FR3119623A1 - POLYAMIDE POWDERS AND THEIR USE IN POWDER AGGLOMERATION PROCESSES BY FUSION - Google Patents

POLYAMIDE POWDERS AND THEIR USE IN POWDER AGGLOMERATION PROCESSES BY FUSION Download PDF

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FR3119623A1
FR3119623A1 FR2201179A FR2201179A FR3119623A1 FR 3119623 A1 FR3119623 A1 FR 3119623A1 FR 2201179 A FR2201179 A FR 2201179A FR 2201179 A FR2201179 A FR 2201179A FR 3119623 A1 FR3119623 A1 FR 3119623A1
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acid
powder
polyamide
melting
chain limiter
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Emilie-Marie SOARES LATOUR
Ornella ZOVI
Arnaud LEMAITRE
Hervé STER
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Arkema France SA
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Arkema France SA
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Priority to FR2201179A priority Critical patent/FR3119623A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/141—Processes of additive manufacturing using only solid materials
    • B29C64/153—Processes of additive manufacturing using only solid materials using layers of powder being selectively joined, e.g. by selective laser sintering or melting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/092—Polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/372—Sulfides, e.g. R-(S)x-R'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

Abstract

La présente invention concerne une poudre de polyamide destinée à être utilisée dans un procédé d’agglomération de poudre par fusion, comprenant au moins un limiteur de chaine. (pas de figure)The present invention relates to a polyamide powder intended to be used in a powder agglomeration process by melting, comprising at least one chain limiter. (no figure)

Description

POUDRES DE POLYAMIDE ET LEUR UTILISATION DANS LES PROCEDES D’AGGLOMERATION DE POUDRES PAR FUSIONPOLYAMIDE POWDERS AND THEIR USE IN POWDER AGGLOMERATION PROCESSES BY FUSION

Domaine de l’inventionField of the invention

La présente invention concerne des poudres de polymères, en particulier de polyamides, destinées à être utilisées dans des procédés d'agglomération de poudres par fusion et pouvant être recyclées plusieurs fois.The present invention relates to powders of polymers, in particular of polyamides, intended to be used in processes for the agglomeration of powders by melting and which can be recycled several times.

Arrière-plan techniqueTechnical background

La technologie d'agglomération de poudres de polyamide sert à fabriquer des objets en trois dimensions par ajout ou agglomération de poudre par fusion couche par couche. Cette technologie est notamment utilisée pour fabriquer des prototypes et des modèles, dans des domaines variés tels que l’automobile, la nautique, l’aéronautique, l’aérospatial, le domaine médical, le textile, l’habillement, la décoration, le domaine des boîtiers pour l’électronique, la téléphonie, la domotique, l’informatique et l’éclairage, la mode, le sport, et l’outillage industriel.Polyamide powder agglomeration technology is used to manufacture three-dimensional objects by adding or agglomeration of powder by melting layer by layer. This technology is used in particular to manufacture prototypes and models, in various fields such as the automobile, nautical, aeronautical, aerospace, medical field, textiles, clothing, decoration, enclosures for electronics, telephony, home automation, IT and lighting, fashion, sport, and industrial tools.

L'agglomération de poudres par fusion (ou « frittage ») est provoquée par un rayonnement, tel que par exemple un faisceau laser (aussi connu sous le nom de frittage laser oulaser sintering), un rayonnement infra-rouge, un rayonnement UV, un rayonnement de type LED, ou toute source de rayonnement électromagnétique permettant de faire fondre la poudre couche par couche pour fabriquer des objets tridimensionnels.The agglomeration of powders by melting (or "sintering") is caused by radiation, such as for example a laser beam (also known as laser sintering or laser sintering ), infrared radiation, UV radiation, LED-type radiation, or any source of electromagnetic radiation allowing the powder to be melted layer by layer to manufacture three-dimensional objects.

