WO2021122299A1 - Blend comprising polyethylene based recyclate - Google Patents

Blend comprising polyethylene based recyclate Download PDF

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Publication number
WO2021122299A1
WO2021122299A1 PCT/EP2020/085509 EP2020085509W WO2021122299A1 WO 2021122299 A1 WO2021122299 A1 WO 2021122299A1 EP 2020085509 W EP2020085509 W EP 2020085509W WO 2021122299 A1 WO2021122299 A1 WO 2021122299A1
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WO
WIPO (PCT)
Prior art keywords
mixed
units
plastic
polyethylene
blend
Prior art date
Application number
PCT/EP2020/085509
Other languages
French (fr)
Inventor
Yi Liu
Susanne Kahlen
Hermann Braun
Elisabeth Ribarits
Christian Goetzloff
Gerhard Hubner
Ruth Dammert
Sanna RONKAINEN
Andreas RÖSSLER-CZERMAK
Jari Äärilä
Original Assignee
Borealis Ag
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Filing date
Publication date
Application filed by Borealis Ag filed Critical Borealis Ag
Priority to EP20820429.7A priority Critical patent/EP4077531A1/en
Priority to KR1020227024711A priority patent/KR102715405B1/en
Priority to BR112022011747A priority patent/BR112022011747A2/en
Priority to US17/785,264 priority patent/US20230114045A1/en
Priority to CN202080086629.6A priority patent/CN114829481B/en
Publication of WO2021122299A1 publication Critical patent/WO2021122299A1/en

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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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/02—Disposition of insulation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
    • 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
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • 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
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • Blend comprising polyethylene based recyclate
  • the present invention relates to upgrading of PE recycling streams using virgin high-density polyethylenes (HDPE) to give jacketing materials that have acceptable ESCR (Environmental Stress Crack Resistance) and/or strain hardening performance.
  • HDPE high-density polyethylenes
  • Polyolefins in particular polyethylene and polypropylene are increasingly consumed in large amounts in a wide range of applications, including packaging for food and other goods, fibres, automotive components, and a great variety of manufactured articles.
  • Polyethylene based materials are a particular problem as these materials are extensively used in packaging. Taking into account the huge amount of waste collected compared to the amount of waste recycled back into the stream, there is still a great potential for intelligent reuse of plastic waste streams and for mechanical recycling of plastic wastes.
  • recycled quantities of polyethylene on the market are mixtures of both polypropylene (PP) and polyethylene (PE), this is especially true for post-consumer waste streams.
  • commercial recyclates from post-consumer waste sources are conventionally cross contaminated with non-polyolefin materials, such as polyethylene terephthalate, polyamide, polystyrene or non polymeric substances like wood, paper, glass or aluminium. These cross-contaminations drastically limit final applications or recycling streams such that no profitable final uses remain.
  • recycled polyolefin materials normally have properties, which are much worse than those of the virgin materials, unless the amount of recycled polyolefin added to the final compound is extremely low.
  • such materials often have limited impact strength and poor mechanical properties (such as e.g. brittleness) and thus, they do not fulfil customer requirements.
  • jacketing materials for cables
  • containers for automotive components
  • household articles This normally excludes the application of recycled materials for high quality parts, and means that they are only used in low-cost, non demanding applications, such as e.g. in construction or in furniture.
  • compatibilizing/coupling agents and elastomeric polymers are added. These materials are generally virgin materials, which are produced from oil.
  • US 8981007 B2 relates to non-crosslinked polyethylene compositions for use in the jacketing of power cables.
  • crosslinked polyethylene is used for power cables, due to its excellent heat resistance, chemical resistance and electrical properties.
  • crosslinked polyethylene resin is a thermoset resin, it is not recyclable. There is, therefore, a demand for an eco-friendly non-crosslinked type thermoplastic polyethylene resin, which is also heat resistant and hence suitable for use in power cables.
  • EP 2417194 B1 also relates to uncrosslinked polyethylene compositions for use in power cables.
  • the compositions disclosed herein are polymer blends comprising MDPE and HDPE and one or more additive(s) selected from a flame retardant, an oxidation stabilizer, a UV stabilizer, a heat stabilizer and a process aid.
  • DE-102011108823-A1 relates to a composite for electrical isolation of electrical cables.
  • the composite comprises a plastic, a material having a heat conductivity of less than 1 W/(mk) and a displacement material (C).
  • the displacement material can be a recycled material.
  • EP 1676283 B1 relates to medium/high voltage electrical energy transport or distribution cables comprising at least one transmissive element and at least one coating layer, said coating layer being made from a coating material comprising at least one recycled polyethylene (obtained from a waste material) with a density not higher than 0.940 g/cm 3 and at least a second polyethylene material having a density higher than 0.940 g/cm 3 .
  • the coating material in some of the examples of EP 1676283 B1 showed improved values with respect to stress cracking resistance with respect to those obtained from recycled polyethylene alone. However, these values were considerably less than those obtained with the virgin material, DFDG-6059® Black.
  • EP 2417 194 B1 relates to power cables comprising an non crosslinked polyethylene composition
  • a non crosslinked polyethylene composition comprising 100 parts by weight of a polymer comprising 60 to 95 wt% of a linear medium density polyethylene resin comprising an alpha-olefin having 4 or more carbon atoms as a comonomer and having a melt index of 0.6-2.2 g/10 min (at 190 °C under a load of 5 kg), a differential scanning calorimetry (DSC) enthalpy of 130-190 joule/g and a molecular weight distribution of 2-30; and 5 to 40 wt% of a high-density polyethylene resin having a melt index of 0.1-0.35 g/10 min (at 190 °C under a load of 5 kg), a DSC enthalpy of 190-250 joule/g and a molecular weight distribution of 3-30; 0.1 to 10 parts by weight of one or more additive(s) selected from a flame retard
  • the present invention provides compositions with acceptable ESCR and strain hardening performance, while maintaining other properties similar to the blend of virgin polyethylene marketed for the purpose of cable jacketing.
  • the present invention is also concerned with maximising the loading of recycled material (with loadings of up to 85 % recycled material) in the composition and with the use of a combination of specific blends of virgin polyethylene to improve the ESCR properties and or strain hardening properties of a mixed-plastic- polyethylene primary recycling blend (A).
  • the present invention relates to a mixed-plastic-polyethylene composition
  • a mixed-plastic-polyethylene composition comprising a total amount of ethylene units (C2 units) of from 90.00 to 99.00 wt%, and a total amount of continuous units having 3 carbon atoms corresponding to polypropylene (continuous C3 units) of from 0.10 to 5.00 wt%, with the total amounts of C2 units and continuous C3 units based on the total weight amount of monomer units in the composition and measured according to quantitative 13 C ⁇ 1 H ⁇ NMR measurement, and wherein the composition has a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 2.0 g/10 min; a density of from 930 kg/m 3 to 955 kg/m 3 , preferably from 932 to 953 kg/m.
  • a melt flow rate ISO 1133, 2.16 kg, 190 °C
  • the present invention relates to a mixed-plastic-polyethylene composition having a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 2.0 g/lOmin; and a density of from 930 kg/m 3 to 955 kg/m 3 , preferably from 932 to 953 kg/m 3 ; obtainable by blending and extruding components comprising
  • a mixed-plastic- polyethylene primary recycling blend (A) wherein at least 90 wt.-%, preferably at least 95 wt.-%, more preferably 100 wt.-% of the mixed-plastic-polyethylene primary blend (A) originates from post-consumer waste and/or post-industrial waste having a limonene content of from 2 to 500 mg/kg; and wherein the mixed-plastic-polyethylene primary blend (A) has a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 1.2 g/lOmin, preferably from 0.3 to 1.1 g/lOmin , a density of from 910 to 945 kg/m 3 , preferably from 915 to 942 kg/m 3 , most preferably from 920 to 940 kg/m 3 , and a total amount of ethylene units (C2 units) of from 80.00 to 96.00 wt
  • the present invention relates to an article, comprising the mixed-plastic-polyethylene composition as described above or below, preferably wherein the article is a cable comprising at least one layer comprising the mixed-plastic-polyethylene composition as described above or below, more preferably wherein the article is a cable comprising a jacketing layer comprising the mixed-plastic-polyethylene composition as described above or below.
  • the present invention relates to a process for preparing the mixed-plastic- polyethylene composition as defined above or below, comprising the steps of: a) providing a mixed-plastic-polyethylene primary recycling blend (A) in an amount of 10 to 85 wt.-% based on the overall weight of the composition, wherein at least 90 wt.-%, preferably at least 95 wt.-%, more preferably 100 wt.-% of the mixed-plastic-polyethylene primary blend (A) originates from post-consumer waste and/or post-industrial waste wherein the mixed-plastic-polyethylene primary blend (A) has a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 1.2 g/lOmin, preferably from 0.3 to 1.1 g/lOmin, a density of from 910 to 945 kg/m 3 , preferably from 915 to 942 kg/m 3 , most preferably from 920 to 940 kg/m 3 , a total melt flow
  • the present invention relates to the use of a mixed-plastic-polyethylene composition as defined above or below for producing a cable layer, preferably a cable jacketing layer, having an ESCR (Bell test failure time) of more than 1000 hours and/or a strain hardening modulus (SH modulus) of from 15.0 to 30.0 MPa.
  • ESCR Bell test failure time
  • SH modulus strain hardening modulus
  • post-consumer waste refers to objects having completed at least a first use cycle (or life cycle), i.e. having already served their first purpose.
  • a blend denotes a mixture of two or more components, wherein one of the components is polymeric.
  • the blend can be prepared by mixing the two or more components. Suitable mixing procedures are known in the art.
  • the term secondary blend (B) refers to a blend comprising at least 90 wt.-% of a reactor made high density polyethylene material. Said high density polyethylene material preferably does not contain carbon black or any other pigments. This high density polyethylene material is a virgin material which has not already been recycled.
  • mixed- plastic-polyethylene indicates a polymer material including predominantly units derived from ethylene apart from other polymeric ingredients of arbitrary nature.
  • polymeric ingredients may for example originate from monomer units derived from alpha olefins such as propylene, butylene, octene, and the like, styrene derivatives such as vinylstyrene, substituted and unsubstituted acrylates, substituted and unsubstituted methacrylates.
  • Said polymeric materials can be identified in the mixed-plastic polyethylene composition by means of quantitative 13 C ⁇ 1 H ⁇ NMR measurements as described herein.
  • the units having 3 carbon atoms can be distinguished in the NMR spectrum as isolated C3 units (isolated C3 units) and as continuous C3 units (continuous C3 units) which indicate that the polymeric material contains a propylene based polymer.
  • isolated C3 units isolated C3 units
  • continuous C3 units continuous C3 units
  • the continuous C3 units thereby can be distinctively attributed to the mixed-plastic-polyethylene primary recycling blend (A) as the secondary blend (B) of virgin high-density polyethylene (HDPE) in the mixed-plastic- polyethylene composition according to the present invention usually does not include any propylene based polymeric components.
  • HDPE high-density polyethylene
  • the units having 3, 4, 6 and 7 carbon atoms describe units in the NMR spectrum which are derived from two carbon atoms in the main chain of the polymer and a short side chain or branch of 1 carbon atom (isolated C3 unit), 2 carbon atoms (C4 units), 4 carbon atoms (C6 units) or 5 carbon atoms (C7 units).
  • the units having 3, 4 and 6 carbon atoms can derive either from incorporated comomoners (propylene, 1 -butene and 1 -hexene comonomers) or from short chain branches formed by radical polymerization.
  • the units having 7 carbon atoms can be distinctively attributed to the mixed- plastic-polyethylene primary recycling blend (A) as they cannot derive from any comonomers. 1-heptene monomers are not used in copolymerization. Instead, the C7 units represent presence of LDPE distinct for the recyclate. It has been found that in LDPE resins the amount of C7 units is always in a distinct range. Thus, the amount of C7 units measured by quantitative 13 C ⁇ 1 H ⁇ NMR measurements can be used to calculate the amount of LDPE in a polyethylene composition. Thus, the amounts of continuous C3 units, isolated C3 units, C4 units, C6 units and C7 units are measured by quantitative 13 C ⁇ 1 H ⁇ NMR measurements as described below, whereas the LDPE content is calculated from the amount of C7 units as described below.
  • the total amount of ethylene units (C2 units) is attributed to units in the polymer chain, which do not have short side chains of 1-5 carbon atoms, in addition to the units attributed to the LDPE (i.e. units which have longer side chains branches of 6 or more carbon atoms).
  • a mixed-plastic-polyethylene primary blend (A) denotes the starting primary blend containing the mixed plastic-polyethylene as described above.
  • further components such as fillers, including organic and inorganic fillers for example talc, chalk, carbon black, and further pigments such as TiCk as well as paper and cellulose may be present.
  • the waste stream is a consumer waste stream, such a waste stream may originate from conventional collecting systems such as those implemented in the European Union.
  • Post-consumer waste material is characterized by a limonene content of from 2 to 500 mg/kg (as determined using solid phase microextraction (HS-SPME-GC-MS) by standard addition).
  • Mixed-plastic-polyethylene primary blend(s) (A) as used herein are commercially available.
  • One suitable recyclate is e.g. available from Ecoplast Kunststoffrecycling GmbH under the brand name NAV 102.
  • jacketing materials refers to materials used in cable jacketing/cable coating applications for electrical/telephone/telecommunications cables. These materials are required to show good ESCR properties, such as a Bell test failure time of > 1000 hours, preferably > 2000 hours.
  • the mixed-plastic-polyethylene composition according to the present invention comprises a mixed-plastic-polyethylene primary recycling blend (A). It is the essence of the present invention that this primary recycling blend is obtained from a post-consumer waste stream and/or a post-industrial waste stream, preferably from a post-consumer waste stream.
  • A mixed-plastic-polyethylene primary recycling blend
  • the mixed-plastic-polyethylene primary recycling blend (A) is generally a blend, wherein at least 90 wt.-%, preferably at least 95 wt.-%, more preferably 100 wt.-% of the mixed-plastic-polyethylene primary blend originates from post consumer waste, such as from conventional collecting systems (curb-side collection), such as those implemented in the European Union, and/or post-industrial waste, preferably from post consumer waste.
  • post consumer waste such as from conventional collecting systems (curb-side collection), such as those implemented in the European Union, and/or post-industrial waste, preferably from post consumer waste.
  • Said post-consumer waste can be identified by its limonene content. It is preferred that the post-consumer waste has a limonene content of from 2 to 500 mg/kg.
  • the mixed-plastic-polyethylene primary recycling blend (A) preferably comprises a total amount of ethylene units (C2 units) of from 80.00 wt% to 96.00 wt%, more preferably of from 82.50 wt% to 95.50 wt%, still more preferably of from 85.00 wt% to 95.50 wt% and most preferably of from 87.50 wt% to 95.00 wt%; a total amount of continuous units having 3 carbon atoms corresponding to polypropylene (continuous C3 units) of from 0.20 to 6.50 wt%, more preferably from 0.40 wt% to 6.00 wt%, still more preferably from 0.60 wt% to 5.50 wt% and most preferably from 0.75 wt% to 5.00 wt%.
  • C2 units ethylene units of from 80.00 wt% to 96.00 wt%, more preferably of from 82.50 wt% to 95.50 wt%, still more
  • the total amounts of C2 units and continuous C3 units thereby are based on the total weight amount of monomer units in the mixed-plastic-polyethylene primary recycling blend (A) and are measured according to quantitative 13 C ⁇ 1 H ⁇ NMR measurement.
  • the mixed-plastic-polyethylene primary recycling blend (A) can further comprise units having 3, 4, 6 or 7 or more carbon atoms so that the mixed-plastic-polyethylene primary recycling blend (A) overall can comprise ethylene units and a mix of units having 3, 4, 6 and 7 or more carbon atoms.
  • the mixed-plastic-polyethylene primary recycling blend (A) preferably comprises one or more in any combination, preferably all of: a total amount of units having 3 carbon atoms as isolated C3 units (isolated C3 units) of from 0.01 wt% to 0.50 wt%, more preferably from 0.02 wt% to 0.40 wt%, still more preferably from 0.03 wt% to 0.30 wt% and most preferably from 0.05 wt% to 0.25 wt%; a total amount of units having 4 carbon atoms (C4 units) of from 0.50 to 5.00 wt%, more preferably from 0.75 wt% to 4.00 wt%, still more preferably from 1.00 wt% to 3.50 wt% and most preferably from 1.25 wt% to 3.00 wt%; a total amount of units having 6 carbon atoms (C6 units) of from 0.50 to 7.50 wt%, more preferably from 0.75 wt% to 6.50 wt
  • the total amounts of C2 units, continuous C3 units, isolated C3 units, C4 units, C6 units, C7 units and LDPE content thereby are based on the total weight amount of monomer units in the mixed-plastic-polyethylene primary recycling blend (A) and are measured or calculated according to quantitative 13 C ⁇ 1 ET ⁇ NMR measurement.
  • the total amount of units, which can be attributed to comonomers (i.e. isolated C3 units, C4 units and C6 units), in the mixed-plastic-polyethylene primary recycling blend (A) is from 4.00 wt% to 20.00 wt%, more preferably from 4.50 wt% to 17.50 wt%, still more preferably from 4.75 wt% to 15.00 wt% and most preferably from 5.00 wt% to 12.50 wt%, and is measured according to quantitative 13 C ⁇ 1 ET ⁇ NMR measurement.
  • the mixed-plastic-polyethylene primary recycling blend (A) preferably shows non-linear viscoelastic behaviour as shown in the below defined Large Oscillatory Shear (LAOS) measurement:
  • the mixed-plastic-polyethylene primary recycling blend (A) preferably has a Large Amplitude Oscillatory Shear Non Linear Factor at a strain of 1000%, LAOS NLF (1000%), of from 2.200 to 10.000, more preferably from 2.400 to 8.500, still more preferably from 2.600 to 7.000 and most preferably from 2.800 to 5.000.
  • LAOS NLF Large Amplitude Oscillatory Shear Non Linear Factor at a strain of 1000%, LAOS NLF (1000%), of from 2.200 to 10.000, more preferably from 2.400 to 8.500, still more preferably from 2.600 to 7.000 and most preferably from 2.800 to 5.000.
  • the mixed-plastic-polyethylene primary recycling blend (A) has a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 1.0 g/10 min, more preferably from 0.3 to 1.1 g/10 min; and/or a density of from 910 to 945 kg/m 3 , more preferably from 915 to 942 kg/m 3 , most preferably from 920 to 940 kg/m 3 .
  • a melt flow rate ISO 1133, 2.16 kg, 190 °C
  • the mixed-plastic-polyethylene primary recycling blend (A) preferably does not comprise carbon black. It is further preferred that the mixed-plastic-polyethylene primary recycling blend (A) does not comprise any pigments other than carbon black.
  • the mixed-plastic-polyethylene primary recycling blend (A) preferably is a natural mixed- plastic-polyethylene primary recycling blend (A).
  • the mixed-plastic-polyethylene primary recycling blend (A) may also include: a) 0 to 10 wt.-% units derived from alpha olefin(s), b) 0 to 3.0 wt.-% stabilizers, c) 0 to 3.0 wt.-% talc, d) 0 to 3.0 wt.-% chalk, e) 0 to 6.0 wt.-% further components all percentages with respect to the mixed-plastic-polyethylene primary recycling blend (A).
