WO2025002949A1 - Particules enrobées stables au stockage et leur préparation - Google Patents

Particules enrobées stables au stockage et leur préparation Download PDF

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Publication number
WO2025002949A1
WO2025002949A1 PCT/EP2024/067124 EP2024067124W WO2025002949A1 WO 2025002949 A1 WO2025002949 A1 WO 2025002949A1 EP 2024067124 W EP2024067124 W EP 2024067124W WO 2025002949 A1 WO2025002949 A1 WO 2025002949A1
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WIPO (PCT)
Prior art keywords
particles
dispersion
polyurethane
coated
beads
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.)
Ceased
Application number
PCT/EP2024/067124
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English (en)
Inventor
Ulrike Licht
Anna Maria CRISTADORO
Elmar Poeselt
Jens Peter Dierssen
Volker VOGELSANG
Martin Vallo
Lionel Gehringer
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BASF SE
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BASF SE
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Priority to CN202480043403.6A priority Critical patent/CN121443663A/zh
Publication of WO2025002949A1 publication Critical patent/WO2025002949A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/3461—Making or treating expandable particles
    • 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
    • C08G18/08—Processes
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
    • C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
    • 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
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    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
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    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • 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
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    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4216—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from mixtures or combinations of aromatic dicarboxylic acids and aliphatic 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
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    • 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
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4808—Mixtures of two or more polyetherdiols
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
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    • 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
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    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
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    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl 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
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/224—Surface treatment
    • 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
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/228—Forming foamed products
    • C08J9/232—Forming foamed products by sintering expandable particles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
    • 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
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    • 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
    • C08J2475/04—Polyurethanes

Definitions

  • the present invention relates to a process for the preparation of storage-stable coated particles of a moldable thermoplastic particle foam comprising the steps of ai) bringing the particles into contact with an aqueous polyurethane dispersion, the polyurethane having at least a first glass transition T gi and a second glass transition temperature T g 2, wherein T gi is below 0°C and T g 2 is higher than 25 °C, resulting in at least partly coated particles; and a 2 ) drying the coated particles.
  • the invention further relates to a process for the preparation of a shaped body, storagestable, at least partly coated particles and shaped bodies thereof.
  • thermoplastic particle foams including thermoplastic elastomer particle foams are used, for example, for the production of any solid foam bodies, for example for exercise mats, body protectors, lining elements in automobile construction, sound and vibration dampers, packaging or shoe soles.
  • Moldable thermoplastic particle foams are known in the art and described, e.g., in Robin Britton (Author), Update on Moldable Particle Foam Technology, Rapra technology Ltd, 2009. Expanded thermoplastic elastomers, especially expanded thermoplastic polyesters (E-TPC), expanded thermoplastic copolyamides (E-TPA), expanded thermoplastic polyurethanes (E-TPU), represent specific moldable thermoplastic particle foams.
  • Expanded thermoplastic elastomers especially expanded thermoplastic polyesters (E-TPC), expanded thermoplastic copolyamides (E-TPA), expanded thermoplastic polyurethanes (E-TPU), represent specific moldable thermoplastic particle foams.
  • Expanded thermoplastic elastomers are known in the art.
  • WO 2018/082984 A1 describes particle foams based on expanded thermoplastic elastomers.
  • WO 2008/087078 A1 describes hybrid systems consisting of foamed thermoplastic elastomers and polyurethanes.
  • thermoplastic polymer is expanded thermoplastic polyurethane (E-TPU), which is commercially available, e.g. marketed by BASF under the name Infinergy®.
  • E-TPU particles represent mainly to fully closed-cell particle foam.
  • Thermoplastic polyurethane e.g. Elastollan®
  • E-TPU grades also absorbs only low amounts of water.
  • TPU on which it is based it can also be characterized by high breaking elongation, tensile strength and abrasion resistance, combined with good chemical resistance.
  • E-TPS different mixtures of E-TPS, E-PS, E-PP, E-TPA, E-TPC, E-TPO and the like.
  • the application of a coating allows as well the adjustment of the mechanical performance and applicability by incorporation of additivities, like for example pigments or dyes, flame retardants or antistatic agents, directly to the particle surface. Filling agents for example allow the increase of the stiffness of the final part, while the use of additives which are for example excitable by an electro-magnetic field allow the moldability of the coating and thereby reducing the required energy for molding.
  • additives can be used pigments, dyes, odor, filling agents, bio-based and/or biodegradable additives, UV-, heat-stabilizer, flame retardants such as expandable graphite, additives which generate antistatic properties, electrical conductivity, additives, which reduce dirt-uptake, antislip additives, antimicrobial additives, wax, crosslinking agents, surface functionalized fillers, foamable additives such as Expancell, additives which can be irradiated by an electromagnetical field, and/or radiofrequency, and/or microwave.
  • flame retardants such as expandable graphite
  • additives which generate antistatic properties, electrical conductivity, additives, which reduce dirt-uptake, antislip additives, antimicrobial additives, wax, crosslinking agents, surface functionalized fillers, foamable additives such as Expancell, additives which can be irradiated by an electromagnetical field, and/or radiofrequency, and/or microwave.
  • WO2022/223438 A1 describes different water-based binders for coating particles that can be brought into the shape of said 3D parts.
  • US 6 616 797 B1 describes the formation of adhesive bonds by a process that includes applying a dispersion containing a polyurethane which has structural units of formula (I) to a surface.
  • the dispersion is first coated onto the surface to form a coating.
  • the coating is dried to give an essentially anhydrous coating.
  • the dried coating is then subjected to heat activation.
  • the adhesive bond is formed by joining the heat-activated coating to itself or to another surface.
  • particle coating is not described.
  • WO 2012/13506 A1 describes the use of an aqueous polyurethane dispersion adhesive for producing biologically disintegratable composite films with at least two substrates being bonded to one another using the polyurethane dispersion adhesive, with at least one of the substrates being a biologically disintegratable polymer film.
  • At least 60% by weight of the polyurethane is made up of diisocyanates, polyester diols and at least one bifunctional carboxylic acid selected from dihydroxycarboxylic acids and diaminocarboxylic acids.
  • WO 2005/003247 A1 relates to a method for bonding substrates with different surface energies.
  • the adhesive used for bonding consists of at least 15% by weight of a polyurethane (water or other organic solvents with a boiling point below 150°C at 1 bar not counted), the adhesive is applied to the substrate with the lower surface energy and the resulting adhesive-coated substrate is bonded to the substrate with the higher surface energy.
  • a polyurethane water or other organic solvents with a boiling point below 150°C at 1 bar not counted
  • WO2021/7249749 describes the recycling of bonded articles, including TPU - foam substrates, by using aqueous polyurethane dispersions of specified molecular weights as adhesives. It is not mentioned, that the foamed particles are coated.
  • WO 2024/083787 A1 describes a process for the preparation of storage-stable coated particles of a moldable thermoplastic particle foam, wherein the particles are at least partly coated with an aqueous polyurethane dispersion, the polyurethane having a K-value according to DIN EN ISO 1628-1 2021 in the range from higher than 50 to lower than 100, preferably from 55 to 95.
  • US 10 669 447 B2 describes a method for producing a coating on a substrate by curing a two- component coating composition resulting in a crosslinked coating, which is no longer thermoplastic.
  • an object of the present invention is to provide a process for the preparation of storagestable coated particles.
  • the object is achieved by a process for the preparation of storage-stable coated particles of a moldable thermoplastic particle foam comprising the steps of ai) bringing the particles into contact with an aqueous polyurethane dispersion, the polyurethane having at least a first glass transition temperature T gi and a second glass transition temperature T g 2, wherein T gi is below 0°C and T g 2 is higher than 25 °C, resulting in at least partly coated particles; a 2 ) drying the coated particles.
