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WO2010010010A1 - Mélanges de polymères thermoplastiques à base de polyuréthanne thermoplastique et de polymère de styrène, mousses fabriquées à partir de ces mélanges et procédés de fabrication correspondants - Google Patents

Mélanges de polymères thermoplastiques à base de polyuréthanne thermoplastique et de polymère de styrène, mousses fabriquées à partir de ces mélanges et procédés de fabrication correspondants Download PDF

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Publication number
WO2010010010A1
WO2010010010A1 PCT/EP2009/059014 EP2009059014W WO2010010010A1 WO 2010010010 A1 WO2010010010 A1 WO 2010010010A1 EP 2009059014 W EP2009059014 W EP 2009059014W WO 2010010010 A1 WO2010010010 A1 WO 2010010010A1
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Prior art keywords
polymer blend
polymer
thermoplastic
weight
styrene
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German (de)
English (en)
Inventor
Carsten Schips
Frank Braun
Frank Prissok
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16—Making expandable particles
    • C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • 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
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/03—Extrusion of the foamable blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/08—Copolymers of styrene
    • C08J2325/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2355/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00
    • C08J2355/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2455/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2423/00 - C08J2453/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene

Definitions

  • thermoplastic polyurethane and styrene polymer foams produced therefrom and related manufacturing processes
  • the invention relates to an expandable, propellant-containing thermoplastic polymer blend comprising thermoplastic polyurethane (TPU) and styrene polymer, wherein preferably the weight percentages of thermoplastic polyurethane are between 5 and 95 and the weight proportions of styrene polymer are between 5 and 95 and the proportions by weight of thermoplastic polyurethane (TPU) and styrene polymer add to 100 parts, wherein the polymer blend contains in a preferred embodiment, at least one further thermoplastic polymer, and the sum of the proportions by weight of the thermoplastic polyurethane and the Styrolpoly- merisates in this preferred embodiment between 50 and 99 and the proportions by weight of thermoplastic polyurethane, styrene polymer and further thermoplastic polymer in this preferred embodiment add to 100 and the polymer blend is preferably present as granules.
  • the invention relates to processes for the preparation of the expandable, blowing agent-containing thermoplastic see polymer blend, in which the TPU and the styrene polymer, optionally together with at least one filler, auxiliary and additive, and / or at least one further thermoplastic polymer to a granulate extruded with a mean diameter of 0.2 mm to 1 cm, as well as processes for the production of foams based on thermoplastic polymer blends and the foams or thermoplastic polymer blends produced by these methods.
  • TPU foams are mentioned, which are produced on an injection molding machine. Densities of 800 g / L and greater are specified in the examples. These are foamed TPU boards, not particle foams. Particle foams based on TPU are disclosed in WO 94/20568.
  • a disadvantage of the TPU foams described in WO 94/20568 is the high energy consumption in the production and processing. It is applied a water vapor pressure of 4.5 bar to 7 bar, ie a temperature of 145 ° C to 165 ° C.
  • WO 94/20568 describes expanded, ie foamed, TPU particles which can be processed into shaped parts. These TPU foam particles are produced at temperatures of 150 ° C. and above 150 ° C. and in the examples have a bulk density of between 55 g / l and 180 g / l, which is disadvantageous during transport and storage of these particles because of the increased space requirement.
  • the object of the present invention was to find expandable, ie foamable, thermoplastic polymer particles with high expansion capacity, thereby low storage volume, and at the same time low propellant loss during storage and a suitable process for their preparation and to produce therefrom a particle foam, which at temperatures below 150 0 C and at the same time has a high elasticity.
  • thermoplastic polyurethane TPU
  • styrene polymer optionally containing at least one further thermoplastic polymer, and in that the polymer blend is processed into a foam using the processes according to the invention.
  • the invention relates to a thermoplastic particle foam which is produced from a polymer blend containing thermoplastic polyurethane, hereinafter referred to as TPU, and styrene polymer.
  • the polymer blend contains at least one further thermoplastic polymer in addition to TPU and styrene polymer.
  • this further thermoplastic polymer is selected from the group consisting of acrylonitrile-butadiene-styrene (ABS), polyamide (PA), polymethylmethacrylate (PMMA), polycarbonate (PC), polyethylene (PE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), cellulose and polyoxymethylene (POM).
  • ABS acrylonitrile-butadiene-styrene
  • PA polyamide
  • PMMA polymethylmethacrylate
  • PC polycarbonate
  • PE polyethylene
  • PP polypropylene
  • PS polystyrene
  • PVC polyvinyl chloride
  • cellulose cellulose and polyoxymethylene
  • TPU, styrene polymer and the at least one further thermoplastic polymer are present in the mixture such that the proportions by weight of TPU, styrene polymer and the at least one further thermoplastic polymer add up to 100, the proportions by weight of the TPU and of the Styrene polymer together comprise between 50 parts by weight and 99 parts by weight, more preferably these parts by weight are between 70 and 99, more preferably between 80 and 99, even more preferably between 90 and 99, even more preferably between 95 and 99.
  • the polymer blend is composed of thermoplastic polyurethane and at least one other thermoplastic polymer that is not styrene polymer.
  • the polymer blend contains, in addition to styrene polymer, at least one further thermoplastic polymer which is not thermoplastic polyurethane.
