WO2024251869A1 - Composition de polypropylène contenant un recyclat pour applications automobiles intérieures - Google Patents

Composition de polypropylène contenant un recyclat pour applications automobiles intérieures Download PDF

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Publication number
WO2024251869A1
WO2024251869A1 PCT/EP2024/065580 EP2024065580W WO2024251869A1 WO 2024251869 A1 WO2024251869 A1 WO 2024251869A1 EP 2024065580 W EP2024065580 W EP 2024065580W WO 2024251869 A1 WO2024251869 A1 WO 2024251869A1
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determined
polypropylene composition
content
iso
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Daniela MILEVA
Markus Gall
Wolfgang Stockreiter
Christophe SALLES
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Borealis GmbH
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Borealis GmbH
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Priority to CN202480037885.4A priority Critical patent/CN121263480A/zh
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/02—Heterophasic composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/20—Recycled plastic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2308/00—Chemical blending or stepwise polymerisation process with the same catalyst
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2310/00—Masterbatches

Definitions

  • PC polypropylene composition
  • PC polypropylene composition
  • Technical background Compositions suitable for the automotive industry typically contain one or more heterophasic polypropylene copolymer(s), and/or random heterophasic copolymers, and conventionally some inorganic filler.
  • PCT/EP2022/084506 discloses polypropylene compositions in which up to 35.0 wt.- % of a recyclate blend originating from post-consumer waste is used, which shows a good balance of properties in regard of mechanical properties, low emissions and excellent surface properties is obtained, which is especially suitable for interior automotive applications.
  • Said polypropylene compositions contain up to 20.0 wt.-% inorganic filler and up to 15.0 wt.-% of ethylene-1-octene elastomer.
  • the present invention is based in the surprising finding of providing a polypropylene composition with a high weight content of recyclate blend and low contents of inorganic filler and ethylene-1-octene elastomer, which shows a good balance of properties in regard of mechanical properties, low emissions and excellent surface properties. Additionally, the inventive polypropylene compositions show a high toughness after processing and show a low coefficient of linear thermal expansion (CLTE). The polypropylene compositions according to the invention are therefore especially suitable for interior automotive applications.
  • the present invention is directed, in its broadest sense, to a polypropylene composition (PC) being a mixed-plastic polypropylene blend, wherein the polypropylene composition (PC) comprises: inclusions attributed to automotive paints, determined on compressed films with a thickness of 35 to 70 ⁇ m, wherein the inclusions are identified by optical microscopy, the chemical composition of the inclusions is characterized by infrared spectroscopy and the physical information of the inclusions is characterized by computed tomography; and a content of low boiling organic substances (LBS), determined by screening of organic emissions by thermos-desorption analysis of not more than 100 ⁇ g/g; wherein the polymeric part of said polypropylene composition (PC) has: i) an ethylene content (C2(total)), determined from crystallization extraction (CRYSTEX) by FT-IR spectroscopy calibrated by quantitative 13 C-NMR spectroscopy, in the range from 7.5 to 35.0 wt.-%
  • the polypropylene composition (PC) is obtainable by blending at least components a) to h): a) from 1.0 to 40.0 wt.-%, relative to the total weight of the polypropylene composition (PC), of a first heterophasic propylene-ethylene copolymer (HECO1), having a melt flow rate (MFR2), determined according to ISO 1133 at 230 °C and 2.16 kg, in the range from 90 to 250 g/10 min and an intrinsic viscosity, determined according to DIN ISO 1628/1, of the soluble fraction (iV(SF)), according to crystallization extraction (CRYSTEX)analysis, in the range from 2.00 to 4.00 dL/g; b) from 0.0 to 35.0 wt.-%, relative to the total weight of the of the polypropylene composition (PC), of a second heterophasic propylene-ethylene copolymer (HECO2), having a melt flow rate (MFR2), determined according to ISO 1133 at 230
  • the present invention is directed to an article, preferably an injection-moulded article, comprising the polypropylene composition of the first aspect in an amount of at least 95 wt.-%, more preferably at least 98 wt.-%, most preferably at least 99 wt.-%.
  • a propylene homopolymer is a polymer that essentially consists of propylene monomer units. Due to impurities especially during commercial polymerization processes, a propylene homopolymer can comprise up to 0.1 mol% comonomer units, preferably up to 0.05 mol% comonomer units and most preferably up to 0.01 mol% comonomer units.
  • a propylene copolymer is a copolymer of propylene monomer units and comonomer units, preferably selected from ethylene and C4-C8 alpha-olefins.
  • a propylene random copolymer is a propylene copolymer wherein the comonomer units are randomly distributed along the polymer chain, whilst a propylene block copolymer comprises blocks of propylene monomer units and blocks of comonomer units.
  • Propylene random copolymers can comprise comonomer units from one or more comonomers different in their amounts of carbon atoms.
  • the heterophasic propylene copolymers typically comprise: a) a crystalline propylene homopolymer or copolymer matrix (M); and b) an elastomeric rubber, preferably a propylene-ethylene copolymer (E);
  • said crystalline matrix phase is a random copolymer of propylene and at least one alpha-olefin comonomer.
  • the elastomeric phase can be a propylene copolymer with a high amount of comonomer that is not randomly distributed in the polymer chain but is distributed in a comonomer-rich block structure and a propylene-rich block structure.
  • a heterophasic polypropylene usually differentiates from a one-phasic propylene copolymer in that it shows two distinct glass transition temperatures Tg which are attributed to the matrix phase and the elastomeric phase.
  • the presence of a heterophasic nature can be easily determined by the number of glass transition points, like in dynamic-mechanical analysis (DMA), and/or high resolution microscopy, like scanning electron microscopy (SEM), transmission electron microscopy (TEM) or atomic force microscopy (AFM).
  • DMA dynamic-mechanical analysis
  • SEM scanning electron microscopy
  • TEM transmission electron microscopy
  • a polypropylene means a polymer being composed of units derived from propylene in an amount of more than 50 mol-%.
  • a polyethylene means a polymer being composed of units derived from ethylene in an amount of more than 50 mol-%.
  • the term “elastomer” denotes a natural or synthetic polymer having elastic properties.
  • the term “plastomer” denotes a natural or synthetic polymer, which combines qualities of elastomers and plastics, such as rubber-like properties with the processing ability of plastic.
  • An ethylene based plastomer means a plastomer being composed of units derived from ethylene in an amount of more than 50 mol- %.
  • the term “recycled waste” is used to indicate a material recovered from post-consumer waste only, as opposed to virgin polymers and material recovered from post industrial waste. Post-consumer waste refers to objects having completed at least a first use cycle (or life cycle), i.e.
  • recycled waste is especially used for mixed-plastics waste collected from end-of live (ELV) vehicles, especially from end-of-life (ELV) car bumpers.
  • EUV end-of live
  • VUV end-of-life
  • the term “virgin” denotes the newly produced materials and/or objects prior to their first use, which have not already been recycled. In case that the origin of the polymer is not explicitly mentioned the polymer is a “virgin” polymer.
  • recycled material such as used herein denotes materials reprocessed from “recycled waste”.
  • a polymer blend denotes a mixture of two or more polymeric components.
  • the blend can be prepared by mixing the two or more polymeric components. Suitable mixing procedures known in the art are post-polymerization blending procedures. Post-polymerization blending can be dry blending of polymeric components such as polymer powders and/or compounded polymer pellets or melt blending by melt mixing the polymeric components.
  • a mixed-plastic polypropylene blend indicates that the blend predominantly comprises polypropylene; however, small amounts of other plastic are present.
  • a mixed-plastic polypropylene blend is preferably used, which results from post-consumer waste from very special sources, which is characterized by the presence of inclusions attributed to automotive paints, preferably post- consumer waste from end-of-live (ELV) vehicles, more preferably from end-of-life (ELV) car bumpers.
  • the presence of such mixed-plastic polypropylene blends can be identified in a polypropylene composition by identifying inclusions attributed to automotive paints e.g. by means of IR spectroscopy in the polypropylene composition.
  • inclusions attributed to automotive paints means particles, which comprise chemical components, which originate from automotive paints, such as styrene-based components, urethane-based components and/or acrylic-based components. Said components in the polypropylene composition usually originate from paint residuals in the mixed-plastic polypropylene blend (B) contained in the polypropylene composition.
  • the inclusions are usually identified by optical microscopy on compressed films of the polypropylene composition and are identified as “inclusions attributed to automotive paints” by characterizing their chemical composition and their physical information.