  • Another aspect of the present invention is a process for the preparation of a shaped body comprising the steps of bi) coating of particles of an expanded thermoplastic elastomer according to the process for the preparation of storage-stable coated particles according to the present invention; b2) shaping the particles obtained from step bi).
  • Another aspect of the present invention is a storage-stable, at least partly coated particle of a moldable thermoplastic particle foam, wherein the coating is a dried aqueous polyurethane dispersion and wherein the polyurethane has at least a first glass transition T gi and a second glass transition temperature T g 2, wherein T gi is below 0°C and T g 2 is higher than 25 °C, preferably obtainable by a process for the preparation of storage-stable coated particles according to the present invention.
  • Another aspect of the present invention is a shaped body comprising storage-stable, at least partly coated particles according to the present invention, preferably obtainable by a process for the preparation of a shaped body according to the present invention.
  • preferred dispersions used for the process of the present invention can have high solid content (>35%), but still show low viscosity. This allows an easy application of the dispersions to the particles.
  • the particles are homogenously coated with a transparent coating, which is tack free at room temperature.
  • the coating melts and allows bridging of beads upon cooling. Only moderate heat is required.
  • the coated particles show surprisingly an improved flow behavior, which is a very important factor when particles are stored for long time, e.g. in octabins, as a clogging of the particles during storage causes unpleasant problems at the customer site, additional to very interesting antistatic properties.
  • a coating on the surface of the particles has moreover additional advantages: Particles of different sizes and chemistry (e.g. E-TPU, E-TPS, E-PS, E-TPO, E-PP, E- PE, E-TPA, E-TPC) can be bond together as the adhesive capability comes from the coating and not from the melting of the wall of the particles.
  • Particles of different sizes and chemistry e.g. E-TPU, E-TPS, E-PS, E-TPO, E-PP, E- PE, E-TPA, E-TPC
  • This has the advantage that also particles with high melting point can be worked at a temperature of, e.g. 100 °C into a 3 D part in a steam-less process.
  • a hot-press can be used with the advantage that steam can be avoided, and low temperature of mold can be used. This results in energy saving and a complexity reduction.
  • Additives can be mixed with the coating and places directly to the beads surface.
  • interesting additives are heat conductive particles, antistatic particle, flame retardants, dyes, UV stabilizers, ferromagnetic particles, anticaking agents, etc.
  • Particles coated with the polyurethane dispersions described herein in a 3 D part (shaped body) can be disassembled, when water-re-dispersible dispersions are used, e.g. by exposing the 3 D part to alkaline conditions under stirring.
  • another material e.g. textile, leader, thermoplastic film, metallic parts, in mold coating
  • another material e.g. textile, leader, thermoplastic film, metallic parts, in mold coating
  • the coated particles can still be worked with a standard steam chest mold process or other heating processes using high energy radiation to increase temperature of the coating as described in EP 3 338 984 B1 for expanded beads, so they are compatible with already existing customer equipment.
  • the process allows realization of 3 D parts of very complex geometries.
  • the 3 D parts can still have empty spaces among the particles (allowing water penetration) or can have no empty spaces among the beads, which is high desirable for the fabrication of shoe soles.
  • the process of the present invention refers to the preparation of coated particles of a moldable thermoplastic particle foam.
  • foams are known in the art (see e.g. Robin Britton (Author), Update on Mouldable Particle Foam Technology, Rapra technology Ltd, 2009).
  • the moldable thermoplastic particle foam is an expanded thermoplastic elastomer.
  • thermoplastic elastomers are, for example, thermoplastic polyurethanes (TPU), thermoplastic polyester elastomers (e.g. polyetherester and polyesterester) (TPC), thermoplastic copolyamides (e.g. Polyether copolyamides) (TPA), thermoplastic polyolefins (TPO) or thermoplastic styrene butadiene block copolymers (TPS).
  • TPU thermoplastic polyurethane
  • TPC thermoplastic polyester elastomers
  • TPA thermoplastic copolyamides
  • TPO thermoplastic polyolefins
  • TPS thermoplastic styrene butadiene block copolymers
  • Foam particles based on thermoplastic polyurethane (TPU) are particularly preferred.
  • the expanded thermoplastic elastomer is E-TPA, E-TPC or E- TPU, especially E-TPU.
  • the particles comprise at least two particles based on different polymers or different particle size.
  • Two or more foam particles in the sense of the present invention refers to a mixture of different lots of loose foam particles, wherein the lots differ in their chemical nature and/or size.
  • thermoplastic foam particles are mixed. More preferably, the foam particles comprise at least two thermoplastic foam particles selected from the group consisting of styrene polymer foam particles, polyamide foam particles, thermoplastic elastomer foam particles, polyolefin foam particles and mixtures thereof.
  • all kind of particles can be used, such as for example shredded foam parts or polymeric foam waste material based on thermosetting, thermoplastic, or elastomeric polymers.
  • additional material can be fused together with the foam particles into a hybrid particle foam molded part.
  • inliners are selected from the group consisting of synthetic or natural textiles, chopped textiles, leather, paper, thermoplastic films, thermoplastic tapes, organo-sheets, in mold coating, pieces of fiber composites, rubber sheets, rubber crumbs, pieces of wood, thermosetting films, plastic agglomerates, chopped foamed materials, and mixtures thereof. Additional materials can be of virgin or of recycled nature.
  • the inliners can be fused together with the foam particles in one step or in a separate processing step.
  • the aqueous polymer dispersion used in the process of the present invention has a solid content of at least 30 wt.-% based on the total weight of the dispersion, more preferably in the range of from 35 wt.-% to 60 wt.-% based on the total weight of the dispersion.
  • the polyurethane of the aqueous polymer dispersion and comprised in the at least partly coated particle and shaped body according to the present invention has a viscosity of less than 300 mPas at 23 °C, preferably less than 200 mPas at 23 °C, measured according to DIN EN ISO 3219-2:2021 at 23°C and a shear rate of 250 S’ 1 .
  • the polyurethane of the aqueous polyurethane dispersion and comprised in the at least partly coated particle and shaped body according to the present invention has at least a first glass transition temperature T gi and a second glass transition temperature T g 2, wherein T gi is below 0°C and T g 2 is higher than 25 °C.
  • T gi is below -10 °C.
  • T g 2 is higher than 40 °C, more preferably higher than 50 °C, even more preferably higher than 60 °C.
  • the polyurethane of the aqueous polyurethane dispersion has a T gi from -10 °C to -60 °C and a T g 2 from 60 °C to 90 °C.
  • the polyurethane has exactly two T g .
  • the glass transition temperature can be determined by differential scanning calorimetry according to DIN EN ISO 11357-2 (2014), as so-called midpoint temperature.
  • the glass transition temperature of the polymer in the polymer dispersion is the glass transition temperature obtained when evaluating the second heating curve (heating rate 20°C/min).
  • aqueous polyurethane dispersion used in the process of the present invention can be prepared by methods known in the art. Exemplary methods are described in WO 2021/249749 A1
  • an aqueous polyurethane dispersion comprises at least one polyurethane as polymeric binder dispersed in water, and optionally additives.
  • Preferred additives are selected from the group consisting of ionic surfactants, non-ionic surfactants, rheology modifiers (including thickeners), anti-blocking additives, other aqueous dispersions, cross-linkers, plasticizers, stabilizers against hydrolytic degradation, biocides, fillers and antifoam agents.
  • the polymeric binder preferably takes the form of dispersion in water or else in a mixture made of predominantly water and of water-soluble organic solvents with boiling points, which are preferably below 150°C (1 bar). Particular preference is given to water as sole solvent.
  • the aqueous polyurethane dispersion comprises at least one additive selected from the group consisting of pigments, dyes, odor, filling agents, biobased and/or biodegradable additives, UV-, heat-stabilizer, flame retardants such as expandable graphite, additives which generate antistatic properties, electrical conductivity, additives, which reduce dirt-uptake, anti-slip additives, antimicrobial additives, wax, crosslinking agents, surface functionalized fillers, foamable additives such as Expancell, additives which can be irradiated by an electromagnetical field, and/or radiofrequency, and/or microwave, ionic surfactants, nonionic surfactants, rheology modifiers, fillers, anti-blocking additives, other aqueous dispersions, crosslinkers, plasticizers, stabilizers against hydrolytic degradation, antifoam agents and biocides.
