US20110172387A1 - Method for increasing the difference between the melting temperature and the crystallization temperature of a polyamide powder - Google Patents

Method for increasing the difference between the melting temperature and the crystallization temperature of a polyamide powder Download PDF

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US20110172387A1
US20110172387A1 US12/990,301 US99030109A US2011172387A1 US 20110172387 A1 US20110172387 A1 US 20110172387A1 US 99030109 A US99030109 A US 99030109A US 2011172387 A1 US2011172387 A1 US 2011172387A1
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polymerization
monomer
powder
minor
acid
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Gregory Filou
Cyrille Mathieu
Holger Senff
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Arkema France SA
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    • 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
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/02—Moulding by agglomerating
    • B29C67/04—Sintering
    • 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
    • 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
    • C08G69/04—Preparatory processes
    • 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
    • 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
    • C08G69/14—Lactams
    • C08G69/16—Preparatory processes
    • 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
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • 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
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/28—Preparatory processes
    • 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
    • C08G69/44—Polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08J3/14—Powdering or granulating by precipitation from solutions
    • 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
    • C08J3/28—Treatment by wave energy or particle radiation
    • 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

Definitions

  • the present invention relates to polyamides, such as copolyamides and copolyesteramides, which have an increased difference between their melting temperature and their crystallization temperature (Tf ⁇ Tc).
  • the present invention also relates to a process for manufacturing powders of such copolyamides or copolyesteramides, irrespective of the type of polymerization used during the process: hydrolytic polycondensation, anionic or cationic polymerization.
  • a large difference between the Tf and the Tc of a polyamide-based powder is particularly useful in many uses, and especially in powder aggregation technology by radiation-mediated melting or sintering, for instance using a laser beam (laser sintering), infrared radiation or UV radiation or any source of electromagnetic radiation that makes it possible to melt the powder in order to manufacture articles.
  • radiation-mediated melting or sintering for instance using a laser beam (laser sintering), infrared radiation or UV radiation or any source of electromagnetic radiation that makes it possible to melt the powder in order to manufacture articles.
  • the technology of aggregation of polyamide powders via a laser beam serves to manufacture three-dimensional articles such as prototypes and models, especially in the motor vehicle, nautical, aeronautics, aerospace, medical (prostheses, auditive systems, cell tissues, etc.), textile, clothing, fashion, decorative, electronic casing, telephony, home automation, information technology and lighting sectors.
  • a thin layer of polyamide powder is deposited on a horizontal plate maintained in a chamber heated to a temperature between the crystallization temperature Tc and the melting temperature Tf of the polyamide powder.
  • the laser aggregates the powder particles at different points in the powder layer according to a geometry corresponding to the article, for example with the aid of a computer which has in its memory the shape of the article and which restitutes this article in the form of slices.
  • the horizontal plate is lowered by a value corresponding to the thickness of the powder layer (for example between 0.05 and 2 mm and generally about 0.1 mm), then a new powder layer is deposited and the laser aggregates powder particles according to a geometry corresponding to this new slice of the article, and so on. The procedure is repeated until the entire article has been manufactured.
  • the temperature of the sample is higher than the crystallization temperature (Tc) of the powder.
  • Tc crystallization temperature
  • the introduction of a new layer of colder powder causes the temperature of the part to drop rapidly, which, when it passes below said Tc, results in deformations (phenomenon known as curling).
  • Tf melting temperature
  • the difference Tf ⁇ Tc of the powder determines the working-temperature window of the device that serves to aggregate the powder particles via radiation-mediated melting.
  • This working window is defined by its upper temperature limit and its lower temperature limit.
  • the upper limit of the working window corresponds to the temperature at which aggregation or caking takes place.
  • the lower limit of the working window corresponds to the temperature at which distortion or deformation or “curling” takes place.
  • This working window of the device is generally estimated as about 10° C. by a person skilled in the art for use of the powder in the machine under good conditions, i.e. without appearance of the phenomena described above, which are the cause of defects on the parts obtained.
  • the highest possible heat of fusion (AHf) is required in order to obtain a good geometrical definition of the manufactured parts. Specifically, if this heat of fusion is too low, the energy provided by the laser is sufficient to sinter by heat conduction the powder particles close to the walls under construction, and thus the geometrical precision of the part is no longer satisfactory.
  • U.S. Pat. No. 6,245,281 (EP 0 911 142) describes the use, for selective laser sintering, of polyamide 12 (PA 12) powders with an increased melting point and heat of fusion.
  • Their Tf is within the range from 185 to 189° C.