  • the mixed-plastic-polyethylene primary recycling blend (A) preferably has one or more, more preferably all, of the following properties in any combination: a melt flow rate (ISO 1133, 5.0 kg, 190 °C) of from 1.5 to 5.0 g/10 min, more preferably from 2.0 to 4.0 g/10 min; a melt flow rate (ISO 1133, 21.6 kg, 190 °C) of from 20.0 to 50.0 g/10 min, more preferably from 25.0 to 40.0 g/10 min; a polydispersity index PI of from 1.0 to 3.5 s 1 , more preferably from 1.3 to 3.0 s 1 ; a shear thinning index SHI2 .
  • a Shore D hardness measured after 15 s according to ISO 868, Shore D 15 s, of from 40 to 60, more preferably of from 45 to 55, a Shore D hardness, measured after 1 s according to ISO 868, Shore D 1 s, of from 45 to 65, more preferably of from 48 to 60, a Shore D hardness, measured after 3 s according to ISO 868, Shore D 3 s, of from 45 to 65, more preferably of from 48 to 60, a strain hardening modulus, SH modulus, of from 12.5 to 20.0 MPa, more preferably from 15.0 to 17.5 MPa, a xylene hot insoluble content, XHU, of from 0.01 to 1.0 wt%, more preferably from 0.1 to 0.5 wt%, a Charpy notched impact strength at 23 °C, Charpy NIS 23 °C, of from 50 to 100 kJ/m
  • the mixed-plastic-polyethylene primary recycling blend (A) has a comparatively low gel content, especially in comparison to other mixed-plastic-polyethylene primary recycling blends.
  • the mixed-plastic-polyethylene primary recycling blend (A) preferably has a gel content for gels with a size of from above 600 pm to 1000 pm of not more than 1000 gels/m 2 , more preferably not more than 850 gels/m 2 .
  • the lower limit of the gel content for gels with a size of from above 600 pm to 1000 pm is usually 100 gels/m 2 , preferably 150 gels/m 2 .
  • the mixed-plastic polyethylene composition preferably has a gel content for gels with a size of from above 1000 pm of not more than 200 gels/m 2 , more preferably not more than 150 gels/m 2 .
  • the lower limit of the gel content for gels with a size of from above 1000 pm is usually 10 gels/m 2 , preferably 25 gels/m 2 .
  • recycled materials perform less well in functional tests such as the ESCR (Bell test failure time), SH modulus and Shore D tests than virgin materials or blends comprising virgin materials.
  • the mixed-plastic-polyethylene primary recycling blend (A) is preferably present in the composition of the present invention in an amount of from 10 to 85 wt%, more preferably 10 to 70 wt%, still more preferably from 15 to 65 wt%, even more preferably from 20 to 55 wt% and most preferably from 25 to 50 wt%, based on the overall weight of the composition.
  • the mixed-plastic-polyethylene composition of the invention comprises a secondary blend (B) of virgin high-density polyethylene (HDPE).
  • B virgin high-density polyethylene
  • the secondary blend (B) preferably has: a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 1.2 g/10 min, preferably from 0.3 to 0.7 g/lOmin; and/or a density of from 940 to 970 kg/m 3 , more preferably from 943 to 965 kg/m 3 ; and/or a polydispersity index from 1.5 to 2.8, more preferably from 1.7 to 2.5.
  • a melt flow rate ISO 1133, 2.16 kg, 190 °C
  • the secondary blend (B) can comprise carbon black or other pigments in an amount of of not more than 5 wt%, preferably not more than 3 wt%.
  • a secondary blend (B) comprising carbon black preferably has a density of from 950 to 970 kg/m 3 , more preferably from 953 to 965 kg/m 3 .
  • the secondary blend (B) does not comprise carbon black. It is further preferred that the secondary blend (B) does not comprise any pigments other than carbon black.
  • the secondary blend (B) of virgin high-density polyethylene (HDPE) is preferably a natural secondary blend (B) of virgin high-density polyethylene (HDPE).
  • the secondary blend (B) of virgin high-density polyethylene (HDPE) preferably has a density of from 940 to 960 kg/m 3 , preferably from 943 to 955 kg/m 3 .
  • the secondary blend (B) includes as polymeric component a copolymer of ethylene and one or more comonomer units selected from alpha-olefins having from 3 to 6 carbon atoms. It is preferred that the polymeric component is a copolymer of ethylene and 1 -butene or a copolymer of ethylene and 1 -hexene.
  • the secondary blend (B) can further comprise additives in an amount of 10 wt% or below, more preferably 9 wt% or below, more preferably 7 wt% or below of the secondary blend (B).
  • Suitable additives are usual additives for utilization with polyolefins, such as stabilizers (e.g. antioxidant agents), metal scavengers and/or UV- stabilizers, antistatic agents and utilization agents (such as processing aid agents).
  • the secondary blend (B) preferably has one or more, more preferably all of the following properties in any combination: a melt flow rate (ISO 1133, 5.0 kg, 190 °C) of from 1.0 to 5.0 g/10 min, more preferably from 1.3 to 4.0 g/10 min; a melt flow rate (ISO 1133, 21.6 kg, 190 °C) of from 20.0 to 50.0 g/10 min, more preferably from 25.0 to 40.0 g/10 min; a shear thinning index SHI2 .
  • a melt flow rate ISO 1133, 5.0 kg, 190 °C
  • a Shore D hardness measured after 15 s according to ISO 868, Shore D 15 s, of from 50 to 70, more preferably of from 55 to 65, a Shore D hardness, measured after 1 s according to ISO 868, Shore D 1 s, of from 55 to 75, more preferably of from 58 to 70, a Shore D hardness, measured after 3 s according to ISO 868, Shore D 3 s, of from 55 to 75, more preferably of from 58 to 70, a strain hardening modulus, SH modulus, of from 20.0 to 35.0 MPa, more preferably from 22.5 to 32.5 MPa, a Charpy notched impact strength at 23 °C, Charpy NIS 23°C, of from 8.0 to 20.0 kJ/m 2 , more preferably from 10.0 to 17.5 kJ/m 2 , a Charpy notched impact strength at 0 °C, Charp
  • recycled materials perform less well in functional tests such as the ESCR (Bell test failure time), SH modulus and Shore D tests than virgin materials or blends comprising virgin materials.
  • the secondary blend (B) is preferably present in the composition of the present invention in an amount of from 15 to 90 wt%, more preferably from 30 to 90 wt%, still more preferably from 35 to 85 wt%, even more preferably from 45 to 80 wt% and most preferably from 50 to 75 wt%, based on the overall weight of the composition.
  • the mixed-plastic-polyethylene composition of the invention additionally comprises a tertiary blend (C) of virgin high-density polyethylene (HDPE).
  • C virgin high-density polyethylene
  • the tertiary blend (C) preferably has: a melt flow rate (ISO 1133, 5 kg, 190 °C) of from 0.01 to 0.5 g/10 min, preferably from 0.1 to 0.4 g/lOmin; and/or a density of from 945 to 970 kg/m 3 , more preferably from 947 to 965 kg/m 3 .
  • a melt flow rate ISO 1133, 5 kg, 190 °C
  • the tertiary blend (C) can comprise carbon black or other pigments in an amount of of not more than 5 wt%, preferably not more than 3 wt%.
  • the presence of carbon black has an influence on the density of the tertiary blend (C).
  • a tertiary blend (C) comprising carbon black preferably has a density of from 955 to 970 kg/m 3 , preferably from 958 to 965 kg/m 3 .
  • the tertiary blend (C) does not comprise carbon black. It is further preferred that the tertiary blend (C) does not comprise any pigments other than carbon black.
  • the tertiary blend (C) of virgin high-density polyethylene (HDPE) is preferably a natural tertiary blend (C) of virgin high-density polyethylene (HDPE).
  • the natural tertiary blend (C) of virgin high-density polyethylene (HDPE) preferably has a density of from 945 to 960 kg/m 3 , preferably from 947 to 955 kg/m 3 .
  • the tertiary blend (C) includes as polymeric component a copolymer of ethylene and one or more comonomer units selected from alpha-olefins having from 3 to 6 carbon atoms. It is preferred that the polymeric component is a copolymer of ethylene and 1 -butene or a copolymer of ethylene and 1 -hexene.
  • the tertiary blend (C) can further comprise additives in an amount of 10 wt% or below, more preferably 9 wt% or below, more preferably 7 wt% or below of the tertiary blend (C).
  • Suitable additives are usual additives for utilization with polyolefins, such as stabilizers (e.g. antioxidant agents), metal scavengers and/or UV- stabilizers, antistatic agents and utilization agents (such as processing aid agents).
  • the tertiary blend (C) consists of said polymeric component and the optional additives.
  • the tertiary blend (C) preferably has one or more, more preferably all of the following properties in any combination: a comonomer content, preferably a 1 -hexene content, of from 0.1 to 1.0 mol%, more preferably from 0.3 to 0.7 mol%, determined using quantitative 13 C-NMR (see method description “Quantification of microstructure by NMR spectroscopy); a melt flow rate (ISO 1133, 21.6 kg, 190 °C) of from 4.0 to 15.0 g/10 min, more preferably from 5.0 to 10.0 g/lOmin; a tensile modulus of from 850 MPa to 1500 MPa, more preferably from 900 MPa to 1250 MPa; a tensile stress at break of from 20 to 50 MPa, more preferably from 22 to 40 MPa, or preferably from 25 to 50 MPa, more preferably from 28 to 40 MPa, a tensile strain at break of from 500 to 1000% more preferably from 600 to 950%
  • the tertiary blend (C) is a bimodal HDPE resin blend which is suitable for pipe applications. It is especially preferred that the tertiary blend is a HDPE resin suitable for PE100 pipes, i.e. pipes withstanding a hoop stress of 10.0 MPa (MRSio . o).
  • the tertiary blend of virgin high-density polyethylene (HDPE) is preferably present in the composition of the present invention in an amount of from 1 to 20 wt%, more preferably from 2 to 18 wt%, still more preferably from 3 to 17 wt%, even more preferably from 4 to 16 wt% and most preferably from 5 to 15 wt%, based on the overall weight of the composition.
  • HDPE high-density polyethylene
  • the present invention seeks to provide a mixed-plastic-polyethylene composition comprising a mixed-plastic-polyethylene primary recycling blend (A) with improved ESCR, impact strength and SH modulus compared to the mixed-plastic-polyethylene primary recycling blend (A), to levels which are suitable for jacketing applications.
  • A mixed-plastic-polyethylene primary recycling blend
  • the mixed-plastic-polyethylene composition as described herein is especially suitable for wire and cable applications, such as jacketing applications.
  • the present invention relates to a mixed-plastic-polyethylene composition comprising a total amount of ethylene units (C2 units) of from 90.00 to 99.00 wt%, and a total amount of continuous units having 3 carbon atoms corresponding to polypropylene (continuous C3 units) of from 0.10 to 5.00 wt%, with the total amounts of C2 units and continuous C3 units being based on the total weight amount of monomer units in the composition and measured according to quantitative 13 C ⁇ 1 H ⁇ NMR measurement, and wherein the composition has a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 2.0 g/10 min; a density of from 930 kg/m 3 to 955 kg/m 3 , preferably from 932 to 953 kg/m.
  • a melt flow rate ISO 1133, 2.16 kg, 190 °C
  • the mixed-plastic-polyethylene composition is preferably obtainable by blending and extruding components comprising
  • a mixed-plastic- polyethylene primary recycling blend (A) wherein at least 90 wt.-%, preferably at least 95 wt.-%, more preferably 100 wt.-% of the mixed-plastic-polyethylene primary blend (A) originates from post-consumer waste and/or post-industrial waste; and wherein the mixed-plastic-polyethylene primary blend (A) has a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 1.2 g/10 min, preferably from 0.3 to 1.1 g/10 min, a density of from 910 to 945 kg/m 3 , preferably from 915 to 942 kg/m 3 , most preferably from 920 to 940 kg/m 3 , a total amount of ethylene units (C2 units) of from 80.00 to 96.00 wt%, and a total amount of continuous units having 3 carbon atoms corresponding to polypropylene
  • the mixed-plastic-polyethylene composition only comprises, preferably consists of the mixed-plastic-polyethylene primary recycling blend (A) and the secondary blend (B) of virgin high-density polyethylene (HDPE) as polymeric components.
  • A mixed-plastic-polyethylene primary recycling blend
  • B secondary blend
  • HDPE virgin high-density polyethylene
  • the mixed-plastic polyethylene composition comprises, preferably consists of the mixed-plastic-polyethylene primary recycling blend (A), the secondary blend (B) of virgin high-density polyethylene (HDPE) and a tertiary blend (C) of virgin high- density polyethylene (HDPE) as polymeric components.
  • the mixed-plastic polyethylene composition has a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 1.0 g/lOmin and being obtainable by blending and extruding components comprising
  • the present invention relates to a mixed-plastic-polyethylene composition having a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 2.0 g/lOmin; and a density of from 930 kg/m 3 to 955 kg/m 3 , preferably from 932 to 953 kg/m; obtainable by blending and extruding components comprising
  • a mixed-plastic- polyethylene primary recycling blend (A) wherein at least 90 wt.-%, preferably at least 95 wt.-%, more preferably 100 wt.-% of the mixed-plastic-polyethylene primary blend (A) originates from post-consumer waste and/or post-industrial waste having a limonene content of from 2 to 500 mg/kg; and wherein the mixed-plastic-polyethylene primary blend (A) has a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 1.2 g/lOmin, preferably from 0.3 to 1.1 g/lOmin , a density of from 910 to 945 kg/m 3 , preferably from 915 to 942 kg/m 3 , most preferably from 920 to 940 kg/m 3 , and a total amount of ethylene units (C2 units) of from 80.00 to 96.00 wt
  • the mixed-plastic polyethylene composition of said aspect has a melt flow rate (ISO 1133, 2.16 kg, 190 °C) offrom O.l to 1.0 g/lOmin and being obtainable by blending and extruding components comprising
  • a melt flow rate ISO 1133, 5 kg, 190 °C
  • the mixed-plastic-polyethylene composition of said aspect only comprises, preferably consists of the mixed-plastic-polyethylene primary recycling blend (A) and the secondary blend (B) of virgin high-density polyethylene (HDPE) as polymeric components.
  • A mixed-plastic-polyethylene primary recycling blend
  • B secondary blend
  • HDPE virgin high-density polyethylene
  • the mixed-plastic polyethylene composition of said aspect comprises, preferably consists of the mixed-plastic-polyethylene primary recycling blend (A), the secondary blend (B) of virgin high-density polyethylene (HDPE) and a tertiary blend (C) of virgin high-density polyethylene (HDPE) as polymeric components.
  • the mixed-plastic-polyethylene composition comprises a total amount of ethylene units (C2 units) of from 90.00 to 99.00 wt%, preferably from 91.00 to 98.00 wt%, more preferably from 92.00 to 97.00 wt%, and a total amount of continuous units having 3 carbon atoms corresponding to polypropylene (continuous C3 units) of from 0.10 to 5.00 wt%, more preferably from 0.15 wt% to 4.50 wt%, still more preferably from 0.20 wt% to 4.00 wt%.
  • C2 units ethylene units of from 90.00 to 99.00 wt%, preferably from 91.00 to 98.00 wt%, more preferably from 92.00 to 97.00 wt%
  • continuous C3 units continuous units of from 0.10 to 5.00 wt%, more preferably from 0.15 wt% to 4.50 wt%, still more preferably from 0.20 wt% to 4.00 wt%.
  • the mixed-plastic-polyethylene composition preferably comprises one or more in any combination of, more preferably all of: a total amount of units having 3 carbon atoms as isolated peaks in the NMR spectrum (isolated C3 units) of from 0 wt% to 0.50 wt%, more preferably from 0 wt% to 0.40 wt%, still more preferably from 0 wt% to 0.30 wt%; a total amount of units having 4 carbon atoms (C4 units) of from 0.20 wt% to 4.00 wt%, more preferably from 0.30 wt% to 3.50 wt%, still more preferably from 0.50 wt% to 3.00 wt%; a total amount of units having 6 carbon atoms (C6 units) of from 0.20 wt% to 5.00 wt%, more preferably from 0.30 wt% to 4.00 wt%, still more preferably from 0.50 wt% to 3.50 wt%; a total amount of
  • the total amounts of C2 units, continuous C3 units, isolated C3 units, C4 units, C6 units, C7 units and LDPE content thereby are based on the total weight amount of monomer units in the composition and are measured or calculated according to quantitative 13 C ⁇ 1 ET ⁇ NMR measurement.
  • the total amounts of units, which can be attributed to comonomers (i.e. isolated C3 units, C4 units and C6 units), in the mixed-plastic-polyethylene composition is from 1.00 wt% to 8.00 wt%, more preferably from 2.00 wt% to 7.00 wt%, still more preferably from 3.00 wt% to 6.00 wt%, and is measured according to quantitative 1 C J 1 H ⁇ NMR measurement.
  • the mixed-plastic polyethylene composition according to the present invention has a a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 2.0 g/10 min, more preferably from 0.2 to 1.8 g/10 min.; and a density of from 930 kg/m 3 to 955 kg/m 3 , preferably from 932 to 953 kg/m 3 .
  • the mixed-plastic polyethylene composition preferably shows non-linear viscoelastic behaviour as shown in the below defined Large Oscillatory Shear (LAOS) measurement:
  • LAOS Large Oscillatory Shear
  • the mixed-plastic polyethylene composition preferably has a Large Amplitude Oscillatory Shear Non Linear Factor at a strain of 1000%, LAOS NLF (1000%), of from 1.900 to 4.000, more preferably from 2.000 to 3.500, still more preferably from 2.100 to 3.000 and most preferably from 2.125 to 2.850.
  • LAOS NLF Large Amplitude Oscillatory Shear Non Linear Factor at a strain of 1000%, LAOS NLF (1000%), of from 1.900 to 4.000, more preferably from 2.000 to 3.500, still more preferably from 2.100 to 3.000 and most preferably from 2.125 to 2.850.
  • the mixed-plastic polyethylene composition preferably has an impact strength at 23 °C (ISO 179-1 eA) of from 10 to 27 kJ/m 2 , preferably from 12 to 26 kJ/m 2 .
  • the impact strength at 23 °C (ISO 179-1 eA) of the composition is higher than that of the secondary blend. It is preferred that the impact strength at 23 °C (ISO 179-1 eA) of the composition is at least 105 %, more preferably at least 110 % of the impact strength of the secondary blend (B).
  • the mixed-plastic polyethylene composition preferably has an impact strength at 0 °C (according to ISO 179-1 eA) of from 5.0 to 12.0 kJ/m 2 , more preferably from 6.0 to 10.0 kJ/m 2
  • the mixed-plastic polyethylene composition preferably has a strain hardening modulus (SH modulus) of from 15.0 to 30.0 MPa, more preferably from 16.0 to 26.0 MPa and most preferably from 17.0 to 25.0 MPa.
  • SH modulus strain hardening modulus
  • the SH modulus of the mixed polyethylene composition is at least 60 %, more preferably at least 65 % of the SH modulus of the secondary blend (B).
  • the mixed-plastic polyethylene composition preferably has an ESCR (Bell test failure time) of more than 1000 hours, preferably more than 1250 hours and still more preferably more than 1500 hours and most preferably more than 1800 hours.
  • the mixed-plastic polyethylene composition can have an ESCR (Bell test failure time) of more than 2000 hours or even more than 5000 hours
  • the upper limit of the ESCR can be as high as 15000 hours, usually up to 10000 hours.
