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WO2024200432A1 - Préparation de particules stables au stockage d'une mousse de particules thermoplastiques moulables et corps façonnés et produits de préparation et leurs utilisations - Google Patents

Préparation de particules stables au stockage d'une mousse de particules thermoplastiques moulables et corps façonnés et produits de préparation et leurs utilisations Download PDF

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Publication number
WO2024200432A1
WO2024200432A1 PCT/EP2024/058101 EP2024058101W WO2024200432A1 WO 2024200432 A1 WO2024200432 A1 WO 2024200432A1 EP 2024058101 W EP2024058101 W EP 2024058101W WO 2024200432 A1 WO2024200432 A1 WO 2024200432A1
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WO
WIPO (PCT)
Prior art keywords
hot melt
particles
melt adhesive
thermoplastic
coated
Prior art date
Application number
PCT/EP2024/058101
Other languages
English (en)
Inventor
Anna Maria CRISTADORO
Elmar Poeselt
Peter Gutmann
Lothar Seidemann
Peter Gast
Julio Albuerne
Po Han Chen
Martin Linnenbrink
Tobias Kramer
Mon Wei HSIAO
Original Assignee
Basf Se
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Se filed Critical Basf Se
Publication of WO2024200432A1 publication Critical patent/WO2024200432A1/fr

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Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/16—Auxiliary treatment of granules
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • 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
    • C08J9/236—Forming foamed products using binding agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/16—Auxiliary treatment of granules
    • B29B2009/163—Coating, i.e. applying a layer of liquid or solid material on the granule
    • 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
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • 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
    • B29C44/3415—Heating or cooling
    • B29C44/3426—Heating by introducing steam in the mould
    • 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
    • B29C44/36—Feeding the material to be shaped
    • B29C44/38—Feeding the material to be shaped into a closed space, i.e. to make articles of definite length
    • B29C44/44—Feeding the material to be shaped into a closed space, i.e. to make articles of definite length in solid form
    • B29C44/445—Feeding the material to be shaped into a closed space, i.e. to make articles of definite length in solid form in the form of expandable granules, particles or beads
    • 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
    • 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 particles (also herein referred to as "beads") of a moldable thermoplastic particle foam at least partly coated with a hot melt adhesive, preferably a non-reactive hot melt adhesive, comprising the steps of ai) bringing the particles into contact with the hot melt adhesive in order to obtain the coated particles; a 2 ) moving the coated particles until the particles are tacky-free.
  • a hot melt adhesive preferably a non-reactive hot melt adhesive
  • the invention also relates to a storage-stable, at least partly coated particle of a moldable thermoplastic particle foam which is at least partly coated with a hot melt adhesive, preferably a non-reactive hot melt adhesive, wherein the coated particle is tacky-free, preferably obtainable by said process as well as to a process for preparing shaped bodies and shaped bodies obtainable by said process and the use of said particles and shaped bodies.
  • a hot melt adhesive preferably a non-reactive hot melt adhesive
  • Moldable thermoplastic 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 polyurethanes (eTPU), 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. Hybrid eTPU systems are also described in ON 109337343 A, ON 110240795 A and ON 109080061 A.
  • thermoplastic polymer is expanded thermoplastic polyurethane (eTPU), which is commercially available, e.g. marketed by BASF under the name Infinergy®.
  • eTPU particles represent mainly closed to fully closed-cell particle foam.
  • Thermoplastic polyurethane e.g. Elastol- lan®
  • Elastol- lan® is expanded resulting in particle foam and can be processed on standard molding machines. Thanks to its closed particle surface and the chemical nature of the used TPU, standard eTPU grades also absorb only low amounts of water. Like the 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.
  • eTPS eTPS
  • ePS ePS
  • ePP eTPA
  • eTPC eTPO
  • additives like for example pigments or dyes, flame retardants or antistatic agents
  • 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, antimicrobial additives, wax, crosslinking agents, surface functionalized fillers, foamable additives such as Expancell®, additives which can be irradiated by an electromagnetical field, and/or radio frequency, and/or microwave.
  • flame retardants such as expandable graphite
  • additives which generate antistatic properties, electrical conductivity, additives, which reduce dirt-uptake, antimicrobial additives, wax, crosslinking agents, surface functionalized fillers, foamable additives such as Expancell®, additives which can be irradiated by an electromagnetical field, and/or radio frequency, and/or microwave.
  • WO 2022/223 438 A1 and European patent application with application number EP 22 202 204.8 describe 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 disintegrable 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 disintegrable 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
  • WO 2021/249749 A1 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.
  • US 2019/367698 A1 describes methods for the preparation of foamed thermoplastic polyurethane elastomer products using hot melt adhesives like Mirathane® H306.
  • the coated particles are not moved until the particles are tacky-free, but instead filled directly into a product mold for vulcanization.
  • the vulcanization process implicates crosslinking happening among the particles, which lead to the realization of a 3 D material, which loses his thermoplastic characteristics, such as re-meltability and re-cyclability.
  • WO 2019/073607 A1 describes a member for shoe soles, a part or the whole of which is formed from a resin composite body that comprises a non-foamed elastic matrix which is composed of an elastomer and a plurality of resin foam particles that are dispersed in the elastic matrix. Furthermore, a shoe is disclosed which is provided with this member for shoe soles.
  • Hot melt can be used as carrier for e.g. stabilizers, pigments etc.;
  • Hot melt can be recycled together with the eTPU
  • Particle foam bodies, made out of hot melt coated particles can be debonded and the eTPU parts can be recovered;
  • Hot melt coated beads can be fused together by easy hotpress or by using other molding technology such as radio frequency and steam chest molding.
  • a tacky-free coating of the particles allows easy filling into e.g. molds or cavities during processing due to better flowability and lower electrostatic charging by friction.
  • 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 particles of a moldable thermoplastic particle foam at least partly coated with a hot melt adhesive, preferably a non-re- active hot melt adhesive, comprising the steps of ai) bringing the particles into contact with the hot melt adhesive in order to obtain the coated particles; a 2 ) moving the coated particles until the particles are tacky-free.
