Flame-retardant polypropylene composition

Abstract

The present invention relates to a polypropylene composition (C) comprising a heterogeneous propylene copolymer (HECO), a mixed plastic polypropylene blend (PPB), a flame retardant (FR), a fiber (F), and optionally an adhesion promoter (AP), and to articles comprising the polypropylene composition (C).

Description

[Technical Field]

[0001] The present invention relates to a polypropylene composition comprising a mixed plastic polypropylene blend (PPB) and a flame retardant (FR), and an article comprising this polypropylene composition. [Background technology]

[0002] Manufacturers of electric motors and power electronics components have traditionally used housings made of steel or die-cast aluminum. However, since many components are now actively cooled, plastics are a viable option for lightweight construction. Some of these existing alternatives are primarily based on PC / ABS or polyamide, which are engineering plastics that are expensive to produce and have a high CO2 footprint.

[0003] In particular, one essential requirement for electronic enclosures is achieving UL94 V-0 flammability class with a thickness of less than 1.5 mm. Materials that meet these requirements are most likely to be metals, halogenated flame-retardant reinforced polymers, polymers with inherent flame retardancy, or non-halogenated flame-retardant reinforced polymers, such as PC / ABS flame retardants. High levels of flame retardant additives in such flame retardants lead to degradation of material performance and conversion problems. Furthermore, anti-dripping agents are usually required to prevent dripping during combustion.

[0004] Propylene polymers are also applicable as base polymers for flame-retardant systems. Generally speaking, glass fibers are used with polypropylene to achieve specific mechanical properties (e.g., stiffness). However, the main drawbacks of glass fiber reinforced polypropylene are, among other things, dimensional stability in the fiber direction and high warpage when high-flow polypropylene is used as the base polymer. However, low warpage is essential, especially for high-precision parts (e.g., cell holders).

[0005] In recent years, polymer waste has been recognized as a major environmental and economic problem. Therefore, efforts have been made to recycle polymer waste and use the recycled polymers for upcycling applications. In this regard, a decrease in mechanical performance is often observed when virgin materials and recycled materials are blended.

[0006] WO 2022 / 189647 A1 discloses a flame-retardant reinforced high-flow polypropylene composition made of virgin components, which meets the requirements of UL94 V-0, shows low warpage, and has mechanical properties remaining at a high level.

[0007] Surprisingly, by replacing up to 30% by weight of the virgin propylene polymer used in the composition of WO 2022 / 189647 A1, preferably with a mixed plastic polypropylene blend (PPB) from consumer used waste, it has been found that, contrary to expectations, no loss in mechanical properties and in the UL94 test is observed.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Summary of the Invention

Means for Solving the Problems

[0009] The present invention relates to a polypropylene composition (C), i) 5.0 to 40.0% by weight of a heterophasic propylene copolymer (HECO) having a melt flow rate MFR2 (230 °C, 2.16 kg) determined according to ISO 1133 of at least 45.0 g / 10 min, ii) 5.0 to 30.0% by weight of a mixed plastic polypropylene blend (PPB), iii) 10.0 to 40.0% by weight of flame retardant (FR), iv) 10.0-40.0% by weight of fiber (F), v) 0.0~5.0 wt% of adhesion promoter (AP) and This includes, and all weight content is based on the total weight of polypropylene composition (C) and pertains to polypropylene composition (C).

[0010] Furthermore, the present invention relates to an article comprising the above or the following polypropylene composition (C).

[0011] definition Unless otherwise specified, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which the present invention pertains. Any methods and materials similar or equivalent to those described herein may be used in practice for testing the present invention, but preferred materials and methods are described herein. In the description and claims of the present invention, the following terms are used according to the definitions set forth below. Unless otherwise explicitly stated, the use of terms such as “a,” “an,” etc., refers to one or more.

[0012] Mixed-plastic(s) are defined as the presence of small amounts of compounds not typically found in virgin polypropylene blends, such as polystyrene, polyamide, polyester, wood, paper, limonene, aldehydes, ketones, fatty acids, metals, and / or long-term degradation products of stabilizers. Virgin polypropylene blends represent blends that originate directly from the manufacturing process without any intermediate use. As a matter of definition, "mixed plastics" can be considered equivalent to detectable amounts of polystyrene and / or polyamide-6 and / or limonene and / or fatty acids. Therefore, as opposed to virgin polymers, mixed plastics may originate from both consumer end-of-life and industrial waste. Consumer end-of-life refers to objects that have completed at least one use cycle (or life cycle), i.e., have already served their primary purpose. In contrast, industrial waste refers to manufacturing scrap or conversion scrap, which typically do not reach consumers.

[0013] The term "virgin" refers to newly manufactured material and / or object that has not been recycled and is not yet used for its first purpose.

[0014] As used herein, the term “recycled material” means material that has been reprocessed from “recycled waste.”

[0015] A polymer blend is a mixture of two or more polymer components. Generally, blends can be prepared by mixing two or more polymer components. A preferred mixing procedure known in the art is post-polymerization blending. Post-polymerization blends can be dry blends of polymer components such as polymer powders and / or polymer pellets obtained through compounding, or melt blends obtained by melt-mixing polymer components.

[0016] A mixed plastic polypropylene blend indicates that the blend primarily consists of polypropylene, but also contains small amounts of other plastics. A mixed plastic polyethylene blend indicates that the blend primarily consists of polyethylene, but also contains small amounts of other plastics. Recycled material blends, especially consumer-recycled material blends, are almost always mixed plastic blends, which reflects the sorting efficiency in state-of-the-art recycling processes.

[0017] Polypropylene refers to a polymer composed of units derived from propylene in amounts exceeding 50 mol%. Polyethylene refers to a polymer composed of units derived from ethylene in amounts exceeding 50 mol%.

[0018] Propylene homopolymers are polymers that essentially consist of propylene monomer units. Due to impurities, particularly in commercial polymerization processes, propylene homopolymers may contain up to 0.1 mol% comonomer units, preferably up to 0.05 mol%, and most preferably up to 0.01 mol% comonomer units.

[0019] The presence of heterophases can be easily determined, for example, by the number of glass transition points in dynamic mechanical analysis (DMA), and / or by high-resolution microscopy such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), or atomic force microscopy (AFM).

[0020] The term "XCS" refers to the cold xylene-soluble fraction (by weight) determined at 25°C according to ISO 16152. The term "XCI" refers to the cold xylene-insoluble fraction (by weight) determined at 25°C according to ISO 16152.

[0021] A reactor blend is a blend produced in a reactor having two or more reactors connected in series, or two or more reaction compartments. Alternatively, a reactor blend may be produced from a blend in solution. Reactor blends are in contrast to compounds (compounds) produced by melt extrusion, for example.

[0022] Unless otherwise specified, "%" refers to weight percentage. [Modes for carrying out the invention]

[0023] The present invention relates to a polypropylene composition (C), i) A heterogeneous propylene copolymer (HECO) having a melt flow rate MFR2 (230°C, 2.16 kg) determined according to ISO 1133, at least 45.0 g / 10 min, in an amount of 5.0 to 40.0 wt%, preferably 10.0 to 38.5 wt%, more preferably 15.0 to 37.5 wt%, and at least 45.0 g / 10 min, ii) A mixed plastic polypropylene blend (PPB) in an amount of 5.0 to 30.0% by weight, preferably 6.5 to 27.5% by weight, more preferably 7.5 to 25.0% by weight, iii) A flame retardant (FR) in an amount of 10.0 to 40.0% by weight, 15.0 to 35.0% by weight, more preferably 20.0 to 32.5% by weight, iv) 10.0 to 40.0% by weight of fiber (F), preferably 12.0 to 38.0% by weight, more preferably 20.0 to 30.0% by weight, v) 0.0 to 5.0% by weight, preferably 0.4 to 3.0% by weight, more preferably 1.0 to 2.0% by weight of an adhesion promoter (AP) and This includes, and all weight content is based on the total weight of polypropylene composition (C) and pertains to polypropylene composition (C).

[0024] Preferably, the total amounts of heterogeneous propylene copolymer (HECO), mixed plastic polypropylene blend (PPB), flame retardant (FR), fiber (F), and optionally adhesion promoter (AP) together constitute at least 90% by weight of the polypropylene composition (C).

[0025] The polypropylene composition (C) according to the present invention may further contain additives (AD), such as acid scavengers, antioxidants, colorants, light stabilizers, slip agents, scratch inhibitors, dispersants, processing aids, lubricants, pigments, and the like.