  • the mixed-plastic polyethylene composition preferably has a Shore D hardness, measured according to ASTM D2240-03 with a measuring time of 1 s, Shore D Is, of from 52.0 to 68.0, more preferably from 55.0 to 65.0 and most preferably from 56.5 to 62.5, and/or a Shore D hardness, measured according to ASTM D2240-03 with a measuring time of 3 s, Shore D 3s, of from 50.0 to 68.0, more preferably from 55.5 to 65.0 and most preferably from 56.5 to 62.5, and/or a Shore D hardness, measured according to ASTM D2240-03 with a measuring time of 15 s, Shore D 15s, of from 48.0 to 65.0, more preferably from 52.5 to 62.5 and most preferably from 54.0 to 60.0.
  • the mixed-plastic polyethylene composition preferably has a Shore D hardness, measured according to ISO 868 with a measuring time of 1 s, Shore D Is, of from 55.0 to 70.0, more preferably from 55.5 to 68.0 and most preferably from 56.0 to 65.0, and/or a Shore D hardness, measured according to ISO 868 with a measuring time of 3 s, Shore D 3s, of from 52.0 to 68.0, more preferably from 53.0 to 65.0 and most preferably from 54.0 to 62.5, and/or a Shore D hardness, measured according to ISO 868 with a measuring time of 15 s, Shore D 15s, of from 50.0 to 67.0 more preferably from 51.5 to 65.0 and most preferably from 52.0 to 60.0.
  • the mixed-plastic polyethylene composition preferably has one or more, preferably all of the following rheological properties, in any combination: a shear thinning index SHIp o ) of from 15 to 40, more preferably from 16 to 35 and/or a complex viscosity at 0.05 rad/s etao .
  • os rad/s of from 10000 to 38000 Pa-s, more preferably from 10100 to 35000 Pa-s, and/or a complex viscosity at 300 rad/s eta3oo rad/s of from 550 to 850 Pa-s, more preferably from 570 to 800 Pa-s, and/or a polydispersity index PI of from 1.0 to 3.5 s 1 , more preferably from 1.3 to 3.0 s 1 .
  • the mixed-plastic polyethylene composition preferably has one or more, preferably all of the following melt flow rate properties, in any combination: a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.2 to 1.8 g/10 min, more preferably from 0.3 to 1.5 g/10 min, and/or a melt flow rate (ISO 1133, 5 kg, 190 °C) of from 1.2 to 5.0 g/10 min, more preferably from 1.4 to 4.8 g/10 min and/or a melt flow rate (ISO 1133, 21 kg, 190 °C) of from 18 to 70 g/10 min, more preferably from 20 to 60 g/10 min.
  • a melt flow rate ISO 1133, 2.16 kg, 190 °C
  • a melt flow rate ISO 1133, 2.16 kg, 190 °C of from 0.2 to 1.8 g/10 min, more preferably from 0.3 to 1.5 g/10 min
  • the mixed-plastic polyethylene composition preferably has one or more, preferably all of the following tensile properties, in any combination: a tensile strain at break, measured according to ISO 527-2 on compression moulded test specimens of type 5A, of from 650% to 900%, more preferably from 700% to 880%; and/or a tensile stress at break, measured according to ISO 527-2 on compression moulded test specimens of type 5 A, of from 18 MPa to 35 MPa, more preferably from 20 MPa to 30 MPa.
  • a tensile strain at break measured according to ISO 527-2 on compression moulded test specimens of type 5A, of from 650% to 900%, more preferably from 700% to 880%
  • a tensile stress at break measured according to ISO 527-2 on compression moulded test specimens of type 5 A, of from 18 MPa to 35 MPa, more preferably from 20 MPa to 30 MPa.
  • the mixed-plastic polyethylene composition After ageing of the 5 A test specimens at 110 °C for 14 days the mixed-plastic polyethylene composition preferably has one or more, preferably all of the following tensile properties, in any combination: a tensile strain at break, measured according to ISO 527-2 on compression moulded test specimens of type 5A after ageing, of from 700% to 950%, more preferably from 750% to 930%; and/or a tensile stress at break, measured according to ISO 527-2 on compression moulded test specimens of type 5 A after ageing, of from 16 MPa to 33 MPa, more preferably from 18 MPa to 28 MPa.
  • the mixed-plastic polyethylene composition preferably has a tear resistance of from 10.0 to 25.0 N/mm, more preferably of from 12.5 to 22.5 N/mm and most preferably of from 15.0 to 20.0 N/mm.
  • the mixed-plastic polyethylene composition has a pressure deformation of not more than 15%, more preferably not more than 13%.
  • the lower limit is usually at least 0 %, meaning that no pressure deformation can be detected, preferably at least 1 %.
  • the mixed-plastic polyethylene composition preferably has a water content of preferably not more than 250 ppm more preferably not more than 248 ppm.
  • the lower limit is usually at least 25 ppm, preferably at least 50 ppm.
  • the mixed-plastic polyethylene composition has a gel content for gels with a size of from above 600 pm to 1000 pm of from 25 to 250 gels/m 2 , more preferably from 35 to 225 gels/m 2 .
  • the mixed-plastic polyethylene composition preferably has a gel content for gels with a size of from above 1000 pm of not more than 35 gels/m 2 , more preferably not more than 30 gels/m 2 .
  • the lower limit is usually at least 0, meaning that no gels of said size can be detected, preferably at least 1.0.
  • the composition can have further components apart from the mixed-plastic-polyethylene primary recycling blend (A) and the secondary blend (B) of virgin high-density polyethylene (HDPE), and the optional tertiary blend (C) of virgin high-density polyethylene (HDPE), such as further polymeric components or additives in amounts of not more than 15 wt%, based on the total weight of the composition.
  • Suitable additives are usual additives for utilization with polyolefins, such as stabilizers, (e.g. antioxidant agents), metal scavengers and/or UV stabilizers, antistatic agents, and utilization agents.
  • stabilizers e.g. antioxidant agents
  • metal scavengers and/or UV stabilizers e.g., sodium sulfide, sodium sulfide, sodium sulfide, sodium scavengers, sodium scavengers and/or UV stabilizers, antistatic agents, and utilization agents.
  • the additives can be present in the composition in an amount of 10 wt% or below, more preferably 9 wt% or below, more preferably 7 wt% or below.
  • composition can comprise carbon black or pigments in an amount of not more than 5 wt%, preferably not more than 3 wt%.
  • the composition does not contain carbon black. It is further preferred that the composition does not contain any pigments other than carbon black.
  • the mixed-plastic-polyethylene composition is preferably a natural mixed- plastic-polyethylene composition.
  • the composition consists of the mixed-plastic-polyethylene primary recycling blend (A) and the secondary blend (B) of virgin high-density polyethylene (HDPE), the optional tertiary blend (C) of virgin high-density polyethylene (HDPE) and optional additives.
  • a composition comprising carbon black preferably has a density of from 935 to 955 kg/m 3 , preferably from 937 to 953 kg/m 3 .
  • a composition free from carbon black preferably has a density of from 930 to 950 kg/m 3 , preferably from 932 to 948 kg/m 3 .
  • the mixed-plastic polyethylene composition comprises, more preferably consists of mixed-plastic-polyethylene primary recycling blend (A) and the secondary blend (B) of virgin high-density polyethylene (HDPE), but does not comprise, i.e. is free of the tertiary secondary blend (C) of virgin high-density polyethylene (HDPE).
  • the mixed-plastic polyethylene composition preferably has the following properties:
  • the mixed-plastic polyethylene composition preferably has one or more, preferably all of the following melt flow rate properties, in any combination: a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.3 to 1.8 g/10 min, more preferably from 0.4 to 1.5 g/10 min, and/or a melt flow rate (ISO 1133, 5 kg, 190 °C) of from 1.5 to 5.0 g/10 min, more preferably from 1.6 to 4.8 g/10 min and/or a melt flow rate (ISO 1133, 21 kg, 190 °C) of from 22 to 70 g/10 min, more preferably from 24 to 60 g/10 min.
  • a melt flow rate ISO 1133, 2.16 kg, 190 °C
  • a melt flow rate ISO 1133, 2.16 kg, 190 °C of from 0.3 to 1.8 g/10 min, more preferably from 0.4 to 1.5 g/10 min
  • mixed-plastic polyethylene composition preferably has one or more, preferably all of the following melt flow rate properties, in any combination: a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 1.0 g/10 min, more preferably from 0.3 to 0.8 g/10 min and most preferably from 0.3 to 0.7 g/10 min and/or a melt flow rate (ISO 1133, 5 kg, 190 °C) of from 1.5 to 2.5 g/10 min, more preferably 5 from 1.6 to 2.3 g/10 min and/or a melt flow rate (ISO 1133, 21 kg, 190 °C) of from 22 to 40 g/10 min, more preferably from 24 to 37 g/10 min.
  • a melt flow rate ISO 1133, 2.16 kg, 190 °C
  • melt flow rate ISO 1133, 2.16 kg, 190 °C
  • melt flow rate ISO 1133, 2.16 kg, 190 °C
  • the mixed-plastic polyethylene composition preferably has one or more, preferably all of the following rheological properties, in any combination: a shear thinning index SHIp o ) of from 15 to 35, more preferably from 16 to 32 and/or a complex viscosity at 0.05 rad/s etao .
  • os rad/s of from 10000 to 28000 Pa-s more preferably from 10100 to 27500 Pa-s
  • a complex viscosity at 300 rad/s eta3oo rad/s of from 550 to 850 Pa-s more preferably from 570 to 800 Pa-s
  • a polydispersity index PI of from 1.0 to 3.5 s 1 more preferably from 1.3 to 3.0 s 1 .
  • the mixed-plastic polyethylene composition preferably has a strain hardening modulus (SH modulus) of from 15.0 to 27.0 MPa, more preferably from 16.0 to 26.0 MPa and most preferably from 17.0 to 25.0 MPa.
  • SH modulus of the mixed polyethylene composition is at least 60 %, more preferably at least 65 % of the SH modulus of the secondary blend (B).
  • All other properties of the mixed-plastic polyethylene composition preferably are in the range as disclosed above.
  • the weight ratio of the mixed-plastic-polyethylene primary recycling blend (A) and the secondary blend (B) of virgin high-density polyethylene (HDPE) is preferably in the range of from 10:90 to 85:15, more preferably from 10:90 to 70:30, still more preferably from 15:85 to 65:35, even more preferably from 20:80 to 60:40, and most preferably from 25:75 to 50:50.
  • the mixed-plastic-polyethylene primary recycling blend (A) and the secondary blend (B) of virgin high-density polyethylene (HDPE) are generally defined as described above or below.
  • One positive aspect of the present invention of said embodiment is that rather high amounts of mixed-plastic-polyethylene primary recycling blend (A) can be used in the composition which still shows acceptable properties especially in regard of ESCRbut also regarding strain hardening and Shore D hardness.
  • the mixed-plastic polyethylene composition comprises, more preferably consists of mixed-plastic-polyethylene primary recycling blend (A), the secondary blend (B) of virgin high-density polyethylene (HDPE) and the tertiary secondary blend (C) of virgin high-density polyethylene (HDPE).
  • the mixed-plastic polyethylene composition preferably has the following properties:
  • the mixed-plastic polyethylene composition preferably has one or more, preferably all of the following melt flow rate properties, in any combination: a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 1.0 g/10 min, more preferably from 0.2 to 0.8 g/10 min, and/or a melt flow rate (ISO 1133, 5 kg, 190 °C) of from 1.2 to 3.5 g/10 min, more preferably from 1.3 to 3.0 g/10 min and/or a melt flow rate (ISO 1133, 21 kg, 190 °C) of from 18 to 50 g/10 min, more preferably from 20 to 40 g/10 min.
  • a melt flow rate ISO 1133, 2.16 kg, 190 °C
  • a melt flow rate ISO 1133, 2.16 kg, 190 °C of from 0.1 to 1.0 g/10 min, more preferably from 0.2 to 0.8 g/10 min
  • the mixed-plastic polyethylene composition preferably has one or more, preferably all of the following melt flow rate properties, in any combination: a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from from 0.1 to 1.0 g/10 min, more preferably from 0.2 to 0.7 g/10 min and most preferably from 0.3 to 0.6 g/10 min and/or a melt flow rate (ISO 1133, 5 kg, 190 °C) of from 1.2 to 2.0 g/10 min, more preferably from 1.3 to 1.9 g/10 min and/or a melt flow rate (ISO 1133, 21.6 kg, 190 °C) of from 18 to 35 g/10 min, more preferably from 20 to 30 g/10 min.
  • a melt flow rate ISO 1133, 2.16 kg, 190 °C
  • the mixed-plastic polyethylene composition preferably has one or more, preferably all of the following rheological properties, in any combination: a shear thinning index SHIp o ) of from 20 to 40, more preferably from 22 to 37 and/or a complex viscosity at 0.05 rad/s etao .
  • os rad/s of from 16000 to 38000 Pa-s, more preferably from 18000 to 35000 Pa-s, and/or a complex viscosity at 300 rad/s eta3oo rad/s of from 550 to 850 Pa-s, more preferably from 570 to 800 Pa-s, and/or a polydispersity index PI of from 1.0 to 3.5 s 1 , more preferably from 1.3 to 3.0 s 1 .
  • the mixed-plastic polyethylene composition preferably has a strain hardening modulus (SH modulus) of from 18.0 to 30.0 MPa, more preferably from 20.0 to 28.0 MPa and most preferably from 21.0 to 27.0 MPa.
  • SH modulus of the mixed polyethylene composition is at least 70 %, more preferably at least 75 % of the SH modulus of the secondary blend (B).
  • All other properties of the mixed-plastic polyethylene composition preferably are in the range as disclosed above.
  • the weight ratio of the mixed-plastic-polyethylene primary recycling blend (A) and the combined blend of the secondary blend (B) of virgin high-density polyethylene (HDPE) and the tertiary blend (C) of virgin high-density polyethylene (HDPE) is preferably in the range of from 10:90 to 83:17, more preferably 10:90 to 70:30, still more preferably from 15:85 to 65:35, even more preferably from 20:80 to 60:40, and most preferably from 25:75 to 50:50.
  • the mixed-plastic-polyethylene primary recycling blend (A), the secondary blend (B) of virgin high-density polyethylene (HDPE) and the tertiary blend (C) of virgin high-density polyethylene (HDPE) are generally defined as described above or below.
  • One positive aspect of the present invention of said embodiment is that rather high amounts of mixed-plastic-polyethylene primary recycling blend (A) can be used in the composition which still shows acceptable properties especially in regard of strain hardening but also regarding ESCR and Shore D hardness.
  • the present application is further directed to an article comprising the mixed-plastic- polyethylene composition as described above.
  • the article is used in jacketing applications i.e. for a cable jacket.
  • the article is a cable comprising at least one layer which comprises the mixed- plastic-polyethylene composition as described above.
  • the cable comprising a layer such as a jacketing layer, which comprises the mixed- plastic-polyethylene composition as described above has a cable shrinkage of not more than 2.0 %, more preferably not more than 1.8 %.
  • the lower limit is usually at least 0.3 %, preferably at least 0.5 %.
  • the cable comprising a layer such as a jacketing layer, which comprises the mixed- plastic-polyethylene composition as described above preferably has the following tensile properties: a tensile strain at break, measured according to EN60811-501 on cable specimen, of from 480% to 870%, more preferably from 500% to 850%; and/or a tensile stress at break, measured according to EN60811-501 on cable specimen, of from 16 MPa to 35 MPa, more preferably from 17 MPa to 33 MPa.
  • the cable comprising a layer such as a jacketing layer, which comprises the mixed-plastic- polyethylene composition comprising, more preferably consisting of the mixed-plastic- polyethylene primary recycling blend (A) and the secondary blend (B) of virgin high-density polyethylene (HDPE), but does not comprise, i.e.
  • a tensile strain at break measured according to EN60811-501 on cable specimen, of from 500% to 870%, more preferably from 525% to 750%; and/or a tensile stress at break, measured according to EN60811-501 on cable specimen, of from 16 MPa to 33 MPa, more preferably from 17 MPa to 30 MPa.
  • the cable comprising a layer such as a jacketing layer, which comprises the mixed-plastic- polyethylene composition comprising, more preferably consisting of the mixed-plastic- polyethylene primary recycling blend (A), the secondary blend (B) of virgin high-density polyethylene (HDPE) and the tertiary secondary blend (C) of virgin high-density polyethylene (HDPE) as described above, preferably has the following tensile properties: a tensile strain at break, measured according to EN60811-501 on cable specimen, of from 480% to 870%, more preferably from 500% to 850%; and/or a tensile stress at break, measured according to EN60811-501 on cable specimen, of from 18 MPa to 35 MPa, more preferably from 19 MPa to 33 MPa.
  • a tensile strain at break measured according to EN60811-501 on cable specimen, of from 480% to 870%, more preferably from 500% to 850%
  • a tensile stress at break measured according to EN60
  • the present invention also relates to a process for preparing the mixed-plastic-polyethylene composition as defined above or below.
  • the process according to the present invention results in an improvement in the mechanical properties of the mixed-plastic-polyethylene primary recycling blend (A).
  • the process according to the present invention comprises the steps of: a) providing a mixed-plastic-polyethylene primary recycling blend (A) in an amount of 10 to 85 wt.-% based on the overall weight of the composition, wherein at least 90 wt.-%, preferably at least 95 wt.-%, more preferably 100 wt.-% of the mixed-plastic-polyethylene primary blend (A) originates from post-consumer waste and/or post-industrial waste wherein the mixed-plastic-polyethylene primary blend (A) has a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 1.2 g/lOmin, preferably from 0.3 to 1.1 g/lOmin, a density of from 910 to 945 kg/m 3 , preferably from 915 to 942 kg/m 3 , most preferably from 920 to 940 kg/m 3 , a total amount of ethylene units (C2 units) of from 80.00 to 96.00 wt%
  • the process of the invention as described above comprises the steps of: a) providing the mixed-plastic-polyethylene primary recycling blend (A) in an amount of 10 to 83 wt.-% based on the overall weight of the composition; b) providing the secondary blend (B) of virgin high-density polyethylene (HDPE) in an amount of 16 to 80 wt.-% based on the overall weight of the composition; and c) providing a tertiary blend (C) of virgin high-density polyethylene (HDPE) in an amount of 1 to 20 wt.-% based on the overall weight of the composition, wherein the tertiary blend (C) has ethylene monomer units and comonomer units derived from olefins having from 3 to 6 carbon atoms, a melt flow rate (ISO 1133, 5 kg, 190 °C) of from 0.01 to 0.5 g/lOmin, and a density of from 945 to 970 kg/m 3 , d) melting
  • the present invention relates to the use of a mixed-plastic-polyethylene composition as defined above or below for producing a cable layer, preferably a cable jacketing layer, having an ESCR (Bell test failure time) of more than 1000 hours, preferably more than 1250 hours and still more preferably more than 1500 hours and most preferably more than 1800 hours.
  • the cable layer, preferably the cable jacketing layer can have an ESCR (Bell test failure time) of more than 2000 hours or even more than 5000 hours.
  • the upper limit of the ESCR can be as high as 15000 hours, usually up to 10000 hours.
  • the cable layer preferably the cable jacketing layer, has a strain hardening modulus (SH modulus) of from 15.0 to 30.0 MPa, more preferably from 16.0 to 26.0 MPa and most preferably from 17.0 to 25.0 MPa.
