EP4433536A1 - Polyamide compositions comprising recycled carbon fibers and uses thereof - Google Patents

Polyamide compositions comprising recycled carbon fibers and uses thereof

Info

Publication number
EP4433536A1
EP4433536A1 EP22823139.5A EP22823139A EP4433536A1 EP 4433536 A1 EP4433536 A1 EP 4433536A1 EP 22823139 A EP22823139 A EP 22823139A EP 4433536 A1 EP4433536 A1 EP 4433536A1
Authority
EP
European Patent Office
Prior art keywords
equal
polyamide
carbon fibers
less
preferentially
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
EP22823139.5A
Other languages
German (de)
French (fr)
Inventor
Guillaume VINCENT
Mathieu SABARD
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 EP4433536A1 publication Critical patent/EP4433536A1/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/004—Additives being defined by their length
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics

Definitions

  • TITLE POLYAMIDE COMPOSITIONS COMPRISING RECYCLED CARBON FIBERS AND THEIR USES
  • the invention relates to polyamide compositions comprising recycled carbon fibers and their uses.
  • polyamides and in particular polyamide 11 (PA 11) reinforced with carbon fibers are well known for their rigidity, lightness and high mechanical performance.
  • Carbon fiber has been used for many years. The reasons why this type of fiber has become essential are simple: the material produced is extremely strong, resistant and ultra-light, characteristics that are highly prized by sports equipment manufacturers who are looking for lightness, rigidity and longevity.
  • a composition reinforced with carbon fibers will have a strong impact on CO2 emissions, in particular because the production of carbon fibers is very energy intensive, and carbon fibers are approximately 100% carbon ( VS).
  • compositions reinforced with carbon fibers but having a much lower impact on CO2 emissions, while maintaining high mechanical properties, in terms of modulus, stress, elongation and impact resistance.
  • One solution is to use recycled carbon fibers.
  • the carbon fiber can be recycled or cellulose-based
  • the plastic material (B) is chosen from the group consisting of polyamides, in particular copolyamides, polyesters, particular of copolyesters, polyurethanes, epoxy resins, polyhydroxyethers, acrylic copolymers, and mixtures or superimposed layers of two or more of these plastic materials
  • the plastic material (A) of component (a) is a thermoplastic chosen from the group consisting of acetal resins, liquid crystalline polymers, polyacrylates, polymethacrylates, olefinic and cycloolefinic polymers, polyamides, polyamide elastomers, in particular polyesteramides, polyetheramides and polyetheresteramides, polyamide-imides, polyethers, polyarylethers including polyphenylethers, polyhydroxyethers, polycarbonates, polysulfones, polyetherimides, polyimides, polyesters, polyester polycarbonates, polyoxyethylenes, polystyrenes, styrene cop
  • compositions have the disadvantage of being fragile with an elongation at break of less than 3%.
  • compositions reinforced with recycled carbon fibers that do not have the disadvantages of impact on CO2 emissions and loss of mechanical properties mentioned above.
  • the present invention therefore relates to a molding composition
  • a molding composition comprising by weight: a) from 50 to 99% of a semi-crystalline aliphatic polyamide having an inherent viscosity less than or equal to 1.10, in particular less than or equal to 1.00, in particular less than or equal to 0.95, in particular less than or equal to 0.9, as determined according to the ISO 307:2007 standard but using m-cresol instead of sulfuric acid, a temperature of 20° C and a concentration of 0.5% by mass, b) from 1 to 50% of recycled carbon fibers having an average length less than or equal to 6 mm before compounding, and surface-coated with a polyamide, in particular an aliphatic polyamide, c) from 0 to 5% of additives, the sum of components a), b) and c) being equal to 100%.
  • the inventors have therefore surprisingly found that by selecting a polyamide having an appropriate inherent viscosity as well as recycled carbon fibers sized with a polyamide, it was possible to improve the mechanical performance of polyamide formulations as well as CO2 emissions compared to polyamide formulations reinforced with virgin carbon fibers.
  • a molding composition is generally prepared by mixing the various ingredients of the latter in the molten state in an extruder, in particular a twin-screw extruder.
  • the compounded material emerges from the extruder in the form of rods which are then cooled and cut into granules.
  • before compounding therefore means that the recycled carbon fibers which are introduced into the extruder at the time of implementation have an average length less than or equal to 6 mm.
  • a semi-crystalline polyamide designates a polyamide which has a glass transition temperature (Tg) and a melting temperature (Tf) determined respectively according to the ISO 11357-2 and 3:2013 standards, and a enthalpy of crystallization during the cooling step at a rate of 20 K/min in DSC measured according to standard ISO 11357-3 of 2013 greater than 30 J/g, preferably greater than 35 J/g.
  • Tg glass transition temperature
  • Tf melting temperature
  • the polyamide can be a homopolyamide or a copolyamide or a mixture thereof.
  • the average number of carbon atoms relative to the nitrogen atom is greater than or equal to 6.
  • the semi-crystalline aliphatic polyamide is excluding PA6 and PA66.
  • the average number of carbon atoms relative to the nitrogen atom is greater than or equal to 8, in particular greater than or equal to 9, in particular greater than or equal to 10.
  • the average number of carbon atoms relative to the nitrogen atom is greater than or equal to 8 and the semi-crystalline aliphatic polyamide is excluding PA612.
  • the number of carbon atoms per nitrogen atom is the average of the X unit and of the Y unit.
  • the number of carbon per nitrogen is calculated according to the same principle. The calculation is carried out in molar proportion of the various amide units.
  • the semi-crystalline aliphatic polyamide is obtained from the polycondensation of at least one aminocarboxylic acid comprising from 6 to 18 carbon atoms, preferably from 9 to 18 carbon atoms, plus preferentially from 10 to 18 carbon atoms, even more preferentially from 10 to 12 carbon atoms.
  • 6-aminohexanoic acid 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, 13-aminotridecanoic acid, 14-aminotetradecanoic acid, 15-aminopentadecanoic acid, 16-aminohexadecanoic acid, 17-aminoheptadecanoic acid, 18-aminooctadecanoic acid.
  • it is obtained from the polycondensation of a single aminocarboxylic acid.
  • the semi-crystalline aliphatic polyamide is obtained from the polycondensation of at least one lactam comprising from 6 to 18 carbon atoms, preferentially from 9 to 18 carbon atoms, more preferentially from 10 to 18 carbon atoms, even more preferably from 10 to 12 carbon atoms.
  • it is obtained from the polycondensation of a single lactam.
  • the semi-crystalline aliphatic polyamide is obtained from the polycondensation of at least one aliphatic diamine comprising from 4 to 36 carbon atoms, advantageously from 6 to 18 carbon atoms, advantageously from 6 to 12 carbon atoms, advantageously from 10 to 12 carbon atoms and from at least one aliphatic dicarboxylic acid comprising from 4 to 36 carbon atoms, advantageously from 6 to 18 carbon atoms, advantageously from 6 to 12 carbon, advantageously from 10 to 12 carbon atoms.
  • the aliphatic diamine used to obtain this repetitive unit X.Y is an aliphatic diamine which has a linear main chain comprising at least 4 carbon atoms.
  • This linear main chain may, where appropriate, comprise one or more methyl and/or ethyl substituents; in this last configuration, one speaks of "branched aliphatic diamine". In the case where the main chain contains no substituent, the aliphatic diamine is called “linear aliphatic diamine”.
  • the aliphatic diamine used to obtain this repeating unit XY comprises from 4 to 36 carbon atoms, advantageously from 4 to 18 carbon atoms, advantageously from 6 to 18 carbon atoms, advantageously from 6 to 14 carbon atoms.
  • this diamine is a linear aliphatic diamine, it then has the formula H2N-(CH2)x-NH2 and can be chosen, for example, from butanediamine, pentanediamine, hexanediamine, heptanediamine, octanediamine, nonanediamine , decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, hexadecanediamine, octadecanediamine and octadecanediamine.
  • the linear aliphatic diamines which have just been cited can all be bioresourced within the meaning of standard ASTM D6866.
  • this diamine is a branched aliphatic diamine, it may in particular be 2-methylpentanediamine, 2-methyl-1,8-octanediamine or trimethylene (2,2,4 or 2,4,4) hexanediamine.
  • the dicarboxylic acid can be chosen from aliphatic, linear or branched dicarboxylic acids.
  • the dicarboxylic acid is aliphatic and linear, it can be chosen from succinic acid (4), pentanedioic acid (5), adipic acid (6), heptanedioic acid (7), octanedioic acid (8), azelaic acid (9), sebacic acid (10), undecanedioic acid (11), dodecanedioic acid (12), brassylic acid (13), tetradecanedioic acid ( 14), hexadecanedioic acid (16), octadecanedioic acid (18), octadecanedioic acid (18), eicosanedioic acid (20), docosanedioic acid (22) and fatty acid dimers containing 36 carbons.
  • succinic acid (4) pentanedioic acid (5), adipic acid (6), heptanedioic acid (7),
  • the fatty acid dimers mentioned above are dimerized fatty acids obtained by oligomerization or polymerization of unsaturated monobasic fatty acids with a long hydrocarbon chain (such as linoleic acid and oleic acid), as described in particular in the document EP 0471 566.
  • the semi-crystalline aliphatic polyamide is obtained from a mixture of these three variants.
  • the semi-crystalline aliphatic polyamide is obtained from the polycondensation of at least one aminocarboxylic acid comprising from 6 to 18 carbon atoms, preferentially from 8 to 12 carbon atoms, plus preferably from 10 to 12 carbon atoms.
  • the semi-crystalline aliphatic polyamide is obtained from the polycondensation of at least one lactam comprising from 6 to 18 carbon atoms, preferentially from 8 to 12 carbon atoms, more preferentially 10 to 12 carbon atoms.
  • said semi-crystalline polyamide is chosen from PA610, PA612, PA1010, PA1012, PA1212, PAU and PA12, in particular PA1010, PA1012, PA1212, PAU, PA12.
  • said semi-crystalline polyamide is chosen from PAU and PA12, in particular PAU.
  • said semi-crystalline polyamide of said composition consists of at least 30% by weight, in particular of at least 50% of recycled semi-crystalline polyamide.
  • the recycled carbon fibers in the semi-crystalline aliphatic polyamide molding composition according to the invention are present preferably from 1.0 to 50.0% by weight, preferably from 10.0 to 40.0%, more preferably from 20.0 to 40.0% by weight, even more preferably from 25.0 to 40.0% by weight, each based on the sum of the constituents of the composition.
  • the recycled carbon fibers used in the semi-crystalline aliphatic polyamide molding composition can be in the form of chopped (or short) fibers or in the form of bundles of chopped (or short) fibers or in the form of ground carbon fibers.
  • the carbon fibers are preferably cut (or short) carbon fibers and have an average length of from 0.1 to 6 mm, in particular from 2 to 6 mm.
  • the ground carbon fibers have an average length ranging from 50 ⁇ m to 400 ⁇ m.
  • the ground carbon fibers After compounding, in the composition to be molded, the ground carbon fibers have an average length of less than 400 ⁇ m.
  • the short carbon fibers After compounding, in the composition to be molded, the short carbon fibers have an average length comprised from 100 to 600 ⁇ m, in particular from 150 to 500 ⁇ m.
  • the recycled carbon fibers used are coated on the surface (size).
  • a coating (size) must be compatible with the plastic matrix in order to ensure good coating, good adhesion and the best possible reinforcement effect.
  • the polyamide size of the recycled carbon fiber can be a semi-aromatic polyamide or an aliphatic polyamide or a mixture of these.
  • said polyamide is an aliphatic polyamide.
