EP2760904A1 - Procédé de fabrication d'un élément en mousse moulé - Google Patents

Procédé de fabrication d'un élément en mousse moulé

Info

Publication number
EP2760904A1
EP2760904A1 EP12723817.8A EP12723817A EP2760904A1 EP 2760904 A1 EP2760904 A1 EP 2760904A1 EP 12723817 A EP12723817 A EP 12723817A EP 2760904 A1 EP2760904 A1 EP 2760904A1
Authority
EP
European Patent Office
Prior art keywords
cyclic oligosaccharide
groups
modified cyclic
modified
koh
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.)
Withdrawn
Application number
EP12723817.8A
Other languages
German (de)
English (en)
Inventor
Günter Baumgartner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eurofoam GmbH
Original Assignee
Eurofoam GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Eurofoam GmbH filed Critical Eurofoam GmbH
Publication of EP2760904A1 publication Critical patent/EP2760904A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/16—Cyclodextrin; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3218—Polyhydroxy compounds containing cyclic groups having at least one oxygen atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3237—Polyamines aromatic
    • C08G18/324—Polyamines aromatic containing only one aromatic ring
    • 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
    • C08G18/4072—Mixtures of compounds of group C08G18/63 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
    • C08G18/28—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
    • C08G18/4081—Mixtures of compounds of group C08G18/64 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
    • C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6484—Polysaccharides and derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—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
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/005—< 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 method for producing a shaped foam element for a padding, a mattress, a carpet, a trim part for a motor vehicle or a furniture based on a polyurethane foam formed by reacting a plurality of components comprising at least one isocyanate, at least one polyol and water in which there is further added at least one modified cyclic oligosaccharide having a cavity, a corresponding molded foam element, and the use of a cyclic oligosaccharide, in particular a cyclodextrin, in the manufacture of a padding, a mattress, a carpet, a trim piece Motor vehicle or a piece of furniture, at least partially consisting of a polyurethane foam.
  • cyclodextrins have also found its way into the patent literature as "odor neutralizers.”
  • WO 2008/112712 A1 discloses a process for producing a hygiene or wound care product from a polyurethane foam absorbing odorous substances, according to which US Pat DE 199 28 689 A1 and WO 01/00723 A1 describe a process for the production of upholstery for furniture, carpets or mattresses, based on flexible polyurethane foams, the production of which is described in US Pat Deactivation of amine catalysts in polyisocyanate polyaddition products in the presence of organic, cyclic compounds Melting with a molecular weight of 200 to 3000 g / mol is performed to get by the inclusion of odors Foggingprobleme under control.
  • Modified cyclic compounds are optionally modified cyclodextrins, resorcinearzenes, cyclophanes and cyclocalixarenes.
  • DE 10 2007 062 525 A1 discloses polyurethanes prepared on the basis of polyols and polyisocyanates which contain 0.1 to 45% by weight, based on the weight of the polyol component, of cyclodextrins and / or cyclodextrin derivatives in chemically bound form.
  • the polyurethanes are prepared using polyester polyols, polyether polyols, glycols and / or C 1 -C 6 alkanediols and using MDI, TDI, HDI and / or IPDI in monomeric or oligomeric form.
  • the cyclodextrin used is ⁇ -, ⁇ - or ⁇ -cyclodextrin in monomeric, dimeric, more primer or higher oligomeric form, it being possible for the cyclodextrin to be completely or partially loaded with an active substance, in particular with odorous substances, insecticides, fungicides or dyes.
  • the object of the present invention is to reduce the odor of mattresses made of polyurethane foams.
  • This object is achieved in each case independently by the method mentioned at the outset, the molded foam element mentioned at the outset and by the use of a cyclic oligosaccharide mentioned at the outset, the process employing a modified cyclic oligosaccharide having a hydroxyl value of not more than 600 mg KOH / g or the molded foam element contains this modified cyclic oligosaccharide which is used for masking odorous compounds which are formed during the foaming process and / or are contained as impurities in the educts used.
