide werden vorzugsweise Ethylenoxid und/oder Propylenoxid eingesetzt, wobei bei Polyetheralkoholen, die für die Herstellung von Polyurethan- Weichschäumen verwendet werden, häufig am Kettenende ein Ethylenoxidblock angelagert wird. Als Katalysatoren bei der Anlagerung der Alkylenoxide kommen insbesondere basische Verbindungen zum Einsatz, wobei hier das Kaliumhydroxid die größte technische Bedeutung hat. Wenn der Gehalt an ungesättigten Bestandteilen in den Polyetheralkoholen gering sein soll, können als Katalysatoren auch Multimetallcyanidverbindungen, sogenannte DMC-Katalysatoren, eingesetzt werden.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. As 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. In particular, 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.
Zur Herstellung von viskoelastischen Weichschäumen und Integralschäumen werden insbesondere zwei- und/oder dreifunktionelle Polyetheralkohole eingesetzt.In particular, two- and / or three-functional polyether alcohols are used to produce viscoelastic flexible foams and integral foams.
Bevorzugt werden zur Herstellung von Weich- und Halbhartschaumstoffen nach dem erfindungsgemäßen Verfahren zwei- und/oder dreifunktionelle Polyetheralkohole eingesetzt, die primäre Hydroxylgruppen aufweisen, insbesondere solche mit einem Ethylenoxidblock am Kettenende oder solche, die nur auf Ethylenoxid basieren.For the production of flexible and semi-rigid foams by the process according to the invention, preference is given to using two- and / or three-functional polyether alcohols which have primary hydroxyl groups, in particular those having an ethylene oxide block at the chain end or those which are based only on ethylene oxide.
Zu den Verbindungen mit mindestens zwei aktiven Wasserstoffatomen gehören auch die Kettenverlängerungs- und Vernetzungsmittel, die gegebenenfalls mitverwendet werden können. Als Kettenverlängerungs- und Vernetzungsmittel werden vorzugsweise 2- und 3-funktioneile Alkohole mit Molekulargewichten unter 400 g/mol, insbesondere im Bereich von 60 bis 150 g/mol, ver- wendet. Beispiele sind Ethylenglykol, Propylenglykol , Diethylen- glykol, Butandiol-1, 4, Glycerin oder Trimethylolpropan. Als Vernetzungsmittel können auch Diamine eingesetzt werden. Falls Kettenverlängerungs- und Vernetzungsmittel eingesetzt werden, beträgt deren Menge vorzugsweise bis zu 5 Gew.-%, bezogen auf das Gewicht der Verbindungen mit mindestens zwei aktiven Wasserstoffatomen.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.
Als Polyisocyanate können die üblichen und bekannten aromatischen Di- und Polyisocyanate einzeln oder in beliebigen Gemischen untereinander eingesetzt werden. Beispiele für aromatische Di- oder Polyisocyanate sind 2, 4-Toluylendiisocyanat (2,4-TDI), 2 , 6-Toluylendiisocyanat (2 , 6-TDI) , 2,4' -Diphenylmethandiisocyanat (2,4'-MDI), 4, 4 '-Diphenylmethandiisocyanat (4,4'-MDI), Poly- phenylpolymethylenpolyisocyanate, wie sie durch Kondensation von Anilin und Formaldehyd und anschließende Phosgenierung hergestellt werden (Polymer-MDI) , p-Phenylendiisocyanat, Toluidindii- socyanat, Xylylendiisocyanat oder 1, 5-Naphthylendiisocyanat (NDI) .The customary and known aromatic di- and polyisocyanates can be used individually or in any mixtures with one another as polyisocyanates. Examples of 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).
Vorzugsweise werden gemeinsam mit oder an Stelle von diesen mono- meren Isocyanaten oder deren Gemischen daraus hergestellte Oligo- oder Polyisocyanate, sogenannte Prepolymere, insbesondere auf Basis von TDI und MDI, eingesetzt. Diese Oligo- oder Polyiso- cyanate lassen sich aus den genannten Di- oder Polyisocyanaten oder deren Mischungen und gegebenenfalls Mono- oder Polyalkoholen durch Verknüpfung mittels Urethan-, Allophanat-, Harnstoff-, Biuret-, Uretdion-, Amid-, Isocyanurat-, Carbodiimid-, Ureton- imin-, Oxadiazintrion- oder Iminooxadiazindion-Strukturen her- stellen. Vorzugsweise werden hier Urethan-, Allophanat-, Carbodiimid-, Uretonimin-, Biuret- oder Isocyanuratgruppen aufweisende Polymere aus TDI oder MDI sowie gegebenenfalls Mono- oder Poly- alkohole verwendet.Oligo- or polyisocyanates, so-called prepolymers, in particular based on TDI and MDI, 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.
