WO2006072461A1 - Method for producing thermoplastic polyurethane particles - Google Patents

Method for producing thermoplastic polyurethane particles Download PDF

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Publication number
WO2006072461A1
WO2006072461A1 PCT/EP2005/014156 EP2005014156W WO2006072461A1 WO 2006072461 A1 WO2006072461 A1 WO 2006072461A1 EP 2005014156 W EP2005014156 W EP 2005014156W WO 2006072461 A1 WO2006072461 A1 WO 2006072461A1
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WO
WIPO (PCT)
Prior art keywords
thermoplastic polyurethane
tpu
diisocyanate
molten
thermoplastic
Prior art date
Application number
PCT/EP2005/014156
Other languages
German (de)
French (fr)
Inventor
Oliver Steffen Henze
Markus Steffen
Michael Senge
Stefan Arenz
Stephan Friederichs
Original Assignee
Basf Aktiengesellschaft
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Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to DE112005003144T priority Critical patent/DE112005003144A5/en
Publication of WO2006072461A1 publication Critical patent/WO2006072461A1/en

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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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/122—Pulverisation by spraying
    • 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
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
    • B01J4/002—Nozzle-type elements
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00119—Heat exchange inside a feeding nozzle or nozzle reactor
    • 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

Definitions

  • the invention relates to processes for the preparation of preferably round thermoplastic polyurethane particles, preferably based on aliphatic isocyanates, more preferably hexamethylene diisocyanate, preferably having a melt index according to DIN ISO 1133 (180 ° C / 2.16 kg) between 5 g / 10min and 300 g / 10min , more preferably between 10 g / 10 min and 200 g / 10 min, in particular between 15 g / 10 min and 200 g / 10 min, preferably a flowability according to DIN EN ISO 6186: 1998 of less than 15 sec / 100 g, preferably less than 10 sec / 100 g and preferably a particle diameter of the powder preferably less than 2000 .mu.m, more preferably between 50 .mu.m and 1000 .mu.m, in particular between 100 .mu.m and 900 .mu.m.
  • particle diameter is meant the maximum diameter of a TPU particle in the powder, preferably the mean particle diameter in the powder.
  • the invention further relates to thermoplastic polyurethane particles obtainable in this way and to processes for producing articles based on thermoplastic polyurethanes by sintering powdered thermoplastic polyurethanes, the thermoplastic polyurethane particles obtainable according to the invention being used as pulverized thermoplastic polyurethanes.
  • 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.
  • Thermoplastic polyurethane (hereinafter referred to as TPU) is an elastomer which finds use in many applications , eg Shoe applications, foils, fibers, ski boots, hoses.
  • the preparation of the TPU is usually carried out batchwise or continuously by the known processes, for example with reaction extruders or the strip process by one-shot or prepolymer process.
  • the components to be reacted in particular diisocyanate and diol, are mixed successively or simultaneously with one another, the reaction beginning 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.
  • the products obtainable by these known processes usually have to be comminuted after granulation, in particular for use in powder slush, e.g. be ground to achieve an acceptable particle size.
  • the granules are ground (cryogenically) at low temperatures.
  • the powders then obtained contain irregular and angular particles, which adversely affect the flowability.
  • TPU powdered TPU is usually distributed in a mold on a surface which, when heated, causes fusion of the TPU powder to produce a TPU "skin."
  • a mold it is as fast and complete as possible Distribution of the TPU powder on the surface is desirable, but this can only be achieved if the flowability of the TPU powder is sufficiently high.
  • thermoplastic polyurethane particles and thermoplastic polyurethane particles obtainable in this way, which have a high flowability, a shape which is as round as possible and, especially in the powder-slush process, rapid and complete coverage of the Enable surface.
  • the expression “dripping” also means “spraying”.
  • 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 dripping invention can be carried out by well-known methods and apparatuses for spraying or dropping liquids. Corresponding processes are described inter alia for molten polyesters in WO 02/18113. Information on process parameters, which should also be content of this document, are also given in WO 01/64326, page 12 to page 14 and in DE-A 101 37 925, page 7, lines 13 to 39, in particular lines 24 to 39.
  • the generation of the spray or the droplets by the spraying and / or dripping of the molten TPU can be carried out by means of conventional devices for spraying or dripping liquids, for example by means of spray nozzles, Vibra- tionsvertropfem and vibrating diaphragm aerosol generators.
  • the process according to the invention can preferably be carried out by dropwise dripping the molten thermoplastic polyurethane by means of a dropletizing nozzle, particularly preferably by particularly preferring the molten thermoplastic polyurethane by means of a vibrated perforated disk, which preferably has a frequency between 50 and 20,000 Hz between 70 and 5000 Hz, dripped.
  • the temperature of the molten TPU during spraying and / or dripping is preferably 140 to 260 0 C, particularly preferably 160-220 0 C.
  • the droplet diameter which is obtained during spraying is preferably less than 2000 .mu.m, more preferably less than 1200 .mu.m, in particular between 50 .mu.m and 1200 .mu.m, according to the invention.
  • the dripping and / or spraying is preferably carried out in apparatus which are also suitable for spray drying.
  • apparatus 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.
  • the process according to the invention is preferably carried out in apparatuses in which the spray droplets can fall freely. Suitable for this purpose are apparatuses as described, for example, in US Pat. No. 5,269,980.
  • the molten thermoplastic polyurethane is dripped into a spray tower.
  • the spray tower preferably has a height between 2 m and 30 m.
  • the device for spraying and / or dripping the TPU is particularly preferably at least at a height of between 2.6 m and 12 m from the bottom of the drop tower. After spraying the mixture at this height into the reaction space, the spray or droplets, driven by gravity, can fall towards the bottom of the drop tower.
  • the TPU is dripped or sprayed on the head of the drop tower.
  • a temperature profile more preferably a downward falling temperature.
  • a fluidized bed may be present at the bottom of the drop tower.
  • Fluidized bed reactors are well known in particular for reactions with solids.
  • This fluidized bed offers the advantage that the addition of liquid and / or solid additives (e.g., flame retardants, color pigments, etc.) is possible. It is therefore preferred to add additives (e) to the liquid and / or solid droplets above and / or in the fluidized bed.
  • the falling tower is preferably powered by 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 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 TPU particles obtainable by the process according to the invention are usually present in powdered form and can be collected in this form, for example, at the bottom of the reactor and purified by generally known methods, e.g. be removed by means of screw conveyor, optionally tempered and further processed, e.g. by extrusion or injection molding.
  • thermoplastic polyurethane is dripped or sprayed in a molten state according to the invention.
  • the TPU e.g. may be in granulated form, are melted in the Vertropfungsapparatur.
