WO2019053238A1 - Procédé de fabrication additive pour fabriquer un objet tridimensionnel à l'aide d'un frittage laser sélectif - Google Patents

Procédé de fabrication additive pour fabriquer un objet tridimensionnel à l'aide d'un frittage laser sélectif Download PDF

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WO2019053238A1
WO2019053238A1 PCT/EP2018/074983 EP2018074983W WO2019053238A1 WO 2019053238 A1 WO2019053238 A1 WO 2019053238A1 EP 2018074983 W EP2018074983 W EP 2018074983W WO 2019053238 A1 WO2019053238 A1 WO 2019053238A1
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polymer
polymer material
ether
pei
peek
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PCT/EP2018/074983
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English (en)
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Stéphane JEOL
Christopher Ward
Vito Leo
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Solvay Specialty Polymers Usa, Llc
Solvay Sa
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Publication of WO2019053238A1 publication Critical patent/WO2019053238A1/fr

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/141—Processes of additive manufacturing using only solid materials
    • B29C64/153—Processes of additive manufacturing using only solid materials using layers of powder being selectively joined, e.g. by selective laser sintering or melting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • 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
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials

Definitions

  • the present disclosure relates to an additive manufacturing (AM) method for making a three-dimensional (3D) object, using a powdered polymer material (M) comprising at least one poly(ether ether ketone) (PEEK) polymer, in particular to a 3D object obtainable by laser sintering from this powdered polymer material (M).
  • AM additive manufacturing
  • Additive manufacturing systems are used to print or otherwise build 3D objects from a digital blueprint created with computer-aided design (CAD) modelling software.
  • Selective laser sintering uses electromagnetic radiation from a laser to fuse powdered materials into a mass. The laser selectively fuses the powdered material by scanning cross-sections generated from the digital blueprint of the object on the surface of a powder bed. After a cross-section is scanned, the powder bed is lowered by one layer thickness, a new layer of material is applied, and the bed is rescanned. Locally full coalescence of polymer particles in the top powder layer is necessary as well as an adhesion with previous sintered layers. This process is repeated until the object is completed.
  • the powdered material is generally preheated to a processing temperature close to the melting point (Tm) of the resin.
  • Tm melting point
  • Tc crystallization temperature
  • the processing temperature must therefore be precisely adjusted between the melting temperature (Tm) and the crystallization temperature (Tc) of the semi crystalline polymer, also called the "sintering window".
  • the preheating of the powder makes it easier for the laser to raise the temperature of the selected regions of layer of unfused powder to the melting point.
  • the laser causes fusion of the powder only in locations specified by the input. Laser energy exposure is typically selected based on the polymer in use and to avoid polymer degradation.
  • the non-fused powder is removed from the 3D object and can be recycled and reused in a subsequent SLS process.
  • the laser sintering 3D printing method of the present invention is based on the use of a powdered material made of a blend of polymers comprising at least a semi-crystalline PEEK polymer and at least one amorphous PEI polymer, without significantly degrading and/or crosslinking the powdered material, thereby allowing unsintered material to be recycled and used in the manufacture of a new 3D object.
  • the present invention relates to an additive manufacturing method for making a three-dimensional (3D) object.
  • the method comprises the steps of:
  • PEEK poly(ether ether ketone)
  • PEI poly(ether imide)
  • Tg (°C) is the glass transition temperature of the PEI polymer, as measured by differential scanning calorimetry (DSC) according to ASTM D3418.
  • the method for manufacturing a 3D object of the present invention employs a powdered polymer material (M) comprising a PEEK polymer as the main element of the polymer material, as well as a PEI polymer.
  • the powdered polymer material (M) can have a regular shape such as a spherical shape, or a complex shape obtained by grinding/milling of pellets or coarse powder.
  • the present invention also relates to a powdered polymer material (M) comprising at least one PEEK polymer and at least one PEI polymer, said material (M) having for example a do.s-value ranging from 25 and 90 pm, as measured by laser scattering in isopropanol, as well as to the method for the production of a powdered polymer material (M) comprising at least one PEEK polymer and at least one PEI polymer, said method comprising a step of grinding a blend of at least the PEEK polymer and the PEI polymer, the blend being optionally cooled down to a temperature a temperature below 25°C before and/or during grinding.
  • the 3D objects or articles obtainable by such method of manufacture can be used in a variety of final applications. Mention can be made in particular of implantable device, medical device, dental prostheses, brackets and complex shaped parts in the aerospace industry and under-the-hood parts in the automotive industry.
  • the present invention relates to an additive manufacturing method for making a three-dimensional (3D) object.
  • the method comprises a first step of providing a powdered polymer material (M) comprising from 55 to 95 wt.% of at least one poly(ether ether ketone) (PEEK) polymer, and from 5 to 45 wt.% of at least one poly(ether imide) (PEI) polymer, based on the total weight of the powdered polymer material (M).