  • the weight proportions of TPU and styrene polymer add up to 100 parts by weight, wherein the weight parts of TPU are between 5 and 95, more preferably between 15 and 85, more preferably between 30 and 70, particularly preferably between 40 and 60.
  • TPU is prepared by reacting from a mixture of isocyanates (a) with isocyanate-reactive compounds (b), preferably having a molecular weight of from 0.5 kg / mol to 10 kg / mol and optionally chain extenders (c), preferably one Molecular weight of 0.05 kg / mol to 0.5 kg / mol.
  • at least one chain regulator (d), a catalyst (d) and optionally at least one filler, auxiliary and / or additive are added to the mixture for the production of TPU.
  • the substance groups which may also be indicated by the lower case letters, are also addressed as components.
  • the components (a), (b), (c), (d), (d) and (e) usually used in the preparation of the TPU are described below by way of example and comprise the following substance groups: isocyanates (a), in relation to isocyanates reactive compounds (b), chain extenders (c), chain regulators (d), catalysts (d) and / or at least one customary filling, auxiliary and / or additive.
  • a mixture of isocyanates (a) and isocyanate-reactive compounds (b) is required for the preparation of TPU.
  • the further addition of the Components (c), (c1), (d) and (e) are optional and may be alone or in all possible variations.
  • component means in each case a single substance or a mixture of the substances belonging to this component.
  • the components isocyanates (a), isocyanate-reactive compounds (b), and chain extenders (c) and, if used, the chain regulators (c1) are addressed as structural components.
  • the organic isocyanates used are (a) aliphatic, cycloaliphatic, araliphatic and / or aromatic isocyanates, further preferred diisocyanates.
  • preferred diisocyanates are 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-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl cyclohexane (isophorone diisocyanate, IPDI), 1, 4 and / or 1, 3-bis (isocyanatomethyl) cyclohexane (HXDI), 1, 4-cyclohexane diisocyanate, 1-methyl-2, 4- and / or -2, 6-cyclohexan
  • polyesterols in preferred embodiments polyesterols, polyetherols and / or polycarbonate diols, which are usually also grouped together under the term "polyols", are used.
  • TPU is preferably prepared from polyether alcohol, polyetherdiol is particularly preferably used.
  • a particularly preferred polyether diol is polytetrahydrofuran.
  • the polyether alcohols and polytetrahydrofuran having a molecular weight between 0.6 kg / mol and 2.5 kg / mol are preferably used.
  • the polyether alcohols are used individually or else as a mixture of different polyether alcohols.
  • TPU is made from polyester alcohol.
  • polyester diol is used for this purpose.
  • a preferred polyester diol is prepared from adipic acid and butane-1, 4-diol.
  • Preferred embodiments of the polyester alcohols have a molecular weight between 0.6 kg / mol and 2.5 kg / mol.
  • these polyols have molecular weights of 0.5 kg / mol to 8 kg / mol, preferably 0.6 kg / mol to 6 kg / mol, in particular 0.8 kg / mol to 4 kg / mol, and in further preferred embodiments have an average functionality of from 1.8 to 2.3, more preferably from 1.9 to 2.2, in particular 2.
  • the polyol is a polyester alcohol, preferably from polyether tetrahydrofuran, and in a further preferred embodiment has a molecular weight between 0.6 kg / mol and 2.5 kg / mol
  • chain extenders (c) in preferred embodiments, aliphatic, aromatic, aromatic and / or cycloaliphatic compounds are used, which in further preferred embodiments have a molecular weight of from 0.05 kg / mol to 0.5 kg / mol.
  • chain extenders (c) are compounds having two functional groups, for example diamines and / or alkanediols having 2 to 10 C atoms in the alkylene radical, in particular butanediol-1, 4, hexanediol-1, 6 and / or Di, tri, tetra, penta, hexa, hepta, octa, nona and / or Dekaalkylenglykole having 3 to 8 carbon atoms and corresponding oligo- and / or polypropylenglykole.
  • mixtures of the chain extenders are used to prepare TPU.
  • chain regulators (d) usually having a molecular weight of 0.03 kg / mol to 0.5 kg / mol.
  • Chain regulators are compounds which have only one functional group compared to isocyanates. Examples of chain regulators are monofunctional alcohols, monofunctional amines, preferably methylamine, and / or monofunctional polyols. Through chain regulators, the flow behavior of the mixtures of the individual components can be specifically adjusted. Chain regulators are in preferred embodiments in an amount of 0 parts by weight to 5 parts by weight, more preferably from 0.1 parts by weight to 1 parts by weight, based on 100 parts by weight of the isocyanate-reactive compound b) used. Chain regulators are used in addition to or instead of chain extenders.
  • At least one catalyst (d) is used for TPU preparation, which accelerates in particular the reaction between the NCO groups of the diisocyanates (a) and the isocyanate-reactive compounds, preferably hydroxyl groups of the synthesis components (b), (c) and d ,
  • the catalyst is selected from the group of tertiary amines such as triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, diazabicyclo (2,2,2) octane and similar substances.
  • the at least one catalyst is selected from the group of organic metal compounds and is, by way of example, titanic acid ester, an iron compound such as iron (Ml) - acetylacetonate, a tin compound, eg Zinndiacetat, Zinndioctoat, tin dilaurate or a Zinndialkylsalz an aliphatic Carboxylic acid such as dibutyltin diacetate, dibutyltin dilaurate or the like.
