CN116490364A - Additive manufacturing method for manufacturing three-dimensional objects - Google Patents
Additive manufacturing method for manufacturing three-dimensional objects Download PDFInfo
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- CN116490364A CN116490364A CN202180080078.7A CN202180080078A CN116490364A CN 116490364 A CN116490364 A CN 116490364A CN 202180080078 A CN202180080078 A CN 202180080078A CN 116490364 A CN116490364 A CN 116490364A
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- 238000000034 method Methods 0.000 claims description 78
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 25
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 24
- 229920002530 polyetherether ketone Polymers 0.000 claims description 24
- 238000001125 extrusion Methods 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 20
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- 125000003118 aryl group Chemical group 0.000 claims description 10
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- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 9
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000005600 alkyl phosphonate group Chemical group 0.000 claims description 8
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- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 claims 23
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Abstract
The present disclosure relates to an Additive Manufacturing (AM) method of manufacturing three-dimensional (3D) objects using a part material (M) comprising at least one PEEK-PEoEK copolymer, in particular to a 3D object obtainable from such a part material (M) by Fused Deposition Modeling (FDM) or fuse manufacturing (FFF).
Description
RELATED APPLICATIONS
The present application claims priority from U.S. provisional application 63/119,171, filed on month 11 and 30 of 2020, and from european patent application 21155706.1 filed on month 2 and 8 of 2021, the entire contents of each of these applications being incorporated herein by reference for all purposes.
Technical Field
The present disclosure relates to an Additive Manufacturing (AM) method of manufacturing three-dimensional (3D) objects using a part material (M) comprising at least one copolymer comprising poly (ether ketone) (PEEK) repeating units and poly (ether o ether ketone) (PEoEK) repeating units, in particular to a 3D object obtainable from such part material (M) by Fused Deposition Modeling (FDM) or fuse manufacturing (FFF).
Background
Additive manufacturing systems are used to print or otherwise build 3D parts from digital representations of the 3D parts using one or more additive manufacturing techniques. Examples of commercially available additive manufacturing techniques include extrusion-based techniques, selective laser sintering, powder/binder jetting, electron beam melting, and stereolithography processes. For each of these techniques, the digital representation of the 3D part is initially cut into multiple horizontal layers. For each sliced layer, a tool path is then generated that provides instructions for the particular additive manufacturing system to print the given layer.
For example, in an extrusion-based additive manufacturing system, a 3D part may be printed from a digital representation of the 3D part in a layer-by-layer manner by extruding and abutting a strip of part material. The part material is extruded through an extrusion tip carried by the print head of the system and deposited as a series of roads on the x-y planar platen. The extruded part material melts to the pre-deposited part material and solidifies as the temperature drops. The position of the printhead relative to the substrate then increases along the z-axis (perpendicular to the x-y plane), and the process is then repeated to form a 3D part similar to the digital representation. An example of an extrusion-based additive manufacturing system starting with filaments is known as fuse fabrication (FFF), also known as Fused Deposition Modeling (FDM). Pellet Additive Manufacturing (PAM) is another example of an extrusion-based 3D printing method that is capable of printing raw materials into pellet form.
Poly (aryl ether ketone) Polymers (PAEK), such as poly (ether ketone) Polymers (PEEK), are well known for their high temperature properties and excellent chemical resistance. Their use for the preparation of 3D objects/articles/parts has been described in the literature. For some semi-crystalline polymers, such as PEEK, the processing temperature is too high, resulting in degradation and/or crosslinking. It is well known that this negatively affects the processability of the material and recovery by Selective Laser Sintering (SLS), another widely used 3D printing method using polymer powder as part material.
The PEEK printability defect in extrusion-based 3D printing methods has been addressed in a number of different ways in the patent literature. WO 2019/055737 A1 (armema) describes in particular PEKK 70/30 copolymers which crystallize more slowly than PEEK, enabling easy printing with advantageous characteristic features and the option of using a post-printing annealing process, which further improves some mechanical properties and chemical resistance. WO 2015/081009 A1 (Stratasys) describes a substantially miscible polymer blend of a semi-crystalline polymer with a second polymer for slowing the crystallization rate of the first semi-crystalline polymer.
PEEK-PEEK copolymers (comprising PEEK units having the formula: ph-Ph-O-Ph-C (O) -Ph-, wherein-Ph-is a1, 4-phenylene unit and comprising greater than 65% PEEK units having the formula-Ph '-O-Ph' -C (O) -Ph '-O-, wherein-Ph' -is 1, 4-phenylene) have also been described as using melting and extrusion of raw materials to make shaped articles. WO 2017/051202 A1 (Victrex) describes a PEEK-PEDEK 75/25 copolymer that provides slower crystallization kinetics than PEEK. While these materials exhibit lower melting temperatures, their mechanical properties are inferior to PEEK.
It is an object of the present invention to provide a PAEK-based polymeric material for extrusion-based 3D printing processes, which material has a lower melting temperature, a slower crystallization speed and high mechanical and chemical resistance properties. As described below, PEEK-PEoEK copolymers comprising PEEK and PEoEK repeat units provide a suitable technical solution for this.
PEEK-PEoEK copolymers have been described in the art. JP 1221426 describes in particular PEEK-PEoEK copolymers in its examples 5 and 6, which are made of hydroquinone, catechol and difluorobenzophenone, said to have an increased glass transition temperature and at the same time excellent heat resistance. Similarly, 50/50 and 70/30 copolymers of PEEK and PEoEK are described in Macromolecules, 2006, 39, 6467-6472 by A.ben-Haida et al, which are prepared by stepwise polycondensation of hydroquinone and catechol with 4,4' -difluorobenzophenone in diphenyl sulfone. However, these documents do not describe PEEK-PEoEK filaments or pellets used in extrusion-based 3D manufacturing.
Disclosure of Invention
The present invention relates to a method for manufacturing a 3D object using an additive manufacturing system, such as an extrusion-based additive manufacturing system (e.g. FFF or FDM).
The 3D object or article obtainable by such a manufacturing method can be used in a variety of end applications. Mention may be made in particular of implantable devices, medical devices, dental prostheses, stents and parts of complex shape in the aerospace industry and parts in the hood of the automobile industry.
The method of the invention comprises the step of printing a layer of the 3D object from the part material (M). The part material (M) may be in filament form and used in extrusion-based additive manufacturing systems (known as fuse fabrication (FFF), also known as Fused Deposition Modeling (FDM)) that originate from filaments. The part material may also be in pellet form and used in 3D printing technology (PAM) capable of printing raw material prints in pellet form.