  • the TPU is preferably introduced in molten state from an extruder into a dropping device.
  • the extruder may be both a reaction extruder in which the TPU is synthesized and an extruder fed with granulated TPU, which may optionally come directly from a belt mill.
  • 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
  • chain extenders having a Molecular weight of 50 to 499 optionally prepared in the presence of (d) catalysts and / or (e) conventional additives.
  • 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, Methyl-pentamethylene-diisocyanate-1, 5, 2-ethyl-butylene-diisocyanate-1, 4, pentamethylene-diisocyanate-1, 5, butylene-diisocyanate-1, 4, 1-iso-cyanato-3,3, 5-trimethyl-5-isocyanato-methylcyclohexane (isophorone diisocyanate, IPDI), 1, 4- and / or 1,3-bis (isocyanatomethyl) cyclohexane (HXDI), 1,4-cyclohexane diisocyanate, 1 Methyl 2,4- and / or
  • NDI 1, 2,4- and / or 2,6-toluene diisocyanate
  • TDI 2,6-toluene diisocyanate
  • diphenylmethane diisocyanate 3,3'-dimethyl-diphenyl-diisocyanate, 1, 2-diphenylethane diisocyanate and / or phenylene diisocyanate.
  • 4,4'-MDI is used.
  • aliphatic isocyanates are also preferred, as is indicated at the outset, particularly preferably i-isocyanato-SS ⁇ -trimethyl- ⁇ -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, due to the pre-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 polyoxytetramethylene glycols.
  • the polyetherols have the advantage that they have a higher hydrolysis stability than polyesterols.
  • low-unsaturated polyols 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 -Atomen in the alkylene radical, in particular 1, 3-propanediol, butanediol-1, 4, hexanediol-1, 6 and / or di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and or Dekaalkylen- glycols having 3 to 8 carbon atoms, preferably corresponding oligo- and / or
  • Polypropylene glycols although mixtures of 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 accelerate the reaction between the NCO groups of the diisocyanates (a) and the hydroxyl groups of the constituent components (b) and (c) are the tertiary amines known and customary in the prior art, such as Triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethylpiperazine, 2- (dimethylamino) ethoxy) 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 (III) - acetylacetonate, tin compounds, eg Zinndiacetat, Zinndi- octoate, tin dilaurate or Zinndialkylsalze aliphatic Carboxylic acids such as di-butyltin diacetate, dibutyltin dilaurate or the like.
  • the catalysts are usually
  • component (e) in addition to catalysts (d) can the constitutional components (a) to (c) and conventional auxiliaries and / or additives (e) are added.
  • auxiliaries and / or additives e.g. blowing agents, surface-active substances, fillers, nucleating agents, lubricants and mold release agents, dyes and pigments, antioxidants, e.g. against hydrolysis, light, heat or discoloration, inorganic and / or organic fillers, flame retardants, reinforcing agents and plasticizers, metal deactivators.
  • 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 preferred in an amount between 0.1 and 60 wt .-%, particularly preferably between 5 and
  • the thermoplastic polyurethane 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.
  • 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, more preferably greater than 700 g / mol and a maximum molecular weight of ⁇ 10,000 g / mol, preferably ⁇ 3,000 g / mol.
  • they are preferred a melting point of less than 18O 0 C.
  • antioxidants are preferably used, which are amorphous or liquid.
  • 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.
  • monofunctional alcohols monofunctional amines and / or monofunctional polyols.
  • 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.
  • thermoplastic polyurethane particles according to the invention for extrusion, injection molding, calendar articles and in particular for powder-slush process.
  • TPUs according to the invention which are present preferably in powder form according to the invention, in the powder-slush process or in injection molding, caulking and extrusion articles, e.g. to the desired films, moldings, rolls, fibers, linings in automobiles, hoses, cable connectors, bellows, trailing cables, cable sheathing, seals, belts or damping elements, can be carried out 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. Particularly preferred are the inventive
  • TPU used for the production of articles which are produced by powder-slush method, in particular instrument panels in automobiles, for example, foils for instrument panels.

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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)
  • Polyurethanes Or Polyureas (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

The invention relates to a method for producing thermoplastic polyurethane particles, characterised in that melted thermoplastic polyurethane is atomised to form droplets.

Description

Verfahren zur Herstellung von thermoplastischen PolyurethanpartikelnProcess for the preparation of thermoplastic polyurethane particles
Beschreibungdescription
Die Erfindung betrifft Verfahren zur Herstellung von bevorzugt runden thermoplastischen Polyurethanpartikeln, bevorzugt basierend auf aliphatischen Isocyanaten, besonders bevorzugt Hexamethylendiisocyanat, bevorzugt mit einem Schmelzindex nach DIN ISO 1133 (180°C/2,16 kg) zwischen 5 g/10min und 300 g/10min, besonders bevorzugt zwischen 10 g/10min und 200 g/10 min, insbesondere zwischen 15 g/10min und 200 g/10 min, bevorzugt einen Rieselfähigkeit nach DIN EN ISO 6186: 1998 von kleiner 15 sec/100g, bevorzugt kleiner 10 sec/100g und bevorzugt einem Partikeldurchmesser des Pulvers bevorzugt kleiner 2000 μm, besonders bevorzugt zwischen 50 μm und 1000 μm insbesondere zwischen 100 μm und 900 μm. Unter Partikeldurchmesser ist der maximale Durchmesser eines TPU-Partikels in dem Pulver zu ver- stehen, bevorzugt der mittlere Partikeldurchmesser in dem Pulver. Des weiteren bezieht sich die Erfindung auf derart erhältliche thermoplastische Polyurethanpartikel sowie Verfahren zur Herstellung von Artikeln auf der Basis von thermoplastischen Polyurethanen durch Sinterung von pulverisierten thermoplastischen Polyurethanen, wobei man als pulverisierte thermoplastische Polyurethane die erfindungsgemäß erhältlichen thermoplastischen Polyurethanpartikel einsetzt. Unter dem Ausdruck „rund" sind in dieser Schrift Formen zu verstehen, die keine Ecken oder Kanten aufweisen. Dabei kann es sich um tröpfchenförmige, kugelige oder andere Formen handeln, die ein Tropfen beim Fallen annehmen kann.The invention relates to processes for the preparation of preferably round thermoplastic polyurethane particles, preferably based on aliphatic isocyanates, more preferably hexamethylene diisocyanate, preferably having a melt index according to DIN ISO 1133 (180 ° C / 2.16 kg) between 5 g / 10min and 300 g / 10min , more preferably between 10 g / 10 min and 200 g / 10 min, in particular between 15 g / 10 min and 200 g / 10 min, preferably a flowability according to DIN EN ISO 6186: 1998 of less than 15 sec / 100 g, preferably less than 10 sec / 100 g and preferably a particle diameter of the powder preferably less than 2000 .mu.m, more preferably between 50 .mu.m and 1000 .mu.m, in particular between 100 .mu.m and 900 .mu.m. By particle diameter is meant the maximum diameter of a TPU particle in the powder, preferably the mean particle diameter in the powder. The invention further relates to thermoplastic polyurethane particles obtainable in this way and to processes for producing articles based on thermoplastic polyurethanes by sintering powdered thermoplastic polyurethanes, the thermoplastic polyurethane particles obtainable according to the invention being used as pulverized thermoplastic polyurethanes. By the term "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.