  • the method of the invention also comprises a step of depositing successive layers of the powdered polymer material and a step of selectively sintering each layer prior to deposition of the subsequent layer.
  • the powdered polymer material (M) is heated before the sintering step to a temperature Tp (°C):
  • Tg (°C) is the glass transition temperature of the PEI polymer, as measured by differential scanning calorimetry (DSC) according to ASTM D3418.
  • the method of the present invention employs a powdered polymer material (M) comprising a PEEK polymer as the main element of the polymer material, as well as a PEI polymer.
  • the powdered polymer material (M) can have a regular shape such as a spherical shape, or a complex shape obtained by grinding/milling of pellets or coarse powder.
  • the powdered polymer material (M) is heated, for example in the powder bed of a SLS printer, prior to the sintering of a selected area of the powder layer (for example, by means of an electromagnetic radiation of the powder), at a processing temperature (Tp) which is Tp ⁇ Tg + 40, where Tg is the glass transition temperature of the PEI amorphous polymer.
  • Tp processing temperature
  • the powdered polymer material (M) is not significantly affected by the long-term exposure to the processing temperature and presents a set of characteristics (namely powder aspect and color, disaggregation and coalescence abilities) which is comparable to a new, unprocessed polymer material.
  • the powdered polymer material (M) employed in the method of the present invention comprises:
  • PEEK poly(ether ether ketone)
  • PEI poly(ether imide)
  • the powdered polymer material (M) of the invention may include other components.
  • the material (M) may comprise at least one additive, notably at least one additive selected from the group consisting of flow agents, fillers, colorants, lubricants, plasticizers, stabilizers, flame retardants, nucleating agents and combinations thereof. Fillers in this context can be reinforcing or non-reinforcing in nature.
  • the amount of flow agents in the material (M) ranges from 0.01 to 10 wt.%, with respect to the total weight of the part material.
  • the amount of fillers in the material (M) ranges from 0.5 wt.% to 30 wt.%, with respect to the total weight of the material (M).
  • Suitable fillers include calcium carbonate, magnesium carbonate, glass fibers, graphite, carbon black, carbon fibers, carbon nanofibers, graphene, graphene oxide, fullerenes, talc, wollastonite, mica, alumina, silica, titanium dioxide, kaolin, silicon carbide, zirconium tungstate, boron nitride and combinations thereof.
  • the material (M) of the present invention comprises:
  • PEEK poly(ether ether ketone)
  • PEI poly(ether imide)
  • wt.% from 0 to 30 wt.% of at least one additive, or from 0.1 to 28 wt.% or from 0.5 to 25 wt.% of at least one additive, for example selected from the group consisting of flow agents, fillers, colorants, dyes, pigments, lubricants, plasticizers, flame retardants (such as halogen and halogen free flame retardants), nucleating agents, heat stabilizer, light stabilizer, antioxidants, processing aids, nanofillers and electomagnetic absorbers,
  • flow agents for example selected from the group consisting of flow agents, fillers, colorants, dyes, pigments, lubricants, plasticizers, flame retardants (such as halogen and halogen free flame retardants), nucleating agents, heat stabilizer, light stabilizer, antioxidants, processing aids, nanofillers and electomagnetic absorbers,
  • a poly(ether ether ketone) denotes any polymer comprising at least 50 mol.% of recurring units (RPEEK) of formula (J-A), based on the total number of moles in the polymer:
  • - R' at each location, is independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; and
  • - j' for each R', is independently zero or an integer ranging from 1 to 4 (for example 1 , 2, 3 or 4).
  • Each phenylene moiety of the recurring unit (RPEEK) may, independently from one another, have a 1 ,2-, a 1 ,3- or a 1 ,4-linkage to the other phenylene moieties.
  • each phenylene moiety of the recurring unit (RPEEK) independently from one another, has a 1 ,3- or a 1 ,4-linkage to the other phenylene moieties.
  • each phenylene moiety of the recurring unit (RPEEK) has a 1 ,4-linkage to the other phenylene moieties.
  • R' is, at each location in formula (J-A) above, independently selected from the group consisting of a C1 -C12 moiety optionally comprising one or more than one heteroatoms; sulfonic acid and sulfonate groups; phosphonic acid and phosphonate groups; amine and quaternary ammonium groups.
  • j' is zero for each R'.
  • the recurring units (RPEEK) are according to fo (J'-A):
  • At least 50 mol. %, at least 60 mol. %, at least 70 mol. %, at least 80 mol. %, at least 90 mol. %, at least 95 mol. %, at least 99 mol. % or all of the recurring units in the PEEK are recurring units (RPEEK) of formulae (J-A) and/or (J'-A).
  • a poly(ether ether ketone) denotes any polymer comprising at least 50 mol.% of the recurring units are recurring units (RPEEK) of formula (J-A”):
  • the mol. % being based on the total number of moles in the polymer.
