EP3727828A1 - Nouvelles mousses polyuréthanes souples - Google Patents

Nouvelles mousses polyuréthanes souples

Info

Publication number
EP3727828A1
EP3727828A1 EP18822362.2A EP18822362A EP3727828A1 EP 3727828 A1 EP3727828 A1 EP 3727828A1 EP 18822362 A EP18822362 A EP 18822362A EP 3727828 A1 EP3727828 A1 EP 3727828A1
Authority
EP
European Patent Office
Prior art keywords
flexible polyurethane
polyurethane foam
thermoplastic polyurethane
component
thermoplastic
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.)
Pending
Application number
EP18822362.2A
Other languages
German (de)
English (en)
Inventor
Julia JAEHNIGEN
Wibke LOELSBERG
Angelika Mueller
Daniela Tepe
Frank Prissok
Dejan Petrovic
Heinz-Dieter Lutter
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of EP3727828A1 publication Critical patent/EP3727828A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B1/00—Footwear characterised by the material
    • A43B1/0063—Footwear characterised by the material made at least partially of material that can be recycled
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B1/00—Footwear characterised by the material
    • A43B1/14—Footwear characterised by the material made of plastics
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A43B13/02—Soles; Sole-and-heel integral units characterised by the material
    • A43B13/04—Plastics, rubber or vulcanised fibre
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    • A43B13/14—Soles; Sole-and-heel integral units characterised by the constructive form
    • A43B13/18—Resilient soles
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    • Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the present invention relates to a process for the preparation of a hot melt thermally recyclable flexible polyurethane foam having a free density of between 30-150 g / L by reacting a reaction mixture comprising
  • an isocyanate component having a functionality between 1, 9-2.2;
  • the flexible polyurethane foams and hybrid materials produced according to the method of the invention comprising the flexible polyurethane foam according to the invention and compact thermoplastic elastomer and / or expanded thermoplastic polyurethane.
  • Polyurethane flexible foams are used industrially in a variety of ways, including automotive interior upholstery, seats, carpets and engine covers, furniture, armchairs, chairs, armrests, sofas, beds, shoes, boots, ski boots, sports equipment, handles, bicycle handles or saddles and wound and patch pads, sponge or for filter materials.
  • flexible polyurethane foams will often also be used in conjunction with other polymers such as thermoplastic elastomers.
  • uppers and decorative elements made of a thermoplastic material containing soft foam padding elements in, for example, the heel and forefoot areas and in the shoe pocket.
  • hybrid materials made of flexible polyurethane foams and other thermoplastic materials are used in furniture (chairs, seats, upholstery) or in the medical sector such as patches.
  • thermoplastic materials obtained after recycling provide a valuable starting raw material for applications such as for use in consumer articles, preferably selected from the group consisting of clothing, in particular shoe and shoe component, in particular outsole and laces; Jewelery and jewelery component, in particular for a smart device or monitoring electronics (in particular for monitoring physical functions such as heart rate, temperature), preferably selected from the group consisting of bracelet, bracelet component, neck strap and neckband component, body belt and thoroughlygurt reallyteil, glasses and spectacle component; Sports accessories, in particular sports band, stretch band; Damping material; Foam particles; woven article; non-woven article; Cleaning articles for mobile vehicles or aircraft, in particular windscreen wipers; medical article, especially bandage or tube.
  • a smart device here is an electronic device which is wirelessly networked or networkable with another device or network, for example devices of consumer electronics, telephone, smartwatch.
  • DE 19514744 C2 describes a process in which after mechanical comminution of the flexible foam and a layer of clothing or leather at low temperatures, the subsequent bonding is achieved by adding a meltable polyamide or polyester powder, thermal decomposition of the Raw material is explicitly desired.
  • the object has been achieved by a method for producing a thermally recyclable flexible polyurethane foam having a free density of between 30 and 150 g / l by reaction comprising the reaction of a reaction mixture
  • an isocyanate component having a functionality between 1, 9-2.2;
  • the isocyanate component (a) contains at least one polyisocyanate.
  • the polyisocyanate composition may also contain two or more polyisocyanates.
  • isocyanate component (a) it is preferred to use aliphatic, cycloaliphatic, araliphatic and / or aromatic isocyanates, more preferably tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methylpentamethylene diisocyanate 1, 5, 2-ethylbutylene diisocyanate 1, 4, pentamethylene diisocyanate 1, 5, butylene diisocyanate 1, 4, 1-iso-cyanato-3,3,5-trimethyl-5 isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1,4-bis (isocyanatomethyl) cyclohexane and / or 1,3-bis (isocyanatomethyl)
  • the isocyanate component (a) used to prepare the polyurethane foams of the invention has an isocyanate content of from 20 to 33.5% by weight, preferably from 25 to 31.5% by weight.
  • the process for producing a soft polyurethane foam having a free space weight between 30-150 g / L comprises the reaction of a reaction mixture comprising
  • an isocyanate component (a) and optionally a part of the polyol component (b) are mixed and reacted to form an isocyanate-terminated prepolymer, and
  • An isocyanate-terminated prepolymer is obtainable according to i), in which the above-described isocyanate component (a) is preferably in excess compared to polyols used in (i), preferably at temperatures of 30 to 150 ° C., more preferably at temperatures of 50 to 120 ° C, more preferably at about 80 ° C, are reacted to the prepolymer.
  • polyisocyanates and polyols having a functionality of between 1.7 and 2.2 based on polyesters and polyethers are preferably used.
  • customary chain extenders with a functionality of between 1.7 and 2.2 are added to said polyols in the preparation of the isocyanate-terminated prepolymer.
  • Such substances are basically known from the prior art or are described below.
  • the ratio of polyisocyanates to polyols and optionally chain extenders is selected such that the isocyanate-terminated prepolymer has an NCO content of from 2 to 30.5%, preferably from 10 to 30%, more preferably from 12 to 29% and most preferably an NCO- Content of 15 to 28%.
  • a polyol component (b) is furthermore used.
  • This polyol component (b) according to (ii) comprises at least one polyester or polyether polyol, in particular at least one polyester or polyether polyol each having a functionality of from 1.7 to 2.2, where according to the invention two or more polyester or polyether polyols are also used Polyetherpolyole or mixtures of polyester and polyether polyols can be used.
  • a "polyester or polyether polyol having a functionality of xx” is meant a nominal xx functional polyester or polyether polyol. In practice, it is departed from the nominal functionality, since various side reactions during the polyol synthesis can lead to a functionality that can be lower than nominally assumed.
  • Polyols are known in principle to the person skilled in the art and described, for example, in Kunststoffhandbuch, Vol 7, Polyurethane ", Carl Hanser Verlag, 3rd edition 1993, chapter 3.1.
  • a polyol component (b) having a functionality of between 1.9 and 2.2 is used, mixtures of polyols also being used here. If polyols having a higher functionality are used in these polyol mixtures, as described below, the functionality of the mixture must not be more than 2.2, preferably. Furthermore, the proportion of polyols having a high functionality must not exceed 10% by weight, preferably not more than 5% by weight, based on the total mixture.
  • Polyester polyols can be prepared, for example, from organic dicarboxylic acids having 2 to 12 carbon atoms, preferably aliphatic dicarboxylic acids having 4 to 6 carbon atoms and polyhydric alcohols, preferably diols, having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms.
  • Suitable dicarboxylic acids are, for example: succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid and terephthalic acid.
  • the dicarboxylic acids can be used both individually and in admixture with each other.
  • dicarboxylic acid derivatives for example dicarboxylic acid esters of alcohols having 1 to 4 carbon atoms or dicarboxylic acid anhydrides.
  • dicarboxylic acid mixtures of succinic, glutaric and adipic acid in proportions of, for example, from 20 to 35:35 to 50:20 to 32 parts by weight, and in particular adipic acid.
  • Examples of mono-, di- and polyhydric alcohols, in particular diols, are: ethanediol, diethylene glycol, 1,2- or 1,3-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1 , 10-decanediol, glycerol and trimethylolpropane.
  • Preferably used are ethanediol, diethy glycol, 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol.
