EP1833878A1 - Fine-grained polyarylene ether ketone powder - Google Patents

Fine-grained polyarylene ether ketone powder

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Publication number
EP1833878A1
EP1833878A1 EP05816251A EP05816251A EP1833878A1 EP 1833878 A1 EP1833878 A1 EP 1833878A1 EP 05816251 A EP05816251 A EP 05816251A EP 05816251 A EP05816251 A EP 05816251A EP 1833878 A1 EP1833878 A1 EP 1833878A1
Authority
EP
European Patent Office
Prior art keywords
ether ketone
polyarylene ether
paek
powder
ketone powder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05816251A
Other languages
German (de)
French (fr)
Inventor
Alexander Richter
Patrick Kreidler
Holger Renners
Wolfgang Christoph
Heinrich Temme
Christian Bierhaus
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Evonik Degussa GmbH
Degussa GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Evonik Degussa GmbH, Degussa GmbH filed Critical Evonik Degussa GmbH
Publication of EP1833878A1 publication Critical patent/EP1833878A1/en
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B13/00—Conditioning or physical treatment of the material to be shaped
    • B29B13/10—Conditioning or physical treatment of the material to be shaped by grinding, e.g. by triturating; by sieving; by filtering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/46—Post-polymerisation treatment, e.g. recovery, purification, drying
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • B29B2009/125—Micropellets, microgranules, microparticles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2071/00—Use of polyethers, e.g. PEEK, i.e. polyether-etherketone or PEK, i.e. polyetherketone or derivatives thereof, as moulding material
    • 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
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
    • C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK

Definitions

  • the invention relates to a fine-grained polyarylene ether ketone (PAEK), its preparation by grinding of porous PAEK and its use.
  • PAEK polyarylene ether ketone
  • the grinding of polymers with different grinding units and grinding processes is an established technology that is already used for a wide variety of grinding products, for example, for polyesters, polyamides or polyolefins. These polymers are usually ground from the corresponding commercial granular form in a cryogenic milling process to the corresponding powders. Usually, pin mills or fluidized bed mills are used at operating temperatures of up to -60 ° C. PAEK and in particular polyetheretherketone (PEEK) are characterized among others by excellent tribological and mechanical properties; They are therefore very difficult and with great effort to a fine powder to be ground.
  • PEEK polyetheretherketone
  • Another method known from WO 99/50339 is to mix PAEK with another polymer and thereby determine the particle shape of the PAEK. After dissolving the other polymer in a suitable solvent, the powdered PAEK is exposed. This method is very expensive. On this basis, the object of the invention was to find a little complicated grinding process with improved Mahlausbeute for the production of fine-grained PAEK powder.
  • This object has been achieved by a process in which a porous PAEK having a BET surface area of more than 1 m 2 / g, preferably of more than 4 m 2 / g, more preferably of more than 8 m 2 / g and particularly preferred of more than 12 m 2 / g is ground to a powder.
  • the porous PAEK is usually prepared by reacting an aromatic dihalogen compound with a bisphenol and / or a halophenol in the presence of alkali or alkaline earth carbonate or bicarbonate in a high boiling aprotic solvent to a PAEK, discharging and solidifying the melt, optionally grinding, z , In a hammer mill, extracting the resulting particles with one or more organic solvents to remove the reaction solvent and with water to remove the inorganic salts, and then drying.
  • the particles to be extracted may be prepared from the reaction mixture other than by milling, also by granulating an extruded strand, applying a drop to a chilled metal strip, prilling or spray-drying.
  • the degree of porosity obtained after the extraction depends in particular on the content of reaction solvent in the material to be extracted. In this respect, it is advantageous to remove only a portion of the reaction solvent during spray drying. Otherwise, the way in which the particles to be extracted are produced is not critical.
  • Method was prepared and is in a compact form, for. B. as granules are dissolved in a suitable high-boiling aprotic solvent, whereupon the hot solution, as described above for the melt obtained in the reaction, converted into particle form and extracted with one or more organic solvents.
  • T represents a direct bond, an oxygen atom or two hydrogen atoms
  • Z and Z ' are hydrogen or phenyl groups. This is preferably diphenylsulfone.
  • the PAEK contains units of the formulas
  • Ar and Ar ' represent a bivalent aromatic radical, preferably 1,4-phenylene, 4,4'-biphenylene and 1,4-, 1,5- or 2,6-naphthylene.
  • X is an electron-withdrawing group, preferably carbonyl or sulfonyl, while Y represents another group such as O, S, CH 2 , isopropylidene or the like.
  • at least 50%, preferably at least 70% and particularly preferably at least 80% of the groups X represent a carbonyl group, while at least 50%, preferably at least 70% and particularly preferably at least 80% of the groups Y should consist of oxygen.
  • the PAEK may be, for example, a polyetheretherketone (PEEK; Formula I), a polyetherketone (PEK; Formula II), a polyetherketone ketone (PEKK; Formula III), or a polyetheretherketone ketone (PEEKK; Formula IV), but of course other arrangements are contemplated the carbonyl and Oxygen groups possible.
  • the PAEK is generally semicrystalline, as evidenced, for example, in the DSC analysis by finding a crystalline melting point T m , which is of the order of magnitude of 300 ° C or higher in most cases.