  • the catalysts are used individually, in other embodiments, mixtures of catalysts are used.
  • the catalyst or mixture of catalysts is in from 0.0001 parts by weight to 0.1 parts by weight per 100 parts by weight of the isocyanate-reactive compound (b), preferably polyhydroxyl compound.
  • auxiliary and / or additive examples include hydrolysis protectants and flame retardants.
  • Other additives and auxiliaries may be standard works such as o.g. Becker and Braun (1996).
  • structural components (a) to (c) and, if appropriate, (d) can also be added to hydrolysis protection agents such as, for example, polymeric and low molecular weight carbodiimides.
  • the TPU may contain a phosphorus compound.
  • organophosphorus compounds of the trivalent phosphorus such as, for example, phosphites and phosphonites, are used as the phosphorus compounds.
  • suitable phosphorus compounds are triphenylphosphite, diphenylalkylphosphite, phenyldialkylphosphite, tris (nonylphenyl) phosphite, trilaurylphosphite, trioctadecylphosphite, di-stearyl-pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, di- (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tristearyl
  • Particularly preferred embodiments contain phosphorus compounds which are difficult to hydrolyze since the hydrolysis of a phosphorus compound to the corresponding acid can lead to damage of the polyurethane, in particular of the polyester urethane. Accordingly, phosphorus compounds are particularly suitable for polyester urethanes, which are particularly difficult to hydrolyze.
  • Preferred embodiments of hardly hydrolyzable phosphorus compounds are di-propylene glycol phenyl phosphite, tri-isodecyl phosphite, triphenyl monodecyl phosphite, trisisononyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4 ' -diphenylylenediphosphonite and di- (2,4-di-tert-butylphenyl) -pentaerythritol diphosphite or mixtures thereof.
  • the structural components (b) and (c) can be varied in relatively wide molar ratios.
  • the molar ratio of component (b) to total chain extender (c) used is from 10: 1 to 1:10, preferably from 5: 1 to 1: 8, more preferably from 1: 1 to 1: 4 the hardness of TPU increases with increasing content of chain extender (c).
  • Shore hardnesses of A44 to D80 can be adjusted, particularly preferred are Shore hardnesses of A44 to A84.
  • the Shore hardnesses are determined according to DIN 53505.
  • the conversion to TPU takes place with customary characteristic numbers.
  • the index is defined by the ratio of the total isocyanate groups of component (a) used in the reaction to the isocyanate-reactive groups, ie the active hydrogens, components (b) and (c).
  • an isocyanate group of component (a) has an active hydrogen atom, ie, an isocyanate-reactive function, components (b) and (c).
  • characteristic numbers above 100 more isocyanate groups than groups reactive toward isocyanates, for example OH groups, are present.
  • the conversion to TPU is carried out at a ratio between 60 and 120, more preferably at a ratio between 80 and 1 10.
  • TPU is preferably carried out according to one of the known methods mentioned below.
  • Preferred embodiments are the continuous process, for example with reaction extruders, the belt process, the one-shot process or the prepolymer process. [Ebnose Eb worker] Preferred embodiments are also the batch process or the prepolymer process process. a) and (b) and optionally (c), (d), (d) and / or (e) are mixed successively or simultaneously with each other, the reaction of the components (a) and (b) being used immediately.
  • the synthesis components (a) and (b) and optionally components (c), (d), (d) and / or (e) are introduced individually or as a mixture into the extruder and at temperatures of 100 0 C to 280 0 C, preferably at 140 0 C to 250 0 C reacted.
  • the resulting TPU is extruded, cooled and granulated.
  • styrene polymer any polymer based on a styrene monomer.
  • the styrene polymer is selected in preferred embodiments from the group: standard polystyrene, impact polystyrene (HIPS), styrene-acrylonitrile copolymers (SAN), acrylonitrile-butadiene-styrene copolymers (ABS), alpha-methyl-styrene-acrylonitrile (AMSAN) and acrylonitrile-styrene-acrylic ester (ASA).
  • HIPS impact polystyrene
  • SAN styrene-acrylonitrile copolymers
  • ABS acrylonitrile-butadiene-styrene copolymers
  • AMSAN alpha-methyl-styrene-acrylonitrile
  • ASA acrylonitrile-styrene-acrylic ester
  • SAN styrene-acrylonitrile copolymer
  • ABS acrylonitrile-butadiene-styrene copolymers
  • SAN styrene-acrylonitrile copolymers
  • ABS acrylonitrile-butadiene-styrene copolymers
  • weight average molecular weights in the range of 100 kg / mol to 250 kg / mol are used.
  • the styrene polymers a viscosity number (in 0.5% DMF) measured according to DIN 53726 in the range from 50 mL / g to 100 mL / g, in particular also SAN and ABS.
  • At least one further polymer which is thermoplastic in a preferred embodiment, is added to the polymer blend of styrene polymer and TPU according to the invention in preferred embodiments.
  • any polymer miscible with the polymer blend consisting of styrene polymer and TPU can be added.
  • Particularly preferred polymers are polyamide (PA), polymethyl methacrylate (PMMA), polycarbonate (PC), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), cellulose and / or polyoxymethylene (POM).