  • polyester polyols from lactones, for example ⁇ -caprolactone or hydroxycarboxylic acids, for example ⁇ -hydroxycaproic acid.
  • the organic e.g. aromatic and preferably aliphatic polycarboxylic acids and / or derivatives and polyhydric alcohols catalyst-free or preferably in the presence of esterification catalysts, conveniently in an atmosphere of inert gas, such. Nitrogen, carbon monoxide, helium, argon and the like. in the melt at temperatures of 150 to 250 ° C, preferably 180 to 220 ° C, optionally under reduced pressure, to the desired acid number, which is preferably less than 10, more preferably less than 2, polycondensed.
  • inert gas such. Nitrogen, carbon monoxide, helium, argon and the like.
  • the esterification mixture is polycondensed at the abovementioned temperatures up to an acid number of 80 to 30, preferably 40 to 30, under normal pressure and then under a pressure of less than 500 mbar, preferably 50 to 150 mbar.
  • Suitable esterification catalysts are, for example, iron, cadmium, cobalt, lead, zinc, antimony, magnesium, titanium and tin catalysts in the form of metals, metal oxides or metal salts.
  • the polycondensation may also be carried out in the liquid phase in the presence of diluents and / or entrainers, e.g.
  • the organic polycarboxylic acids and / or derivatives and polyhydric alcohols are advantageously polycondensed in a molar ratio of 1: 1 to 1.8, preferably 1: 1, 05 to 1.2.
  • the polyester polyols used preferably have a functionality of 1 to 4, in particular of 2 to 3, and for example a number average molecular weight of 480 to 3000 g / mol, preferably 1000 to 3000 g / mol.
  • Polyetheroic be prepared by known methods, for example by anionic polymerization with alkali metal hydroxides or alkali metal as catalysts and with the addition of at least one starter molecule containing 2 to 3 reactive hydrogen atoms bonded, or by cationic polymerization with Lewis acids such as antimony pentachloride or borofluoro etherate or by bases such as potassium hydroxide of one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene radical.
  • Suitable alkylene oxides are, for example, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide and preferably ethylene oxide and 1,2-propylene oxide.
  • tetrahydrofuran monomer can be used.
  • the alkylene oxides can be used individually, alternately in succession or as mixtures. Preference is given to 1,2-propylene oxide, ethylene oxide and mixtures of 1, 2-propylene oxide and ethylene oxide, wherein the ethylene oxide is used in amounts of 1 to 50% and is more preferably used as ethylene oxide endblock ("EO-cap"), so that the resulting polyols contain more than 70% primary OH end groups.
  • EO-cap ethylene oxide endblock
  • mixtures of starter molecules are used such that the average number of reactive hydrogen atoms of the starter molecules is between 2 to 6.
  • Water or 2- to 8-hydric alcohols such as ethylene glycol, 1, 2- and 1, 3-propanediol, diethylene glycol, dipropylene glycol, 1,4-butanediol, glycerol or trimethylolpropane, pentaerythritol, sugar alcohols, such as sorbitol or sugar, are preferably used as starter molecules.
  • cakers such as Saacherose, aminic compounds such as ethylenediamine, diethanolamine or toluenediamine or mixtures of starter molecules into consideration.
  • the particularly preferred polyether polyols preferably polyoxypropylene-polyoxyethylene polyols or polyoxypropylene polyols, preferably have a functionality of from 1.3 to 5.8, preferably a functionality of from 1.5 to 5 and very particularly preferably a functionality of 1.7 to 2.2 and number average molecular weights of from 1000 g / mol to 12,000 g / mol (or an OH number of 7 to 325 mg KOH / g), preferably from 1,500 g / mol to 8,000 g / mol (or an OH Number from 12 to 190 mg KOH / g), in particular from 2,000 g / mol to 6,000 g / mol (or an OH number of 17 to 125 mg / KOH).
  • polymer polyol dispersions also called "graft polyols" are used.
  • suitable polyols of the polyol composition according to (ii) are polymer-modified polyols, preferably polymer-modified polyester oil or polyether oil, particularly preferably graft polyether or graft polyesterols, in particular graft polyetherols.
  • polymer polyol which usually has a content of, preferably thermoplastic, polymers of 5 to 60 wt .-%, preferably 10 to 55 wt .-%, particularly preferably 30 to 55 wt .-% and in particular 40 to 50% by weight.
  • These polymer polyesterols are described, for example, in WO 05/098763 and EPA 250 351 and are usually prepared by free-radical polymerization of suitable olefinic monomers, for example styrene, acrylonitrile, (meth) acrylates, (meth) acrylic acid and / or acrylamide prepared in a polyesterol serving as a graft base.
  • the side chains are generally formed by transferring the radicals from growing polymer chains to polyester oil or polyether oxide.
  • the polymer polyol predominantly contains the homopolymers of the olefins dispersed in unchanged polyesterol or polyetherol.
  • the monomers used are acrylonitrile, styrene, preferably acrylonitrile and styrene.
  • the monomers are polymerized in the presence of further monomers, a macromer, ie an unsaturated, free-radically polymerizable polyol, a moderator and using a free-radical initiator, usually azo or peroxide compounds, in a polyesterol or polyetherol as the continuous phase.
  • a macromer ie an unsaturated, free-radically polymerizable polyol
  • a moderator and using a free-radical initiator, usually azo or peroxide compounds, in a polyesterol or polyetherol as the continuous phase.
  • the macro- mers are incorporated into the copolymer chain.
  • the proportion of macromers is usually 1 to 20 wt .-%, based on the total weight of the monomers used for the preparation of the polymer polyols. If polymer polyol is present in the graft polyol, this is preferably present together with other polyols, for example polyether oils, polyester oils or mixtures of polyether oils and polyester oils.
  • the proportion of polymer polyol is greater than 5 wt .-%, based on the total weight of component (ii).
  • the polymer polyols may be contained, for example, based on the total weight of component (ii) in an amount of 7 to 90 wt .-%, or from 1 1 to 80 wt .-%.
  • the polymer polyol is polymer polyesterol or polymer polyetherol.
  • the polyol composition b) used is preferably mixtures containing polyetheroie.
  • the proportion of polyether oils in the polyol composition (b) is preferably at least 30% by weight, particularly preferably at least 70% by weight, and in particular polyetherol is used exclusively as the polyol composition (b).
  • the polyol component (b) comprises at least one polyester or polyether polyol.
  • the number-average molecular weight Mn of the polyols of the polyol composition (b) used according to the invention is preferably between 480 g / mol and 12,000 g / mol, preferably between 800 g / mol and 8000 g / mol, in particular between 1000 g / mol and 6000 g / mol.
  • polyester diols preferably polycaprolactone
  • polyether polyols preferably polyether diols, more preferably those based on ethylene oxide, propylene oxide and / or butylene oxide, preferably polypropylene glycol.
  • a particularly preferred polyether is polytetrahydrofuran (PTHF), in particular polyether oxide.
  • Particularly preferred polyols are selected from the following group: Copolyester based on adipic acid, succinic acid, pentanedioic acid, sebacic acid or mixtures thereof and mixtures of 1, 2-ethanediol and 1, 4-butanediol, copolyester based on adipic acid , Succinic acid, pentanedioic acid, sebacic acid or mixtures thereof and mixtures of 1,4-butanediol and 1,6-hexanediol, polyesters based on adipic acid and 3-methyl-pentanediol-1, 5 and / or polytetramethylene glycol (polytetrahydrofuran, PTHF), particularly preferably copolyesters based on adipic acid and mixtures of 1,2-ethanediol and 1,4-butanediol or polyesters based on adipic acid, succinic acid, pentaned
  • the polyol component (b) may contain a chain extender or a chain extender composition.
  • Preferred chain extenders are aliphatic, araliphatic, aromatic and / or cycloaliphatic compounds having a molecular weight of from 50 g / mol to 499 g / mol, preferably with 2 isocyanate-reactive compounds, which are also referred to as functional groups.
  • Preferred chain extenders are diamines and / or alkanediols, more preferably alkanediols having 2 to 10 carbon atoms, preferably having 3 to 8 carbon atoms in the alkylene radical, which more preferably have only primary hydroxyl groups.
