Powdered material (P) containing poly(arylene sulfide) (PAS) polymer and use thereof for additive manufacturing

Abstract

The present invention relates to a pulverous material (M) containing at least one poly(arylene sulfide) (PAS) polymer comprising recurring units p, q and r according to formulae (I), (II) and (III): wherein n p , n q and n r are the mole % of each recurring unit p, q and r, respectively; the recurring units p, q and r are arranged in blocks, in alternation or randomly; 1% ≤ (n q +n r ) / (n p +n q +n r ) ≤ 12%; nq is ≥ 0% and nr is ≥ 0%; j is zero or an integer varying between 1 and 4; R 1 is selected from the group consisting of a halogen atom, a C1-C 12 alkyl group, a C7-C 24 alkylaryl group, a C7-C 24 aralkyl group, a C6-C 24 arylene group, a C1-C 12 alkoxy group, and a C6-C 18 aryloxy group.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to U.S. Provisional Application 62 / 987,423, filed March 10, 2020, and European Patent Application 20185792.7, filed July 14, 2020, the entire contents of each of these applications are incorporated herein by reference for all purposes. Technical Field

[0003] This invention relates to a powdered material (M) containing at least one poly(aryl sulfide) (PAS) polymer and a method for manufacturing three-dimensional (3D) articles, parts, or composite materials from such powdered material (M). The invention also relates to 3D articles, parts, or composite materials obtainable from this method, and the use of such articles, parts, or composite materials in oil and gas applications, automotive applications, electrical and electronic applications, or aerospace and consumer products. Background Technology

[0004] Many objects, from everyday items to automotive parts, are made from a single piece of material, or milled or sculpted from a larger piece. An alternative method for manufacturing objects is to deposit thin layers of material, such as powder, and then add another layer on top, followed by another, and so on. This additive process is called additive manufacturing (AM), more commonly known as 3D printing. Currently, the market offers a wide range of specially designed 3D-printed products, from automotive parts to dental implants. Notably, they can be made using plastics. Additive manufacturing is expected to disrupt established practices and overturn conventional assumptions about mass production in remote factories. Local manufacturing of small batches, or even single items, closer to the end user will become feasible.

[0005] One of the fundamental limitations associated with known additive manufacturing methods that use polymer part materials in powder form is the lack of identification of materials that exhibit the correct set of properties in order to print 3D parts / objects with acceptable density and mechanical properties.

[0006] Poly(aryl sulfides) (PAS) polymers are semi-crystalline thermoplastic polymers with remarkable mechanical properties, such as high tensile modulus and high tensile strength, as well as significant stability against thermal degradation and chemical reactivity. They are also characterized by excellent melt processability, such as injection molding.

[0007] This wide range of properties makes PAS polymers suitable for a wide range of applications, such as the automotive, electrical, electronics, aerospace, and appliance markets.

[0008] Despite the aforementioned advantages, PAS polymers are known to have low impact resistance and low elongation at break, in other words, poor ductility and poor toughness.

[0009] Therefore, there is a need for a PAS polymer for additive manufacturing that has improved ductility and toughness while maintaining high tensile strength.

[0010] WO 2017 / 1226484 (Toray Industries, Inc.) describes the use of PAS resin as a powder for the production of three-dimensional models by powder sintering via a 3D printer.

[0011] WO 2020 / 011991 (Solvay) relates to a PAS polymer that can be used in additive manufacturing. This PAS exhibits a calcium content of less than 200 ppm as a key technical feature, measured by X-ray fluorescence (XRF) analysis calibrated with standards via ICP-OES.

[0012] WO 2020 / 011990 (Solvay) describes PAS polymers exhibiting flowability, which makes the powder ideal for applications such as manufacturing 3D objects using laser sintering-based additive manufacturing systems, where the powder must exhibit good flow behavior to facilitate powder deposition during the printing process.

[0013] JP 2019165004 (Toray Industries, Inc.) relates to an insulating tube with excellent durability, electrical properties, and flame retardancy. In its Reference Example 1, D1 describes the preparation of PPS based on 90 mol of p-dichlorobenzene and 10 mol of m-dichlorobenzene. However, this document does not describe the resin in powder form with a specific PSD, which is highly suitable for 3D printing.

[0014] JP S63 10633 (Idemitsu Corporation) relates to a method for producing polyarylene sulfides for use as engineering plastics.

[0015] EP 3530701 (Toray Industries, Inc.) relates to a polyarylether sulfide resin powder granular mixture suitable for producing three-dimensional molded articles using a selective laser sintering (SLS) 3D printer, and a method for producing three-dimensional molded articles using such polyarylether sulfide resin powder granular mixture.

[0016] These documents do not describe powdered materials containing PAS polymers as described herein for additive manufacturing. The use of such materials has been shown to produce better printability and improved final part properties (mechanical and aesthetic) compared to powders used in existing technologies. Summary of the Invention

[0017] In a first aspect, the present invention relates to a powdered material (M) containing a poly(aryl sulfide) (PAS) polymer, said PAS polymer comprising repeating units p, q, and r according to formulas (I), (II), and (III):

[0018]

[0019] in

[0020] n p n q and n r These represent the mole percent of each repeating unit p, q, and r, respectively;

[0021] Repeating units p, q, and r are arranged in blocks, alternately, or randomly;

[0022] 1%≤(n) q +n r ) / (n p +n q +n r )≤12%; n q It is ≥0% and n r It is ≥0%;

[0023] j is zero or an integer varying between 1 and 4;

[0024] R 1 Choose from the following groups: halogen atoms, C1-C 12 Alkyl, C7-C 24 Alkyl aryl, C7-C 24 Aryl group, C6-C 24 aryl, C1-C 12 Alkoxy groups and C6-C 18 aryloxy,

[0025] In another aspect, the present invention relates to a method for manufacturing three-dimensional (3D) articles, parts, or composite materials, comprising:

[0026] a) Deposition of a continuous layer of powdered material (M) as described herein, and

[0027] b) Print the layer before depositing subsequent layers.

[0028] According to this aspect, step b) preferably includes selectively sintering the powder by electromagnetic radiation.

