EP4363222A1 - Poudre de polymère thermoplastique pour impression 3d à la stabilité et à la recyclabilité améliorées - Google Patents

Poudre de polymère thermoplastique pour impression 3d à la stabilité et à la recyclabilité améliorées

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Publication number
EP4363222A1
EP4363222A1 EP22747075.4A EP22747075A EP4363222A1 EP 4363222 A1 EP4363222 A1 EP 4363222A1 EP 22747075 A EP22747075 A EP 22747075A EP 4363222 A1 EP4363222 A1 EP 4363222A1
Authority
EP
European Patent Office
Prior art keywords
powder
sulfonate
weight
thermoplastic polymer
sodium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22747075.4A
Other languages
German (de)
English (en)
French (fr)
Inventor
Ornella ZOVI
Jean-Charles Durand
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Arkema France SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Arkema France SA filed Critical Arkema France SA
Publication of EP4363222A1 publication Critical patent/EP4363222A1/fr
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • 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
    • B29C64/307—Handling of material to be used in additive manufacturing
    • B29C64/314—Preparation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/372—Sulfides, e.g. R-(S)x-R'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • 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
    • B29K2045/00—Use of polymers of unsaturated cyclic compounds having no unsaturated aliphatic groups in a side-chain, e.g. coumarone-indene resins 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
    • 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
    • B29K2105/0094—Condition, form or state of moulded material or of the material to be shaped having particular viscosity
    • 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
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/16—Fillers
    • 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
    • B29K2105/25—Solid
    • B29K2105/251—Particles, powder or granules
    • 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
    • B29K2995/004—Semi-crystalline
    • 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
    • B29K2995/0094—Geometrical properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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

Definitions

  • the present invention relates to a polymer powder for the manufacture of articles by 3D printing, in particular by sintering, comprising a thermoplastic polymer and a particular antioxidant, having improved stability and recyclability.
  • the invention also relates to a process for preparing this powder as well as its use in a manufacturing process by sintering, and the articles made from said powder.
  • SLS Selective Laser Sintering
  • HSS High Speed Sintering
  • MTF Multi-Jet Fusion
  • thermoplastic polymer powder for example a polyamide powder
  • thermoplastic polymer powder having good thermal stability, more particularly in an air sintering process, in order to be able to be recycled.
  • thermal stability means reduced thermo-oxidative degradation, namely, in particular limited yellowing of the non-agglomerated powder during sintering. It is known to employ an antioxidant in a powder formulation to improve the recyclability of the powder and/or to limit its yellowing.
  • Document CN104910616 describes a powder of an elastomer based on polyamide
  • the powder may also comprise an antioxidant of the phenolic, phosphite or thioether type.
  • Document FR 3087198 describes a powder intended for 3D printing based on a thermoplastic polymer, comprising at least 0.1% by weight of at least one thioether antioxidant relative to the total weight of powder.
  • the aim of the present invention is to propose a solution to one or more problems mentioned above.
  • the aim of the invention is to provide a thermoplastic polymer powder, preferably a polyamide powder, comprising a particular antioxidant, having improved thermal stability and thus better recyclability.
  • a powder with improved thermal stability is understood to mean a powder having a yellowness index (Yl), measured after having been exposed in air at 177° C. in a volume of approximately 50 ml_ for 72 hours, which is at least 30% less than the index measured under the same conditions for the same powder without the particular antioxidant.
  • Yl yellowness index
  • the present invention relates to a polymer powder suitable for 3D printing by sintering, comprising a thermoplastic polymer (a), preferably a polyamide, and an aliphatic sulfonate (b) according to the formula R-SO 3 X , or aromatic according to the formula RY-SO 3 X, in which,
  • R represents an aliphatic carbon chain having 4 to 30 carbon atoms, linear or branched, saturated or unsaturated, which may comprise a group (in particular a single group) chosen from ester, amide, carboxylic acid, alcohol, nitrile, ketone and/or aldehyde, preferably chosen from ester, amide, carboxylic acid and alcohol (R possibly consisting in particular of an aliphatic carbon chain having 4 to 30 carbon atoms, linear or branched, saturated or unsaturated),
  • - Y represents one or more aromatic rings
  • - X represents a monovalent ion chosen from alkali metals, preferably a sodium ion.