  • chain extenders are used, these are preferably aliphatic, araliphatic, aromatic and / or cycloaliphatic compounds having a molecular weight of 50 g / mol to 499 g / mol, preferably with 2 isocyanate-reactive groups, which are also referred to as functional groups.
  • the chain extender is at least one chain extender selected from the group consisting of 1, 2-ethylene glycol, 1, 3-propanediol, 1, 10-decanediol, 1, 2, 1, 3, 1, 4-dihydroxycyclohexane, diethylene glycol, dipropylene glycol , Tripropylene glycol and 1, 4-butanediol, 1, 6-hexanediol and bis (2-hydroxyethyl) hydroquinone and low molecular weight hydroxyl-containing polyalkylene oxides based on ethylene and / or 1, 2-propylene oxide and the aforementioned Dio len as starter molecules , Further, also aromatic amines such as diethyltoluenediamine, 3,3 'dichloro-4,4'-diaminodiphenylmethane, 3,5-diamino-4 can chlorisobutylbenzoat as a chain extender, 4-methyl-2,6-bis (methylthio) -1, 3-diamin
  • Such aromatic aminic chain extenders can be obtained from various manufacturers and are generally known to the expert under various abbreviations such as MOCA, MBOCA, MCDEA, DETA.
  • the proportion of the chain extender is at least 0.2 wt .-%, preferably 1, 0 to 5 wt .-%, particularly preferably 1, 5 to 4 wt.%, Most preferably at least 2 , 0 to 3.5% by weight.
  • blowing agent (c) are present in the preparation of the flexible polyurethane foams according to the invention.
  • blowing agent (c) chemically acting blowing agents and / or physically acting compounds can be used.
  • chemicalmaschinemit- stuffs are compounds that form gaseous products by reaction with isocyanate, such as water and carboxylic acids or carboxylic acid derivatives, for example Hydrogencitrate, bicarbonates or azodicarbonamides, as Celegoene ®, Tracel ®, hydro- CEROL ®, or mixtures thereof, wherein Water is a preferred propellant.
  • Physical blowing agents are compounds which are dissolved or emulsified in the starting materials of the polyurethane preparation and evaporate under the conditions of polyurethane formation.
  • These are, for example, hydrocarbons, halogenated hydrocarbons, and other compounds, such as perfluorinated alkanes, such as perfluorohexane, chlorofluorocarbons, and ethers, esters, ketones and / or acetals, for example (cyclo) aliphatic hydrocarbons with 4 to 8 carbon atoms, Flu- orkohlenwasserstoffe as Solkane ® 365 mfc, or thereof gases such as carbon dioxide, or mixtures thereof.
  • the blowing agent used is a mixture of these blowing agents, comprising water, particularly preferably exclusively water.
  • the content of water in a preferred embodiment is from 0.1 to 6 wt .-%, preferably 1 to 5 wt .-%, particularly preferably 2.5 to 4 wt .-%, based on the total weight of the flexible polyurethane foam.
  • the content of physical blowing agent (c), if present, is in a preferred embodiment in the range between 1 and 20 wt .-%, in particular 5 and 20 wt .-%, the amount of water preferably in the range between 0.1 and 2.0 wt .-%, particularly preferably between 0.3 and 1, 0 wt .-% and in particular between 0.5 and 0.8 wt .-%, each based on the total weight of the used in the Reatkion components.
  • blowing agent-loaded polystyrene or styrene-acrylonitrile polymers such as, for example, blowing agent-loaded polystyrene or styrene-acrylonitrile polymers (SAN).
  • propellant-filled plastic hollow bodies are preferably used.
  • Suitable blowing agent-filled plastic hollow bodies are preferably based on a plastic which has a lower polarity than the thermoplastic polyurethane used.
  • they are based on polystyrene or styrene-acrylonitrile polymers (SAN).
  • so-called expandable microspheres are used as blowing agents filled plastic hollow body.
  • Expandable microspheres are hollow microspheres which consist of a thin plastic shell, preferably of polyacrylonitrile or copolymers thereof. These hollow microspheres are filled with gas or low-boiling liquids, preferably with hydrocarbons. Due to the acting temperature in the thermoplastic processing, it softens the plastic shell and at the same time to an expansion of the enclosed gas. This leads to an expansion of the microspheres.
  • the expansion capacity of the microspheres can be described by determining the TMA density [kg / m 3 ] (Stare Thermal Analysis System Fa Mettler Toledo, heating rate 20 ° C / min).
  • the TMA density here is the minimum achievable density at a certain temperature T max under normal pressure before the microspheres collapse.
  • the propellant-filled hollow plastic body preferably have a diameter between 20 pm and 40 gm.
  • Such propellant-filled Kunststoffhohl- are the body, for example, available from Akzo Nobel, Casco Products GmbH, Essen under the trademark Expancel ®.
  • propellant-filled plastic hollow bodies having a TMA density of less than 10 kg / m 3 preferably from 2 to 10 kg / m 3 and particularly preferably from 2 to 7 kg / m 3
  • a particularly fine cell structure a suppression of voids formation and no formation of sink marks to observe and also the processing range, for example, in terms of temperature, much larger, so that microspheres are particularly preferred with such a TMA density.
  • suitable propellant-filled plastic hollow bodies have a bimodal particle size distribution. The particle sizes are chosen so that the best possible space filling of the expanded particles is possible and thus the lowest possible density of the resulting foam is obtained.
  • the content of propellant-filled plastic hollow bodies in the mixture used is dependent on the desired density of the flexible polyurethane foam. Preference is given per 100 parts by weight of the polyurethane to be foamed, between 1 part by weight and 20 parts by weight, preferably used between 2 parts by weight and 10 parts by weight of the propellant-filled plastic hollow body.
  • mixtures of various blowing agents in particular mixtures comprising at least one encapsulated blowing agent and at least one chemical blowing agent or mixtures comprising at least one encapsulated blowing agent and at least one physical blowing agent.
  • catalysts (d) for the preparation of the flexible polyurethane foams according to the invention it is preferred to use compounds which greatly accelerate the reaction of the hydroxyl-containing compounds of component (b) with the polyisocyanates (a) and / or the reaction of the isocyanates with water.
  • Suitable catalysts are, for example, amines selected from the group consisting of tertiary amines, preferably selected from the group consisting of tributylamine, triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylethanolamine, N-methyl -morpholine, N-ethyl-morpholine, N, N, N ', N'-tetramethylethylenediamine, pentamethyldiethylenetriamine; 1,4-diaza-bicyclo- (2,2,2) -octane, N-methyl-N'-dimethylaminoethylpiperazine, bis (dimethylaminoalkyl) -piperazine, N, N-dimethylbenzylamine, N, N-dimethylcyclohexylamine, N , N-diethylbenzylamine, bis (N, N-diethylaminoethy
  • organic metal compounds Preference is given to using organic metal compounds based on tin, zinc, bismuth, titanium, zirconium, manganese, iron, cobalt, copper, aluminum.
  • organic tin compounds such as tin (II) salts of organic carboxylic acids, e.g. Tin (II) acetate, stannous octoate, stannous (II) ethyl hexoate, and stannous laurate and the dialkyltin (IV) salts of organic carboxylic acids, e.g.
  • the organic metal compounds can be used alone or in combination with strongly basic amines. In a preferred embodiment, no organic metal compounds, but only amines are used as catalysts.
  • the catalysts are usually used in amounts of 0 to 2000 ppm, preferably 1 ppm to 1000 ppm, more preferably 2 ppm to 500 ppm, and most preferably from 5 ppm to 300 ppm.
  • the organic metal compounds can be used alone or preferably in combination with strongly basic amines.
  • catalysts (d) Preferably, only amine catalysts are used as catalysts (d).
  • the catalyst or catalyst combination are usually used in amounts of 0 to 2000 ppm, preferably 1 ppm to 1000 ppm, more preferably 2 ppm to 500 ppm, and most preferably from 5 ppm to 300 ppm, based on the weight of component (b) used.