[0026] Therefore, polypropylene composition (C) is i) A heterogeneous propylene copolymer (HECO) having a melt flow rate MFR2 (230°C, 2.16 kg) determined according to ISO 1133, at least 45.0 g / 10 min, in an amount of 5.0 to 40.0 wt%, preferably 10.0 to 38.5 wt%, more preferably 15.0 to 37.5 wt%, and at least 45.0 g / 10 min, ii) A mixed plastic polypropylene blend (PPB) in an amount of 5.0 to 30.0% by weight, preferably 6.5 to 27.5% by weight, more preferably 7.5 to 25.0% by weight, iii) A flame retardant (FR) in an amount of 10.0 to 40.0% by weight, 15.0 to 35.0% by weight, more preferably 20.0 to 32.5% by weight, iv) 10.0 to 40.0% by weight of fiber (F), preferably 12.0 to 38.0% by weight, more preferably 20.0 to 30.0% by weight, v) 0.0 to 5.0% by weight, preferably 0.4 to 3.0% by weight, more preferably 1.0 to 2.0% by weight of an adhesion promoter (AP), vi) Additive (AD) in an amount of 0.01 to 5.0% by weight, preferably 0.1 to 3.5% by weight, more preferably 0.2 to 2.0% by weight It is preferable to include, and more preferably to consist of, these, and all weight contents are based on the total weight of the polypropylene composition (C). Additives (AD) are described in more detail below.

[0027] Preferably, the total amount of heterogeneous propylene copolymer (HECO), mixed plastic polypropylene blend (PPB), flame retardant (FR), fiber (F), adhesion promoter (AP), and additive (AD) constitutes at least 90% by weight of the polypropylene composition (C), and more preferably 100% by weight in total.

[0028] According to preferred embodiments of the present invention, the polypropylene composition (C) does not contain a fluoropolymer. In particular, it is preferable that the polypropylene composition (C) does not contain an amount of fluoropolymer exceeding 0.5% by weight, more preferably 0.1% by weight, and even more preferably 0.01% by weight, for example, 0.001% by weight. It is especially preferable that no fluoropolymer is used in the production of the polypropylene composition (C).

[0029] As used herein, the term "fluoropolymer" refers to a polymer compound containing a fluorine atom. Examples of fluoropolymers include poly(tetrafluoroethylene) (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and polychlorotrifluoroethylene (PCTFE).

[0030] The polypropylene composition (C) according to the present invention preferably has a melt flow rate MFR2 determined at 2.16 kg and 230°C according to ISO 1133, with a melt flow rate of 2.5 to 20.0 g / 10 min, preferably 3.0 to 15.0 g / 10 min, and more preferably 4.0 to 12.5 g / 10 min.

[0031] With respect to mechanical properties, the polypropylene composition (C) preferably has a tensile modulus determined at 23°C according to ISO 527-1A, at least 5500 MPa, for example 5500 to 10000 MPa, preferably 6000 to 9500 MPa, and more preferably 6250 to 9000 MPa.

[0032] Furthermore, it is preferable that the polypropylene composition (C) has a tensile strength determined at 23°C according to ISO 527-1A, at least 50 MPa, for example 50 to 100 MPa, preferably 55 to 95 MPa, and more preferably 60 to 90 MPa.

[0033] Furthermore, it is preferable that the polypropylene composition (C) has a tensile fracture stress determined at 23°C according to ISO 527-1A, which is at least 1.7%, for example, 1.7 to 5.0%, preferably 2.0 to 4.5%, and more preferably 2.3 to 4.0%.

[0034] In addition to or instead of the preceding paragraph, polypropylene composition (C) contains at least 7.0 kJ / m 2 For example, 7.0~15.0 kJ / m 2 Preferably 7.5 to 12.5 kJ / m³ 2 It is preferable to have a notched Charpy impact strength of 7.7 to 11.0 kJ / m, determined at 23°C according to ISO 179 1eA.

[0035] Preferably, the polypropylene composition (C) satisfies the requirements of the Standard for Safety of Flammability of Plastic Materials UL94 V-0 when determined using a 1.5 mm thick test specimen and applying Condition Part 1 (i.e., conditioning the sample at a constant room temperature of 23 ± 2 °C and a humidity of 50 ± 10% for 48 hours) according to the method "UL94 Vertical Flammage Test" described herein in the "Measurement Method" section.

[0036] Furthermore, the polypropylene composition (C) preferably meets the requirements of the Standard for Safety of Flammability of Plastic Materials UL94 V-0 when determined according to the method "UL94 Vertical Flammage Test" described herein in the "Measurement Method" section, using a 1.5 mm thick test specimen and applying Condition Part 1 (i.e., conditioning the sample in an air-circulating oven at 70 ± 1°C for 168 hours, and then cooling in a desiccator at room temperature for at least 4 hours).

[0037] The polypropylene composition (C) is preferably obtained by blending, preferably by melt blending, a heterogeneous propylene copolymer (HECO), a mixed plastic polypropylene blend (PPB), a flame retardant (FR), glass fiber (GF), an adhesion promoter (AP), and optionally an additive (AD).

[0038] The following provides a more detailed explanation of heterogeneous propylene copolymers (HECOs), mixed plastic polypropylene blends (PPBs), flame retardants (FRs), glass fibers (GFs), and adhesion promoters (APs).

[0039] Heterophase propylene copolymer (HECO) The polypropylene composition (C) contains a heterophasic propylene copolymer (HECO). The heterophasic propylene copolymer (HECO) may be a mixture of two or more heterophasic propylene copolymer components.

[0040] The heterogeneous propylene copolymer (HECO) has a melt flow rate MFR2 (230°C, 2.16 kg) determined according to ISO 1133, at least 45.0 g / 10 min, more preferably in the range of 45.0 to 300 g / 10 min, and even more preferably in the range of 60.0 to 200 g / 10 min, for example, in the range of 80.0 to 120 g / 10 min.

[0041] Preferably, the heterogeneous propylene copolymer (HECO) is i) A matrix (M) which is a propylene polymer, ii) Elastomer (E), which is a copolymer containing units derived from propylene and ethylene and / or C4-C8a-olefins, preferably units derived from propylene and ethylene. Includes.

[0042] Heterophase propylene copolymers (HECOs) can be characterized by CRYSTEX QC analysis. CRYSTEX QC analysis yields crystalline fractions (CF) and soluble fractions (SF), which can be quantified and analyzed in terms of monomer and comonomer content and intrinsic viscosity (iV).

[0043] Heterophase propylene copolymers (HECOs) preferably exhibit the following properties in CRYSTEX QC analysis. • A crystalline fraction (CF) content determined by CRYSTEX QC analysis, in the range of 80.5 to 92.0% by weight, preferably 82.0 to 90.0% by weight, and more preferably 83.0 to 86.0% by weight, and • Soluble fraction (SF) content determined by CRYSTEX QC analysis, in the range of 8.0 to 19.5% by weight, preferably 10.0 to 18.0% by weight, and more preferably 13.0 to 17.0% by weight. Show one or all of them.

[0044] The above crystalline fraction (CF) preferably has the following properties • Quantitatively, 0.1 to 5.0% by weight, preferably 0.2 to 4.0% by weight, more preferably 0.5 to 3.0% by weight 13 Ethylene content (C2(CF)) determined by FT-IR spectroscopy calibrated by 13C-NMR spectroscopy, and / or • Intrinsic viscosity (iV(CF)) measured at 135°C in decalin according to DIN ISO 1628 / 1, less than 1.8 dl / g, preferably 0.8 to 1.6 dl / g, more preferably 0.9 to 1.3 dl / g. It has one or more, preferably all, of the following.

[0045] The above soluble fraction (SF) preferably has the following characteristics • A quantitative amount in the range of 25.0 to 45.0% by weight, preferably 27.5 to 43.0% by weight, and more preferably 30.0 to 42.0% by weight. 13 Ethylene content (C2(SF)) determined by FT-IR spectroscopy calibrated by 13C-NMR spectroscopy, and / or • Intrinsic viscosity (iV(SF)) measured at 135°C in decalin according to DIN ISO 1628 / 1, between 1.50 and 4.00 dl / g, preferably 1.60 and 3.00 dl / g, and more preferably 1.70 and 2.50 dl / g. It has one or more, preferably all, of the following.

[0046] In certain embodiments, the heterogeneous propylene copolymer (HECO) has an intrinsic viscosity (iV(SF)) measured at 135°C in decalin according to DIN ISO 1628 / 1, preferably 2.00 to 4.00 dl / g, preferably 2.30 to 3.70 dl / g, and more preferably 2.50 to 3.30 dl / g.

[0047] The heterophase propylene copolymer (HECO) preferably contains ethylene-derived units in an amount of 2.5 to 12.5% ​​by weight, more preferably 4.0 to 10.0% by weight, and even more preferably 5.0 to 7.5% by weight.

[0048] The ratio of the intrinsic viscosity of the soluble fraction to the crystalline fraction (IV(SF) / IV(CF)) is preferably greater than 1.0, more preferably 1.3 to 2.5, and even more preferably 1.4 to 2.0.

[0049] The ratio of ethylene content between the soluble fraction and the crystalline fraction (C2(SF) / C2(CF)) is preferably in the range of 7.5 to 22.5, more preferably in the range of 10.0 to 20.0, and even more preferably in the range of 15.0 to 17.5.