Dans le cas du frittage laser, on dépose une fine couche de poudre de polyamide sur une plaque horizontale maintenue dans une enceinte chauffée à une température située entre la température de cristallisation Tc et la température de fusion TF de la poudre de polyamide. Le laser permet de fusionner des particules de poudre en différents points de la couche qui cristallisent lentement après le passage du laser selon une géométrie correspondant à l'objet, par exemple à l'aide d'un ordinateur ayant en mémoire la forme de l'objet 3D et restituant cette dernière sous forme de tranches 2D. Ensuite, on abaisse la plaque horizontale d'une valeur correspondant à l'épaisseur d'une couche de poudre (par exemple entre 0,05 et 2 mm et généralement de l'ordre de 0,1 mm) puis on dépose une nouvelle couche de poudre, le laser permet de fusionner des particules de poudre selon une géométrie correspondant à cette nouvelle couche qui cristallise lentement selon une géométrie correspondant à l'objet et ainsi de suite. La procédure est répétée jusqu'à ce que l’on ait fabriqué tout l'objet. On obtient à l’intérieur de l’enceinte un objet entouré de poudre. Les parties qui n'ont pas été agglomérées sont donc restées à l'état de poudre.In the case of laser sintering, a thin layer of polyamide powder is deposited on a horizontal plate held in an enclosure heated to a temperature between the crystallization temperature Tc and the melting temperature TF of the polyamide powder. The laser makes it possible to merge powder particles at different points of the layer which crystallize slowly after the passage of the laser according to a geometry corresponding to the object, for example using a computer having in memory the shape of the 3D object and rendering it in the form of 2D slices. Then, the horizontal plate is lowered by a value corresponding to the thickness of a layer of powder (for example between 0.05 and 2 mm and generally of the order of 0.1 mm) then a new layer is deposited. of powder, the laser makes it possible to fuse powder particles according to a geometry corresponding to this new layer which crystallizes slowly according to a geometry corresponding to the object and so on. The procedure is repeated until the entire object has been made. An object surrounded by powder is obtained inside the enclosure. The parts which were not agglomerated thus remained in the state of powder.

Dans le cas du frittage laser au moins 50% de la poudre n’est pas visée par le laser. Il est donc avantageux de pouvoir réutiliser, c’est-à-dire recycler, cette poudre lors de la construction (ou «run») suivante. Pour cela, la poudre de polyamide doit autant que possible avoir conservé ses propriétés initiales : granulométrie, coulabilité, couleur, viscosité, etc.In the case of laser sintering at least 50% of the powder is not targeted by the laser. It is therefore advantageous to be able to reuse, that is to say recycle, this powder during the following construction (or “ run ”). For this, the polyamide powder must as far as possible have retained its initial properties: particle size, flowability, color, viscosity, etc.

Lors d’une construction par frittage, la poudre environnante, c’est-à-dire non touchée par le rayonnement, reste plusieurs heures au-dessus de sa température de cristallisation (Tc) ce qui peut entraîner une augmentation de la masse moléculaire et donc de la viscosité du polyamide. Par la suite, la coalescence entre grains de poudre devient de plus en plus difficile au cours des runs successifs. Ainsi, certaines poudres de polyamide nécessitent de modifier les paramètres du dispositif de frittage, en particulier d’augmenter de manière drastique la puissance du rayonnement, à chaque recyclage de la poudre lors de runs successifs. En outre, un déclin très net des propriétés mécaniques des pièces obtenues au fur et à mesure des runs est constaté.During a construction by sintering, the surrounding powder, that is to say not affected by the radiation, remains several hours above its crystallization temperature (Tc) which can lead to an increase in the molecular mass and therefore the viscosity of the polyamide. Subsequently, the coalescence between powder grains becomes increasingly difficult during successive runs. Thus, some polyamide powders require modifying the parameters of the sintering device, in particular drastically increasing the power of the radiation, each time the powder is recycled during successive runs. In addition, a very clear decline in the mechanical properties of the parts obtained as the runs progress is observed.

Afin de limiter l’augmentation de masse moléculaire des poudres de polyamide, des savons métalliques (0,5%) ont été ajoutés à la poudre de polyamide (US2004106691). Toutefois, lorsqu’ils sont au contact de certains solvants, les objets fabriqués à partir de ces poudres ont tendance à relarguer des dérivés de sels métalliques ce qui restreint leur utilisation à certaines applications.In order to limit the increase in molecular weight of polyamide powders, metallic soaps (0.5%) were added to the polyamide powder (US2004106691). However, when in contact with certain solvents, objects made from these powders tend to release metal salt derivatives, which restricts their use to certain applications.

En outre, des traitements à la vapeur d’eau à haute température, de la poudre utilisée lors d’un run, ont été effectués avant de recycler la poudre traitée dans un run ultérieur (US20090291308). Toutefois, ce procédé nécessite, entre 2 runs successifs, et à proximité du dispositif de frittage, de traiter la poudre à la vapeur d’eau et de la sécher ce qui nécessite de nombreuses étapes intermédiaires entre les runs et n’est pas viable économiquement.In addition, high temperature water vapor treatments of the powder used during a run were carried out before recycling the treated powder in a subsequent run (US20090291308). However, this process requires, between 2 successive runs, and near the sintering device, to treat the powder with steam and to dry it, which requires numerous intermediate steps between the runs and is not economically viable. .

