Classifications

• • 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
  • C08J11/00—Recovery or working-up of waste materials
  • C08J11/04—Recovery or working-up of waste materials of polymers
  • C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
  • B05B14/00—Arrangements for collecting, re-using or eliminating excess spraying material
  • B05B14/10—Arrangements for collecting, re-using or eliminating excess spraying material the excess material being particulate
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
  • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
  • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
  • B09B3/30—Destroying solid waste or transforming solid waste into something useful or harmless involving mechanical treatment
  • B09B3/35—Shredding, crushing or cutting
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
  • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
  • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
  • B09B3/30—Destroying solid waste or transforming solid waste into something useful or harmless involving mechanical treatment
  • B09B3/38—Stirring or kneading
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
  • B29B17/0026—Recovery of plastics or other constituents of waste material containing plastics by agglomeration or compacting
  • B29B17/0042—Recovery of plastics or other constituents of waste material containing plastics by agglomeration or compacting for shaping parts, e.g. multilayered parts with at least one layer containing regenerated plastic
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
  • B29B17/04—Disintegrating plastics, e.g. by milling
  • B29B17/0404—Disintegrating plastics, e.g. by milling to powder
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B9/00—Making granules
  • B29B9/02—Making granules by dividing preformed material
  • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
• • 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
  • 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
  • B29C64/30—Auxiliary operations or equipment
  • B29C64/357—Recycling
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—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
  • B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
• • 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
  • C08J3/005—Processes for mixing polymers
• • 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
  • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
  • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
  • B09B2101/00—Type of solid waste
  • B09B2101/75—Plastic waste
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
  • B29B17/04—Disintegrating plastics, e.g. by milling
  • B29B2017/042—Mixing disintegrated particles or powders with other materials, e.g. with virgin materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/26—Scrap or recycled material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
  • B29K2995/0037—Other properties
  • B29K2995/0088—Molecular weight
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—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
  • B33Y10/00—Processes of 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
  • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2207/00—Properties characterising the ingredient of the composition
  • C08L2207/20—Recycled plastic
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
  • Y02W30/00—Technologies for solid waste management
  • Y02W30/50—Reuse, recycling or recovery technologies
  • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

• TITLE Polyamide composition prepared from polyamide powder to be recycled
• 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 by electrostatic spraying or from powder obtained by grinding a part based on polyamide of an object to be recycled, a composition of polyamides, and its use for the preparation of articles.
• AM additive manufacturing
• the agglomeration of powders by fusion 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 make three-dimensional objects.
• a laser beam (“laser sintering” or “selective laser sintering” SLS in English)
• infrared radiation such as for example a laser beam (“laser sintering” or “selective laser sintering” SLS in English)
• infrared radiation such as for example a laser beam (“laser sintering” or “selective laser sintering” SLS in English)
• infrared radiation such as for example a laser beam (“laser sintering” or “selective laser sintering” SLS in English)
• UV radiation such as for example a laser beam
• HSS High Speed Sintering
• MTF Multi-Jet Fusion
• these degraded powders generally cannot be directly reused in the next sintering additive manufacturing, 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, for example an orange peel appearance, and diminished mechanical properties, in particular lower elongation at break, as the defects play the role of initiator to rupture during tensile tests.
• waste PA12 powder can account for up to 50%, or even up to 90%, of the total powder used in the process. This represents a significant loss of PA12 powder, since this powder waste must be eliminated.
• polymer powders to manufacture substrate coatings, particularly metallic ones, typically by powder coating or by electrostatic projection.
• a powdery polymer composition is applied to the substrate in the form of a loose powder, for example by electrostatic spraying or by immersion of 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.
• One of the objectives of the present application is to make it possible to recycle unprocessed powders resulting from additive manufacturing or from a powder coating or electrostatic spraying process, or powders obtained by grinding a part based on polyamide d 'an object to recycle.
• One of the objectives is to reduce the environmental impact and reduce the cost price:
• One of the objectives of the application is to provide a PA1 1 or PA12 polyamide composition having certain mechanical and/or physicochemical properties better than those of a polyamide composition prepared from exclusively virgin polyamides.
