WO2022110037A1 - Composition renforcée par des fibres de verre présentant une ininflammabilité et un faible gauchissement - Google Patents

Composition renforcée par des fibres de verre présentant une ininflammabilité et un faible gauchissement Download PDF

Info

Publication number
WO2022110037A1
WO2022110037A1 PCT/CN2020/132320 CN2020132320W WO2022110037A1 WO 2022110037 A1 WO2022110037 A1 WO 2022110037A1 CN 2020132320 W CN2020132320 W CN 2020132320W WO 2022110037 A1 WO2022110037 A1 WO 2022110037A1
Authority
WO
WIPO (PCT)
Prior art keywords
range
flame
composition
polypropylene
base composition
Prior art date
Application number
PCT/CN2020/132320
Other languages
English (en)
Inventor
Xiangyang Zhu
Shengquan ZHU
Feild SHEN
Original Assignee
Borouge Compounding Shanghai Co., Ltd.
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 Borouge Compounding Shanghai Co., Ltd. filed Critical Borouge Compounding Shanghai Co., Ltd.
Priority to PCT/CN2020/132320 priority Critical patent/WO2022110037A1/fr
Priority to CN202080107131.3A priority patent/CN117999313A/zh
Publication of WO2022110037A1 publication Critical patent/WO2022110037A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/24—Crystallisation aids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus

