EP3651960A1 - Compositions rendues stables à la chaleur - Google Patents

Compositions rendues stables à la chaleur

Info

Publication number
EP3651960A1
EP3651960A1 EP18738336.9A EP18738336A EP3651960A1 EP 3651960 A1 EP3651960 A1 EP 3651960A1 EP 18738336 A EP18738336 A EP 18738336A EP 3651960 A1 EP3651960 A1 EP 3651960A1
Authority
EP
European Patent Office
Prior art keywords
component
parts
polyamide
compositions
components
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.)
Withdrawn
Application number
EP18738336.9A
Other languages
German (de)
English (en)
Inventor
Detlev Joachimi
Thomas Linder
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.)
Lanxess Deutschland GmbH
Original Assignee
Lanxess Deutschland GmbH
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 Lanxess Deutschland GmbH filed Critical Lanxess Deutschland GmbH
Publication of EP3651960A1 publication Critical patent/EP3651960A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B11/00—Making preforms
    • B29B11/06—Making preforms by moulding the material
    • B29B11/10—Extrusion moulding
    • 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
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B29C48/023—Extruding materials comprising incompatible ingredients
    • 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
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
    • B29C49/04—Extrusion blow-moulding
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • 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
    • C08K7/14—Glass
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B77/00—Component parts, details or accessories, not otherwise provided for
    • F02B77/11—Thermal or acoustic insulation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0044—Stabilisers, e.g. against oxydation, light or heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/748—Machines or parts thereof not otherwise provided for
    • B29L2031/749—Motors