  • the sulphonate according to the invention can be chosen from:
  • an aliphatic sulfonate comprising a saturated carbon chain, linear or branched, having 4 to 12 carbon atoms, preferably 6 to 10 carbon atoms, for example, sodium hexane sulfonate, sodium heptane sulfonate, sodium octane sulfonate, sodium nonane sulfonate, sodium decane sulfonate, sodium undecane sulfonate, sodium dodecane sulfonate;
  • an aliphatic sulfonate comprising an unsaturated carbon chain, linear or branched, having 4 to 30 carbon atoms, preferably 12 to 18 carbon atoms, for example a sodium olefin sulfonate having 12 to 18 carbon atoms; and or
  • an aliphatic or aromatic sulfonate comprising a carbon chain having 4 to 30 carbon atoms, linear or branched, saturated or unsaturated, the chain comprising a group (in particular a single group) chosen from ester, amide, acid, alcohol, nitrile and/or or aldehyde, preferably chosen from ester, amide, acid and alcohol.
  • the aliphatic sulfonate may for example comprise a carbon chain having 4 to 30 carbon atoms, preferably having 4 to 20 carbon atoms, saturated or unsaturated, comprising an ester or amide group.
  • the aromatic sulphonate can for example be an alkylbenzene sulphonate, in which the benzene is substituted by at least one carbon chain having 4 to 18 carbon atoms, linear or branched, saturated or unsaturated, for example, dodecylbenzene sulphonate.
  • the sulphonate has a melting point below 300° C., preferably below 250° C., more preferably below 200° C., and in particular below that of the polymer powder.
  • thermoplastic polymer which can be used according to the invention can be chosen from: polyolefin, polyamide, polyester, polyarylether ketone, polyphenylene sulfide, polyacetal, polyimide, vinylidene fluoride polymer and/or their mixture, preferably polyamide, polyarylether ketone, and/ or their mixture.
  • thermoplastic polymer according to the invention is a semi-crystalline thermoplastic polymer.
  • the polymer powder further comprises a thioether, fillers or reinforcements, and/or one or more additional additives.
  • thermoplastic polymer powder preferably a polyamide powder
  • the addition of the sulphonate makes it possible to very advantageously limit the yellowing of the powder during the successive constructions.
  • this thermal stabilization improvement was observed not only on the powder but also on the printed part.
  • the presence of sulfonate makes it possible to avoid an excessive rise in the inherent viscosity of the non-agglomerated powder, and thus makes it possible to increase the possibility of recycling the powder in a sintering process and ultimately makes it possible to obtain 3D parts with high-performance mechanical properties.
  • the present invention thus provides a powder having excellent recyclability, even when the sintering process is carried out under severe conditions, typically in air, at high temperature (namely, generally a few tens of degrees below the melting temperature) and /or extended term under construction.
  • the polymer powder according to the invention comprises a thermoplastic polymer (a), a sulphonate (b), and optionally a thioether (c), fillers or reinforcements (d) and/or one or more additives additional (e).
  • the invention relates to a method for preparing a powder as defined above.
  • the present invention also relates to the use of a sulfonate to improve the thermal stability, preferably to limit yellowing, of a thermoplastic polymer powder suitable for 3D printing by sintering.
  • the polymer powder further comprises a thioether.
  • the present invention also relates to a 3D printing process, preferably a sintering process caused by electromagnetic radiation, using the powder as defined above, or a powder comprising a part of said non-agglomerated powder and recovered after a or more constructions within the same printing process or a different printing process.
  • the electromagnetic radiation is chosen from a laser beam, infrared radiation or UV radiation, with or without an absorber.
  • the present invention also relates to an article obtained by the 3D printing process as defined above.
  • the article can be chosen from among prototypes, models and parts, in particular in the automotive, nautical, aeronautical, aerospace, medical (prostheses, hearing systems, cellular tissues, etc.) fields, textiles, clothing, fashion, decoration, design, boxes for electronics, telephony, IT, lighting, sports, industrial tools.
  • the inherent viscosity in solution (also called “inherent viscosity”) of the printed part is greater than 0.8, so that the article has acceptable mechanical properties. More preferably, the inherent viscosity of the printed part is greater than 1.0. Generally, the inherent viscosity of the printed part is less than 4.0, preferably less than 3.0.
  • the Dv50 also called here “volume median diameter”, corresponds to the value of the particle size which divides the population of particles examined exactly in two. Dv50 is measured according to ISO 13320-1. In the present description, a Malvern Insitec particle size analyzer and RTSizer software are used to obtain the particle size distribution of the powder and to deduce the Dv50 therefrom.
