Polypropylene composition for external automotive applications

Abstract

A composition suitable for automotive applications, which can be obtained by blending at least components (A), (B), (C) and (D): (A) 15% to 50% by weight, preferably 18 to 44% by weight, more preferably 20 to 40% by weight of a mixed plastic polypropylene blend; (B) 20% to 50% by weight, preferably 22 to 47% by weight, more preferably 25 to 45% by weight of a multiphase propylene copolymer; (C) 5% to 25% by weight, preferably 7 to 23% by weight, more preferably 10 to 22% by weight of an ethylene-based plastomer, and (D) 5% to 25% by weight, preferably 7 to 22% by weight, more preferably 10 to 20% by weight of an inorganic filler.

Description

Technical Field

[0001] The present invention relates to a polypropylene composition particularly suitable for automotive exterior applications, which polypropylene composition comprises a blended plastic polypropylene-based blend and an inorganic filler. Background Art

[0002] Compositions suitable for the automotive industry typically comprise one or more polyphase polypropylene copolymers and / or random polyphase copolymers, as well as some conventional inorganic fillers.

[0003] One fundamental problem in the polymer industry is recycling. Currently, the market for recyclates, especially those from household waste, which are commonly referred to as PCR ("post-consumer resin"), is somewhat limited. Starting from household waste, the sorting and separation processes employed will not be able to produce pure polymers, i.e., there will always be some contaminants, or these processes may even result in blends of different polymers. When it comes to polyolefins, which constitute the vast majority of the polymer portion of the collected household waste, it is almost impossible to perfectly separate polypropylene and polyethylene. Recycled polyolefin materials, especially post-consumer resins, are usually cross-contaminated with non-polyolefin materials such as polyethylene terephthalate, polyamide, polystyrene, or non-polymeric substances such as wood, paper, glass, or aluminum. Even worse, these post-consumer recycled polyolefin materials are readily available on a scale of several tons, but unfortunately, these post-consumer recycled polyolefin materials have limited mechanical properties and often suffer from serious odor and / or emission problems.

[0004] For exterior applications in the automotive industry, materials are required to have good flowability, coatability, surface appearance, and mechanical properties balanced in terms of stiffness and toughness. Recently, to meet specific requirements, the market demand has expanded in the direction of using recycled polyolefins in blends with virgin polymers.

[0005] However, there is a great need to allow the dumping and reuse of post-consumer polyolefin recyclates in the final product without health and safety hazards.

[0006] The unpublished patent application EP 20 190 838.1 relates to a polypropylene composition for automotive applications, which polypropylene composition comprises a blended plastic polypropylene-based blend derived from a post-consumer recycled polyolefin stream, an ethylene-based plastomer, and an inorganic filler (such as talc). These compositions exhibit beneficial VOC properties and impact properties, and thus these compositions can replace complex polyphase polypropylene copolymers in automotive applications. However, these compositions still show deficiencies in terms of mechanical properties and flowability.

[0007] The present invention is based on the surprising finding that, by carefully selecting the original components based on multiphase propylene copolymers in a polypropylene-based composition, the polypropylene-based composition comprising a mixed plastic polypropylene-based blend derived from a post-consumer recycled polyolefin stream, an ethylene-based plastomer, and an inorganic filler (such as talc), the polypropylene-based composition has an excellent balance in terms of impact properties, thermal stability, coatability, and especially mechanical properties (such as tensile properties) and flowability (expressed as a high melt flow rate). Thus, the composition of the present invention comprising a mixed plastic polypropylene-based blend derived from a post-consumer recycled polyolefin stream is suitable for injection molding applications, especially in the automotive field, such as external automotive applications, and can replace complex multiphase polypropylene copolymers. SUMMARY OF THE INVENTION

[0008] The present invention relates to a composition suitable for automotive applications, which can be obtained by blending at least components (A), (B), (C), and (D)

[0009] (A) 15% to 50% by weight, preferably 18% to 44% by weight, more preferably 20% to 40% by weight of a mixed plastic polypropylene blend;

[0010] (B) 20% to 50% by weight, preferably 22% to 47% by weight, more preferably 25% to 45% by weight of a multiphase propylene copolymer;

[0011] (C) 5% to 25% by weight, preferably 7% to 23% by weight, more preferably 10% to 22% by weight of an ethylene-based plastomer, and

[0012] (D) 5% to 25% by weight, preferably 7% to 22% by weight, more preferably 10% to 20% by weight of an inorganic filler;

[0013] wherein all percentages refer to the total composition, and wherein

[0014] the mixed plastic polypropylene blend (A) has

[0015] - a crystalline fraction (CF) content, determined according to 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

[0016] - a soluble fraction (SF) content, determined according to 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, wherein

[0017] - the crystalline fraction (CF) has a content of 1.0 to 10.0% by weight, preferably in the range of 1.5 to 9.5% by weight, determined by quantitative 13Determination of the ethylene content (C2(CF)) by FT-IR spectroscopy calibrated by 13C-NMR spectroscopy; and

[0018] - The soluble fraction (SF) has an intrinsic viscosity (iV(SF)) determined in decalin at 135 °C 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;

[0019] The multiphase propylene copolymer (B) comprises a matrix phase and an elastomeric phase dispersed therein and has

[0020] - A melt flow rate MFR of 85 to 250 g / 10 min, preferably 90 to 150 g / 10 min, more preferably 95 to 125 g / 10 min 2 (230 °C, 2.16 kg, ISO 1133);

[0021] - A soluble fraction (SF) content determined by CRYSTEX QC analysis in the range of greater than 20.0 wt% to 30.0 wt%; and

[0022] - An intrinsic viscosity of the soluble fraction iV(SF) measured in decalin at 135 °C according to DINISO 1628 / 1 in the range of 2.0 to 4.5 dl / g, preferably 2.4 to 3.8 dl / g, more preferably 2.5 to 3.7 dl / g;

[0023] The ethylene-based plastomer (C) is a copolymer of ethylene and comonomer units selected from α-olefins having 3 to 12 carbon atoms, preferably α-olefins having 4 to 10 carbon atoms, most preferably 1-butene or 1-octene, and the ethylene-based plastomer (C) has

[0024] - A melt flow rate MFR of 0.2 to 2.5 g / 10 min, preferably 0.3 to 2.0 g / 10 min 2 (190 °C, 2.16 kg, ISO 1133); and

[0025] - A density of 850 to 870 kg / m 3 preferably 855 to 865 kg / m 3 ;

[0026] The composition has

[0027] - A melt flow rate MFR of 8 to 50 g / 10 min, preferably 10 to 48 g / 10 min, more preferably 11 to 45 g / 10 min 2(230 °C, 2.16 kg, ISO 1133).

[0028] Furthermore, the present invention relates to an article comprising a composition as described above or below, preferably a molded article, more preferably a molded automotive article.

[0029] Still further, the present invention relates to the use of a composition as described above or below for injection molding of an article, preferably an automotive article, more preferably an automotive exterior article.

[0030] Definitions

[0031] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although, in practice, any methods and materials similar or equivalent to those described herein can be used to test the present invention, the preferred materials and methods are described herein. When describing and claiming the present invention, the following terms will be used according to the definitions set forth below. Unless otherwise clearly specified, the use of the terms "a", "an", etc. refers to one or more.

[0032] Blended plastics are defined as the presence of small amounts of compounds not normally found in the original polypropylene blend, such as polystyrene, polyamide, polyester, wood, paper, limonene, aldehydes, ketones, fatty acids, metals, and / or long-term decomposition products of stabilizers. The original polypropylene blend refers to a blend that directly originates from the production process without intermediate use.

[0033] By definition, "blended plastics" can be equated with detectable amounts of polystyrene and / or polyamide-6 and / or limonene and / or fatty acids.

[0034] Thus, blended plastics can originate from post-consumer waste and industrial waste, rather than virgin polymers. Post-consumer waste refers to articles that have at least completed their first use cycle (or life cycle), i.e., have been used for their first purpose. In contrast, industrial waste refers to manufacturing scrap or conversion scrap, which generally does not reach the consumer.

[0035] Those skilled in the art will understand that the soluble fraction (SF) having an intrinsic viscosity (iV(SF)) in the range of 0.9 to less than 2.2 dl / g obtained by CRYSTEX QC analysis is typically found in materials from recycle streams. In a preferred aspect of the present invention, the soluble fraction (SF) obtained by CRYSTEX QC analysis has an intrinsic viscosity (iV(SF)) in the range of 0.9 to 2.1 dl / g.

[0036] A polymer blend is a mixture of two or more polymer components. Generally, the blend can be prepared by mixing two or more polymer components. Suitable mixing procedures known in the art are post-polymerization blending. Post-polymerization blending can be dry blending of polymer components such as polymer powders and / or compounded polymer pellets, or melt blending by melt mixing the polymer components.