  • said aliphatic polyamide is a semi-crystalline polyamide, in particular having an average number of carbon atoms per nitrogen atom (C/N) less than or equal to 10, in particular less than or equal to 9, in particular less than or equal to 8, in particular less than or equal to 6.
  • said semi-crystalline aliphatic polyamide is chosen from PA6, PA66 and a mixture thereof.
  • the recycled carbon fibers are sized with said polyamide, in particular said aliphatic polyamide, in a range ranging from 0.5 to 6%, in particular from 1 to 5%, in particular from 1.5 to 4% by weight per ratio of total carbon fibers-sizing.
  • the carbon footprint of the recycled carbon fibers is at least halved compared to the footprint of the virgin carbon fibers as determined according to the LCA (Life Cycle Analysis) method in order to determine the environmental impact according to international standards ISO 14040:2006, ISO 14044:2006 and/or ISO 14067:2018.
  • LCA Life Cycle Analysis
  • the additive is optional and comprised from 0 to 5.0%, in particular from 0.1 to 5.0% by weight.
  • the additive is selected from fillers, glass beads, colorants, stabilizers, plasticizers, surfactants, nucleating agents, pigments, brighteners, antioxidants, lubricants, flame retardants, natural waxes and their mixtures.
  • fillers are excluding carbon fibers, whether recycled or not.
  • the additive is chosen from fillers, colorants, stabilizers, plasticizers, surfactants, nucleating agents, pigments, brighteners, antioxidants, flame retardants, natural waxes and mixtures thereof.
  • the additive is chosen from dyes, stabilizers, nucleating agents, pigments, brighteners, antioxidants, natural waxes and mixtures thereof.
  • the stabilizer can be a UV stabilizer, an organic stabilizer or more generally a combination of organic stabilizers, such as a phenol-type antioxidant (for example of the type of that of irganox 245 or 1098 or 1010 of the company Ciba-BASF), a phosphite-type antioxidant (for example irgafos® 126 from Ciba-BASF) and even possibly other stabilizers such as a HALS, which means Hindered Amine Light Stabilizer or amine-type light stabilizer encumbered (for example Tinuvin 770 from the company Ciba-BASF), an anti-UV (for example Tinuvin 312 from the company Ciba), a stabilizer based on phosphorus. It is also possible to use antioxidants of the amine type such as Naugard 445 from the company Crompton or alternatively polyfunctional stabilizers such as Nylostab S-EED from the company Clariant.
  • organic stabilizers such as a phenol-type antioxidant (
  • This stabilizer can also be an inorganic stabilizer, such as a copper-based stabilizer.
  • a copper-based stabilizer By way of example of such mineral stabilizers, mention may be made of copper halides and acetates. Incidentally, one can possibly consider other metals such as silver, but these are known to be less effective. These copper-based compounds are typically associated with alkali metal halides, particularly potassium.
  • the plasticizers are chosen from benzene sulfonamide derivatives, such as n-butyl benzene sulfonamide (BBSA); ethyl toluene sulfonamide or N-cyclohexyl toluene sulfonamide; hydroxybenzoic acid esters, such as ethyl-2-parahydroxybenzoate hexyl and decyl-2-hexyl parahydroxybenzoate; tetrahydrofurfuryl alcohol esters or ethers, such as oligoethyleneoxytetrahydrofurfuryl alcohol; and esters of citric acid or hydroxy-malonic acid, such as oligoethyleneoxy malonate.
  • BBSA n-butyl benzene sulfonamide
  • ethyl toluene sulfonamide or N-cyclohexyl toluene sulfonamide hydroxybenzoic acid esters,
  • the fillers can be chosen from silica, graphite, expanded graphite, carbon black, kaolin, magnesia, slag, talc, wollastonite, nanofillers (carbon nanotubes), pigments, metal oxides (titanium oxide), metals, advantageously wollastonite and talc, preferentially talc.
  • the molding composition is as defined above and comprises in a first embodiment by weight: a) from 50 to 99% of a semi-crystalline aliphatic polyamide having an inherent viscosity less than or equal to 1.10, in in particular less than or equal to 1.00, in particular less than or equal to 0.95, in particular less than or equal to 0.9, as determined according to standard ISO 307:2007 but using m-cresol instead of l sulfuric acid, a temperature of 20° C.
  • recycled carbon fibers having an average length less than or equal to 6 mm before compounding, said recycled carbon fibers being surface-coated (sized) with a polyamide, in particular an aliphatic polyamide, c) from 0 to 5% of at least one additive, the sum of components a), b) and c) being equal to 100%.
  • it comprises by weight: a) from 50 to 98.9% of a semi-crystalline aliphatic polyamide having an inherent viscosity less than or equal to 1.10, in particular less than or equal to 1.00, in particular less than or equal to 0.95, in particular less than or equal to 0.9, as determined according to standard ISO 307:2007 but using m-cresol instead of sulfuric acid, a temperature of 20°C and a concentration from 0.5% by mass, b) from 1 to 50% of recycled carbon fibers having an average length less than or equal to 6 mm before compounding, said recycled carbon fibers being surface-coated (sized) with a polyamide, in particular an aliphatic polyamide, c) from 0.1 to 5% of at least one additive, the sum of the components a), b) and c) being equal to 100%.
  • a semi-crystalline aliphatic polyamide having an inherent viscosity less than or equal to 1.10, in particular less than or equal to 1.00, in particular less than or equal to 0.95, in particular
  • it comprises by weight: a) from 60 to 89.9% of a semi-crystalline aliphatic polyamide having an inherent viscosity less than or equal to 1.10, in particular less than or equal to 1.00, in particular less than or equal to 0.95, in particular less than or equal to 0.9, as determined according to ISO 307:2007 but using m-cresol instead of sulfuric acid, a temperature of 20°C and a concentration of 0.5% by mass, b) from 10 to 40% of recycled carbon fibers having an average length less than or equal to 6 mm before compounding, said recycled carbon fibers being surface-coated (sized) with a polyamide, in particular a aliphatic polyamide, c) from 0.1 to 5% of at least one additive, the sum of components a), b) and c) being equal to 100%.
  • it comprises by weight: a) from 60 to 79.9% of a semi-crystalline aliphatic polyamide having an inherent viscosity less than or equal to 1.10, in particular less than or equal to 1.00, in particular less than or equal to 0.95, in particular less than or equal to 0.9, as determined according to standard ISO 307:2007 but using m-cresol instead of sulfuric acid, a temperature of 20°C and a concentration of 0.5% by mass, b) from 20 to 40% of recycled carbon fibers having an average length less than or equal to to 6 mm before compounding, said recycled carbon fibers being surface-coated (sized) with a polyamide, in particular an aliphatic polyamide, c) from 0.1 to 5% of at least one additive, the sum of the components a) , b) and c) being equal to 100%.
  • a third variant it comprises by weight: a) from 60 to 75% of a semi-crystalline aliphatic polyamide having an inherent viscosity less than or equal to 1.10, in particular less than or equal to 1.00, in particular less or equal to 0.95, in particular less than or equal to 0.9, as determined according to standard ISO 307:2007 but using m-cresol instead of sulfuric acid, a temperature of 20°C and a concentration from 0.5% by mass, b) from 25 to 40% of recycled carbon fibers having an average length less than or equal to 6 mm before compounding, said recycled carbon fibers being surface-coated (sized) with a polyamide, in particular an aliphatic polyamide, c) from 0 to 5% of at least one additive, the sum of the components a), b) and c) being equal to 100%.
  • it comprises by weight: a) from 60 to 74.9% of a semi-crystalline aliphatic polyamide having an inherent viscosity less than or equal to 1.10, in particular less than or equal to 1.00, in particular less than or equal to 0.95, in particular less than or equal to 0.9, as determined according to standard ISO 307:2007 but using m-cresol instead of sulfuric acid, a temperature of 20°C and a concentration from 0.5% by mass, b) from 25 to 40% of recycled carbon fibers having an average length less than or equal to 6 mm before compounding, said recycled carbon fibers being surface-coated (sized) with a polyamide, in particular an aliphatic polyamide, c) from 0.1 to 5% of at least one additive, the sum of the components a), b) and c) being equal to 100%.
  • a semi-crystalline aliphatic polyamide having an inherent viscosity less than or equal to 1.10, in particular less than or equal to 1.00, in particular less than or equal to 0.95, in particular
  • said composition of the invention consists of the various elements a, b and c, their sum being equal to 100% by weight defined in the first embodiment and of the three variants with their particular embodiment defined above.
  • said composition is characterized in that the mechanical properties thereof are at least equivalent to those of the same composition but comprising virgin carbon fibers having a length average less than or equal to 6 mm in place of recycled carbon fibers before the compounding step, said virgin carbon fibers being surface-coated (sized) with the same polyamide or a polymer other than a polyamide.
  • the resilience as measured by charpy impact on unnotched bars leU at 23° C. of the compositions according to the invention is more than 10% higher than that obtained with virgin carbon fibers sized with a polyamide or with fibers recycled carbon but sized with a polymer other than a polyamide.
  • the elongation at break of the compositions according to the invention is more than 10% greater than that obtained with virgin carbon fibers sized with a polyamide or with recycled carbon fibers but sized with a polymer other than a polyamide.
  • the resilience as measured by charpy impact on unnotched bars leU at 23° C. of the compositions according to the invention is greater by more than 10% than that obtained with virgin carbon fibers sized with a polyamide or with recycled carbon fibers but sized with a polymer other than a polyamide.
  • the resilience as measured by Charpy impact on unnotched bars leU at 23° C. and the elongation at break of the compositions according to the invention are more than 10% higher than those obtained with fibers of virgin carbon sized with a polyamide or with recycled carbon fibers but sized with a polymer other than a polyamide.
  • the present invention relates to the use of a composition as defined above, for the manufacture of articles obtained by injection chosen from a sports article, in particular a sports shoe, in particular a ski or a part of a ski boot or a rigid shoe with cleats, such as a soccer, rugby or American football shoe, a hockey shoe or a part of a hockey shoe, or a running shoe, a golf ball or a part of a golf ball, or a stick in the sport of lacrosse, a hockey article such as a helmet, and sports articles for the protection of the head, shoulders, elbows, hands, knees, back or shin, such as helmet, gloves, shoulder pads, elbow pads, knee pads or shin guards.
  • a sports article in particular a sports shoe, in particular a ski or a part of a ski boot or a rigid shoe with cleats, such as a soccer, rugby or American football shoe, a hockey shoe or a part of a hockey shoe, or a running shoe, a golf ball or
  • the present invention relates to the use of a molding composition as defined above, for the manufacture of an article for electronics, for the automobile, for telecom applications or for the exchange of data, such as for an autonomous vehicle or for applications connected to each other.
  • the present invention relates to an article obtained by injection molding of a composition as defined above.
  • compositions in Table I were prepared by melt blending the polymer pellets with the carbon fibers and the additives. This mixture was carried out by compounding on a co-rotating twin-screw extruder with a diameter of 26 mm with a temperature profile (T°) flat at 240°C. The screw speed is 200 rpm and the flow rate is 16 kg/h.
  • the introduction of the carbon fibers is carried out by lateral force-feeding.
  • the polyamide(s) and the additives are added during the compounding process in the main hopper.
  • compositions were then molded on an injection molding machine at a material temperature of 260°C and a mold temperature of 60°C in the form of dumbbells or bars in order to study the mechanical properties according to the standards below [Table I]
  • Virgin PAN and recycled PAN carbon fibers with polyurethane or polyamide sizing are marketed for example by Mitsubishi, SGL, ACECA, Teijin, Zoltek or Hexcel.
  • the tensile modulus, the elongation and the breaking stress were measured at 23° C. according to the ISO 527-1: 2012 standard on a dry sample.