Definitions

  • the present invention relates to a fiber-reinforced polypropylene composition
  • a fiber-reinforced polypropylene composition comprising glass fibers and a polypropylene base composition, which in turn comprises a heterophasic propylene-ethylene copolymer, a flame-retardant, and additives, as well as articles comprising said composition.
  • normal petrol-and diesel-powered vehicles will contain a battery, both for starting the motor and powering the various electrical components in said vehicle.
  • batteries can be bulky and heavy, housing large quantities of electrolytic solutions. Furthermore, there is the ever-present risk, as in any electric component, of fire. As such, the housing materials for such batteries are required to have highly optimised mechanical properties and minimized warpage, as well as flame-retardancy properties.
  • Vehicle battery covers have been traditionally made of metals, which are non-flammable and provide a good balance of mechanical properties.
  • Polymer-based battery covers are considerably lighter than those made from metal, and thus are advantageous as a lightweight alternative. It is, however, required that specialised polymer compositions are developed in order to avoid having a battery cover with inferior mechanical and flame retardance properties. In addition, the polymer compositions are required to have a low warpage, so as to avoid any spilling or overflowing of battery liquid.
  • Flame-retardants are chemicals used in polymers that inhibit or resist the spread of fire.
  • compounds containing halides have historically been added to the polymer. These compounds function via the release of relatively stable halogen radicals that are able to quench the radical chain reactions involved in the combustion process.
  • Another approach to achieve high flame-retardant properties in halogen-free polymer compositions has been to add large amounts, typically above 60 wt%of inorganic flame-retardant fillers such as hydrated and hydroxy compounds.
  • Such fillers which include Al (OH) 3 and Mg (OH) 2 decomposes endothermically at temperatures between 200 and 300 °C, liberating inert gases.
  • Another group of non-halogenated flame-retardants is the class of organophosphorus. These compounds typically operate by creating a thermal insulation barrier between the burning sections and the unburned plastic, typically a layer of charred phosphoric acid.
  • PC fiber-reinforced polypropylene composition
  • HECO heterophasic propylene-ethylene copolymer
  • heterophasic propylene-ethylene copolymer HECO has a melt flow rate (MFR 2 ) measured according to ISO 1133 at 230 °C and 2.16 kg in the range from 70.0 to 150.0 g/10 min;
  • heterophasic propylene-ethylene copolymer has one or more, preferably all, of the following properties:
  • XCS xylene cold solubles
  • a total ethylene (C2) content in the range from 3.0 to 10.0 wt. -%, preferably in the range from 4.5 to 8.5 wt. -%, most preferably in the range from 5.5 to 7.5 wt. -%;
  • heterophasic propylene-ethylene copolymer has one or more, preferably all, of the following properties:
  • a melting temperature measured by DSC analysis, in the range from 160 to 169 °C, more preferably in the range from 161 to 168 °C, most preferably in the range from 162 to 168 °C;
  • a flexural modulus measured according to according to ISO 178 on 80x10x4 mm 3 test bars injection molded in line with EN ISO 1873-2, in the range from 1000 to 2500 MPa, more preferably in the range from 1200 to 2000 MPa, most preferably in the range from 1400 to 1700 MPa;
  • a Charpy notched impact strength measured at 23 °C according to ISO 179-1 1eA using injection-molded bar test specimens of 80x10x4 mm 3 prepared in accordance with ISO 1873-2: 2007, in the range from 1.0 to 10.0 kJ/m 2 , more preferably in the range from 3.0 to 8.0 kJ/m 2 , most preferably in the range from 4.0 to 6.0 kJ/m 2 .
  • the heterophasic propylene-ethylene copolymer contains a polymeric nucleating agent, preferably being a vinyl cycloalkane polymer, more preferably a vinyl cyclohexane polymer, most preferably a vinyl cyclohexane homopolymer.
  • the crystalline propylene homopolymer matrix (M) of the heterophasic propylene-ethylene copolymer (HECO) has a melt flow rate (MFR 2 ) measured according to ISO 1133 at 230 °C and 2.16 kg in the range from 100.0 to 300.0 g/10 min, more preferably in the range from 130 to 260 g/10 min, most preferably in the range from 160 to 220 g/10 min.
  • the flame-retardant (FR) is a non-halogenated flame-retardant, more preferably a non-halogenated organophosphorus flame-retardant, most preferably selected from piperazine pyrophosphate, melamine polyphosphate, calcium bis (dihydrogenorthophosphate) , calcium hydrogen phosphonate and mixtures thereof.
  • the glass fibers (GF) are continuous glass fibers that have been introduced to the composition using an LFT-D extruder, preferably wherein the continuous glass fibers have a nominal diameter in the range from 5 to 30 ⁇ m, preferably in the range from 10 to 20 ⁇ m, most preferably in the range from 13 to 17 ⁇ m.
  • the polypropylene base composition (BC) further comprises:
  • PMP polar-modified polypropylene
  • the polar-modified polypropylene (PMP) has a content of polar groups in the range from 0.5 to 3.0 wt. -%.
  • the fiber-reinforced polypropylene composition has a flame-retardancy classification, as measured according to test standard UL94-2013, of V-0.
  • the present invention is directed to an article comprising more than 75 wt. -%of the fiber-reinforced polypropylene composition (PC) according to any one of claims 1 to 10, preferably a molded article, most preferably a compression molded article.
  • PC polypropylene composition
  • the article is an automotive article, preferably the article is a vehicle battery cover.
  • the present invention is directed to a use of a polypropylene base composition (BC) , comprising:
  • HECO heterophasic propylene-ethylene copolymer
  • heterophasic propylene-ethylene copolymer HECO has a melt flow rate (MFR 2 ) measured according to ISO 1133 at 230 °C and 2.16 kg in the range from 70.0 to 150.0 g/10 min;
  • d) optionally from 0.1 to 3. wt. -%, based on the total weight of the base composition, of a polar-modified polypropylene (PMP) , preferably a maleic anhydride-modified polypropylene, in an LFT-D process with continuous glass fibers to form a compression molded article, preferably a vehicle battery cover, wherein the article contains 60 to 80 wt. -%of the polypropylene base composition (BC) and 20 to 40 wt. -%continuous glass fibers.
  • PMP polar-modified polypropylene
  • a maleic anhydride-modified polypropylene in an LFT-D process with continuous glass fibers to form a compression molded article, preferably a vehicle battery cover, wherein the article contains 60 to 80 wt. -%of the polypropylene base composition (BC) and 20 to 40 wt. -%continuous glass fibers.
  • heterophasic propylene-ethylene copolymer HECO
  • the main component of the polyolefin base composition (BC) is the heterophasic propylene-ethylene copolymer (HECO) .
  • a heterophasic propylene-ethylene copolymer comprises at least two distinct phases, namely a propylene homopolymer crystalline matrix phase (M) and an elastomeric ethylene-propylene copolymer (EC) .
  • M propylene homopolymer crystalline matrix phase
  • EC elastomeric ethylene-propylene copolymer
  • the crystalline matrix (M) of the heterophasic propylene-ethylene copolymer (HECO) of the present invention is bimodal or unimodal, most preferably bimodal, whilst the elastomeric ethylene-propylene copolymer (EC) is unimodal.
  • the heterophasic propylene-ethylene copolymer (HECO) of the present invention has a melt flow rate (MFR 2 ) measured according to ISO 1133 at 230°C and 2.16 kg in the range from 70.0 to 150.0 g/10 min, preferably in the range from 80.0 to 130.0 g/10 min, more preferably in the range from 85.0 to 120.0 g/10 min, most preferably in the range from 90.0 to 110.0 g/10 min.