Definitions

  • thermostabilized polyamide 66 based compositions additionally comprising at least a partially aromatic polyamide, at least one phenolic antioxidant and at least one polyhydric alcohol, molding compositions to be prepared therefrom, and injection molded, blown or extruded products to be produced therefrom.
  • Polyamides in particular partially crystalline polyamides, are frequently used as materials for moldings which are exposed during their service life to elevated temperatures over an extended period of time.
  • materials are sufficiently stable against the resulting thermal oxidative damage, especially for applications in the engine compartment of motor vehicles.
  • thermal oxidative damage see: P.Gijsman, e-Polymers, 2008, no.065.
  • glass fiber reinforced polyamide 66 compounds have been established in the automotive industry for the production of high thermal stress products, where "high temperature” means temperatures in the range of 180 ° C to 240 ° C, temperatures that may occur in the engine compartment of motor vehicles with internal combustion engines today,
  • high temperature means temperatures in the range of 180 ° C to 240 ° C
  • temperatures that may occur in the engine compartment of motor vehicles with internal combustion engines today
  • the products are turbocharged air ducts, intake pipes, valve covers, intercoolers or engine covers, because of the increase in the performance of automotive engines in recent years, there are ever-higher demands on the manufacturer for the materials to be used for the production of these products.
  • Polyamides generally show a deterioration in their mechanical properties when exposed to elevated temperatures for extended periods of time. This effect is based primarily on the oxidative damage of the polyamide at elevated temperatures (thermo-oxidative damage).
  • a longer period in the sense of the present invention means longer than 100 hours, elevated temperatures in the sense of the present invention means higher than 80 ° C.
  • thermoplastic molding compositions or products made therefrom against thermo-oxidative damage is usually by comparing mechanical Properties, in particular the impact strength according to ISO180, the tensile stress and elongation at break measured in the tensile test according to ISO 527, and the modulus of elasticity at a defined temperature over a defined period of time.
  • the thermo-oxidative degradation of thermoplastic, polyamide-based molding compounds at elevated temperatures over a longer period of time can generally not be prevented with stabilizer systems, but only delayed in time.
  • the requirements of polyamide-based molding compositions or of products to be produced therefrom in high-temperature applications are not sufficiently satisfied with the thermostabilizing systems known from the prior art.
  • components of polyamide-based molding compositions which also have at least one weld by vibration, Schuelement-, infrared, hot gas, ultrasonic, rotary or laser welding, show reduced stability, especially in the weld after aging at temperatures in the above Area.
  • metal-free stabilizers As traditional stabilizer systems based on metal salts such as copper iodide can under certain conditions lead to corrosion of metal parts also installed in the engine compartment.
  • poly (/ V, / V-hexamethylene adipamide), or poly (hexamethylene adipamide), also referred to below as polyamide 66 or PA 66 (CAS No. 32131 -17-2), with the aid of a polyhydric alcohol and with a copper compound is known for example from WO 2010/014801 A1.
  • WO 2010/014791 A1 also describes the thermal stabilization of PA66 with ethylene vinyl alcohol copolymer and copper iodide / potassium iodide.
  • metal salts or metal salt-containing stabilizers in combination with a polyhydric alcohol can lead to undesirable side effects. These preferably occur in the form of a deterioration in the mechanical properties of products after 2500 hours hot air aging at temperatures above 200 ° C, e.g. in the most important area around 220 ° C, in particular the impact resistance is affected.
  • the object of the present invention was to contrast the stabilization of reinforcing materials containing polyamide 66 based compositions and the products to be produced therefrom thermooxidative damage after 2500 h Hot air aging at temperatures around 220 ° C waiving the use of metal-containing stabilizers to improve so that the impact strength does not fall to a value below 50% of the value measured on fresh test specimens.
  • the used in the present application marking the polyamides corresponds to international standard, wherein the first digit (s) indicate the C atomic number of Trustdiamins and the last digit (s) the C atomic number of the dicarboxylic acid. If only one number is given, as in the case of PA 6, this means that an ⁇ , ⁇ -aminocarboxylic acid or the lactam derived therefrom, in the case of PA 6, ie ⁇ -caprolactam, has been used as starting material; Incidentally, reference is made to DIN EN ISO 1874-1: 201 1 -03.
  • Impact resistance describes the ability of a material to absorb impact energy and impact energy.
  • the impact resistance is calculated as the ratio Impact work and specimen cross section (unit of measurement kJ / m 2 ).
  • Charpy, Izod the impact strength can be determined.
  • the notched impact strength of the impact strength of the specimens is not notched.
  • tests were carried out with the test specimen standing upright, the pendulum striking the free end of the test specimen and determining the impact resistance on the non-notched or unnotched specimen according to IZOD according to ISO 180 1 U.
  • compositions according to the invention which are collectively referred to as molding compounds in plastics technology, are preferably obtained as granules, in strand form or as powder in the processing of the components A) to E) to be used according to the invention.
  • the compositions according to the invention are prepared by mixing the components to be used according to the invention in at least one mixing unit, preferably in a compounder, more preferably in a co-rotating twin-screw extruder, wherein compositions, also referred to as preparations, in the sense of the invention also purely physical mixtures which are mixed during mixing Components arise, include.
  • thermoplastic molding compositions can either consist exclusively of the components A), B), C), D) and E), or in addition to the components A), B), C), D) and E ) contain at least one further component.
  • d10, d50 and d90 values in this application their determination and their meaning, reference is made to Chemie Ingenieurtechnik (72) pp. 273-276, 3/2000, Wiley-VCH Verlags GmbH, Weinheim, 2000, according to which the d10 Value is the particle size below which 10% of the particle quantity lies, the d50 value is the particle size below which 50% of the particle quantity lies (median value) and the d90 value is that particle size below which 90% of the particle quantity lies.
  • PA6I or PA6T preferably PA6I
  • combustion engine components in particular motor vehicle combustion engine components based on compositions containing
  • combustion engine components in particular motor vehicle combustion engine components based on compositions containing
  • PA6I or PA6T preferably PA6I
  • the present invention preferably relates to molding compositions and products based on the compositions according to the invention, preferably engine components, in particular motor vehicle engine components, in which from 6.0 parts to 50.0 parts by weight of component B) per 100 parts by weight of component A), from 0.2 to 5.0 parts by mass Component C), 1 to 5 parts by mass of component D) and 17.5 to 185 parts by mass of component E) are used.