• One of the objectives of the application is to provide a polyamide composition whose processability (suitability for implementation, transformation) by extrusion, by injection or by overmolding is improved.
• the invention relates to a process for preparing a polyamide composition
• 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, of 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 projection, 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) recovery of said polyamide composition.
• the process comprises a step a) of supplying 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.
• vPA means a virgin polyamide. This has not undergone any prior transformation, and in particular it has not been used in a prior additive manufacturing process by sintering or powder coating or by electrostatic spraying and it does not come from a part of 'a pre-existing article.
• rPA means a polyamide to be recycled, also called recycled polyamide. The latter appears:
• untransformed powder from additive manufacturing by sintering we mean the powder which was not targeted by the radiation during a previous additive manufacturing process by sintering and which was not used to form the object formed during the previous additive manufacturing process. Typically, this powder has spent at least 1 minute at a temperature above 100°C in an additive manufacturing device.
• unprocessed powder from a powder coating or electrostatic spray coating process is meant the powder which was not used to form the coating on the substrate in the previous powder coating or electrostatic spray coating process. Typically, this powder has been used in a process of coating a substrate by powder coating or by electrostatic projection (electrospray).
• the unprocessed powder used as polyamide to be recycled in the process according to the invention corresponds to waste polyamide powder from a previous process.
• the polyamide to be recycled rPA has therefore undergone degradation, generally thermal.
• polyamide-based part of an object to be recycled we mean a part having been obtained by a previous transformation, for example injection, extrusion or overmolding.
• the object to be recycled (or part) may be used, broken, of poor quality, and/or incapable of performing its function.
• the polyamide in this part is therefore also waste.
• the unprocessed powder or 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 mixture of polyamides) in weight relative to the weight of the powder.
• the proportion of polyamides is generally less than 99.9% by weight.
• 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 from 5 to 200 pm, preferably in the range of 10 to 150 pm.
• the “volume average diameter” or “Dv” the volume average diameter of a powdery material is as measured according to standard ISO 9276 - parts 1 to 6: “Representation of data obtained by particle size analysis” , in its version effective in 2022.
• the Dv50 designates the median diameter by volume, that is to say that corresponding to the 50th percentile by volume
• the Dv10 and Dv90 respectively designate the volume average diameters below which 10 or 90% by volume of the particles are located.
• the volume average diameter can be measured in particular by means of a laser particle size analyzer, for example a laser particle size analyzer (Malvern Insitec System).
• An associated software then makes it possible to obtain the volumetric distribution of a powder and to deduce the Dv10, the Dv50 and the Dv90.
• the polyamide rPA and vPA may independently be a homopolyamide, a copolyamide, a polyamide block and polyether block copolymer (PEBA) or a mixture thereof.
• the polyamide rPA and the vPA can 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.
• the polyamide rPA and the vPA are independently a condensation product:
• amino acid it is possible to cite alpha-omega amino acids, such as aminocaproic, amino-7-heptanoic, amino-11-undecanoic, n-heptyl-1 1 -aminoundecanoic and amino- 12-dodecanoic.
• aminocaproic amino-7-heptanoic
• amino-11-undecanoic amino-11-undecanoic
• n-heptyl-1 1 -aminoundecanoic amino- 12-dodecanoic.
• Lactam monomers preferably comprise between 3 and 12 carbon atoms on the main ring and may be substituted.
• lactam it is possible to cite p,p-dimethylpropriolactam, a,a-dimethylpropriolactam, amylolactam, caprolactam, capryllactam, oenantholactam, 2-pyrrolidone and lauryllactam.
• the diamine used in the composition of the polyamide rPA and/or vPA is an aliphatic diamine, an aryl diamine and/or a saturated cyclic diamine having 6 to 12 carbon atoms.