  • a molded foam element is understood as meaning a foam product that can already be readily removed from the foam mold, or that is cut out of larger molded foam blocks, for example cut out.
  • a padding for example, for seating, a mattress, a carpet layer, a Covering part for a motor vehicle, such as a side trim part or furniture, such as seat cushions, etc., or a (cleaning) sponge or a filter foam understood.
  • odor-intensive molecules resulting from the covalent incorporation of the oligosaccharide in the preparation of the polyurethane foam or introduced into the reaction mixture are already "neutralized” at a very early stage, whereby the subsequent removal time of the molded foam element can be significantly reduced the incorporation of these molecules into the oligosaccharide is advantageous because of the relatively high temperature of the foaming process, since, on the one hand, the cavity of the oligosaccharide is not unintentionally occupied, and, on the other hand, the mobility of these molecules is so great compared with that at room temperature that storage takes place more rapidly In other words, the incorporation of these molecules takes place from the beginning and not in the course of a later decay of molecules.
  • odor-intensive molecules in the context of the invention means molecules which are already small Odor concentrations of substance trigger an odor sensation (cf. also DIN EN 13725). Likewise, they are understood to mean molecules which are formed as short-lived compounds during the foaming process or are already present in the raw materials and must be classified as “odor-intensive molecules” or precursors thereof "are incorporated into the oligosaccharide, in order to prevent or reduce the odor impairment in this way.
  • the modified cyclic oligosaccharide has a hydroxyl number between 50 mg KOH / g and 370 mg KOH / g.
  • a modified cyclic oligosaccharide is used whose free hydroxyl groups are at least partially replaced by groups which are inert to isocyanate groups. It is thus avoided by the reduction of the acidity of the oligosaccharide a higher cross-linking of the oligosaccharide with the polyurethane foam, whereby the storage of odor-intensive molecules less harmful to the oligosaccharide. In addition, too high a hardness or a stiffening of the polyurethane foam is avoided, also due to the lower reactivity of the oligosaccharide compared to the isocyanate groups.
  • these groups for inerting the oligosaccharide with respect to isocyanate groups are selected from a group comprising branched (cis and trans forms) and unbranched Cl, C2, C3, C4, C5, C6, C7, C8, C9, C10 alkyl groups, for example methyl, ethyl, propyl, n-butyl, iso-butyl, n-pentyl, iso-pentyl, neo-pentyl, n-hexyl, 2-methylpentyl , 3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-
  • ethers resulting from the reaction of the cyclic oligosaccharide in particular cyclodextrin, OH groups with branched or unbranched, aromatic or aliphatic (saturated and unsaturated) silylalkyl halides, for example triisopropylsilyl chloride, t-butyldimethylsilyl chloride, t-butyldiphenylsilyl chloride, and tosylate be used
  • a specific adaptation of the cavity to the odor-intensive molecules to be stored is possible.
  • a relatively simple adaptation of the cavity of the oligosaccharide (with regard to the reactivity and the size) to certain odor-intensive molecules can thus be achieved even on a large-scale, so that the oligosaccharide is specifically targeted to a certain type of molecule or a particular class of compound or group. which is to be stored in the cavity conditioned can be used to increase the selectivity of the odor reduction by the oligosaccharide.
  • a modified cyclic oligosaccharide is used whose free hydroxyl groups are at least 50% inertized, since this significantly improves these effects.
  • a "conical" modified cyclic oligosaccharide is used whose cone has an upper diameter between 0.045 nm, in particular 0.47 nm, and 0.53 nm, in particular 0.51 nm.
  • the oligosaccharide is particularly suitable for the incorporation of esters, aldehydes, phthalates, cleavage products of urethanes and aromatic compounds, ie primarily of compounds that can occur in the production process of the polyurethane foam.