  • their Tc is within the range from 138 to 143° C. (and so 42° C. ⁇ Tf ⁇ Tc ⁇ 51° C.)
  • their ⁇ Hf is 112 ⁇ 17 J/g.
  • This process requires several steps, in which PA 12 is first manufactured by condensation and is then dissolved in ethanol between 130 and 150° C., and the ethanol solution is cooled slowly to below 125° C. with stirring, to make the PA 12 precipitate in powder form.
  • One drawback of the powders obtained via this process is the evolution of gas during the process of sintering residual monomers present in these powders, in particular when the manufacturing chamber is maintained at a temperature just below the melting temperature of the polymer. These gaseous monomers, after sublimation, become deposited on the components of the machine, which damages it. In particular, the condensation of these monomers on optical surfaces impairs the manufacturing conditions and leads to reduced performance and precision.
  • a complicated intermediate step may be added during the preparation of the polyamide powder. This additional step consists in extracting the residual monomers from the polyamide in hot alcohol, and necessitates an expensive manipulation.
  • Patent FR 2 867 190 describes a process for manufacturing a polyamide 12 powder with a high Tf (the Tc remaining unchanged) via a synthetic process of anionic type starting with lauryllactam dissolved in a solvent in the presence of a filler and an amide of formula R1-NH—CO—R2.
  • the process of said document consists in placing the solvent in lactam supersaturation state, i.e. at a temperature below the Tc of the lactam in the solvent.
  • the polyamide 12 powders obtained via this process contain very few residual monomers, have a melting point of at least 180° C. and preferably within the temperature range from 182° C. to 184° C., and a crystallization temperature of about 135 ⁇ 1° C. This process involves very precise control and monitoring of the temperature under industrial conditions.
  • Patent FR 2 873 380 describes a process for increasing the melting temperature and the heat of fusion of a polyamide, without modifying the crystallization temperature of the powder.
  • this process it is a matter of increasing the Tf of pre-manufactured polyamides, for example of PA 11, via a water treatment.
  • Polyamide in divided form (granules or powder) is placed in contact in the solid state with water or water vapor at a temperature close to its crystallization temperature Tc, and is then separated from the water and dried.
  • This process thus involves several steps subsequent to the manufacture of the polyamide itself, the drying step being a limiting step of the process.
  • French patent application 06/56029 relates to a process for manufacturing a seeded powder particle formed from a polyamide shell and a polyamide core.
  • the process uses the anionic polymerization of lauryllactam or caprolactam monomer or a blend thereof dissolved in a solvent in the presence of seeds that are polyamide powder particles.
  • This characteristic core/shell structure of the seeded polyamide powder leads to a much lower Tc, the Tf being unchanged.
  • the powders obtained have a difference Tf ⁇ Tc absolute value higher than that of the powders of the prior art. However, the difference obtained between Tf and Tc is not as great as with the process of the abovementioned patent FR 2 867 190.
  • One aim of the present invention is thus to provide a process for efficiently increasing the difference Tf ⁇ Tc of existing polyamides.
  • one aim of the present invention is to provide a process for manufacturing polyamide, especially in the form of powder or granules, with an enlarged difference Tf ⁇ Tc, which is simple, quick (comprising the fewest possible steps) and easy to perform and which entrains few or no residual monomers liable to affect the functioning of the machines used for the manufacture of articles by powder aggregation.
  • copolymers are especially PA 12/6/6.12 (in a mass percentage ratio of 40/30/30) and PA 12/6/6.6 (in a mass percentage ratio of 33/33/33 or of 60/25/15).
  • the use of these copolymer powders is directed toward implementing the aggregation process at lower temperatures than with conventional powders.
  • the materials obtained with the copolymer powders described are soft and do not have a sufficient modulus or sufficient resistance to the working temperatures, for example at room temperature, or at the heating temperature of an engine in the aeronautical or motor vehicle field, or alternatively in the information technology field (heat given off by batteries).
  • One aim of the present invention is thus to increase the difference between the Tf and the Tc of polyamide powders while at the same time conserving their mechanical properties, in order for the final article obtained by aggregation of these powders to have properties that are compatible with its use.
  • the material of the final article should have sufficient strength and flexibility, in particular with an elastic modulus of greater than 1500 N/mm 2 and an elongation at break of greater than 15% and preferably greater than 20%.
  • the Applicant Company has now found a process for manufacturing polyamides that are designed to satisfy these various requirements.
  • the process according to the invention is a process for increasing the difference Tf ⁇ Tc of polyamides, which is simple, quick (in one step) and which produces few residual monomers.