  • the chemical composition of said inclusions can be determined by IR spectroscopy.
  • the shape and other physical information of the particles can be characterized by computed tomography.
  • the inclusions usually show a sharp edged and platelet-like 3D shape, usually with a multilayer structure, and a grey value, which is at least 50 % higher compared to the average grey value of the surrounding polypropylene composition and therefore differentiates from other inclusions such as pigment particles or talc particles, which have a rounder 3D shape or have smooth edges or show grey values below the threshold of at least 50 % higher compared to the average grey value of the surrounding polypropylene composition.
  • the measurement method is described in the example section.
  • PC Polypropylene composition
  • the present invention is directed, in a first aspect, to a polypropylene composition (PC) being a mixed-plastic polypropylene blend.
  • the polypropylene composition (PC) is characterized by the presence of inclusions attributed to automotive paints.
  • the polypropylene composition (PC) further has a content of low boiling organic substances (LBS) determined by screening of organic emissions by thermo- desorption analysis of not more than 100 ⁇ g/g, such as in the range from 5 to 100 ⁇ g/g, preferably in the range from 5 to 80 ⁇ g/g, most preferably in the range from 5 to 75 ⁇ g/g.
  • LBS low boiling organic substances
  • the polypropylene composition (PC) preferably has a content of acetaldehyde of not more than 50 mg/m3, more preferably not more than 40 mg/m3.
  • the lower limit is usually at least 5 mg/m3, preferably at least 10 mg/m3.
  • Acetaldehyde is the most significant odour marker. Such a low amount of acetaldehyde indicates the suitability of the polypropylene composition (PC) for interior automotive applications.
  • the polypropylene composition (PC) preferably has a content of high boiling organic substances (HBS) determined by screening of organic emissions by thermo- desorption analysis in the range from 10 to 300 ⁇ g/g, more preferably in the range from 20 to 280 ⁇ g/g, most preferably in the range from 30 to 250 ⁇ g/g.
  • the polypropylene composition (PC) preferably has an amount of fogging, determined according to the gravimetric method DI 75201:2011-11, method B, in the range from 0.05 to 1.00 mg, more preferably in the range from 0.10 to 0.80 mg, most preferably in the range from 0.10 to 0.75 mg.
  • the polypropylene composition (PC) usually has a low limonene content, determined by solid phase microextraction (HS-SPME-GC-MS).
  • HS-SPME-GC-MS solid phase microextraction
  • the limonene content in the polypropylene composition is less than 0.1 ppm.
  • the limonene content is even below the detection limit of the HS- SPME-GC-MS method.
  • the low limonene content in these embodiments results from the use of mixed-plastic polypropylene blends (B) which themselves only contain traces of limonene as they do not originate from post-consumer household waste.
  • the mixed-plastic polypropylene blends (B) include recycled blends, which in an earlier life cycle originate from post-consumer household waste typically in amounts of up to 50 wt.-%, based on the total amounts of mixed plastic polypropylene blends (B).
  • the polypropylene composition (PC) can contain a limonene content, determined by solid phase microextraction (HS-SPME-GC-MS) an amount of not more than 5.0 ppm, such as in the range of 0.05 to 5.0 ppm.
  • the polypropylene composition (PC) preferably has a melt flow rate (MFR 2 ), determined according to ISO 1133 at 230 °C and 2.16 kg, in the range from 5.0 to 50.0 g/10 min, more preferably in the range from 7.5 to 35.0 g/10 min, most preferably in the range from 9.0 to 25.0 g/10 min.
  • the polypropylene composition (PC) preferably has a flexural modulus, determined according to ISO 178 using 80 ⁇ 10 ⁇ 4 mm 3 test bars injection-moulded in line with ISO 19069-2, in the range from 900 to 2500 MPa, more preferably in the range from 1000 to 2300 MPa, most preferably in the range from 1250 to 2250 MPa.
  • the polypropylene composition (PC) preferably has a Charpy Notched impact strength at 23 °C, determined according to ISO 179 using 80 ⁇ 10 ⁇ 4 mm 3 test bars injection-moulded in line with ISO 19069-2, in the range from 10.0 to 70.0 kJ/m 2 , more preferably in the range from 13 to 60 kJ/m 2 , most preferably in the range from 15 to 55 kJ/m 2 .
  • the polypropylene composition (PC) preferably has a Charpy Notched impact strength at -20 °C, determined according to ISO 179 using 80 ⁇ 10 ⁇ 4 mm 3 test bars injection-moulded in line with ISO 19069-2, in the range from 2.5 to 12.0 kJ/m 2 , more preferably in the range from 3.0 to 10.0 kJ/m 2 , most preferably in the range from 3.5 to 7.5 kJ/m 2 .
  • the polymeric part of the polypropylene composition (PC) may be characterized according to the crystallization extraction (CRYSTEX) method using trichlorobenzene (TCB) as a solvent. This method is described below in the determination methods section.
  • the crystalline fraction (CF) contains for the most part the matrix phase and only a small part of the elastomeric phase and the soluble fraction (SF) contains for the most part the elastomeric phase and only a small part of the matrix phase.
  • this method results in more useful data, since the crystalline fraction (CF) and the soluble fraction (SF) more accurately correspond to the matrix and elastomeric phases respectively. Due to the differences in the separation methods of xylene extraction and crystallization extraction (CRYSTEX)method the properties of XCS/XCI fractions on the one hand and crystalline/soluble (CF/SF) fractions on the other hand are not exactly the same, meaning that the amounts of matrix phase and elastomeric phase can differ as well as the properties.
  • the crystalline fraction (CF) content and the soluble (SF) content of a composition only relate to its polymeric components, i.e. without other components, which are insoluble and therefore not part of the dissolution and crystallization cycles as described below in the determination method, such as the inorganic filler (F).
  • the crystalline fraction (CF) content and the soluble (SF) content therefore are based on the weight amount of the polymeric components of the polypropylene composition (PC).
  • the polymeric part of the polypropylene composition has an ethylene content (C2(total)), determined from crystallization extraction (CRYSTEX) by FT-IR spectroscopy calibrated by quantitative 13 C-NMR spectroscopy, in the range from 7.5 to 35.0 wt.-%, preferably in the range from 10.0 to 30.0 wt.-%, most preferably in the range from 12.0 to 22.0 wt.-%.
  • the polymeric part of the polypropylene composition (PC) preferably has an intrinsic viscosity (iV(total)), determined from crystallization extraction (CRYSTEX) according to DIN ISO 1628/1, in the range from 1.00 to 2.50 dL/g, more preferably in the range from 1.20 to 2.30 dL/g, most preferably in the range from 1.40 to 2.20 dL/g.
  • iV(total) intrinsic viscosity
  • the polymeric part of the polypropylene composition (PC) has a soluble fraction (SF) content, determined by crystallization extraction (CRYSTEX) analysis, in the range from 20.0 to 40.0 wt.-%, more preferably in the range from 20.0 to 35.0 wt.-%, most preferably in the range from 20.0 to 30.0 wt.-%
  • Said soluble fraction (SF) preferably has an ethylene content (C2(SF)) determined by FT-IR spectroscopy calibrated by quantitative 13 C-NMR spectroscopy, in the range from 25.0 to 70.0 wt.-%, more preferably in the range from 30.0 to 65.0 wt.-%, still more preferably in the range from 35.0 to 60.0 wt.-%, most preferably in the range from 40.0 to 58.0 wt.-%.
  • Said soluble fraction (SF) also has an intrinsic viscosity (iV(SF)), determined according to DIN ISO 1628/1, in the range from 1.80 to 3.60 dL/g, more preferably in the range from 1.90 to 3.30 dL/g, most preferably in the range from 2.00 to 3.00 dL/g.
  • iV(SF) intrinsic viscosity
  • the polymeric part of the polypropylene composition (PC) has a crystalline fraction (CF) content, determined by crystallization extraction (CRYSTEX) analysis, in the range from 60.0 to 80.0 wt.-%, more preferably in the range from 65.0 to 80.0 wt.-%, most preferably in the range from 70.0 to 80.0 wt.-%
  • Said crystalline fraction (CF) has an ethylene content (C2(CF)) determined by FT-IR spectroscopy calibrated by quantitative 13 C-NMR spectroscopy, in the range from 1.0 to 15.0 wt.-%, preferably in the range from 2.0 to 15.0 wt.-%, more preferably in the range from 2.5 to 15.0 wt.-%, most preferably in the range from 3.0 to 10.0 wt.- %.
