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WO2025040343A1 - Pastilles renforcées par des fibres de verre ignifuges, leur procédé de production et article renforcé obtenu à partir de celles-ci - Google Patents

Pastilles renforcées par des fibres de verre ignifuges, leur procédé de production et article renforcé obtenu à partir de celles-ci Download PDF

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Publication number
WO2025040343A1
WO2025040343A1 PCT/EP2024/070737 EP2024070737W WO2025040343A1 WO 2025040343 A1 WO2025040343 A1 WO 2025040343A1 EP 2024070737 W EP2024070737 W EP 2024070737W WO 2025040343 A1 WO2025040343 A1 WO 2025040343A1
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WO
WIPO (PCT)
Prior art keywords
pellet
filaments
range
core
sheath
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
PCT/EP2024/070737
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English (en)
Inventor
Xiqiang LIU
Chaodong JIANG
Christelle Marie Hélène Grein
Liang Wen
Ting Huang
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.)
SABIC Global Technologies BV
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SABIC Global Technologies BV
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 SABIC Global Technologies BV filed Critical SABIC Global Technologies BV
Publication of WO2025040343A1 publication Critical patent/WO2025040343A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • B29B9/12—Making granules characterised by structure or composition
    • 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
    • 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
    • B29B9/12—Making granules characterised by structure or composition
    • B29B9/14—Making granules characterised by structure or composition fibre-reinforced
    • 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
    • B29C48/15—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor incorporating preformed parts or layers, e.g. extrusion moulding around inserts
    • B29C48/156—Coating two or more articles simultaneously
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/201—Pre-melted polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
    • 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
    • B29K2105/0026—Flame proofing or flame retarding agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/08—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns
    • B29K2105/10—Cords, strands or rovings, e.g. oriented cords, strands or rovings
    • B29K2105/101—Oriented
    • B29K2105/105—Oriented uni directionally
    • B29K2105/106—Oriented uni directionally longitudinally
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/25—Solid
    • B29K2105/251—Particles, powder or granules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof

Definitions

  • the invention relates to flame retardant glass fiber reinforced pellets, production method thereof and reinforced article obtained therefrom.
  • fiber-reinforced plastics are composite materials with a wide range of applications in industry, for example in the aerospace, automotive, chipping, building and construction industries.
  • a reinforced article can comprise any combination of individual materials, for example, a thermoplastic polymer (the matrix) in which fibers (reinforcing fiber) have been dispersed.
  • a thermoplastic polymer the matrix
  • fibers reinforcing fiber
  • Glass fibers are generally supplied as a plurality of continuous, very long filaments, and can be in the form of strands or bundles, rovings or yarns.
  • a filament is an individual fiber of reinforcing material.
  • a bundle is a plurality of bundled filaments.
  • Yarns are collections of filaments or bundles twisted together.
  • a roving refers to a collection of bundles/strands wound into a package.
  • a process for producing reinforced compositions is for example described in W02009/080281.
  • a process is described for producing a long glass fiber- reinforced thermoplastic polymer composition, which comprises the subsequent steps of: a. Unwinding from a package of at least one continuous glass multifilament strand containing a sizing composition; b. Applying an impregnating agent to said at least one continuous glass multifilament strand to form an impregnated continuous multifilament strand; c. Applying a sheath of thermoplastic polymer around the impregnated continuous multifilament strand to form a sheathed continuous multifilament strand; and d. Cutting the sheathed continuous glass multifilament strand into pellets.
  • the thermoplastic polymer around the core is usually comprised of polypropylene and a coupling agent is normally needed.
  • Glass fiber reinforced articles are widely used in various fields including automotive applications. In some of the applications, flame retardancy of the glass fiber reinforced articles is desired. Flame retardancy is usually obtained by addition of flame retardant additives into the thermoplastic polymer composition. However, such an addition usually results in deterioration of mechanical performance of the reinforced articles.
  • the present invention relates to a pellet having an axial direction; said pellet comprising a core that extends in the axial direction and comprising a polymer sheath which has been applied around said core, wherein said core comprises a plurality of filaments, preferably glass filaments, that extends in the axial direction; wherein said polymer sheath is at least substantially free of said (glass) filaments and wherein said polymer sheath comprises or consists of at least one aliphatic polyamide and a non-halogen flame retardant composition.
  • the present invention relates to a solid object obtained from molding a plurality of said pellets according to the invention.