  • additives selected from the group consisting of pigments, dyes, odor, filling agents, biobased and/or biodegradable additive
  • Preferred other dispersions are those described in WO 2022/223438 A1 .
  • the polyurethane dispersion used in the process of the invention and comprised in the at least partly coated particle and shaped body according to the present invention in dried form comprises at least one polyurethane.
  • Suitable polyurethanes are obtainable in principle through reaction of at least one polyisocyanate with at least one compound, which has at least two groups reactive toward isocyanate groups with the specific requirements mentioned below in order to obtain a polyurethane with at least two T g as mentioned above.
  • the polyurethane of the aqueous polyurethane dispersion can be prepared from a) at least one organic diisocyanate, selected from diisocyanates of the formula X(NCO)2, where X is a noncyclic aliphatic hydrocarbon radical having 4 to 15 carbon atoms, a cy- cloaliphatic hydrocarbon radical having 6 to 15 carbon atoms, an aromatic hydrocarbon radical having 6 to 15 carbon atoms, or an araliphatic hydrocarbon radical having 7 to 15 carbon atoms, wherein the amount of aromatic diisocyanates is less than 60 mol-%, based on the sum of all organic diisocyanates a); b1 ) at least one dihydroxy compound having a molecular weight of 500 g/mol to 5000 g/mol and selected from the group consisting of polyesterdiols, polyetherols and polytetrahydrofuran; b2) at least one dihydroxy compound selected from the group consisting of branched or unbranched
  • the polyurethane dispersion, the at least partly coated particle and shaped body according to the present invention preferably comprises at least one polyurethane which comprises in copolymerized form at least one polyisocyanate and at least two polyols as mentioned above.
  • the polyurethane dispersion and the at least partly coated particle and shaped body according to the present invention preferably comprise at least one polyurethane which comprises in copolymerized form the at least one polyisocyanate and diol components, of which a) 10 -90 mol%, based on the total amount of the diols b1) and b) 90- 10 mol%, based on the total amount of the diols b2).
  • the polymeric polyol preferably has a number-average molecular weight in the range from about 500 to 5000 g/mol.
  • the polyurethane is preferably synthesized to an extent of at least 35% by weight, more preferably at least 60% by weight, and very preferably at least 80% by weight, based on the total weight of the monomers used in preparing the polyurethane, of at least one diisocyanate and at the least two diols.
  • Suitable further synthesis components to 100% by weight are, for example, the below-specified polyisocyanates having at least three NCO groups, and compounds that are different from the polymeric polyols and have at least two groups reactive toward isocyanate groups.
  • non-polymeric diols include, for example, non-polymeric diols; diamines; polymers different from polymeric polyols and having at least two active hydrogen atoms per molecule; compounds which have two active hydrogen atoms and at least one ionogenic or ionic group per molecule; and mixtures thereof.
  • Preferred polyurethanes are synthesized from: a) at least one monomeric diisocyanate, b) the at least diols b1) and b2), c) at least one monomer, different from the monomers (a) and (b), having at least one isocyanate group or at least one group reactive toward isocyanate groups, and additionally carrying at least one hydrophilic group or potentially hydrophilic group, d) optionally at least one further compound, different from the monomers (a) to (c), having at least two reactive groups selected from alcoholic hydroxyl groups, primary or secondary amino groups or isocyanate groups, and e) optionally at least one monofunctional compound, different from the monomers (a) to (d), having a reactive group which is an alcoholic hydroxyl group, a primary or secondary amino group or an isocyanate group.
  • the polyurethane dispersion is an anionic polyurethane dispersion made with low amount of aromatic diisocyanates or no aromatic diisocyanates, e.g. less than 60 mol%, based on the sum of all organic diisocyanates a).
  • the anionic groups of the anionic polyurethane are preferably selected from carboxylate groups and sulfonate groups. The same applies to the polyurethane comprised in the at least partly coated particle and shaped body according to the present invention.
  • Component b) is composed preferably of b1 ) 10 to 90 mol%, based on the total amount of component b), of diols b1 ), b2) 10 to 90 mol%, based on the total amount of component b), of diols b2).
  • the molar ratio of the diols b1) to the monomers b2) is more preferably 1 :5 to 5:1 , more preferably 1 : 2 to 2 : 1.
  • X is a noncyclic aliphatic hydrocarbon radical having 4 to 15 carbon atoms, a cycloaliphatic or aromatic hydrocarbon radical having 6 to 15 carbon atoms, or an araliphatic hydrocarbon radical having 7 to 15 carbon atoms.
  • diisocyanates examples include tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1 ,4-diiso- cyanatocy- clohexane, 1-isocyanato-3,5,5-trimethyl-3-isocyanatomethyl-cyclohexane (I PDI), 2,2- bis(4- isocyanatocyclohexyl)-propane, trimethylhexane diisocyanate, 1 ,4-diisocyanatobenzene, 2,4- diisocyanatotoluene, 2,6-diisocyanatotoluene (TDI), 4,4’-diisocyanato-diphenylmethane, 2,4’- diisocyanatodiphenylmethane, p-xylylene diisocyanate, tetramethylxylylene diisocyanate (TM
  • Diisocyanates of this kind are available commercially.
  • the diisocyanate is selected from the group consisting of hexamethylene diisocyanate, 1-isocyanato-3,5,5-trimethyl-3-isocyanato- methylcyclohexane, 2,6-diisocyanatotoluene, and tetramethylxylylene diisocyanate, or a mixture thereof.
  • Particularly important mixtures of these isocyanates are the mixtures of the respective structural isomers of diisocyanatotoluene and diisocyanatodiphenylmethane; the mixture of 80 mol% 2,4-diisocyanatotoluene and 20 mol% 2,6-diisocyanatotoluene is particularly suitable.
  • aromatic isocyanates such as 2,4- diisocyanatotoluene and/or 2,6-diisocyanatotoluene
  • aliphatic or cycloaliphatic isocyanates such as hexa- methylene diisocyanate or IPDI
  • the preferred molar mixing ratio of the aliphatic to the aromatic isocyanates is 1 :9 to 9:1 , more particularly 4:1 to 1 :4. It is also preferred that only aliphatic isocyanates are used.
  • the diols (b1) may be polyester polyols, which are known, for example, from Ullmanns En- zyklopadie der ischen Chemie, 4th edition, volume 19, pp. 62 to 65. It is preferred to use polyester polyols which are obtained by reacting dihydric alcohols with dibasic carboxylic acids. Instead of the free polycarboxylic acids it is also possible to use the corresponding polycarboxylic anhydrides or corresponding polycarboxylic esters of lower alcohols or mixtures thereof to prepare the polyester polyols.
  • the polycarboxylic acids can be aliphatic, cyclo aliphatic, arali- phatic, aromatic or heterocyclic and can optionally be substituted, by halogen atoms for example, and/or unsaturated. Examples thereof include the following: suberic acid, azelaic acid, phthalic acid, isophthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylene tetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, and dimeric fatty acids.
  • Preferred dicarboxylic acids are those of the general formula HOOC-(CH2) y -COOH, where y is a number from 1 to 20, preferably an even number from 2 to 20, examples being succinic acid, adipic acid, sebacic acid, and dodecane dicarboxylic acid.
  • dihydric alcohols examples include ethylene glycol, propane-1 ,2- diol, propane-1 , 3-diol, butane-1 , 3-diol, butene-1 , 4- diol, butyne-1 ,4-diol, pentane-1 , 5-diol, neopentyl glycol, bis(hydroxymethyl) cyclohexanes such as 1 ,4-bis(hydroxymethyl)cyclohexane, 2-methylpropane-1 , 3-diol, methylpentanediols, and also diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, and dibutylene glycol and polybutylene glycols.