[0029] According to a third aspect, the present invention relates to a three-dimensional (3D) article, part or composite material that can be obtained from the powdered material (M) described herein by additive manufacturing, wherein the additive manufacturing is preferably selective laser sintering (SLS), composite material-based additive manufacturing technology (“CBAM”) or multi-jet melting (MJF).

[0030] According to a fourth aspect, the present invention relates to the use of the powdered material (M) described herein for manufacturing three-dimensional (3D) objects using additive manufacturing, preferably selective laser sintering (SLS), composite material-based additive manufacturing technology (“CBAM”) or multi-jet melting (MJF).

[0031] According to a fifth aspect, the present invention relates to the use of a polymeric component (P) comprising at least one poly(aryl sulfide) (PAS) polymer described herein, optionally in combination with one or more flow aids (F) and / or one or more additives (A), for the manufacture of a powdered material (M) for additive manufacturing, preferably selective laser sintering (SLS), composite material-based additive manufacturing technology (“CBAM”), or multi-jet fusion (MJF).

[0032] According to a sixth aspect, the present invention relates to the use of articles, parts or composite materials in oil and gas applications, automotive applications, electrical and electronic applications, or aerospace and consumer products.

[0033] Disclosure of the invention

[0034] This document discloses a powdered material (M) and a method for manufacturing 3D objects (i.e., articles, parts, or composites) from such powdered material (M) comprising at least one poly(aryl sulfide) polymer (also referred to herein as "poly(aryl sulfide)" or PAS). References to poly(aryl sulfide) polymers specifically include, but are not limited to, polyphenylene sulfide polymers, also referred to herein as "polyphenylene sulfide" or PPS.

[0035] The powdered material (M) of the present invention can have a regular shape such as a sphere, or a complex shape obtained by grinding / milling a polymer component (P) (i.e., at least a PAS polymer) in the form of granules or coarse powder.

[0036] In this application:

[0037] -Even any description relating to a specific embodiment may be applied to and interchanged with other embodiments disclosed herein;

[0038] - When an element or component is referred to as being included in and / or selected from the list of enumerated elements or components, it should be understood that in the relevant embodiments explicitly considered herein, the element or component may also be any one of these enumerated individual elements or components, or may be a group consisting of any two or more of the explicitly enumerated elements or components; any element or component listed in the list of elements or components may be omitted from this list; and

[0039] - Any enumeration of numerical ranges by endpoints in this document includes all numbers contained within the enumerated range, as well as the endpoints and equivalents of that range.

[0040] Powdered material (M)

[0041] The powdered material (M) of the present invention comprises at least one polymer component (P). The polymer component (P) of the powdered material (M) may comprise one or more PAS as described below. It may also comprise at least one additional polymer material, i.e., at least one polymer or copolymer different from the PAS polymer described herein. This additional polymer material may, for example, be selected from the group consisting of: poly(aryl ether sulfone) (PAES) polymers, such as poly(diphenyl ether sulfone) (PPSU) polymers or polysulfone (PSU) polymers, and poly(aryl ether ketone) (PAEK) polymers, such as poly(ether ether ketone) (PEEK) polymers. This additional polymer material may also be a homopolymer of poly(aryl sulfide) (PAS*) polymers, such as poly(phenylene sulfide) (PPS) polymers, different from the PAS described herein.

[0042] The PAS described herein comprises repeating units p, q, and r according to equations (I), (II), and (III), respectively:

[0043]

[0044] The repeating units p, q, and r are arranged in blocks, alternately, or randomly.

[0045] In equation (I), j is zero or an integer varying between 1 and 4.

[0046] Preferably, j in equations (I), (II), and / or (III) is zero, which means that the aromatic ring is unsubstituted. Therefore, the repeating units p, q, and r are defined according to equations (IV), (V), and (VI), respectively:

[0047]

[0048] When j varies between 1 and 4, R 1 You can choose from the following groups: halogen atoms, C1-C 12 Alkyl, C7-C24 Alkyl aryl, C7-C 24 Aryl group, C6-C 24 aryl, C1-C 12 Alkoxy groups and C6-C 18 Aryloxy.

[0049] The molar percentages of repeating units p, q, and r in equation (I) (denoted as n) p n q and n r ) is such that 1% ≤ (n q +n r) / (n p +n q +n r) ≤12%, which means that the PAS polymer with formula (I) contains between 1 and 12 mol.% of repeating units q and r, based on the total number of repeating units p, q and r in the polymer.

[0050] The PAS polymer described herein comprises repeating units p, and also comprises repeating units q and / or r. When the PAS polymer comprises repeating units p, q, and r, n in the above equation... q and n r All are >0%. Alternatively, the PAS polymer described herein may contain repeating units p and q, but not repeating unit r. In this case, n q It is ≥1%, but n r =0%. According to the third possibility, the PAS polymer described herein may contain repeating units p and r, but not repeating unit q. In this case, n r It is ≥1%, but n q =0%.

[0051] In some preferred embodiments, the PAS described herein comprises repeating units p and q according to equations (I) and (II), respectively:

[0052]

[0053] The repeating units p and q are arranged in blocks, alternately, or randomly. Preferably, j in formula (I) and / or (II) is zero, which means that at least one aromatic ring is unsubstituted. More preferably, j in formula (I) and (II) is zero, which means that both aromatic rings are unsubstituted.

[0054] In some other preferred embodiments, the PAS described herein comprises repeating units p and r according to equations (I) and (III), respectively:

[0055]

[0056] The repeating units p and r are arranged in blocks, alternately, or randomly. Preferably, j in formula (I) and / or (III) is zero, which means that at least one aromatic ring is unsubstituted. More preferably, j in formula (I) and (III) is zero, which means that both aromatic rings are unsubstituted.