  • the machine used is of the INSTRON 5966 type.
  • the speed of the crosshead is 1 mm/min for measuring the modulus and 5 mm/min for the stress at break and the elongation at break.
  • the test conditions are 23°C +/- 2°C, on dry samples.
  • the impact resistance was determined according to ISO 179-1: 2010 (Charpy impact) on bars measuring 80mm x 10mm x 4mm, notched and unnotched, at a temperature of 23°C +/- 2°C under humidity. relative humidity of 50% +/- 10% or at -30°C +/-2°C under a relative humidity of 50% +/- 10% on dry samples.
  • compositions based on recycled carbon fibers sized with a polyamide are better than those of compositions based on virgin carbon fibers sized with a polyamide or virgin carbon fibers sized with another polymer.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to a molding composition comprising by weight: a) from 50% to 99% of a semi-crystalline aliphatic polyamide having an inherent viscosity of less than or equal to 1.10, in particular less than or equal to 1.00, in particular less than or equal to 0.95, notably less than or equal to 0.9, as determined according to standard ISO 307:2007 but using m-cresol in place of sulfuric acid, a temperature of 20°C and a concentration of 0.5% by weight, b) from 1% to 50% of recycled carbon fibers having an average length of less than or equal to 6 mm before compounding, said recycled carbon fibers being surface-coated (sized) with a polyamide, in particular an aliphatic polyamide, c) from 0 to 5% of at least one additive, the sum of the components a), b) and c) being equal to 100%.

Description

DESCRIPTION DESCRIPTION
TITRE : COMPOSITIONS DE POLYAMIDE COMPRENANT DES FIBRES DE CARBONE RECYCLEES ET LEURS UTILISATIONS TITLE: POLYAMIDE COMPOSITIONS COMPRISING RECYCLED CARBON FIBERS AND THEIR USES
L'invention porte sur des compositions de polyamide comprenant des fibres de carbone recyclées et leurs utilisations. The invention relates to polyamide compositions comprising recycled carbon fibers and their uses.
[Technique antérieure] [prior technique]
Dans les applications liées au sport, les polyamides et en particulier le polyamide 11 (PA 11) renforcés avec des fibres de carbone sont bien connus pour leur rigidité, leur légèreté et leurs performances mécaniques élevées. In sports-related applications, polyamides and in particular polyamide 11 (PA 11) reinforced with carbon fibers are well known for their rigidity, lightness and high mechanical performance.
La fibre de carbone est utilisée depuis de nombreuses années. Les raisons pour lesquelles ce type de fibre est devenu incontournable sont simples : le matériel fabriqué est extrêmement solide, résistant et ultraléger, des caractéristiques qui sont très prisées par des équipementiers sportifs qui recherchent légèreté, rigidité et longévité. Carbon fiber has been used for many years. The reasons why this type of fiber has become essential are simple: the material produced is extremely strong, resistant and ultra-light, characteristics that are highly prized by sports equipment manufacturers who are looking for lightness, rigidity and longevity.
Aujourd'hui, la durabilité d'un produit est essentielle pour le consommateur et est devenue une exigence clé pour les grandes marques de sport. Today, the durability of a product is essential for the consumer and has become a key requirement for major sports brands.
Une composition renforcée avec des fibres de carbone aura un impact fort sur les émissions de CO2, en particulier parce que la production de fibres de carbone est fortement consommatrice d'énergie, et que les fibres de carbone sont à environ 100 % constituées de carbone (C). A composition reinforced with carbon fibers will have a strong impact on CO2 emissions, in particular because the production of carbon fibers is very energy intensive, and carbon fibers are approximately 100% carbon ( VS).
Il est donc nécessaire de disposer de compositions renforcées par des fibres de carbone mais présentant un impact bien moins important sur les émissions de CO2, tout en maintenant des propriétés mécaniques élevées, en termes de module, contrainte, allongement et résistance à l'impact. It is therefore necessary to have compositions reinforced with carbon fibers but having a much lower impact on CO2 emissions, while maintaining high mechanical properties, in terms of modulus, stress, elongation and impact resistance.
Une solution consiste à utiliser des fibres de carbone recyclées. One solution is to use recycled carbon fibers.
Ainsi la demande internationale WO 2015/074945 décrit une masse de moulage ayant la composition suivante : Thus international application WO 2015/074945 describes a molding mass having the following composition:
(a) de 49 à 97 % en poids d'au moins une matière plastique (A) formant une matrice, (a) from 49 to 97% by weight of at least one plastic material (A) forming a matrix,
(b) de 3 à 40 % en poids d'au moins une fibre de carbone recouverte au moins d'une matière plastique (B), (b) from 3 to 40% by weight of at least one carbon fiber covered with at least one plastic material (B),
(c) de 0 à 48 % en poids d'au moins un autre additif (C), (c) from 0 to 48% by weight of at least one other additive (C),
La somme des composants (a) à (c) représentant 100 % en poids, caractérisée en ce que la masse de moulage plastique a une résistance surfacique spécifique de lxlO7 à lxlO22 ohm et une résistance volumique spécifique de lxlO5 à lxlO20 ohm*m, toutes deux déterminées conformément à la CEI 60093. The sum of components (a) to (c) representing 100% by weight, characterized in that the plastic molding mass has a specific surface resistance of 1x10 7 to 1x10 22 ohm and a specific volumetric resistance of 1x10 5 to 1x10 20 ohm *m, both determined according to IEC 60093.
La fibre de carbone peut être recyclée ou à base de cellulose, la matière plastique (B) est choisie à partir du groupe composé de polyamides, en particulier de copolyamides, de polyesters, en particulier de copolyesters, de polyuréthanes, résines époxy, polyhydroxyéthers, copolymères acryliques, et des mélanges ou des couches superposées de deux ou plus de ces matières plastiques, et la matière plastique (A) du composant (a) est un thermoplastique choisi à partir du groupe composé de résines acétal, de polymères liquides cristallins, polyacrylates, polyméthacrylates, polymères oléfiniques et cyclooléfiniques, polyamides, élastomères polyamides, en particulier des polyesteramides, des polyétheramides et des polyétherestéramides, polyamide-imides, polyéthers, des polyaryléthers en ce compris des polyphényléthers, des polyhydroxyéthers, polycarbonates, polysulfones, polyétherimides, polyimides, polyesters, polycarbonates de polyester, polyoxyéthylènes, polystyrènes, copolymères de styrène, polysulfones, polymères vinyliques comme le polychlorure de vinyle et le polyacétate de vinyle, et des mélanges de deux ou plus des thermoplastiques mentionnés, ou un duroplaste choisi à partir du groupe composé de résines de mélamine, phénoplastes, résines de polyester, aminoplastes, résines époxy, polyuréthanes, polyacrylates réticulés, et des mélanges de deux ou plus des duroplastes mentionnés. The carbon fiber can be recycled or cellulose-based, the plastic material (B) is chosen from the group consisting of polyamides, in particular copolyamides, polyesters, particular of copolyesters, polyurethanes, epoxy resins, polyhydroxyethers, acrylic copolymers, and mixtures or superimposed layers of two or more of these plastic materials, and the plastic material (A) of component (a) is a thermoplastic chosen from the group consisting of acetal resins, liquid crystalline polymers, polyacrylates, polymethacrylates, olefinic and cycloolefinic polymers, polyamides, polyamide elastomers, in particular polyesteramides, polyetheramides and polyetheresteramides, polyamide-imides, polyethers, polyarylethers including polyphenylethers, polyhydroxyethers, polycarbonates, polysulfones, polyetherimides, polyimides, polyesters, polyester polycarbonates, polyoxyethylenes, polystyrenes, styrene copolymers, polysulfones, vinyl polymers such as polyvinyl chloride and polyvinyl acetate, and mixtures of two or more of the mentioned thermoplastics , or a duroplast selected from the group consisting of melamine resins, phenoplasts, polyester resins, aminoplasts, epoxy resins, cross-linked polyurethanes, polyacrylates, and mixtures of two or more of the mentioned duroplasts.
Néanmoins ces compositions présentent le désavantage d'être fragiles avec un allongement à la rupture inférieur à 3%. Nevertheless, these compositions have the disadvantage of being fragile with an elongation at break of less than 3%.
Il arrive que certaines matières recyclées aient été altérés de par leur historique et leur vécu et donc que leurs performances, en particulier mécaniques, soient inférieures par rapport aux matériaux vierges, ce qui ne satisfait pas aux exigences des compositions à base de polymères de hautes performances tel que le PA11. It happens that some recycled materials have been altered by their history and their experience and therefore that their performance, in particular mechanical, is lower compared to virgin materials, which does not meet the requirements of compositions based on high performance polymers. such as the PA11.
Il est donc nécessaire de disposer de compositions renforcées par des fibres de carbone recyclées ne présentant pas les inconvénients d'impact sur les émissions de CO2 et de perte de propriétés mécaniques cités ci-dessus. It is therefore necessary to have compositions reinforced with recycled carbon fibers that do not have the disadvantages of impact on CO2 emissions and loss of mechanical properties mentioned above.
La présente invention concerne donc une composition de moulage comprenant en poids : a) de 50 à 99% d'un polyamide aliphatique semi-cristallin présentant une viscosité inhérente inférieure ou égale à 1,10, en particulier inférieur ou égale à 1,00, en particulier inférieur ou égale à 0,95, notamment inférieur ou égale à 0,9, telle que déterminée selon la norme ISO 307 :2007 mais en utilisant du m-crésol à la place de l'acide sulfurique, une température de 20°C et une concentration de 0,5% massique, b) de 1 à 50% de fibres de carbone recyclées présentant une longueur moyenne inférieure ou égale à 6 mm avant compoundage, et revêtues en surface par un polyamide, en particulier un polyamide aliphatique, c) de 0 à 5% d'additifs, la somme des composants a), b) et c) étant égale à 100%. The present invention therefore relates to a molding composition comprising by weight: a) from 50 to 99% of a semi-crystalline aliphatic polyamide having an inherent viscosity less than or equal to 1.10, in particular less than or equal to 1.00, in particular less than or equal to 0.95, in particular less than or equal to 0.9, as determined according to the ISO 307:2007 standard but using m-cresol instead of sulfuric acid, a temperature of 20° C and a concentration of 0.5% by mass, b) from 1 to 50% of recycled carbon fibers having an average length less than or equal to 6 mm before compounding, and surface-coated with a polyamide, in particular an aliphatic polyamide, c) from 0 to 5% of additives, the sum of components a), b) and c) being equal to 100%.
Les inventeurs ont donc trouvé de manière étonnante qu'en sélectionnant un polyamide présentant une viscosité inhérente appropriée ainsi que des fibres de carbone recyclées ensimées avec un polyamide, il était possible d'améliorer les performances mécaniques de formulations de polyamide ainsi que les émissions de CO2 en comparaison de formulations de polyamides renforcées avec des fibres de carbone vierges. The inventors have therefore surprisingly found that by selecting a polyamide having an appropriate inherent viscosity as well as recycled carbon fibers sized with a polyamide, it was possible to improve the mechanical performance of polyamide formulations as well as CO2 emissions compared to polyamide formulations reinforced with virgin carbon fibers.
Une composition de moulage est en règle général préparée par mélange à l'état fondu des différents ingrédients de celle-ci dans une extrudeuse, en particulier une extrudeuse bi-vis. La matière compoundée ressort de l'extrudeuse sous forme de joncs qui sont ensuite refroidis et découpés en granulés. A molding composition is generally prepared by mixing the various ingredients of the latter in the molten state in an extruder, in particular a twin-screw extruder. The compounded material emerges from the extruder in the form of rods which are then cooled and cut into granules.