  • preferred alcohols are those of the general formula HO-(CH2)x-OH, where x is a number from 1 to 20, preferably an even number from 2 to 20.
  • examples of such alcohols are ethylene glycol, butane-1 , 4-diol, hexane-1 , 6-diol, octane-1 , 8-diol, and dodecane-1 ,12-diol.
  • the diols (b1) may also be polytetrahydrofuran.
  • Suitable polytetrahydrofurans can be prepared by cationic polymerization of tetra hydrofuran in the presence of acidic catalysts, such as sulfuric acid or fluorosulfuric acid, for example. Preparation processes of this kind are known to the skilled person.
  • the diols (b1) may also be polyether diols.
  • Polyether diols are obtainable in particular by polymerizing ethylene oxide, propylene oxide, butylene oxide, tetra hydrofuran, styrene oxide or epichlorohydrin with itself, in the presence of BF3 for example, or by subjecting these compounds, optionally in a mixture or in succession, to addition reaction with starter components containing reactive hydrogen atoms, such as alcohols or amines, examples being water, ethylene glycol, propane-1 , 2-diol, propane-1 , 3-diol, 2,2-bis(4-hydroxyphenyl)propane, and aniline. Particular preference is given to polyether diols with a molecular weight of 500 to 5000, and in particular 600 to 4500.
  • Compounds subsumed under b1) include only those polyether diols composed to an extent of less than 20% by weight of ethylene oxide, based on their total weight. Polyether diols with at least 20% by weight of incorporated ethylene oxide units are hydrophilic polyether diols, which are counted as monomers c).
  • the hardness and the elasticity modulus of the polyurethanes can be increased by using as diols (b) not only the diols (b1) but also low molecular weight diols (b2) having a molecular weight of from about 60 to less than 500, preferably from 62 to 200 g/mol.
  • Monomers (b2) are at least one dihydroxy compound selected from the group consisting of branched or unbranched acyclic diols having 2 to 8 C atoms, preferably 2 to 6 carbon atoms, or cyclic diols having 3 to 8 C atoms, preferably 3 to 6 carbon atoms.
  • Suitable diols b2) include ethylene glycol, propane-1 , 2-diol, propane-1 , 3-diol, butane-1 , 3-diol, butane-1 ,4-diol, butene- 1 , 4-diol, butyne-1 ,4-diol, pentane-1 , 5-diol, neopentyl glycol, hexane-1 , 6-diol, 2- methylpropane- 1 , 3-diol, methyl pentane diols, octane-1 , 8-diol, bis- (hydroxyme- thyl)cyclohexanes such as 1 ,4-bis(hydroxymethyl)cyclohexane, additionally diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, dibutylene glycol. Preference is given to acyclic dihydroxy compounds (b2).
  • the polyurethanes In order to make the polyurethanes dispersible in water they comprise as synthesis components monomers (c), which carry at least one isocyanate group or at least one group reactive toward isocyanate groups and, furthermore, at least one hydrophilic group or a group which can be converted into a hydrophilic group.
  • monomers (c) which carry at least one isocyanate group or at least one group reactive toward isocyanate groups and, furthermore, at least one hydrophilic group or a group which can be converted into a hydrophilic group.
  • hydrophilic groups or potentially hydrophilic groups is abbreviated to “(potentially) hydrophilic groups”. The (potentially) hydrophilic groups react with isocyanates at a substantially slower rate than do the functional groups of the monomers used to synthesize the polymer main chain.
  • the fraction of the components having (potentially) hydrophilic groups among the total quantity of components (a) to (e) is generally such that the molar amount of the (potentially) hydrophilic groups, based on the amount by weight of all monomers (a) to (e), is from 30 to 1000, preferably 50 to 500, and more preferably 80 to 300 mmol/kg.
  • the (potentially) hydrophilic groups can be nonionic or, preferably, (potentially) ionic hydrophilic groups.
  • nonionic hydrophilic groups are polyethylene glycol ethers composed of preferably 5 to 100, more preferably 10 to 80 repeating ethylene oxide units.
  • the amount of polyethylene oxide units is generally 0 to 10%, preferably 0 to 6% by weight, based on the amount by weight of all monomers (a) to (e).
  • Preferred monomers containing nonionic hydrophilic groups are polyethylene oxide diols containing at least 20% by weight of ethylene oxide, polyethylene oxide monools, and the reaction products of a polyethylene glycol and a diisocyanate which carry a terminally etherified polyethylene glycol radical. Diisocyanates of this kind and processes for preparing them are specified in patents US-A 3,905,929 and US-A 3,920,598.
  • Ionic hydrophilic groups are, in particular, anionic groups such as the sulfonate, the carboxylate, and the phosphate groups in the form of their alkali metal salts or ammonium salts, and also cationic groups such as ammonium groups, especially protonated tertiary amino groups or quaternary ammonium groups.
  • Potentially ionic hydrophilic groups are, in particular, those which can be converted into the abovementioned ionic hydrophilic groups by simple neutralization, hydrolysis or quaternization reactions, in other words, for example, carboxylic acid groups or tertiary amino groups.
  • Acid groups of the polyurethane are neutralized preferably to an extent of at least 10 mol%, more preferably at least 40 mol%, more preferably at least 70 mol%, very preferably at least 90 mol%, and more particularly completely (100 mol%) with a suitable neutralizing agent, and are therefore present in salt form, with the acid group being the anion and with the neutralizing agent being present as cation.
  • Neutralizing agents are, for example, ammonia, alkali metal hydroxides such as NaOH or KOH, or alkanol- amines.
  • cationic monomers (c) are, in particular, monomers containing tertiary amino groups, examples being tris(hydroxyalkyl)amines, N,N’- bis(hydroxyalkyl)alkylamines, N-hydroxyalkyldialkylamines, tris(aminoalkyl)amines, N,N’- bis(aminoalkyl)alkylamines, and N-aminoalkyldialkylamines, the alkyl radicals and alkanediyl units of these tertiary amines consisting independently of one another of 1 to 6 carbon atoms.
  • polyethers containing tertiary nitrogen atoms and preferably two terminal hydroxyl groups such as are obtainable in a conventional manner, for example, by alkoxylating amines containing two hydrogen atoms attached to amine nitrogen, such as methylamine, aniline or N,N ’-dimethylhydrazine.
  • Polyethers of this kind generally have a molar weight of between 500 and 6000 g/mol.
  • tertiary amines are converted into the ammonium salts either with acids, preferably strong mineral acids such as phosphoric acid, sulfuric acid, hydrohalic acids, or strong organic acids, or by reaction with suitable quaternizing agents such as Ci to C6 alkyl halides or benzyl halides, e.g., bromides or chlorides.
  • acids preferably strong mineral acids such as phosphoric acid, sulfuric acid, hydrohalic acids, or strong organic acids
  • suitable quaternizing agents such as Ci to C6 alkyl halides or benzyl halides, e.g., bromides or chlorides.
  • Suitable monomers having (potentially) anionic groups normally include aliphatic, cycloaliphatic, araliphatic or aromatic carboxylic acids and sulfonic acids which carry at least one alcoholic hydroxyl group or at least one primary or secondary amino group.
  • dihydroxyalkylcarboxylic acids especially those having 3 to 10 C atoms, such as are also described in US-A 3,412,054.
  • Particular preference is given to compounds of the general formula (ci) in which R 1 and R 2 are a Ci to C4 alkanediyl (unit) and R 3 is a Ci to C4 alkyl (unit), and especially to dimethylolpropionic acid (DM PA).
  • dihydroxysulfonic acids and dihydroxyphosphonic acids such as 2,3-dihydroxypropanephosphonic acid.