  • Said crystalline fraction (CF) also has an intrinsic viscosity (iV(CF)), determined according to DIN ISO 1628/1, in the range from 1.00 to 2.00 dL/g, more preferably in the range from 1.20 to 1.90 dL/g, most preferably in the range from 1.30 to 1.80 dL/g.
  • iV(CF) intrinsic viscosity
  • the polypropylene composition (PC) preferably comprises a) from 5.0 to 65.0 wt.-%, preferably from 6.0 to 62.5 wt.-%, more preferably from 15.0 to 62.0 wt.-%, still more preferably from 25.0 to 62.0 wt.-% of heterophasic propylene-ethylene copolymer (HECO); b) from 7.5 to 85.0 wt.-%, preferably from 9.0 to 82.5 wt.-%, more preferably from 10.0 to 50.0 wt.-%, still more preferably from 15.0 to 45.0 wt.-% of a mixed- plastic polypropylene blend (B) comprising inclusions attributed to automotive paints; c) from 0 to 7.5 wt.-%, preferably from 0 to 6.5 wt.-% of ethylene-1-octene elastomer (EC); d) from 0 to 25.0 wt.-%, preferably from 0 to 21.0 w
  • the polypropylene composition (PC) preferably comprises i. from 40.0 to 75.0 wt.-%, preferably from 45.0 to 72.5 wt.-% of a total amount of heterophasic propylene-ethylene copolymer; ii. from 10.0 to 25.0 wt.-%, preferably from 15.0 to 22.5 wt.-% of a total amount of an ethylene-based elastomer; iii. from 0.5 to 30.0 wt.-%, preferably from 0.5 to 27.5 wt.-% of a total amount of inorganic filler; iv.
  • a pigment masterbatch which comprises one or more pigments, wherein the total pigment content is in the range from 40.0 to 80.0 wt.-%, relative to the total weight of the pigment masterbatch (P); and v. from 0.2 to 5.0 wt.-% of further additives (A), wherein the total contents of components i. to v. add up to at least 95 wt.-%, more preferably at least 98 wt.-%, most preferably 100 wt.-%, relative to the total weight of the polypropylene composition (PC).
  • PC polypropylene composition
  • the ethylene-based elastomer is preferably copolymer of ethylene with a comonomer selected from alpha olefin comonomer(s) having from 3 to 10 carbon atoms.
  • the ethylene-based elastomer can be a mixture of copolymers of ethylene with different comonomers selected from alpha olefin comonomer(s) having from 3 to 10 carbon atoms.
  • the polypropylene composition (PC) is preferably obtainable by blending at least components a) to h): a) from 1.0 to 40.0 wt.-%, relative to the total weight of the polypropylene composition (PC), of a first heterophasic propylene-ethylene copolymer (HECO1); b) from 0 to 35.0 wt.-%, relative to the total weight of the of the polypropylene composition (PC), of a second heterophasic propylene-ethylene copolymer (HECO2); c) from 0 to 35.0 wt.-%, relative to the total weight of the of the polypropylene composition (PC), of a third heterophasic propylene-ethylene copolymer (HECO3); d) from 7.5 to 85.0 wt.-%, relative to the total weight of the polypropylene composition (PC), of a mixed-plastic polypropylene blend (B) comprising inclusions attributed to automotive paints; e) from 0 to
  • the properties of each of these components are given in the respective sections below.
  • the total contents of components a) to h) add up to at least 95 wt.-%, more preferably at least 98 wt.-%, most preferably 100 wt.-%, relative to the total weight of the polypropylene composition (PC).
  • the polypropylene composition (PC) is obtainable by blending at least components a) to h): a) from 2.5 to 35.0 wt.-%, relative to the total weight of the polypropylene composition (PC), of a first heterophasic propylene-ethylene copolymer (HECO1); b) from 2.5 to 35.0 wt.-%, relative to the total weight of the of the polypropylene composition (PC), of a second heterophasic propylene-ethylene copolymer (HECO2); c) 0 wt.-%, relative to the total weight of the of the polypropylene composition (PC), of a third heterophasic propylene-ethylene copolymer (HECO3); d) from 9.0 to 82.5 wt.-%, relative to the total weight of the polypropylene composition (PC), of a mixed-plastic polypropylene blend (B) comprising inclusions attributed to automotive paints; e) from 0 to 6.5 wt
  • the polypropylene composition (PC) is obtainable by blending at least components a) to h): a) from 7.5 to 35.0 wt.-%, relative to the total weight of the polypropylene composition (PC), of a first heterophasic propylene-ethylene copolymer (HECO1); b) from 7.5 to 35.0 wt.-%, relative to the total weight of the of the polypropylene composition (PC), of a second heterophasic propylene-ethylene copolymer (HECO2); c) 0 wt.-%, relative to the total weight of the of the polypropylene composition (PC), of a third heterophasic propylene-ethylene copolymer (HECO3); d) from 10.0 to 50.0 wt.-%, relative to the total weight of the polypropylene composition (PC), of a mixed-plastic polypropylene blend (B) comprising inclusions attributed to automotive paints; e) from 0 to 6.5
  • the polypropylene composition (PC) is obtainable by blending at least components a) to h): a) from 10.0 to 35.0 wt.-%, relative to the total weight of the polypropylene composition (PC), of a first heterophasic propylene-ethylene copolymer (HECO1); b) from 10.0 to 35.0 wt.-%, relative to the total weight of the of the polypropylene composition (PC), of a second heterophasic propylene-ethylene copolymer (HECO2); c) 0 wt.-%, relative to the total weight of the of the polypropylene composition (PC), of a third heterophasic propylene-ethylene copolymer (HECO3); d) from 15.0 to 45.0 wt.-%, relative to the total weight of the polypropylene composition (PC), of a mixed-plastic polypropylene blend (B) comprising inclusions attributed to automotive paints; e) from 0 to 6.5
  • the blending of the polypropylene composition (PC) may be carried out according to a process comprising the steps of: a) providing the first heterophasic propylene-ethylene copolymer (HECO1), the optional second heterophasic propylene-ethylene copolymer (HECO2), the optional third heterophasic propylene-ethylene copolymer (HECO3), the mixed- plastic polypropylene blend (B), the ethylene-octene elastomer (EC), the inorganic filler (F), the optional pigment masterbatch and the further additives (A); b) blending and extruding the first heterophasic propylene-ethylene copolymer (HECO1), the optional second heterophasic propylene-ethylene copolymer (HECO2), the optional third heterophasic propylene-ethylene copolymer (HECO3), the mixed-plastic polypropylene blend (B), the ethylene-octene elastomer (EC), the inorganic filler (F),
  • a conventional compounding or blending apparatus e.g. a Banbury mixer, a 2-roll rubber mill, Buss-co-kneader or a twin- screw extruder. More preferably, mixing is accomplished in a co-rotating twin-screw extruder.
  • the polymer materials recovered from the extruder are usually in the form of pellets.
  • the first heterophasic propylene ethylene copolymer (HECO1) is preferably provided in an amount in the range from 1.0 to 40.0 wt.-%, more preferably in the range from 2.5 to 35.0 wt.-%, relative to the total weight of the polypropylene composition (PC).
  • the first heterophasic propylene ethylene copolymer (HECO1) has a melt flow rate (MFR 2 ), determined according to ISO 1133 at 230 °C and 2.16 kg, in the range from 90 to 250 g/10 min, more preferably in the range from 93 to 200 g/10 min, most preferably in the range from 95 to 150 g/10 min.
  • the first heterophasic propylene ethylene copolymer preferably has a soluble fraction (SF) content, determined by crystallization extraction (CRYSTEX) analysis, in the range from 8.0 to 19.5 wt.-%, more preferably in the range from 10.0 to 18.0 wt.-%, most preferably in the range from 13.0 to 17.0 wt.-%.
  • SF soluble fraction
  • the first heterophasic propylene ethylene copolymer preferably has an ethylene content of the soluble fraction (C2(SF)), according to crystallization extraction (CRYSTEX)analysis, determined by FT-IR spectroscopy calibrated by quantitative 13 C-NMR spectroscopy, in the range from 31.0 to 45.0 wt.-%, more preferably in the range from 33.0 to 43.0 wt.-%, most preferably in the range from 36.0 to 42.0 wt.-%.