The invention relates generally to an AM method for manufacturing a 3D object, comprising extruding a part material (M) comprising a polymer component comprising at least one PEEK-PEoEK copolymer, wherein the copolymer comprises a total of at least 50mol.% of repeating units (R PEEK ) And repeating units (R) PEoEK ) Wherein：
(a) Repeating unit (R) PEEK ) Is a repeating unit having formula (a):
and is also provided with
(b) Repeating unit (R) PEoEK ) Is a repeating unit having the formula (B):
wherein the method comprises the steps of
-each R 1 And R is 2 Identical to or different from each other, are independently selected at each occurrence from the group consisting of: halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium,
-each a and b, equal to or different from each other, is independently selected from the group consisting of integers ranging from 0 to 4, and
the PEEK-PEoEK copolymer comprises the following components in molar ratio R PEEK /R PEoEK These repeat units R range from 95/5 to 5/95 PEEK And R is PEoEK 。
Applicants' advantage is the unexpected discovery that PEEK-PEoEK copolymers, alone or blended with other polymers (e.g., PEEK), have a slow crystallization rate and a lower percent crystallinity than neat PEEK. These properties in particular enable more reliable printing of objects and their use for 3D printing of larger and complex objects, due to the reduced crystallinity compared to pure PEEK. Interestingly, the crystallization rate was not so slow as to completely eliminate crystallization from 3D printed objects. The 3D printed parts of these compositions still have some crystallinity after printing, and unexpectedly, parts printed from these compositions have little warpage when printed at oven temperatures near the glass transition temperature (Tg) of the polymer.
The expression "polymer" or "copolymer" is used herein to designate a homopolymer containing substantially 100 mole% of the same repeat units, as well as terephthalic acid and hexamethylenediamine comprising at least 50 mole%, for example at least about 60 mole%, at least about 65 mole%, at least about 70 mole%, at least about 75 mole%, at least about 80 mole%, at least about 85 mole%, at least about 90 mole%, at least about 95 mole%, or at least about 98 mole%, added to the condensation mixture.
The expression "part material" is here intended to mean a material forming a 3D object or a part of a 3D object, notably a blend of polymer compounds. According to the invention, the part material (M) is used as a raw material to be used for manufacturing 3D objects or parts of 3D objects.
The method of the present invention employs PEEK-PEoEK copolymers as the primary element of a part material that can be shaped, for example, in the form of filaments to build up a 3D object (e.g., a 3D model, a 3D article, or a 3D part). The polymer may also be printed in the form of pellets (e.g., pellets of a polymer blend).
In the present application:
any description, even with respect to specific embodiments, is applicable to and interchangeable with other embodiments of the invention;
When an element or component is said to be included in and/or selected from the list of enumerated elements or components, it is to be understood that in the relevant embodiments explicitly contemplated herein, the element or component may also be any one of these enumerated independent elements or components, or may also be selected from the group consisting of any two or more of the enumerated elements or components; any elements or components recited in a list of elements or components may be omitted from this list; and is also provided with
Any recitation of numerical ranges herein by endpoints includes all numbers subsumed within that range, and the endpoints and equivalents of that range.
According to an embodiment, the part material is in the form of filaments. The expression "filaments" refers to linear objects or fibers or filaments (strands) formed from a material or blend of materials according to the invention comprising at least the PEEK-PEoEK copolymer described herein.
The filaments may have a cylindrical or substantially cylindrical geometry, or may have a non-cylindrical geometry, such as a ribbon filament geometry; furthermore, the filaments may have a hollow geometry or may have a core-shell geometry, wherein another polymer composition is used to form the core or shell.
According to an embodiment of the invention, the method for manufacturing a 3D object using an AM system comprises the steps of extruding a part material (M). This step may occur, for example, when printing or depositing a strip or layer of part material (M). Methods of manufacturing 3D objects with extrusion-based additive manufacturing systems are also known as fuse fabrication techniques (FFF), fused Deposition Modeling (FDM), and pellet additive manufacturing techniques (PAM).
For example, the FFF/FDM 3D printer is a printer manufactured by Apium, roboze, hyrel, or Sttatus (under the trade name) Are commercially available. For example, SLS 3D printer is available from EOS under the trade name +.>P is available. For example, FRTP 3D printers are available from Markforged corporation.
For example, PAM 3D printers are commercially available from the bellen company. BAAM (large area additive manufacturing) is an industrial-scale additive manufacturing machine commercially available from Cincinnati inc.
Material for parts
The part material (M) employed in the process of the invention comprises a polymer component comprising at least one PEEK-PEoEK copolymer, wherein the copolymer comprises a total of at least 50mol.% of recurring units (R PEEK ) And repeating units (R) PEoEK ) Wherein:
(a) Repeating unit (R) PEEK ) Is a repeating unit having formula (a):
and is also provided with
(b) Repeating unit (R) PEoEK ) Is a repeating unit having the formula (B):
wherein the method comprises the steps of
-each R 1 And R is 2 Identical to or different from each other, are independently selected at each occurrence from the group consisting of: halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium,
-each a and b, equal to or different from each other, is independently selected from the group consisting of integers ranging from 0 to 4, and
the PEEK-PEoEK copolymer comprises the following components in molar ratio R PEEK /R PEoEK These repeat units R range from 95/5 to 5/95 PEEK And R is PEoEK 。
The applicant has found that the part material (M) based on PEEK-PEoEK copolymer, possibly blended with other polymers (e.g. PEEK), has a slow crystallization rate, which enables 3D printing of large and complex objects/articles. 3D printed parts from part materials comprising PEEK-PEoEK copolymer (possibly blended with other polymers such as PEEK) have some crystallinity after printing but little warpage when printed at oven temperatures near Tg.
The inventive part material (M) may comprise further components. For example, the part material may comprise at least one additive, notably at least one additive selected from the group consisting of: fillers, colorants, lubricants, plasticizers, stabilizers, flame retardants, nucleating agents, flow enhancers, and combinations thereof. In this context, the filler may be reinforcing or non-reinforcing in nature. For example, the part material may comprise from 0.1wt.% to 60wt.% of at least one additive, relative to the total weight of material (M). For example, the amount of additive in material (M) ranges from 0.5wt.% to 50wt.%, from 1wt.% to 40wt.%, from 5wt.% to 30wt.%, or from 10wt.% to 20wt.%, relative to the total weight of material (M).
In embodiments including filler, the concentration of filler in the part material (M) ranges from 0.1wt.% to 60wt.%, relative to the total weight of the part material (M). Suitable fillers include calcium carbonate, magnesium carbonate, glass fibers, graphite, carbon black, carbon fibers, carbon nanofibers, graphene oxide, fullerenes, talc, wollastonite, mica, alumina, silica, titania, kaolin, silicon carbide, zirconium tungstate, boron nitride, and combinations thereof. For example, the amount of filler in material (M) may range from 0.5wt.% to 50wt.%, from 1wt.% to 40wt.%, from 5wt.% to 30wt.%, or from 10wt.% to 20wt.%, relative to the total weight of material (M).
According to a first embodiment, the part material (M) of the invention comprises a polymer component comprising: from 20 to 100wt.%, from 30 to 99wt.%, from 40 to 95wt.%, or from 50 to 90wt.% of at least one PEEK-PEoEK copolymer, based on the total weight of the polymer components.