  • a modified ⁇ -, ⁇ - or ⁇ -cyclodextrin is particularly preferably used as the modified cyclic oligosaccharide, since these cyclodextrins are readily available on an industrial scale, whereby a significant increase in cost in the production of the molded foam element can be avoided.
  • the steric adaptation of the cavity of these molecules is easier to carry out.
  • modified a-, ß- or ⁇ -cyclodextrin is used in foam form or foamed to the foam character, i. the foam structure, the polyurethane foam not or only slightly to change.
  • the modified cyclic oligosaccharide may have a molecular weight between 1100 g / mol and 6000 g / mol, in particular between 1000 g / mol and 3000 g / mol, whereby the temperature stability in the production process of the polyurethane foam is better.
  • the foaming of the polyurethane foam is preferably at a temperature between 100 ° C, in particular 100 ° C, and 170 ° C, in particular 150 ° C, for the production of block foams or at a temperature between 20 ° C, in particular 25 ° C, and 45 ° C, in particular 40 ° C, performed for the production of molded foams, because it can be used to reduce the occupancy of the cavities with other than the odorous molecules.
  • the modified cyclic oligosaccharide is added in an amount such that a ratio of the hydroxyl functionality of the polyol (s) to the hydroxyl functionality of the oligosaccharide is between 250 mg KOH / g: 50 mg KOH / g, especially between 150 mg KOH / g: 50 mg KOH / g, and 27 mg KOH / g: 600 mg KOH / g, in particular between 27 mg KOH / g: 400 mg KOH / g. It can thus be better avoided a stiffening of the polyurethane foam.
  • the cyclic oligosaccharide in particular the cyclodextrin, in a proportion between 0.5 pphp and 25 pphp (parts per hundred parts polyol, parts by weight calculated on 100 parts by weight of polyol), in particular between 0.9 pphp and 19 pphp used.
  • the modified cyclic oligosaccharide may be added as a suspension in the or one of the polyols. This has the advantage that an additional solvent or suspending agent for metering the oligosaccharide into the reaction mass for the polyurethane foam can be avoided. In particular, this type of addition is also suitable for poorly soluble oligosaccharides. As a side effect, a better homogenization of the oligosaccharide with respect to the polyol is achieved.
  • the modified cyclic oligosaccharide may be added to avoid an additional process chemical as a solution in the water.
  • the modified cyclic oligosaccharide is added as a particulate solid in order to reduce the energy required for the foaming process, since the solvent or suspending agent need not be removed during foaming or after foaming, although the latter of Advantage in terms of that Cooling behavior of the polyurethane foam can be.
  • the introduction as a solid also has the advantage of a higher environmental impact of the process.
  • the modified cyclic oligosaccharide can be used with a particle size between 5 ⁇ m and 100 ⁇ m, in particular between 12 ⁇ m and 60 ⁇ m, in order to improve its homogenizability.
  • the modified cyclic oligosaccharide is loaded with at least one active substance, so that not only odor-intensive molecules are bound with a manufacturing step but at the same time an odor improvement or an odor control of the molded foam element can be achieved.
  • other active ingredients that are not aimed at improving the odor of the molded foam element, without additional manufacturing step in the polyurethane foam.
  • the active ingredient may preferably be selected from a group comprising insecticides, especially active against arthropods such as bed bugs or mites, medicinal agents, and fragrances.
  • the fragrances may be selected from a group comprising substances having a citrus-like odor, flower-like odor, freshness smell, geranium-like smell, grape-like smell, grapefruit-like smell, grassy smell, green note, herbaceous smell, lavender-like smell, lemon-like smell, mint-like Odor, orange peel-like odor, peppermint-like odor, pine-like odor, rose-like odor, spearmint-like odor, woody odor, and mixtures thereof.