  • the first heterophasic propylene ethylene copolymer has an intrinsic viscosity, determined according to DIN ISO 1628/1, of the soluble fraction (iV(SF)), according to crystallization extraction (CRYSTEX) analysis, in the range from 2.00 to 4.00 dL/g, more preferably in the range from 2.30 to 3.70 dL/g, most preferably in the range from 2.50 to 3.30 dL/g.
  • the second heterophasic propylene ethylene copolymer (HECO2) is preferably provided in an amount in the range from 0 to 35.0 wt.-%, more preferably in the range from 2.5 to 35.0 wt.-%, relative to the total weight of the polypropylene composition (PC).
  • the second heterophasic propylene ethylene copolymer (HECO2) has a melt flow rate (MFR 2 ), determined according to ISO 1133 at 230 °C and 2.16 kg, in the range from 3.0 to 30.0 g/10 min, more preferably in the range from 4.0 to 20.0 g/10 min, most preferably in the range from 4.5 to 10.0 g/10 min.
  • the second heterophasic propylene ethylene copolymer preferably has a soluble fraction (SF) content, determined by crystallization extraction (CRYSTEX) analysis, in the range from 20.0 to 40.0 wt.-%, more preferably in the range from 20.0 to 30.0 wt.-%, most preferably in the range from 20.0 to 26.0 wt.-%.
  • SF soluble fraction
  • the second heterophasic propylene ethylene copolymer preferably has an ethylene content of the soluble fraction (C2(SF)), according to crystallization extraction (CRYSTEX) analysis, determined by FT-IR spectroscopy calibrated by quantitative 13 C-NMR spectroscopy, in the range from 18.0 to 30.0 wt.-%, more preferably in the range from 19.0 to 28.0 wt.-%, most preferably in the range from 20.0 to 26.0 wt.-%.
  • the second heterophasic propylene ethylene copolymer has an intrinsic viscosity, determined according to DIN ISO 1628/1, of the soluble fraction (iV(SF)), according to crystallization extraction (CRYSTEX) analysis, in the range from 4.10 to 10.00 dL/g, more preferably in the range from 4.50 to 8.00 dL/g, most preferably in the range from 5.00 to 6.00 dL/g.
  • the third heterophasic propylene ethylene copolymer (HECO3) is preferably provided in an amount in the range from 0 to 35.0 wt.-%, more preferably in an amount of 0 wt.-%, relative to the total weight of the polypropylene composition (PC).
  • the third heterophasic propylene ethylene copolymer (HECO3) has a melt flow rate (MFR 2 ), determined according to ISO 1133 at 230 °C and 2.16 kg, in the range from 5.0 to 30.0 g/10 min, more preferably in the range from 10.0 to 25.0 g/10 min, most preferably in the range from 12.0 to 20.0 g/10 min.
  • the third heterophasic propylene ethylene copolymer preferably has a soluble fraction (SF) content, determined by crystallization extraction (CRYSTEX) analysis, in the range from 20.0 to 40.0 wt.-%, more preferably in the range from 24.0 to 36.0 wt.-%, most preferably in the range from 27.0 to 33.0 wt.-%.
  • SF soluble fraction
  • the third heterophasic propylene ethylene copolymer preferably has an ethylene content of the soluble fraction (C2(SF)), according to crystallization extraction (CRYSTEX) analysis, determined by FT-IR spectroscopy calibrated by quantitative 13 C-NMR spectroscopy, in the range from 31.0 to 45.0 wt.-%, more preferably in the range from 34.0 to 44.0 wt.-%, most preferably in the range from 37.0 to 43.0 wt.-%.
  • the third heterophasic propylene ethylene copolymer has an intrinsic viscosity, determined according to DIN ISO 1628/1, of the soluble fraction (iV(SF)), according to crystallization extraction (CRYSTEX) analysis, in the range from 2.00 to 4.00 dL/g, more preferably in the range from 2.10 to 3.50 dL/g, most preferably in the range from 2.20 to 3.00 dL/g.
  • the mixed-plastic polypropylene blend (B) is preferably provided in an amount in the range from 7.5 to 85.0 wt.-%, more preferably in the range from 9.0 to 82.5 wt.-%, relative to the total weight of the polypropylene composition (PC).
  • the mixed-plastic polypropylene blend (B) is a polypropylene rich recycled material, meaning that it comprises significantly more polypropylene than polyethylene. Recycled waste streams, which are high in polypropylene can be obtained for example from the automobile industry, particularly as some automobile parts such as bumpers are sources of fairly pure polypropylene material in a recycling stream.
  • the mixed-plastic polypropylene blend (B) originates from post-consumer waste from very special sources, preferably from end-of life vehicle (ELV) recycled feedstock, more preferably from shredded bumpers. It is especially preferred that the mixed-plastic polypropylene blend (B) in its last product cycle does not originate from post-consumer household waste.
  • the mixed mixed-plastic polypropylene blend (B) originates from post-consumer waste from very special sources, preferably from end-of life vehicle (ELV) recycled feedstock, more preferably from shredded bumpers, which comprises up to 50 wt.-% of a mixed-plastic polypropylene blend which in an earlier product cycle originated from post-consumer household waste.
  • the polypropylene composition used for the production of the industrial purpose are mixed-plastics polypropylene blends as described e.g. in PCT/EP2022/084506.
  • any reasonable measure will usually be taken for any components other than polyethylene and polypropylene to be reduced/removed as far as the final application or use suggests such measures; however, other components are often present in small amounts.
  • Such components include e.g. inorganic filler, which can be present in the mixed- plastic polypropylene blend (B) in an amount of from 2.5 to 30 wt.-%, preferably 3.5 to 25 wt.-%, relative to the total weight of the mixed-plastic polypropylene blend (B).
  • the mixed-plastic polypropylene blend (B) is characterized by the presence of inclusions attributed to automotive paints. Said inclusions are determined in the example section on compressed films with a thickness of 35 to 70 ⁇ m, wherein the inclusions are identified by optical microscopy, the chemical composition of the inclusions is characterized by infrared spectroscopy and the physical information of the inclusions is characterized by computed tomography
  • the inclusions attributed to automotive paints are typically particles, which comprise styrene-based components, urethane-based components and/or acrylic-based components and usually originate from paint residuals from the mixed-plastic polypropylene blend (B) such as e.g. from the painted car parts, such as bumpers.
  • the mixed-plastic polypropylene blend (B) preferably has a limonene content, determined by solid phase microextraction (HS-SPME-GC-MS), of less than 0.1 ppm. In some embodiments, the limonene content is even below the detection limit of the HS-SPME-GC-MS method.
  • the low limonene content in these embodiments results from mixed-plastic polypropylene blends (B), which do not originate from post-consumer household waste or do not contain any content of mixed plastics polypropylene blends, which in an earlier life cycle originated from post-consumer household waste.
  • the mixed-plastic polypropylene blends (B) include recycled blends, which in an earlier life cycle originate from post-consumer household waste typically in amounts of up to 50 wt.-%, based on the total amounts of mixed plastic polypropylene blends (B).
  • the mixed-plastic polypropylene blends (B) can contain a limonene content, determined by solid phase microextraction (HS-SPME-GC-MS) an amount of not more than 10.0 ppm, such as in the range of 0.1 to 10.0 ppm.
  • Other such components include inorganic residue content, as determined by calcination analysis according to DIN ISO 1172:1996, of 0.5 to 10.0 wt.-%.
  • Further components include a content of derivatives from organic acids and/or organic aldehydes, of 1 to 100 ppm.
  • the mixed-plastic polypropylene blend (B) preferably has a melt flow (MFR2), determined according to ISO 1133 at 230 °C and 2.16 kg, in the range from 5.0 to 30.0 g/10 min, more preferably in the range from 6.0 to 27.5 g/10 min, most preferably in the range from 7.5 to 25.0 g/10 min.
  • MFR2 melt flow
  • the mixed-plastic polypropylene blend (B) preferably has an ethylene content (C2(total)), determined from crystallization extraction (CRYSTEX) by FT-IR spectroscopy calibrated by quantitative 13 C-NMR spectroscopy, in the range from 15.0 to 30.0 wt.-%, more preferably in the range from 17.5 to 28.5 wt.-%, most preferably in the range from 15.0 to 27.5 wt.-%.
  • the mixed-plastic polypropylene blend (B) preferably has a soluble fraction (SF) content of the polymeric part of the mixed-plastic polypropylene blend (B), determined by crystallization extraction (CRYSTEX) analysis, in the range from 10.0 to 50.0 wt.-%, more preferably in the range from 15.0 to 45.0 wt.-%, most preferably in the range from 20.0 to 40.0 wt.-%.