Zur Durchführung des erfindungsgemäßen Verfahrens können weitere Einsatzstoffe, insbesondere Katalysatoren, Treibmittel sowie Hilfs- und/oder Zusatzstoffe mitverwendet werden, zu denen im einzelnen folgendes zu sagen ist:To carry out the process according to the invention, further starting materials, in particular catalysts, blowing agents and auxiliaries and / or additives, can be used, for which the following should be said in detail:
Als Katalysatoren für die Herstellung der erfindungsgemäßen Polyurethan-Schaumstoffe werden die üblichen und bekannten Polyurethanbildungskatalysatoren eingesetzt, beispielsweise organische Zinnverbindungen, wie Zinndiacetat , Zinndioctoat, Dibutylzinn- dilaurat, und/oder stark basische Amine wie Diazabicyclooctan, Diazabicyclononan, Diazabicycloundecan, Triethylamin, Penta- methyldiethylentriamin, Tetramethyldiaminoethylether, Imidazole oder vorzugsweise Triethylendiamin oder Bis (N,N-Dimethylamino- ethyDether. Weiterhin werden Carbonsäuresalze, wie z.B. Kalium- acetat, Cäsiumacetat oder Tetraalkylammoniumsalze von Carbonsäuren eingesetzt. In letzter Zeit kommen verstärkt einbaubare Katalysatoren zum Einsatz, die funktioneile Gruppen wie Hydroxyl-, primäre oder sekundäre Amino- oder andere Gruppen enthalten, die mit Isocyanaten reagieren können, zum Einsatz. Diese Katalysatoren werden kovalent in die Polyurethanmatrix eingebunden und können nicht aus dem Schaum emittieren, was zu geringerem Geruch und allgemein geringeren Emissionen beiträgt, wie es aktuell vom Markt gefordert wird. Beispiele für solche bevorzugten, einbaubaren Katalysatoren sind 3-Aminopropylimidazol, N,N, '-Trimethyl-N -hydroxyethylbisaminoethylether, 6-Dimethyl- amino-1-hexanol, N- (2-Hydroxypropyl) imidazol, Bis (dimethylamino- propyl)amin oder 2- (2-(N,N-Dimethylamino)ethoxy) ethanol oder z.B. die kommerziell erhältlichen Katalysatoren Dabco NE 200, Dabco NE 1060. Die Katalysatoren werden vorzugsweise in einer Menge von 0,01 bis 10 Gew.-%, vorzugsweise 0,05 bis 5 Gew.-%, eingesetzt.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. Carboxylic acid salts, such as, for example, potassium acetate, cesium acetate or tetraalkylammonium salts of carboxylic acids, are also used. Recently, 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.
Als Treibmittel zur Herstellung der Polyurethan-Schaumstoffe wird bevorzugt Wasser eingesetzt, das mit den Isocyanatgruppen unter Freisetzung von Kohlendioxid reagiert. Gemeinsam mit oder an Stelle von Wasser können auch physikalisch wirkende Treibmittel, beispielsweise Kohlendioxid, Kohlenwasserstoffe, wie n-, iso- oder Cyclopentan, Cyclohexan oder halogenierte Kohlenwasser- Stoffe, wie Tetrafluorethan, Pentafluorpropan, Heptafluorpropan, Pentafluorbutan, Hexafluorbutan oder Dichlormonofluorethan, eingesetzt werden. Die Menge des physikalischen Treibmittels liegt dabei vorzugsweise im Bereich zwischen 1 bis 15 Gew.-%, insbesondere 1 bis 10 Gew.-%, die Menge an Wasser vorzugsweise im Bereich zwischen 0,5 bis 10 Gew.-%, insbesondere 1 bis 5 Gew.-%.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 .-%.
Als Hilfsmittel und/oder Zusatzstoffe werden beispielsweise oberflächenaktive Substanzen, Schaumstabilisatoren, Zellregler, äußere und innere Trennmittel, Füllstoffe, Flammschutzmittel, Pigmente, Hydrolyseschutzmittel sowie fungistatisch und bakteri- statisch wirkende Substanzen eingesetzt.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.
Bei der technischen Herstellung von Polyurethan-Schaumstoffen ist es üblich, die Verbindungen mit mindestens zwei aktiven Wasserstoffatomen b) und die weiteren Einsatzstoffe sowie Hilfsund/oder Zusatzstoffe vor der Umsetzung zu einer sogenannten Polyolkomponente zu vereinigen. Weitere Angaben über die verwendeten Ausgangsstoffe finden sich beispielsweise im Kunststoffhandbuch, Band 7, Polyurethane, herausgegeben von Günter Oertel, Carl-Hanser-Verlag, München, 3. Auflage 1993.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, Munich, 3rd edition 1993.
Zur Herstellung der erfindungsgemäßen Polyurethane werden die organischen Polyisocyanate a) mit den Verbindungen mit mindestens zwei aktiven Wasserstoffatomen b) sowie den genannten Treibmitteln, Katalysatoren und Hilfs- und/oder Zusatzstoffen (Polyol- komponente) zur Reaktion gebracht, wobei die erfindungsgemäß verwendeten Acrylatpolyole vorzugsweise der Polyolkomponente zugesetzt werden.To produce the polyurethanes according to the invention, 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.
Bei der Herstellung der erfindungsgemäßen Polyurethane werden Isocyanat- und Polyolkomponente in einer solchen Menge zusammengebracht, daß das Äquivalenzverhältnis von Isocyanatgruppen zur Summe der aktiven Wasserstoffatome, auch als Index bezeichnet, 0,6 bis 1,4, vorzugsweise 0,7 bis 1,2 beträgt. Wie aufgeführt, werden sehr weiche Schaumstoffe mit viskoelastischen Eigen- schatten vorzugsweise bei einem Index im Bereich zwischen 0,45 bis 1,0, bevorzugt 0,55 bis 0,95, besonders bevorzugt 0,6 bis 0,9 hergestellt.In the production of the polyurethanes according to the invention, 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 , As mentioned, 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.
Die Herstellung der Polyurethan-Schaumstoffe erfolgt vorzugs- weise nach dem one-shot-Verfahren, beispielsweise mit Hilfe der Hochdruck- oder Niederdrucktechnik. Die Schaumstoffe können in offenen oder geschlossenen metallischen Formwerkzeugen oder durch das kontinuierliche Auftragen des Reaktionsgemisches auf Bandstraßen zur Erzeugung von Schaumblöcken hergestellt werden.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.