  • T m crystalline melting point
  • the teaching of the invention is also applicable to amorphous PAEK.
  • sulfonyl groups, biphenylene groups, naphthylene groups or bulky groups Y such as.
  • As an isopropylidene group reduce the crystallinity.
  • the viscosity number measured according to DIN EN ISO 307, on a solution of 250 mg PAEK in 50 ml of 96% by weight H 2 SO 4 at 25 ° C, about 20 to 150 cmVg and preferably 50 to 120 cmVg.
  • the BET surface area is determined according to DIN ISO 9277.
  • the porous PAEK can be ground at room temperature or elevated temperature, but to improve grinding and milling yield it is advantageous to ground at a lower temperature, preferably below 0 ° C, more preferably below -20 ° C, and most preferably below ⁇ 40 ° C.
  • a lower temperature preferably below 0 ° C, more preferably below -20 ° C, and most preferably below ⁇ 40 ° C.
  • pin mills fluidized bed counter-jet mills or baffle mills are suitable.
  • the porous structure of the PAEK to be grounded provides weak points which lead to breakage under the abovementioned conditions.
  • the regrind can be subsequently screened or sieved.
  • a finely powdered PAEK having a number average particle diameter (d 50 ) of 1 to 300 .mu.m, preferably from 4 to 200 .mu.m, more preferably from 10 to 150 .mu.m, particularly preferably from 15 to 120 .mu.m and very particularly preferably from 20 to 100 microns are obtained.
  • the determination of the particle diameter and its distribution is carried out by laser diffraction according to DIN ISO 13320-1.
  • the PAEK powder can then additives such.
  • inorganic pigments such as titanium dioxide, carbon black and the like or processing aids may be added, for example as a dry blend.
  • the ultrafine powdery PAEK thus obtained can be used for coating, e.g. As of metal (eg., Steel) or ceramic objects by means of electrostatic coating, vortex sintering or
  • Coating with a PAEK suspension in water can be used. In these cases can it as an inorganic processing aid z.
  • Example 1 Particles of PEEK with a BET surface area of 50 m 2 / g and an average grain diameter of 500 ⁇ m were ground using a cryogen-working pin mill (Hosokawa Alpine CW 160).
  • the PEEK particles were conveyed via a screw conveyor into a grinding chamber and, in the meantime, cooled down to - 50 ° C with liquid nitrogen.
  • the PEEK particles were accelerated by rotating pin disks to 220 m / s. At this speed, they impacted the pins on the pin disks, exposing them to strong impact, causing the particles to break. This happened with a throughput of PEEK particles of 15 kg / h.
  • the grinding chamber left a micronized product with a proportion of particles smaller than 100 microns of 30 wt .-% (sieve analysis with Alpine air jet sieve according to DIN EN ISO 4610).
  • the process cut of separation followed.
  • the crushed PEEK particles were fractionated using an Alpine air jet screen with a downstream cyclone.
  • the fractionation was carried out at a mesh size of 80 microns.
  • the powder thus obtained was characterized by a d 10 of 16.7 ⁇ m, d 50 of 52.6 ⁇ m and d 90 of 113.8 ⁇ m.
  • Example 2 The procedure was as in Example 1, but with a throughput of 20 kg / h.
  • the grinding chamber left a micronized product with a proportion of particles smaller than 100 microns of 30 wt .-%. After micronization, the process intersection of separation took place.
  • the crushed PEEK particles were fractionated using a zigzag sifter.
  • the operating parameters of the zigzag sifter were: revolutions 10,000 min -1 , drag air 65 mVh
  • the powder thus obtained was characterized by a d 10 of 8.5 ⁇ m, d 50 of 21.4 ⁇ m and d 90 of 54.9 ⁇ m.

Abstract

The invention relates to a milling method for producing fine-grained polyarylene ether ketone. Said method is characterised in that a porous polyarylene ether ketone with a BET surface area greater than 1 m2/g is milled.

Description

Feinkörniges PolyarylenetherketonpulverFine-grained polyarylene ether ketone powder
Die Erfindung betrifft ein feinkörniges Polyarylenetherketon (PAEK), seine Herstellung durch Mahlen von porösem PAEK sowie seine Verwendung.The invention relates to a fine-grained polyarylene ether ketone (PAEK), its preparation by grinding of porous PAEK and its use.