  • Polyurethane foams are known to consist of one or a mixture of at least two isocyanate (s) having an NCO functionality of 2 or greater, for example TDI (toluene-2,4-diisocyanate) or MDI ((diphenylmethane diisocyanate), optionally used as prepolymer, one or a mixture of several polyol (s) with an OH Functionality of 2 or greater, for example a polyether polyol or a polyester terpolyol, and water as base components for the polyurethane foam, and one or more auxiliaries, such as a catalyst or activator, a defoamer, colorants, etc., produced.
  • auxiliaries such as a catalyst or activator, a defoamer, colorants, etc.
  • the at least one isocyanate and the at least one polyol are preferably added in an amount such that a ratio of the number of NCO / OH in a range between 0.95: 1, in particular 0.98: 1, and 1.20: 1, in particular 1, 15: 1, is obtained.
  • waste foams in particular of polyurthane soft foams, in particulate form and to connect them with new foam to form a so-called composite foam.
  • a polyurethane foam is understood as meaning, in particular, an open-cell flexible polyurethane foam having a bulk density according to EN ISO 845 selected from a range with a lower limit of 15 kg / m 3, in particular 20 kg / m 3, and an upper limit of 130 kg / m 3, in particular 60 kg / m 3, and a hardness according to DIN EN 3386 of not more than 6.5 kPa, in particular not more than 6 kPa, understood, as commonly found in the above products, especially in mattresses, use.
  • At least one modified cyclic oligosaccharide is used for the preparation of the polyurethane foam having a hydroxyl value of not more than 600 mg KOH / g, in particular between 50 mg KOH / g and 370 mg KOH / g, according to DIN 53240, in order to mask odor-intensive compounds which are formed during the foaming process and / or are contained as impurities in the educts used. If appropriate, it is also possible to use a mixture of at least two differently modified cyclic oligosaccharides in order to be able to mask different odor substances more selectively.
  • cyclic oligosaccharide (s) will modify esters, for example methyl 2-ethylhexanoate, and / or aldehydes, for example butanal or 2-methyl-2-pentenal, and / or phthalates, for example benzyl butyl phthalate, and / or cleavage products Urethanes, and / or aromatic compounds, for example m- or p-xylene, masked.
  • ⁇ - and / or ⁇ - and / or ⁇ -cyclodextrin are used as the cyclic oligosaccharide, preference being given to using ⁇ -cyclodextrin.
  • the unmodified or already modified - multiple modifications are possible, which may optionally be carried out simultaneously - in particular with acetyl chloride or dimethyl sulfate, to be reacted accordingly (AA Sutyagin, et al, "Regioselective Acetylation of b-cyclodextrin", Russian Journal of General Chemistry; (72); 2002; 147-150 and Peter Bako et al; "Methylation of cyclodextrins by phase transfer catalysis"; Journal of Inclusion Phenomena and Macrocyclic Chemistry; (18); 1994; 307-
  • cyclic oligosaccharides whose free OH groups are at least partially replaced by groups which are inert to the isocyanate groups of the isocyanates used, so that a reaction and crosslinking of the oligosaccharides takes place only partially with the isocyanates.
  • methylated, acetylated or saturated cyclic oligosaccharides are prepared by this modification.
  • the abovementioned branched (also cyclic, saturated or unsaturated) or unbranched (saturated or unsaturated) C 1 -C 10 -alkyl groups can be used as chemical groups, especially methyl groups, cyclohexyl groups, (iso) -butyl groups, (iso) -hexenyl groups, branched (also cyclic, saturated or unsaturated), and / or unbranched (saturated or unsaturated) C 1 -C 10 -alkoxy groups and their isomers, such as, for example, methoxy groups, ethoxy groups, heptenoxy groups, cyclohexannoxy groups, (iso) -propoxy groups, (iso) -nonoxy groups, ( iso) -decoxy, branched (also cyclic, saturated or unsaturated) or unbranched (saturated or unsaturated) C 1 -C 10 -carboxylic acids and their isomers (
  • ethers derived from the reaction of the cyclodextrin OH groups with branched or unbranched, aromatic or aliphatic (saturated or unsaturated Silylalkyl halides such as triisopropylsilyl chloride, t-butyldimethylsilyl chloride t-butyldiphenylsilyl chloride, are used.