  • auxiliaries and / or additives are known per se to the person skilled in the art. Suitable auxiliaries and additives, for example, the Plastics Handbook, Volume 7, Carl Hanser Verlag, Kunststoff 1966 (pp 103-1 13) are removed. Surfactants, flame retardants, nucleating agents, oxidation stabilizers, antioxidants, lubricants and mold release agents, dyes and pigments, stabilizers, eg. As against hydrolysis, light, heat or discoloration, inorganic and / or organic fillers, reinforcing agents and plasticizers.
  • auxiliaries and / or additives for example, surface-active substances, foam stabilizers, cell regulators, external and internal release agents, fillers, pigments, dyes, flame retardants, antistatic agents, nucleating agents, oxidation stabilizers, antioxidants, lubricants and mold release agents, dyes and pigments, stabilizers, for , As against hydrolysis, light, heat or discoloration, inorganic and / or organic fillers, reinforcing agents and plasticizers and fungistatic and bactericidal substances used. Further information on the starting materials used can be found, for example, in the Plastics Handbook, Volume 7, Polyurethanes, edited by Günter Oertel, Carl Hanser Verlag, Kunststoff, 3rd edition 1993, Chapter 5, Flexible Polyurethane Foams.
  • the polyol component (b), the catalysts (d), the blowing agent (c) and, if appropriate, the auxiliaries and / or additives used are conventionally mixed in advance and in this form with the polyisocyanates a) brought to implementation.
  • the polyisocyanate component (a) is reacted with the polyol component (b) in the presence of the abovementioned blowing agents (c), catalysts (d) and auxiliaries and / or additives.
  • the mixing ratios are selected such that the equivalence ratio of NCO groups of the polyisocyanates (a) to the sum of the reactive hydrogen atoms of components (b) and, if present, (c) and (d) are in the range 0.4 : 1 to 1: 120, preferably 0.5 to 0.95 to 1.2, preferably 0.6 to 0.8 to 1.2 and in particular 0.65 to 0.75 to 1.1.
  • a ratio of 1 to 1 corresponds to an isocyanate index of 100.
  • the flexible polyurethane foams according to the invention are preferably produced by the one-shot process, for example by means of high-pressure or low-pressure technology.
  • the foams according to the invention are produced, for example, on a belt or preferably in a mold.
  • the polyurethane molded foams can be produced in open or closed, for example metallic molds.
  • a polyol component is prepared and mixed with polyisocyanate a). foams.
  • the components are preferably mixed at a temperature in the range between 15 to 120 ° C, preferably 20 to 80 ° C and brought into the mold or on the strip line.
  • the temperature in the mold is usually in the range between 15 and 120 ° C, preferably between 30 and 80 ° C.
  • the resultant polyurethane molded foam is likewise an object of the present invention.
  • the polyurethane molded foam has a tack-free surface, which improves workplace hygiene and consumer acceptance, in particular in the furniture and mattress sector, but also in the shoe sector (wearing comfort, cushioning effect when used in the heel and forefoot area and as a shoe bag) ,
  • the present invention relates to the flexible polyurethane foams obtained by the above-described processes.
  • the flexible polyurethane foams according to the invention are fusible, open-celled foams with low free space weight under elevated pressure and corresponding temperature.
  • the flexible polyurethane foams according to the invention preferably have a softening point lower than 160 ° C., more preferably lower than 150 ° C., determined under a hot press at a contact pressure of 25-50 kN for 60-180 sec.
  • Another property of the flexible polyurethane foams according to the invention is that they can be compacted under the action of elevated pressure and corresponding temperature to form compact elastomers with surprisingly good mechanical properties.
  • Another object of the present invention are hybrid materials comprising the novel flexible polyurethane foam in combination with a compact thermoplastic elastomer, preferably thermoplastic polyurethane.
  • a further subject of the present invention are hybrid materials comprising the flexible polyurethane foam according to the invention in combination with expanded thermoplastic polyurethane in the form of particles or interconnected particles (particle foam structure).
  • hybrid materials comprising the novel flexible polyurethane foam in combination with expanded thermoplastic polyurethane in the form of particles or interconnected particles (particulate material structure), as well as thermoplastic elastomer, preferably polyurethane.
  • the flexible polyurethane foam in the form of an insert or poster element can be connected to a compact thermoplastic polyurethane.
  • Ways of producing are welding, gluing, sewing or pouring.
  • thermoplastic elastomers are thermoplastic elastomers with a density of at least 1 g / cm 3 measured without fillers, preferably a density of 1 g / cm 3 to 1, 5 g / cm 3 , particularly preferably 1, 05 g / cm 3 to 1 , 35 g / cm 3 .
  • thermoplastic polyether esters and polyester esters can be prepared by all conventional methods known from the literature by transesterification or esterification of aromatic and aliphatic dicarboxylic acids having 4 to 20 carbon atoms or esters thereof with suitable aliphatic and aromatic diols and polyols. Corresponding preparation methods are described, for example, in "Polymer Chemistry", Interscience Publ., New York, 1961, pp. 11-127; Kunststoffhandbuch, Volume VIII, C. Hanser Verlag, Kunststoff 1973 and Journal of Polymer Science, Part A1, 4, pages 1851-1859 (1966).
  • Suitable aromatic dicarboxylic acids are, for example, phthalic acid, isophthalic acid and terephthalic acid or their esters.
  • Suitable aliphatic dicarboxylic acids are, for example, cyclohexane-1,4-dicarboxylic acid, adipic acid, sebacic acid, azelaic acid and decanedicarboxylic acid as saturated dicarboxylic acids and maleic acid, fumaric acid, aconitic acid, itaconic acid, tetrahydrophthalic acid and tetrahydroterephthalic acid as unsaturated dicarboxylic acids.
  • Suitable diol components are, for example, diols of the general formula HO- (CH 2) n -OH, where n is an integer from 2 to 20.
  • Suitable diols are, for example, ethylene glycol, propanediol (1, 3), butanediol (1, 4) or hexanediol (1, 6).
  • Polyetheroie by the transesterification of which the thermoplastic polyetherester can be prepared, are preferably those of the general formula H0- (CH 2 ) n -O- (CH 2 ) m -OH, where n and m may be the same or different and n and m independently each represent an integer between 2 and 20.
  • Unsaturated diols and polyetheroils which can be used to prepare the polyetherester include, for example, butene diol (1,4) as well as diols containing aromatic moieties and polyether oil.
  • the hard phases of the block copolymers are usually formed from aromatic dicarboxylic acids and short-chain diols, the soft phases from preformed aliphatic, difunctional polyesters having a molecular weight Mw between 500 and 3000 g / mol.
  • a coupling of the hard and soft phases can additionally be effected by reactive compounds such as diisocyanates, which react, for example, with terminal alcohol groups.
  • Thermoplastic polyetheramides suitable for the hybrid materials according to the invention can be obtained by all conventional methods known from the literature by reaction of amines and carboxylic acids or their esters. Amines and / or carboxylic acids also contain here ether units of the type R-O-R, wherein R is an aliphatic or aromatic organic radical. In general, monomers selected from the following classes of compounds are used:
  • R ' can be aromatic or aliphatic and preferably contains ether units of the type R-O-R.
  • R stands for an aliphatic or aromatic organic radical
  • aromatic dicarboxylic acids for example phthalic acid, isophthalic acid and terephthalic acid or their esters, and aromatic dicarboxylic acids containing ether units of the R-O-R type, where R is an aliphatic or aromatic organic radical,
  • aliphatic dicarboxylic acids for example cyclohexane-1, 4-dicarboxylic acid, adipic acid, sebacic acid, azelaic acid and decanedicarboxylic acid as saturated dicarboxylic acids and maleic acid, fumaric acid, aconitic acid, itaconic acid, tetrahydrophthalic acid and tetrahydohydroterephthalic acid as unsaturated dicarboxylic acids, and aliphatic dicarboxylic acids containing ether units of the type ROR, where R is an aliphatic and / or aromatic organic radical,
  • Diamines of the general formula H 2 NR "-NH 2 where R” may be aromatic and aliphatic and preferably contains ROR-type ether units and R is an aliphatic and / or aromatic organic radical,
  • Lactams for example e-caprolactam, pyrrolidone or laurolactam and
  • thermoplastic elastomers having a block copolymer structure which can be used for the hybrid materials according to the invention preferably contain vinylaromatic, butadiene and isoprene and also polyolefin and vinylic units, for example ethylene, propylene and vinyl acetate units. Preference is given to styrene-butadiene copolymers.