[0050] Heterogenetic propylene copolymers (HECOs) more preferably have the following properties • A melting temperature Tm of 155-175°C, more preferably 157-172°C, even more preferably 160-170°C, and / or Crystallization temperature Tc of 115-135°C, more preferably 117-132°C, and even more preferably 119-130°C. The system has one or more, preferably all, of the above temperatures, all of which are determined by differential scanning calorimetry (DSC).

[0051] Heterophase propylene copolymers (HECOs) preferably exhibit a good balance of properties with respect to mechanical properties, impact properties, and thermal stability.

[0052] The heterogeneous propylene copolymer (HECO) preferably has a tensile modulus of 1200 to 1600 MPa, more preferably 1250 to 1550 MPa, and even more preferably 1300 to 1500 MPa.

[0053] Furthermore, the heterogeneous propylene copolymer (HECO) preferably has a concentration of 1.0 to 7.5 kJ / m³. 2 , more preferably 2.0~5.0 kJ / m 2 It has a notched Charpy impact strength (CNIS at 23°C) at 23°C.

[0054] The heterogeneous propylene copolymer (HECO) preferably consists only of propylene units and ethylene units. Although not measured, the content of units derived from propylene in the soluble fraction (SF) (C3) is preferably 100% by weight when combined with the content of units derived from ethylene in the soluble fraction (SF) (C2). The content of units derived from propylene (C3) in the soluble fraction (SF) is preferably 55.0 to 75.0% by weight, more preferably 57.0 to 72.5% by weight, and even more preferably 58.0 to 70.0% by weight. Although not measured, the content of units derived from propylene in the crystalline fraction (CF) (C3) is preferably 100% by weight when combined with the content of units derived from ethylene in the crystalline fraction (CF) (C2). The content of units derived from propylene (C3) in the crystalline fraction (CF) is preferably 95.0 to 99.9% by weight, more preferably 96.0 to 99.8% by weight, and even more preferably 97.0 to 99.5% by weight. The total content (C3) of units derived from propylene in the heterophase propylene copolymer (HECO) is preferably 87.5 to 97.5% by weight, more preferably 90.0 to 96.0% by weight, and even more preferably 92.5 to 95.0% by weight.

[0055] The heterogeneous propylene copolymer (HECO) is preferably a virgin polymer.

[0056] Suitable heterogeneous propylene copolymers (HECOs) are commercially available.

[0057] Before blending with other components for preparing the polypropylene composition (C), the heterogeneous propylene copolymer (HECO) can be aerated to remove volatile components, for example, as described in European Patent Application Publication No. 3786190A1.

[0058] Mixed plastic polypropylene blend (PPB) Polypropylene composition (C) contains a mixed plastic polypropylene blend (PPB).

[0059] Mixed plastic polypropylene blends (PPBs) are polypropylene-rich recycled materials, meaning they contain significantly more polypropylene than polyethylene. Polypropylene-rich recycled waste streams can be obtained, for example, from the automotive industry, as certain automotive parts, such as bumpers, are a fairly pure source of polypropylene material in the recycling stream.

[0060] Preferably, polypropylene-rich recycled materials are obtained from recycled waste by plastic recycling processes known in the art. Such recycled materials are commercially available from companies such as Corepla (an Italian consortium for the collection, recovery and recycling of packaging plastic waste), Resource Plastics Corp. (Brampton, Ontario), Kruschitz GmbH, Plastics and Recycling (Austria), Vogt Plastik GmbH (Germany), Mtm ​​Plastics GmbH (Germany), and Borealis AG (Austria). Non-exclusive examples of polypropylene-rich recycled materials include Dipolen® PP (Mtm Plastics GmbH), Axpoly® recycled polypropylene pellets (Axion Ltd), and polypropylene copolymers (BSP Compounds).

[0061] During recycling, any reasonable measures are usually taken to reduce or remove any components other than polyethylene and polypropylene, insofar as the final application or use suggests such measures. However, other components are often present in small amounts.

[0062] Other such components include polystyrene (PS), polyamide (PA), and polyethylene terephthalate (PET), all of which are present in the smallest possible amounts, preferably below the detection limit.

[0063] The mixed plastic polypropylene blend (PPB) has a melt flow MFR2 determined at 230°C and 2.16 kg according to ISO 1133, preferably in the range of 9.0 to 25.0 g / 10 min, more preferably in the range of 10.0 to 15.0 g / 10 min.

[0064] Furthermore, the mixed plastic polypropylene blend (PPB) preferably has a density determined in accordance with ISO 1183 of 900 to 930 kg / m 3 , more preferably 905 to 925 kg / m 3 , even more preferably 910 to 920 kg / m 3 .

[0065] The mixed plastic polypropylene blend (PPB) can be characterized by CRYSTEX QC analysis. In CRYSTEX QC analysis, a crystalline fraction (CF) and a soluble fraction (SF) are obtained, and these can be quantified and analyzed with respect to the monomer and comonomer contents and the intrinsic viscosity (iV).

[0066] The mixed plastic polypropylene blend (PPB) preferably has the following characteristics in CRYSTEX QC analysis · A crystalline fraction (CF) content determined in accordance with CRYSTEX QC analysis in the range of 85.0 to 96.0% by weight, preferably 86.5 to 95.5% by weight, more preferably 89.0 to 95.0% by weight, and · A soluble fraction (SF) content determined in accordance with CRYSTEX QC analysis in the range of 4.0 to 15.0% by weight, preferably 4.5 to 13.5% by weight, more preferably 5.0 to 11.0% by weight showing one or all of these.

[0067] The above crystalline fraction (CF) preferably has one or more, preferably all, of the following characteristics · An ethylene content (C2(CF)) determined by FT-IR spectroscopy calibrated by quantitative 13 C-NMR spectroscopy in the range of 1.0 to 10.0% by weight, preferably 1.5 to 9.5% by weight, more preferably 2.0 to 7.5% by weight, and / or · An intrinsic viscosity (iV(CF)) measured at 135 °C in decalin in accordance with DIN ISO 1628 / 1 of less than 2.5 dl / g, preferably 1.1 to 2.3 dl / g, more preferably 1.4 to 2.0 dl / g ​

[0068] The above soluble fraction (SF) preferably has the following characteristics • A quantitative amount in the range of 20.0 to 55.0% by weight, preferably 22.0 to 50.0% by weight, more preferably 24.0 to 48.0% by weight. 13 Ethylene content (C2(SF)) determined by FT-IR spectroscopy calibrated by 13C-NMR spectroscopy, and / or • Intrinsic viscosity (iV(SF)) measured at 135°C in decalin according to DIN ISO 1628 / 1, in the range of 0.9 to 2.1 dl / g, preferably in the range of 1.0 to 2.0 dl / g, more preferably in the range of 1.1 to 1.9 dl / g. It has one or more, preferably all, of the following.

[0069] The mixed plastic polypropylene blend (PPB) preferably contains units derived from ethylene in an amount of 2.5 to 10.0% by weight, more preferably 3.0 to 9.0% by weight, and even more preferably 3.5 to 8.0% by weight.

[0070] The mixed plastic polypropylene blend (PPB) has an inorganic residue content determined by calcination analysis according to DIN ISO 1172:1996, preferably in the range of 0.05 to 3.0% by weight, more preferably in the range of 0.5 to 2.5% by weight, and most preferably in the range of 1.0 to 2.5% by weight.

[0071] The mixed plastic polypropylene blend (PPB) is preferably derived from post-industrial waste or post-consumer waste, and most preferably from post-consumer waste.

[0072] The mixed plastic polypropylene blend (PPB) is preferably 1 to 250 mg / m². 3 It has a limonene content within the range determined by solid-phase microextraction (HS-SPME-GC-MS).

[0073] The presence of limonene indicates that the mixed plastic polypropylene blend (PPB) originates from consumer used waste.

[0074] Further indicators of the recycled nature of mixed plastic polypropylene blends (PPBs) include the presence of other polymers, such as polystyrene and polyamide-6, as well as the presence of fatty acids.

[0075] Therefore, the mixed plastic polypropylene blend (PPB) contains one or more of polystyrene, polyamide-6, and fatty acids, and more preferably contains each of polystyrene, polyamide-6, and fatty acids.

[0076] Mixed plastic polypropylene blend (PPB) is preferably, i) L of 50.0 to 97.0, more preferably 80.0 to 97.0 * , ii) a of -5.0~0.0 * , iii) b 0.0~22.0 (excluding 22.0) * CIELAB color space (L * a * (b) has

[0077] The mixed plastic polypropylene blend (PPB) preferably has a tensile modulus of 1000 MPa to 1500 MPa, preferably 1100 MPa to 1400 MPa, and more preferably 1150 to 1300 MPa.

[0078] Furthermore, the mixed plastic polypropylene blend (PPB) preferably has a concentration of 3.0 to 7.5 kJ / m³. 2 More preferably 4.0 to 7.0 kJ / m 2 It has a notched Charpy impact strength (CNIS at 23°C) at 23°C.