[0057] In some embodiments, the molar percentages of repeating units p, q, and r in PAS are such that:

[0058] 1.2%≤(n) q +n r ) / (n p +n q +n r) ≤10.8% or

[0059] 1.5% ≤ (n q +n r ) / (n p +n q +n r) ≤10.5% or

[0060] 1.8% ≤ (n q +n r ) / (n p +n q +n r) ≤10.2% or

[0061] 2.0% ≤ (n q +n r ) / (n p +n q +n r) ≤10.0%

[0062] In some preferred embodiments where the PAS contains repeating units p and q, but not repeating unit r, the molar percentages of repeating units p and q in the PAS are such that:

[0063] 1.2% ≤ n q / (n p +n q ≤10.8% or

[0064] 1.5% ≤ n q / (n p +n q ≤10.5% or

[0065] 1.8% ≤ n q / (n p +n q ≤10.2% or

[0066] 2.0%≤n q / (np +n q ≤10.0%

[0067] As an example of implementation, n q / (n p +n q () equals 2.5 mol.%, 3.0 mol.%, 5.0 mol.%, and 7.0 mol.%.

[0068] In some preferred embodiments where the PAS includes repeating units p and r, but does not contain repeating unit q, the molar percentages of repeating units p and r in the PAS are such that:

[0069] 1.2% ≤ n r / (n p +n r ≤10.8% or

[0070] 1.5% ≤ n r / (n p +n r ≤10.5% or

[0071] 1.8% ≤ n r / (n p +n r ≤10.2% or

[0072] 2.0%≤n r / (n p +n r ≤10.0%

[0073] As an example of implementation, n r / (n p +n r () equals 2.5 mol.%, 3.0 mol.%, 5.0 mol.%, and 7.0 mol.%.

[0074] According to the embodiment, n p +n q +n r The sum is at least 50%, meaning that based on the total number of moles of repeating units in the PAS polymer, PAS contains at least 50 mol.% of repeating units p, q, and r. For example, based on the total number of moles of repeating units in the PAS polymer, n p +n q +n r The sum can be at least 60%, at least 70%, at least 80%, at least 90%, or even at least 95%.

[0075] According to the embodiments described herein, PAS consists of repeating units p, and repeating units q and / or r, or is substantially composed of them. The expression "substantially composed of..." means that PAS includes repeating units p, and repeating units q and / or r, and other repeating units different from repeating units p, q, and r, based on the total molar number of repeating units in the PAS polymer, less than 10 mol.%, preferably less than 5 mol.%, more preferably less than 3 mol.%, and even more preferably less than 1 mol.%.

[0076] According to the embodiment, n p +n q +n r The sum is 100%, where n q and n r At least one of them is >0 mol.%.

[0077] According to another embodiment, n p +n q The sum is 100%.

[0078] According to yet another embodiment, n p +n r The sum is 100%.

[0079] According to the embodiment, n p +n q +n r The sum is less than 100%. In this embodiment, the PAS polymer contains at least one repeating unit different from p, r, and q, for example, repeating units according to formulas (VII) to (XVII):

[0080]

[0081] Where R 2 You can choose from the following groups: halogen atoms, C1-C 12 Alkyl, C7-C 24 Alkyl aryl, C7-C 24 Aryl group, C6-C 24 aryl, C1-C 12 Alkoxy groups and C6-C 18 The aryloxy group, k is zero or an integer varying between 1 and 4.

[0082] Preferably, the melt flow rate of PAS (according to ASTM D1238, Procedure B, at 315.6°C and 1.27 kg by weight) is at most 700 g / 10 min, more preferably at most 500 g / 10 min, and even more preferably at most 200 g / 10 min.

[0083] Preferably, the melt flow rate of PAS (according to ASTM D1238, Procedure B, at 315.6°C and 1.27 kg by weight) is at least 1 g / 10 min, more preferably at least 5 g / 10 min, even more preferably at least 10 g / 10 min, even more preferably at least 15 g / 10 min, and even more preferably at least 50 g / 10 min.

[0084] Preferably, when determined in a differential scanning calorimeter (DSC) during the second thermal scan using a heating and cooling rate of 20°C / min according to ASTM D3418, the PAS has a melting point of at least 220°C, more preferably at least 225°C, and even more preferably at least 230°C.

[0085] Preferably, when determined in a differential scanning calorimeter (DSC) during the second thermal scan using a heating and cooling rate of 20°C / min according to ASTM D3418, the PAS has a melting point of up to 290°C, more preferably up to 285°C, and even more preferably up to 280°C.

[0086] In some embodiments, PAS has a heat of fusion greater than 20 J / g, preferably greater than 21 J / g or greater than 22 J / g, as determined in the second thermal scan of a differential scanning calorimeter (DSC) using a heating and cooling rate of 20 °C / min according to ASTM D3418.

[0087] The powdered material (M) of the present invention comprises a polymer component (P) that contains at least one PAS polymer as described above. The powdered material (M) of the present invention may consist substantially of one or more polymers, for example, it may consist substantially of one PAS polymer as described herein, or it may also contain additional components as described below (e.g., flow aids / flow promoters (F)) and / or one or more additives (A). When the powdered material (M) of the present invention contains additional components, they may be added before, during, or after the milling step or blended with the polymer component described herein.

[0088] In some embodiments of the invention, the powdered material (M) has a di of less than 100 μm, as measured by laser scattering in isopropanol. 50 Value. According to an embodiment, the powdered material (M) has a dm of less than 90 μm, preferably less than 80 μm or less than 75 μm, as measured by laser scattering in isopropanol. 50 value.

[0089] In some embodiments of the invention, the powdered material (M) has a dm greater than 10 μm, as measured by laser scattering in isopropanol. 50Value. According to an embodiment, the powdered material (M) has a dm value greater than 15 μm, preferably greater than 20 μm, greater than 25 μm, or greater than 30 μm, as measured by laser scattering in isopropanol. 50 value.

[0090] In some embodiments of the invention, the powdered material (M) has a di of less than 150 μm, as measured by laser scattering in isopropanol. 90 Value. According to an embodiment, the powdered material (M) has a dm of less than 120 μm, preferably less than 110 μm or less than 100 μm, as measured by laser scattering in isopropanol. 90 value.

[0091] In some embodiments of the invention, the powdered material (M) has a dm greater than 0.1 μm, as measured by laser scattering in isopropanol. 10 Value. According to a preferred embodiment, the powdered material (M) has a dm greater than 1 μm, preferably greater than 5 μm, or greater than 10 μm, as measured by laser scattering in isopropanol. 10 value.