  • dihydroxyl compounds having a molecular weight of more than 500 to 10000 g/mol and at least 2 carboxylate groups, which are known from DE-A 39 11 827. They are obtainable by reacting dihydroxyl compounds with tetracarboxylic dianhydrides such as pyromellitic dianhydride or cyclopentanetetracarboxylic dianhydride in a molar ratio of 2 : 1 to 1 .05 : 1 in a polyaddition reaction.
  • Particularly suitable dihydroxyl compounds are the monomers (b2) cited as chain extenders and also the diols (b1 ).
  • Suitable monomers (c) containing amino groups reactive toward isocyanates include aminocarboxylic acids such as lysine, b-alanine or the adducts of aliphatic diprimary diamines with alpha, beta-unsaturated carboxylic or sulfonic acids that are specified in DE-A 20 34479.
  • aminocarboxylic acids such as lysine, b-alanine or the adducts of aliphatic diprimary diamines with alpha, beta-unsaturated carboxylic or sulfonic acids that are specified in DE-A 20 34479.
  • Such compounds obey, for example, the formula (C2)
  • R 4 and R 5 independently of one another are a Ci to Ce alkanediyl unit, preferably ethylene and X is COOH or SO3 H.
  • Particularly preferred compounds of the formula (c 2 ) are N-(2- aminoethyl)-2-aminoethanecarboxylic acid and also N-(2-aminoethyl)-2-aminoethane- sulfonic acid and the corresponding alkali metal salts, with Na being a particularly preferred counterion.
  • adducts of the abovementioned aliphatic diprimary diamines with 2-acrylamido-2-methylpropanesulfonic acid are also particularly preferred.
  • monomers with potentially ionic groups are used, their conversion into the ionic form may take place before, during or, preferably, after the isocyanate polyaddition, since the ionic monomers do not frequently dissolve well in the reaction mixture.
  • neutralizing agents include ammonia, NaOH, triethanolamine (TEA), triisopropylamine (TIPA) or morpholine, or its derivatives.
  • the sulfonate or carboxylate groups are more preferably in the form of their salts with an alkali metal ion or ammonium ion as counterion.
  • the monomers (d), which are different from the monomers (a) to (c) and which may also be constituents of the polyurethane, may serve for crosslinking or chain extension. They may comprise nonphenolic alcohols with a functionality of more than 2, amines having 2 or more primary and/or secondary amino groups, and compounds which as well as one or more alcoholic hydroxyl groups carry one or more primary and/or secondary amino groups. Alcohols having a functionality of more than 2, which may be used in order to set a certain degree of branching or crosslinking, include for example trimethylolpropane, glycerol, or sugars.
  • suitable compounds (d) are alpha, omega-diaminopolyethers, which are preparable by aminating polyalkylene oxides with ammonia.
  • Compounds (d) are, for example, also isocyanates, which as well as free isocyanate groups carry further, masked isocyanate groups, e.g., uretdione groups or carbodiimide groups.
  • monoalcohols which as well as the hydroxyl group carry a further isocyanatereactive group, such as monoalcohols having one or more primary and/or secondary amino groups, monoethanolamine for example.
  • Polyamines having 2 or more primary and/or secondary amino groups are used especially when the chain extension and/or crosslinking is to take place in the presence of water, since amines generally react more quickly than alcohols or water with isocyanates. This is frequently necessary when the desire is for aqueous dispersions of crosslinked polyurethanes or polyurethanes having a high molar weight. In such cases the approach taken is to prepare prepolymers with isocyanate groups, to disperse them rapidly in water, and then to subject them to chain extension or crosslinking by adding compounds having two or more isocyanate-reactive amino groups.
  • Amines suitable for this purpose are generally polyfunctional amines of the molar weight range from 32 to 500 g/mol, preferably from 60 to 300 g/mol, which comprise at least two amino groups selected from the group consisting of primary and secondary amino groups.
  • examples of such amines are diamines such as diaminoethane, diaminopropanes, diaminobutanes, diaminohexanes, piperazine, 2,5-dimethylpiperazine, amino-3-aminomethyl-3, 5, 5-trimethyl- cyclohexane (isophoronediamine, IPDA), 4,4’-diaminodicyclohexylmethane, 1 ,4-diaminocyclo- hexane, aminoethyl ethanolamine, hydrazine, hydrazine hydrate or triamines such as diethylenetriamine or 1 ,8-diamino-4-a ino ethyloctane.
  • the amines can also be used in blocked form, e.g., in the form of the corresponding ketimines (see for example CA-A 1 129 128), ketazines (cf. , e.g., US-A 4,269,748) or amine salts (see US-A 4,292,226).
  • Oxazolidines as well, as used for example in US-A 4,192,937, represent blocked polyamines which can be used for the preparation of the polyurethanes of the invention, for chain extension of the prepolymers.
  • blocked polyamines of this kind are used they are generally mixed with the prepolymers in the absence of water and this mixture is then mixed with the dispersion water or with a portion of the dispersion water, so that the corresponding polyamines are liberated by hydrolysis. It is preferred to use mixtures or combinations of diamines and triamines, more preferably mixtures or combinations of isophoronediamine (I PDA) and diethylenetriamine (DETA).
  • I PDA isophoronediamine
  • DETA diethylenetriamine
  • the polyurethanes comprise preferably 1 to 30 mol%, more preferably 4 to 25 mol%, based on the total amount of components (b) and (d), of a polyamine having at least 2 isocyanate-reactive amino groups as monomers (d).
  • isocyanates having a functionality of more than two.
  • isocyanurate or the biuret of hexamethylene diisocyanate.
  • Monomers (e), which are used optionally, are monoisocyanates, monoalcohols, and mono primary and -secondary amines. Their fraction is generally not more than 10 mol%, based on the total molar amount of the monomers. These monofunctional compounds customarily carry further functional groups such as olefinic groups or carbonyl groups and serve to introduce into the polyurethane functional groups, which facilitate the dispersing and/or the crosslinking or further polymer-analogous reaction of the polyurethane.
  • Monomers suitable for this purpose include those such as isopropenyl-a,a’ -dimethylbenzyl isocyanate (TMI) and esters of acrylic or methacrylic acid such as hydroxyethyl acrylate or hydroxyethyl methacrylate.
  • TMI isopropenyl-a,a’ -dimethylbenzyl isocyanate
  • esters of acrylic or methacrylic acid such as hydroxyethyl acrylate or hydroxyethyl methacrylate.
  • the polyurethane of the aqueous polyurethane dispersion and comprised in the at least partly coated particle and shaped body according to the present invention has preferably a K-value from higher than 40 and lower than 100, preferably, from 55 to 95.
  • the K value is a relative viscosity number, which is determined in analogy to DIN EN ISO 1628- 1 2021 at 25 °C. It comprises the flow rate of a 1 weight-% strength solution of the polyurethane in DMF, relative to the flow rate of pure DMF, and characterizes the average molecular weight of the polyurethane.
  • A) is the molar amount of isocyanate groups
  • B) is the sum of the molar amount of the hydroxyl groups and the molar amount of the functional groups which are able to react with isocyanates in an addition reaction, is 0.5:1 to 2:1 , preferably 0.8:1 to 1.5:1 , more preferably 0.9:1 to 1.2:1 . With very particular preference the ratio A:B is as close as possible to 1 :1 .
  • the monomers (a) to (e) employed carry on average usually 1 .5 to 2.5, preferably 1 .9 to 2.1 , more preferably 2.0 isocyanate groups and/or functional groups which are able to react with isocyanates in an addition reaction. Very high K-values are achieved be using monomers (a) to (e) with functionalities >2,5 in small amounts or monomers which additionally carry crosslinking groups like carbodiimide, silane, aziridine etc.
  • the polyaddition of components (a) to (e) for preparing the polyurethane takes place preferably at reaction temperatures of up to 180°C, more preferably up to 150°C, for example from 20 to 180°C, preferably from 70 to 150°C, under atmospheric pressure or under autogenous pressure.