[0037] An isotactic polypropylene is a polymer consisting essentially of propylene monomer units. Due to impurities, especially during industrial polymerization processes, the isotactic polypropylene can contain up to 0.1 mol% of comonomer units, preferably up to 0.05 mol% of comonomer units, and most preferably up to 0.01 mol% of comonomer units.

[0038] “Polypropylene - polyethylene blend” refers to a composition containing both polypropylene and polyethylene, and also includes polypropylene copolymers and polyethylene copolymers. Since it is impossible to directly determine the polypropylene content and polyethylene content, the weight ratio of polypropylene (A - 1) to polyethylene (A - 2) of 19:1 to 7:3 represents the equivalent ratio calibrated with iPP and HDPE and determined by IR spectroscopy.

[0039] Polypropylene refers to a polymer composed of units derived from propylene in an amount greater than 50 mol%.

[0040] Polyethylene refers to a polymer composed of units derived from ethylene in an amount greater than 50 mol%.

[0041] The term “elastomer” refers to a natural or synthetic polymer having elastic properties. The term “plastomer” refers to a natural or synthetic polymer that combines the characteristics of an elastomer and a plastic, such as rubber-like properties and plastic processing capabilities. An ethylene-based plastomer refers to a plastomer composed of units derived from ethylene in an amount greater than 50 mol%.

[0042] The presence of a multiphase nature can be easily determined by the number of glass transition points, as in dynamic mechanical analysis (DMA) and / or high-resolution microscopy, such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), or atomic force microscopy (AFM).

[0043] The term “XCS” refers to the xylene cold-soluble fraction (XCS wt%) determined at 25 °C according to ISO 16152. The term “XCI” refers to the xylene cold-insoluble fraction (XCI wt%) determined at 25 °C according to ISO 16152.

[0044] A reactor blend is a blend resulting from production in two or more reactors coupled in series or in a reactor having two or more reaction chambers. Optionally, the reactor blend can be produced by blending in solution. The reactor blend is contrasted with a compounded material produced by melt extrusion.

[0045] Unless otherwise specified, "%" means weight percent (wt%). Detailed Description

[0046] Composition

[0047] In a first aspect, the present invention relates to a composition suitable for automotive applications, which can be obtained by blending at least components (A), (B), (C), and (D).

[0048] (A) 15 wt% to 50 wt%, preferably 18 to 44 wt%, more preferably 20 to 40 wt% of a blended plastic polypropylene blend;

[0049] (B) 20 wt% to 50 wt%, preferably 22 to 47 wt%, more preferably 25 to 45 wt% of a multiphase propylene copolymer;

[0050] (C) 5 wt% to 25 wt%, preferably 7 to 23 wt%, more preferably 10 to 22 wt% of an ethylene-based plastomer, and

[0051] (D) 5 wt% to 25 wt%, preferably 7 to 22 wt%, more preferably 10 to 20 wt% of an inorganic filler;

[0052] wherein all percentages refer to the total composition, and wherein

[0053] the blended plastic polypropylene blend (A) has

[0054] - a crystalline fraction (CF) content, as determined by CRYSTEX QC analysis, in the range of 85.0 to 96.0 wt%, preferably in the range of 86.5 to 95.5 wt%, and

[0055] - a soluble fraction (SF) content, as determined by CRYSTEX QC analysis, in the range of 4.0 to 15.0 wt%, preferably in the range of 4.5 to 13.5 wt%, wherein

[0056] - the crystalline fraction (CF) has 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 wt%, preferably in the range of 1.5 to 9.5 wt%; and

[0057] - The soluble fraction (SF) has an intrinsic viscosity (iV(SF)) measured in decalin at 135 °C 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;

[0058] The multiphase propylene copolymer (B) comprises a matrix phase and an elastomeric phase dispersed therein, and has

[0059] - A melt flow rate MFR of 85 to 250 g / 10 min, preferably 90 to 150 g / 10 min, more preferably 95 to 125 g / 10 min 2 (230 °C, 2.16 kg, ISO 1133);

[0060] - A soluble fraction (SF) content determined by CRYSTEX QC analysis in the range of greater than 20.0 wt% to 30.0 wt%; and

[0061] - An intrinsic viscosity iV(SF) of the soluble fraction measured in decalin at 135 °C according to DIN ISO 1628 / 1 in the range of 2.0 to 4.5 dl / g, preferably 2.4 to 3.8 dl / g, more preferably 2.5 to 3.7 dl / g;

[0062] The ethylene-based plastomer (C) is a copolymer of ethylene and comonomer units selected from α-olefins having 3 to 12 carbon atoms, preferably α-olefins having 4 to 10 carbon atoms, most preferably 1-butene or 1-octene, and the ethylene-based plastomer (C) has

[0063] - A melt flow rate MFR of 0.2 to 2.5 g / 10 min, preferably 0.3 to 2.0 g / 10 min 2 (190 °C, 2.16 kg, ISO 1133); and

[0064] - A density of 850 to 870 kg / m 3 , preferably 855 to 865 kg / m 3 ;

[0065] The composition has

[0066] - A melt flow rate MFR of 8 to 50 g / 10 min, preferably 10 to 48 g / 10 min, more preferably 11 to 45 g / 10 min 2 (230 °C, 2.16 kg, ISO 1133).

[0067] The composition according to the invention for automotive applications is particularly suitable for injection molding of articles for use on the exterior of a vehicle.

[0068] The composition according to the invention for automotive applications has one or more of the following characteristics:

[0069] The composition has a melt flow rate MFR of 8 to 50 g / 10 min, preferably 10 to 48 g / 10 min, more preferably 11 to 45 g / 10 min 2 (230 °C, 2.16 kg, ISO 1133).

[0070] The composition can be characterized by CRYSTEX QC analysis. In the CRYSTEX QC analysis, a crystalline fraction (CF) and a soluble fraction (SF) are obtained that can be quantified and analyzed based on monomer and comonomer content and intrinsic viscosity (iV).

[0071] Preferably, in the CRYSTEX QC analysis, the composition exhibits one or all of the following properties:

[0072] - A crystalline fraction (CF) content, determined by CRYSTEX QC analysis, in the range of 55.0 to 75.0 wt%, preferably 60.0 to 72.0 wt%, and

[0073] - A soluble fraction (SF) content, determined by CRYSTEX QC analysis, in the range of 25.0 to 45.0 wt%, preferably 28.0 to 40.0 wt%.

[0074] Preferably, the crystalline fraction (CF) has one or more of the following properties, preferably all of the following properties:

[0075] - An ethylene content (C2(CF)) determined by FT-IR spectroscopy calibrated by quantitative 13 C-NMR spectroscopy of less than 10.0 wt%, preferably 2.5 to 7.5 wt%; and / or

[0076] - An intrinsic viscosity (iV(CF)) measured in decalin at 135 °C according to DIN ISO 1628 / 1 of less than 1.8 dl / g, preferably 0.8 to 1.6 dl / g.

[0077] Preferably, the soluble fraction (SF) has one or more of the following properties, preferably all of the following properties:

[0078] - In the range of 45.0 to 65.0 wt%, preferably 46.0 to 63.0 wt% of 13Ethylene content (C2(SF)) determined by FT-IR spectroscopy calibrated by 13C-NMR spectroscopy; and / or

[0079] - Intrinsic viscosity (iV(SF)) measured in decalin at 135 °C according to DIN ISO 1628 / 1, greater than 1.6 dl / g, preferably 1.7 to 2.7 dl / g.

[0080] Preferably, the composition comprises from 12.5 to 32.5% by weight, more preferably from 15.0 to 30.0% by weight, still more preferably from 17.0 to 28.0% by weight of units derived from ethylene.

[0081] Preferably, the composition according to the invention exhibits an excellent balance of properties in terms of impact performance, thermal stability, flowability (which can be derived from the melt flow rate described above), especially mechanical properties (such as in terms of flexural modulus or tensile properties).

[0082] Preferably, the composition has a flexural modulus of from 1400 MPa to 2000 MPa, preferably from 1450 MPa to 1950 MPa.

[0083] Furthermore, preferably, the composition has a Charpy notched impact strength at 23 °C (CNIS at 23 °C) of from 20.0 kJ / m 2 to 65.0 kJ / m 2 , preferably from 21.0 kJ / m 2 to 60.0 kJ / m 2 .

[0084] Furthermore, preferably, the composition has a Charpy notched impact strength at -20 °C (CNIS at -20 °C) of from 4.0 kJ / m 2 to 10.0 kJ / m 2 , preferably from 4.5 kJ / m 2 to 7.5 kJ / m 2 .

[0085] Even more preferably, the composition has very good impact strength in an instrumented puncture test:

[0086] Preferably, the composition has a puncture energy measured at 23 °C of from 25 to 55 J, preferably from 30 to 50 J.

[0087] Preferably, the composition has a maximum force energy measured at 23 °C of from 15 to 45 J, preferably from 18 to 40 J.

[0088] Furthermore, preferably, the composition has a puncture energy measured at -30 °C of from 12 to 40 J, preferably from 13 to 38 J.