  • the inherent viscosity in solution is measured according to the following steps: - Sampling of polymer samples between 0.07 and 0.10 g and preferably 0.15 g maximum,
  • the analysis of the thermal characteristics of the polyamide is made by DSC according to the standard ISO 11357-3 "Plastics - Differential Scanning Calorimetry (DSC) Part 3: Determination of temperature and enthalpy of melting and crystallization".
  • the temperatures which are of particular interest here to the invention are the melting temperature during the first heating (Tf1), the crystallization temperature (Te) and the enthalpy of melting,
  • thermoplastic polymer By “semi-crystalline thermoplastic polymer”, is meant a thermoplastic polymer which has: a crystallization temperature (Te) determined according to standard ISO 11357-3:2013, during the cooling step at a rate of 20 K/min in DSC (differential scanning calorimetry or “differential scanning calorimetry”);
  • Tf melting temperature
  • DH ⁇ enthalpy of fusion
  • the yellowness is quantified by the yellowness index (Yl) measured according to the ASTM E313-96 standard (D65), in particular using a Konica Minolta spectrocolorimeter illuminating D65 under 10° in specular reflection mode included ( SCI).
  • the mechanical properties in particular the tensile modulus and the elongation at break, are measured according to the ISO 527-1 B: 2012 standard. In the present description, it is specified that when reference is made to intervals, expressions of the type "between... and" include the limits of the interval. Unless otherwise stated, the percentages expressed are percentages by mass. Unless otherwise stated, the parameters referred to are measured at atmospheric pressure and ambient temperature (23°C).
  • PA XY designating a polyamide resulting from the condensation of a diamine with a dicarboxylic acid
  • X represents the number of carbon atoms of the diamine
  • Y represents the number of carbon atoms of the dicarboxylic acid
  • Z represents the number of carbon atoms of the polyamide units resulting from the condensation of an amino acid or lactam.
  • PA X/Y, PA X/Y/Z, etc. refers to copolyamides in which X, Y, Z, etc. represent homopolyamide units X, Y, Z as described in the present invention.
  • thermoplastic polymer is a semi-crystalline thermoplastic polymer, preferably a polyamide.
  • the polyamide can be a homopolyamide (i.e. PA “XY” and PA “Z”), a copolyamide (i.e. PA “X/Y”), or mixtures thereof.
  • Type “Z” polyamides come from the condensation of one or more a,w-aminocarboxylic acids and/or one or more lactams.
  • alpha-omega amino acids such as aminocaproic, amino-7-heptanoic, amino-11-undecanoic, n-heptyl-11-aminoundecanoic and amino-12-dodecanoic.
  • lactams By way of example of lactams, mention may be made of those having from 3 to 12 carbon atoms on the main ring and which may be substituted. We can cite for example the b,b- dimethylpropriolactam, ⁇ , ⁇ -dimethylpropriolactam, amylolactam, caprolactam, capryllactam, oenantholactam, 2-pyrrolidone and lauryllactam.
  • XY type polyamides come from the condensation of a dicarboxylic acid with an aliphatic, cycloaliphatic or aromatic diamine.
  • a diamine mention may be made of aliphatic diamines having from 6 to 12 atoms, the diamine X possibly also being aryl and/or saturated cyclic.
  • Examples include hexamethylenediamine, piperazine, tetramethylenediamine, octamethylenediamine, decamethylenediamine, dodecamethylenediamine, 1,5 diaminohexane, 2,2,4-trimethyl-1,6 -diamino-hexane, diamine polyols, isophorone diamine (I PD), methyl pentamethylenediamine (MPDM), bis(aminocyclohexyl) methane (BACM), bis(3-methyl-4 aminocyclohexyl) methane (BMACM), methoxylyenediamine, trimethylhexamethylene diamine.
  • I PD isophorone diamine
  • MPDM methyl pentamethylenediamine
  • BAM bis(aminocyclohexyl) methane
  • BMACM bis(3-methyl-4 aminocyclohexyl) methane
  • a dicarboxylic acid By way of example of a dicarboxylic acid, mention may be made of acids having between 4 and 18 carbon atoms, preferably from 9 to 12 carbon atoms. Mention may be made, for example, of adipic acid, sebacic acid, azelaic acid, suberic acid, isophthalic acid, butanedioic acid, 1,4-cyclohexyldicarboxylic acid, terephthalic acid, sodium or lithium salt of sulfoisophthalic acid, dimerized fatty acids (especially those having a dimer content of at least 98% and/or hydrogenated) and 1,2-dodecanedioic acid HOOC-( CH2) IO -COOH.