  • At least 50 mol. %, at least 60 mol. %, at least 70 mol. %, at least 80 mol. %, at least 90 mol. %, at least 95 mol. %, at least 99 mol. % or all of the recurring units in the PEEK are recurring units (RPEEK) of formula (J"-A).
  • the PEEK polymer of the present disclosure can therefore be a homopolymer or a copolymer. If it is a copolymer, it can be a random, alternate or block copolymer.
  • PEEK poly(ether ether ketone)
  • R*PEEK recurring units
  • RPEEK recurring units of formula (J-D):
  • R' at each location, is independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; and
  • - j' for each R', is independently zero or an integer ranging from 1 to 4.
  • R' is, at each location in formula (J-D) above, independently selected from the group consisting of a C1 -C12 moiety optionally comprising one or more than one heteroatoms; sulfonic acid and sulfonate groups; phosphonic acid and phosphonate groups; amine and quaternary ammonium groups.
  • j' is zero for each R'.
  • the recurring units (R*PEEK) are according to formula (J'-D):
  • the recurring units (R*PEEK) are according to formula (J-D"):
  • less than 50 mol. %, less than 40 mol. %, less than 30 mol. %, less than 20 mol. %, less than 10 mol. %, less than 5 mol. %, less than 1 mol. % or all of the recurring units in the PEEK are recurring units (R*PEEK) of formulas (J-D), (J'-D), and/or (J"-D).
  • the PEEK polymer is a PEEK-PEDEK copolymer.
  • a PEEK-PEDEK copolymer denotes a polymer comprising recurring units (RPEEK) of formula (J-A), (J'-A) and/or (J"-A) and recurring units (R*PEEK) of formulas (J-D), (J'D) or (J"-D) (also called hereby recurring units (RPEDEK)).
  • the PEEK-PEDEK copolymer may include relative molar proportions of recurring units (RPEEK/RPEDEK) ranging from 95/5 to 51/49, from 90/10 to 55/45, or from 85/15 to 56/44.
  • the sum of recurring units (RPEEK) and (RPEDEK) can for example represent at least 60 mol.%, 70 mol.%, 80 mol.%, 90 mol.%, 95 mol.%, 99 mol.%, of recurring units in the PEEK copolymer.
  • the sum of recurring units (RPEEK) and (RPEDEK) can also represent 100 mol.%, of recurring units in the PEEK copolymer.
  • PEEK is commercially available as KetaSpire® PEEK from Solvay Specialty Polymers USA, LLC.
  • PEEK can be prepared by any method known in the art. It can for example result from the condensation of 4,4'-difluorobenzophenone and hydroquinone in presence of a base.
  • the reactor of monomer units takes place through a nucleophilic aromatic substitution.
  • the molecular weight (for example the weight average molecular weight Mw) can be adjusted by adjusting the monomers molar ratio and measuring the yield of polymerisation (e.g. measure of the torque of the impeller that stirs the reaction mixture).
  • the powdered polymer material (M) comprises at least one PEEK polymer having a weight average molecular weight (Mw) ranging from 50,000 to 150,000 g/mol, for example from 55,000 to 130,000 g/mol, from 60,000 to 120,000 g/mol, from 65,000 to 1 10,000 g/mol, or from 70,000 to 100,000 g/mol (as determined by gel permeation chromatography (GPC) using phenol and trichlorobenzene (1 :1 ) at 160°C, with polystyrene standards).
  • Mw weight average molecular weight
  • the powdered polymer material (M) comprises at least two PEEK polymers of different Mw.
  • the blend may for example comprise:
  • the weight average molecular weight (Mw) of PEEK can be determined by gel permeation chromatography (GPC) using phenol and trichlorobenzene (1 :1 ) at 160°C (2x PL Gel mixed B, 10m, 300 x 7.5 mm using a Polymer Laboratories PL-220 unit; flow rate: 1.0 mL/min; injection volume: 200 pL of a 0.2w/v% sample solution), with polystyrene standards.
  • GPC gel permeation chromatography
  • the weight average molecular weight (Mw) can be measured by gel permeation chromatography (GPC) as described in the experimental section.
  • GPC gel permeation chromatography
  • samples are dissolved in a 1 :1 mixture of phenol and 1 ,2,4-trichlorobenzene at 190°C temperature.
  • Samples are then passed through 2x PL Gel mixed B, 10m, 300 x 7.5 mm using a Polymer Laboratories PL-220 unit maintained at 160°C equipped with a differential refractive index detector and calibrated with 12 narrow molecular weight polystyrene standards (Peak molecular weight range: 1 ,000 - 1 ,000,000).
  • a flow rate of 1 .0 mL/min and injection volume of 200 pL of a 0.2w/v% sample solution are selected.
  • the polymers can be characterized by their weight average molecular weight (Mw), and they can also be characterized by their polydispersity index (“PDI” or "PDI index” herewith), also called sometimes polymolecularity index.