  • a hot melt adhesive preferably a non-re- active hot melt adhesive
  • the object is also achieved by a process for the preparation of a shaped body comprising the steps of bi) coating of particles according to the process for the preparation of storage-stable particles according to the present invention; b2) shaping the particles obtained from step bi).
  • the object is also achieved by a storage-stable, at least partly coated particle of a moldable thermoplastic particle foam which is at least partly coated with a hot melt adhesive, preferably a non-reactive hot melt adhesive, wherein the coated particle is tacky-free, preferably obtainable by a process for the preparation of storage-stable particles according to the present invention.
  • the object is also achieved by a shaped body obtainable from a process for the preparation of a shaped body according to the present invention or obtained by molding of particle foams according to the present invention.
  • the hot melt adhesive is brought into contact in form of its molten state.
  • a typical temperature used is in the range from 60 °C to 200 °C, preferably from 60 °C to 180 °C, more preferably from 80 °C to 180 °C.
  • the hot melt adhesive in its molten state has a viscosity in the range from 0.1 mPas to 800000 mPas, more preferably from 1 mPas to 600000 mPas, even more preferably from 10 mPas to 500000 mPas, measured at 160°C.
  • the viscosity is measured by using a Brookfield viscosimeter.
  • the Brookfield viscometer measures the torque required to rotate the selected spindle in a fluid. This torque value is directly related to the viscosity of a fluid.
  • a Brookfield/Ametek rotationviscosimeter (HB DV2T Extra) can be used, which measures the torque required to rotate the spindle (SC4-27) in a fluid at 0.4 rpm.
  • the particles are kept under agitation (kitchen mixer, cement mixer or spray coating drum).
  • the mixer is preferably kept at a temperature from 15 °C to 100 °C, preferably from 30 °C to 100 °C, even more preferably, from 60 °C to 100 °C.
  • the particles are tempered before step ai) so that the temperature of the particles at least at the beginning of step ai), preferably during the whole step ai), is from 15 °C to 100 °C, preferably from 30 °C to 100 °C, even more preferably, from 60 °C to 100 °C.
  • the hot melt adhesive is brought into contact in form of its solid state by powder coating.
  • Powder coating is a well-known method and a person skilled in the art is able to conduct said powder coating.
  • the hot melt adhesive is brought into contact in form of a solution, wherein the hot melt adhesive is dissolved in an organic solvent, followed by the step of as) removing the organic solvent and/or drying the particles after step a 2 ) at a temperature below the melting point of the hot melt adhesive in order to obtain the coated particles.
  • Suitable organic solvents are organic solvents, like acetone, acetonitrile, butanol, t-butyl alcohol, butanone (MEK), chlorobenzene, chloroform, cyclohexane, diethylene glycol, diethyl ether, dimethoxy ethane, dimethylformamide, dioxane, ethanol, ethyl acetate, ethylene glycol, glycerin, heptane, hexane, methanol, methyl t-butyl ether, N-methyl-2-pyrrolidinone, methylene chloride, pentane, propanol, pyridine, tetrahydrofuran, toluene, triethyl amine, xylene.
  • a preferred organic solvent is MEK.
  • the draying in step as) can be carried out by conventional methods.
  • a most preferred embodiment is the use of the hot melt adhesive in form of its molten state.
  • the processes of the present invention refer 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 eTPU.
  • the glass transition temperature (Tg) of the moldable thermoplastic particle foam is, according to the named patents, ⁇ 100 °C and is measured via DSC according to DIN EN ISO 11357-3:2013, preferably with a heating rate of 20 °C/min after a first pre-drying step at 100 °C for 10 min.
  • the Tg of the soft phase can be measured in the first heating run.
  • the bringing into contact is realized by mixing the foamed beads with the hot melt adhesive using kitchen or cement mixers or spraying, like mixing with a Vollrath mixer or spray drying.
  • the amount of liquid/solution 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 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 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 as) refers to the drying the coated particles in case the hot melt adhesive is brought into contact in form of a solution, wherein the hot melt adhesive is dissolved in an organic solvent.
  • all suitable methods are possible, like convective drying, contact drying, infrared drying and also microwave technology. In case of the use of a hot melt in the molten state such it is only required to bring the coated particles to room temperature.
  • 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.
  • step 82 the coated particles are moved until the particles are tacky-free.
  • tacky-free refers to the realization of a non-sticky surface at room temperature, preferably in the range from 20 °C to 25 °C. This is given when the coated particles do not agglomerate in contact with each other and do not adhere to a second surface at room temperature. This translates to a Tfb (further described in the following) of the hot melt higher than 40 °C, preferentially higher than 60 °C. Tacky-free particles are important to provide storage-stable particles.
  • step 82) can take place simultaneously with step ai) or afterwards or both, starting with or during step ai) and continued after completion of step ai).
  • 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. Also, this option prevents agglomeration of the particles.
  • the hot melt adhesive is a composition comprising a thermoplastic polymer, preferably a thermoplastic polyurethane.
  • a hot melt adhesive typically is solid at room temperature, solvent-free and meltable above room temperature.
  • the hot melt adhesive generally is an unreactive thermoplastic.
  • Hot-melt adhesives are adhesive systems which are solid at room temperature, become tacky or sticky upon heating and melt to a liquid or fluid state. They typically solidify rapidly upon cooling at ambient temperatures to develop internal strength and cohesion.
  • Hot melt adhesives are one- part, solvent free thermoplastic adhesives which are characterized by low to medium viscosity when applied at the required dispensing temperature. Once applied, hot melt adhesives cool and solidify to form a strong bond between articles. Bonds formed with thermoplastic hot melt adhesives are reversible. Under sufficiently high thermal stress, thermoplastic hot melt adhesives will liquefy and lose their cohesive strength.
  • the melting point, measured by differential scanning calorimetry (DSC), of the composition comprising the thermoplastic polymer, in particular the thermoplastic polyurethane, is preferably from about 50 °C to about 180 °C, or from about 50 °C to about 160 °C.
