Polyamide composition prepared from a powder of polyamides to be recycled

Abstract

The application relates to a method for preparing a polyamide composition, which comprises the steps of: a) providing a mixture comprising a virgin polyamide vPA and a polyamide to be recycled rPA in the form of an untransformed powder resulting from additive manufacturing by sintering or from a coating method by powdering or by electrostatic spraying, or powder obtained by grinding a polyamide-based part of an object to be recycled; b) kneading the mixture in the molten state, as a result of which a polyamide composition is obtained; and c) recovering the polyamide composition. The invention also relates to the polyamide composition obtained and to the uses thereof for preparing articles by extrusion, injection or overmoulding.

Description

[0001] DESCRIPTION

[0002] TITLE: Polyamide composition prepared from polyamide powder to be recycled

[0003] The present invention relates to a process for preparing a polyamide composition from unprocessed powder resulting from additive manufacturing by sintering or from a powder coating process or from electrostatic spraying or from powder obtained by grinding a polyamide-based part of an object to be recycled, a polyamide composition, and its use for the preparation of articles.

[0004] Additive manufacturing (AM) has grown rapidly in recent years, thanks in part to the ability to design objects in a wide variety of shapes, the short time between design and production, and the associated environmental and economic benefits.

[0005] The agglomeration of powders by fusion (hereinafter "sintering") is caused by radiation, such as for example a laser beam ("laser sintering" or "selective laser sintering" SLS in English), infrared radiation, UV radiation, or any source of electromagnetic radiation allowing the powder to be melted layer by layer to manufacture three-dimensional objects. The SLS technique produces a part by applying powders layer by layer, each layer being in the form of a thin powder bed, generally of the order of 100 μm. A laser is used to melt a portion of this powder at the desired location, then a new layer of powder is deposited. The process is repeated until a thermoplastic polymer object is formed layer by layer.

[0006] Selective sintering processes using an absorber can also be mentioned, in particular the technologies known as "High Speed ​​Sintering" (HSS) and "Multi-Jet Fusion" (MJF). In these technologies, the manufacturing of 3D objects is also done layer by layer, using a polyamide-based powder which is melted in a controlled manner for each layer constituting the 3D object: an absorber is deposited on the layer (for example by means of a liquid ink in the "inkjet process") before exposing the layer to electromagnetic radiation (for example infrared) which causes the fusion of the areas containing said absorber.

[0007] Sintering generates a large amount of untransformed powder. For each layer, the powder that was not targeted by the radiation is not incorporated into the final object. This leaves a lot of untransformed powder. This is difficult to recycle because it is generally degraded. Indeed, the powder bed is preheated and maintained at a temperature close to the melting point of the powder, typically 5 to 15°C below its melting point. This allows for good melting of the powder targeted by the laser and good definition of each layer of the object formed by the laser. At this temperature, the untransformed powder undergoes degradation due to aging such as solid-state polycondensation and oxidation reactions. This leads to an increase in the polymer chain length, resulting in a decrease in the melt flow rate (MFR).Therefore, these degraded powders generally cannot be directly reused in the next additive manufacturing by sintering, especially when the viscosity of the degraded powder is too different from that of the initial powder. Any attempt to reuse these powders results in parts with poor surface finish, e.g., an orange peel appearance, and reduced mechanical properties, in particular a lower elongation at break, because the defects act as a fracture initiator during tensile tests.

[0008] Recycling this unprocessed powder for other types of processing (extrusion, injection) is not easy. Indeed, heating during the sintering technique affects the intrinsic viscosity of the powder. Generally, extrusion or molding of this degraded powder leads to spongy articles and / or articles whose mechanical properties, particularly strength, and aesthetic properties, particularly with regard to the color which tends towards brown, are less good than those of articles formed from virgin polymer.

[0009] A large amount of waste is generated by additive manufacturing processes using sintering in the form of degraded, unprocessed powder. This powder is rarely recycled.

[0010] Taking polyamide 12 (PA12) as an example, which is the main type of plastic used in the SLS process, PA12 powder waste can represent up to 50%, or even 90%, of the total powder used in the process. This represents a significant loss of PA12 powder, since this powder waste must be disposed of.

[0011] The literature reports some attempts to recycle this polyamide powder waste. Application US 2022 / 0064405 describes a recycled polyamide composition comprising a polyamide waste preferably from additive manufacturing, a lubricating agent and a crystallization agent. The invention that is the subject of this application is based on the increase in the crystallization temperature and the improvement in fluidity conferred by these agents. The composition of this application is free of virgin polyamide. There is therefore a need to recycle polyamide powder waste from additive manufacturing.

[0012] Furthermore, it is known to use polymer powders to manufacture coatings for substrates, particularly metallic ones, typically by powder coating or electrostatic spraying. A powdered polymer composition is applied to the substrate in the form of a loose powder, for example by electrostatic spraying or by immersing the substrate to be coated in a fluidized bed of powder. The polymers used for the manufacture of powders are usually thermosetting resins, but it is also possible to use thermoplastic polymers. Polyamides are, due to their high chemical and thermal resistance, polymers of choice for demanding applications, such as the coating of dishwasher baskets for example.

[0013] However, these powders are not easily recyclable. Indeed, the fraction of powder that does not reach the substrate during spraying, called "overspray", which is of interest to recover for recycling, generally does not have the same composition and / or the same properties as the powder initially used and the coatings obtained from it therefore do not correspond to it in terms of appearance and properties.

[0014] There is therefore a need to recycle polyamide powder waste from a powder coating or electrostatic spraying process.

[0015] The lower mechanical properties of polyamide powder waste from additive manufacturing or from a powder coating or electrostatic spraying process, in particular the reduced elongation at break, make them less attractive than virgin polyamides, particularly for the preparation of articles.

[0016] Finally, there is a need to recycle many polyamide-based parts belonging to defective objects and / or in need of recycling in order to promote the circular economy and the reuse of the material. Due to the previous use that these parts have undergone, the polyamide they contain generally does not have properties as good as those of virgin polyamide.

[0017] One of the objectives of this application is to enable the recycling of unprocessed powders resulting from additive manufacturing or from a powder coating or electrostatic spraying process, or powders obtained by grinding a polyamide-based part of an object to be recycled.

[0018] One of the objectives is to reduce the environmental impact and lower the cost price:

[0019] - additive manufacturing or powder coating or electrostatic spraying processes by recycling their unprocessed powders, - processes for preparing new polyamide articles using as raw material said unprocessed powders or a powder obtained by grinding a polyamide-based part of an object to be recycled.

[0020] One of the objectives of the application is to provide a polyamide PA1 1 or PA12 composition having certain mechanical and / or physicochemical properties better than those of a polyamide composition prepared from exclusively virgin polyamides.

[0021] One of the objectives of the application is to provide a polyamide composition whose processability (suitability for implementation, transformation) by extrusion, injection or overmolding is improved.

