Powder materials (P) containing poly(arylene sulfide) (PAS) polymers and their use for additive manufacturing

Abstract

The present invention relates to compounds of formula (I), (II), and (III): [Formula 1] TIFF2023517899000013.tif45170 (in the formula, n p , n q and n r are the mole percentages of each repeat unit p, q, and r, respectively; The repeat units p, q and r are arranged in blocks, alternating, or randomly; 1%≦(n q +n r ) / (n p +n q +n r )≦12%;n q ≧0% and n r ≥ 0%; j is zero or an integer varying between 1 and 4; R 1 is a halogen atom, C1-C 12 Alkyl groups, C7-C 24 Alkylaryl group, C7-C 24 Aralkyl groups, C6-C 24 Arylene groups, C1-C 12 Alkoxy groups and C6-C 18 aryloxy groups) The present invention relates to a powder material (M) comprising at least one poly(arylene sulfide) (PAS) polymer comprising repeating units p, q, and r according to the formula:

Description

[Technical Field]

[0001] Related Applications This application claims priority to U.S. Provisional Patent Application No. 62 / 987,423, filed March 10, 2020, and European Patent Application Publication No. 20185792.7, filed July 14, 2020, the entire contents of each of which are incorporated herein by reference for all purposes.

[0002] The present invention relates to a powder material (M) comprising at least one poly(arylene sulfide) (PAS) polymer, and to a method for producing three-dimensional (3D) articles, parts, or composites from such powder material (M).The present invention also relates to the 3D articles, parts, or composites obtained from such processes, and to the use of the articles, parts, or composites in oil and gas applications, automotive applications, electrical and electronic applications, or aerospace and consumer goods. [Background technology]

[0003] Many objects, from household items to motor parts, are manufactured from a single lump of material, or they are milled or sculpted from a larger block of material. Another approach to manufacturing an object is to deposit a thin layer of material as a powder, then add another layer on top of it, followed by another layer, and so on. This additive process gave rise to the name additive manufacturing (AM), more commonly known as 3D printing. The range of specifically designed 3D printed products on the market, from motor parts to dental implants, is now substantial. They can be manufactured using plastics, among other things. Additive manufacturing promises to disrupt established practices and overturn traditional assumptions about mass production in distant factories. Local manufacturing of small quantities, or even single items, close to the end user, will become viable.

[0004] One of the fundamental limitations associated with known additive manufacturing methods that use polymer part materials in powder form is based on the lack of identification of materials that exhibit a suitable set of properties for printing 3D parts / objects with acceptable density and mechanical properties.

[0005] Poly(arylene sulfide) (PAS) polymers are semi-crystalline thermoplastic polymers that possess remarkable mechanical properties, such as high tensile modulus and strength, and exceptional stability against thermal degradation and chemical reactivity. They also feature excellent melt processing, such as injection molding.

[0006] This wide range of properties makes PAS polymers suitable for many applications, for example in the automotive, electrical, electronic, aerospace and appliance markets.

[0007] Despite the above advantages, PAS polymers are known to exhibit low impact resistance and low elongation at break, in other words, poor ductility and poor toughness.

[0008] Therefore, there is a need for PAS polymers for use in additive manufacturing that have improved ductility and toughness while maintaining high tensile strength.

[0009] WO 2017 / 1226484 (Toray) describes the use of PAS resin as a powder for producing three-dimensional models by powder sintering with a 3D printer.

[0010] WO 2020 / 011991 (Solvay) relates to PAS polymers that can be used in additive manufacturing, which have as their main technical feature a calcium content of less than 200 ppm as measured by standard calibrated X-ray fluorescence (XRF) analysis with ICP-OES.

[0011] WO 2020 / 011990 (Solvay) describes PAS polymers that exhibit flowability that makes them well-suited powders for applications such as the production of 3D objects using laser sintering-based additive manufacturing systems, in which the powder must exhibit good flow behavior to facilitate powder packing during the printing process.

[0012] JP 2019-165004 A (Toray) relates to an insulating tube with excellent durability, electrical properties, and flame retardancy. In Reference Example 1, D1 describes the preparation of PPS based on 90 moles of p-dichlorobenzene and 10 moles of m-dichlorobenzene. However, this document does not describe a specific PSD powder resin suitable for 3D printing.

[0013] JP 63-10633 (Idemitsu) relates to a method for producing polyarylene sulfides used as engineering plastics.

[0014] EP 3530701 (Toray) relates to a polyarylene sulfide resin powder particulate 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 a polyarylene sulfide resin powder particulate mixture.