  • Mw weight average molecular weight
  • PDI index polydispersity index
  • the PDI index corresponds to the molar weight distribution of the various macromolecules within the polymer.
  • the PDI index corresponds to the ratio Mw/Mn, Mn being the number average molecular weight and determined by GPC.
  • the PDI index of the PEEK polymer or PEEK polymers blend is from 1.8 to 2.5, for example from 1.9 to 2.4 or 1.95 to 2.3.
  • the melt flow rate or melt flow index (at 400°C under a weight of 2.16 kg according to ASTM D1238) (MFR or MFI) of the PEEK may be from 1 to 60 g/10 min, for example from 2 to 50 g/10 min or from 2 to 40 g/10 min.
  • the melt flow rate (at 400°C under a weight of 2.16 kg according to ASTM D1238) of the PEEK is from 1 to 10 g/10 min, for example from 1.5 to 8 g/10 min or from 2 to 5 g/10 min.
  • the melt flow rate (at 400°C under a weight of 2.16 kg according to ASTM D1238) of the PEEK is from 20 to 60 g/10 min, for example from 25 to 55 g/10 min or from 27 to 50 g/10 min.
  • a poly(ether imide) denotes any polymer comprising at least 50 mol.%, based on the total number of moles in the polymer, of recurring units (RPEI) comprising at least one aromatic ring, at least one imide group, as such and/or in its amic acid form, and at least one ether group.
  • RPEI recurring units
  • Recurring units (RPEI) may optionally further comprise at least one amide group which is not included in the amic acid form of an imide group.
  • the recurring units (RPEI) are selected from the group consisting of following formulas (I), (II), (III), (IV), (V) and mixtures thereof:
  • - Ar is a tetravalent aromatic moiety and is selected from the group consisting of a substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic group having 5 to 50 carbon atoms;
  • - Ar' is a trivalent aromatic moiety and is selected from the group consisting of a substituted, unsubstituted, saturated, unsaturated, aromatic monocyclic and aromatic polycyclic group having from 5 to 50 C atoms;
  • - R is selected from the group consisting of substituted and unsubstituted divalent organic radicals, for example selected from the group consisting of
  • - Y is selected from the group consisting of alkylenes of 1 to 6 carbon atoms, for example -C(CH3)2 and -CnH n- (n being an integer from 1 to 6); perfluoroalkylenes of 1 to 6 carbon atoms, for example -C(CF 3 )2 and -C n F2n- (n being an integer from 1 to 6) ; cycloalkylenes of 4 to 8 carbon atoms ; alkylidenes of 1 to 6 carbon atoms ; cycloalkylidenes of 4 to 8 carbon atoms ; -O- ; -S- ; -C(O)- ; -S0 2 - ; -SO-, and
  • R" is selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali earth metal sulfonate, alkaline earth metal sulfonate, alkyl sulfonate, alkali earth metal phosphonate, alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium and
  • Ar is selected from the group consisting of formulas:
  • X is a divalent moiety, having divalent bonds in the 3,3', 3,4', 4,3" or the 4,4' positions and is selected from the group consisting of alkylenes of 1 to 6 carbon atoms, for example -C(CH3)2 and -C n H2n- (n being an integer from 1 to 6); perfluoroalkylenes of 1 to 6 carbon atoms, for example -C(CF 3 )2 and -C n F2n— (n being an integer from 1 to 6) ; cycloalkylenes of 4 to 8 carbon atoms ; alkylidenes of 1 to 6 carbon atoms ; cycloalkylidenes of 4 to 8 carbon atoms ; -O- ; -S- ; -C(O)- ; -S0 2 - ; -SO-;
  • X is a group of the formula -O-Ar"-O- wherein Ar" is a aromatic moiety selected from the group consisting of a substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic group having 5 to 50 carbon atoms.
  • Ar' is selected from the group consisting of formulas:
  • X is a divalent moiety, having divalent bonds in the 3,3', 3,4', 4,3" or the 4,4' positions and is selected from the group consisting of alkylenes of 1 to 6 carbon atoms, for example -C(CH3)2 and -C n H2n- (n being an integer from 1 to 6); perfluoroalkylenes of 1 to 6 carbon atoms, for example -C(CF 3 )2 and -Cn F2n- (n being an integer from 1 to 6) ; cycloalkylenes of 4 to 8 carbon atoms ; alkylidenes of 1 to 6 carbon atoms ; cycloalkylidenes of 4 to 8 carbon atoms ; -O- ; -S- ; -C(O)- ; -S0 2 - ; -SO-;
  • X is a group of the formula -O-Ar"-O- wherein Ar" is a aromatic moiety selected from the group consisting of a substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic group having 5 to 50 carbon atoms.