  • MFR 2 melt flow rate measured according to ISO 1133 at 230°C and 2.16 kg in the range from 70.0 to 150.0 g/10 min, preferably in the range from 80.0 to 130.0 g/10 min, more preferably in the range from 85.0 to 120.0 g/10 min, most preferably in the range from 90.0 to 110.0 g/10 min.
  • the heterophasic propylene-ethylene copolymer (HECO) of the present invention preferably has a xylene cold solubles (XCS) content in the range from 5.0 to 20.0 wt. -%, preferably in the range from 10.0 to 18.0 wt. -%, most preferably in the range from 13.0 to 16.0 wt. -%.
  • XCS xylene cold solubles
  • heterophasic propylene-ethylene copolymer (HECO) of the present invention has an ethylene content of the xylene cold soluble fraction (C2 (XCS) ) in the range from 30.0 to 50.0 wt. -%, preferably in the range from 35.0 to 45.0 wt. -%, most preferably in the range from 37.0 to 41.0 wt. -%.
  • C2 (XCS) xylene cold soluble fraction
  • heterophasic propylene-ethylene copolymer (HECO) of the present invention has a total ethylene (C2) content in the range from 3.0 to 10.0 wt. -%, preferably in the range from 4.5 to 8.5 wt. -%, most preferably in the range from 5.5 to 7.5 wt. -%.
  • heterophasic propylene-ethylene copolymer (HECO) of the present invention has an intrinsic viscosity of the xylene cold soluble fraction (IV (XCS) ) in the range from 1.5 to 3.0 dl/g, preferably in the range from 1.8 to 2.7 dl/g, most preferably in the range from 2.1 to 2.5 dl/g.
  • the crystalline propylene homopolymer matrix (M) has a melt flow rate (MFR 2 ) measured according to ISO 1133 at 230°C and 2.16 kg in the range from 100.0 to 300.0 g/10 min, more preferably in the range from 130 to 260 g/10 min, most preferably in the range from 160 to 220 g/10 min.
  • MFR 2 melt flow rate measured according to ISO 1133 at 230°C and 2.16 kg in the range from 100.0 to 300.0 g/10 min, more preferably in the range from 130 to 260 g/10 min, most preferably in the range from 160 to 220 g/10 min.
  • heterophasic propylene-ethylene copolymer (HECO) of the present invention has a flexural modulus measured according to ISO 178 in the range from 1000 to 2500 MPa, more preferably in the range from 1200 to 2000 MPa, most preferably in the range from 1400 to 1700 MPa.
  • the heterophasic propylene-ethylene copolymer (HECO) of the present invention has a Charpy Notched Impact Strength measured according to ISO 179/1eA at +23 °C in the range from 1.0 to 10.0 kJ/m 2 , more preferably in the range from 3.0 to 8.0 kJ/m 2 , most preferably in the range from 4.0 to 6.0 kJ/m 2 .
  • heterophasic propylene-ethylene copolymer (HECO) of the present invention may either be synthesized or selected from commercially available polypropylenes.
  • the heterophasic propylene-ethylene copolymer preferably comprises a polymeric nucleating agent.
  • a preferred example of such a polymeric nucleating agent is a vinyl polymer, such as a vinyl polymer derived from monomers of the formula
  • R 1 and R 2 together with the carbon atom they are attached to, form an optionally substituted saturated or unsaturated or aromatic ring or a fused ring system, wherein the ring or fused ring moiety contains four to 20 carbon atoms, preferably 5 to 12 membered saturated or unsaturated or aromatic ring or a fused ring system or independently represent a linear or branched C4-C30 alkane, C4-C20 cycloalkane or C4-C20 aromatic ring.
  • R 1 and R 2 together with the C-atom wherein they are attached to, form a five-or six-membered saturated or unsaturated or aromatic ring or independently represent a lower alkyl group comprising from 1 to 4 carbon atoms.
  • Preferred vinyl compounds for the preparation of a polymeric nucleating agent to be used in accordance with the present invention are in particular vinyl cycloalkanes, in particular vinyl cyclohexane (VCH) , vinyl cyclopentane, and vinyl-2-methyl cyclohexane, 3-methyl-1-butene, 3-ethyl-1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene or mixtures thereof.
  • the vinyl polymer is a vinyl cycloalkane polymer, preferably selected from vinyl cyclohexane (VCH) , vinyl cyclopentane and vinyl-2-methyl cyclohexane, with vinyl cyclohexane polymer being a particularly preferred embodiment.
  • VCH vinyl cyclohexane
  • vinyl cyclopentane vinyl cyclopentane
  • vinyl-2-methyl cyclohexane vinyl cyclohexane
  • the vinyl polymer of the polymeric nucleating agent is a homopolymer, most preferably a vinyl cyclohexane homopolymer.
  • heterophasic propylene-ethylene copolymer (HECO) of the present invention may either be synthesized or selected from commercially available polypropylenes.
  • heterophasic propylene-ethylene copolymer (HECO) comprised in the composition according to this invention is preferably produced in a sequential polymerization process in the presence of a Ziegler-Natta catalyst, more preferably in the presence of a catalyst (system) as defined below.
  • heterophasic propylene-ethylene copolymer is reactor made, preferably has been produced in a sequential polymerization process, wherein the crystalline matrix (M) has been produced in at least one reactor, preferably in two reactors, and subsequently the elastomeric ethylene-propylene copolymer (EC) has been produced in at least one further reactor, preferably in one further reactor.
  • M crystalline matrix
  • EC elastomeric ethylene-propylene copolymer
  • polymerization reactor shall indicate that the main polymerization takes place. Thus in case the process consists of three polymerization reactors, this definition does not exclude the option that the overall process comprises for instance a pre-polymerization step in a pre-polymerization reactor.
  • consist of is only a closing formulation in view of the main polymerization reactors, i.e. does not exclude prepolymerisation reactors prior to the three reactors.
  • said process comprises the steps of
  • step (d1) transferring the crystalline propylene homopolymer matrix (M) of step (c1) into a third reactor (R3) ,
  • step (e1) polymerizing propylene and ethylene in the third reactor (R3) and in the presence of the crystalline propylene homopolymer matrix (M) obtained in step (c1) , obtaining thereby the elastomeric ethylene-propylene copolymer (EC) , said crystalline propylene homopolymer matrix (M) and said elastomeric ethylene-propylene copolymer (EC) forming the heterophasic propylene-ethylene copolymer (HECO) .
  • HECO heterophasic propylene-ethylene copolymer
  • heterophasic propylene copolymer HECO
  • crystalline matrix M
  • first propylene homopolymer h-PP1
  • second propylene homopolymer h-PP2
  • EC elastomeric ethylene-propylene copolymer
  • the first reactor (R1) is preferably a slurry reactor (SR) and can be any continuous or simple stirred batch tank reactor or loop reactor operating in bulk or slurry.
  • Bulk means a polymerization in a reaction medium that comprises of at least 60 % (w/w) monomer.
  • the slurry reactor (SR) is preferably a (bulk) loop reactor (LR) .
  • the second reactor (R2) and the third reactor (R3) are preferably gas phase reactors (GPR) .
  • gas phase reactors (GPR) can be any mechanically mixed or fluid bed reactors.
  • the gas phase reactors (GPR) comprise a mechanically agitated fluid bed reactor with gas velocities of at least 0.2 m/sec.
  • the gas phase reactor is a fluidized bed type reactor preferably with a mechanical stirrer.
  • the first reactor (R1) is a slurry reactor (SR) , like loop reactor (LR)
  • the second reactor (R2) and the third reactor (R3) are gas phase reactors (GPR)
  • at least three, preferably three polymerization reactors namely a slurry reactor (SR) , like loop reactor (LR) , a first gas phase reactor (GPR-1) and a second gas phase reactor (GPR-2) connected in series are used. If needed prior to the slurry reactor (SR) a pre-polymerization reactor is placed.