[0015] These documents do not describe powder materials for use in additive manufacturing, including PAS polymers as described herein, the use of which has been shown to result in superior printing characteristics and improved final part properties (mechanical and part aesthetics) over prior art powders. Summary of the Invention

[0016] In a first aspect, the present invention provides a powder material (M) comprising a poly(arylene sulfide) (PAS) polymer, wherein said PAS polymer has formulas (I), (II), and (III): [ka] (In the formula, n p , n q and n r are the mole percentages of each repeat unit p, q, and r, respectively; The repeat units p, q and r are arranged in blocks, alternating, or randomly; 1%≦(n q +n r ) / (n p +n q +n r )≦12%;n q ≧0% and n r ≥ 0%; j is zero or an integer varying between 1 and 4; R 1 is a halogen atom, C1 to C 12 Alkyl groups, C7-C 24 Alkylaryl group, C7-C 24 Aralkyl groups, C6-C 24 Arylene groups, C1-C 12 Alkoxy groups and C6-C 18 The present invention relates to a powder material (M) comprising repeating units p, q, and r according to the formula (I) (a) selected from the group consisting of aryloxy groups.

[0017] In another aspect, the present invention provides a method for producing a three-dimensional (3D) article, component, or composite material, comprising: a) depositing successive layers of the powder material (M) described herein; b) printing a layer before the deposition of a subsequent layer; The present invention relates to a method comprising:

[0018] According to this embodiment, step b) preferably comprises selective sintering of the powder by electromagnetic radiation.

[0019] According to a third aspect, the present invention relates to a three-dimensional (3D) article, part or composite obtained by additive manufacturing from a powder material (M) as described herein, wherein said additive manufacturing is preferably selective laser sintering (SLS), composite-based additive manufacturing ("CBAM") or multi-jet fusion (MJF).

[0020] According to a fourth aspect, the present invention relates to the use of a powder material (M) as described herein for the production of a three-dimensional (3D) object using additive manufacturing, preferably selective laser sintering (SLS), composite-based additive manufacturing ("CBAM"), or multi-jet fusion (MJF).

[0021] According to a fifth aspect, the present invention relates to the use of a polymer component (P) for producing a powder material (M) for additive manufacturing, preferably selective laser sintering (SLS), composite-based additive manufacturing ("CBAM"), or multi-jet fusion (MJF), wherein the polymer component (P) comprises at least one poly(arylene sulfide) (PAS) polymer as described herein, optionally in combination with one or more flow agents (F) and / or one or more additives (A).

[0022] According to a sixth aspect, the invention relates to the use of the article, part or composite material in oil and gas applications, automotive applications, electrical and electronic applications, or aerospace and consumer goods. DETAILED DESCRIPTION OF THE INVENTION

[0023] Disclosed herein are methods for fabricating a 3D object (i.e., an article, part, or composite) from a powder material (M) comprising at least one poly(arylene sulfide) polymer, also referred to herein as "poly(arylene sulfide)" or PAS. Reference to poly(arylene sulfide) polymer specifically includes, but is not limited to, polyphenylene sulfide polymer, also referred to herein as "polyphenylene sulfide" or PPS.

[0024] The powder material (M) of the present invention can have a regular shape, such as a sphere, or it can have a complex shape obtained by grinding / crushing the polymer component (P), i.e. at least the PAS polymer, in the form of pellets or coarse powder.

[0025] In this application: - any description, even if made in relation to a particular embodiment, is applicable to and interchangeable with other embodiments of the present disclosure; - when an element or component is said to be included in and / or selected from a list of enumerated elements or components, it is to be understood that in the relevant embodiments expressly contemplated herein, the element or component may be any one of the individually enumerated elements or components, or may be selected from a group consisting of any two or more of the explicitly enumerated elements or components, and that any element or component enumerated in a list of elements or components may be omitted from such list; - Any recitation herein of numerical ranges by endpoints includes all numbers subsumed within the recited range, as well as the endpoints of the range and equivalents thereof.

[0026] Powdered polymer material (M) The powder material (M) of the present invention comprises at least one polymer component (P). The polymer component (P) of the powder material (M) may comprise one or more PASs described below. It may also comprise at least one additional polymeric material, i.e., at least one polymer or copolymer, different from the PAS polymers described herein. This additional polymeric material may be selected from the group consisting of poly(aryl ether sulfone) (PAES) polymers, such as poly(biphenyl 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 polymeric material may also be a homopolymer of a poly(arylene sulfide) (PAS*) different from the PASs described herein, such as a poly(phenylene sulfide) (PPS) polymer.

[0027] The PASs described herein are represented by formulas (I), (II), and (III), respectively: [ka] wherein the repeating units p, q and r are arranged in blocks, alternating, or randomly.

[0028] In formula (I), j is zero or an integer varying between 1 and 4.

[0029] Preferably, j is zero in formula (I), (II), and / or (III), meaning that the aromatic ring is unsubstituted. Accordingly, repeat units p, q, and r conform to the following formulas (IV), (V), and (VI), respectively: [ka]

[0030] When j varies between 1 and 4, R 1 is a halogen atom, C1 to C 12 Alkyl groups, C7-C24 Alkylaryl group, C7-C 24 Aralkyl groups, C6-C 24 Arylene groups, C1-C 12 Alkoxy groups and C6-C 18 The alkyl group may be selected from the group consisting of aryloxy groups.

[0031] n respectively p , n q and n r The molar percentage of repeating units p, q and r in formula (I) is 1%≦(n q +n r) / (n p +n q +n r) ≦12%, which means that the PAS polymer of formula (I) contains 1 to 12 mole % of repeat units q and r, based on the total number of repeat units p, q and r in the polymer.