  • the present invention relates to a method of preparing a pellet comprising the steps of: i) Unwinding from a package of a plurality of continuous (glass) filaments; ii) Optionally applying an impregnating composition to said plurality of (glass) filaments to form an impregnated plurality of (glass) filaments; iii) Applying a sheath of polymer around the plurality of (glass) filaments to form a sheathed bundle comprising a core comprising said plurality of (glass) filaments and comprising a sheath surrounding said core, and iv) Cutting the sheathed bundle into individual pellets comprising a core that extends in the axial direction and comprising a polymer sheath which has been applied around said core, wherein said polymer sheath is at least substantially free of said (glass) filaments and said polymer sheath comprises or consists of at least one aliphatic polyamide and a non-halogen flame retardant composition.
  • composite means comprising at least two individual materials.
  • the pellet according to the present invention may be regarded as being a composite pellet.
  • pellet means a rounded or tube-like solid object, such as a compressed mass of a substance.
  • filament means a thin thread or thread-like object or fiber.
  • glass fiber filament means a filament made of glass fiber.
  • multifilament means a plurality of filaments, e.g. in the form of a strand or bundle.
  • bundle means a plurality of filaments that is held together or wrapper up together.
  • mass and “weight” are used interchangeably.
  • mass% has the same meaning as the term “weight%” or simply “wt%”.
  • the term “degree Celsius” or “°C” is sometimes simplified as “C”.
  • “190C” means “190°C”, as is known to a skilled person in the field.
  • an amount of a certain component is at least 1wt%, preferably at least 2wt%, and at most 5%, preferably at most 4wt%, being in one example specifically 3wt%
  • the amount ranges of 1-2wt%, 2- 3wt%, 3-4wt%, 4-5wt%, 1-5wt%, 2-4wt% etc, are all inherently disclosed, as if they were explicitly described in the present invention.
  • an amount of a certain component is in the range of 1-5wt%, preferably 2-4wt%, being in one example specifically 3wt%, then the amount ranges of 1-2wt%, 2-3wt%, 3-4wt%, 4- 5wt%, etc, are all inherently disclosed, as if they were explicitly described in the present invention.
  • the present invention relates to a pellet having an axial direction; said pellet comprising a core that extends in the axial direction and comprising a polymer sheath which has been applied around said core, wherein: * said core comprises a plurality of (glass) filaments that extends in the axial direction; * said polymer sheath is at least substantially free of said filaments; * said polymer sheath comprises or consists of at least one aliphatic polyamide and a non-halogen flame retardant composition.
  • a pellet comprising a glass filament core surrounded by a polymer sheath comprising or consisting of at least one aliphatic polyamide and a non-halogen flame retardant composition. This pellet may be used to prepare reinforced articles.
  • a sum of the amounts of the core and the sheath is at least 90wt% of the total weight of the pellet, preferably at least 95wt%, more preferably at least 97wt%.
  • said polymer sheath consists of the at least one aliphatic polyamide and the non-halogen flame retardant composition.
  • the pellet comprises 10-50wt% of the core and 50-90wt% of the sheath. In an embodiment, the pellet comprises 15-45wt% of the core, such as 20, 30 or 40 wt%. In an embodiment, the pellet comprises 55-85wt% of the sheath, such as 60, 70 or 80 wt%.
  • the pellet comprises 20-40 wt% of the glass filament, 40-60 wt% of the at least one aliphatic polyamide, and 10-25 wt% of the non-halogen flame retardant composition.
  • the pellet does not comprise a different thermoplastic polymer than the at least one aliphatic polyamide.
  • the pellet sheath does not comprise a polyolefin, such as a polypropylene, in particular, a polypropylene homopolymer or a polypropylene copolymer.
  • the aliphatic polyamide is PA6. In an embodiment, the aliphatic polyamide is PA6 with a viscosity number tested according to ISO307 in the range of 90- 160 ml/g, preferably in the range of 110-130 ml/g, more preferably about 120ml/g.
  • the polymer sheath does not comprise PA46 and/or PA66.
  • a weight percentage of a pellet is described with respect to a single pellet, or equally to a numerical average of a plurality of pellets.
  • the pellet does not comprise a coupling agent.
  • the pellet does not comprise an impregnating agent.
  • the pellet used in the present invention has a generally cylindrical shape having an axial length, i.e. the length in the direction perpendicular to the cross section of the cylinder.