Die Vermahlung von Polymeren mit unterschiedlichsten Mahlaggregaten und Mahlverfahren ist eine etablierte Technologie, die bereits für verschiedenste Mahlprodukte eingesetzt wird, beispielsweise für Polyester, Polyamide oder Polyolefine. Diese Polymere werden üblicherweise aus der entsprechenden handelsüblichen Granulatform in einem kryogenen Mahlverfahren zu den entsprechenden Pulvern vermählen. Dazu werden normalerweise Stiftmühlen oder Fließbettmühlen bei Betriebstemperaturen von bis zu -60 °C eingesetzt. PAEK und insbesondere Polyetheretherketon (PEEK) zeichnen sich unter anderem durch hervorragende tribologische und mechanische Eigenschaften aus; sie sind daher nur sehr schwer und mit hohem Aufwand zu einem Feinpulver zu vermählen. In der DE 38 44 457 Al wird die Kaltvermahlung von PAEK auf einer Fließbettmühle beschrieben, wobei Feinpulver mit einer mittleren Korngröße von 40 μm oder weniger erhalten werden. Nachteilig ist hier jedoch die Ausbeute, die mit maximal 7,5 kg/h deutlich unter den üblichen Durchsätzen einer Mahleinrichtung zurückbleibt. Hier kommen die technischen Schwierigkeiten, ein PAEK zu vermählen, zum Ausdruck.The grinding of polymers with different grinding units and grinding processes is an established technology that is already used for a wide variety of grinding products, for example, for polyesters, polyamides or polyolefins. These polymers are usually ground from the corresponding commercial granular form in a cryogenic milling process to the corresponding powders. Usually, pin mills or fluidized bed mills are used at operating temperatures of up to -60 ° C. PAEK and in particular polyetheretherketone (PEEK) are characterized among others by excellent tribological and mechanical properties; They are therefore very difficult and with great effort to a fine powder to be ground. In DE 38 44 457 Al, the cold milling of PAEK is described on a fluidized bed mill, whereby fine powder having an average particle size of 40 microns or less are obtained. However, the disadvantage here is the yield, which remains at a maximum of 7.5 kg / h, well below the usual throughputs of a grinder. Here are the technical difficulties to marry a PAEK.
Es gab daher gelegentlich Ansätze, den Mahlschritt bei der Pulverherstellung zu umgehen und auf alternativen Routen zu pulverförmigem oder feinst-pulverförmigem PAEK zu gelangen. So wird in der US 5 910 558 die Herstellung von PAEK-Mikropulvern durch Prillen von Schmelzen oder durch Sprühtrocknen der Lösungen beschrieben. Dieses Verfahren hat sich jedoch wegen des hohen apparativen Aufwands und der geringen Prozessstabilität nicht durchsetzen können.Therefore, there were occasional attempts to circumvent the grinding step in powder production and to arrive at alternative routes to powdery or ultrafine powdered PAEK. For example, US Pat. No. 5,910,558 describes the preparation of PAEK micropowders by prilling melts or by spray-drying the solutions. However, this method has not been able to prevail because of the high equipment cost and the low process stability.
Eine weitere aus der WO 99/50339 bekannte Methode besteht darin, PAEK mit einem anderen Polymer zu mischen und dabei die Partikelform des PAEK festzulegen. Nach Auflösen des anderen Polymers in einem geeigneten Lösemittel wird das pulverförmige PAEK freigelegt. Diese Methode ist allerdings sehr aufwendig. Hiervon ausgehend bestand die Aufgabe der Erfindung darin, ein wenig aufwendiges Mahlverfahren mit verbesserter Mahlausbeute zur Herstellung von feinkörnigem PAEK-Pulver aufzufinden.Another method known from WO 99/50339 is to mix PAEK with another polymer and thereby determine the particle shape of the PAEK. After dissolving the other polymer in a suitable solvent, the powdered PAEK is exposed. This method is very expensive. On this basis, the object of the invention was to find a little complicated grinding process with improved Mahlausbeute for the production of fine-grained PAEK powder.
Diese Aufgabe wurde durch ein Verfahren gelöst, bei dem ein poröses PAEK mit einer BET- Oberfläche von mehr als 1 m2/g, bevorzugt von mehr als 4 m2/g, besonders bevorzugt von mehr als 8 m2/g und insbesondere bevorzugt von mehr als 12 m2/g zu einem Pulver vermählen wird.This object has been achieved by a process in which a porous PAEK having a BET surface area of more than 1 m 2 / g, preferably of more than 4 m 2 / g, more preferably of more than 8 m 2 / g and particularly preferred of more than 12 m 2 / g is ground to a powder.
Das poröse PAEK wird in der Regel hergestellt durch Umsetzung einer aromatischen Dihalogenverbindung mit einem Bisphenol und/oder eines Halogenphenols in Gegenwart von Alkali- oder Erdalkalicarbonat oder -hydrogencarbonat in einem hochsiedenden aprotischen Lösemittel zu einem PAEK, Austragen und Erstarrenlassen der Schmelze, gegebenenfalls Mahlen, z. B. in einer Hammermühle, Extrahieren der entstandenen Partikel mit einem oder mehreren organischen Lösemitteln zwecks Entfernung des Reaktionslösemittels sowie mit Wasser zwecks Entfernung der anorganischen Salze, und anschließendes Trocknen. Die zu extrahierenden Partikel können aus dem Reaktionsgemisch außer durch Mahlen auch durch Granulieren eines extrudierten Strangs, Tropfenauftrag auf ein gekühltes Metallband, Prillen oder Sprühtrocknen hergestellt werden. Der Grad der nach der Extraktion erhaltenen Porosität hängt insbesondere vom Gehalt an Reaktionslösemittel im zu extrahierenden Gut ab. Insofern ist es vorteilhaft, beim Sprühtrocknen nur einen Teil des Reaktionslösemittels zu entfernen. Ansonsten ist die Art, wie die zu extrahierenden Partikel erzeugt werden, unkritisch.The porous PAEK is usually prepared by reacting an aromatic dihalogen compound with a bisphenol and / or a halophenol in the presence of alkali or alkaline earth carbonate or bicarbonate in a high boiling aprotic solvent to a PAEK, discharging and solidifying the melt, optionally grinding, z , In a hammer mill, extracting the resulting particles with one or more organic solvents to remove the reaction solvent and with water to remove the inorganic salts, and then drying. The particles to be extracted may be prepared from the reaction mixture other than by milling, also by granulating an extruded strand, applying a drop to a chilled metal strip, prilling or spray-drying. The degree of porosity obtained after the extraction depends in particular on the content of reaction solvent in the material to be extracted. In this respect, it is advantageous to remove only a portion of the reaction solvent during spray drying. Otherwise, the way in which the particles to be extracted are produced is not critical.
