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WO2006072462A1 - Poudres de polyurethane thermoplastiques produites par condensation par pulverisation - Google Patents

Poudres de polyurethane thermoplastiques produites par condensation par pulverisation Download PDF

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Publication number
WO2006072462A1
WO2006072462A1 PCT/EP2005/014158 EP2005014158W WO2006072462A1 WO 2006072462 A1 WO2006072462 A1 WO 2006072462A1 EP 2005014158 W EP2005014158 W EP 2005014158W WO 2006072462 A1 WO2006072462 A1 WO 2006072462A1
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WIPO (PCT)
Prior art keywords
starting materials
thermoplastic polyurethanes
reactor
preparation
spray
Prior art date
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Ceased
Application number
PCT/EP2005/014158
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German (de)
English (en)
Inventor
Ekaterina Helwig
Carolin Nadine DÜCKER
Ulrike Licht
Volker Seidl
Oliver Steffen Henze
Dirk Kempfert
Stefan Arenz
Stephan Friederichs
Hans-Ulrich Moritz
Lars Buksch
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BASF SE
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BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to DE112005003149T priority Critical patent/DE112005003149A5/de
Publication of WO2006072462A1 publication Critical patent/WO2006072462A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/26—Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised 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
    • 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
    • C08G18/0895—Manufacture of polymers by continuous processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic

Definitions

  • the invention relates to round thermoplastic polyurethanes, preferably based on aliphatic isocyanates, more preferably hexamethylene diisocyanate, having a melt flow rate (MFR) according to DIN ISO 1133 (180 ° C./2.16 kg) between 5 g / 10 min and 300 g / 10 min, preferably between 10 g / 10min and 200 g / 10 min, more preferably between 15 g / 10min and 200 g / 10 min, preferably a flowability according to DIN EN ISO 6186: 1998 of less than 15 sec / 100g, preferably less than 10 sec / 100g and preferably a particle diameter of the powder preferably less than 1000 .mu.m, more preferably between 50 .mu.m to 1000 .mu.m, in particular less than 600 .mu.m, in particular 100 .mu.m to 600 .mu.m, particularly preferably less than 500 .mu.m, particularly particularly preferably 10 .mu
  • the particle diameter is to be understood as meaning the maximum diameter of a TPU particle in the powder, preferably the mean particle diameter in the powder.
  • the average particle diameter d 50 is preferably between 10 ⁇ m and 200 ⁇ m.
  • Particularly preferred are thermoplastic polyurethanes with a weight fraction greater than 1 wt .-%, more preferably between 1 and 30 wt .-% of particles having a particle size of less than 63 microns, said particle size distribution is measured according to the DIN standard EN-ISO 4610
  • the invention relates to processes for the production of thermoplastic polyurethane and thermoplastic polyurethanes obtainable in this way.
  • round is meant in this document shapes that have no corners or edges, which may be droplet-shaped, spherical, or other shapes that a drop may take on falling.
  • Thermoplastics are plastics that remain thermoplastic when repeatedly heated and cooled in the temperature range typical of the material for processing and application.
  • thermoplastic is meant the property of a plastic to soften in a typical temperature range for him repeatedly in the heat and to harden on cooling and be repeatedly formed in the softened state by flowing as a molded part, extrudate or forming part to semifinished or articles.
  • Thermoplastics are widely used in the art and are in the form of fibers, sheets, films, moldings, bottles, jackets, packages, etc.
  • TPU is an elastomer used in many applications, e.g. Shoe applications, foils, fibers, ski boots, hoses.
  • the preparation of the TPU is usually carried out batchwise or by the known methods continuously, for example with reaction extruders or the tape process by one-shot or prepolymer process.
  • the components to be reacted in particular diisocyanate and diol, are sequentially or mixed together at the same time, the reaction starting immediately.
  • the starting components are introduced individually or as a mixture in the extruder, for example at temperatures of 100 to 28O 0 C, preferably 140 to 25O 0 C reacted, the resulting TPU is extruded, cooled and granulated.
  • thermoplastic polyurethane which are accessible via a simple, fast and inexpensive production process and in particular have the above properties.
  • thermoplastic polyurethanes should be provided which are suitable for direct processing. in the powder-slush process, i. in the production of films or moldings in a mold in which powdered TPUs are melted.
  • a particular task was to optimize the behavior of the TPU powder in the mold during the powder-slush process in order to ensure as complete, rapid and uniform filling of the mold as possible.
  • thermoplastic polyurethanes described above.
  • the round TPU according to the invention are very suitable for powder-slush processing, since they are very easy pourable due to their round shape and therefore can be easily and quickly applied in the mold and fill them well. So far, ground TPUs have been used in powder slush, but due to the milling process they have a non-optimal flowability and therefore have an improvement potential in the powder-slush application.
  • the round shape according to the invention is achieved by the method according to the invention, in which the liquid reaction system forms this shape after spraying. This excellent suitability is supported by the inventively preferred melt index of the TPU.
  • a further object was to provide an improved, simpler, faster, more reproducible and / or more economical process for producing TPU, in particular by reacting (a) isocyanates with (b) isocyanate-reactive compounds, usually having a molecular weight (M w ). from 500 to 10,000, preferably 500 to 5000, particularly preferably 800 to 3000 and (c) chain lengthening to develop agents having a molecular weight of 50 to 499 optionally in the presence of (d) catalysts and / or (e) conventional additives.
  • M w molecular weight
  • a more uniform product quality should be available with overall lower cleaning and process management costs and low reactor costs.
  • thermoplastic polyurethanes in particular isocyanate (a), diol (b) and preferably chain extenders (c), and spraying the mixture containing the starting materials.
  • the inventive method is characterized in that due to the excellent dissipation of the heat of reaction damage to the TPU is avoided during the manufacturing process.
  • the performance of the polyaddition reaction i. the exothermic reaction of the isocyanate groups with, in particular, the hydroxyl groups of the diols and chain extenders in the small-volume droplets of the spray leads to a very good ratio of surface area of the reaction space (drops) to volume of the reaction space.
  • a very exact, preferably isothermal reaction regime with respect to the reaction temperature is made accessible by this process according to the invention since a very constant, precise temperature control is possible via the gas surrounding the "reaction droplets".
  • the inventive method is also characterized by the fact that at low reactor costs in a quasi-closed system there is only a small amount of personnel and cleaning.
  • the TPU obtainable by the process according to the invention are usually in powdered form and can be collected in this form, for example, at the bottom of the reactor and further processed by generally known processes, for example by extrusion or injection molding.