  • the process of the invention concerns the mechanical properties (breaking modulus and elongation at break) of the usual polyamides in the powders obtained, and likewise in 3D articles, such as those obtained via the techniques of aggregation by electromagnetic radiation-mediated melting of these powders.
  • One subject of the present invention is thus the use of at least one minor comonomer in a process for polymerizing at least one major monomer in order to reduce the crystallization temperature and the melting temperature of a polyamide derived from the polymerization of said at least one major monomer, and in order for the decrease in crystallization temperature to be greater than the decrease in melting temperature, respectively, relative to the crystallization temperature and the melting temperature of the polyamide resulting from the polymerization of said at least one major monomer, said melting and crystallization temperatures being measured by DSC according to standard ISO 11357-3, said at least one minor comonomer being polymerized according to the same polymerization process as said at least one major monomer, and said at least one minor comonomer being chosen from aminocarboxylic acids, diamine-diacid couples, lactams and/or lactones, and said at least one minor comonomer representing from 0.1% to 20% by mass of the total blend of said monomer(s) and comonomer(s),
  • the polymerization between the various minor and major monomers is an anionic polymerization.
  • the polymerization between the various minor and major monomers is a hydrolytic polycondensation.
  • said at least one major monomer comprises 11-aminoundecanoic acid and/or lactam 12 and/or the decanediamine-sebacic acid couple (10/10).
  • said at least one minor comonomer is chosen from aminocarboxylic acids, preferably ⁇ , ⁇ -aminocarboxylic acids, comprising from 4 to 18 carbon atoms, diamine-diacid couples comprising from 4 to 18 carbon atoms, lactams comprising from 3 to 18 carbon atoms, lactones comprising from 3 to 18 carbon atoms, and mixtures thereof.
  • said at least one minor comonomer comprises 11-aminoundecanoic acid, 11-n-heptylaminoundecanoic acid, lauryllactam, caprolactam and/or caprolactone.
  • said at least one minor comonomer comprises at least one of the following diamine-diacid couples: 6.6, 6.10, 6.11, 6.12, 6.14, 6.18, 10.10, 10.12, 10.14, 10.18, 10.T, T being terephthalic acid.
  • a subject of the present invention is also a process for reducing the crystallization temperature and the melting temperature of a polyamide (homopolyamide or copolyamide) derived from the polymerization of at least one major monomer, in which the reduction of the crystallization temperature is greater than the reduction of the melting temperature, said process comprising a step of polymerizing said at least one major monomer with at least one different minor comonomer polymerized according to the same polymerization process as said at least one major monomer, said at least one minor comonomer being chosen from aminocarboxylic acids, diamine-diacid couples, lactams and/or lactones, and said at least one minor comonomer representing from 0.1% to 20% by mass of the total blend of said monomer(s) and comonomer(s), preferably from 0.5% to 15% by mass of said total blend and preferably from 1% to 10% by mass of said total blend.
  • a polyamide homopolyamide or copolyamide
  • said at least one minor comonomer represents from 1% to 7% by mass of the total blend of said monomer(s) and comonomer(s), preferably from 1% to 5% by mass of said total blend, and said at least one minor comonomer comprises 11-aminoundecanoic acid and/or lauryllactam and/or caprolactam and/or caprolactone and/or at least one of the following diamine-diacid couples: 6.6, 6.10, 6.11, 6.12, 6.14, 6.18, 10.10, 10.12, 10.14, 10.18 and/or 10.T, T being terephthalic acid.
  • the polymerization between the various minor and major monomers is an anionic polymerization.
  • the polymerization between the various minor and major monomers is a hydrolytic polycondensation.
  • said at least one major monomer comprises 11-aminoundecanoic acid and/or lactam 12 and/or the decanediamine-sebacic acid couple (10.10).
  • said process also comprises, after said polymerization step, at least one step chosen from: dissolution, precipitation, extrusion, atomization, spraying, cold nebulization, hot nebulization, milling, cryogenic milling, screening, viscosity raising, and combinations thereof.
  • a subject of the present invention is also a copolyamide or copolyesteramide powder, which may be manufactured according to the process defined previously, said powder being derived from the polymerization of at least two different monomers polymerized according to the same polymerization process, at least one of the comonomers being minor and chosen from aminocarboxylic acids, diamine-diacid couples, lactams and/or lactones, and said at least one minor comonomer representing from 0.1% to 20% by mass of the total blend of said monomer(s) and comonomer(s), preferably from 0.5% to 15% by mass of said total blend, and preferably from 1% to 10% by mass of said total blend.