  • At least 50 mol. %, at least 60 mol. %, at least 70 mol. %, at least 80 mol. %, at least 90 mol. %, at least 95 mol. %, at least 99 mol. % or all of the recurring units in the PEI are recurring units (RPEI) of formulas (I), (II), (I II), (IV), (V) and/or mixtures thereof, as defined above.
  • a poly(ether imide) denotes any polymer comprising at least 50 mol.%, based on the total number of moles in the (VII):
  • - R is selected from the group consisting of substituted and unsubstituted divalent organic radicals, for example selected from the group consisting of
  • - Y is selected from the group consisting of alkylenes of 1 to 6 carbon atoms, for example -C(CH3)2 and -CnH n- (n being an integer from 1 to 6); perfluoroalkylenes of 1 to 6 carbon atoms, for example -C(CF 3 )2 and -C n F2n- (n being an integer from 1 to 6) ; cycloalkylenes of 4 to 8 carbon atoms ; alkylidenes of 1 to 6 carbon atoms ; cycloalkylidenes of 4 to 8 carbon atoms ; -O- ; -S- ; -C(O)- ; -S0 2 - ; -SO-, and
  • R" is selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali earth metal sulfonate, alkaline earth metal sulfonate, alkyl sulfonate, alkali earth metal phosphonate, alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium and
  • - i, for each R" is independently zero or an integer ranging from 1 to 4, with the provisio that at least one of Ar, Ar' and R comprise at least one ether group and that the ether group is present in the polymer chain backbone.
  • Ar is a aromatic moiety selected from the group consisting of a substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic group having 5 to 50 carbon atoms, for example a substituted or unsubtitutated phenylene, a substitued or unsubstituted biphenyl group, a susbtituted ou unsubstituted naphtalene group or a moiety comprising two substituted or unsubtitutated phenylene.
  • Ar is of the general formula (VI), as detailed above ; for example, Ar" is of formula (XIX):
  • polyetherimides (PEI) of the present invention may be prepared by any of the methods well-known to those skilled in the art including the reaction of a diamino compound of the formula H2N-R-NH2 (XX), where R is as defined before, with any aromatic bis(ether anhydride)s of the formula (XXI):
  • the preparation can be carried out in solvents, e.g., o-dichlorobenzene, m-cresol/toluene, ⁇ , ⁇ -dimethylacetamide, at temperatures ranging from 20°C to 250°C.
  • solvents e.g., o-dichlorobenzene, m-cresol/toluene, ⁇ , ⁇ -dimethylacetamide
  • these polyetherimides can be prepared by melt polymerization of any dianhydrides of formula (XXI) with any diamino compound of formula (XX) while heating the mixture of the ingredients at elevated temperatures with concurrent intermixing.
  • aromatic bis(ether anhydride)s of formula (XXI) include, for example:
  • the organic diamines of formula (XX) are chosen from the group consisting of m-phenylenediamine, p-phenylenediamine, 2,2-bis(p-aminophenyl)propane, 4,4'-diaminodiphenyl-methane, 4,4'-diaminodiphenyl sulfide, 4,4'-diamino diphenyl sulfone, 4,4'-diaminodiphenyl ether, 1 ,5-diaminonaphthalene, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, and mixtures thereof; preferably, the organic diamines of formula (XX) are chosen from the group consisting of m-phenylenedi
  • a poly(ether imide) denotes any polymer comprising at least 50 mol.%, based on the total number of moles in the polymer, of recurring units (RPEI) of formulas (XXIII) or (XXIV), in imide forms, or their corresponding amic acid forms and mixtures thereof:
  • At least 50 mol. %, at least 60 mol. %, at least 70 mol. %, at least 80 mol. %, at least 90 mol. %, at least 95 mol. %, at least 99 mol. % or all of the recurring units in the PEI are recurring units (RPEI) of formulas (XXIII) or (XXIV), in imide forms, or their corresponding amic acid forms and mixtures thereof.
  • Such aromatic polyimides are notably commercially available from Sabic Innovative Plastics as ULTEM ® polyetherimides.
  • the material (M) can comprise only one PEI. Alternatively, it can comprise several PEI, for example two, three, or even more than three PEI.
  • the PEI polymer has a weight average molecular weight (Mw) of 10,000 to 150,000 g/mol, as measured by gel permeation chromatography, using a polystyrene standard.
  • the PEI polymer has an intrinsic viscosity greater than 0.2 deciliters per gram (dl/g), beneficially 0.35 to 0.7 dl/g measured in m- cresol at 25°C.
  • the melt flow rate or melt flow index (at 337°C under a weight of 6.6 kg according to ASTM D1238) (MFR or MFI) of the PEI may be from 0.1 to 40 g/10 min, for example from 2 to 30 g/10 min or from 3 to 25 g/10 min.
  • the PEI polymer has a Tg ranging from 160 and 270°C, as measured by differential scanning calorimetry (DSC) according to ASTM D3418, for example ranging from 170 and 260°C, from 180 and 250 °C, or from 190 and 240°C.