Das Herstellverfahren von PAEK mit anschließender Extraktion ist in einer großen Anzahl von Patentanmeldungen beschrieben, beispielsweise EP-A-O 001 879, EP-A-O 182 648, EP-A- 0 244 167 und EP-A-O 322 151.The production process of PAEK with subsequent extraction is described in a large number of patent applications, for example EP-A-0 001 879, EP-A-0 182 648, EP-A-0 244 167 and EP-A-0 322 151.
Im Rahmen der Erfindung kann jedoch auch ein PAEK, das eventuell nach einem anderenHowever, within the scope of the invention may also be a PAEK, possibly after another
Verfahren hergestellt wurde und das in kompakter Form vorliegt, z. B. als Granulat, in einem geeigneten hochsiedenden aprotischen Lösemittel aufgelöst werden, worauf die heiße Lösung, so wie oben für die bei der Reaktion erhaltene Schmelze beschrieben, in Partikelform überführt und mit einem oder mehreren organischen Lösemitteln extrahiert wird.Method was prepared and is in a compact form, for. B. as granules are dissolved in a suitable high-boiling aprotic solvent, whereupon the hot solution, as described above for the melt obtained in the reaction, converted into particle form and extracted with one or more organic solvents.
Das hochsiedende aprotische Lösemittel ist gemäß dem Stand der Technik vorzugsweise eine Verbindung der FormelThe high-boiling aprotic solvent is preferably a compound of the formula according to the prior art
wobei T eine direkte Bindung, ein Sauerstoffatom oder zwei Wasserstoffatome darstellt; Z und Z' sind Wasserstoff oder Phenylgruppen. Bevorzugt handelt es sich hier um Diphenylsulfon.wherein T represents a direct bond, an oxygen atom or two hydrogen atoms; Z and Z 'are hydrogen or phenyl groups. This is preferably diphenylsulfone.
Das PAEK enthält Einheiten der FormelnThe PAEK contains units of the formulas
(-Ar-X-) und (-Ar' -Y-),(-Ar-X-) and (-Ar'-Y-),
wobei Ar und Ar' einen zweiwertigen aromatischen Rest darstellen, vorzugsweise 1,4- Phenylen, 4,4 '-Biphenylen sowie 1,4-, 1,5- oder 2,6-Naphthylen. X ist eine elektronenziehende Gruppe, bevorzugt Carbonyl oder Sulfonyl, während Y eine andere Gruppe wie O, S, CH2, Isopropyliden oder dergleichen darstellt. Hierbei sollten mindestens 50 %, bevorzugt mindestens 70 % und besonders bevorzugt mindestens 80 % der Gruppen X eine Carbonylgruppe darstellen, während mindestens 50 %, bevorzugt mindestens 70 % und besonders bevorzugt mindestens 80 % der Gruppen Y aus Sauerstoff bestehen sollten.wherein Ar and Ar 'represent a bivalent aromatic radical, preferably 1,4-phenylene, 4,4'-biphenylene and 1,4-, 1,5- or 2,6-naphthylene. X is an electron-withdrawing group, preferably carbonyl or sulfonyl, while Y represents another group such as O, S, CH 2 , isopropylidene or the like. In this case, at least 50%, preferably at least 70% and particularly preferably at least 80% of the groups X represent a carbonyl group, while at least 50%, preferably at least 70% and particularly preferably at least 80% of the groups Y should consist of oxygen.
In der insbesondere bevorzugten Ausführungsform bestehen 100 % der Gruppen X aus Carbonylgruppen und 100 % der Gruppen Y aus Sauerstoff. In dieser Ausführungsform kann das PAEK beispielsweise ein Polyetheretherketon (PEEK; Formel I), ein Polyetherketon (PEK; Formel II), ein Polyetherketonketon (PEKK; Formel III) oder ein Polyetheretherketonketon (PEEKK; Formel IV) sein, jedoch sind natürlich auch andere Anordnungen der Carbonyl- und Sauerstoffgruppen möglich.In the most preferred embodiment, 100% of the X groups are carbonyl groups and 100% of the Y groups are oxygen. In this embodiment, the PAEK may be, for example, a polyetheretherketone (PEEK; Formula I), a polyetherketone (PEK; Formula II), a polyetherketone ketone (PEKK; Formula III), or a polyetheretherketone ketone (PEEKK; Formula IV), but of course other arrangements are contemplated the carbonyl and Oxygen groups possible.