  • thermoplastic elastomers having a block copolymer structure which can be used for the hybrid materials according to the invention, such as polyetheramides, polyether esters and polyester esters, preferably have a Shore hardness in the range from A44 to D80. Particularly preferred are shore Hardness in the range of A40 to A 99, especially in the range of A44 to A96. The Shore hardnesses are determined according to DIN 53505.
  • the elastomers having a block copolymer structure such as polyetheramides, polyether esters and polyester esters which can be used for the hybrid materials according to the invention are chosen such that their melting points are below 300.degree. C., preferably at a maximum of 250.degree. C. and in particular at a maximum of 220.degree.
  • the elastomers with block copolymer structure such as polyetheramides, polyether esters and polyester esters, which can be used for the hybrid materials according to the invention can be partially crystalline or amorphous.
  • thermoplastic elastomers may contain in effective amounts other additives such as dyes, pigments, fillers, flame retardants, synergists for flame retardants, antistatic agents, stabilizers, surface-active substances, plasticizers and infrared opacifiers.
  • Suitable infrared opacifiers for reducing the radiation contribution to the thermal conductivity are, for example, metal oxides, nonmetal oxides, metal powders, for example aluminum powder, carbon, for example carbon black, graphite or diamond, or organic dyes and colored pigments.
  • the use of infrared opacifiers is particularly advantageous for high temperature applications.
  • Particularly preferred as infrared opacifiers are carbon black, titanium dioxide, iron oxides or zirconium dioxide.
  • the abovementioned materials can be used both individually and in combination, that is to say in the form of a mixture of a plurality of materials. If fillers are used, they can be inorganic and / or organic.
  • fillers are, for example, organic and inorganic powders or fibrous materials and mixtures thereof.
  • organic fillers for example, wood flour, starch, flax, hemp, ramie, jute, sisal, cotton, cellulose or aramid fibers can be used.
  • Suitable inorganic fillers are, for example, silicates, barite, glass beads, zeolites, metals or metal oxides.
  • pulverulent inorganic substances such as chalk, kaolin, aluminum hydroxide, magnesium hydroxide, aluminum nitrite, aluminum silicate, barium sulfate, calcium carbonate, calcium sulfate, silica, quartz flour, aerosil, alumina, mica or wollastonite or spherical or fibrous inorganic substances, for example Iron powder, glass beads, glass fibers or carbon fibers, used.
  • the average particle diameter or, in the case of fibrous fillers, the length of the fibers should be in the range of the cell size or smaller. Preference is given to an average particle diameter or an average length of the fibers in the range from 0.1 to 100 ⁇ m, in particular in the range from 1 to 50 ⁇ m.
  • thermoplastic elastomers Preference is given to expandable, blowing agent-containing thermoplastic elastomers, thermoplastic elastomers having a block copolymer structure, polyetheramides, polyether esters Polyester esters containing between 5 and 80% by weight of organic and / or inorganic fillers, based on the total weight of the blowing agent-containing system.
  • thermoplastic molding compositions which may be contained in the thermoplastic molding composition are, for example, compounds which serve to assist the homogenization of the starting materials and may also be suitable for regulating the cell structure.
  • suitable surface-active substances are emulsifiers, for example sodium salts of castor oil sulfates or of fatty acids and salts of fatty acids with amines, for example diethylamine oily diethanolamine, diethanolamine stearate, diethanolamine ricinoleic acid, salts of sulfonic acids, for example alkali metal or ammonium salts of dodecylbenzene or dinaphthylmethanedisulfonic acid and ricinoleic acid; Foam stabilizers such as Siloxanoxalkylen- copolymers and other organosiloxanes, oxyethylated alkylphenols, oxyethylated Fettal alcohols, paraffin oils, castor oil or Rizinolklad, turquoise oil and peanut
  • oligomeric polyacrylates with polyoxyalkylene and fluoroalkane radicals are also suitable as side groups.
  • the surface-active substances are usually used in amounts of from 0.01 to 5% by weight, based on the total weight of the blowing agent-containing system.
  • thermoplastic elastomers the elastomers which can be used for the hybrid materials according to the invention are thermoplastic polyurethanes.
  • Thermoplastic polyurethanes are well known.
  • the preparation is carried out by reacting (a) isocyanates with (b) isocyanate-reactive compounds / polyol having a number average molecular weight of 500 g / mol to 100,000 g / mol and optionally chain extenders having a molecular weight of 50 g / mol to 499 g if appropriate in the presence of (c) catalysts and / or (d) customary auxiliaries and / or additives.
  • the components (a) isocyanate, (b) isocyanate-reactive compounds / polyol optionally chain extenders are individually or together also addressed as constituent components.
  • the synthesis components including the catalyst and / or the usual auxiliaries and / or additives are also called feedstocks.
  • the amounts used of the synthesis components (b) can be varied in their molar ratios, the hardness and the melt viscosity increasing with increasing content of chain extender in the component (b), while Melt index decreases.
  • thermoplastic polyurethanes To prepare the thermoplastic polyurethanes, the synthesis components (a), (b), wherein (b) in a preferred embodiment also contains chain extenders, in the presence of a catalyst (d) and optionally auxiliaries and / or additives in such quantities Reaction brought that the equivalence ratio of NCO groups of Diisocyanates (a) to the sum of the hydroxyl groups of the polyol component (b) and (c) 0.95 to 1, 10: 1, preferably 0.98 to 1, 08: 1 and in particular about 1, 0 to 1, 05: 1 ,
  • thermoplastic polyurethanes are preferably prepared in which the thermoplastic polyurethane has a weight-average molecular weight of at least 60,000 g / mol, preferably of at least 80,000 g / mol and in particular greater than 10,000 g / mol.
  • the upper limit for the weight-average molecular weight of the thermoplastic polyurethanes is generally determined by the processability as well as the desired property spectrum.
  • the number-average molecular weight of the thermoplastic polyurethanes is preferably between 80,000 and 200,000 g / mol.
  • the average molecular weights given above for the thermoplastic polyurethane as well as the constituent components (a) and (b) are the weight average determined by gel permeation chromatography.
  • organic isocyanates it is preferred to use aliphatic, cycloaliphatic, araliphatic and / or aromatic isocyanates, more preferably tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methylpentamethylene diisocyanate 1, 5, 2-ethyl-butylene-diisocyanate-1, 4, pentamethylene-diisocyanate-1, 5, butylene-diisocyanate-1, 4, 1-iso-cyanato-3,3,5-trimethyl-5-isocyanatomethyl cyclohexane (isophorone diisocyanate, IPDI), 1,4-bis (isocyanatomethyl) cyclohexane and / or 1,3-bis (isocyanatomethyl) cyclohexane (HXDI), 2,4-paraphenylene diisocyanate (PPDI), 2,4-paraphen
  • Preferred isocyanate-reactive compounds (b) are those having a molecular weight between 500 g / mol and 8000 g / mol, preferably 700 g / mol to 6000 g / mol, in particular 800 g / mol to 4000 g / mol ,
  • the isocyanate-reactive compound (b) has on statistical average at least 1, 8 and at most 2.2, preferably 2, Zerewitinoffepte hydrogen atoms, this number is also referred to as functionality of the isocyanate-reactive compound (b) and gives the theoretical amount of a substance to a molecule downsized amount of the isocyanate-reactive groups of the molecule.
  • the isocyanate-reactive compound is substantially linear and is an isocyanate-reactive substance or a mixture of various substances, in which case the mixture satisfies the said requirement.
  • These long-chain compounds are used with a mole fraction of from 1 equivalent mol% to 80 equivalent mol%, based on the isocyanate group content of the polyisocyanate.
  • the isocyanate-reactive compound (b) has a reactive group selected from the hydroxyl group, the amino group, the mercapto group or the carboxylic acid group. It is preferably the hydroxyl group.
  • the isocyanate-reactive compound (b) is particularly preferably selected from the group of the polyester oil, the polyether oil or the polycarbonate diols, which are also combined under the term "polyols".