Besonders vorteilhaft ist es, nach dem sogenannten Zweikomponentenverfahren zu arbeiten, bei dem, wie oben ausgeführt, eine Polyol- und eine Isocyanatkomponente hergestellt und verschäumt werden. Die Komponenten werden vorzugsweise bei einer Temperatur im Bereich zwischen 15 bis 120°C, vorzugsweise 20 bis 80°C vermischt und in das Formwerkzeug beziehungsweise auf die Bandstraße gebracht. Die Temperatur im Formwerkzeug liegt zumeist im Bereich zwischen 15 und 120°C, vorzugsweise zwischen 30 und 80°C.It is particularly advantageous to work according to the so-called two-component process, in which, as stated above, 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.
Die erfindungsgemäß eingesetzten Acrylatpolyole erlauben die Herstellung von elastischen und viskoelastischen Weich- und Halbhartschaumstoffen mit Raumgewichten unter 200 g/1 und hervorragenden mechanischen Eigenschaften, z.B. einer sehr guten Dehnung, Zugfestigkeit und Härte. Überraschenderweise kann durch den Einsatz der Acrylatpolyole die Rückprallelastizität der Poly- urethan-Schaumstoffe verringert werden, so dass die erwünschten viskoelastischen Eigenschaften noch verstärkt werden.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.
Die Erfindung soll an nachstehenden Beispielen näher erläutert werden.The invention is illustrated by the examples below.
In Tabelle 1 sind Polyacrylatpolyole dargestellt, die zur Herstellung der erfindungsgemäßen Schaumstoffe eingesetzt werden können.Table 1 shows polyacrylate polyols which can be used to produce the foams according to the invention.
Tabelle 1: Beispiele für PolyacrylatpolyoleTable 1: Examples of polyacrylate polyols
BA: n-Butylacrylat BA: n-butyl acrylate
HEA: 2-Hydroxyethylacrylat EHA: 2-EthylhexylacrylatHEA: 2-hydroxyethyl acrylate EHA: 2-ethylhexyl acrylate
Die Beschreibung der übrigen zur Herstellung der Polyurethan- Schaumstoffe eingesetzten Ausgangsstoffe erfolgt unten.The description of the other starting materials used for the production of the polyurethane foams is given below.
Um Bedingungen zu simulieren, wie sie bei Spezialanwendungen, bei denen Polyurethanwerkstoffe hydrolytischen Belastungen ausgesetzt sind, auftreten und, um Schaumstoffe mit messbaren Gehalten an aromatischen Aminen zu erhalten, wurden die hergestellten Schaumstoffe einer Feuchtwärmelagerung unterzogen. Hierzu wurden jeweils Probenwürfel der Kantenlänge 3 cm bei 90 % relativer Luftfeuchtigkeit und 90°C für 72 Stunden in einem Klimaschrank gelagert. Die anschließende Extraktion der gebildeten aromatischen Amine wurde mittels einer von Prof. Skarping, Universität Lund, entwickelten Methode durchgeführt. Hierzu wird der Schaum in 10 ml Essigsäure (w = 1 Gew.-%) 10 mal ausgedrückt. Die Essigsäure wurde bei zusammengedrückter Schaumprobe in einen 50-ml-Meßkolben überführt. Der Vorgang wird zweimal wiederholt und der Meßkolben anschließend bis zur Messmarke mit Essigsäure (w = 1 Gew.-%) aufgefüllt. Anschließend wurde der MDA-Gehalt der vereinigten Extrakte mittels Kapillarelektrophorese mit UV-Detektion (Gerätetyp: Biofocus 3000, Messung der Peakflachen und Vergleich mit Imidazol als internem Standard) bestimmt. Die Nachweisgrenze der kapillarelektrophoretisehen Bestimmung beträgt 1 ppm. Die in den Beispielen angegebenen MDA-Gehalte entsprechen den Absolut- gehalten des gebildeten MDA im PUR-Schaum.In order to simulate conditions such as occur in special applications in which polyurethane materials are exposed to hydrolytic loads and to obtain foams with measurable aromatic amine contents, the foams produced were subjected to a moist heat storage. For this purpose, 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. For this purpose, the foam is squeezed out 10 times in 10 ml of acetic acid (w = 1% by weight). The acetic acid was transferred to a 50 ml volumetric flask with the foam sample compressed. The process is repeated twice and the volumetric flask is then filled up to the measuring mark with acetic acid (w = 1% by weight). 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.
Formweichschäume: Verringerung des Gehaltes an aromatischen Aminen nach Feuchtwärmelagerung:Molded flexible foams: Reduction in the content of aromatic amines after moist heat storage:
Beispiel 1 (Vergleichsbeispiel)Example 1 (comparative example)
Zur Herstellung eines Polyurethan-Formweichschaums wurdenTo produce a flexible molded polyurethane foam
750 g einer Polyolkomponente aus 97 Gew. -Teilen Lupranol 2090750 g of a polyol component from 97 parts by weight of Lupranol 2090
(Elastogran GmbH), 3 Gew. -Teilen Lupranol® 2047 (Elastogran GmbH), 3,31 Gew. -Teilen Wasser, 0,22 Gew. -Teilen Triethylendi- amin, 0,14 Gew. -Teilen Lupragen® N 206 (BASF Aktiengesellschaft), 0,5 Gew. -Teilen Tegostab® B 8631 (Goldschmidt AG) mit 350 g einer Isocyanatkomponente aus 42 Gew. -Teilen Lupranat M 20 W (Polymer- MDI, Elastogran GmbH) und einem Gemisch aus 2,4'- und 4,4X-MDI (11 Gew. -Teile Lupranat® ME und 47 Gew. -Teile Lupranat® MI, Elastogran GmbH) bei einem Index von 0,9 vermischt und das aufschäumende Gemisch in eine auf 53°C temperierte Aluminiumform mit den Maßen 40 cm x 40 cm x 10 cm gegeben.(Elastogran GmbH), 3 parts by weight of Lupranol ® 2047 (Elastogran GmbH), 3.31 parts by weight of water, 0.22 parts by weight of triethylene diamine, 0.14 parts by weight of Lupragen ® N 206 ( BASF Aktiengesellschaft), 0.5 wt. parts by Tegostab ® B 8631 (Goldschmidt AG) with 350 g of an isocyanate component of 42 wt. parts by Lupranat M 20 W (polymer MDI, Elastogran GmbH) and a mixture of 2,4 ' - and 4.4 X MDI (.. 11 Parts by weight Lupranat.RTM ME and 47 parts by weight of Lupranat MI ®, Elastogran GmbH) at an index of 0.9 and the foaming mixture into a temperature-controlled at 53 ° C aluminum mold with the dimensions 40 cm x 40 cm x 10 cm.