  • the method according to the invention differs not only from known processes for the production of thermoplastic polyurethanes but also from spray processes for the production of crosslinked polyurethane films or coatings.
  • these known processes for the preparation of crosslinked polyurethane coatings on a substrate only a small proportion of the reaction of the isocyanates with the higher-functional polyols in the spray, the predominant reaction is carried out on the substrate, ie in the coating or the film. Only in this way is a possible closed surface of the crosslinked polyurethane coating accessible.
  • EP-B 303 305 describes the preparation of a crosslinked, gel-forming polyurethane layer on a surface.
  • the reaction takes place predominantly in the droplets of the spray. This can prevent sticking, making it possible to access a powdered, non-bonded, thermoplastic product.
  • the starting materials for the preparation of the thermoplastic polyurethanes are mixed before or during the spraying.
  • the mixing of the starting materials, in particular the components (a) with (b) and preferably (c) can be effected by means of static or dynamic mixing elements. Preference is given to mixing the starting materials for the preparation of the thermoplastic polyurethanes in a low-pressure mixing head. It is also possible to use prepolymers having isocyanate groups as starting materials to be mixed, both in admixture with further isocyanates and as the sole isocyanate component.
  • the mixed or mixed by the spraying starting materials are sprayed into a space, preferably a reactor.
  • the generation of the spray or of the droplets by the spraying of the mixture containing the starting materials can be carried out by means of conventional devices for spraying liquids, for example by means of spray nozzles, vibrating inverters and vibrating diaphragm aerosol generators.
  • the mixture containing the starting materials for the preparation of the thermoplastic polyurethanes by means of spray nozzles in a usually filled with gas, preferably with inert gas reaction space, preferably reactor spray.
  • the temperature of the mixture containing the starting materials for the preparation of the thermoplastic polyurethanes during spraying is preferably between 60 and 19O 0 C.
  • the dynamic viscosity of the mixture is preferably between 20 mPas and 80 mPas.
  • the droplet diameter which is obtained during the spraying is preferably less than 1000 .mu.m, more preferably between 50 .mu.m and 1000 .mu.m, in particular less than 600 .mu.m, in particular 100 .mu.m to 600 .mu.m, particularly preferably less than 500 .mu.m, particularly particularly preferably 10 .mu.m to 400 .mu.m.
  • the reaction is preferably carried out in apparatuses which are also suitable for spray drying.
  • Such reactors are described, for example, in K. Masters, Spray Drying Handbook, 5th Edition, Longman, 1991, pages 23-66.
  • Processes for spray polymerization are known for polymerizable monomers, in particular acrylic acid, from EP-A 348 180, US Pat. No. 5,269,980, WO 96/40427 and EP-A 816 383. known.
  • these polymerization reactions are fundamentally different from the polyaddition reaction of isocyanates with diols in the production of TPU.
  • two different components react with each other, usually and preferably not in the presence of solvents, and preferably at individually adjusted molar ratios.
  • the viscosity of the reaction system is usually much higher than in known systems for spray polymerization.
  • the heat produced during the polyaddition is usually removed only by the inert gas stream (no evaporation of starting components / of the solvent).
  • the reaction is preferably carried out in apparatuses in which the spray droplets containing the mixture containing the starting materials for the preparation of the thermoplastic polyurethanes can fall freely.
  • apparatuses as described, for example, in US Pat. No. 5,269,980.
  • the conversion to the TPU preferably takes place largely in the spray / droplet, it is preferred to use reactors which, by virtue of their height, provide the spray droplets with a minimum residence time before the droplets undergo e.g. collect on the bottom of the reactor. It is therefore preferred to spray the mixture containing starting materials for the preparation of the thermoplastic polyurethanes in a reactor with a height between 2 m and 30 m. Particularly preferred is the device for spraying the mixture containing the starting components at least at a height between 2.6 m and 12 m from the bottom of the reactor. After spraying the mixture at this height into the reaction space, the spray can be driven by gravity to fall towards the bottom of the reactor.
  • the starting materials are preferably sprayed into the reactor at the top of the tower-shaped reactor.
  • a temperature profile in the reactor in the vertical direction, i. depending on its height, a temperature profile, particularly preferably a temperature falling down.
  • a fluidized bed may be present at the bottom of the reactor.
  • Fluidized bed reactors are well known in particular for reactions with solids. This fluidized bed has the advantage that the residence time and thus the conversion in the polyaddition reaction can be increased. Furthermore, the addition of liquid and / or solid additives (e.g., flame retardants, color pigments, etc.) is possible.
  • additives (e) to the liquid and / or solid droplets above and / or in the fluidized bed.
  • the reaction of the starting materials is preferably carried out isothermally at a temperature between 80 and 19O 0 C.
  • the temperature can be adjusted by means of a preferably tempered gas, which is passed into the reactor.
  • the starting materials in the droplets of the spray it is preferable to convert to at least 80%. This can be achieved by a suitable temperature control, a corresponding residence time of the droplets in the reactor, e.g. due to the drop height of the spray or suitable catalysis can be achieved.