  • SH modulus strain hardening modulus
  • melt flow rates were measured with a load of 2.16 kg (MFR2), 5.0 kg (MFR5) or 21.6 kg (MFR21) at 190°C as indicated.
  • the melt flow rate is that quantity of polymer in grams which the test apparatus standardized to ISO 1133 extrudes within 10 minutes at a temperature of or 190°C under a load of 2.16 kg, 5.0 kg or 21.6 kg.
  • the NMR tube was further heated in a rotatory oven for at least 1 hour. Upon insertion into the magnet the tube was spun at 10 Hz.
  • This setup was chosen primarily for the high resolution and quantitatively needed for accurate ethylene content quantification. Standard single-pulse excitation was employed without NOE, using an optimised tip angle, 1 s recycle delay and a bi-level WALTZ16 decoupling scheme ⁇ zhou07,busico07 ⁇ . A total of 6144 (6k) transients were acquired per spectra.
  • Quantitative 13 C ⁇ 1 H ⁇ NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals using proprietary computer programs. All chemical shifts were indirectly referenced to the central methylene group of the ethylene block (EEE) at 30.00 ppm using the chemical shift of the solvent. Characteristic signals corresponding to polyethylene with different short chain branches (Bl, B2, B4, B5, B6plus) and polypropylene were observed ⁇ randall89, brandoliniOO ⁇ .
  • Characteristic signals corresponding to the presence of polyethylene containing isolated Bl branches (starBl 33.3 ppm), isolated B2 branches (starB2 39.8 ppm), isolated B4 branches (twoB423.4 ppm), isolated B5 branches (threeB5 32.8 ppm), all branches longer than 4 carbons (starB4plus 38.3 ppm) and the third carbon from a saturated aliphatic chain end (3s
  • the weight percent of the C2 fraction and the polypropylene can be quantified according following equations:
  • WtC2fraction fCc2total * 100 / (fCc2total + fCpp)
  • wtpp fCpp * 100 / (fCc2total + fCpp)
  • the impact strength is determined as Charpy Notched Impact Strength according to ISO 179- 1 eA at +23 °C and at 0 °C on compression moulded specimens of 80 x 10 x 4 mm prepared according to ISO 17855-2. e) Tensile testing of 5A specimen and that after ageing of 5A specimen at 110 °C, 14 days (336h)
  • dog bone specimens of 5A are prepared according to ISO 527-2/5A by die cutting from compression moulded plaques of 2mm’ thickness. If ageing is needed, the 5A specimens are kept at 110 °C in a cell oven for 14 days (336 hours). All specimens are conditioned for at least 16 hours at 23°C and 50% relative humidity before testing.
  • Tensile properties are measured according to ISO 527-1/2 at 23°C and 50% relative humidity with Alwetron R24, lkN load cell. Tensile testing speed is 50mm/min, grip distance is 50mm and gauge length is 20mm. f) Rheological measurements
  • Dynamic test results are typically expressed by means of several different rheological functions, namely the shear storage modulus G’, the shear loss modulus, G”, the complex shear modulus, G*, the complex shear viscosity, h*, the dynamic shear viscosity, h', the out- of-phase component of the complex shear viscosity h” and the loss tangent, tan d which can be expressed as follows:
  • Shear Thinning Index which correlates with MWD and is independent of Mw
  • the SHIp o is defined by the value of the complex viscosity, in Pa s, determined for a value of G* equal to 2.7 kPa, divided by the value of the complex viscosity, in Pa s, determined for a value of G* equal to 210 kPa.
  • the loss tangent tan (delta) is defined as the ratio of the loss modulus (G") and the storage modulus (G) at a given frequency.
  • tano . os is used as abbreviation for the ratio of the loss modulus (G") and the storage modulus (G) at 0.05 rad/s
  • tamoo is used as abbreviation for the ratio of the loss modulus (G") and the storage modulus (G) at 300 rad/s.
  • the elasticity balance tano . os/tamoo is defined as the ratio of the loss tangent tano . os and the loss tangent tamoo.
  • the elasticity index EI(x) is the value of the storage modulus (G) determined for a value of the loss modulus (G") of x kPa and can be described by equation 10.
  • the ///(5k Pa) is the defined by the value of the storage modulus (G), determined for a value of G" equal to 5 kPa.
  • the polydispersity index, PI is defined by equation 11.
  • COCOP is the cross-over angular frequency, determined as the angular frequency for which the storage modulus, G, equals the loss modulus, G".
  • the values are determined by means of a single point interpolation procedure, as defined by Rheoplus software. In situations for which a given G* value is not experimentally reached, the value is determined by means of an extrapolation, using the same procedure as before. In both cases (interpolation or extrapolation), the option from Rheoplus " Interpolate y-values to x-values from parameter" and the "logarithmic interpolation type" were applied.
  • LAOS Large Amplitude Oscillatory Shear
  • the investigation of the non-linear viscoelastic behaviour under shear flow was done resorting to Large Amplitude Oscillatory Shear.
  • the method requires the application of a sinusoidal strain amplitude, go, imposed at a given angular frequency, co, for a given time, t.
  • a non-linear response is generated.
  • the stress, s is in this case a function of the applied strain amplitude, time and the angular frequency. Under these conditions, the non-linear stress response is still a periodic function; however, it can no longer be expressed by a single harmonic sinusoid.
  • LAOSNLF Large Amplitude Oscillatory Shear
  • G' 3 with G’i first order elastic Fourier coefficient
  • Gri third order elastic Fourier coefficient
  • ESCR environment stress cracking resistance
  • the ESCR is determined in accordance with IEC 60811-406, method B.
  • the reagent employed is 10 weight% Igepal CO 630 in water.
  • the materials were prepared according to instructions for HDPE as follows: The materials were pressed at 165°C to a thickness of 1.75 - 2.00 mm. The notch was 0.30 - 0.40 mm deep. i) Shore D hardness
  • Shore D hardness is determined according to ISO 868 on moulded specimen with a thickness of 4 mm.
  • the shore hardness is determined after 1 sec, 3 sec or 15 sec after the pressure foot is in firm contact with the test specimen.
  • the sample is compression moulded according to ISO 17855-2 and milled into specimens of 80x10x4 mm.
  • Shore D hardness is determined according to ASTM D2240-03. The same samples as for the Shore D hardness according to ISO 868 were used. j) Strain hardening (SH) modulus
  • the strain hardening test is a modified tensile test performed at 80 °C on a specially prepared thin sample.
  • the Strain Hardening Modulus (MPa), ⁇ Gp>, is calculated from True Strain- True Stress curves; by using the slope of the curve in the region of True Strain, l, is between 8 and 12.
  • the true strain, l is calculated from the length, 1 (mm), and the gauge length, 10 (mm), as shown by Equation 1.
  • x 1 + r « where D1 is the increase in the specimen length between the gauge marks, (mm).
  • the true stress, otrue (MPa) is calculated according to formula 2, assuming conservation of volume between the gauge marks: where sh is the engineering stress.
  • the Neo-Hookean constitutive model (Equation 3) is used to fit the true strain- true stress data from which ⁇ Gp> (MPa) for 8 ⁇ l ⁇ 12 is calculated.
  • the sheets were annealed to remove any orientation or thermal history and maintain isotropic sheets. Annealing of the sheets was performed for 1 h in an oven at a temperature of (120 ⁇ 2) °C followed by slowly cooling down to room temperature by switching off the temperature chamber. During this operation free movement of the sheets was allowed.
  • test pieces were punched from the pressed sheets.
  • the specimen geometry of the modified ISO 37:1994 Type 3 ( Figure 3) was used.
  • the sample has a large clamping area to prevent grip slip, dimensions given in Table 1.
  • the punching procedure is carried out in such a way that no deformation, crazes or other irregularities are present in the test pieces.
  • the thickness of the samples was measured at three points of the parallel area of the specimen; the lowest measured value of the thickness of these measurements was used for data treatment.
  • the water content was determined as described in ISO15512:2019 Method A - Extraction with anhydrous methanol. There the test portion is extracted with anhydrous methanol and the extracted water is determined by a coulometric Karl Fischer Titrator. l) Cable extrusion
  • the cable extrusion is done on a Nokia-Maillefer cable line.
  • the extruder has five temperature zones with temperatures of 170/175/180/190/190°C and the extruder head has three zones with temperatures of 210/210/210°C.
  • the extruder screw is a barrier screw of the design Elise.
  • the die is a semi-tube on type with 5.9 mm diameter and the outer diameter of the cable is 5 mm.
  • the compound is extruded on a 3 mm in diameter, solid aluminum conductor to investigate the extrusion properties. Line speed is 75 m/min.
  • the pressure at the screen and the current consumption of the extruder is recorded for each material. m) Pressure deformation
  • Tensile testing of cable is conducted according to EN60811-501. At least 24 hours later after cable extrusion, the conductor is removed and the cable is cut into specimens of 15cm’ s long. The specimens are conditioned for at least 16 hours at 23°C and 50% relative humidity before testing.
  • Tensile properties are measured at 23°C and 50% relative humidity with Zwick Z005, 500N load cell. Tensile testing speed is 25mm/min, grip distance is 50mm and gauge length is 20mm. o) Cable shrinkage
  • the shrinkage of the composition is determined with the cable samples obtained from the cable extrusion.
  • the cables are conditioned in the constant room at least 24 hours before the cutting of the samples.
  • the conditions in the constant room are 23 ⁇ 2°C and 50 ⁇ 5% humidity.
  • Samples are cut to 400 mm at least 2 m away from the cable ends. They are further conditioned in the constant room for 24 hours after which they are place in an oven on a talcum bed at 100°C for 24 hours. After removal of the sample from the oven they are allowed to cool down to room temperature and then measured.
  • the shrinkage is calculated according to formula below:
  • Tear resistance is measured on compression moulded plaques of 1 mm thickness according to BS 6469 section 99.1. A test piece with a cut is used to measure the tear force by means of a tensile testing machine. The tear resistance is calculated by dividing the maximum force needed to tear the specimen by its thickness. q) Ash content
  • Thermogravimetric Analysis (TGA) experiments were performed with a Perkin Elmer TGA 8000. Approximately 10-20 mg of materials were placed in a platinum pan. The temperature was equilibrated at 50°C for 10 minutes, and afterwards raised to 950°C under nitrogen at 20°C/min. The ash content was evaluated as the weight % at 850 °C. r) Amount of Limonene This method allows nature of a raw mixed-plastic-polyethylene primary recycling blend to be determined.
  • Enrichment of the volatile fraction was carried out by headspace solid phase microextraction with a 2 cm stable flex 50/30 pm DVB/C arboxen/PDMS fibre at 60°C for 20 minutes. Desorption was carried out directly in the heated injection port of a GCMS system at 270°C.
  • the gel count was measured with a gel counting apparatus consisting of a measuring extruder, ME 25 / 5200 VI, 25*25D, with five temperature conditioning zones adjusted to a temperature profile of 170/180/190/190/190°C), an adapter and a slit die (with an opening of 0.5 * 150 mm). Attached to this were a chill roll unit (with a diameter of 13 cm with a temperature set of 50°C), a line camera (CCD 4096 pixel for dynamic digital processing of grey tone images) and a winding unit.
  • a gel counting apparatus consisting of a measuring extruder, ME 25 / 5200 VI, 25*25D, with five temperature conditioning zones adjusted to a temperature profile of 170/180/190/190/190°C), an adapter and a slit die (with an opening of 0.5 * 150 mm). Attached to this were a chill roll unit (with a diameter of 13 cm with a temperature set of 50°C), a line camera (CCD 4096 pixel
  • the materials were extruded at a screw speed of 30 rounds per minute, a drawing speed of 3-3.5 m/min and a chill roll temperature of 50°C to make thin cast films with a thickness of 70 pm and a width of approximately 110 mm.
  • the resolution of the camera is 25 pm x 25 pm on the film.
  • a sensitivity level dark of 25% is used for detecting gels.
  • the line camera was set to differentiate the gel dot size according to the following:
  • HE6063 is a natural bimodal high density polyethylene jacketing compound for energy and communication cables (available from Borealis AG).
  • HE3493-LS-H is a natural bimodal high density polyethylene compound for pipes (available from Borealis AG).
  • Additive package The additive package consists of 27.3 wt% of pentaerythrityl-tetrakis(3- (3’,5’-di-tert. butyl-4-hydroxyphenyl)-propionate (CAS No. 6683-19-8), 9.1 wt% of tris (2,4- di-t-butylphenyl) phosphite (CAS No. 31570-04-4), 9.1 wt% of calcium stearate (CAS No.
  • NAV 102 is a mixed-plastic-low density polyethylene (LDPE) primary recycling blend available from Ecoplast Kunststoffrecycling GmbH. Samples of NAV 102 (NAV 102-1 with the Lot No 190206-1, NAV- 102-2 with the Lot No 190611 -II and NAV 102-5 with the Lot No 200312-1) differing as to melt flow rate and also rheology were tested, the properties of these samples are shown in table A.
  • LDPE mixed-plastic-low density polyethylene
  • NAV-102 NAV 102-3 with the Lot No 190612-1 and NAV 102-4 with the Lot No 190611-1
  • the properties of these samples were not measured but should be similar to those of NAV 102-1, NAV 102-2 and NAV 102-5.
  • CE1 (comparative example 1) are 100 % reactor-made HE6063 pellets.
  • CE2 (comparative example 2) is 100 % compounded HE6063 (blank extrusion of CE1). b) Inventive examples:
  • inventive example 1 25 wt% HE6063 was melt mixed with 75 wt% NAV 102-2.
  • inventive example 2 50 wt% HE6063 was melt mixed with 50 wt% NAV 102-2.
  • inventive example 3 60 wt% HE6063 was melt mixed with 40 wt% NAV 102-2.
  • inventive example 4 75 wt% HE6063 was melt mixed with 25 wt% NAV 102-2.
  • inventive example 5 25 wt% HE6063 was melt mixed with 75 wt% NAV 102-3.
  • inventive example 6 50 wt% HE6063 was melt mixed with 50 wt% NAV 102-3.
  • inventive example 7 75 wt% HE6063 was melt mixed with 25 wt% NAV 102-3.
  • inventive example 8 50 wt% HE6063 was melt mixed with 50 wt% NAV 102-4.
  • inventive example 9 50 wt% HE6063 was melt mixed with 50 wt% NAV 102-1.
  • inventive example 10 75 wt% HE6063 was melt mixed with 25 wt% NAV 102-1.
  • inventive example 11 49.7 wt% HE6063 was melt mixed with 50 wt% NAV 102-5 and 0.3 wt% additive package.
  • inventive example 12 49.7 wt% HE6063 was melt mixed with 50 wt% NAV 102-5 and 0.3 wt% additive package.
  • inventive example 13 50 wt% HE6063 was melt mixed with 40 wt% NAV 102-1 and 10 wt% HE3493-LS-H.
  • inventive example 14 50 wt% HE6063 was melt mixed with 40 wt% NAV 102-2 and 10 wt% HE3493-LS-H.
  • inventive example 15 40 wt% HE6063 was melt mixed with 50 wt% NAV 102-2 and 10 wt% HE3493-LS-H.
  • inventive example 16 40 wt% HE6063 was melt mixed with 50 wt% NAV 102-3 and 10 wt% HE3493-LS-H.
  • inventive example 17 40 wt% HE6063 was melt mixed with 50 wt% NAV 102-4 and 10 wt% HE3493-LS-H.
  • inventive example 18 39.7 wt% HE6063 was melt mixed with 50 wt% NAV 102-5, 10 wt% HE3493-LS-H and 0.3 wt% additive package.
  • inventive example 19 39.7 wt% HE6063 was melt mixed with 50 wt% NAV 102-5, 10 wt% HE3493-LS-H and 0.3 wt% additive package.
  • compositions of examples IE11, IE12, IE18 and IE19 were prepared via melt blending on a Berstoff ZE110 extruder at 200°C in the first two barrels after the feeding zone and 230°C in all the following barrels, a screw speed of 420 rpm for IE11, 280-300 rpm for IE12, IE18 and IE19 and a throughput rate of about 1.8 to 2.0 ton/h..
  • the polymer melt mixtures were discharged and pelletized. Mechanical properties were tested as described above. Thereby, the final MFR of the compounds is influenced by the compounding condition, e.g, the screw speed.
  • compositions and cables made from these compositions are shown below in Table B for the compositions of examples CE1-CE2, IE1-IE4 and IE8, in Table C for the compositions of examples CE1-CE2 and IE5, IE6, IE7, IE9, IE10, IE11 and IE12 and in Table D for the compositions of examples CE1-CE2 and IE13, IE14, IE15, IE16, IE17, IE18 and IE 19.
  • the values for the LDPE content have been calculated according to the content of NAV 102 and the LDPE content of the used batch of NAV 102. For all other examples, where listed, the values for the LDPE content has been measured as described in the test method section.
  • the examples according to the invention show an improved balance of properties especially in regard of ESCR, SH index and Shore D hardness while maintaining good tensile properties and impact properties. Additionally, the example according to the invention show a surprisingly low gel content due to the use of NAV 102 recycling blends, which themselves have a low gel content indicating a high purity. It is believed that especially the surprisingly high ESCR values result from said high purity indicated in the low gel contents. The > in the ESCR data means that the measurement is still running. Table B: Properties of CE1-CE2, IE1-IE4 and IE8
  • Table D Properties of CE1, CE2 and IE13, IE14, IE15, IE16, IE17, IE18 and IE19

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Abstract

The present invention relates to a mixed-plastic-polyethylene composition comprising: - a total amount of ethylene units (C2 units) of from 90.00 to 99.00 wt%, and - a total amount of continuous units having 3 carbon atoms corresponding to polypropylene (continuous C3 units) of from 0.01 to 5.00 wt%, with the total amounts of C2 units and continuous C3 units being based on the total weight amount of monomer units in the composition and measured according to quantitative 13C{1H} NMR measurement, and wherein the composition has - a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 2.0 g/10 min; and - a density of from 930 kg/m³ to 955 kg/m³, preferably from 932 to 953 kg/m³, a process for producing said mixed-plastic-polyethylene composition, an article comprising said mixed-plastic-polyethylene composition and the use of said mixed-plastic-polyethylene composition for producing a cable layer.

Description

Blend comprising polyethylene based recyclate
Field of the Invention
The present invention relates to upgrading of PE recycling streams using virgin high-density polyethylenes (HDPE) to give jacketing materials that have acceptable ESCR (Environmental Stress Crack Resistance) and/or strain hardening performance.
Background
Polyolefins, in particular polyethylene and polypropylene are increasingly consumed in large amounts in a wide range of applications, including packaging for food and other goods, fibres, automotive components, and a great variety of manufactured articles.
Polyethylene based materials are a particular problem as these materials are extensively used in packaging. Taking into account the huge amount of waste collected compared to the amount of waste recycled back into the stream, there is still a great potential for intelligent reuse of plastic waste streams and for mechanical recycling of plastic wastes.
Generally, recycled quantities of polyethylene on the market are mixtures of both polypropylene (PP) and polyethylene (PE), this is especially true for post-consumer waste streams. Moreover, commercial recyclates from post-consumer waste sources are conventionally cross contaminated with non-polyolefin materials, such as polyethylene terephthalate, polyamide, polystyrene or non polymeric substances like wood, paper, glass or aluminium. These cross-contaminations drastically limit final applications or recycling streams such that no profitable final uses remain.