  • engine components in particular motor vehicle engine components, in which from 6.0 parts to 50.0 parts by weight of component B) per 100 parts by weight of component A), from 0.2 to 5.0 parts by mass Component C), 1 to 5 parts by mass of component D) and 17.5 to 185 parts by mass of component E) are used.
  • component A 20 to 25 parts by mass of component B
  • component C 0.01 to 0.1 parts by mass of component C
  • component D 4 to 5 mass fractions of component D
  • 70 to 80 parts by mass of component E are used.
  • compositions, and also the molding compositions and products to be produced therefrom preferably combustion engine components, in particular motor vehicle engine components, in addition to the components A) to E), F) at least one mold release agent, preferably in amounts in the range of 0.05 to 0 , 50 parts by mass per 100 parts by mass of component A).
  • the compositions, as well as the molding compositions and products to be produced therefrom preferably contain engine components, in particular motor vehicle engine components, in addition to the components A) to F) or in place of the components F) G) at least one of the components B) to F) various other additive, preferably in amounts ranging from 0.05 to 3.00 parts by mass per 100 parts by mass of component A).
  • Polyamide 66 having a relative solution viscosity in m-cresol in the range from 2.0 to 4.0 is preferably used as component A).
  • Polyamide 66 with a relative solution viscosity in m-cresol in the range from 2.6 to 3.2 is particularly preferably used.
  • the transit times of a dissolved polymer are measured by an Ubbelohde viscometer to subsequently determine the viscosity difference between the polymer solution and its solvent, here m-cresol (1% solution).
  • Applicable standards are DIN 51562; DIN ISO 1628 or equivalent standards.
  • the viscosity measurement in the context of the present invention is carried out in sulfuric acid using an Ubbelohde viscometer according to DIN 51562 part 1, with the capillary II at 25 ° C. ( ⁇ 0.02 ° C.).
  • the polyamide 66 to be used according to the invention as component A) preferably has 20 to 80 milliequivalent of amino end groups / 1 kg PA and 20 to 80 milliequivalent acid end groups / 1 kg PA, more preferably 35 to 60 milliequivalent amino end groups / 1 kg PA and 40 to 75 milliequivalent acid end groups / 1 kg PA, where PA stands for polyamide.
  • the determination of the amino end groups was carried out in the context of the present invention according to: GB Taylor, J. Am. Chem. Soc. 69, 635, 1947.
  • Polyamide 66 [CAS No. 32131 -17-2] to be used according to the invention as component A) is available, for example, from Ascend Performance Materials LLC under the brand Vydyne®.
  • Partaromatic polyamides are polyamides whose monomers are derived in part from aromatic bases.
  • the polyamides to be used as component B) can be prepared by various processes and synthesized from different building blocks.
  • For the preparation of partially aromatic polyamides a variety of procedures are known, depending on the desired end product different monomer units, various chain regulators for setting a desired molecular weight or monomers can be used with reactive groups for later intended aftertreatments.
  • the technically relevant processes for the preparation of the polyamides to be used as component B) usually proceed via the polycondensation in the melt.
  • the hydrolytic polymerization of lactams is understood as polycondensation.
  • Partially aromatic polyamides to be used according to the invention as component B) are based on ⁇ , ⁇ -diamines and at least one benzenedicarboxylic acid.
  • Preferred benzenedicarboxylic acids are isophthalic acid or terephthalic acid, preferably isophthalic acid.
  • Preferred optional additional aromatic units are selected from phenylenediamine or xylylenediamine.
  • Preferred ⁇ , ⁇ -diamines are 1,4-diaminobutane (hexabutylenediamine) or 1,6-diaminobutane (hexamethylenediamine), in particular hexamethylenediamine.
  • Partially aromatic polyamides to be used particularly preferably as component B) are based on isophthalic acid (PA6I) [CAS No. 25668-34-2] or terephthalic acid (PA6T) [CAS No. 24938-70-3]. and hexamethylenediamine [CAS No. 124-09-4].
  • PA6I isophthalic acid
  • PA6T terephthalic acid
  • hexamethylenediamine CAS No. 124-09-4
  • Very particular preference is PA6I, which is available inter alia as Durethan® T40 at LANXESS Deutschland GmbH, Cologne.
  • component C) at least one sterically hindered phenol, commonly referred to as phenolic antioxidant used.
  • component C) contains at least one unit of the formula
  • At least one polyhydric alcohol is used.
  • a polyhydric alcohol having more than two hydroxyl groups is used.
  • Very particular preference is given to using at least one polyhydric alcohol from the group consisting of dipentaerythritol, tripentaerythritol, pentaerythritol and mixtures thereof.
  • Particularly preferred according to the invention is dipentaerythritol [CAS No. 126-58-9], which can be obtained, for example, from Sigma-Aldrich.
  • component E preferably fibrous, needle-shaped or particulate fillers and reinforcing agents are used.
  • a “fiber” in the sense of the present invention is a macroscopically homogeneous body with a high ratio of length to its cross-sectional area
  • the fiber cross-section may be of any shape but is generally round or oval According to "http: //en.wikipedia. org / wiki / fiber-plastic composite "makes a distinction
  • Endless fibers with a mean length L> 50 mm can be determined, for example, by microfocus X-ray computed tomography ( ⁇ -CT); J. Kastner et. al., Quantitative measurement of fiber lengths and distribution in fiber-reinforced plastic parts by means of ⁇ -ray computed tomography, DGZfP Annual Meeting 2007 - Lecture 47, pages 1-8. Particular preference is given to using glass fibers, very particular preference being given to glass fibers made of E glass.
  • the glass fibers are particularly preferably used as short glass fibers for molding compositions which are used in injection molding. In the case of the use of the compositions according to the invention as a matrix polymer for composites, the glass fibers are preferably used as continuous fibers and / or long fibers.
  • the fibrous or particulate fillers and reinforcing agents are provided in a preferred embodiment for better compatibility with the component A) with suitable surface modifications, preferably with surface modifications containing silane compounds.
  • suitable surface modifications preferably with surface modifications containing silane compounds.
  • the glass fiber CS7928 from Lanxess Deutschland GmbH can be used.
  • Cross-sectional area or filament diameter are determined in the context of the present invention by means of at least one optical method according to DIN 65571.
  • Optical methods are a) light microscope and micrometer eyepiece (distance measurement cylinder diameter), b) Light microscope and digital camera with subsequent planimetry (cross-section measurement), c) laser interferometry and d) projection.
  • d 50 value All length, width or diameter data for the fillers and reinforcing materials listed here are averaged (d 50 value) and refer to the state before compounding. With regard to the d 50 values in this application, their determination and their significance, reference is made to Chemie Ingenieurtechnik 72, 273-276, 3/2000, Wiley-VCH Verlags GmbH, Weinheim, 2000, according to which the d 50 value is that particle size , below which 50% of the particle quantity lie (median value).