  • the test method refers to ASTM D 3418 - 12 (Standard Test Method for Transition Temperatures and Enthalpies of Fusion and Crystallization of Polymers by Differential Scanning Calorimetry) by using the Hitachi High-Tech Co., DSC7000X with a heating rate of 10 °C/min and a cooling rate of 10 °C/min.
  • the flow beginning temperature (Tfb) of the composition comprising the thermoplastic polymer has an influence on the coating properties of the composition.
  • the adjustment of the flow beginning temperature in a suitable range can be used to influence the temperature behaviour of the adhesive strength to obtain good coating properties under conditions of usage, but also to allow for easy recycling.
  • an advantageous combination of good coating using mild conditions can be achieved using the composition comprising a thermoplastic polymer which has a flow beginning temperature (Tfb) of at least 50°C, preferably at least 60°C, more preferably at least 70°C as measured according to Example 1 referring to JSI K7311-1995 and K7210-1999 and by using the Shimadzu Flowtester Capillary Rheometer CFT- 500D.
  • the present invention is also directed to process according to the present invention, wherein the thermoplastic polymer composition has flow beginning temperature (Tfb) measured according to Example 1 of in the range from 50 °C to 160 °C, preferably from 60 °C to 160 °C, more preferably from 70 °C to 160 °C, more preferably from 70 °C to 150 °C.
  • Tfb flow beginning temperature
  • the composition comprising the thermoplastic polymer, used according to the present invention has a relatively low softening temperature and also a low flow beginning temperature.
  • the composition comprising the thermoplastic polymer can include a variety of polymers commonly used in adhesive.
  • the composition can include at least one polymer selected from a polyurethane, a polychloroprene, a latex, a polystyrene, a polyamide, a polyolefin, a polyacrylate, a polyester, a polyether, a copolymer thereof, and any combination thereof.
  • the polystyrene is or includes a polystyrene block copolymer.
  • Suitable polystyrenes can include poly(styrene-isoprene-styrene), poly(styrene-butadiene-styrene), poly(sty- rene-ethylene-butene-styrene), and a poly(styrene-ethylene-propene).
  • the composition comprising the thermoplastic polymer includes at least one thermoplastic polymer selected from a thermoplastic polyurethane, a thermoplastic polyamide, a thermoplastic polyolefin, a thermoplastic polyester, a thermoplastic polyether, a thermoplastic copolymer thereof, and any combination thereof.
  • the composition includes a polyolefin such as a polyethylene, a polypropylene, a copolymer thereof, or any combination thereof.
  • the polyolefin can be an ethylene copolymer.
  • the composition includes a thermoplastic polyolefin.
  • the thermoplastic polyolefin in some aspects, includes a thermoplastic polyethylene, a thermoplastic polypropylene, a thermoplastic copolymer thereof, or any combination thereof.
  • the thermoplastic polyolefin can include a thermoplastic ethylene copolymer.
  • the thermoplastic ethylene copolymer is ethylene vinyl acetate (EVA).
  • the composition includes at least one thermoplastic polymer which is a polymer or copolymer including a plurality of functional groups in its chemical structure, wherein the plurality of functional groups are selected from hydroxyl groups, carboxyl groups, amine groups, amide groups, urethane groups, and combinations thereof.
  • the present invention is also directed to the processes as disclosed herein, wherein the thermoplastic polymer composition comprises at least one polymer selected from a thermoplastic polyurethane, a polychloroprene, a polystyrene, a polyamide, a polyolefin, a polyacrylate, or a mixture thereof.
  • the thermoplastic polymer composition comprises at least one polymer selected from a thermoplastic polyurethane, a polychloroprene, a polystyrene, a polyamide, a polyolefin, a polyacrylate, or a mixture thereof.
  • the composition typically is applied at elevated temperature to produce adhesive coatings.
  • the composition can for example be applied as a melt at temperatures from preferably 60 °C to 220 °C, more preferably from 80 °C to 200 °C, even more preferably, from 80 °C to 200 °C the foam to be coated, the coated surface being coated at least partly with the composition comprising the thermoplastic polymer.
  • the application amount of the composition comprising the thermoplastic polymer is preferably in the range from 1 wt.-% to 30 wt.-%, more preferred from 5 wt.-% to 20 wt.-% based on the total weight of the coated particle.
  • the composition comprises a thermoplastic polyurethane.
  • the present invention is also directed to a process as disclosed herein, wherein the thermoplastic polymer is a thermoplastic polyurethane.
  • Suitable thermoplastic polyurethanes typically comprise the reaction product of a) a polyisocyanate component, b) a polyol component, and c) optionally a chain extender component.
  • thermoplastic polyurethane is the reaction product of the building components a polyol, an isocyanate and eventually a chain extender.
  • the starting materials are preferably selected to adjust the flow beginning temperature of the thermoplastic polyurethane.
  • the flow beginning temperature may for example be adjusted by reducing the hard segment content of the thermoplastic polyurethane.
  • mixtures of polyols or mixtures of chain extenders may be used to adjust the flow beginning temperature.
  • the structure of the polyol might be adjusted by choosing suitable monomers or mixtures of monomers to influence the flow beginning temperature.
  • the molecular weight and/or chain length of the chain extender used may be adjusted to influence the flow beginning temperature.
  • Adjustment of the molecular weight of the thermoplastic polyurethane by choosing a suitable molar ratio of the NCO/OH groups also influences the flow beginning temperature.
  • two or more of these adjustments can be used to achieve an ideal combination of hardness, flow beginning temperature, and other properties.
  • the present invention is also directed to a process as disclosed herein, wherein the isocyanate is an aromatic isocyanate, an aliphatic isocyanate, an alicyclic isocyanate, and combinations thereof.
  • the isocyanate component may comprise one or more polyisocyanates.
  • the polyisocyanate component includes one or more diisocyanates. Suitable polyisocyanates include aromatic diisocyanates, aliphatic diisocyanates, cyclo aliphatic diisocyanates or combinations thereof.
  • the polyisocyanate component includes one or more aromatic diisocyanates.