[0032] The PAS polymers described herein contain repeating units p, which in turn contain repeating units q and / or r. When a PAS polymer contains repeating units p, q, and r, n in the above equation q and n r are both greater than 0%. Alternatively, the PAS polymers described herein may contain repeat units p and q, but no repeat unit r. In this case, n q is more than 1%, but n r is 0%. According to a third possibility, the PAS polymers described herein may contain repeat units p and r, but no repeat unit q. In this case, n r is more than 1%, but n q is 0%.

[0033] In some preferred embodiments, the PAS described herein has formula (I) and (II), respectively: [ka] wherein the repeating units p, q, and r are arranged in blocks, alternating, or randomly. Preferably, j is zero in formula (I) and / or (II), meaning that at least one of the aromatic rings is unsubstituted. More preferably, j is zero in formula (I) and (II), meaning that both aromatic rings are unsubstituted.

[0034] In some other preferred embodiments, the PAS described herein has formula (I) and (III), respectively: [ka] wherein the repeating units p and r are arranged in blocks, alternating, or randomly. Preferably, j is zero in formula (I) and / or (III), meaning that at least one of the aromatic rings is unsubstituted. More preferably, j is zero in formula (I) and (III), meaning that both aromatic rings are unsubstituted.

[0035] In some embodiments, the mole percentages of repeat units p, q, and r in the PAS are: 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% It is as if.

[0036] In some preferred embodiments, where the PAS comprises repeat units p and q but no repeat unit r, the mole percentage of repeat units p and q in the PAS is: 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% It is as if.

[0037] For example, n q / (n p +n q ) is equal to 2.5 mol%, 3.0 mol%, 5.0 mol%, and 7.0 mol%.

[0038] In some preferred embodiments, where the PAS comprises repeat units p and r but no repeat unit q, the mole percentage of repeat units p and r in the PAS is: 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% It is as if.

[0039] For example, n r / (n p +n r ) is equal to 2.5 mol%, 3.0 mol%, 5.0 mol%, and 7.0 mol%.

[0040] According to one embodiment, the total number n p +n q +n r is at least 50%, meaning that the PAS contains at least 50 mole % of repeat units p, q, and r based on the total number of moles of repeat units in the PAS polymer. For example, a total of n p +n q +n r can be at least 60%, at least 70%, at least 80%, at least 90%, or even at least 95%, based on the total number of moles of repeat units in the PAS polymer.

[0041] According to embodiments described herein, the PAS consists or consists essentially of repeat unit p and repeat units q and / or r. By "consisting essentially of," we mean that the PAS includes repeat unit p and repeat units q and / or r, and also less than 10 mol %, preferably less than 5 mol %, more preferably less than 3 mol, and even more preferably less than 1 mol %, based on the total number of moles of repeat units in the PAS polymer, of other repeat units different from repeat units p, q, and r.

[0042] According to one embodiment, the total number n p +n q +n r is 100%, and n q and n r At least one of them is greater than 0 mol %.

[0043] According to another embodiment, the sum of n p +n q is 100%.

[0044] According to yet another embodiment, the sum of n p +nr is 100%.

[0045] According to one embodiment, the total number n p +n q +n r In this embodiment, the PAS polymer has at least one repeat unit different from p, r, and q, such as those of the following formulae (VII) to (XVII): [ka] (In the formula, R 2 is a halogen atom, C1 to C 12 Alkyl groups, C7-C 24 Alkylaryl group, C7-C 24 Aralkyl groups, C6-C 24 Arylene groups, C1-C 12 Alkoxy groups and C6-C 18 aryloxy groups, and k is 0 or an integer varying between 1 and 4).

[0046] Preferably, the PAS has a melt flow rate (ASTM D1238, Procedure B, 315.6°C under a load of 1.27 kg) of at most 700 g / 10 min, more preferably at most 500 g / 10 min, and even more preferably at most 200 g / 10 min.

[0047] Preferably, the PAS has a melt flow rate (ASTM D1238, Procedure B, 315.6°C under a load of 1.27 kg) of 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, even more preferably at least 50 g / 10 min.

[0048] Preferably, 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, as determined by a second heating scan in a differential scanning calorimeter (DSC) using a heating and cooling rate of 20°C / min according to ASTM D3418.

[0049] Preferably, the PAS has a melting point of at most 290°C, more preferably at most 285°C, and even more preferably at most 280°C, as determined by a second heating scan in a differential scanning calorimeter (DSC) according to ASTM D3418 using a heating and cooling rate of 20°C / min.

[0050] In some embodiments, the PAS has a heat of fusion of greater than 20 J / g, preferably greater than 21 J / g, or greater than 22 J / g, as determined by the second heat scan of a differential scanning calorimeter (DSC) using a heating and cooling rate of 20°C / min according to ASTM D3418.

[0051] The powder material (M) of the present invention comprises one polymer component (P) comprising at least one PAS polymer as described above. The powder material (M) of the present invention may consist essentially of one or more polymers, for example, it may consist essentially of one PAS polymer as described herein, or it may further comprise additional components, such as a flow aid / agent (F) and / or one or more additives (A) as described below. When the powder material (M) of the present invention comprises additional components, they can be added or blended with the polymer component described herein before, during, or after the milling process.