[0022] For this purpose, according to a first subject, the invention relates to a process for preparing a polyamide composition comprising the steps of: a) providing a mixture comprising: from 5 to 90% by weight of virgin polyamide vPA, from 10 to 95% by weight of polyamide to be recycled rPA, the polyamide to be recycled rPA being in the form of an unprocessed powder resulting from additive manufacturing by sintering or from a powder coating process or by electrostatic spraying, or of powder obtained by grinding a polyamide-based part of an object to be recycled, b) kneading said mixture in the molten state, whereby a polyamide composition is obtained, c) recovering said polyamide composition.

[0023] The method comprises a step a) of providing a mixture comprising a virgin polyamide vPA, a polyamide to be recycled rPA, the polyamide to be recycled rPA being in the form of a powder.

[0024] For the purposes of the application, "vPA" means a virgin polyamide. This has not undergone any prior processing, and in particular it has not been used in a prior additive manufacturing process by sintering or coating by powder or electrostatic spraying and it does not originate from a part of a pre-existing article.

[0025] By "prior" is meant a process taking place before step a) of the process according to the invention.

[0026] In the sense of the application, "rPA" means a polyamide to be recycled, also called recycled polyamide. The latter is:

[0027] - either in the form of unprocessed powder resulting from additive manufacturing by sintering or from a powder coating process or electrostatic spraying, preferably in the form of unprocessed powder resulting from additive manufacturing by sintering, also called 3D printing by sintering,

[0028] - either in the form of powder obtained by grinding a polyamide-based part of an object to be recycled.

[0029] “Unprocessed powder from additive manufacturing by sintering” means powder that has not been subjected to radiation in a prior additive manufacturing by sintering process and that has not been used to form the object formed in the prior additive manufacturing process. Typically, this powder has spent at least 1 minute at a temperature above 100°C in an additive manufacturing device.

[0030] Unprocessed powder from a powder coating or electrostatic spraying process means powder that was not used to form the coating on the substrate in the prior powder coating or electrostatic spraying process. Typically, this powder has been used in a process for coating a substrate by powder coating or electrostatic spraying (electrospray).

[0031] In both cases, the unprocessed powder used as polyamide to be recycled in the process according to the invention corresponds to polyamide powder waste from a previous process. The polyamide to be recycled rPA has therefore undergone degradation, generally thermal.

[0032] A "polyamide-based part of an object to be recycled" means a part obtained by a previous transformation, for example injection, extrusion or overmolding. The object to be recycled (or the part) may be used, broken, of poor quality, and / or unfit for its function. The polyamide in this part is therefore also waste.

[0033] The unprocessed powder, or powder obtained by grinding a polyamide-based part of an object to be recycled, generally comprises more than 10%, typically more than 50%, or even more than 75% of polyamide (or polyamide mixture) by weight relative to the weight of the powder. The proportion of polyamides is generally less than 99.9% by weight.

[0034] The powder is generally such that the volume median diameter (Dv50) of the particles it contains is in the range of 5 to 250 pm, in particular 5 to 200 pm, preferably in the range of 10 to 150 pm. According to the present application, the "volume mean diameter" or "Dv" the volume mean diameter of a powdery material is as measured according to ISO 9276 - parts 1 to 6: "Representation of data obtained by particle size analysis", in its version in force in 2022. Different diameters are distinguished. More specifically, Dv50 designates the volume median diameter, that is to say that corresponding to the 50th percentile by volume, and Dv10 and Dv90 designate respectively the volume mean diameters below which 10 or 90% by volume of the particles are located. The volume average diameter can be measured in particular using a laser granulometer, for example a laser granulometer (Malvern Insitec System).Associated software (RT sizer) then makes it possible to obtain the volumetric distribution of a powder and to deduce the Dv10, the Dv50 and the Dv90.

[0035] The rPA polyamide and vPA may independently be a homopolyamide, a copolyamide, a polyamide block copolymer with a polyether block (PEBA) or a mixture thereof. The rPA polyamide and vPA may independently also be a mixture of polyamide and at least one other polymer, the polyamide forming the matrix and the other polymer(s) forming the dispersed phase.

[0036] Preferably, the polyamide rPA and the vPA are independently a condensation product:

[0037] - one or more amino acids;

[0038] - one or more lactams; or

[0039] - one or more salts or mixtures of diamines with diacids.

[0040] Examples of amino acids include alpha-omega amino acids, such as aminocaproic, 7-aminoheptanoic, 11-aminoundecanoic, n-heptyl-11-aminoundecanoic and 12-aminododecanoic acids.

[0041] The lactam monomers preferably comprise between 3 and 12 carbon atoms on the main ring and may be substituted. Examples of lactams include p,p-dimethylpropriolactam, a,a-dimethylpropriolactam, amylolactam, caprolactam, capryllactam, oenantholactam, 2-pyrrolidone and lauryllactam.

[0042] Preferably, the diamine used in the composition of the rPA and / or vPA polyamide is an aliphatic diamine, an aryl diamine and / or a saturated cyclic diamine having from 6 to 12 carbon atoms. Examples of diamines include hexamethylenediamine, decanediamine, piperazine, tetramethylenediamine, octamethylenediamine, decamethylenediamine, dodecamethylenediamine, 1,5-diaminohexane, 2,2,4-trimethyl-1,6-diaminohexane, diamine polyols, isophoronediamine (IPD), methylpentamethylenediamine (MPDM), bis(aminocyclohexyl)methane (BACM), bis(3-methyl-4-aminocyclohexyl)methane (BMACM), methaxylyenediamine, bis-p-aminocyclohexylmethane, and trimethylhexamethylenediamine.

[0043] Preferably, the dicarboxylic acid used in the composition of the rPA and / or vPA polyamide has between 4 and 18 carbon atoms. Examples of dicarboxylic acids that may be mentioned are adipic acid, sebacic acid, azelaic acid, suberic acid, isophthalic acid, butanedioic acid, 1,4-cyclohexyldicarboxylic acid, terephthalic acid, the sodium or lithium salt of sulfoisophthalic acid, dimerized fatty acids (these dimerized fatty acids have a dimer content of at least 98% and are preferably hydrogenated) and dodecanedioic acid HOOC-(CH2)10-COOH.

[0044] Preferably, the rPA and / or vPA copolyamide results from the condensation of at least two different monomers, for example at least two different alpha-omega aminocarboxylic acids or two different lactams or a lactam and an alpha-omega aminocarboxylic acid of different carbon numbers. It is also possible to cite copolyamides resulting from the condensation of at least one alpha-omega aminocarboxylic acid (or a lactam), at least one diamine and at least one dicarboxylic acid. It is also possible to cite copolyamides resulting from the condensation of an aliphatic diamine with an aliphatic dicarboxylic acid and at least one other monomer chosen from aliphatic diamines different from the previous one and aliphatic diacids different from the previous one.

[0045] Preferably, the rPA and / or vPA polyamide powder comprises at least one polyamide or copolyamide comprising at least one monomer selected from the group consisting of 4.6, 4T, 5.4, 5.9, 5.10, 5.12, 5.13, 5.14, 5.16, 5.18, 5.36, 6, 6.4, 6.9, 6.10, 6.12, 6.13, 6.14, 6.16, 6.18, 6.36, 6T, 9, 10.4, 10.9, 10.10, 10.11, 10.12, 10.13, 10.14, 10.16, 10.18, 10.36, 10T, 11, 12, 12.4, 12.9, 12.10, 12.12, 12.13, 12.14, 12.16, 12.18, 12.36, 12T, MXD6, MXD10, MXD12, MXD14, and mixtures thereof.