  • said at least one minor comonomer represents from 1% to 7% by mass of the total blend of said monomer(s) and comonomer(s), preferably from 1% to 5% by mass of said total blend, and said at least one minor comonomer comprises 11-aminoundecanoic acid and/or lauryllactam and/or caprolactam and/or caprolactone and/or at least one of the following diamine-diacid couples: 6.6, 6.10, 6.11, 6.12, 6.14, 6.18, 10.10, 10.12, 10.14, 10.18 and/or 10.T, T being terephthalic acid.
  • the powder of the invention comprises an 11-aminoundecanoic acid major monomer and at least one minor monomer chosen from the hexamethylenediamine-adipic acid couple (6.6), lauryllactam, caprolactam and/or caprolactone.
  • the powder comprises a lauryllactam major monomer and a minor monomer chosen from caprolactam, caprolactone and/or the hexamethylenediamine-adipic acid couple (6.6).
  • the powder according to the invention is chosen from the following polyamides: PA 11/6.6 comprising from 1% to 7% of 11-aminoundecanoic acid, PA 11/N-heptylamino acid comprising from 1% to 5% of N-heptylamino acid, PA 12/11 comprising from 1% to 12% and preferably from 2% to 5% of 11-aminoundecanoic acid, and PA 12/6 comprising from 1% to 5% of lactam 6, all the percentages being given as mass relative to the total mass of the blend of monomer and comonomer of each preferred PA.
  • PA 11/6.6 comprising from 1% to 7% of 11-aminoundecanoic acid
  • PA 11/N-heptylamino acid comprising from 1% to 5% of N-heptylamino acid
  • PA 12/11 comprising from 1% to 12% and preferably from 2% to 5% of 11-aminoundecanoic acid
  • PA 12/6 comprising from 1% to
  • a subject of the present invention is also the use of the powder according to the invention as defined previously, in coatings, such as paints, varnishes, anticorrosion compositions, textile coatings, cosmetics; paper additives; powder aggregation technologies via electromagnetic radiation-mediated melting or sintering for the manufacture of articles; electrophoresis gels, multilayer composite materials; the packaging industry; the toy industry; the textile industry; the motor vehicle industry and/or the electronics industry.
  • coatings such as paints, varnishes, anticorrosion compositions, textile coatings, cosmetics; paper additives; powder aggregation technologies via electromagnetic radiation-mediated melting or sintering for the manufacture of articles; electrophoresis gels, multilayer composite materials; the packaging industry; the toy industry; the textile industry; the motor vehicle industry and/or the electronics industry.
  • a subject of the present invention is also a process for manufacturing polyamide articles by powder aggregation via electromagnetic radiation-mediated melting, the polyamide powder having been obtained beforehand according to the process defined previously or being in accordance with the powder defined previously.
  • a subject of the present invention is also a manufactured article obtained by electromagnetic radiation-mediated melting of a powder according to the invention.
  • the process of the invention makes it possible simultaneously to reduce the crystallization temperature and the melting temperature of polyamides.
  • the process of the invention substantially reduces the crystallization temperature of polyamides, whereas the melting temperature remains virtually unchanged. This results in polyamides for which the difference Tf ⁇ Tc is greater as an absolute value compared with the usual polyamides not manufactured according to the process of the invention.
  • polyamide means products of condensation of lactams, amino acids or diacids with diamines and, as a general rule, any polymer formed by units connected together via amide groups.
  • the process of the invention involves polymerizing at least two different monomers, known as “comonomers”, i.e. at least one monomer and at least one comonomer (monomer different than the first monomer) to form a copolymer such as a copolyamide, abbreviated as CoPA, or a copolyesteramide, abbreviated as CoPEA, as defined hereinbelow.
  • Comonomers i.e. at least one monomer and at least one comonomer (monomer different than the first monomer) to form a copolymer such as a copolyamide, abbreviated as CoPA, or a copolyesteramide, abbreviated as CoPEA, as defined hereinbelow.
  • the term “monomer” should be understood in the sense of a “repeating unit”.
  • a repeating unit is formed from the combination of a diacid with a diamine. It is considered that it is the combination of a diamine and a diacid, i.e. the diamine-diacid couple (in equimolar amount) that corresponds to the monomer. This may be explained by the fact that, individually, the diacid or the diamine is only a structural unit, which is insufficient in itself to form a polymer.
  • the process of the invention comprises the polymerization of at least one major monomer, i.e. a monomer representing at least 80% by mass of the total mass of the monomer blend, and at least one minor comonomer, representing not more than 20% by mass of the total mass of the total blend of said monomer(s) and comonomer(s).