Thermoplastische Kunststoffe sind Kunststoffe, die, wenn es in dem für den Werkstoff für Verarbeitung und Anwendung typischen Temperaturbereich wiederholt erwärmt und abgekühlt wird, thermoplastisch bleiben. Unter thermoplastisch wird die Eigenschaft eines Kunststoffes verstanden, in einem für ihn typischen Temperaturbereich wiederholt in der Wärme zu erweichen und beim Abkühlen zu erhärten und im erweichten Zustand wiederholt durch Fließen als Formteil, Extrudat oder Umformteil zu Halbzeug oder Gegenständen formbar zu sein. Thermoplastische Kunststoffe sind in der Technik weit verbreitet und finden sich in der Form von Fasern, Platten, Folien, Formkörpern, Flaschen, Ummantelungen, Verpackungen usw. Thermoplastisches Polyurethan (nachstehend als TPU bezeichnet) ist ein Elastomer, der in vielen Anwendungen Ver- wendung findet, z.B. Schuhapplikationen, Folien, Fasern, Skistiefel, Schläuche.Thermoplastics are plastics that remain thermoplastic when repeatedly heated and cooled in the temperature range typical of the material for processing and application. By 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. Thermoplastic polyurethane (hereinafter referred to as TPU) is an elastomer which finds use in many applications , eg Shoe applications, foils, fibers, ski boots, hoses.
Die Herstellung der TPU erfolgt üblicherweise diskontinuierlich oder nach den bekannten Verfahren kontinuierlich, beispielsweise mit Reaktionsextrudern oder dem Bandverfahren nach One-shot- oder Prepolymerverfahren. Bei diesen Verfahren werden die zur Reaktion kommenden Komponenten, insbesondere Diisocyanat und Diol nacheinander oder gleichzeitig miteinander vermischt, wobei die Reaktion unmittelbar einsetzt. Beim Extruderverfahren werden die Ausgangskomponenten einzeln oder als Gemisch in den Extruder eingeführt, z.B. bei Temperaturen von 100 bis 28O0C, vorzugsweise 140 bis 25O0C zur Reaktion gebracht, das erhaltene TPU wird extrudiert, abgekühlt und granuliert.The preparation of the TPU is usually carried out batchwise or continuously by the known processes, for example with reaction extruders or the strip process by one-shot or prepolymer process. In these processes, the components to be reacted, in particular diisocyanate and diol, are mixed successively or simultaneously with one another, the reaction beginning immediately. In the extruder process, 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.
Die mit diesen bekannten Verfahren zugänglichen Produkte müssen nach einer Granu- lierung üblicherweise insbesondere zum Einsatz im powder-slush noch zerkleinert, z.B. gemahlen werden, um eine akzeptable Partikelgröße zu erreichen. Üblicherweise werden die Granulate bei tiefen Temperaturen (kryogen) gemahlen. Die dann erhaltenen Pulver enthalten unregelmäßige und kantige Partikel, die die Rieselfähigkeit negativ beeinflussen. Für bestimmte Anwendungen ist es allerdings erwünscht, das die TPU- Partikel eine möglichst ausgeprägte Rieselfähigkeit aufweisen. Dies gilt insbesondere im allgemein bekannten powder-slush. In diesem Verfahren wird pulverisiertes TPU überlicherweise in einer Form auf einer Oberfläche verteilt, die aufgeheizt ein Verschmelzen des TPU- Pulvers und damit die Herstellung einer TPU- „Haut" bewirkt. Wird bei diesem Verfahren eine Form verwendet, so ist eine möglichst schnelle und vollständige Verteilung des TPU- Pulvers auf der Oberfläche wünschenswert. Dies ist allerdings nur dann zu erreichen, wenn die Rieselfähigkeit des TPU- Pulvers ausreichend hoch ist.The products obtainable by these known processes usually have to be comminuted after granulation, in particular for use in powder slush, e.g. be ground to achieve an acceptable particle size. Usually, the granules are ground (cryogenically) at low temperatures. The powders then obtained contain irregular and angular particles, which adversely affect the flowability. For certain applications, however, it is desirable that the TPU particles have the greatest possible flowability. This is especially true in the well-known powder-slush. In this process, powdered TPU is usually distributed in a mold on a surface which, when heated, causes fusion of the TPU powder to produce a TPU "skin." When a mold is used in this process, it is as fast and complete as possible Distribution of the TPU powder on the surface is desirable, but this can only be achieved if the flowability of the TPU powder is sufficiently high.
Aufgabe der vorliegenden Erfindung war es somit, Verfahren zur Herstellung von ther- moplastischen Polyurethanpartikeln und derart erhältliche thermoplastische Polyurethanpartikel zu entwickeln, die über eine hohe Rieselfähigkeit verfügen, eine möglichst runde Form aufweisen und insbesondere im powder-slush- Verfahren eine schnelle und vollständige Bedeckung der Oberfläche ermöglichen.It was therefore an object of the present invention to develop processes for the production of thermoplastic polyurethane particles and thermoplastic polyurethane particles obtainable in this way, which have a high flowability, a shape which is as round as possible and, especially in the powder-slush process, rapid and complete coverage of the Enable surface.
Diese Aufgaben konnten dadurch gelöst werden, dass man geschmolzenes thermoplastisches Polyurethan vertropft. Unter dem Ausdruck „Vertropfen" ist in Sinne dieser Erfindung auch ein „Versprühen" zu verstehen. Gerade die erfindungsgemäßen runden TPU eigenen sich hervorragend für powder-slush- Verarbeitungen, da sie aufgrund ihrer runden Form sehr gut rieselfähig sind und deshalb einfach und schnell in die Form appliziert werden können und diese gut ausfüllen. Bislang werden gemahlene TPU im powder-slush eingesetzt, die allerdings aufgrund des Mahlvorgangs über eine nicht optimale Rieselfähigkeit verfügen und daher in der powder-slush- Anwendung ein Verbesserungspotential aufweisen.These tasks could be solved by dropping molten thermoplastic polyurethane. For the purposes of this invention, the expression "dripping" also means "spraying". Especially 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.