Das PAEK ist im Allgemeinen teilkristallin, was sich beispielsweise in der DSC-Analyse durch Auffinden eines Kristallitschmelzpunkts Tm äußert, der größenordnungsmäßig in den meisten Fällen um 300 °C oder darüber liegt. Jedoch ist die Lehre der Erfindung auch auf amorphe PAEK anwendbar. Im Allgemeinen gilt, dass Sulfonylgruppen, Biphenylengruppen, Naphthylengruppen oder sperrige Gruppen Y, wie z. B. eine Isopropylidengruppe, die Kristallinität verringern.The PAEK is generally semicrystalline, as evidenced, for example, in the DSC analysis by finding a crystalline melting point T m , which is of the order of magnitude of 300 ° C or higher in most cases. However, the teaching of the invention is also applicable to amorphous PAEK. In general, it is true that sulfonyl groups, biphenylene groups, naphthylene groups or bulky groups Y, such as. As an isopropylidene group, reduce the crystallinity.
In einer bevorzugten Ausführungsform beträgt die Viskositätszahl, gemessen entsprechend DIN EN ISO 307 an einer Lösung von 250 mg PAEK in 50 ml 96-gewichtsprozentiger H2SO4 bei 25 °C, etwa 20 bis 150 cmVg und bevorzugt 50 bis 120 cmVg.In a preferred embodiment, the viscosity number, measured according to DIN EN ISO 307, on a solution of 250 mg PAEK in 50 ml of 96% by weight H 2 SO 4 at 25 ° C, about 20 to 150 cmVg and preferably 50 to 120 cmVg.
Die BET-Oberfläche wird gemäß DIN ISO 9277 bestimmt.The BET surface area is determined according to DIN ISO 9277.
Das poröse PAEK kann bei Raumtemperatur oder erhöhter Temperatur vermählen werden, jedoch ist es zur Verbesserung der Vermahlung und der Mahlausbeute vorteilhaft, bei tieferer Temperatur zu vermählen, bevorzugt unterhalb von 0 °C, besonders bevorzugt unterhalb von -20 °C und insbesondere bevorzugt unterhalb von →40 °C. Zum Vermählen eignen sich unter anderem Stiftmühlen, Fließbettgegenstrahlmühlen oder Pralltellermühlen. Hierbei sorgt die poröse Struktur des zu mahlenden PAEK für Schwachstellen, die unter den obengenannten Bedingungen zum Bruch führen.The porous PAEK can be ground at room temperature or elevated temperature, but to improve grinding and milling yield it is advantageous to ground at a lower temperature, preferably below 0 ° C, more preferably below -20 ° C, and most preferably below → 40 ° C. For grinding, among other things pin mills, fluidized bed counter-jet mills or baffle mills are suitable. In this case, the porous structure of the PAEK to be grounded provides weak points which lead to breakage under the abovementioned conditions.
Das Mahlgut kann nachträglich gesichtet oder gesiebt werden. Je nach eingesetztem Mahlgut und anschließendem Trennverfahren kann ein feinpulvriges PAEK mit einem zahlenmittleren Partikeldurchmesser (d50) von 1 bis 300 μm, bevorzugt von 4 bis 200 μm, besonders bevorzugt von 10 bis 150 μm, insbesondere bevorzugt von 15 bis 120 μm und ganz besonders bevorzugt von 20 bis 100 μm erhalten werden. In einer besonders vorteilhaften Ausführungsform stellt man auf diese Weise ein feinstpulveriges PAEK mit einem d50 von 15 bis 80 μm und einem d90 von kleiner als 160 μm und bevorzugt eines mit einem d50 von 20 bis 50 μm und einem d90 von kleiner als 100 μm her.The regrind can be subsequently screened or sieved. Depending on the millbase used and subsequent separation process, a finely powdered PAEK having a number average particle diameter (d 50 ) of 1 to 300 .mu.m, preferably from 4 to 200 .mu.m, more preferably from 10 to 150 .mu.m, particularly preferably from 15 to 120 .mu.m and very particularly preferably from 20 to 100 microns are obtained. In a particularly advantageous embodiment, a very finely powdered PAEK with a d 50 of 15 to 80 μm and a d 90 of less than 160 μm and preferably one with a d 50 of 20 to 50 μm and a d 90 of less than 100 μm ago.
Die Bestimmung der Teilchendurchmesser und deren Verteilung erfolgt durch Laserbeugung nach DIN ISO 13320-1.The determination of the particle diameter and its distribution is carried out by laser diffraction according to DIN ISO 13320-1.
Dem PAEK-Pulver können anschließend Zusatzstoffe wie z. B. anorganische Pigmente wie Titandioxid, Ruß und dergleichen oder Verarbeitungshilfsmittel zugesetzt werden, beispielsweise als Trockenmischung.The PAEK powder can then additives such. For example, inorganic pigments such as titanium dioxide, carbon black and the like or processing aids may be added, for example as a dry blend.
