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WO2025045719A1 - Composition de polymère thermoplastique renforcée par des fibres - Google Patents

Composition de polymère thermoplastique renforcée par des fibres Download PDF

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Publication number
WO2025045719A1
WO2025045719A1 PCT/EP2024/073552 EP2024073552W WO2025045719A1 WO 2025045719 A1 WO2025045719 A1 WO 2025045719A1 EP 2024073552 W EP2024073552 W EP 2024073552W WO 2025045719 A1 WO2025045719 A1 WO 2025045719A1
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WO
WIPO (PCT)
Prior art keywords
filaments
pellet
thermoplastic polymer
filament
multifilament strand
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/EP2024/073552
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English (en)
Inventor
Rob DONNERS
Gerard Jan Eduard BIEMOND
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
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Filing date
Publication date
Application filed by SABIC Global Technologies BV filed Critical SABIC Global Technologies BV
Publication of WO2025045719A1 publication Critical patent/WO2025045719A1/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
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/72—Measuring, controlling or regulating
    • B29B7/726—Measuring properties of mixture, e.g. temperature or density
    • 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
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
    • B29B7/905—Fillers or reinforcements, e.g. fibres with means for pretreatment of the charges or fibres
    • 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
    • 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
    • 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
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • 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
    • 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

Definitions

  • the present invention relates to a pellet comprising a fiber reinforced thermoplastic polymer composition and a process for producing such pellet.
  • the present invention further relates to a molded article made from such pellet.
  • a fiber reinforced thermoplastic polymer composition in which a thermoplastic polymer is reinforced by glass fibers is widely used.
  • the glass fibers may be chopped before being melt-mixed with the thermoplastic polymer to be dispersed therein.
  • the glass fibers may be combined with the thermoplastic polymer as long glass fibers without chopping.
  • thermoplastic compositions having high electromagnetic/radio frequency interference (EMI/RFI) shielding effectiveness by the use of conductive fibers are known.
  • EMI/RFI electromagnetic/radio frequency interference
  • US4566990 discloses a thermoplastic polymeric composition having high electromagnetic interference shielding effectiveness comprising a thermoplastic resin or resin blend, metal flake, and metal or metal coated fiber.
  • US20170001336A1 discloses a fiber-reinforced multilayered pellet comprising a sheath layer; and a core layer, the sheath layer comprising a resin composition comprising a thermoplastic resin (a1) and a fibrous filler (b1), wherein the fibrous filler (b1) has a weight-average fiber length (Lw) of 0.1 mm to less than 0.5 mm and a weight-average fiber length/number-average fiber length ratio (Lw/Ln) of 1 .0 to less than 1 .8, the core layer comprising a resin composition comprising a thermoplastic resin (a2) and a fibrous filler (b2), wherein the fibrous filler (b2) has a weight-average fiber length (Lw) of 0.5 mm to less than 15.0 mm and a weight-average fiber length/number-average fiber length ratio (Lw/Ln) of 1 .8 to less than 5.0.
  • US2010068518 discloses a molding material comprising: (i) 1 to 50% by weight of a bundle of continuous reinforcing fibers (A); (ii) 0.1 to 10% by weight of a polyarylene sulfide prepolymer (B) comprising at least 50% by weight of cyclic polyarylene sulfide and having a weight average molecular weight of less than 10,000 or polyarylene sulfide (B') having a weight average molecular weight of 10,000 or greater and having the degree of dispersion represented by weight average molecular weight/number average molecular weight of 2.5 or smaller; and (iii) 40 to 98.9% by weight of a thermoplastic resin (C), wherein component (C) is adhered to a composite of component (A) and component (B) or (B').
  • a polyarylene sulfide prepolymer comprising at least 50% by weight of cyclic polyarylene sulfide and having a weight average molecular weight of less than 10,000 or
  • US5935508A discloses a process for the manufacture of fibre-reinforced intermediates useful in thermoplastic processing methods, which comprises impregnating continuous fibres with a resin composition comprising at least one radiation-polymerisable component; exposing the impregnated fibres to radiation to effect polymerisation of such component; and cutting the product to form thermoplastically processible intermediates.
  • the present invention provides a pellet comprising a fiber reinforced thermoplastic polymer composition comprising a thermoplastic polymer and a plurality of co-filaments, wherein each of the co-filaments comprises a first filament and a second filament, the first filament consisting of an inorganic material, the first filament having a glass transition temperature of greater than or equal to 400°C, the second filament consisting of a metallic material, and the second filament contacting the first filament, wherein the weight average length of the co-filaments in the pellet is at least 5.0 mm.
  • the pellet comprises or consists of the fiber reinforced thermoplastic polymer composition.
  • the co-filaments used in the present invention have a high shielding property against electromagnetic waves.
  • the present inventors have realized that the relatively large average length of the co-filaments in the pellet according to the invention allows, in a molded article made from the pellets according to the invention, the co-filaments to be close to each other to form a network for improving the EMI shielding property.
  • the co-filaments may be present in the pellet according to the invention as bundled co- filaments or may be dispersed in the pellet.
  • a pellet comprising bundled co- filaments can be obtained by the so-called wire-coating process, and a pellet comprising dispersed co-filaments can be obtained by the so-called pultrusion process, explained herein in detail.
  • the filaments in the pellet may consist of the co-filaments.
  • the filaments in the pellet may further comprise glass filaments. The presence of the glass filaments may be beneficial for production cost and/or mechanical properties of the molded article made from the pellets.
  • the weight ratio between the co-filaments and the glass filaments in the pellet may be any ratio, for example 10:90 to 90: 10, for example 10:90 to 50:50 or 50:50 to 90: 10.
  • the weight ratio may be selected based on the desired EMI shielding property and the cost and mechanical properties.
  • the invention provides a pellet comprising a sheathed continuous multifilament strand comprising a core that extends in the longitudinal direction and a polymer sheath which intimately surrounds said core, wherein the core comprises an impregnated continuous bicomponent multifilament strand comprising at least one continuous bicomponent multifilament strand comprising the plurality of co-filaments which are bundled and the polymer sheath consists of a thermoplastic polymer composition comprising the thermoplastic polymer.
  • the pellet consists of the sheathed continuous multifilament strand.
  • the core-sheath structure of such sheathed continuous multifilament strand is per se known and is described in detail e.g. in W02009/080281 , incorporated herein by reference.