[0046] Preferably, the polyamide rPA and / or vPA is selected from the group consisting of PA 6, PA 6.6, PA 10.10, PA 11, PA 12, PA 10.11, PA 6.10, PA6.12, PA 6.13 and mixtures thereof.

[0047] Examples of copolyamides include copolymers of caprolactam and lauryllactam (PA 6.12), copolymers of caprolactam, adipic acid and hexamethylenediamine (PA 6.66), copolymers of caprolactam, lauryllactam, adipic acid and hexamethylenediamine (PA 6.12.66), copolymers of caprolactam, lauryllactam, 11-aminoundecanoic acid, azelaic acid and hexamethylenediamine (PA 6.69.11.12), copolymers of caprolactam, lauryllactam, 11-aminoundecanoic acid, adipic acid and hexamethylenediamine (PA 6.66.1 1.12), copolymers of lauryllactam, azelaic acid and hexamethylenediamine (PA 69.12), copolymers of 11-aminoundecanoic acid, terephthalic acid and decamethylenediamine (PA 11.10T).

[0048] Preferably, the average number of carbon atoms (C) relative to the nitrogen atom (N) of the polyamide rPA and / or vPA is greater than or equal to 8, in particular greater than or equal to 10, preferably greater than or equal to 11. In a particularly preferred manner, the average number of carbon atoms (C) relative to the nitrogen atom (N) of the polyamide rPA and / or vPA is 1 or 12.

[0049] Preferably, the polyamide rPA and vPA are independently selected from PA 11, PA 10.10, PA 10.12, PA 12, PA 12.12, PA 10.14 or PA 12.14 and mixtures thereof, preferably PA1 1 or PA12 or a mixture thereof.

[0050] The nomenclature used to define polyamides is described in ISO 1874-1:2010 "Plastics - Polyamide (PA) materials for molding and extrusion - Part 1: Designation", particularly on page 3 (tables 1 and 2) and is well known to those skilled in the art.

[0051] Preferably, the polyamide of the rPA polyamide and the vPA polyamide are of identical nature. For example, the virgin polyamide is vPA1 1 , the polyamide to be recycled rPA is rPA11. According to another example, the virgin polyamide is vPA12, the polyamide to be recycled rPA is rPA12.

[0052] Virgin polyamide vPA generally has an inherent viscosity of less than or equal to 1.50, in particular less than or equal to 1.40, preferably less than or equal to 1.30. For the purposes of the application, the inherent viscosity is as measured using an Ubbelohde tube at 20°C on a 0.5% by weight solution in m-cresol according to ISO 307 of 2019.

[0053] Generally, the inherent viscosity of the virgin polyamide vPA is lower than that of the powder of the mixture, typically the inherent viscosity of the virgin polyamide vPA is lower by at least 10%, in particular by at least 20%, preferably by at least 30% than that of the powder of the mixture.

[0054] The powder of the mixture generally has an inherent viscosity greater than or equal to 1.50, preferably greater than or equal to 1.60, and most often in the range of 1.70 to 5.00.

[0055] Generally, the weight polydispersity index Ip of the virgin polyamide vPA is lower than that of the polyamide to be recycled rPA. Typically the polydispersity index Ip of the virgin polyamide vPA is at least 20%, in particular at least 35%, preferably at least 50% lower than the polydispersity index Ip of the polyamide to be recycled rPA. The weight polydispersity index Ip is the ratio of the weight average molecular mass Mw to the number average molecular mass Mn.

[0056] Preferably, the weight polydispersity index Ip of the virgin polyamide vPA is from 1.6 to 2.2, in particular from 1.6 to 2.1 and / or the weight polydispersity index Ip of the polyamide to be recycled rPA is from 2.5 to 15.0, in particular from 2.8 to 10.0.

[0057] Generally, the z-polydispersity index Iz of the virgin polyamide vPA is lower than that of the polyamide to be recycled rPA. Typically the polydispersity index Iz of the virgin polyamide vPA is at least 30%, in particular at least 50%, preferably at least 70% lower than the polydispersity index Iz of the polyamide to be recycled rPA. The z-polydispersity index Iz is the ratio of the z-average molecular weight Mz to the number-average molecular weight Mn.

[0058] Preferably, the z-polydispersity index Iz of the virgin polyamide vPA is from 1.5 to 3.5, in particular from 2.0 to 3.0 and / or the z-polydispersity index Iz of the polyamide to be recycled rPA is from 3.5 to 50.0, in particular from 4.0 to 30.0.

[0059] The number-average molecular masses Mn, weight-average molecular masses Mw and z-average molecular masses Mz are measured by size exclusion chromatography (or gel permeation chromatography) according to ISO 16014-1 of 2012. Typically, the polyamide is solubilized in hexafluoroisoproponol stabilized with 0.05 M potassium trifluoroacetate for 24 h at room temperature (20°C) at a concentration of 1 g / L. The solution obtained is then filtered through a PTFE membrane with a porosity of 0.2 pm, then injected at a flow rate of 1 mL / min, into a liquid chromatography system equipped with a set of PFG columns from Polymer Standards Service consisting of a pre-column with dimensions of 50 x 8 mm, a 1000 Å column with dimensions of 300 x 8 mm and particle size of 7 pm, and a 100 Å column with dimensions of 300 x 8 mm and particle size of 7 pm. The molar masses are measured by the refractive index and are expressed in PMMA equivalents, used as a calibration standard, then converted to g / mol.

[0060] rPA polyamides to be recycled have particularities, and in particular new species resulting from oxidation mechanisms.

[0061] The expression "new species resulting from oxidation mechanisms" is intended to designate, within the meaning of the invention, the primary amide functions, the nitriles, the methyl groups at the end of the chain, the alkenes, the formamides, the imides, the carboxylic acids and the alcohols which may appear in the polyamide to be recycled rPA of the invention.

[0062] The rPA polyamide to be recycled of the invention has functions resulting from oxidation reactions chosen from primary amide functions, nitriles, methyl groups at the end of the chain, alkenes, formamides, imides, carboxylic acids and alcohols.

[0063] According to a preferred embodiment of the invention, the polyamide to be recycled rPA of the invention has functions resulting from oxidation reactions chosen from nitriles and methyl groups at the end of the chain.

[0064] According to a preferred embodiment of the invention, the polyamide to be recycled rPA of the invention has functions resulting from oxidation reactions chosen from nitriles and methyl groups at the end of the chain in a molar ratio relative to the secondary amide functions higher than that of the same virgin polyamide, and primary amine functions in a molar ratio relative to the secondary amide functions lower than that of the same virgin polyamide.

[0065] These functions can be identified and quantified using infrared spectroscopy and / or proton or carbon NMR.