  • DSC differential scanning calorimetry
  • the powdered polymer material (M) of the present invention may further comprise a flow agent, also called sometimes flow aid.
  • This flow agent may for example be hydrophilic.
  • hydrophilic flow aids are inorganic pigments notably selected from the group consisting of silicas, aluminas and titanium oxide. Mention can be made of fumed silica.
  • Fumed silicas are commercially available under the trade name Aerosil® (Evonik) and Cab-O-Sil® (Cabot).
  • the powdered polymer material (M) comprises from 0.01 to 10 wt.%, preferably from 0.05 to 5 wt.%, more preferably from 0.25 to 1 wt.%, of a flow agent, for example of fumed silica.
  • silicas are composed of nanometric primary particles (typically between 5 and 50 nm for fumed silicas). These primary particles are combined to form aggregates. In use as flow agent, silicas are found in various forms (elementary particles and aggregates).
  • the powdered polymer material (M) of the present invention may further comprise one or several additives, such as lubricants, heat stabilizers, light stabilizers, antioxidants, pigments, processing aids, dyes, fillers, nanofillers or electomagnetic absorbers.
  • additives such as lubricants, heat stabilizers, light stabilizers, antioxidants, pigments, processing aids, dyes, fillers, nanofillers or electomagnetic absorbers.
  • additives such as lubricants, heat stabilizers, light stabilizers, antioxidants, pigments, processing aids, dyes, fillers, nanofillers or electomagnetic absorbers.
  • additives such as lubricants, heat stabilizers, light stabilizers, antioxidants, pigments, processing aids, dyes, fillers, nanofillers or electomagnetic absorbers.
  • these optional additives are titanium dioxide, zinc oxide, cerium oxide, silica or zinc sulphide, glass fibers, carbon fibers.
  • the powdered polymer material (M) of the present invention may further comprise flame retardants such as halogen and halogen free flame retardants.
  • the additive manufacturing method for making a three-dimensional (3D) object of the present invention comprises:
  • the method of the present invention is conducted at a temperature where the thermal aging of the powdered polymer material, which can be assessed by the polymer aspect (for example color), the coalescence ability and the disaggregation ability, is significantly reduced.
  • the powdered material shows no significant signs of thermal aging, can be recycled and use to prepare a new article by laser sintering 3D printing, as such or in
  • the step of printing layers comprises selective sintering by means of a high power energy source, for example a high power laser source such as an electromagnetic beam source.
  • a high power energy source for example a high power laser source such as an electromagnetic beam source.
  • the 3D object/article/part may be built on substrate, for example an horizontal substrate and/or on a planar substrate.
  • the substrate may be moveable in all directions, for example in the horizontal or vertical direction.
  • the substrate can, for example, be lowered, in order for the successive layer of unsintered polymeric material to be sintered on top of the former layer of sintered polymeric material.
  • the process further comprises a step consisting in producing a support structure.
  • the 3D object/article/part is built upon the support structure and both the support structure and the 3D object/article/part are produced using the same AM method.
  • the support structure may be useful in multiple situations.
  • the support structure may be useful in providing sufficient support to the printed or under-printing, 3D object/article/part, in order to avoid distortion of the shape 3D object/article/part, especially when this 3D object/article/part is not planar. This is particularly true when the temperature used to maintain the printed or under-printing, 3D object/article/part is below the re- solidification temperature of the powder.
  • the method of manufacture usually takes place using a printer.
  • the printer may comprise a sintering chamber and a powder bed, both maintained at determined at specific temperatures.
  • the powder to be printed can be pre-heated to a processing
  • Tp glass transition temperature
  • Tg glass transition temperature
  • the powder is not significantly affected by the long-term exposure to the processing temperature and presents a set of characteristics (namely powder aspect and color, disaggregation and coalescence abilities) which is comparable to a new, unprocessed polymer material.
  • the present invention also relates to a method for the production of a powdered polymer material (M), comprising at least one PEEK polymer and at least one PEI polymer, said method comprising: a) a step of mixing the polymers together, for example blend compounding the polymers, and b) a step of grinding the resulting blended formulation, for example in the form of pellets, in order to obtain a powdered polymer material (M) having for example a do.s-value ranging from 25 from 90 pm, for example from 35 to 88 pm, or from 45 to 85 pm, as measured by laser scattering in isopropanol.
  • M powdered polymer material having for example a do.s-value ranging from 25 from 90 pm, for example from 35 to 88 pm, or from 45 to 85 pm, as measured by laser scattering in isopropanol.
  • the do.s also called D50, is known as the median diameter or the medium value of the particle size distribution, it is the value of the particle diameter at 50% in the cumulative distribution. It means that 50% of the particles in the sample are larger than the do.s-value, and 50% of the particles in the sample are smaller than the do.s-value. D50 is usually used to represent the particle size of group of particles.