  • a preferred multistage process is a “loop-gas phase” -process, such as developed by Borealis A/S, Denmark (known as technology) described e.g. in patent literature, such as in EP 0 887 379, WO 92/12182 WO 2004/000899, WO 2004/111095, WO 99/24478, WO 99/24479 or in WO 00/68315.
  • a further suitable slurry-gas phase process is the process of Basell described e.g. in figure 20 of the paper by Galli and Vecello, Prog. Polym. Sci. 26 (2001) 1287-1336.
  • step (a1) the conditions for the first reactor (R1) , i.e. the slurry reactor (SR) , like a loop reactor (LR) , of step (a1) may be as follows:
  • the temperature is within the range of 40 °C to 110 °C, preferably between 60 °C and 100 °C, like 68 to 95 °C,
  • the pressure is within the range of 20 bar to 80 bar, preferably between 40 bar to 70 bar,
  • reaction mixture from step (a1) containing preferably the first propylene homopolymer fraction (h-PP1) is transferred to the second reactor (R2) , i.e. the first gas phase reactor (GPR-1) , whereby the conditions are preferably as follows:
  • the temperature is within the range of 50 °C to 130 °C, preferably between 60 °C and 100 °C,
  • the pressure is within the range of 5 bar to 50 bar, preferably between 15 bar to 35 bar,
  • the polymerization may be effected in a known manner under supercritical conditions in the first reactor (R1) , i.e. in the slurry reactor (SR) , like in the loop reactor (LR) , and/or as a condensed mode in the gas phase reactor (GPR-1) .
  • R1 first reactor
  • SR slurry reactor
  • LR loop reactor
  • GPR-1 gas phase reactor
  • the second gas phase reactor (GPR-2) of step (e1) is preferably also operated within the above conditions, preferably with the exception that in the second gas phase reactor (GPR-2)
  • the pressure is within the range of 5 bar to 50 bar, preferably between 10 bar to 30 bar.
  • the residence time can vary in the above different reactors.
  • the residence time the first reactor (R1) i.e. the slurry reactor (SR) , like a loop reactor (LR)
  • the residence time in the gas phase reactors (GPR1 to GPR2) will generally be 0.2 to 6.0 hours, like 0.5 to 4.0 hours.
  • a well-known prepolymerization step may precede before the actual polymerization in the reactors (R1) to (R3) .
  • the prepolymerisation step is typically conducted at a temperature of 0 to 50 °C, preferably from 10 to 45 °C, and more preferably from 15 to 40 °C.
  • heterophasic propylene-ethylene copolymer HECO
  • process according to the present invention includes the following process steps:
  • a vinyl compound as defined above preferably vinyl cyclohexane (VCH)
  • VCH vinyl cyclohexane
  • the weight ratio (g) of the polymer of the vinyl compound to the solid catalyst system is up to 5 (5: 1) , preferably up to 3 (3: 1) most preferably is from 0.5 (1: 2) to 2 (2: 1)
  • the obtained modified catalyst system is fed to polymerization step (a1) of the process for producing the heterophasic propylene copolymer (HECO) .
  • the used catalyst is preferably a Ziegler-Natta catalyst system and even more preferred a modified Ziegler Natta catalyst system as defined in more detail below.
  • Such a Ziegler-Natta catalyst system typically comprises a solid catalyst component, preferably a solid transition metal component, and a cocatalyst, and optionally an external donor.
  • the solid catalyst component comprises most preferably a magnesium halide, a titanium halide and an internal electron donor.
  • Such catalysts are well known in the art. Examples of such solid catalyst components are disclosed, among others, in WO 87/07620, WO 92/21705, WO 93/11165, WO 93/11166, WO 93/19100, WO 97/36939, WO 98/12234, WO 99/33842.
  • Suitable electron donors are, among others, esters of carboxylic acids, like phthalates, citraconates, and succinates. Also oxygen-or nitrogen-containing silicon compounds may be used. Examples of suitable compounds are shown in WO 92/19659, WO 92/19653, WO 92/19658, US 4,347,160, US 4,382,019, US 4,435,550, US 4,465,782, US 4,473,660, US 4,530,912 and US 4,560,671.
  • said solid catalyst components are preferably used in combination with well known external electron donors, including without limiting to, ethers, ketones, amines, alcohols, phenols, phosphines and silanes, for example organosilane compounds containing Si-OCOR, Si-OR, or Si-NR 2 bonds, having silicon as the central atom, and R is an alkyl, alkenyl, aryl, arylalkyl or cycloalkyl with 1-20 carbon atoms; and well known cocatalysts, which preferably comprise an aluminium alkyl compound as known in the art, to polymerise the propylene copolymer.
  • well known external electron donors including without limiting to, ethers, ketones, amines, alcohols, phenols, phosphines and silanes, for example organosilane compounds containing Si-OCOR, Si-OR, or Si-NR 2 bonds, having silicon as the central atom, and R is an alkyl, alkenyl,
  • the amount of nucleating agent present in the heterophasic propylene-ethylene copolymer (HECO) is preferably not more than 500 ppm, more preferably is 0.025 to 200 ppm, still more preferably is 1 to 100 ppm, and most preferably is 5 to 100 ppm, based on the heterophasic propylene-ethylene copolymer (HECO) and the nucleating agent, preferably based on the total weight of the heterophasic propylene-ethylene copolymer (HECO) including all additives.
  • the flame-retardant (FR) The flame-retardant (FR)
  • the polypropylene base composition (BC) comprises flame-retardant (FR) .
  • flame-retardant refers to any compound typically used in the art for improving the flame-retardant properties of polypropylene compositions.
  • Said flame-retardant (FR) may either be a halogenated flame-retardant or a non-halogenated flame-retardant.
  • the flame-retardant (FR) is a non-halogenated flame-retardant.
  • Typical halogenated flame-retardants include organohalogen compounds, selected from organochlorines such as chlorendic acid derivatives and chlorinated paraffins; organobromines such as decabromodiphenyl ether (decaBDE) , decabromodiphenyl ethane (areplacement for decaBDE) , polymeric brominated compounds such as brominated polystyrenes, brominated carbonate oligomers (BCOs) , brominated epoxy oligomers (BEOs) , tetrabromophthalic anyhydride, tetrabromobisphenol A (TBBPA) and hexabromocyclododecane (HBCD) ;
  • organochlorines such as chlorendic acid derivatives and chlorinated paraffins
  • organobromines such as decabromodiphenyl ether (decaBDE) , decabromodiphenyl ethane (areplacement for de
  • inorganic synergists such as antimony pentoxide, sodium antimonite and antimony trioxide.
  • the flame-retardant of the present invention is a halogenated flame-retardant, then it is preferably selected from the above list or mixtures of the flame-retardants from the above list.
  • the halogenated flame-retardant would be a mixture of decabromodiphenyl ethane and antimony trioxide.
  • Typical non-halogenated flame-retardants include minerals such as aluminium hydroxide (ATH) , magnesium hydroxide (MDH) , huntite and hydromagnesite, red phosphorus and borates, as well as organophosphorus compounds including ammonium polyphosphate, melamine polyphosphate, triphenyl phosphate (TPP) , resorcinol bis (diphenylphosphate) (RDP) , bisphenol A diphenyl phosphate (BADP) , tricresyl phosphate (TCP) , dimethyl methylphosphonate (DMMP) , aluminium diethyl phosphinate, piperazine pyrophosphate, melamine polyphosphate, calcium bis (dihydrogenorthophosphate) and calcium hydrogen phosphonate.
  • ATH aluminium hydroxide
  • MDH magnesium hydroxide
  • RDP resorcinol bis
  • BADP bisphenol A diphenyl phosphate
  • TCP tricre
  • the flame-retardant of the present invention is preferably a non-halogenated flame-retardant, more preferably a non-halogenated organophosphorus flame-retardant, most preferably selected from piperazine pyrophosphate, melamine polyphosphate, calcium bis (dihydrogenorthophosphate) , calcium hydrogen phosphonate and mixtures thereof.