  • PA 612 resulting from the condensation of hexamethylenediamine and 1,12-dodecanedioic acid
  • PA 613 resulting from the condensation of hexamethylene diamine and brassylic acid
  • PA 912 resulting from the condensation of 1,9-nonanediamine and 1,12-dodecanedioic acid
  • PA 1010 resulting from the condensation of 1,10-decanediamine and sebacic acid
  • PA 1012 resulting from the condensation of 1,10-decanediamine and 1,12-dodecanedioic acid.
  • the polyamide can also be a copolyamide resulting from the condensation: - of at least two different monomers, for example of at least two different a,w-amino carboxylic acids or - of two different lactams or - a lactam and an a,w-amino carboxylic acid with different carbon numbers or
  • polyamides which may be mixtures of aliphatic polyamides and of semi-aromatic polyamides and mixtures of aliphatic polyamides and of cycloaliphatic polyamides.
  • the polyamide of the present invention can also be a copolymer with polyamide blocks and with polyether blocks (PEBA) or a mixture of a copolymer with polyamide blocks and with polyether blocks with at least one of the aforementioned polyamides.
  • PEBA polyether blocks
  • the PEBA copolymers can result from the copolycondensation of polyamide blocks with reactive ends with polyether blocks with reactive ends, such as, among others: 1) polyamide blocks with diamine chain ends with polyoxyalkylene blocks with dicarboxylic chain ends;
  • the polyamide blocks can be a homopolyamide or a copolyamide as described above for homopolyamides and copolyamides.
  • the polyamide blocks with dicarboxylic chain ends come, for example, from the condensation of polyamide precursors in the presence of a chain limiter of the dicarboxylic acid type.
  • the polyamide blocks with diamine chain ends come, for example, from the condensation of polyamide precursors in the presence of a chain limiter of the diamine type.
  • the polyether blocks of PEBA can be derived from alkylene glycols such as PEG (polyethylene glycol), PPG (propylene glycol), P03G (polytrimethylene glycol) or PTMG (polytetramethylene glycol), preferably PTMG.
  • the polymers containing polyamide blocks and polyether blocks can comprise units distributed randomly. These polymers can be prepared by the simultaneous reaction of the polyether and the precursors of the polyamide blocks.
  • polyetherdiol blocks are either used as such and copolycondensed with polyamide blocks with carboxylic ends, or they are aminated to be transformed into polyether diamines and condensed with polyamide blocks with carboxylic ends. They can also be mixed with polyamide precursors and a chain limiter to make polymers with polyamide blocks and polyether blocks having randomly distributed units.
  • the ratio of the amount of copolymer containing polyamide blocks and polyether blocks to the amount of polyamide is advantageously between 1/99 and 15/85 by weight.
  • the mixture of polyamide and at least one other polymer it is in the form of a mixture with a polyamide matrix and the other polymer(s) form(s) the dispersed phase.
  • this other polymer mention may be made of polyolefins, polyesters, polycarbonate, PPO (abbreviation of polyphenylene oxide), PPS (abbreviation of polyphenylene sulfide), elastomers.
  • the powder compositions comprise at least one polyamide chosen from polyamides, copolyamides and/or PEBA copolymers comprising at least one of the following XY or Z monomers: 46, 4T, 54, 59, 510, 512, 513, 514, 516, 518, 536, 6, 64, 66, 69, 610, 612, 613, 614, 616, 618, 636, 6T, 9, 104, 109, 1010,
  • the powder of the invention can advantageously comprise a thioether.
  • the thioether is preferably selected from: dilauryl thiodipropionate (DLTDP), ditridecyl thiodipropionate (DTDTDP), distearyl thiodipropionate (DSTDP), dimyrystil thiodipropionate (DMTDP), pentaerythritol tetrakis (3-dodecylthio propionate or 3-laurylthiopropionate), 3,3'- thiodipropionate, alkyl (C12-14) thiopropionate, dilauryl 3,3'-thiodipropionate, ditridecyl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, dioctadecyl 3,3'-thiodiprop
  • the thioether according to the invention is selected from the group consisting of dilauryl thiodipropionate (DLTDP), ditridecyl thiodipropionate (DTDTDP), distearyl thiodipropionate (DSTDP), dimyrystil thiodipropionate (DMTDP), pentaerythritol tetrakis (3-dodecylthio propionate or 3- laurylthiopropionate), and/or mixtures thereof.