Il est donc nécessaire de fournir des poudres faciles à mettre en œuvre et recyclables plusieurs fois sans qu’il soit nécessaire de modifier les conditions d’utilisation du dispositif de frittage et permettant ainsi d’obtenir des objets aux propriétés mécaniques reproductibles.It is therefore necessary to provide powders that are easy to use and recyclable several times without it being necessary to modify the conditions of use of the sintering device and thus making it possible to obtain objects with reproducible mechanical properties.

La présente invention découle de la mise en évidence inattendue, par les inventeurs, que l’ajout d’au moins un limiteur de chaine à l’état solide ou liquide, en particulier un monoacide, un acide dicarboxylique, une monoamine ou une diamine, dans une poudre de polyamide permet de contrôler, en particulier d’abaisser, de stabiliser ou de supprimer, l’augmentation de la viscosité et de la température de fusion de la poudre de polyamide non agglomérée qui se produit aux cours des cycles, ou runs, successifs d’un procédé d’agglomération par fusion. Ceci permet de réutiliser ou de recycler la poudre non agglomérée, et d’obtenir des objets aux propriétés reproductibles au cours derunssuccessifs.The present invention stems from the unexpected demonstration, by the inventors, that the addition of at least one chain limiter in the solid or liquid state, in particular a monoacid, a dicarboxylic acid, a monoamine or a diamine, in a polyamide powder makes it possible to control, in particular to lower, stabilize or eliminate, the increase in the viscosity and the melting temperature of the non-agglomerated polyamide powder which occurs during the cycles, or runs , successive of an agglomeration process by fusion. This makes it possible to reuse or recycle the non-agglomerated powder, and to obtain objects with reproducible properties during successive runs .

Ainsi, la présente invention concerne une poudre de polyamide destinée à être utilisée dans un procédé d’agglomération de poudre par fusion, comprenant au moins un limiteur de chaine.Thus, the present invention relates to a polyamide powder intended to be used in a process for agglomeration of powder by melting, comprising at least one chain limiter.

La présente invention concerne également l’utilisation de poudre de polyamide telle que définie ci-dessus, pour fabriquer des objets par agglomération de ladite poudre par fusion.The present invention also relates to the use of polyamide powder as defined above, to manufacture objects by agglomeration of said powder by fusion.

La présente invention concerne également un procédé de fabrication d’objet dans lequel on agglomère une poudre de polyamide telle que définie ci-dessus par fusion.The present invention also relates to a process for manufacturing an object in which a polyamide powder as defined above is agglomerated by melting.

La présente invention concerne également un objet fabriqué en utilisant au moins une poudre de polyamide telle que définie ci-dessus.The present invention also relates to an object manufactured using at least one polyamide powder as defined above.

La présente invention concerne également un procédé tel que défini ci-dessus dans lequel la poudre de polyamide non agglomérée est récupérée.The present invention also relates to a process as defined above in which the non-agglomerated polyamide powder is recovered.

La présente invention concerne également l’utilisation d’une poudre de polyamide non agglomérée et récupérée selon le procédé ci-dessus pour la fabrication d’objets par agglomération de la poudre par fusion.The present invention also relates to the use of a non-agglomerated polyamide powder recovered according to the above process for the manufacture of objects by agglomeration of the powder by fusion.

La présente invention concerne également l’utilisation d’au moins un limiteur de chaine pour contrôler l’augmentation de viscosité ou de température de fusion d’une poudre de polyamide destinée à être utilisée dans un procédé de fabrication d’objet par agglomération de poudre par fusion.The present invention also relates to the use of at least one chain limiter to control the increase in viscosity or melting temperature of a polyamide powder intended to be used in a process for manufacturing an object by powder agglomeration. by merger.

La présente invention concerne également l’utilisation d’au moins un limiteur de chaine pour améliorer la recyclabilité d’une poudre de polyamide destinée à être utilisée dans un procédé d’agglomération de poudre par fusion.The present invention also relates to the use of at least one chain limiter to improve the recyclability of a polyamide powder intended to be used in a powder agglomeration process by melting.