  • the polyisocyanate component is essentially free of, or even completely free of, aliphatic diisocyanates.
  • the polyisocyanate component includes one or more aliphatic diisocyanates and/or cyclo aliphatic diisocyanates.
  • the polyisocyanate component is essentially free of, or even completely free of, aromatic diisocyanates.
  • mixtures of aliphatic and aromatic diisocyanates may be useful.
  • useful polyisocyanates include aromatic diisocyanates such as 4,4'-methylenebis(phenyl isocyanate (4,4’-M DI), 2,4-diphenylmethane diisocyanate (2,4-MDI), 2,2'-diphenylmethane diisocyanate (2,2’-M DI), m-xylene diisocyanate (XDI), phenylene-1 ,4-diisocyanate (1 ,4-PDI), naphthalene-l,5-diisocyanate (NDI), 4,4'-diisocyanato- 1 ,2-diphenylethane, 3,3'-dimethyl-4,4'-biphenylene diisocyanate (TODI) and toluen
  • the polyisocyanate is MDI and/or H12MDL In some embodiments, the polyisocyanate consists essentially of MDI. In some embodiments, the polyisocyanate consists essentially of H12MDL
  • the present invention is also directed to a process as disclosed herein, wherein the aromatic isocyanate more preferably selected from the group consisting of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, urethane-modified liquid 4,4'-diphenylmethane diisocyanate and/or 2,4-diphenylmethane diisocyanate, 4,4’-diisocy- anato-1 ,2-diphenylethane, 1 ,5-naphthalene diisocyanate, and combinations thereof.
  • the present invention is also directed to a process as disclosed herein, wherein the aromatic isocyanate most preferably is 4,4'-diphenylmethane diisocyan
  • the present invention is also directed to a process as disclosed herein, wherein the aliphatic isocyanate is more preferably selected from the group consisting of 1 ,4-tetramethylene diisocyanate, 1 ,6-hexamethylene diisocyanate, 1 ,12-docecane diisocyanate, and combinations thereof.
  • the present invention is also directed to a process as disclosed herein, wherein the aliphatic isocyanate most preferably is 1 ,6-hexamethylene diisocyanate (HDI).
  • the aliphatic isocyanate most preferably is 1 ,6-hexamethylene diisocyanate (HDI).
  • the present invention is also directed to a process as disclosed herein, wherein the alicyclic isocyanate more preferably selected from the group consisting of isophorone diisocyanate, 1 ,4-cyclohexane diisocyanate, 1-methyl-2,4-cyclohexane diisocyanate, 1-methyl-2,6-cyclohexane diisocyanate and its corresponding isomer mixture, 4,4'-, 2,4-, and 2,2'-dicyclohexylmethane diisocyanate and their corresponding isomer mixtures, and combinations thereof.
  • the alicyclic isocyanate more preferably selected from the group consisting of isophorone diisocyanate, 1 ,4-cyclohexane diisocyanate, 1-methyl-2,4-cyclohexane diisocyanate, 1-methyl-2,6-cyclohexane diisocyanate and its corresponding isomer mixture, 4,4'-, 2,4-, and 2,2
  • the present invention is also directed to a process as disclosed herein, wherein the alicyclic isocyanate most preferably is 4,4'-dicyclohexyl-methane diisocyanate (H12MDI).
  • H12MDI 4,4'-dicyclohexyl-methane diisocyanate
  • the thermoplastic polyurethanes are also made using b) a polyol component.
  • Polyols which may also be described as hydroxyl terminated intermediates, useful in the present invention include polyester polyols, polyether polyols, polycarbonate polyols and combinations thereof.
  • the polyester polyols preferably are linear polyesters.
  • Hydroxyl terminated polymeric intermediates having a number average molecular weight (Mn) of preferably from about 300 to about 10,000, 10 for example, about 400 to about 8,000 Daltons, further for example about 500 to about 6,000 Daltons.
  • Mn number average molecular weight
  • the molecular weight is determined by assay of the terminal functional groups and is related to the number average molecular weight. Unless otherwise noted, the molecular weight can be determined via end group quantification or can be calculated from the OH number according to EN ISO 4629-1 :2016 in the context of the present invention.
  • the present invention is also directed to a process as disclosed herein, wherein the polyol is a polyol with a number average molecular weight between 0.4 x 103 g/mol and 6 x 103 g/mol, measured according to end group quantification.
  • Suitable polyester intermediates may be produced by (1) an esterification reaction of one or more glycols with one or more dicarboxylic acids or anhydrides, or (2) by transesterification reaction, i.e., the reaction of one or more glycols with esters of dicarboxylic acids, or (3) ring opening polymerization, ex. polycaprolactone diol (PCL-diol), Polylactide diol (PLA-diol), etc. Mole ratios generally in excess of more than one mole of glycol to acid are preferred so as to obtain linear chains having a preponderance of terminal hydroxyl groups.
  • the dicarboxylic acids of the desired polyester can be aliphatic, cycloaliphatic, aromatic, or combinations thereof.
  • Suitable dicarboxylic acids which may be used alone or in mixtures generally have a total of from 4 to 44 carbon atoms and include: succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, isophthalic, terephthalic, cyclohexane dicarboxylic, dimer fatty acid and the like.
  • Anhydrides of the above dicarboxylic acids such as phthalic anhydride, tetrahydrophthalic anhydride, or the like, can also be used.
  • the glycols which are reacted to form a desirable polyester intermediate can be aliphatic, aromatic, or combinations thereof, and have a total of from 2 to 44 or from 2 to 36 carbon atoms.
  • Suitable examples include ethylene glycol, 1 ,2-propanediol, 1 ,3-propanediol, 2-methyl-1 ,3-propanediol,1 ,3-butanediol, 1 ,4-butanediol, 1 ,5-pentanediol, 3-methyl-1 ,5-pentane- diol, 1 ,6-hexanediol, 2,2-dimethyl-1 ,3-propanediol, 1 ,4-cyclohexanedimethanol, decamethylene glycol, dodecamethylene glycol, dimer fatty diol and mixtures thereof.