[0079] Before blending with other components to prepare the polypropylene composition (C), the mixed plastic polypropylene blend (PPB) can be aerated to remove volatile components, for example, as described in European Patent Application Publication No. 3786190A1.

[0080] Flame retardant (FR) The polypropylene composition (C) contains a flame retardant (FR). The flame retardant (FR) may be a mixture of two or more flame retardants (FR). The flame retardant product may be any flame retardant product suitable for polypropylene resins.

[0081] Preferably, the flame retardant (FR) is halogen-free. That is, it is preferable that the flame retardant (FR) is not an organic or inorganic compound containing a halogen atom. As used herein, the term "halogen" refers to an element of Group 17 of the periodic table.

[0082] The polypropylene composition (C) preferably contains a nitrogen-containing flame retardant (FR).

[0083] The nitrogen-containing flame retardant (FR) preferably contains at least one nitrogen-containing phosphate (phosphate ester), preferably at least one organic nitrogen-containing phosphate. Preferably, this organic nitrogen-containing phosphate is a heterocyclic C3-C6- phosphate, and more preferably a C3-C4-alkyl or aryl compound phosphate containing at least one N atom.

[0084] According to a preferred embodiment of the present invention, the nitrogen-containing flame retardant (FR) comprises a first nitrogen-containing phosphate (FR1) and a second nitrogen-containing phosphate (FR2) different from the first nitrogen-containing phosphate (FR1).

[0085] Preferably, the first nitrogen-containing phosphate (FR1) and the second nitrogen-containing phosphate (FR2) are organic nitrogen-containing phosphates. It is particularly preferable that the first nitrogen-containing phosphate (FR1) and the second nitrogen-containing phosphate (FR2) are heterocyclic C3-C6 phosphates, more preferably C3-C4 alkyl or aryl compound phosphates containing at least one N atom.

[0086] The first nitrogen-containing phosphate (FR1) is preferably an organic nitrogen-containing polyphosphate. More preferably, the first nitrogen-containing phosphate (FR1) is a heterocyclic C3-C6- polyphosphate, and more preferably a polyphosphate of a C3-C4-aryl compound containing at least one N atom. It is particularly preferable that the first nitrogen-containing phosphate (FR1) is a melamine polyphosphate (melamine polyphosphate).

[0087] The second nitrogen-containing phosphate (FR2) is preferably an organic nitrogen-containing diphosphate. More preferably, the second nitrogen-containing phosphate (FR2) is a heterocyclic C3-C6- diphosphate, and more preferably, a diphosphate of a C3-C4-alkyl compound containing at least one N atom, for example, two N atoms. It is particularly preferable that the second nitrogen-containing phosphate (FR2) is a piperazine pyrophosphate (piperazine pyrophosphate).

[0088] According to a preferred embodiment of the present invention, the weight ratio of the first nitrogen-containing phosphate (FR1) to the second nitrogen-containing phosphate (FR2) is in the range of 60:40 to 40:60.

[0089] Suitable nitrogen-containing flame retardants (FRs) are preferably commercially available. A very suitable example of a commercially available nitrogen-containing flame retardant (FR) is the flame retardant product manufactured and supplied by SULI (Soli) and sold under the trade name Phlamoon-1090A.

[0090] As outlined above, the polypropylene composition (C) according to the present invention contains 10.0 to 40.0% by weight, preferably 18.0 to 35.0% by weight, more preferably 20.0 to 38.0% by weight, even more preferably 20.0 to 30.0% by weight, and even more preferably 20.0 to 27.0% by weight, for example, 20.0 to 25.0% by weight of a flame retardant (FR) based on the total weight of the polypropylene composition (C).

[0091] In this specification, the amount of flame retardant (FR) refers to the amount of flame retardant (FR) supplied by the manufacturer relative to the total weight of the polypropylene composition (C). Therefore, the flame retardant (FR) may contain small amounts of further components such as additives, flame retardant synergens, and / or carrier media. It should be understood that such further components are included in the amount of flame retardant (FR).

[0092] Fiber (F) The essential component of the polypropylene composition (C) is fiber (F).

[0093] Preferably, the fiber (F) is selected from the group consisting of glass fibers, carbon fibers, polymer fibers, cellulose fibers, metal fibers, mineral fibers, ceramic fibers, and mixtures thereof. More preferably, the fiber (F) is glass fiber and / or carbon fiber.

[0094] It is particularly preferable that the fiber (F) is a glass fiber (GF). Preferably, the glass fiber (GF) is a cut glass fiber, also known as a glass short fiber (SGF) or chopped strand, and / or a glass long fiber (LGF), preferably a glass long fiber (LGF) obtained from glass roving.

[0095] It is particularly preferable that the fiber (F) is a glass short fiber (SGF).

[0096] The cut glass fibers or glass short fibers (SGF) in the fiber-reinforced composition (C) preferably have a weight-average fiber length in the range of 0.2 to 1.2 mm, more preferably in the range of 0.25 to 1.0 mm, and even more preferably in the range of 0.3 to 0.8 mm, determined according to FASEP after injection molding the fiber-reinforced composition (C) according to EN ISO 1873-2.

[0097] The initial average length of the glass staple fibers (SGF) provided by the supplier, i.e., the average length of the short fibers (SFG) before melt-blending with the propylene polymer (PP), flame retardant (FR), and optional adhesion promoter (AP), differs from the weight-average fiber length of the glass staple fibers (SGF) in the fiber-reinforced composition (C).

[0098] The cut glass fibers or glass short fibers (SGF) used in the fiber-reinforced composition (C) preferably have an initial average length in the range of 2.0 to 10.0 mm, more preferably in the range of 2.3 to 9.0 mm, and even more preferably in the range of 2.5 to 8.0 mm, for example, in the range of 3.0 to 7.0 mm.

[0099] The cut glass fibers or glass short fibers (SGF) used in the fiber-reinforced composition (C) preferably have an average diameter of 5 to 20 μm, more preferably 6 to 18 μm, and even more preferably 8 to 16 μm.

[0100] Preferably, the glass short fibers (SGF) have an initial aspect ratio of 125 to 650, preferably 150 to 500, and more preferably 200 to 450. The aspect ratio is the relationship between the average length and average diameter of the fiber.

[0101] The initial average length and initial average aspect ratio of glass short fibers (SGF) refer to the raw material values ​​provided by the supplier.

[0102] Adhesion promoter (AP) According to the present invention, the polypropylene composition (C) optionally further comprises an adhesion promoter (AP). The adhesion promoter (AP) is specified as a polar-modified polypropylene (PM-PP) homopolymer or copolymer.

[0103] In embodiments of the present invention in which the fiber (F) is glass fiber and / or carbon fiber, it is preferable that the polypropylene composition (C) contains an adhesion promoter (AP).

[0104] Polarized modified polypropylene (PM-PP) homopolymers or copolymers contain low molecular weight compounds having reactive polar groups. Modified polypropylene homopolymers and copolymers include, for example, propylene and ethylene or other α-olefins, such as C4-C4. 10 Copolymers with α-olefins are most preferred because they are highly compatible with the propylene polymer (PP) of the polypropylene composition (C).

[0105] In terms of structure, polar-modified polypropylene (PM-PP) homopolymers or copolymers are preferably selected from grafted homopolymers or grafted copolymers.

[0106] In this regard, polar-modified polypropylene (PM-PP) homopolymers or copolymers containing polar compounds, particularly polar compounds selected from the group consisting of acid anhydrides, carboxylic acids, carboxylic acid derivatives, primary and secondary amines, hydroxyl compounds, oxazolines, and epoxides, as well as groups derived from ionic compounds, are preferred.

[0107] Specific examples of the above polar compounds include unsaturated cyclic anhydrides and their aliphatic diesters, and dibasic acid derivatives. In particular, maleic anhydride, and maleic acid C1-C1 10 Linear and branched dialkyls, fumarates C1-C 10 Linear and branched dialkyl groups, itaconic anhydride, itaconic acid C1-C1 10 Compounds selected from linear and branched dialkyl esters, acrylic acid, maleic acid, fumaric acid, itaconic acid, and mixtures thereof can be used.

[0108] It is particularly preferable to use a polypropylene homopolymer or copolymer grafted with maleic anhydride or acrylic acid as a polarity-modified polypropylene (PM-PP) homopolymer or copolymer, i.e., an adhesion promoter (AP).

[0109] The above-mentioned modified polymer, i.e., adhesion promoter, can be produced by a simple method, such as reaction extrusion of the polymer with, for example, maleic anhydride or acrylic acid, in the presence of a free radical generator (such as an organic peroxide), as disclosed in, for example, U.S. Patent No. 4,506,056, U.S. Patent No. 4,753,997, or European Patent Application Publication No. 1805238.

[0110] The preferred amount of groups derived from polar compounds in polar-modified polypropylene (PM-PP) homopolymers or copolymers, i.e., adhesion promoters (APs), is 0.5 to 5.0% by weight. For example, this amount may be in the range of 0.5% to 4.5% by weight, preferably 0.5% to 4.0% by weight, and more preferably 0.5% to 3.5% by weight.