Der resultierende Schaumstoff enthielt ungealtert keine nachweisbaren Mengen an MDA und nach Feuchtwärmealterung 32 ppm 4,4λ-MDA und 78 ppm 2,4,-MDA.The resulting foam contained no detectable amounts of MDA when aged and 32 ppm of 4.4 λ -MDA and 78 ppm of 2,4 , -MDA after aging under moist heat.
Beispiel 2 (Erfindungsgemäß)Example 2
Es wurde verfahren wie in Beispiel 1 mit dem Unterschied, dass in der Polyolkomponente anstelle von Lupranol® 2090 97 Gew. -Teile des Acrylatpolyols 1 aus Tabelle 1 verwendet wurden. Die Ver- schäumung erfolgte ebenfalls bei einem Index von 0,9.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.
Der resultierende Schaumstoff enthielt ungealtert keine nachweisbaren Mengen an MDA und nach Feuchtwärmealterung 6 ppm 4,4 -MDA und 20 ppm 2,4V-MDA. Es wurde gezeigt, daß der MDA-Gehalt des gealterten Schaums durch Einsatz des erfindungsgemäßen Acrylatpolyols deutlich reduziert werden konnte.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.
Beispiel 3 (Vergleichsbeispiel)Example 3 (comparative example)
Es erfolgte die Herstellung eines Polyurethan-Formweichschaums durch Vermischen von 750 g einer Polyolkomponente wie in Vergleichsbeispiel 1, bei der jedoch an Stelle von Triethylendiamin 0,8 Gew. -Teile 3-Aminopropylimidazol und an Stelle von 0,14 Gew.- Teilen 0,8 Gew. -Teile Lupragen® N 206 verwendet wurden, mit 360 g der Isocyanatkomponente aus Vergleichsbeispiel 1 (Index = 1,0) und Überführen des aufschäumenden Gemisches in eine auf 53°C temperierte Aluminiumform der Maße 40 cm x 40 cm x 10 cm.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. Lupragen ® N were used 206, with 360 g of the isocyanate component of Comparative example 1 (index = 1.0) and transferring the foaming mixture cm in a temperature-controlled at 53 ° C aluminum mold of dimensions 40 x 40 cm x 10 cm ,
Der resultierende Schaumstoff enthielt ungealtert keine nachweisbaren Mengen an MDA und nach Feuchtwärmealterung 397 ppm 4, 4 * -MDA und 687 ppm 2, 4' -MDA.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.
Beispiel 4 (Erfindungsgemäß)Example 4
Es wurde verfahren wie in Beispiel 3 (lndex=l,0) mit dem Unterschied, dass in der Polyolkomponente 48,5 Teile des Acrylatpolyols 1 aus Tabelle 1 und nur 48,5 Teile Lupranol® 2090 verwendet wurden.The procedure with the difference that 48.5 parts of the acrylate polyol 1 of Table 1, and only 48.5 parts of Lupranol ® 2090 were used in Example 3 (0 index = l) in the polyol component.
Der resultierende Schaumstoff enthielt ungealtert keine nachweisbaren Mengen an MDA und nach Feuchtwärmealterung 58 ppm 4, 4* -MDA und 127 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.
Der MDA-Gehalt des gealterten Schaums konnte also durch Einsatz des erfindungsgemäßen Acrylatpolyols deutlich reduziert werden.The MDA content of the aged foam could thus be significantly reduced by using the acrylate polyol according to the invention.
Blockweichschäume: Verringerung des Gehaltes an aromatischen Aminen nach Feuchtwärmelagerung:Block flexible foams: Reduction in the content of aromatic amines after moist heat storage:
Beispiel 5 (Vergleichsbeispiel)Example 5 (comparative example)
Zur Herstellung eines Polyurethan-Blockweichschaums wurden 441 g einer Polyolkomponente aus 100 Gew. -Teilen Lupranol® 2080 (Elastogran GmbH), 2,7 Gew. -Teilen Wasser, 0,63 Gew. -Teilen Tegostab® BF 2370 und 0,17 Gew. -Teilen Kosmos® 29 (Goldschmidt AG), 0,09 Gew. -Teilen Lupragen® N 201 und 0,04 Teilen Lupragen® N 101 (BASF Aktiengesellschaft) mit 159 g Toluylendiisocyanat (Isomerengemisch 80/20, Lupranat® T 80, Elastogran GmbH) bei einem Index von 1,1 vermischt und das aufschäumende Gemisch in eine oben offene Pappschachtel mit den Maßen 22 cm x 22 cm x 22 cm gegeben.For preparing a flexible polyurethane slabstock foam were 441 g of a polyol component, 100 wt. Parts by Lupranol ® 2080 (Elastogran GmbH), 2.7 wt. Parts by water, 0.63 wt. Parts by Tegostab ® BF 2370, and 0.17 wt . Parts Kosmos ® 29 (Goldschmidt AG), 0.09 parts by weight Lupragen ® N 201 and 0.04 parts Lupragen ® N 101 (BASF Aktiengesellschaft) with 159 g tolylene diisocyanate (mixture of isomers 80/20, Lupranat ® T 80, Elastogran GmbH) mixed at an index of 1.1 and the foaming mixture in given a cardboard box with the dimensions 22 cm x 22 cm x 22 cm open at the top.