Le terme « avant compoundage » signifie donc que les fibres de carbone recyclées qui sont introduites dans l'extrudeuse au moment de la mise en oeuvre présentent une longueur moyenne inférieure ou égale à 6 mm. The term “before compounding” therefore means that the recycled carbon fibers which are introduced into the extruder at the time of implementation have an average length less than or equal to 6 mm.
S'agissant du polyamide aliphatique semi-cristallin (a): Regarding the semi-crystalline aliphatic polyamide (a):
La nomenclature utilisée pour définir les polyamides est décrite dans la norme ISO 1874-1:2011 "Plastiques - Matériaux polyamides (PA) pour moulage et extrusion - Partie 1 : Désignation", notamment en page 3 (tableaux 1 et 2) et est bien connue de l'homme du métier. The nomenclature used to define polyamides is described in standard ISO 1874-1:2011 "Plastics - Polyamide (PA) materials for molding and extrusion - Part 1: Designation", in particular on page 3 (tables 1 and 2) and is well known to those skilled in the art.
Un polyamide semi-cristallin, au sens de l'invention, désigne un polyamide qui présente une température de transition vitreuse (Tg) et une température de fusion (Tf) déterminées respectivement selon la norme ISO 11357-2 et 3 :2013, et une enthalpie de cristallisation lors de l'étape de refroidissement à une vitesse de 20K/min en DSC mesurée selon la norme ISO 11357-3 de 2013 supérieure à 30 J/g, de préférence supérieure à 35 J/g. A semi-crystalline polyamide, within the meaning of the invention, designates a polyamide which has a glass transition temperature (Tg) and a melting temperature (Tf) determined respectively according to the ISO 11357-2 and 3:2013 standards, and a enthalpy of crystallization during the cooling step at a rate of 20 K/min in DSC measured according to standard ISO 11357-3 of 2013 greater than 30 J/g, preferably greater than 35 J/g.
Le polyamide peut être un homopolyamide ou un copolyamide ou un mélange de ceux-ci. The polyamide can be a homopolyamide or a copolyamide or a mixture thereof.
Le polyamide aliphatique semi-cristallin présentant une viscosité inhérente inférieure ou égale à 1,10, en particulier inférieur ou égale à 1,00, en particulier inférieur ou égale à 0,95, notamment inférieur ou égale à 0,9, telle que déterminée selon la norme ISO 307 :2007 mais en utilisant du m-crésol à la place de l'acide sulfurique, une température de 20°C et une concentration de 0,5% massique, est présent de 50 à 99% dans la composition, de préférence de 60,0 à 90,0%, plus préférentiellement de 60,0 à 80,0% en poids, encore plus préférentiellement de 65,0 à 80,0% en poids, chacun basé sur la somme des constituants de la composition. The semi-crystalline aliphatic polyamide having an inherent viscosity less than or equal to 1.10, in particular less than or equal to 1.00, in particular less than or equal to 0.95, in particular less than or equal to 0.9, as determined according to ISO 307:2007 but using m-cresol instead of sulfuric acid, a temperature of 20°C and a concentration of 0.5% by mass, is present from 50 to 99% in the composition, preferably 60.0 to 90.0%, more preferably 60.0 to 80.0% by weight, even more preferably 65.0 to 80.0% by weight, each based on the sum of the constituents of the composition.
Le nombre moyen d'atome de carbone par rapport à l'atome d'azote est supérieur à ou égal à 6. Avantageusement, le polyamide aliphatique semi-cristallin est à l'exclusion de PA6 et PA66. The average number of carbon atoms relative to the nitrogen atom is greater than or equal to 6. Advantageously, the semi-crystalline aliphatic polyamide is excluding PA6 and PA66.
Avantageusement, le nombre moyen d'atome de carbone par rapport à l'atome d'azote est supérieur ou égal à 8, en particulier supérieur ou égal à 9, notamment supérieur ou égal à 10. Advantageously, the average number of carbon atoms relative to the nitrogen atom is greater than or equal to 8, in particular greater than or equal to 9, in particular greater than or equal to 10.
Avantageusement, le nombre moyen d'atome de carbone par rapport à l'atome d'azote est supérieur ou égal à 8 et le polyamide aliphatique semi-cristallin est à l'exclusion de PA612. Advantageously, the average number of carbon atoms relative to the nitrogen atom is greater than or equal to 8 and the semi-crystalline aliphatic polyamide is excluding PA612.
Dans le cas d'un homopolyamide de type PA-X.Y, le nombre d'atomes de carbone par atome d'azote est la moyenne du motif X et du motif Y. Dans le cas d'un copolyamide, le nombre de carbone par azote se calcule selon le même principe. Le calcul est réalisé au prorata molaire des différents motifs amides. In the case of a homopolyamide of the PA-XY type, the number of carbon atoms per nitrogen atom is the average of the X unit and of the Y unit. In the case of a copolyamide, the number of carbon per nitrogen is calculated according to the same principle. The calculation is carried out in molar proportion of the various amide units.
Dans un premier mode de réalisation : In a first embodiment:
Dans une première variante de ce premier mode de réalisation, le polyamide aliphatique semi-cristallin est obtenu à partir de la polycondensation d'au moins un acide aminocarboxylique comprenant de 6 à 18 atomes de carbone, préférentiellement de 9 à 18 atomes de carbone, plus préférentiellement de 10 à 18 atomes de carbone, encore plus préférentiellement de 10 à 12 atomes de carbone. Il peut ainsi être choisi parmi l'acide 6-aminohexanoïque, l'acide 7-aminoheptanoïque, l'acide 8-aminooctanoïque, l'acide 9-aminononanoïque, l'acide 10-aminodécanoïque, l'acide 11-aminoundécanoïque et l'acide 12- aminododécanoïque, l'acide 13-aminotridécanoïque, l'acide 14-aminotetradécanoïque, l'acide 15- aminopentadécanoïque, l'acide 16-aminohexadécanoïque, l'acide 17-aminoheptadécanoïque, l'acide 18-aminooctadécanoïque. In a first variant of this first embodiment, the semi-crystalline aliphatic polyamide is obtained from the polycondensation of at least one aminocarboxylic acid comprising from 6 to 18 carbon atoms, preferably from 9 to 18 carbon atoms, plus preferentially from 10 to 18 carbon atoms, even more preferentially from 10 to 12 carbon atoms. It can thus be chosen from 6-aminohexanoic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, 13-aminotridecanoic acid, 14-aminotetradecanoic acid, 15-aminopentadecanoic acid, 16-aminohexadecanoic acid, 17-aminoheptadecanoic acid, 18-aminooctadecanoic acid.
Préférentiellement, il est obtenu à partir de la polycondensation d'un seul acide aminocarboxylique.Preferably, it is obtained from the polycondensation of a single aminocarboxylic acid.
Dans une deuxième variante de ce premier mode de réalisation, le polyamide aliphatique semi- cristallin est obtenu à partir de la polycondensation d'au moins un lactame comprenant de 6 à 18 atomes de carbone, préférentiellement de 9 à 18 atomes de carbone, plus préférentiellement de 10 à 18 atomes de carbone, encore plus préférentiellement de 10 à 12 atomes de carbone. In a second variant of this first embodiment, the semi-crystalline aliphatic polyamide is obtained from the polycondensation of at least one lactam comprising from 6 to 18 carbon atoms, preferentially from 9 to 18 carbon atoms, more preferentially from 10 to 18 carbon atoms, even more preferably from 10 to 12 carbon atoms.
Préférentiellement, il est obtenu à partir de la polycondensation d'un seul lactame. Preferably, it is obtained from the polycondensation of a single lactam.
Dans une troisième variante de ce premier mode de réalisation, le polyamide aliphatique semi- cristallin est obtenu à partir de la polycondensation d'au moins une diamine aliphatique comprenant de 4 à 36 atomes de carbones, avantageusement de 6 à 18 atomes de carbone, avantageusement de 6 à 12 atomes de carbone, avantageusement de 10 à 12 atomes de carbone et d'au moins un acide dicarboxylique aliphatique comprenant de 4 à 36 atomes de carbones, avantageusement de 6 à 18 atomes de carbone, avantageusement de 6 à 12 atomes de carbone, avantageusement de 10 à 12 atomes de carbone . In a third variant of this first embodiment, the semi-crystalline aliphatic polyamide is obtained from the polycondensation of at least one aliphatic diamine comprising from 4 to 36 carbon atoms, advantageously from 6 to 18 carbon atoms, advantageously from 6 to 12 carbon atoms, advantageously from 10 to 12 carbon atoms and from at least one aliphatic dicarboxylic acid comprising from 4 to 36 carbon atoms, advantageously from 6 to 18 carbon atoms, advantageously from 6 to 12 carbon, advantageously from 10 to 12 carbon atoms.
La diamine aliphatique utilisée pour l'obtention de ce motif répétitif X.Y est une diamine aliphatique qui présente une chaine principale linéaire comprenant au moins 4 atomes de carbone. The aliphatic diamine used to obtain this repetitive unit X.Y is an aliphatic diamine which has a linear main chain comprising at least 4 carbon atoms.
Cette chaine principale linéaire peut, le cas échéant, comporter un ou plusieurs substituant méthyle et/ou éthyle ; dans cette dernière configuration, on parle de "diamine aliphatique ramifiée". Dans le cas où la chaine principale ne comporte aucun substituant, la diamine aliphatique est dite "diamine aliphatique linéaire". This linear main chain may, where appropriate, comprise one or more methyl and/or ethyl substituents; in this last configuration, one speaks of "branched aliphatic diamine". In the case where the main chain contains no substituent, the aliphatic diamine is called "linear aliphatic diamine".
Qu'elle comporte ou non des substituant méthyle et/ou éthyle sur la chaine principale, la diamine aliphatique utilisée pour l'obtention de ce motif répétitif X.Y comprend de 4 à 36 atomes de carbones, avantageusement de 4 à 18 atomes de carbone, avantageusement de 6 à 18 atomes de carbone, avantageusement de 6 à 14 atomes de carbone. Lorsque cette diamine est une diamine aliphatique linéaire, elle répond alors à la formule H2N-(CH2)x- NH2 et peut être choisie par exemple parmi la butanediamine, la pentanediamine, l'hexanediamine, l'heptanediamine, l'octanediamine, la nonanediamine, la décanediamine, l'undécanediamine, la dodécanediamine, la tridécanediamine, la tétradécanediamine, l'hexadécanediamine, l'octadécanedia-mine et l'octadécènediamine. Les diamines aliphatiques linéaires qui viennent d'être citées peuvent être toutes bio ressourcées au sens de la norme ASTM D6866. Whether or not it comprises methyl and/or ethyl substituents on the main chain, the aliphatic diamine used to obtain this repeating unit XY comprises from 4 to 36 carbon atoms, advantageously from 4 to 18 carbon atoms, advantageously from 6 to 18 carbon atoms, advantageously from 6 to 14 carbon atoms. When this diamine is a linear aliphatic diamine, it then has the formula H2N-(CH2)x-NH2 and can be chosen, for example, from butanediamine, pentanediamine, hexanediamine, heptanediamine, octanediamine, nonanediamine , decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, hexadecanediamine, octadecanediamine and octadecanediamine. The linear aliphatic diamines which have just been cited can all be bioresourced within the meaning of standard ASTM D6866.
Lorsque cette diamine est une diamine aliphatique ramifiée, elle peut notamment être la méthyl-2 pentanediamine, la 2-méthyl-l,8-octanediamine ou la triméthylène (2,2,4 ou 2,4,4) hexanediamine,. Le diacide carboxylique peut être choisi parmi les diacides carboxyliques aliphatiques, linéaires ou ramifiés. When this diamine is a branched aliphatic diamine, it may in particular be 2-methylpentanediamine, 2-methyl-1,8-octanediamine or trimethylene (2,2,4 or 2,4,4) hexanediamine. The dicarboxylic acid can be chosen from aliphatic, linear or branched dicarboxylic acids.