[0092] In some embodiments of the invention, the powdered material (M) has a dm as measured by laser scattering in isopropanol, between 40 μm and 70 μm, preferably between 40 μm and 60 μm, or between 43 μm and 58 μm, or between 45 μm and 55 μm. 50 Value. Powdered materials (M) with this particle size distribution are, for example, very suitable for selective laser sintering (SLS).

[0093] In some embodiments of the invention, the powdered material (M) has a di of less than 195 μm, as measured by laser scattering in isopropanol. 99 Value. According to a preferred embodiment, the powdered material (M) has a dm of less than 190 μm, preferably less than 180 μm or less than 170 μm, as measured by laser scattering in isopropanol. 99 value.

[0094] The powdered material (M) of the present invention can have an immersion / evacuation temperature range of 0 to 30 m³, as measured by ISO 9277 using a maximum immersion / evacuation temperature of 25°C. 2 / g, preferably from 2 to 25m 2 / g, more preferably from 4 to 20m 2 / g of BET surface area.

[0095] The powdered material (M) of the present invention can have a content of at least 0.35 g / cm³. 3 Preferably at least 0.45 g / cm³ 3 The optimal value is at least 0.50 g / cm³. 3The bulk density (or dumping bulk density).

[0096] According to one embodiment, based on the total weight of the powdered material (M), the powdered material (M) of the present invention comprises at least 50 wt.% of a polymer component (P), such as at least 60 wt.% of a polymer component (P), at least 70 wt.% of a polymer component (P), at least 80 wt.% of a polymer component (P), at least 90 wt.% of a polymer component (P), at least 95 wt.% of a polymer component (P), at least 98 wt.% of a polymer component (P) as described herein.

[0097] According to one embodiment, based on the total weight of the powder, the polymer component (P) contains at least 50 wt.% of the PAS described herein, such as at least 60 wt.% of the PAS described herein, at least 70 wt.% of, at least 80 wt.% of, at least 90 wt.% of, at least 95 wt.% of, at least 98 wt.% of, or at least 99 wt.% of the PAS described herein.

[0098] Before using the powder in additive manufacturing, an additional component may be added to the polymer component (P) before, during, or after the grinding step of the polymer component (P) (note the grinding step of PAS as described herein). For example, the additional component may be a flow aid (F). This flow aid (F) may be, for example, hydrophilic. Examples of hydrophilic flow aids are inorganic pigments, particularly selected from the group consisting of silica, alumina, and titanium dioxide. Fumed silica may be mentioned. Fumed silica is a trade name. (Evonik) and It is commercially available from Cabot Corporation. Fumed alumina is marketed under the trade name. (Cabote) is available for commercial purchase.

[0099] In one embodiment of the invention, based on the total weight of the powder, the powdered material (M) contains from 0.01 to 10 wt.% of a flow aid (F), such as from 0.05 to 8 wt.%, from 0.1 to 6 wt.%, or from 0.15 to 5 wt.% of at least one flow aid (F), such as at least fumed silica or fumed alumina.

[0100] These silica or alumina particles consist of primary particles at the nanoscale (typically between 5 and 50 nm for fumed silica or alumina). These primary particles combine to form aggregates. When used as a flow aid, silica or alumina is found to exist in various forms (basic particles and aggregates).

[0101] The powdered material (M) of the present invention may also contain one or more additives (A) selected from the group consisting of: fillers (such as carbon fiber, glass fiber, milled carbon fiber, glass beads, glass microspheres, milled glass fiber, wollastonite, silica beads, talc, calcium carbonate), colorants, dyes, pigments, lubricants, plasticizers, flame retardants (such as halogenated and halogen-free flame retardants), nucleating agents, heat stabilizers, light stabilizers, antioxidants, processing aids, thermally conductive fillers (such as boron nitride), fluxes, and electromagnetic absorbers. Specific examples of these optional additives (A) are titanium dioxide, zinc oxide, cerium oxide, silica or zinc sulfide, glass fiber, and carbon fiber.

[0102] The powdered material (M) of the present invention may also contain flame retardants, such as halogens and halogen-free flame retardants.

[0103] In another embodiment of the invention, based on the total weight of the powder, the powdered material (M) contains at least one additive (A) ranging from 0.01 to 30 wt.%, for example, from 0.05 to 25 wt.%, from 0.1 to 20 wt.%, or from 0.15 to 10 wt.%.

[0104] According to one embodiment, the powdered material (M) of the present invention comprises:

[0105] - At least 50 wt.% of polymer component (P),

[0106] - at least one flow aid (F) from 0.01 wt.% to 10 wt.%, from 0.05 to 8 wt.%, from 0.1 to 6 wt.%, or from 0.15 to 5 wt.%, and

[0107] -Optionally, at least one additive (A) selected from the group consisting of: fillers (e.g., carbon fiber, glass fiber, milled carbon fiber, glass beads, glass microspheres, silica beads, talc, calcium carbonate, milled glass fiber, wollastonite), colorants, dyes, pigments, lubricants, plasticizers, flame retardants (e.g., halogenated and halogen-free flame retardants), nucleating agents, heat stabilizers, light stabilizers, antioxidants, processing aids, thermally conductive fillers (e.g., boron nitride), fluxes, and electromagnetic absorbers.

[0108] % is based on the total weight of the powder.

[0109] The PAS polymers of the present invention can be obtained by methods known in the art. Notably, reference can be made to WO 2015 / 095362 A1 (Chevron Philipps), WO 2015 / 177857 A1 (Solvay), and WO 2016 / 079243 A1 (Solvay), which are incorporated herein by reference.

[0110] The PAS polymer used in the method of the present invention can notably be obtained by the following method, which includes:

[0111] Step 1) Polymerize the reactants in a reaction vessel to produce a PAS reaction mixture;

[0112] Step 2) Process the PAS reaction mixture to obtain PAS polymer and byproduct slurry;

[0113] Step 3) Recover the PAS polymer, for example, by precipitation or by evaporation; and

[0114] Step 4) Treat the PAS polymer with water and / or an aqueous acid solution and / or a calcium solution.

[0115] In some embodiments, when step 4) includes treating the PAS polymer with water and / or an aqueous acid solution (not a calcium solution), the PAS preparation method produces treated PAS having a low calcium content, as measured by X-ray fluorescence (XRF) analysis calibrated with standards via ICP-OES. Step 4) may include treating (or washing) the PAS polymer with water, an aqueous acid solution, or a combination of both. The PAS polymer may be treated or washed several times. The PAS polymer treated in step 4) may be in dried form or dispersed in a solvent.