  • thermoplastic polyurethane a process for preparing pulverized thermoplastic polyurethane, wherein the starting materials for the preparation of the thermoplastic polyurethanes, in particular isocyanate (a), diol (b) and preferably chain extender (c) is mixed and the mixture containing the starting materials in a Reaction space, preferably a reactor sprays, which converts starting materials in the droplets of the spray and the solid droplets containing the thermoplastic polyurethane as a reaction product in powdered form preferably with a particle diameter of the powder preferably less than 1000 microns, more preferably between 50 .mu.m to 1000 .mu.m, in particular less than 600 microns, in particular
  • the reactor is preferably of an inert gas, i. in particular a substance which is present in the gaseous state at the selected temperature and the pressure in the reactor and is inert toward isocyanates, particularly preferably nitrogen, flows through.
  • an inert gas i. in particular a substance which is present in the gaseous state at the selected temperature and the pressure in the reactor and is inert toward isocyanates, particularly preferably nitrogen, flows through.
  • the Gleichstromfahrweise that is, the inert gas flows through the reactor from top to bottom.
  • the inert gas velocity is preferably adjusted so that the flow in the reactor is preferably laminar and is preferably 0.02 to 1.5 m / s, preferably 0.05 to 0.4 m / s.
  • the reaction product can usually be removed from the reactor, preferably at the bottom via a screw conveyor, and optionally tempered to the desired degree of conversion.
  • TPUs are prepared by reacting (a) isocyanates with (b) isocyanate-reactive compounds, usually having a molecular weight (M w ) of 500 to 10,000, preferably 500 to 5000, more preferably 800 to 3000 and (c) chain extenders having a Molecular weight of 50 to 499 optionally prepared in the presence of (d) catalysts and / or (e) conventional additives.
  • M w molecular weight
  • organic isocyanates it is possible to use generally known aliphatic, cycloaliphatic, araliphatic and / or aromatic isocyanates, for example tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, Methylpentamethylene diisocyanate 1, 5, 2-ethylbutylene diisocyanate 1, 4, pentamethylene diisocyanate-1, 5, butylene diisocyanate 1, 4, 1-iso-cyanato-3,3, 5-trimethyl-5-isocyanato-methyl-cyclohexane (isophorone diisocyanate, IPDI), 1, 4- and / or 1, 3-bis (isocyanatomethyl) cyclohexane (HXDI), 1, 4-cyclohexane diisocyanate, 1 Methyl 2,4- and / or 2,6-cyclohexane diisocyanate
  • aliphatic isocyanates are also preferred, particularly preferably i-isocyanato-SS ⁇ -trimethyl-S-isocyanato-methylcyclohexane (isophorone diisocyanate, IPDI) and / or hexamethylene diisocyanate (HDI), in particular hexamethylene diisocyanate.
  • IPDI isophorone diisocyanate
  • HDI hexamethylene diisocyanate
  • isocyanate (a) prepolymers which have free isocyanate groups.
  • the NCO content of these prepolymers is preferably between 10 and 25%.
  • the prepolymers can offer the advantage that, owing to the preliminary reaction in the preparation of the prepolymers, a shorter reaction time is required in the production of the TPU.
  • isocyanate-reactive compounds for example polyesterols, polyetherols and / or polycarbonatediols, which are usually also grouped under the term "polyols", with molecular weights between 500 and 8000 , preferably 600 to 6000, in particular 800 to less than 3000, and preferably an average functionality to isocyanates of 1, 8 to 2.3, preferably 1, 9 to 2.2, in particular 2.
  • Polyether polyols are preferably used, for example those the basis of generally known starter substances and customary alkylene oxides, for example
  • Ethylene oxide, propylene oxide and / or butylene oxide preferably polyetherols based on propylene oxide-1, 2 and ethylene oxide and in particular polyoxytetramethyl len glycols.
  • the polyetherols have the advantage that they have a higher hydrolysis stability than polyesterols.
  • low-unsaturated polyetherols are understood as meaning, in particular, polyether alcohols having an unsaturated compound content of less than 0.02 meg / g, preferably less than 0.01 meg / g.
  • Such polyether alcohols are usually prepared by addition of alkylene oxides, in particular ethylene oxide, propylene oxide and mixtures thereof, to the diols or triols described above in the presence of highly active catalysts.
  • highly active catalysts are, for example, cesium hydroxide and multimetal cyanide catalysts, also referred to as DMC catalysts.
  • DMC catalysts A frequently used DMC catalyst is zinc hexacyanocobaltate.
  • the DMC catalyst can be left in the polyether alcohol after the reaction, usually it is removed, for example by sedimentation or filtration.
  • polybutadiene diols having a molecular weight of 500-10,000 g / mol, preferably 1,000-5,000 g / mol, in particular 2,000-3,000 g / mol, can be used.
  • TPUs made using these polyols can be radiation crosslinked after thermoplastic processing. This leads e.g. to a better burning behavior.
  • chain extenders (c) it is possible to use generally known aliphatic, araliphatic, aromatic and / or cycloaliphatic compounds having a molecular weight of 50 to 499, preferably 2-functional compounds, for example diamines and / or alkanediols having 2 to 10C In the
  • Alkylene in particular 1, 3-propanediol, butanediol-1, 4, hexanediol-1, 6 and / or di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and / or Dekaalkylengly - Cole having 3 to 8 carbon atoms, preferably corresponding oligo- and / or polypropylene glycols, wherein mixtures of the chain extenders can be used.
  • components a) to c) are difunctional compounds, i. Diisocyanates (a), difunctional polyols, preferably polyetherols (b) and difunctional chain extenders, preferably diols.
  • suitable catalysts which, in particular, the reaction between the NCO groups of the diisocyanates (a) and the hydroxyl groups of the everydaykom- components (b) and (c) are the tertiary amines known and customary in the prior art, such as, for example, triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethylpiperazine, 2- (dimethylaminoethoxy) - ethanol, diazabicyclo- (2,2,2) -octane and the like, and in particular organic metal compounds such as titanic acid esters, iron compounds such as iron (111) - acetylacetonate, tin compounds, for example tin diacetate, Zinndi- octoate, tin dilaurate or Zinndialkylsalze aliphatic carboxylic acids such as di butyltin diacetate, dibutyltin dilaurate or the like.