The polymer component of the part material (M) may comprise another polymer than PEEK-PEoEK as described herein. It may for example comprise poly (aryl ether ketone) (PAEK) other than such PEEK-PEoEK. As used herein, PAEK means a composition comprising more than 50mol.% of recurring units (R PAEK ) These repeating units comprise Ar '-C (=o) -Ar groups, wherein Ar' and Ar are identical or different from each other and are aromatic groups. Advantageously, the PEAK polymer is a poly (ether ketone) (PEEK) homopolymer or copolymer (hereinafter PEEK (co) polymer).
According to a second embodiment, the part material (M) of the invention comprises a polymer component comprising: based on the total weight of the polymer component,
from 20 to 99wt.%, from 30 to 98wt.%, from 40 to 95wt.%, or from 50 to 90wt.% of at least one PEEK-PEoEK copolymer,
from 1 to 80wt.%, from 2 to 70wt.%, from 5 to 60wt.%, or from 10 to 50wt.% of at least one PEEK (co) polymer.
According to a third embodiment, the inventive part material (M) comprises a polymer component comprising or consisting of: based on the total weight of the part material (M),
from 20 to 99wt.%, from 30 to 98wt.%, from 40 to 95wt.%, or from 50 to 90wt.% of at least one PEEK-PEoEK copolymer,
from 1 to 80wt.%, from 2 to 70wt.%, from 5 to 60wt.%, or from 10 to 50wt.% of at least one PEEK (co) polymer,
optionally up to 60wt.% of at least one additive, for example selected from the group consisting of: fillers, colorants, lubricants, plasticizers, stabilizers, flame retardants, nucleating agents, flow enhancers, and combinations thereof.
In some embodiments, the polymer component of the part material (M) comprises at least 80wt.% of a PEEK-PEoEK copolymer, based on the total weight of the polymer component of the part material (M). For example, the polymer component comprises at least 85wt.% of PEEK-PEoEK copolymer, at least 90wt.%, at least 95wt.%, at least 96wt.%, at least 97wt.%, at least 98wt.%, or at least 99wt.% of PEEK-PEoEK copolymer, based on the polymer component of the part material (M).
In some embodiments, the polymer component of the part material (M) consists of a PEEK-PEoEK copolymer.
In some embodiments, the part material (M) comprises at least 80wt.% PEEK-PEoEK copolymer based on the total weight of the part material (M). For example, the part material (M) comprises at least 85wt.% PEEK-PEoEK copolymer, at least 90wt.%, at least 95wt.%, at least 96wt.%, at least 97wt.%, at least 98wt.%, or at least 99wt.% PEEK-PEoEK copolymer, based on the total weight of the part material (M).
In some embodiments, the part material (M) consists of or consists essentially of a PEEK-PEoEK copolymer. As used herein, the expression "consisting essentially of PEEK-PEoEK copolymer" means that the part material (M) may contain up to 2wt.%, up to 1wt.%, or up to 0.5wt.% of other components relative to the total weight of the part material (M), so as not to substantially alter the advantageous properties of such material.
PEEK-PEoEK copolymer
As used herein, a "PEEK-PEoEK copolymer" comprises at least 50mol.% total of recurring units (R PEEK ) And repeating units (R) PEoEK ). In some embodiments, the PEEK-PEoEK copolymer comprises at least 51mol.%, at least 55mol.%, at least 60mol.%, at least 70mol.%, at least 80mol.%, at least 90mol.%, at least 95mol.%, and most preferably at least 99mol.% of recurring units (R) relative to the total moles of recurring units in the PEEK-PEoEK copolymer PEEK ) And (R) PEoEK )。
Repeating unit (R) PEEK ) Represented by formula (a):
and is also provided with
Repeating unit (R) PEoEK ) Represented by formula (B):
each R1 and R2, equal to or different from each other, is independently selected at each occurrence from the group consisting of: halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium,
each of a and b, equal to or different from each other, is independently selected from the group consisting of integers ranging from 0 to 4, and
the PEEK-PEoEK copolymer comprises the following components in molar ratio R PEEK /R PEoEK These repeat units R range from 95/5 to 5/95 PEEK And R is PEoEK 。
In some preferred embodiments, each a is zero, such that the repeating unit (R PEEK ) Is a repeating unit having the formula (A-1):
in some preferred embodiments, each b is zero, such that the repeating unit (R PEoEK ) Is a repeating unit having the formula (B-1):
preferably, the repeating unit (R PEEK ) Is a repeating unit having the formula (A-1), and the repeating unit (R) PEoEK ) Is a repeating unit having the formula (B-1).
The PEEK-PEoEK copolymer of the present invention may additionally comprise repeating units (R) PEEK ) And (R) PEoEK ) Repeating units (R) PAEK ). In this case, the repeating unit (R PAEK ) The amount of (c) may be comprised between 0.1 and less than 50mol.%, preferably less than 10mol.%, more preferably less than 5mol.%, most preferably less than 2mol.%, relative to the total moles of recurring units of the PEEK-PEoEK copolymer.
When different from the repeating unit (R) PEEK ) And (R) PEoEK ) Repeating units (R) PAEK ) When present in the PEEK-PEoEK copolymer of the present invention, it is different from the repeating unit (R PEEK ) And (R) PEoEK ) Is a repeating unit (R) PAEK ) Generally, any one of the following formulas (K-A) to (K-M) is satisfied:
wherein in the above formulae (K-A) to (K-M), each R' is the same or different from each other and is independently selected at each occurrence from C optionally containing one or more heteroatoms 1 -C 12 A group; sulfonic acid and sulfonate groups; phosphonic acid and phosphonate groups; amine and quaternary ammonium groups; and each j 'is the same or different from each other and is independently selected at each occurrence from 0 and an integer from 1 to 4, preferably j' is equal to zero.
However, it is generally preferred that the PEEK-PEoEK copolymers of the present invention consist essentially of recurring units (R PEEK ) And (R) PEoEK ) The composition is formed. Thus, in some preferred embodiments, the PEEK-PEoEK copolymer consists essentially of repeat units R PEEK And R is PEoEK Composition is prepared. The expression "essentially consisting of repeat units R", as used herein PEEK And R is PEoEK By composition "is meant a repeat unit R different from that as detailed above PEEK And R is PEoEK May be present in the PEEK-PEoEK copolymer in an amount of at most 2mol.%, at most 1mol.%, or at most 0.5mol.%, relative to the total moles of repeating units in the PEEK-PEoEK copolymer, and so as not to substantially alter the advantageous properties of the PEEK-PEoEK copolymer.
Repeat unit R PEEK And R is PEoEK With R ranging from 95/5 to 5/95 PEEK /R PEoEK The molar ratio is present in the PEEK-PEoEK copolymer. Preferably, the PEEK-PEoEK copolymer suitable for the powder of the invention is a polymer comprising a major part of R PEEK Those of units, i.e. where R PEEK /R PEoEK The molar ratio ranges from 95/5 to greater than 50/50, even more preferably from 95/5 to 60/40, still more preferably from 90/10 to 65/35, most preferably from 85/15 to 70/30.