[0116] According to the embodiment of step 4), PAS is contacted with water and / or an acidic aqueous solution (e.g., blended) to form a mixture. Based on the total weight of the mixture, the concentration of PAS in the mixture can range from about 1 wt.% to about 50 wt.%, from about 5 wt.% to about 40 wt.%, or from about 10 wt.% to about 30 wt.%.

[0117] The acidic aqueous solution that can be used in step 4) may include an acidic compound. The acidic compound can be any water-soluble organic or inorganic acid. According to embodiments, the organic acids that can be used are C1 to C15 carboxylic acids, such as C1 to C10 or C1 to C5 carboxylic acids. According to embodiments, the organic acids that can be used are selected from the group consisting of: acetic acid, formic acid, oxalic acid, fumaric acid, and potassium phthalate. Preferably, the organic acid is acetic acid. The inorganic acids that can be used are selected from the group consisting of: hydrochloric acid, monoammonium phosphate, sulfuric acid, phosphoric acid, boric acid, nitric acid, sodium dihydrogen phosphate, ammonium dihydrogen phosphate, carbonic acid, and sulfurous acid. Based on the total amount of water in the solution / mixture, the amount of the acidic compound present in the acidic aqueous solution or mixture can range from 0.01 wt.% to 10 wt.%, from 0.025 wt.% to 5 wt.%, or from 0.075 wt.% to 1 wt.%.

[0118] The solution / mixture can be heated to a temperature below the melting point of PAS. The temperature range of the solution / mixture in step 4) can be from about 10°C to 190°C, from 15°C to 185°C, or from about 20°C to 180°C.

[0119] In some embodiments, the PAS polymer is such that it exhibits a calcium content of less than 800 ppm, preferably less than 500 ppm, less than 200 ppm, less than 100 ppm, less than 50 ppm, or less than 10 ppm, as measured by X-ray fluorescence (XRF) analysis calibrated with standards via ICP-OES.

[0120] In some embodiments, the PAS polymer is such that it exhibits a calcium content greater than 1 ppm, preferably greater than 2 ppm or greater than 5 ppm, as measured by X-ray fluorescence (XRF) analysis calibrated with standards via ICP-OES.

[0121] In some embodiments, the PAS polymer is such that it exhibits a sodium content of less than 2000 ppm, preferably less than 1500 ppm, less than 1000 ppm, less than 800 ppm, less than 500 ppm, or less than 100 ppm, as measured by X-ray fluorescence (XRF) analysis calibrated with standards via ICP-OES.

[0122] In some embodiments, the PAS polymer is such that it exhibits a sodium content greater than 1 ppm, preferably greater than 2 ppm or greater than 5 ppm, as measured by X-ray fluorescence (XRF) analysis calibrated with standards via ICP-OES.

[0123] Calcium and sodium content can be measured by X-ray fluorescence (XRF) analysis calibrated to a standard with known calcium content determined by inductively coupled plasma optical emission spectrometry (ICP-OES) according to ASTM UOP714-07.

[0124] The present invention also relates to a method for producing a powdered material (M) for a layer-by-layer manufacturing method of three-dimensional parts, wherein fine powder is produced by grinding, solvent precipitation, melt spraying, or spray drying of coarse powder or particles.

[0125] The powdered material (M) used in the additive manufacturing method of the present invention can be obtained by the following:

[0126] Step 1') Grinding the polymer component (P), notably grinding the PAS polymer described herein; and

[0127] Step 2') blends the polymer component (P) from step 1') with an optional component, such as at least one flow aid (F).

[0128] The powdered material (M) used in the additive manufacturing method of the present invention can be alternatively obtained by the following:

[0129] Step 1) involves blending the polymer component (P) with an optional component, such as at least one flow aid (F), and

[0130] Step 2) Grind the blend from Step 1), notably grinding the PAS polymer described herein.

[0131] The grinding process can be carried out in a pin mill, a jet mill / fluidized jet mill with a classifier, an impact mill with a classifier, a pin / pin-beater mill, or a wet grinding mill, or a combination of these devices.

[0132] The ground powdered material can preferably be separated or screened in an air separator or classifier to obtain a predetermined fraction spectrum. The powdered material (M) is preferably screened before use in a printer. Screening includes removing particles larger than 200 μm, 150 μm, 140 μm, 130 μm, 120 μm, 110 μm, or 100 μm using appropriate equipment.

[0133] According to another aspect, the present invention relates to a method for manufacturing three-dimensional (3D) articles, parts or composite materials, the method comprising depositing a continuous layer of powdered material (M) and selectively sintering each layer before depositing subsequent layers, for example by subjecting the powder to electromagnetic radiation.

[0134] The additive manufacturing method of the present invention is preferably selected from the group consisting of selective laser sintering (SLS), composite material-based additive manufacturing technology (“CBAM”), or multi-jet melting (MJF).

[0135] Additive manufacturing methods typically use 3D printers.

[0136] For example, the SLS 3D printer is from EOS Corporation under the trade name... P is available.

[0137] For example, the MJF 3D printer is available from Hewlett-Packard Company under the trade name MultiJet Fusion.

[0138] Powders can also be used to produce continuous fiber composites in the CBAM process, for example, those developed by Impossible Objects.

[0139] According to an embodiment, the step of printing the layer includes selectively sintering the powdered material (M) by subjecting it to electromagnetic radiation (e.g., a high-power laser source such as an electromagnetic beam source).

[0140] 3D objects / articles / parts can be constructed on a substrate (e.g., a horizontal substrate and / or a planar substrate). The substrate can be movable in all directions (e.g., horizontally or vertically). During the 3D printing process, the substrate can be lowered, for example, to sinter a continuous layer of unsintered polymer material on top of a previously sintered polymer material layer.