  • the invention also provides a process for preparing the pellet according to the invention, comprising the sequential steps of: a) unwinding from a package of the at least one continuous bicomponent multifilament strand, b) applying an impregnating agent to said at least one continuous bicomponent multifilament strand to form the impregnated continuous bicomponent multifilament strand, c) applying a sheath of the thermoplastic polymer composition around the impregnated continuous bicomponent multifilament strand to form the sheathed continuous multifilament strand and d) cutting the sheathed continuous multifilament strand into pellets.
  • the weight average length of the co-filaments in the pellet is substantially the same as the pellet length, and preferably is 10 to 55 mm, preferably 10 to 40 mm, more preferably 10 to 30 mm and most preferably from 10 to 20 mm.
  • the core may comprise an impregnated continuous bicomponent multifilament strand comprising at least one continuous bicomponent multifilament strand and an impregnated continuous glass multifilament strand comprising at least one continuous glass multifilament strand.
  • the pellet may be prepared by a process comprising the steps of: a) unwinding from a package of the at least one continuous bicomponent multifilament strand, a2) unwinding from a package of at least one continuous glass multifilament strand, b) applying an impregnating agent to said at least one continuous bicomponent multifilament strand to form the impregnated continuous bicomponent multifilament strand, b2) applying an impregnating agent to said at least one continuous glass multifilament strand to form an impregnated continuous glass multifilament strand, c’) applying a sheath of thermoplastic polymer around the impregnated continuous bicomponent multifilament strand and the impregnated continuous glass multifilament strand to form the sheathed continuous multifilament strand and d) cutting the strand into the pellets.
  • Steps a) and a2) can be performed in any order.
  • Steps b) and b2) may be performed as separate steps, but are preferably performed as one step of applying an impregnating agent to said at least one continuous bicomponent multifilament strand and said at least one continuous glass multifilament strand to form the impregnated continuous bicomponent multifilament strand and the impregnated continuous glass multifilament strand.
  • the invention provides a pellet wherein the plurality of co-filaments are dispersed in a matrix of the thermoplastic polymer.
  • thermoplastic polymer of the matrix of the pellet are those described herein as examples of the thermoplastic polymer in the thermoplastic polymer composition of the polymer sheath of the sheathed continuous multifilament strand.
  • the pellet may further comprise additives.
  • Suitable examples of the additives are those described herein as examples of the additives in the thermoplastic polymer composition of the polymer sheath of the sheathed continuous multifilament strand.
  • Such pellet can be obtained e.g. by a pultrusion method as described in US6291064B1 , hereby incorporated by reference.
  • the invention also provides a process for preparing the pellet according to the invention, comprising the sequential steps of: i) unwinding from a package of the at least one continuous bicomponent multifilament strand, ii) spreading the at least one continuous bicomponent multifilament strand into individual co-filaments, iii) drawing the co-filaments through a melt of a thermoplastic polymer composition comprising the thermoplastic polymer to impregnate the co-filaments with the thermoplastic polymer to obtain a strand wherein the co-filaments are dispersed in the matrix of the thermoplastic polymer, and iv) cutting the strand to obtain pellets.
  • the weight average length of the filaments in the pellet is substantially the same as the pellet length, and is preferably 5.0 to 10 mm, preferably 5.0 to 8.0 mm.
  • the pellet may be prepared by a process comprising the steps of: i) unwinding from a package of the at least one continuous bicomponent multifilament strand, i2) unwinding from a package of at least one continuous glass multifilament strand, ii) spreading the at least one continuous bicomponent multifilament strand into individual co-filaments, H2) spreading the at least one continuous glass multifilament strand into individual glass filaments,
  • the order of steps to be performed is i) and i2), then ii and ii2), then Hi’) and then d).
  • Steps i) and i2) can be performed in any order.
  • Steps ii) and H2) can be performed in any order.
  • the molded article according to the invention is made by molding pellets comprising the pellets according to the invention.
  • the pellets used for molding may consist of the pellets according to the invention.
  • the pellets used for molding may further comprise other types of pellets in addition to the invention.
  • said other types of pellets may be pellets comprising a thermoplastic polymer and glass filaments or pellets of a thermoplastic polymer not comprising glass filaments.
  • Suitable examples of such further polymer are those described herein as examples of the thermoplastic polymer in the thermoplastic polymer composition of the polymer sheath of the sheathed continuous multifilament strand.
  • the invention provides a molded article made by molding of the pellets according to the invention and optionally pellets of a thermoplastic composition comprising a thermoplastic polymer and optionally glass filaments.
  • thermoplastic polymer in the optional pellets are preferably the same as the thermoplastic polymer in the pellet according to the invention and preferably is polypropylene.
  • the optional pellets not comprising glass filaments may be made by standard methods.
  • the optional pellets comprising glass filaments are preferably pellets made by wirecoating process or pultrusion process.
  • the optional pellet comprises a sheathed continuous multifilament strand comprising a core that extends in the longitudinal direction and a polymer sheath which intimately surrounds said core, wherein the core comprises an impregnated continuous glass multifilament strand comprising at least one continuous glass multifilament strand and the polymer sheath consists of a thermoplastic polymer composition comprising a thermoplastic polymer.
  • the optional pellet comprises glass filaments dispersed in a matrix of a thermoplastic polymer.
  • the optional pellets have the same structure as the pellets according to the invention, i.e. when the pellets according to the invention have the sheathed core structure, the optional pellets used in combination also have the sheathed core structure and when the pellets according to the invention have a structure in which filaments are dispersed in a matrix, the optional pellets used in combination also have such structure.
  • the amount of the pellets according to the invention with respect to the total pellets used for making the molded article may be 5 to 100 wt%, for example 5 to 50 wt% or 50 to 100 wt%.
  • Suitable examples of molding processes include injection molding, compression molding, extrusion (optionally followed by thermoforming) and extrusion compression molding.
  • the molded article is an injection molded article.
  • the weight average length of the co-filaments in the article is at least 1 .0 mm, preferably 1 .0 to 2.0 mm, for example 1 .3 to 1.7 mm.
  • the molded article is an extrusion molded article.
  • the weight average length of the co-filaments in the article is at least 0.5 mm, preferably at least 1 .0 mm, preferably 1 .0 to 2.0 mm, for example 1 .3 to 1 .7 mm.
  • the type of equipment used for extrusion has an effect on the weight average length of the co-filaments in the article.
  • Use of a single screw extruder generally results in a longer weight average length of the co-filaments than a double screw extruder.
  • the molded article may preferably be selected from the group consisting of battery housing, battery tray, battery charging station, power tools, building and construction shielding boxes, scaffolding, construction frames and flooring.
  • Each of the co-filaments comprises a first filament and a second filament, the first filament consisting of an inorganic material, the first filament having a glass transition temperature of greater than or equal to 400°C, the second filament consisting of a metallic material, and the second filament contacting the first filament.