  • Mold release agents or amide derivatives of long-chain fatty acids in particular ethylene-bis-stearylamide, glycerol tristearate, stearyl stearate, montan ester waxes, in particular esters of montan acids with ethylene glycol and low molecular weight polyethylene or polypropylene waxes in oxidized and non-oxidized form are preferably used as component F).
  • Particularly preferred release agents according to the invention are contained in the group of esters or amides of saturated or unsaturated aliphatic carboxylic acids having 8 to 40 carbon atoms with saturated aliphatic alcohols or amines having 2 to 40 carbon atoms.
  • the compositions or molding compositions according to the invention comprise mixtures of said mold release agents.
  • Montan ester waxes preferably used as mold release agents are esters of mixtures of straight-chain, saturated carboxylic acids with chain lengths in the range from 28 to 32 carbon atoms.
  • Corresponding montan ester waxes are obtained, for example, from Clariant International Ltd. offered as Licowax®.
  • Particularly preferred according to the invention is Licowax® E, or a mixture of waxes, preferably mixtures of ester waxes and amide waxes, as described in EP2607419 A1.
  • the additive to be used as component G) is preferably at least one substance from the group of thermostabilizers other than components C) and D), UV stabilizers, gamma ray stabilizers, hydrolysis stabilizers, antistatic agents, nucleating agents, plasticizers, processing aids, impact modifiers, dyes, pigments and flame retardants.
  • thermostabilizers other than components C) and D UV stabilizers, gamma ray stabilizers, hydrolysis stabilizers, antistatic agents, nucleating agents, plasticizers, processing aids, impact modifiers, dyes, pigments and flame retardants.
  • the above-mentioned and other suitable additives are state of the art and can be used by the person skilled in the art, for example, in the Plastics Additives Handbook, 5th Edition, Hanser Verlag, Kunststoff, 2001, pp. 80-84, 546-547, 688, 872-874, 938, 966.
  • the additives to be used as component G) can be used alone or in mixture or in the form
  • Additional heat stabilizers to be used according to the invention are preferably sterically hindered phosphites, hydroquinones, substituted resorcinols, salicylates, benzotriazoles or benzophenones, as well as variously substituted representatives of these groups and / or mixtures thereof.
  • Explicitly excluded are aromatic secondary amines and hindered aromatic amines (HALS).
  • UV stabilizers are preferably substituted resorcinols, salicylates, benzotriazoles or benzophenones.
  • impact modifiers or elastomer modifiers are preferably copolymers, which are preferably composed of at least two monomers of the following series: ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile and acrylic acid esters or methacrylic acid esters with 1 to 18 carbon atoms in the alcohol component.
  • the copolymers may contain compatibilizing groups, preferably maleic anhydride or epoxide.
  • Dyes or pigments to be used as an additive according to the invention are preferably inorganic pigments, more preferably titanium dioxide, ultramarine blue, iron oxide, zinc sulfide or carbon black, and also organic pigments, more preferably phthalocyanines, quinacridones, perylenes and dyes, more preferably nigrosine or anthraquinones, and other colorants.
  • Nucleating agents to be used as an additive according to the invention are preferably sodium or calcium phenylphosphinate, aluminum oxide, silicon dioxide or talc. Particularly preferred as the nucleating agent talc [CAS No.14807-96-6] is used, in particular microcrystalline talc, microcrystalline talc having an average particle size d 5 o, measured by Sedigraph, in the range of 0.5 to 10 ⁇ . See: Micromeritics Instrument Corp, The Science and Technology of Small Particles, Norcross, USA, Part # 512/42901/00.
  • Flame retardants to be used according to the invention as an additive are preferably mineral flame retardants, nitrogen-containing flame retardants or phosphorus-containing flame retardants. Among the mineral flame retardants magnesium hydroxide is particularly preferred.
  • Magnesium hydroxide may be contaminated due to its origin and method of production. Typical impurities are, for example, silicon, iron, calcium and / or aluminum-containing species, which may be incorporated in the magnesium hydroxide crystals, for example in the form of oxides.
  • the magnesium hydroxide to be used according to the invention can be uncoated or else provided with a size, a size being understood to mean an impregnating liquid in order to give the surface of a substance specific properties.
  • the magnesium hydroxide to be used according to the invention is provided with sizes based on stearates or aminosiloxanes, particularly preferably with aminosiloxanes.
  • Preferably used magnesium hydroxide has an average particle size d50 in the range of 0.5 ⁇ to 6 ⁇ , with a d50 in the range of 0.7 ⁇ to 3.8 ⁇ preferred and a d50 in the range of 1, 0 ⁇ to 2.6 ⁇ is particularly preferred and the mean particle size is determined according to ISO 13320 by laser diffractometry.
  • Suitable magnesium hydroxide types according to the invention are, for example, Magnifin® H5IV from Martinswerk GmbH, Bergheim, Germany or Hidromag® Q2015 TC from Penoles, Mexico City, Mexico.
  • Preferred nitrogen-containing flame retardants are the reaction products of trichlorotriazine, piperazine and morpholine according to CAS No. 1078142-02-5, in particular MCA PPM triazine HF from the company MCA Technologies GmbH, Biel-Benken, Switzerland, furthermore melamine cyanurate and condensation products of melamine such as e.g. Meiern, Melam, Melon or higher condensed compounds of this type.
  • Preferred inorganic nitrogen-containing compounds are ammonium salts.
  • salts of aliphatic and aromatic sulfonic acids and mineral flame retardant additives such as aluminum hydroxide, Ca-Mg-carbonate hydrates (for example DE-A 4 236 122) can also be used.
  • flame retardant synergists from the group of the oxygen-nitrogen or sulfur-containing metal compounds, where zinc-free compounds, in particular molybdenum oxide, magnesium oxide, magnesium carbonate, calcium carbonate, Calcium oxide, titanium nitride, magnesium nitride, calcium phosphate, calcium borate, magnesium borate or mixtures thereof are particularly preferred.
  • components which contain zinc may also be used as component G), if required.
  • These preferably include zinc oxide, zinc borate, zinc stannate, zinc hydroxystannate, zinc sulfide and zinc nitride, or mixtures thereof.
  • Preferred phosphorus-containing flame retardants are organic metal phosphinates such as e.g. Aluminum tris (diethylphosphinate), aluminum salts of phosphonic acid, red phosphorus, inorganic metal hypophosphites, in particular aluminum hypophosphite, further metal phosphonates, in particular calcium phosphonate, derivatives of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxides (DOPO derivatives), resorcinol bis
  • organic metal phosphinates such as e.g. Aluminum tris (diethylphosphinate), aluminum salts of phosphonic acid, red phosphorus, inorganic metal hypophosphites, in particular aluminum hypophosphite, further metal phosphonates, in particular calcium phosphonate, derivatives of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxides (DOPO derivatives), resorcinol bis
