EP4433536A1 - Polyamidzusammensetzungen mit recycelten kohlenstofffasern und verwendungen davon - Google Patents

Polyamidzusammensetzungen mit recycelten kohlenstofffasern und verwendungen davon

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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
English (en)
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/de
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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0005—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor using fibre reinforcements
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
    • B29K2077/10—Aromatic polyamides [polyaramides] or derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2307/00—Use of elements other than metals as reinforcement
    • B29K2307/04—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0089—Impact strength or toughness
    • 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
    • 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
    • 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 Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP22823139.5A 2021-11-17 2022-11-15 Polyamidzusammensetzungen mit recycelten kohlenstofffasern und verwendungen davon Pending EP4433536A1 (de)

Applications Claiming Priority (2)

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FR2112118A FR3129154B1 (fr) 2021-11-17 2021-11-17 Compositions de polyamide comprenant des fibres de carbone recyclees et leurs utilisations
PCT/FR2022/000110 WO2023089250A1 (fr) 2021-11-17 2022-11-15 Compositions de polyamide comprenant des fibres de carbone recyclees et leurs utilisations

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EP4433536A1 true EP4433536A1 (de) 2024-09-25

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US (1) US20250002678A1 (de)
EP (1) EP4433536A1 (de)
JP (1) JP2024540488A (de)
KR (1) KR20240101846A (de)
CN (1) CN118251452A (de)
FR (1) FR3129154B1 (de)
WO (1) WO2023089250A1 (de)

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GB9018144D0 (en) 1990-08-17 1990-10-03 Unilever Plc Polymerisation process
JP6333803B2 (ja) * 2013-03-06 2018-05-30 住友精化株式会社 繊維用処理剤および該繊維用処理剤で処理した炭素繊維、並びに当該炭素繊維を含む炭素繊維複合化材料
CH708727B1 (de) 2013-11-21 2020-08-31 Ems Patent Ag Kohlenstofffaser-verstärkte Kunststoff-Formmassen.
JP2021055198A (ja) * 2019-09-27 2021-04-08 カーボンファイバーリサイクル工業株式会社 炭素繊維集合体

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CN118251452A (zh) 2024-06-25
JP2024540488A (ja) 2024-10-31
FR3129154B1 (fr) 2025-05-30
WO2023089250A1 (fr) 2023-05-25
US20250002678A1 (en) 2025-01-02
KR20240101846A (ko) 2024-07-02
FR3129154A1 (fr) 2023-05-19

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