  • the co-filament preferably consists of the first filament and the second filament.
  • an “inorganic material” is understood to mean a material that contains no plant or animal components or has them only to a lesser extent as impurities.
  • An inorganic material may be a natural stone, in particular granite, basalt, slate, sandstone or limestone.
  • An inorganic material is preferably understood to mean a material which contains little or no carbon as an impurity.
  • An inorganic material may be a ceramic, a glass (a crystalline glass or an amorphous glass), in particular an E glass, an S glass or a C glass.
  • the "glass transition temperature" of a material in particular a glass, a polymer or a ceramic, describes the temperature at which the material changes from its solid state to a viscous or liquid state.
  • the first filament is a glass filament or a basalt filament.
  • a "metallic material” is understood to mean a substance that is located specifically to the left and below a dividing line from boron to astatine in the periodic table of the elements.
  • the second filament has an aluminum content of at least 98 wt%, at least 99 wt% or at least 99.5 wt% or a copper content of at least 98 wt%, at least 99 wt% or at least 99.5 wt%.
  • a “co-filament” describes a filament with a practically endless length, which has at least two partial filaments of different material properties extending in the longitudinal direction, wherein the two materially different filaments are physically and/or chemically connected to one another to form the co-filament.
  • a co-filament may have a ratio of length to diameter of greater than or equal to 1000.
  • the first filament and the second filament are physically and/or chemically connected to one another to form the co-filament and a contact region between the first filament and the second filament is at least 5% of the circumference of the first filament.
  • a contact area between the first filament and the second filament is 5 to 95%, more preferably 10 to 90%, more preferably 15 to 85%, of the circumference of the first filament.
  • the pellet comprising the sheathed continuous multifilament strand according to the invention has an advantage that its manufacturing process can be performed at higher speed than the pultrusion process and that materials with low MFI can be used.
  • the pellet comprises or consists of the sheathed continuous multifilament strand.
  • the sheathed continuous multifilament strand comprises or consists of a core and a polymer sheath.
  • the core has a generally cylindrical shape and comprises an impregnated continuous bicomponent multifilament strand comprising the co-filaments.
  • the core is intimately surrounded around its circumference by a polymer sheath having a generally tubular shape and consisting of a thermoplastic polymer composition.
  • the co-filaments have a length substantially equal to the axial length of the pellet.
  • the core does not substantially contain the material of the sheath.
  • 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.
  • the polymer sheath is substantially free of co-filaments, meaning it comprises less than 2 wt% of filaments based on the total weight of the polymer sheath.
  • the radius of the core is between 800 and 4000 micrometer and/or the thickness of the polymer sheath is between 500 and 1500 micrometer.
  • the core comprises between 35 and 60 % of the cross section area of the pellet and the sheath comprises between 40 and 65 % of the cross section area of the pellet.
  • the core comprises between 3 and 35 % of the cross section area of the sheathed continuous multifilament strand and the sheath comprises between 65 and 97 % of the cross section area of the sheathed continuous multifilament strand. In some embodiments, the core comprises between 35 and 60 % of the cross section area of the sheathed continuous multifilament strand and the sheath comprises between 40 and 65 % of the cross section area of the sheathed continuous multifilament strand.
  • the amount of the core is 10 to 80 wt%, for example 10 to 50 wt% (for example 25 to 45 wt%) or 50 to 80 wt% (for example 60 to 75 wt%), with respect to the sheathed continuous multifilament strand.
  • the amount of the sheath is 20 to 90 wt%, for example 20 to 50 wt% (for example 25 to 40 wt%) or 50 to 90 wt% (for example 55 to 75 wt%), with respect to the sheathed continuous multifilament strand.
  • the total amount of the core and the sheath is 100 wt% with respect to the sheathed continuous multifilament strand.
  • the sheath intimately surrounds the core.
  • intimately surrounding as used herein is to be understood as meaning that the polymer sheath substantially entirely contacts the core. Said in another way the sheath is applied in such a manner onto the core that there is no deliberate gap between an inner surface of the sheath and the core containing the impregnated continuous multifilament strands. A skilled person will nevertheless understand that a certain small gap between the polymer sheath and the core may be formed as a result of process variations.
  • the polymer sheath consists of a thermoplastic polymer composition.
  • thermoplastic polymer composition comprises a thermoplastic polymer.
  • thermoplastic polymer composition consists of the thermoplastic polymer and additives described below.
  • the thermoplastic polymer composition may have a melt flow index as measured according to ISO1133-1 :2011 (2.16kg/230°C) of 1.0 to 150 dg/min, for example at least 1 .0 dg/min and less than 20 dg/min, or 20 to 150 dg/min.
  • Thermoplastic polymer in thermoplastic polymer composition of polymer sheath may be at least 50 wt%, for example 50 to 99.9 wt%, 75 to 99.9 wt% or 95 to 99.9 wt%.
  • thermoplastic polymers include but are not limited to polyamide, such as polyamide 6, polyamide, 66 or polyamide 46; polyolefins, for example polypropylenes and polyethylenes; polyesters, such as polyethylene terephthalate, polybutylene terephthalate; polycarbonates; polyphenylene sulphide; polyurethanes and and mixtures thereof.
  • the thermoplastic polymer is preferably a polyolefin, more preferably a polyolefin chosen from the group of polypropylenes or elastomers of ethylene and a-olefin comonomer having 4 to 8 carbon atoms, and any mixtures thereof.
  • the thermoplastic polymer composition comprises at least 80wt% of the thermoplastic polymer, for example at least 90wt%, at least 93wt%, at least 95wt%, at least 97wt% at least 98wt% or at least 99wt% of the thermoplastic polymer based on the thermoplastic polymer composition.
  • the thermoplastic polymer composition consists of the thermoplastic polymer.
  • the thermoplastic polymer composition comprises at least 60wt%, for example at least 70wt%, for example at least 75wt% and/or at most 99wt%, for example at most 95wt%, for example at most 90wt% of the thermoplastic polymer.
  • the thermoplastic polymer may have a melt flow index in the range from 1.0 to 150 dg/min as measured according to ISO1133-1 :2011 (2.16kg/230°C). In some embodiments, the thermoplastic polymer has a melt flow index of at least 1 .0 dg/min and less than 20 dg/min preferably 5.0 to 19 dg/min, more preferably 6.0 to 18 dg/min, as measured according to ISO1133-1 :2011 (2.16kg/230°C). In some embodiments, the thermoplastic polymer has a melt flow index of 20 to 150 dg/min, for example in the range from 30 to 140 dg/min as measured according to ISO1133-1 :2011 (2.16kg/230°C). Preferably, the thermoplastic polymer has a melt flow index in the range from 50 to 130 dg/min as measured according to ISO1133-1 :2011 (2.16kg/230°C). This leads to good mechanical properties of the obtained composition.