In addition, recycled polyolefin materials normally have properties, which are much worse than those of the virgin materials, unless the amount of recycled polyolefin added to the final compound is extremely low. For example, such materials often have limited impact strength and poor mechanical properties (such as e.g. brittleness) and thus, they do not fulfil customer requirements. For several applications, e.g. jacketing materials (for cables), containers, automotive components or household articles. This normally excludes the application of recycled materials for high quality parts, and means that they are only used in low-cost, non demanding applications, such as e.g. in construction or in furniture. In order to improve the mechanical properties of these recycled materials, generally relatively large amounts of compatibilizing/coupling agents and elastomeric polymers are added. These materials are generally virgin materials, which are produced from oil.
US 8981007 B2 relates to non-crosslinked polyethylene compositions for use in the jacketing of power cables. Generally crosslinked polyethylene is used for power cables, due to its excellent heat resistance, chemical resistance and electrical properties. However, since crosslinked polyethylene resin is a thermoset resin, it is not recyclable. There is, therefore, a demand for an eco-friendly non-crosslinked type thermoplastic polyethylene resin, which is also heat resistant and hence suitable for use in power cables.
EP 2417194 B1 also relates to uncrosslinked polyethylene compositions for use in power cables. The compositions disclosed herein are polymer blends comprising MDPE and HDPE and one or more additive(s) selected from a flame retardant, an oxidation stabilizer, a UV stabilizer, a heat stabilizer and a process aid.
DE-102011108823-A1 relates to a composite for electrical isolation of electrical cables. The composite comprises a plastic, a material having a heat conductivity of less than 1 W/(mk) and a displacement material (C). In certain embodiments, the displacement material can be a recycled material.
EP 1676283 B1 relates to medium/high voltage electrical energy transport or distribution cables comprising at least one transmissive element and at least one coating layer, said coating layer being made from a coating material comprising at least one recycled polyethylene (obtained from a waste material) with a density not higher than 0.940 g/cm3 and at least a second polyethylene material having a density higher than 0.940 g/cm3. The coating material in some of the examples of EP 1676283 B1 showed improved values with respect to stress cracking resistance with respect to those obtained from recycled polyethylene alone. However, these values were considerably less than those obtained with the virgin material, DFDG-6059® Black. EP 2417 194 B1 relates to power cables comprising an non crosslinked polyethylene composition comprising 100 parts by weight of a polymer comprising 60 to 95 wt% of a linear medium density polyethylene resin comprising an alpha-olefin having 4 or more carbon atoms as a comonomer and having a melt index of 0.6-2.2 g/10 min (at 190 °C under a load of 5 kg), a differential scanning calorimetry (DSC) enthalpy of 130-190 joule/g and a molecular weight distribution of 2-30; and 5 to 40 wt% of a high-density polyethylene resin having a melt index of 0.1-0.35 g/10 min (at 190 °C under a load of 5 kg), a DSC enthalpy of 190-250 joule/g and a molecular weight distribution of 3-30; 0.1 to 10 parts by weight of one or more additive(s) selected from a flame retardant, an oxidation stabilizer, a UV stabilizer, a heat stabilizer and a process aid, based on 100 parts by weight of the polymer. None of the resins is recycled material.
Another particular problem in recycled polyethylene materials is that variations in ESCR (Environmental Stress Crack Resistance) properties can also be observed in recycled polyethylene blends depending on the waste origin. Thus, there is need for addressing these limitations in a flexible way. For jacketing applications generally an ESCR (Bell test failure time) of greater than 1000 hours is desirable.
Thus, there remains a need in the art to provide recycled polyethylene solutions for wire and cable applications, especially for jacketing materials, that have acceptable and constant ESCR (Environmental Stress Crack Resistance) performance (e.g. tensile properties), with Bell test failure time >1000 hours and good strain hardening (SH) performance with a strain hardening (SH) modulus of at least 15.0 MPa with other properties which are similar to blends of virgin polyethylene marketed for the purpose of cable jacketing. It is also desirable to maximize the loading of recycled polyethylene material.
Summary of the Invention
The present invention provides compositions with acceptable ESCR and strain hardening performance, while maintaining other properties similar to the blend of virgin polyethylene marketed for the purpose of cable jacketing. The present invention is also concerned with maximising the loading of recycled material (with loadings of up to 85 % recycled material) in the composition and with the use of a combination of specific blends of virgin polyethylene to improve the ESCR properties and or strain hardening properties of a mixed-plastic- polyethylene primary recycling blend (A).
In a first aspect the present invention relates to a mixed-plastic-polyethylene composition comprising a total amount of ethylene units (C2 units) of from 90.00 to 99.00 wt%, and a total amount of continuous units having 3 carbon atoms corresponding to polypropylene (continuous C3 units) of from 0.10 to 5.00 wt%, with the total amounts of C2 units and continuous C3 units based on the total weight amount of monomer units in the composition and measured according to quantitative 13C{ 1H} NMR measurement, and wherein the composition has a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 2.0 g/10 min; a density of from 930 kg/m3 to 955 kg/m3, preferably from 932 to 953 kg/m.
In a second aspect the present invention relates to a mixed-plastic-polyethylene composition having a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 2.0 g/lOmin; and a density of from 930 kg/m3 to 955 kg/m3, preferably from 932 to 953 kg/m3; obtainable by blending and extruding components comprising
10 to 85 wt.-%, based on the overall weight of the composition, of a mixed-plastic- polyethylene primary recycling blend (A) wherein at least 90 wt.-%, preferably at least 95 wt.-%, more preferably 100 wt.-% of the mixed-plastic-polyethylene primary blend (A) originates from post-consumer waste and/or post-industrial waste having a limonene content of from 2 to 500 mg/kg; and wherein the mixed-plastic-polyethylene primary blend (A) has a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 1.2 g/lOmin, preferably from 0.3 to 1.1 g/lOmin , a density of from 910 to 945 kg/m3, preferably from 915 to 942 kg/m3, most preferably from 920 to 940 kg/m3, and a total amount of ethylene units (C2 units) of from 80.00 to 96.00 wt%, with the total amounts of C2 units being based on the total weight amount of monomer units in the mixed-plastic-polyethylene primary blend (A) and measured according to quantitative 13C{ 1H} NMR measurement;
15 to 90 wt.-%, based on the overall weight of the composition, of a secondary blend (B) of virgin high-density polyethylene (HDPE), wherein the secondary blend (B) has ethylene monomer units and comonomer units derived from olefins having from 3 to 6 carbon atoms, a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 1.2 g/10 min, preferably from 0.3 to 0.7 g/10 min; a density of from 940 to 970 kg/m3, a polydispersity index PI of from 1.0 to 2.8 s 1 as obtained from rheological measurement, and
- preferably a limonene content below 2 ppm.
Further, the present invention relates to an article, comprising the mixed-plastic-polyethylene composition as described above or below, preferably wherein the article is a cable comprising at least one layer comprising the mixed-plastic-polyethylene composition as described above or below, more preferably wherein the article is a cable comprising a jacketing layer comprising the mixed-plastic-polyethylene composition as described above or below.
Still further, the present invention relates to a process for preparing the mixed-plastic- polyethylene composition as defined above or below, comprising the steps of: a) providing a mixed-plastic-polyethylene primary recycling blend (A) in an amount of 10 to 85 wt.-% based on the overall weight of the composition, wherein at least 90 wt.-%, preferably at least 95 wt.-%, more preferably 100 wt.-% of the mixed-plastic-polyethylene primary blend (A) originates from post-consumer waste and/or post-industrial waste wherein the mixed-plastic-polyethylene primary blend (A) has a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 1.2 g/lOmin, preferably from 0.3 to 1.1 g/lOmin, a density of from 910 to 945 kg/m3, preferably from 915 to 942 kg/m3, most preferably from 920 to 940 kg/m3, a total amount of ethylene units (C2 units) of from 80.00 to 96.00 wt%, and a total amount of continuous units having 3 carbon atoms corresponding to polypropylene (continuous C3 units) of from 0.20 to 6.50 wt%; with the total amounts of C2 units and continuous C3 units being based on the total weight amount of monomer units in the mixed-plastic-polyethylene primary blend (A) and measured according to quantitative 13C{ 1H} NMR measurement, b) providing a secondary blend (B) of virgin high-density polyethylene (HDPE) in an amount of 15 to 90 wt.-% based on the overall weight of the composition, wherein the secondary blend (B) has ethylene monomer units and comonomer units derived from olefins having from 3 to 6 carbon atoms, a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 1.2 g/10 min, preferably from 0.3 to 0.7 g/10 min; a density of from 940 to 970 kg/m3, a polydispersity index PI of from 1.0 to 2.8 s 1 as obtained from rheological measurement, c) melting and mixing the blend of mixed-plastic-polyethylene primary blend (A) and the secondary blend (B) in an extruder, optionally a twin screw extruder, and d) optionally pelletizing the obtained mixed-plastic-polyethylene composition.
Finally, the present invention relates to the use of a mixed-plastic-polyethylene composition as defined above or below for producing a cable layer, preferably a cable jacketing layer, having an ESCR (Bell test failure time) of more than 1000 hours and/or a strain hardening modulus (SH modulus) of from 15.0 to 30.0 MPa.
Definitions
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention pertains. Although, any methods and materials similar or equivalent to those described herein can be used in practice for testing of the present invention, the preferred materials and methods are described herein. In describing and claiming the present invention, the following terminology will be used in accordance with the definitions set out below. Unless clearly indicated otherwise, use of the terms “a,” “an,” and the like refers to one or more.
For the purposes of the present description and of the subsequent claims, the term “recycled waste” is used to indicate a material recovered from post-consumer waste, as opposed to virgin polymers and/or materials. Post-consumer waste refers to objects having completed at least a first use cycle (or life cycle), i.e. having already served their first purpose.
The term “virgin” denotes the newly produced materials and/or objects prior to their first use, which have not already been recycled. The term “recycled material” such as used herein denotes materials reprocessed from “recycled waste”.
The term “natural” in the context of the present invention means that the components are of natural colour. This means that no pigments (including carbon black) are included in the components of the mixed-plastic-polyethylene composition of the present invention.
A blend denotes a mixture of two or more components, wherein one of the components is polymeric. In general, the blend can be prepared by mixing the two or more components. Suitable mixing procedures are known in the art. The term secondary blend (B) refers to a blend comprising at least 90 wt.-% of a reactor made high density polyethylene material. Said high density polyethylene material preferably does not contain carbon black or any other pigments. This high density polyethylene material is a virgin material which has not already been recycled.
For the purposes of the present description and of the subsequent claims, the term “mixed- plastic-polyethylene” indicates a polymer material including predominantly units derived from ethylene apart from other polymeric ingredients of arbitrary nature. Such polymeric ingredients may for example originate from monomer units derived from alpha olefins such as propylene, butylene, octene, and the like, styrene derivatives such as vinylstyrene, substituted and unsubstituted acrylates, substituted and unsubstituted methacrylates. Said polymeric materials can be identified in the mixed-plastic polyethylene composition by means of quantitative 13C{ 1H} NMR measurements as described herein. In the quantitative 13C{ 1H} NMR measurement used herein and described below in the measurement methods different units in the polymeric chain can be distinguished and quantified. These units are ethylene units (C2 units), units having 3, 4 and 6 carbons and units having 7 carbon atoms.
Thereby, the units having 3 carbon atoms (C3 units) can be distinguished in the NMR spectrum as isolated C3 units (isolated C3 units) and as continuous C3 units (continuous C3 units) which indicate that the polymeric material contains a propylene based polymer. These continuous C3 units can also be identified as iPP units. The continuous C3 units thereby can be distinctively attributed to the mixed-plastic-polyethylene primary recycling blend (A) as the secondary blend (B) of virgin high-density polyethylene (HDPE) in the mixed-plastic- polyethylene composition according to the present invention usually does not include any propylene based polymeric components.
The units having 3, 4, 6 and 7 carbon atoms describe units in the NMR spectrum which are derived from two carbon atoms in the main chain of the polymer and a short side chain or branch of 1 carbon atom (isolated C3 unit), 2 carbon atoms (C4 units), 4 carbon atoms (C6 units) or 5 carbon atoms (C7 units).
The units having 3, 4 and 6 carbon atoms (isolated C3, C4 and C6 units) can derive either from incorporated comomoners (propylene, 1 -butene and 1 -hexene comonomers) or from short chain branches formed by radical polymerization.
The units having 7 carbon atoms (C7 units) can be distinctively attributed to the mixed- plastic-polyethylene primary recycling blend (A) as they cannot derive from any comonomers. 1-heptene monomers are not used in copolymerization. Instead, the C7 units represent presence of LDPE distinct for the recyclate. It has been found that in LDPE resins the amount of C7 units is always in a distinct range. Thus, the amount of C7 units measured by quantitative 13C{ 1H} NMR measurements can be used to calculate the amount of LDPE in a polyethylene composition. Thus, the amounts of continuous C3 units, isolated C3 units, C4 units, C6 units and C7 units are measured by quantitative 13C{ 1H} NMR measurements as described below, whereas the LDPE content is calculated from the amount of C7 units as described below.
The total amount of ethylene units (C2 units) is attributed to units in the polymer chain, which do not have short side chains of 1-5 carbon atoms, in addition to the units attributed to the LDPE (i.e. units which have longer side chains branches of 6 or more carbon atoms).
A mixed-plastic-polyethylene primary blend (A) denotes the starting primary blend containing the mixed plastic-polyethylene as described above. Conventionally further components such as fillers, including organic and inorganic fillers for example talc, chalk, carbon black, and further pigments such as TiCk as well as paper and cellulose may be present. In a specific and preferred embodiment the waste stream is a consumer waste stream, such a waste stream may originate from conventional collecting systems such as those implemented in the European Union. Post-consumer waste material is characterized by a limonene content of from 2 to 500 mg/kg (as determined using solid phase microextraction (HS-SPME-GC-MS) by standard addition).
Mixed-plastic-polyethylene primary blend(s) (A) as used herein are commercially available. One suitable recyclate is e.g. available from Ecoplast Kunststoffrecycling GmbH under the brand name NAV 102.
Within the meaning of this invention the term “jacketing materials” refers to materials used in cable jacketing/cable coating applications for electrical/telephone/telecommunications cables. These materials are required to show good ESCR properties, such as a Bell test failure time of > 1000 hours, preferably > 2000 hours.
If not indicated otherwise “%” refers to weight-%. Detailed Description
Natural mixed-plastic-polyethylene primary recycling blend (A)
The mixed-plastic-polyethylene composition according to the present invention comprises a mixed-plastic-polyethylene primary recycling blend (A). It is the essence of the present invention that this primary recycling blend is obtained from a post-consumer waste stream and/or a post-industrial waste stream, preferably from a post-consumer waste stream.
According to the present invention the mixed-plastic-polyethylene primary recycling blend (A) is generally a blend, wherein at least 90 wt.-%, preferably at least 95 wt.-%, more preferably 100 wt.-% of the mixed-plastic-polyethylene primary blend originates from post consumer waste, such as from conventional collecting systems (curb-side collection), such as those implemented in the European Union, and/or post-industrial waste, preferably from post consumer waste.
Said post-consumer waste can be identified by its limonene content. It is preferred that the post-consumer waste has a limonene content of from 2 to 500 mg/kg.
The mixed-plastic-polyethylene primary recycling blend (A) preferably comprises a total amount of ethylene units (C2 units) of from 80.00 wt% to 96.00 wt%, more preferably of from 82.50 wt% to 95.50 wt%, still more preferably of from 85.00 wt% to 95.50 wt% and most preferably of from 87.50 wt% to 95.00 wt%; a total amount of continuous units having 3 carbon atoms corresponding to polypropylene (continuous C3 units) of from 0.20 to 6.50 wt%, more preferably from 0.40 wt% to 6.00 wt%, still more preferably from 0.60 wt% to 5.50 wt% and most preferably from 0.75 wt% to 5.00 wt%.
The total amounts of C2 units and continuous C3 units thereby are based on the total weight amount of monomer units in the mixed-plastic-polyethylene primary recycling blend (A) and are measured according to quantitative 13C{ 1H} NMR measurement.
In addition to C2 units and continuous C3 units the mixed-plastic-polyethylene primary recycling blend (A) can further comprise units having 3, 4, 6 or 7 or more carbon atoms so that the mixed-plastic-polyethylene primary recycling blend (A) overall can comprise ethylene units and a mix of units having 3, 4, 6 and 7 or more carbon atoms.
The mixed-plastic-polyethylene primary recycling blend (A) preferably comprises one or more in any combination, preferably all of: a total amount of units having 3 carbon atoms as isolated C3 units (isolated C3 units) of from 0.01 wt% to 0.50 wt%, more preferably from 0.02 wt% to 0.40 wt%, still more preferably from 0.03 wt% to 0.30 wt% and most preferably from 0.05 wt% to 0.25 wt%; a total amount of units having 4 carbon atoms (C4 units) of from 0.50 to 5.00 wt%, more preferably from 0.75 wt% to 4.00 wt%, still more preferably from 1.00 wt% to 3.50 wt% and most preferably from 1.25 wt% to 3.00 wt%; a total amount of units having 6 carbon atoms (C6 units) of from 0.50 to 7.50 wt%, more preferably from 0.75 wt% to 6.50 wt%, still more preferably from 1.00 wt% to 5.50 wt% and most preferably from 1.25 wt% to 5.00 wt%; a total amount of units having 7 carbon atoms (C7 units) of from 0.20 wt% to 2.50 wt%, of from 0.30 wt% to 2.00 wt%, still more preferably of from 0.40 to 1.50 wt% and most preferably of from 0.50 wt% to 1.25 wt%, and a LDPE content of from 20.00 to 65.00 wt%, more preferably from 25.00 wt% to 62.50 wt%, still more preferably from 30.00 wt% to 60.00 wt% and most preferably from 35.00 wt% to 55.00 wt%.
The total amounts of C2 units, continuous C3 units, isolated C3 units, C4 units, C6 units, C7 units and LDPE content thereby are based on the total weight amount of monomer units in the mixed-plastic-polyethylene primary recycling blend (A) and are measured or calculated according to quantitative 13C{ 1ET} NMR measurement.
Preferably, the total amount of units, which can be attributed to comonomers (i.e. isolated C3 units, C4 units and C6 units), in the mixed-plastic-polyethylene primary recycling blend (A) is from 4.00 wt% to 20.00 wt%, more preferably from 4.50 wt% to 17.50 wt%, still more preferably from 4.75 wt% to 15.00 wt% and most preferably from 5.00 wt% to 12.50 wt%, and is measured according to quantitative 13C{ 1ET} NMR measurement. Additionally, the mixed-plastic-polyethylene primary recycling blend (A) preferably shows non-linear viscoelastic behaviour as shown in the below defined Large Oscillatory Shear (LAOS) measurement:
The mixed-plastic-polyethylene primary recycling blend (A) preferably has a Large Amplitude Oscillatory Shear Non Linear Factor at a strain of 1000%, LAOSNLF (1000%), of from 2.200 to 10.000, more preferably from 2.400 to 8.500, still more preferably from 2.600 to 7.000 and most preferably from 2.800 to 5.000.
It is preferred that the mixed-plastic-polyethylene primary recycling blend (A) has a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 1.0 g/10 min, more preferably from 0.3 to 1.1 g/10 min; and/or a density of from 910 to 945 kg/m3, more preferably from 915 to 942 kg/m3, most preferably from 920 to 940 kg/m3.