  • a major monomer i.e. a monomer representing at least 80% by mass of the total mass of the monomer blend
  • minor comonomer representing not more than 20% by mass of the total mass of the total blend of said monomer(s) and comonomer(s).
  • the polymerization of the major monomer(s) may be performed using one or more amide monomers individually comprising from 4 to 30 carbon atoms and preferably from 8 to 28 carbon atoms.
  • said at least one minor comonomer represents from 0.1% to 20% by mass of said total blend of said monomer(s) and comonomer(s), preferably from 0.5% to 15% by mass of said total blend, preferably from 1% to 10% by mass of said total blend. Even more preferably, said at least one minor comonomer represents from 1% to 7% by mass of the total blend of said monomer(s) and comonomer(s), preferably from 1% to 5% by mass of said total blend.
  • the process for increasing the difference Tf ⁇ Tc of polyamide-based powders comprises the manufacture of CoPA powders from:
  • copolyamide (abbreviated as CoPA) means products of polymerization of at least two different monomers chosen from:
  • ⁇ , ⁇ -amino acids examples include those containing from 4 to 18 carbon atoms, such as aminocaproic acid, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 11-n-heptylaminoundecanoic acid and 12-aminododecanoic acid.
  • lactams examples include those containing from 3 to 18 carbon atoms on the main ring and which may be substituted. Examples that may be mentioned include ⁇ , ⁇ -dimethylpropiolactam, ⁇ , ⁇ -dimethylpropiolactam, amylolactam, caprolactam, also known as lactam 6, capryllactam, also known as lactam 8, oenantholactam, 2-pyrrolidone and lauryllactam, also known as a lactam 12.
  • dicarboxylic acids examples include acids containing between 4 and 18 carbon atoms. Examples that may be mentioned include adipic acid, sebacic acid, azelaic acid, suberic acid, isophthalic acid, butanedioic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, the sodium or lithium salt of sulfoisophthalic acid, dimerized fatty acids (these dimerized fatty acids have a dimer content of at least 98% and are preferably hydrogenated) and dodecanedioic acid HOOC—(CH 2 ) 10 —COOH.
  • diamines examples include aliphatic diamines containing from 4 to 18 atoms, which may be aryl and/or saturated cyclic diamines. Examples that may be mentioned include hexamethylenediamine, piperazine, tetramethylenediamine, octamethylenediamine, decamethylenediamine, dodecamethylenediamine, 1,5-diaminohexane, 2,2,4-trimethyl-1,6-diaminohexane, diamine polyols, isophorone diamine (IPD), methylpentamethylenediamine (MPDM), bis(aminocyclohexyl)methane (BACM), bis(3-methyl-4-aminocyclohexyl)methane (BMACM), meta-xylylenediamine, bis(p-aminocyclohexyl)methane and trimethylhexamethylenediamine.
  • IPD isophorone diamine
  • MPDM methylpent
  • Examples of monomers of “diamine-diacid” type include those resulting from the condensation of hexamethylenediamine with a C6 to C36 diacid, especially the monomers: 6.6, 6.10, 6.11, 6.12, 6.14, 6.18. Mention may be made of monomers resulting from the condensation of decanediamine with a C6 to C36 diacid, especially the monomers: 10.10, 10.12, 10.14, 10.18; or resulting from the condensation of decanediamine with a terephthalic acid, i.e. the monomer 10.T.
  • copolyamides formed from the various types of monomers described above mention may be made of copolyamides resulting from the condensation of at least two ⁇ , ⁇ -aminocarboxylic acids or from two lactams or from one lactam and one ⁇ , ⁇ -aminocarboxylic acid. Mention may also be made of copolyamides resulting from the condensation of at least one ⁇ , ⁇ -aminocarboxylic acid (or a lactam), at least one diamine and at least one dicarboxylic acid.
  • copolyamides resulting from the condensation of an aliphatic diamine with an aliphatic dicarboxylic acid and at least one other monomer chosen from aliphatic diamines different than the preceding one and aliphatic diacids different than the preceding one.