[0052] According to some embodiments of the present invention, the powder material (M) has a d of less than 100 μm, as measured by laser scattering in isopropanol. 50 According to one embodiment, the powder material (M) has a d value of less than 90 μm, preferably less than 80 μm or less than 75 μm, measured by laser scattering in isopropanol. 50 It has a value.

[0053] According to some embodiments of the present invention, the powder material (M) has a d of more than 10 μm, as measured by laser scattering in isopropanol. 50According to one embodiment, the powder material (M) has a d value of more than 15 μm, preferably more than 20 μm, more than 25 or more than 30 μm, measured by laser scattering in isopropanol. 50 It has a value.

[0054] According to some embodiments of the present invention, the powder material (M) has a d of less than 150 μm, as measured by laser scattering in isopropanol. 90 According to one embodiment, the powder material (M) has a d value of less than 120 μm, preferably less than 110 μm or less than 100 μm, measured by laser scattering in isopropanol. 90 It has a value.

[0055] According to some embodiments of the present invention, the powder material (M) has a d of greater than 0.1 μm, as measured by laser scattering in isopropanol. 10 According to a preferred embodiment, the powder material (M) has a d value, measured by laser scattering in isopropanol, of greater than 1 μm, preferably greater than 5 μm or greater than 10 μm. 10 It has a value.

[0056] According to some embodiments of the present invention, the powder material (M) has a particle size of 40 to 70 μm, preferably 40 to 60 μm, or 43 to 58 μm, or 45 to 55 μm, measured by laser scattering in isopropanol. 50 A powder material (M) having such a particle size distribution is suitable for example for selective laser sintering (SLS).

[0057] In some embodiments of the present invention, the powder material (M) has a d of less than 195 μm as measured by laser scattering in isopropanol. 99 According to a preferred embodiment, the powder material (M) has a d value of less than 190 μm, preferably less than 180 μm or less than 170 μm, measured by laser scattering in isopropanol. 99 It has a value.

[0058] The powder material (M) of the present invention has a viscosity of 0 to 30 m, measured according to ISO 9277 using a immersion / evacuation temperature of up to 25°C. 2 / g, preferably 2 to 25m 2 / g, more preferably 4 to 20m 2 / g.

[0059] The powder material (M) of the present disclosure has a density of at least 0.35 g / cm 3 , preferably at least 0.45 g / cm 3 , most preferably at least 0.50 g / cm 3 The bulk density of the powder may be 0.15 to 1.005 g / cm².

[0060] According to one embodiment, the powder material (M) of the present invention comprises at least 50 wt. % of the polymer component (P), such as at least 60 wt. % of the polymer component (P), at least 70 wt. %, at least 80 wt. %, at least 90 wt. %, at least 95 wt. %, at least 98 wt. %, or at least 99 wt. % of the polymer component (P) described herein, based on the total weight of the powder material (M).

[0061] According to one embodiment, the polymer component (P) comprises at least 50 wt. % of a PAS described herein, such as at least 60 wt. % of a PAS described herein, at least 70 wt. %, at least 80 wt. %, at least 90 wt. %, at least 95 wt. %, at least 98 wt. %, or at least 99 wt. % of a PAS described herein, based on the total weight of the powder.

[0062] Before, during, or after the grinding process of the polymer component (P), in particular the grinding process of the PAS described herein, additional components can be added to the polymer component (P) before using the powder for additive manufacturing. For example, the further component can be a flow agent (F). This flow agent (F) can be, for example, hydrophilic. Examples of hydrophilic flow aids are inorganic pigments selected, among others, from the group consisting of silica, alumina, and titanium dioxide. Mention can be made of fumed silica. Fumed silica is commercially available under the trade names Aerosil® (Evonik) and Cab-O-Sil® (Cabot). Fumed alumina is commercially available under the trade name SpectraAl® (Cabot).

[0063] According to one embodiment of the present invention, the powder material (M) comprises 0.01 to 10 wt. % of a flow agent (F), such as 0.05 to 8 wt. %, 0.1 to 6 wt. %, or 0.15 to 5 wt. % of at least one flow agent (F), such as at least fumed silica or fumed alumina, based on the total weight of the powder.

[0064] These silicas or aluminas are composed of nanometer primary particles (usually 5-50 nm for fumed silica or alumina), which combine to form aggregates. In their use as flow agents, silicas or aluminas are found in various forms (elementary particles and aggregates).

[0065] The powder material (M) of the present invention may also contain one or more additives (A), such as fillers (carbon fiber, glass fiber, crushed carbon fiber, glass beads, glass microspheres, crushed glass fiber, wollastonite, silica beads, talc, calcium carbonate, etc.), colorants, dyes, pigments, lubricants, plasticizers, flame retardants (halogen and halogen-free flame retardants, etc.), nucleating agents, heat stabilizers, light stabilizers, antioxidants, processing aids, thermally conductive fillers (boron nitride, etc.), fusing agents, 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.