[0141] According to an embodiment, the method further includes a step of producing a support structure. According to this embodiment, a 3D object is constructed on the support structure, and both the support structure and the 3D object are produced using the same AM method. The support structure can be used in a variety of situations. For example, the support structure can be used to provide sufficient support for a printed or being printed object to prevent deformation of the formed 3D object, especially when the 3D object is not planar. This is particularly true when the temperature used to maintain the printed or being printed 3D object is below the resolidification temperature of the polymer component (e.g., PAS polymer).

[0142] A 3D printer may include a sintering chamber and a powder bed, both of which are maintained at a defined specific temperature.

[0143] The powdered material (M) to be printed can be preheated to a processing temperature (Tp) above the powder's glass transition temperature (Tg) but below its melting temperature (Tm). Preheating the powdered material (M) makes it easier for the laser to raise the temperature of selected areas of the unfused powder layer to their melting point. The laser induces fusion of the material only at the locations specified by the input information. Typically, the laser energy exposure is selected based on the polymer used and to avoid polymer degradation.

[0144] Products and Applications

[0145] The present invention also relates to articles, parts or composites comprising poly(aryl sulfides) (PAS) as described herein, which are obtainable by the additive manufacturing method of the present invention, and the use of said articles, parts or composites in oil and gas applications, automotive applications, electrical and electronic applications, or aerospace and consumer products.

[0146] For automotive applications, the articles can be bases (e.g., oil pans), panels (e.g., exterior body panels, including but not limited to rear side panels, trunks, and hoods; and interior body panels, including but not limited to door panels and dashboards), side panels, rearview mirrors, bumpers, bars (e.g., torsion bars and rocker arms), rods, suspension components (e.g., suspension rods, leaf springs, and suspension arms), and turbocharger components (e.g., housings, volutes, compressor wheels, and impellers), pipes (for conveying, for example, fuel, coolant, air, and brake fluid), and supports. For oil and gas applications, the articles can be drilling components, such as downhole drilling pipes, chemical injection pipes, subsea umbilicals, and hydraulic control lines. The articles can also be components for mobile electronic devices.

[0147] According to embodiments, the composite material obtainable by the additive manufacturing method of the present invention is a continuous fiber-reinforced thermoplastic composite material. The fibers may be composed of carbon, glass, or organic fibers (such as aramid fibers).

[0148] The present invention also relates to the use of the powdered material (M) described herein for manufacturing three-dimensional (3D) objects using additive manufacturing, preferably selective laser sintering (SLS), composite material-based additive manufacturing technology (“CBAM”) or multi-jet melting (MJF).

[0149] The present invention also relates to the use of a polymeric component (P) comprising at least one poly(aryl sulfide) (PAS) polymer as described above for the manufacture of a powdered material (M) for additive manufacturing, preferably selective laser sintering (SLS), composite material-based additive manufacturing technology (“CBAM”) or multi-jet fusion (MJF).

[0150] The invention will now be described with reference to the following examples, which are merely illustrative and not intended to limit the scope of the invention.

[0151] Experimental Section

[0152] Material

[0153] NaSH (approximately 55-60 wt.%) is commercially available from Nouryan.

[0154] 1,3-Dichlorobenzene was obtained from Tulstar.

[0155] NaOH is commercially available from Columbus Chemical Industries Inc.

[0156] Sodium acetate is commercially available from Jarchem.

[0157] NMP is commercially available from Ashland.

[0158] Synthesis Example

[0159] PAS polymer #1 (This invention)

[0160] The polymer was synthesized in a 340-liter reactor containing 41.26 kg of NaSH (57.0 wt%), 30.84 kg of NaOH (50.6 wt%), 12.07 kg of NaOAc, and 123.05 kg of NMP. Following a dehydration step, 55.65 kg of 1,4-dichlorobenzene and 2.93 kg of 1,3-dichlorobenzene were added, and the mixture was heated to a maximum temperature of 275 °C. After the addition of 7.71 kg of additional NMP, the mixture was gradually cooled to obtain granular PPS, which was washed with a solution of NMP, water, and acetic acid at 60 °C–75 °C. The resulting product was poly(phenylene sulfide), wherein n p =95%, n q =5% and n r =0%.

[0161] PAS polymer #2 (comparison)

[0162] The polymer was synthesized and recovered from the reaction mixture according to the method described in U.S. Patent Nos. 3,919,177 and 4,415,729, washed with deionized water at 60°C for at least 5 minutes, then contacted with an aqueous acetic acid solution having a pH of <6.0 at 60°C for at least 5 minutes, and subsequently rinsed with deionized water at 60°C.

[0163] The product obtained is poly(phenylene sulfide), where n p =100%, n q =0% and n r =0%.

[0164] PAS polymer #3 (comparison)

[0165] The polymer was synthesized and recovered from the reaction mixture according to the method described in U.S. Patent Nos. 3,919,177 and 4,415,729, washed with deionized water at 60°C for at least 5 minutes, then contacted with an aqueous solution of about 0.01 mol / L calcium acetate at 60°C for at least 5 minutes, and subsequently rinsed with deionized water at 60°C.

[0166] The product obtained is poly(phenylene sulfide), where n p =100%, n q =0% and n r =0%.

[0167] Characterization of polymer components

[0168] DSC / Heat of Melting

[0169] DSC analysis was performed according to ASTM D3418 on a DSC Q200-5293 TA instrument, and data were collected using a two-heat-one-cooling method. The protocol used was as follows: First heating cycle: from 30.00℃ to 350.00℃ at 20.00℃ / min; isothermal duration 5 minutes; First cooling cycle: from 350.00℃ to 30.00℃ at 20.00℃ / min; Second heating cycle: from 30.00℃ to 350.00℃ at 20.00℃ / min. The melting temperature (T) was recorded during the first and second heating cycles. m During the cooling cycle, the melting and crystallization temperature (T) is recorded. mc During the second heating cycle, the glass transition temperature (T) was recorded. g ), and record the enthalpy of melting (ΔH) during the second heating cycle.

[0170] Molecular weight (Mw)

[0171] The weight-average molecular weight (Mw) was determined by gel permeation chromatography (GPC) at 210 °C using PL 220 high-temperature GPC with 1-chloronaphthalene mobile phase and polystyrene standards.

[0172] melt flow rate

[0173] MFR was measured on an extrusion plasticizer at 315.6°C after a 5-minute equilibration period using a 5 kg weight and a 0.0825 inch × 0.315 inch die (in g / 10 min).