In some embodiments, the PEEK-PEoEK copolymer has a melting temperature (Tm) of less than or equal to 340 ℃, preferably less than or equal to 335 ℃. The melting temperatures described herein are measured as the peak temperatures of the melting endotherm curves at the second heating scan in a Differential Scanning Calorimeter (DSC) according to ASTM D3418-03 and E794-06 and using heating and cooling rates of 20 ℃/min.
In some embodiments, the PEEK-PEoEK copolymer has a glass transition temperature (Tg) of at least 135℃and at most 155 ℃, preferably at least 140℃as determined according to ASTM D3418-03, E1356-03, E793-06, E794-06 upon a second heat scan.
In some embodiments, the PEEK-PEoEK copolymer has a heat of fusion (. DELTA.H) of at least 1J/g, preferably at least 2J/g, at least 5J/g. The heat of fusion described herein is determined as the area under the melting endotherm curve at the second heat scan in a Differential Scanning Calorimeter (DSC) using heating and cooling rates of 20 ℃/min according to ASTM D3418-03 and E793-06. In some aspects, the PEEK-PEoEK copolymer may have a heat of fusion (. DELTA.H) of at most 65J/g, preferably at most 60J/g.
According to certain embodiments, the PEEK-PEoEK copolymer has a microstructure such that its FT-IR spectrum, when measured at 600 and 1,000cm on a polymer powder -1 When recorded in ATR mode, such that the following inequality is satisfied:
(i)wherein->Is at 700cm -1 Absorbance at, and->Is at 704cm -1 Absorbance at;
(ii)wherein->Is at 816cm -1 Absorbance at and->Is at 835cm -1 Absorbance at; />
(iii)Wherein->Is at 623cm -1 Absorbance at and->Is 557cm -1 Absorbance at;
(iv)wherein->Is at 928cm -1 Absorbance at and->Is at 924cm -1 Absorbance at.
The PEEK-PEoEK copolymer can be such that it has a calcium content of less than 5ppm, which is measured by inductively coupled plasma optical emission spectrometry (ICP-OES) calibrated with standards of known calcium content. This particularly low and controlled Ca content is particularly beneficial when the PEEK-PEoEK copolymer is used in metal joints where very stringent dielectric properties are required. According to these preferred embodiments, the PEEK-PEoEK copolymer may have a calcium content of less than 4ppm, less than 3ppm, or even more preferably less than 2.5 ppm.
In these preferred embodiments, the PEEK-PEoEK copolymer can also be such that it has a sodium content of less than 1,000ppm, as measured by inductively coupled plasma optical emission spectroscopy (ICP-OES) calibrated with standards of known sodium content. Preferably, the PEEK-PEoEK copolymer may have a sodium content of less than 900ppm, less than 800ppm or even more preferably less than 500 ppm.
In some embodiments, the PEEK-PEoEK copolymer can be such that it has a phosphorus content of at least 6ppm, as measured by inductively coupled plasma optical emission spectroscopy (ICP-OES) calibrated using standards of known phosphorus content. Preferably, the PEEK-PEoEK copolymer has a phosphorus content of at least 10ppm, at least 15ppm or even more preferably at least 20 ppm.
In the powder of the invention, it may be advantageous to select PEEK-PEoEK copolymers with increased thermal stability, which may be particularly beneficial in certain fields of use, for example for preparing 3D objects by additive manufacturing. The PEEK-PEoEK copolymer may in particular have a peak degradation temperature of at least 550 ℃, more preferably at least 551 ℃, and even more preferably at least 552 ℃ as measured by TGA according to ASTM D3850.
Methods suitable for making PEEK-PEoEK copolymers are generally known in the art. They are described in particular in co-pending patent applications EP 2020/065154 and EP 2020/066177 (not yet published).
PAEK copolymers
As used herein, poly (aryl ether ketone) (PAEK) means a polymer comprising greater than 50mol.% of repeating units (R PAEK ) These repeating units comprise Ar '-C (=o) -Ar groups, wherein Ar' and Ar are identical or different from each other and are aromatic groups.
Repeating unit (R) PAEK ) May be selected from the group consisting of units of the following formulae (J-A) to (J-D):
wherein the method comprises the steps of
Each R', equal to or different from each other, is selected from the group consisting of: halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; and is also provided with
j' is zero or an integer ranging from 1 to 4.
In repeating units (R) PAEK ) In which the corresponding phenylene moiety may independently have a structural unit (R PAEK ) Other moieties different from R' in (a) are 1, 2-linkages, 1, 4-linkages or 1, 3-linkages. Preferably, the phenylene moieties have 1, 3-linkages or 1, 4-linkages, more preferably they have 1, 4-linkages.
In repeating units (R) PAEK ) In j' is preferably zero at each occurrence such that the phenylene moiety has no other substituents other than those attached to the backbone of the polymer.
In some embodiments, the PAEK is poly (ether ketone) (PEEK). As used herein, poly (ether ketone ether) (PEEK) means any polymer comprising greater than 50mol.% of repeat units (R) having the formula (J' -a) PAEK ) Is a polymer of (a):
preferably, at least 60 mole%, 70 mole%, 80 mole%, 90 mole%, 95 mole%, 99 mole% and most preferably all of the repeat units (R) PAEK ) Is a repeating unit (J' -A).
Method for manufacturing a three-dimensional (3D) object
An Additive Manufacturing (AM) method for manufacturing a three-dimensional (3D) object of the invention comprises the steps of extruding a part material (M).
The methods of the present invention are typically performed using an additive manufacturing system or printer (also referred to as a 3D printer).
The method of the present invention may further comprise at least one of the following steps, in combination with a 3D printer:
-feeding the part material (M) to a discharge head member having a through hole ending in a discharge tip and a circumferential heater melting the material (M) in the through hole;
-heating the part material (M) to a temperature of at least 350 ℃ before extrusion;
-compressing the part material (M) in the through-hole with a piston, for example with unmelted filaments acting as piston;
-ensuring relative movement of the discharge tip and the receiving platform in X-and Y-directions while discharging the part material (M) on the receiving platform to form a cross-sectional shape;
-ensuring a relative movement of the discharge tip and the receiving platform in Z-direction while discharging the part material (M) on the receiving platform to form a 3D object or part in height.
The 3D object/article/part may be built on a substrate (e.g., a horizontal substrate and/or a planar substrate). The substrate may be movable in all directions (e.g., in a horizontal or vertical direction). During the 3D printing process, the substrate may be lowered, for example, to extrude a continuous layer of part material on top of a previous layer of polymer material.
According to an embodiment, the method further comprises a step comprising producing the support structure. According to this embodiment, a 3D object/article/part is built on a 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 used in a variety of situations. For example, the support structure may be used to provide sufficient support for a printed or printing 3D object/article/part in order to avoid shape deformation of the 3D object/article/part, especially when such 3D object/article/part is not planar. This is especially true when used to maintain the temperature of the 3D object/article/part being printed or being printed below the resolidification temperature of the powder.