[0066] The powder material (M) of the present invention may also contain flame retardants, such as halogen flame retardants and halogen-free flame retardants.

[0067] In another embodiment of the present invention, the powder material (M) comprises 0.01 to 30 wt. % of at least one additive (A), for example 0.05 to 25 wt. %, 0.1 to 20 wt. %, or 0.15 to 10 wt. % of at least one additive (A), based on the total weight of the powder.

[0068] According to one embodiment, the powder material (M) of the present invention comprises: - at least 50% by weight of a polymer component (P), - 0.01 to 10% by weight, 0.05 to 8% by weight, 0.1 to 6% by weight, or 0.15 to 5% by weight of at least one flow agent (F), - at least one optional additive (A), for example an additive selected from the group consisting of fillers (such as carbon fibers, glass fibers, crushed carbon fibers, glass beads, glass microspheres, silica beads, talc, calcium carbonate, crushed glass fibers, wollastonite, etc.), colorants, dyes, pigments, lubricants, plasticizers, flame retardants (such as halogen and halogen-free flame retardants), nucleating agents, heat stabilizers, light stabilizers, antioxidants, processing aids, thermally conductive fillers (such as boron nitride), fusing agents, and electromagnetic absorbers; and % is based on the total weight of the powder.

[0069] The PAS polymers of the present invention can be obtained by processes known in the art, see in particular WO 2015 / 095362 A1 (Chevron Philips), WO 2015 / 177857 A1 (Solvay) and WO 2016 / 079243 A1 (Solvay), which are incorporated herein by reference.

[0070] The PAS polymers used in the method of the present invention are in particular Step 1) polymerizing the reactants in a reaction vessel to form a PAS reaction mixture; step 2) treating the PAS reaction mixture to obtain a PAS polymer and by-product slurry; step 3) recovering the PAS polymer, for example by precipitation or evaporation; Step 4) treating the PAS polymer with water and / or an aqueous acid and / or a calcium solution; It can be obtained by a method comprising:

[0071] In some embodiments, when step 4) comprises treating the PAS polymer with water and / or an aqueous acid solution (but not a calcium solution), the PAS preparation process results in a treated PAS with a low calcium content as measured by standard-calibrated X-ray fluorescence (XRF) analysis by ICP-OES. Step 4) can include treating (or washing) the PAS polymer with water, an aqueous acid solution, and a combination of both. The PAS polymer can be treated or washed several times. The PAS polymer undergoing treatment in step 4) can be either in dry form or as a dispersion in a solvent.

[0072] According to an embodiment of step 4), the PAS is contacted, e.g., blended, with water and / or an acidic aqueous solution to form a mixture. The concentration of the PAS in the mixture can range from about 1 wt. % to about 50 wt. %, about 5 wt. % to about 40 wt. %, or about 10 wt. % to about 30 wt. %, based on the total weight of the mixture.

[0073] The acidic aqueous solution that can be used in step 4) may contain an acidic compound. The acidic compound may be any water-soluble organic or inorganic acid. According to one embodiment, the organic acid that can be used is a C1-C15 carboxylic acid, such as a C1-C10 carboxylic acid or a C1-C5 carboxylic acid. According to one embodiment, the organic acid that can be used is selected from the group consisting of acetic acid, formic acid, oxalic acid, fumaric acid, and monopotassium phthalate. Preferably, the organic acid is acetic acid. The inorganic acid that can be used may be 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. The amount of the acidic compound present in the acidic aqueous solution or mixture may range from 0.01% to 10% by weight, 0.025% to 5% by weight, or 0.075% to 1% by weight, based on the total amount of water in the solution / mixture.

[0074] The solution / mixture can be heated to a temperature below the melting point of the PAS. The temperature of the solution / mixture in step 4) can be in the range of about 10 to 190°C, 15 to 185°C, or about 20 to 180°C.

[0075] In some embodiments, the PAS polymer 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 standard-calibrated X-ray fluorescence (XRF) analysis by ICP-OES.

[0076] In some embodiments, the PAS polymer exhibits a calcium content of greater than 1 ppm, preferably greater than 2 ppm, or greater than 5 ppm as measured by standard-calibrated X-ray fluorescence (XRF) analysis by ICP-OES.

[0077] In some embodiments, the PAS polymer exhibits a calcium 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 standard-calibrated X-ray fluorescence (XRF) analysis by ICP-OES.

[0078] In some embodiments, the PAS polymer exhibits a calcium content of greater than 1 ppm, preferably greater than 2 ppm, or greater than 5 ppm as measured by standard-calibrated X-ray fluorescence (XRF) analysis by ICP-OES.

[0079] Calcium and sodium content may be measured by X-ray fluorescence (XRF) analysis calibrated with standards of known calcium content determined by inductively coupled plasma optical emission spectroscopy (ICP-OES) in accordance with ASTM UOP714-07.

[0080] The present invention also relates to a method for producing a powder material (M) for use in a method for the layer-by-layer production of three-dimensional parts, in which a fine powder is produced by grinding, a precipitation process from a solvent, melt spraying or spray drying from a coarse powder or granules.