[0089] Preferably, the composition has a maximum force energy measured at -30 °C of 10 to 30 J, preferably 11 to 28 J.

[0090] Furthermore, preferably, the composition has a heat distortion temperature (ISO 75 B) of greater than 90 °C, preferably 91 °C to 110 °C.

[0091] Furthermore, preferably, the composition has a coefficient of linear thermal expansion (CLTE) of 60 to 100 μm / mK, preferably 65 to 90 μm / mK.

[0092] The composition according to the invention compulsorily contains the components (A), (B), (C) and (D) in the amounts described accordingly above or below.

[0093] The composition may optionally contain additional polymer components such that the composition can be obtained by blending the components (A), (B), (C) and one or more of the following components:

[0094] (E) 0 to 20 wt%, preferably 0 to 18 wt%, more preferably 0 to 17 wt% of a second multiphase propylene copolymer; and

[0095] (F) 0 to 10 wt%, preferably 0 to 9 wt%, more preferably 0 to 8 wt% of a propylene homopolymer;

[0096] wherein all percentages refer to the total composition, and wherein

[0097] the second multiphase propylene copolymer (E) comprises a matrix phase and an elastomeric phase dispersed therein and has

[0098] - a melt flow rate MFR of -2 to 10 g / 10 min, preferably 3 to 8 g / 10 min, more preferably 3.5 to 7.5 g / 10 min 2 (230 °C, 2.16 kg, ISO 1133);

[0099] - a soluble fraction (SF) content of greater than 20.0 to 50.0 wt%, preferably 21.0 to 45.0 wt% as determined by CRYSTEX QC analysis; and

[0100] - an intrinsic viscosity iV(SF) of the soluble fraction measured in decalin at 135 °C of 4.0 dl / g to 10.0 dl / g, preferably 4.5 to 9.5 dl / g, more preferably 5.0 to 9.0 dl / g according to DIN ISO 1628 / 1;

[0101] the propylene homopolymer (F) has

[0102] A melt flow rate MFR of -800 to 2000 g / 10 min, preferably 900 to 1600 g / 10 min, more preferably 1000 to 1500 g / 10 min 2 (230 °C, 2.16 kg, ISO 1133).

[0103] In one embodiment, the composition can be obtained by blending components (A), (B), (C) and (D), in the absence of (E) and (F),

[0104] (A) 15 wt% to 50 wt%, preferably 18 to 44 wt%, more preferably 20 to 40 wt% of a blended plastic polypropylene blend;

[0105] (B) 30 wt% to 50 wt%, preferably 32 to 47 wt%, more preferably 35 to 45 wt% of a multiphase propylene copolymer;

[0106] (C) 5 wt% to 25 wt%, preferably 7 to 23 wt%, more preferably 10 to 22 wt% of an ethylene-based plastomer, and

[0107] (D) 5 wt% to 25 wt%, preferably 7 to 22 wt%, more preferably 10 to 20 wt% of an inorganic filler,

[0108] wherein all percentages refer to the total composition.

[0109] In another embodiment, the composition can be obtained by blending components (A), (B), (C), (D) and (E), in the absence of (F),

[0110] (A) 15 wt% to 40 wt%, preferably 18 to 37 wt%, more preferably 20 to 38 wt% of a blended plastic polypropylene blend;

[0111] (B) 20 wt% to 50 wt%, preferably 22 to 47 wt%, more preferably 25 to 45 wt% of a multiphase propylene copolymer;

[0112] (C) 5 wt% to 25 wt%, preferably 7 to 23 wt%, more preferably 10 to 22 wt% of an ethylene-based plastomer;

[0113] (D) 5 wt% to 25 wt%, preferably 7 to 22 wt%, more preferably 10 to 20 wt% of an inorganic filler; and

[0114] (E) 5 to 20 wt%, preferably 7 to 18 wt%, more preferably 10 to 17 wt% of a second multiphase propylene copolymer,

[0115] wherein all percentages refer to the total composition.

[0116] In yet another embodiment, the composition can be obtained by blending components (A), (B), (C), (D) and (F), in the absence of (E),

[0117] (A) 15 wt% to 40 wt%, preferably 18 to 37 wt%, more preferably 20 to 38 wt% of a mixed plastic polypropylene blend;

[0118] (B) 20 wt% to 50 wt%, preferably 22 to 47 wt%, more preferably 25 to 45 wt% of a multiphase propylene copolymer;

[0119] (C) 5 wt% to 25 wt%, preferably 7 to 23 wt%, more preferably 10 to 22 wt% of an ethylene-based plastomer;

[0120] (D) 5 wt% to 25 wt%, preferably 7 to 22 wt%, more preferably 10 to 20 wt% of an inorganic filler; and

[0121] (F) 2 wt% to 10 wt%, preferably 3 to 9 wt%, more preferably 4 to 8 wt% of a propylene homopolymer,

[0122] wherein all percentages refer to the total composition.

[0123] Mixed plastic polypropylene blend (A)

[0124] The mixed plastic polypropylene blend (A) is suitable for characterization by CRYSTEX QC analysis. In the CRYSTEX QC analysis, a crystalline fraction (CF) and a soluble fraction (SF) are obtained that can be quantified and analyzed based on monomer and comonomer content and intrinsic viscosity (iV).

[0125] In the CRYSTEX QC analysis, the mixed plastic polypropylene blend (A) exhibits the following properties:

[0126] - A crystalline fraction (CF) content, as determined by CRYSTEX QC analysis, in the range of 85.0 to 96.0 wt%, preferably in the range of 86.5 to 95.5 wt%, more preferably in the range of 88.0 to 95.0 wt%; and

[0127] - A soluble fraction (SF) content, as determined by CRYSTEX QC analysis, in the range of 4.0 to 15.0 wt%, preferably in the range of 4.5 to 13.5 wt%, more preferably in the range of 5.0 to 12.0 wt%.

[0128] The crystalline fraction (CF) has one or more of the following properties, preferably all of the following properties:

[0129] - in the range of 1.0 to 10.0% by weight, preferably in the range of 1.5 to 9.5% by weight, more preferably in the range of 2.0 to 9.0% by weight, of ethylene content (C2(CF)) determined by FT-IR spectroscopy calibrated by quantitative 13 13C-NMR spectroscopy; and / or

[0130] - preferably in the range of 1.0 to less than 2.6 dl / g, more preferably in the range of 1.2 to 2.5 dl / g, still more preferably in the range of 1.3 to 2.4 dl / g, of intrinsic viscosity (iV(CF)) measured in decalin at 135 °C according to DIN ISO 1628 / 1.

[0131] The soluble fraction (SF) has one or more of the following properties, preferably all of the following properties:

[0132] - preferably in the range of 20.0 to 55.0% by weight, preferably in the range of 22.0 to 50.0% by weight, more preferably in the range of 24.0 to 48.0% by weight, of ethylene content (C2(SF)) determined by FT-IR spectroscopy calibrated by quantitative 13 13C-NMR spectroscopy; and / or

[0133] - 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, of intrinsic viscosity (iV(SF)) measured in decalin at 135 °C according to DIN ISO 1628 / 1.

[0134] Preferably, the mixed plastic polypropylene blend (A) comprises polypropylene and polyethylene.

[0135] Preferably, the weight ratio of polypropylene to polyethylene is from 19:1 to 7:3.

[0136] Preferably, the mixed plastic polypropylene blend (A) comprises more than 50 mol% of units derived from propylene.

[0137] Preferably, the mixed plastic polypropylene blend (A) comprises from 2.5 to 15.0% by weight, more preferably from 4.0 to 12.5% by weight, still more preferably from 5.0 to 10.0% by weight, of units derived from ethylene.

[0138] Furthermore, preferably, the mixed plastic polypropylene blend (A) has one or more of the following properties, preferably all of the following properties:

[0139] - Melt flow rate MFR of -8.0 to 40 g / 10 min, preferably 9.0 to 35 g / 10 min, more preferably 10.0 to 30 g / 10 min 2 (at 230 °C, 2.16 kg, ISO 1133); and / or

[0140] - Limonene content determined by using headspace solid-phase microextraction (HS-SPME-GC-MS): 0.1 ppm to 50 ppm; and / or

[0141] - Tensile modulus of 1000 MPa to 1500 MPa, preferably 1100 MPa to 1400 MPa; and / or

[0142] - 3.0 to 7.5 kJ / m 2 , preferably 4.0 to 7.0 kJ / m 2 of the notched Izod impact strength at 23 °C (CNIS at 23 °C).

[0143] The hybrid plastic polypropylene blend according to the invention preferably exists in the form of pellets. Pelletizing helps with low amounts of volatile substances.

[0144] Heterophasic propylene copolymer (B)

[0145] The multiphase polypropylene copolymer (B) comprises a matrix phase and an elastomeric phase dispersed therein.