  • diphenyl phosphate (diphenyl phosphate) (RDP), including oligomers and bisphenol A bis-diphenyl phosphate (BDP) including oligomers, furthermore melamine pyrophosphate and melamine polyphosphate, furthermore melamine poly (aluminum phosphate), melamine poly (zinc phosphate) or Phenoxyphosphazenoligomere and mixtures thereof.
  • flame retardants to be used as component G) are carbon formers, particularly preferably phenol-formaldehyde resins, polycarbonates, polyimides, polysulfones, polyethersulfones or polyether ketones, and also anti-dripping agents, in particular tetrafluoroethylene polymers.
  • the flame retardants to be used as component G) can be added in pure form, as well as via masterbatches or compactates.
  • flame retardants may also be used - if necessary, taking into account the disadvantages of the loss of halogen freedom of the flame retardants - halogen-containing flame retardants.
  • Preferred halogen-containing flame retardants are commercially available organic halogen compounds, more preferably ethylene-1, 2-bistetrabromophthalimide, decabromodiphenylethane, tetrabromobisphenol A epoxyoligomer, tetrabromobisphenol A oligocarbonate, tetrachlorobisphenol A oligocarbonate, polypentabromobenzyl acrylate, brominated polystyrene or brominated polyphenylene ethers which are used alone or in Combination with synergists, especially antimony trioxide or antimony pentoxide, can be used, among the halogen-containing flame retardants brominated polystyrene is particularly preferred.
  • Brominated polystyrene is available in various product qualities commercially available. Examples include FireMaster ® PBS64 the Fa.. Lanxess, Cologne, Germany and Saytex ® HP-3010 from the company Albemarle, Baton Rouge, United States.
  • flame retardants to be used as component G are aluminum tris (diethylphosphinate)] [CAS no. No. 225789-38-8] and the combination of aluminum tris (diethylphosphinate) and melamine polyphosphate or the combination of aluminum tris (diethylphosphinate) and at least one aluminum salt of phosphonic acid are very particularly preferred, with the latter combination being particularly preferred.
  • a suitable aluminum tris takes the Exolit ® OP1230 or OP1240, Exolit ® of the company, for example. Clariant International Ltd. Muttenz, Switzerland in question.
  • Melamine polyphosphate is commercially available in various product qualities. Examples of these are, for example, Melapur® 200/70 from BASF, Ludwigshafen, Germany and Budit® 3141 from Budenheim, Budenheim, Germany.
  • Preferred aluminum salts of phosphonic acid are selected from the group of primary aluminum phosphonate [Al (H 2 P0 3 ) 3 ],
  • AI 2 (HP0 3) 3 Al 2 0 3 x n H 2 0 with x in the range 2.27 to 1 and n ranges from 0 to 4,
  • M is alkali metal ion (s) and z ranges from 0.01 to 1.5, y is from 2.63 to 3.5, v is from 0 to 2 and w is from 0 to 4, and
  • u is in the range of 2 to 2.99
  • t is in the range of 2 to 0.01
  • s is in the range of 0 to 4
  • Preferred alkali metals in formula (Z2) are sodium and potassium.
  • the aluminum salts of phosphonic acid described can be used individually or in a mixture.
  • Particularly preferred aluminum salts of phosphonic acid are selected from the group
  • AI 2 (HP0 3) 3 Al 2 0 3 x n H 2 0 with x in the range 2.27 to 1 and n is in the range from 0 to 4th
  • secondary aluminum phosphonate Al 2 (HPO 3 ) 3 , CAS no. 71449-76-8
  • secondary aluminum phosphonate tetrahydrate Al 2 (HPO 3 ) 3 -4H 2 O, CAS No. 156024-71 -4
  • secondary aluminum phosphonate Al 2 (HPO 3 ) 3 ].
  • polyamide 6 (PA 6) can be used as component G), with the proviso that the PA 6 does not form a copolymer with either component A) or component B).
  • PA 6 [CAS No. 25038-54-4] is a partially crystalline thermoplastic, available for example from Lanxess Deutschland GmbH, Cologne, under the name Durethan®. According to DE 10 2011 084 519 A1, partially crystalline polyamides have a melting enthalpy in the range from 4 to 25 J / g, measured by the DSC method according to ISO 1 1357 during the second heating and integration of the melt peak.
  • the present invention preferably relates to compositions comprising A) PA 66, B) PA6I, C) phenolic antioxidant, D) dipentaerythritol, E) glass fibers, as well as molding compositions and products to be produced therefrom.
  • the present invention preferably relates to compositions comprising A) PA 66, B) PA6T, C) phenolic antioxidant, D) dipentaerythritol, E) glass fibers, as well as molding compositions and products to be produced therefrom.
  • the present invention preferably relates to compositions containing A) PA
  • the present invention preferably relates to compositions containing A) PA
  • the present invention preferably relates to compositions comprising A) PA 66, B) PA6I, C) 1, 6-bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamido) hexane, D) dipentaerythritol, E) glass fibers, and mixtures thereof Moldings and products to be produced.
  • the present invention preferably relates to compositions comprising A) PA 66, B) PA6T, C) 1, 6-bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamido) hexane, D) dipentaerythritol, E) glass fibers, and mixtures thereof Moldings and products to be produced.
  • the present invention preferably relates to compositions comprising A) PA 66, B) partially aromatic PA, C) 1, 6-bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamido) hexane, D) dipentaerythritol, E) glass fibers and G ) PA 6, as well as molding compounds and products to be produced therefrom.
  • the present invention preferably relates to compositions comprising A) PA 66, B) partially aromatic PA, C) 1, 6-bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamido) hexane, D) dipentaerythritol, E) glass fibers and G ) PA 6 in proportions less than or equal to the proportions of component B), as well as molding compositions and products to be produced therefrom.
  • the present invention also relates to a process for the preparation of products by mixing the components of the compositions according to the invention, to form a molding compound in the form of a strand, cooled to Granuliernote and granulated and as a matrix material of injection molding, blow molding or extrusion processing, preferred subjected to injection molding.
  • Products according to the invention may also be composites based on continuous fibers or long fibers, preferably glass-based continuous fibers or glass-based long fibers, as known to the person skilled in the art, for example from DE 10 2006 013 684 A1 or DE 10 2004 060 009 A1.
  • the mixing of the components occurs at temperatures in the range of 220 to 400 ° C by mixing together, mixing, kneading, extruding or rolling.
  • Preferred mixing units are to be selected from compounder, co-rotating twin-screw extruder or Buss kneader. It may be advantageous to premix individual components.
  • Compounds are mixtures of raw materials to which fillers, reinforcing agents or other additives have additionally been added. By compounding thus at least two substances are connected together to form a homogeneous mixture. The process of making a compound is called compounding.
  • a first step at least one of components B), C), D) or E) is mixed with component A) or with PA6 as component G) to form a premix.
  • This first step is preferably carried out at temperatures ⁇ 50 ° C. in a spiral mixer, double-cone mixer, Lodige mixer or similar mixing units suitable for mixing solids.
  • premixing on a co-rotating twin-screw extruder, Buss kneader or planetary roller extruder at a temperature above the melting point of component A) or G) PA6 may be advantageous.
  • the mixing units are equipped with a degassing function.