Lorsque l'acide dicarboxylique est aliphatique et linéaire, il peut être choisi parmi l'acide succinique (4), l'acide pentanedioïque (5), l'acide adipique (6), l'acide heptanedioïque (7), l'acide octanedioïque (8), l'acide azélaïque (9), l'acide sébacique (10), l'acide undécanedioïque (11), l'acide dodécanedioïque (12), l'acide brassylique (13), l'acide tétradécanedioïque (14), l'acide hexadécanedioïque (16), l'acide octadécanedioïque (18), l'acide octadécènedioïque (18), l'acide eicosanedioïque (20), l'acide docosanedioïque (22) et les dimères d'acides gras contenant 36 carbones. When the dicarboxylic acid is aliphatic and linear, it can be chosen from succinic acid (4), pentanedioic acid (5), adipic acid (6), heptanedioic acid (7), octanedioic acid (8), azelaic acid (9), sebacic acid (10), undecanedioic acid (11), dodecanedioic acid (12), brassylic acid (13), tetradecanedioic acid ( 14), hexadecanedioic acid (16), octadecanedioic acid (18), octadecanedioic acid (18), eicosanedioic acid (20), docosanedioic acid (22) and fatty acid dimers containing 36 carbons.
Les dimères d'acides gras mentionnés ci-dessus sont des acides gras dimérisés obtenus par oligomérisation ou polymérisation d'acides gras monobasiques insaturés à longue chaîne hydrocarbonée (tels que l'acide linoléïque et l'acide oléïque), comme décrit notamment dans le document EP 0471 566. The fatty acid dimers mentioned above are dimerized fatty acids obtained by oligomerization or polymerization of unsaturated monobasic fatty acids with a long hydrocarbon chain (such as linoleic acid and oleic acid), as described in particular in the document EP 0471 566.
Dans une quatrième variante de ce premier mode de réalisation, le polyamide aliphatique semi- cristallin est obtenu à partir d'un mélange de ces trois variantes. In a fourth variant of this first embodiment, the semi-crystalline aliphatic polyamide is obtained from a mixture of these three variants.
Dans un second mode de réalisation : In a second embodiment:
Dans une première variante de ce second mode de réalisation, le polyamide aliphatique semi-cristallin est obtenu à partir de la polycondensation d'au moins un acide aminocarboxylique comprenant de 6 à 18 atomes de carbone, préférentiellement de 8 à 12 atomes de carbone, plus préférentiellement de 10 à 12 atomes de carbone. In a first variant of this second embodiment, the semi-crystalline aliphatic polyamide is obtained from the polycondensation of at least one aminocarboxylic acid comprising from 6 to 18 carbon atoms, preferentially from 8 to 12 carbon atoms, plus preferably from 10 to 12 carbon atoms.
Préférentiellement, il est obtenu à partir de la polycondensation d'un seul acide aminocarboxylique. Dans une deuxième variante de ce second mode de réalisation, le polyamide aliphatique semi-cristallin est obtenu à partir de la polycondensation d'au moins un lactame comprenant de 6 à 18 atomes de carbone, préférentiellement de 8 à 12 atomes de carbone, plus préférentiellement de 10 à 12 atomes de carbone. Preferably, it is obtained from the polycondensation of a single aminocarboxylic acid. In a second variant of this second embodiment, the semi-crystalline aliphatic polyamide is obtained from the polycondensation of at least one lactam comprising from 6 to 18 carbon atoms, preferentially from 8 to 12 carbon atoms, more preferentially 10 to 12 carbon atoms.
Préférentiellement, il est obtenu à partir de la polycondensation d'un seul lactame. Dans un troisième mode de réalisation, ledit polyamide semi-cristallin est choisi parmi les PA610, PA612, PA1010, PA1012, PA1212, PAU et le PA12, en particulier les PA1010, PA1012, PA1212, PAU, PA12. Preferably, it is obtained from the polycondensation of a single lactam. In a third embodiment, said semi-crystalline polyamide is chosen from PA610, PA612, PA1010, PA1012, PA1212, PAU and PA12, in particular PA1010, PA1012, PA1212, PAU, PA12.
Avantageusement, ledit polyamide semi-cristallin est choisi parmi le PAU et le PA12, en particulier le PAU. Advantageously, said semi-crystalline polyamide is chosen from PAU and PA12, in particular PAU.
Dans un mode de réalisation, ledit polyamide semi-cristallin de ladite composition est constitué d'au moins 30% en poids, en particulier d'au moins 50% de polyamide semi-cristallin recyclé. In one embodiment, said semi-crystalline polyamide of said composition consists of at least 30% by weight, in particular of at least 50% of recycled semi-crystalline polyamide.
S'agissant des fibres de carbone Regarding carbon fibers
Les fibres de carbone recyclées dans la composition de moulage de polyamide aliphatique semi- cristallin selon l'invention sont présentes de préférence de 1,0 à 50,0% en poids, de préférence de 10,0 à 40,0%, plus préférentiellement de 20,0 à 40,0% en poids, encore plus préférentiellement de 25,0 à 40,0% en poids, chacun basé sur la somme des constituants de la composition. The recycled carbon fibers in the semi-crystalline aliphatic polyamide molding composition according to the invention are present preferably from 1.0 to 50.0% by weight, preferably from 10.0 to 40.0%, more preferably from 20.0 to 40.0% by weight, even more preferably from 25.0 to 40.0% by weight, each based on the sum of the constituents of the composition.
Les fibres de carbone recyclées utilisées dans la composition de moulage polyamide aliphatique semi-cristallin peuvent se présenter sous forme de fibres coupées (ou courtes) ou sous forme de faisceaux de fibres coupées (ou courtes) ou sous forme de fibres de carbone broyées. The recycled carbon fibers used in the semi-crystalline aliphatic polyamide molding composition can be in the form of chopped (or short) fibers or in the form of bundles of chopped (or short) fibers or in the form of ground carbon fibers.
Avant compoundage, les fibres de carbone sont préférentiellement des fibres de carbone coupées (ou courtes) et ont une longueur moyenne comprise de 0,1 à 6 mm, en particulier de 2 et à 6 mm. Avant compoundage, les fibres de carbone broyées ont une longueur moyenne comprise de 50 pm à 400 pm. Before compounding, the carbon fibers are preferably cut (or short) carbon fibers and have an average length of from 0.1 to 6 mm, in particular from 2 to 6 mm. Before compounding, the ground carbon fibers have an average length ranging from 50 μm to 400 μm.
Après compoundage, dans la composition à mouler, les fibres de carbone broyées ont une longueur moyenne inférieure à 400 pm. After compounding, in the composition to be molded, the ground carbon fibers have an average length of less than 400 μm.
Après compoundage, dans la composition à mouler, les fibres de carbone courtes ont une longueur moyenne comprise de 100 à 600pm, en particulier de 150 à 500pm. After compounding, in the composition to be molded, the short carbon fibers have an average length comprised from 100 to 600 μm, in particular from 150 to 500 μm.
Les fibres de carbone recyclées utilisées sont revêtues en surface (ensimage). Un revêtement (ensimage) doit être compatible avec la matrice plastique afin d'assurer un bon enrobage, une bonne adhérence et le meilleur effet de renforcement possible. The recycled carbon fibers used are coated on the surface (size). A coating (size) must be compatible with the plastic matrix in order to ensure good coating, good adhesion and the best possible reinforcement effect.
L'ensimage polyamide de la fibre de carbone recyclée peut être un polyamide semi-aromatique ou un polyamide aliphatique ou un mélange de ceux-ci. The polyamide size of the recycled carbon fiber can be a semi-aromatic polyamide or an aliphatic polyamide or a mixture of these.
Avantageusement ledit polyamide est un polyamide aliphatique. Advantageously, said polyamide is an aliphatic polyamide.
Avantageusement, ledit polyamide aliphatique est un polyamide semi-cristallin, en particulier présentant un nombre moyen d'atome de carbone par atome d'azote(C/N) inférieur ou égal à 10, en particulier inférieur ou égal à 9, notamment inférieur ou égal à 8, en particulier inférieur ou égal à 6. Dans un mode de réalisation, ledit polyamide aliphatique semi-cristallin est choisi parmi le PA6, le PA66 et un mélange de ceux-ci. Advantageously, said aliphatic polyamide is a semi-crystalline polyamide, in particular having an average number of carbon atoms per nitrogen atom (C/N) less than or equal to 10, in particular less than or equal to 9, in particular less than or equal to 8, in particular less than or equal to 6. In one embodiment, said semi-crystalline aliphatic polyamide is chosen from PA6, PA66 and a mixture thereof.
Des exemples de polyamides aliphatiques en particulier semi-cristallins sont donnés ci-dessus. Avantageusement, les fibres de carbones recyclées sont ensimées par ledit polyamide, en particulier ledit polyamide aliphatique, dans une gamme allant de 0,5 à 6%, en particulier de 1 à 5%, notamment de 1,5 à 4% en poids par rapport au total fibres de carbone-ensimage. Examples of aliphatic polyamides, in particular semi-crystalline, are given above. Advantageously, the recycled carbon fibers are sized with said polyamide, in particular said aliphatic polyamide, in a range ranging from 0.5 to 6%, in particular from 1 to 5%, in particular from 1.5 to 4% by weight per ratio of total carbon fibers-sizing.
Dans un mode de réalisation, l'empreinte carbone des fibres de carbone recyclées est au moins divisée par deux par rapport à l'empreinte des fibres de carbone vierges telle que déterminée selon la méthode ACV (Analyse du Cycle de Vie) afin de déterminer l'impact environnemental suivant notamment les normes internationales ISO 14040:2006, ISO 14044:2006 et/ou ISO 14067:2018.In one embodiment, the carbon footprint of the recycled carbon fibers is at least halved compared to the footprint of the virgin carbon fibers as determined according to the LCA (Life Cycle Analysis) method in order to determine the environmental impact according to international standards ISO 14040:2006, ISO 14044:2006 and/or ISO 14067:2018.
S'agissant des additifs (c) With regard to additives (c)
L'additif est optionnel et compris de 0 à 5,0%, en particulier de 0,1 à 5,0% en poids. The additive is optional and comprised from 0 to 5.0%, in particular from 0.1 to 5.0% by weight.
L'additif est choisi parmi les charges, les billes de verre, les colorants, les stabilisants, les plastifiants, les agents tensioactifs, les agents nucléants, les pigments, les azurants, les antioxydants, les lubrifiants, les ignifugeants, les cires naturelles et leurs mélanges. The additive is selected from fillers, glass beads, colorants, stabilizers, plasticizers, surfactants, nucleating agents, pigments, brighteners, antioxidants, lubricants, flame retardants, natural waxes and their mixtures.
Il est bien évident que les charges sont à l'exclusion de fibres de carbones recyclées ou non. It is quite obvious that the fillers are excluding carbon fibers, whether recycled or not.
Avantageusement, l'additif est choisi parmi les charges, les colorants, les stabilisants, les plastifiants, les agents tensioactifs, les agents nucléants, les pigments, les azurants, les antioxydants, les ignifugeants, les cires naturelles et leurs mélanges. Advantageously, the additive is chosen from fillers, colorants, stabilizers, plasticizers, surfactants, nucleating agents, pigments, brighteners, antioxidants, flame retardants, natural waxes and mixtures thereof.
Avantageusement, l'additif est choisi parmi les colorants, les stabilisants, les agents nucléants, les pigments, les azurants, les antioxydants, les cires naturelles et leurs mélanges. Advantageously, the additive is chosen from dyes, stabilizers, nucleating agents, pigments, brighteners, antioxidants, natural waxes and mixtures thereof.