The mixed-plastic-polyethylene primary recycling blend (A) preferably does not comprise carbon black. It is further preferred that the mixed-plastic-polyethylene primary recycling blend (A) does not comprise any pigments other than carbon black.
The mixed-plastic-polyethylene primary recycling blend (A) preferably is a natural mixed- plastic-polyethylene primary recycling blend (A).
The mixed-plastic-polyethylene primary recycling blend (A) may also include: a) 0 to 10 wt.-% units derived from alpha olefin(s), b) 0 to 3.0 wt.-% stabilizers, c) 0 to 3.0 wt.-% talc, d) 0 to 3.0 wt.-% chalk, e) 0 to 6.0 wt.-% further components all percentages with respect to the mixed-plastic-polyethylene primary recycling blend (A).
The mixed-plastic-polyethylene primary recycling blend (A) preferably has one or more, more preferably all, of the following properties in any combination: a melt flow rate (ISO 1133, 5.0 kg, 190 °C) of from 1.5 to 5.0 g/10 min, more preferably from 2.0 to 4.0 g/10 min; a melt flow rate (ISO 1133, 21.6 kg, 190 °C) of from 20.0 to 50.0 g/10 min, more preferably from 25.0 to 40.0 g/10 min; a polydispersity index PI of from 1.0 to 3.5 s 1, more preferably from 1.3 to 3.0 s 1; a shear thinning index SHI2.7/210 of from 15 to 40, more preferably from 20 to 35; a complex viscosity at the frequency of 300 rad/s, eta3oo, of from 500 to 750 Pa-s, more preferably from 550 to 700 Pa-s; a complex viscosity at the frequency of 0.05 rad/s, etao.05, of from 15000 to 30000 Pa-s, more preferably from 17500 to 27500 Pa-s; a Shore D hardness, measured after 15 s according to ISO 868, Shore D 15 s, of from 40 to 60, more preferably of from 45 to 55, a Shore D hardness, measured after 1 s according to ISO 868, Shore D 1 s, of from 45 to 65, more preferably of from 48 to 60, a Shore D hardness, measured after 3 s according to ISO 868, Shore D 3 s, of from 45 to 65, more preferably of from 48 to 60, a strain hardening modulus, SH modulus, of from 12.5 to 20.0 MPa, more preferably from 15.0 to 17.5 MPa, a xylene hot insoluble content, XHU, of from 0.01 to 1.0 wt%, more preferably from 0.1 to 0.5 wt%, a Charpy notched impact strength at 23 °C, Charpy NIS 23 °C, of from 50 to 100 kJ/m2, more preferably from 55 to 90 kJ/m2, an ash content of from 0.01 to 2.5 wt%, more preferably of from 0.1 to 2.0 wt%, and/or a limonene content of from 2 to 500 mg/kg.
It is preferred that the mixed-plastic-polyethylene primary recycling blend (A) has a comparatively low gel content, especially in comparison to other mixed-plastic-polyethylene primary recycling blends.
The mixed-plastic-polyethylene primary recycling blend (A) preferably has a gel content for gels with a size of from above 600 pm to 1000 pm of not more than 1000 gels/m2, more preferably not more than 850 gels/m2. The lower limit of the gel content for gels with a size of from above 600 pm to 1000 pm is usually 100 gels/m2, preferably 150 gels/m2. Still further, the mixed-plastic polyethylene composition preferably has a gel content for gels with a size of from above 1000 pm of not more than 200 gels/m2, more preferably not more than 150 gels/m2. The lower limit of the gel content for gels with a size of from above 1000 pm is usually 10 gels/m2, preferably 25 gels/m2.
Generally, recycled materials perform less well in functional tests such as the ESCR (Bell test failure time), SH modulus and Shore D tests than virgin materials or blends comprising virgin materials.
The mixed-plastic-polyethylene primary recycling blend (A) is preferably present in the composition of the present invention in an amount of from 10 to 85 wt%, more preferably 10 to 70 wt%, still more preferably from 15 to 65 wt%, even more preferably from 20 to 55 wt% and most preferably from 25 to 50 wt%, based on the overall weight of the composition.
Secondary blend (B) of virgin high-density polyethylene (HDPE)
The mixed-plastic-polyethylene composition of the invention comprises a secondary blend (B) of virgin high-density polyethylene (HDPE).
The secondary blend (B) preferably has: a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 1.2 g/10 min, preferably from 0.3 to 0.7 g/lOmin; and/or a density of from 940 to 970 kg/m3, more preferably from 943 to 965 kg/m3; and/or a polydispersity index from 1.5 to 2.8, more preferably from 1.7 to 2.5.
The secondary blend (B) can comprise carbon black or other pigments in an amount of of not more than 5 wt%, preferably not more than 3 wt%.
The presence of carbon black has an influence on the density of the secondary blend (B). A secondary blend (B) comprising carbon black preferably has a density of from 950 to 970 kg/m3, more preferably from 953 to 965 kg/m3.
In a preferred embodiment the secondary blend (B) does not comprise carbon black. It is further preferred that the secondary blend (B) does not comprise any pigments other than carbon black. In said embodiment the secondary blend (B) of virgin high-density polyethylene (HDPE) is preferably a natural secondary blend (B) of virgin high-density polyethylene (HDPE).
The secondary blend (B) of virgin high-density polyethylene (HDPE) preferably has a density of from 940 to 960 kg/m3, preferably from 943 to 955 kg/m3.
The secondary blend (B) includes as polymeric component a copolymer of ethylene and one or more comonomer units selected from alpha-olefins having from 3 to 6 carbon atoms. It is preferred that the polymeric component is a copolymer of ethylene and 1 -butene or a copolymer of ethylene and 1 -hexene.
Apart from the polymeric component the secondary blend (B) can further comprise additives in an amount of 10 wt% or below, more preferably 9 wt% or below, more preferably 7 wt% or below of the secondary blend (B). Suitable additives are usual additives for utilization with polyolefins, such as stabilizers (e.g. antioxidant agents), metal scavengers and/or UV- stabilizers, antistatic agents and utilization agents (such as processing aid agents).
The secondary blend (B) preferably has one or more, more preferably all of the following properties in any combination: a melt flow rate (ISO 1133, 5.0 kg, 190 °C) of from 1.0 to 5.0 g/10 min, more preferably from 1.3 to 4.0 g/10 min; a melt flow rate (ISO 1133, 21.6 kg, 190 °C) of from 20.0 to 50.0 g/10 min, more preferably from 25.0 to 40.0 g/10 min; a shear thinning index SHI2.7/210 of from 15 to 40, more preferably from 20 to 35; a complex viscosity at the frequency of 300 rad/s, eta3oo, of from 500 to 900 Pa-s, more preferably from 600 to 850 Pa-s; a complex viscosity at the frequency of 0.05 rad/s, etao.05, of from 15000 to 30000 Pa-s, more preferably from 17500 to 27500 Pa-s; a Shore D hardness, measured after 15 s according to ISO 868, Shore D 15 s, of from 50 to 70, more preferably of from 55 to 65, a Shore D hardness, measured after 1 s according to ISO 868, Shore D 1 s, of from 55 to 75, more preferably of from 58 to 70, a Shore D hardness, measured after 3 s according to ISO 868, Shore D 3 s, of from 55 to 75, more preferably of from 58 to 70, a strain hardening modulus, SH modulus, of from 20.0 to 35.0 MPa, more preferably from 22.5 to 32.5 MPa, a Charpy notched impact strength at 23 °C, Charpy NIS 23°C, of from 8.0 to 20.0 kJ/m2, more preferably from 10.0 to 17.5 kJ/m2, a Charpy notched impact strength at 0 °C, Charpy NIS 0°C, of from 4.0 to 15.0 kJ/m2, more preferably from 6.0 to 12.5 kJ/m2, a tensile stress at break of from 25 to 50 MPa, more preferably from 28 to 40 MPa, a tensile strain at break of from 700 to 1000 %, more preferably from 800 to 950 %, an environmental stress crack resistance, ESCR, of at least 2500 hours, more preferably at least 3000 hours, and/or a limonene content of less than 2 ppm.
Generally, recycled materials perform less well in functional tests such as the ESCR (Bell test failure time), SH modulus and Shore D tests than virgin materials or blends comprising virgin materials.
The secondary blend (B) is preferably present in the composition of the present invention in an amount of from 15 to 90 wt%, more preferably from 30 to 90 wt%, still more preferably from 35 to 85 wt%, even more preferably from 45 to 80 wt% and most preferably from 50 to 75 wt%, based on the overall weight of the composition.
Tertiary blend (C) of virgin high-density polyethylene (HDPE)
In one specific embodiment the mixed-plastic-polyethylene composition of the invention additionally comprises a tertiary blend (C) of virgin high-density polyethylene (HDPE).
The tertiary blend (C) preferably has: a melt flow rate (ISO 1133, 5 kg, 190 °C) of from 0.01 to 0.5 g/10 min, preferably from 0.1 to 0.4 g/lOmin; and/or a density of from 945 to 970 kg/m3, more preferably from 947 to 965 kg/m3.
The tertiary blend (C) can comprise carbon black or other pigments in an amount of of not more than 5 wt%, preferably not more than 3 wt%. The presence of carbon black has an influence on the density of the tertiary blend (C). A tertiary blend (C) comprising carbon black preferably has a density of from 955 to 970 kg/m3, preferably from 958 to 965 kg/m3.
In a preferred embodiment the tertiary blend (C) does not comprise carbon black. It is further preferred that the tertiary blend (C) does not comprise any pigments other than carbon black. In said embodiment the tertiary blend (C) of virgin high-density polyethylene (HDPE) is preferably a natural tertiary blend (C) of virgin high-density polyethylene (HDPE).
The natural tertiary blend (C) of virgin high-density polyethylene (HDPE) preferably has a density of from 945 to 960 kg/m3, preferably from 947 to 955 kg/m3.
The tertiary blend (C) includes as polymeric component a copolymer of ethylene and one or more comonomer units selected from alpha-olefins having from 3 to 6 carbon atoms. It is preferred that the polymeric component is a copolymer of ethylene and 1 -butene or a copolymer of ethylene and 1 -hexene.
Apart from the polymeric component the tertiary blend (C) can further comprise additives in an amount of 10 wt% or below, more preferably 9 wt% or below, more preferably 7 wt% or below of the tertiary blend (C). Suitable additives are usual additives for utilization with polyolefins, such as stabilizers (e.g. antioxidant agents), metal scavengers and/or UV- stabilizers, antistatic agents and utilization agents (such as processing aid agents).
It is preferred that the tertiary blend (C) consists of said polymeric component and the optional additives.
The tertiary blend (C) preferably has one or more, more preferably all of the following properties in any combination: a comonomer content, preferably a 1 -hexene content, of from 0.1 to 1.0 mol%, more preferably from 0.3 to 0.7 mol%, determined using quantitative 13C-NMR (see method description “Quantification of microstructure by NMR spectroscopy); a melt flow rate (ISO 1133, 21.6 kg, 190 °C) of from 4.0 to 15.0 g/10 min, more preferably from 5.0 to 10.0 g/lOmin; a tensile modulus of from 850 MPa to 1500 MPa, more preferably from 900 MPa to 1250 MPa; a tensile stress at break of from 20 to 50 MPa, more preferably from 22 to 40 MPa, or preferably from 25 to 50 MPa, more preferably from 28 to 40 MPa, a tensile strain at break of from 500 to 1000% more preferably from 600 to 950%, or preferably from 700 to 1000%, more preferably from 800 to 950% a Charpy notched impact strength of from 30 to 75 kJ/m2, more preferably from 40 to 65 kJ/m2, determined according to ISO 179-1 eA at +23 °C on compression moulded specimens of 80 x 10 x 4 mm prepared according to ISO 17855-2, a resistance to rapid crack propagation in a S4 test with Pc at 0°C using a SDR11 test pipe of 250 mm according to ISO 13477 of at least 9 bar, preferably at least 10 bar, a resistance to slow crack growth according to ISO 13479 at 9.2 bar and 80°C of at least 2000 h, more preferably at least 3000 h, and/or a limonene content of less than 2 ppm.
The tensile properties of tensile modulus, tensile stress at break and tensile strain at break are thereby measured according to ISO 527-2 (cross head speed = 1 mm/min; test speed 50 mm/min at 23 °C) using compression moulded specimens as described in ISO 17855-2 (dog bone shape, 4 mm thickness).
It is preferred that the tertiary blend (C) is a bimodal HDPE resin blend which is suitable for pipe applications. It is especially preferred that the tertiary blend is a HDPE resin suitable for PE100 pipes, i.e. pipes withstanding a hoop stress of 10.0 MPa (MRSio.o).
If present, the tertiary blend of virgin high-density polyethylene (HDPE) is preferably present in the composition of the present invention in an amount of from 1 to 20 wt%, more preferably from 2 to 18 wt%, still more preferably from 3 to 17 wt%, even more preferably from 4 to 16 wt% and most preferably from 5 to 15 wt%, based on the overall weight of the composition.
Mixed-plastic-polyethylene composition
The present invention seeks to provide a mixed-plastic-polyethylene composition comprising a mixed-plastic-polyethylene primary recycling blend (A) with improved ESCR, impact strength and SH modulus compared to the mixed-plastic-polyethylene primary recycling blend (A), to levels which are suitable for jacketing applications.
The mixed-plastic-polyethylene composition as described herein is especially suitable for wire and cable applications, such as jacketing applications. In a first aspect the present invention relates to a mixed-plastic-polyethylene composition comprising a total amount of ethylene units (C2 units) of from 90.00 to 99.00 wt%, and a total amount of continuous units having 3 carbon atoms corresponding to polypropylene (continuous C3 units) of from 0.10 to 5.00 wt%, with the total amounts of C2 units and continuous C3 units being based on the total weight amount of monomer units in the composition and measured according to quantitative 13C{ 1H} NMR measurement, and wherein the composition has a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 2.0 g/10 min; a density of from 930 kg/m3 to 955 kg/m3, preferably from 932 to 953 kg/m.
In said aspect the mixed-plastic-polyethylene composition is preferably obtainable by blending and extruding components comprising
10 to 85 wt.-%, based on the overall weight of the composition, of a mixed-plastic- polyethylene primary recycling blend (A) wherein at least 90 wt.-%, preferably at least 95 wt.-%, more preferably 100 wt.-% of the mixed-plastic-polyethylene primary blend (A) originates from post-consumer waste and/or post-industrial waste; and wherein the mixed-plastic-polyethylene primary blend (A) has a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 1.2 g/10 min, preferably from 0.3 to 1.1 g/10 min, a density of from 910 to 945 kg/m3, preferably from 915 to 942 kg/m3, most preferably from 920 to 940 kg/m3, a total amount of ethylene units (C2 units) of from 80.00 to 96.00 wt%, and a total amount of continuous units having 3 carbon atoms corresponding to polypropylene ( continuous C3 units) of from 0.20 to 6.50 wt%; with the total amounts of C2 units and continuous C3 units being based on the total weight amount of monomer units in the natural mixed-plastic-polyethylene primary blend (A) and measured according to quantitative 13C{ 1H} NMR measurement; and 15 to 90 wt.-%, based on the overall weight of the composition, of a secondary blend (B) of virgin high-density polyethylene (HDPE), wherein the secondary blend (B) has ethylene monomer units and comonomer units derived from olefins having from 3 to 6 carbon atoms, a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 1.2 g/10 min, preferably from 0.3 to 0.7 g/10 min; a density of from 940 to 970 kg/m3, a polydispersity index PI of from 1.0 to 2.8 s 1 as obtained from rheological measurement.
In one embodiment the mixed-plastic-polyethylene composition only comprises, preferably consists of the mixed-plastic-polyethylene primary recycling blend (A) and the secondary blend (B) of virgin high-density polyethylene (HDPE) as polymeric components.
In another embodiment the mixed-plastic polyethylene composition comprises, preferably consists of the mixed-plastic-polyethylene primary recycling blend (A), the secondary blend (B) of virgin high-density polyethylene (HDPE) and a tertiary blend (C) of virgin high- density polyethylene (HDPE) as polymeric components.
In said embodiment the mixed-plastic polyethylene composition has a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 1.0 g/lOmin and being obtainable by blending and extruding components comprising
10 to 83 wt.-%, based on the overall weight of the composition, of the mixed-plastic- polyethylene primary recycling blend (A);
16 to 80 wt.-%, based on the overall weight of the composition, of a secondary blend (B) of virgin high-density polyethylene (HDPE); and
1 to 20 wt.-%, based on the overall weight of the composition, of a tertiary blend (C) of virgin high-density polyethylene (HDPE), the blend (C) having ethylene monomer units and comonomer units derived from olefins having from 3 to 6 carbon atoms, a melt flow rate (ISO 1133, 5 kg, 190 °C) of from 0.01 to 0.5 g/lOmin, and a density of from 945 to 970 kg/m3. In a second aspect the present invention relates to a mixed-plastic-polyethylene composition having a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 2.0 g/lOmin; and a density of from 930 kg/m3 to 955 kg/m3, preferably from 932 to 953 kg/m; obtainable by blending and extruding components comprising
10 to 85 wt.-%, based on the overall weight of the composition, of a mixed-plastic- polyethylene primary recycling blend (A) wherein at least 90 wt.-%, preferably at least 95 wt.-%, more preferably 100 wt.-% of the mixed-plastic-polyethylene primary blend (A) originates from post-consumer waste and/or post-industrial waste having a limonene content of from 2 to 500 mg/kg; and wherein the mixed-plastic-polyethylene primary blend (A) has a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 1.2 g/lOmin, preferably from 0.3 to 1.1 g/lOmin , a density of from 910 to 945 kg/m3, preferably from 915 to 942 kg/m3, most preferably from 920 to 940 kg/m3, and a total amount of ethylene units (C2 units) of from 80.00 to 96.00 wt%, with the total amounts of C2 units being based on the total weight amount of monomer units in the mixed-plastic-polyethylene primary blend (A) and measured according to quantitative 13C{ 1H} NMR measurement;
15 to 90 wt.-%, based on the overall weight of the composition, of a secondary blend (B) of virgin high-density polyethylene (HDPE), wherein the secondary blend (B) has ethylene monomer units and comonomer units derived from olefins having from 3 to 6 carbon atoms, a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 1.2 g/10 min, preferably from 0.3 to 0.7 g/10 min; a density of from 940 to 970 kg/m3, a polydispersity index PI of from 1.0 to 2.8 s 1 as obtained from rheological measurement, and
- preferably a limonene content below 2 ppm. In one embodiment the mixed-plastic polyethylene composition of said aspect has a melt flow rate (ISO 1133, 2.16 kg, 190 °C) offrom O.l to 1.0 g/lOmin and being obtainable by blending and extruding components comprising
10 to 83 wt.-%, based on the overall weight of the composition, of the mixed-plastic- polyethylene primary recycling blend (A);
16 to 80 wt.-%, based on the overall weight of the composition, of a secondary blend (B) of virgin high-density polyethylene (HDPE); and
1 to 20 wt.-%, based on the overall weight of the composition, of a tertiary blend (C) of virgin high-density polyethylene (HDPE), the blend (C) having ethylene monomer units and comonomer units derived from olefins having from 3 to 6 carbon atoms, a melt flow rate (ISO 1133, 5 kg, 190 °C) of from 0.01 to 0.5 g/lOmin, and a density of from 945 to 970 kg/m3, and preferably a limonene content below 2 ppm.