  • the resulting molding compositions are preferably discharged as a strand, cooled to Granuliernote and granulated.
  • the resulting granules are dried, preferably at temperatures in the range of 70 to 130 ° C, preferably in a vacuum oven or in a dry air dryer.
  • the residual moisture should be set to a value preferably less than 0.12%.
  • a residual moisture content of a maximum of 0.06% should be maintained.
  • so-called semi-finished products from a physical mixture prepared at room temperature, preferably at a temperature in the range from 10 to 40 ° C., a so-called dry blend, premixed components and / or individual components.
  • Semi-finished products in the context of the present invention are prefabricated objects and arise in a first step in the production process of a product.
  • semi-finished products are not bulk materials, granules or powders because, unlike semifinished products, they are not geometrically determined, solid bodies and thus no "half-completion" of a final product has yet occurred.
  • the term product therefore also includes semi-finished products.
  • thermoplastic molding materials are known to the person skilled in the art.
  • Processes according to the invention for producing polyamide-based products by extrusion or injection molding are used at melt temperatures in the range from 250 to 330 ° C., preferably in the range from 260 to 310 ° C., more preferably in the range from 270 to 300 ° C., and in the case of injection molding at filling pressures of up to 2500 bar, preferably at filling pressures of at most 2000 bar, more preferably at filling pressures of at most 1500 bar and very particularly preferably carried out at filling pressures of a maximum of 750 bar.
  • the products to be produced from the molding compositions according to the invention can preferably be used for applications for which a high stability against heat aging is required, preferably in the automotive, electrical, electronic, telecommunications, solar, information technology, computer industries, in the household , in sports, medicine or the entertainment industry.
  • Preferred for such applications is the use for products in vehicles, particularly preferably in motor vehicles (motor vehicles) with an internal combustion engine, in particular in the motor vehicle engine compartment.
  • the compositions according to the invention are particularly preferably suitable for producing welded components which have at least one weld seam by means of vibration, heating element, infrared, hot gas, ultrasound, rotational or laser welding methods.
  • the present invention therefore also relates to the use of thermoplastic molding compositions containing the above-mentioned components in the form of compositions for producing products with increased stability against thermo-oxidative damage, preferably of motor vehicle products, more preferably of motor vehicle compartment products, in particular preferably of products having at least one weld, in particular a weld by vibration, heating element, infrared, hot gas, ultrasonic, rotary or laser welding.
  • the molding compositions according to the invention are also suitable for applications or moldings or articles, where in addition to the thermo-oxidative stability, a stability to photo-oxidative damage is required, preferably solar systems.
  • the products to be produced according to the invention are semi-finished products in the form of thermally stabilized composites Basis of continuous fibers, also referred to as organic sheets, but also to overmolded or overmolded composite structures.
  • the compositions according to the invention or the heat stabilizer system according to the invention can be used either in the thermoplastic matrix of the composite structure or in the molding compound to be sprayed or in both components or contained therein.
  • Thermostabilized composites are known, for example, from WO 2011/014754 A1, overmolded composite structures are described, for example, in WO 2011/014751 A1.
  • the present invention also relates to a process for thermostabilization of polyamide 66 and in particular the welds of polyamide 66 based components by using a stabilizer system of partially aromatic polyamide, dipentaerythritol and phenolic antioxidant, preferably a stabilizer system of PA6I, dipentaerythritol, and phenolic antioxidant, wherein the Polyamide 66 is not present as a copolymer with the partially aromatic polyamide.
  • the present application also relates to a method for reducing photooxidative damage and / or thermo-oxidative damage of offset with at least one reinforcing polyamide 66 or products to be produced therefrom in the form of films, fibers or moldings, by a stabilizer system based on a partially aromatic polyamide, at least a polyhydric alcohol and at least one phenolic antioxidant, and the polyamide 66 is not present as a copolymer with the partially aromatic polyamide.
  • the products are preferably composite structures based on polyamide 66 and overmoulded composite structures, but also polyamide 66 based components provided with weld seams.
  • the stabilizer system used is preferably partially aromatic polyamide, dipentaerythritol and phenolic antioxidant, particularly preferably a stabilizer system of PA6I, dipentaerythritol and phenolic antioxidant.
  • the invention relates to the use of a stabilizer system based on a partially aromatic polyamide, at least one polyhydric alcohol and at least one phenolic antioxidant for reducing photooxidative damage and / or thermo-oxidative damage to polyamide 66 mixed with at least one reinforcing substance or to films to be produced therefrom in the form of films.
  • the preferred subject of the present invention are also combustion engine components, in particular motor vehicle combustion engine components, based on compositions containing
  • PA6I or PA6T preferably PA6I
  • A) and B) do not form a copolymer, which are turbocharged air ducts, intake manifolds, valve covers, intercoolers or engine covers.
  • molding compositions were first prepared in the extruder. Products obtained by injection molding from the molding compositions in the form of flat bars were then tested as unnotched test specimens, in a fresh state and after prior aging, in the impact test according to DIN EN ISO 180 1 -U.
  • Component A Polyamide 66, Vydyne® 50 BWFS from Ascend Performance Materials
  • Component B partly aromatic polyamide PA6I, Durethan® T40 from Lanxess
  • Component C) Irganox® 1098 from BASF
  • Component D dipentaerythritol [CAS No. 126-58-9]
  • Component E Glass fibers, Chopped Strands CS7928 from Lanxess Deutschland GmbH
  • Soot masterbatch 50% in polyethylene
  • the glass fiber content was in all molding compounds 35% of the total weight. Since the compositions are based on 100 parts by mass of PA 66 and this proportion changes due to the different amounts of admixtures, the different numerical values for the mass fractions of glass fibers are obtained.
  • the injection molding of the resulting molding compositions was carried out on an injection molding machine type SG370-173732 Fa. Arburg.
  • the melt temperature was 290 ° C and the mold temperature 80 ° C.
  • Flat bars were sprayed as test specimens according to DIN EN ISO 180 1 -U of the nominal size 80 mm x 10 mm x 4 mm. Aging and testing:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Acoustics & Sound (AREA)
  • Combustion & Propulsion (AREA)
  • General Engineering & Computer Science (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Cylinder Crankcases Of Internal Combustion Engines (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