Die erfindungsgemäße Vertropfung kann durch allgemein bekannte Verfahren und Apparaturen zum Versprühen oder Vertropfen von Flüssigkeiten erfolgen. Entsprechende Verfahren sind unter anderem beschrieben für geschmolzene Polyester in WO 02/18113. Angaben über Prozessparameter, die auch Inhalt dieser Schrift sein sollen, sind ferner gegeben in WO 01/64326, Seite 12 bis Seite 14 sowie in DE-A 101 37 925, Seite 7, Zeilen 13 bis 39, insbesondere Zeilen 24 bis 39. Die Erzeugung des Sprühnebels bzw. der Tröpfchen durch das Versprühen und/oder Vertropfen des geschmolzenen TPU kann mittels gängiger Vorrichtungen zum Sprühen oder Vertropfen von Flüssigkeiten erfolgen, beispielsweise mittels Sprühdüsen, Vibra- tionsvertropfem und Schwingblenden-Aerosolgeneratoren.The dripping invention can be carried out by well-known methods and apparatuses for spraying or dropping liquids. Corresponding processes are described inter alia for molten polyesters in WO 02/18113. Information on process parameters, which should also be content of this document, are also given in WO 01/64326, page 12 to page 14 and in DE-A 101 37 925, page 7, lines 13 to 39, in particular lines 24 to 39. The generation of the spray or the droplets by the spraying and / or dripping of the molten TPU can be carried out by means of conventional devices for spraying or dripping liquids, for example by means of spray nozzles, Vibra- tionsvertropfem and vibrating diaphragm aerosol generators.
Das erfindungsgemäße Verfahren kann bevorzugt derart erfolgen, dass man das geschmolzene thermoplastische Polyurethan mittels einer Vertropfungsdüse zu Tropfen vertropft, besonders bevorzugt indem man das geschmolzene thermoplastische Polyurethan mittels einer in Schwingung versetzten Lochscheibe, die bevorzugt eine Fre- quenz zwischen 50 und 20000 Hz, besonders bevorzugt zwischen 70 und 5000 Hz aufweist, vertropft.The process according to the invention can preferably be carried out by dropwise dripping the molten thermoplastic polyurethane by means of a dropletizing nozzle, particularly preferably by particularly preferring the molten thermoplastic polyurethane by means of a vibrated perforated disk, which preferably has a frequency between 50 and 20,000 Hz between 70 and 5000 Hz, dripped.
Die Temperatur des geschmolzenen TPU beim Versprühen und/oder Vertropfen beträgt bevorzugt zwischen 140 und 2600C, besonders bevorzugt zwischen 160 und 2200C.The temperature of the molten TPU during spraying and / or dripping is preferably 140 to 260 0 C, particularly preferably 160-220 0 C.
Der sich beim Versprühen einstellende Tröpfchendurchmesser beträgt erfindungsgemäß bevorzugt kleiner 2000 μm, besonders bevorzugt kleiner 1200 μm, insbesondere zwischen 50 μm bis 1200 μm.The droplet diameter which is obtained during spraying is preferably less than 2000 .mu.m, more preferably less than 1200 .mu.m, in particular between 50 .mu.m and 1200 .mu.m, according to the invention.
Das Vertropfen und/oder Versprühen wird vorzugsweise in Apparaten durchgeführt, die auch für die Sprühtrocknung geeignet sind. Derartige Reaktoren werden beispielsweise in K. Masters, Spray Drying Handbook, 5th Edition, Longman, 1991 , Seiten 23 bis 66, beschrieben.The dripping and / or spraying is preferably carried out in apparatus 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.
Bevorzugt wird das erfindungsgemäße Verfahren in Apparaten durchgeführt, in denen die Sprühtröpfchen frei fallen können. Geeignet dazu sind Apparaturen, wie beispielsweise in der Patentschrift US 5 269 980 beschrieben.The process according to the invention is preferably carried out in apparatuses in which the spray droplets can fall freely. Suitable for this purpose are apparatuses as described, for example, in US Pat. No. 5,269,980.
Bevorzugt werden Reaktoren eingesetzt, die aufgrund ihrer Höhe den Sprühtröpfchen eine Mindestverweilzeit bieten, bevor die Tröpfchen sich z.B. auf dem Boden des Reaktors sammeln. Bevorzugt wird man somit das geschmolzene thermoplastische Polyurethan in einen Sprühturm vertropfen. Dabei weist der Sprühturm bevorzugt eine Höhe zwischen 2 m und 30 m auf. Besonders bevorzugt ist dabei die Vorrichtung zum Sprühen und/oder Vertropfen der TPU mindestens in einer Höhe zwischen 2,6 m und 12 m vom Boden des Fallturms entfernt. Nach dem Sprühen der Mischung in dieser Höhe in den Reaktionsraum kann der Sprühnebel bzw. die Tropfen getrieben durch die Schwerkraft Richtung Boden des Fallturms fallen. Bevorzugt vertropft oder versprüht man das TPU am Kopf des Fallturms. Bevorzugt kann in dem Fallturm in vertikaler Richtung, d.h. in Abhängigkeit seiner Höhe, ein Temperaturprofil, besonders bevorzugt eine nach unten fallende Temperatur vorliegen.Preference is given to using reactors which, owing to their height, provide the spray droplets with a minimum residence time before the droplets collect, for example, on the bottom of the reactor. Preferably, therefore, the molten thermoplastic polyurethane is dripped into a spray tower. In this case, the spray tower preferably has a height between 2 m and 30 m. In this case, the device for spraying and / or dripping the TPU is particularly preferably at least at a height of between 2.6 m and 12 m from the bottom of the drop tower. After spraying the mixture at this height into the reaction space, the spray or droplets, driven by gravity, can fall towards the bottom of the drop tower. Preferably, the TPU is dripped or sprayed on the head of the drop tower. Preferably, in the fall tower in the vertical direction, that is, depending on its height, a temperature profile, more preferably a downward falling temperature.
Bevorzugt kann am Boden des Fallturms eine Wirbelschicht vorliegen. Wirbelschichtreaktoren sind insbesondere für Umsetzungen mit Feststoffen allgemein bekannt. Diese Wirbelschicht bietet den Vorteil, dass die Zugabe von flüssigen und/oder festen Additiven (z.B. Flammschutzmitteln, Farbpigmenten, etc.) möglich ist. Bevorzugt wird man somit oberhalb und/oder in der Wirbelschicht den flüssigen und/oder festen Tropfen Zusatzstoffe (e) zugeben.Preferably, a fluidized bed may be present at the bottom of the drop tower. Fluidized bed reactors are well known in particular for reactions with solids. This fluidized bed offers the advantage that the addition of liquid and / or solid additives (e.g., flame retardants, color pigments, etc.) is possible. It is therefore preferred to add additives (e) to the liquid and / or solid droplets above and / or in the fluidized bed.