  • the addition of the at least one further polymer is carried out in preferred embodiments in amounts of 0.1% by weight to 70% by weight, preferably 0.1% by weight to 50% by weight, more preferably 0.1% to 30% by weight. , more preferably 0.1% by weight to 20% by weight, more preferably 0.1% by weight to 15% by weight, more preferably 0.1% by weight to 10% by weight, and particularly preferably 0.1% by weight. % to 5 wt.% Based on the total weight of the polymer blend without the addition of the filler, auxiliary and / or additive.
  • the constituents TPU, styrene polymer and further thermoplastic polymer may furthermore each contain, individually or in admixture, at least one filler, auxiliary and / or additive.
  • surface-active substances z.
  • compounds which serve to assist the homogenization of the starting materials and, if appropriate, are also suitable for regulating the cell structure.
  • examples include emulsifiers, such as.
  • emulsifiers such as.
  • sodium salts of castor oil or of fatty acids and salts of fatty acids with amines eg. Diethylamine, stearic acid diethanolamine, ricinoleic diethanolamine, salts of sulfonic acids, eg.
  • Foam stabilizers such as siloxane-oxalkylene copolymers and other organosiloxanes, ethoxylated alkylphenols, ethoxylated fatty alcohols, paraffin oils, castor oil or ricinoleic acid esters, turkey red oil and peanut oil and cell regulators, such as paraffins, fatty alcohols and dimethylpolysiloxanes.
  • oligomeric polyacrylates having polyoxyalkylene and fluoroalkane radicals as side groups are also suitable.
  • the surface-active substances are usually used in amounts of from 0.01 to 5 parts by weight, based on 100 parts by weight of the relatively high molecular weight polyhydroxyl compounds (b) (without consideration of mixed magnetisable particles).
  • Suitable flame retardants are, for example, tricresyl phosphate, tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate, tris (1, 3-dichloropropyl) phosphate, tris (2,3-dibromopropyl) phosphate and tetrakis. (2-chloroethyl) ethylene diphosphate.
  • Flame retardants such as red phosphorus, alumina hydrate, antimony trioxide, arsenic trioxide, ammonium polyphosphate and calcium sulfate or cyanuric acid derivatives, such as.
  • melamine or mixtures of at least two flame retardants such as.
  • ammonium phosphates and melamine and optionally starch and / or expandable graphite for flameproofing the cellular PU elastomers according to the invention can be used.
  • it has proven expedient to 5 to 50 parts by weight, preferably 5 to 25 parts by weight of said flame retardants or - mixtures for every 100 parts by weight of the structural components (a) to (c), wherein the Weight of possibly mixed magnetisable particles is not taken into account.
  • Suitable antioxidants and heat stabilizers which can be added to the cellular PU elastomers according to the invention are, for example, halides of Group I metals of the periodic system, e.g. For example, sodium, potassium, lithium halides, optionally in combination with copper (l) halides, eg.
  • hydrolysis protectants are various substituted carbodiimides, such as 2,2 ', 6,6'-tetraisopropyldiphenylcarbodiimide, which are generally present in amounts of up to 2.0% by weight, based on the weight of the constituent components (a) to (c). , Wherein the weight of possibly admixed magnetisable particles is not taken into consideration, can be used.
  • Lubricants and mold release agents used in the also in amounts of up to 1% by weight, based on the weight of the constituent components (a) to (c), wherein the weight of possibly admixed magnetizable particles is not taken into account are stearic acid, stearyl alcohol, stearic acid esters and amides and the fatty acid esters of pentaerythritol.
  • organic dyes such as nigrosine, pigments, such as.
  • titanium dioxide, cadmium sulfide, cadmium sulfide selenide, phthalocyanines or ultramarine blue are added.
  • microbial inhibitors and / or organic colorants may be added.
  • athermane materials such as graphite, carbon black or aluminum powder may be added.
  • Preferred embodiments of the polymer blend contain as fillers organic and inorganic powders or fibrous materials, as well as mixtures thereof.
  • organic fillers are wood flour, starch, flax, hemp, ramie, jute, leather, sisal, cotton, cellulose or aramid fibers.
  • Preferred embodiments with inorganic fillers are selected from the following group: silicates,
  • Barite, glass beads, zeolites, metals, metal oxides or pulverulent inorganic substances such as talc, chalk, kaolin (Ab ⁇ Os) (OH) 4 ), aluminum hydroxide, magnesium hydroxide, aluminum nitrite, aluminum silicate, barium sulfate, calcium carbonate, calcium sulfate, silicic acid, quartz powder , Aerosil, alumina, mica or wollastonite and spherical or fibrous inorganic substances such as iron powder, glass beads, glass fibers or carbon fibers.
  • the average particle diameter or, in the case of fibrous fillers, the mean length is in preferred embodiments in the range of the cell size of the expanded granulate or of the molded foam or is smaller.
  • Preferred embodiments contain fillers having an average particle diameter in the range from 0.1 ⁇ m to 100 ⁇ m, more preferably in the range from 1 ⁇ m to 50 ⁇ m.
  • contents of fillers between 5% by weight and 80% by weight are preferred, inorganic and / or organic fillers being used.
  • auxiliaries and additives can be found in the specialist literature, see, for example, Kunststoffhandbuch, Volume VII, edited by Vieweg and Hochtlen, Carl Hanser Verlag, Kunststoff 1966 (S103-1 13).