  • Suitable hydroxyl terminated polyether intermediates include polyether polyols derived from a diol or polyol having a total of from 2 to 15 carbon atoms.
  • the hydroxyl terminated polyether is an alkyl diol or glycol which is reacted with an ether comprising an alkylene oxide having from 2 to 6 carbon atoms, typically ethylene oxide or propylene oxide or mixtures thereof.
  • hydroxyl functional polyether can be produced by first reacting propylene glycol with propylene oxide followed by subsequent reaction with ethylene oxide.
  • Useful commercial polyether polyols include poly(ethylene glycol) comprising ethylene oxide reacted with ethylene glycol, polypropylene glycol) comprising propylene oxide reacted with propylene glycol, poly(tetramethylene glycol) comprising water reacted with tetrahydrofuran which can be described as polymerized tetrahydrofuran, and which is commonly referred to as PTMEG.
  • Suitable polyurethanes described herein are made using optionally c) a chain extender component.
  • Suitable chain extenders include low molecular weight diols (molecular weight less than 500 g/mol), diamines, and combination thereof.
  • Suitable chain extenders include relatively small polyhydroxy compounds, for example lower aliphatic or short chain glycols having from 2 to 20, or 2 to 12, or 2 to 10 carbon atoms.
  • Suitable examples include ethylene glycol (EDO), diethylene glycol (DEG), propylene glycol (PDO), dipropylene glycol (DPG), 1 ,4-butanediol (BDO), 2- methyl-1 ,3-propanediol (MPO), 1 ,6-hexanediol (HDO), 1 ,3-butanediol (1 ,3-BDO), 1 ,5-pentane- diol (1 ,5-PDO), neopentyl glycol (NPG), 1 ,4-cyclohexanedimethanol (CHDM), 2,2-bis[4-(2-hy- droxyethoxy)phenylpropane (HEPP), hexamethylenediol (HDO), heptanediol, nonanediol (NDO), dodecanediol (DDO), 3-methyl-1 ,5-pentanediol (
  • the chain extender includes BDO, HDO, 3-methyl-1 ,5-pentanediol, or a combination thereof.
  • the chain extender includes BDO.
  • Other glycols, such as aromatic glycols could be used.
  • the composition is formed using less than 40% by weight, for example only less than 30% by weight, preferably less than 25%, for example, less than 15%, further for example, less than 12%, in particular less than 8% by weight of the total reactants of a chain extender.
  • the thermoplastic polyurethanes are essentially free of or even completely free of chain extender.
  • the present invention is also directed to a process as disclosed herein, wherein the chain extender is selected from ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, or is a mixture thereof, more preferably the chain extender is butanediol, hexanediol, cyclohexane dimethanol (CHDM), hydroquinone bis(2-hydroxyethyl)ether (HQEE), or is a mixture thereof.
  • CHDM butanediol, hexanediol, cyclohexane dimethanol
  • HQEE hydroquinone bis(2-hydroxyethyl)ether
  • thermoplastic polyurethanes used according to the present invention typically have a hard segment content less than 50 wt%, preferred less than 40 wt%.
  • one or more polymerization catalysts may be present during the polymerization reaction.
  • any conventional catalyst can be utilized to react the diisocyanate with the polyol intermediates or the chain extender.
  • suitable catalysts which in particular accelerate the reaction between the NCO groups of the diisocyanates and the hydroxy groups of the polyols and chain extenders are the conventional tertiary amines known from the prior art, e.g.
  • organometallic compounds such as titanic esters, iron compounds, e.g. ferric acetylacetonate, tin compounds, e.g. stannous diacetate, stannous octoate, stannous dilaurate, bismuth compounds, e.g. bismuth trineodecanoate, or the dialkyltin salts of aliphatic carboxylic acids, e.g.
  • the reaction to form the thermoplastic PU used according to the present invention is substantially free of or completely free of catalyst.
  • additives include but are not limited to antioxidants, such as phenolic types, rheology modifiers, such as hydrophobic or hydrophilic fumed silica, and adhesion promoters, such as malonic acid, fumaric acid, chlorinated rubber, vinyl chlo- ride/vinyl acetate copolymers, vinyl chloride/vinyl acetate/maleic acid terpolymers.
  • antioxidants such as phenolic types
  • rheology modifiers such as hydrophobic or hydrophilic fumed silica
  • adhesion promoters such as malonic acid, fumaric acid, chlorinated rubber, vinyl chlo- ride/vinyl acetate copolymers, vinyl chloride/vinyl acetate/maleic acid terpolymers.
  • additives may be used to enhance the performance of the composition or blended product, such as other resins, including but not limited to coumarone-indene or terpene-phenolic which may help increase the tackiness of the hot-melt adhesive when hot and slow the recrystallization time. All of the additives described above may be used in an effective amount customary for these substances.
  • additives can be used including 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, antimicrobial additives, wax, crosslinking agents, surface functionalized fillers, foamable additives such as Expancell®, heat conductive additives and additives which can be irradiated by an electromagnetical field, and/or radio frequency, and/or microwave.
  • flame retardants such as expandable graphite
  • additives which generate antistatic properties, electrical conductivity, additives, which reduce dirt- uptake, antimicrobial additives, wax, crosslinking agents, surface functionalized fillers
  • foamable additives such as Expancell®
  • heat conductive additives and additives which can be irradiated by an electromagnetical field, and/or radio frequency, and/or microwave.
  • Exemplary additives are mentioned in DE 102021 205 928 A1 , like heat conductive additives, e.g. a metal nitride, a metal oxide, a metal carbide, a metal sulfide, a metal silicate, a silicon carbide and silicon nitride, particularly preferably boron nitride, BN, SILATHERM® (a mixture of AI2O3 and SiC>2) or SILATHERM® Advance.
  • a metal nitride e.g. a metal nitride, a metal oxide, a metal carbide, a metal sulfide, a metal silicate, a silicon carbide and silicon nitride, particularly preferably boron nitride, BN, SILATHERM® (a mixture of AI2O3 and SiC>2) or SILATHERM® Advance.