  • DLTDP dilauryl thiodipropionate
  • DTDTDP ditridecyl thiodipropionate
  • DSTDP distearyl thiodipropionate
  • DMTDP dimyrystil thiodipropionate
  • pentaerythritol tetrakis (3-dodecylthio propionate or 3- laurylthiopropionate
  • the thioether is DLTDP.
  • the thioether is pentaerythritol tetrakis (3-dodecylthio propionate).
  • a compound is in particular marketed by the companies Songnox, or Adeka under the trade name ADK STAB AO-412S.
  • the thioether has a melting point less than or equal to 180° C., preferably less than or equal to 160° C., preferably less than or equal to 140° C., even more preferably less than or equal to 130° C., or 100°C.
  • the polymer powder according to the invention comprises a thermoplastic polymer (a), a sulphonate (b), and optionally a thioether (c), fillers or reinforcements (d) and/or one or more additives additional (e).
  • the powder according to the invention comprises:
  • thermoplastic polymer (a) 30 to 99.9%, preferably 40 to 95%, by weight of a thermoplastic polymer as defined above;
  • the powder according to the invention comprises: (a) 75 to 99.9%, preferably 85 to 99%, by weight of a thermoplastic polymer as defined above;
  • Component (e) may include one or more of these additives.
  • the sulfonate represents from 0.1 to 3% or from 3 to 5%, or from 5 to 10%, or from 10 to 15%, or from 15 to 20% by weight relative to the total weight polymer powder.
  • the sulfonate can represent from 0.5 to 10% by weight, or from 0.5 to 5% by weight, relative to the total weight of the polymer powder.
  • the thioether represents at least 0.1%, preferably from 0.1 to 5%, preferably from 0.1 to 3%, preferably from 0.1 to 2%, preferably from 0.1 to 1%, by weight relative to the total weight of the polymer powder.
  • the thioether represents at least 0.2%, for example at least 0.3%, typically at least 0.4%, and typically less than 5%, for example, less than 4%, preferably less than 3% by weight relative to the total weight of the polymer powder.
  • the polymer powder has a first heating melting temperature (Tf 1 ) of between 80 and 220°C, preferably between 100 and 200°C.
  • Tf 1 first heating melting temperature
  • the powder may have a crystallization temperature (Te) of 40 to 250°C, and preferably of 45 to 200°C, for example 45 to 150°C.
  • Te crystallization temperature
  • Tf the lowest Tf in the mixture
  • Te the highest Te in the mixture.
  • the difference between the Te and the Tf of the powder is preferably greater than or equal to 20°C, or more preferably greater than or equal to 30°C.
  • the inherent viscosity in solution of the powder before its use in a sintering process is typically less than 3, preferably less than 2.
  • the inherent viscosity of the powder, unaffected by the radiation electromagnetic after a first construction in a sintering process is between 0.8 and 3, preferably between 1 and 2.
  • the polymer powder according to the invention has a diameter Dv50 of 40 to 150 ⁇ m, and preferably of 40 to 100 ⁇ m.
  • the diameter Dv50 of the polymer powder can be 40 to 45 ⁇ m; or 45 to 50 ⁇ m; or 50 to 55 ⁇ m; or 55 to 60 ⁇ m; or 60 to 65 ⁇ m; or 65 to 70 ⁇ m; or 70 to 75 ⁇ m; or 75 to 80 ⁇ m; 80 to 85 ⁇ m; or 85 to 90 ⁇ m; or 90 to 95 ⁇ m; or 95 to 100 ⁇ m; or from 100 to 105 ⁇ m; or 105 to 110 ⁇ m; or 110 to 115 ⁇ m; or 115 to 120 ⁇ m; or from 120 to 125 ⁇ m; or from 125 to 130 ⁇ m; or from 130 to 135 ⁇ m; or from 135 to 140 ⁇ m; or 140 to 145 ⁇ m; or from 145 to 150 pm.
  • the polymer powder according to the invention may moreover optionally comprise fillers or reinforcements, in particular in order to ensure that the printed article has sufficient mechanical properties, in particular in terms of modulus.