La présente invention concerne des compositions à base de polyamide 66 rendu stable à la chaleur, contenant des matières de renfort, qui sont à base d'au moins un polyamide semi-aromatique, d'au moins un antioxydant phénolique et d'au moins un alcool polyhydrique, des matières à mouler qu'elles permettent d'obtenir et des produits moulés par injection, moulés par soufflage ou extrudés qu'elles permettent d'obtenir.
EP18738336.9A 2017-07-13 2018-07-12 Compositions rendues stables à la chaleur Withdrawn EP3651960A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP17181105 2017-07-13
PCT/EP2018/069000 WO2019012064A1 (fr) 2017-07-13 2018-07-12 Compositions rendues stables à la chaleur

Publications (1)

Publication Number Publication Date
EP3651960A1 true EP3651960A1 (fr) 2020-05-20

Family

ID=59362941

Family Applications (1)

Application Number Title Priority Date Filing Date
EP18738336.9A Withdrawn EP3651960A1 (fr) 2017-07-13 2018-07-12 Compositions rendues stables à la chaleur

Country Status (8)

Country Link
US (1) US20210087390A1 (fr)
EP (1) EP3651960A1 (fr)
JP (1) JP2020527183A (fr)
KR (1) KR20200030530A (fr)
CN (1) CN110891753A (fr)
BR (1) BR112020000246A2 (fr)
DE (1) DE202018006637U1 (fr)
WO (1) WO2019012064A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3587085A1 (fr) * 2018-06-27 2020-01-01 Basf Se Poudre de frittage comportant un alcool polyvalent destiné à la fabrication de corps moulés
JP2021050323A (ja) * 2019-09-19 2021-04-01 旭化成株式会社 ポリアミド組成物及びその製造方法、並びに、成形品
CA3154604C (fr) 2019-10-24 2024-01-30 Chee Sern LIM Compositions a base de polyamide et articles fabriques a partir de celles-ci
CN115315485A (zh) * 2020-03-19 2022-11-08 Ｕｂｅ株式会社 聚酰胺树脂组合物
WO2024091994A1 (fr) * 2022-10-26 2024-05-02 Celanese International Corporation Composition de polymère thermoplastique renforcée par des fibres contenant une enveloppe ignifuge
KR102646823B1 (ko) * 2023-12-07 2024-03-11 정필성 친환경 덕트
KR102646824B1 (ko) * 2023-12-07 2024-03-11 정필성 친환경 필터 고정프레임