[0146] The multiphase polypropylene copolymer (B) is characterized by

[0147] - Melt flow rate MFR of 85 to 250 g / 10 min, preferably 90 to 150 g / 10 min, more preferably 95 to 125 g / 10 min 2 (at 230 °C, 2.16 kg, ISO 1133);

[0148] - Solubles fraction (SF) content determined according to CRYSTEX QC analysis in the range of 20.0 to 30.0 wt%, preferably in the range of 21.0 to 28.0 wt%, more preferably in the range of 21.0 to 26.0 wt%; and

[0149] - Intrinsic viscosity iV(SF) of the solubles fraction measured in decalin at 135 °C according to DIN ISO 1628 / 1 of 2.0 dl / g to 4.5 dl / g, preferably 2.4 to 3.8 dl / g, more preferably 2.5 to 3.7 dl / g.

[0150] Preferably, the multiphase polypropylene copolymer (B) has one or more of the following properties, preferably all of the following properties:

[0151] - From 30 to 45% by weight, preferably from 32 to 40% by weight, more preferably from 33 to 38% by weight of the content of units derived from ethylene (C2) in the soluble fraction (SF); and / or

[0152] - From 0.1 to 5.0% by weight, preferably from 0.2 to 4.0% by weight, more preferably from 0.5 to 3.0% by weight of the content of units derived from ethylene (C2) in the crystalline fraction (CF); and / or

[0153] - From 5.0 to 15.0% by weight, preferably from 6.0 to 12.0% by weight, more preferably from 7.0 to 10.0% by weight of the total content of units derived from ethylene (C2); and / or

[0154] - From 0.8 to 2.0 dl / g, preferably from 0.9 to 1.8 dl / g of the intrinsic viscosity iV(CF) of the crystalline fraction measured according to the CRYSTEX QC analysis and measured in decalin at 135 °C according to DIN ISO 1628 / 1; and / or

[0155] - A melting temperature Tm of from 155 to 175 °C, preferably from 157 to 172 °C, more preferably from 160 to 170 °C; and / or

[0156] - A crystallization temperature Tc of from 120 to 140 °C, preferably from 122 to 137 °C, more preferably from 125 to 135 °C; and / or

[0157] - A tensile modulus of from 1250 MPa to 1800 MPa, preferably from 1300 MPa to 1750 MPa, more preferably from 1350 to 1700 MPa; and / or

[0158] - From 4.0 to 8.5 kJ / m 2 preferably from 5.0 to 7.0 kJ / m 2 of the Charpy notched impact strength at 23 °C (CNIS at 23 °C).

[0159] Preferably, the multiphase propylene copolymer (B) consists of propylene units and ethylene units.

[0160] Although not measured, the content of units derived from propylene (C3) in the soluble fraction (SF) and the content of units derived from ethylene (C2) in the soluble fraction (SF) preferably total 100% by weight.

[0161] Preferably, the content of units derived from propylene (C3) in the soluble fraction (SF) is in the range of from 55 to 70% by weight, more preferably in the range of from 60 to 68% by weight, still more preferably in the range of from 62 to 67% by weight.

[0162] Although not measured, the content of units derived from propylene (C3) in the crystalline fraction (CF) and the content of units derived from ethylene (C2) in the crystalline fraction (CF) preferably total 100% by weight.

[0163] Preferably, the content of units derived from propylene (C3) in the crystalline fraction (CF) is 95.0 to 99.9% by weight, more preferably 96.0 to 99.8% by weight, still more preferably 97.0 to 99.5% by weight.

[0164] Preferably, the total content of units derived from propylene (C3) in the multiphase propylene copolymer (B) is 85.0 to 95.0% by weight, more preferably 88.0 to 94.0% by weight, still more preferably 90.0 to 93.0% by weight.

[0165] These multiphase propylene copolymers are commercially available.

[0166] Ethylene-based plastomer (C)

[0167] Preferably, the ethylene-based plastomer (C) is a copolymer of ethylene and comonomer units selected from α-olefins having 3 to 12 carbon atoms, preferably α-olefins having 4 to 10 carbon atoms, most preferably 1-butene or 1-octene.

[0168] The ethylene-based plastomer is usually added to further improve the impact properties of the composition.

[0169] Preferably, the ethylene-based plastomer (C) has one or more of the following properties, preferably all of the following properties:

[0170] - A melt flow rate MFR of 0.2 to 2.5 g / 10 min, preferably 0.3 to 2.0 g / 10 min 2 (190 °C, 2.16 kg, ISO 1133); and

[0171] - A density of 850 to 870 kg / m 3 , preferably 855 to 865 kg / m 3 of the density.

[0172] These ethylene-based plastomers are commercially available under the trade names Engage, Exact, Queo, Tafmer, etc.

[0173] Inorganic filler (D)

[0174] Preferably, the inorganic filler (D) is talc.

[0175] Preferably, the inorganic filler (preferably talc) (D) has a median particle size d before compounding of from 0.3 to 30.0 µm, more preferably from 0.5 to 15.0 µm 50 .

[0176] Furthermore, preferably, the inorganic filler (preferably talc) (D) has a top cut particle size d before compounding of from 1.0 to 50.0 µm, preferably from 1.5 to 35.0 µm 95 .

[0177] These inorganic fillers are commercially available.

[0178] Additive

[0179] Additives are generally used in the compositions according to the invention. Preferably, the additives are selected from one or more of antioxidants, UV stabilizers, slip agents, nucleating agents, pigments, lubricants, masterbatch polymers and / or anti-fogging agents.

[0180] Based on the total composition, the additives are generally present in the composition in an amount of from 0.01 to 4.0% by weight, preferably from 0.05 to 3.0% by weight.

[0181] Second heterophasic propylene copolymer (E)

[0182] The optional polypropylene copolymer (E) comprises a matrix phase and an elastomeric phase dispersed therein.

[0183] If a second polypropylene copolymer (E) is present in the composition, preferably, the second polypropylene copolymer (E) has a melt flow rate lower than that of the polypropylene copolymer (B).

[0184] The optional second polypropylene copolymer (E) has a melt flow rate MFR of from 2 to 10 g / 10 min, preferably from 3 to 8 g / 10 min, more preferably from 4 to 7 g / 10 min 2 (230 °C, 2.16 kg, ISO 1133).

[0185] Furthermore, the optional second polypropylene copolymer (E) has a soluble fraction (SF) content determined according to CRYSTEX QC analysis in the range of greater than 20.0 to 50.0% by weight, preferably in the range of 21.0 to 45.0% by weight, more preferably in the range of 22.0 to 40.0% by weight.

[0186] Preferably, the soluble fraction has an intrinsic viscosity iV(SF) measured in decalin at 135 °C according to DIN ISO 1628 / 1 in the range from 4.0 dl / g to 10.0 dl / g, preferably from 4.5 to 9.5 dl / g, more preferably from 5.0 to 9.0 dl / g.

[0187] Preferably, the optional second multiphase propylene copolymer (E) has a crystalline fraction (CF) content determined by CRYSTEX QC analysis in the range from 50.0 to 80.0% by weight, preferably from 55.0 to 79.0% by weight, more preferably from 60.0 to 78.0% by weight.

[0188] Preferably, the optional second multiphase propylene copolymer (E) has one or more of the following properties, preferably all of the following properties:

[0189] - a content of units derived from ethylene (C2) in the soluble fraction (SF) in the range from 25 to 35% by weight, preferably from 27 to 34% by weight, more preferably from 28 to 33% by weight; and / or

[0190] - a content of units derived from ethylene in the crystalline fraction (CF) in the range from 0.5 to 7.5% by weight, preferably from 1.0 to 5.0% by weight, more preferably from 1.5 to 4.0% by weight; and / or

[0191] - a total content of units derived from ethylene in the range from 4.0 to 15.0% by weight, preferably from 5.0 to 12.0% by weight, more preferably from 6.0 to 10.0% by weight; and / or

[0192] - an intrinsic viscosity iV(CF) of the crystalline fraction determined by CRYSTEX QC analysis and measured in decalin at 135 °C according to DIN ISO 1628 / 1 in the range from 1.8 to 3.5 dl / g, preferably from 2.0 to 3.0 dl / g; and / or

[0193] - a melting temperature Tm in the range from 155 to 175 °C, preferably from 157 to 172 °C, more preferably from 160 to 170 °C; and / or

[0194] - a crystallization temperature Tc in the range from 105 to 125 °C, preferably from 107 to 122 °C, more preferably from 110 to 120 °C.

[0195] Preferably, the optional multiphase propylene copolymer (E) consists of propylene units and ethylene units.

[0196] Although not measured, the content of units derived from propylene (C3) in the soluble fraction (SF) and the content of units derived from ethylene (C2) in the soluble fraction (SF) preferably total 100% by weight.

[0197] Preferably, the content of units derived from propylene (C3) in the soluble fraction (SF) is 65 to 75% by weight, more preferably 66 to 73% by weight, still more preferably 67 to 72% by weight.