  • These fillers may in particular be carbonated minerals, in particular carbonate of calcium, magnesium carbonate, dolomite, calcite, barium sulphate, calcium sulphate, dolomite, alumina hydrate, wollastonite, montmorillonite, zeolite, perlite, nanofillers (fillers having a dimension of the order of a nanometer) such as nano-clays, calcium silicates, magnesium silicates, such as talc, mica, kaolin, attapulgite and mixtures thereof.
  • Component (c) may include one or more fillers and/or reinforcements.
  • the fillers and reinforcements do not include pigments as defined above for the pigmentary composition.
  • the powder of the invention can comprise 0 to 60%; or from 5 to 50%; or 10 to 40%; or from 10 to 30% by weight of component (c).
  • the polymer powder is devoid of fillers and reinforcements.
  • the polymer powder may include, where appropriate, additional additives usual in polymer powders used in 3D printing by sintering.
  • additives in powder form or not, which contribute to improving the behavior of the powder in 3D printing by sintering and those which make it possible to improve the properties of the printed articles, in particular the mechanical strength, the thermal resistance, fire resistance, and in particular elongation at break and impact resistance.
  • additives can in particular be chosen from flow agents, chain limiters, flame retardants, flame retardants, anti-UV agents, antioxidants, anti-abrasion agents, light stabilizers, impact modifiers, antistatic agents. , pigments and waxes.
  • the flow agent may for example be chosen from silicas, in particular hydrophobic fumed silica, for example, mention may be made of the product marketed under the name Cab-o-Sil® TS610 by Cabot Corporation, precipitated silica, hydrated silica, vitreous silica, fumed silica, vitreous oxides, in particular glassy phosphates, glassy borates, alumina, such as amorphous alumina, and mixtures thereof.
  • the powder of the invention may comprise a phenolic antioxidant, such as 3,3'-Bis(3,5-di-tert-butyl-4-hydroxyphenyl)-N,N'-hexamethylenedipropionamide marketed in particular under the name Palmarole AO.
  • a phenolic antioxidant such as 3,3'-Bis(3,5-di-tert-butyl-4-hydroxyphenyl)-N,N'-hexamethylenedipropionamide marketed in particular under the name Palmarole AO.
  • the powder may also comprise antioxidants such as compounds comprising aromatic or aliphatic phosphonites (such as the Hostanox® P-EPQ® product marketed by Clariant), alkaline salts of phenyl- phosphonic or hypophosphorous acid, compounds comprising phosphite functions, such as trialkyl- and trialkylaryl-phosphites and cyclic diphosphites derived from pentaerythritol. Mention may be made of Irgafos® 168 sold by BASF.
  • antioxidants such as compounds comprising aromatic or aliphatic phosphonites (such as the Hostanox® P-EPQ® product marketed by Clariant), alkaline salts of phenyl- phosphonic or hypophosphorous acid, compounds comprising phosphite functions, such as trialkyl- and trialkylaryl-phosphites and cyclic diphosphites derived from pentaerythritol. Mention may be made of Irgafos®
  • trialkyl- and trialkylaryl-phosphites mention may be made of trinonyl-, tri(nonylphenyl)- and tri[(2,4-di-tert-butyl-5-methyl)phenyl] phosphites.
  • cyclic diphosphites derived from pentaerythritol mention may be made of distearylpentaerythritol diphosphite.
  • the pigment may be a pigment having an absorbance of light with a wavelength of 1000 nm, as measured according to the ASTM E1790 standard, of less than 40%, for example chosen from metal oxides and metal oxides of transition as well as their mixtures, mixed oxides, and corresponding doped oxides.
  • an oxide selected from oxides of titanium, tin, magnesium, copper, zinc, iron, manganese, cobalt, nickel, aluminum, antimony, chromium, titanium , silicon or a mixture thereof, mixed oxides or corresponding doped oxides.
  • Wax Wax may include polyethylene and polypropylene wax, polytetrafluoroethylene, ketones, acid, partially esterified acid, acid anhydride, ester, aldehydes, amides, their derivatives as well as mixtures thereof.
  • the wax may in particular comprise a product marketed under the name Crayvallac®
  • the wax is present in the composition in the form of a coating at least partially covering the polymer powder.
  • the powder of the invention may comprise a chain limiter chosen from dicarboxylic acids, monocarboxylic acids, diamines and monoamines, each of which may be linear or cyclic.