[0111] For polar-modified polypropylene (PM-PP) homopolymers or copolymers, i.e., for adhesion promoters (APs), a preferred melt flow rate MFR2 (230°C, 2.16 kg) is 20.0 to 400 g / 10 min. It is particularly preferable that the polar-modified polypropylene (PM-PP) homopolymer or copolymer has a melt flow rate MFR2 (230°C, 2.16 kg) in the range of 40.0 to 300 g / 10 min, more preferably in the range of 50.0 to 250 g / 10 min.

[0112] In one preferred embodiment of the present invention, the adhesion promoter (AP) is a maleic anhydride-modified polypropylene homopolymer or copolymer, and / or an acrylic acid-modified polypropylene homopolymer or copolymer. Preferably, the adhesion promoter (AP) is a maleic anhydride-modified polypropylene homopolymer and / or an acrylic acid-modified polypropylene homopolymer, preferably a maleic anhydride-modified polypropylene homopolymer. For example, suitable polarity-modified polypropylene (PM-PP) homopolymers or copolymers include, for example, polypropylene homopolymers grafted with maleic anhydride (PP-g-MAH) and polypropylene homopolymers grafted with acrylic acid (PP-g-AA).

[0113] Additives (AD) In addition to heterogeneous propylene copolymer (HECO), mixed plastic polypropylene blend (PPB), nitrogen-containing flame retardant (FR), fiber (F), and optional adhesion promoter (AP), the polypropylene composition (C) may also contain additives (AD). Typical additives include acid scavengers, antioxidants, colorants, light stabilizers, slip agents, scratch inhibitors, dispersants, processing aids, lubricants, and pigments.

[0114] The content of additives in the polypropylene composition (C) of the present invention does not usually exceed 5.0% by weight, and is preferably in the range of 0.5 to 3.5% by weight.

[0115] Such additives are commercially available and are described, for example, in Hans Zweifel's "Plastic Additives Handbook," 6th edition, 2009 (pp. 1141-1190).

[0116] Furthermore, the term "additive (AD)" in the present invention also includes carrier materials, particularly polymer carrier materials.

[0117] Polymer carrier materials Preferably, the polypropylene composition (C) does not contain any further polymers (multiple types) other than the heterogeneous propylene copolymer (HECO), the mixed plastic polypropylene blend (PPB), and the adhesion promoter (AP) in amounts exceeding 5.0% by weight, preferably exceeding 3.0% by weight, and more preferably exceeding 2.0% by weight, based on the weight of the polypropylene composition (C). Any polymer that is a carrier material for the additive (AD) is counted in the amount of the respective additive, rather than the amount of the polymer compound as shown in the present invention.

[0118] The polymer carrier material of additive (AD) is a carrier polymer for ensuring uniform distribution in the polypropylene composition (C) of the present invention. This polymer carrier material is not limited to a specific polymer. The polymer carrier material may be an ethylene homopolymer, an ethylene copolymer obtained from ethylene and α-olefin comonomers such as C3-C8α-olefin comonomers, a propylene homopolymer, and / or a propylene copolymer obtained from propylene and ethylene and / or α-olefin comonomers such as C4-C8α-olefin comonomers. It is preferable that the polymer carrier material does not contain monomer units that can be derived from styrene or its derivatives.

[0119] Goods The present invention also relates to articles comprising the polypropylene composition (C) defined above or below. The present invention particularly relates to articles comprising at least 60% by weight, more preferably at least 80% by weight, even more preferably at least 90% by weight, for example, at least 95% by weight or at least 99% by weight of the polypropylene composition (C) defined above or below. In a particularly preferred embodiment, the present invention relates to articles comprising the polypropylene composition (C) defined above or below.

[0120] Preferably, the articles are automotive articles in the field of electronic components such as electrical cable insulators and housings for electrical equipment, as well as containers and parts for power electronics components of automotive parts and home appliance parts.

[0121] The present invention will be described in more detail by the embodiments provided below. [Examples]

[0122] A.Measurement method The following definitions and methods of determining terms apply to the above general description of the present invention and the following embodiments, unless otherwise defined.

[0123] MFR2 (230°C) was measured according to ISO 1133 (230°C, 2.16 kg load). MFR2 (190°C) was measured according to ISO 1133 (190°C, 2.16 kg load).

[0124] Quantification of fine structure by NMR spectroscopy Quantitative nuclear magnetic resonance (NMR) spectroscopy was used to quantify the comonomer content and comonomer arrangement distribution of the polymer. 13 C{ 1 The H}NMR spectrum is, 1 H and 13 For each C, the spectra were recorded in solution using a Bruker Advance III 400 NMR spectrometer operating at 400.15 MHz and 100.62 MHz, respectively. All spectra were recorded at 125°C. 13A 10 mm extended temperature probe head optimized for C was used, and nitrogen gas was used to record all air pressures. Approximately 200 mg of the material was dissolved in 3 ml of 1,2-tetrachloroethane-d2 (TCE-d2) with chromium(III) acetylacetonate (Cr(acac)3) giving a 65 mM solution of the mitigating agent in the solvent (Singh, G., Kothari, A., Gupta, V., Polymer Testing 28 5(2009), 475). To ensure a homogeneous solution, after the initial sample preparation in a heat block, the NMR tube was further heated in a rotary oven for at least 1 hour. After insertion into the magnet, the tube was rotated at 10 Hz. This setting was chosen primarily for the high resolution and quantitative accuracy required for accurate ethylene content determination. Standard single-pulse excitation without NOE was employed using an optimized tip angle, a 1-series recycle delay, and a bilevel Waltz 16 decoupling scheme (Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh, D., Winniford, B., J. Mag. Reson. 187(2007)225; Busico, V., Carbonniere, P., Cipullo, R., Pellecchia, R., Severn, J., Talarico, G., Macromol. Rapid Commun. 2007, 28, 1128). A total of 6144 (6k) transient signals were acquired per spectrum. quantitative 13 C{ 1 The ¹H NMR spectra were processed and integrated using a proprietary computer program, and relevant quantitative properties were determined from the integrated values. All chemical shifts were indirectly referenced to the central methylene group of the 30.00 ppm ethylene block (EEE) using the chemical shift of the solvent. This approach allowed for comparable reference setting even in the absence of this structural unit. Characteristic signals corresponding to ethylene incorporation were observed (Cheng, HN, Macromolecules 17 (1984), 1950). For polypropylene homopolymers, all chemical shifts are based on an internal standard of 21.85 ppm methyl isotactic pentad (mmmm). Characteristic signals corresponding to locative defects (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253; Wang, WJ., Zhu, S., Macromolecules 33 (2000), 1157; Cheng, HN, Macromolecules 17 (1984), 1950) or comonomers were observed. The tacticity distribution was quantified by integrating the methyl region from 23.6 to 19.7 ppm, correcting for any regions unrelated to the desired stereochemistry (Busico, V., Cipullo, R., Prog.Polym.Sci. 26(2001) 443; Busico, V., Cipullo, R., Monaco, G., Vacatello, M., Segre, AL, Macromolecules 30(1997) 6251). Specifically, the influence of positional defects and comonomers on the quantification of tacticity distribution was corrected by subtracting the integral values ​​of representative positional defects and comonomers from a specific integral region of the stereochemical arrangement. Iso-tacticity was determined at the pentad level and reported as the percentage of isotactic pentad (mmmm) sequences relative to all pentad sequences. [mmmm]% = 100 × (mmmm / sum of all pentads) The presence of a 2,1-erythrocyte defect was indicated by the presence of two methyl sites at 17.7 and 17.2 ppm, and confirmed by other characteristic sites. No characteristic signals corresponding to other types of locative defects were observed (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253). The amount of 2,1-erythrocyte defects was quantified using the average integral values ​​of two characteristic methyl sites, 17.7 and 17.2 ppm. P 21e=(I e6 +I e8 ) / 2 The amount of primary inserted propene was quantified based on the methyl region. Corrections were made for sites within this region that are not related to primary insertion, and primary insertion sites that are excluded from this region. P 12 =I CH3 +P 12e The total amount of propene was quantified as the sum of the primary insertion propene and all other present situational defects. P 全 =P 12 +P 21e The molar percentage of 2,1-erythrocyte locative defects was quantified relative to the total propene. [21e] Mole% = 100 × (P 21e / P 全 ) For copolymers, we observed characteristic signals corresponding to the incorporation of ethylene (Cheng, HN, Macromolecules 17 (1984), 1950). When positional defects were also observed (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253; Wang, WJ., Zhu, S., Macromolecules 33(2000), 1157); Cheng, HN, Macromolecules 17(1984), 1950), correction for the effect of such defects on the comonomer content was necessary. The comonomer fraction is 13 C{ 1 The quantification was performed by integrating multiple signals across the entire spectral region of the H} spectrum using the method of Wang et al. (Wang, WJ., Zhu, S., Macromolecules 33(2000) 1157). This method was chosen for its robustness and, if necessary, its ability to account for the presence of locative defects. The integration region was slightly adjusted to enhance its applicability across the entire range of comonomer content. For systems where only isolated ethylenes in the PPEPP sequence are observed, Wang et al.'s method was modified to reduce the effect of non-zero integrals from known non-existent sites. This approach reduces overestimation of the ethylene content for such systems by reducing the number of sites used to determine the absolute ethylene content. E=0.5(Sββ+Sβγ+Sβδ+0.5(Sαβ+Sαγ)) It was accomplished. By using this set of parts, the corresponding integral equation can be expressed using the same notation as used in Wang et al.'s paper (Wang, WJ., Zhu, S., Macromolecules 33(2000), 1157), E=0.5(I H +I G +0.5(I C +I D )) The equation used for the absolute propylene content was not modified. The comonomer incorporation in mole percentage was calculated from the mole fraction. E [mol%] = 100 × fE The weight percentage of comonomer incorporation was calculated from the mole fraction. E[weight%]=100×(fE×28.06) / ((fE×28.06)+((1-fE)×42.08)) The comonomer sequence distribution at the triad level was determined using the analytical method of Kakugo et al. (Kakugo, M., Naito, Y., Mizunuma, K., Miyatake, T. Macromolecules 15(1982)1150). This method was chosen for its robustness and the integration region, which is slightly adjusted to enhance its applicability to a wider range of comonomer content.