  • polyester diols preferably polycaprolactone
  • polyether polyols preferably polyether diols, more preferably those based on ethylene oxide, propylene oxide and / or butylene oxide, preferably polypropylene glycol.
  • a particularly preferred polyether is polytetrahydrofuran (PTHF), in particular polyether oxide.
  • Particularly preferred polyols are those selected from the following group: copolyesters based on adipic acid, succinic acid, pentanedioic acid, sebacic acid or mixtures thereof and mixtures of 1,2-ethanediol and 1,4-butanediol, copolyester based on adipic acid, Succinic acid, pentanedioic acid, sebacic acid or mixtures thereof and mixtures of 1,4-butanediol and 1,6-hexanediol, polyesters based on adipic acid and 3-methyl-pentanediol-1, 5 and / or polytetramethylene glycol (polytetrahydrofuran, PTHF), in particular preferably copolyesters based on adipic acid and mixtures of 1, 2-ethanediol and
  • adipic acid succinic acid
  • pentanedioic acid pentanedioic acid
  • sebacic acid sebacic acid or mixtures thereof
  • polytetramethylene glycol (PTHF) polytetramethylene glycol
  • the chain extenders used are preferably aliphatic, araliphatic, aromatic and / or cycloaliphatic compounds having a molecular weight of from 50 g / mol to 499 g / mol, preferably with 2 isocyanate-reactive compounds, which are also referred to as functional groups.
  • Preferred chain extenders are diamines and / or alkanediols, more preferably alkanediols having 2 to 10 carbon atoms, preferably 3 to
  • chain extenders (c) are used, these are preferably aliphatic, araliphatic, aromatic and / or cycloaliphatic compounds having a molecular weight of 50 g / mol to 0499 g / mol, preferably with 2 isocyanate-reactive groups, which are also known as functional groups.
  • the chain extender is at least one chain extender selected from the group consisting of 1, 2-ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 2,3-butanediol, 1, 5-pentanediol, 1 , 6-hexanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol,
  • 1,4-dimethanolcyclohexane 1,4-dimethanolcyclohexane, neopentyl glycol and hydroquinone bis (beta-hydroxyethyl) ethers (HQEE).
  • chain extenders selected from the group consisting of 1, 2-ethylene glycol, 1, 3-propanediol, 1, 4-butanediol and 1, 6-hexanediol.
  • Very particularly preferred chain extenders are 1,4-butanediol, 1,6-hexanediol and ethanediol.
  • catalysts (d) are used with the synthesis components. These are in particular catalysts which accelerate the reaction between the NCO groups of the isocyanates (a) and the hydroxyl groups of the isocyanate-reactive compound (b) and, when used, the chain extender.
  • Preferred catalysts are tertiary amines, in particular triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, diazabicyclo (2,2,2) octane.
  • the catalysts are more preferably organic metal compounds such as titanic acid esters, iron compounds, preferably iron (III) acetylacetonate, tin compounds, preferably those of carboxylic acids, particularly preferably tin diacetate, tin dioctoate, tin dilaurate or the tin dialkyl salts Dibutyltin diacetate, dibutyltin dilaurate, or bismuth salts of carboxylic acids, preferably bismuth decanoate.
  • Particularly preferred catalysts are tin dioctoate, bismuth decanoate and titanic acid esters.
  • the catalyst (d) is preferably used in amounts of from 0.0001 to 0.1 parts by weight per 100 parts by weight of the isocyanate-reactive compound (b).
  • auxiliaries (d) it is also possible to add conventional auxiliaries (d) to structural components (a) to (b). Mention may be made, for example, of surface-active substances, fillers, flame retardants, nucleating agents, oxidation stabilizers, lubricants and mold release agents, dyes and pigments, optionally stabilizers, preferably against hydrolysis, light, heat or discoloration, inorganic and / or organic fillers, reinforcing agents and / or plasticizers ,
  • Stabilizers in the context of the present invention are additives which protect a plastic or a plastic mixture against harmful environmental influences.
  • examples are primary and secondary antioxidants, hindered phenols, hindered amine light stabilizers, UV absorbers, hydrolysis protectors, quenchers and flame retardants.
  • examples of commercial stabilizers are given in Plastics Additives Handbook, 5th Edition, H. Zweifel, ed., Hanser Publishers, Kunststoff, 2001 ([1]), p.98-S136.
  • the UV absorbers have a number average molecular weight of greater than 300 g / mol, in particular greater than 390 g / mol. Furthermore, the UV absorbers preferably used should have a molecular weight of not greater than 5000 g / mol, particularly preferably not greater than 2000 g / mol.
  • UV absorber is the group comprising cinnamates, oxanilides and benzotriazoles, particularly preferred are benzotriazoles.
  • benzotriazoles are Tinuvin® 213, Tinuvin® 234, Tinuvin® 571, Tinuvin® 384 and Eversorb®82.
  • the UV absorbers are usually metered in amounts of from 0.01% by weight to 5% by weight, based on the total mass, of thermoplastic polyurethane, preferably from 0.1% by weight to 2.0% by weight, in particular 0.2 Wt .-% to 0.5 wt .-%.
  • a UV stabilization based on an antioxidant and a UV absorber described above is still not sufficient to ensure good stability of the thermoplastic polyurethane according to the invention against the harmful influence of UV rays.
  • a hindered amine light stabilizer can also be added to the thermoplastic polyurethane according to the invention.
  • the activity of the HALS compounds is based on their ability to form nitroxyl radicals, which interfere with the mechanism of oxidation of polymers. HALS are considered to be highly efficient UV stabilizers for most polymers.
  • HALS compounds are well known and commercially available. Examples of commercially available HALS stabilizers can be found in Plastics Additive Handbook, 5th edition, H. Zweifel, Hanser Publishers, Kunststoff, 2001, pp. 123-136.
  • Hindered Amine Light Stabilizers are preferably Hindered Amine Light Stabilizers in which the number average molecular weight is greater than 500 g / mol. Furthermore, the molecular weight of the preferred HALS compounds should not be greater than 10,000 g / mol, more preferably not greater than 5,000 g / mol.
  • Particularly preferred hindered amine light stabilizers are bis (1, 2,2,6,6-pentamethylpiperidyl) sebacate (Tinuvin® 765, Ciba Spezialitätenchemie AG) and the condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl- 4-hydroxypiperidine and succinic acid (Tinuvin® 622).
  • the condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidines and succinic acid is particularly preferred if the titanium content of the finished product is less than 150 ppm, preferably less than 50 ppm, in particular less than 10 ppm, based on the starting components used.
  • HALS compounds are preferably used in a concentration of 0.01% by weight to 5% by weight, more preferably of 0.1% by weight to 1% by weight, in particular of 0.15% by weight. up to 0.3% by weight, based on the total weight of the thermoplastic polyurethane, of the starting components used.
  • a particularly preferred UV stabilization comprises a mixture of a phenolic stabilizer, a benzotriazole and a HALS compound in the preferred amounts described above. Further details on the auxiliaries and additives mentioned above can be found in the specialist literature, eg from Plastics Additives Handbook, 5th edition, H. Zweifel, ed., Hanser Publishers, Kunststoff, 2001.
  • thermoplastic polyurethanes can be carried out continuously or continuously, for example using reaction extruders or the strip process, by the "one-shot” or the prepolymer process, preferably by the “one-shot” process, according to the known processes.
  • the synthesis components (a), (b) and in preferred embodiments also (c), (d) and / or (e) are introduced individually or as a mixture into the extruder and, preferably at temperatures of 100 ° C to 280 ° C, preferably 140 ° C to 250 ° C, reacted.
  • the resulting polyurethane is extruded, cooled and granulated.
  • thermoplastic polyurethane is prepared in a first step from the synthesis components isocanate (a), isocyanate-reactive compound (b) including chain extenders and in preferred embodiments the other starting materials (c) and / or (d) and in a second Extrusion step incorporated the additives or excipients.
  • the preparation described above is preferably used for the production as injection molding, calendering, powder sintering or extrusion articles.
  • twin-screw extruder is used, since the twin-screw extruder works positively conveying and so a more precise adjustment of the temperature and discharge rate is possible on the extruder.