[0066] NMR measurements can be performed in the HFIP / CD2CI2 mixture. For example, 20 mg of polymer can be dissolved in 0.7 mL of solvent with a HFIP / CD2CI2 ratio of 1 / 3. Dichloromethane (CD2CI2) / trifluoroacetic anhydride (TFAA) mixture can also be used.

[0067] This method is described in the doctoral thesis of E. Goncalves in chapter II.2.3 published in 2011, incorporated by reference. Analyses in these two solvents make it possible to identify a majority of functions formed during the life of the polyamide.

[0068] Thus, for example, in infrared spectroscopy, the absorption band from 1700 to 1740cm -1 corresponds to an imide, that of 1680 to 1720 cm -1 to the carbonyl of the carboxylic acid and that of 3580 to 3670 cm -1 corresponds to the alcohol function of the carboxylic acid.

[0069] The absorption band from 3580 to 3670 cm -1 corresponds to the free alcohol function.

[0070] The amide function is characterized on the one hand by a pair of absorption bands from 3100 to 3500 cm -1 and from 15560 to 1640 cm -1 which corresponds to the NH group of the amide and on the other hand by the absorption band from 1650 to 1700 cm -1 which corresponds to the carbonyl group of the amide.

[0071] The absorption bands of 1180 and 1723 cm -1 corresponds to the formates. The bands at 900 and 1660 cm -1 correspond to alkenes.

[0072] Quantification by NMR is, for example, carried out by comparing the intensity of the lines of the functions not present in the virgin polymer with the lines corresponding to the CH2 in a of the amide, ether or other CH2 functions in the context of proton NMR. In carbon NMR, the intensity of the lines of the functions formed during the life of the polymer is compared with the intensity of the lines of the carbons of the amides or CH2.

[0073] Some of the above-mentioned functions can be observed, for example, in 13C NMR in the HFIP / CD2CI2 solvent. Thus, the line at 36 ppm corresponds to the CH2 in a of the primary amide, that at 34 ppm corresponds to the CH2 in a of the carboxylic acid. These species can be quantified by integrating the area under the lines and comparing them to the area under the 37.1 ppm line corresponding to the secondary amide. Similarly, the lines corresponding to the carbonyl groups of the primary amide, carboxylic acid and secondary amide functions are observed at 181.2 ppm, 179.6 ppm and 177.4 ppm respectively. The line at 16.7 ppm corresponds to the CH2 in a of the nitrile group. The formamide group gives a chemical shift at 163.0 ppm and 166.3 ppm.

[0074] Other functions mentioned above can be observed by proton NMR (1 H NMR) in the HFIP / CD2CI2 solvent as described above. The line of the CHO groups of formamides appears at 7.92 and 8.01 ppm. The line corresponding to the CH2 in a of primary amides can be observed at 2.30 ppm. The line at 0.9 ppm corresponds to the CH3 groups of the CH3-(CH2) type. n The line at 2.40 ppm corresponds to the CH2 in a of the nitrile function. The line corresponding to the proton of the formate function is observed at 8.1 ppm. The line corresponding to the proton of the aldehyde function is observed at 9.7 ppm. Similar to what is described for carbon NMR, the ratios of new functions to secondary amides can be determined by integrating the area under the lines and comparing them to the area under the line corresponding to the CH2 in a of the secondary amide (2.20 ppm) or to the area under the line corresponding to the CONH proton of the secondary amide (6.0 - 6.1 ppm).

[0075] According to any one of the embodiments of the invention, in a polyamide to be recycled rPA of the invention, the molar ratio of the functions resulting from oxidation reactions relative to the secondary amide functions is between 0.0005 and 0.3.

[0076] According to any one of the embodiments of the invention, in a polyamide to be recycled rPA of the invention, the molar ratio of the imide functions relative to the secondary amide functions is between 0.0005 and 0.1, in particular between 0.001 and 0.08, in particular between 0.005 and 0.05.

[0077] According to any one of the embodiments of the invention, in a polyamide to be recycled rPA of the invention, the molar ratio of the carboxylic acid functions relative to the secondary amide functions is between 0.0005 and 0.1, in particular between 0.001 and 0.08, in particular between 0.005 and 0.05.

[0078] According to any one of the embodiments of the invention, in a polyamide to be recycled rPA of the invention, the molar ratio of the alcohol functions relative to the secondary amide functions is between 0.0005 and 0.1, in particular between 0.001 and 0.08, in particular between 0.005 and 0.05.

[0079] According to any one of the embodiments of the invention, in a polyamide to be recycled rPA of the invention, the molar ratio of the primary amide functions relative to the secondary amide functions is between 0.0005 and 0.1, in particular between 0.001 and 0.08, in particular between 0.005 and 0.05.

[0080] According to any one of the embodiments of the invention, in a polyamide to be recycled rPA of the invention, the molar ratio of the nitrile functions relative to the secondary amide functions is between 0.0005 and 0.1, in particular between 0.001 and 0.08, in particular between 0.005 and 0.05.

[0081] According to any one of the embodiments of the invention, in a polyamide to be recycled rPA of the invention, the molar ratio of the alkene functions relative to the secondary amide functions is between 0.0005 and 0.1, in particular between 0.001 and 0.08, in particular between 0.005 and 0.05.

[0082] According to any one of the embodiments of the invention, in a polyamide to be recycled rPA of the invention, the molar ratio of the formamide functions relative to the secondary amide functions is between 0.0005 and 0.1, in particular between 0.001 and 0.08, in particular between 0.005 and 0.05.

[0083] According to any one of the embodiments of the invention, in a polyamide to be recycled rPA of the invention, the molar ratio of the methyl functions at the end of the chain relative to the secondary amide functions is between 0.0005 and 0.2, in particular between 0.001 and 0.08, in particular between 0.005 and 0.05.

[0084] It is obvious that depending on the waste and the exposure to which it has been subjected, one or more functions resulting from oxidation reactions may be present.

[0085] The mixture of step a) comprises: from 5 to 90% by weight, generally from 5 to 70% by weight, in particular from 20 to 65% by weight, preferably from 40 to 60% by weight, of virgin polyamide vPA, from 10 to 95% by weight, generally from 30 to 95% by weight, in particular from 35 to 80% by weight, preferably from 40 to 60% by weight, of polyamide to be recycled rPA, relative to the total weight of the mixture.

[0086] The mixture of step a) may comprise other components than virgin polyamide vPA or polyamide to be recycled rPA.

[0087] The mixture of step a) may comprise a chain-limiting agent comprising at least one, preferably at least two functions, each chosen independently from carboxylic acids and amines. This embodiment is particularly preferred when the proportion of polyamide to be recycled rPA within the mixture is greater than 50% by weight.

[0088] This chain limiting agent can be a dicarboxylic acid, a diamine or an amino acid. It makes it possible to react with the amide, amine or carboxylic acid functions of rPA and / or vPA during melt mixing and to reduce the inherent viscosity of the polyamide composition obtained by the process.

[0089] The amino acid may be chosen from aminocaproic acids, amino-7-heptanoic acid, amino-11-undecanoic acid, amino-12-dodecanoic acid, and / or a mixture thereof. The proportion by weight of chain limiting agent within the mixture is generally between 0 and 4% by weight, in particular between 0.01 and 4% by weight, typically less than or equal to 1.5%, advantageously less than or equal to 1%, for example less than or equal to 1.0%, preferably from 0.1 to 1%, advantageously from 0.2 to 0.8%.