Der resultierende Schaumstoff enthielt ungealtert keine nach- weisbaren Mengen an TDA und nach Feuchtwärmealterung 33 ppm 2,4-TDA und 9 ppm 2,6-TDA.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.
Beispiel 6 (Erfindungsgemäß)Example 6
Es wurde verfahren wie in Beispiel 5 mit dem Unterschied, dass in der Polyolkomponente 50 Teile Lupranol 2080 und 50 Teile des Acrylatpolyols 3 (Tabelle 1) verwendet wurden. Die Verschäumung erfolgte ebenfalls bei einem Index von 1,1.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.
Der resultierende Schaumstoff enthielt ungealtert keine nachweisbaren Mengen an TDA und nach Feuchtwärmealterung 20 ppm 2,4-TDA und 7 ppm 2,6-TDA.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.
Der TDA-Gehalt des gealterten Schaums konnte also durch Einsatz des erfindungsgemäßen Acrylatpolyols deutlich reduziert werden.The TDA content of the aged foam could thus be significantly reduced by using the acrylate polyol according to the invention.
Beispiel 7 (Erfindungsgemäß)Example 7
Es wurde verfahren wie in Beispiel 5 mit dem Unterschied, dass in der Polyolkomponente nur 1,7 Teile Lupranol 2080 und 98,3 Teile des Acrylatpolyols 3 (Tabelle 1) verwendet wurden. Die Verschäumung erfolgte ebenfalls bei einem Index von 1,1.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.
Der resultierende Schaumstoff enthielt ungealtert keine nach- weisbaren Mengen an TDA und nach Feuchtwärmealterung 11 ppm 2,4-TDA und 4 ppm 2,6-TDA.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.
Der TDA-Gehalt des gealterten Schaums konnte also durch Einsatz des erfindungsgemäßen Acrylatpolyols deutlich reduziert werden.The TDA content of the aged foam could thus be significantly reduced by using the acrylate polyol according to the invention.
Beispiel 8 (Erfindungsgemäß)Example 8
Es wurde verfahren wie in Beispiel 5 mit dem Unterschied, dass in der Polyolkomponente 70 Teile Lupranol 2080 und 30 Teile des Acrylatpolyols 6 (Tabelle 1) verwendet wurden. Die Verschäumung erfolgte ebenfalls bei einem Index von 1,1.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.
Der resultierende Schaumstoff enthielt ungealtert keine nachweisbaren Mengen an TDA und nach Feuchtwärmealterung 13 ppm 2,4-TDA und 3 ppm 2,6-TDA. Der TDA-Gehalt des gealterten Schaums konnte also durch Einsatz des erfindungsgemäßen Acrylatpolyols deutlich reduziert werden.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.
Beispiel 9 (Erfindungsgemäß)Example 9
Es wurde verfahren wie in Beispiel 5 mit dem Unterschied, dass in der Polyolkomponente 30 Teile Lupranol 2080 und 70 Teile des Acrylatpolyols 6 (Tabelle 1) verwendet wurden. Die Verschäumung erfolgte ebenfalls bei einem Index von 1,1.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.
Der resultierende Schaumstoff enthielt ungealtert keine nachweisbaren Mengen an TDA und nach Feuchtwärmealterung 10 ppm 2,4-TDA und 3 ppm 2,6-TDA.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.
Der TDA-Gehalt des gealterten Schaums konnte also durch Einsatz des erfindungsgemäßen Acrylatpolyols deutlich reduziert werden.The TDA content of the aged foam could thus be significantly reduced by using the acrylate polyol according to the invention.
Beispiel 10 (Erfindungsgemäß)Example 10
Es wurde verfahren wie in Beispiel 5 mit dem Unterschied, dass in der Polyolkomponente nur 1,7 Teile Lupranol 2080 und 98,3 Teile des Acrylatpolyols 6 (Tabelle 1) verwendet wurden. Die Verschäumung erfolgte ebenfalls bei einem Index von 1,1.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.
Der resultierende Schaumstoff enthielt ungealtert keine nachweisbaren Mengen an TDA und nach Feuchtwärmealterung 9 ppm 2,4-TDA und 3 ppm 2,6-TDA.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.
Der TDA-Gehalt des gealterten Schaums konnte also durch Einsatz des erfindungsgemäßen Acrylatpolyols deutlich reduziert werden.The TDA content of the aged foam could thus be significantly reduced by using the acrylate polyol according to the invention.
Einstellung von Viskoelastizität bzw. Rückprallelastizität bei viskoelastischen BlockweichschäumenAdjustment of viscoelasticity or rebound elasticity in viscoelastic block flexible foams
Im Vergleich zu dem Standard-System (Vergleichsbeispiel 11) vermindert die Zugabe von Acrylatpolyolen deutlich die Rückprallelastizität der Schaumstoffe.In comparison to the standard system (comparative example 11), the addition of acrylate polyols significantly reduces the resilience of the foams.