[0125] Crystallization extraction (CRYSTEX) Determination of crystalline fraction and soluble fraction, and their respective properties (IV and ethylene content). The crystalline fraction (CF) and soluble fraction (SF) of the polypropylene composition, as well as the comonomer content and intrinsic viscosity of each fraction, were analyzed using a CRYSTEX apparatus and Polymer Char (Valencia, Spain). Technical and methodological details can be found in the literature (Ljiljana Jeremic, Andreas Albrecht, Martina Sandholzer, and Markus Gahleitner (2020) Rapid characterization of high-impact ethylene-propylene copolymer composition by crystallization extraction separation: compareability to standard separation methods, International Journal of Polymer Analysis and Characterization, 25:8, 581-596). Crystalline and amorphous fractions are separated by a temperature cycle of dissolution at 160°C, crystallization at 40°C, and redissolution in 1,2,4-trichlorobenzene at 160°C. Quantification of SF and CF, as well as determination of ethylene content (C2), are achieved using an integrated infrared detector (IR4), and an online two-capillary viscometer is used to determine the intrinsic viscosity (iV). The IR4 detector uses two different frequency bands (concentration and CH3 extensional oscillation (approximately 2960 cm) which helps determine the ethylene content in ethylene-propylene copolymers). -1 (centered around) and CH extension vibration (2700~3000cm) -1 )) is a multi-wavelength detector that measures IR absorbance. The IR4 detector measures ethylene content in the range of 2 wt% to 69 wt% ( 13 A series of eight EP copolymers (determined by 13C-NMR) were used, each calibrated at various concentrations ranging from 2 to 13 mg / ml. The following calibration equation was applied to simultaneously encounter both characteristics, concentrations, and ethylene content for the various polymer concentrations expected during crystal analysis. Concentration=a+b×Abs(CH)+c×(Abs(CH)) 2 +d × Abs(CH3) + e × (Abs(CH3) 2 +f×Abs(CH)×Abs(CH3) (Formula 1) CH3 / 1000C=a+b×Abs(CH)+c×Abs(CH3)+d×(Abs(CH3) / Abs(CH))+e×(Abs(CH3) / Abs(CH)) 2 (Formula 2)

[0126] The constants a to e in Equation 1 and a to f in Equation 2 were determined using least squares regression analysis. CH3 / 1000C is converted to ethylene content (weight %) using the following relationship: Weight % (ethylene in EP copolymer) = 100 - CH3 / 1000 TC × 0.3 (Equation 3)

[0127] The amounts of the soluble fraction (SF) and crystalline fraction (CF) are correlated with the amounts of the "cold xylene soluble fraction" (XCS) and cold xylene insoluble fraction (XCI), respectively, determined by XS calibration according to the standard gravimetric method of ISO 16152. XS calibration is achieved by testing various EP copolymers having XS content ranging from 2 to 31% by weight. The determined XS calibration is linear. Weight%XS=1.01×Weight%SF (Formula 4)

[0128] The intrinsic viscosity (iV) of the parent EP copolymer and its soluble and crystalline fractions is determined using an online two-capillary viscometer and correlated with the corresponding iV determined by a standard method in decalin according to ISO 1628-3. Calibration is achieved using various EPPP copolymers with iV = 2–4 dL / g. The determined calibration curve is linear. iV(dL / g)=a×Vsp / c (Formula 5)

[0129] The sample to be analyzed was weighed at a concentration of 10 mg / ml to 20 mg / ml. To avoid the injection of gels and / or polymers that may be present and do not dissolve in TCB at 160°C, such as PET and PA, the weighed sample was packed into a stainless steel mesh MW0.077 / D0.05 mm. After automatically filling vials with 1,2,4-TCB containing 250 mg / l 2,6-tert-butyl-4-methylphenol (BHT) as an antioxidant, the sample is dissolved at 160°C for typically 60 minutes, with continuous stirring at 400 rpm, until complete dissolution is achieved. To avoid sample degradation, the polymer solution is covered with an N2 atmosphere during dissolution. A specified volume of sample solution is injected into a column packed with an inert support that allows for the crystallization of the sample and the separation of the soluble fraction from the crystalline portion. This process is repeated twice. During the first injection, the entire sample is measured at high temperature to determine the iV [dl / g] and C2 [wt%] of the PP composition. During the second injection, the soluble fraction (at low temperature) and crystalline fraction (at high temperature) are measured in the crystallization cycle (wt%SF, wt%C2, iV).

[0130] intrinsic viscosity Intrinsic viscosity was measured according to DIN ISO 1628 / 1, October 1999 (135°C in decalin).

[0131] Density: Measured according to ISO 1183 on a compression-molded plate (plaque).

[0132] DSC analysis, melting temperature (T m ) and heat of fusion (H f ), crystallization temperature (T c ) and heat of crystallization (H c ) 5–7 mg samples were measured using differential scanning calorimetry (DSC) with a TA Instrument Q200. DSC was performed according to ISO 11357 / Part 3 / Method C2, in a heating / cooling / heating cycle at a scanning rate of 10°C / min in the temperature range of -30 to +225°C. Crystallization temperature (T c ) and crystallization enthalpy (H cThe melting temperature (T) is determined from the cooling process. m ) and enthalpy of melting (H m ) is determined from the second heating process.

[0133] Cold xylene soluble fraction (XCS, wt%): The content of the cold xylene soluble fraction (XCS) was determined at 25°C according to ISO 16152; 1st edition; 2005-07-01.

[0134] The notched Charpy impact strength was determined at 23°C according to ISO 179-1 / 1eA using injection-molded test specimens (80 × 10 × 4 mm) prepared according to EN ISO 1873-2.

[0135] Tensile properties were determined for injection-molded dogbone specimens with a thickness of 4 mm, prepared according to EN ISO 1873-2. The tensile modulus was determined according to ISO 527-1A at a strain rate of 1 mm / min and at 23°C, 80°C, and 120°C, and the yield stress was determined at a strain rate of 50 mm / min and at 23°C, 80°C, and 120°C.

[0136] The flexural modulus was determined for 80 mm × 10 mm × 4 mm test specimens according to ISO 178 Method A (three-point bending test). A test speed of 2 mm / min and a support distance of 16 times the thickness were used, as per the standard. The test temperature was 23 ± 2 °C. Injection molding was performed according to ISO 19069-2, using a melting temperature of 230 °C for all materials, regardless of the material's melt flow rate.

[0137] The ash content was measured according to the ISO 3451-1 (1997) standard.