• a diamine it is possible to cite hexamethylenediamine, decanediamine, piperazine, tetramethylenediamine, octamethylenediamine, decamethylenediamine, dodecamethylenediamine, 1,5 diaminohexane, 2,2 ,4-trimethyl-1,6-diamino-hexane, diamine polyols, isophorone diamine (IPD), methyl-pentamethylenediamine (MPDM), bis(aminocyclohexyl)methane (BACM), bis(3-methyl- 4 aminocyclohexyl)methane (BMACM), methaxylenediamine, bis-p-aminocyclohexylme
• the dicarboxylic acid used in the composition of the rPA and/or vPA polyamide has between 4 and 18 carbon atoms.
• a dicarboxylic acid it is possible to cite adipic acid, sebacic acid, azelaic acid, suberic acid, isophthalic acid, butanedioic acid, 1,4 cyclohexyldicarboxylic acid, terephthalic acid, sodium or lithium salt of sulfo-isophthalic acid, dimerized fatty acids (these dimerized fatty acids have a dimer content of at least 98% and are preferably hydrogenated) and dodecanedioic acid HOOC-(CH 2 )10-COOH.
• the copolyamide rPA and/or vPA 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 acid. 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.
• 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, 1 1 , 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.
• 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 10.1 1, PA 6.10, PA6.12, PA 6.13 and their mixtures.
• copolyamide As an example of copolyamide, it is possible to cite copolymers of caprolactam and lauryllactam (PA 6.12), copolymers of caprolactam, adipic acid and hexamethylene diamine (PA 6.66), copolymers of caprolactam, lauryllactam, adipic acid and hexamethylene diamine (PA 6.12.66), copolymers of caprolactam, lauryllactam, 11-aminoundecanoic acid, azelaic acid and hexamethylene diamine (PA 6.69.11.12) , copolymers of caprolactam, lauryllactam, 11-amino-undecanoic acid, adipic acid and hexamethylene diamine (PA 6.66.1 1.12), copolymers of lauryllactam, azelaic acid and hexamethylene diamine (PA 6.66.1 1.12), PA 69.12), copolymers of 11
• 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 or equal to 11.
• the average number of carbon atoms (C) relative to the nitrogen atom (N) of the polyamide rPA and/or vPA is 1 1 or 12.
• the polyamide rPA and vPA are independently chosen from PA 11, PA 10.10, PA 10.12, PA 12, PA 12.12, PA 10.14 or PA 12.14 and their mixtures, preferably PA1 1 or PA12 or a mixture thereof.
• the polyamide of the polyamide rPA and the polyamide vPA are of identical nature.
• the virgin polyamide is vPA1 1
• the polyamide to be recycled rPA is rPA11.
• the virgin polyamide is vPA12
• the polyamide to be recycled rPA is rPA12.
• the virgin polyamide vPA generally has an inherent viscosity less than or equal to 1.50, in particular less than or equal to 1.40, preferably less than or equal to 1.30.
• the inherent viscosity is as measured using an Ubbelohde tube at 20°C on a 0.5% solution by weight in m-cresol according to ISO 307 of 2019.
• 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% to that of the powder in the mixture.
• 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 of the order of 1.70 to 5.00.
• the polydispersity index by weight Ip of virgin polyamide vPA is lower than that of polyamide to be recycled rPA.
• the polydispersity index Ip of the virgin polyamide vPA is lower by at least 20%, in particular by at least 35%, preferably by at least 50%, 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 molecular mass Mn.
• the polydispersity index by weight Ip of the virgin polyamide vPA is from 1.6 to 2.2, in particular from 1.6 to 2.1 and/or the polydispersity index by weight Ip of the polyamide to be recycled rPA is 2.5 to 15.0, especially 2.8 to 10.0.
• the polydispersity index in z Iz of the virgin polyamide vPA is lower than that of the polyamide to be recycled rPA.
• the polydispersity index Iz of virgin polyamide vPA is lower by at least 30%, in particular by at least 50%, preferably by at least 70%, than the polydispersity index Iz of the polyamide to be recycled rPA.
• the polydispersity index in z Iz is the ratio of the average molecular mass in z Mz relative to the molecular mass in number Mn.
• the polydispersity index in z Iz of the virgin polyamide vPA is from 1.5 to 3.5, in particular from 2.0 to 3.0 and/or the polydispersity index in z Iz of the polyamide to be recycled rPA is 3.5 to 50.0, especially 4.0 to 30.0.