Beispiel 11 (Vergleichsbeispiel)Example 11 (comparative example)
Es wurde ein Polyurethan-Weichschaum durch Vermischen vonIt became a flexible polyurethane foam by mixing
1000 g einer Polyolkomponente aus 100 Gew. -Teilen Lupranol 20801000 g of a polyol component from 100 parts by weight of Lupranol 2080
(Elastogran GmbH), 2,65 Gew. -Teilen Wasser, 0,25 Gew. -Teilen Lupragen® N 101 (BASF Aktiengesellschaft), 0,04 Gew. -Teilen Lupragen® N 206 (BASF Aktiengesellschaft), 0,2 Gew. -Teilen Kosmos® 29 (Goldschmidt AG) 0,8 Gew. -Teilen Tegostab® BF 2370(Elastogran GmbH), 2.65 wt. Parts by water, 0.25 wt. Parts by Lupragen ® N 101 (BASF Aktiengesellschaft), 0.04 wt. Parts by Lupragen® N 206 (BASF Aktiengesellschaft), 0.2 wt . Parts Kosmos ® 29 (Goldschmidt AG) 0.8 parts by weight Tegostab ® BF 2370
(Goldschmidt AG) mit 374 g Toluylendiisocyanat (Isomerengemisch 80/20, Lupranat® T 80, Elastogran GmbH), Index = 1,15, und Überführen des aufschäumenden Gemisches in eine oben offene Kiste mit den Maßen 40 cm x 40 cm x 40 cm hergestellt.(Goldschmidt AG) with 374 g tolylene diisocyanate (mixture of isomers 80/20, Lupranat ® T 80, Elastogran GmbH), index = 1.15, and transferring the foaming mixture into an open-top box with the dimensions 40 cm x 40 cm x 40 cm.
5 Die Rückprallelastizität des resultierenden Schaumes ist in Tabelle 2 aufgeführt.5 The resilience of the resulting foam is shown in Table 2.
Beispiel 12 (Erfindungsgemäß) 0 Es wurde verfahren wie in Beispiel 11 mit dem Unterschied, dass in der Polyolkomponente 5 Teile des Acrylatpolyols 2 aus Tabelle 1 und 95 Teile Lupranol 2080 verwendet wurden. Die Verschäumung erfolgte ebenfalls bei einem Index von 1,15 5Example 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
Die Rückprallelastizität ist in Tabelle 2 aufgeführt.The resilience is shown in Table 2.
Beispiel 13 (Erfindungsgemäß)Example 13
Q Es wurde verfahren wie in Beispiel 11 mit dem Unterschied, dass in der Polyolkomponente 10 Teile des Acrylatpolyols 2 aus Tabelle 1 und 90 Teile Lupranol 2080 verwendet wurden. Die Verschäumung erfolgte ebenfalls bei einem Index von 1,15. Q The procedure was as in Example 11, with the difference that 10 parts of the acrylate polyol 2 from Table 1 and 90 parts of Lupranol 2080 were used in the polyol component. Foaming also took place at an index of 1.15.
5 Die Rückprallelastizität ist in Tabelle 2 aufgeführt.5 The resilience is shown in Table 2.
Beispiel 14 (Erfindungsgemäß)Example 14
Es wurde verfahren wie in Beispiel 11 mit dem Unterschied, 0 dass in der Polyolkomponente 20 Teile des Acrylatpolyols 2 aus Tabelle 1 und 80 Teile Lupranol 2080 verwendet wurden. Die Verschäumung erfolgte ebenfalls bei einem Index von 1,15.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.
Die Rückprallelastizität ist in Tabelle 2 aufgeführt. 5The resilience is shown in Table 2. 5
Tabelle 2Table 2
00
5 Wie Tabelle 2 zeigt, kann bei konventionellen Blockschäumen vergleichbarer Dichte durch Zugabe eines geeigneten Acrylatpolyols die Elastizität deutlich abgesenkt werden, so dass viskoelastische Schaumstoffe entstehen. 5 5 As shown in Table 2, with conventional block foams of comparable density, the elasticity can be significantly reduced by adding a suitable acrylate polyol, so that viscoelastic foams are formed. 5
Halbhartschäume: Verbesserung der AlterungsbeständigkeitSemi-rigid foams: improvement of aging resistance
Beispiel 15 (Vergleichsbeispiel)Example 15 (comparative example)
10 Zur Herstellung eines Polyurethan-Halbhartschaums wurden eine Polyolkomponente aus 92 Gew. -Teilen Lupranol® 2090 (Elastogran GmbH), 8 Gew. -Teilen Polyol PP50 (Perstorp AB), 2 Gew. -Teilen eines Amin gestarteten Polyoxypropylendiol , Hydroxyzahl: 250, 2,81 Gew. -Teilen Wasser, 0,26 Gew. -Teilen Jeffcat® ZF10 (Huntsman., 10 for preparing a polyurethane semirigid foam 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
15 Corporation), 0,26 Gew. -Teilen Kaliumacetat (47%ig in Ethylen- glykol) mit einer Isocyanatkomponente bestehend aus einer Mischung aus 31,5 Gew. -Teilen Lupranat® M 20 W (Polymer-MDI , Elastogran GmbH) und 68,5 Gew. -Teilen eines Prepolymers (NCO- Gehalt: 26 %) aus Lupranat® MM103, Lupranat® ME (Elastrogan GmbH)15 Corporation), 0.26 wt. Parts by potassium acetate (47% in ethylene glycol) with an isocyanate component consisting of a mixture of 31.5 wt. Parts by Lupranat ® M 20 W (polymeric MDI, Elastogran GmbH) and 68.5 parts by weight of a prepolymer (NCO content: 26%) made of Lupranat ® MM103, Lupranat ® ME (Elastrogan GmbH)
20 und Tripropylenglykol bei einem Index von 0,97 vermischt und das aufschäumende Gemisch in eine auf 44°C temperierte Aluminiumform mit den Maßen 20 cm x 20 cm x 4 cm gegeben und ein Kissen mit der Dichte 95 kg/m3 erhalten.20 and tripropylene glycol are mixed at an index of 0.97 and the foaming mixture is placed in an aluminum mold with the dimensions 20 cm x 20 cm x 4 cm and heated to 44 ° C. and a cushion with a density of 95 kg / m 3 is obtained.