  • reaction temperatures of up to 180°C, more preferably up to 150°C, for example from 20 to 180°C, preferably from 70 to 150°C, under atmospheric pressure or under autogenous pressure.
  • the preparation of polyurethanes, and of aqueous polyurethane dispersions is known to the skilled person.
  • the polyaddition of the synthesis components for the preparation of the poly urethanes can be catalyzed using organic or organometallic compounds.
  • Suitable catalysts include dibutyltin dilaurate (DBTL), tin(ll) octoate, tetrabutoxytitanium (TBOT), or diazabicyclo- [2.2.2]octane.
  • DBTL dibutyltin dilaurate
  • TBOT tetrabutoxytitanium
  • Other suitable catalysts are salts of cesium, especially cesium carboxylates such as, for example, the formiate, acetate, propionate, hexanoate, or 2-ethylhexanoate of cesium.
  • An aqueous polyurethane dispersion for the purposes of the present invention is a dispersion which has an aqueous solvent as a continuous phase.
  • Suitable aqueous solvents are water and mixtures of water with water-miscible solvents, examples being alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-hexanol and cyclohexanol; glycols, such as ethylene glycol, propylene glycol, and butylene glycol; the methyl or ethyl ethers of the dihydric alcohols, diethylene glycol, triethylene glycol, polyethylene glycols having number-average molecular weights of up to about 3000, glycerol and dioxane and also ketones, such as acetone in particular.
  • alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-hexano
  • the polyurethane dispersion is substantially free from organic solvents.
  • substantially free from organic solvents here is meant that the fraction of organic solvents is not more than 5% by weight, more preferably not more than 1 % by weight, more particularly not more than 0.1 % by weight, based on the total weight of the solvent.
  • the polyurethanes are prepared in the presence of at least one organic solvent.
  • organic solvents for preparing the polyurethanes are ketones, such as acetone and methyl ethyl ketone, and also N-methylpyrrolidone. Acetone is used with particular preference.
  • the polyurethane dispersion of the invention may comprise, in addition to water, the organic solvent used for the preparation. It will be appreciated that the polyurethane dispersions of the invention can be prepared in the presence of at least one organic solvent which is subsequently replaced in whole or in part by water.
  • the polyurethane dispersions may be prepared for example by one of the following processes: According to the "acetone process", an ionic polyurethane is prepared from the synthesis components in a solvent which is miscible with water and which boils below 100°C under atmospheric pressure. Sufficient water is added to form a dispersion in which water represents the coherent phase.
  • the "prepolymer mixing process” differs from the acetone process in that, rather than a fully reacted (potentially) ionic polyurethane, a prepolymer is first of all prepared that carries isocyanate groups.
  • the components in this case are selected such that the as- defined ratio A : B is greater than 1 .0 and up to 3, preferably from 1 .05 to 1 .5.
  • the prepolymer is first dispersed in water and then optionally crosslinked by reaction of the isocyanate groups with amines which carry more than 2 isocyanate-reactive amino groups, or chain extended by reaction of the isocyanate groups with amines which carry 2 isocyanate-reactive amino groups. Chain extension also takes place when no amine is added. In that case, isocyanate groups are hydrolyzed to amino groups, which are consumed by reaction with remaining isocyanate groups in the prepolymers, with chain extension.
  • the dispersions preferably have a solvent content of less than 10 weight% and with particular preference are free from solvents.
  • Solvents are understood to mean organic solvents.
  • the particles are brought into contact with an aqueous polyurethane dispersion, the polyurethane the polyurethane having at least a first glass transition T gi and a second glass transition temperature T g 2, wherein T gi is below 0°C and Tg2 is higher than 25 °C, resulting in at least partly coated particles.
  • the bringing into contact is realized by mixing the foamed beads with the dispersion using kitchen or cement mixers or spraying, like mixing with a Vollrath mixer or spray drying.
  • the amount of liquid/suspension relative to the product weight may be in the range of from 1 ml/kg/min to 1000 ml/g/min.
  • the size of droplets may vary from 1 mm to 1000 mm in diameter.
  • Suitable nozzles would be hollow cone nozzles, full cone nozzles or flat jet nozzles, as well as spray discs that produce droplets through rotational movement and centrifugal force.
  • a suitable mixer that can be used is an EMT 30 L.
  • EMT L 30 is a discontinuous paddle mixer.
  • It is suitable for mixing, agglomeration and coating experiments. It consists of a rigid vessel with rotatable mixing tools. Depending on the field of application there are various available installation possibilities nozzles.
  • the mixer is heatable due to a double jacket.
  • the rotation speed is adjustable via a mechanical variator. Melt containers and pressure vessels are used for the addition of liquids.
  • the bringing into contact is realized by mixing or spraying, preferably by mixing from 0.5 minutes to 6 hours, preferably 5 minutes to 1 hour, most preferably from 5 minutes to 30 minutes and/or until a residual water content of 3 % or lower based on the total weight of the at least partly coated particle.
  • the contact time can be very low.
  • the coated particles can be then for example dried down to the desired water content by using e.g. a fluidized bed.
  • the particles are spray-coated keeping them in motion via blowing them with e.g. air or mixtures of different gases.
  • the at least partly coated particles are preferably coated in an amount of from 0.1 wt.-% to 40 wt.-%, preferably from 5 wt.-% to 25 wt.-% based on the total weight of particle and coating.
  • the at least partly coated particles are coated in an amount of at least 90 %, preferably at least 95 %, more preferably at least 99 %, more preferably fully coated based on the total surface of the particle.
  • the step a 2 ) refers to the drying the coated particles.
  • all suitable methods are possible, like convective drying, contact drying, infrared drying and also microwave technology.
  • the temperature difference between the product and the wall in should be limited to 1 - 100 K, in the case of convective drying the gas composition can be N2 or air.
  • the gas quantity is preferably 1-1000 liters/min per 1 kg product and the product temperature in the mixer should be between 1 °C and 100°C, preferably 10°C to 60°C.
  • the at least partly coated particles are kept moving. This can prevent agglomeration of the particles.
  • the at least partly coated particles are kept moving until the particles are tacky-free, preferably until a residual water content of 3 % or lower based on the total weight of the at least partly coated particle.
  • step ai) and before step 82) the particles are separated from each other. This can be achieved, e.g. by using a vibrating belt or the like. In addition, this option prevents agglomeration of the particles.
  • Another aspect of the present invention is a process for the preparation of a shaped body comprising the steps of bi) coating of particles of an expanded thermoplastic elastomer according to the process of the present invention. b2) shaping the particles obtained from step bi).
  • the shaping in step b2) is carried out by steam-less thermo-pressing.
  • thermo-pressing also called hot press or heat press
  • the thermo-pressing is carried out at a temperature of from 60 °C to 160 °C, more preferably from 80 °C to 160 °C, even more preferably from 90 °C to 150 °C, even more preferably from 90 °C to 140 °C.
  • the machinery that can be used for the compression molding of fer example EVA polymers will be then suitable for obtaining parts out of the preferred E-TPU particles.
  • the resulting shaped bodies are cooled down to room temperature, which can improve mechanical properties.
  • the molding (shaping) process can be carried out by using an electro-magnetic field in order to generate completely or partly the required heat.
  • the electro-magnetic field is preferably in the range of 30 kHz to 1 GHz (corresponding to radio frequency (RF) and microwave molding) and more preferably from 30 kHz to 300 MHz (corresponding to RF molding).
  • the shaping is carried out by heat, wherein the heat is produced partly or completely by an electro-magnetic field in the range of 30 kHz to 1 GHz, preferably in the radio frequency range (30 kHz to 300 MHz).
  • Shaping by energetic radiation is generally carried out in the microwave-frequency range of 300 MHz - 300 GHz or in the radio-frequency range of 30 kHz - 300 MHz.