[0138] Limonene detection Estimated Limonene The determination of benzene and limonene is based on a static headspace (HS) approach. This analysis uses an HS sampler in combination with gas chromatography (GC) and mass spectrometry (MS) for screening purposes. Samples were delivered to the laboratory in sealed aluminum-coated polyethylene (PE) bags. Prior to analysis, the samples were freeze-dried and ground, and portions of 2,000 ± 0.100 g were weighed into 20 ml HS vials and sealed. Duplicate measurements were performed for all samples. HS / GC / MS parameters • HS parameters (Agilent G1888 headspace sampler) Vial equilibration time: 120 minutes (sample), 5 minutes (standard) Oven temperature: 100°C (sample), 200°C (standard) Loop temperature: 110°C (sample), 205°C (standard) Transfer line temperature: 120°C (sample), 210°C (standard) low shaking • GC parameters (Agilent 7890A GC system) Column: ZB-WAX 7HG-G007-22 (30m x 250μm x 1μm) Carrier gas: Helium 5.0 Flow rate: 2ml / min Split: 5:1 GC Oven Program: 35°C for 0.1 minutes Up to 250°C at 10°C / min 1 minute at 250℃ • MS parameters (Agilent 5975C inert XL MSD) Acquisition mode: Scan Scan parameters: Low mass: 20 High mass:200 Threshold: 10 • Software / Data Evaluation MSD ChemStation E.02.02.1431 MassHunter GC / MS Acquisition B.07.05.2479 AMDIS GC / MS Analysis version 2.71 NIST / EPA / NIH Mass Spectral Library (2011 edition) NIST Mass Spectral Search Program version 2.0 g AMDIS deconvolution parameters Minimize match factor: 80 Threshold: Low Scan direction: High to Low Data file format: Agilent files are Agilent files. Instrument type: Quadrupole Component width: 20 Adjacent peak subtraction: Two (2) Resolution: High Sensitivity: Very high Shape requirements: Medium Solvent tailing: 91 m / z Column bleed: 207 m / z Minimum model peaks: 2 Min.S / N: 10 Min. certain peaks: 0.5 MSD ChemStation integration parameters Integrator:ChemStation Initial area rejection: 0 Initial peak width: 0.005 Shoulder detection: off Initial threshold: 10.5

[0139] In this study, the description "below the detection limit (<LOD)" describes the condition that either the match factor is less than 80 (AMDIS) or the signal-to-noise (noise) ratio of the peak in the sample run (Pk-Pk S / N = corrected signal / Pk-Pk noise, MSD ChemStation signal-to-noise report) is less than 3. The results refer only to the measured sample, the measurement time, and the parameters applied.

[0140] Standard solution For the positive identification and comparison with the (lowest) odour detection threshold (ODT), limonene standards were used. For HS / GC / MS analysis, 5 μl of each standard was injected into a 20 ml HS vial, sealed, and measured. Assuming complete vaporization of the standard substance, the limonene concentration c in HS G was estimated as listed in the following table.

[0141] [Table 1]

[0142] Data evaluation The concentration c of the analyte in HS G is calculated taking into account the amount of substance m G and the available HS volume V G (Equation 1). [Equation] To estimate the concentration of the analyte in HS above the polymer sample, a response factor Rf for single-point calibration is required (Equation 2). The peak area of the analyte is obtained by integrating the extracted ion chromatogram (EIC). The corresponding target ions are listed in the above table. [Equation] Concentration of the analyte in HS above the polymer sample 0[Equation] This is calculated by multiplying the response factor by the EIC peak area of ​​the sample (Equation 3).

number

number

number

[0143] Considerations and limitations It must be considered that the ODT for some substances falls below the detection limit (LOD) of the method. Therefore, components below the LOD may still be present in the overall odor but may be missed. OAV is based on the assumption that the HS parameter is somewhat related to the measurement conditions for ODT determination. Of course, this assumption is not entirely applicable, as a temperature setting of 100°C is not always chosen for such experiments and therefore has limited practical value. Nevertheless, this approach can at least demonstrate the odor relevance of a defined marker substance. Considering all the assumptions and limitations mentioned, the concentrations and odor activity values ​​in HS above the determined sample should be interpreted as merely rough estimates. References [1] Van Gemert LJ, Odour Thresholds: Compilations of odor threshold values ​​in air, water and other media, Utrecht, Oliemans Punter & Partners BV, 2011.

[0144] The average fiber diameter was determined according to ISO 1888:2006(E), Method B.

[0145] The weight-average fiber length and fiber length distribution were determined according to the FASEP (FAser (German; fiber) SEParation) method for injection-molded specimens prepared in accordance with EN ISO 1873-2. Fibers were separated from the polymer matrix by thermal decomposition in a TGA oven (625°C for glass fibers, 500°C for carbon fibers), or by solution separation and physical separation. The separated fibers were suspended in deionized water, and the suspension was diluted until the number of fibers and fiber overlap were well balanced. The average fiber length was determined by grayscale image processing on FASEP 1.9.44.0 (IDM Systems, Darmstadt, Germany), and statistically examined by calculating the average fiber length and fiber length distribution. Accurate results will be achieved for images with a small number of fiber clusters and fibers cut in any manner. This is achieved by realizing a specific fiber-to-water fraction. For glass fibers, the fraction must be 30 mg / L or less, and for carbon fibers, the fraction must be 20 mg / L or less. The number of clusters relative to free fibers should be less than 20% for short fibers and less than 15% for long fibers. For evaluation, FASEP software (ImageProPlus including the FASEP module) is used to separate fibers from the background, remove dust and other irrelevant features, separate fibers where they overlap, and automatically measure the length of each fiber. The average fiber length Ln and weight-average fiber length Lp are determined according to ISO 22314:05:2006.

number

[0146] The investigation report must include the following values ​​in addition to the settings used. • The total number of fibers in all images combined for each sample Ln, Lp (as defined above) • Lmin and Lmax of fibers in all combined images for each sample. • Fiber length distribution • Fiber mass • Local fiber content

[0147] The UL94 vertical combustion test was performed in accordance with UL94:2016. The sample was injection molded into a piece measuring 125±5 mm in length, 13.0±0.5 mm in width, and 0.8–3.2 mm in thickness (1.5 mm thickness was used in the example section). Under condition part 1, the sample had to be conditioned for 48 hours at a constant room temperature of 23±2°C and 50±10% humidity. Under condition part 2, the sample had to be conditioned for 168 hours at 70±1°C in an air-circulating oven, and then cooled in a desiccator at room temperature for at least 4 hours prior to the test. The test had to be performed within 30 minutes of removing the sample from conditioning. The sample was suspended vertically in the test chamber and subjected to a first ignition for 10 seconds, followed by a second ignition for another 10 seconds. The burning time after each ignition is recorded, and attention is also paid to whether there is afterglow, whether there is any dripping of combustion fluid at the bottom of the chamber to ignite the cotton, and whether there is a flame or red-hot light up to the retaining clamp. The classification is V-0, V-1, V-2, or unclassified, and the classification depends on the thickness of the test object.

[0148] B Experiment Heterophase propylene copolymer HECO The catalyst used to produce the heterogeneous propylene copolymer HECO was the Ziegler-Natta catalyst, commercially available from Lyondell Basell (Italy) under the trade name ZN180M.

[0149] HECO was prepared using a prepolymerization / loop reactor / gas-phase reactor 1 / gas-phase reactor 2 configuration, followed by a pelletization process. For HECO, the catalyst system specified above was used in combination with triethylaluminum (TEAL) as a co-catalyst and dicyclopentadienyl-dimethoxysilane (donor D) as an external donor. The polymerization conditions are shown in Table 1.

[0150] [Table 2]

[0151] The heterogeneous copolymer HECO was compounded in a co-rotating twin-screw extruder Coperion ZSK 47 at 220°C with 0.15 wt% antioxidant (Irganox B215FF from BASF, Germany; this is a 1:2 mixture of pentaerythrityl-tetrakis(3-(3',5'-di-tert-butyl-4-hydroxyphenyl)-propionate, CAS No. 6683-19-8, and tris(2,4-di-t-butylphenyl)phosphite, CAS No. 31570-04-4); and 0.05 wt% calcium stearate (CAS No. 1592-23-0, commercially available from Faci, Italy).

[0152] Mixed plastic polypropylene blend (PPB) Table 2 shows the properties of the polypropylene / polyethylene blends (PPBs) used in the evaluation. Since these compositions originate from mechanical recycling processes, the properties are shown as ranges.

[0153] [Table 3]

[0154] Preparation of polypropylene composition (C) HECO or PP1 (for CE1) and PPB were melt-blended with the amounts of flame retardant composition (FR), glass fiber (GF), adhesion promoter (AP), and additive (AD) shown in Table 3 below using a co-rotating twin-screw extruder.

[0155] [Table 4] PP1 is Borealis' commercially available propylene homopolymer HL504FB, which has a melt flow rate of 450 g / 10 min (ISO1133; 230°C, 2.16 kg load), a melting temperature Tm of 161°C, and a flexural modulus of 1519 MPa, and is manufactured by bis-breaking from a base polymer produced using a post-phthalate Ziegler-Natta type catalyst. FR is SULI's commercially available flame retardant composition Phlamoon-1090A, which contains 55-60% by weight of melamine polyphosphate and 40-55% by weight of piperazine pyrophosphate. The GF is the commercially available ECS 03 T-480H from Nippon Electric Glass Co., Ltd., which has a filament diameter of 13.0 μm and a strand length of 3 mm. AP is a bonding promoter from Scona, SCONA TPPP 8112 GA, which is polypropylene functionalized with maleic anhydride, containing 1.4% by weight maleic anhydride and having an MFR (at 190°C, 2.16 kg) greater than 80 g / 10 min. CB is a masterbatch containing 40% by weight of carbon black. AO1 is the antioxidant 2,2'-oxamidobis-(ethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), which is commercially available as Naugard XL-1 from Addivant. AO2 is tris(2,4-di-t-butylphenyl) phosphite, an antioxidant marketed as Irgafos 168 by BASF. AO3 is pentaerythrityl-tetrakis(3-(3',5'-di-tert-butyl-4-hydroxyphenyl)-propionate, an antioxidant commercially available from BASF as Irganox 1010.