  • copolyamides examples include copolymers of caprolactam and of lauryllactam (PA 6/12), copolymers of caprolactam, of hexamethylenediamine and of adipic acid (PA 6/6.6), copolymers of caprolactam, of lauryllactam, of hexamethylenediamine and of adipic acid (PA 6/12/6.6), copolymers of caprolactam, of hexamethylenediamine and of azelaic acid, of 11-aminoundecanoic acid, and of lauryllactam (PA 6/6.9/11/12), copolymers of caprolactam, of adipic acid and of hexamethylenediamine, of 11-aminoundecanoic acid, of lauryllactam (PA 6/6.6/11/12), copolymers of hexamethylenediamine, of azelaic acid and of lauryllactam (PA 6.9/12),
  • said at least one major monomer and/or said at least one minor comonomer used in the process of the invention comprise(s) 11-aminoundecanoic acid or lactam 12.
  • the process for increasing the difference Tf ⁇ Tc of polyamide-based powders includes the manufacture of copolyesteramide (CoPEA) powders, by polymerization of at least one major monomer, corresponding to the constituent monomer(s) of the base polyamide whose difference Tf ⁇ Tc it is desired to increase, and of at least one minor comonomer, comprising a lactone.
  • CoPEA copolyesteramide
  • the major monomers that may be used to manufacture the copolyesteramides are the same as those described above.
  • At least one lactam preferably chosen from caprolactam and lauryllactam, is advantageously used.
  • lactones that may be mentioned include caprolactone, valerolactone and butyrolactone.
  • Caprolactone and/or butyrolactone is preferably used.
  • said at least one major monomer and said at least one minor comonomer comprising the lactone are advantageously used in the following respective proportions of major-minor monomers (mass %) ranging from: 80-20% to 99.5-0.5% (the total being 100%).
  • the process according to the invention uses blends of copolyamide and/or of copolyesteramide.
  • the CoPAs or the CoPEAs and similarly the various monomers (minor and major) included in the composition of these CoPAs or CoPEAs, in particular the possible monomers of diamine-diacid type, are derived from the same polymerization process, irrespective of its type: hydrolytic polycondensation, anionic polymerization, cationic polymerization, etc.
  • the polymerization between the various monomers (minor and major) is of the hydrolytic polycondensation type.
  • Hydrolytic polymerization used above all for lactams, is induced by water at high temperature.
  • the hydrolytic polymerization of lactams consists in opening the lactam with water and then in heating under pressure to polymerize.
  • a catalyst such as phosphoric acid may also be employed in the hydrolytic process.
  • CoPAs or CoPEAs derived from hydrolytic polymerization mention may be made of those comprising an 11-aminoundecanoic acid major monomer and at least one minor monomer chosen from the hexamethylenediamineadipic acid couple (6.6), lauryllactam, caprolactam and/or 11-n-heptylaminoundecanoic acid.
  • the polymerization between the various monomers (minor and major) is of the anionic polymerization type.
  • Anionic polymerization is performed at temperatures much lower than those used for hydrolytic or cationic mechanisms.
  • Anionic polymerization is performed continuously or, preferably, in batch mode in a solvent.
  • the anionic route more specifically concerns cyclic molecules, such as lactams and lactones.
  • the mechanism of anionic polymerization of lactams proceeds in three steps: an initiation step to form the lactamate anion, then an activation reaction which leads to the acyllactam and finally a propagation step.
  • the anionic polymerization method is thus based essentially on the use of a catalyst and an activator optionally in the presence of a finely divided mineral or organic filler that serves as a crystallization seed and in the presence of an amide.
  • the process is described in patents EP 192 515 and EP 303 530.
  • the catalyst mention may be made of sodium or a compound thereof, such as sodium hydride or sodium methoxide.
  • lactam-N-carboxyanilides isocyanates, carbodiimides, cyanimides, acyllactams, triazines, ureas, N-substituted imides and esters, inter alia.
  • PA powder for example Orgasol® powder, silica, talc, etc.
  • N,N′-alkylenebisamide mention may be made more particularly of N,N′-ethylenebisstearamide (EBS), N,N′-ethylenebisoleamide, N,N′-ethylenebispalmitamide, gadoleamide, cetoleamide and erucamide, N,N′-dioleyldipamide and N,N′-dierucylamide, etc.
  • EBS N,N′-ethylenebisstearamide
  • N,N′-ethylenebisoleamide N,N′-ethylenebispalmitamide
  • gadoleamide cetoleamide and erucamide
  • N,N′-dioleyldipamide and N,N′-dierucylamide etc.
  • CoPAs or CoPEAs derived from anionic polymerization mention may be made of those comprising a lauryllactam major monomer and a minor monomer chosen from caprolactam, caprolactone and/or the hexamethylenediamine-adipic acid couple (6.6).