  • the polypropylene may for example be a propylene homopolymer or a random propylene copolymer or a heterophasic propylene copolymer.
  • a propylene homopolymer can be obtained by polymerizing propylene under suitable polymerization conditions.
  • a propylene copolymer can be obtained by copolymerizing propylene and one or more other a-olefins, preferably ethylene, under suitable polymerization conditions.
  • the preparation of propylene homopolymers and copolymers is, for example, described in Moore, E. P. (1996) Polypropylene Handbook. Polymerization, Characterization, Properties, Processing, Applications, Hanser Publishers: New York.
  • the random propylene copolymer may comprise as the comonomer ethylene or an a- olefin chosen from the group of a-olefins having 4 to 10 C-atoms, preferably ethylene, 1 -butene, 1 -hexene or any mixtures thereof.
  • the amount of the comonomer is preferably at most 10wt% based on the random propylene copolymer, for example in the range from 2-7wt% based on the random propylene copolymer.
  • Polypropylenes can be made by any known polymerization technique as well as with any known polymerization catalyst system.
  • techniques reference can be given to slurry, solution or gas phase polymerizations; regarding the catalyst system reference can be given to Ziegler-Natta, metallocene or single-site catalyst systems. All are, in themselves, known in the art.
  • Heterophasic propylene copolymers are generally prepared in one or more reactors, by polymerization of propylene in the presence of a catalyst and subsequent polymerization of an ethylene-a-olefin mixture.
  • the resulting polymeric materials are heterophasic, but the specific morphology usually depends on the preparation method and monomer ratios used.
  • the heterophasic propylene copolymers can be produced using any conventional technique known to the skilled person, for example multistage process polymerization, such as bulk polymerization, gas phase polymerization, slurry polymerization, solution polymerization or any combinations thereof.
  • Any conventional catalyst systems for example, Ziegler-Natta or metallocene may be used.
  • the heterophasic propylene copolymer is made using Ziegler-Natta catalyst.
  • the heterophasic propylene copolymer may be prepared by a process comprising
  • the steps are preferably performed in different reactors.
  • the catalyst systems for the first step and for the second step may be different or same.
  • the heterophasic propylene copolymer of the composition consists of a propylene- based matrix and a dispersed ethylene-a-olefin copolymer.
  • the propylene-based matrix typically forms the continuous phase in the heterophasic propylene copolymer.
  • the amounts of the propylene-based matrix and the dispersed ethylene-a-olefin copolymer may be determined by 13 C-NMR, as well known in the art.
  • the propylene-based matrix consists of a propylene homopolymer and/or a propylene copolymer consisting of at least 70 wt% of propylene monomer units and at most 30 wt% of comonomer units selected from ethylene monomer units and a-olefin monomer units having 4 to 10 carbon atoms, for example consisting of at least 80 wt% of propylene monomer units and at most 20 wt% of the comonomer units, at least 90 wt% of propylene monomer units and at most 10 wt% of the comonomer units or at least 95 wt% of propylene monomer units and at most 5 wt% of the comonomer units, based on the total weight of the propylene-based matrix.
  • the comonomer in the propylene copolymer of the propylene-based matrix is selected from the group of ethylene, 1-butene, 1-pentene, 4-methyl-1 -pentene, 1- hexen, 1 -heptene and 1 -octene, and is preferably ethylene.
  • the propylene-based matrix consists of a propylene homopolymer.
  • the melt flow index (MFI) of the propylene-based matrix (before the heterophasic propylene copolymer is mixed into the composition), MFI PP . may be for example at least 0.1 dg/min, at least 0.2 dg/min, at least 0.3 dg/min, at least 0.5 dg/min, at least 1 dg/min, at least 1 .5 dg/min, and/or for example at most 50 dg/min, at most 40 dg/min, at most 30 dg/min, at most 25 dg/min, at most 20 dg/min, measured according to ISO1133 (2.16 kg/230°C).
  • the MFI PP may be in the range of for example 0.1 to 50 dg/min, for example from 0.2 to 40 dg/min, for example 0.3 to 30 dg/min, for example 0.5 to 25 dg/min, for example from 1 to 20 dg/min, for example from 1.5 to 10 dg/min, measured according to ISO1133 (2.16 kg/230°C).
  • the propylene-based matrix may e.g. be present in an amount of 50 to 95wt%.
  • the propylene-based matrix is present in an amount of 60 to 85wt%, for example at least 65 wt% or at least 70 wt% and/or at most 78 wt%, based on the total heterophasic propylene copolymer.
  • the propylene-based matrix is preferably semi-crystalline, that is it is not 100% amorphous, nor is it 100% crystalline.
  • the propylene-based matrix is at least 40% crystalline, for example at least 50%, for example at least 60% crystalline and/or for example at most 80% crystalline, for example at most 70% crystalline.
  • the propylene-based matrix has a crystallinity of 60 to 70%.
  • the degree of crystallinity of the propylene-based matrix is measured using differential scanning calorimetry (DSC) according to ISO11357-1 and ISO11357- 3 of 1997, using a scan rate of 10°C/min, a sample of 5mg and the second heating curve using as a theoretical standard for a 100% crystalline material 207.1 J/g.
  • DSC differential scanning calorimetry
  • the heterophasic propylene copolymer also comprises a dispersed ethylene-a-olefin copolymer.
  • the dispersed ethylene-a-olefin copolymer is also referred to herein as the ‘dispersed phase’.
  • the dispersed phase is embedded in the heterophasic propylene copolymer in a discontinuous form.
  • the particle size of the dispersed phase is typically in the range of 0.05 to 2.0 microns, as may be determined by transmission electron microscopy (TEM).
  • TEM transmission electron microscopy
  • the amount of the dispersed ethylene-a-olefin copolymer in the heterophasic propylene copolymer may herein be sometimes referred as RC.
  • the amount of ethylene monomer units in the ethylene-a-olefin copolymer may e.g. be 20 to 65 wt%.
  • the amount of ethylene monomer units in the dispersed ethylene-a- olefin copolymer in the heterophasic propylene copolymer may herein be sometimes referred as RCC2.
  • the a-olefin in the ethylene-a-olefin copolymer is preferably chosen from the group of a-olefins having 3 to 8 carbon atoms.
  • suitable a-olefins having 3 to 8 carbon atoms include but are not limited to propylene, 1 -butene, 1 -pentene, 4-methyl- 1 -pentene, 1-hexen, 1 -heptene and 1 -octene.