[0081] The powder material (M) used in the additive manufacturing method of the present invention is Step 1') grinding the polymer component (P), in particular grinding the PAS polymer described herein; Step 2') blending the polymer component (P) from step 1') with optional components, such as at least one flow agent (F); can be obtained by

[0082] Alternatively, the powder material (M) used in the additive manufacturing method of the present invention may be Step 1″) blending the polymer component (P) with optional components, such as at least one flow agent (F); step 2″) grinding the blend from step 1″), in particular grinding the PAS polymer described herein; can be obtained by

[0083] The grinding step can be carried out in a pin disc mill, a jet mill with classifier / fluidized jet mill, an impact mill and classifier, a pin / pin-beater mill or a wet grinding mill or a combination of such devices.

[0084] The crushed powder material is preferably separated or sieved in an air separator or classifier to obtain a predetermined fraction spectrum. The powder material (M) is preferably sieved before use in the printer. Sieving involves removing particles larger than 200 μm, 150 μm, 140 μm, 130 μm, 120 μm, 110 μm or 100 μm using a suitable device.

[0085] According to another aspect, the present invention relates to a method for manufacturing a three-dimensional (3D) article, part, or composite material, comprising depositing successive layers of a powder material (M) and selectively sintering each layer before depositing a subsequent layer, for example by electromagnetic radiation of the powder.

[0086] The additive manufacturing method of the present invention is preferably selected from the group consisting of selective laser sintering (SLS), composite-based additive manufacturing ("CBAM"), or multi-jet fusion (MJF).

[0087] Additive manufacturing methods are typically performed using 3D printers.

[0088] SLS 3D printers are available, for example, from EOS Corporation under the trade name EOSINT® P.

[0089] MJF 3D printers are available, for example, from Hewlett-Packard Company under the trademark name Multi Jet Fusion.

[0090] The powders can also be used to make continuous fiber composites, for example in the CBAM process developed by Impossible Objects.

[0091] According to one embodiment, the step of printing the layer comprises selective sintering of the powder material (M) by electromagnetic radiation, for example a high power laser source, such as an electromagnetic beam source.

[0092] The 3D object / article / part can be built on a substrate, for example, a horizontal substrate and / or a planar substrate. The substrate can be movable in any direction, for example, horizontally or vertically. During the 3D printing process, the substrate can, for example, be lowered so that successive layers of unsintered polymer material are sintered on top of previous layers of sintered polymer material.

[0093] According to one embodiment, the process further includes a step comprising fabricating a support structure. According to this embodiment, the 3D object is built on the support structure, and the support structure and the 3D object are both fabricated using the same AM method. The support structure can be useful in several situations. For example, the support structure can be useful to provide sufficient support to the printed or printing 3D object to avoid distortion of the molded 3D object, especially if the 3D object is not planar. This is particularly true when the temperature used to maintain the printed or printing 3D object is lower than the re-solidification temperature of the polymer component, e.g., the PAS polymer.

[0094] The 3D printer may include a sintering chamber and a powder bed, both of which are maintained at a specific predetermined temperature.

[0095] The powder material (M) to be printed can be preheated to a processing temperature (Tp) above the powder's glass transition temperature (Tg) and below its melting temperature (Tm). Preheating the powder material (M) makes it easier for the laser to raise the temperature of selected areas of the layer of unfused powder to the melting point. The laser causes the material to fuse only where specified by the input. The laser energy exposure is typically selected based on the polymer being used and to avoid polymer degradation.

[0096] Articles and uses The present invention also relates to articles, parts, or composites comprising the poly(arylene sulfide) (PAS) described herein obtained from the additive manufacturing methods 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 goods.

[0097] For automotive applications, the article can be a pan (e.g., an oil pan), a panel (e.g., an exterior body panel, including, but not limited to, a quarter panel, a trunk, and a hood; and an interior body panel, including, but not limited to, a door panel and a dash panel), a side panel, a mirror, a bumper, a bar (e.g., a torsion bar and a sway bar), a rod, a suspension component (e.g., a suspension rod, a leaf spring, a suspension arm), and a turbocharger component (e.g., a housing, a volute, a compressor wheel, and an impeller), a pipe (e.g., for carrying fuel, coolant, air, brake fluid), and a bracket. For oil and gas applications, the article can be a mining component, such as a downhole drilling pipe, a chemical injection pipe, a subsea umbilical, and a hydraulic control line. The article can also be a portable electronic device component.

[0098] According to one embodiment, the composite material resulting from the additive manufacturing process 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.

[0099] The present invention also relates to the use of the powder material (M) described herein for the production of three-dimensional (3D) objects using additive manufacturing, preferably selective laser sintering (SLS), composite-based additive manufacturing ("CBAM"), or multi-jet fusion (MJF).

[0100] The present invention also relates to the use of a polymer component (P) comprising at least one poly(arylene sulfide) (PAS) polymer as described above for producing a powder material (M) for additive manufacturing, preferably for selective laser sintering (SLS), composite-based additive manufacturing ("CBAM"), or multi-jet fusion (MJF).