  • the reaction of the hydroxy groups of the cyclic oligosaccharide is preferably carried out to a degree of conversion of at least 50%, preferably at least 60%, based on the total number of hydroxyl groups in the oligosaccharide.
  • the acetylation can take place up to a degree of conversion of 66% to 96%.
  • an inertization of the hydroxyl groups is to be preferred, although a 100% conversion should be avoided if the cyclic oligosaccharide is to be covalently bound into the polyurethane foam.
  • the latter variant is the preferred within the scope of the invention.
  • the degree of implementation should not exceed 96%, in particular not more than 88%.
  • the degree of inertization may e.g. in the case of acetylation via acid scavenger and amount of acetylating be regulated.
  • the modification can also serve to adapt the size of the cavity of the cyclic oligosaccharide, in particular of the cyclodextrin, to the molecule (s) to be incorporated, in particular to those mentioned above Links.
  • a modified cyclic oligosaccharide with a "cone-shaped” structure is used whose cone (cavity) has an upper diameter between 0.045 nm, in particular 0.47 nm , and 0.53 nm, in particular 0.51 nm, and a lower diameter between 0.35 nm in particular 0.37 nm, and 0.47 nm, in particular 0.44 nm, or whose cone has an upper diameter between 0, 83 nm, in particular 0.86 nm, and 1.3 nm, in particular 1.11 nm, and a lower diameter between 0.75 nm, in particular 0.81 nm, and 1 nm, esp re 0.92 nm, and which has a height
  • oligosaccharide falls under the general group "polyols"
  • polyols it is possible that a part of the at least one other, primarily used, above-mentioned polyol for producing the polyurethane foam is replaced by the cyclic oligosaccharide.
  • the modified cyclic oligosaccharide may be added in an amount such that a ratio of the hydroxyl functionality of the polyol (s) present in the reaction mixture and the oligosaccharide to the hydroxyl functionality of the oligosaccharide is between 250 mg KOH / g: 50 mg KOH / g and 27 mg KOH / g: 600 mg KOH / g, in particular between 150 mg KOH / g: 50 mg KOH / g and 27 mg KOH / g: 400 mg KOH / g, according to DIN 53240.
  • the cyclic oligosaccharide can be introduced in several ways into the reaction mixture to produce the polyurethane foam. On the one hand, there is the possibility that the modified cyclic oligosaccharide is added as a suspension in or further to the polyol (s) added to the reaction mixture. On the other hand, the modified cyclic oligosaccharide may be added as a solution in the water used in foaming to produce the C0 2 .
  • the modified cyclic oligosaccharide can also be added as a particulate solid. In the latter case, it is advantageous if the modified cyclic oligosaccharide with a particle size between 5 ⁇ and 100 ⁇ , in particular between 12 ⁇ and 60 ⁇ , is used.
  • the cyclic polysaccharide in particular the cyclodextrin, to be applied on an (inert) support as a coating in the polyurethane foam. is brought. It is thus achievable to improve the efficiency based on the amount of cyclic polysaccharide used.
  • the preparation of the polyurethane foam is preferably carried out at a temperature between 100 ° C. and 170 ° C., in particular between 100 ° C. and 150 °
  • the molecular weight of the modified cyclic oligosaccharide used may be between 1000 g / mol and 6000 g / mol, in particular between 1000 g / mol and 3000 g / mol.
  • the modified cyclic oligosaccharide is loaded with at least one active substance.
  • the active ingredient is in particular selected from a group comprising insecticides, especially effective against arthropods such as bedbugs or mites, medicinal agents, and fragrances.