25 Die prozentuale Abnahme der Reißfestigkeit bzw. der Dehnung nach Wärmelagerung (7 Tage 140°C) betrug 35 % bzw. 60 %. Die prozentuale Abnahme der Stauchhärte bei 40 % Stauchung betrug nach Feucht-Wärme-Lagerung (5 h 120°C bei 100 % Luftfeuchtigkeit, 3 Zyklen) 53 %.25 The percentage decrease in tear strength or elongation after heat storage (7 days at 140 ° C.) was 35% and 60%, respectively. The percentage decrease in compression hardness at 40% compression was 53% after storage under moist heat (120 ° C for 5 h at 100% humidity, 3 cycles).
3030
Beispiel 16 (Erfindungsgemäß)Example 16 (According to the Invention)
Es wurde verfahren wie in Beispiel 1 mit dem Unterschied, dass in der Polyolkomponente anstelle von 92 Gew. -Teilen Lupranol 2090The procedure was as in Example 1, with the difference that in the polyol component instead of 92 parts by weight of Lupranol 2090
35 61 Gew. -Teile Lupranol® 2090 und 31 Gew. -Teile des Acrylatpolyols 7 aus Tabelle 1 verwendet wurden. Des weiteren wurde der Gehalt des Polyols PP50 von 8 Gew. -Teile auf 2 Gew. -Teile reduziert und zusätzlich 0,25 Teile Tegostab® BF 2370 (Goldschmidt AG) eingesetzt. Die Dichte des resultierenden Kissens betrug 77 kg/m3.35 61 parts by wt. Lupranol ® 2090 and 31 parts by wt. Of the acrylate polyol were 7 of Table 1 was used. Further, the content of the polyol PP50 of 8 parts by wt., 2 parts by wt. Was reduced and additionally 0.25 parts Tegostab ® BF 2370 (Goldschmidt AG). The density of the resulting cushion was 77 kg / m 3 .
4040
Die prozentuale Abnahme der Reißfestigkeit bzw. der Dehnung nach Wärmelagerung (7 Tage 140°C) betrug 18 % bzw. 14 %. Die prozentuale Abnahme der Stauchhärte bei 40 % Stauchung betrug nach Feucht-Wärme-Lagerung (5 h 120°C bei 100 % Luftfeuchtigkeit,The percentage decrease in tensile strength or elongation after heat storage (7 days at 140 ° C.) was 18% and 14%, respectively. The percentage decrease in compression hardness at 40% compression after storage under moist and warm conditions (5 h 120 ° C at 100% humidity,
45 3 Zyklen) 37 %. 45 3 cycles) 37%.

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von Polyurethan-Schaumstoffen mit einer Dichte von unter 200 g/1, durch Umsetzung von1. Process for the production of polyurethane foams with a density of less than 200 g / 1, by reaction of
a) Polyisocyanaten mita) with polyisocyanates
b) Verbindungen mit mindestens zwei mit Isocyanatgruppen reaktiven Wasserstoffatomen,b) compounds with at least two hydrogen atoms reactive with isocyanate groups,
dadurch gekennzeichnet, dass die Polyisocyanate a) aromatische Di- oder Polyisocyanate sind und die Verbindungen mit mindestens zwei mit Isocyanatgruppen reaktiven Wasserstoffatomen b) mindestens ein Acrylatpolyol enthalten.characterized in that the polyisocyanates a) are aromatic di- or polyisocyanates and the compounds with at least two hydrogen atoms reactive with isocyanate groups b) contain at least one acrylate polyol.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Acrylatpolyole ein mittleres Molekulargewicht Mn von maximal 12000 g/mol aufweisen.2. The method according to claim 1, characterized in that the acrylate polyols have an average molecular weight Mn of at most 12000 g / mol.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Acrylatpolyole ein mittleres Molekulargewicht Mn von maximal 8000 g/mol aufweisen.3. The method according to claim 1, characterized in that the acrylate polyols have an average molecular weight Mn of at most 8000 g / mol.
4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Acrylatpolyole ein mittleres Molekulargewicht Mn von maximal 6000 g/mol aufweisen.4. The method according to claim 1, characterized in that the acrylate polyols have an average molecular weight Mn of at most 6000 g / mol.
5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Acrylatpolyole durch Polymerisation von hydroxyfunktionalisierten (Meth) acrylaten hergestellt werden.5. The method according to claim 1, characterized in that the acrylate polyols are prepared by polymerizing hydroxy-functionalized (meth) acrylates.
6. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Acrylatpolyole durch Copolymerisation von hydroxyfunktionalisierten (Meth) acrylaten mit nicht hydroxyfunktionellen, olefinische Doppelbindungen enthaltenden Monomeren hergestellt werden.6. The method according to claim 1, characterized in that the acrylate polyols are prepared by copolymerization of hydroxy-functionalized (meth) acrylates with non-hydroxy-functional monomers containing olefinic double bonds.
7. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Acrylatpolyole durch Copolymerisation von hydroxyfunktionalisierten (Meth) acrylaten mit Ethen, Propen, Buten, Isobuten, Diisobuten, Acrylnitril, Acrylamid, Acrolein, Styrol, Methyl- styrol, Divinylbenzol, Maleinsäureanhydrid, Vinylester von Carbonsäuren oder ungesättigten Carbonsäuren, wie zum Bei- spiel Maleinsäure, Fumarsäure oder Crotonsäure oder deren Derivaten, hergestellt werden.7. The method according to claim 1, characterized in that the acrylate polyols by copolymerization of hydroxy-functionalized (meth) acrylates with ethene, propene, butene, isobutene, diisobutene, acrylonitrile, acrylamide, acrolein, styrene, methyl styrene, divinylbenzene, maleic anhydride, vinyl ester of Carboxylic acids or unsaturated carboxylic acids, such as game maleic acid, fumaric acid or crotonic acid or their derivatives.
8. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die8. The method according to claim 1, characterized in that the
5 Acrylatpolyole durch Copolymerisation von hydroxyfunktionalisierten (Meth) acrylaten mit nicht hydroxylfunktionellen (Meth) acrylaten hergestellt werden.5 acrylate polyols can be prepared by copolymerizing hydroxy-functionalized (meth) acrylates with non-hydroxyl-functional (meth) acrylates.
9. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die 10 Acrylatpolyole durch Polymerisation von Ci-bis C8-Hydroxy- alkyl (meth) acrylaten hergestellt werden.9. The method according to claim 1, characterized in that the 10 acrylate polyols are prepared by polymerizing C 1 -C 8 -hydroxyalkyl (meth) acrylates.
10. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Acrylatpolyole durch Copolymerisation von Cχ-bis C8-Hydroxy-10. The method according to claim 1, characterized in that the acrylate polyols by copolymerization of Cχ-to C 8 -hydroxy-
15 alkyl (meth) acrylaten mit Alkyl (meth) acrylaten mit Cι~ bis Cι0- Alkylgruppen hergestellt werden.15 alkyl (meth) acrylates with alkyl (meth) acrylates with C 1 to C 0 alkyl groups can be prepared.
11. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Verbindungen mit mindestens zwei mit Isocyanatgruppen11. The method according to claim 1, characterized in that the compounds having at least two with isocyanate groups
20 reaktiven Wasserstoffatomen b) mindestens ein Acrylatpolyol und mindestens einen Polyetheralkohol oder Polyesteralkohol enthalten.20 reactive hydrogen atoms b) contain at least one acrylate polyol and at least one polyether alcohol or polyester alcohol.
12. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass 25 Acrylatpolyole in einer Menge von 0,1 bis 50 Gew. -Teilen, bezogen auf 100 Gew. -Teile der Verbindungen mit mindestens zwei mit Isocyanatgruppen reaktiven Wasserstoffatomen b) , eingesetzt werden.12. The method according to claim 1, characterized in that 25 acrylate polyols are used in an amount of 0.1 to 50 parts by weight, based on 100 parts by weight of the compounds having at least two hydrogen atoms b) which are reactive with isocyanate groups.
30 13. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass30 13. The method according to claim 1, characterized in that
Acrylatpolyole in einer Menge von 0,5 bis 40 Gew. -Teilen, bezogen auf 100 Gew. -Teile der Verbindungen mit mindestens zwei mit Isocyanatgruppen reaktiven Wasserstoffatomen b) , eingesetzt werden.Acrylate polyols are used in an amount of 0.5 to 40 parts by weight, based on 100 parts by weight of the compounds having at least two hydrogen atoms b) which are reactive with isocyanate groups.
3535
14. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Acrylatpolyole in einer Menge von 1 bis 30 Gew-Teilen, bezogen auf 100 Gew. -Teile der Verbindungen mit mindestens zwei mit Isocyanatgruppen reaktiven Wasserstoffatomen b) ,14. The method according to claim 1, characterized in that the acrylate polyols in an amount of 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),
40 eingesetzt werden.40 are used.
15. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass als Polyisocyanate a) Toluylendiisocyanat, Diphenylmethandiisocyanat, Polyphenylpolymethylenpolyisocyanat, Phenylen-15. The method according to claim 1, characterized in that as polyisocyanates a) tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylpolymethylene polyisocyanate, phenylene
45 diisocyanat, Xylylendiisocyanat , Naphthylendiisocyanat, Tolidindiisocyanat, oder Gemische der genannten Isocyanate eingesetzt werden.45 diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, Tolidine diisocyanate, or mixtures of the isocyanates mentioned.
16. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die 5 Polyisocyanate a) durch Einbau von Urethan-, Allophanat-,16. The method according to claim 1, characterized in that the 5 polyisocyanates a) by incorporating urethane, allophanate,
Harnstoff-, Biuret-, Uretdion-, Amid-, Isocyanurat-, Carbodi- imid-, Uretonimin-, Oxadiazintrion- oder Iminooxadiazindion- Strukturen modifiziert wurden.Urea, biuret, uretdione, amide, isocyanurate, carbodimide, uretonimine, oxadiazinetrione or iminooxadiazinedione structures were modified.
10 17. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Polyisocyanate a) durch Einbau von Urethan-, Allophanat-, Uretdion-, Carbodiimid-, Uretonimin-, Biuret- oder Iso- cyanurat-Strukturen modifiziert wurden.17. The method according to claim 1, characterized in that the polyisocyanates a) have been modified by incorporating urethane, allophanate, uretdione, carbodiimide, uretonimine, biuret or isocyanurate structures.
15 18. Polyurethan-Schaumstoff, herstellbar nach einem der Ansprüche 1 bis 17.15 18. Polyurethane foam, producible according to one of claims 1 to 17.
19. Polyolmischung zur Herstellung von Polyurethan-Schaumstoffen, enthaltend mindestens ein Acrylatpolyol und mindestens einen 20 Polyetheralkohol oder einen Polyesteralkohol .19. Polyol mixture for the production of polyurethane foams, containing at least one acrylate polyol and at least one polyether alcohol or a polyester alcohol.
2525
3030
3535
4040
45 45
EP03740193A 2002-06-13 2003-06-06 Method for the production of polyurethane foam materials Withdrawn EP1516005A1 (en)

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DE10226414A DE10226414A1 (en) 2002-06-13 2002-06-13 Process for the production of polyurethane foams
DE10226414 2002-06-13
PCT/EP2003/005935 WO2003106528A1 (en) 2002-06-13 2003-06-06 Method for the production of polyurethane foam materials

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JP5973130B2 (en) * 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 Method for producing an upper layer containing an inorganic material for floor covering
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