[0101] The present invention will now be described with reference to the following examples, which are for illustrative purposes only and are not intended to limit the scope of the invention.

[0102] Experimental section material NaSH (approximately 55-60% by weight) commercially available from Nouryan 1,3-Dichlorobenzene was obtained from Tulstar NaOH commercially available from Columbus Chemical Industries Inc. Sodium acetate commercially available from Jarchem NMP commercially available from Ashland

[0103] Synthesis Examples PAS Polymer #1 (Invention) This polymer was synthesized in a 340-liter reactor using 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. After 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 adding 7.71 kg of additional NMP, the mixture was gradually cooled to obtain granular PPS, which was then rinsed with NMP, water, and acetic acid solution at 60°C to 75°C. The resulting product was poly(phenylene sulfide) (n p = 95%, n q =5%, n r =0%).

[0104] PAS Polymer #2 (Comparison) The polymer was synthesized according to the methods described in U.S. Pat. Nos. 3,919,177 and 4,415,729, recovered from the reaction mixture, washed with deionized water at 60° C. for at least 5 minutes, then contacted with an aqueous solution of acetic acid having a pH less than 6.0 at 60° C. for at least 5 minutes, and then rinsed with deionized water at 60° C.

[0105] The resulting product was poly(phenylene sulfide) (n p =100%, n q =0%, n r =0%).

[0106] PAS Polymer #3 (Comparison) The polymer was synthesized according to the methods described in U.S. Pat. Nos. 3,919,177 and 4,415,729, recovered from the reaction mixture, washed with deionized water at 60° C. for at least 5 minutes, then contacted with an approximately 0.01 mol / L aqueous solution of calcium acetate at 60° C. for at least 5 minutes, and then rinsed with deionized water at 60° C.

[0107] The resulting product was poly(phenylene sulfide) (n p =100%, n q =0%, nr =0%).

[0108] Characterization of polymer components DSC / Heat of Fusion DSC analysis was performed on a DSC Q200-5293 TA instrument according to ASTM D3418, and data were collected using a two-heat and one-cool procedure. The protocol used was as follows: first heating cycle from 30.00 °C to 350.00 °C at 20.00 °C / min; 5-minute isothermal; first cooling cycle from 350.00 °C to 30.00 °C at 20.00 °C / min; second heating cycle from 30.00 °C to 350.00 °C at 20.00 °C / min. Melting temperature (T m ) was recorded between the first and second heating cycles, and the melt-crystallization temperature (T mc ) was recorded during the cooling cycle, and the glass transition temperature (T g ) is recorded during the second heating cycle and the enthalpy of fusion (ΔH) is recorded during the second heating cycle.

[0109] Molecular weight (Mw) Weight average molecular weights Mw were determined by gel permeation chromatography (GPC) at 210°C using a PL 220 high temperature GPC with a 1-chloronaphthalene mobile phase and polystyrene standards.

[0110] Melt Flow Rate MFR is measured in g / 10 min on an extrusion plastometer at 315.6° C. using a 5 kg weight and a 0.0825 inch by 0.315 inch die after a 5 minute equilibration period.

[0111] Milling of polymer components - Preparation of powder materials The PAS polymer was powdered by grinding in a rotor attrition mill (Retsch Rotor Mill SR300) until the following PSD was reached: d 10 >20 microns, 30 <d 50 <70 microns, and d 90<110 microns.

[0112] Particle size was determined for polymers by averaging three runs using laser scattering techniques on a Microtrac S3500 analyzer in wet mode (128 channels, 0.0215-1408 μm). The solvent used was isopropanol with a refractive index of 1.38, and the particles were assumed to have a refractive index of 1.59. Ultrasonic mode was enabled (25 W / 60 s) and the flow rate was set to 55%.

[0113] The powder was then mixed with 0.3% fumed silica (Cab-O-Sil® M-5 from Cabot Corporation) by drum rolling and sieved through a No. 120 mesh tensioned sieve silk (pore size 147 μm).

[0114] The BET surface area (multipoint) of the final powder was determined by nitrogen (N2) gas adsorption according to ISO 9277 on a TriStar II Plus version 3.01 surface area and pore analyzer.

[0115] The bulk density of the powder was determined by Method A of ASTM D1895.

[0116] [Table 1]

[0117] printing Printing was carried out on an EOSINT® P800 SLS printer using the following print settings: hatch laser power 12 watts, contour laser power 8.5 watts, laser speed 2.65 m / s, and cooling rate after printing was completed less than 10° C. / min. The powder material was sintered into ASTM Type I tensile bars.

[0118] Characterization of printed rods ASTM Type I tensile bars were tested according to ASTM D638. The results reported in Table 3 are the average of five bars.

[0119] result

[0120] [Table 2]

[0121] [Table 3]

[0122] Powders containing PAS Polymer #2 or PAS Polymer #3 (comparative powders) were initially printed at a processing temperature of 250° C., which resulted in curl. Therefore, to avoid curl, the processing temperature was adjusted to 275° C. for comparative powder #2 and 270° C. for comparative powder #3. Powders based on inventive PAS Polymer #1 were printed at a processing temperature of 250° C. and did not curl.