[0198] Although not measured, the content of units derived from propylene (C3) in the crystalline fraction (CF) and the content of units derived from ethylene (C2) in the crystalline fraction (CF) preferably total 100% by weight.

[0199] Preferably, the content of units derived from propylene (C3) in the crystalline fraction (CF) is 92.5 to 99.5% by weight, more preferably 95.0 to 99.0% by weight, still more preferably 96.0 to 98.5% by weight.

[0200] Preferably, the total content of units derived from propylene (C3) in the multiphase propylene copolymer (B) is 85.0 to 96.0% by weight, more preferably 88.0 to 95.0% by weight, still more preferably 90.0 to 94.0% by weight.

[0201] Preferably, the optional multiphase propylene copolymer (E) has a tensile modulus of 800 MPa to 1200 MPa, preferably 850 MPa to 1150 MPa.

[0202] Furthermore, preferably, the optional multiphase propylene copolymer (E) has a Charpy notched impact strength (CNIS, 23 °C) at 23 °C of 25 to 75 kJ / m 2 , preferably 35 to 60 kJ / m 2 of the Charpy notched impact strength (CNIS, 23 °C) at 23 °C.

[0203] These multiphase propylene copolymers are commercially available.

[0204] Polypropylene homopolymer (F)

[0205] Preferably, the optional propylene homopolymer (F) has a very high melt flow rate MFR of 800 to 2000 g / 10 min, preferably 900 to 1600 g / 10 min, more preferably 1000 to 1500 g / 10 min 2 (230 °C, 2.16 kg, ISO 1133).

[0206] Furthermore, preferably, the optional propylene homopolymer (F) has a melting temperature Tm measured by DSC according to ISO 11357-3 of 150 to 170 °C, preferably 155 to 166 °C.

[0207] These propylene homopolymers are usually added to further improve the fluidity of the composition.

[0208] These propylene homopolymers are commercially available.

[0209] Product

[0210] On the other hand, the present invention relates to an article comprising the composition as described above or below, preferably a molded article, more preferably a molded automotive article.

[0211] Preferably, the article is used on the exterior of a vehicle.

[0212] Preferably, the article exhibits paint adhesion with a coated area evaluated as failed or delaminated.

[0213] Preferably, the article has a failed or delaminated coated area of less than 50 mm 2 , preferably 0 to 45 mm 2 of the failed or delaminated coated area.

[0214] Use

[0215] In another aspect, the present invention relates to the use of the composition as described above or below for injection molding of articles, preferably automotive articles, more preferably automotive exterior articles.

[0216] Experimental section

[0217] The following examples are included to illustrate certain aspects and embodiments of the present invention as set forth in the claims. However, those skilled in the art should understand that the following description is merely illustrative and should not be construed as limiting the present invention in any way.

[0218] Test methods

[0219] a) CRYSTEX

[0220] Determination of the crystalline fraction and the soluble fraction and their respective properties (IV and ethylene content)

[0221] By using a CRYSTEX instrument, Polymer Char (Valencia, Spain) analyzes the crystalline fraction (CF) and the soluble fraction (SF) of polypropylene (PP) compositions, as well as the comonomer content and intrinsic viscosity of each fraction. Details of the technique and method can be found in the literature (Ljiljana Jeremic, Andreas Albrecht, Martina Sandholzer & Markus Gahleitner (2020) Rapid characterization of high-impact ethylene–propylene copolymer composition by crystallization extraction separation: comparability to standard separation methods, International Journal of Polymer Analysis and Characterization, 25:8, pp. 581-596).

[0222] The crystalline and amorphous fractions were separated by a temperature cycle of dissolution at 160 °C, crystallization at 40 °C, and re-dissolution at 160 °C in 1,2,4-trichlorobenzene. Quantification of SF and CF and determination of ethylene content (C2) were achieved by an integrated infrared detector (IR4), and the intrinsic viscosity (iV) was measured using an on-line 2-capillary viscometer.

[0223] The IR4 detector is a multi-wavelength detector that detects IR absorbance at two different bands (CH 3 stretching vibration (centered at approximately 2960 cm -1 −1) and CH stretching vibration (2700 to 3000 cm -1 −1)), and the IR absorbance at these two different bands is used to determine the concentration and ethylene content in ethylene-propylene copolymers. The IR4 detector was calibrated with a series of 8 EP copolymers having known ethylene contents in the range of 2 wt% to 69 wt% (determined by 13 13C-NMR spectroscopy), and each EP copolymer used for calibration had multiple concentrations between 2 and 13 mg / ml. To simultaneously experience the two characteristics, concentration and ethylene content, of polymers at various concentrations during Crystex analysis, the following calibration equation was applied:

[0224] Concentration = a + b * Absorbance(CH) + c * (Absorbance(CH)) 2 + d * Absorbance(CH 3 ) + e * Absorbance(CH3 ) 2 + f × Absorbance(CH) × Absorbance(CH 3 ) (Equation 1)

[0225] CH 3 / 1000C = a + b × Absorbance(CH) + c × Absorbance(CH 3 ) + d × (Absorbance(CH 3 ) / Absorbance(CH)) + e × (Absorbance(CH 3 ) / Absorbance(CH)) 2 (Equation 2)

[0226] The constants a to e of Equation 1 and the constants a to f of Equation 2 are determined by using least squares regression analysis.

[0227] Using the following relationship, CH 3 / 1000C is converted to the ethylene content in wt%:

[0228] wt% (ethylene in EP copolymer) = 100 - CH 3 / 1000TC × 0.3 (Equation 3)

[0229] The amounts of the soluble fraction (SF) and the crystalline fraction (CF) are related to the amounts of "xylene cold soluble" (XCS) and the xylene cold insoluble (XCI) fraction determined by the standard gravimetric method according to ISO 16152 through XS calibration. The XS calibration is achieved by testing various EP copolymers with XS contents in the range of 2 to 31 wt%. The determined XS calibration is linear:

[0230] wt% XS = 1.01 × wt% SF (Equation 4)

[0231] The intrinsic viscosities (iV) of the parent EP copolymer and its soluble and crystalline fractions are determined using an on-line 2-capillary viscometer and correlated with the corresponding iV determined by the standard method in decalin according to ISO 1628-3. Calibration is achieved using various EP PP copolymers with iV = 2 to 4 dL / g. The determined calibration curve is linear:

[0232] iV (dL / g) = a × Vsp / c (Equation 5)

[0233] Weigh out the samples to be analyzed at a concentration of 10 mg / ml to 20 mg / ml. To avoid injecting gels and / or polymers that are insoluble in TCB at 160 °C, such as PET and PA, the weighed samples are extruded through a stainless steel mesh MW 0.077 / D 0.05 mm m.

[0234] After automatically filling the vials with 1,2,4-TCB containing 250 mg / l of 2,6-di-tert-butyl-4-methylphenol (BHT) as antioxidant, the sample was dissolved at 160 °C until completely dissolved, usually for 60 min, with continuous stirring at 400 rpm. To avoid sample degradation, the polymer solution was covered with an N2 atmosphere during dissolution.

[0235] A defined volume of the sample solution was injected into a column filled with an inert support, where crystallization of the sample and separation of the soluble fraction from the crystalline part took place. This process was repeated twice. During the first injection, the entire sample was 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 the crystalline fraction (CF) (at high temperature) (wt% SF, wt% C2, iV) were measured using a crystallization cycle.

[0236] b) Cold xylene soluble fraction (XCS, wt%)

[0237] The cold xylene soluble fraction (XCS) was determined at 25 °C according to ISO 16152; First edition; 2005-07-01. The fraction remaining insoluble was the cold xylene insoluble (XCI) fraction.

[0238] c) Intrinsic viscosity

[0239] The intrinsic viscosity was measured according to DIN ISO 1628 / 1, October 1999 (in decalin, at 135 °C).

[0240] d) Izod notched impact strength

[0241] Determined according to ISO 179-1eA at +23 °C and -20 °C on injection molded specimens of 80×10×4 mm 3 prepared according to EN ISO 1873-2. The measurement was carried out after a conditioning time of 96 h at 23 °C on the specimens.

[0242] e) Flexural modulus

[0243] The flexural modulus was determined according to ISO 178 at a test speed of 2 mm / min and a force of 100 N on test specimens of dimensions 80×10×4 mm 3 (length × width × thickness) prepared by injection molding according to EN ISO 1873-2, where the span length between the supports was 64 mm.

[0244] f) Tensile modulus

[0245] Measured according to ISO 527-2 (crosshead speed = 1 mm / min; test speed at 23° C. is 50 mm / min) using injection molded test specimens 1B (dog bone shape, 4 mm thick) prepared as described in EN ISO 1873-2. The measurement is carried out after a conditioning time of 96 hours at 23° C. of the sample.

[0246] g) Instrumented puncture test

[0247] The instrumented puncture test was performed according to ISO6603-2:2000 at 23°C and -30°C on a 60×60×3 mm 3 The measurements were carried out on injection-molded plaques of 1.30 °C. The measurements were carried out after a conditioning time of 96 hours at 23 °C of the samples.