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4236122A1 (de) 1992-10-27 1994-04-28 Bayer Ag Flammgeschützte, mineralgefüllte, thermoplastische Formmassen mit hoher Kriechstromfestigkeit
JPH079945A (ja) * 1993-06-22 1995-01-13 Showa Denko Kk 自動車用電気部品
JP3405583B2 (ja) * 1994-01-26 2003-05-12 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー ポリアミド樹脂組成物およびその成形品
US20040242737A1 (en) * 2003-04-14 2004-12-02 Georgios Topulos Polyamide composition for blow molded articles
DE102004060009B4 (de) 2004-12-14 2015-05-28 Bayerische Motoren Werke Aktiengesellschaft Verfahren zur Herstellung eines Schichtkörpers
DE102006013684A1 (de) 2006-03-20 2007-09-27 Geiger Technik Gesellschaft mit beschränkter Haftung Oberflächenoptimiertes Kunststoffbauteil
JP2011529990A (ja) 2008-07-30 2011-12-15 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー コポリエーテルエステル組成物およびそれから作製された物品
US20110027571A1 (en) 2009-07-30 2011-02-03 E.I. Du Pont De Nemours And Company Heat resistant polyamide composite structures and processes for their preparation
US20110039470A1 (en) 2009-07-30 2011-02-17 E.I. Du Pont De Nemours And Company Overmolded heat resistant polyamide composite structures and processes for their preparation
CN102464881A (zh) * 2010-11-10 2012-05-23 杜邦公司 无卤的阻燃聚酰胺组合物
DE102011084519A1 (de) 2011-10-14 2013-04-18 Evonik Industries Ag Verwendung einer Mehrschichtfolie für die Herstellung photovoltaischer Module
DE102011120200A1 (de) 2011-12-05 2013-06-06 Clariant International Ltd. Flammschutzmittel-Mischungen enthaltend Flammschutzmittel und Aluminiumphosphite, Verfahren zu ihrer Herstellung und ihre Verwendung
EP2607418A1 (fr) 2011-12-21 2013-06-26 LANXESS Deutschland GmbH Combinaisons d'agents de démoulage
US20140288220A1 (en) * 2013-03-25 2014-09-25 E I Du Pont De Nemours And Company Heat resistant polyamide compositions
KR20170003927A (ko) * 2014-05-05 2017-01-10 사빅 글로벌 테크놀러지스 비.브이. 보강된 폴리프탈아미드/폴리(페닐렌 에테르) 조성물
EP3115406A1 (fr) * 2015-07-10 2017-01-11 LANXESS Deutschland GmbH Masses de moulage thermoplastiques

Also Published As

Publication number Publication date
US20210087390A1 (en) 2021-03-25
JP2020527183A (ja) 2020-09-03
DE202018006637U1 (de) 2021-09-28
WO2019012064A1 (fr) 2019-01-17
BR112020000246A2 (pt) 2020-07-14
CN110891753A (zh) 2020-03-17
KR20200030530A (ko) 2020-03-20

Similar Documents

Publication Publication Date Title
EP3651960A1 (fr) Compositions rendues stables à la chaleur
EP2060596B1 (fr) Compositions de moulage renforcées à base de polyamide chargé
EP3039077B1 (fr) Matières moulables à base de polyamide et articles moulés à partir de ces matières
EP3034554B1 (fr) Compositions de polyamide
WO2019012061A1 (fr) Compositions rendues stables à la chaleur
EP3133104B1 (fr) Compositions de polyamide
EP3526283B1 (fr) Polyamides ignifugés
EP3546511A1 (fr) Compositions de polyamide
DE102017214048A1 (de) Flammhemmende Polyamidzusammensetzungen mit hoher Glühdrahtentzündungstemperatur und deren Verwendung
EP3514198B1 (fr) Fibres de verre hr dans des composants oscillants
DE102017212098A1 (de) Flammhemmende Polyamidzusammensetzungen mit hoher Wärmeformbeständigkeit und deren Verwendung
EP3511366B1 (fr) Fibres de verre hr dans des composants oscillants
WO2019048308A1 (fr) Compositions de polyamide ignifuges ayant une résistance à la déformation à chaud élevée et leur utilisation
DE102008053797A1 (de) Thermoplastische Formmassen mit verbesserter thermischer Stabilität
EP3670589A1 (fr) Compositions de polyamide
EP1846487A1 (fr) Polyamides thermoplastiques remplis de verre spherique
DE102008052055A1 (de) Thermoplastische Formmassen mit verbesserter thermischer Stabilität
EP4314140A1 (fr) Compositions de polyamide
WO2019030253A1 (fr) Compositions de polyamide ignifuges ayant une résistance à la déformation à chaud élevée et leur utilisation
DE202008018386U1 (de) Thermoplastische Formmassen mit verbesserter thermischer Stabilität

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20200213

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: LANXESS DEUTSCHLAND GMBH

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20230201