[0123] The inventive powders exhibited superior printing characteristics and final printed part properties (mechanical and part aesthetics) over the comparative powders. During printing, the inventive powders exhibited a smooth bed surface throughout the entire print. This is important for achieving a stable print that results in successful print completion and acceptable parts.

[0124] The bars printed from the powder of the present invention exhibited a smooth surface.

[0125] The use of the powder of the present invention containing 5% repeating units q resulted in parts with better mechanical properties (tensile strength) than the comparative powder made with only repeating units p.

Claims

1. d of 10-100 μm measured by laser scattering in isopropanol ５０ A powder material (M) for additive manufacturing having a value, Formulas (I), (II) and (III): 【Chemical 1】 (In the formula, n ｐ , n ｑ and n ｒ are the mole percentages of each repeat unit p, q, and r, respectively; The repeat units p, q and r are arranged in blocks, alternating, or randomly; 1%≦(n ｑ +n ｒ ) / (n ｐ +n ｑ +n ｒ ) ≦12%; n ｑ ≧0% and n ｒ ≧0%; j is zero or an integer varying between 1 and 4; R １ is a halogen atom, C １ ~C １２ Alkyl group, C ７ ~C ２４ Alkylaryl group, C ７ ~C ２４ Aralkyl group, C ６ ~C ２４ Arylene group, C １ ~C １２ Alkoxy groups, and C ６ ~C １８ a polymer component (P) comprising at least one poly(arylene sulfide) (PAS) polymer comprising repeating units p, q, and r according to the formula (I), where p, q, and r are selected from the group consisting of aryloxy groups; - optionally one or more flow agents (F), - one or more optional additives (A) selected from the group consisting of lubricants, heat stabilizers, light stabilizers, antioxidants, pigments, processing aids, dyes, fillers, nanofillers or electromagnetic absorbers, and flame retardants; A powder material (M) comprising:

2. The PAS is ｐ +n ｑ +n ｒ ≧50% of the powder material (M) according to claim 1 .

3. The powder material (M) according to claim 1 or 2, wherein the PAS consists of repeating units p and repeating units q and / or r.

4. The powder material (M) according to any one of claims 1 to 3, wherein the PAS is one in which j in formula (I) is zero.

5. The powder material (M) according to any one of claims 1 to 4, wherein the PAS has a heat of fusion of more than 20 J / g as determined in the second heating scan of a differential scanning calorimeter (DSC) using a heating and cooling rate of 20 ° C. / min according to ASTM D3418.

6. The powder material (M) according to any one of claims 1 to 5, wherein the PAS has a melting point of at most 280°C and / or at least 245°C as determined in a second heating scan of a differential scanning calorimeter (DSC) using a heating and cooling rate of 20°C / min according to ASTM D3418.

7. The powder material (M) according to any one of claims 1 to 6, wherein the flow agent (F) is an inorganic pigment selected from the group consisting of silica, alumina, and titanium oxide.

8. The powder material (M) according to any one of claims 1 to 7, wherein the flow agent (F) is fumed silica.

9. The material (M) has a d in the range of 15 to 80 μm as measured by laser scattering in isopropanol. ５０ Powder material (M) according to any one of claims 1 to 7, having a value.

10. 1. A method for manufacturing a three-dimensional (3D) article, part, or composite material, comprising: a) depositing successive layers of a powder material (M) according to any one of claims 1 to 9, and b) printing a layer before the deposition of a subsequent layer; A method comprising:

11. The method of claim 10 wherein step b) comprises selective sintering of the powder by electromagnetic radiation.

12. A three-dimensional (3D) article, part or composite obtained by additive manufacturing from a powder material (M) according to any one of claims 1 to 9.

13. Use of the powder material (M) according to any one of claims 1 to 9 for producing a three-dimensional (3D) object using additive manufacturing.

14. Formulas (I), (II), and (III), optionally in combination with one or more flow agents (F) and / or one or more additives (A): 【Chemistry 2】 (In the formula, n ｐ , n ｑ and n ｒ are the mole percentages of each repeat unit p, q, and r, respectively; The repeat units p, q and r are arranged in blocks, alternating, or randomly; 1%≦(n ｑ +n ｒ ) / (n ｐ +n ｑ +n ｒ ) ≦12%; n ｑ ≧0% and nr ≧0%; j is zero or an integer varying between 1 and 4; R １ is a halogen atom, C １ ~C １２ Alkyl group, C ７ ~C ２４ Alkylaryl group, C ７ ~C ２４ Aralkyl group, C ６ ~C ２４ Arylene group, C １ ~C １２ Alkoxy groups, and C ６ ~C １８ a polymer component (P) comprising at least one poly(arylene sulfide) (PAS) polymer comprising repeating units p, q, and r according to the formula (I), wherein p, q, and r are selected from the group consisting of aryloxy groups; Use for producing powder materials (M) for additive manufacturing.

15. 13. Use of the article, part, or composite material of claim 12 in oil and gas applications, automotive applications, electrical and electronic applications, or aerospace and consumer goods.

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