  • thermoplastic polymer blends are used according to the invention for the preparation of expandable, preferably particulate and more preferably propellant-containing thermoplastic polymer blends, furthermore for the production of expanded thermoplastic polymer blends and for the production of molded foam based on thermoplastic polymer blends.
  • the preparation of these materials from the thermoplastic polymer blends is described below.
  • the expanded thermoplastic polymer blend particles according to the invention can in principle be prepared by suspension or extrusion processes directly or indirectly via expandable particles of polymer blend and foaming in a pressure prefoamer with steam or hot air.
  • the polymer blend is used as granules, more preferably as minigranules having an average diameter of 0.2 mm to 1 cm, in particular from 0.5 mm to 5 mm.
  • the minigranule is cylindrical or round and is prepared by extruding the polymer blend, in a preferred embodiment with at least one filler, auxiliary and / or additive, then extruding from the extruder, optionally cooling, and granulating.
  • the granules are heated with water, a suspension aid and the blowing agent in a closed reactor to above the softening temperature of the granules. In this way, the propellant penetrates into the granules.
  • This process is also referred to as impregnating the polymer particles with blowing agent.
  • the hot suspension is cooled, whereby the particles solidify to include the blowing agent, and then the reactor is expanded.
  • the blowing agent-containing expandable particles obtained in this way expand upon heating, resulting in expanded particles having a foam structure.
  • the hot suspension is suddenly expanded without cooling (explosion expansion process), wherein the softened, blowing agent-containing particles foam directly to the expanded particles. This method is i.a. disclosed in WO 94/20568.
  • the polymer blend is melt-mixed in an extruder with a blowing agent supplied to the extruder under pressure.
  • the polymer blend is used as premixed granules consisting of TPU and styrene polymer, optionally with at least one further thermoplastic polymer.
  • the polymer blend of the present invention is made in-situ in the extruder from TPU and styrene polymer, and in a preferred embodiment with at least one other thermoplastic polymer
  • the polymer blend of the invention is formed from the TPU components (a), (b), (c), (d), (d) and (e) and styrene polymer and, in a preferred embodiment, with at least one further thermoplastic polymer
  • the propellant-containing mixture is either in an environment with such Pressed and temperature conditions pressed and granulated that the granules of the polymer blend does not foam, so does not expand.This can be achieved for example by an underwater granulation, which is operated at a water pressure of more than 2 bar low temperature propellant-containing, expandable particles, which by anschlie gently heating the expanded particles to be foamed.
  • the mixture is squeezed out into an environment without overpressure. This results in a foaming of the expandable polymer blend.
  • this foaming takes place by pressing the blowing agent-containing melt through a corresponding nozzle, so that directly expanded plates of the desired size are formed from the expandable polymer blend.
  • the melt is pressed through a suitable nozzle.
  • the melt strand pressed out of the extruder foams up and solidifies.
  • the expanded particles are obtained by subsequent granulation of the expanded melt strand.
  • the expandable particles of thermoplastic polymer blend according to the invention are preferably prepared by the suspension process or by the extrusion process.
  • the preferred blowing agents vary.
  • the suspension process is preferably used as a propellant organic liquids or inorganic gases or mixtures thereof.
  • the organic liquids are halogenated hydrocarbons, but preferred are saturated aliphatic hydrocarbons, especially those having 3 to 8 carbon atoms.
  • Preferred inorganic gases are nitrogen, air, ammonia or carbon dioxide.
  • blowing agents are hydrocarbons (preferably halogen-free), in particular C4-io-alkanes, for example, the isomers of butane, pentane , Hexanes, heptanes and octanes, particularly preferred is s-pentane.
  • Suitable propellants are also compounds such as alcohols, ketones, esters, ethers and organic carbonates.
  • the organic liquids are halogenated hydrocarbons, but preferred are saturated aliphatic hydrocarbons, especially those having 3 to 8 carbon atoms.
  • Preferred inorganic gases are nitrogen, air, ammonia or carbon dioxide.
  • halocarbons are used as blowing agents, but preferably the blowing agent is halogen-free.
  • the blowing agent amount is 0.1 to 40 parts by weight, in particular 0.5 parts by weight to 35 parts by weight and particularly preferably 1 to 30 parts by weight, based on 100 parts by weight of polymer used -Blend.
  • the suspension process is usually carried out batchwise in an impregnation vessel, e.g. in a stirred tank reactor.
  • the polymer blend are metered in as granules, also water or another suspension medium, and the blowing agent and optionally a suspension aid.
  • the suspension aid used is at least one water-insoluble inorganic stabilizer, such as tricalcium phosphate, magnesium pyrophosphate, metal carbonate; also used polyvinyl alcohol and surfactants such as sodium dodecylarylsulfonate.
  • the stabilizer is used as a single substance or in mixtures, in preferred embodiments in amounts of from 0.01% by weight to 10% by weight, based on the polymer blend.
  • the reactor is closed and the reactor contents are heated to an impregnation temperature, in a preferred embodiment this is from 100 ° C. to 150 ° C.
  • the propellant is added before, during or after the reactor contents have been heated.
  • the impregnation temperature is in the vicinity of the softening temperature of the polymer blend.
  • Preferred impregnation temperatures are between 100 ° C and 200 0 C, in particular between 110 ° C and 145 ° C.
  • a pressure is set, which is in preferred embodiments between 2 bar and 100 bar (absolute).
  • the pressure is regulated by a pressure regulating valve or by repressing propellant.