  • the chain limiter has a melting temperature below 180°C.
  • the monocarboxylic acid preferably has 2 to 20 carbon atoms.
  • a monocarboxylic acid By way of example of a monocarboxylic acid, mention may be made of acetic acid, propionic acid, benzoic acid, and stearic acid, lauric acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, hexadecanoic acid, octodecanoic acid, tetradecanoic acid.
  • the dicarboxylic acid preferably has 2 to 20 carbon atoms, more preferably 6 to 10 carbon atoms.
  • dicarboxylic acid mention may be made of sebacic acid, adipic acid, azelaic acid, suberic acid, dodecanedicarboxylic acid, butane-dioic acid, and ortho phthalic acid. .
  • the monoamine may in particular be a primary amine having from 2 to 18 carbon atoms.
  • Examples of monoamine include 1-aminopentane, 1-aminohexane, 1-aminoheptane, 1-aminooctane, 1-aminononane, 1-aminodecane, 1-aminoundecane, 1-aminododecane , benzylamine, and oleylamine.
  • the diamine may in particular be a primary diamine comprising 4 to 20 carbon atoms.
  • Examples of diamines include the isomers of bis-(4-aminocyclohexyl)methane (BACM), bis-(3-methyl-4-aminocyclohexyl)methane
  • BMACM 2-2-bis-(3-methyl-4-aminocyclohexyl)-propane
  • PAM para-amino-di-cyclo-hexyl-methane
  • IPDA isophoronediamine
  • BAMN 2,6-bis-(aminomethyl)-norbornane
  • the chain limiter represents from 0.01 to 10%, preferably from 0.01 to 5%, preferably from 0.01 to 4%, preferably from 0.01 to 3%, preferably from 0.01 to 2%, preferably from 0.01 to 1% by weight relative to the total weight of the thermoplastic polymer, or relative to the total weight of the polyamide when the thermoplastic polymer is a polyamide.
  • the chain limiter can represent from 0.01 to 2% by weight relative to the total weight of the thermoplastic polymer, or relative to the total weight of the polyamide when the thermoplastic polymer is a polyamide.
  • the chain limiter represents from 0.01 to 0.5%, from 0.01 to 0.4%, from 0.01 to 0.3%, from 0.01 to 0.2% by weight per relative to the total weight of the thermoplastic polymer, or relative to the total weight of the polyamide when the thermoplastic polymer is a polyamide.
  • the polymer powder can be manufactured according to the usual methods.
  • component (a) can be used, especially in the form of granules, flakes or powder. If necessary, component (a) can be transformed into powder, by means of known methods, in particular by grinding.
  • the milling may be ambient temperature milling.
  • the grinding may be cryogenic grinding.
  • the material to be ground is cooled, for example by means of liquid nitrogen, liquid carbon dioxide or liquid helium, to make the material more fragile and therefore facilitate the grinding.
  • the grinding can be carried out, for example, in a counter-rotating pin mill (pin mill), a hammer mill (hammer mill) or in a whirl mill (whirl mill).
  • the process for preparing a powder according to the invention comprises the steps of: (i) grinding a thermoplastic polymer (a) into a powder with a diameter Dv50 of
  • thermoplastic polymer (component (a)) before the grinding can be carried out according to the methods known to those skilled in the art.
  • the addition can be carried out by melting, for example in an extruder (compounding) or by wet impregnation (reference can be made, for example, to the method described in EP 3 325 535 B1).
  • the components are added after grinding, for example, by dry addition (dry blend), it is preferable that the components are in powder form with a Dv suitable for 3D printing.
  • the sulfonate (component (b)), if necessary, one or more components (c) to (e), can be added to the thermoplastic polymer during the synthesis thereof.
  • the method for preparing a powder according to the invention comprises the steps of:
  • thermoplastic polymer (a) (i) synthesis of a thermoplastic polymer (a), during or after,
  • the sulfonate (component (b)), if necessary, one or more components can be added by dry addition (dry blend) to the thermoplastic polymer (a).
  • the method for preparing a powder according to the invention comprises a step in which the sulfonate (b), where appropriate, one or more components (c) to (e) are incorporated into the powder by dry addition. It is also possible to use several of these methods, depending on the additives, for their introduction into the polymer composition.
  • the powder thus obtained can then be sieved or subjected to a selection step to obtain the desired particle size profile.