  • One suitable commercially available non-halogenated flame-retardant is Amgard PP1, available from Solvay S.A. (China) .
  • the polypropylene base composition (BC) of the present invention may contain additives (A) in an amount of from 0.1 to 5.0 wt. -%.
  • additives (A) in an amount of from 0.1 to 5.0 wt. -%.
  • suitable additives that are well known in the art.
  • the additives (A) are preferably selected from antioxidants, UV-stabilisers, anti-scratch agents, mold release agents, acid scavengers, lubricants, anti-static agents, colorant or pigment, and mixtures thereof.
  • the content of additives (A) given with respect to the total weight of the polypropylene base composition (BC) , includes any carrier polymers used to introduce the additives to said polypropylene base composition (BC) , i.e. masterbatch carrier polymers.
  • An example of such a carrier polymer would be a polypropylene homopolymer in the form of powder.
  • the polypropylene base composition (BC) of the invention may further comprise a polar-modified polypropylene (PMP) .
  • PMP polar-modified polypropylene
  • the polar-modified polypropylene (PMP) is used as a compatibilizer in the composition, which further helps to disperse the glass fibers within the fiber-reinforced polypropylene composition (PC) .
  • the polar-modified polypropyplene (PMP) has a content of polar groups content in the range from 0.5 to 3.0 wt. -%, more preferably in the range from 0.7 to 2.0 wt. -%, most preferably in the range from 0.8 to 1.5 wt. -%.
  • the polar-modified polypropylene (PMP) has a melt flow rate (MFR 2 ) measured according to ISO 1133 at 230°C and 2.16 kg in the range from 30.0 to 150.0 g/10 min, more preferably in the range from 40.0 to 120.0 g/10 min, most preferably in the range from 50.0 to 100.0 g/10 min.
  • MFR 2 melt flow rate measured according to ISO 1133 at 230°C and 2.16 kg in the range from 30.0 to 150.0 g/10 min, more preferably in the range from 40.0 to 120.0 g/10 min, most preferably in the range from 50.0 to 100.0 g/10 min.
  • the polar-modified polypropylene is a maleic anhydride-modified polypropylene.
  • Suitable commercially available polar-modified polypropylenes include CMG5701, available from Fine-Blend Compatibilizer Jiangsu Co., Ltd. (China) .
  • the polypropylene base composition (BC) is the polypropylene base composition (BC)
  • the polypropylene base composition of the present invention comprises several essential components, including the heterophasic propylene-ethylene copolymer (HECO) , the flame-retardant (FR) , and the at least one additive (A) other than the flame-retardant (FR) .
  • the polypropylene base composition (BC) comprises:
  • HECO heterophasic propylene-ethylene copolymer
  • heterophasic propylene-ethylene copolymer HECO has a melt flow rate (MFR 2 ) measured according to ISO 1133 at 230 °C and 2.16 kg in the range from 70.0 to 150.0 g/10 min;
  • the polypropylene base composition (BC) may further comprise:
  • the polypropylene base composition (BC) of the present invention can comprise further components, in addition to the essential components as defined above. However, it is preferred that the individual contents of the heterophasic propylene-ethylene copolymer (HECO) , the flame-retardant (FR) , and the at least one additive (A) and the optional polar-modified polypropylene (PMP) add up to at least 90 wt. -%, more preferably to at least 95 wt. -%, based on the total weight of the polypropylene base composition (BC) .
  • HECO heterophasic propylene-ethylene copolymer
  • FR flame-retardant
  • PMP optional polar-modified polypropylene
  • the polypropylene base composition (BC) consists of only the heterophasic propylene-ethylene copolymer (HECO) , the flame-retardant (FR) , and the at least one additive (A) and the optional polar-modified polypropylene (PMP) .
  • HECO heterophasic propylene-ethylene copolymer
  • FR flame-retardant
  • A additive
  • PMP optional polar-modified polypropylene
  • the heterophasic propylene-ethylene copolymer is present in the polypropylene base composition (BC) in an amount of from 50.0 to 75.0 wt. -%, based on the total weight of the base composition, more preferably in an amount of from 55.0 to 72.0 wt. -%, most preferably in an amount from 60.0 to 70.0 wt. -%, based on the total weight of the base composition.
  • the flame-retardant (FR) is present in the polypropylene base composition (BC) in an amount of from 20.0 to 45.0 wt. -%, based on the total weight of the base composition, more preferably in an amount of from 23 to 40.0 wt. -%, most preferably in an amount of from 26.0 to 35.0 wt. -%based on the total weight of the base composition.
  • the polar-modified polypropylene (PMP) is present in the polypropylene composition in an amount of from 0.1 to 5.0 wt. -%, based on the total weight of the base composition, more preferably in an amount of from 1.0 to 4.0 wt. -%, most preferably in an amount of from 2.0 to 3.0 wt. -%based on the total weight of the base composition.
  • the polypropylene base composition (BC) comprises, preferably consists of:
  • HECO heterophasic propylene-ethylene copolymer
  • heterophasic propylene-ethylene copolymer HECO has a melt flow rate (MFR 2 ) measured according to ISO 1133 at 230 °C and 2.16 kg in the range from 70.0 to 150.0 g/10 min;
  • d) optionally from 0.1 to 5.0 wt. -%, based on the total weight of the base composition, of a polar-modified polypropylene (PMP) .
  • PMP polar-modified polypropylene
  • the polypropylene base composition (BC) comprises, preferably consists of:
  • HECO heterophasic propylene-ethylene copolymer
  • heterophasic propylene-ethylene copolymer HECO has a melt flow rate (MFR 2 ) measured according to ISO 1133 at 230 °C and 2.16 kg in the range from 70.0 to 150.0 g/10 min;
  • d) optionally from 1.0 to 4.0 wt. -%, based on the total weight of the base composition, of a polar-modified polypropylene (PMP) .
  • PMP polar-modified polypropylene
  • the polypropylene base composition (BC) comprises, preferably consists of:
  • HECO heterophasic propylene-ethylene copolymer
  • heterophasic propylene-ethylene copolymer HECO has a melt flow rate (MFR 2 ) measured according to ISO 1133 at 230 °C and 2.16 kg in the range from 70.0 to 150.0 g/10 min;
  • d) optionally from 2.0 to 3.0 wt. -%, based on the total weight of the base composition, of a polar-modified polypropylene (PMP) .
  • PMP polar-modified polypropylene
  • the glass fibers (GF) are The glass fibers (GF)
  • PC fiber-reinforced polypropylene composition
  • GF glass fibers
  • the glass fibers are preferably provided in the form of continuous glass fibers.
  • the continuous glass fibers have a nominal diameter in the range from 5 to 30 ⁇ m, preferably in the range from 10 to 20 ⁇ m, most preferably in the range from 13 to 17 ⁇ m.
  • the glass fibers have been introduced to the composition using an LFT-D (Long Fiber Reinforced Thermoplastics -Direct) extruder.
  • LFT-D Long Fiber Reinforced Thermoplastics -Direct
  • Introduction using an LFT-D extruder has the consequence that the glass fibers are mixed with a precompounded base composition, which has already been subjected to a compounding process, rather than all of the components of the fiber-reinforced composition being mixed in the same extruder.
  • the glass fibers are introduced into a middle section of the LFT-D extruder, rather than with the precompounded base composition at the beginning of the barrel. This ensures that the base composition is already in a molten state when the fibers are added, reducing stress on the fibers.
  • the compounded fiber-reinforced composition is extruded directly into blank sheets that are delivered directly into a compression-molding machine and compression molded to form fiber-reinforced articles. Consequently, this process does not involve the pelletisation of fiber-reinforced composition at any stage.
