EP1516005A1

EP1516005A1 - Method for the production of polyurethane foam materials

Info

Publication number: EP1516005A1
Application number: EP03740193A
Authority: EP
Inventors: Dieter Rodewald; Bernd Bruchmann; Horst Binder; Heinz-Dieter Lutter; Ansgar Frericks; Markus Templin; Martin Kreyenschmidt
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2002-06-13
Filing date: 2003-06-06
Publication date: 2005-03-23
Also published as: KR20050008814A; CA2488636A1; AU2003276909A1; CN1313508C; WO2003106528A1; US20050176838A1; CN1659203A; JP2005534731A; DE10226414A1

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

Process for the production of polyurethane foams

description

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. 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.

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).

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. 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.

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.

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.

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.

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.

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

a) with polyisocyanates

b) compounds with at least two hydrogen atoms reactive with isocyanate groups,

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.

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. 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.

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. For example, the production of the acrylate polyols used according to the invention is preferably carried out without the use of polymerization regulators.

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.

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.

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.

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, propyl (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, ethylhexyl (meth) acrylate and / or hexanediol di

(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.

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.

The number-average molar masses (Mn) of the acrylate polyols used according to the invention are particularly preferably between

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.

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.

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.

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.

In particular, two- and / or three-functional polyether alcohols are used to produce viscoelastic flexible foams and integral foams.

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.

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.

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).

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.

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:

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.

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.

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.

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.

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.

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.

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.

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.

The invention is illustrated by the examples below.

Table 1 shows polyacrylate polyols which can be used to produce the foams according to the invention.

Table 1: Examples of polyacrylate polyols

BA: n-butyl acrylate

HEA: 2-hydroxyethyl acrylate EHA: 2-ethylhexyl acrylate

The description of the other starting materials used for the production of the polyurethane foams is given below.

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.

Molded flexible foams: Reduction in the content of aromatic amines after moist heat storage:

Example 1 (comparative example)

To produce a flexible molded polyurethane foam

750 g of a polyol component from 97 parts by weight of Lupranol 2090

(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.

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.

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.

Example 3 (comparative example)

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 ,

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.

Example 4

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.

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:

Example 5 (comparative example)

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.

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 6

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 7

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.

Example 8

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 9

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.

Example 10

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.

Adjustment of viscoelasticity or rebound elasticity in viscoelastic block flexible foams

In comparison to the standard system (comparative example 11), the addition of acrylate polyols significantly reduces the resilience of the foams.

Example 11 (comparative example)

It became a flexible polyurethane foam by mixing

1000 g of a polyol component from 100 parts by weight of Lupranol 2080

(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) 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 The resilience of the resulting foam is shown in Table 2.

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

The resilience is shown in Table 2.

Example 13

_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 The resilience is shown in Table 2.

Example 14

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.

The resilience is shown in Table 2. 5

Table 2

0

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

Semi-rigid foams: improvement of aging resistance

Example 15 (comparative example)

., 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 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 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 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).

30

Example 16 (According to the Invention)

The 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 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 .

40

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 cycles) 37%.

Claims

claims

1. Process for the production of polyurethane foams with a density of less than 200 g / 1, by reaction of

a) with polyisocyanates

b) compounds with at least two hydrogen atoms reactive with isocyanate groups,

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. 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. 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. 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. The method according to claim 1, characterized in that the acrylate polyols are prepared by polymerizing hydroxy-functionalized (meth) acrylates.

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. 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. The method according to claim 1, characterized in that the

5 acrylate polyols can be prepared by copolymerizing hydroxy-functionalized (meth) acrylates with non-hydroxyl-functional (meth) acrylates.

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. The method according to claim 1, characterized in that the acrylate polyols by copolymerization of Cχ-to C ₈ -hydroxy-

15 alkyl (meth) acrylates with alkyl (meth) acrylates with C 1 to C ₀ alkyl groups can be prepared.

11. The method according to claim 1, characterized in that the compounds having at least two with isocyanate groups

20 reactive hydrogen atoms b) contain at least one acrylate polyol and at least one polyether alcohol or polyester alcohol.

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. The method according to claim 1, characterized in that

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.

35

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 are used.

15. The method according to claim 1, characterized in that as polyisocyanates a) tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylpolymethylene polyisocyanate, phenylene

45 diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, Tolidine diisocyanate, or mixtures of the isocyanates mentioned.

16. The method according to claim 1, characterized in that the 5 polyisocyanates a) by incorporating urethane, allophanate,

Urea, biuret, uretdione, amide, isocyanurate, carbodimide, uretonimine, oxadiazinetrione or iminooxadiazinedione structures were modified.

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. Polyurethane foam, producible according to one of claims 1 to 17.

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.

25

30

35

40

45