  • the pellets of blended formulations can for example be ground in a pinned disk mill, a jet mill / fluidized jet mil with classifier, an impact mill plus classifier, a pin/pin-beater mill or a wet grinding mill, or a combination of those equipment.
  • the pellets of blended formulations can be cooled before step c) to a temperature below the temperature at which the material becomes brittle, for example below 25°C before being ground.
  • the step of grinding can also take place with additional cooling. Cooling can take place by means of liquid nitrogen or dry ice.
  • the ground powder can be separated, preferably in an air separator or classifier, to obtain a predetermined fraction spectrum.
  • the method for the production of a powdered polymer material (M) may further comprise, a step consisting in exposing the powder to a temperature (Ta) ranging from the glass transition temperature (Tg) of the PEEK polymer and the melting temperature (Tm) of the PEEK polymer, both Tg and Tm being measured using differential scanning calorimetry (DSC) according to ASTM D3418.
  • the temperature Ta can be selected to be at least 20°C above the Tg of the PEEK polymer, for example at least 30, 40 or 50 °C above the Tg of the PEEK polymer.
  • the temperature Ta can be selected to be at least 5°C below the Tm of the PEEK polymer, for example at least 10, 20 or 30 °C below the Tm of the PEEK polymer.
  • the exposition of the powder to the temperature Ta can for example be by heat-treatment and can take place in an oven (static, continuous, batch, convection), fluid bed heaters.
  • the exposition of the powder to the temperature Ta can alternatively be by irradiation with electromagnetic or particle radiation.
  • the heat treatment can be conducted under air or under inert atmosphere.
  • the heat treatment is conducted under inert atmosphere, more preferably under an atmosphere containing less than 2% oxygen.
  • the present invention also relates to the powdered polymer material (M), comprising at least one PEEK polymer and at least one PEI polymer, obtainable by the process described above, for use in the manufacture of a 3D object using SLS.
  • M powdered polymer material
  • the 3D objects or articles obtainable by such method of manufacture can be used in a variety of final applications. Mention can be made in particular of implantable device, medical device, dental prostheses, brackets and complex shaped parts in the aerospace industry and under-the-hood parts in the automotive industry.
  • PEEK a poly(ether ether ketone) (PEEK) having a MFI of 3 g/10 min (400°C/2.16 kg), prepared according to the following process:
  • reaction mixture was heated slowly to 150°C.
  • 150°C a mixture of 28.43 g of dry Na2C0 3 and 0.18 g of dry K2C0 3 was added via a powder dispenser to the reaction mixture over 30 minutes.
  • the reaction mixture was heated to 320°C at 1 °C/minute.
  • the solid was broken up and ground.
  • the polymer was recovered by filtration of the salts, washing and drying.
  • PEI Ultem® 1000 having a MFI of 9 g/10 min (337°C/6.6 kg)
  • the glass transition and melting temperatures of the polymers were measured using differential scanning calorimetry (DSC) according to ASTM D3418 employing a heating and cooling rate of 20°C/min. Three scans were used for each DSC test: a first heat up to 400°C, followed by a first cool down to 30°C, followed by a second heat up to 400°C. The Tg and the Tm were determined from the second heat up. DSC was performed on a TA Instruments DSC Q20 with nitrogen as carrier gas (99.998 % purity, 50 mL/min).
  • melt flow indices of the polymers were measured according to ASTM D-1238, using a weight of either 2.16 kg or 6.6 kg and a temperature of 400 °C or 337 °C. The measurements were conducted on a Dynisco D4001 Melt Flow Indexer. [001 10] * PSD (do.s)
  • the PSD (volume distribution) of the powdered polymer materials were determined by an average of 3 runs using laser scattering Microtrac S3500 analyzer in wet mode (128 channels, between 0.0215 and 1408 pm).
  • the solvent was isopropanol with a refractive index of 1 .38 and the particles were assumed to have a refractive index of 1 .59.
  • the ultrasonic mode was enabled (25 W/60 seconds) and the flow was set at 55%.
  • the formulations were melt compounded using a 26 mm diameter Coperion® ZSK-26 co-rotating partially intermeshing twin screw extruder having an L/D ratio of 48: 1 .
  • the barrel sections 2 through 12 and the die were heated to set point temperatures as follows:
  • the aim of the heat treatments was to simulate long-term printing conditions within the print bed of an SLS printer and evaluate recyclability of the materials. More precisely, the materials were subjected to different heat treatment temperatures for 16 hours in an air convection oven and then tested for their retained sintering (coalescence) capability, thereby simulating a printing cycle. Recyclability was tested by examining remaining particle coalescence ability. Additionally, the powders were evaluated for their aspect and their disaggregation following heat treatments, that-is-to-say their ability to be broken apart by traditional sieving.
  • the aim of the hot stage microscopy tests was to study particle coalescence under experimental conditions that simulate the sintering step of the method for making a 3D object of the present invention, in order to compare sintering behaviour as a function of the exposition of different materials to high- temperature conditions within an air convection oven for 16 hours.