  • the expanded particles may be obtained by melt impregnation of molten thermoplastic polyurethane with a blowing agent and subsequent granulation.
  • the production of corresponding particle foams can be carried out by superheated steam welding (eg at temperatures between 100-200 ° C., optionally under pressure (eg 1-6 bar)) or high-frequency electromagnetic radiation, in particular microwave radiation or radio waves.
  • Suitable processes for producing the foam particles and the resulting particle foams are described, for example, in WO 2005023920, WO 2007082838, WO2010 / 136398 WO 2013/153190, WO 2013/153190; WO 2014198779, WO2015 / 05581, WO2017030835,
  • the hybrid materials according to the invention of the flexible polyurethane foam according to the invention and thermoplastic polyurethane or expanded thermoplastic polyurethane are characterized in that at least 50% by weight of the polyol component (b) used for building up the flexible polyurethane foam and the isocyanate-reactive compounds (b) of the thermoplastic polyurethane or expanded thermoplastic polyurethane are identical.
  • the hybrid materials according to the invention of the flexible polyurethane foam according to the invention and thermoplastic polyurethane are characterized in that at least 50% by weight of the isocyanate component a) used to build up the flexible polyurethane foam and the organic isocyanate (a) of the thermoplastic Polyurethane or expanded thermoplastic polyurethane are identical.
  • the hybrid materials according to the invention comprising the flexible polyurethane foam according to the invention and thermoplastic polyurethane or expanded thermoplastic polyurethane are characterized in that at least 50% by weight of the isocyanate component a) and the organic isocyanates (a) used to build up the flexible polyurethane foam of the thermoplastic polyurethane or expanded thermoplastic polyurethane and at least 50% by weight of the isocyanate component a) used to build up the flexible polyurethane foam and the organic isocyanates (a) of the thermoplastic polyurethane or expanded thermoplastic polyurethane are identical.
  • the hybrid materials according to the invention of the flexible polyurethane foam according to the invention and thermoplastic polyurethane or expanded thermoplastic polyurethane are characterized in that at least 85% by weight of the isocyanate component a) and the organic isocyanates used to build up the flexible polyurethane foam a) of the thermoplastic polyurethane or expanded thermoplastic polyurethane and at least 85% by weight of the isocyanate component a) used to build up the flexible polyurethane foam and the organic isocyanates (a) of the thermoplastic polyurethane or expanded thermoplastic polyurethane are identical.
  • the isocyanate component a) or the organic isocyanate (a) of the thermoplastic polyurethane or of the expanded thermoplastic polyurethane used to build up the flexible polyurethane foam is selected from the group consisting of 2,2 ', 2,4' - And / or 4,4'-diphenylmethane diisocyanate (MDI), mixtures thereof and / or Prepoylmere used on their basis.
  • MDI 4,4'-diphenylmethane diisocyanate
  • the polyol component (b) or the isocyanate-reactive compounds (b) of the thermoplastic polyurethane or of the expanded thermoplastic polyurethane selected from the group consisting of polyether diols is further preferably those based on ethylene oxide, propylene oxide and / or butylene oxide, based on polytetrahydrofuran (PTHF) and polyesterdiols based on adipic acid and mixtures of 1,2-ethanediol and 1,4-butanediol or polyesters based on adipic acid, Succinic acid, pentanedioic, sebacic acid or mixtures thereof.
  • PTHF polytetrahydrofuran
  • Kettenverimerer of 1, 4-butanediol, 1, 6-hexanediol and ethanediol preferably included.
  • Another object of the present invention is a process for recycling a novel flexible polyurethane foam or a hybrid material according to the invention comprising collecting, crushing, cleaning and melting of the hybrid material, preferably in a twin-screw extruder.
  • the flexible polyurethane foam according to the invention or the hybrid material according to the invention is correspondingly comminuted.
  • the extrusion is carried out at temperatures of 120 to 260 ° C, preferably 160 to 220 ° C, wherein the pressure is selected depending on the machine, material and temperature.
  • the melting of the previously comminuted flexible polyurethane foam is carried out together with thermoplastic elastomer, preferably thermoplastic polyurethane, wherein the melting is carried out in an extruder.
  • the proportion of the thermoplastic elastomer, preferably thermoplastic polyurethane, based on the total mixture is preferably more than 30% by weight, preferably more than 50% by weight, very particularly preferably more than 70% by weight.
  • the added thermoplastic polyurethane is characterized in that at least 50% by weight of the polyol component (b) or of the polyol component used to build up the flexible polyurethane foam (b) and the isocyanate-reactive compounds (b) of the hybrid material are identical to the isocyanate-reactive compounds (b) of the added thermoplastic polyurethane.
  • the added thermoplastic polyurethane is characterized in that at least 50% by weight of the isocyanate component a) or the isocyanate component a) and the organic isocyanates (a) of the hybrid material used for the synthesis of the flexible polyurethane foam are identical to the isocyanate component a) of the added thermoplastic polyurethane.
  • the added thermoplastic polyurethane is characterized in that
  • (B) at least 50 wt .-% of the isocyanate component used for the construction of the flexible polyurethane foam a) or used isocyanate component a) and the organic isocyanates (a) of the hybrid material with the isocyanate component a) of the added thermoplastic polyurethane are identical.
  • the added thermoplastic polyurethane is characterized in that
  • (B) at least 85 wt .-% of the isocyanate component used for the construction of the flexible polyurethane foam a) or isocyanate component used a) and the organic isocyanates (a) of the hybrid material with the isocyanate component a) of the added thermoplastic polyurethane are identical.
  • the isocyanate component a) or the organic isocyanate (a) of the thermoplastic polyurethane used for the construction of the polyurethane soft-shell is selected from the group consisting of 2,2'-, 2,4'- and / or 4 , 4'-diphenylmethane diisocyanate (MDI), mixtures thereof and / or Prepoylmere used on their basis.
  • MDI 4,'-diphenylmethane diisocyanate
  • polyetherdiols more preferably those based on the soft polyurethane material of ethylene oxide, propylene oxide and / or butylene oxide based on polyte
  • thermoplastic polyurethane preferably contains thermoplastic polyurethane
  • thermoplastic elastomer preferably thermoplastic polyurethane
  • the proportion of the thermoplastic elastomer, preferably thermoplastic polyurethane, based on the total mixture is preferably more than 30% by weight, preferably more than 50% by weight, very particularly preferably more than 70% by weight.
  • the invention furthermore relates to the use of a flexible polyurethane foam according to the invention as described above or a hybrid material according to the invention for consumer articles, preferably selected from the group consisting of articles of clothing, in particular shoe and shoe component, in particular shoe soles and upholstery; Jewelery and jewelery component, in particular for a smart device or for monitoring electronics, preferably selected from the group consisting of bracelet, bracelet component, neck strap and neckband component, body belt and body belt component, spectacles and spectacle component; Sports accessories; Damping material; Foam particles; Cleaning articles for mobile vehicles or aircraft; medical article, in particular dressing article, transdermal system, component of a transdermal system, in particular paving, constituent of a plaster, wound covering, component of a wound covering; Furniture part; Cushion, kisssen allocateteil; Mattress, mattress component; Awning or airframe accessory, in particular automotive accessory, in particular seat, seat component, carpet backing, engine cover, instrument panel, steering wheels; Body and airborne sound absorbing component; Design element for electrical components; and seal; Article for the agricultural industry,
  • hybrid material or polyurethane flexible foam according to the invention for articles of clothing, in particular shoes, boots, ski boots, as well as shoe and shoe components, the use as shoe and shoe components being preferred, in particular as shoe soles and padding.
  • the present invention therefore provides padding of the flexible polyurethane foam for shoes according to the invention.
  • Another object of the present invention is an insert of the flexible polyurethane foam according to the invention for shoes.
  • a further subject of the present invention is therefore also a shoe, preferably a sports shoe, in which the flexible polyurethane foam according to the invention is used as upholstery in the e.g. Heel area, forefoot area or in the shoe pocket, and the center hole is made of expanded thermoplastic polyurethane.