  • auxiliaries and / or additives (e) can also be added to the synthesis components (a) to (c).
  • component (e) also includes hydrolysis protectants such as, for example, polymeric and low molecular weight carbodiimides.
  • thermoplastic polyurethane in the materials according to the invention particularly preferably contains melamine cyanurate, which acts as a flame retardant.
  • Melamine cyanurate is preferably used in an amount of between 0.1 and 60% by weight, more preferably between 5 and 40% by weight, in particular between 15 and 25% by weight, in each case based on the total weight of the TPU.
  • the thermoplastic polyurethane preferably contains
  • Triazole and / or triazole derivative and antioxidants in an amount of 0.1 to 5 wt .-% based on the total weight of the thermoplastic polyurethane.
  • antioxidants are generally suitable substances which inhibit or prevent unwanted oxidative processes in the plastic to be protected. In general, antioxidants are commercially available. Examples of antioxidants are hindered phenols, aromatic amines, thiosynergists, trivalent phosphorus organophosphorus compounds, and hindered amine light stabilizers. Examples of hindered phenols can be found in Plastics Additive Handbook, 5 th edition, H. Zweifel, ed, Hanser Publishers, Kunststoff, 2001 ([1]), pp. 98-107 and pp. 161-121.
  • Examples of aromatic amines can be found in [1] p.107-108.
  • Examples of thiosynergists are given in [1], p.104-105 and p.112-113.
  • Examples of phosphites can be found in [1], p.109-112.
  • Examples of hindered amine light stabilizers are given in [1], p.123-136.
  • Phenolic antioxidants are preferred for use in the antioxidant mixture according to the invention.
  • the antioxidants in particular the phenolic antioxidants, have a molecular weight of greater than 350 g / mol, particularly preferably greater than 700 g / mol and a maximum len molecular weight ⁇ 10000 g / mol, preferably ⁇ 3000 g / mol. Furthermore, they preferably have a melting point of less than 180 ° C. Furthermore, preference is given to using antioxidants which are amorphous or liquid. Also, as component (i), mixtures of two or more antioxidants can be used.
  • chain regulators usually having a molecular weight of from 31 to 3000.
  • Such chain regulators are compounds which have only one isocyanate-reactive functional group, such as e.g. monofunctional alcohols, monofunctional amines and / or monofunctional polyols.
  • a flow behavior in particular with TPUs, can be adjusted in a targeted manner.
  • Chain regulators can generally be used in an amount of 0 to 5, preferably 0.1 to 1, parts by weight, based on 100 parts by weight of component b), and fall by definition under component (c).
  • the structural components (b) and (c) can be varied in relatively wide molar ratios.
  • thermoplastically processable polyurethane elastomers according to the invention can be used for extrusion, injection molding, calendar articles and powder slush processes.
  • the processing of the TPUs according to the invention which are present preferably in powder form, in the powder-slush process or in injection molding, caulking and extrusion articles, for example to the desired films, moldings, rolls, fibers, linings in automobiles, Hoses, cable plugs, bellows, trailing cables, cable sheathing, gaskets, belts or damping elements can be made by conventional methods.
  • Such injection molding and extrusion articles can also be made of compounds containing the TPU according to the invention and at least one further thermoplastic, especially a polyethylene, polypropylene, polyester, polyether, polystyrene, PVC, ABS, ASA, SAN, polyacrylonitrile, EVA, PBT, PET, polyoxymethylene, consist.
  • the TPUs according to the invention are particularly preferably used for the production of articles which are produced by means of powder-slush processes, in particular instrument panels in automobiles, for example films for instrument panels. Examples:
  • TPU particles having an average diameter d 50 of 50 microns generates a MFR of 60g / 10 min (DIN ISO 1133, 180 0 C, 2.16kg) and a free-flowing properties of ⁇ 15 sec / 100g (DIN EN ISO 6186).
  • a stainless steel spray tower with a diameter of 3 m and a height of 9 m, equipped with a vibrating unit was used. Through several heating zones, temperature profiles could be realized along the reactor length.
  • 330 parts of hexamethylene diisocyanate, 1000 parts of a polyether polyol having the OH number of 113.8 mg KOH / g and 89 parts of 1, 4-butanediol were mixed in a low-pressure mixing head and then sprayed directly into the reactor space.
  • Particles having a mean diameter d 50 in the range of 150-200 ⁇ m, an MFR of 70 g / 10 min (DIN ISO 1133, 180 ° C., 2.16 kg) and a flowability of ⁇ 10 sec / 100 g were generated.
  • a spray tower made of stainless steel with a diameter of 2 m and a height of 12 m, equipped with a vibrating unit was used. Through several heating zones, temperature profiles could be realized along the reactor length.
  • the mass flow rates in the spray tower were in the range of 20 kg / h.
  • the nitrogen mass flow was 100-1000 kg / h.
  • 330 parts of hexamethylene diisocyanate, 1000 parts of a polyether polyol having the OH number of 113.8 mg KOH / g and 89 parts of 1, 4-butanediol were mixed in a low-pressure mixing head and then sprayed directly into the reactor space.
  • TPU particles with a mean diameter dso in the range of 150-200 microns, an MFR of 70 g / 10 min (DIN ISO 1133, 18O 0 C, 2.16 kg) and a flowability of ⁇ 10 sec / 100 g generated.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Combustion & Propulsion (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un procédé de production de polyuréthane thermoplastique, caractérisé en ce qu'il consiste à mélanger les produits de départ pour la production des polyuréthanes thermoplastiques et à pulvériser le mélange contenant les produits de départ.
PCT/EP2005/014158 2005-01-07 2005-12-31 Poudres de polyurethane thermoplastiques produites par condensation par pulverisation Ceased WO2006072462A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE112005003149T DE112005003149A5 (de) 2005-01-07 2005-12-31 Thermoplastische Polyurethane Pulver hergestellt durch Sprühkondensation