[0248] h) Comonomer content

[0249] Poly(propylene-co-ethylene)-ethylene content-IR spectroscopy

[0250] Quantitative infrared (IR) spectroscopy was used to quantify the ethylene content of poly(ethylene-co-propylene) copolymers by calibration to the primary method. 13 In-house non-commercial calibration standards of known ethylene content, determined by C solution state nuclear magnetic resonance (NMR) spectroscopy, facilitate calibration. The calibration procedure was performed in a conventional manner well documented in the literature. The calibration set consisted of 38 calibration standards with ethylene contents ranging from 0.2 to 75.0 wt %, produced at pilot or full scale under a variety of conditions. The calibration set was selected to reflect the typical types of copolymers encountered by the final quantitative IR spectroscopy.

[0251] Solid-state quantitative IR spectra were recorded using a Bruker Vertex 70 FTIR spectrometer. Spectra were recorded at 180 to 210°C and 4 to 6 MPa on 300 μm thick 25×25 mm square films prepared by compression molding. For samples with very high ethylene content (>50 mol%), 100 μm thick films were used. A standard transmission FTIR spectrometer was used using a 5000-500 cm -1 spectral range, 6mm hole, 2cm -1 spectral resolution, 16 background scans, 16 spectral scans, an interferogram zero filling factor of 64, and the Blackmann-Harris 3-term apodization method. 2 ) >2 The structural unit is between 730 and 720 cm -1 (A Q ) 2 Total area of ​​rocking deformation (integration method G, limits 762 and 694 cm-1 ) Perform quantitative analysis. The quantitative band is normalized to the area of the CH band corresponding to the CH structural unit at 4323 cm -1 (A R ) (integration method G, limits 4650, 4007 cm -1 ). Then, the ethylene content in weight percentage is predicted from the normalized absorbance (A Q / A R ) using a quadratic calibration curve. This calibration curve has been previously constructed by ordinary least squares (OLS) regression of the normalized absorbance and the major comonomer content measured on the calibration set.

[0252] Poly(propylene-co-ethylene) - Ethylene content - 13 CNMR spectroscopy

[0253] Quantitative 1 H and 13 C NMR spectra are recorded in solution state using a Bruker Avance III 400 NMR spectrometer operating at 400.15 and 100.62 MHz for 13 C{ 1 H} NMR spectroscopy, respectively. Nitrogen is used for all pneumatic devices and all spectra are recorded at 125 °C using a 13 C-optimized 10 mm extended temperature probe. Approximately 200 mg of the material is dissolved in 3 ml of 1,2-tetrachloroethane-d 3 (TCE-d 2 ) together with chromium(III) acetylacetonate (Cr(acac) 2 ) to obtain a 65 mM solution of the relaxant in the solvent (Singh, G., Kothari, A., Gupta, V., Polymer Testing 28 5 (2009), 475).

[0254] To ensure a homogeneous solution, after initial sample preparation in a heating block, the NMR tube is further heated in a spinning oven for at least 1 hour. After insertion into the magnet, the tube is spun at 10 Hz. This setting is chosen mainly for high resolution and accurate ethylene content quantification, which is required quantitatively. Standard single pulse excitation without NOE is used, with an optimized tip angle, a 1 s recycle delay, and a two-stage WALTZ16 decoupling scheme (Zhou, Z. et al., J. Mag. Reson. 187 (2007) 225, and Busico, V. et al., Macromol. Rapid Commun. 2007, 28, 1128). A total of 6144 (6k) transients are acquired for each spectrum. For quantitative 13 C{ 1The {H} NMR spectra were processed, integrated, and the relevant quantitative properties were determined from the integrals. Using the chemical shift of the solvent, all chemical shifts were indirectly referenced to the central methylene group of the ethylene block (EEE) at 30.00 ppm. Even if this structural unit was absent, this method allowed for comparable referencing. Characteristic signals corresponding to the incorporation of ethylene were observed (Cheng, H. N., Macromolecules 17 (1984), 1950), and the comonomer fraction was calculated as the fraction of ethylene in the polymer relative to all monomers in the polymer: fE = (E / (P + E)). Using the method of Wang et al. (Wang, W-J., Zhu, S., Macromolecules 33 (2000), 1157), the comonomer fraction was quantified by the integration of multiple signals over the entire spectral area in the 13 C{ 1 H} spectrum. This method was chosen because of its robustness and the ability to account for the presence of area defects when needed. The integrated areas were slightly adjusted to improve applicability over the entire range of comonomer contents encountered. For systems where only isolated ethylene with very low ethylene content in the PPEPP sequence was observed, the method of Wang et al. was modified to reduce the influence of the integration of sites that were no longer present. This method reduced the overestimation of the ethylene content in such systems and was achieved by reducing the number of sites used to determine the absolute ethylene content to the following: E = 0.5(Sββ + Sβγ + Sβδ + 0.5(Sαβ + Sαγ)). By using this set of sites, the corresponding integration equation became: E = 0.5(I H + I G + 0.5(I C + I D ). The same symbols used in the article by Wang et al. (Wang, W-J., Zhu, S., Macromolecules 33 (2000), 1157) were used. The equation for the absolute propylene content was not modified. The mole percent of comonomer incorporation was calculated from the mole fraction: E [mol%] = 100*fE. The weight percent of comonomer incorporation was calculated from the mole fraction: E [wt%] = 100*(fE*28.06) / ((fE*28.06)+((1 - fE)*42.08)).

[0255] i) Comonomer content

[0256] Using the film thickness method, using the intensity of the quantitative band I(q) and the thickness of the pressed film T, the content was determined using the following relationship: [I(q) / T]m + c = C, where m and c are coefficients determined from a calibration curve constructed using the comonomer content obtained from the 13 C-NMR spectrum.

[0257] The comonomer content was measured in a known manner based on Fourier transform infrared spectroscopy (FTIR) calibrated with 13 C-NMR using a Nicolet Magna 550IR spectrometer and Nicolet Omnic FTIR software. Films with a thickness of approximately 250 μm were compression molded from the samples. Similar films were made from calibration samples with known comonomer contents. The comonomer content was determined from spectra in the wavenumber range of 1430 to 1100 cm -1 . The absorbance was measured as the height of the peak by selecting a so-called short baseline or long baseline or both. The short baseline was drawn through the lowest point at approximately 1410 to 1320 cm -1 , and the long baseline was drawn between approximately 1410 and 1220 cm -1 . Special calibration was required for each baseline type. In addition, the comonomer content of the unknown sample was within the comonomer content range of the calibration samples.

[0258] j) MFR

[0259] The melt flow rate (MFR 2 ) was measured at 230 °C (polypropylene-based materials) or 190 °C (polyethylene-based materials) under a load of 2.16 kg. The melt flow rate is the amount of polymer extruded in 10 minutes at a temperature of 230 °C (or 190 °C) under a load of 2.16 kg using the test equipment according to ISO 1133, and the unit is grams.

[0260] k) Density

[0261] The density was measured according to ISO 1183-187. Sample preparation was carried out by compression molding according to ISO 1872-2:2007.

[0262] 1) Heat distortion temperature (HDT)

[0263] The HDT was determined on injection molded test specimens of 80×10×4 mm 3 prepared according to ISO 1873-2, and stored at +23 °C for at least 96 hours before measurement. The horizontally supported specimens were tested according to ISO 75, Condition B, with a nominal surface stress of 0.45 MPa.

[0264] m) Coefficient of linear thermal expansion (CLTE)

[0265] The coefficient of linear thermal expansion (CLTE) was determined on 10 mm long pieces of 20 cut from the same injection molded specimens used for the determination of the tensile modulus according to ISO 11359-2:1999. The measurements were carried out longitudinally (MD) at a heating rate of 1 °C / min in the temperature range from -30 to +80 °C and at a heating rate of 1 °C / min in the temperature range from 23 to +80 °C.

[0266] n) Coating adhesion

[0267] Adhesion is characterized as the resistance of decorative coatings (such as paints) when subjected to a high-pressure cleaner wash under certain conditions as described below.

[0268] Injection molded sample plates (150 mm × 80 mm × 3 mm) were produced at a melt temperature of 240 °C and a mold temperature of 50 °C. The flow front velocity was 100 mm / s. Before coating, the plates were cleaned with Zeller Gmelin mm / s for 5 minutes. Subsequently, the surface was activated by combustion, where a burner dispersed a mixture of propane (9 l / min) and air (180 l / min) in a ratio of 1:20 at a speed of 670 mm / s onto the polymer substrate. After that, the polymer substrate was coated with 3 layers, namely a primer, a base coat (black), and a clear coat. The combustion step was carried out twice.

[0269] The decorative coating was cut down to the substrate with a cutting tool to a total depth of approximately 500 □m (including the coating and the substrate), and a cross was formed with 100 mm long branches. On each coated substrate, 3 lines with corresponding crosses were cut. The cut area was further exposed to hot water vapor at a temperature of T, which was directed at an angle α to the surface of the test plate at a distance d for a time t. The pressure of the water jet was generated by the water flow rate and determined by the type of nozzle installed at the end of the water pipe.