Das so erhaltene feinstpulverige PAEK kann zum Beschichten, z. B. von Metall- (z. B. Stahl-) oder Keramikgegenständen mittels elektrostatischer Beschichtung, Wirbelsintern oderThe ultrafine powdery PAEK thus obtained can be used for coating, e.g. As of metal (eg., Steel) or ceramic objects by means of electrostatic coating, vortex sintering or
Beschichtung mit einer PAEK-Suspension in Wasser, verwendet werden. In diesen Fällen kann es als anorganisches Verarbeitungshilfsmittel z. B. Al2O3 oder SiO2 (etwa Aerosil) enthalten. Es ist darüber hinaus geeignet zur Herstellung von Composites, beispielsweise durch Imprägnieren von Verstärkungsfasergewebe mit dem Pulver und anschließendes Verpressen bei ausreichend hoher Temperatur. Darüber hinaus kann es auch z. B. durch Sintern oder heißisostatisches Pressen zu Formteilen verarbeitet werden.Coating with a PAEK suspension in water, can be used. In these cases can it as an inorganic processing aid z. B. Al 2 O 3 or SiO 2 (such as Aerosil) included. It is also suitable for the production of composites, for example by impregnating reinforcing fiber fabric with the powder and then pressing at a sufficiently high temperature. In addition, it may also be z. B. processed by sintering or hot isostatic pressing to form parts.
Die Erfindung soll im Folgenden beispielhaft erläutert werden.The invention will be explained by way of example below.
Beispiel 1: Partikel aus PEEK mit einer BET-Oberfläche von 50 m2/g und einem mittleren Korndurchmesser von 500 μm wurden mit Hilfe einer cryogen arbeitenden Stiftmühle (Hosokawa Alpine CW 160) gemahlen. Dabei wurden die PEEK-Partikel über eine Förderschnecke in einen Mahlraum gefördert und währenddessen mit flüssigem Stickstoff auf - 50 °C heruntergekühlt. In diesem Mahlraum wurden die PEEK-Partikel durch rotierende Stiftscheiben auf 220 m/s beschleunigt. Mit dieser Geschwindigkeit prallten sie auf die auf den Stiftscheiben angebrachten Stifte und wurden so einer starken Prallbeanspruchung ausgesetzt, die zum Bruch der Partikel führte. Dies geschah mit einem Durchsatz an PEEK-Partikeln von 15 kg/h. Den Mahlraum verließ ein micronisiertes Produkt mit einem Anteil von Partikeln kleiner als 100 μm von 30 Gew.-% (Siebanalyse mit Alpine Luftstrahlsieb nach DIN EN ISO 4610).Example 1 Particles of PEEK with a BET surface area of 50 m 2 / g and an average grain diameter of 500 μm were ground using a cryogen-working pin mill (Hosokawa Alpine CW 160). The PEEK particles were conveyed via a screw conveyor into a grinding chamber and, in the meantime, cooled down to - 50 ° C with liquid nitrogen. In this grinding chamber, the PEEK particles were accelerated by rotating pin disks to 220 m / s. At this speed, they impacted the pins on the pin disks, exposing them to strong impact, causing the particles to break. This happened with a throughput of PEEK particles of 15 kg / h. The grinding chamber left a micronized product with a proportion of particles smaller than 100 microns of 30 wt .-% (sieve analysis with Alpine air jet sieve according to DIN EN ISO 4610).
Nach dem Micronisieren schloss sich der Prozessschnitt des Separierens an. Dabei wurden die zerkleinerten PEEK-Partikel mit Hilfe eines Alpine Luftstrahlsiebes mit nachgeschaltetem Zyklon fraktioniert. Die Fraktionierung erfolgte bei einer Maschenweite von 80 μm. Das so erhaltene Pulver war charakterisiert durch einen d10 von 16,7 μm, d50 von 52,6 μm und d90 von 113,8 μm.After micronization, the process cut of separation followed. The crushed PEEK particles were fractionated using an Alpine air jet screen with a downstream cyclone. The fractionation was carried out at a mesh size of 80 microns. The powder thus obtained was characterized by a d 10 of 16.7 μm, d 50 of 52.6 μm and d 90 of 113.8 μm.
Beispiel 2:Example 2:
Es wurde wie im Beispiel 1 gearbeitet, jedoch mit einem Durchsatz von 20 kg/h. Den Mahlraum verließ ein micronisiertes Produkt mit einem Anteil von Partikeln kleiner als 100 μm von 30 Gew.-%. Nach dem Micronisieren fügte sich der Prozessschnitt des Separierens an. Dabei wurden die zerkleinerten PEEK-Partikel mit Hilfe eines Zickzacksichters fraktioniert. Die Betriebsparameter des Zickzacksichters waren: Umdrehungen 10.000 min"1, Schleppluft 65 mVh. Das so erhaltene Pulver war charakterisiert durch einen d10 von 8,5 μm, d50 von 21,4 μm und d90 von 54,9 μm.The procedure was as in Example 1, but with a throughput of 20 kg / h. The grinding chamber left a micronized product with a proportion of particles smaller than 100 microns of 30 wt .-%. After micronization, the process intersection of separation took place. The crushed PEEK particles were fractionated using a zigzag sifter. The operating parameters of the zigzag sifter were: revolutions 10,000 min -1 , drag air 65 mVh The powder thus obtained was characterized by a d 10 of 8.5 μm, d 50 of 21.4 μm and d 90 of 54.9 μm.