  • the fragrances can be selected from a group comprising substances with:
  • Citrusy odor such as preferably linalyl pentanoate, heptanal, linalyl isopentanoate dodecanal, linalyl formate, ⁇ -p-dimethylstyrene, p-cymenol, nonanal, ⁇ -cubebene, (Z) -lione oxide, cis-6-ethenyl-tetrahydro-2,2 , 6-trimethylpyran-3-ol, cis-pyranoidlinalooloxide, dihydrolinalool, 6 (10) -dihydromyrcenol, dihydromyrcenol, ⁇ -farnesene, (Z) - ⁇ -Farnesene, (Z) -cime, (E) -liminene oxide, dihydrotypinyl acetate, (+) - limonene, (epoxymethylbutyl) methylfuran and / or p -c
  • flower-like odor such as, preferably, benzyl alcohol, phenylacetic acid, tridecanal, p-anisyl alcohol, hexanol, (E, E) -farnesylacetone, methyl geranate, trans-crotonaldehyde, tetradecylaldehyde, methyl anthranilate, linalooloxide, epoxylinalool, phytol, 10-epi ⁇ -eudesmol, nerol oxide, ethyldihydrocinnamate, ⁇ -dodecalactone, hexadecanol, 4-mercapto-4-methyl-2-pentanol, (Z) -oximes, cetyl alcohol, nerolidol, ethyl (E) -cinnamate, elemicin, pinocarveol, ⁇ - Bisabolol, (2R, 4R) -Tetrahydro-4-methyl
  • freshness odor such as, preferably, methylhexanoate, undecanone, (Z) -imimonial oxide, benzylacetate, ethylhydroxyhexanoate, isopropylhexanoate, pentadecanal, ⁇ -elemene, ⁇ -zingiberene, (E) -liminene oxide, (E) -p-mentha-2 , 8-dien-l-ol, menthone, piperone, (E) -3-hexenol and / or carveol or
  • freshness odor such as, preferably, methylhexanoate, undecanone, (Z) -imimonial oxide, benzylacetate, ethylhydroxyhexanoate, isopropylhexanoate, pentadecanal, ⁇ -elemene, ⁇ -zingiberene, (E) -liminene oxide, (E) -p-mentha-2
  • Geranium-like odor such as preferably geraniol, (E, Z) -2,4-nonadienal, octadienone and / or o-xylene or
  • a grape-like odor such as preferably ethyl decanoate and / or hexanone or
  • grapefruit-like odor such as preferably (+) - 5,6-dimethyl-8-isopropenylbicyclo [4.4.0] dec-1-en-3-oo and / or p-menthenethiol or
  • grassy odor such as preferably 2-ethylpyridine, 2,6-dimethylnaphthalene, hexanal and / or (Z) -3-hexenol or
  • (h) green note preferably 2-ethylhexanol, 6-decenal, dimethylheptenal, hexanol, hep- tanol, methyl-2-butenal, hexyloctanoate, nonanoic acid, undecanone, methyl geranate, isobornyl formate, butanal, octanal, nonanal, epoxy-2 -decenal, cis-linalool, pyranoxide, nonanol, ⁇ , ⁇ -dimethylallylalcohol, (Z) -2-penten-1-ol, (Z) -3-hexenylbutanoate, isobutylthiazole, (E) -2-nonenal, 2-dodecenal , (Z) -4-decenal, 2-octenal, 2-hepten-1-al, bicyclogermacrene, 2-octenal, ⁇ -thiols
  • (k) lemon-like odor preferably neral, octanal, ⁇ -3-carene, limonene, geranial, 4-mercapto-4-methyl-2-pentanol, citral, 2,3-dehydro-1, 8-cineol and / or ⁇ -Terpines or
  • Minty odor preferably menthone, ethyl salicylate, p-anisaldehyde, 2,4,5,7-tetrahydro-3,6-dimethylbenzofuran, epoxy-p-menthene, geranial, (methylbutenyl) methyl furan , Dihydrocarvylacetate, ⁇ -cyclocitral, 1,8-cineole, ⁇ -phellandrene, methylpentanone, (+) - limonene, dihydrocarveol (-) - carvone, (E) -p-mentha-2,8-dien-1-ol, Isopulegyl acetate, piperi- ton, 2,3-dehydro-1, 8-cineol, ⁇ -terpineol, DL-carvone and / or ⁇ -phellandrene or