  • Microwaves are preferably applied in the frequency range between 0.5 and 100 GHz, especially preferably in the range between 0.8 and 10 GHz and irradiation times between 0.1 and 15 min are used.
  • Radio waves are preferably applied in the frequency range between 500 kHz and 100 MHz, especially preferably in the range between 1 MHz and 80 MHz and irradiation times between 0.1 and 30 min are used.
  • the shaped body is a composite material of the particles with other materials, like textile, leather, a thermoplastic film or parts containing metals, especially electronic parts.
  • Another aspect of the present invention relates to a method for disposing a shaped body comprising the steps of
  • Ci preparing a shaped body according to the process of the present invention
  • C2 disassembling the particles by subjecting the shaped body to an alkaline aqueous fluid that may comprise surfactants.
  • the at least partly coated particles according to the present invention can be used pure, as a mixture of different particles and/or other materials to obtain 3D parts for industrial, consumer, transportation, and construction-application used solely or as a component for sealing, insolation of e.g.
  • Viscosity is measured according to DIN EN ISO 3219-2:2021 (at 23°C and a shear rate of 250 S’ 1 .
  • the dispersions are dried in a mold at 40°C for 3 days and then at 23°C for 7 days. Thermal properties are measured by differential scanning calorimetry.
  • the K-value was determined according to DIN EN ISO 1628-1 :2021 Examples EX1 : Dispersion with two Tgs. The highest Tg is higher than RT (allowing storagestable coated E-TPU single beads)
  • the mixture was diluted with 1852 g acetone and cooled to 40°C and expanded to atmospheric pressure.
  • the NCO-value was determined to 1 .2%.
  • 10.2 g of Isophoronediamine (monomer d) were added in a shot, followed by 81 g Diethylethanolamine (neutralization agent) in 5 min.
  • the dispersion step was continued with 3567 g deionized water in 37 min at 30°C, followed by an addition of 19.8 Diethylenetriamine (monomer d) in 340 g deionized water in 30min.
  • the acetone was removed by vacuum distillation with the help of 0.23 g of defoamer (FoamStar PB 2724, BASF) and the solids content was 37.4%.
  • the dispersion step was continued with 3294 g deionized water in 37 min at 39°C, followed by an addition of 19,8 Diethylenetriamine (monomer d)) in 346 g deionized water in 30 min.
  • the acetone was removed by vacuum distillation with the help of 0.58 g of defoamer (FoamStar PB 2724, BASF) and the solids content was 37%.
  • Comparative example C1 amorphous dispersion with one Tg ⁇ RT (generating sticky and not storage-stable coated E-TPU beads)
  • Comparative example C2 amorphous dispersion with one Tg ⁇ RT (generating sticky and not storage-stable coated E-TPU beads)
  • the acetone was removed by vacuum distillation with the help of two drops of defoamer (FoamStar PB 2724, BASF) and the solids content of the obtained semicrystalline dispersion adjusted to 50% by addition of controlled amount of water.
  • defoamer FraamStar PB 2724, BASF
  • the properties of the obtained dispersion are shown in Table 1 .
  • the polyurethane dispersion described in example Ex1.1 was mixed with E-TPU beads (particles), made according to example 1 of WO 2013/153190 A1 having a bulk density 130 g/l and a particle weight of 27 mg with a Vollrath dissolver for 60 second at room temperature. Later the beads were let drying at RT on a Teflon foil, keeping attention to isolate them from each other. After a time of around 10 minutes the beads were collected. The coated beads are non-sticky, storage stable and can be collected without agglomeration.
  • Sample 1 E-TPU beads coated with 5% dispersion
  • Sample 2 E-TPU beads coated with 10% dispersion
  • the polyurethane dispersion, described in Ex 1.1 was mixed with E-TPU beads, made according to example 1 of WO 2013/153190 A1 having a bulk density 130 g/l and a particle weight of 27 mg with the help of a kitchen mixer (Bosch), equipped with a dough hook.
  • the beads were coated with 10% w/w of the dispersion, described in Ex 1 .1.
  • the beads were mixed until the water was evaporated. For 100 g of product around 15 minutes until drying of the particles. The process leads to coated beads, tack-free and storage stable.
  • E-TPU beads made accordingly to example 1 of WO 2013/153190 A1 having a bulk density 130 g/l and a particle weight of 27 mg were placed in a cement mixer of the company Scheppach, model mix 140, which was equipped with a sieve drum. 481g of dispersion of example Ex 1.1 including 1 % blue dye were slowly added to the cement mixer, under rotation. Within 90 seconds the beads were completely coated. The beads were then allowed to reach the sieve drum, which allowed separation of coated single beads and collection on the underneath Teflon belt. Within 10 minutes after coating the beads were tack free and could be collected and stored.
  • E-TPU beads made accordingly to example 1 of WO 2013/153190 A1 having a bulk density 130 g/l and a particle weight of 27 mg
  • a 30-liter paddle mixer of the company EMT GmbH year of manufacturing was 2013
  • the TPU precursor synthesis was carried out in a twin-screw extruder, ZSK58 MC, of the company Coperion with a process length of 48D (12 housings).
  • the melt discharge from the extruder was carried out by a gear pump.
  • After melt filtration, the polymer melt was processed by underwater granulation into granules, which were continuously dried in a heating vortex bed, at 40 - 90 °C.
  • Polyols, chain extender and diisocyanate (Table 2) were dosed into the first zone.
  • the housing temperatures are in the range 150 - 230 °C.
  • the melt discharge and underwater pelletizing are carried out at melt temperatures of 210 - 245°C.
  • the screw speed was between 180 and 240 1/min.
  • the throughput was in the range of 180 - 220 kg/h.
  • the dried TPU and further raw materials listed in table 3 were fed into a twin screw extruder (ZE40, KraussMaffei Berstorff) and melted in a temperature range of 160 °C to 220 °C.
  • ZE40 twin screw extruder
  • ZE40 KraussMaffei Berstorff
  • blowing agents 1.12 wt.% CO2 (based on the weight of the polymer composition) and 0.194 wt.% N2 (based on the weight of the polymer composition) were injected into the melt in the extruder and mixed with the thermoplastic polyurethane and the other additives to form a ho- mogenic melt.
  • the melting mixture was then pressed via a gear pump at 160-200 0 C into a perforated plate having a temperature of 180 - 200 0 C and cut in the cutting chamber of the underwater granulating (having a temperature of 49 °C and a pressure of 8.7 bar) to granules, which subsequently expanded under water.
  • the expanded granules were dried at 60 °C for 2 h.
  • the obtained E-TPU having a bulk density of 95 g/L and a particle weight of 20 mg was mixed with the polyurethane dispersion, described in Ex 1.1 , with the help of a kitchen mixer, equipped with a dough hook.
  • the beads were coated with 10% w/w of the dispersion, described in Ex 1 .1.
  • the beads were mixed until the water was evaporated. For 100 g of product around 15 minutes until drying of the particles. The process leads to coated beads, tack-free and storage stable.
  • the polyurethane dispersion, described in Ex 1 .1 was mixed with E-TPA, made according to Example 9 of WO2017220671 (having a bulk density 64 g/l and a particle weight of 19 mg) with the help of a kitchen mixer, equipped with a dough hook.
  • the beads were coated with 10% w/w of the dispersion, described in Ex 1.1 .
  • the beads were mixed until the water was evaporated. For 100 g of product around 15 minutes until drying of the particles. The process leads to coated beads, tack-free and storage stable.
  • the polyurethane dispersion, described in Ex 1 .1 was mixed with E-TPA, made according to Example 12 of WO2017220671 (having a bulk density 40 g/l and a particle weight of 17 mg) with the help of a kitchen mixer, equipped with a dough hook.
  • the beads were coated with 10% w/w of the dispersion, described in Ex 1.1. The beads were mixed until the water was evaporated. For 100 g of product around 15 minutes until drying of the particles. The process leads to coated beads, tack-free and storage stable.