  • Exemplary electrical conductive additives are a mixture of a carbon material and an inorganic material, carbon fiber, glassy carbon, carbon nanotubes, carbon nanobuds, aerographite, linear acetylenic carbon, q-carbon, graphene, a salt, a monocrystalline powder, a polycrystalline powder, an amorphous powder, a glass fiber.
  • the additives can be incorporated into the components of, or into the reaction mixture for the preparation of the thermoplastic polymer and then melted or they can be incorporated directly into the melt of the thermoplastic polymer.
  • thermoplastic polyurethane can be manufactured by any means known to those of ordinary skill in the art, such as for example batch processes, REX line procedure or Belt line procedure.
  • the components: (a) the diisocyanate component, (b) the polyol component, and (c) the optional chain extender component are reacted together to form the thermoplastic PU useful in this invention.
  • Any known processes to react the reactants may be used to make the thermoplastic PU.
  • the process is a so-called "one-shot” process where all the reactants are added together, mixed and reacted.
  • the equivalent weight amount of the diisocyanate to the total equivalent weight amount of the hydroxyl containing components, that is, the polyol intermediate and, if included, the chain extender glycol can be from about 0.5 to about 1.30, or, from about 0.6 to about 1 .20, or from about 0.7 to about 1.10.
  • Reaction temperatures utilizing a urethane catalyst can be from about 175 °C to about 245 °C preferably from 180 °C to 220 °C in the reaction zone of a Twin-Screw Reactive Extruder (REX line) procedure; or from about 80°C to about 160°C preferably from 90°C to 150°C in the reaction zone of a Belt line procedure.
  • thermoplastic PU can also be prepared utilizing a pre-polymer process.
  • the polyol component is reacted with generally an equivalent excess of one or more diisocyanates to form a pre-polymer solution having free or unreacted diisocyanate therein in the presence of a suitable urethane catalyst.
  • a chain extender as noted above, is added in an equivalent amount generally equal to the isocyanate end groups as well as to any free or unreacted diisocyanate compounds.
  • the overall equivalent ratio of the total diisocyanate to the total equivalent of the polyol intermediate and the chain extender is thus from about can be from about 0.5 to about 1 .30, or, from about 0.6 to about 1.20, or from about 0.7 to about 1.10.
  • the pre-polymer route can be carried out in any conventional device.
  • the described process for preparing the thermoplastic PU includes both the "pre-polymer” process and the “one-shot” process, in either a batch or continuous manner. That is, in some embodiments the thermoplastic PU may be made by reacting the components together in a "one shot” polymerization process wherein all of the components, including reactants are added together simultaneously or substantially simultaneously to a mixer and reacted to form the thermoplastic PU.
  • thermoplastic PU may be made by first reacting the polyisocyanate component with some portion of the polyol component forming a pre-polymer, and then completing the reaction by reacting the pre- polymer with the remaining reactants, resulting in the thermoplastic PU. After exiting the extruder, the composition may be pelletized and stored and is ultimately sold in pellet form; or could be extruded directly from the reaction extruder through a die into a final product profile.
  • the chemical nature of the particles and the coating is the same, especially a PU hot melt adhesive and eTPU 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 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, steam chest molding and/or by means of an electromagnetic field, especially radio frequency, preferably 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 140 °C, even more preferably from 100 °C to 140 °C.
  • the resulting shaped bodies are cooled down to room temperature, which can improve mechanical properties.
  • 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
  • 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, like the shaped bodies of the present invention, for various utilities including industrial, consumer, transportation, and construction-application used solely or as a component for sealing, insolation of e.g.
  • another aspect of the present invention is the use of a storage-stable, at least partly coated particle or a shaped body of the present invention for industrial, consumer, transportation, and/or construction-applications, especially for the utilities mentioned above.
  • Figure 1 shows a structure drawing Shimadzu Flowtester CFT-500EX.
  • control unit CPU
  • the sample is charged in the cylinder and heated by the heater outside the cylinder.
  • the force generated by the weight is multiplied by the load lever, applied to the piston through the load shaft and extrudes the sample through the die orifice.
  • the piston stroke is detected by the potentiometer.
  • the potentiometer value is read by the instrument control unit.
  • the now rate is then calculated from the relationship between the extrusion time and the piston stroke to obtain shear rate and viscosity.
  • the loading mechanism generates load force 10 times larger than the weights by combining the wheel set with lever ratio 1 :2 and the load lever with lever ratio 1 :5.
  • the wheel set and the load lever operate in unison via the connecting steel strip.
  • the load shaft moves vertically but its horizontal movement is restricted.
  • the load force is not generated by the weights.
  • the load force is generated in the load shaft, which extrudes the sample.
  • the weight lever movement supporting point moves on the flat supporting point bearing horizontally to prevent any force other than the horizontal force from applying to the load shaft.
  • Figure 2 shows a schematic view of the cylinder unit.
  • the cylinder (c) comprises the die holder (dh) and the heater (h).
  • the sample (s) is placed between the die (d) and the piston (p).
  • Figure 3 shows a schematic view of the die.
  • the die (d) has a die length (dl), a die orifice diameter (ddi) and a die width (do).
  • Figure 4 shows a schematic flow test curve with a constant heating-rate method.
  • the piston stroke PS, y-axis
  • the points A and B mark the preheating period.
  • B and C determine the softening region.
  • Starting at D and continuing over point E a flow region is shown.
  • the softening temperature (Ts) and the flow beginning temperature (Tfb) are also marked.
  • Figure 5 shows a set up involving a more direct coating unit which made up of a jacketed hot melt container (19) up to 170 ml and 4 bar connected to a Schlick atomise nozzle (20), which is heated by a gas heater unit (21) and process air (arrows).
  • a ploughshare (22) has been chosen in order to enable thorough mixing properties until the beads are tacky-free.
  • the set up temperature is controlled by a thermostat (23).