Der Fallturm wird bevorzugt von einem Inertgas, d.h. insbesondere einem Stoff, der bei der gewählten Temperatur und dem Druck im Reaktor im gasförmigen Zustand vorliegt und gegenüber Isocyanaten inert ist, besonders bevorzugt Stickstoff, durchströmt. Be- vorzugt ist die Gleichstromfahrweise, das heißt, das Inertgas durchströmt den Reaktor von oben nach unten. Die Inertgasgeschwindigkeit wird vorzugsweise so eingestellt, dass die Strömung im Reaktor bevorzugt laminar ist und beträgt bevorzugt 0,02 bis 1 ,5 m/s, bevorzugt 0,05 bis 0,4 m/s.The falling tower is preferably powered by 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. Preferred is the DC mode, 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.
Die mit dem erfindungsgemäßen Verfahren erhältlichen TPU- Partikel liegen üblicherweise in pulverisierter Form vor und können in dieser Form zum Beispiel am Boden des Reaktors gesammelt und nach allgemein bekannten Verfahren, z.B. mittels Förderschnecke entnommen, gegebenenfalls getempert und weiterverarbeitet werden, z.B. durch Extrusion oder Spritzguss.The TPU particles obtainable by the process according to the invention are usually present in powdered form and can be collected in this form, for example, at the bottom of the reactor and purified by generally known methods, e.g. be removed by means of screw conveyor, optionally tempered and further processed, e.g. by extrusion or injection molding.
Das thermoplastische Polyurethan wird erfindungsgemäß in geschmolzenem Zustand vertropft bzw. versprüht. Dabei kann das TPU, das z.B. in granulierter Form vorliegen kann, in der Vertropfungsapparatur geschmolzen werden. Bevorzugt wird das TPU allerdings in geschmolzenen Zustand aus einem Extruder in eine Vertropfungsvorrich- tung eingeführt. Dabei kann es sich bei dem Extruder sowohl um einen Reaktionsextruder handeln, in dem das TPU synthetisiert wird, als auch um einen Extruder, der mit granuliertem TPU gespeist wird, das gegebenenfalls direkt von einer Bandanlage kommen kann.The thermoplastic polyurethane is dripped or sprayed in a molten state according to the invention. In this case, the TPU, e.g. may be in granulated form, are melted in the Vertropfungsapparatur. However, the TPU is preferably introduced in molten state from an extruder into a dropping device. The extruder may be both a reaction extruder in which the TPU is synthesized and an extruder fed with granulated TPU, which may optionally come directly from a belt mill.
Verfahren zur Herstellung von thermoplastischen Polyurethanen, in dieser Schrift auch als TPU bezeichnet, sind allgemein bekannt. Im allgemeinen werden TPUs durch Umsetzung von (a) Isocyanaten mit (b) gegenüber Isocyanaten reaktiven Verbindungen, üblicherweise mit einem Molekulargewicht (Mw) von 500 bis 10000, bevorzugt 500 bis 5000, besonders bevorzugt 800 bis 3000 und (c) Kettenverlängerungsmitteln mit einem Molekulargewicht von 50 bis 499 gegebenenfalls in Gegenwart von (d) Katalysatoren und/oder (e) üblichen Zusatzstoffen hergestellt. Im Folgenden sollen beispielhaft die Ausgangskomponenten und Verfahren zur Herstellung der bevorzugten Polyurethane dargestellt werden. Die bei der Herstellung der Polyurethane üblicherweise verwendeten Komponenten (a), (b), (c) sowie gegebenenfalls (d) und/oder (e) sollen im Folgenden beispielhaft beschrieben werden:Processes for the production of thermoplastic polyurethanes, also referred to in this document as TPU, are well known. In general, 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. In the following, by way of example, the starting components and processes for the preparation of the preferred polyurethanes are shown. The components (a), (b), (c) and optionally (d) and / or (e) usually used in the preparation of the polyurethanes are described below by way of example:
a) Als organische Isocyanate (a) können allgemein bekannte aliphatische, cyclo- aliphatische, araliphatische und/oder aromatische Isocyanate eingesetzt werden, beispielsweise Tri-, Tetra-, Penta-, Hexa-, Hepta- und/oder Oktamethylendiiso- cyanat, 2-MethyI-pentamethylen-düsocyanat-1 ,5, 2-Ethyl-butylen-diiso- cyanat-1 ,4, Pentamethylen-diisocyanat-1 ,5, Butylen-diisocyanat-1 ,4, 1 -Iso- cyanato-3,3,5-trimethyl-5-isocyanato-methyl-cyclohexan (Isophoron-diisocyanat, IPDI), 1 ,4- und/oder 1,3-Bis(isocyanatomethyl)cyclohexan (HXDI), 1 ,4-Cyclo- hexan-diisocyanat, 1-Methyl-2,4- und/oder -2,6-cyclohexan-di-isocyanat und/oder 4,4-, 2,4- und 2,2'-Dicyclohexylmethan-diisocyanat, 2,2'-, 2,4'- und/oder 4,4'-Diphenylmethandiisocyanat (MDI), 1 ,5-Naphthylendiisocyanata) As organic isocyanates (a) 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, Methyl-pentamethylene-diisocyanate-1, 5, 2-ethyl-butylene-diisocyanate-1, 4, pentamethylene-diisocyanate-1, 5, butylene-diisocyanate-1, 4, 1-iso-cyanato-3,3, 5-trimethyl-5-isocyanato-methylcyclohexane (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 and / or 4,4-, 2,4- and 2,2'-dicyclohexylmethane diisocyanate, 2,2'-, 2, 4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), 1, 5-naphthylene diisocyanate
(NDI)1 2,4- und/oder 2,6-Toluylendiisocyanat (TDI), Diphenylmethandiisocyanat, 3,3'-Dimethyl-diphenyl-diisocyanat, 1 ,2-Diphenylethandiisocyanat und/oder Phenylendiisocyanat. Bevorzugt wird 4,4'-MDI verwendet. Für powder-slush- Anwendungen sind, wie eingangs dargestellt auch aliphatische Isocyanate be- vorzugt, besonders bevorzugt i-lsocyanato-S.S.δ-trimethyl-δ-isocyanato-methyl- cyclohexan (Isophoron-diisocyanat, IPDI) und/oder Hexamethylendiisocyanat (HDI), insbesondere Hexamethylendiisocyanat. Wie bereits eingangs dargestellt können als Isocyanat (a) auch Prepolymer eingesetzt werden, die frei Isocya- natgruppen aufweisen. Der NCO-Gehalt dieser Prepolymere beträgt bevorzugt zwischen 10 und 25 %. Die Prepolymere können den Vorteil bieten, dass aufgrund der Vorreaktion bei der Herstellung der Prepolymere eine geringere Reaktionszeit bei der Herstellung der TPU benötigt wird.(NDI) 1 2,4- and / or 2,6-toluene diisocyanate (TDI), diphenylmethane diisocyanate, 3,3'-dimethyl-diphenyl-diisocyanate, 1, 2-diphenylethane diisocyanate and / or phenylene diisocyanate. Preferably, 4,4'-MDI is used. For powder slush applications, aliphatic isocyanates are also preferred, as is indicated at the outset, particularly preferably i-isocyanato-SSδ-trimethyl-δ-isocyanato-methylcyclohexane (isophorone diisocyanate, IPDI) and / or hexamethylene diisocyanate (HDI), in particular hexamethylene diisocyanate. As already mentioned at the outset, it is also possible to use, as 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, due to the pre-reaction in the preparation of the prepolymers, a shorter reaction time is required in the production of the TPU.