  • the very narrow particle size distribution of the powders advantageously obtained by anionic polymerization promotes their use for the manufacture of parts via radiation-mediated aggregation (infrared, UV curing, etc.) since it leads to a very fine definition of the parts, and it reduces the problems of formation of dusts during the use of the powder. Furthermore, the molecular mass of the polymer does not increase, even after long exposure to temperatures close to and below the melting temperature of the powder. This means that the powder can be recycled a large number of times without modification of its behavior during the manufacture of parts via radiation-mediated aggregation, the properties of said parts also remaining constant during the process. In addition, this process allows the manufacture via powder aggregation of an article that has good mechanical properties.
  • any other polymerization process may also be envisioned provided that all the (co)monomers used for manufacturing a CoPA or a CoPEA according to the invention can be polymerized together in the same polymerization process.
  • cationic polymerization catalyzed with acids under anhydrous conditions.
  • acids such as hydrochloric acid, phosphoric acid or hydrobromic acid are the most reactive, but the use of Lewis acids or ammonium salts is also possible.
  • Lewis acids or ammonium salts There are essentially two types of activation and of chain growth. Either the activated monomer reacts with the neutral reactive center, or it is the reactive center that is activated and the monomer is neutral.
  • CoPA or CoPEA powder or CoPA or CoPEA granules are obtained directly.
  • examples that may be mentioned include dissolution-precipitation, i.e. solubilization of the CoPA or CoPEA polymer in a hot solvent followed by precipitation of the powder by slow cooling.
  • Mention may also be made of atomization, i.e. spraying of a solution of the cooled polymer. This technique is also known as “cold nebulization” or “spray cooling”. There is also a process of polymer extrusion, followed by atomization with a heated high-pressure nozzle, and then cooling of the powder obtained. This technique is also known as “hot nebulization” or “spray drying”.
  • Mention may also be made of the milling/screening of polymer granules, optionally followed by raising the viscosity. The milling may be cryogenic. All these powder production techniques are already known to those skilled in the art.
  • powders or granules are particles of any shape from a few mm to 1 cm. They are, for example, granules obtained at an extruder outlet. Powders are preferentially used in the melting or sintering aggregation process. These powders may be up to 350 ⁇ m in size and are advantageously between 10 and 100 ⁇ m in size. Preferably, the D50 is 60 ⁇ m (i.e. 50% of the particles are less than 60 ⁇ m in size).
  • a subject of the present invention is also a copolyamide or copolyesteramide powder manufactured according to the process described previously, said powder being derived from the polymerization of at least two different monomers polymerized according to the same polymerization process, at least one of the comonomers being minor and chosen from aminocarboxylic acids, diamine-diacid couples, lactams and/or lactones as described previously, and said at least one minor comonomer representing 0.1% to 20% by mass of the total monomer blend, preferably from 0.5% to 15% by mass of the total monomer blend, preferably from 1% to 10% by mass of the total monomer blend.
  • said at least one minor comonomer represents from 1% to 7% by mass of the total blend of said monomer(s) and comonomer(s), preferably from 1% to 5% by mass of said total blend and said at least one minor comonomer comprises 11-aminoundecanoic acid and/or lauryllactam and/or caprolactam and/or caprolactone and/or at least one of the following diamine-diacid couples: 6.6, 6.10, 6.11, 6.12, 6.14, 6.18, 10.10, 10.12, 10.14, 10.18 and/or 10.T, T being terephthalic acid.
  • the powders according to the invention may also comprise additives that contribute toward improving the properties of the powder for its use in the aggregation technique.
  • additives that contribute toward improving the properties of the powder for its use in the aggregation technique. Examples that may be mentioned include pigments for coloration, TiO 2 , fillers or pigments for infrared absorption, carbon black, mineral fillers for reducing the internal stresses, and flame-retardant additives.
  • Additives for improving the mechanical properties (ultimate stress and elongation at break) of the parts obtained by melting may also be added. These fillers are, for example, glass fibers, carbon fibers, nanofillers, nanoclays and carbon nanotubes. Introducing these fillers at the time of synthesis improves their dispersion and their efficacy.
  • the powders according to the invention may be advantageously used in coatings, paints, anticorrosion compositions, paper additives, powder aggregation techniques via radiation-mediated melting or sintering for the manufacture of articles, electrophoresis gels, multilayer composite materials, the packaging industry, the toy industry, the textile industry, the motor vehicle industry and/or the electronics industry.
  • a subject of the present invention is also a process for manufacturing polyamide articles by melt-induced powder aggregation via radiation, the polyamide powder having been obtained beforehand according to the process mentioned above.