  • pine-like odor preferably ⁇ - ⁇ -dimethylstyrene, ⁇ -pinene, bornyl benzoate, ⁇ -terpinene, dihydroterpinyl acetate and / or ⁇ -pinene or (p) rose-like odor, preferably ⁇ -phenethyl acetate, 2-ethylhexanol , Geranyl valerate, geranyl acetate, citronellol, geraniol, geranyl butyrate, geranyl isovalerate, citronellyl butyrate, citronellyl acetate, isogeraniol, tetrahydro-4-methyl-2- (2-methyl-1-propenyl) -2,5-cis-2H-pyran, isogeraniol, 2 Phenylethyl alcohol, citronellyl valerate and / or citronellyl isobutyrate, or
  • spearmint-like odor preferably carvylacetate and / or carveol
  • woody odor preferably ⁇ -muurolene, cadina-1, 4-dien-3-ol, isocaryophyllene, eudesmol, a-ionone, bomylbutyrate, (E) -a-Bergamoten, Linalooloxid, ethylpyrazine, lO-epi- ⁇ -Eudesmol, a-ionone, Bomylbutyrat, Germacrene B, trans-Sabine hydrate, Dihydrolinalool, Isodihydrohydrove, ß-Farnesene, ß-Sesquiphellandren, ⁇ -Elemene , ⁇ -calacorene, epoxy- ⁇ -ionone, germacrene D, bicyclo-mercacea, alloaromadendrene, ⁇ -thujen
  • ⁇ -Muurolene Sabinene, ⁇ -Guaiene, ⁇ -Copaene, ⁇ -Cadinene, Nerolidol, ⁇ -Eudesmol, ⁇ -Cadinol, ⁇ -Cadinene, 4,5-Dimethoxy-6- (2-propenyl) -l, 3 benzodioxole, ⁇ -gurjunes, guaiol, ⁇ -farnesene, ⁇ -selenene, 4- (1-methylethyl) benzene-ethanol, perillene, elemole, ⁇ -humulenes, ⁇ -caryophyllene and / or ⁇ -guaienes and mixtures of these compounds.
  • Example A Formulation or Reference Foaming Formulations with Glycerol Propoxylate (Mn: -2800 g / mol)
  • the components were weighed in order of listing (table above) in 60 ml polypropylene (PP) centrifuge tubes and homogenized by shaking after each of the individual components. After completion of the addition of TDI 80, the mixture was again homogenized and rapidly transferred to the foaming vessel. The foaming started after a short delay, and the soft foam body received its final volume after about 30 seconds.
  • PP polypropylene
  • Example B Formulations of foams made with industrial raw materials.
  • Polyalkylene oxide methylsiloxane copolymer 0.35 0.34 0.33 0.33 0.32
  • the amines and silicones are weighed in and mixed well after the addition of all polyols (including that in which the cyclodextrin is dispersed). In the next step, the water is added and well homogenized. Thereafter, the Zinnoctoat is weighed and stirred again. Finally, the required amount of T80 is added with stirring and the mixture poured into a ready-made mold.
  • the amines and the silicones are weighed in and mixed well after the addition of Polyolelbis 3.
  • the water containing 30 wt .-% methylated cyclodextrin
  • the Zinnoctoat is weighed and stirred again.
  • the required amount of T80 is added with stirring and the mixture poured into a ready-made mold.