[0090] In order to ensure good properties (flexibility, burst strength, tear strength, rheology, alloy morphology, compatibilization, homogeneity, consistency, adhesion) and, in particular, good impact resistance and impact properties after aging (in particular oxidative aging at high temperature), it is possible to add an impact modifier to the mixture, in particular of an elastomeric nature and preferably polar.

[0091] Thus, the mixture may comprise up to 20% by weight, relative to the total weight of the mixture, of an impact modifier consisting of a non-rigid polymer having a flexural modulus of less than 100 MPa measured according to ISO 178 of 2010.

[0092] This non-rigid polymer is preferably as flexible as possible and has the lowest possible glass transition temperature Tg, i.e. less than 0°C. This impact modifier is chemically functionalized if necessary so that it can react with the polyamide and form an alloy compatible with them.

[0093] The impact modifier is preferably made up of one or more polyolefins, some or all of which carry a function chosen from carboxylic acid, carboxylic acid anhydride, epoxide and any other function capable of reacting chemically with polyamides, typically with its amine chain ends (case of carboxylic acid, maleic anhydride) or its acid chain ends (case of epoxide, in particular glycidyl methacrylate). For example, the polyolefin is chosen from: an ethylene and propylene copolymer with an elastomeric character (EPR), an ethylene-butene copolymer, an ethylene-octene copolymer, an ethylene-propylene-diene copolymer with an elastomeric character (EPDM) and an ethylene / alkyl (meth)acrylate copolymer, for example anhydride-grafted EPR such as Exxelor VA1803 from Exxon, or a copolymer of polyethylene, ethyl acrylate and maleic anhydride (coPE / EA / MAH) such as Lotader 4700 from SK.

[0094] The mixture may also comprise additives to the polyamides, such as: pigments, dyes, light (UV) and / or heat stabilizers, plasticizers, surfactants, optical brighteners, antioxidants, natural waxes, mold release agents, fillers, reinforcing fibers or mixtures thereof. The fillers envisaged include mineral fillers, such as those chosen from the group, given without limitation, comprising talc, kaolin, magnesia, slag, silica, carbon black, carbon nanotubes, expanded or non-expanded graphite, titanium oxide.

[0095] Reinforcing fibers are chosen from fibers, particularly short fibers. The fibers can be of synthetic origin, including glass or carbon fibers, or natural, typically of plant origin such as flax, reed, bamboo, or hemp fibers.

[0096] Common stabilizers used with polymers are phenols, phosphites, UV absorbers, HALS (Hindered Amine Light Stabilizer) stabilizers, metal iodides or thioethers. Examples include Irganox 1010, 245, 1098, Irgafos 168, 126, Tinuvin 312, 770, Iodide P201 from Ciba, Nylostab S-EED from Clariant, AO 412S from Adeka Palmarole.

[0097] Preferably, the additives of the mixture may be present in an amount less than or equal to 10%, and more particularly less than 5% by weight relative to the weight of the mixture.

[0098] The sum of virgin polyamide vPa and powder comprising polyamide to be recycled rPa generally represents at least 40% by weight, in particular at least 60% by weight, or even at least 80% by weight of the mixture, sometimes at least 95% of the mixture, or even 100% of the mixture.

[0099] Preferably, the mixture is free of crystallizing agent (such as an inorganic salt of an organic acid, for example sodium, potassium or calcium benzoate) and / or lubricating agent (such as zinc, calcium or magnesium stearate).

[0100] Preferably, the mixture is free of H3PO2 and / or H3PO3. For the purposes of the application, H3PC>2 and H3PO3 are not considered additives. Recycled unprocessed powders resulting from additive manufacturing by sintering have the advantage of containing few or no precursor species for the formation of phosphine, unlike virgin polyamide powders. This advantage makes it possible to process (by extrusion, injection in particular) recycled 3D powders more safely than virgin polyamide powders.

[0101] In one embodiment, the mixture consists of a mixture of: from 5 to 70% by weight, in particular from 20 to 65% by weight, preferably from 40 to 60% by weight, of virgin polyamide vPA, from 30 to 95% by weight, in particular from 35 to 80% by weight, preferably from 40 to 60% by weight, of polyamide to be recycled rPA, from 0 to 4% by weight, in particular between 0.01 and 4% by weight, preferably from 0.1 to 1%, advantageously from 0.2 to 0.8% of a chain limiting agent, in particular as defined above, from 0 to 20% by weight, in particular 0 to 10% by weight of an impact modifier, in particular as defined above, and from 0 to 10% by weight, in particular 0 to 5% by weight of additives, in particular as defined above. above, relative to the total weight of the mixture.

[0102] The method comprises a step b) of kneading said mixture in the molten state, whereby a polyamide composition is obtained.

[0103] The composition according to the invention is particularly simple to prepare since it is sufficient to carry out a melted kneading of a mixture of vPA and rPA.

[0104] Typically, the temperature during kneading is at least 5°C higher, preferably at least 10°C higher than the highest melting temperature of vPA and rPA. This temperature should generally remain below 330°C to avoid thermal degradation of the polyamides.

[0105] Typically, the temperature during kneading is greater than 200°C and less than 330°C, preferably greater than 220°C and less than 320°C, for example between 220°C and 310°C, or for example between 230°C and 300°C.

[0106] Generally, the residence time of the mixture during mixing is less than 10 minutes, especially less than 5 minutes, or less than 3 minutes or even less.

[0107] This melt mixing process is preferably carried out in single-screw, co-rotating twin-screw or BUSS type co-kneader.

[0108] The process comprises a step c) of recovering the polyamide composition obtained after kneading in the molten state. The recovery step c) can be carried out using methods known to those skilled in the art.

[0109] It generally involves an extrusion of the polyamide composition obtained after melt mixing.

[0110] Extrusion can be carried out in a shear mixer such as a single or twin screw extruder.

[0111] Extrusion can be carried out through a granulation die to produce granules. The volume median diameter Dv50 of the granules is advantageously in a range from 1 to 10 mm and in particular from 2 to 4 mm. Alternatively, extrusion can be carried out through a die to a cooled rolling mill in which the mixture solidifies or using a calender. Then, the solidified mixture can be fed to a crusher to produce flakes. These flakes typically have an average size of 5x5x1 mm.

[0112] Typically, the recovery step consists of an extrusion step, a step of cooling the composition in the molten state using a coolant generally containing water, a step of cutting the composition into pellet form, and a step of separating the coolant and the cooled composition.

[0113] The cutting step can be performed during the cooling step, or after the cooling step, and before the separation step or after the separation step.

[0114] The recovery step can be followed by a grinding step to obtain the composition in the form of flakes or powder.

[0115] These shapes are suitable for subsequent shaping by extrusion, injection or overmolding.

[0116] The process can be discontinuous (“batch” in English).

[0117] The process can be continuous.