[0156] Table 4 summarizes the flame retardancy and mechanical properties of comparative examples and the compositions of the present invention.

[0157] [Table 5] * The UL94 vertical combustion test was conducted under the conditions described in Part 1 of the "Measurement Method - UL94 Vertical Combustion Test" section, specifically, the sample was conditioned for 48 hours at a constant room temperature of 23±2°C and a humidity of 50±10%. ** The UL94 vertical combustion test was conducted under the conditions described in Part 2 of the "Measurement Method - UL94 Vertical Combustion Test" section, specifically, the sample was conditioned in an air-circulating oven at 70±1°C for 168 hours, and then cooled in a desiccator at room temperature for at least 4 hours.

[0158] Examples IE1 and IE2, which include 8.9% by weight and 22.2% by weight of mixed plastic polypropylene blends PPB, surprisingly exhibit properties comparable to Reference Example RE1, which includes only virgin heterogeneous propylene copolymer HECO as the propylene polymer. Comparative Example CE1, which contains 18.0 wt% mixed plastic polypropylene blend PPB and high-flow propylene homopolymer PP1 instead of HECO, failed the UL94 vertical combustion test under Condition Part 2 and is therefore unsuitable as a flame-retardant material for electronic equipment housings.

Claims

1. A polypropylene composition (C), i) Melt flow rate MFR of 5.0–40.0% by weight, at least 45.0 g / 10 min as determined according to ISO 1133 ２ A heterogeneous propylene copolymer (HECO) having (230°C, 2.16 kg), ii) A mixed plastic polypropylene blend (PPB) in an amount of 5.0 to 30.0% by weight, iii) 10.0 to 40.0% by weight of flame retardant (FR), iv) 10.0 to 40.0% by weight of fiber (F), v) 0.0 to 5.0% by weight of an adhesion promoter (AP) and A polypropylene composition (C) comprising, where all weight content is based on the total weight of the polypropylene composition (C).

2. Melt flow rate MFR determined at 2.16 kg and 230°C according to ISO 1133, in a range of 2.5 to 20.0 g / 10 min, preferably 3.0 to 15.0 g / 10 min, and more preferably 4.0 to 12.5 g / 10 min. ２ The polypropylene composition (C) according to claim 1, having the following characteristics.

3. At least 7.0 kJ / m ２ For example, 7.0 to 15.0 kJ / m ２ Preferably 7.5 to 12.5 kJ / m ２ More preferably 7.7 to 11.0 kJ / m ２ The polypropylene composition (C) according to claim 1 or 2, having a notched Charpy impact strength at 23°C determined at 23°C in accordance with ISO 179-1 / 1eA.

4. The following characteristics A tensile modulus of at least 5500 MPa, for example 5500 to 10000 MPa, preferably 6000 to 9500 MPa, more preferably 6250 to 9000 MPa, A tensile strength of at least 50 MPa, for example 50 to 100 MPa, preferably 55 to 95 MPa, more preferably 60 to 90 MPa, Tensile fracture stress of at least 1.7%, for example 1.7 to 5.0%, preferably 2.0 to 4.5%, and more preferably 2.3 to 4.0% A polypropylene composition (C) according to any one of claims 1 to 3, comprising one or more or all of the above, all of which are determined at 23°C according to ISO 527-1A.

5. The following characteristics UL94 classification V-0 in UL94 flame retardancy testing after 48 hours of conditioning according to Condition Part 1. UL94 classification V-0 in UL94 flame retardancy test after 168 hours of conditioning according to Condition Part 1. A polypropylene composition (C) according to any one of claims 1 to 4, comprising one or more or all of the above, each of which has been performed on an injection-molded sample having a length of 125 ± 5 mm, a width of 13.0 ± 0.5 mm, and a thickness of 1.5 mm.

6. i) The polypropylene composition (C) is free of fluoropolymers in an amount exceeding 0.5% by weight, more preferably 0.1% by weight, even more preferably 0.01% by weight, for example, more than 0.001% by weight, most preferably free of fluoropolymers, and / or ii) Nitrogen-containing flame retardants (FR) do not contain halogens. A polypropylene composition (C) according to any one of claims 1 to 5.

7. The aforementioned mixed plastic polypropylene blend (PPB) is A crystalline fraction (CF) content determined by CRYSTEX QC analysis, in the range of 85.0 to 96.0% by weight, preferably in the range of 86.5 to 95.5% by weight, and Soluble fraction (SF) content determined by CRYSTEX QC analysis, in the range of 4.0 to 15.0% by weight, preferably in the range of 4.5 to 13.5% by weight. It has, The crystalline fraction (CF) is quantitatively measured in the range of 1.0 to 10.0% by weight, preferably in the range of 1.5 to 9.5% by weight. １３ It has an ethylene content (C2(CF)) determined by FT-IR spectroscopy calibrated by C-NMR spectroscopy, The crystalline fraction (CF) has an intrinsic viscosity (iV(CF)) of less than 2.5 dl / g, preferably in the range of 1.1 to 2.3 dl / g. The soluble fraction (SF) is quantitatively measured in the range of 20.0 to 55.0% by weight, preferably in the range of 22.0 to 50.0% by weight. １３ It has an ethylene content (C2(SF)) determined by FT-IR spectroscopy calibrated by C-NMR spectroscopy, The soluble fraction (SF) has an intrinsic viscosity (iV(SF)) in the range of 0.9 to 2.1 dl / g, preferably in the range of 1.0 to 2.0 dl / g. A polypropylene composition (C) according to any one of claims 1 to 6.

8. The aforementioned mixed plastic polypropylene blend (PPB) has the following characteristics The melt flow rate MFR determined according to ISO 1133 at 2.16 kg and 230°C of 8.0 to 40 g / 10 min, preferably 9.0 to 25.0 g / 10 min, more preferably 10.0 to 15.0 g / 10 min ２ , 900-930kg / m ３ Preferably 905 to 925 kg / m ３ , more preferably 910 to 920 kg / m ３ The density determined according to ISO 1183, 1-250 mg / m² ３ The limonene content was determined by using solid-phase microextraction (HS-SPME-GC-MS). A tensile modulus determined according to ISO 527-2, with a tensile modulus of 1000 MPa to 1500 MPa, preferably 1100 MPa to 1400 MPa. 3.0-7.5kJ / m ２ Preferably 4.0 to 7.0 kJ / m ２ The notched Charpy impact strength at 23°C, as determined at 23°C according to ISO 179-1 / 1eA. A polypropylene composition (C) according to any one of claims 1 to 7, having one or more or all of the above.

9. The polypropylene composition (C) according to any one of claims 1 to 8, wherein the flame retardant (FR) is a nitrogen-containing flame retardant (FR), more preferably comprising a first nitrogen-containing phosphate (FR1) and a second nitrogen-containing phosphate (FR2), and optionally the weight ratio of the first nitrogen-containing phosphate (FR1) to the second nitrogen-containing phosphate (FR2) is in the range of 60:40 to 40:

60.

10. The polypropylene composition (C) according to claim 9, wherein the first nitrogen-containing phosphate (FR1) is melamine polyphosphate and the second nitrogen-containing phosphate (FR2) is piperazine pyrophosphate.

11. The heterogeneous propylene copolymer (HECO) has a cold xylene-soluble fraction (XCS) in the range of 7.0 to 25.0% by weight based on the total weight of the heterogeneous propylene copolymer (HECO), and the xylene-soluble fraction (XCS) of the heterogeneous propylene copolymer (HECO) is preferably i) Comonomer content exceeding 35.0 mol%, and / or ii) Intrinsic viscosity (IV) less than 3.5 dl / g, measured according to ISO 1628 / 1 (in decalin at 135°C) A polypropylene composition (C) according to any one of claims 1 to 10, having the characteristics of the polypropylene composition (C).

12. The polypropylene composition (C) according to any one of claims 1 to 11, wherein the fiber (F) is a glass fiber (GF), preferably a glass short fiber (SGF) having a weight-average fiber length determined according to the FASEP method described in "Method" after injection molding in accordance with EN ISO 1873-2 in the range of 0.2 to 1.2 mm.

13. The adhesion promoter (AP) is at least 20.0 g / 10 min of melt flow rate MFR determined according to ISO 1133. ２ A polypropylene composition (C) according to any one of claims 1 to 12, which is a polar-modified polypropylene (PM-PP) that is a homopolymer or copolymer of maleic anhydride-grafted propylene having (230°C, 2.16 kg).

14. The polypropylene composition (C) according to any one of claims 1 to 13, wherein the total amount of the propylene polymer (PP), the flame retardant (FR), the fiber (F), and optionally the adhesion promoter (AP) together constitutes at least 90% by weight of the polypropylene composition (C).

15. An article comprising the polypropylene composition (C) according to any one of claims 1 to 14.

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