  • Example 2.8 Coated E-TPU expanded beads by using a kitchen mixer
  • the polyurethane dispersion, described in Ex 1 .1 was mixed with E-TPU, made according to example E-TPU5 made of TPU1 of W02020136239 (having a bulk density of 77 g/L and a particle weight of 40 mg), with the help of a kitchen mixer, equipped with a dough hook.
  • E-TPU5 made of TPU1 of W02020136239 (having a bulk density of 77 g/L and a particle weight of 40 mg)
  • the beads were coated with 10% w/w of the dispersion, described in Ex 1 .1 .
  • the beads were mixed until the water was evaporated. For 100 g of product around 15 minutes until drying of the particles. The process leads to coated beads, tack-free and storage stable.
  • Example 2.9 The polyurethane dispersion described in example C1 and C2 (Ex. 2.2, sample 2) were mixed with E-TPU beads (particles), made according to example 1 of WO 2013/153190 A1 having a bulk density 130 g/l and a particle weight of 27 mg with a Vollrath dissolver for 60 second at room temperature. Later the beads were let drying at RT on a Teflon foil, keeping attention to isolate them from each other. After a time of around 10 minutes the beads were collected. The beads are extremely sticky and a collection without agglomeration cannot be reached.
  • Sample 1 E-TPU beads coated with 5% dispersion
  • Example 3.1 Hotpress plates with E-TPU beads according to experiment 2.1
  • Example 2 65 g of coated beads according to experiment 2.1 (sample 2) were placed in a preheated mold of dimension ((16.3x9.6x3.3) cm 3 (length, bright, depth), which was previously sprayed with a silicone-based release agent (Indrosil 2000). The filled mold was covered with a mold lid (also sprayed with Indrosil 2000), which allows a compression/compactaction of 50%.
  • the time in the heated press and the residual time for cooling down the 3 D parts prior to demolding are summarized in the following table.
  • E-TPU beads according to example 1 of WO 2013/153190 A1 having a bulk density 130 g/l were placed in a preheated mold of dimension (16.3x9.6x3.3) cm 3 (length, bright, depth)).
  • the filled mold was covered with a mold lid, which allows a compres- sion/compactation of 50%.
  • the hot press molded 3 D parts obtainable be not coated E-TPU beads are reported respectively.
  • Ref-1 is the reference example of our patent, where a plate is made out of non-coated beads
  • Example 3.2 Hot-press plates obtained by using e-TPU beads, coated according to Ex. 2.5
  • 60 g of coated beads e-TPU according to experiment 2.5 were placed in a preheated mold of dimension ((16.3x9.6x3.3) cm 3 (length, bright, depth), which was previously sprayed with a silicone-based release agent (Indrosil 2000).
  • the filled mold was covered with a mold lid (also sprayed with Indrosil 2000), which allows a compression/compactaction of 50%.
  • the material was pressed in the compression molded at 140C for 10 Minutes and actively cooled down to 23 °C for 5 minutes, by circulating water into the walls of the closed mold.
  • a stable plate could be then demolded
  • Example 3.3 Hot-press plates obtained by using e-TPA beads, coated according to Ex. 2.6
  • the material was pressed in the compression molded at 140C for 10 Minutes and actively cooled down to 23 °C for 5 minutes, by circulating water into the walls of the closed mold.
  • a stable plate could be then demolded
  • Example 3.4 Hot-press plates obtained by using e-TPU beads, coated according to Ex. 2.8
  • the material was pressed in the compression molded at 140 °C for 10 Minutes and actively cooled down to 23 °C for 5 minutes, by circulating water into the walls of the closed mold. A stable plate could be then demolded
  • Example 3.5 Hot-press plates obtained by using e-TPU beads, coated according to Ex. 2.1 (sample 2) and e-TPA beads, coated according to Ex. 2.6
  • Example 2 35 g of coated E-TPU beads according to Ex. 2.1 (sample 2) were placed in a preheated mold of dimension ((16.3x9.6x3.3) cm 3 (length, bright, depth), which was previously sprayed with a silicone-based release agent (Indrosil 2000). 20 g of e-TPA, coated according to Ex. 2.6 were placed on top of the E-TPU beads. The filled mold was covered with a mold lid (also sprayed with Indrosil 2000), which allows a compression/compactaction of 50%.
  • the material was pressed in the compression molded at 140 °C for 10 Minutes and actively cooled down to 23C for 5 minutes, by circulating water into the walls of the closed mold.
  • a stable plate could be the demolded.
  • the plate comprises beads of different density and chemical nature. This experiment shows the possibility to realize plates, bearing localized density and chemical differences, with the possibility to tune the mechanical properties of the 3 D object, depending on the dedicated application.
  • Example 3.6 Hot-press plates obtained by using e-TPU beads, coated according to Ex. 2.5 Lower temperature molding
  • 60 g of coated beads e-TPU according to experiment 2.5 were placed in a preheated mold of dimension ((16.3x9.6x3.3) cm 3 (length, bright, depth), which was previously sprayed with a silicone-based release agent (Indrosil 2000).
  • the filled mold was covered with a mold lid (also sprayed with Indrosil 2000), which allows a compression/compactaction of 50%.
  • the material was pressed in the compression molded at 120°C for 10 Minutes and actively cooled down to 23 °C for 5 minutes, by circulating water into the walls of the closed mold.
  • a stable plate could be then demolded
  • E-TPU beads according to example 1 of WO 2013/153190 A1 having a bulk density 130 g/l, coated with 10 w/w% of the dispersion of example 1.1 , were placed in a 15 cm high cylinder of 11 cm in diameter.
  • An 800 g heavy lid was placed on the filled cylinder, which was stored at a temperature of 60 °C.
  • the same experimental set up was used for evaluating the agglomeration behavior of the coated beads over a time of 24 hours.
  • the coated beads could flow out without agglomeration also after 24 hours of storage at 60 °C.
  • E-TPU beads according to example 1 of WO 2013/153190 A1 having a bulk density 130 g/l, coated with 10w/w% of the dispersion of the comparative example C3, were placed in a 15 cm high cylinder of 11 cm in diameter.
  • An 800 g heavy lid was placed on the filled cylinder, which was stored at which was stored at a temperature of 60 C. Upon remotion of the lid after 1 hour of storage, the beads did no flow out of the cylinder and agglomeration was observed.
  • coated beads of example 2.1 show the positive phenomenon of avoiding agglomeration upon storage under defined pressure also at elevated temperature.
  • coating beads by using a 9:1 w/w mixture of the polyurethane dispersion of the example 1.1 and of the comparative example C3 also allows obtaining coated beads which did not agglomerate after performing the caking test at higher temperature as described in Experiment 4.
  • the molded plate made according to example 3.6, was placed in a 2L Becher glass, filled with 1000 mL Water and 5g Persil Kraftgel equipped with a magnet stirrer. The plate was stirred for 30 minutes at a temperature of 90 °C. The loan beads could be recovered.

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Abstract

La présente invention se rapporte à un procédé de préparation de particules enrobées stables au stockage d'une mousse de particules thermoplastiques moulables comprenant les étapes consistant à a1) mettre les particules en contact avec une dispersion aqueuse de polyuréthane, le polyuréthane ayant au moins une première température de transition vitreuse Tg1 et une seconde température de transition vitreuse Tg2, Tg1 étant inférieure à 0 °C et Tg2 étant supérieure à 25 °C, conduisant à des particules au moins partiellement enrobées ; et a2) sécher les particules enrobées. L'invention se rapporte en outre à un procédé de préparation d'un corps façonné, de particules au moins partiellement enrobées stables au stockage et de corps façonnés de celles-ci.
PCT/EP2024/067124 2023-06-28 2024-06-19 Particules enrobées stables au stockage et leur préparation Ceased WO2025002949A1 (fr)

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