A titre d'exemple, le stabilisant peut être un stabilisant UV, un stabilisant organique ou plus généralement une combinaison de stabilisants organiques, tel un antioxydant de type phénol (par exemple du type de celle de l'irganox 245 ou 1098 ou 1010 de la société Ciba-BASF), un antioxydant de type phosphite (par exemple l'irgafos® 126 de la société Ciba-BASF) et voire éventuellement d'autres stabilisants comme un HALS, ce qui signifie Hindered Amine Light Stabiliser ou stabilisant lumière de type amine encombrée (par exemple le Tinuvin 770 de la société Ciba-BASF), un anti-UV (par exemple le Tinuvin 312 de la société Ciba), un stabilisant à base de phosphore. On peut également utiliser des antioxydants de type amine tel le Naugard 445 de la société Crompton ou encore des stabilisants polyfonctionnels tel le Nylostab S-EED de la société Clariant. By way of example, the stabilizer can be a UV stabilizer, an organic stabilizer or more generally a combination of organic stabilizers, such as a phenol-type antioxidant (for example of the type of that of irganox 245 or 1098 or 1010 of the company Ciba-BASF), a phosphite-type antioxidant (for example irgafos® 126 from Ciba-BASF) and even possibly other stabilizers such as a HALS, which means Hindered Amine Light Stabilizer or amine-type light stabilizer encumbered (for example Tinuvin 770 from the company Ciba-BASF), an anti-UV (for example Tinuvin 312 from the company Ciba), a stabilizer based on phosphorus. It is also possible to use antioxidants of the amine type such as Naugard 445 from the company Crompton or alternatively polyfunctional stabilizers such as Nylostab S-EED from the company Clariant.
Ce stabilisant peut également être un stabilisant minéral, tel qu'un stabilisant à base de cuivre. A titre d'exemple de tels stabilisants minéraux, on peut citer les halogénures et les acétates de cuivre. Accessoirement, on peut considérer éventuellement d'autres métaux tel l'argent, mais ceux-ci sont connus pour être moins efficaces. Ces composés à base de cuivre sont typiquement associés à des halogénures de métaux alcalins, en particulier le potassium. This stabilizer can also be an inorganic stabilizer, such as a copper-based stabilizer. By way of example of such mineral stabilizers, mention may be made of copper halides and acetates. Incidentally, one can possibly consider other metals such as silver, but these are known to be less effective. These copper-based compounds are typically associated with alkali metal halides, particularly potassium.
A titre d'exemple, les plastifiants sont choisis parmi les dérivés de benzène sulfonamide, tels que le n- butyl benzène sulfonamide (BBSA) ; l'éthyl toluène sulfonamide ou le N-cyclohexyl toluène sulfonamide ; les esters d'acides hydroxy-benzoïques, tels que le parahydroxybenzoate d'éthyl-2- hexyle et le parahydroxybenzoate de décyl-2-hexyle ; les esters ou éthers du tétrahydrofurfuryl alcool, comme l'oligoéthylèneoxytétrahydrofurfurylalcool ; et les esters de l'acide citrique ou de l'acide hydroxy-malonique, tel que l'oligoéthylèneoxy malonate. By way of example, the plasticizers are chosen from benzene sulfonamide derivatives, such as n-butyl benzene sulfonamide (BBSA); ethyl toluene sulfonamide or N-cyclohexyl toluene sulfonamide; hydroxybenzoic acid esters, such as ethyl-2-parahydroxybenzoate hexyl and decyl-2-hexyl parahydroxybenzoate; tetrahydrofurfuryl alcohol esters or ethers, such as oligoethyleneoxytetrahydrofurfuryl alcohol; and esters of citric acid or hydroxy-malonic acid, such as oligoethyleneoxy malonate.
On ne sortirait pas du cadre de l'invention en utilisant un mélange de plastifiants. It would not be departing from the scope of the invention to use a mixture of plasticizers.
A titre d'exemple, les charges peuvent être choisies parmi la silice, le graphite, le graphite expansé, le noir de carbone, le kaolin, la magnésie, les scories, le talc, la wollastonite, les nanocharges (nanotubes de carbone), les pigments, les oxydes métalliques (oxyde de titane), les métaux, avantageusement la wollastonite et le talc, préférentiellement le talc. By way of example, the fillers can be chosen from silica, graphite, expanded graphite, carbon black, kaolin, magnesia, slag, talc, wollastonite, nanofillers (carbon nanotubes), pigments, metal oxides (titanium oxide), metals, advantageously wollastonite and talc, preferentially talc.
S'agissant de la composition Regarding the composition
La composition de moulage est telle que définie ci-dessus et comprend dans un premier mode de réalisation en poids : a) de 50 à 99% d'un polyamide aliphatique semi-cristallin présentant une viscosité inhérente inférieure ou égale à 1,10, en particulier inférieure ou égale à 1,00, en particulier inférieure ou égale à 0,95, notamment inférieure ou égale à 0,9, telle que déterminée selon la norme ISO 307 :2007 mais en utilisant du m-crésol à la place de l'acide sulfurique, une température de 20°C et une concentration de 0,5% massique, b) de 1 à 50% de fibres de carbone recyclées présentant une longueur moyenne inférieure ou égale à 6 mm avant compoundage, lesdites fibres de carbone recyclées étant revêtues en surface (ensimées) par un polyamide, en particulier un polyamide aliphatique, c) de 0 à 5% d'au moins un additif, la somme des composants a), b) et c) étant égale à 100%. The molding composition is as defined above and comprises in a first embodiment by weight: a) from 50 to 99% of a semi-crystalline aliphatic polyamide having an inherent viscosity less than or equal to 1.10, in in particular less than or equal to 1.00, in particular less than or equal to 0.95, in particular less than or equal to 0.9, as determined according to standard ISO 307:2007 but using m-cresol instead of l sulfuric acid, a temperature of 20° C. and a concentration of 0.5% by mass, b) from 1 to 50% of recycled carbon fibers having an average length less than or equal to 6 mm before compounding, said recycled carbon fibers being surface-coated (sized) with a polyamide, in particular an aliphatic polyamide, c) from 0 to 5% of at least one additive, the sum of components a), b) and c) being equal to 100%.
Avantageusement, elle comprend en poids : a) de 50 à 98,9% d'un polyamide aliphatique semi-cristallin présentant une viscosité inhérente inférieure ou égale à 1,10, en particulier inférieure ou égal à 1,00, en particulier inférieure ou égale à 0,95, notamment inférieure ou égale à 0,9, telle que déterminée selon la norme ISO 307 :2007 mais en utilisant du m-crésol à la place de l'acide sulfurique, une température de 20°C et une concentration de 0,5% massique, b) de 1 à 50% de fibres de carbone recyclées présentant une longueur moyenne inférieure ou égale à 6 mm avant compoundage, lesdites fibres de carbone recyclées étant revêtues en surface (ensimées) par un polyamide, en particulier un polyamide aliphatique, c) de 0,1 à 5% d'au moins un additif, la somme des composants a), b) et c) étant égale à 100%. Advantageously, it comprises by weight: a) from 50 to 98.9% of a semi-crystalline aliphatic polyamide having an inherent viscosity less than or equal to 1.10, in particular less than or equal to 1.00, in particular less than or equal to 0.95, in particular less than or equal to 0.9, as determined according to standard ISO 307:2007 but using m-cresol instead of sulfuric acid, a temperature of 20°C and a concentration from 0.5% by mass, b) from 1 to 50% of recycled carbon fibers having an average length less than or equal to 6 mm before compounding, said recycled carbon fibers being surface-coated (sized) with a polyamide, in particular an aliphatic polyamide, c) from 0.1 to 5% of at least one additive, the sum of the components a), b) and c) being equal to 100%.
Selon une première variante, elle comprend en poids : a) de 60 à 90% d'un polyamide aliphatique semi-cristallin présentant une viscosité inhérente inférieure ou égale à 1,10, en particulier inférieure ou égale à 1,00, en particulier inférieure ou égale à 0,95, notamment inférieure ou égale à 0,9, telle que déterminée selon la norme ISO 307 :2007 mais en utilisant du m-crésol à la place de l'acide sulfurique, une température de 20°C et une concentration de 0,5% massique, b) de 10 à 40% de fibres de carbone recyclées présentant une longueur moyenne inférieure ou égale à 6 mm avant compoundage, lesdites fibres de carbone recyclées étant revêtues en surface (ensimées) par un polyamide, en particulier un polyamide aliphatique, c) de 0 à 5% d'au moins un additif, la somme des composants a), b) et c) étant égale à 100%. According to a first variant, it comprises by weight: a) from 60 to 90% of a semi-crystalline aliphatic polyamide having an inherent viscosity less than or equal to 1.10, in particular less than or equal to 1.00, in particular less or equal to 0.95, in particular less than or equal to 0.9, as determined according to ISO 307:2007 but using m-cresol instead of sulfuric acid, a temperature of 20°C and a concentration of 0.5% by mass, b) from 10 to 40% of recycled carbon fibers having an average length less than or equal to 6 mm before compounding, said recycled carbon fibers being surface-coated (sized) with a polyamide, in particular a aliphatic polyamide, c) from 0 to 5% of at least one additive, the sum of the components a), b) and c) being equal to 100%.
Avantageusement, elle comprend en poids : a) de 60 à 89,9% d'un polyamide aliphatique semi-cristallin présentant une viscosité inhérente inférieure ou égale à 1,10, en particulier inférieure ou égal à 1,00, en particulier inférieure ou égale à 0,95, notamment inférieure ou égale 0,9, telle que déterminée selon la norme ISO 307 :2007 mais en utilisant du m-crésol à la place de l'acide sulfurique, une température de 20°C et une concentration de 0,5% massique, b) de 10 à 40% de fibres de carbone recyclées présentant une longueur moyenne inférieure ou égale à 6 mm avant compoundage, lesdites fibres de carbone recyclées étant revêtues en surface (ensimées) par un polyamide, en particulier un polyamide aliphatique, c) de 0,1 à 5% d'au moins un additif, la somme des composants a), b) et c) étant égale à 100%. Advantageously, it comprises by weight: a) from 60 to 89.9% of a semi-crystalline aliphatic polyamide having an inherent viscosity less than or equal to 1.10, in particular less than or equal to 1.00, in particular less than or equal to 0.95, in particular less than or equal to 0.9, as determined according to ISO 307:2007 but using m-cresol instead of sulfuric acid, a temperature of 20°C and a concentration of 0.5% by mass, b) from 10 to 40% of recycled carbon fibers having an average length less than or equal to 6 mm before compounding, said recycled carbon fibers being surface-coated (sized) with a polyamide, in particular a aliphatic polyamide, c) from 0.1 to 5% of at least one additive, the sum of components a), b) and c) being equal to 100%.