[0270] The following parameters were used:

[0271] T (water) = 68 °C; t = 30 s; d = 100 mm, α = 90°, water pressure 65 bar, nozzle type = Walter 13 / 32.

[0272] Adhesion was evaluated by quantifying the coated area of failure or delamination for each test line, in units of mm 2 . For each example, 5 plates (150 mm × 80 mm × 3 mm) were tested. For this purpose, images of the test lines were taken before and after exposure to the steam jet. Then, the delamination area was calculated using image processing software. The average non-conforming area of the 3 test lines on 5 test specimens (i.e., the average of a total of 15 test points) was recorded as the average non-conforming area. The SD is the standard deviation determined according to the following formula:

[0273]

[0274] Wherein:

[0275] x is the observed value;

[0276] is the average value of the observed values; and

[0277] n is the number of observations.

[0278] Experiment

[0279] Catalyst system:

[0280] For the polymerization process of HECO 1, the invention examples for WO 2016 / 066446 A1 were used and described as a Ziegler-Natta type catalyst nucleated with poly(vinylcyclohexane) by pre-polymerization with vinylcyclohexane.

[0281] The nucleation by pre-polymerization with vinylcyclohexane is described in detail in EP 2 960 256 B1 and EP 2 960 279 B1. These documents are incorporated by reference.

[0282] For the polymerization processes of HECO 2 and HECO 3, a conventional transesterification high-yield MgCl 2 supported Ziegler-Natta polypropylene catalyst component containing diethyl phthalate as an internal donor was used. The catalyst component and its preparation are generally described in, for example, patent publications EP491566, EP591224, and EP586390.

[0283] Therefore, the catalyst component was prepared as follows: First, at atmospheric pressure, 0.1 mole of MgCl 2 x 3EtOH was suspended in 250 ml of decane in the reactor under inert conditions. The solution was cooled to -15°C, and 300 ml of cold TiCl 4 was added while maintaining the temperature at this temperature. Then, the temperature of the slurry was slowly raised to 20°C. At this temperature, 0.02 mole of dioctyl phthalate (DOP) was added to the slurry. After the addition of the phthalate, the temperature was raised to 135°C within 90 minutes, and the slurry was allowed to stand for 60 minutes. Then, another 300 ml of TiCl 4 was added, and the temperature was maintained at 135°C for 120 minutes. Thereafter, the catalyst was filtered out from the liquid and washed six times with 300 ml of heptane at 80°C. Then, the solid catalyst component was filtered out and dried.

[0284] HECO 1, HECO 2, and HECO 3 are prepared in a prepolymerization / loop reactor / gas phase reactor 1 / gas phase reactor 2 / gas phase reactor 3 configuration, followed by a pelletizing step. The catalyst system defined above is used in combination with triethylaluminum (TEAL) as a cocatalyst and dicyclopentadienyl-dimethoxysilane (Donor D) as an external donor.

[0285] Table 1: Preparation of HECO 1, HECO 2, and HECO 3

[0286]

[0287]

[0288] The multiphase copolymers HECO 1, HECO 2, and HECO 3 are compounded in a co-rotating twin-screw extruder Coperion ZSK 47 at 220 °C with 0.15 wt% antioxidant (Irganox B215FF, from BASF AG, Germany; this is a 1:2 mixture of pentaerythritol tetrakis(3-(3’,5’-di-tert-butyl-4-hydroxyphenyl)propionate) (CAS-number 6683-19-8) and tris(2,4-di-tert-butylphenyl) phosphite (CAS-number 31570-04-4)); 0.05 wt% calcium stearate (CAS-number 1592-23-0, commercially available from Faci, Italy). The CRYSTEX QC analysis of these three copolymers gives the results listed in Table 2.

[0289] Table 2: CRYSTEX QC Analysis of HECO 1, HECO 2, and HECO 3

[0290] HECO 1 HECO 2 HECO 3 CF wt% 78.0 85.3 78.2 C2(CF) wt% 1.1 2.4 2.0 iV(CF) dl / g 1.0 1.2 1.8 SF wt% 22.0 14.7 23.3 C2(SF) wt% 35.0 39.5 23 iV(SF) dl / g 3.4 3.1 5.5

[0291] Table 3 shows the properties of the polypropylene / polyethylene blend (A) used for evaluation. Since these compositions are from a mechanical recycling process, the properties are indicated as ranges.

[0292] Table 3: Properties of the Polypropylene / Polyethylene Blend (Blend A)

[0293]

[0294]

[0295] Plastomer 1 is Engage HM 7487, which has a density of 860 kg / m 3 and an MFR 2(2.16 kg, 190 °C, ISO1133) is an ethylene-1-butene plastomer commercially available from The Dow Chemical Company with a melt flow rate of less than 0.5 g / 10 min.

[0296] Plastomer 2 is Engage 8842, which has a density of 857 kg / m 3 and an MFR 2 (2.16 kg, 190 °C, ISO1133) of 1.0 g / 10 min and is an ethylene-1-octene plastomer commercially available from The Dow Chemical Company.

[0297] Talc 1 is Jetfine 3CA, with a d 50 of 1.2 μm and a d 95 of 3.3 μm (measured by sedimentation diagram), and is commercially available from IMERYS in France.

[0298] Talc 2 is Luzenac HAR T84, with a d 50 of 2.0 μm and a d 95 of 10.0 μm (measured by sedimentation diagram), and is commercially available from IMERYS.

[0299] PP-Homo is a commercially available propylene homopolymer HL712FB, with an MFR 2 (2.16 kg, 230 °C, ISO1133) of 1200 g / 10 min and a Tm (DSC, ISO 11357-3) of 158 °C.

[0300] The final composition was compounded at 220 °C in a Coperin ZSK40 twin-screw extruder using the polymer, talc, and antioxidants, UV-stabilizers, slip agents, nucleating agents, carbon black masterbatch, calcium stearate, and anti-fog agents. The compositions of the examples are shown in Table 4.

[0301] Table 4: Compositions of the examples

[0302]

[0303]

[0304] Table 5 shows the properties of the examples.

[0305] Table 5: Properties of the examples

[0306] CE1 CE2 IE1 IE2 IE3 IE4 <![CDATA[MFR 2 , g / 10min]]> 20 10.5 17 12 25 40 C2(Comp), wt% 19.1 21.4 20.8 18.0 26.1 20.1 iV(Comp), dl / g 1.78 1.89 1.67 1.84 1.41 1.43 CF(CRYSTEX), wt% 66.1 66.4 66.7 69.7 63.0 69.0 C2(CF), wt% 3.1 5.5 5.6 5.2 5.5 4.2 iV(CF), dl / g 1.26 1.70 1.38 1.52 1.22 1.22 SF(CRYSTEX), wt% 33.9 33.6 33.3 30.3 37.0 31.0 C2(SF), wt% 53.5 54.5 52.5 47.3 62.0 58.0 iV(SF), dl / g 2.60 2.3 2.25 2.55 1.78 1.92 Flexural modulus, MPa 1760 1571 1595 1644 1526 1918 Tensile modulus, MPa 1684 1465 1531 1596 n.m. n.m. <![CDATA[Simply supported beam NIS, +23 °C, kJ / m 2 > 27 51 35 45 47 22 <![CDATA[Simply supported beam NIS, -20 °C, kJ / m 2 > 5.8 5.9 5.2 5.0 6.7 4.6 Maximum force energy, +23°C, J 21 21 21 21 20 21 Puncture energy, +23°C, J 36 37 34 37 35 38 Maximum force energy, -30°C, J 28 24 17 12 26 19 Puncture energy, -30°C, J 31 26 19 14 32 19 HDT(ISO 75B), °C 102 92 97 98 92 104 CLTE, +23 / 80°C, μm / mK, MD 73 74 80 83 70 79 <![CDATA[Stratified spraying area, mm 2 > 25 2 6 8 22 44

[0307] n.m. = not measured

[0308] Example IE2 shows that by using HECO 1 to replace HECO 2 in CE2, better mechanical properties, better thermal stability, and comparable impact properties, fluidity, and good paint adhesion can be obtained.

[0309] Example IE1 shows that omitting HECO 3 can further increase fluidity without sacrificing other properties.

[0310] The addition of PP-Homo in Examples IE3 and IE4 shows an increase in fluidity. Thus, when a lower amount of plastomer is used in IE4, very good mechanical properties and thermal stability can be obtained. However, the addition of PP-Homo comes at the cost of impaired coatability.