  • the a-olefin in the ethylene-a-olefin copolymer is chosen from the group of a-olefins having 3 to 4 carbon atoms and any mixture thereof, more preferably the a-olefin is propylene, in which case the ethylene-a-olefin copolymer is ethylene-propylene copolymer.
  • the MFI of the dispersed ethylene a-olefin copolymer (before the heterophasic propylene copolymer is mixed into the composition), MFIrubber, may be for example at least 0.001 dg/min, at least 0.01 dg/min, at least 0.1 dg/min, at least 0.3 dg/min, at least 0.7 dg/min, at least 1 dg/min, and/or for example at most 30 dg/min, at most 20 dg/min, at most 15 dg/min at most 10 dg/min, at most 5 dg/min or at most 3 dg/min.
  • the MFIrubber may be in the range for example from 0.001 to 30 dg/min, for example from 0.01 to 20 dg/min, for example 0.1 to 15 dg/min, for example 0.3 to 10 dg/min, for example from 0.7 to 5 dg/min, for example from 1 to 3 dg/min.
  • MFIrubber is calculated according to the following formula: wherein
  • MFIheterophasic is the MFI (dg/min) of the heterophasic propylene copolymer measured according to ISO1133 (2.16kg/230°C),
  • MFImatrix is the MFI (dg/min) of the propylene-based matrix measured according to ISO1133 (2.16kg/230°C)
  • matrix content is the fraction of the propylene-based matrix in the heterophasic propylene copolymer
  • rubber content is the fraction of the dispersed ethylene-a-olefin copolymer in the heterophasic propylene copolymer.
  • the sum of the matrix content and the rubber content is 1.
  • Log in the formula means logic.
  • the dispersed ethylene-a-olefin copolymer is present in an amount of 50 to 5 wt% based on the total heterophasic propylene copolymer.
  • the dispersed ethylene-a-olefin copolymer is present in an amount of 40 to 15 wt%, for example in an amount of at least 22 wt% and/or for example in an amount of at most 35 wt% or at most 30 wt% based on the total heterophasic propylene copolymer.
  • the sum of the total weight of the propylene-based matrix and the total weight of the dispersed ethylene-a-olefin copolymer is 100 wt% of the heterophasic propylene copolymer.
  • the a-olefin in the ethylene-a-olefin copolymer is preferably chosen from the group of a-olefins having 3 to 8 carbon atoms and any mixtures thereof, preferably the a-olefin in the ethylene-a-olefin copolymer is chosen from the group of a-olefins having 3 to 4 carbon atoms and any mixture thereof, more preferably the a-olefin is propylene, in which case the ethylene-a-olefin copolymer is ethylene-propylene copolymer.
  • Suitable a-olefins having 3 to 8 carbon atoms which may be employed as ethylene comonomers to form the ethylene a-olefin copolymer include but are not limited to propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexen, 1-heptene and 1 -octene.
  • the elastomer of ethylene and a-olefin comonomer having 4 to 8 carbon atoms may for example have a density in the range from 0.850 to 0.915 g/cm 3 .
  • Such elastomers are sometimes also referred to as plastomers.
  • the a-olefin comonomer in the elastomer is preferably an acyclic monoolefin such as 1-butene, 1-pentene, 1 -hexene, 1 -octene, or 4-methylpentene.
  • the elastomer is preferably selected from the group consisting of ethylene- 1-butene copolymer , ethylene-1 -hexene copolymer, ethylene-1 -octene copolymer and mixtures thereof, more preferably wherein the elastomer is selected from ethylene- 1 -octene copolymer. Most preferably, the elastomer is an ethylene-1- octene copolymer.
  • the density of the elastomer is at least 0.865 g/cm 3 and/or at most 0.910 g/cm 3 .
  • the density of the elastomer is at least 0.850, for example at least 0.865, for example at least 0.88, for example at least 0.90 and/or for example at most 0.915, for example at most 0.910, for example at most 0.907, for example at most 0.906 g/cm 3 .
  • the density of the elastomer is in the range from 0.88 up to an including 0.907 g/cm 3 , most preferably, the density of the elastomer is in the range from 0.90 up to and including 0.906 g/cm 3 .
  • the elastomers may be prepared using methods known in the art, for example by using a single site catalyst, i.e. , a catalyst the transition metal components of which is an organometallic compound and at least one ligand of which has a cyclopentadienyl anion structure through which such ligand bondingly coordinates to the transition metal cation.
  • a single site catalyst i.e. , a catalyst the transition metal components of which is an organometallic compound and at least one ligand of which has a cyclopentadienyl anion structure through which such ligand bondingly coordinates to the transition metal cation.
  • This type of catalyst is also known as "metallocene" catalyst.
  • Metallocene catalysts are for example described in U.S. Patent Nos. 5,017,714 and 5,324,820.
  • the elastomer s may also be prepared using traditional types of heterogeneous multi-sited Ziegler-Natta catalysts.
  • the elastomer has a melt flow index of 0.1 to 40 dg/min (ISO1133, 2.16kg, 190°C), for example at least 1 dg/min and/or at most 35 dg/min. More preferably, the elastomer has a melt flow index of at least 1 .5 dg/min, for example of at least 2 dg/min, for example of at least 2.5 dg/min, for example of at least 3 dg/min, more preferably at least 5 dg/min and/or preferably at most 30 dg/min, more preferably at most 20 dg/min, more preferably at most 10 dg/min measured in accordance with ISO 1133 using a 2.16 kg weight and at a temperature of 190 °C.
  • the amount of ethylene incorporated into the elastomer is at least 50 mol %. More preferably, the amount of ethylene incorporated into the elastomer is at least 57 mol%, for example at least 60 mol %, at least 65 mol% or at least 70 mol%. Even more preferably, the amount of ethylene incorporated into the elastomer is at least 75 mol%. The amount of ethylene incorporated into the elastomer may typically be at most 97.5 mol%, for example at most 95 mol% or at most 90 mol%. In preferred embodiments, the thermoplastic polymer in the thermoplastic polymer composition is a propylene homopolymer.
  • the thermoplastic polymer is a non-visbroken polypropylene, also known as a reactor grade. This results in better smell properties than visborken polypropylene made by visbreaking a reactor grade polypropylene with a lower melt flow index to increase its melt flow index.