In one embodiment the mixed-plastic-polyethylene composition of said aspect only comprises, preferably consists of the mixed-plastic-polyethylene primary recycling blend (A) and the secondary blend (B) of virgin high-density polyethylene (HDPE) as polymeric components.
In another embodiment the mixed-plastic polyethylene composition of said aspect comprises, preferably consists of the mixed-plastic-polyethylene primary recycling blend (A), the secondary blend (B) of virgin high-density polyethylene (HDPE) and a tertiary blend (C) of virgin high-density polyethylene (HDPE) as polymeric components.
The following properties apply to all aspects of the mixed-plastic polyethylene composition:
The mixed-plastic-polyethylene composition comprises a total amount of ethylene units (C2 units) of from 90.00 to 99.00 wt%, preferably from 91.00 to 98.00 wt%, more preferably from 92.00 to 97.00 wt%, and a total amount of continuous units having 3 carbon atoms corresponding to polypropylene (continuous C3 units) of from 0.10 to 5.00 wt%, more preferably from 0.15 wt% to 4.50 wt%, still more preferably from 0.20 wt% to 4.00 wt%.
Further, the mixed-plastic-polyethylene composition preferably comprises one or more in any combination of, more preferably all of: a total amount of units having 3 carbon atoms as isolated peaks in the NMR spectrum (isolated C3 units) of from 0 wt% to 0.50 wt%, more preferably from 0 wt% to 0.40 wt%, still more preferably from 0 wt% to 0.30 wt%; a total amount of units having 4 carbon atoms (C4 units) of from 0.20 wt% to 4.00 wt%, more preferably from 0.30 wt% to 3.50 wt%, still more preferably from 0.50 wt% to 3.00 wt%; a total amount of units having 6 carbon atoms (C6 units) of from 0.20 wt% to 5.00 wt%, more preferably from 0.30 wt% to 4.00 wt%, still more preferably from 0.50 wt% to 3.50 wt%; a total amount of units having 7 carbon atoms (C7 units) of from 0 wt% to 0.80 wt%, more preferably from 0 wt% to 0.70 wt%, still more preferably from 0 wt% to 0.65 wt%; in one embodiment the lower limit of the total amount of units having 7 carbon atoms (C7 units) is preferably 0.10 wt%, more preferably 0.15 wt%, still more preferably 0.20 wt%; a LDPE content of from 5.00 to 50.00 wt%, more preferably from 8.00 wt% to 48.00 wt%, still more preferably from 10.00 wt% to 46.00 wt% and most preferably from 11.50 wt% to 45.00 wt%.
The total amounts of C2 units, continuous C3 units, isolated C3 units, C4 units, C6 units, C7 units and LDPE content thereby are based on the total weight amount of monomer units in the composition and are measured or calculated according to quantitative 13C{ 1ET} NMR measurement.
Preferably, the total amounts of units, which can be attributed to comonomers (i.e. isolated C3 units, C4 units and C6 units), in the mixed-plastic-polyethylene composition is from 1.00 wt% to 8.00 wt%, more preferably from 2.00 wt% to 7.00 wt%, still more preferably from 3.00 wt% to 6.00 wt%, and is measured according to quantitative 1 C J 1 H } NMR measurement. The mixed-plastic polyethylene composition according to the present invention has a a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 2.0 g/10 min, more preferably from 0.2 to 1.8 g/10 min.; and a density of from 930 kg/m3 to 955 kg/m3, preferably from 932 to 953 kg/m3.
Additionally, the mixed-plastic polyethylene composition preferably shows non-linear viscoelastic behaviour as shown in the below defined Large Oscillatory Shear (LAOS) measurement:
The mixed-plastic polyethylene composition preferably has a Large Amplitude Oscillatory Shear Non Linear Factor at a strain of 1000%, LAOSNLF (1000%), of from 1.900 to 4.000, more preferably from 2.000 to 3.500, still more preferably from 2.100 to 3.000 and most preferably from 2.125 to 2.850.
The mixed-plastic polyethylene composition preferably has an impact strength at 23 °C (ISO 179-1 eA) of from 10 to 27 kJ/m2, preferably from 12 to 26 kJ/m2.
Preferably, the impact strength at 23 °C (ISO 179-1 eA) of the composition is higher than that of the secondary blend. It is preferred that the impact strength at 23 °C (ISO 179-1 eA) of the composition is at least 105 %, more preferably at least 110 % of the impact strength of the secondary blend (B).
Further, the mixed-plastic polyethylene composition preferably has an impact strength at 0 °C (according to ISO 179-1 eA) of from 5.0 to 12.0 kJ/m2, more preferably from 6.0 to 10.0 kJ/m2
The mixed-plastic polyethylene composition preferably has a strain hardening modulus (SH modulus) of from 15.0 to 30.0 MPa, more preferably from 16.0 to 26.0 MPa and most preferably from 17.0 to 25.0 MPa. Preferably, the SH modulus of the mixed polyethylene composition is at least 60 %, more preferably at least 65 % of the SH modulus of the secondary blend (B).
Further, the mixed-plastic polyethylene composition preferably has an ESCR (Bell test failure time) of more than 1000 hours, preferably more than 1250 hours and still more preferably more than 1500 hours and most preferably more than 1800 hours. In some embodiments the mixed-plastic polyethylene composition can have an ESCR (Bell test failure time) of more than 2000 hours or even more than 5000 hours The upper limit of the ESCR can be as high as 15000 hours, usually up to 10000 hours.
It is preferred that the mixed-plastic polyethylene composition preferably has a Shore D hardness, measured according to ASTM D2240-03 with a measuring time of 1 s, Shore D Is, of from 52.0 to 68.0, more preferably from 55.0 to 65.0 and most preferably from 56.5 to 62.5, and/or a Shore D hardness, measured according to ASTM D2240-03 with a measuring time of 3 s, Shore D 3s, of from 50.0 to 68.0, more preferably from 55.5 to 65.0 and most preferably from 56.5 to 62.5, and/or a Shore D hardness, measured according to ASTM D2240-03 with a measuring time of 15 s, Shore D 15s, of from 48.0 to 65.0, more preferably from 52.5 to 62.5 and most preferably from 54.0 to 60.0.
It is further preferred that that the mixed-plastic polyethylene composition preferably has a Shore D hardness, measured according to ISO 868 with a measuring time of 1 s, Shore D Is, of from 55.0 to 70.0, more preferably from 55.5 to 68.0 and most preferably from 56.0 to 65.0, and/or a Shore D hardness, measured according to ISO 868 with a measuring time of 3 s, Shore D 3s, of from 52.0 to 68.0, more preferably from 53.0 to 65.0 and most preferably from 54.0 to 62.5, and/or a Shore D hardness, measured according to ISO 868 with a measuring time of 15 s, Shore D 15s, of from 50.0 to 67.0 more preferably from 51.5 to 65.0 and most preferably from 52.0 to 60.0.
The mixed-plastic polyethylene composition preferably has one or more, preferably all of the following rheological properties, in any combination: a shear thinning index SHIp o) of from 15 to 40, more preferably from 16 to 35 and/or a complex viscosity at 0.05 rad/s etao.os rad/s of from 10000 to 38000 Pa-s, more preferably from 10100 to 35000 Pa-s, and/or a complex viscosity at 300 rad/s eta3oo rad/s of from 550 to 850 Pa-s, more preferably from 570 to 800 Pa-s, and/or a polydispersity index PI of from 1.0 to 3.5 s 1, more preferably from 1.3 to 3.0 s 1.
Further, the mixed-plastic polyethylene composition preferably has one or more, preferably all of the following melt flow rate properties, in any combination: a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.2 to 1.8 g/10 min, more preferably from 0.3 to 1.5 g/10 min, and/or a melt flow rate (ISO 1133, 5 kg, 190 °C) of from 1.2 to 5.0 g/10 min, more preferably from 1.4 to 4.8 g/10 min and/or a melt flow rate (ISO 1133, 21 kg, 190 °C) of from 18 to 70 g/10 min, more preferably from 20 to 60 g/10 min.
Still further, the mixed-plastic polyethylene composition preferably has one or more, preferably all of the following tensile properties, in any combination: a tensile strain at break, measured according to ISO 527-2 on compression moulded test specimens of type 5A, of from 650% to 900%, more preferably from 700% to 880%; and/or a tensile stress at break, measured according to ISO 527-2 on compression moulded test specimens of type 5 A, of from 18 MPa to 35 MPa, more preferably from 20 MPa to 30 MPa.
After ageing of the 5 A test specimens at 110 °C for 14 days the mixed-plastic polyethylene composition preferably has one or more, preferably all of the following tensile properties, in any combination: a tensile strain at break, measured according to ISO 527-2 on compression moulded test specimens of type 5A after ageing, of from 700% to 950%, more preferably from 750% to 930%; and/or a tensile stress at break, measured according to ISO 527-2 on compression moulded test specimens of type 5 A after ageing, of from 16 MPa to 33 MPa, more preferably from 18 MPa to 28 MPa. Further, the mixed-plastic polyethylene composition preferably has a tear resistance of from 10.0 to 25.0 N/mm, more preferably of from 12.5 to 22.5 N/mm and most preferably of from 15.0 to 20.0 N/mm.
It is further preferred that the mixed-plastic polyethylene composition has a pressure deformation of not more than 15%, more preferably not more than 13%. The lower limit is usually at least 0 %, meaning that no pressure deformation can be detected, preferably at least 1 %.
Still further, the mixed-plastic polyethylene composition preferably has a water content of preferably not more than 250 ppm more preferably not more than 248 ppm. The lower limit is usually at least 25 ppm, preferably at least 50 ppm.
It is further preferred that the mixed-plastic polyethylene composition has a gel content for gels with a size of from above 600 pm to 1000 pm of from 25 to 250 gels/m2, more preferably from 35 to 225 gels/m2.
Still further, the mixed-plastic polyethylene composition preferably has a gel content for gels with a size of from above 1000 pm of not more than 35 gels/m2, more preferably not more than 30 gels/m2. The lower limit is usually at least 0, meaning that no gels of said size can be detected, preferably at least 1.0.
The composition can have further components apart from the mixed-plastic-polyethylene primary recycling blend (A) and the secondary blend (B) of virgin high-density polyethylene (HDPE), and the optional tertiary blend (C) of virgin high-density polyethylene (HDPE), such as further polymeric components or additives in amounts of not more than 15 wt%, based on the total weight of the composition.
Suitable additives are usual additives for utilization with polyolefins, such as stabilizers, (e.g. antioxidant agents), metal scavengers and/or UV stabilizers, antistatic agents, and utilization agents. The additives can be present in the composition in an amount of 10 wt% or below, more preferably 9 wt% or below, more preferably 7 wt% or below.
Carbon black or other pigments are not enclosed in the definition of additives. The composition can comprise carbon black or pigments in an amount of not more than 5 wt%, preferably not more than 3 wt%.
It is thereby preferred that the composition does not contain carbon black. It is further preferred that the composition does not contain any pigments other than carbon black. In said embodiment the mixed-plastic-polyethylene composition is preferably a natural mixed- plastic-polyethylene composition.
It is, however, preferred that the composition consists of the mixed-plastic-polyethylene primary recycling blend (A) and the secondary blend (B) of virgin high-density polyethylene (HDPE), the optional tertiary blend (C) of virgin high-density polyethylene (HDPE) and optional additives.
The presence of carbon black has an influence on the density of the composition. A composition comprising carbon black preferably has a density of from 935 to 955 kg/m3, preferably from 937 to 953 kg/m3.
A composition free from carbon black preferably has a density of from 930 to 950 kg/m3, preferably from 932 to 948 kg/m3.
In one embodiment the mixed-plastic polyethylene composition comprises, more preferably consists of mixed-plastic-polyethylene primary recycling blend (A) and the secondary blend (B) of virgin high-density polyethylene (HDPE), but does not comprise, i.e. is free of the tertiary secondary blend (C) of virgin high-density polyethylene (HDPE).
In said embodiment, the mixed-plastic polyethylene composition preferably has the following properties:
The mixed-plastic polyethylene composition preferably has one or more, preferably all of the following melt flow rate properties, in any combination: a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.3 to 1.8 g/10 min, more preferably from 0.4 to 1.5 g/10 min, and/or a melt flow rate (ISO 1133, 5 kg, 190 °C) of from 1.5 to 5.0 g/10 min, more preferably from 1.6 to 4.8 g/10 min and/or a melt flow rate (ISO 1133, 21 kg, 190 °C) of from 22 to 70 g/10 min, more preferably from 24 to 60 g/10 min. In one embodiment mixed-plastic polyethylene composition preferably has one or more, preferably all of the following melt flow rate properties, in any combination: a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 1.0 g/10 min, more preferably from 0.3 to 0.8 g/10 min and most preferably from 0.3 to 0.7 g/10 min and/or a melt flow rate (ISO 1133, 5 kg, 190 °C) of from 1.5 to 2.5 g/10 min, more preferably 5 from 1.6 to 2.3 g/10 min and/or a melt flow rate (ISO 1133, 21 kg, 190 °C) of from 22 to 40 g/10 min, more preferably from 24 to 37 g/10 min.
Further, the mixed-plastic polyethylene composition preferably has one or more, preferably all of the following rheological properties, in any combination: a shear thinning index SHIp o) of from 15 to 35, more preferably from 16 to 32 and/or a complex viscosity at 0.05 rad/s etao.os rad/s of from 10000 to 28000 Pa-s, more preferably from 10100 to 27500 Pa-s, and/or a complex viscosity at 300 rad/s eta3oo rad/s of from 550 to 850 Pa-s, more preferably from 570 to 800 Pa-s, and/or a polydispersity index PI of from 1.0 to 3.5 s 1, more preferably from 1.3 to 3.0 s 1.
Still further, the mixed-plastic polyethylene composition preferably has a strain hardening modulus (SH modulus) of from 15.0 to 27.0 MPa, more preferably from 16.0 to 26.0 MPa and most preferably from 17.0 to 25.0 MPa. Preferably, the SH modulus of the mixed polyethylene composition is at least 60 %, more preferably at least 65 % of the SH modulus of the secondary blend (B).
All other properties of the mixed-plastic polyethylene composition preferably are in the range as disclosed above.
The weight ratio of the mixed-plastic-polyethylene primary recycling blend (A) and the secondary blend (B) of virgin high-density polyethylene (HDPE) is preferably in the range of from 10:90 to 85:15, more preferably from 10:90 to 70:30, still more preferably from 15:85 to 65:35, even more preferably from 20:80 to 60:40, and most preferably from 25:75 to 50:50. The mixed-plastic-polyethylene primary recycling blend (A) and the secondary blend (B) of virgin high-density polyethylene (HDPE) are generally defined as described above or below.
One positive aspect of the present invention of said embodiment is that rather high amounts of mixed-plastic-polyethylene primary recycling blend (A) can be used in the composition which still shows acceptable properties especially in regard of ESCRbut also regarding strain hardening and Shore D hardness.
In another embodiment the mixed-plastic polyethylene composition comprises, more preferably consists of mixed-plastic-polyethylene primary recycling blend (A), the secondary blend (B) of virgin high-density polyethylene (HDPE) and the tertiary secondary blend (C) of virgin high-density polyethylene (HDPE).
In said embodiment, the mixed-plastic polyethylene composition preferably has the following properties:
The mixed-plastic polyethylene composition preferably has one or more, preferably all of the following melt flow rate properties, in any combination: a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 1.0 g/10 min, more preferably from 0.2 to 0.8 g/10 min, and/or a melt flow rate (ISO 1133, 5 kg, 190 °C) of from 1.2 to 3.5 g/10 min, more preferably from 1.3 to 3.0 g/10 min and/or a melt flow rate (ISO 1133, 21 kg, 190 °C) of from 18 to 50 g/10 min, more preferably from 20 to 40 g/10 min.
In one embodiment the mixed-plastic polyethylene composition preferably has one or more, preferably all of the following melt flow rate properties, in any combination: a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from from 0.1 to 1.0 g/10 min, more preferably from 0.2 to 0.7 g/10 min and most preferably from 0.3 to 0.6 g/10 min and/or a melt flow rate (ISO 1133, 5 kg, 190 °C) of from 1.2 to 2.0 g/10 min, more preferably from 1.3 to 1.9 g/10 min and/or a melt flow rate (ISO 1133, 21.6 kg, 190 °C) of from 18 to 35 g/10 min, more preferably from 20 to 30 g/10 min.
Further, the mixed-plastic polyethylene composition preferably has one or more, preferably all of the following rheological properties, in any combination: a shear thinning index SHIp o) of from 20 to 40, more preferably from 22 to 37 and/or a complex viscosity at 0.05 rad/s etao.os rad/s of from 16000 to 38000 Pa-s, more preferably from 18000 to 35000 Pa-s, and/or a complex viscosity at 300 rad/s eta3oo rad/s of from 550 to 850 Pa-s, more preferably from 570 to 800 Pa-s, and/or a polydispersity index PI of from 1.0 to 3.5 s 1, more preferably from 1.3 to 3.0 s 1.
Still further, the mixed-plastic polyethylene composition preferably has a strain hardening modulus (SH modulus) of from 18.0 to 30.0 MPa, more preferably from 20.0 to 28.0 MPa and most preferably from 21.0 to 27.0 MPa. Preferably, the SH modulus of the mixed polyethylene composition is at least 70 %, more preferably at least 75 % of the SH modulus of the secondary blend (B).
All other properties of the mixed-plastic polyethylene composition preferably are in the range as disclosed above.
The weight ratio of the mixed-plastic-polyethylene primary recycling blend (A) and the combined blend of the secondary blend (B) of virgin high-density polyethylene (HDPE) and the tertiary blend (C) of virgin high-density polyethylene (HDPE) is preferably in the range of from 10:90 to 83:17, more preferably 10:90 to 70:30, still more preferably from 15:85 to 65:35, even more preferably from 20:80 to 60:40, and most preferably from 25:75 to 50:50.
The mixed-plastic-polyethylene primary recycling blend (A), the secondary blend (B) of virgin high-density polyethylene (HDPE) and the tertiary blend (C) of virgin high-density polyethylene (HDPE) are generally defined as described above or below. One positive aspect of the present invention of said embodiment is that rather high amounts of mixed-plastic-polyethylene primary recycling blend (A) can be used in the composition which still shows acceptable properties especially in regard of strain hardening but also regarding ESCR and Shore D hardness.
It has been found that the addition of the tertiary blend (C) of virgin high-density polyethylene (HDPE) to the composition in small amounts thereby especially improves the strain hardening behavior and the tensile properties without sacrificing the impact properties.
Article
The present application is further directed to an article comprising the mixed-plastic- polyethylene composition as described above.
In a preferred embodiment, the article is used in jacketing applications i.e. for a cable jacket. Preferably the article is a cable comprising at least one layer which comprises the mixed- plastic-polyethylene composition as described above.
Preferably, the cable comprising a layer such as a jacketing layer, which comprises the mixed- plastic-polyethylene composition as described above, has a cable shrinkage of not more than 2.0 %, more preferably not more than 1.8 %. The lower limit is usually at least 0.3 %, preferably at least 0.5 %.
Further, the cable comprising a layer such as a jacketing layer, which comprises the mixed- plastic-polyethylene composition as described above, preferably has the following tensile properties: a tensile strain at break, measured according to EN60811-501 on cable specimen, of from 480% to 870%, more preferably from 500% to 850%; and/or a tensile stress at break, measured according to EN60811-501 on cable specimen, of from 16 MPa to 35 MPa, more preferably from 17 MPa to 33 MPa.