Claims

1. A composition suitable for automotive applications, The composition can be obtained by blending at least components (A), (B), (C) and (D) (A) 15 wt% to 50 wt% of a mixed plastic polypropylene blend, wherein the mixed plastic polypropylene blend is derived from post-consumer waste and / or industrial waste and comprises polypropylene and polyethylene; (B) 20 wt% to 50 wt% of a multiphase propylene copolymer; (C) 5 wt% to 25 wt% of an ethylene-based plastomer, and (D) 5 wt% to 25 wt% of an inorganic filler; wherein all percentages refer to the total composition, and wherein the mixed plastic polypropylene blend (A) has - a crystalline fraction CF content in the range of 85.0 to 96.0 wt% determined by temperature cycling of dissolving at 160 °C, crystallizing at 40 °C and redissolving at 160 °C in 1,2,4-trichlorobenzene to separate the crystalline fraction CF and analyzed according to CRYSTEX QC, and - a soluble fraction SF content in the range of 4.0 to 15.0 wt% determined by temperature cycling of dissolving at 160 °C, crystallizing at 40 °C and redissolving at 160 °C in 1,2,4-trichlorobenzene to separate the soluble fraction SF and analyzed according to CRYSTEX QC, wherein - The crystalline fraction CF has 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; and - the soluble fraction SF has an intrinsic viscosity iV(SF) measured in decalin at 135 °C in the range of 0.9 to 2.1 dl / g according to DIN ISO 1628 / 1; the multiphase propylene copolymer (B) comprises a matrix phase and an elastomeric phase dispersed therein, and has - Melt flow rate MFR measured according to ISO 1133 at 230 °C and 2.16 kg of 85 to 250 g / 10 min 2 ; - a soluble fraction SF content in the range of greater than 20.0 wt% to 30.0 wt% determined by temperature cycling of dissolving at 160 °C, crystallizing at 40 °C and redissolving at 160 °C in 1,2,4-trichlorobenzene to separate the soluble fraction SF and analyzed according to CRYSTEX QC; and - an intrinsic viscosity iV(SF) of the soluble fraction measured in decalin at 135 °C in the range of 2.0 dl / g to 4.5 dl / g according to DIN ISO 1628 / 1; the ethylene-based plastomer (C) is a copolymer of ethylene and comonomer units selected from α-olefins having 3 to 12 carbon atoms, and the ethylene-based plastomer (C) has -0.2 to 2.5 g / 10 min of melt flow rate MFR determined according to ISO 1133 at 190 °C and 2.16 kg 2 ; and -850 to 870 kg / m 3 of density; The composition has - 8 to 50 g / 10 min melt flow rate (MFR) measured according to ISO 1133 at 230 °C and 2.16 kg 2 .

2. The composition according to claim 1, wherein the composition can be obtained by blending components (A), (B), (C), (D) and one or more of the following components (E) 0 to 20 wt% of a second multiphase propylene copolymer; and (F) 0 to 10 wt% of a propylene homopolymer; wherein all percentages refer to the total composition, and wherein the second multiphase propylene copolymer (E) comprises a matrix phase and an elastomeric phase dispersed therein, and has - 2 to 10 g / 10 min melt flow rate (MFR) measured according to ISO 1133 at 230 °C and 2.16 kg 2 ; - a soluble fraction SF content of greater than 20.0 to 50.0% by weight, separated by a temperature cycle of dissolving at 160 °C, crystallizing at 40 °C and redissolving at 160 °C in 1,2,4-trichlorobenzene and determined according to CRYSTEX QC analysis; and - an intrinsic viscosity iV(SF) of the soluble fraction measured in decalin at 135 °C according to DIN ISO 1628 / 1 in the range of 4.0 dl / g to 10.0 dl / g; The propylene homopolymer (F) has - 800 to 2000 g / 10 min melt flow rate (MFR) measured according to ISO 1133 at 230 °C and 2.16 kg 2 .

3. The composition according to claim 2, wherein the composition can be obtained by blending components (A), (B), (C) and (D), in the absence of the second multiphase propylene copolymer (E) and the propylene homopolymer (F), (A) 15% to 50% by weight of a mixed plastic polypropylene blend; (B) 30% to 50% by weight of a multiphase propylene copolymer; (C) 5% to 25% by weight of an ethylene-based plastomer and (D) 5% to 25% by weight of an inorganic filler.

4. The composition according to claim 2, wherein the composition can be obtained by blending components (A), (B), (C), (D) and (E), in the absence of the propylene homopolymer (F), (A) 15% to 40% by weight of a mixed plastic polypropylene blend; (B) 20% to 50% by weight of a multiphase propylene copolymer; (C) 5% to 25% by weight of an ethylene-based plastomer; (D) 5% to 25% by weight of an inorganic filler; and (E) 5% to 20% by weight of a second multiphase propylene copolymer.

5. The composition according to claim 2, wherein the composition can be obtained by blending components (A), (B), (C), (D) and (F), wherein the second multiphase propylene copolymer (E) is absent, (A) 15% to 40% by weight of a mixed plastic polypropylene blend; (B) 20% to 50% by weight of a multiphase propylene copolymer; (C) 5% to 25% by weight of an ethylene-based plastomer; (D) 5% to 25% by weight of an inorganic filler; and (F) 2% to 10% by weight of a propylene homopolymer.

6. The composition according to claim 1, wherein the inorganic filler (D) is talc, having - 0.3 to 30.0 micrometers median particle size d before compounding 50 ; and / or - The top cut size d before compounding, from 1.0 to 50.0 µm 95 .

7. The composition according to claim 1, wherein the composition has - a crystalline fraction CF content in the range of 55.0 to 75.0% by weight, separated by a temperature cycle of dissolving at 160 °C, crystallizing at 40 °C and redissolving at 160 °C in 1,2,4-trichlorobenzene and determined according to CRYSTEX QC analysis, and - a soluble fraction SF content in the range of 25.0 to 45.0% by weight, separated by a temperature cycle of dissolving at 160 °C, crystallizing at 40 °C and redissolving at 160 °C in 1,2,4-trichlorobenzene and determined according to CRYSTEX QC analysis, wherein - The crystalline fraction CF has an ethylene content C2(CF) determined by FT-IR spectroscopy calibrated by quantitative 13 C-NMR spectroscopy of less than 10.0% by weight; - The crystalline fraction CF has an intrinsic viscosity iV(CF) measured in decalin at 135 °C according to DIN ISO 1628 / 1 of less than 1.8 dl / g; - The soluble fraction SF has an ethylene content C2(SF) determined by FT-IR spectroscopy calibrated by quantitative 13 C-NMR spectroscopy in the range of 45.0 to 65.0% by weight; and - The soluble fraction SF has an intrinsic viscosity iV(SF) measured in decalin at 135 °C according to DIN ISO 1628 / 1 of greater than 1.6 dl / g.

8. The composition according to claim 1, wherein the composition has a flexural modulus of 1400 MPa to 2000 MPa measured on a test specimen having dimensions of 80×10×4 mm prepared by injection molding according to EN ISO 1873-2 at a test speed of 2 mm / min and a force of 100 N according to ISO 178. 3 ​ 9. The composition according to claim 1, wherein the composition has a Charpy notched impact strength, determined according to ISO 179-1eA at 23 °C on an injection-molded specimen prepared according to EN ISO 1873-2 and having dimensions of 80×10×4 mm, of from 20.0 kJ / m 2 to 65.0 kJ / m 2 and / or a Charpy notched impact strength, determined according to ISO 179-1eA at -20 °C on an injection-molded specimen prepared according to EN ISO 1873-2 and having dimensions of 80×10×4 mm, of from 4.0 kJ / m 3 to 10.0 kJ / m 2 2 2 and / or a Charpy notched impact strength, determined according to ISO 179-1eA at -20 °C on an injection-molded specimen prepared according to EN ISO 1873-2 and having dimensions of 80×10×4 mm, of from 4.0 kJ / m 3 to 10.0 kJ / m.

10. The composition according to claim 1, wherein the composition has a heat distortion temperature determined according to ISO 75B of greater than 90 °C and / or a coefficient of linear thermal expansion CLTE of 60 to 100 μm / mK.

11. The composition according to claim 1, wherein when determined at 23 °C in an instrumented impact test according to ISO 6603-2, the composition has a puncture energy of 25 to 55 J and / or a maximum force energy of 15 to 45 J, and / or when determined at -30 °C in an instrumented impact test according to ISO 6603-2, the composition has a puncture energy of 12 to 40 J and / or a maximum force energy of 10 to 30 J.

12. An article comprising the composition according to any one of claims 1 to 11.

13. The article according to claim 12, wherein the article has a coating adhesion of less than 50 mm 2 evaluated as the coating area of failure or delamination in mm 2 ; wherein the coating adhesion is measured on an injection molded sample plate of 150 mm × 80 mm × 3 mm produced at a melting temperature of 240 °C and a mold temperature of 50 °C by exposing the injection molded sample plate to hot water vapor at a temperature of 68 °C, a water pressure of 65 bar, a surface distance of 100 mm from the injection molded sample plate and at an angle of 90° thereto for 30 s.

14. Use of a composition according to any one of claims 1 to 11 for injection molding of an article.

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