  • SF soluble fraction
  • the mixed-plastic polypropylene blend (B) preferably has a crystalline fraction (CF) content of the polymeric part of the mixed-plastic polypropylene blend (B), determined by crystallization extraction (CRYSTEX) analysis, in the range from 50.0 to 90.0 wt.-%, more preferably in the range from 55.0 to 85.0 wt.-%, most preferably in the range from 60.0 to 80.0 wt.-%.
  • CF crystalline fraction
  • the mixed-plastic polypropylene blend (B) preferably has an ethylene content of the soluble fraction (C2(SF)), according to crystallization extraction (CRYSTEX) analysis, determined by FT-IR spectroscopy calibrated by quantitative 13 C-NMR spectroscopy, in the range from 30.0 to 60.0 wt.-%, more preferably in the range from 32.5 to 57.5 wt.-%, most preferably in the range from 35.0 to 55.0 wt.-%.
  • C2(SF) crystallization extraction
  • the mixed-plastic polypropylene blend (B) preferably has an ethylene content of the crystalline fraction (C2(CF)), according to crystallization extraction (CRYSTEX) analysis, determined by FT-IR spectroscopy calibrated by quantitative 13 C-NMR spectroscopy, in the range from 5.0 to 25.0 wt.-%, more preferably in the range from 6.5 to 22.5 wt.-%, most preferably in the range from 7.5 to 20.0 wt.-%.
  • C2(CF) crystallization extraction
  • the mixed-plastic polypropylene blend (B) preferably has an intrinsic viscosity, determined according to DIN ISO 1628/1, of the soluble fraction (iV(SF)), according to crystallization extraction (CRYSTEX) analysis, in the range from 1.10 to 2.75 dL/g, more preferably in the range from 1.25 to 2.60 dL/g, most preferably in the range from 1.40 to 2.50 dL/g.
  • the mixed-plastic polypropylene blend (B) preferably has an intrinsic viscosity, determined according to DIN ISO 1628/1, of the crystalline fraction (iV(CF)), according to crystallization extraction (CRYSTEX) analysis, in the range from 0.90 to 2.10 dL/g, more preferably in the range from 1.00 to 2.00 dL/g, most preferably in the range from 1.10 to 1.90 dL/g.
  • the mixed-plastics blend (B) preferably has a density in the range of 900 to 1050 kg/m3, determined according to ISO 1183.
  • the mixed-plastics blend (B) preferably has a flexural modulus, determined according to ISO 178 using 80 ⁇ 10 ⁇ 4 mm 3 test bars injection-moulded in line with ISO 19069-2, of from 900 to 2200 MPa, more preferably from 950 to 2000 MPa. Still more preferably, the mixed-plastics blend (B) preferably has a Charpy Notched impact strength at 23 °C, determined according to ISO 179 using 80 ⁇ 10 ⁇ 4 mm 3 test bars injection-moulded in line with ISO 19069-2, in the range from 10.0 to 70.0 kJ/m 2 , preferably from 15.0 to 60 kJ/m2.
  • Ethylene-1-octene elastomer The ethylene-1-octene elastomer (EC) is an elastomeric copolymer containing ethylene monomers and 1-octene comonomers.
  • the ethylene-1-octene elastomer (EC) is preferably provided in an amount in the range from 0 to 7.5 wt.-%, more preferably in the range from 0 to 6.5 wt.-%, relative to the total weight of the polypropylene composition (PC).
  • the ethylene-1-octene elastomer (EC) preferably is a virgin polymer, which is compounded to the other components.
  • the ethylene-1-octene elastomer (EC) preferably has a melt flow rate (MFR2), determined according to ISO 1133 at 190 °C and 2.16 kg, in the range from 0.2 to 2.5 g/10 min, more preferably in the range from 0.3 to 1.5 g/10 min, most preferably in the range from 0.4 to 1.0 g/10 min.
  • the ethylene-1-octene elastomer (EC) preferably has a density, determined according to ISO 1183-187, in the range from 850 to 870 kg/m 3 , more preferably in the range from 855 to 867 kg/m 3 , most preferably in the range from 860 to 865 kg/m 3 .
  • Inorganic filler (F) The inorganic filler (F) is preferably provided in an amount in the range from 0 to 25.0 wt.-%, more preferably in the range from 0 to 21.0 wt.-%, most preferably in the range from 12.0 to 18.0 wt.-%, relative to the total weight of the polypropylene composition (PC).
  • the inorganic filler (F) preferably is a virgin filler, which is compounded to the other components. Residual inorganic filler, which may be present in the mixed-plastic polypropylene blend (B) is not subsumed under inorganic filler (F). It is preferred that the inorganic filler is selected from the group containing talc, calcium carbonate, barium sulfate, mica, and mixtures thereof. Most preferably, the inorganic filler (F) is talc.
  • the inorganic filler (F) has a median diameter (d50) in the range from 1.0 to 15.0 ⁇ m, more preferably in the range from 2.0 to 10.0 ⁇ m, most preferably in the range from 2.5 to 5.0 ⁇ m. It is preferred that the inorganic filler (F) has a top cut diameter (d95) in the range from 2.0 to 30.0 ⁇ m, more preferably in the range from 4.0 to 20.0 ⁇ m, most preferably in the range from 5.0 to 10.0 ⁇ m.
  • Pigment masterbatch (P) The polypropylene composition (PC) is preferably a pigmented polypropylene composition.
  • a pigment masterbatch (P) is preferably provided in an amount in the range from 0.5 to 10.0 wt.-%, more preferably in the range from 2.0 to 10.0 wt.-%, relative to the total weight of the polypropylene composition (PC).
  • the pigment masterbatch has a total pigment content in the range from 40.0 to 80.0 wt.-%, relative to the total weight of the pigment masterbatch (P).
  • the pigment masterbatch (P) may comprise one pigment, or it may comprise multiple pigments.
  • the pigment masterbatch (P) comprises more than one pigment
  • the pigment masterbatch may be provided as multiple pigment masterbatches, each containing a single pigment, wherein the sum of the amounts of the individual pigment masterbatches equals the total weight of the pigment masterbatch (P) according to the present invention.
  • the selection of the pigment depends on the intended colour of the polypropylene composition (PC). Beyond such considerations, the choice of suitable pigment is not restricted. The person skilled in the art would be able to select suitable pigment(s) to achieve a certain end colour of the composition.
  • Additives (A) The further additives (A) are preferably provided in an amount in the range from 0.2 to 5.0 wt.-%. The skilled practitioner would be able to select suitable additives that are well known in the art.
  • the additives (A) are preferably selected from antioxidants, UV-stabilisers, anti- scratch agents, mold release agents, acid scavengers, lubricants, anti-static agents, and mixtures thereof. It is understood that the content of additives (A), given with respect to the total weight of the polypropylene composition (PC), includes any carrier polymers used to introduce the additives to said polypropylene composition (PC), i.e. masterbatch carrier polymers. An example of such a carrier polymer would be a polypropylene homopolymer in the form of powder.
  • the present invention is directed to an article, preferably an injection-moulded article, comprising the polypropylene composition according to any one of the preceding claims in an amount of at least 95 wt.-%, more preferably at least 98 wt.-%, most preferably at least 99 wt.-%.
  • the article, more preferably the injection-moulded article is an automotive interior article, more preferably selected from the group consisting of dashboards, step assists, interior trims, ash trays, interior body panels and gear shift levers.
  • the article comprising, preferably consisting of the polypropylene composition (PC) has been found to show a good balance of properties in regard of surface quality and toughness after processing.
  • the article preferably has a scratch resistance at 10 N in the range from -0.20 to 1.00, more preferably in the range from 0.00 to 0.75. Further, the article preferably has an average coefficient of linear thermal expansion at a temperature range from +23 to +80°C at a heating rate of 1 °C/min in machine direction (average CLTE 23-80°C) of below 150 ⁇ m/m°C, such as not more than 140 ⁇ m/m°C, more preferably not more than 135 ⁇ m/m°C, still more preferably not more than 115 ⁇ m/m°C , most preferably not more than 112 ⁇ m/m°C.
  • the lower limit of the average CLTE 23-80°C is usually at least 70 ⁇ m/m°C, preferably at least 75 ⁇ m/m°C.
  • the average CLTE 23-80°C can be the arithmetic mean of CLTE 23-80°C, MD and CLTE 23-80°C, TD.