[0118] According to a second subject, the invention relates to a polyamide composition capable of being obtained by the process described above.

[0119] The embodiments described above, in particular for the mixture and its constituents and their proportions, and the form of the composition obtained, are of course applicable, since the polyamide composition is capable of being obtained from the process described above.

[0120] Advantageously, the composition according to the invention has a better elongation at break as measured by the ISO 527 1 A standard of 2019 than an identical composition except that the polyamide to be recycled rPA is replaced by virgin polyamide vPA (therefore compared to a composition free of rPA).

[0121] Advantageously, the composition according to the invention has a better cold impact resistance than an identical composition except that the polyamide to be recycled rPA is replaced by virgin polyamide vPA (therefore compared to a composition free of rPA). The cold impact resistance is advantageously improved by at least 10%, preferably by at least 30%, in particular by at least 50%. The impact resistance can be determined according to the ISO 179-1 eA standard of 2010.

[0122] Advantageously, in the molten state, the composition according to the invention has better rheological properties at representative processing frequencies (for example at an angular frequency between 5 and 500 rad / s) by extrusion, injection or overmolding than an identical composition except that the polyamide to be recycled rPA is replaced by virgin polyamide vPA (therefore compared to a composition free of rPA), which is an advantage for shaping the composition by extrusion or injection.

[0123] Without wishing to be bound by particular theories, the polyamide to be recycled rPA from the powder generally has a higher molecular weight and a polydispersity index Iz (Mz / Mn) and / or Ip (Mw / Mn) higher than the virgin polyamide vPA of identical nature. For example, rPA11 generally has a higher molecular weight and a polydispersity index Iz (Mz / Mn) and / or Ip (Mw / Mn) higher than that of vPA1 1. This makes it possible, when adding this powder to a virgin polyamide grade, to increase the cold impact resistance as well as the elongation at break of the articles (compared to an article free of rPA).

[0124] This also makes it possible to improve the processability / implementation of the composition according to the invention. Indeed, the higher polydispersity index Iz (Mz / Mn) of the polyamide composition according to the invention compared to that of virgin polyamide vPA makes it possible to improve the melt strength (composition in the molten state) during extrusion, molding or overmolding to form an article or part.

[0125] In addition, rPA has more oxidized functions than vPA, and therefore more polar groups. The addition of rPA in a vPA grade provides better adhesion properties and thus promotes the implementation of the composition according to the invention by overmolding. The improvement in adhesion properties can, for example, be demonstrated with a peel test at the interface of two parts joined by overmolding.

[0126] Indeed, during the additive manufacturing process, new species resulting from oxidation mechanisms, in particular functions resulting from the degradation of primary amides and / or methylene in alpha of said amide functions, such as primary amide functions, nitriles, methyl groups at the end of the chain (CH3(CH2) n , alkenes (CH2=CH-), formamides, imides, carboxylic acids and alcohols, appear in the structure of polyamides. These functions are described above.

[0127] Infrared allows the detection of the presence or absence of said new species resulting from oxidation mechanisms.

[0128] Thus the absorption band from 1700 to 1740cm -1 corresponds to an imide, that of 1680 to 1720 cm -1 to the carbonyl of the carboxylic acid and that from 3580 to 3670 cm-1 corresponds to the alcohol function of the carboxylic acid.

[0129] The absorption band from 3580 to 3670 cm -1corresponds to the free alcohol function.

[0130] The amide function is characterized on the one hand by a pair of absorption bands from 3100 to 3500 cm -1 and from 1560 to 1640 cm -1 which corresponds to the NH group of the amide and on the other hand by the absorption band from 1650 to 1700 cm -1 which corresponds to the carbonyl group of the amide. The quantification of said new species resulting from the oxidation mechanisms is carried out by proton NMR in dichloromethane-d 2 , by adding HFIP (hexafluoroisopropanol) to solubilize the polyamide.

[0131] For example, 20 mg of polymer can be dissolved in 0.7 mL of solvent with a HFIP / CD2CI2 ratio of 1 / 3.

[0132] Some of the functions mentioned below can be observed, for example, in 13C NMR. Thus, the 36 ppm line corresponds to the CHp in a of the primary amide, that at 34 ppm corresponds to the CH2 in a of the carboxylic acid. These species can be quantified by integrating the area under the lines and comparing them to the area under the 37.1 ppm line corresponding to the secondary amide.

[0133] Similarly, the lines corresponding to the carbonyl groups of the primary amide, carboxylic acid and secondary amide functions are observed at 181.2 ppm, 179.6 ppm and 177.4 ppm respectively.

[0134] The line at 16.7 ppm corresponds to the CH2 in a of the nitrile group.

[0135] The formamide group gives a chemical shift at 163.0 ppm and 166.3 ppm.

[0136] Other functions mentioned above can be observed in proton NMR (1 H NMR) of the HFIP / CD2CI2 solvent as described above. The line of the CHO groups of the formamides appears at 7.92 and 8.01 ppm. The line corresponding to the CH2 in a of the primary amides can be observed at 2.30 ppm. The 0.9 ppm line corresponds to the CH3 groups of the CH3-(CH2) type. n The line at 2.40 ppm corresponds to the CH2 in a of the nitrile function. Similar to what is described for carbon NMR, the ratios of new functions to secondary amides can be determined by integrating the area under the lines and comparing them to the area under the line corresponding to the CH2 in a of the secondary amide (2.20 ppm).

[0137] Preferably, the inherent viscosity of the polyamide composition according to the invention is lower by at least 10%, in particular by at least 20%, preferably by at least 30%, compared to that of the powder of the mixture used in step a).

[0138] Preferably, when the average number of carbon atoms (C) relative to the nitrogen atom (N) of the polyamide rPA and of the vPA is greater than or equal to 8, in particular greater than or equal to 10, preferably greater than or equal to 11, in particular when the virgin polyamide and the polyamide to be recycled used as starting products in the mixture are independently PA11 or PA12, the inherent viscosity of the polyamide composition according to the invention is less than or equal to 1.50, preferably less than or equal to 1.40, 1.30, 1.25, 1.20, 1.15, or even less than or equal to 1.10. For example, the inherent viscosity of the polyamide composition may be between 0.80 and 1.50, preferably between 0.90 and 1.40, between 0.90 and 1.30, between 0.90 and 1.20 (inclusive).

[0139] Preferably, when the average number of carbon atoms (C) relative to the nitrogen atom (N) of the polyamide rPA and vPA is greater than or equal to 8, in particular greater than or equal to 10, preferably greater than or equal to 11, in particular when the virgin polyamide and the polyamide to be recycled used as starting products in the mixture are independently PA11 or PA12, the melt flow index (MFI or melt flow rate MFR in English) of the composition according to the invention, as measured at 235°C, under 2.16 kg, is between 0.1 and 60 cm 3 / 10 min, advantageously between 0.2 and 45 cm 3 / 10 min. Preferably, the fluidity index of the composition according to the invention measured according to standard ISO 1133 at 250°C under a weight of 5 kg is greater than 30, advantageously greater than 40, in particular greater than 50, and preferably greater than 60 cm 3 / 10 min.