  • Polyurethane based hot melts All selected PU hot melts are not sticky at room temperature, remain stable under storage condition, and will activate when temperature increase. Unlike cross-linking TPU, mechanical properties (hardness, tensile strength%) are given by hydrogen bonding (or other intermolecular force such as VDW and IT- IT interaction) between polymer chain which are reversible. The following are specified properties for selected hot melts:
  • Hardness of the PU hot melts was measured according to ASTM D2240 - 15 Standard Test Method for Rubber Property — Durometer Hardness
  • the amount of hard segments (HS) in wt.-% was calculated according to the following equation, wherein m(CE) is the mass in g/mol of the chain extender, m(iso) the mass in g/mol of the isocyanate and m(polyol) the mass in g/mol of the polyol:
  • the melting point was measured via DSC according to ASTM D3418 - 12 Standard Test Method for Transition Temperatures and Enthalpies of Fusion and Crystallization of Polymers by Differential Scanning Calorimetry, heating rate: 10 °C/min, cooling rate: 10 °C/min.
  • a mixture of each component was heated to 80 °C with stirring by using a paddle mixer (SHIN KWANG GR-150R) for 1 -3 minutes at a rotation speed of 500-1 ,000 revolutions per 25 minutes (rpm).
  • the TPU HMA is then discharged.
  • the TPU HMA was post-heat treated at 100°C for 1-5 hours and then pelletized.
  • Hot melt adhesive Dynacoll® 7130 Solid, amorphous, saturated copolyester. Chemical structure according to WO 2009/010324 A1 .
  • the experimental setup is described in JIS K 7311 and JIS K 7210 standard.
  • the general setup of the apparatus used is shown in Figure 1.
  • the hole of the cylinder is closed on the bottom with a die comprising a channel as in detail described in Figure 3.
  • This cylinder is placed in a device for determining the Tfb.
  • the device is constructed to allow the channel of the die to be closed by screwing the die presser at the bottom of the cylinder and press the die strictly fitting to the bottom of the cylinder. Closing of the channel of the die is important for removing air from the sample before the experiment starts.
  • Removing the air is done by compressing the sample in the hole of the cylinder with a piston being pressed towards the die with a specific load without increasing the temperature of the cylinder.
  • the piston with a specific load is set on the sample and the sample is heated by heating the cylinder with a constant increase of the temperature and in parallel plotting the temperature around the sample.
  • Tfb flow beginning temperature
  • the temperature, the piston starts to move is detected by a suitable move detecting means.
  • the temperature the piston starts to move is the flow beginning temperature (Tfb).
  • the device used in all experiments is Shimadzu CFT-500D, from Shimadzu Corporation, Tokyo, Japan.
  • the sample was collected and cut to pieces not greater in maximal diameter than not larger than the diameter of the cylinder, preferable not larger than 5 mm, most preferable not larger than 2 mm.
  • the temperature of the cylinder with the piston was conditioned to 30 ° C +/- 2 °C well before the measurement.
  • the channel of the die then was closed with the means for closing the channel and the air was removed from the sample by pressing the piston 3 times repeatedly towards the sample with a load of 100 kg. After that, the means for closing the channel was removed to open the channel again.
  • the sample under the piston with a load of 100 kg then was held at a temperature of 30°C for 240 seconds. After that, under continued load of 100 kg the sample was heated with a heating rate of 3 °C/min and the temperature close to the sample was continuously plotted.
  • the flow beginning temperature (Tfb) is the temperature when the piston started to move under the load when molten sample started to pass through the channel of the die.
  • a typical diagram for determining the flow beginning temperature (Tfb) can be taken from Figure 4.
  • the selected PU hot melt adhesive was dissolved in MEK solution, the solution viscosity should below 100 cps (25 °C) which can be achieve by adjust solid content.
  • Above solution were mixed with eTPU beads (made according to W02013/153190 A1 , Infinergy 230 based on Diisocyanate 4, BDO, and Polyol 1 , company BASF SE) using mechanical agitator for 30 second at room temperature.
  • the beads were dried on a Teflon coated plate at RT, keeping attention to isolate them from each other. After 5 - 20 minutes drying, the coated beads are tack-free and storage stable.
  • the coating amount of hot melt were 7% to 12% to the beads.
  • Cooling time 5 - 15 min eTPU beads coated with hot melt 1 and 2, accordingly to the procedure described in experiment 2 were heat press (15 minutes, heating at 140 °C and 15 minutes cooling, mold temperature 140 °C). The mechanical properties are reported in the table below. As a comparison a eTPU plate made via steam chest molding is reported.
  • thermoplastic particle foams eTPU foamed particles
  • the setup according to Figure 4 was used and successfully tested with the commercial non-re- active hot melt adhesive Dynacoll® 7130.
  • the setup works at maximum of 200 °C and a viscosity of 10 mPas.
  • the thermoplastic particle foams eTPU foamed particles
  • the following conditions were used:
  • T3 nozzle gas ahead of nozzle 166°C T emperature hot melt container: 165°C Pressure hot melt container: 2.5 bar
  • Coated eTPU beads were obtained.
  • the hot melt 5 in granular form was placed in the cartridge unit (TR 80 LCD cartridge) of a spray gun (Reka Klebetechnik).
  • the hot melt 5 was molten at a temperature of 160 °C and then spraying by using a pressure of 6 bar.
  • eTPU beads made according to WO 2013/153190 A1 , Infinergy 230 based on Diisocyanate 4, BDO, and Polyol 1 , company BASF SE
  • a kitchen machine Cooking Chef XL KCL95
  • the molten hot melt was sprayed on the beads, kept under motion for a period of time of two minutes. A coating amount of 10 w/w% was achieved.
  • 65 g of eTPU beads, coated with hot melt 6 according to experiment 4 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 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.
  • 65 g of eTPU beads according to W02013/153190 A1 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 compression/compactation of 50%. This results in a plate with the following dimensions: 16x9.5x1.6 cm 3 .
  • the hot press molded 3 D parts obtainable be not coated eTPU beads are reported respectively.
  • the selected PU hot melt adhesive 6 was milled to fine powder (100 to 600pm).