Selon une seconde variante, elle comprend en poids : a) de 60 à 80% d'un polyamide aliphatique semi-cristallin présentant une viscosité inhérente inférieure ou égale à 1,10, en particulier inférieure ou égale à 1,00, en particulier inférieure ou égale à 0,95, notamment inférieure ou égal 0,9, telle que déterminée selon la norme ISO 307 :2007 mais en utilisant du m-crésol à la place de l'acide sulfurique, une température de 20°C et une concentration de 0,5% massique, b) de 20 à 40% de fibres de carbone recyclées présentant une longueur moyenne inférieure ou égale à 6 mm avant compoundage, lesdites fibres de carbone recyclées étant revêtues en surface (ensimées) par un polyamide, en particulier un polyamide aliphatique, c) de 0 à 5% d'au moins un additif, la somme des composants a), b) et c) étant égale à 100%. According to a second variant, it comprises by weight: a) from 60 to 80% of a semi-crystalline aliphatic polyamide having an inherent viscosity less than or equal to 1.10, in particular less than or equal to 1.00, in particular less or equal to 0.95, in particular less than or equal to 0.9, as determined according to ISO 307:2007 but using m-cresol instead of sulfuric acid, a temperature of 20°C and a concentration from 0.5% by mass, b) from 20 to 40% of recycled carbon fibers having an average length less than or equal to 6 mm before compounding, said recycled carbon fibers being surface-coated (sized) with a polyamide, in particular an aliphatic polyamide, c) from 0 to 5% of at least one additive, the sum of the components a), b) and c) being equal to 100%.
Avantageusement, elle comprend en poids : a) de 60 à 79,9% d'un polyamide aliphatique semi-cristallin présentant une viscosité inhérente inférieure ou égale à 1,10, en particulier inférieur ou égal à 1,00, en particulier inférieure ou égale à 0,95, notamment inférieure ou égale à 0,9, telle que déterminée selon la norme ISO 307 :2007 mais en utilisant du m-crésol à la place de l'acide sulfurique, une température de 20°C et une concentration de 0,5% massique, b) de 20 à 40% de fibres de carbone recyclées présentant une longueur moyenne inférieure ou égale à 6 mm avant compoundage, lesdites fibres de carbone recyclées étant revêtues en surface (ensimées) par un polyamide, en particulier un polyamide aliphatique, c) de 0,1 à 5% d'au moins un additif, la somme des composants a), b) et c) étant égale à 100%. Advantageously, it comprises by weight: a) from 60 to 79.9% of a semi-crystalline aliphatic polyamide having an inherent viscosity less than or equal to 1.10, in particular less than or equal to 1.00, in particular less than or equal to 0.95, in particular less than or equal to 0.9, as determined according to standard ISO 307:2007 but using m-cresol instead of sulfuric acid, a temperature of 20°C and a concentration of 0.5% by mass, b) from 20 to 40% of recycled carbon fibers having an average length less than or equal to to 6 mm before compounding, said recycled carbon fibers being surface-coated (sized) with a polyamide, in particular an aliphatic polyamide, c) from 0.1 to 5% of at least one additive, the sum of the components a) , b) and c) being equal to 100%.
Selon une troisième variante, elle comprend en poids : a) de 60 à 75% d'un polyamide aliphatique semi-cristallin présentant une viscosité inhérente inférieure ou égale à 1,10, en particulier inférieure ou égal à 1,00, en particulier inférieure ou égal à 0,95, notamment inférieure ou égale 0,9, telle que déterminée selon la norme ISO 307 :2007 mais en utilisant du m-crésol à la place de l'acide sulfurique, une température de 20°C et une concentration de 0,5% massique, b) de 25 à 40% de fibres de carbone recyclées présentant une longueur moyenne inférieure ou égale à 6 mm avant compoundage, lesdites fibres de carbone recyclées étant revêtues en surface (ensimées) par un polyamide, en particulier un polyamide aliphatique, c) de 0 à 5% d'au moins un additif, la somme des composants a), b) et c) étant égale à 100%. According to a third variant, it comprises by weight: a) from 60 to 75% of a semi-crystalline aliphatic polyamide having an inherent viscosity less than or equal to 1.10, in particular less than or equal to 1.00, in particular less or equal to 0.95, in particular less than or equal to 0.9, as determined according to standard ISO 307:2007 but using m-cresol instead of sulfuric acid, a temperature of 20°C and a concentration from 0.5% by mass, b) from 25 to 40% of recycled carbon fibers having an average length less than or equal to 6 mm before compounding, said recycled carbon fibers being surface-coated (sized) with a polyamide, in particular an aliphatic polyamide, c) from 0 to 5% of at least one additive, the sum of the components a), b) and c) being equal to 100%.
Avantageusement, elle comprend en poids : a) de 60 à 74,9% d'un polyamide aliphatique semi-cristallin présentant une viscosité inhérente inférieure ou égale à 1,10, en particulier inférieure ou égale à 1,00, en particulier inférieure ou égale à 0,95, notamment inférieure ou égale à 0,9, telle que déterminée selon la norme ISO 307 :2007 mais en utilisant du m-crésol à la place de l'acide sulfurique, une température de 20°C et une concentration de 0,5% massique, b) de 25 à 40% de fibres de carbone recyclées présentant une longueur moyenne inférieure ou égale à 6 mm avant compoundage, lesdites fibres de carbone recyclées étant revêtues en surface (ensimées) par un polyamide, en particulier un polyamide aliphatique, c) de 0,1 à 5% d'au moins un additif, la somme des composants a), b) et c) étant égale à 100%. Advantageously, it comprises by weight: a) from 60 to 74.9% of a semi-crystalline aliphatic polyamide having an inherent viscosity less than or equal to 1.10, in particular less than or equal to 1.00, in particular less than or equal to 0.95, in particular less than or equal to 0.9, as determined according to standard ISO 307:2007 but using m-cresol instead of sulfuric acid, a temperature of 20°C and a concentration from 0.5% by mass, b) from 25 to 40% of recycled carbon fibers having an average length less than or equal to 6 mm before compounding, said recycled carbon fibers being surface-coated (sized) with a polyamide, in particular an aliphatic polyamide, c) from 0.1 to 5% of at least one additive, the sum of the components a), b) and c) being equal to 100%.
Dans un second mode de réalisation, ladite composition de l'invention est constituée des divers éléments a, b et c, leur somme étant égale à 100% en poids définis dans le premier mode de réalisation et des trois variantes avec leur mode de réalisation particulier définis ci-dessus. In a second embodiment, said composition of the invention consists of the various elements a, b and c, their sum being equal to 100% by weight defined in the first embodiment and of the three variants with their particular embodiment defined above.
Quels que soient les modes de réalisation des compositions décrite ci-dessus, ladite composition est caractérisée en ce que les propriétés mécaniques de celle-ci sont au moins équivalentes à celle de la même composition mais comprenant des fibres de carbone vierges présentant une longueur moyenne inférieure ou égale à 6 mm à la place des fibres de carbone recyclées avant étape de compoundage, lesdites fibres de carbone vierges étant revêtues en surface (ensimées) par le même polyamide ou un polymère autre qu'un polyamide. Whatever the embodiments of the compositions described above, said composition is characterized in that the mechanical properties thereof are at least equivalent to those of the same composition but comprising virgin carbon fibers having a length average less than or equal to 6 mm in place of recycled carbon fibers before the compounding step, said virgin carbon fibers being surface-coated (sized) with the same polyamide or a polymer other than a polyamide.
En particulier, la résilience telle que mesurée par choc charpy sur barreaux non entaillés leU à 23°C des compositions selon l'invention est supérieure de plus de 10% à celle obtenue avec des fibres de carbone vierges ensimée par un polyamide ou avec des fibres de carbone recyclées mais ensimées par un polymère autre qu'un polyamide. In particular, the resilience as measured by charpy impact on unnotched bars leU at 23° C. of the compositions according to the invention is more than 10% higher than that obtained with virgin carbon fibers sized with a polyamide or with fibers recycled carbon but sized with a polymer other than a polyamide.
Avantageusement, l'élongation à la rupture des compositions selon l'invention est supérieure de plus de 10% à celle obtenue avec des fibres de carbone vierges ensimée par un polyamide ou avec des fibres de carbone recyclées mais ensimées par un polymère autre qu'un polyamide. Advantageously, the elongation at break of the compositions according to the invention is more than 10% greater than that obtained with virgin carbon fibers sized with a polyamide or with recycled carbon fibers but sized with a polymer other than a polyamide.
Dans un mode de réalisation, la résilience telle que mesurée par choc charpy sur barreaux non entaillés leU à 23°C des compositions selon l'invention est supérieure de plus de 10% à celle obtenue avec des fibres de carbone vierges ensimée par un polyamide ou avec des fibres de carbone recyclées mais ensimées par un polymère autre qu'un polyamide. In one embodiment, the resilience as measured by charpy impact on unnotched bars leU at 23° C. of the compositions according to the invention is greater by more than 10% than that obtained with virgin carbon fibers sized with a polyamide or with recycled carbon fibers but sized with a polymer other than a polyamide.
Dans un autre mode de réalisation, la résilience telle que mesurée par choc charpy sur barreaux non entaillés leU à 23°C et l'élongation à la rupture des compositions selon l'invention sont supérieures de plus de 10% à celles obtenues avec des fibres de carbone vierges ensimée par un polyamide ou avec des fibres de carbone recyclées mais ensimées par un polymère autre qu'un polyamide. In another embodiment, the resilience as measured by Charpy impact on unnotched bars leU at 23° C. and the elongation at break of the compositions according to the invention are more than 10% higher than those obtained with fibers of virgin carbon sized with a polyamide or with recycled carbon fibers but sized with a polymer other than a polyamide.
Selon un autre aspect, la présente invention concerne l'utilisation d'une composition telle que définie ci-dessus, pour la fabrication d'articles obtenus par injection choisis parmi un article de sport, notamment une chaussure de sport, en particulier une chaussure de ski ou une partie de chaussure de ski ou une chaussure rigide à crampon, telle que chaussure de soccer, de rugby ou de football américain une chaussure de hockey ou une partie de chaussure de hockey, ou une chaussure de running, une balle de golf ou une partie de balle de golf, ou une crosse dans le sport lacrosse, un article de hockey tel qu'un casque et des articles de sport pour la protection de la tête, des épaules, des coudes, des mains, des genoux, du dos ou du tibia, tels que casque, gants, épaulettes, coudières, genouillères ou protèges tibia. According to another aspect, the present invention relates to the use of a composition as defined above, for the manufacture of articles obtained by injection chosen from a sports article, in particular a sports shoe, in particular a ski or a part of a ski boot or a rigid shoe with cleats, such as a soccer, rugby or American football shoe, a hockey shoe or a part of a hockey shoe, or a running shoe, a golf ball or a part of a golf ball, or a stick in the sport of lacrosse, a hockey article such as a helmet, and sports articles for the protection of the head, shoulders, elbows, hands, knees, back or shin, such as helmet, gloves, shoulder pads, elbow pads, knee pads or shin guards.
Selon encore un autre aspect, la présente invention concerne l'utilisation d'une composition de moulage telle que définie ci-dessus, pour la fabrication d'un article pour l'électronique, pour l'automobile, pour des applications télécom ou pour l'échange de donnée, tel que pour un véhicule autonome ou pour des applications connectées entre elles. According to yet another aspect, the present invention relates to the use of a molding composition as defined above, for the manufacture of an article for electronics, for the automobile, for telecom applications or for the exchange of data, such as for an autonomous vehicle or for applications connected to each other.
Selon un autre aspect, la présente invention concerne un article obtenu par moulage par injection d'une composition telle que définie ci-dessus. According to another aspect, the present invention relates to an article obtained by injection molding of a composition as defined above.
Exemples : La présente invention va être maintenant illustrée par les exemples suivants sans pour autant être limitatifs de l'invention. Examples: The present invention will now be illustrated by the following examples without however being limiting of the invention.
Préparation des compositions de l'invention et propriétés mécaniques: Preparation of the compositions of the invention and mechanical properties:
Les compositions du tableau I ont été préparées par mélange à l'état fondu des granulés de polymères avec les fibres de carbone et les additifs. Ce mélange a été effectué par compoundage sur extrudeuse bi-vis co-rotative de diamètre 26 mm avec un profil de température (T°) plat à 240°C. La vitesse de vis est de 200 rpm et le débit de 16 kg/h. The compositions in Table I were prepared by melt blending the polymer pellets with the carbon fibers and the additives. This mixture was carried out by compounding on a co-rotating twin-screw extruder with a diameter of 26 mm with a temperature profile (T°) flat at 240°C. The screw speed is 200 rpm and the flow rate is 16 kg/h.