[0140] Generally, the polydispersity index in z Iz of the polyamides of the composition according to the invention is greater than that of the virgin polyamide used as starting product in the mixture, and / or the polydispersity index by weight Ip of the polyamides of the composition is greater than that of the virgin polyamide used as starting product in the mixture.

[0141] Preferably, the polydispersity index in z Iz (Mz / Mn) of the polyamides of the composition according to the invention is greater than or equal to 3.0, typically greater than or equal to 3.5, in particular greater than or equal to 4.0, preferably greater than or equal to 5.0 and / or the polydispersity index by weight Ip (Mw / Mn) of the polyamides of the composition is greater than or equal to 1.5, typically greater than 2.0, in particular greater than or equal to 2.5, preferably greater than 3.0, or even greater than 4.0. Generally, the z-polydispersity index Iz is less than 30.0, in particular less than 25.0, preferably less than 15.0 and / or the weight polydispersity index Ip is less than 20.0, in particular less than 15.0, preferably less than 8.0, particularly preferably less than 7.0.

[0142] According to a third subject, the invention relates to the process for preparing an article comprising a step of extrusion, molding or overmolding of the composition according to the invention, whereby an article is obtained.

[0143] According to a fourth subject, the invention relates to a method for preparing an article comprising the steps of: a) providing a mixture comprising: from 5 to 90% by weight of virgin polyamide vPA, from 10 to 95% by weight of polyamide to be recycled rPA, relative to the total weight of the mixture, the polyamide to be recycled rPA being in the form of an unprocessed powder resulting from additive manufacturing by sintering or from a coating process by powder coating or by electrostatic spraying, b) melt mixing of said mixture, whereby a polyamide composition is obtained, c) recovery of said polyamide composition, d) extrusion, molding or overmolding of the recovered composition, whereby an article is obtained.

[0144] According to a fifth object, the invention relates to the article capable of being obtained according to the above method.

[0145] The article is preferably a shaped article, such as fiber, fabric, film, sheet, rod, tube, extruded part, injected part, comprising the composition as defined above. Thus, the composition according to the present invention is advantageous for the manufacture of articles, in particular articles or elements of sporting articles, which must in particular have both good impact resistance and good endurance to mechanical, chemical, UV and thermal aggression. Among these sporting articles, mention may be made of elements of sports shoes, sports utensils such as ice skates or other winter sports and mountaineering articles, ski bindings, snowshoes, sports bats, boards, horseshoes, fins, golf balls, leisure vehicles, in particular those intended for activities in cold weather.We can also mention, in general, leisure and DIY articles, tools and road equipment subject to climatic and mechanical aggression, protective articles, such as helmet visors, glasses, as well as glasses arms. We can also cite, by way of non-limiting examples, car components, such as headlight protectors, rearview mirrors, small parts of off-road vehicles, tanks, in particular, of mopeds, motorcycles, scooters, subject to mechanical and chemical aggression, screws, cosmetic articles subject to mechanical and chemical aggression, lipsticks, pressure gauges, aesthetic protection elements such as gas bottles. We can also mention objects or parts of objects for electronics requiring compliance with dimensions, for example parts of mobile phones, computers, tablets.

[0146] Advantageously, the article according to the invention generally exhibits less exudation than an article prepared from a composition in which the polyamide to be recycled rPA is replaced by virgin polyamide vPA (therefore compared to a composition free of rPA11 or rPA12). Typically, exudation is determined on 1 mm plates which are placed for 7 days at 70°C and 62% RH (relative humidity). Exudation is manifested by the appearance of a deposit on the surface and is estimated visually.

[0147] Without wishing to be bound by any particular theory, the increase in the molar masses of the polyamide chains in powder waste would imply a lower proportion of oligomers in them. However, these oligomers are generally responsible for exudation. The article according to the invention thus has lower exudation than that of an article obtained from exclusively virgin polyamide.

[0148] The invention is illustrated with the following figure and examples, which are provided without limitation.

[0149] Figure 1 [fig. 1] represents rheology curves of virgin PA 11 (vPA1 1 ), virgin PA 12 (vPA12), an unprocessed PA1 1 powder to be recycled (rPA1 1 ) resulting from additive manufacturing by sintering, an unprocessed PA12 powder to be recycled (rPA12) resulting from additive manufacturing by sintering, a composition obtained by hot mixing of 50% by weight of vPA11 and 50% by weight of vPA1 1 powder, and a composition obtained by hot mixing of 50% by weight of vPA12 and 50% by weight of vPA12 powder.

[0150] Examples

[0151] Example 1: Rheology of compositions according to the invention

[0152] For two types of PA homopolymers (PA11 (with an inherent viscosity of 1.0 and supplied by Arkema) and PA12 (with an inherent viscosity of 1.0 and supplied by Arkema)) the rheology of the polyamides in the molten state used as starting materials in the mixture (virgin PA and unprocessed PA powder to be recycled from additive manufacturing by sintering) was determined. These polyamides, mixed with a proportion of 50% by weight of vPA and 50% by weight of rPA relative to the weight of the mixture, were then kneaded in the molten state in accordance with the process according to the invention to form two polyamide compositions.

[0153] The rheology curves are illustrated in Figure 1.

[0154] Capillary rheology analyses show that, at frequencies representative of implementation by extrusion or injection, the two compositions according to the invention have better resistance in molten form than virgin vPA polyamides, which is an advantage for shaping the composition by extrusion or injection. Example 2: Inherent viscosity, polydispersity index Ip and Iz of a composition based on vPA1 1 and rPA1 1 according to the invention

[0155] A virgin vPA1 1 and an unprocessed rPA11 powder to be recycled from additive manufacturing by sintering were mixed with a proportion of 50% by weight of vPA1 1 and 50% by weight of rPA relative to the weight of the mixture, and were then kneaded in the molten state in accordance with the process according to the invention to form a polyamide composition.

[0156] It proved impossible to implement rPA11 powder by injection. Since the inherent viscosity of rPA11 was too high (large Ip and Iz), the mixture was too viscous to be used in injection and did not fill the molds correctly, leading to parts with defects and poor surface appearance. On the other hand, the composition obtained by mixing could be injected without difficulty.

[0157] Table 1 below provides the inherent viscosities and polydispersity indices Ip and Iz of the starting products and the composition according to the invention. [Table 1] * as measured using an Ubbelohde tube at 20°C on a 0.5% by weight solution in m-cresol except that the measurement temperature is 20°C instead of 25°C Inherent viscosities and polydispersity indices Ip and Iz of the starting products and of the composition according to the invention

[0158] Example 3: Inherent viscosity, polydispersity index Ip and Iz of a composition based on vPA12 and rPA12 according to the invention

[0159] A virgin vPA12 and an unprocessed rPA12 powder to be recycled from additive manufacturing by sintering were mixed with a proportion of 70% by weight of vPA12 and 30% by weight of rPA12 relative to the weight of the mixture, and were then kneaded in the molten state in accordance with the process according to the invention to form a polyamide composition.