  • thermoplastic polymer composition of polymer sheath additives in thermoplastic polymer composition of polymer sheath
  • the thermoplastic polymer composition of the polymer sheath may contain other usual additives, for instance nucleating agents and clarifiers, stabilizers, fillers, plasticizers, anti-oxidants, lubricants, antistatics, scratch resistance agents, impact modifiers, acid scavengers, recycling additives, coupling agents, anti-microbials, anti-fogging additives, slip additives, anti-blocking additives, polymer processing aids, flame retardants, colorants and the like.
  • additives are well known in the art. The skilled person will know how to choose the type and amount of additives such that they do not detrimentally influence the aimed properties.
  • the amount of the additives may e.g. be 0.1 to 5.0 wt% of the thermoplastic polymer composition.
  • the amount of the additives may e.g. be 0.1 to 50 wt% of the thermoplastic polymer composition.
  • the additives in the thermoplastic polymer composition of the polymer sheath comprises a flame retardant.
  • the flame retardant may comprise an organic flame retardant and/or an inorganic flame retardant.
  • the organic flame retardant preferably comprises at least one phosphate selected from the group consisting of melamine phosphate, melamine polyphosphate, melamine pyrophosphate, piperazine phosphate, piperazine polyphosphate, piperazine pyrophosphate, 2-methylpiperazine monophosphate, tricresyl phosphate, alkyl phosphates, haloalkyl phosphates, tetraphenyl pyrophosphate, poly(2-hydroxy propylene spirocyclic pentaerythritol bisphosphate) and poly(2,2-dimethylpropylene spirocyclic pentaerythritol bisphosphonate).
  • a phosphate selected from the group consisting of melamine phosphate, melamine polyphosphate, melamine pyrophosphate, piperazine phosphate, piperazine polyphosphate, piperazine pyrophosphate, 2-methylpiperazine monophosphate, tricresyl phosphate,
  • the organic flame retardant preferably comprises ammonium polyphosphate. In some preferred embodiments, the organic flame retardant comprises ammonium polyphosphate and at least one of the above-mentioned phosphate. In some preferred embodiments, the organic flame retardant comprises ammonium polyphosphate and at least two of the above-mentioned phosphate.
  • the organic flame retardant comprises ammonium polyphosphate, melamine polyphosphate and piperazine phosphate.
  • the organic flame retardant comprises melamine phosphate and piperazine pyrophosphate.
  • the inorganic flame retardant may comprise e.g. zinc oxide.
  • the flame retardant may be particles comprising the organic flame retardant and zinc oxide.
  • the amount of zinc oxide with respect to the particles is 1 to 10 wt%.
  • the organic flame retardant comprises an aromatic phosphate ester.
  • the amount of the flame retardant, in particular the organic flame retardant, with respect to thermoplastic polymer composition of the polymer sheath is 0.1 to 50 wt%, e.g. at least 1 .0 wt%, at least 5.0 wt%, at least 10 wt%, at least 20 wt%, at least 30 wt% and/or at most 45 wt% or at most 40 wt%.
  • the flame retardant described above, in particular the phosphates, may serve as part of an intumescent flame retardant composition.
  • An intumescent flame retardant composition may comprise various components to produce an outer char coating when exposed to flame and/or high heat.
  • a thermoplastic polymer composition comprising an intumescent flame retardant comprises a carbon source and the intumescent flame retardant composition may comprise a film-forming binder, an acid source and a blowing agent.
  • the carbon source can be an organic material that decomposes to a char consisting primarily of carbon when exposed to fire or heat.
  • the carbon source may be the polyolefin in the thermoplastic polymer composition.
  • the carbon source can generate an expanded, insulating, cellular structure that can be several times thicker than the original thickness, when exposed to fire or heat.
  • the additives in the thermoplastic polymer composition of the polymer sheath comprises a coupling agent.
  • Suitable examples of the coupling agent include a functionalized polyolefin grafted with an acid or acid anhydride functional group.
  • the polyolefin is preferably polyethylene or polypropylene, more preferably polypropylene.
  • the polypropylene may be a propylene homopolymer or a propylene copolymer.
  • the propylene copolymer may be a propylene- a-olefin copolymer consisting of at least 70 wt% of propylene and up to 30 wt% of a-olefin, for example ethylene, for example consisting of at least 80 wt% of propylene and up to 20 wt% of a-olefin, for example consisting of at least 90 wt% of propylene and up to 10 wt% of a-olefin, based on the total weight of the propylene- based matrix.
  • a propylene- a-olefin copolymer consisting of at least 70 wt% of propylene and up to 30 wt% of a-olefin, for example ethylene, for example consisting of at least 80 wt% of propylene and up to 20 wt% of a-olefin, for example consisting of at least 90 wt% of propylene and up to 10
  • the a-olefin in the propylene- a-olefin copolymer is selected from the group of a-olefins having 2 or 4-10 carbon atoms and is preferably ethylene.
  • the acid or acid anhydride functional groups include (meth)acrylic acid and maleic anhydride.
  • a particularly suitable material is for example maleic acid functionalized propylene homopolymer (for example Exxelor PO 1020 supplied by ExxonMobil and Fine-Blend® CMG5701 supplied by Fine-Blend Compatibilizer Jiangsu Co., Ltd).
  • maleic acid functionalized propylene homopolymer with low odor and TVOC is preferred, an example being Fine-Blend® CMG5701.
  • the amount of the coupling agent may e.g. be 0.5 to 3.0 wt%, preferably 1.0 to 2.0 wt%, based on the sheathed continuous multifilament strand.
  • the sheathed continuous multifilament strand comprises a core that extends in the longitudinal direction.
  • the core comprises an impregnated continuous bicomponent multifilament strand comprising at least one continuous bicomponent multifilament strand and an impregnating agent.
  • the impregnated continuous bicomponent multifilament strand is prepared from a continuous bicomponent multifilament strand and an impregnating agent by impregnating the continuous bicomponent multifilament strand with the impregnating agent.
  • the total of the impregnated continuous bicomponent multifilament strand and any impregnated continuous glass multifilament strand form at least 90wt%, more preferably at least 93wt%, even more preferably at least 95wt%, even more preferably at least 97wt%, even more preferably at least 98wt%, for example at least 99wt% of the core.
  • the core consists of the impregnated continuous bicomponent multifilament strand and any impregnated continuous glass multifilament strand.
  • the continuous bicomponent multifilament strands comprising the co-filaments are generally supplied as a plurality of continuous, very long filaments, and can be in the form of strands, rovings or yarns.
  • a filament is an individual fibre of reinforcing material.
  • a strand is a plurality of bundled filaments.
  • Yarns are collections of strands, for example strands twisted together.
  • a roving refers to a collection of strands wound into a package.
  • a multifilament strand is defined as a plurality of bundled co-filaments.