• the number average molecular masses Mn, weight Mw and z Mz are measured by size exclusion chromatography (or gel permeation chromatography) according to ISO 16014-1 of 2012.
• 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 on 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 of dimensions 50 x 8 mm, a column 1000 ⁇ , dimensions 300 x 8 mm and particle size 7 pm, and a column 100 ⁇ , dimensions 300 x 8 mm and particle size 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.
• the polyamides to be recycled rPA have particularities, and in particular new species resulting from oxidation mechanisms.
• new species resulting from oxidation mechanisms is intended to designate, within the meaning of the invention, the primary amide functions, nitriles, methyl groups at the end of the chain, alkenes, formamides, imides, acids. carboxylic acids and alcohols which may appear in the polyamide to be recycled rPA of the invention.
• the polyamide to be recycled rPA 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.
• 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.
• 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 functions secondary amides higher than that of the same virgin polyamide, and primary amine functions in a molar ratio relative to secondary amide functions lower than that of the same virgin polyamide.
• NMR measurements can be carried out in the HFIP/CD2CI2 mixture.
• 20 mg of polymer can be dissolved in 0.7 mL of solvent with an HFIP/CD2CI2 ratio of 1/3.
• the dichloromethane (CD2CI2)/trifluoroacetic anhydride (ATFA) mixture can also be used.
• the absorption band from 1700 to 1740 cm -1 corresponds to an imide, that from 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.
• the absorption band from 3580 to 3670 cm -1 corresponds to the free alcohol function.
• 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 band d absorption from 1650 to 1700 cm -1 which corresponds to the carbonyl group of the amide.
• the absorption bands of 1180 and 1723 cm -1 correspond to the formates.
• the bands at 900 and 1660 cm -1 correspond to alkenes.
• Quantification by NMR is, for example, carried out by comparing the intensity of the lines of functions not present in the virgin polymer to the lines corresponding to CH2 in a amide, ether or other CH2 functions in the context of proton NMR. .
• the intensity of the lines of the functions formed during the life of the polymer is compared to the intensities of the carbon lines of amides or CH2.
• the line at 36 ppm corresponds to CH2 at a of the primary amide, that at 34 ppm corresponds to CH2 at 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 line 37.1 ppm corresponding to the secondary amide.
• 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 CH 2 in a nitrile group.
• the formamide group gives a chemical shift at 163.0 ppm and 166.3 ppm.
• the ratios of new functions relative to secondary amides can be determined by integrating the area under the lines and comparing them to the area under the line corresponding to CH2 in to 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).
• the molar ratio of the functions resulting from oxidation reactions relative to the secondary amide functions is between 0.0005 and 0 ,3.
• 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, especially between 0.005 and 0.05.
• 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.
• 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, especially between 0.005 and 0.05.
• 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.
• the molar ratio of the nitrile functions relative to the functions secondary amides is between 0.0005 and 0.1, in particular between 0.001 and 0.08, in particular between 0.005 and 0.05.
• 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, especially between 0.005 and 0.05.
• 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, especially between 0.005 and 0.05.
• 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.
• 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 .
• the mixture of step a) may include components other than the virgin polyamide vPA or the polyamide to be recycled rPA.
• 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.
• This chain limiting agent may 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.
• the amino acid may be chosen from aminocaproic acid, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and/or their mixture.
• the proportion by weight of chain limiting agent within the mixture is generally between 0 and 4% by weight, in particular between 0.01 to 4% by weight, typically less than or equal to 1.5%, advantageously less or equal to 1%, for example less than or equal to 1.0%, preferably 0.1 to 1%, advantageously 0.2 to 0.8%.
• 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 less than 100 MPa measured according to standard ISO 178 of 2010 .
• This non-rigid polymer is preferably as flexible as possible and has the lowest possible glass transition temperature Tg, that is to say less than 0°C.
• This impact modifier is, if necessary, chemically functionalized so as to be able to react with the polyamide and to form an alloy compatible with them.
• the impact modifier is preferably made up of one or more polyolefins, part or all of these carrying a function chosen from the functions 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).