b) Als gegenüber Isocyanaten reaktive Verbindungen (b) können die allgemein be- kannten gegenüber Isocyanaten reaktiven Verbindungen eingesetzt werden, beispielsweise Polyesterole, Polyetherole und/oder Polycarbonatdiole, die üblicherweise auch unter dem Begriff "Polyole" zusammengefasst werden, mit Molekulargewichten zwischen 500 und 8000, bevorzugt 600 bis 6000, insbesondere 800 bis weniger als 3000, und bevorzugt einer mittleren Funktionalität gegenüber Isocyanaten von 1 ,8 bis 2,3, bevorzugt 1 ,9 bis 2,2, insbesondere 2. Bevorzugt setzt man Polyetherpolyole ein, beispielsweise solche auf der Basis von allgemein bekannten Startersubstanzen und üblichen Alkylenoxiden, beispielsweise Ethylenoxid, Propylenoxid und/oder Butylenoxid, bevorzugt Polyetherole basierend auf Propylenoxid-1 ,2 und Ethylenoxid und insbesondere Polyoxy- tetramethylen-glykole. Die Polyetherole weisen den Vorteil auf, dass sie eine höhere Hydrolysestabilität als Polyesterole besitzen. Weiterhin können als Polyetherole sogenannte niedrig ungesättigte Polyetherole verwendet werden. Unter niedrig ungesättigten Polyolen werden im Rahmen dieser Erfindung insbesondere Polyetheralkohole mit einem Gehalt an ungesättigten Verbindungen von kleiner als 0,02 meg/g, bevorzugt kleiner als 0,01 meg/g, verstanden.b) As isocyanate-reactive compounds (b) it is possible to use the generally known 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 polyoxytetramethylene glycols. The polyetherols have the advantage that they have a higher hydrolysis stability than polyesterols. Furthermore, it is possible to use as polyetherols so-called low-unsaturated polyetherols. In the context of this invention, low-unsaturated polyols 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.
Derartige Polyetheralkohole werden zumeist durch Anlagerung von Alkylenoxiden, insbesondere Ethylenoxid, Propylenoxid und Mischungen daraus, an die oben beschriebenen Diole oder Triole in Gegenwart von hochaktiven Katalysatoren hergestellt. Derartige hochaktive Katalysatoren sind beispielsweise Cäsiumhydroxid und Multi- metallcyanidkatalysatoren, auch als DMC-Katalysatoren bezeichnet. Ein häufig eingesetzter DMC-Katalysator ist das Zinkhexacyanocobaltat. Der DMC-Katalysator kann nach der Umsetzung im Polyetheralkohol belassen werden, üblicherweise wird er entfernt, beispielsweise durch Sedimentation oder Filtration.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. Such highly active catalysts are, for example, cesium hydroxide and multimetal cyanide catalysts, also referred to as 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.
Weiterhin können Polybutadiendiole mit einer Molmasse von 500 - 10000 g/mol bevorzugt 1000-5000 g/mol, insbesondere 2000 - 3000 g/mol verwendet werden. TPU's welche unter der Verwendung dieser Polyole hergestellt wurden, können nach thermoplastischer Verarbeitung strahlenvernetzt werden. Dies führt z.B. zu einem besseren Abbrennverhalten.Furthermore, 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.
Statt eines Polyols können auch Mischungen verschiedener Polyole eingesetzt werden.Instead of a polyol, it is also possible to use mixtures of different polyols.
c) Als Kettenverlängerungsmittel (c) können allgemein bekannte aliphatische, arali- phatische, aromatische und/oder cycloaliphatische Verbindungen mit einem Molekulargewicht von 50 bis 499, bevorzugt 2-funktionelle Verbindungen, eingesetzt werden, beispielsweise Diamine und/oder Alkandiole mit 2 bis 10 C-Atomen im Alkylenrest, insbesondere 1 ,3-Propandiol, Butandiol-1 ,4, Hexandiol-1 ,6 und/oder Di-, Tri-, Tetra-, Penta-, Hexa-, Hepta-, Okta-, Nona- und/oder Dekaalkylen- glykole mit 3 bis 8 Kohlenstoffatomen, bevorzugt entsprechende Oligo- und/oderc) As 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 -Atomen in the alkylene radical, in particular 1, 3-propanediol, butanediol-1, 4, hexanediol-1, 6 and / or di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and or Dekaalkylen- glycols having 3 to 8 carbon atoms, preferably corresponding oligo- and / or
Polypropylenglykole, wobei auch Mischungen der Kettenverlängerer eingesetzt werden können.Polypropylene glycols, although mixtures of chain extenders can be used.