  • the core of the pellet has a generally cylindrical shape and comprises a multifilament (bundle) made of (glass) fibers optionally impregnated with an impregnating agent.
  • the fibers have a length substantially equal to the axial length of the pellet.
  • the core of the pellet is surrounded around its circumference by a sheath having a generally tubular shape consisting of a thermoplastic polymer.
  • the pellet has a core sheath structure wherein the core comprises the optional impregnating agent and the glass multifilament.
  • the sheath surrounds the core.
  • the core glass filament
  • the sheath is substantially free of filaments.
  • Such a pellet structure is obtainable by a wire-coating process such as for example disclosed in WO 2009/080281 and is distinct from the pellet structure that is obtained via the typical pultrusion type of processes such as disclosed in US 6,291 ,064.
  • said plurality of filaments is a continuous, multifilament glass.
  • said plurality of filaments preferably comprise from 2000 to 5000 filaments.
  • said filaments preferably each individually having a diameter from 5 to 50 microns, more preferably from 10 to 30 microns and most preferably from 15 to 25 microns.
  • said filaments each have substantially the same diameter, e.g. where at least 90 % of all filaments forming said multifilament have a diameter that is within a range +10% and -10% from an average diameter.
  • said filaments preferably having an average diameter (mathematical average of all filaments) from 5 to 50 microns, more preferably from 10 to 30 microns and most preferably from 15 to 25 microns.
  • the exposed ratio (the number of filaments that is (visually) observed at the cutting edge of the pellet divided by the total number of filaments times 100 %) is at least 95%.
  • the polymer sheath comprises less than 5 wt.% of filament, preferably less than 2 wt.% of filament based on the total weight of the polymer sheath. This is meant with substantially free of filament.
  • the core comprises between 35 and 60% of the cross section area of the pellet and wherein the sheath comprises between 40 and 65% of the cross section area of the pellet.
  • the cross section area of the pellet is determined and separately the cross section area of the filament core is determined. The difference between the two values is the cross section area of the polymer sheath.
  • the longitudinal variation in the radius of the core over the length of the pellet in view of the average radius is between - 5% and + 5 %.
  • the variation in the radius of the core from one individual pellet to another individual pellet in view of the average radius is between - 5% and + 5 %.
  • the longitudinal variation in the diameter of the pellet over the length of the pellet in view of the average diameter is between - 5% and + 5 %.
  • the variation in the diameter of the core from one individual pellet to another individual pellet in view of the average diameter is between - 5% and + 5 %.
  • average diameter over the length as well as the average diameter over several individual pellets is meant unless specified otherwise.
  • the present inventors assume that due to the cutting step in the production of said pellets, the diameter and shape of one or both ends of said pellet may show a variation with respect to the center of said pellet.
  • the radius of the core is between 800 and 4000 micrometer. In an embodiment, the thickness of the sheath is between 500 and 1500 micrometer
  • the pellet has a tensile modulus tested according to ISO 527-2(1A) (2012) at 23°C in the range of 6000-15000MPa, preferably in the range of 6500-13000M Pa, more preferably in the range of 8000-9000MPa.
  • the pellet has a tensile stress at break tested according to ISO 527-2(1 A) (2012) at 23°C in the range of 70-150 MPa, preferably in the range of 80-130MPa, more preferably in the range of 100-125MPa.
  • the pellet has a flexural modulus tested according to ISO 178 (II) at 23°C in the range of 4000-11000 MPa, preferably in the range of 5000-9000MPa.
  • the pellet has a flexural stress tested according to ISO 178 (II) at 23°C in the range of 130-300MPa, preferably in the range of 150-250MPa, more preferably in the range of 170-190MPa.
  • Multifilament bundles (preferably glass multifilament bundles) and their preparation are known in the art.
  • the fibers, preferably glass fibers, in the bundles may have been formed by any method known to those skilled in the art. Particularly, the fibers may have been formed by a melt spinning process.
  • the length of the fibers in the bundle is determined by the length of the pellet and may vary in a wide range. For example, the average length of the filaments in the pellet may vary between 10 to 50 mm, preferably between 10-25 mm, more preferably between 10-20 mm.
  • the average length of the filaments in the object formed from the pellets is less than the average length of the filaments in the pellet due to breakage of the filaments because of mechanical forces during production of said objects.