[0174] Grinding of polymer components - preparation of powder materials

[0175] PAS polymers are ground into powder by grinding them on a rotary mill (Retsch SR300 rotary mill) until they reach the following PSD:

[0176] ·d 10 >20 micrometers,

[0177] ·30 <d 50 <70 micrometers, and

[0178] ·d 90 <110 micrometers.

[0179] The particle size of the polymer was determined by laser scattering on a Microtrac S3500 analyzer in wet mode (128 channels, between 0.0215 and 1408 μm) with an average of three runs. Isopropanol with a refractive index of 1.38 was used as the solvent, and a particle refractive index of 1.59 was assumed. Ultrasonic mode was enabled (25 W / 60 s), and the flow rate was set to 55%.

[0180] The powder is then passed through a roller with 0.3% fumed silica (from Cabot Corporation). M-5) was blended and sieved through a 120-mesh tension bolt cloth (147 μm aperture).

[0181] The final BET surface area (multipoint) of the powder was determined by nitrogen (N2) adsorption on a TriStar II Plus 3.01 surface and porosity analyzer according to ISO 9277.

[0182] The bulk density of the powder was determined using Method A of ASTM D1895.

[0183] Characterization of powdered materials

[0184] Table 1

[0185]

[0186] Print

[0187] exist Print on the P800SLS printer using the following print settings: 12 watts of hatch laser power, 8.5 watts of contour laser power, 2.65 m / s laser speed, and a post-printing cooling rate of less than 10 °C / min.

[0188] Powdered materials are sintered into ASTM Type I tensile bars.

[0189] Characterization of the printed strip

[0190] ASTM Type I tensile bars were tested according to ASTM D638, and the results reported in Table 3 are the average of five bars.

[0191] result

[0192] Table 2

[0193]

[0194]

[0195] Table 3

[0196]

[0197] Powders containing PAS polymer #2 or PAS polymer #3 (comparison powders) were first printed at a processing temperature of 250°C, but this caused curling. Therefore, to avoid curling, the processing temperature was adjusted to 275°C for comparison powder #2 and to 270°C for comparison powder #3. Powders based on PAS polymer #1 of the present invention were printed at a processing temperature of 250°C, and no curling occurred.

[0198] Compared to comparative powders, the powder of this invention exhibits superior printing properties and superior final printed part properties (mechanical and aesthetic). During printing, the powder of this invention maintains a smooth bed surface throughout the entire printing process. This is crucial for obtaining stable prints, which leads to successful printing and acceptable parts.

[0199] The strips printed with the powder of this invention exhibit a smooth surface.

[0200] Parts produced using the powder of the present invention containing 5% repeating unit q have superior mechanical properties (ultimate tensile strength) compared to the comparative powder made only of repeating unit p.

Claims

1. A powdered material M for additive manufacturing, having a d value in the range of 10 to 100 μm as measured by laser scattering in isopropanol. 50 Values, which include: - A polymer component P comprising at least one poly(aryl sulfide) (PAS) polymer containing repeating units p, q, and r according to formulas (I), (II), and (III): in n p n q and n r These represent the mole percent of each repeating unit p, q, and r, respectively; Repeating units p, q, and r are arranged in blocks, alternately, or randomly; 1%≤(n) q +n r ) / (n p +n q +n r )≤12%; n q It is ≥0% and n r It is ≥0%; j is zero or an integer varying between 1 and 4; R 1 Choose from the following groups: halogen atoms, C1-C 12 Alkyl, C7-C 24 Alkyl aryl, C7-C 24 Aryl group, C6-C 24 aryl, C1-C 12 Alkoxy groups and C6-C 18 aryloxy, -Optionally, one or more flow aids F, -Optionally, one or more additives A, selected from the group consisting of: lubricants, heat stabilizers, light stabilizers, antioxidants, pigments, dyes, fillers or electromagnetic absorbers and flame retardants.

2. The powdered material M as described in claim 1, wherein, This PAS makes n p +n q +n r ≥50%.

3. The powdered material M as described in claim 1, wherein, The filler is a nanofiller.

4. The powdered material M as described in claim 1 or 2, wherein, The PAS is composed of repeating units p, and repeating units q and / or r.

5. The powdered material M as described in claim 1 or 2, wherein, This PAS is essentially composed of repeating units p, and repeating units q and / or r.

6. The powdered material M as described in claim 1 or 2, wherein, The PAS makes j in equation (I) zero.

7. The powdered material M as described in claim 1 or 2, wherein, The PAS has a heat of fusion greater than 20 J / g as determined in the second thermal scan using a differential scanning calorimeter (DSC) at a heating and cooling rate of 20 °C / min, according to ASTM D3418.

8. The powdered material M as described in claim 1 or 2, wherein, When determined in a differential scanning calorimeter (DSC) during the second thermal scan using a heating and cooling rate of 20 °C / min according to ASTM D3418, the PAS results in a melting point of up to 280 °C and / or at least 245 °C.

9. The powdered material M as described in claim 8, wherein, This gives it a melting point of up to 278°C.

10. The powdered material M as described in claim 8, wherein, This gives it a melting point of up to 275°C.

11. The powdered material M as described in claim 8, wherein, This gives PAS a melting point of at least 248°C.

12. The powdered material M as described in claim 8, wherein, This gives PAS a melting point of at least 250°C.

13. The powdered material M as described in claim 1 or 2, wherein, The flow aid F is an inorganic pigment selected from the group consisting of silica, alumina and titanium dioxide.

14. The powdered material M as described in claim 1 or 2, wherein, The flow aid F is fumed silica.

15. The powdered material M as described in claim 1 or 2, wherein, The material M has a d value in the range of 15 to 80 μm as measured by laser scattering in isopropanol. 50 value.