Vergleichsbeispiel 1:Comparative Example 1
Es wurde versucht, PEEK-Granulat (BET-Oberfläche kleiner als 0,1 m7g) mit Hilfe einer cryogen arbeitenden Stiftmühle (Hosokawa Alpine CW 160) zu zerkleinern. Dabei wurden die PEEK-Partikel über eine Förderschnecke in einen Mahlraum gefördert und währenddessen mit flüssigem Stickstoff auf -70 °C herunter gekühlt. In diesem Mahlraum wurden die PEEK- Partikel durch rotierende Stiftscheiben auf 220 m/s beschleunigt. Mit dieser Geschwindigkeit prallten sie auf die auf den Stiftscheiben angebrachten Stifte und wurden so einer starken Prallbeanspruchung ausgesetzt. Der Durchsatz an PEEK-Granulat betrug 15 kg/h. Den Mahlraum verließ ein Produkt mit einem Anteil von Partikeln kleiner als 100 μm von 2 Gew.- %. Nach dreimaligem Durchführen dieser Prozedur ergab sich ein Anteil kleiner als 100 μm von 7 Gew.-%. Aufgrund des niedrigen Wirkungsgrades bei der Vermahlung wurde auf eine Separierung verzichtet. An attempt was made to crush PEEK granules (BET surface area less than 0.1 m7g) using a cryogenic pencil mill (Hosokawa Alpine CW 160). The PEEK particles were conveyed via a screw conveyor into a grinding chamber and cooled down to -70 ° C with liquid nitrogen. In this grinding chamber, the PEEK particles were accelerated by rotating pin disks to 220 m / s. With this speed, they hit the pins on the pin disks and were subjected to a strong impact load. The throughput of PEEK granules was 15 kg / h. The grinding chamber left a product with a proportion of particles smaller than 100 microns of 2% by weight. After performing this procedure three times, the proportion was less than 100 μm by 7% by weight. Due to the low efficiency in the milling was dispensed with a separation.

Claims

Patentansprüche: claims:
1. Verfahren zur Herstellung eines Polyarylenetherketon-Pulvers, dadurch gekennzeichnet, dass ein poröses Polyarylenetherketon mit einer BET-Oberfläche von mehr als 1 m2/g vermählen wird.1. A process for the preparation of a polyarylene ether ketone powder, characterized in that a porous polyarylene ether ketone having a BET surface area of more than 1 m 2 / g is ground.
2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, dass das poröse Polyarylenetherketon bei einer Temperatur unterhalb von 0 °C vermählen wird.2. The method according to claim 1, characterized in that the porous polyarylene ether ketone is ground at a temperature below 0 ° C.
3. Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das vermahlene Produkt gesichtet oder gesiebt wird.A method according to any one of the preceding claims, characterized in that the milled product is sifted or sieved.
4. Verfahren gemäß Anspruch 3, dadurch gekennzeichnet, dass das erhaltene Polyarylenetherketon-Pulver einen zahlenmittleren Partikeldurchmesser d50 von 1 bis 300 μm besitzt.4. The method according to claim 3, characterized in that the resulting polyarylene ether ketone powder has a number average particle diameter d 50 of 1 to 300 microns.
5. Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Polyarylenetherketon ein PEEK, ein PEK, ein PEKK oder ein PEEKK ist.5. The method according to any one of the preceding claims, characterized in that the polyarylene ether ketone is a PEEK, a PEK, a PEKK or a PEEKK.
6. Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Polyarylenetherketon eine Viskositätszahl von 20 bis 150 cmVg besitzt.6. The method according to any one of the preceding claims, characterized in that the polyarylene ether ketone has a viscosity number of 20 to 150 cmVg.
7. Polyarylenetherketon-Pulver, hergestellt gemäß einem der vorhergehenden Ansprüche. 7. Polyarylene ether ketone powder prepared according to one of the preceding claims.
8. Polyarylenetherketonpulver gemäß Anspruch 7, dadurch gekennzeichnet, dass es zugemischte anorganische Pigmente oder Verarbeitungshilfsmittel enthält.8. Polyarylene ether ketone powder according to claim 7, characterized in that it contains admixed inorganic pigments or processing aids.
9. Verwendung eines Polyarylenetherketon-Pulvers gemäß einem der Ansprüche 7 und 8 zum Beschichten oder zur Herstellung von Composites oder Formteilen. 9. Use of a polyarylene ether ketone powder according to any one of claims 7 and 8 for coating or for the production of composites or molded parts.