  • the fiber density of the fibers in the bundle may vary within wide limits.
  • the bundle may have from 500 to 10000 fibers/bundle and more preferably from 2000 to 5000 fibers/ bundle.
  • the diameter of the fibers in the bundle may widely vary.
  • the diameter of the fibers in the bundle ranges from 5 to 50 microns, more preferably from 10 to 30 microns and most preferably from 15 to 25 microns. Fiber diameters outside these ranges tend to result in a decrease of mechanical properties and/or enhanced abrasion of the equipment used.
  • the diameter of the multifilament bundle in the pellet may e.g. be between 1 and 7 mm.
  • the multifilament bundle may comprise a sizing composition.
  • Suitable examples of conventional sizing compositions include solvent-based compositions, such as an organic material dissolved in aqueous solutions or dispersed in water and melt- or radiation curebased compositions. More particularly, an aqueous sizing composition is applied on the individual fibers, but also oil-based sizing compositions can be applied.
  • an aqueous sizing composition typically includes film formers, coupling agents and other additional components. The film formers are generally present in effective amount to protect fibers from inter-filament abrasion and to provide integrity and processability for fiber bundles after they are dried.
  • Suitable examples of film formers generally include polyurethanes, polyesters, such as polycaprolactone, polyolefins, such as polypropylene, polyamides. It is already recognized in the art that the film former should be miscible with the polymer to be reinforced.
  • polycaprolactone may be used as film former when nylon is used as polymer to be reinforced; for reinforcing polypropylenes, suitable film formers generally comprise polyolefin waxes.
  • the core of the pellet, or the multifilament bundle does not comprise polyolefin waxes.
  • Coupling agents in the sizing composition
  • Suitable examples of coupling agents known in the art as being used for the fibers include organofunctional silanes.
  • the coupling agent which has been added to the sizing composition is an aminosilane, such as aminomethyl-trimethoxysilane, N-(beta-aminoethyl)-gamma-aminopropyl-trimethoxysilane, gamma-aminopropyl- trimethoxysilane gamma-methylaminopropyl-trimethoxysilane, delta-aminobutyl- triethoxysilane, 1 ,4-aminophenyl-trimethoxysilane.
  • aminosilane such as aminomethyl-trimethoxysilane, N-(beta-aminoethyl)-gamma-aminopropyl-trimethoxysilane, gamma-aminopropyl- trimethoxysilane gamma-methylaminopropyl-trimethoxysilane, delta-aminobutyl- triethoxys
  • the pellet of the present application in particular the filaments of the present application, does not comprise a coupling agent.
  • any other additional components known to the skilled person may be present in the sizing composition. Suitable examples include lubricants, used to prevent damage to the bundles by abrasion, antistatic agents, crosslinking agents, plasticizers, surfactants, nucleation agents, antioxidants, pigments and any combinations thereof. Applying a sizing composition to the formed filaments is well-known in the art.
  • the fibers are bundled into bundle and then wound on bobbins to form a package.
  • a multifilament bundle which contains at most 2 wt.% of a sizing composition based on the total weight of the fibers in the multifilament bundle is preferably employed in the pellets of the invention.
  • the amount of the sizing composition can be determined by loss on ignition (LOI).
  • the LOI is a well-known technique for determining the amount of sizing on fibers. More preferably, a multifilament bundle containing from 0.1 to 1 wt.% of sizing composition, as determined by loss on ignition (LOI) is used.
  • bundle(s) comprising (glass) fibers on which a sizing composition has been applied as aqueous dispersion are employed in the pellet according to the invention.
  • Sizing is usually a solvent based material that is applied on the surface of the fibers to improve production process of fibers; preferably more than 90% of the sizing composition is solvent which will be removed during a drying process.
  • An impregnating agent is usually low molecular weight material that acts mainly as a lubricant and remains in the product during whole process.
  • the impregnating agent that may be used in the process according to the present invention comprises at least one compound that is compatible with the thermoplastic polymer.
  • the impregnating agent enables the enhanced dispersion of the fibers in the thermoplastic polymer matrix during the molding process.
  • the application temperature is chosen such that the desired viscosity range is obtained.
  • the application temperature of the impregnating agent can be from 225-290°C.
  • the amount of impregnating agent applied to the multifilament bundle comprising fibers depends on the thermoplastic matrix, on the size (diameter) and concentration of the fibers forming the bundle, and on type of sizing that is on the surface of the fibers.