Although not strictly necessary, the 3D object/article/part may also be heat treated (also referred to as annealed or tempered) after manufacture. In this case, the 3D object/article/part may be placed in an oven at a temperature ranging from 170 ℃ to 260 ℃, preferably from 180 ℃ to 220 ℃ for a period of time ranging from about 30 minutes to 24 hours, preferably from 1 hour to 8 hours.
The 3D object of the present invention preferably exhibits a level of crystallinity corresponding to an enthalpy of fusion or heat of fusion of at least 30J/g, as measured according to ASTM D3418 using a heating rate of 20 ℃/min prior to any annealing heat treatment of the second heat scan in a Differential Scanning Calorimeter (DSC) and calculated as the difference between the absolute value of the area of melting endotherm minus the absolute value of any crystallization endotherm detectable during the first heating scan. In some embodiments, the heat of fusion of the 3D object as printed prior to any heat treatment and as measured according to the above description is at least 32J/g, at least 33J/g, or at least 34J/g.
The 3D object of the present invention preferably exhibits a Z-direction yield or tensile stress at break of greater than about 50%, preferably at least 55%, even more preferably 60% of the x-y direction yield or tensile stress at break.
Details material (M)
The part material (M) of the present invention can be manufactured by methods well known to those of ordinary skill in the art. For example, such methods include, but are not limited to, melt mixing methods. Melt mixing processes are typically performed by heating the polymer components above the melt temperature of the thermoplastic polymer to form a melt of the thermoplastic polymer. In some embodiments, the processing temperature ranges from about 280 ℃ to 450 ℃, preferably from about 290 ℃ to 440 ℃, from about 300 ℃ to 430 ℃, or from about 310 ℃ to 420 ℃. Suitable melt mixing devices are, for example, kneaders, banbury mixers, single-screw extruders and twin-screw extruders. Preferably, an extruder is used which is equipped with means for feeding all the required components into the extruder (into the throat of the extruder or into the melt). In a method for preparing a part material, components of the part material (e.g., PEEK-PEoEK polymer, optionally other polymers such as PEEK polymer, optional additives) are fed into and melt mixed in a melt mixing device. The components may be fed simultaneously as a powder mixture or a particulate mixture (also known as a dry blend) or may be fed separately.
The order of combination of the components during melt mixing is not particularly limited. In one embodiment, the components may be mixed in a single batch such that the desired amounts of the components are added together and then mixed. In other embodiments, a first subset of the components may be initially mixed together, and one or more of the remaining components may be added to the mixture for further mixing. The desired total amounts of the components need not be mixed as separate amounts for clarity. For example, for one or more of the components, a partial amount may be initially added and mixed, and then some or all of the remainder may be added and mixed.
The part material may be used in pellet form, for example, in a Pellet Additive Manufacturing (PAM) 3D printing process.
When the part material is in pellet form, the pellets may have a size ranging from 1mm to 1cm, for example from 2mm to 5mm or from 2.5mm to 4.5 mm.
Filament material
The invention also relates to a filament material (F) comprising a polymer component comprising at least one PEEK-PEoEK copolymer as described above.
According to this aspect of the invention, the PEEK-PEoEK copolymer is as described above.
According to one embodiment, the filament material further comprises one or several other polymers, such as at least one PEEK polymer.
The filament material is well suited for use in a method for manufacturing a three-dimensional object.
The filaments may have a cylindrical or substantially cylindrical geometry, or may have a non-cylindrical geometry, such as a ribbon filament geometry; furthermore, the filaments may have a hollow geometry or may have a core-shell geometry, wherein the support material of the present invention is used to form a core or shell.
When the filaments have a cylindrical geometry, their diameter may vary between 0.5mm and 5mm, for example between 0.8 and 4mm or for example between 1mm and 3.5 mm. The diameter of the filaments may be selected to feed a particular FFF 3D printer. Examples of filament diameters widely used in FFF processes are 1.75mm or 2.85mm diameters. The diameter of the filaments is accurate to +/-200 microns, for example +/-100 microns or +/-50 microns.
Filaments of the present invention can be prepared by a two-step process in which the compound will first be produced as part material in pellet form and then the pellets are extruded to produce the filaments. Alternatively, the filaments of the present invention may be prepared by an integrated process wherein the compound and filaments are prepared in a one-step process.
Filaments of the present invention may be made from part materials by methods including, but not limited to, melt mixing processes. The melt mixing process is typically performed by heating the polymer components above the highest melting temperature and glass transition temperature of the thermoplastic polymer, thereby forming a melt of the thermoplastic polymer. In some embodiments, the processing temperature ranges from about 280 ℃ to 450 ℃, preferably from about 290 ℃ to 440 ℃, from about 300 ℃ to 430 ℃, or from about 310 ℃ to 420 ℃.
The process for preparing the filaments may be carried out in a melt mixing device, wherein any melt mixing device known to those skilled in the art of preparing polymer compositions by melt mixing may be used. Suitable melt mixing devices are, for example, kneaders, banbury mixers, single-screw extruders and twin-screw extruders. Preferably, an extruder is used which is equipped with means for feeding all the required components into the extruder (into the throat of the extruder or into the melt). In a process for preparing filaments, the components of the part material are fed into a melt mixing device and melt mixed in the device. The components may be fed simultaneously as a powder mixture or a particulate mixture (also known as a dry blend) or may be fed separately.
The order of combination of the components during melt mixing is not particularly limited. In one embodiment, the components may be mixed in a single batch such that the desired amounts of the components are added together and then mixed. In other embodiments, a first subset of the components may be initially mixed together, and one or more of the remaining components may be added to the mixture for further mixing. The desired total amounts of the components need not be mixed as separate amounts for clarity. For example, for one or more of the components, a partial amount may be initially added and mixed, and then some or all of the remainder may be added and mixed.
The method for manufacturing filaments further comprises an extrusion step, for example with a die. Any standard molding technique may be used for this purpose; standard techniques including shaping the polymer composition in molten/softened form may be advantageously applied and notably include compression molding, extrusion molding, injection molding, transfer molding, and the like. Extrusion molding is preferred. If the article is a filament of cylindrical geometry, the article may be shaped using a die, for example a die having a circular orifice.
In some embodiments, the filaments are obtained by a melt mixing process by heating the polymer component above the melting temperature of the polymer component and melt mixing the components of the part material.
The process may comprise (if desired) several successive steps of melt mixing or extrusion under different conditions.
The process itself, or each step of the process if relevant, may also comprise a step comprising cooling of the molten mixture.
Support material
The method of the present invention may also employ another polymer component to support the 3D object being built. This polymer component, which is similar or different from the part material used to construct the 3D object, is referred to herein as a support material. Support material may be required during 3D printing to provide vertical and/or lateral support for the part material being built. The support material will need to have similar thermal characteristics to the part material in the sense that it can remain strong and rigid to provide the desired support for the part material in the hollow or overhanging regions of the part.