Claims (13)

Poudre de polyamide destinée à être utilisée dans un procédé d’agglomération de poudre par fusion, comprenant au moins un limiteur de chaine et comprenant au moins un antioxydant thioéther. Polyamide powder intended for use in a powder agglomeration process by fusion, comprising at least one chain limiter and comprising at least one thioether antioxidant. Poudre selon la revendication 1, dans laquelle le limiteur de chaine représente de 0,01 à 10%, de préférence 0,01 à 5%, de préférence de 0,01 à 4%, de préférence de 0,01 à 3%, de préférence de 0,01 à 2%, de préférence de 0,01 à 1% en masse sur la masse totale de poudre de polyamide représentant 100%. Powder according to claim 1, in which the chain limiter represents from 0.01 to 10%, preferably from 0.01 to 5%, preferably from 0.01 to 4%, preferably from 0.01 to 3%, preferably from 0.01 to 2%, preferably from 0.01 to 1% by mass on the total mass of polyamide powder representing 100%. Poudre selon la revendication 1 ou 2, dans laquelle le limiteur de chaine est sélectionné dans le groupe constitué des diacides carboxylique, des monoacides carboxylique, des diamines et des monoamines. Powder according to claim 1 or 2, wherein the chain limiter is selected from the group consisting of dicarboxylic acids, monocarboxylic acids, diamines and monoamines. Poudre selon l’une quelconque des revendications 1 à 3, dans laquelle le limiteur de chaine est sélectionné dans le groupe constitué de l'acide acétique, l'acide propionique, l'acide benzoïque, l'acide stéarique, l’acide laurique, l’acide butanoïque, l’acide pentanoïque, l’acide hexanoïque, l’acide heptanoïque, l’acide octanoïque, l’acide nonanoïque, l’acide décanoïque, l’acide undécanoïque, l’acide acrylique, l’acide méthacrylique, l’acide crotonique, l’acide cinnamique, l’acide hexadécanoïque, l’acide octodécanoïque, l’acide tétradécanoïque, l’acide sébacique, l’acide adipique, l’acide azélaïque, l’acide subérique, l’acide dodécanedicarboxylique, et l'acide ortho-phtalique, l’acide butane-dioïque, la 1-aminopentane, la 1-aminohexane, la 1-aminoheptane, la 1-aminooctane, la 1- aminononane, la 1-aminodécane, la 1-aminoundécane, la 1-aminododécane, la benzylamine, et l'oleylamine, les isomères des bis-(4-aminocyclohexyl)-méthane (BACM), bis-(3-méthyl-4-aminocyclohexyl)méthane (BMACM), et 2-2-bis-(3-méthyl-4-aminocyclohexyl)-propane(BMACP), et para-amino-di-cyclo-hexyl-méthane (PACM), l'isophoronediamine (IPDA), la 2,6-bis-(aminométhyl)-norbornane (BAMN) et la pipérazine. Powder according to any one of Claims 1 to 3, in which the chain limiter is selected from the group consisting of acetic acid, propionic acid, benzoic acid, stearic acid, lauric acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, hexadecanoic acid, octodecanoic acid, tetradecanoic acid, sebacic acid, adipic acid, azelaic acid, suberic acid, dodecanedicarboxylic acid, and ortho-phthalic acid, butane-dioic acid, 1-aminopentane, 1-aminohexane, 1-aminoheptane, 1-aminooctane, 1-aminononane, 1-aminodecane, 1-aminoundecane, 1-aminododecane, benzylamine, and oleylamine, isomers of bis-(4-aminocyclohexyl)-methane (BACM), bis-(3-methyl-4-aminocyclohexyl)methane (BMACM), and t 2-2-bis-(3-methyl-4-aminocyclohexyl)-propane(BMACP), and para-amino-di-cyclo-hexyl-methane (PACM), isophoronediamine (IPDA), 2,6- bis-(aminomethyl)-norbornane (BAMN) and piperazine. Poudre selon l’une des revendications 1 à 4, dans laquelle le polyamide comprend au moins un monomère sélectionné dans le groupe constitué du 46, 4T, 54, 59, 510, 512, 513, 514, 516, 518, 536, 6, 66, 64, 69, 610, 612, 613, 614, 616, 618, 636, 6T, 9, 104, 109, 1010, 1011, 1012, 1013, 1014, 1016, 1018, 1036, 10T, 11, 12, 124, 129, 1210, 1212, 1213, 1214, 1216, 1218, 1236, 12T, MXD6, MXD10, MXD12, MXD14, et de leurs mélanges, de préférence le polyamide est sélectionné dans le groupe constitué du PA 6, le PA 66, le PA 1010, le PA 11, le PA 12, le PA 1011, le PA 610, le PA 612, le PA 613, et de leurs mélanges. Powder