Besonders bevorzugt handelt es sich bei den Komponenten a) bis c) um difunktionelle Verbindungen, d.h. Diisocyanate (a), difunktionelle Polyole, bevorzugt Polyetherole (b) und difunktionelle Kettenverlängerungsmittel, bevorzugt Diole.Most preferably, components a) to c) are difunctional compounds, i. Diisocyanates (a), difunctional polyols, preferably polyetherols (b) and difunctional chain extenders, preferably diols.
d) Geeignete Katalysatoren, welche insbesondere die Reaktion zwischen den NCO-Gruppen der Diisocyanate (a) und den Hydroxylgruppen der Aufbau- komponenten (b) und (c) beschleunigen, sind die nach dem Stand der Technik bekannten und üblichen tertiären Amine, wie z.B. Triethylamin, Dimethylcyclo- hexylamin, N-Methylmorpholin, N,N'-Dimethylpiperazin, 2-(Dimethylamino- ethoxy)-ethanol, Diazabicyclo-(2,2,2)-octan und ähnliche sowie insbesondere organische Metallverbindungen wie Titansäureester, Eisenverbindungen wie z.B. Eisen— (III)— acetylacetonat, Zinnverbindungen, z.B. Zinndiacetat, Zinndi- octoat, Zinndilaurat oder die Zinndialkylsalze aliphatischer Carbonsäuren wie Di- butylzinndiacetat, Dibutylzinndilaurat oder ähnliche. Die Katalysatoren werden üblicherweise in Mengen von 0,0001 bis 0,1 Gew. -Teilen pro 100 Gew. -Teile Po- lyhydroxylverbindung (b) eingesetzt.d) Suitable catalysts which in particular accelerate the reaction between the NCO groups of the diisocyanates (a) and the hydroxyl groups of the constituent components (b) and (c) are the tertiary amines known and customary in the prior art, such as Triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethylpiperazine, 2- (dimethylamino) ethoxy) 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 (III) - acetylacetonate, tin compounds, eg Zinndiacetat, Zinndi- octoate, tin dilaurate or Zinndialkylsalze aliphatic Carboxylic acids such as di-butyltin diacetate, dibutyltin dilaurate or the like. The catalysts are usually used in amounts of from 0.0001 to 0.1 parts by weight per 100 parts by weight of polyhydroxyl compound (b).
e) Neben Katalysatoren (d) können den Aufbaukomponenten (a) bis (c) auch übliche Hilfsmittel und/oder Zusatzstoffe (e) hinzugefügt werden. Genannt seien beispielsweise Treibmittel, oberflächenaktive Substanzen, Füllstoffe, Keimbildungsmittel, Gleit- und Entformungshilfen, Farbstoffe und Pigmente, Anti- oxidantien, z.B. gegen Hydrolyse, Licht, Hitze oder Verfärbung, anorganische und/oder organische Füllstoffe, Flammschutzmittel, Verstärkungsmittel und Weichmacher, Metalldeaktivatoren. In einer bevorzugten Ausführungsform fallen unter die Komponente (e) auch Hydrolyseschutzmittel wie beispielsweise polymere und niedermolekulare Carbodiimide. Besonders bevorzugt enthält das thermoplastische Polyurethan in den erfindungsgemäßen Materialien Melamin- cyanurat, das als Flammschutzmittel wirkt. Bevorzugt wird Melamincyanurat in einer Menge zwischen 0,1 und 60 Gew.-%, besonders bevorzugt zwischen 5 unde) In addition to catalysts (d) can the constitutional components (a) to (c) and conventional auxiliaries and / or additives (e) are added. Examples which may be mentioned are blowing agents, surface-active substances, fillers, nucleating agents, lubricants and mold release agents, dyes and pigments, antioxidants, e.g. against hydrolysis, light, heat or discoloration, inorganic and / or organic fillers, flame retardants, reinforcing agents and plasticizers, metal deactivators. In a preferred embodiment, component (e) also includes hydrolysis protectants such as, for example, polymeric and low molecular weight carbodiimides. The thermoplastic polyurethane in the materials according to the invention particularly preferably contains melamine cyanurate, which acts as a flame retardant. Melamine cyanurate is preferred in an amount between 0.1 and 60 wt .-%, particularly preferably between 5 and
40 Gew.-%, insbesondere zwischen 15 und 25 Gew.-% eingesetzt, jeweils bezogen auf das Gesamtgewicht des TPU. Bevorzugt enthält das thermoplastische Polyurethan Triazol und/oder Triazolderivat und Antioxidantien in einer Menge von 0,1 bis 5 Gew.-% bezogen auf das Gesamtgewicht des thermoplastischen Polyurethans. Als Antioxidantien sind im allgemeinen Stoffe geeignet, welche unerwünschte oxidative Prozesse im zu schützenden Kunststoff hemmen oder verhindern. Im allgemeinen sind Antioxidantien kommerziell erhältlich. Beispiele für Antioxidantien sind sterisch gehinderte Phenole, aromatische Amine, Thiosynergisten, Organophosphorverbindungen des trivalenten Phosphors, und Hindered Amine Light Stabilizers. Beispiele für Sterisch gehinderte Phenole finden sich in Plastics Additive Handbook, 5m edition, H. Zweifel, ed, Hanser Publishers, München, 2001 ([1]), S.98-107 und S.116- 121. Beispiele für Aromatische Amine finden sich in [1] S.107-108. Beispiele für Thiosynergisten sind gegeben in [1], S.104-105 und S.112-113. Beispiele für Phosphite finden sich in [1], S.109-112.Beispiele für Hindered Amine Light40 wt .-%, in particular between 15 and 25 wt .-% used, each based on the total weight of the TPU. Preferably, the thermoplastic polyurethane 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. As 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 sterically hindered phenols can be found in Plastics Additive Handbook, 5 m edition, H. Zweifel, ed, Hanser Publishers, Munich, 2001 ([1]), p.98-107 and p.116-121. 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
Stabilizer sind gegeben in [1], S.123-136. Zur Verwendung im erfindungsgemäßem Antioxidantiengemisch eignen sich bevorzugt phenolische Antioxidantien. In einer bevorzugten Ausführungsform weisen die Antioxidantien, insbesondere die phenolischen Antioxidantien, eine Molmasse von größer 350 g/mol, besonders bevorzugt von größer 700g/mol und einer maximalen Molmasse < 10000 g/mol bevorzugt < 3000 g/mol auf. Ferner besitzen sie bevorzugt einen Schmelzpunkt von kleiner 18O0C. Weiterhin werden bevorzugt Antioxidantien verwendet, die amorph oder flüssig sind.Stabilizers are given in [1], p.123-136. Phenolic antioxidants are preferred for use in the antioxidant mixture according to the invention. In a preferred embodiment, the antioxidants, in particular the phenolic antioxidants, have a molecular weight of greater than 350 g / mol, more preferably greater than 700 g / mol and a maximum molecular weight of <10,000 g / mol, preferably <3,000 g / mol. Furthermore, they are preferred a melting point of less than 18O 0 C. Further, antioxidants are preferably used, which are amorphous or liquid.