  • a further subject of the present invention is therefore a shoe in which the flexible polyurethane foam according to the invention is used as upholstery in the e.g. Heel area, forefoot area or in the shoe pocket or is used as an insert, wherein the thermoplastic elastomer, preferably thermoplastic polyurethane, the outsole, the upper and / or other shoe components represents.
  • the insert can be connected to the outer sole made of thermoplastic elastomer, preferably thermoplastic polyurethane, whereby the hybrid material according to the invention is obtained, or inserted into the shoe.
  • a further object of the present invention is therefore also a shoe, preferably a sports shoe, in which the flexible polyurethane foam according to the invention is used as upholstery in the e.g. Heel area, forefoot area or in the shoe pocket, the midsole is made of expanded thermoplastic polyurethane, and the outsole, the upper and / or other shoe components is a thermoplastic elastomer, preferably thermoplastic polyurethane.
  • the insert may be connected to the midsole of expanded thermoplastic polyurethane, whereby the erfindugnsdorfe hybrid material is obtained, o- be inserted into the shoe.
  • the recycled hybrid material may preferably be used for injection molding applications such as pads, stoppers, stops, shoe soles, shoe parts, rail pads, mats, animal ear tags.
  • a process for producing a thermally recyclable flexible polyurethane foam having a free density of between 30-150 g / L comprising the reaction of a reaction mixture
  • an isocyanate component having a functionality between 1, 9-2.2;
  • polyol component (b) is a polyester or polyether polyol having an average molecular weight of 500 g / mol and 12,000 g / mol. 3. Process according to embodiment 1 or 2, wherein the polyol component (b) additionally contains a chain extender.
  • Thermally recyclable flexible polyurethane foam obtainable by a process according to one of the embodiments 1 to 4.
  • hybrid material comprising the flexible polyurethane foam according to the invention according to embodiment 5 and compact thermoplastic elastomer.
  • Hybrid material according to embodiment 6 comprising the flexible polyurethane foam according to the invention according to embodiment 5 and expanded thermoplastic polyurethane
  • thermoplastic polyurethane 8. hybrid material according to embodiment 6 or 7, wherein at least 50% by weight of the polyol used for the construction of the flexible polyurethane foam polyol component (b) and the isocyanate-reactive compounds (b) of the thermoplastic polyurethane are identical.
  • a flexible polyurethane foam according to embodiment 5 or of the hybrid material according to any one of embodiments 6 to 8 for clothing articles of en- gagement, jewelery and jewelery components, sports accessories, damping materials, foam particles, cleaning articles for mobile vehicles or aircraft, medical articles; Furniture parts; Cushion, kisssen decorateteil; Mattress, mattress component; Drive or aircar accessories; Body and airborne sound absorbing component; Design element for electrical components and seals as well as articles for the agricultural industry and hydroponic substrates.
  • Shoe comprising a flexible polyurethane foam according to embodiment 5 as a padding in the heel area, forefoot area or in the shoehorn or as an insert.
  • Shoe comprising a flexible polyurethane foam according to embodiment 5 as padding in the heel area and / or forefoot area and / or in the shoe pocket and / or as insert and a midsole of expanded thermoplastic polyurethane and / or the outsole, the upper and / or or other shoe components made of thermoplastic polyurethane.
  • the feedstocks of the polyol component were mixed with a Vollrath stirrer at 1800 revolutions per minute for 10 minutes.
  • the isocyanate component was processed at 30 ° C. Due to the viscosity, polyether polyols were processed at 25 ° C and polyester components at 45 ° C. Polyol component and polyisocyanate component were then mixed with a Vollrath stirrer at 1800 revolutions per minute for 10 seconds and placed in a mold. All amounts given in the following tables to the starting substances are parts by weight (% by weight).
  • a conventional, commercially available flexible foam system was added as a reference system.
  • a conventional soft foam system usually consists of a polyol component with feedstocks (polyols and chain extenders / crosslinkers) with functionalities> 2.
  • the isocyanate component often a prepolymer, usually contains a proportion of polymeric MDI (pMDl). , as well as polyols and chain extenders / crosslinkers with functionalities of 3 and greater.
  • pMDl polymeric MDI
  • a commercially available seat foam system based on polyhydric polyether polyols and pMDl, for the vehicle and furniture sector, was selected as reference system, available as Elastoflex® W 5165/142 from BASF SE.
  • the resulting soft foam test specimens were conditioned for 2 days under standard conditions before the mechanical characterization was carried out. Test specimens were punched or cut out of these samples and the tear propagation resistance according to DIN ISO 34-1A, and the tensile strength and elongation at break according to DIN 53543 were determined. The abrasion with 10 N was determined according to DIN ISO 4649 and the density of foams according to method A of DIN EN ISO 1 183-1.
  • the melting point was determined with the aid of a hot press at a defined contact pressure over a defined time [sec].
  • Foam cubes with an edge length of 5 cm were prepared for this purpose.
  • the desired temperatures were set on the heating press on the upper and lower plate and temp. For about half an hour. riert.
  • the foam cube was placed between upper and lower plate of the hot press without first deforming the test specimen.
  • the plates of the hot press were then brought together with the desired contact pressure, the time was determined by a stopwatch. After the residence time had elapsed, the upper and lower plates of the hot press were moved apart again, and the test specimen was removed and evaluated.
  • compositions as well as the results of the measurements are given in Tables 1-3.
  • nb not determined Table 2. Index variations (polyester-polyether based).
  • the foam test specimens produced as described above were compacted by means of a hot press.
  • a foam body measuring 5 ⁇ 10 ⁇ 5 cm was placed between the Teflon-coated, 180 ° C hot metal plates of the press and the metal plates were brought together until a pressure of 25-30 kN was reached. After about 5-7 minutes, the pressure was constant, so that the metal plates were moved apart and the compacted test specimen was removed.
  • the foam specimens were sawn into small cubes and pressed with a hot press at 160 ° C for one minute at about 50 kN.
  • the resulting compacts were then ground with a 5 mm sieve and the foam granules were then dried for 3 hours at 110 ° C. in a heating cabinet.
  • thermoplastic polyurethane samples described above were comminuted in a mill to form pourable granules, dried again for 3 hours at 110 ° C. in a heating cabinet and filled in aluminum-coated PE bags for further use.
  • the foam granules were mixed in different proportions with a mixture of thermoplastic polyurethane 1 and thermoplastic polyurethane 2 in the ratio 1: 1.
  • Extrusion of the blend of thermoplastic recyclable foam and the thermoplastic polyurethane was performed on an APV twin-bladed Cone extruder, which provides a strand diameter of about 2 mm. The following parameters have been set:

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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)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Public Health (AREA)
  • Epidemiology (AREA)
  • General Health & Medical Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)

Abstract

La présente invention concerne un procédé de fabrication d'une mousse polyuréthane souple pouvant être recyclée thermiquement par fusion, ainsi que des matériaux hybrides en mousse polyuréthane souple et en élastomère thermoplastique compact et/ou polyuréthane thermoplastique expansé.
EP18822362.2A 2017-12-20 2018-12-20 Nouvelles mousses polyuréthanes souples Pending EP3727828A1 (fr)

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EP17208739 2017-12-20
PCT/EP2018/086186 WO2019122122A1 (fr) 2017-12-20 2018-12-20 Nouvelles mousses polyuréthanes souples

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EP3727828A1 true EP3727828A1 (fr) 2020-10-28

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JP (1) JP2021508350A (fr)
KR (1) KR20200094220A (fr)
CN (1) CN111511537A (fr)
BR (1) BR112020012516A2 (fr)
CA (1) CA3083860A1 (fr)
MX (1) MX2020006558A (fr)
RU (1) RU2020123773A (fr)
TW (1) TW201936684A (fr)
WO (1) WO2019122122A1 (fr)

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CA3083860A1 (fr) 2019-06-27
JP2021508350A (ja) 2021-03-04
WO2019122122A1 (fr) 2019-06-27
RU2020123773A (ru) 2022-01-20
TW201936684A (zh) 2019-09-16
KR20200094220A (ko) 2020-08-06
MX2020006558A (es) 2020-09-24
US20200339735A1 (en) 2020-10-29
US11945904B2 (en) 2024-04-02
CN111511537A (zh) 2020-08-07

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