  • the LFT-D process is understood to reduce excess breakage of the continuous fibers, ensuring that the fibers in the final fiber-reinforced composition (and fiber-reinforced article) are longer than would be the case if other extrusion techniques were to be used, or indeed if chopped fibers were to be employed.
  • PC polypropylene composition
  • the fiber-reinforced polypropylene composition according to the present invention comprises, preferably consists of, from 60 to 80 wt. -%of the polypropylene base composition (BC) and from 20 to 40 wt. -%of the glass fibers (GF) , based on the weight of the fiber-reinforced polypropylene composition.
  • the fiber reinforced polypropylene composition comprises, preferably consists of, from 63 to 75 wt. -%of the polypropylene base composition (BC) and from 25 to 37 wt. -%of the glass fibers (GF) , based on the weight of the fiber-reinforced polypropylene composition.
  • the fiber reinforced polypropylene composition comprises, preferably consists of, from 65 to 70 wt. -%of the polypropylene base composition (BC) and from 30 to 35 wt. -%of the glass fibers (GF) , based on the weight of the fiber-reinforced polypropylene composition.
  • the fiber-reinforced polypropylene composition (PC) according to the present invention requires beneficial mechanical properties, such as flexural strength and impact strength, low warpage, in addition to good flame resistance properties.
  • the fiber-reinforced polypropylene composition has a flexural strength measured according to ISO 178 of at least 80 MPa, more preferably of at least 83 MPa, most preferably of at least 86 MPa.
  • the flexural strength will not typically exceed 100 MPa.
  • the fiber-reinforced polypropylene composition has a Charpy unnotched impact strength measured according to ISO 179-1 1eA at +23°C of at least 20 kJ/m 2 , more preferably of at least 22 kJ/m 2 .
  • the Charpy unnotched impact strength will not typically exceed 40 kJ/m 2 .
  • the fiber-reinforced polypropylene composition has a flame-retardancy classification, as measured according to test standard UL94-2013, of V-0.
  • the polypropylene composition (PC) has a low warpage.
  • the present invention is additionally directed to a process for the preparation of the fiber-reinforced polypropylene composition (PC) of the present invention, comprising the steps of:
  • HECO heterophasic propylene-ethylene copolymer
  • PMP optional polar-modified polypropylene
  • HECO heterophasic propylene-ethylene copolymer
  • A additive
  • FR flame-retardant
  • a temperature in the range from 120 °C to 220 °C in an ‘compounding’ extruder, preferably a twin-screw extruder, thus forming a polypropylene base composition (BC) in the form of pellets;
  • the polypropylene base composition (BC) in the form of pellets, e.g. a Banbury mixer, a 2-roll rubber mill, Buss-co-kneader or a twin-screw extruder. More preferably, mixing is accomplished in a co-rotating twin-screw extruder.
  • the polymer materials recovered from the extruder in this case the polypropylene base composition (BC) are usually in the form of pellets.
  • LFT-D extruder for compounding and blending the polypropylene base composition (BC) and continuous glass fibers to form the fiber-reinforced polypropylene composition (PC) .
  • the LFT-D extruder is similar to the extruder of compounding process in the structure, but has a weaker shear stress.
  • the LFT-D extruder has a platy die.
  • the present invention also relates to articles comprising the fiber-reinforced polypropylene composition (PC) of the invention.
  • PC polypropylene composition
  • the article of the invention comprises more than 75 wt. -%of the fiber-reinforced polypropylene composition (PC) , more preferably more than 85 wt. -%, yet more preferably more than 90 wt. -%, most preferably more than 95 wt. -%of the of the fiber-reinforced polypropylene composition (PC) .
  • the article is preferably a molded article, most preferably an compression molded article.
  • the article is an automotive article, more preferably the article is the housing for a storage battery in an electric vehicle.
  • the present invention also relates to a use of a polypropylene base composition (BC) comprising:
  • HECO heterophasic propylene-ethylene copolymer
  • heterophasic propylene-ethylene copolymer HECO has a melt flow rate (MFR 2 ) measured according to ISO 1133 at 230 °C and 2.16 kg in the range from 70.0 to 150.0 g/10 min;
  • d) optionally from 0.1 to 3. wt. -%, based on the total weight of the base composition, of a polar-modified polypropylene (PMP) , preferably a maleic anhydride-modified polypropylene,
  • PMP polar-modified polypropylene
  • a compression molded article preferably a vehicle battery cover
  • the article contains 60 to 80 wt. -%of the polypropylene base composition (BC) and 20 to 40 wt. -%continuous glass fibers.
  • Melting temperature Tm is measured according to ISO 11357-3.
  • MFR 2 The melt flow rate (MFR) is determined according to ISO 1133 and is indicated in g/10 min.
  • the MFR is an indication of the flowability, and hence the processability, of the polymer. The higher the melt flow rate, the lower the viscosity of the polymer.
  • the MFR 2 of polypropylene is determined at a temperature of 230 °C and a load of 2.16 kg.
  • NMR nuclear-magnetic resonance
  • the NMR tube was further heated in a rotatory oven for at least 1 hour. Upon insertion into the magnet the tube was spun at 10 Hz.
  • This setup was chosen primarily for the high resolution and quantitatively needed for accurate ethylene content quantification. Standard single-pulse excitation was employed without NOE, using an optimised tip angle, 1 s recycle delay and a bi-level WALTZ16 decoupling scheme as described in Z. Zhou, R. Kuemmerle, X. Qiu, D. Redwine, R. Cong, A. Taha, D. Baugh, B. Winniford, J. Mag. Reson. 187 (2007) 225 and V. Busico, P.
  • the comonomer fraction was quantified using the method of W-J. Wang and S. Zhu, Macromolecules 2000, 33 1157, through integration of multiple signals across the whole spectral region in the 13 C ⁇ 1 H ⁇ spectra. This method was chosen for its robust nature and ability to account for the presence of regio-defects when needed. Integral regions were slightly adjusted to increase applicability across the whole range of encountered comonomer contents.
  • the mole percent comonomer incorporation was calculated from the mole fraction.
  • the weight percent comonomer incorporation was calculated from the weight fraction.
  • EC elastomeric propylene-ethylene copolymer fraction
  • HECO heterophasic propylene copolymer
  • FT-IR standards are prepared by blending a PP homopolymer with different amounts of MAH to create a calibration curve (absorption/thickness in cm versus MAH content in weight %) .
  • the MAH content is determined in the solid-state by IR spectroscopy using a Bruker Vertex 70 FTIR spectrometer on 25x25 mm square films of 100 ⁇ m thickness (with an accuracy of ⁇ 1 ⁇ m) prepared by compression molding at 190 °C with 4 -6 mPa clamping force.
  • Standard transmission FTIR spectroscopy is employed using a spectral range of 4000-400 cm -1 , an aperture of 6 mm, a spectral resolution of 2 cm -1 , 16 background scans, 16 spectrum scans, an interferogram zero filling factor of 32 and Norton Beer strong apodisation.
  • the xylene soluble fraction (XCS) at room temperature (XCS, wt. -%) : The amount of the polymer soluble in xylene is determined at 25 °C according to ISO 16152; first edition; 2005-07-01. The remaining part is the xylene cold insoluble (XCU) fraction.
  • the intrinsic viscosity (IV) is measured according to ISO 1628-1 (at 135 °C in decalin) .
  • Charpy impact test The Charpy notched impact strength (NIS) and Charpy unnotched impact strength (UIS) were measured according to ISO 179-1 eA at +23 °C, using injection-molded bar test specimens of 80x10x4 mm 3 prepared in accordance with ISO 1873-2: 2007.