  • blowing agent diffuses into the polymer granules particles.
  • the impregnation time is preferably between 0.5 hours and 10 hours.
  • the impregnated suspension is cooled to below 100 0 C, whereby the polymer blend solidifies again and includes the blowing agent. After solidification of the polymer blend is relaxed.
  • Adhesive water is removed in a preferred embodiment by drying, for example in a stream dryer.
  • the adhering suspension aid is removed by treating the particles with a suitable reagent.
  • the polymer blend is mixed with an acid such as nitric acid, hydrochloric acid or sulfur. acid to remove acid-soluble suspension aids, such as metal carbonates or tricalcium phosphate.
  • a mixture is prepared from the solid components.
  • first of all TPU and styrene polymer and, if appropriate, filler, auxiliary and / or additive (s), and in a preferred embodiment, at least one further thermoplastic polymer are mixed and the mixture is fed to the extruder, then the blowing agent is fed to the extruder ie the extruder mixes the blowing agent into a polymer melt.
  • a mixture of blowing agent and fillers, auxiliaries and / or additives is fed to the extruder, i. the fillers, auxiliaries, and / or additives are added first with the propellant.
  • extruder In the extruder, the starting materials mentioned are mixed with melting. Suitable extruders are all conventional screw machines, in particular single screw and twin screw extruders (eg type ZSK from Werner & Pfleiderer), co-kneaders, Kombiplast machines, MPC kneading mixers, FCM mixers, KEX kneading screw extruders and Shear roll extruder, as described, for example, in Saechtling (ed.), Kunststoff-Taschenbuch, 27th edition, Hanser-Verlag, Kunststoff 1998, chap. 3.2.1 and 3.2.4 are described.
  • the extruder is preferably operated at a temperature at which the polymer blend is present as a melt, for example at 150 0 C to 250 0 C, particularly at 180 ° C to 210 0 C.
  • the speed, length, diameter and configuration of the extruder screw (s), supplied quantities and extruder throughput are selected by the person skilled in the art such that the fillers, auxiliaries and / or additives are uniformly distributed in the extruded polymer blend.
  • expandable particles are produced.
  • the temperature and pressure conditions are coordinated so that the melt strand practically does not foam up (expands) during extrusion. These conditions depend on the type and amount of the polymers, the fillers, auxiliaries, and / or additives and in particular the blowing agent.
  • the expert routinely determines the optimum conditions by means of appropriate preliminary tests.
  • a technically advantageous embodiment is the underwater granulation in a water bath, which has a temperature below 100 0 C and under a pressure of at least 2 bar (absolute).
  • the temperature range results in practice from two limit parameters. On the one hand, depending on the material properties, the temperature must be set so high that the melt on the nozzle plate does not solidify, and at the same time, it must be chosen so low that the melt does not expand.
  • the propellant s-pentane is the optimum water bath temperature at 30 0 C to 60 0 C and the optimum water pressure at 8 bar to 12 bar (absolute).
  • cooling media are used instead of water.
  • water ring granulation is used. In this case, the cutting space is encapsulated in such a way that the granulating device can be operated under pressure.
  • expandable particles of polymer blend are obtained, which are subsequently separated off from the water and optionally dried. Thereafter, they are foamed to expanded particles of polymer blend as described below.
  • a preferred process for making expandable blowing agent-containing polymer blend particles comprises the following steps:
  • step ii Another preferred process for the preparation of expandable, blowing agent-containing particles of polymer blend comprises the following steps:
  • Propellant and optionally with fillers, auxiliaries and / or additives on an extruder ii) pressing the melt and underwater granulation of the melt strand at
  • Particularly preferred and subject of the present invention is thus also a process for the preparation of expandable, blowing agent-containing polymer blend, wherein a TPU and a styrene polymer, optionally together with at least one filler, auxiliary and / or additive, in a preferred embodiment with additionally at least one thermoplastic polymer, extruded to a granulate having a mean diameter of 0.2 mm to 1 cm, the granules with 0.1 wt .-% to 40 wt.%, Based on the total weight of the granules, a preferred volatile blowing agent in aqueous suspension under pressure, preferably at a pressure between 5 bar and 100 bar, impregnated at temperatures in the range of 100 0 C to 200 0 C, the suspension containing the blowing agent-containing polymer blends to 20 0 C to 95 ° C and then cooling relaxes the propellant-containing polymer blends.
  • a preferred volatile blowing agent in aqueous suspension under pressure preferably at a
  • Also particularly preferred and subject of the present invention is also a process for the preparation of expandable, preferably particulate, blowing agent-containing polymer blend, wherein a TPU and a styrene polymer, together with 0.1 wt .-% to 40 wt .-%, based on the total weight of the granules, a preferred volatile blowing agent and optionally with fillers, auxiliaries and additives, in a preferred embodiment further with at least one thermoplastic polymer, melts on an extruder and the melt under water at pressures of 2 bar to 20 bar and Granulated temperatures between 5 0 C and 95 0 C.
  • expandable particles they can be foamed (foamed) in a manner known per se to give a foam, the expanded particles according to the invention being produced from polymer blend.
  • the foaming is generally carried out by heating the expandable particles in conventional VerDumungsvor- directions, eg with hot air or superheated steam in a so-called. Druckvor- foamer, as is customary for processing of expandable polystyrene (EPS).