  • the pellet according to the invention may comprise 0-10 wt.% impregnating agent based on the weight of the fibers in the multifilament bundle in the pellet.
  • Suitable examples of impregnating agents include low molar mass compounds, for example low molar mass or oligomeric polyurethanes, polyesters such as unsaturated polyesters, polycaprolactones, polyethyleneterephthalate, poly(alpha-olefins), such as branched polyethylenes and polypropylenes, polyamides, such as nylons, and other hydrocarbon resins.
  • a polar thermoplastic polymer matrix requires the use of an impregnating agent containing polar functional groups; a non-polar polymer matrix involves using an impregnating agent having non-polar character, respectively.
  • the impregnating agent may comprise low molecular weight polyurethanes or polyesters, like a polycaprolactone.
  • the impregnating agent may comprise branched poly(alpha-olefins), such as polyethylene waxes, modified low molecular weight polypropylenes, mineral oils, such as, paraffin or silicon and any mixtures of these compounds.
  • the impregnating agent is non-volatile, and substantially solvent-free. Being non-volatile means that the impregnating agent does not evaporate under the application and processing conditions applied; that is it has a boiling point or range higher than said processing temperatures.
  • substantially solvent-free means that impregnating agent contains less than 10 percent by mass of solvent, preferably less than 5 percent by mass solvent. Most preferably, the impregnating agent does not contain any organic solvent.
  • the polymer sheath is made of a thermoplastic polymer and a non-halogen flame retardant composition.
  • the thermoplastic polymer comprises or consists of at least one aliphatic polyamide.
  • the thermoplastic polymer comprises at least 90wt%, preferably at least 95wt%, and more preferably at least 98wt%, of the at least one aliphatic polyamide.
  • the thermoplastic polymer consists of the at least one aliphatic polyamide.
  • Polyamide (PA) is a polymer containing recurring amide groups (R — CO — NH — R’) as integral parts of the main polymer chain. According to composition of their main chain, polyamides are classified as aliphatic, semi-aromatic and aromatic. Examples of Aliphatic type polyamides are PA6(Nylon 6) and PA 66(Nylon 6,6).
  • Polyamides can be synthesized by two main methods, a) polycondensation of diacid and diamind and b) ring opening polymerization of lactams.
  • Aliphatic Polyamides can be synthesized by condensation of bifunctional monomers.
  • Polyamide 6 can be synthesized by ring-opening anionic polymerization of epsilon-caprolactam in the presence of sodium caprolactamate as a catalyst and caprolactam-functionalized silica as an initiator.
  • the aliphatic polyamide is preferably PA6.
  • the thermoplastic polymer is comprised of PA6.
  • the thermoplastic polymer does not comprise other aliphatic polyamides, such as PA46 and PA66.
  • the polymer sheath comprises a non-halogen flame retardant composition.
  • the non-halogen flame retardant composition comprises at least one non-halogen flame retardant compound.
  • the non-halogen flame retardant compound include ammonium phosphate, ammonium polyphosphate; melamine orthophosphate, melamine pyrophosphate, melamine polyphosphate, and melamine phosphate; piperazine orthophosphate, piperazine phosphate, piperazine polyphosphate, and piperazine pyrophosphate.
  • non-halogen flame retardant compound examples include phosphinates of the following phosphinic acids: dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylphosphinic acid, methanedi(methylphosphinic acid), benzene-1 ,4-(dimethylphosphinic acid), methylphenylphosphinic acid and diphenylphosphinic acid.
  • phosphinates of the following phosphinic acids dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylphosphinic acid, methanedi(methylphosphinic acid), benzene-1 ,4-(dimethylphosphinic acid), methylphenylphosphinic acid and diphenylphosphinic acid.
  • Examples also include metal salts of the above dialkyl or diaryl or arylalkyl phosphinic acid, where metal is an alkali metal, Li, Na, K and Cs and the like or alkaline earth metal, Be, Ca, Mg, Ba, Sr and the like or a transition metal, Zn, Ti and the like or other main group elements such as Al, Sn, Sb and the like, such as aluminum diethyl phosphinate.
  • metal is an alkali metal, Li, Na, K and Cs and the like or alkaline earth metal, Be, Ca, Mg, Ba, Sr and the like or a transition metal, Zn, Ti and the like or other main group elements such as Al, Sn, Sb and the like, such as aluminum diethyl phosphinate.