  • Example 3 Cold foam with 5php of an acetylated cyclodextrin (incorporated as solid) phb g OH number description
  • the polyols, glycerine and sorbitol are weighed in turn. Thereafter, the required amount of cyclodextrin is added while stirring. In the next step, the addition of the activator mixture (amine, urea, silicone) takes place. After addition of the water is redispersed. After addition of the tin octoate, the T80 is finally metered in with stirring.
  • the activator mixture amine, urea, silicone
  • a foam with the lowest odor intensity is rated 0 and the strongest 5, corresponding to the rising odor.
  • the evaluators were served coffee beans. The test was always conducted as a single survey and care was taken to keep information and external influences, such as light and noise, constant.
  • Sample No. 10 was found to be the least odorous sample with 21 out of 200 total points (10.5%). Striking is the fact that the odor load in the modified flexible polyurethane foam with 5 wt.% Of cyclodextrin based on the polyol component in contrast to the model foam reduced adsorption performance is recognizable. Comparison of the compression hardness of modified cyclodextrins with different OH numbers (2.5 pphp each).
  • the availability and the universal Einlagerseigenschaften is preferably a ß-cyclodextrin used.
  • the cyclic oligosaccharide, in particular the cyclodextrin may be contained in the molded foam element in a concentration of at most 25 pphp, in particular between 0.5 pphp and 25 pphp.
  • the cyclic, modified oligosaccharide is used as a solid dispersion.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un procédé de fabrication d'un élément en mousse moulé à base d'une mousse polyuréthane, formé par réaction de plusieurs constituants contenant au moins un isocanate, au moins un polyol et de l'eau. Au moins un oligosaccharide cyclique modifié, présentant un indice hydroxyl maximal de 600 mg KOH/g est ajouté.
EP12723817.8A 2011-04-06 2012-04-05 Procédé de fabrication d'un élément en mousse moulé Withdrawn EP2760904A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ATA484/2011A AT511328B1 (de) 2011-04-06 2011-04-06 Verfahren zur herstellung eines formschaumelementes
PCT/AT2012/050043 WO2012135888A1 (fr) 2011-04-06 2012-04-05 Procédé de fabrication d'un élément en mousse moulé

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EP2760904A1 true EP2760904A1 (fr) 2014-08-06

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DE102013201825A1 (de) * 2013-02-05 2014-08-07 Evonik Industries Ag Zusammensetzung zur Verwendung bei der Herstellung von Polyurethansystemen
SG11202109011QA (en) 2019-03-25 2021-09-29 Greiner Aerospace Gmbh Cushion for a plane seat, having antimicrobial effect

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US3454530A (en) * 1966-03-07 1969-07-08 Leslie C Case Novel polyols which are reaction products of a monoepoxide and a cyclic monoanhydride
US5063251A (en) * 1990-05-04 1991-11-05 American Maize-Products Company Blowing and curing of resins and plastics materials with cyclodextrin complexes
JPH0753658A (ja) * 1993-08-17 1995-02-28 Takeda Chem Ind Ltd ポリウレタンフオームの製造方法
DE19745527A1 (de) * 1997-10-15 1999-04-22 Basf Ag Verfahren zur Herstellung von Polyurethanen mit alkoxylierten zyklischen Mehrfachzuckern
DE19928687A1 (de) 1999-06-23 2000-12-28 Basf Ag Polyisocyanat-Polyadditionsprodukte
DE19928689A1 (de) * 1999-06-23 2000-12-28 Basf Ag Polyisocyanat-Polyadditionsprodukte
US8741977B2 (en) * 2007-03-13 2014-06-03 Avery Dennison Corporation Foam compositions and articles including cyclodextrin crosslinked with polyurethane prepolymer and preparation thereof
DE102007062525A1 (de) 2007-12-20 2009-06-25 Tag Composites & Carpets Gmbh Polyurethane mit Cyclodextrinen als Synthesebausteinen

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