  • EPS expandable polystyrene
  • the particles are foamed at a temperature at which they soften (Softening range), more preferably at temperatures between 100 0 C to 140 0 C.
  • the present invention also relates to processes for producing foams based on polymer blend to give the expandable according to the invention, preferably particulate, blowing agent-containing polymer blend at a temperature between 100 0 C and 140 0 C foamed.
  • the present invention further provides foams based on polymer blend which are obtainable in this way.
  • the pressure of the water vapor is usually 0.5 bar to 4 bar, preferably 1, 0 bar to 3.5 bar (absolutely). Higher pressures result in lower densities of the foamed polymer blend, i. with the water vapor pressure you can set the desired density.
  • the duration of the foaming is usually 1 sec to 300 sec, preferably 1 sec to 30 sec. After the foaming is relaxed and cooled.
  • the expansion factor during foaming is 2 to 50. The expansion factor describes the ratio of the volume of the foamed product to the volume of the unfoamed product.
  • the heated suspension consisting of the polymer blend and blowing agent, and optionally fillers, auxiliaries and / or additives, is not cooled, but suddenly released hot without cooling .
  • the blowing agent previously diffused or mixed into the particles of polymer blend expands "explosively" and foams up the softened particles, resulting in expanded particles of polymer blend.
  • the suspension is depressurized through a nozzle, valve or other suitable device.
  • the suspension can be immediately cooled to atmospheric pressure, about 1 bar, for example 1013 mbar.
  • atmospheric pressure about 1 bar, for example 1013 mbar.
  • the pressure is released to a pressure of, for example, 0.5 bar to 5 bar, in particular 1 bar to 3 bar (absolute).
  • the impregnation pressure is kept constant during the expansion in the impregnation container by repressing the propellant.
  • the suspension is cooled after relaxing, the expanded particles of polymer blend separated from the suspension, if necessary before or after adhering suspension auxiliary removed and finally washed and dried the particles.
  • the blowing agent-containing melt of the polymer blend is squeezed and granulated without underwater granulation, water ring granulation, or other precautions that prevent foaming. For example, it is squeezed directly into the atmosphere. In the process, the extruded melt strand foams up and, by granulating the foamed strand, expanded particles of polymer blend are obtained.
  • a preferred process for producing expanded foam particles from polymer blend comprises the steps
  • minigranules having a mean diameter of 0.2 mm to 1 cm, ii) impregnating the minigranules with 0.1% by weight to 40 wt .-%, based on the total weight of the granules, of a volatile blowing agent in aqueous suspension under pressure, preferably at a pressure between 5 bar and 100 bar at temperatures in the range of 100 0 C to 200 0 C and iii) subsequent expansion.
  • Polymer blend includes the steps:
  • a process for the preparation of expanded polymer blend wherein a TPU and a styrene polymer, optionally together with fillers, auxiliaries, and / or additives, in a preferred embodiment with at least one further thermoplastic polymer to a granule extruded with an average diameter of 0.2 mm to 1 cm, the granules with 0.1 wt .-% to 40 wt .-%, based on the total weight of the granules, a preferred volatile blowing agent, more preferably in aqueous suspension under pressure , Preferably at a pressure between 5 bar and 100 bar at temperatures in the range of 100 0 C to 200 0 C impregnated and then relaxed.
  • a particularly preferred process of the present invention is the preparation of expanded polymer blend which comprises a TPU and a styrenic polymer together with from 0.1% to 40% by weight, based on the total weight of the granules, of a preferred volatile blowing agent optionally with at least one filler, auxiliary and / or additive, in a preferred embodiment with at least one further thermoplastic polymer, melts on an extruder and the melt granules without devices that prevent foaming.
  • the present invention further provides expanded polymer blends obtainable by such processes.
  • the particles of polymer blends are provided in preferred embodiments before and / or after foaming with a coating agent.
  • Preferred coating agents are e.g. Talc, metal compounds such as tricalcium phosphate, calcium carbonate, silicic acids, in particular fumed silicas such as Aerosil® from Degussa, salts of long-chain carboxylic acids, for example stearic acid salts such as calcium stearate, esters of long-chain carboxylic acids, e.g. Glycerinester as Glycerinstea- rates, and silicone oils. Long chain carboxylic acids are preferably those having 10 to 22 carbon atoms.
  • the coating compositions are used alone or as a mixture.
  • the coating composition is preferably applied to the polymer blend particles by mixing, spraying, tumbling or other conventional methods.
  • the coating compositions are preferably used in amounts of 0.01 part by weight to 20 parts by weight, more preferably 0.05 part by weight to 10 parts by weight, particularly preferably 0.1 part by weight to 6 weight. Parts, based on 100 parts by weight of the polymer blend used.
  • expanded particles of polymer blend are obtained. They preferably have densities of from 5 g / l to 600 g / l, and more preferably from 10 g / l to 300 g / l.
  • the expanded particles are generally at least approximately spherical and usually have a diameter of 0.1 mm to 20 mm, preferably 0.2 mm to 15 mm and particularly preferably 0.5 mm to 12 mm.
  • non-spherical, e.g. elongated or cylindrical particles, by diameter is meant the longest dimension.
  • the expanded particles preferably have cells of a mean cell size in the range of 10 .mu.m to 500 .mu.m.