according to one of Claims 1 to 4, in which the polyamide comprises at least one monomer selected from the group consisting of 46, 4T, 54, 59, 510, 512, 513, 514, 516, 518, 536, 6, 66, 64, 69, 610, 612, 613, 614, 616, 618, 636, 6T, 9, 104, 109, 1010, 1011, 1012, 1013, 1014, 1016, 1018, 1036, 10T, 11, 12, 124, 129, 1210, 1212, 1213, 1214, 1216, 1218, 1236, 12T, MXD6, MXD10, MXD12, MXD14, and mixtures thereof, preferably the polyamide is selected from the group consisting of PA 6, PA 66 , PA 1010, PA 11, PA 12, PA 1011, PA 610, PA 612, PA 613, and mixtures thereof. Poudre selon la revendication 1, dans laquelle ledit au moins un antioxydant thioéther est sélectionné dans le groupe constitué de dilauryl thiodipropionate (DLTDP), ditridecyl thiodipropionate (DTDTDP), distearyl thiodipropionate (DSTDP), dimyrystil thiodipropionate (DMTDP), pentaerythritol tetrakis (3-dodecylthio propionate ou 3-laurylthiopropionate), et de leurs mélanges. A powder according to claim 1, wherein said at least one thioether antioxidant is selected from the group consisting of dilauryl thiodipropionate (DLTDP), ditridecyl thiodipropionate (DTDTDP), distearyl thiodipropionate (DSTDP), dimyrystil thiodipropionate (DMTDP), pentaerythritol tetrakis (3- dodecylthio propionate or 3-laurylthiopropionate), and mixtures thereof. Poudre selon la revendication 1 ou 6, dans laquelle ledit au moins un antioxydant thioéther représente de 0,1 à 5%, de préférence 0,1 à 4%, de préférence de 0,1 à 3%, de préférence de 0,1 à 2%, de préférence de 0,1 à 1% en masse sur la masse totale de poudre représentant 100%. Powder according to Claim 1 or 6, in which the said at least one thioether antioxidant represents from 0.1 to 5%, preferably 0.1 to 4%, preferably from 0.1 to 3%, preferably from 0.1 at 2%, preferably from 0.1 to 1% by mass on the total mass of powder representing 100%. Procédé de fabrication d’objet dans lequel on agglomère une poudre de polyamide telle que définie dans l’une des revendications 1 à 7 par fusion. Process for manufacturing an object in which a polyamide powder as defined in one of Claims 1 to 7 is agglomerated by melting. Objet fabriqué en utilisant au moins une poudre de polyamide telle que définie dans l’une quelconque des revendications 1 à 7. Object manufactured using at least one polyamide powder as defined in any one of claims 1 to 7. Procédé selon la revendication 8, dans lequel la poudre de polyamide non agglomérée est récupérée. Process according to Claim 8, in which the unagglomerated polyamide powder is recovered. Utilisation de la poudre de polyamide non agglomérée et récupérée selon le procédé tel que défini dans la revendication 10 pour la fabrication d’objets par agglomération de la poudre par fusion. Use of non-agglomerated polyamide powder recovered according to the process as defined in claim 10 for the manufacture of objects by agglomeration of the powder by melting. Utilisation d’au moins un limiteur de chaine et d’au moins un antioxydant thioéther pour contrôler l’augmentation de viscosité ou de température de fusion d’une poudre de polyamide destinée à être utilisée dans un procédé d’agglomération de poudre par fusion. Use of at least one chain limiter and at least one thioether antioxidant to control the increase in viscosity or melting temperature of a polyamide powder intended to be used in a powder agglomeration process by melting. Utilisation d’au moins un limiteur de chaine et d’au moins un antioxydant thioéther pour améliorer la recyclabilité d’une poudre de polyamide destinée à être utilisée dans un procédé d’agglomération de poudre par fusion. Use of at least one chain limiter and at least one thioether antioxidant to improve the recyclability of a polyamide powder intended to be used in a powder agglomeration process by melting.
FR2201179A 2022-02-10 2022-02-10 POLYAMIDE POWDERS AND THEIR USE IN POWDER AGGLOMERATION PROCESSES BY FUSION Pending FR3119623A1 (en)

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