  • Flexural Strength The flexural strength is determined in 3-point-bending at 23 °C according to ISO 178 on 80x10x4 mm 3 test bars injection molded in line with EN ISO 1873-2.
  • Flame-retardancy test The flame-retardant properties of the compositions were tested according to standard UL94-2013.
  • the specimens Before testing, the specimens must be conditioned. Such conditioning requires to maintain the specimens at 23°C and 50%relative humidity for at least 48 hours prior to the test.
  • a specimen with a size of 125mm (length) *13mm (width) *1.5 mm (thickness) is used in the test.
  • One end of the specimen is held by a clamp and the other end is free, and the specimen hangs vertically down.
  • a burner flame is applied to the free end of the specimen for the first 10 seconds, and then taken away. After the flame of the specimen goes out (if any) , the burner flame is applied again to the free end of the specimen for the second 10 seconds, and then taken away.
  • One set of 5 specimens is tested.
  • a small mass of cotton batt is placed under the flaming specimen during the test. The test results are recorded for each specimen as follows:
  • Table 1 the rating standard of flame-retardancy classes V-0 to V-2
  • class V-1 and V-2 The major difference between class V-1 and V-2 is whether the flaming drippings ignite the cotton placed under the specimen.
  • flaming drippings ignite the cotton placed under the specimen.
  • For polypropylene based material it is very easy to change from class V-0 to V-2 (no transition state of class V-1) , because the flaming drippings of polypropylene very easily ignite the cotton.
  • Warpage test In order to measure the warpage, the battery cover produced by LFT-D process is put on a horizontal surface (x-y surface --see Figure 1) . Then heights of 6 points on a surface of the compression molded battery cover in z direction are measured, i.e. 3 points (A, B, C) near the center on the surface of the cover, 1 point at the center of left side on the surface of the cover, 1 point at the center of right side on the surface of the cover, and 1 point at the center of back side on the surface of the cover. The difference of the measured height at a given point from the corresponding height in the compression-molding mold as originally designed, in z direction, is recorded as ⁇ h at said point. The data ⁇ h is used to quantify the warpage at this point: the larger the ⁇ h, the worse the warpage at the given point is.
  • the catalyst used in the polymerizations was a Ziegler-Natta catalyst from Borealis having Ti-content of 1.9 wt. -% (as described in EP 591 224) .
  • the catalyst was prepolymerized with vinyl-cyclohexane (VCH) as described in EP 1 028 984 and EP 1 183 307.
  • VCH vinyl-cyclohexane
  • the ratio of VCH to catalyst of 1: 1 was used in the preparation, thus the final Poly-VCH content was less than 100 ppm.
  • the catalyst described above was fed into prepolymerization reactor together with propylene and small amount of hydrogen (2.5 g/h) and ethylene (330 g/h) .
  • Triethylaluminium as a cocatalyst and dicyclopentyldimethoxysilane as a donor was used.
  • the aluminium to donor ratio was 7.5 mol/mol and aluminium to titanium ratio was 300 mol/mol.
  • Reactor was operated at a temperature of 30 °Cand a pressure of 55 barg.
  • the subsequent polymerization has been effected under the following conditions.
  • the polypropylene base compositions of Inventive examples IE1 to IE4 and comparative example CE1 were prepared based on the recipes indicated in Table 3 by compounding in a ‘compounding’ co-rotating twin-screw extruder under the conditions described in Table 4.
  • the extruder has 12 heating zones.
  • CE1 represents the market benchmark for compositions used in similar LFT-D processes.
  • h-PP propylene homopolymer having a melt flow rate of 80 g/10 min, .
  • FR1 flame-retardant comprising 20%piperazine pyrophosphate, 20%melamine polyphosphate, 30%calcium bis (dihydrogenorthophosphate) , and 30%calcium hydrogen phosphonate.
  • FR2 a mixture of 70%decabromodiphenyl ethane (CAS-no. 84852-53-9) and 30%antimony trioxide (CAS-no. 1309-64-4) .
  • a an additive masterbatch consisting of 0.6 wt. -%of a carrier propylene homopolymer with a trade name of PP-H 225, available from Hongji petrochemical (China) , having an MFR 2 (230 °C, 2.16 kg) of 27 g/10 min, 1.3 wt. -%of a heat stabilizer with a trade name of Irganox PS 802 FL (CAS-no. 693-36-7) , available from BASF SE (Germany) , 0.8 wt. -%of an antioxidant with a trade name of Irganox 3114 (CAS-no. 27676-62-6) , available from BASF SE (Germany) , 0.7 wt.
  • CMB a colour masterbatch with a trade name TP90002452BG, available from PolyOne (Shanghai) Co., Ltd (China) .
  • Table 4 Compounding conditions for the inventive polypropylene base compositions in a twin-screw extruder
  • these polypropylene base compositions were further compounded with long glass fibers in a LFT-D (long fiber thermoplastics -direct) process.
  • the polypropylene base composition is fed into the main feeder of the LFT-D twin-screw extruder, which has 7 heating zones, with a tradename “CTE PLUS” commercially available from Coperion Machine Co. Ltd (Nanjing, China) .
  • Continuous glass fiber commercially available from Owens Corning Composites (China) , having nominal diameter of 15 ⁇ m
  • heating zone 4 where the temperature is around 190°C.
  • the mixture is extruded in the form of a blank sheet with a thickness of 20 mm, and is cut into pieces with a width of 200 mm, length of 200 mm and thickness of 20 mm.
  • a piece of the blank sheet is delivered directly into a compressor machine (model “TM-500” available from Tianma Co. Ltd., (China) ; molding pressure 3000 ton, temperature 170 °C to 180 °C) which compresses the sheet into the desired part (in this case a battery cover as shown in Figure 1) .
  • the LFT-D twin-screw extruder is operated under the conditions given in Table 5, with the throughput rates suitable adjusted such that the final LFT-D products contain 33 wt. -%of glass fibers and 67 wt. -%of the polypropylene base composition, the properties of the final fiber-reinforced compositions being shown in Table 6.
  • the inventive examples display notably improved warpage characteristics, both at the edge of the formed articles and in the centre. It can be seen from a comparison of IE1 to IE4 that the resistance to warpage surprisingly improves with the addition of flame retardant, as the flame retardant in the form of inorganic powder can inhibit the warpage in addition to increasing flame retardancy. A further effect can be seen in the increasing flexural strength. Depending on the precise requirements of the end product, the content of the flame retardant can be adjusted within the claimed ranges to optimise either warpage/flame retardancy/flexural strength or impact strength (which appears to decrease with the addition of more flame retardant) .
  • IE3 in particular has the same amount of each component as CE1, with the selection of the base polypropylene and the choice of the flame retardant as the only differences. All mechanical/warpage properties (flexural strength, impact strength and warpage) are improved for IE3 relative to CE1 due to the presence of the heterophasic propylene-ethylene copolymer (HECO) , and the flame retardancy is maintained at V-0.
  • HECO heterophasic propylene-ethylene copolymer
  • heterophasic propylene-ethylene copolymer HECO
  • the heterophasic propylene-ethylene copolymer has a lower degree of crystallization than the propylene homopolymer used in CE1, which is believed to help reduce shrinkage and inhibit the warpage of the final article.
  • poly vinylcyclohexane as nucleating agent leads to smaller crystal sizes and more even distribution of small crystals in the nucleated composition, and thus improved resistance to warpage.