  • the present invention furthermore relates to processes for the production of foam on the basis of polymer blend, wherein the expanded polymer blend is welded by means of steam to form a shaped body.
  • the temperature in the welding of the expanded particles of polymer blend is preferably between 100 0 C and 140 0 C.
  • foam is made from the expanded polymer blend particles, for example, by heat sealing them together in a closed mold.
  • the particles are filled into a mold and, upon closure of the mold, introduce steam or hot air, thereby further expanding the particles and welding them together to the foam, preferably at a density in the range of 8 g / l to 600 g / l.
  • the foams are semi-finished products, such as plates, profiles or sheets, or finished moldings of simple or complicated geometry. Accordingly, the term includes foam particles of polymer blend, foam semi-finished and foam moldings with a.
  • the invention furthermore also relates to the use of the expanded polymer blend polymer particles for the production of polymer blend foams, as well as polymer blend foams obtainable from the expanded polymer blend particles.
  • foams according to the invention can be easily recycled thermoplastically.
  • the foamed polymer blends are extruded using an extruder with a degasser, the extrusion in a preferred embodiment preceded by mechanical comminution. Thereafter, they can be re-processed into foams in the manner described above.
  • TPUs of the following composition were used to prepare the polymer blend: Table 1
  • the foam particles prepared according to Example 1 were filled under pressure and compression in a preheated mold. This was mutually heated with steam.

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Abstract

L'invention concerne un mélange de polymères thermoplastique expansible contenant un agent d'expansion, ce mélange contenant du polyuréthanne thermoplastique et un polymère de styrène, et éventuellement au moins un autre polymère thermoplastique. L'invention concerne également des procédés de fabrication de ce mélange de polymères thermoplastique et des procédés de fabrication de mousses à base de mélanges de polymères thermoplastiques, ainsi que les mousses fabriquées par ces procédés.
PCT/EP2009/059014 2008-07-25 2009-07-15 Mélanges de polymères thermoplastiques à base de polyuréthanne thermoplastique et de polymère de styrène, mousses fabriquées à partir de ces mélanges et procédés de fabrication correspondants Ceased WO2010010010A1 (fr)

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WO2022161995A1 (fr) 2021-01-29 2022-08-04 Basf Se Procédé de fabrication d'un materiau composite
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WO2022161994A1 (fr) 2021-01-29 2022-08-04 Basf Se Préparation pour corps moulé
WO2023025638A1 (fr) 2021-08-27 2023-03-02 Basf Se Mélange maître antistatique à base de polyuréthane thermoplastique ayant des propriétés améliorées pour l'utilisation dans des polymères
WO2023111012A1 (fr) 2021-12-15 2023-06-22 Basf Se Mousse moulée à base de pentaméthylène diisocyanate (pdi)
WO2023152056A1 (fr) 2022-02-11 2023-08-17 Basf Se Procédé mis en œuvre par ordinateur pour la commande et/ou le suivi d'au moins un processus de moulage de mousse particulaire
WO2023186805A1 (fr) 2022-03-29 2023-10-05 Basf Se Polyuréthane thermoplastique ignifuge (tpu) à base de poly-propane diol
WO2023198755A1 (fr) 2022-04-14 2023-10-19 Basf Se Ensemble roue pour roues non pneumatiques
WO2024002869A1 (fr) 2022-06-27 2024-01-04 Basf Se Composition de polyuréthane thermoplastique (tpu) présentant des propriétés améliorées
WO2024089016A1 (fr) 2022-10-28 2024-05-02 Basf Se Moulage de mousse particulaire avec différentes couches
WO2024089264A1 (fr) 2022-10-28 2024-05-02 Basf Se Polyuréthane thermoplastique expansé pour procédé de moulage spécial
WO2024115593A1 (fr) 2022-11-30 2024-06-06 Basf Se Structure phono-absorbante
WO2024141587A1 (fr) 2022-12-29 2024-07-04 Basf Se Encapsulation de granules de tpu
WO2024200661A1 (fr) 2023-03-31 2024-10-03 Basf Se Polyuréthane thermoplastique expansé pour processus de moulage spécial
WO2024200488A1 (fr) 2023-03-31 2024-10-03 Basf Se Procédé de préparation de pièces moulées en mousse avec des particules revêtues
WO2024200654A1 (fr) 2023-03-31 2024-10-03 Basf Se Polyuréthane thermoplastique expansé pour processus de moulage spécial
WO2024246322A1 (fr) 2023-06-01 2024-12-05 Basf Se Tpu avec additifs cycliques
WO2025051729A1 (fr) 2023-09-04 2025-03-13 Basf Se Aide au démoulage de polyuréthane thermoplastique (tpu)
WO2025083191A1 (fr) 2023-10-20 2025-04-24 Basf Se Polyuréthane thermoplastique (tpu) présentant de bonnes propriétés mécaniques et une bonne stabilité dimensionnelle thermique
WO2025114458A1 (fr) 2023-11-29 2025-06-05 Basf Se Procédé de réalisation d'une semelle intermédiaire en e-tpu/semelle en tpu en une seule étape de moulage
WO2025114423A1 (fr) 2023-11-29 2025-06-05 Basf Se Procédé de préparation de particules de mousse comportant un revêtement de surface pigmenté
WO2025125440A1 (fr) 2023-12-15 2025-06-19 Basf Se Procédés de préparation de pièces moulées en particules de mousse revêtues

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