  • the article preferably has an average coefficient of linear thermal expansion at a temperature range from -30 to +80°C at a heating rate of 1 °C/min in machine direction (average CLTE -30-80°C) of below 120 ⁇ m/m°C, such as not more than 115 ⁇ m/m°C, more preferably not more than 95 ⁇ m/m°C, still more preferably not more than 91 ⁇ m/m°C , most preferably not more than 90 ⁇ m/m°C.
  • the lower limit of the average CLTE -30-80°C is usually at least 55 ⁇ m/m°C, preferably at least 60 ⁇ m/m°C.
  • the average CLTE -30-80°C can be the arithmetic mean of CLTE -30-80°C, MD and CLTE -30-80°C, TD.
  • the coefficient of linear thermal expansion is usually measured on 10 mm long pieces cut from the center of injection moulded bar test specimens of 80 ⁇ 10 ⁇ 4 mm3 prepared in accordance with ISO 19069-2.
  • the average CLTE 23-80°C and the average CLTE -30-80°C can also be determined from test specimens of the accordant dimensions cut out of injection moulded articles, like injection moulded automotive articles, from the arithmetic mean of the coefficient of linear thermal expansion coefficients measured on said test specimens in two orthogonal directions.
  • the article preferably has an isotropic area shrinkage of not more than 1.50%, more preferably not more than 1.40%, still more preferably not more than 1.15%, most preferably not more than 1.10%, determined on injection moulded samples.
  • the lower limit of the isotropic area shrinkage, determined on injection moulded samples, is usually at least 0.25%, preferably 0.50%. Examples 1. Measuring methods The following definitions of terms and determination methods apply for the above general description of the invention including the claims as well as to the below examples unless otherwise defined. Quantification of microstructure by NMR spectroscopy Quantitative nuclear-magnetic resonance (NMR) spectroscopy was used to quantify the comonomer content of the polymers.
  • NMR nuclear-magnetic resonance
  • Standard single-pulse excitation was employed utilising the NOE at short recycle delays of 3 s ⁇ pollard04, klimke06 ⁇ and the RS- HEPT decoupling scheme ⁇ fillip05,griffin07 ⁇ .
  • a total of 1024 (1k) transients were acquired per spectra.
  • Quantitative 13 C ⁇ 1 H ⁇ NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals. All chemical shifts are internally referenced to the methyl isotactic pentad (mmmm) at 21.85 ppm. Characteristic signals corresponding to the incorporation of 1-butene were observed ⁇ brandolini01 ⁇ and the comonomer content quantified.
  • Btotal B + BB Characteristic signals corresponding to the incorporation of ethylene were observed ⁇ brandolini01 ⁇ and the comonomer content quantified.
  • Literature (as referred to above): klimke06 Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, H.W., Wilhelm, M., Macromol. Chem. Phys. 2006;207:382. parkinson07 Parkinson, M., Klimke, K., Spiess, H.W., Wilhelm, M., Macromol. Chem. Phys. 2007;208:2128. pollard04 Pollard, M., Klimke, K., Graf, R., Spiess, H.W., Wilhelm, M., Sperber, O., Piel, C., Kaminsky, W., Macromolecules 2004;37:813.
  • Crystallization extraction (CRYSTEX) analysis analyses the polymeric part of each component, with non-polymeric parts, such as any fillers or particulate pigments, not contributing to the reported CRYSTEX data presented. Determination of Crystalline and soluble fractions and their respective properties (iV and Ethylene content) The crystalline (CF) and soluble fractions (SF) of the polypropylene compositions as well as the comonomer content and intrinsic viscosities of the respective fractions were analyzed by use of the Crystex (crystallisation extraction) method.
  • Crystex QC or Crystex 42 Polymer Char; Valencia, Spain. Details of the technique and the method can be found in 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, 581-596). The crystalline and amorphous fractions are separated through temperature cycles of dissolution at 160°C, crystallization at 40°C and re-dissolution in 1,2,4- trichlorobenzene at 160°C.
  • Quantification of SF and CF and determination of ethylene content (C2) are achieved by means of an integrated infrared detector (IR4) and for the determination of the intrinsic viscosity (IV) an online 2-capillary viscometer is used.
  • the IR4 detector is a multiple wavelength detector measuring IR absorbance at two different bands (CH3 stretching vibration (centred at app.2960 cm -1 ) and the CH stretching vibration (2700-3000 cm -1 ) that are serving for the determination of the concentration and the Ethylene content in Ethylene-Propylene copolymers.
  • the IR4 detector is calibrated with series of 8 EP copolymers with known Ethylene content in the range of 2 wt.-% to 69 wt.-% (determined by 13C-NMR) and each at various concentrations, in the range of 2 and 13mg/ml.
  • the samples to be analyzed are weighed out in concentrations of 10mg/ml to 20mg/ml.
  • the weighed out sample was packed into a stainless steel mesh MW 0,077/D 0,05mmm.
  • 1,2,4-TCB containing 250 mg/l 2,6-tert-butyl-4- methylphenol (BHT) as antioxidant the sample is dissolved at 160°C until complete dissolution is achieved, usually for 60 min, with constant stirring of 400rpm.
  • the polymer solution is blanketed with the N2 atmosphere during dissolution. A defined volume of the sample solution is injected into the column filled with inert support where the crystallization of the sample and separation of the soluble fraction from the crystalline part is taking place.
  • the MFR 2 of polypropylene is determined at a temperature of 230 °C and a load of 2.16 kg.
  • the MFR 2 of polyethylene is determined at a temperature of 190 °C and a load of 2.16 kg.
  • Density The density is measured according to ISO 1183-187. Sample preparation is done by compression moulding in accordance with ISO 1872-2:2007.
  • the Flexural Modulus is determined according to ISO 178 method A (3-point bending test) on 80 mm ⁇ 10 mm ⁇ 4 mm specimens. Following the standard, a test speed of 2 mm/min and a span length of 16 times the thickness was used. The testing temperature was 23 ⁇ 2° C. Injection moulding was carried out according to ISO 19069-2 using a melt temperature of 230°C for all materials irrespective of material melt flow rate.
  • Notched impact strength The Charpy notched impact strength (NIS) was measured according to ISO 1791eA at +23°C or -20 °C, using injection moulded bar test specimens of 80 ⁇ 10 ⁇ 4 mm3 prepared in accordance with ISO 19069-2 using a melt temperature of 230°C for all materials irrespective of material melt flow rate.
  • Instrumented Puncture Test Instrumented puncture test was performed on 60 x 60 x 3 mm 3 injection-molded plaques, prepared in accordance with ISO 19069-2, at -30°C according to ISO 6603-2:2000. The measurement was done after 96 h conditioning time of the specimen at +23°C, the test was conducted at -30°C.
  • Test specimens of the accordant dimensions can also be cut from samples of injection moulded articles, such as injection moulded automotive articles.
  • Average particle size (diameter) d 50 and top cut d 95 The particle size defintions were calculated from the particle size distribution [mass percent] as determined by laser diffraction method, using Laser Mastersizer, according to ISO 13320-1.
  • the d50 is defined as the median diameter, whilst d95 is the diameter at the 95 th percentile, as observed from the particle size distribution.
  • Scratch Resistance To determine the scratch visibility, a Cross Hatch Cutter Model 420P, manufactured by Erichsen, was used.
  • the period between injection moulding of specimens and scratch-testing was 7 days.
  • Limonene detection can be carried out using solid phase microextraction (HS- SPME-GC-MS) by standard addition. 50 mg ground samples are weighed into 20 mL headspace vials and after the addition of limonene in different concentrations and a glass-coated magnetic stir bar, the vial is closed with a magnetic cap lined with silicone/PTFE.
  • Micro capillaries (10 pL) are used to add diluted limonene standards of known concentrations to the sample. Addition of 0, 2, 20 and 100 ng equals 0 mg/kg, 0.1 mg/kg, 1mg/kg and 5 mg/kg limonene, in addition standard amounts of 6.6 mg/kg, 11 mg/kg and 16.5 mg/kg limonene is used in combination with some of the samples tested in this application. For quantification, ion-93 acquired in SIM mode is used. Enrichment of the volatile fraction is carried out by headspace solid phase microextraction with a 2 cm stable flex 50/30 pm DVB/Carboxen/PDMS fibre at 60°C for 20 minutes.
  • the purpose of this test method is to identify the presence of paint particles in PP compounds based on end-of-life vehicle PP raw materials.