Abstract

L'invention concerne une composition de polypropylène renforcée par des fibres (PC) comprenant : A) de 60 à 80 % en poids d'une composition de base de polypropylène (BC), comprenant : a) de 50,0 à 75,0 % en poids d'un copolymère propylène-éthylène hétérophasique (HECO), constitué par : i) une matrice d'homopolymère de propylène cristallin (M) ; ii) un copolymère éthylène-propylène élastomère (EC) ; le copolymère propylène-éthylène hétérophasique (HECO) ayant un MFR2 dans la plage de 70,0 à 150,0 g/10 min ; b) de 20,0 à 45,0 % en poids d'un agent ignifuge (FR) ; et c) de 0,1 à 5,0 % en poids d'au moins un additif (A) autre que l'agent ignifuge (FR), B) de 20 à 40 % en poids de fibres de verre.
PCT/CN2020/132320 2020-11-27 2020-11-27 Composition renforcée par des fibres de verre présentant une ininflammabilité et un faible gauchissement WO2022110037A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/CN2020/132320 WO2022110037A1 (fr) 2020-11-27 2020-11-27 Composition renforcée par des fibres de verre présentant une ininflammabilité et un faible gauchissement
CN202080107131.3A CN117999313A (zh) 2020-11-27 2020-11-27 具有阻燃性和低翘曲的玻璃纤维增强组合物

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2020/132320 WO2022110037A1 (fr) 2020-11-27 2020-11-27 Composition renforcée par des fibres de verre présentant une ininflammabilité et un faible gauchissement

Publications (1)

Publication Number Publication Date
WO2022110037A1 true WO2022110037A1 (fr) 2022-06-02

Family

ID=81753824

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2020/132320 WO2022110037A1 (fr) 2020-11-27 2020-11-27 Composition renforcée par des fibres de verre présentant une ininflammabilité et un faible gauchissement

Country Status (2)

Country Link
CN (1) CN117999313A (fr)
WO (1) WO2022110037A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016066453A2 (fr) * 2014-10-27 2016-05-06 Borealis Ag Polypropylène hétérophasique présentant un meilleur équilibre résistance au choc/rigidité, une meilleure aptitude à l'écoulement des poudres, des émissions réduites et un faible retrait
CN109486021A (zh) * 2018-12-28 2019-03-19 广东圆融新材料有限公司 玻纤增强的阻燃pp材料及其制备方法
CN110914360A (zh) * 2017-07-13 2020-03-24 博禄塑料（上海）有限公司 低气味的玻璃纤维增强组合物
WO2020064752A1 (fr) * 2018-09-25 2020-04-02 Sabic Global Technologies B.V. Composition de propylène ignifuge chargée de fibres de verre

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016066453A2 (fr) * 2014-10-27 2016-05-06 Borealis Ag Polypropylène hétérophasique présentant un meilleur équilibre résistance au choc/rigidité, une meilleure aptitude à l'écoulement des poudres, des émissions réduites et un faible retrait
CN110914360A (zh) * 2017-07-13 2020-03-24 博禄塑料（上海）有限公司 低气味的玻璃纤维增强组合物
WO2020064752A1 (fr) * 2018-09-25 2020-04-02 Sabic Global Technologies B.V. Composition de propylène ignifuge chargée de fibres de verre
CN109486021A (zh) * 2018-12-28 2019-03-19 广东圆融新材料有限公司 玻纤增强的阻燃pp材料及其制备方法

Also Published As

Publication number Publication date
CN117999313A (zh) 2024-05-07

Similar Documents

Publication Publication Date Title
EP3495423B1 (fr) Article comprenant une composition de polypropylène renforcée par des fibres
EP1801155B1 (fr) Composition de polypropylène comprenant un homopolymère de propylène
US10544297B2 (en) Fiber reinforced polymer composition
US10550253B2 (en) Polypropylene—carbon fiber composite
US10717832B2 (en) Low density carbon fibers filled materials
EP1801157A1 (fr) Composition de polypropylène comprenant un copolymère de propylène
CN107075010B (zh) 一种具有改善的耐刮擦性、平衡的冲击强度和刚度的聚丙烯组合物
DE19983137B4 (de) Flammwidrige Polyolefinzusammensetzung
WO2022030480A1 (fr) Composition de résine à base de polypropylène et objet moulé la comprenant
WO2022110037A1 (fr) Composition renforcée par des fibres de verre présentant une ininflammabilité et un faible gauchissement
WO1998031744A1 (fr) Composition de polypropylene choc dotee d'une resilience et d'une rigidite elevees
US20220112324A1 (en) Propylene Resin Composition With Excellent Melt Flowability And Impact Resistance
WO2022088020A1 (fr) Composition renforcée par des fibres de verre présentant des propriétés ignifuges
EP3433315A1 (fr) Tubes tampons pour câbles à fibres optiques
WO2021109071A1 (fr) Compositions de polyoléfine ayant des propriétés de protection contre les interférences électromagnétiques
WO2020229597A1 (fr) Composition de polypropylène hétérophasique
WO2022120648A1 (fr) Compositions de polyoléfine remplies de fibres de verre à faibles retrait et gauchissement
US11584834B2 (en) Fiber reinforced polypropylene compositions
EP4305101A1 (fr) Composition de polypropylène ignifuge
WO2022088019A1 (fr) Composition renforcée avec de la fibre de verre ayant une résistance améliorée aux chocs
WO2024029197A1 (fr) Composition de résine de polypropylène et corps moulé la contenant
JPH10231397A (ja) 難燃性ポリオレフィン組成物
EA043459B1 (ru) Изделие, содержащее армированную волокном композицию полипропилена
BR112020010032B1 (pt) Composição de polipropileno reforçada com fibra

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20962927

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20962927

Country of ref document: EP

Kind code of ref document: A1