  • the powder was mixed with eTPU beads (made according to W02013/153190 A1 , Infinergy 230 based on Diisocyanate 4, BDO, and Polyol 1 , company BASF SE), in defined weight ratio in order to achieve a coating amount of 5w/w%, 10w/w% and 15w/w% respectively.
  • the eTPU beads were pre-heated to at least 120 °C. After homogeneously mixing, remove residue powder by filtration. The coated beads are take-free and storage stable.
  • the coating amount of hot melt were 5% to 15% to the beads.
  • Plates out of the coated beads were realized according to experiment 5 by using the same bead art or by mixing beads of different chemistry coated with the same hot melt.
  • a piece (16.3x9.6cm2) of cotton canvas (0,45mm thickness, standard cotton tissue, Type 10A of Fa. Rocholl) was placed in the mold described in experiment 5. Then, the coated eTPU beads were inserted in the preheated mold at 140 °C and a plate was realized according to the procedure described in experiment 5. A plate, bonded to the cotton canvas textile was realized.
  • an eTPU plate, bonded with the cotton canvas textile, according to experiment 7 was placed in a water bath kept at a temperature of 80 °C under agitation (650 rpm). After 30 minutes delamination of the plate from the textile was observed. The same procedure war repeated, by keeping the water batch temperature at 90 °C. After 30 Minutes, not only the textile was delaminated from the plate, but also the beads of the plates got separated from each other and recovered. The identical procedure, repeated, by keeping the water batch temperature of 60 °C or lower than 60C did not results in delamination or bead disassembly. This guarantees the stability of the assembly during lifetime, such as washing cycle at temperature identical/small than 60 °C.

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Abstract

La présente invention concerne un procédé de préparation de particules stables au stockage d'une mousse de particules thermoplastiques moulables au moins partiellement revêtues d'un adhésif thermofusible, de préférence d'un adhésif thermofusible non réactif, comprenant les étapes consistant à a1) mettre les particules en contact avec l'adhésif thermofusible afin d'obtenir les particules revêtues ; a2) remuer les particules revêtues jusqu'à ce que les particules soient non collantes. L'invention concerne également une particule, stable au stockage, au moins partiellement revêtue, d'une mousse de particules thermoplastiques moulables qui est au moins partiellement revêtue d'un adhésif thermofusible, de préférence d'un adhésif thermofusible non réactif, la particule revêtue étant non collante, ainsi qu'un procédé de préparation de corps façonnés et des corps façonnés pouvant être obtenus par ledit procédé et l'utilisation desdites particules et desdits corps façonnés.
PCT/EP2024/058101 2023-03-31 2024-03-26 Préparation de particules stables au stockage d'une mousse de particules thermoplastiques moulables et corps façonnés et produits de préparation et leurs utilisations WO2024200432A1 (fr)

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EP23165855.0 2023-03-31
EP23165855 2023-03-31

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WO2024200432A1 true WO2024200432A1 (fr) 2024-10-03

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EP0009727A1 (fr) 1978-09-28 1980-04-16 Siemens Aktiengesellschaft Electrode en carbone implantable
US6616797B1 (en) 1999-02-03 2003-09-09 Basf Aktiengesellschaft Preparation of adhesive bonds using carbodiimide-containing dispersions with heat activation
JP2001181437A (ja) * 1999-12-27 2001-07-03 Sekisui Chem Co Ltd 複合材及びその原料組成物並びに複合材の製造方法
WO2005003247A1 (fr) 2003-07-07 2005-01-13 Basf Aktiengesellschaft Procede pour assembler des substrats par collage avec des adhesifs polyurethane
WO2007082838A1 (fr) 2006-01-18 2007-07-26 Basf Se Mousse a base de polyurethane thermoplastique
WO2008087078A1 (fr) 2007-01-16 2008-07-24 Basf Se Systèmes hybrides composés d'élastomères thermoplastiques moussés et de polyuréthanes
WO2009010324A2 (fr) 2007-07-17 2009-01-22 Evonik Degussa Gmbh Adhésif thermofusible durcissant à l'humidité avec une bonne adhésion
WO2012013506A1 (fr) 2010-07-29 2012-02-02 Basf Se Feuilles composites biologiquement désintégrables
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WO2018082984A1 (fr) 2016-11-04 2018-05-11 Basf Se Mousses particulaires à base d'élastomères thermoplastiques expansés
US20190367698A1 (en) 2017-01-16 2019-12-05 Miracll Chemicals Co., Ltd. Method for preparing foamed thermoplastic polyurethane elastomer product
WO2019073607A1 (fr) 2017-10-13 2019-04-18 株式会社アシックス Élément pour semelles de chaussure et chaussure
CN109080061A (zh) 2018-07-25 2018-12-25 南通德亿新材料有限公司 一种热塑性弹性体发泡颗粒浇注成型工艺
CN109337343A (zh) 2018-09-03 2019-02-15 美瑞新材料股份有限公司 一种高载荷缓冲材料及其制备方法
CN110240795A (zh) 2019-05-16 2019-09-17 美瑞新材料股份有限公司 一种嵌段聚醚酰胺弹性体发泡颗粒与聚氨酯的复合材料及其制备方法和应用
WO2021052881A1 (fr) 2019-09-17 2021-03-25 Basf Se Particules de mousse de polyamide à cristallinité élevée et moulages en mousse
WO2021249749A1 (fr) 2020-06-09 2021-12-16 Basf Se Procédé de recyclage d'articles collés
WO2022117331A1 (fr) * 2020-12-02 2022-06-09 Evonik Operations Gmbh Adhérence de particules contenant un agent gonflant à base de polyimides ou de polyacrylates
DE102021205928A1 (de) 2021-01-28 2022-07-28 Adidas Ag Form und Verfahren zur Herstellung einer Komponente durch Formen,Komponente davon und Schuh mit einer solchen Komponente
WO2022223438A1 (fr) 2021-04-22 2022-10-27 Basf Se Procédé pour la préparation de corps façonnés enrobés et leur utilisation

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