  • Sample preparation Around 1-2 grams of polymer compound material taken from real parts or pellets are compressed into films of around 35-70 ⁇ m thickness by compression molding providing good visibility of inclusions and enough IR transmittance. The diameter of each compression molded film is around 8 cm. Compression molding is performed at 190°C at around 80 bar pressure. At least 5 inclusions that are clearly visible under the optical microscope (OM) are identified and individually marked for detailed characterization by IR and CT. Inclusions of interest are chosen by OM such that the size is preferably > 100 ⁇ m, that the shape is showing sharp edges and that the color is different from that of the surrounding polymer matrix. 2.
  • IR microscopic measurements are carried out to identify the chemistry of the inclusions. Two sets of inclusions, viz., “inclusions of interest” and “comparative inclusions” are defined for chemical characterization by IR microscope. IR microscopic measurements are carried out in Bruker Vertex 70 Spectrometer equipped with Hyperion 200 microscope. Infrared or FT-IR microscopy combines FT-IR spectroscopy with traditional light microscopy. This provides an easy, “point and shoot” approach to chemical analysis of very small structures.
  • a sample/ film is first visually examined and from there, a region of interest on the film is selected, which in the present case are inclusions for chemical analysis or identification.
  • FTIR spectra are obtained using IR microscope with spectral window between 600 cm -1 to 4000 cm -1 and spectral resolution of 2 cm -1 . Spectra are processed with zero filling factor of 32 and Norton Beer strong apodization. The “inclusions of interests” result in IR spectra with certain specific characteristics. In the FTIR spectra of inclusions of interest, sharp bands at around 700 cm -1 and 760 cm -1 are observed.
  • CT Computed tomography
  • 3D shape, grey value distribution and average grey value are determined.
  • the source of grey value contrast between paint residues and PP is the color pigments having higher density.
  • X-ray Computed Tomography (CT) is performed using a Thermo Fisher Scientific Heliscan MK2 (Thermo Fisher Scientific) device. Around the inclusions, ca. 1 cm wide parts are cut out of the compression molded films.
  • the Voxelsize is set to 4.5 ⁇ m.
  • the X-ray tube is operated with LaB6 filament, voltage is set to 60 kV, focal spot size is set to medium and a pre-filter made of steel with 0.1 mm thickness is used.
  • the specimens are scanned with Space Filling trajectory. Together with the specimens, discs with 5 mm in diameter and 500 ⁇ m in thickness, made of different polymers, glass and aluminum, are scanned at once. These discs act as reference for the determination of relevant grey value regimes since grey values correlate with density.
  • the software Avizo for industrial inspection (Thermo Fisher Scientific) is used for data analysis.
  • the grey value distribution of a inclusion can be inhomogeneous showing pigments with different sizes. 4. Definition of criteria for paint residue identification (“inclusions of interest”) - The appearance under the optical microscope is sharp edged and of different color compared to the polymer matrix background. - The IR spectrum contains the features indicating the presence of styrene modifications, acrylates or urethanes in the way as described above. - The CT determined 3D shape of paint residues is sharp edged and platelet-like. Single inclusions can consist of more than one platelet resulting in a multilayered structure. - Paint residues have average CT grey values that are at least 50 % higher compared to the average PP grey value.
  • Applied headspace parameters for the analyses of standards and samples differed in the vial equilibration time and the HS oven temperature. Apart from that, method parameters were kept the same for standard and sample runs.
  • the mass spectrometer was operated in scan mode and a total ion chromatogram (TIC) was recorded for each analysis. Identification of substances was supported by deconvolution and a retention time comparison to the respective marker substance in the standard.
  • ⁇ HS parameter (Agilent G1888 Headspace Sampler) Vial equilibration time: 5 min (standard), 120 min (sample) Oven temperature: 200 °C (standard), 100 °C (sample) Loop temperature: 205 °C Transfer line temperature: 210 °C Low shaking
  • ⁇ GC parameter (Agilent 7890A GC System) Column: ZB-WAX 7HG-G007-22 (30 m x 250 ⁇ m x 1 ⁇ m) Carrier gas: Helium 5.0 Flow: 2 ml/min Split: 10:1 GC oven program: 35 °C for 0.1 min 10 °C/min until 250 °C 250 °C for 1 min ⁇ MS parameter (Agilent 5975C inert XL MSD) Acquisition mode: Scan Scan parameters: Low mass: 20 High mass: 200 Threshold: 10 ⁇ Software/Data evaluation MSD ChemStation F.01.03.23
  • the corresponing target ions are depicted in table 1.
  • Table 1 Retention times and substance specific target ions of selected marker substances.
  • Substance Retention time / min Target ion (m/z) Acetaldehyde 1.6 44 Acetone 2.3 58 D-Limonene 7.6 136 Acetic acid 11.5 60
  • the standard concentration of a marker substance in the HS vial ( ⁇ ⁇ [mg/ m ⁇ ]) was calculated according to equation 1, where the marker substance concentration in the liquid standard ( ⁇ ⁇ ⁇ [ ⁇ g/ml]) was multiplied by the injection volume of the standard and divided by the volume of HS vial ( ⁇ [ ⁇ ⁇ ]).
  • a HS volume of 20 ml is used by default.
  • Equation 1 For each marker compound in the standard a response factor ( ⁇ ⁇ ) was calculated according to equation 2. Equation Therein, the marker compound concentration is divided by the integrated peak area of the corresponding marker compound in the EIC ( ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ). In order to estimate the respective marker compound concentration in the headspace of a sample ( ⁇ ⁇ [mg/m ⁇ ]), equation 3 was used. Therefore, the obtained response factor from equation 2 is multiplied by the peak area of the corresponding marker compound in the EIC of the sample run ( ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ).
  • Fogging Fogging was measured according to ISO 75201:2011-11, method B (gravimetric method) on specimens (diameter 80 mm +/- 1mm, thickness 3 mm) cut out from an injection moulded plate.
  • the injection-moulded plates has dimensions of 148.5 x 210 x 3 mm.
  • the plate was produced on an injection-moulding machine Engel ES 1050/250 HL having melting temperature of 240 °C, using holding pressure of 419 bar at 3.5 s. After production, the plates were stored at ambient conditions for 24 h and subsequently packed in Al-bags. With this method, the mass of fogging condensate on aluminium foil in mg by means weighing of foil before and after the fogging test is determined.
  • thermo-desorption analysis refers to a fraction of volatile substances condensed on glass parts as e.g. the windscreen of a vehicle. Screening of organic emissions by thermo-desorption analysis (LBS and HBS) This method describes the semi-quantitative determination of organic compounds emitting from polyolefins. It is similar to the VDA 278 (October 2011) but includes specific adjustments. After the production the sample (injection moulded plaque, DIN-A5) is stored for 24 h at ambient temperature and sealed in an aluminium-coated polyethylene bag and provided to the lab within 14 days. After this period, an aliquot of 60 ⁇ 5 mg is prepared from the stored sample. Trimming the aliquot should aim for a maximum coherent area.
  • LBS and HBS thermo-desorption analysis
  • the diameter of the sample injection tube should be used first. Length and thickness should be chosen accordingly, considering the specified aliquot weight.
  • the aliquot is directly desorbed using heat and a flow of helium gas. Volatile and semi-volatile organic compounds are extracted into the gas stream and cryo-focused prior to the injection into a gas chromatographic (GC) system for analysis.
  • the method comprises two extraction stages: In the analysis of low-boiling substances (LBS) the aliquot is desorbed at 90 °C for 30 min to determine volatile organic compounds in the boiling / elution range up to n-C25 (n- pentacosane).
  • LBS low-boiling substances
  • HBS high-boiling substances
  • the method requires a Thermal Desorption System TDS 3 (Gerstel) and a Cooled Injection System CIS 4 (Gerstel) as well as a GC system with a flame ionisation detector (FID) but does not involve a mass spectrometer. Instead of 280 °C the CIS end temperature is always set to 380 °C.
  • Coefficient of linear thermal expansion (CLTE) The coefficient of linear thermal expansion (CLTE) was determined in accordance with ISO 11359-2:1999 on 10 mm long pieces cut from the center of same injection molded specimens as used for the flexural modulus determination or Charpy notched impact strength determination.
  • the dimension of CLTE specimen was 10x10x4mm3 for CLTE MD measurement and 8x10x4mm3 for CLTE TD measurement.