  • radiation examples include that provided by a laser beam (the process is then known as “laser sintering”). Mention may also be made of the process in which a mask is deposited between the layer of powder and the radiation source, the powder particles protected from the radiation by the mask not being aggregated.
  • a subject of the present invention is also a manufactured 3D article obtained by melting of a powder using electromagnetic radiation.
  • This article may be chosen from prototypes and models, especially in the motor vehicle, nautical, aeronautics, aerospace, medical (prostheses, auditive systems, cell tissues, etc.), textile, clothing, fashion, decorative, electronic casing, telephony, home automation, information technology and lighting sectors.
  • the comparative products 1 and the products of Examples 1.1 to 1.3 are prepared according to the same procedure in the following manner:
  • the anionic catalyst 2.7 g of sodium hydride at a purity of 60% in oil, is then added rapidly under nitrogen and the stirring is increased to 550 rpm under nitrogen at 105° C. for 30 minutes.
  • the chosen activator namely stearyl isocyanate (19.2 g made up to 220.5 g with solvent) is injected continuously into the reaction medium according to the following program:
  • the temperature is maintained at 105° C. for 180 minutes during the injection, and is then raised to 130° C. over 90 minutes and maintained at 130° C. for a further 150 minutes after the end of introduction of the isocyanate.
  • the reactor is virtually clean. After cooling to 80° C., separation by settling and drying, the powder obtained is subjected to DSC analysis.
  • Examples 1 to 3 are manufactured according to the same procedure as in the Comparative Example 1. In these Examples 1 to 3 according to the invention, a small amount of lactam 6 comonomer is used in addition to the lactam 12.
  • Examples 1.1 to 1.3 which contain a lauryllactam major monomer (lactam 12) and a caprolactam minor monomer (lactam 6), have a lower melting temperature and crystallization temperature and a greater difference
  • the various powders according to the invention are each introduced into a melt-induced powder aggregation machine and are subjected to laser radiation. After cooling the various specimens obtained, they are evaluated visually by a panel of experts.
  • Table 2 shows the influence of the process of the invention on the magnitude of the powder “caking” or “setting” or “lumps” or “clumps” defects at the surface of a 3D article obtained by laser sintering.
  • the parts thus obtained by laser sintering with the powders of Examples 1.1 to 1.3 have mechanical properties (especially the breaking modulus and the elongation at break) comparable to those of the Comparative Example 1.
  • the anionic polymerization advantageously used in the process of the invention makes it possible to limit the amount of residual monomers in the final powder, which are liable to condense on the parts of the melt-induced powder aggregation machine.
  • the precision of the 3D articles thus remains optimal and unchanged even after several manufacturing cycles.
  • the graph of FIG. 1 illustrates the impact of the content of comonomer (in this case lactam 12 or monomer 6.6) in a polyamide 11 (PA 11) on the change in the difference between Tf and Tc.
  • the graph shows that it is the comonomer 6.6 that most broadens the window (Tf ⁇ Tc) for contents of between 5% and 20%.
  • a CoPA 11/6.6 powder (7% of 6.6) is synthesized from granules obtained from hydrolytic polymerization, which are reduced to powder by cryogenic milling.
  • the powder obtained has a relative viscosity equal to 1 (20° C., as a solution at 0.5% by mass in meta-cresol).
  • Tf1 first heating
  • Tf2 second heating
  • Tc collated in Table 3 below.
  • the three powders are tested in a laser sintering machine.
  • the transformation window of the CoPA 11/6.6 powder in the machine is 14° C., which allows the SLS machine to be used under good conditions.
  • the parts manufactured from CoPA 11/6.6 have a modulus of 1786 MPa, which is close to that of PA 12 and PA 11, and an elongation at break in the range 25-30%.
  • the elongation at break of CoPA 11/6.6 is between that of polyamide 12 and that of polyamide 11.
  • the DSC values according to standard ISO 11357 are compared (Table 5) between a PA 12 (Comparative) and a polyamide 12 modified, respectively, with 6% and 12% by weight of 11-aminoundecanoic acid (examples according to the invention).
  • a decrease of 3 to 8° C. in the crystallization temperature and an increase in the difference Tf1 ⁇ Tc are found for the two PA 12 modified according to the process of the invention, compared with the homopolyamide PA 12.
  • the DSC values according to standard ISO 11357 are compared (in Table 6) between a PA 11 (Comparative) and a polyamide 11 modified, respectively, with 1% and 5% by weight of N-heptylamino acid (examples according to the invention).
  • Tf1 ⁇ Tc is greater with 1% of N-heptylamino acid than with 5% of N-heptylamino acid.

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