  • the filament density of the continuous bicomponent multifilament strand may vary within wide limits.
  • the continuous bicomponent multifilament strand may have a density of 1000 to 10000 grams per 1000 meter.
  • the continuous bicomponent multifilament strand has a density of 1000 to 2900 grams per 1000 meter, more preferably 1500 to 2800 grams per 1000 meter.
  • the continuous bicomponent multifilament strand may have a filament diameter of 5 to 50 pm, more preferably from 10 to 30 pm, even more preferably from 15 to 25 pm.
  • the bicomponent filaments may be circular in cross section meaning the thickness as defined above would mean diameter.
  • the ratio between the length of the bicomponent filament and the diameter of the bicomponent filament (L/D ratio) in the pellets is 500 to 1000.
  • the bicomponent multifilament strand is coated with a sizing composition (i.e. , a coating) to improve adhesion to the polymer matrix.
  • a sizing composition i.e. , a coating
  • the sizing composition can be disposed on substantially all of the bicomponent filaments or on a portion of the bicomponent filaments in the thermoplastic composition.
  • the sizing provides coated bicomponent filaments that can be either bonding or non-bonding towards bicomponent thermoplastic polymer composition of the sheath.
  • the coated bicomponent filaments are bonding towards the polymer in the thermoplastic polymer composition of the sheath.
  • the sizing composition can include a polyepoxide, a poly(meth)acrylate, a poly(arylene ether), a polyurethane, or a combination thereof.
  • the polyepoxide can be a phenolic epoxy resin, an epoxylated carboxylic acid derivative (e.g., a reaction product of an ester of a polycarboxylic acid having one or more unesterified carboxyl groups with a compound including more than one epoxy group), an epoxidized diene polymer, an epoxidized polyene polymer, or a combination thereof.
  • the sizing composition can further include a silane coupling agent to facilitate bonding with the glass fiber.
  • the silane coupling agent can be tri(Ci_ 6 alkoxy)mono amino silane, tri(Ci_ 6 alkoxy)diamino silane, tri(Ci_ 6 alkoxy)(Ci_ 6 alkyl ureido) silane, tri(Ci_ 6 alkoxy)(epoxy Ci_ 6 alkyl) silane, tri(Ci_ 6 alkoxy)(glycidoxy Ci_ 6 alkyl) silane, tri(Ci_ 6 alkoxy) (mercapto Ci_ 6 alkyl) silane, or a combination thereof.
  • the silane coupling agent is (3 -aminopropyl)triethoxy silane, (3-glycidoxypropyl)trimethoxysilane, (2-(3,4- epoxycyclohexyl)ethyl)triethoxysilane, (3-mercaptopropyl)trimethoxysilane, (3- (2- aminoethylamino)propyl)triethoxysilane, (3 -ureidopropyl)triethoxy silane, or a combination thereof.
  • the silane coupling agent is aminopropyltriethoxysilane, glycidylpropyltrimethoxysilane, or a combination thereof.
  • sizing compositions include, but are not limited to, anti-static agents, coupling agents, lubricants, wetting agents, or the like.
  • the sizing composition can be present in an amount from 0.1 to 5.0 wt% based on the weight of the at least one continuous bicomponent multifilament strand.
  • the sizing composition may be applied to the co-filaments by any means, such as immersing the multifilament strand in the sizing composition or contacting the multifilament strand with an aqueous emulsion, or suspension of the sizing composition.
  • Other coating methods include using an aqueous dispersion of the sizing composition applied to the uncoated multifilament strand by a roller in a continuous fashion, which can be followed by a heat treatment or curing step.
  • the filaments are bundled into the continuous bicomponent multifilament strands and then wound onto bobbins to form a package.
  • the amount of the impregnating agent is preferably in an amount from 0.50 to 18.0 wt%, for example from 0.5 to 10.0 wt% or for example from 10.0 to 18.0 wt% based on the total weight of the pellet.
  • the optimal amount of impregnating agent depends on the polymer sheath, on the size (diameter) of the filaments forming the continuous strand, and on the type of sizing composition.
  • the amount of impregnating agent applied to the continuous multifilament strand is for example at least 0.50 wt%, preferably at least 1 .0wt%, preferably at least 1 ,5wt%, preferably at least 2wt%, preferably at least 2.5 wt% and/or at most 10.0wt%, preferably at most 9.0 wt%, more preferably at most 8.0 wt%, even more preferably at most 7.0 wt%, even more preferably at most 6.0wt%, even more preferably at most 5.5wt%, or for example at least 10.0 wt%, preferably at least 11wt%, preferably at least 12wt% and/or at most 18 wt%, preferably at most 16 wt%, preferably at most 14% based on the amount
  • the amount of impregnating agent is in the range from 1 .5 to 8.0 wt%, even more preferably in the range from 2.5 wt% to 6.0 wt% based on the sheathed continuous multifilament strand.
  • a higher amount of impregnating agent increases the Impact Energy per unit of thickness (J/mm).
  • the amount of impregnating agent should also not become too high.
  • the ratio of impregnating agent to continuous glass multifilament strand is in the range from 1 :4 to 1 :30, preferably in the range from 1 :5 to 1 :20.
  • the viscosity of the impregnating agent is in the range from 2.5 to 200cSt at 160°C, more preferably at least 5.0 cSt, more preferably at least 7.0 cSt and/or at most 150.0 cSt, preferably at most 125.0 cSt, preferably at most 100.0cSt at 160°C.
  • an impregnating agent having a viscosity higher than 200 cSt is difficult to apply to the continuous glass multifilament strand. Low viscosity is needed to facilitate good wetting performance of the fibres, but an impregnating agent having a viscosity lower than 2.5 cSt is difficult to handle, e.g., the amount to be applied is difficult to control; and the impregnating agent could become volatile.
  • the viscosity of the impregnating agent is measured in accordance with ASTM D 3236-15 (standard test method for apparent viscosity of hot melt adhesives and coating materials, Brookfield viscometer Model RVDV 2, #27 spindle, 5 r/min) at 160°C.
  • the melting point of (that is the lowest melting temperature in a melting temperature range) the impregnating agent is at least 20°C below the melting point of the thermoplastic polymer composition. More preferably, the impregnating agent has a melting point of at least 25 or 30°C below the melting point of the thermoplastic polymer composition. For instance, when the thermoplastic polymer composition has a melting point of about 160°C, the melting point of the impregnating agent may be at most about 140°C.
  • Suitable impregnating agents are compatible with the thermoplastic polymer to be reinforced, and may even be soluble in said polymer.
  • the skilled man can select suitable combinations based on general knowledge, and may also find such combinations in the art.