• the polyolefin is chosen from: a copolymer of ethylene and propylene 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 the copolymer of polyethylene, ethyl acrylate and maleic anhydride (coPE/EA/ MAH) such as the Lotader 4700 from the SK company.
• EPR elastomeric character
• EPDM ethylene-propylene-diene copolymer with an elastomeric character
• the mixture may also include polyamide additives, such as: pigments, dyes, light (UV) and/or heat stabilizers, plasticizers, surfactants, optical brighteners, anti- oxidants, natural waxes, mold release agents, fillers, reinforcing fibers or their mixtures.
• polyamide additives such as: pigments, dyes, light (UV) and/or heat stabilizers, plasticizers, surfactants, optical brighteners, anti- oxidants, natural waxes, mold release agents, fillers, reinforcing fibers or their mixtures.
• the fillers envisaged include mineral fillers, such as those chosen from the group, given on a non-limiting basis, including talc, kaolin, magnesia, slag, silica, carbon black, carbon nanotubes, graphite expanded or not, titanium oxide.
• the reinforcing fibers are chosen from fibers, in particular short ones.
• the fibers can be of synthetic origin, in particular glass or carbon fibers, or natural, typically of plant origin such as flax, reed, bamboo or hemp fibers.
• the usual stabilizers used with polymers are phenols, phosphites, UV absorbers, HALS (Hindered Amine Light Stabilizer) type stabilizers, metal iodides or thioethers.
• HALS Hindered Amine Light Stabilizer
• the additives in 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.
• the sum of the virgin polyamide vPa and the powder comprising the 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.
• the mixture is free of crystallization agent (such as an inorganic salt of organic acid, for example sodium, potassium or calcium benzoate) and/or lubricating agent (such as a stearate of zinc, calcium or magnesium).
• crystallization agent such as an inorganic salt of organic acid, for example sodium, potassium or calcium benzoate
• lubricating agent such as a stearate of zinc, calcium or magnesium
• the mixture is free of H 3 PO2 and/or H 3 PO 3 .
• H 3 PC>2 and H 3 PO 3 are not considered additives.
• Unprocessed powders from recycled additive manufacturing by sintering have the advantage of containing little or no precursor species for the formation of phosphine, unlike virgin polyamide powders. This advantage makes it possible to transform (by extrusion, injection in particular) recycled 3D powders more safely than virgin polyamide powders.
• 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, of 30 at 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 to 4% by weight, preferably from 0.1 to 1%, advantageously from 0.2 to 0.8% of a chain limiting agent, in particular such as defined above, from 0 to 20% by weight, in particular 0 to 10% by weight of a shock 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, relative to the total weight of the mixture.
• the process comprises a step b) of melt mixing of said mixture, whereby a polyamide composition is obtained.
• composition according to the invention is particularly simple to prepare since it suffices to knead a mixture of vPA and rPA in the molten state.
• the temperature during mixing is at least 5°C higher, preferably at least 10°C higher than the highest melting temperature between that of vPA and rPA. This temperature must generally remain below 330°C in order to avoid thermal degradation of the polyamides.
• the temperature during mixing 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.
• the residence time of the mixture during mixing is less than 10 minutes, in particular less than 5 minutes, or less than 3 minutes or even less.
• This melt mixing process is preferably carried out in a single-screw, co-rotating twin-screw or BUSS type co-mixer.
• the process comprises a step c) of recovering the polyamide composition obtained after mixing in the melt state.
• Recovery step c) can be carried out using methods known to those skilled in the art.
• Extrusion can be carried out in a shear mixer such as a single or twin screw extruder.
• Extrusion can be carried out through a granulation die to produce granules.
• the median volume diameter Dv50 of the granules is advantageously included in a range going from 1 to 10 mm and in particular from 2 to 4 mm.
• 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 taken to a crusher to produce flakes.
• These scales typically have an average size of 5x5x1 mm.
• the recovery step consists of an extrusion step, a step of cooling the composition in the molten state using a cooling liquid generally containing water, a cutting step of the composition in the form of granules, and a step of separating the coolant and the cooled composition.