  • Coalescence was evaluated on a Keyence VHX 600K optical microscope with a digital zoom of 200X.
  • a Linkam T96-PE hot-stage attachment was utilized in order to increase the temperature of the material in order to simulate the increased temperature of the material within an SLS printer upon printing.
  • the material was heated quickly (100 °C/min) to 260 °C. Following the rapid pre-heat, the material was subjected to a temperature increase at 20 °C/min until reaching 400 °C, at which point the temperature was held constant in order to observe coalescence.
  • the temperature of 400°C hereby simulates the energy source (for example laser) used to sinter selected regions of layer of unfused powder in a SLS equipment.
  • Coalescence was measured by observing two particles that were adjacent prior to heating. During the heating and isothermal phase at 400°C, the particles were observed to coalesce together, with a neck or bridge, formed between the two during intermediate steps.
  • the powder of example E4c however demonstrates difficult disaggregation ability.
  • the powder of example E4C treated 16 hours at a temperature of 255°C (temperature 40 °C higher than the glass transition of the PEI polymer) cannot be recycled.
  • the powder of example E5c demonstrates a non-acceptable change of color, no possible disaggregation and no coalescence, which make it not recyclable at all.

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Abstract

La présente invention concerne un procédé de fabrication additive (AM) pour fabriquer un objet tridimensionnel (3D), consistant à a) utiliser un matériau polymère (M) en poudre comprenant au moins un polymère de polyétheréthercétone (PEEK), et au moins un polymère de polyétherimide (PEI), b) déposer des couches successives du matériau polymère en poudre ; et c) fritter sélectivement chaque couche avant le dépôt de la couche suivante, le matériau polymère (M) en poudre étant chauffé avant l'étape c) à une température Tp (°C) : Tp < Tg + 40, dans laquelle Tg (°C) représente la température de transition vitreuse du polymère de PEI, telle que mesurée par calorimétrie différentielle à balayage (DSC) conformément à la norme ASTM D3418.
PCT/EP2018/074983 2017-09-18 2018-09-14 Procédé de fabrication additive pour fabriquer un objet tridimensionnel à l'aide d'un frittage laser sélectif WO2019053238A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021089747A1 (fr) 2019-11-08 2021-05-14 Solvay Specialty Polymers Usa, Llc Mélange de copolymère de polyaryléthercétone
EP3854834A1 (fr) 2020-01-21 2021-07-28 Solvay Specialty Polymers USA, LLC. Mélange de copolymère de cétone polyaryléther
WO2021214400A1 (fr) * 2020-04-21 2021-10-28 Safran Composition pour fabrication additive
CN114641519A (zh) * 2019-11-21 2022-06-17 索尔维特殊聚合物美国有限责任公司 用于通过3d打印制造制品的聚合物、组合物和方法
US11661521B2 (en) 2019-12-17 2023-05-30 Ticona Llc Three-dimensional printing system employing a thermotropic liquid crystalline polymer

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US20150145168A1 (en) * 2012-11-21 2015-05-28 Stratasys, Inc. Method for printing three-dimensional parts wtih crystallization kinetics control
WO2017180972A1 (fr) * 2016-04-15 2017-10-19 Sabic Global Technologies B.V. Compositions polyisoindolinone, procédés de fabrication et compositions et articles formés à partir de ces dernières
JP2017217881A (ja) * 2016-06-10 2017-12-14 株式会社リコー 立体造形用材料、立体造形物の製造方法、及び立体造形物製造装置

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US20150145168A1 (en) * 2012-11-21 2015-05-28 Stratasys, Inc. Method for printing three-dimensional parts wtih crystallization kinetics control
WO2017180972A1 (fr) * 2016-04-15 2017-10-19 Sabic Global Technologies B.V. Compositions polyisoindolinone, procédés de fabrication et compositions et articles formés à partir de ces dernières
JP2017217881A (ja) * 2016-06-10 2017-12-14 株式会社リコー 立体造形用材料、立体造形物の製造方法、及び立体造形物製造装置

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021089747A1 (fr) 2019-11-08 2021-05-14 Solvay Specialty Polymers Usa, Llc Mélange de copolymère de polyaryléthercétone
CN114641519A (zh) * 2019-11-21 2022-06-17 索尔维特殊聚合物美国有限责任公司 用于通过3d打印制造制品的聚合物、组合物和方法
US11661521B2 (en) 2019-12-17 2023-05-30 Ticona Llc Three-dimensional printing system employing a thermotropic liquid crystalline polymer
EP3854834A1 (fr) 2020-01-21 2021-07-28 Solvay Specialty Polymers USA, LLC. Mélange de copolymère de cétone polyaryléther
WO2021214400A1 (fr) * 2020-04-21 2021-10-28 Safran Composition pour fabrication additive

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