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DE102005000923.9 2005-01-07
DE200510000923 DE102005000923A1 (de) 2005-01-07 2005-01-07 Thermoplastische Polyurethane

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WO2006072462A1 true WO2006072462A1 (fr) 2006-07-13

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EP3838392A1 (fr) * 2019-12-17 2021-06-23 Covestro Deutschland AG Procédé et dispositif de fabrication de polymères thermoplastiques dans un réacteur de pulvérisation

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DE202011107371U1 (de) 2011-10-31 2011-11-16 Schaeffler Technologies Gmbh & Co. Kg Strahlenvernetzte Thermoplastpatronen für Überdruckventile eines hydraulischen Zugmittelspanners
KR20160143700A (ko) * 2014-03-25 2016-12-14 바스프 에스이 Tpu 공압 호스

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WO2002014396A1 (fr) * 2000-08-15 2002-02-21 Kilzer, Andreas Procede de fabrication de particules de polyurethane
WO2004085050A2 (fr) * 2003-03-28 2004-10-07 Basf Aktiengesellschaft Procede pour produire des resines condensees sous forme pulverulente

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Publication number Priority date Publication date Assignee Title
EP3838392A1 (fr) * 2019-12-17 2021-06-23 Covestro Deutschland AG Procédé et dispositif de fabrication de polymères thermoplastiques dans un réacteur de pulvérisation
WO2021122281A1 (fr) * 2019-12-17 2021-06-24 Covestro Intellectual Property Gmbh & Co. Kg Procédé et dispositif de production de polymères thermoplastiques dans un réacteur de pulvérisation

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