Support materials that may be used in the context of the present method advantageously have a high melting temperature (i.e. above 260 ℃) in order to resist high temperature applications. The support material may also have a water absorption behavior or solubility in water at temperatures below 110 ℃ so as to fully swell or deform upon exposure to moisture.
According to an embodiment of the invention, the method for manufacturing a three-dimensional object with an additive manufacturing system further comprises the steps of:
-printing a support structure layer from the support material
-removing at least a portion of the support structure from the three-dimensional object.
A variety of polymer components may be used as support materials. Notably, the support material may comprise a polyamide or copolyamide, such as those described in PCT applications WO 2017/167691 and WO 2017/167692, for example.
Application of
The invention also relates to the use of a part material (M) comprising a polymer component as described above for producing a three-dimensional object.
The invention also relates to the use of a filament material comprising a polymer component as described above for the manufacture of a three-dimensional object.
All of the embodiments described above in relation to the part material apply equally to the use of the part material or the use of the filament material.
The invention also relates to the use of a part material (M) for producing filaments for use in the production of three-dimensional objects, the part material comprising a polymer component as described above.
The invention also relates to a 3D object or 3D article obtainable at least in part by the manufacturing method of the invention using the part materials described herein. These 3D objects or 3D articles preferably exhibit a density comparable to injection molded objects or articles. They also exhibit comparable or improved mechanical properties.
The 3D object or article obtainable by such a manufacturing method can be used in a variety of end applications. Mention may be made in particular of implantable devices, dental prostheses, stents and parts of complex shape in the aerospace industry, parts in the hood in the automotive industry, oil and gas applications and as electronic components.
The 3D objects or articles obtainable by such a manufacturing method may be used in many aircraft applications including, for example, passenger service units, stairways, windowsills, ceilings, information displays, window covers, ceilings, sidewall panels, wall partitions, display cases, mirrors, sun visors, curtains, storage boxes, storage doors, overhead stowage bins, service trays, seat backs, cabin partitions and pipes.
The 3D objects or articles obtainable by such manufacturing methods are useful in many automotive applications including, for example, connectors, fittings, emission control systems, and injection molded parts.
The 3D objects or articles obtainable by this manufacturing method can be used in oil and gas applications, such as offshore solutions, to prevent corrosion, chemical attack and ageing.
The 3D object or article obtainable by such a manufacturing method can be used as electronic components including, for example, wire and cable applications requiring high excellent heat and chemical resistance as well as good flame, smoke and toxicity characteristics, as well as components requiring dimensional stability.
The disclosure of any patent, patent application, and publication incorporated by reference herein should be given priority if it conflicts with the description of the present application to the extent that the term "does not become clear".
Examples
The present disclosure will now be described in more detail with reference to the following examples, which are intended to be illustrative only and are not intended to limit the scope of the present disclosure.
Starting materials
Hydroquinone, optical grade, obtained from Eastman company (Eastman) of the united states. It contained 0.38wt% moisture, which was used to adjust the feed weight. All indicated weights include moisture.
Resorcinol, ACS reagent grade, was obtained from Aldrich, usa.
4,4' -biphenol, polymerization grade, was obtained from the United states SI company (SI, USA).
Catechol, flakes, obtained from Solvey Inc. (Solvay USA). The purity was 99.85% by GC. It contained 680ppm of moisture, which was used to adjust the feed weight. All indicated weights include moisture.
4,4' -difluorobenzophenone, polymer grade (99.8% +) was obtained from Malwa, india.
Diphenyl sulfone (polymeric grade) was obtained from pranlon corporation (Proviron) (99.8% pure).
Sodium carbonate, light soda ash, is obtained from Solvay s.a., france.
Potassium carbonate, having a d90<45 μm, is obtained from the Armand products.
Lithium chloride (anhydrous grade) is obtained from Acros corporation.
Preparation of the resin
PEEK
Into a 500mL 4-necked reaction flask (equipped with stirrer, N2 inlet tube, crisen adapter with thermocouple inserted into the reaction medium, and dean-Stark trap with condenser and dry ice trap) were introduced 127.82g of diphenyl sulfone, 28.685g of hydroquinone, and 57.326g of 4,4' -difluorobenzophenone. The flask contents were evacuated under vacuum and then filled with high purity nitrogen (containing less than 10ppm O2). The reaction mixture was then placed under a constant nitrogen sweep (60 mL/min).
The reaction mixture was slowly heated to 150 ℃. 28.481g of Na was introduced into a powder dispenser at 150 DEG C 2 CO 3 And 0.180g of K 2 CO 3 Is added to the reaction mixture within 30 minutes. At the end of the addition, the reaction mixture was heated to 320 ℃ at 1 ℃/min. After 14 minutes at 320 ℃, the reaction was terminated in 3 stages: 6.818g of 4,4' -difluorobenzophenone was added to the reaction mixture while maintaining a nitrogen sweep over the reactor. After 5 minutes, 0.444g of lithium chloride was added to the reaction mixture. After 10 minutes, an additional2.273g of 4,4' -difluorobenzophenone was added to the reactor and the reaction mixture was held at this temperature for 15 minutes.
The reactor contents were then poured from the reactor into SS trays and cooled. The solid was broken up and ground in a grinder (through a 2mm screen). Diphenyl sulfone and salts were extracted from the mixture using acetone and water.
The powder was then dried under vacuum at 120 ℃ for 12 hours, yielding 65g of white powder.
The melt viscosity, measured by capillary rheology at 400℃for 1000s-1, was 0.30kN-s/m2.
PEEK-PEoEK copolymer 80/20
Into a 1000mL 4-neck reaction flask equipped with a stirrer, an N2 inlet tube, a claisen adapter with thermocouple inserted into the reaction medium, and a dean-Stark trap with condenser and dry ice trap were introduced 343.63g of diphenyl sulfone, 61.852g of hydroquinone, 15.426g of catechol, and 153.809g of 4,4' -difluorobenzophenone. The flask contents were evacuated under vacuum and then filled with high purity nitrogen (containing less than 10ppm O2). The reaction mixture was then placed under a constant nitrogen sweep (60 mL/min).
The reaction mixture was slowly heated to 150 ℃. A mixture of 76.938g of Na2CO3 and 0.484g of K2CO3 was added to the reaction mixture by a powder dispenser over 30 minutes at 150 ℃. At the end of the addition, the reaction mixture was heated to 320 ℃ at 1 ℃/min. After 25 minutes at 320 ℃, the reaction was terminated in 3 stages: 18.329g of 4,4' -difluorobenzophenone was added to the reaction mixture while maintaining a nitrogen sweep over the reactor. After 5 minutes, 2.388g of lithium chloride was added to the reaction mixture. After 10 minutes, a further 6.110g of 4,4' -difluorobenzophenone was added to the reactor and the reaction mixture was kept at this temperature for 15 minutes.