  • Test specimens of the accordant dimensions can also be cut from samples of injection moulded articles, such as injection moulded automotive articles. The measurement was performed in a temperature range from -30 to +80°C at a heating rate of 1 °C/min and a temperature range from 23 to +80°C at a heating rate of 1 °C/min in machine direction, respectively.
  • the average CLTE is the average value of the CLTE MD measurement and the CLTE TD measurement.
  • Isotropic area shrinkage The area shrinkage was calculated from shrinkage data determined on circular sector plates of 320 mm radius, 20 ° opening angle and 2.8 mm thickness produced by injection moulding with an Engel ES 1350/350 machine and filled through a rectangular gate of 7.6 x 2.8 mm2 at the base of the sector. Test specimens of the accordant dimensions can also be cut from samples of injection moulded articles, such as injection moulded automotive articles. A melt temperature of 240 °C, a mould temperature of 25 °C and a filling time of 3.5 s were used, followed by a holding time of 20 s at a holding pressure of 400 bar.
  • a pattern of circular dots was generated on the plates by eroded spots of 1 mm diameter at distances between 5 and 10 mm.
  • the original pattern is recorded immediately after de- moulding by an OGP Smartscope Flash 400 optical gauging system and used as dimensional reference. After 96 h at 23 °C, the post-shrinkage moulding pattern is determined and all deviations of point-to-point distances are recorded. For calculating the isotropic area shrinkage, a number of measuring points is connected by vectors and the resulting area determined, with A being the area after 96 h and A0 the area before that period.
  • HECOs heterophasic propylene-ethylene copolymers
  • the catalyst used for producing HECO1 was a Ziegler-Natta catalyst commercially available from Lyondell Basell (IT), under the trade name ZN180M.
  • the catalyst used for producing HECO2 was a Ziegler-Natta catalyst from Borealis having Ti-content of 1.9 wt.-% (as described in EP 591224). Before the polymerization, the catalyst was prepolymerized with vinyl-cyclohexane (VCH) as described in EP 1028984 and EP 1183307.
  • VCH vinyl-cyclohexane
  • the ratio of VCH to catalyst of 1:1 was used in the preparation, thus the final poly-VCH content was less than 100 ppm.
  • the catalyst described above was fed into prepolymerization reactor together with propylene and small amount of hydrogen (2.5 g/h) and ethylene (330 g/h).
  • Triethylaluminium as a cocatalyst and dicyclopentyldimethoxysilane as a donor was used.
  • the aluminium to donor ratio was 7.5 mol/mol and aluminium to titanium ratio was 300 mol/mol.
  • Reactor was operated at a temperature of 30 °C and a pressure of 55 barg. The subsequent polymerization has been effected under the following conditions.
  • B-ELV1 and B-ELV2 shredded flakes from bumper parts from end of life vehicles were received and pelletized on a double-screw extruder using 200 ⁇ m melt filter and adding 0.30 wt% of a 1:1 mixture of pentaerythrityl-tetrakis(3-(3’,5’-di- tert. butyl-4-hydroxyphenyl)-propionate from BASF and Tris (2,4-di-t-butylphenyl) phosphite from BASF.
  • EC an elastomeric ethylene-1-octene copolymer with a trade name of Engage 8180, commercially available from Dow Chemicals (USA), having an MFR2 (190 °C) of 0.5 g/10 min and a density of 863 kg/m 3 .
  • F talc with a trade name of Jetfine 3CA, commercially available from Imerys (France), with median diameter d50 of 3.9 ⁇ m and top cut diameter d95 of 7.8 ⁇ m.
  • Black MB a polyethylene based masterbatch CBMB LD-09 A02 from Borealis AG (Norway).
  • White MB a polyethylene based masterbatch Masterminds PE white 90/1111 from QolorTech (The Netherlands). It contains 70 wt.-% of pigment.
  • Additives MB an additive masterbatch, consisting of 2.40 wt.-% of a carrier propylene homopolymer with a trade name of HC001 A, commercially available from Borealis AG (Austria), 0.10 wt.-% of an antioxidant with a trade name of Irgafos 168 (CAS-no. 31570-04-4), available from BASF AG (Germany), 0.25 wt.-% of an antioxidant with a trade name of Irganox 1076 (CAS-no.
  • Figures 1-5 show examples for IR spectra from exemplary inclusions selected from compressed films having a thickness of about 70 ⁇ m prepared from the compositions of examples CE1, IE3, IE7 and IE8.
  • Fig 1 the spectra of the polypropylene composition matrix of CE1 and two transparent inclusions (inclusions 1 and 2) are shown. The spectra show comparable peaks so that the two transparent inclusions are identified as inclusions, which are composed of the polypropylene composition which differs from the matrix in a lower silicone content and lower talc content.
  • Fig. 2 the spectra of the polypropylene composition matrix of CE1 and two different transparent inclusions (inclusions 3 and 4) are shown.
  • Fig. 3 the spectra three inclusions of IE3 are shown.
  • Fig. 4 the spectra of three inclusions of IE7 are shown.
  • Figures 6-12 show examples for CT pictures of exemplary inclusions selected from compressed films having a thickness of about 70 ⁇ m prepared from the compositions of examples CE5, CE4, IE6, IE7 and IE8.
  • Fig 6 shows an inclusion of example CE5 with an irregular round 3D shape, which has been identified as an ethylene-vinylacetate (EVA) particle.
  • Fig 7 shows an inclusion of example CE5 with an irregular round 3D shape, which has been identified as a silicone rubber particle.
  • Fig 8 shows an inclusion of example CE4 with a round shape, which has been identified as talc particle.
  • Fig 9 shows an inclusion of example IE6 with a multilayer sharp edged and platelet- like 3D shape and has been identified as paint particle.
  • Fig 10 shows a second inclusion of example IE6 with a sharp edged and platelet-like 3D shape and has been identified as paint particle.
  • Fig 11 shows an inclusion of example IE7 with a sharp edged and platelet-like 3D shape and has been identified as paint particle.
  • Fig 12 shows an inclusion of example IE8 with a sharp edged and platelet-like 3D shape and has been identified as paint particle.
  • Fig. 6- 8 show CT pictures of comparative inclusions
  • Fig. 39-12 show CT pictures of inclusions of interest.
  • the compositions have been prepared as such that several inventive compositions comprising an ELV mixed plastics polypropylene blend can be directly compared to several comparative compositions comprising a PCR mixed plastics polypropylene blend.
  • compositions can be directly compared: CE1, IE1 and IE3 (in addition IE2 and IE4 with the same general composition obtained with higher amounts of ELV mixed plastics polypropylene blend of about 45 wt.-% and IE7 with the same general composition obtained with a lower amount of ELV mixed plastics polypropylene blend of 23 wt.-%)
  • CE3 and IE6 with the same general composition as CE1, IE1 and IE3 with an amount of ELV mixed plastics polypropylene blend of 50 wt.-%
  • CE5 and IE9 with a high overall amount of inorganic filler (24.5 wt.-% ash content) It can be seen that a comparable balance of properties can

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de polypropylène (PC) qui est un mélange de polypropylène de plastiques mixtes contenant un matériau recyclé et comprenant des inclusions attribuées à des peintures automobiles et des articles comprenant ladite composition de polypropylène (PC).
PCT/EP2024/065580 2023-06-07 2024-06-06 Composition de polypropylène contenant un recyclat pour applications automobiles intérieures Pending WO2024251869A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1028984A1 (fr) 1997-11-07 2000-08-23 Borealis A/S Procede de preparation de polypropylene
EP1183307A1 (fr) 1999-05-07 2002-03-06 Borealis Technology Oy Polymeres de propylene de haute rigidite et leur obtention
EP4101890A1 (fr) * 2021-06-09 2022-12-14 Borealis AG Compositions de polypropylène pour applications automobiles extérieures
EP4194504A1 (fr) * 2021-12-07 2023-06-14 Borealis AG Compositions de polypropylène contenant des recyclats et présentant une excellente qualité de surface

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1028984A1 (fr) 1997-11-07 2000-08-23 Borealis A/S Procede de preparation de polypropylene
EP1183307A1 (fr) 1999-05-07 2002-03-06 Borealis Technology Oy Polymeres de propylene de haute rigidite et leur obtention
EP4101890A1 (fr) * 2021-06-09 2022-12-14 Borealis AG Compositions de polypropylène pour applications automobiles extérieures
EP4194504A1 (fr) * 2021-12-07 2023-06-14 Borealis AG Compositions de polypropylène contenant des recyclats et présentant une excellente qualité de surface

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