  • the non-halogen flame retardant composition comprises a melamine polyphosphate and an aluminum diethyl phosphinate. In an embodiment, the non-halogen flame retardant composition consists of a melamine polyphosphate and an aluminum diethyl phosphinate in a weight ratio of 0.5-2, such as 1 .
  • the sheath may further contain one or more common additives, for example stabilizers, processing aids, impact-modifiers, flame-retardants, acid scavengers, inorganic fillers, and colorants.
  • common additives for example stabilizers, processing aids, impact-modifiers, flame-retardants, acid scavengers, inorganic fillers, and colorants.
  • the pellets of the present invention can be produced by a wire-coating process such as for example disclosed in WO 2009/080281.
  • a method for producing pellets of the present invention comprises the following steps: i) Unwinding from a package of a plurality of continuous glass fiber filaments; iii) Applying a polymer sheath around the plurality of filaments to form a sheathed bundle comprising a core comprising said plurality of filaments and a sheath intimately surrounding said core, and iv) Cutting the sheathed bundle into individual pellets.
  • said polymer sheath is substantially free of said filaments; and said polymer sheath comprises or consists of at least one aliphatic polyamide.
  • the process of the present invention may comprise a step of ii) applying an impregnating agent to said plurality of filaments to form an impregnated plurality of filaments.
  • the pellets according to the present invention may be used to prepare a reinforcing article.
  • a reinforcing article is prepared using a molding composition.
  • Said molding composition can be provided by the pellets according to the invention alone or may e.g. be obtained by mixing the pellets and one or more (non-reinforcing) fillers as separate components.
  • Molding is performed at an elevated temperature, which is a temperature at which the molding composition has enough flowability to be molded (i.e. the polymers in the composition are melted).
  • the elevated temperature is above the melting point of the thermoplastic polymer that is present in the sheath of the pellets.
  • the elevated temperature may be suitably chosen by the skilled person. Generally, the elevated temperature may e.g. be 150-500 °C, 180-400 °C or 200-300 °C. In the cases where the thermoplastic polymer in the pellet is PA6, the elevated temperature is preferably 220-300 °C.
  • Suitable examples of molding processes include injection molding, compression molding, extrusion and extrusion compression molding.
  • Injection molding is widely used to produce articles such as automotive exterior parts like bumpers, automotive interior parts like instrument panels, or automotive parts under the bonnet.
  • Extrusion is widely used to produce articles such rods, sheets and pipes.
  • the molding involves injection molding in the process according to the invention.
  • reinforced articles are made.
  • the article is an automotive part.
  • the reinforced article according to the present invention may for example be an EV battery cover.
  • the reinforced article has a tensile modulus tested according to ISO 527- 2(1A) (2012) at 23°C in the range of 6000-15000M Pa, preferably in the range of 6500- 13000MPa, more preferably in the range of 8000-9000MPa.
  • the reinforced article has a tensile stress at break tested according to ISO 527-2(1 A) (2012) at 23°C in the range of 70-150 MPa, preferably in the range of 80- 130MPa, more preferably in the range of 100-125MPa.
  • the reinforced article has a flexural stress tested according to ISO 178 (II) at 23°C in the range of 100-300MPa, preferably in the range of 150-250 MPa, more preferably in the range of 170-190MPa.
  • the invention relates to all possible combinations of features described herein, preferred in particular are those combinations of features that are present in the claims. It is also to be understood that a description on a product comprising certain components also discloses a product consisting of these components. Similarly, it is also to be understood that a description on a process comprising certain steps also discloses a process consisting of these steps. The invention will now be elucidated by way of the following examples without however being limited thereto.
  • the following materials were used to produce glass fiber reinforced pellets according to the method disclosed in W02009/080281 .
  • the method also referred to as wire-coating process, mainly comprises a step of applying a sheath of thermoplastic polymer around a multifilament strand.
  • the barrel temperature set was 270°C.
  • Ultramid® B24 NE 01 is a polyamide 6 commercially available from BASF with a viscosity number tested according to ISO 307 in the range of 115-135 ml/g.
  • Ultramid® B27 E 01 is a polyamide 6 commercially available from BASF with a viscosity number tested according to ISO 307 in the range of 142-158 ml/g.