The reactor contents were then poured from the reactor into SS trays and cooled. The solid was broken up and ground in a grinder (through a 2mm screen). Diphenyl sulfone and salts were extracted from the mixture using acetone and water.
The powder was then dried under vacuum at 120 ℃ for 12 hours, yielding 191g of white powder.
The repeating units of the polymer are:
the melt viscosity, measured by capillary rheology at 400℃for 1000s-1, was 0.37kN-s/m2.
The blend PEEK/PEEK-PEoEK (formulation 3 in Table 1) was prepared as follows: by first tumbling the polymer to be compounded in the form of a resin for about 20 minutes. Then 26mm diameter with an L/D ratio of 48:1 was used The formulation was melt compounded in a twin screw extruder with intermeshing co-rotating parts of ZSK-26. Barrel sections 2 to 12 and the die were heated to the following set point temperatures: barrel 2-12:350 ℃, die opening: 350 ℃. The resin blend was fed at barrel section 1 using a gravity feeder at a throughput rate in the range of 30-40 lb/h. The extruder was operated at a screw speed of about 200 RPM. Vacuum is applied at barrel zone 10 at a vacuum level of about 27 inches of mercury. A single orifice die was used for all compounds to give filaments with a diameter of about 2.4 to 2.5mm, and the polymer filaments exiting the die were cooled in water and fed into a granulator to produce pellets with a length of about 2.0 mm. The pellets were annealed prior to filament extrusion as follows: at 200℃for 2h.
Preparation of filaments
The raw materials used for filament production consist of pure polymers (PEEK or PEEK-PEoEK) or dry blends of polymer resins. The polymer to be extruded into filaments in the form of a resin is tumbled for about 20 minutes. UsingIntelli-Torque/>A Torque Rheometer extruder equipped with a 0.75 "(1.905 cm) 32L/D universal single screw, a heated capillary die attachment, a 3/32 'diameter nozzle with a land (land) of length 1.5' and downstream custom designed filament conveying equipment was used to prepare filaments of 1.80mm diameter for each composition. Other downstream equipment includes belt retractors and duplex winders (Dual Station Coiler), both manufactured by ESI extrusion solutions company (ESI-Extrusion Services). Using Beta with DataPro 1000 data controller 5012 monitors filament size. The molten strands were cooled with air. />The zone setpoint temperature is as follows: region 1, 395 ℃; region 2 and region 3, 400 ℃; die head, 340 ℃. />The speed range is from 35 to 45rpm and the retractor speed range is from 33 to 36 feet per minute (10.058 to 10.973 meters per minute).
3D printing
The filaments described above were printed on an F900 extrusion-based additive manufacturing system commercially available from Stratasys, inc. The filaments were printed as model material, and Stratasys SUP8000B separate support material was used as support material. High temperature (PPSU) build sheets are used as print object substrates. During the print test, the model extruder temperature was set between 400 and 420 ℃, the support extruder temperature was set to about 400 ℃, and the heating chamber was set at 155 ℃. The Stratasys T20D tip was used for model materials with a layer thickness of 0.013 "and the Stratasys T16 tip was used for support materials. The modeling material is extruded in a layer-by-layer fashion into a series of roads to print the structure in the heating chamber. Using 100% fill and 45 °/-45 ° alternating gratings, one 6"x2mm substrate (plaque) was printed for each formulation, and immediately after printing the object was removed from the heating chamber and build sheet.
Test method
DSC (Tg, tc, heat of fusion)
Tg is determined in accordance with ASTM D3418 using a heating and cooling rate of 20 ℃/min in a Differential Scanning Calorimeter (DSC) at heat scan 2.
Tc is determined in accordance with ASTM D3418 using a heating and cooling rate of 20 ℃/min in a Differential Scanning Calorimeter (DSC) at cold scan 1.
The heat of fusion was determined according to ASTM D3418 using a heating rate of 20 ℃/min in a Differential Scanning Calorimeter (DSC) with a 2 nd heat scan.
Results
Table 1 provides an overview of the composition of the filaments used in examples 1, 2 and 3.
TABLE 1
Table 2 provides the first cooling and second heating DSC data for formulations 1, 2 and 3. The last column in table 2 shows the (Tm-Tc)/(Tm-Tg) parameter, which is a method of comparing crystallization rates between similar types of polymers (i.e., PAEKs in this case) having different glass transition temperatures and melt transition temperatures. The closer this value is to 0.0, the closer Tc is to Tm and the faster the crystallization speed is; the closer this value is to 1.0, the closer the Tc is to Tg and the slower the crystallization speed. This ratio effectively measures the supercooling thermal driving force required to effect crystallization.
TABLE 2
PEEK has a highest relative crystallization rate of 0.27, whereas PEEK-PEoEK is 0.45 slowest, with a 50/50 blend compromise of 0.33. In the melting enthalpy column (. DELTA.Hm), the absolute crystallinity of the PEEK-PEoEK copolymer was also lower than that of PEEK, 41J/g and 52J/g, respectively, while the crystallinity of the 50/50 blend was similar to that of pure PEEK, 55J/g and 52J/g, respectively.
The melting point of the pure PEEK-PEoEK copolymer (303 ℃) and its 50/50 blend with PEEK (333 ℃) is also advantageously lower than that of pure PEEK (343 ℃), which provides easier melt processing and also lower thermal degradation opportunities than pure PEEK, since all of these polymers have similar degradation temperatures, which is caused by essentially the same ether and ketone bonds and their resulting bond dissociation energies.
A 6"x 2mm substrate was printed using the above materials. For PEEK materials, during the printing process, some undesirable warpage occurs in the left front corner of the object, which curls upward. The center defect in all three printed objects is a shear for DSC analysis of the printed parts, as will be further described below. The PEEK-PEoEK copolymer did not warp during the 3D printing process. After removal from the PPSU build sheet, it showed a slight downward bend. The 3D printed substrate from the 50/50 blend material advantageously sits flat during the 3D printing process and also after removal from the PPSU build sheet without exhibiting any curl or warp.
Table 3 provides the first thermal DSC thermal transition of the cut from the 3D printed object. The heating chamber is maintained at 155℃which is very close to the T of all these polymers g 。
TABLE 3 Table 3
The PEEK printed parts were fully crystallized during the printing process, as indicated by the absence of cold crystallization peaks during the DSC first heat scan. The pure PEEK-PEoEK copolymer has a cold crystallization enthalpy (. DELTA.H) of 27J/g c ) While the 50/50 blend has a lower ΔH of 15J/g c Indicating that more of the 50/50 blend crystallized during the printing process than the PEEK-PEoEK copolymer.