• the cutting step can be carried out during the cooling step, or after the cooling step, and before the separation step or after the separation step.
• the recovery step can be followed by a grinding step to obtain the composition in the form of scales or powder.
• the process can be discontinuous (“batch” in English).
• the process can be continuous.
• the invention relates to a polyamide composition capable of being obtained by the process described above.
• the composition according to the invention has a better elongation at break as measured by standard ISO 527 1 A 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).
• the composition according to the invention has better resistance to cold impact 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 resistance to cold impact 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.
• the composition according to the invention has better rheological properties at representative frequencies of implementation (for example at an angular frequency between 5 and 500 rad/s) by extrusion, injection or overmolding than a 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.
• the polyamide to be recycled rPA of the powder generally has a higher molecular mass and a polydispersity index Iz (Mz/Mn) and/or Ip (Mw/Mn) greater than the virgin polyamide vPA of identical nature.
• rPA11 generally has a higher molecular mass and a polydispersity index Iz (Mz/Mn) and/or Ip (Mw/Mn) higher than that of vPA1 1. This allows, when adding to this powder in a grade of virgin polyamide, to increase the cold impact resistance as well as the elongation at break of the articles (compared to an article free of rPA).
• the higher polydispersity index Iz (Mz/Mn) of the polyamide composition according to the invention compared to that of the virgin polyamide vPA makes it possible to improve the resistance of the melt (composition in the molten state) during extrusion, molding or overmolding to form an article or part.
• rPA has more oxidized functions than vPA, and therefore more polar groups.
• the addition of rPA in a vPA grade confers 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 associated by overmolding.
• functions are described above.
• Infra red allows the detection of the presence or absence of said new species resulting from oxidation mechanisms.
• the absorption band from 1700 to 1740cm -1 corresponds to an imide, that from 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 acid carboxylic.
• the absorption band from 3580 to 3670 cm -1 corresponds to the free alcohol function.
• 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 band d absorption from 1650 to 1700 cm -1 which corresponds to the carbonyl group of the amide.
• the quantification of said new species resulting from oxidation mechanisms is carried out by proton NMR in dichloromethane-d 2 , by adding HFIP (hexafluoroisopropanol) to solubilize the polyamide.
• 20 mg of polymer can be dissolved in 0.7 mL of solvent with an HFIP/CD2CI2 ratio of 1/3.
• the line at 36 ppm corresponds to the CHp at a of the primary amide, that at 34 ppm corresponds to the CH2 at 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 line 37.1 ppm corresponding to the secondary amide.
• the line at 16.7 ppm corresponds to CH2 in a of the nitrile group.
• the formamide group gives a chemical shift at 163.0 ppm and 166.3 ppm.
• 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).
• 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.
• 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 (limits inclusive).
• the melt flow index MFI or “melt flow rate » MFR in English) of the composition according to the invention is between 0.1 and 60 cm 3 /10 min, advantageously between 0.2 and 45 cm 3/10 mins.
• 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.
• 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 material in the mixture, and/or the polydispersity index by weight Ip of the polyamides of the composition is higher than that of the virgin polyamide used as the starting material in the mixture.
• 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 or equal to 2.5, preferably greater than 3.0, or even greater than 4.0.
• the polydispersity index in z Iz is less than 30.0, in particular less than 25.0, preferably less than 15.0 and/or the polydispersity index in weight Ip is less than 20.0, in particular less than 15.0, preferably less than 8.0, particularly preferably less than 7.0.
• 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, by which an article is obtained.
• the invention relates to a process for preparing an article comprising the steps of: a) supplying 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 or electrostatic spraying process, b) mixing in the molten state of said mixture, by which is obtained a polyamide composition, c) recovering said polyamide composition, d) extrusion, molding or overmolding of the recovered composition, whereby an article is obtained.
• the invention relates to the article capable of being obtained according to the above process.
• 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.
• 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 and chemical attacks. , UV, thermal.
• these sporting articles we can cite elements of sports shoes, sports utensils such as ice skates or other winter sports and mountaineering articles, ski bindings, snowshoes, bats sports, boards, horseshoes, fins, golf balls, recreational vehicles, especially those intended for cold weather activities.