  • the polymer powder can then, if necessary, be subjected to different treatments, in particular thermal or hydraulic treatments, so that it is better suited to 3D printing by sintering.
  • the components may be used in any suitable form depending on the method of preparation. According to one embodiment, one or more components are used in powder form.
  • the shape and size of the particles forming the powder are not particularly limited except by the application of sintering 3D printing. The particles most often have a spherical shape. But their use in other forms such as in the form of rods or in lamellar form is not excluded.
  • the components When the components are added to the polymer in dry-blend, they advantageously have a median diameter by volume Dv50 substantially equal to or less than that of the powder with which they will be mixed. More specifically, the volume median diameter Dv50 of the components is preferably between 0.01 and 50 ⁇ m, preferably between 0.05 and 30 ⁇ m, more preferably between 0.1 and 20 ⁇ m, in particular between 0.2 and 10 ⁇ m and most particularly between 0.5 and 5 ⁇ m.
  • compositions according to the present invention are not limited to this embodiment, but can comprise any type of polymer, in particular polyamide, alone or in combination.
  • the base powder 1 used is a powder comprising polyamide 11 at 99.2% by weight, an antioxidant N,N'-1,6-hexanediylbis[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropanamide at 0.6% by weight and a flow agent (hydrophobic fumed silica) at 0.2% by weight, based on the total weight of base powder 1.
  • the polyamide 11 was prepared according to the method described in EP 2247646 B1, in which the antioxidant was incorporated into the polyamide prepolymer by compounding.
  • the flow agent was then added through the dry mix as follows. In a Henschel IAM 6L mixer, the compounds to be mixed are introduced in the proportions indicated above and the mixture is stirred at 900 revolutions/min for 100 s at room temperature.
  • the Dv50 of the powder measured is 50 ⁇ m.
  • a sulfonate was added to the base powder by dry mixing as follows.
  • the polyamide powder is introduced with a sulphonate in the proportions indicated in Table 1 below and the mixture is stirred at 900 revolutions/min for 100 s at room temperature.
  • Hostapon® TPHC is a sodium 2-(methyloleoylamino)ethane-1-sulphonate, a product marketed by Clariant.
  • Hostapon® SCI 85 is a 2-butanoyloxyethanesulfonate (also called sodium cocoyl isethionate), a product marketed by Clariant. Aging test and measurement of the yellow index (Yl) of the powder a) In solid form
  • the test consists of exposing the powder of the examples to 177°C in a glass bottle placed in a ventilated oven in the air for 72 hours. The results are shown in Table 2.
  • the molten film is peeled off and the measurement is taken by placing it in front of the white part of a Leneta form 2A opacity plate.
  • This test simulates the exposure conditions that a part can undergo in a 3D machine, during its construction.
  • the base powders 2 and 3 used comprise a polyamide 11 at 98.9% by weight, an antioxidant triethylene glycol bis(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate at 0.4% by weight , a flow agent (hydrophobic fumed silica) at 0.2% by weight, and a thioether at 0.5% by weight, based on the total weight of the base powder.
  • the Dv50 of the powder measured is 50 ⁇ m.
  • the thioether used in base powder 2 is pentaerythritol tetrakis (3-dodecylthio propionate), marketed by Adeka.
  • the thioether used in the base powder 3 is a dilauryl thiodipropionate (DLTDP), marketed by Songnox.
  • Base powders 2 and 3 were prepared according to the method as described in EP 2247646 B1, in which the antioxidant and the thioether were added to the polymer by compounding. The flow agent was then added by dry mixing into the powder according to the method described in Example I.
  • Example 9 shows that the inherent viscosity increases less than the inherent viscosity of Examples 4 and 5 (without sulfonate). This shows that the addition of the sulfonate in a powder makes it possible to stabilize its inherent viscosity, as well as to recycle it better because it is less reactive.

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EP22747075.4A 2021-06-29 2022-06-28 Poudre de polymère thermoplastique pour impression 3d à la stabilité et à la recyclabilité améliorées Pending EP4363222A1 (fr)

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DE19708946A1 (de) 1997-03-05 1998-09-10 Huels Chemische Werke Ag Herstellung von Polyamid-Fällpulvern mit enger Korngrößenverteilung und niedriger Porosität
CN1188464C (zh) * 2002-04-26 2005-02-09 北京北方恒利科技发展有限公司 用于激光烧结快速成型制品的尼龙粉末材料
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