  • Suitable examples of impregnating agents include low molar mass compounds, for example low molar mass oligomeric polyurethanes, polyesters such as unsaturated polyesters, polycaprolactones, polyethyleneterephthalate, poly(alpha-olefins), such as highly branched polyethylenes and polypropylenes, polyamides, such as nylons, and other hydrocarbon resins.
  • low molar mass compounds for example low molar mass oligomeric polyurethanes, polyesters such as unsaturated polyesters, polycaprolactones, polyethyleneterephthalate, poly(alpha-olefins), such as highly branched polyethylenes and polypropylenes, polyamides, such as nylons, and other hydrocarbon resins.
  • the impregnating agent preferably comprises highly branched poly(alpha-olefins), such as highly branched polyethylenes, modified low molecular weight polypropylenes, mineral oils, such as, paraffin or silicon and any mixtures of these compounds.
  • the impregnating agent preferably comprises at least 20wt%, more preferably at least 30wt%, more preferably at least 50wt%, for example at least 99.5wt%, for example 100wt% of a branched poly(alpha-olefin), most preferably a branched polyethylene.
  • the branched poly(alpha-olefin) may be mixed with an oil, wherein the oil is chosen from the group consisting of of mineral oils, such as a paraffin oil or silicon oil; hydrocarbon oils; and any mixtures thereof.
  • the impregnating agent is non-volatile, and/or substantially solvent-free.
  • non-volatile means that the impregnating agent has a boiling point or range higher than the temperatures at which the impregnating agent is applied to the continuous multifilament glass strand.
  • substantially solvent-free means that impregnating agent contains less than 10 wt% of solvent, preferably less than 5wt% of solvent based on the impregnating agent. In a preferred embodiment, the impregnating agent does not contain any organic solvent.
  • the impregnating agent may further be mixed with other additives known in the art. Suitable examples include lubricants; antistatic agents; UV stabilizers; plasticizers; surfactants; nucleation agents; antioxidants; pigments; dyes; and adhesion promoters, such as a modified polypropylene having maleated reactive groups; and any combinations thereof, provided the viscosity remains within the desired range. Any method known in the art may be used for applying the impregnating agent to the continuous glass multifilament strand. The application of the impregnating agent may be performed using a die. Other suitable methods for applying the impregnating agent to the continuous multifilament strands include applicators having belts, rollers, and hot melt applicators.
  • the weight average length of the co-filaments in the pellet or molded article can be determined e.g. by creating a photo image of the pellet or article for allowing an image processing algorithm to detect the length of all the individual filaments in the image and calculating the weigh average length from the detected lengths.
  • a photo image can be created e.g. by incinerating the pellet or article and taking a photo of the ash under an optical microscope. This can be done e.g. by incinerating the pellet or article at a temperature of 700°C, using a brush to gently spread the ash obtained by incineration and taking a photo under an optical microscope of the spread ash.
  • the individual filament length in the pellet can also be determined by direct measurement of the pellet length.
  • the weight average length of the co-filaments can be calculated using the following equation: wherein L w is the weight average length of the co-filaments, l i is the individual co-filament length.
  • the term ‘comprising’ does not exclude the presence of other elements.
  • a description on a product/composition comprising certain components also discloses a product/composition consisting of these components.
  • the product/composition consisting of these components may be advantageous in that it offers a simpler, more economical process for the preparation of the product/composition.
  • a description on a process comprising certain steps also discloses a process consisting of these steps. The process consisting of these steps may be advantageous in that it offers a simpler, more economical process.
  • Materials used GF1 a glass roving having a diameter of 19 micron and a tex of 3000 (tex means grams glass per 1000m) containing a sizing composition comprising a silane coupling agent.
  • GF2 a roving having a diameter of 19 micron and a tex of 2200, wherein the roving consists of bundled co-filaments of a basalt filament in contact with an aluminum filament, containing a sizing composition comprising a silane coupling agent and polyurethane
  • Impregnating agent 1 wax commercially available as IGI Paraflex 4838A
  • PP1 SABIC PP 595A Polypropylene homopolymer with following properties: density: 905 kg/m 3 , melt flow index: 45 dg/min at 230°C and 2.16kg (test method: ISO1133)
  • Exxelor P01020 polypropylene grafted with maleic anhydride from ExxonMobil: density: 900 kg/m 3 , melting point: 162°C, melt flow index: 430 dg/min at 230°C and 2.16kg (testing method: ASTM D1238)
  • AOB225 antioxidant B225 from BASF
  • UV119 UV stabilizer UV 119 from SABO SpA
  • Pellets of sheathed continuous glass multifilament strands were prepared using components given in Table 1 using the wire coating process as described in details in the examples of W02009/080281A1.
  • Impregnating agent 1 was applied to GF1 to obtain an impregnated continuous glass multifilament strand.
  • Polypropylene and additives shown in table 1 were fed to the extruder to sheath the impregnated continuous glass multifilament strand using an extruder-head wire-coating die.
  • the sheathing step was performed in-line directly after the impregnating step.
  • the obtained sheathed continuous multifilament strand was cut into pellets having length of 8-15 mm and diameter of 3-4 mm.
  • the obtained pellets were molded using ARBURG 320T injection molding machine to prepare the samples for testing.
  • Pellets of sheathed continuous multifilament strands were prepared using components given in Table 1 using the process as in CEx 1 . Following properties were measured and are shown in Table 1.
  • Charpy performance was tested after 7 days at 23 °C aging according to IS0179/1 eU at 23°C.
  • Weight average filament length of the filaments in an injection molded plaque was determined by heating the sample to collect ash, dispersing the ash residue in a liquid followed by analysis with a microscopy with an imaging software.
  • compositions of Ex 2 and 4 made using long co-filaments of basalt filament and aluminum filament have better shielding properties than the compositions of CEx 1 and CEx 3 made using glass filaments, respectively.

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Abstract

L'invention concerne une pastille comprenant une composition polymère thermoplastique renforcée par des fibres comprenant un polymère thermoplastique et une pluralité de co-filaments, chacun des co-filaments comprenant un premier filament et un deuxième filament, le premier filament étant constitué d'un matériau inorganique, le premier filament ayant une température de transition vitreuse supérieure ou égale à 400 °C, le deuxième filament étant constitué d'un matériau métallique, et le deuxième filament étant en contact avec le premier filament, la longueur moyenne en poids des co-filaments dans la pastille étant d'au moins 5,0 mm.
PCT/EP2024/073552 2023-09-01 2024-08-22 Composition de polymère thermoplastique renforcée par des fibres Pending WO2025045719A1 (fr)

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