  • PP copol K7760H is a polypropylene copolymer commercially available from Sinopec with an MFR tested according to GB/T3682-2000 at 230 °C and 2.16 kg of 60 dg/min.
  • Glass fiber 1 T ufRovTM 4510 is a long glass fiber roving commercially available from Nippon Electric Glass (NEG) with a fiber diameter of 17pm and a roving TEX of 2400 g/km. Glass fiber_1 shows excellent wet out and saturation in polyamide resin.
  • Glass fiber_2 is a long glass fiber roving commercially available from Chongqing Polycomp International Corp (CPIC) with a fiber diameter of 19pm and a roving TEX of 3000 g/km. Glass fiber_2 is suitable for the wire-coating process in which the thermoplastic polymer is a polypropylene.
  • Glass fiber_3: ECS13-4.5-508A is a short glass fiber commercially available from JIISHI with a typical fiber diameter of 13 pm and a fiber length of 4.5 mm.
  • FR MB_1 : JLS-MB52E01 is a PA based flame retardant masterbatch comprising 30wt% of PA6 and 70wt% of flame retardant compounds of melamine polyphosphate and aluminum diethyl phosphinic acid.
  • FR MB_2: MB-2500-60 is a PP based flame retardant masterbatch comprising 40wt% of polypropylene and 60wt% of a flame retardant ADK FP2500S comprising melamine phosphate, piperazine phosphate, and ZnO.
  • Antioxidant B225 is a mixture of Irganox® 1010 (50%) and Irgafos® 168 (50%) from BASF.
  • Bondyram® 1010 is a maleic anhydride modified polypropylene with a maleic anhydride graft level of 0.6-1%.
  • the produced pellets were injection molded at the below condition to prepare samples for testing according to the test methods.
  • Tensile modulus and tensile strength at break were obtained via tensile test carried out at 23 °C after 7 days according to ISO 527/1A (II). The shape of specimen for this test has been defined in the used norm.
  • Flexural modulus and flexural stress were obtained via 3-point flexural test carried out according to ISO178 (II) at 23 °C after 7 days. The shape of specimen for this test has been defined in the used norm.
  • Notched Charpy impact test was performed according to ISO 179/1eA (II) at 23 ° and -30°C after 7 days. The shape of specimen for this test has been defined in the used norm.
  • Un-notched Charpy impact test was performed according to ISO 179/1eU (II) at 23 ° and - 30°C after 7 days. The shape of specimen for this test has been defined in the used norm. Thermal distortion temperature (HDT) at 1.8MPa was tested according to ISO75-2.
  • the pellet of comparative example 2 is produced by a typical polymer compounding process described as follows: The base resin and additives were premixed together and then dosed into a twin-screw extruder through main feeder. The glass fiber was dosed into the twin-screw extruder through the side feeder at zone 5.
  • the twin-screw extruder used was ZSK26mc with L/D 40 and screw diameter 26mm. Melting temperature was 250°C. Screw speed was 350rpm and output was 20kg/hr. The extruded strips were water cooled and then chopped into pellets.
  • Comparative example 1 represents conventional pellets with a polypropylene sheath produced with the wire-coating process using a coupling agent.
  • the sheath polymer consists of PA6 instead of PP
  • the mechanical properties of the pellets are substantively enhanced, especially with respect to tensile strength, flexural strength, and HDT, while some of the mechanical properties are largely maintained.
  • the use of the coupling agent is not needed in examples 1-2, representing a process simplification.
  • the 3mm plaque sample maintained for about 5 mins before broke up (burnt through), it was also ignited but self-extinguished after removing the flame.
  • the situation for the 2mm plaque was similar but only lasted for 3 mins before burnt through.
  • both 2mm and 3mm plaques quickly showed sagging after the burning test started and broke up within less than 2mins. After removing the flame, the plaques did not self-extinguish and finally burnt out.

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Abstract

L'invention concerne des pastilles renforcées de fibres de verre ignifuges, leur procédé de production et un article renforcé obtenu à partir de celles-ci. La pastille présente une direction axiale ; ladite pastille comprend un noyau qui s'étend dans la direction axiale et comprend une gaine polymère, qui a été appliquée autour dudit noyau, ledit noyau comprenant une pluralité de filaments de verre qui s'étendent dans la direction axiale ; ladite gaine polymère est au moins sensiblement exempte desdits filaments ; ladite gaine polymère comprend ou est constituée d'au moins un polyamide aliphatique et d'une composition ignifuge non halogénée.