[0160] It proved impossible to implement the rPA12 powder by injection. Since the inherent viscosity of rPA12 was too high (large Ip and Iz), the mixture was too viscous to be used in injection and did not fill the molds correctly, leading to parts with defects and poor surface appearance. On the other hand, the composition obtained by mixing could be injected without difficulty.

[0161] Table 2 below provides the inherent viscosities and polydispersity indices Ip and Iz of the starting products and the composition according to the invention.

[0162] [Table 2]

[0163]

[0164] * as measured using an Ubbelohde tube at 20°C on a 0.5% by weight solution in m-cresol except that the measurement temperature is 20°C instead of 25°C Inherent viscosities and polydispersity indices Ip and Iz of the starting products and of the composition according to the invention

[0165] Example 4: Influence of the chain-limiting agent content in a composition based on vPA11 and rPA11 according to the invention

[0166] Adipic acid has been used as a chain limiter.

[0167] A virgin vPA11 and an unprocessed rPA11 powder to be recycled from additive manufacturing by sintering were mixed with a proportion of: either 70% by weight of vPA11 and 30% by weight of rPA11 relative to the weight of the mixture, or 28.8% by weight of vPA11 and 70% by weight of rPA11 and 1.2% of adipic acid relative to the weight of the mixture, or 29.4% by weight of vPA11 and 70% by weight of rPA11 and 0.6% of adipic acid relative to the weight of the mixture, or 29.8% by weight of vPA11 and 70% by weight of rPA11 and 0.2% of adipic acid relative to the weight of the mixture, and were then kneaded in the molten state in accordance with the method according to the invention to form a composition of polyamides.

[0168] The compositions obtained by mixing could be injected without difficulty.

[0169] Table 3 below provides the inherent viscosities and polydispersity indices Ip and Iz of the virgin PA11 used as starting material and of the compositions according to the invention. The properties of the rPA11 and vPA11 used as starting materials are shown in Table 1 above.

[0170] [Table 3]

[0171]

[0172] * as measured using an Ubbelohde tube at 20°C on a 0.5% by weight solution in m-cresol except that the measurement temperature is 20°C instead of 25°C Inherent viscosities and polydispersity indices Ip and Iz of the starting products and compositions according to the invention comprising a chain limiting agent

[0173] The results show a degradation of the mechanical resistance of the polyamide composition for a chain limiting agent content of 1.2% by weight.

Claims

CLAIMS 1. Process for preparing a polyamide composition comprising the steps of: a) providing a mixture comprising: from 5 to 90% by weight of virgin polyamide vPA, from 10 to 95% by weight of polyamide to be recycled rPA, relative to the total weight of the mixture, the polyamide to be recycled rPA being in the form of an unprocessed powder resulting from additive manufacturing by sintering or from a powder coating process or by electrostatic spraying or powder obtained by grinding a polyamide-based part of an object to be recycled, the polydispersity index by weight Ip (Mw / Mn) of the virgin polyamide vPA being lower than the polydispersity index Ip of the polyamide to be recycled rPA, where Mw and Mn are measured by size exclusion chromatography according to ISO 16014-1 of 2012, b) melt kneading of said mixture, whereby a composition of polyamides whose polydispersity index by weight Ip is greater than or equal to 1.5,c) recovery of said polyamide composition., 2. Method according to claim 1, in which the polyamide to be recycled rPA and the virgin polyamide vPA are homopolyamides.

3. Method according to claim 1 or 2, in which the average number of carbon atoms (C) relative to the nitrogen atom (N) of the polyamide to be recycled rPA and / or of the virgin polyamide vPA is greater than or equal to 8, in particular greater than or equal to 10, preferably greater than or equal to 11.

4. Method according to any one of claims 1 to 3, in which the polyamide to be recycled rPA and the virgin polyamide vPA are independently chosen from PA11 or PA12.

5. Method according to any one of claims 1 to 4, in which the polyamide to be recycled rPA and the virgin polyamide vPA are of identical nature, preferably: the virgin polyamide is vPA1 1 and the polyamide to be recycled rPA is rPA1 1 , or the virgin polyamide is vPA12 and the polyamide to be recycled rPA is rPA12.

6. Process according to any one of claims 1 to 5, in which the inherent viscosity of the virgin polyamide vPA is less than or equal to 1.50, in particular less than or equal to 1.40, preferably less than or equal to 1.30, and / or the powder of the mixture has an inherent viscosity greater than or equal to 1.50, in particular greater than or equal to 1.60, typically from 1.70 to 5.

00.

7. Method according to any one of claims 1 to 6, in which the polydispersity index by weight Ip (Mw / Mn) of the virgin polyamide vPA is at least 20%, in particular at least 35%, preferably at least 50% lower than the polydispersity index Ip of the polyamide to be recycled rPA, or the polydispersity index Iz (Mz / Mn) of the virgin polyamide vPA is at least 30%, in particular at least 50%, preferably at least 70% lower than the polydispersity index Iz of the polyamide to be recycled rPA, where Mn and Mz are measured by size exclusion chromatography according to ISO 16014-1 of 2012.

8. Process according to any one of claims 1 to 7, in which the weight polydispersity index Ip of the virgin polyamide vPA is from 1.6 to 2.2, in particular from 1.6 to 2.1 and / or the weight polydispersity index Ip of the polyamide to be recycled rPA is from 2.5 to 15, in particular from 2.8 to 10.

9. Method according to any one of claims 1 to 8, in which the proportion by weight of chain limiting agent within the mixture is less than or equal to 1.0%.

10. Polyamide composition obtainable according to the process according to any one of claims 1 to 9, in which the polydispersity index by weight Ip (Mw / Mn) of the polyamides is greater than or equal to 1.5, typically greater than 2.0, where Mw and Mn are measured by size exclusion chromatography according to ISO 16014-1 of 2012.

11. Polyamide composition according to claim 10, wherein the z-polydispersity index Iz (Mz / Mn) of the polyamides of the composition is greater than that of the virgin polyamide used as starting material in the mixture, and / or the weight polydispersity index Ip of the polyamides of the composition is greater than that of the virgin polyamide used as starting material in the mixture, where Mn and Mz are measured by size exclusion chromatography according to ISO 16014-1 of 2012.

12. Polyamide composition according to claim 10 or 11, in which the polydispersity index in z Iz of the polyamides of the composition (Mz / Mn) is greater than or equal to 3.0, typically greater than or equal to 3.5, in particular greater than or equal to 4.0, preferably greater than or equal to 5.0 and / or the polydispersity index by weight Ip of the polyamides of the composition (Mw / Mn) is greater than 2.0, in particular greater than or equal to 2.5, preferably greater than 3.0, or even greater than 4.

0.

13. Polyamide composition according to any one of claims 10 to 12, the inherent viscosity of which, as measured using an Ubbelohde tube at 20°C on a 0.5% by weight solution in m-cresol according to ISO 307 of 2019, is between 0.80 and 1.50, preferably between 0.90 and 1.40, between 0.90 and 1.30, between 0.90 and 1.

20.

14. A method of preparing an article comprising a step of extruding, molding or overmolding the composition according to any one of claims 10 to 13, whereby an article is obtained.

15. Article obtainable according to the method according to claim 14.

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