16. The powdered material M as described in claim 1, wherein, The molar percentages of repeating units p, q, and r in PAS are such that: 1.2%≤(n) q +n r ) / (n p +n q +n r) ≤10.8% or 1.5% ≤ (n q +n r ) / (n p +n q +n r) ≤10.5% or 1.8% ≤ (n q +n r ) / (n p +n q +n r) ≤10.2% or 2.0%≤(n q +n r ) / (n p +n q +n r) ≤10.0%。 17. The powdered material M as claimed in claim 1, wherein PAS comprises repeating units p and q, but does not contain repeating unit r, and the molar percentages of repeating units p and q in PAS are such that: 1.2% ≤ n q / (n p +n q ≤10.8% or 1.5% ≤ n q / (n p +n q ≤10.5% or 1.8% ≤ n q / (n p +n q ≤10.2% or 2.0%≤n q / (n p +n q )≤10.0%。 18. The powdered material M as claimed in claim 1, wherein PAS comprises repeating units p and r, but does not contain repeating unit q, and the molar percentages of repeating units p and r in PAS are such that: 1.2% ≤ n r / (n p +n r ≤10.8% or 1.5% ≤ n r / (n p +n r ≤10.5% or 1.8% ≤ n r / (n p +n r ≤10.2% or 2.0%≤n r / (n p +n r )≤10.0%。 19. The powdered material M as described in claim 1, wherein, Based on the total number of moles of repeating units in the PAS polymer, n p +n q +n r The sum is at least 95%.

20. A method for manufacturing three-dimensional (3D) articles, parts, or composite materials, comprising: a) Depositing a continuous layer of the powdered material M as described in any one of claims 1-19, and b) Print the layer before depositing subsequent layers.

21. The method of claim 20, wherein, Step b) includes selectively sintering the powder by electromagnetic radiation.

22. The method of claim 20, wherein, The molar percentages of repeating units p, q, and r in PAS are such that: 1.2%≤(n) q +n r ) / (n p +n q +n r) ≤10.8% or 1.5% ≤ (n q +n r ) / (n p +n q +n r) ≤10.5% or 1.8% ≤ (n q +n r ) / (n p +n q +n r) ≤10.2% or 2.0%≤(n q +n r ) / (n p +n q +n r) ≤10.0%。 23. The method of claim 20, wherein the PAS comprises repeating units p and q, but does not contain repeating unit r, and the molar percentages of repeating units p and q in the PAS are such that: 1.2% ≤ n q / (n p +n q ≤10.8% or 1.5% ≤ n q / (n p +n q ≤10.5% or 1.8% ≤ n q / (n p +n q ≤10.2% or 2.0%≤n q / (n p +n q )≤10.0%。 24. The method of claim 20, wherein the PAS comprises repeating units p and r, but does not contain repeating unit q, and the molar percentages of repeating units p and r in the PAS are such that: 1.2% ≤ n r / (n p +n r ≤10.8% or 1.5% ≤ n r / (n p +n r ≤10.5% or 1.8% ≤ n r / (n p +n r ≤10.2% or 2.0%≤n r / (n p +n r )≤10.0%。 25. The method of claim 20, wherein, Based on the total number of moles of repeating units in the PAS polymer, n p +n q +n r The sum is at least 95%.

26. A three-dimensional (3D) article, part, or composite material that is obtainable by additive manufacturing from the powdered material M as described in any one of claims 1-19.

27. The three-dimensional (3D) article, part or composite material as claimed in claim 26, wherein the additive manufacturing is selective laser sintering (SLS), composite material-based additive manufacturing ("CBAM") or multi-jet melting (MJF).

28. Use of the powdered material M as described in any one of claims 1-19 for manufacturing three-dimensional (3D) objects using additive manufacturing.

29. The use as claimed in claim 28, wherein the additive manufacturing is selective laser sintering (SLS), composite material-based additive manufacturing ("CBAM"), or multi-jet melting (MJF).

30. The use as described in claim 28, wherein, The molar percentages of repeating units p, q, and r in PAS are such that: 1.2%≤(n) q +n r ) / (n p +n q +n r) ≤10.8% or 1.5% ≤ (n q +n r ) / (n p +n q +n r) ≤10.5% or 1.8% ≤ (n q +n r ) / (n p +n q +n r) ≤10.2% or 2.0%≤(n q +n r ) / (n p +n q +n r) ≤10.0%。 31. The use as described in claim 28, wherein the PAS comprises repeating units p and q, but does not contain repeating unit r, and the molar percentages of repeating units p and q in the PAS are such that: 1.2% ≤ n q / (n p +n q ≤10.8% or 1.5% ≤ n q / (n p +n q ≤10.5% or 1.8% ≤ n q / (n p +n q ≤10.2% or 2.0%≤n q / (n p +n q )≤10.0%。 32. The use as described in claim 28, wherein the PAS comprises repeating units p and r, but does not contain repeating unit q, and the molar percentages of repeating units p and r in the PAS are such that: 1.2% ≤ n r / (n p +n r ≤10.8% or 1.5% ≤ n r / (n p +n r ≤10.5% or 1.8% ≤ n r / (n p +n r ≤10.2% or 2.0%≤n r / (n p +n r )≤10.0%。 33. The use as described in claim 28, wherein, Based on the total number of moles of repeating units in the PAS polymer, n p +n q +n r The sum is at least 95%.

34. Use of polymer component P in the manufacture of powdered material M for additive manufacturing, wherein said polymer component P comprises at least one poly(aryl sulfide) (PAS) polymer comprising repeating units p, q, and r according to formulas (I), (II), and (III): in n p n q and n r These represent the mole percent of each repeating unit p, q, and r, respectively; Repeating units p, q, and r are arranged in blocks, alternately, or randomly; 1%≤(n) q +n r ) / (n p +n q +n r )≤12%; n q It is ≥0% and n r It is ≥0%; j is zero or an integer varying between 1 and 4; R 1 Choose from the following groups: halogen atoms, C1-C 12 Alkyl, C7-C 24 Alkyl aryl, C7-C 24 Aryl group, C6-C 24 aryl, C1-C 12 Alkoxy groups and C6-C 18 aryloxy, Optionally combined with one or more flow aids F and / or one or more additives A.

35. The use as described in claim 34, wherein the additive manufacturing is selective laser sintering (SLS), composite material-based additive manufacturing ("CBAM"), or multi-jet melting (MJF).

36. Use of the article, part or composite material as described in claim 26 in oil and gas applications, automotive applications, electrical and electronic applications or aerospace applications.

37. Use of the article, part or composite material as described in claim 26 in a consumer product.

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