PCT/EP2024/070737 2023-08-23 2024-07-22 Pastilles renforcées par des fibres de verre ignifuges, leur procédé de production et article renforcé obtenu à partir de celles-ci Pending WO2025040343A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CNPCT/CN2023/114419 2023-08-23
CN2023114419 2023-08-23
EP23197644 2023-09-15
EP23197644.0 2023-09-15

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WO2025040343A1 true WO2025040343A1 (fr) 2025-02-27

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4338233A (en) 1981-06-15 1982-07-06 Ppg Industries, Inc. Aqueous sizing composition and sized glass fibers and method
EP0206189A1 (fr) 1985-06-25 1986-12-30 Ppg Industries, Inc. Fibres de verre traitées chimiquement pour renforcer des matériaux polymères et procédé
US20020019182A1 (en) * 1996-11-06 2002-02-14 Toray Industries, Inc. Molding material and production process
EP1460166A1 (fr) 2001-12-27 2004-09-22 Asahi Fiber Glass Company, Limited Liant pour fibre de verre, fibre de verre utilisee pour renforcer une resine olefinique et procede de production d'une composition de resine olefinique destinee a un moulage renforce par des fibres
WO2005116139A2 (fr) * 2004-05-04 2005-12-08 General Electric Company Composition de polyamide ignifuge exempt d'halogene presentant des proprietes electriques ameliorees
EP1982814A1 (fr) * 2006-02-06 2008-10-22 Nitto Boseki Co., Ltd. Pastille contenant des fibres de verre plates, resine thermoplastique moulee contenant des fibres de verre plates et leurs procedes de fabrication
WO2009080281A1 (fr) 2007-12-21 2009-07-02 Saudi Basic Industries Corporation Procédé pour produire des compositions thermoplastiques renforcées par des fibres de verre longues
US20160272770A1 (en) * 2013-10-29 2016-09-22 Carmela Tufano Glass fibre reinforced polyolefin composition
US20170361498A1 (en) * 2012-10-04 2017-12-21 Saudi Basic Industries Corporation Device for manufacturing of a fibre-reinforced polymer composition
CN110290907A (zh) * 2016-12-15 2019-09-27 Sabic环球技术有限责任公司 包含轴向芯和聚合物护套的粒料、及其制造

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4338233A (en) 1981-06-15 1982-07-06 Ppg Industries, Inc. Aqueous sizing composition and sized glass fibers and method
EP0206189A1 (fr) 1985-06-25 1986-12-30 Ppg Industries, Inc. Fibres de verre traitées chimiquement pour renforcer des matériaux polymères et procédé
US20020019182A1 (en) * 1996-11-06 2002-02-14 Toray Industries, Inc. Molding material and production process
EP1460166A1 (fr) 2001-12-27 2004-09-22 Asahi Fiber Glass Company, Limited Liant pour fibre de verre, fibre de verre utilisee pour renforcer une resine olefinique et procede de production d'une composition de resine olefinique destinee a un moulage renforce par des fibres
WO2005116139A2 (fr) * 2004-05-04 2005-12-08 General Electric Company Composition de polyamide ignifuge exempt d'halogene presentant des proprietes electriques ameliorees
EP1753821B1 (fr) * 2004-05-04 2012-10-03 SABIC Innovative Plastics IP B.V. Composition de polyamide ignifuge exempt d'halogene presentant des proprietes electriques ameliorees
EP1982814A1 (fr) * 2006-02-06 2008-10-22 Nitto Boseki Co., Ltd. Pastille contenant des fibres de verre plates, resine thermoplastique moulee contenant des fibres de verre plates et leurs procedes de fabrication
WO2009080281A1 (fr) 2007-12-21 2009-07-02 Saudi Basic Industries Corporation Procédé pour produire des compositions thermoplastiques renforcées par des fibres de verre longues
US20170361498A1 (en) * 2012-10-04 2017-12-21 Saudi Basic Industries Corporation Device for manufacturing of a fibre-reinforced polymer composition
US20160272770A1 (en) * 2013-10-29 2016-09-22 Carmela Tufano Glass fibre reinforced polyolefin composition
CN110290907A (zh) * 2016-12-15 2019-09-27 Sabic环球技术有限责任公司 包含轴向芯和聚合物护套的粒料、及其制造

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