All the above results, taken together, are evident that PEEK-PEoEK and its blends with PEEK advantageously have lower crystallinity and slower crystallization speed than PEEK, while retaining crystallinity during 3D printing. Although PEEK-PEoEK and its blends with PEEK are partially crystallized during the 3D printing process, they surprisingly and advantageously do not warp when printed. This is in contrast to pure PEEK, which warps during the 3D printing process. This retained crystallinity of PEEK-PEoEK and its blends with PEEK contributes to the heat, mechanical and chemical resistance properties of the printed part, as well as maintaining the shape of the part when the end user decides to perform a post-print annealing step to further increase the crystallinity of the part.
Claims (15)
1. An Additive Manufacturing (AM) method for manufacturing a three-dimensional (3D) object, comprising extruding a part material (M) comprising a polymer component comprising at least one PEEK-PEoEK copolymer, wherein the copolymer comprises a total of at least 50mol.% of repeating units (R PEEK ) And repeating units (R) PEoEK ) Wherein:
(a) Repeating unit (R) PEEK ) Is a repeating unit having formula (a):
and is also provided with
(b) Repeating unit (R) PEoEK ) Is a repeating unit having the formula (B):
wherein the method comprises the steps of
-each R 1 And R is 2 Identical to or different from each other, are independently selected at each occurrence from the group consisting of: halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkyl sulfonate, alkali metalOr alkaline earth metal phosphonates, alkylphosphonates, amines and quaternary ammonium,
-each a and b is independently selected from the group consisting of integers ranging from 0 to 4, and
the PEEK-PEoEK copolymer comprises the following components in molar ratio R PEEK /R PEoEK These repeat units R range from 95/5 to 5/95 PEEK And R is PEoEK 。
2. The method of claim 1, wherein the repeating units (R PEEK ) Is a repeating unit having the formula:
3. the method of claim 1 or 2, wherein the repeating units (R PEoEK ) Is a repeating unit having the formula:
4. a method according to any one of claims 1 to 3, wherein the PEEK-PEoEK copolymer consists essentially of recurring units (R PEEK ) And (R) PEoEK ) Is constituted by repeating units R PEEK And R is PEoEK Any additional repeat units that are different are not present, or may be present in an amount of up to 2mol.%, up to 1mol.%, or up to 0.5mol.% relative to the total moles of repeat units in the PEEK-PEoEK copolymer.
5. The process according to any one of claims 1 to 4, wherein the repeating unit R PEEK And R is PEoEK With R ranging from 95/5 to greater than 50/50, preferably from 95/5 to 60/40, still more preferably from 90/10 to 65/35 PEEK /R PEoEK The molar ratio is present in the PEEK-PEoEK copolymer.
6. The method of any of claims 1-5, wherein the part material (M) further comprises 0.1wt.% to 60wt.% of an additive selected from the group consisting of: flow agents, fillers, colorants, lubricants, plasticizers, stabilizers, flame retardants, nucleating agents, and combinations thereof.
7. The method of any of claims 1-6, wherein the polymer component of the part material (M) further comprises at least one polymer different from the PEEK-PEoEK copolymer, preferably at least one PEEK (co) polymer.
8. The method of any one of claims 1-7, wherein the part material (M) is in the form of filaments having a cylindrical or ribbon filament geometry, the diameter or at least one of its cross-sections having dimensions that vary between 0.5mm and 5mm, preferably between 0.8 and 4mm, or even more preferably between 1mm and 3.5 mm.
9. The method of any of claims 1-6, wherein the part material (M) is in the form of pellets having a size ranging from 1mm to 1 cm.
10. The method of any one of claims 1-9, wherein the part material (M) comprises a polymer component comprising: based on the total weight of the polymer component,
-from 20 to 99wt.% of at least one PEEK-PEoEK copolymer, and
from 1 to 80wt.% of at least one PEEK (co) polymer.
11. A filament material having a cylindrical geometry and a diameter of between 0.5 and 5mm ± 0.15mm, the filament material comprising a polymer component comprising at least one PEEK-PEoEK copolymer, wherein the copolymer comprises relative to the PEEK-PEoEK copolymerIn total of at least 50mol.% of the total number of repeating units (R PEEK ) And repeating units (R) PEoEK ) Wherein:
(a) Repeating unit (R) PEEK ) Is a repeating unit having formula (a):
and is also provided with
(b) Repeating unit (R) PEoEK ) Is a repeating unit having the formula (B):
wherein the method comprises the steps of
-each R 1 And R is 2 Identical to or different from each other, are independently selected at each occurrence from the group consisting of: halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium,
-each a and b is independently selected from the group consisting of integers ranging from 0 to 4, and
the PEEK-PEoEK copolymer comprises the following components in molar ratio R PEEK /R PEoEK These repeat units R range from 95/5 to 5/95 PEEK And R is PEoEK 。
12. The filament material of claim 11, wherein the filament is obtained by a melt mixing process by heating the polymer component above the melting temperature of the polymer component and melt mixing the components of the part material.
13. The filament material of claim 11 or 12, wherein the polymer component comprises at least 80wt.% of the PEEK-PEoEK copolymer based on the total weight of the polymer component of the filament.
14. A three-dimensional (3D) object obtainable by an extrusion-based 3D printing method from a part material (M) comprising a polymer component comprising at least one PEEK-PEoEK copolymer, wherein the copolymer comprises a total of at least 50mol.% of repeating units (R PEEK ) And repeating units (R) PEoEK ) Wherein:
(a) Repeating unit (R) PEEK ) Is a repeating unit having formula (a):
and is also provided with
(b) Repeating unit (R) PEoEK ) Is a repeating unit having the formula (B):
Wherein the method comprises the steps of
-each R 1 And R is 2 Identical to or different from each other, are independently selected at each occurrence from the group consisting of: halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium,
-each a and b is independently selected from the group consisting of integers ranging from 0 to 4, and
the PEEK-PEoEK copolymer comprises the following components in molar ratio R PEEK /R PEoEK These repeat units R range from 95/5 to 5/95 PEEK And R is PEoEK 。
15. Use of a part material (M) comprising a polymer component for manufacturing 3D objects using an extrusion-based 3D printing methodThe material is preferably in the form of filaments, and the polymer component comprises at least one PEEK-PEoEK copolymer, wherein the copolymer comprises at least 50mol.% total of recurring units (R PEEK ) And repeating units (R) PEoEK ) Wherein:
(a) Repeating unit (R) PEEK ) Is a repeating unit having formula (a):
and is also provided with
(b) Repeating unit (R) PEoEK ) Is a repeating unit having the formula (B):
wherein the method comprises the steps of
-each R 1 And R is 2 Identical to or different from each other, are independently selected at each occurrence from the group consisting of: halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium,
-each a and b is independently selected from the group consisting of integers ranging from 0 to 4, and
the PEEK-PEoEK copolymer comprises the following components in molar ratio R PEEK /R PEoEK These repeat units R range from 95/5 to 5/95 PEEK And R is PEoEK 。
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| EP21155706.1 | 2021-02-08 | ||
| PCT/EP2021/082569 WO2022112194A1 (en) | 2020-11-30 | 2021-11-23 | Additive manufacturing method for making a three-dimensional object |
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