L'introduction des fibres de carbone est effectuée en gavage latéral. The introduction of the carbon fibers is carried out by lateral force-feeding.
Le ou les polyamide(s) et les additifs sont additionnés lors du procédé de compoundage en trémie principale. The polyamide(s) and the additives are added during the compounding process in the main hopper.
Les compositions ont ensuite été moulées sur presse à injecter à une température matière de 260°C et une température de moule de 60°C sous forme d'haltères ou de barreaux afin d'étudier les propriétés mécaniques selon les normes ci-dessous [Tableau I] The compositions were then molded on an injection molding machine at a material temperature of 260°C and a mold temperature of 60°C in the form of dumbbells or bars in order to study the mechanical properties according to the standards below [Table I]
CE : Contre-exemple CE: Counterexample
E : exemples de l'invention E: examples of the invention
Les proportions sont indiquées en proportion massique (%) The proportions are indicated in mass proportion (%)
Les fibres de carbone vierge PAN et recyclées PAN avec ensimage polyuréthane ou polyamide sont commercialisées par exemple par Mitsubishi, SGL, ACECA, Teijin, Zoltek ou Hexcel. Virgin PAN and recycled PAN carbon fibers with polyurethane or polyamide sizing are marketed for example by Mitsubishi, SGL, ACECA, Teijin, Zoltek or Hexcel.
PAU : synthétisé par la demanderesse PAU: synthesized by the applicant
Le module de traction, l'allongement et la contrainte à la rupture ont été mesurés à 23°C selon la norme ISO 527-1 : 2012 sur échantillon sec. The tensile modulus, the elongation and the breaking stress were measured at 23° C. according to the ISO 527-1: 2012 standard on a dry sample.
La machine utilisée est de type INSTRON 5966. La vitesse de la traverse est de 1 mm/min pour la mesure du module et de 5 mm/min pour la contrainte à la rupture et l'élongation à la rupture. Les conditions de test sont 23°C +/- 2°C, sur échantillons secs. The machine used is of the INSTRON 5966 type. The speed of the crosshead is 1 mm/min for measuring the modulus and 5 mm/min for the stress at break and the elongation at break. The test conditions are 23°C +/- 2°C, on dry samples.
La résistance au choc a été déterminée selon ISO 179-1 : 2010 (choc Charpy) sur des barreaux de dimension 80mm x 10mm x 4mm, entaillées et non entaillées, à une température de 23°C +/- 2°C sous une humidité relative de 50% +/- 10 % ou à -30°C +/-2°C sous une humidité relative de 50% +/- 10 % sur échantillons secs. The impact resistance was determined according to ISO 179-1: 2010 (Charpy impact) on bars measuring 80mm x 10mm x 4mm, notched and unnotched, at a temperature of 23°C +/- 2°C under humidity. relative humidity of 50% +/- 10% or at -30°C +/-2°C under a relative humidity of 50% +/- 10% on dry samples.
Les exemples et contre exemples ci-dessus montrent que les propriétés mécaniques de compositions à base de fibres de carbones recyclée ensimées avec un polyamide sont meilleures que celles de compositions à base de fibres de carbone vierge ensimées avec un polyamide ou de fibres de carbone vierge ensimées avec un autre polymère. The examples and counterexamples above show that the mechanical properties of compositions based on recycled carbon fibers sized with a polyamide are better than those of compositions based on virgin carbon fibers sized with a polyamide or virgin carbon fibers sized with another polymer.

Claims

REVENDICATIONS
1. Composition de moulage comprenant en poids : a) de 50 à 99% d'un polyamide aliphatique semi-cristallin présentant une viscosité inhérente inférieure ou égale à 1,10, en particulier inférieur ou égal à 1,00, en particulier inférieur ou égal à 0,95, notamment inférieur ou égale à 0,9, telle que déterminée selon la norme ISO 307 :2007 mais en utilisant du m-crésol à la place de l'acide sulfurique, une température de 20°C et une concentration de 0,5% massique, b) de 1 à 50% de fibres de carbone recyclées présentant une longueur moyenne inférieure ou égale à 6 mm avant compoundage, lesdites fibres de carbone recyclées étant revêtues en surface (ensimées) par un polyamide, en particulier un polyamide aliphatique, c) de 0 à 5% d'au moins un additif, la somme des composants a), b) et c) étant égale à 100%. 1. Molding composition comprising by weight: a) from 50 to 99% of a semi-crystalline aliphatic polyamide having an inherent viscosity less than or equal to 1.10, in particular less than or equal to 1.00, in particular less than or equal to 0.95, in particular less than or equal to 0.9, as determined according to standard ISO 307:2007 but using m-cresol instead of sulfuric acid, a temperature of 20°C and a concentration from 0.5% by mass, b) from 1 to 50% of recycled carbon fibers having an average length less than or equal to 6 mm before compounding, said recycled carbon fibers being surface-coated (sized) with a polyamide, in particular an aliphatic polyamide, c) from 0 to 5% of at least one additive, the sum of the components a), b) and c) being equal to 100%.
2. Composition de moulage selon la revendication 1, caractérisée en ce que le polyamide aliphatique semi-cristallin (a) est obtenu par polycondensation : d'au moins un acide aminocarboxylique en Cg à Cis, préférentiellement en Cg à Cis, plus préférentiellement en Cio à Cis, notamment en Cio à C12, ou d'au moins un lactame en Cg à Cis, préférentiellement en Cg à Cis, plus préférentiellement en Cio à Ci8, notamment en Cio à C12, ou d'au moins une diamine Ca en C^Cgg, préférentiellement Cg-Ci8, préférentiellement Cg-Ci2, plus préférentiellement C10-C12, avec au moins un acide dicarboxylique Cb en C^Cgg, préférentiellement Cg-Ci8, préférentiellement Cg-Ci2, plus préférentiellement C10-C12. 2. Molding composition according to claim 1, characterized in that the semi-crystalline aliphatic polyamide (a) is obtained by polycondensation: of at least one Cg to Cis aminocarboxylic acid, preferably Cg to Cis, more preferably Cio to Cis, in particular Cio to C12, or of at least one lactam in Cg to Cis, preferentially in Cg to Cis, more preferentially in Cio to Ci8, in particular in Cio to C12, or of at least one diamine Ca in C ^Cgg, preferentially Cg-Ci8, preferentially Cg-Ci2, more preferentially C10-C12, with at least one dicarboxylic acid Cb in C^Cgg, preferentially Cg-Ci8, preferentially Cg-Ci2, more preferentially C10-C12.
3. Composition de moulage selon l'une des revendications 1 ou 2, caractérisée en ce que ledit polyamide (a) présente un nombre moyen d'atome de carbone par atome d'azote supérieur ou égal à 8, en particulier supérieur ou égal à 9, notamment supérieur ou égal à 10. 3. Molding composition according to one of claims 1 or 2, characterized in that said polyamide (a) has an average number of carbon atoms per nitrogen atom greater than or equal to 8, in particular greater than or equal to 9, in particular greater than or equal to 10.
4. Composition de moulage selon la revendication 3, caractérisée en ce que ledit polyamide (a) est choisi parmi PA610, PA612, PA1010, PA1012, PA1212, PAU et PA12, en particulier les PA1010, PA1012, PA1212, PAU, PA12, plus particulièrement PAU et PA12, notamment PAU. 4. Molding composition according to claim 3, characterized in that said polyamide (a) is chosen from PA610, PA612, PA1010, PA1012, PA1212, PAU and PA12, in particular PA1010, PA1012, PA1212, PAU, PA12, plus particularly PAU and PA12, in particular PAU.
5. Composition de moulage selon l'une des revendications 1 à 4, caractérisée en ce que la résilience telle que mesurée par choc charpy sur barreaux non entaillés leU à 23°C desdites compositions est supérieure de plus de 10% à celle obtenue avec des fibres de carbone vierges ensimée par un polyamide ou avec des fibres de carbone recyclées mais ensimées par un polymère autre qu'un polyamide. Composition de moulage selon l'une des revendications 1 à 4, caractérisée en ce que la résilience telle que mesurée par choc charpy sur barreaux non entaillés leU à 23°C et l'élongation à la rupture desdites compositions sont supérieures de plus de 10% à celles obtenues avec des fibres de carbone vierges ensimée par un polyamide ou avec des fibres de carbone recyclées mais ensimées par un polymère autre qu'un polyamide. Utilisation d'une composition telle que définie dans l'une des revendications 1 à 6, pour la fabrication d'articles obtenus par injection choisis parmi un article de sport, notamment une chaussure de sport, en particulier une chaussure de ski ou une partie de chaussure de ski ou une chaussure rigide à crampon, telle que chaussure de soccer, de rugby ou de football américain une chaussure de hockey ou une partie de chaussure de hockey, ou une chaussure de running, une balle de golf ou une partie de balle de golf, ou une crosse dans le sport lacrosse, un article de hockey tel qu'un casque et des articles de sport pour la protection de la tête, des épaules, des coudes, des mains, des genoux, du dos ou du tibia, tels que casque, gants, épaulettes, coudières, genouillères ou protèges tibia. Utilisation d'une composition de moulage telle que définie l'une des revendications 1 à 6, pour la fabrication d'un article pour l'électronique, pour l'automobile, pour des applications télécom ou pour l'échange de donnée, tel que pour un véhicule autonome ou pour des applications connectées entre elles. Article obtenu par moulage par injection d'une composition telle que définie dans l'une des revendications 1 à 6. 5. Molding composition according to one of claims 1 to 4, characterized in that the resilience as measured by charpy impact on unnotched bars leU at 23 ° C of said compositions is more than 10% higher than that obtained with virgin carbon fibers sized with a polyamide or with recycled carbon fibers but sized with a polymer other than a polyamide. Molding composition according to one of Claims 1 to 4, characterized in that the resilience as measured by Charpy impact on unnotched bars leU at 23°C and the elongation at break of the said compositions are greater by more than 10% to those obtained with virgin carbon fibers sized with a polyamide or with recycled carbon fibers but sized with a polymer other than a polyamide. Use of a composition as defined in one of Claims 1 to 6, for the manufacture of articles obtained by injection chosen from a sports article, in particular a sports shoe, in particular a ski boot or part of ski boot or a rigid shoe with cleats, such as a soccer, rugby or American football boot, a hockey boot or part of a hockey boot, or a running shoe, a golf ball or part of a ball golf, or a stick in the sport of lacrosse, a hockey article such as a helmet and sports articles for the protection of the head, shoulders, elbows, hands, knees, back or shin, such as a helmet, gloves, shoulder pads, elbow pads, knee pads or shin pads. Use of a molding composition as defined in one of Claims 1 to 6, for the manufacture of an article for electronics, for automobiles, for telecom applications or for data exchange, such as for an autonomous vehicle or for applications connected to each other. Article obtained by injection molding of a composition as defined in one of claims 1 to 6.
EP22823139.5A 2021-11-17 2022-11-15 Polyamide compositions comprising recycled carbon fibers and uses thereof Pending EP4433536A1 (en)

Applications Claiming Priority (2)

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FR2112118A FR3129154A1 (en) 2021-11-17 2021-11-17 POLYAMIDE COMPOSITIONS COMPRISING RECYCLED CARBON FIBERS AND THEIR USES
PCT/FR2022/000110 WO2023089250A1 (en) 2021-11-17 2022-11-15 Polyamide compositions comprising recycled carbon fibers and uses thereof

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