Neben den genannten Komponenten a), b) und c) und gegebenenfalls d) und e) können auch Kettenregler, üblicherweise mit einem Molekulargewicht von 31 bis 3000, eingesetzt werden. Solche Kettenregler sind Verbindungen, die lediglich eine gegenüber Isocyanaten reaktive funktionelle Gruppe aufweisen, wie z. B. monofunktionelle Alkohole, monofunktionelle Amine und/oder monofunktionelle Polyole. Durch solche Kettenregler kann ein Fließverhalten, insbesondere bei TPUs, gezielt eingestellt werden. Kettenregler können im allgemeinen in einer Menge von 0 bis 5, bevorzugt 0,1 bis 1 Gew.-Teile, bezogen auf 100 Gew.-Teile der Komponente b) eingesetzt werden und fallen definitionsgemäß unter die Komponente (c).In addition to the abovementioned components a), b) and c) and optionally d) and e) it is also possible to use 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. As monofunctional alcohols, monofunctional amines and / or monofunctional polyols. By means of such chain regulators, 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).
Alle in dieser Schrift genannten Molekulargewichte weisen die Einheit [g/mol] auf.All molecular weights mentioned in this document have the unit [g / mol].
Zur Einstellung der Härte der TPUs können die Aufbaukomponenten (b) und (c) in relativ breiten molaren Verhältnissen variiert werden. Bewährt haben sich molare Verhältnisse von Komponente (b) zu insgesamt einzusetzenden Kettenverlängerungsmitteln (c) von 10 : 1 bis 1 : 10, insbesondere von 1 : 1 bis 1 : 4, wobei die Härte der TPU mit zunehmendem Gehalt an (c) ansteigt.To adjust the hardness of the TPUs, the structural components (b) and (c) can be varied in relatively wide molar ratios. Proven molar ratios of component (b) to total used chain extenders (c) of 10: 1 to 1:10, in particular from 1: 1 to 1: 4, the hardness of the TPU increases with increasing content of (c).
Verwendung können die erfindungsgemäßen thermoplastisch verarbeitbaren Polyurethanpartikel für Extrusions-, Spritzguss-, Kalenderartikel sowie insbesondere für Powder-slush-Verfahren finden.Use can find the thermoplastic polyurethane particles according to the invention for extrusion, injection molding, calendar articles and in particular for powder-slush process.
Die Verarbeitung der erfindungsgemäß hergestellten TPUs, die erfindungsgemäß bevorzugt in Pulverform vorliegen, im Powder-Slush-Verfahren oder zu Spritzguss-, Ka- lendar- und Extrusionsartikeln, z.B. zu den gewünschten Folien, Formteilen, Rollen, Fasern, Verkleidungen in Automobilen, Schläuchen, Kabelsteckern, Faltenbälgen, Schleppkabeln, Kabelummantelungen, Dichtungen, Riemen oder Dämpfungselementen, kann nach üblichen Verfahren erfolgen. Derartige Spritzguss und Extrusionsartikel können auch aus Compounds, enthaltend das erfindungsgemäße TPU und mindestens einen weiteren thermoplastischen Kunststoff, besonders ein Polyethylen, Polypropylen, Polyester, Polyether, Polystyrol, PVC, ABS, ASA, SAN, Polyacrylnitril, EVA, PBT, PET, Polyoxymethylen, bestehen. Besonders bevorzugt werden die erfindungsgemäßenThe processing of the TPUs according to the invention, which are present preferably in powder form according to the invention, in the powder-slush process or in injection molding, caulking and extrusion articles, e.g. to the desired films, moldings, rolls, fibers, linings in automobiles, hoses, cable connectors, bellows, trailing cables, cable sheathing, seals, belts or damping elements, can be carried out 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. Particularly preferred are the inventive
TPU zur Herstellung von Artikeln eingesetzt, die mittels powder-slush Verfahren hergestellt werden, insbesondere Instrumententafeln in Automobilen, beispielweise Folien für Instrumententafeln. TPU used for the production of articles which are produced by powder-slush method, in particular instrument panels in automobiles, for example, foils for instrument panels.

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von thermoplastischen Polyurethanpartikeln, dadurch gekennzeichnet, dass man geschmolzenes thermoplastisches Polyurethan ver- tropft.1. A process for the preparation of thermoplastic polyurethane particles, characterized in that dripping molten thermoplastic polyurethane.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass man das geschmolzene thermoplastische Polyurethane mittels einer Vertropfungsdüse zu Tropfen vertropft.2. The method according to claim 1, characterized in that the molten thermoplastic polyurethane is dripped by means of a drip nozzle to drip.
3. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass man das geschmolzene thermoplastische Polyurethane mittels einer in Schwingung versetzten Lochscheibe vertropft.3. The method according to claim 1, characterized in that the molten thermoplastic polyurethane is dripped by means of a vibrated perforated disc.
4. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass man das geschmolzene thermoplastische Polyurethan in einen Sprühturm vertropft.4. The method according to claim 1, characterized in that dripping the molten thermoplastic polyurethane in a spray tower.
5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, dass der Sprühturm eine Höhe zwischen 2 m und 30 m aufweist.5. The method according to claim 4, characterized in that the spray tower has a height between 2 m and 30 m.
6. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass Tropfen des thermoplastischen Polyurethans einen Durchmesser zwischen 50 und 2000 μm aufweisen.6. The method according to claim 1, characterized in that drops of the thermoplastic polyurethane have a diameter between 50 and 2000 microns.
7. Verfahren gemäß Anspruch 1 , dadurch gekennzeichnet, dann man das thermoplastische Polyurethan in geschmolzenem Zustand aus einem Extruder in eine Vertropfungsvorrichtung einführt.7. The method according to claim 1, characterized by then introducing the thermoplastic polyurethane in a molten state from an extruder into a dropletizer.
8. Thermoplastische Polyurethanpartikel erhältlich durch ein Verfahren gemäß ei- nem der Ansprüche 1 bis 7.8. Thermoplastic polyurethane particles obtainable by a process according to one of claims 1 to 7.
9. Verfahren zur Herstellung von Artikeln auf der Basis von thermoplastischen Polyurethanen durch Sinterung von pulverisierten thermoplastischen Polyurethanen, dadurch gekennzeichnet, dass man als pulverisierte thermoplastische PoIy- urethane thermoplastische Polyurethanpartikel gemäß Anspruch 8 einsetzt. 9. A process for the preparation of articles based on thermoplastic polyurethanes by sintering powdered thermoplastic polyurethanes, characterized in that is used as powdered thermoplastic polyurethanes thermoplastic polyurethane particles according to claim 8.
PCT/EP2005/014156 2005-01-10 2005-12-31 Method for producing thermoplastic polyurethane particles WO2006072461A1 (en)

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