• the article according to the invention generally has 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 rPA1 1 or rPA12).
• 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.
• the increase in the molar masses of the polyamide chains of waste powders would imply a lower proportion of oligomers in them.
• these oligomers are generally responsible for exudation.
• the article according to the invention thus has a lower exudation than that of an article obtained from exclusively virgin polyamide.
• Figure 1 represents rheology curves of virgin PA 11 (vPA1 1), virgin PA 12 (vPA12), an untransformed PA1 1 powder to be recycled (rPA1 1) resulting from additive manufacturing by sintering, a unprocessed PA12 powder to be recycled (rPA12) from additive manufacturing by sintering, of a composition obtained by hot mixing of 50% by weight of vPA11 and 50% by weight of vPA1 1 powder, and of a composition obtained by hot mixing of 50% by weight of vPA12 and 50% by weight of vPA12 powder.
• Example 1 Rheology of compositions according to the invention
• PA11 with an inherent viscosity of 1.0 and supplied by Arkema
• PA12 with an inherent viscosity of 1.0 and supplied by Arkema
• the rheology of the polyamides in the molten state used was determined. as starting products in the mixture (virgin PA and unprocessed PA powder to be recycled from additive manufacturing by sintering).
• Example 2 Inherent viscosity, polydispersity index Ip and Iz of a composition based on vPA1 1 and rPA1 1 according to the invention
• 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.
• Table 1 below provides the inherent viscosities and polydispersity indices Ip and Iz of the starting products and the composition according to the invention.
• Example 3 Inherent viscosity, polydispersity index Ip and Iz of a composition based on vPA12 and rPA12 according to the invention
• 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 then been kneaded in the molten state in accordance with the process according to the invention to form a polyamide composition.
• Table 2 below provides the inherent viscosities and polydispersity indices Ip and Iz of the starting products and the composition according to the invention.
• Example 4 Influence of the content of chain limiting agent in a composition based on vPA11 and rPA11 according to the invention
• Adipic acid was used as a chain limiter.
• a virgin vPA1 1 and an unprocessed rPA11 powder to be recycled from additive manufacturing by sintering were mixed with a proportion of: 70% by weight of vPA11 and 30% by weight of rPA11 relative to the weight of the mixture, either 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, i.e.
• compositions obtained by mixing could be injected without difficulty.
• Table 3 below provides the inherent viscosities and polydispersity indices Ip and Iz of the virgin PA1 1 used as a starting product and of the compositions according to the invention.
• the properties of rPA11 and vPA11 used as starting materials are shown in Table 1 above.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Health & Medical Sciences (AREA)
• Organic Chemistry (AREA)
• Polymers & Plastics (AREA)
• Medicinal Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Mechanical Engineering (AREA)
• Environmental & Geological Engineering (AREA)
• Materials Engineering (AREA)
• Optics & Photonics (AREA)
• Physics & Mathematics (AREA)
• Manufacturing & Machinery (AREA)
• Sustainable Development (AREA)
• Life Sciences & Earth Sciences (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Processes Of Treating Macromolecular Substances (AREA)
• Paints Or Removers (AREA)
• Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
• Polyamides (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=84053154

Family Applications (1)

Country Status (7)

Family Cites Families (3)

• 2022
  • 2022-09-23 FR FR2209690A patent/FR3140087B1/fr active Active
• 2023
  • 2023-09-22 JP JP2025517463A patent/JP2025532818A/ja active Pending
  • 2023-09-22 EP EP23776358.6A patent/EP4590449A1/de active Pending
  • 2023-09-22 US US19/114,586 patent/US20260125532A1/en active Pending
  • 2023-09-22 CN CN202380074716.3A patent/CN120112370A/zh active Pending
  • 2023-09-22 WO PCT/EP2023/076263 patent/WO2024062105A1/fr not_active Ceased
  • 2023-09-22 KR KR1020257013436A patent/KR20250115376A/ko active Pending

Also Published As

Similar Documents

Legal Events