EP05816251A 2004-12-21 2005-11-22 Fine-grained polyarylene ether ketone powder Withdrawn EP1833878A1 (en)

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Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004062761A1 (en) * 2004-12-21 2006-06-22 Degussa Ag Use of polyarylene ether ketone powder in a three-dimensional powder-based tool-less production process, and moldings produced therefrom
DE102007016656B4 (en) * 2007-04-05 2018-10-11 Eos Gmbh Electro Optical Systems PAEK powder, in particular for use in a process for producing a three-dimensional object in layers, and method for its production
CN104109250B (en) * 2008-05-21 2017-04-12 东丽株式会社 Method For Producing Polymer Fine Particle
GB0813093D0 (en) * 2008-07-17 2008-08-27 Invibio Ltd Polymeric materials
FR2982519B1 (en) * 2011-11-10 2020-02-21 Arkema France PROCESS OF CRUSHING POLYARYL ETHER CETONES
CN103566827A (en) * 2012-07-12 2014-02-12 金发科技股份有限公司 Homogeneous solution polymerized high molecular polymer and refining method thereof
WO2014100320A1 (en) 2012-12-19 2014-06-26 Oxford Performance Materials, Inc. Method for preparing fine powders for use in selective laser sintering processes
WO2014130275A2 (en) 2013-02-22 2014-08-28 Ticona Llc High performance polymer composition with improved flow properties
FR3015506B1 (en) * 2013-12-20 2017-04-21 Arkema France COMPOSITION OF POLY-ARYLENE-ETHER-KETONE-KETONES POWDERS ALLOWING EXCELLENT COMPROMISE COULABILITY AND COALESCENCE ADAPTED FOR LASER SINTERING
GB2526243B (en) 2014-02-24 2021-07-14 Victrex Mfg Ltd Polymeric materials
US20160053107A1 (en) 2014-08-21 2016-02-25 Ticona Llc Composition Containing a Polyaryletherketone and Low Naphthenic Liquid Crystalline Polymer
KR102367667B1 (en) 2014-08-21 2022-02-24 티코나 엘엘씨 Polyaryletherketone composition
WO2016057253A1 (en) 2014-10-08 2016-04-14 Ticona Llc Dispersant for use in synthesis of polyaryletherketones
FR3027834B1 (en) * 2014-11-03 2017-11-10 Arkema France PROCESS FOR THE DENSIFICATION OF POLYARYLENE ETHER-KETONE POWDERS
US10882215B2 (en) 2015-12-28 2021-01-05 Arkema Inc. Processes for producing polymer powders
US11352480B2 (en) 2016-03-18 2022-06-07 Ticona Llc Polyaryletherketone composition
PL3293232T3 (en) 2016-09-08 2021-01-25 Igp Pulvertechnik Ag Powder paint and method of preparing a powder paint
JP7046489B2 (en) 2017-01-06 2022-04-04 住友化学株式会社 Manufacturing method of resin fine particles, resin particles
CN107618122B (en) * 2017-10-31 2019-08-30 山东凯盛新材料股份有限公司 The preparation method of polyether ketone ketone fine powder
CN107674560A (en) * 2017-10-31 2018-02-09 山东凯盛新材料股份有限公司 The preparation method of the antistatic spray coating powder paint of PEKK
US11118053B2 (en) 2018-03-09 2021-09-14 Ticona Llc Polyaryletherketone/polyarylene sulfide composition
JP7338316B2 (en) * 2018-08-31 2023-09-05 株式会社リコー RESIN POWDER AND METHOD FOR MANUFACTURING 3D MODEL
WO2020156950A1 (en) 2019-01-31 2020-08-06 Solvay Specialty Polymers Usa, Llc Method of grinding poly(ether ketone ketone) (pekk)
US20200247012A1 (en) * 2019-02-05 2020-08-06 Scott DeFelice Method for Grinding Materials for Additive Manufacturing
RU2691409C1 (en) * 2019-02-18 2019-06-13 Российская Федерация, от имени которой выступает ФОНД ПЕРСПЕКТИВНЫХ ИССЛЕДОВАНИЙ Method of producing heat-resistant aromatic polyester ester- and copolyester ether ketones with improved physical and mechanical properties
FR3127496A1 (en) 2021-09-28 2023-03-31 Arkema France Powder based on polyaryletherketone(s) for the manufacture of ductile objects.

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5670057A (en) * 1979-11-12 1981-06-11 Asahi Chem Ind Co Ltd Preparation of powdered resin composition
DE3518277A1 (en) 1984-10-06 1986-04-10 Hüls AG, 4370 Marl THERMOPLASTIC MASSES BASED ON POLYPHENYLENE ETHERS AND POLYOCTENYLENE AND METHOD FOR THE PRODUCTION THEREOF
US5247052A (en) * 1988-12-31 1993-09-21 Hoechst Aktiengesellschaft Fine-grained polyether-ketone powder, process for the manufacture thereof, and the use thereof
DE3844457A1 (en) * 1988-12-31 1990-07-12 Hoechst Ag FINE-GRINED POLYETHERKETONE POWDER, METHOD FOR THE PRODUCTION AND USE THEREOF
JPH08323748A (en) * 1995-05-29 1996-12-10 Toho Rayon Co Ltd Molding material and manufacture thereof
JPH11320691A (en) * 1998-05-21 1999-11-24 Tosoh Corp Thermoplastic resin powder and molding made of it
JP4152521B2 (en) * 1999-04-16 2008-09-17 旭化成ケミカルズ株式会社 Production method of polyphenylene ether powder with improved particle size distribution
AU2002354454A1 (en) 2001-12-11 2003-06-23 Mitsui Chemicals, Inc. Polyether ketone and method for production thereof
JP2004203919A (en) * 2002-12-24 2004-07-22 Inoac Corp Method for producing thermoplastic resin powder
US20050207931A1 (en) * 2004-03-21 2005-09-22 Toyota Motorsport Gmbh unknown
DE102004062761A1 (en) 2004-12-21 2006-06-22 Degussa Ag Use of polyarylene ether ketone powder in a three-dimensional powder-based tool-less production process, and moldings produced therefrom

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006067017A1 *

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