The cable comprising a layer such as a jacketing layer, which comprises the mixed-plastic- polyethylene composition comprising, more preferably consisting of the mixed-plastic- polyethylene primary recycling blend (A) and the secondary blend (B) of virgin high-density polyethylene (HDPE), but does not comprise, i.e. is free of the tertiary secondary blend (C) of virgin high-density polyethylene (HDPE) as described above, preferably has the following tensile properties: a tensile strain at break, measured according to EN60811-501 on cable specimen, of from 500% to 870%, more preferably from 525% to 750%; and/or a tensile stress at break, measured according to EN60811-501 on cable specimen, of from 16 MPa to 33 MPa, more preferably from 17 MPa to 30 MPa.
The cable comprising a layer such as a jacketing layer, which comprises the mixed-plastic- polyethylene composition comprising, more preferably consisting of the mixed-plastic- polyethylene primary recycling blend (A), the secondary blend (B) of virgin high-density polyethylene (HDPE) and the tertiary secondary blend (C) of virgin high-density polyethylene (HDPE) as described above, preferably has the following tensile properties: a tensile strain at break, measured according to EN60811-501 on cable specimen, of from 480% to 870%, more preferably from 500% to 850%; and/or a tensile stress at break, measured according to EN60811-501 on cable specimen, of from 18 MPa to 35 MPa, more preferably from 19 MPa to 33 MPa.
All preferred aspects and embodiments as described above shall also hold for the article.
Process
The present invention also relates to a process for preparing the mixed-plastic-polyethylene composition as defined above or below. The process according to the present invention results in an improvement in the mechanical properties of the mixed-plastic-polyethylene primary recycling blend (A).
The process according to the present invention comprises the steps of: a) providing a mixed-plastic-polyethylene primary recycling blend (A) in an amount of 10 to 85 wt.-% based on the overall weight of the composition, wherein at least 90 wt.-%, preferably at least 95 wt.-%, more preferably 100 wt.-% of the mixed-plastic-polyethylene primary blend (A) originates from post-consumer waste and/or post-industrial waste wherein the mixed-plastic-polyethylene primary blend (A) has a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 1.2 g/lOmin, preferably from 0.3 to 1.1 g/lOmin, a density of from 910 to 945 kg/m3, preferably from 915 to 942 kg/m3, most preferably from 920 to 940 kg/m3, a total amount of ethylene units (C2 units) of from 80.00 to 96.00 wt%, and a total amount of continuous units having 3 carbon atoms corresponding to polypropylene (continuous C3 units) of from 0.20 to 6.50 wt%; with the total amounts of C2 units and continuous C3 units being based on the total weight amount of monomer units in the mixed-plastic-polyethylene primary blend (A) and measured according to quantitative 13C{ 1H} NMR measurement, b) providing a secondary blend (B) of virgin high-density polyethylene (HDPE) in an amount of 15 to 90 wt.-% based on the overall weight of the composition, wherein the secondary blend (B) has ethylene monomer units and comonomer units derived from olefins having from 3 to 6 carbon atoms, a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 1.2 g/10 min, preferably from 0.3 to 0.7 g/10 min; a density of from 940 to 970 kg/m3, a polydispersity index PI of from 1.0 to 2.8 s 1 as obtained from rheological measurement, c) melting and mixing the blend of mixed-plastic-polyethylene primary blend (A) and the secondary blend (B) in an extruder, optionally a twin screw extruder, and d) optionally pelletizing the obtained mixed-plastic-polyethylene composition.
In one embodiment the process of the invention as described above comprises the steps of: a) providing the mixed-plastic-polyethylene primary recycling blend (A) in an amount of 10 to 83 wt.-% based on the overall weight of the composition; b) providing the secondary blend (B) of virgin high-density polyethylene (HDPE) in an amount of 16 to 80 wt.-% based on the overall weight of the composition; and c) providing a tertiary blend (C) of virgin high-density polyethylene (HDPE) in an amount of 1 to 20 wt.-% based on the overall weight of the composition, wherein the tertiary blend (C) has ethylene monomer units and comonomer units derived from olefins having from 3 to 6 carbon atoms, a melt flow rate (ISO 1133, 5 kg, 190 °C) of from 0.01 to 0.5 g/lOmin, and a density of from 945 to 970 kg/m3, d) melting and mixing the blend of mixed-plastic-polyethylene primary blend (A), the secondary blend (B) and the tertiary blend (C) in an extruder, optionally a twin screw extruder, and e) optionally pelletizing the obtained mixed-plastic-polyethylene composition.
All preferred aspects, definitions and embodiments as described above shall also hold for the process.
Use
The present invention relates to the use of a mixed-plastic-polyethylene composition as defined above or below for producing a cable layer, preferably a cable jacketing layer, having an ESCR (Bell test failure time) of more than 1000 hours, preferably more than 1250 hours and still more preferably more than 1500 hours and most preferably more than 1800 hours. In some embodiments the cable layer, preferably the cable jacketing layer, can have an ESCR (Bell test failure time) of more than 2000 hours or even more than 5000 hours. The upper limit of the ESCR can be as high as 15000 hours, usually up to 10000 hours.
It is preferred that the cable layer, preferably the cable jacketing layer, has a strain hardening modulus (SH modulus) of from 15.0 to 30.0 MPa, more preferably from 16.0 to 26.0 MPa and most preferably from 17.0 to 25.0 MPa.
All preferred aspects, definitions and embodiments as described above shall also hold for the use. Examples 1. Test Methods a) Melt Flow rate
Melt flow rates were measured with a load of 2.16 kg (MFR2), 5.0 kg (MFR5) or 21.6 kg (MFR21) at 190°C as indicated. The melt flow rate is that quantity of polymer in grams which the test apparatus standardized to ISO 1133 extrudes within 10 minutes at a temperature of or 190°C under a load of 2.16 kg, 5.0 kg or 21.6 kg. b) Density
Density is measured according to ISO 1183-187. Sample preparation is done by compression moulding in accordance with ISO 17855-2. c) Comonomer content
Quantification of C2, iPP (continuous C3), LDPE and polyethylene short chain branches in polyethylene based recylates
Quantitative 13C{ 1H} NMR spectra were recorded in the solution-state using a Bruker Avancelll 400MHz NMR spectrometer operating at 400.15 and 100.62 MHz for 'H and 13C respectively. All spectra were recorded using a 13C optimised 10 mm extended temperature probehead at 125°C using nitrogen gas for all pneumatics. Approximately 200 mg of material was dissolved in 3 ml of 7,2-tetrachloroethane-ife (TCE-r/?) along with chromium-(III)- acetylacetonate (Cr(acac)3) resulting in a 65 mM solution of relaxation agent in solvent {singh09}. To ensure a homogenous solution, after initial sample preparation in a heat block, the NMR tube was further heated in a rotatory oven for at least 1 hour. Upon insertion into the magnet the tube was spun at 10 Hz. This setup was chosen primarily for the high resolution and quantitatively needed for accurate ethylene content quantification. Standard single-pulse excitation was employed without NOE, using an optimised tip angle, 1 s recycle delay and a bi-level WALTZ16 decoupling scheme {zhou07,busico07}. A total of 6144 (6k) transients were acquired per spectra.
Quantitative 13C{1H} NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals using proprietary computer programs. All chemical shifts were indirectly referenced to the central methylene group of the ethylene block (EEE) at 30.00 ppm using the chemical shift of the solvent. Characteristic signals corresponding to polyethylene with different short chain branches (Bl, B2, B4, B5, B6plus) and polypropylene were observed {randall89, brandoliniOO}.
Characteristic signals corresponding to the presence of polyethylene containing isolated Bl branches (starBl 33.3 ppm), isolated B2 branches (starB2 39.8 ppm), isolated B4 branches (twoB423.4 ppm), isolated B5 branches (threeB5 32.8 ppm), all branches longer than 4 carbons (starB4plus 38.3 ppm) and the third carbon from a saturated aliphatic chain end (3s
32.2 ppm) were observed. The intensity of the combined ethylene backbone methine carbons (ddg) containing the polyethylene backbone carbons (dd 30.0 ppm), g-carbons (g 29.6 ppm) the 4s and the threeB4 carbon (to be compensated for later on) is taken between 30.9 ppm and
29.3 ppm excluding the Tbb from polypropylene. The amount of C2 related carbons was quantified using all mentioned signals according to the following equation: fCc2totai = (Iddg -ItwoB4) + (IstarBl*6) + (IstarB2*7) + (ItwoB4*9) + I(threeB5*10) + ((IstarB4plus-ItwoB4-IthreeB5)*7) + (I3s*3)
Characteristic signals corresponding to the presence of polypropylene (iPP, continuous C3)) were observed at 46.7 ppm, 29.0 ppm and 22.0 ppm. The amount of PP related carbons was quantified using the integral of Saa at 46.6 ppm: fCpp = Isaa * 3
The weight percent of the C2 fraction and the polypropylene can be quantified according following equations:
WtC2fraction = fCc2total * 100 / (fCc2total + fCpp) wtpp = fCpp * 100 / (fCc2total + fCpp)
Characteristic signals corresponding to various short chain branches were observed and their weight percentages quantified as the related branch would be an alpha-olefin, starting by quantifying the weight fraction of each: fwtC2 = fCc2totai - ((IstarBl*3) - (IstarB2*4) - (ItwoB4*6) - (IthreeB5*7) fwtC3 (isolated C3) = IstarBl*3 fwtC4 = IstarB2*4 fwtC6 = ItwoB4*6 fwtC7 = IthreeB5*7
Normalisation of all weight fractions leads to the amount of weight percent for all related branches: fsumwt%totai= fwtC2 + fwtC3 + fwtC4 + fwtC6 + fwtC7 + fCpp wtC2total = fwtC2 * 100 / fsumwt%totai wtC3total = fwtC3 * 100 / fsumwt%totai wtC4total = fwtC4 * 100 / fsumwt%totai wtC6total = fwtC6 * 100 / fsumwt%totai wtC7total = fwtC7 * 100 / fsumwt%totai
The content of LDPE can be estimated assuming the B5 branch, which only arises from ethylene being polymerised under high pressure process, being almost constant in LDPE. We found the average amount of B5 if quantified as C7 at 1.46 wt%. With this assumption it is possible to estimate the LDPE content within certain ranges (approximately between 20 wt% and 80 wt%), which are depending on the SNR ratio of the threeB5 signal: wt%LDPE = wtC7total * 100 / 1.46
References: zhou07 Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh, D. Winniford, B., J. Mag. Reson. 187 (2007) 225 busico07 Busico, V., Carbonniere, P., Cipullo, R., Pellecchia, R., Severn, J., Talarico, G., Macromol. Rapid Commun. 2007, 28, 1128 singh09 Singh, G., Kothari, A., Gupta, V., Polymer Testing 28 5 (2009), 475 randall89 J. Randall, Macromol. Sci., Rev. Macromol. Chem. Phys. 1989, C29, 201. brandoliniOO A. J. Brandolini, D. D. Hills, NMR Spectra of Polymers and Polymer Additives, Marcel Dekker Inc., 2000 d) Impact strength
The impact strength is determined as Charpy Notched Impact Strength according to ISO 179- 1 eA at +23 °C and at 0 °C on compression moulded specimens of 80 x 10 x 4 mm prepared according to ISO 17855-2. e) Tensile testing of 5A specimen and that after ageing of 5A specimen at 110 °C, 14 days (336h)
For tensile testing, dog bone specimens of 5A are prepared according to ISO 527-2/5A by die cutting from compression moulded plaques of 2mm’ thickness. If ageing is needed, the 5A specimens are kept at 110 °C in a cell oven for 14 days (336 hours). All specimens are conditioned for at least 16 hours at 23°C and 50% relative humidity before testing.
Tensile properties are measured according to ISO 527-1/2 at 23°C and 50% relative humidity with Alwetron R24, lkN load cell. Tensile testing speed is 50mm/min, grip distance is 50mm and gauge length is 20mm. f) Rheological measurements
Dynamic Shear Measurements (frequency sweep measurements)
The characterisation of melt of polymer composition or polymer as given above or below in the context by dynamic shear measurements complies with ISO standards 6721-1 and 6721- 10. The measurements were performed on an Anton Paar MCR501 stress controlled rotational rheometer, equipped with a 25 mm parallel plate geometry. Measurements were undertaken on compression moulded plates, using nitrogen atmosphere and setting a strain within the linear viscoelastic regime. The oscillatory shear tests were done at 190 °C applying a frequency range between 0.01 and 600 rad/s and setting a gap of 1.3 mm.
In a dynamic shear experiment the probe is subjected to a homogeneous deformation at a sinusoidal varying shear strain or shear stress (strain and stress controlled mode, respectively). On a controlled strain experiment, the probe is subjected to a sinusoidal strain that can be expressed by y(t) = To sin(mt) (1)
If the applied strain is within the linear viscoelastic regime, the resulting sinusoidal stress response can be given by a(t) = s0 sin(u>t + d ) (2) where s0 and y0 are the stress and strain amplitudes, respectively w is the angular frequency d is the phase shift (loss angle between applied strain and stress response) t is the time
Dynamic test results are typically expressed by means of several different rheological functions, namely the shear storage modulus G’, the shear loss modulus, G”, the complex shear modulus, G*, the complex shear viscosity, h*, the dynamic shear viscosity, h', the out- of-phase component of the complex shear viscosity h” and the loss tangent, tan d which can be expressed as follows:
G' = —cosS [Pa] (3)
Yo
G" = — sinri [Pa] (4)
Yo
G* = G' + iG" [Pa] (5) h* = h' - ίh" [Pa.s] (6)
Figure imgf000041_0001
The determination of so-called Shear Thinning Index, which correlates with MWD and is independent of Mw, is done as described in equation 9.
„UT _ Eta* for (G* = x kPa) ^ (x/y) — Eta* for (G* = y kPa) (9)
For example, the SHIp o) is defined by the value of the complex viscosity, in Pa s, determined for a value of G* equal to 2.7 kPa, divided by the value of the complex viscosity, in Pa s, determined for a value of G* equal to 210 kPa.
The values of storage modulus (G), loss modulus (G"), complex modulus (G*) and complex viscosity (h*) were obtained as a function of frequency (co). Thereby, e.g. r|*3oorad/s (eta*3oorad/s) is used as abbreviation for the complex viscosity at the frequency of 300 rad/s and p*o.o5rad/s (eta*o.o5rad/s) is used as abbreviation for the complex viscosity at the frequency of 0.05 rad/s.
The loss tangent tan (delta) is defined as the ratio of the loss modulus (G") and the storage modulus (G) at a given frequency. Thereby, e.g. tano.os is used as abbreviation for the ratio of the loss modulus (G") and the storage modulus (G) at 0.05 rad/s and tamoo is used as abbreviation for the ratio of the loss modulus (G") and the storage modulus (G) at 300 rad/s.
The elasticity balance tano.os/tamoo is defined as the ratio of the loss tangent tano.os and the loss tangent tamoo.
Besides the above mentioned rheological functions one can also determine other rheological parameters such as the so-called elasticity index EI(x). The elasticity index EI(x) is the value of the storage modulus (G) determined for a value of the loss modulus (G") of x kPa and can be described by equation 10.
EI(x ) = G' for (G" = x kPa ) [Pa] (10)
For example, the ///(5k Pa) is the defined by the value of the storage modulus (G), determined for a value of G" equal to 5 kPa.
The polydispersity index, PI, is defined by equation 11.
Figure imgf000042_0001
where COCOP is the cross-over angular frequency, determined as the angular frequency for which the storage modulus, G, equals the loss modulus, G".
The values are determined by means of a single point interpolation procedure, as defined by Rheoplus software. In situations for which a given G* value is not experimentally reached, the value is determined by means of an extrapolation, using the same procedure as before. In both cases (interpolation or extrapolation), the option from Rheoplus " Interpolate y-values to x-values from parameter" and the "logarithmic interpolation type" were applied.
References: [1] Rheological characterization of polyethylene fractions” Heino, E.L., Lehtinen, A., Tanner T, Seppala, I, Neste Oy, Porvoo, Finland, Theor. Appl. Rheol., Proc. Int. Congr. Rheol, 11th (1992), 1, 360-362
[2] The influence of molecular structure on some rheological properties of polyethylene”, Heino, E.L., Borealis Polymers Oy, Porvoo, Finland, Annual Transactions of the Nordic Rheology Society, 1995.).
[3] Definition of terms relating to the non-ultimate mechanical properties of polymers, Pure & Appl. Chem., Vol. 70, No. 3, pp. 701-754, 1998. g) Large Amplitude Oscillatory Shear (LAOS)
The investigation of the non-linear viscoelastic behaviour under shear flow was done resorting to Large Amplitude Oscillatory Shear. The method requires the application of a sinusoidal strain amplitude, go, imposed at a given angular frequency, co, for a given time, t. Provided that the applied sinusoidal strain is high enough, a non-linear response is generated. The stress, s, is in this case a function of the applied strain amplitude, time and the angular frequency. Under these conditions, the non-linear stress response is still a periodic function; however, it can no longer be expressed by a single harmonic sinusoid. The stress resulting from linear viscoelastic response [1-3] can be expressed by a Fourier series, which includes higher harmonics contributions: (nmt) + G"n(u>,y0) cos(nmt)]
Figure imgf000043_0001
with s = stress response t = time co = frequency go = strain amplitude n = harmonic number G’n = n order elastic Fourier coefficient G”n = n order viscous Fourier coefficient
The non-linear viscoelastic response was analysed applying Large Amplitude Oscillatory Shear (LAOS). Time sweep measurements were undertaken on an RPA 2000 rheometer from Alpha Technologies coupled with a standard biconical die. During the course of the measurement the test chamber is sealed and a pressure of about 6 MPa is applied. The LAOS test is done applying a temperature of 190 °C, an angular frequency of 0.628 rad/s and a strain of 1000 % (LAOSNLF (1000%)). In order to ensure that steady state conditions are reached, the non-linear response is only determined after at least 20 cycles per measurement are completed. The Large Amplitude Oscillatory Shear Non-Linear Factor (LAOSNLF) is defined by:
G' 1
LAOSNLF(X%)
G' 3 with G’i = first order elastic Fourier coefficient Gri = third order elastic Fourier coefficient
References:
1. J. M. Dealy, K. F. Wissbrun, Melt Rheology and Its Role in Plastics Processing: Theory and Applications; edited by Van Nostrand Reinhold, New York (1990)
2. S. Filipe, Non-Linear Rheology of Polymer Melts, AIP Conference Proceedings 1152, pp. 168-174 (2009) 3.
3. M. Wilhelm, Macromol. Mat. Eng. 287, 83-105 (2002)
4. S. Filipe, K. Hofstadler, K. Klimke, A. T. Tran, Non-Linear Rheological Parameters for Characterisation of Molecular Structural Properties in Polyolefins, Proceedings of Annual European Rheology Conference, 135 (2010)
5. S. Filipe, K. Klimke, A. T. Tran, J. Reussner, Proceedings of Novel Non-Linear Rheological Parameters for Molecular Structural Characterisation of Polyolefins, Novel Trends in Rheology IV, Zlin, Check Republik (2011)
6. K. Klimke, S. Filipe, A. T. Tran, Non-linear rheological parameters for characterization of molecular structural properties in polyolefins, Proceedings of European Polymer Conference, Granada, Spain (2011) h) ESCR (Bell test, h)
By the term ESCR (environmental stress cracking resistance) is meant the resistance of the polymer to crack formation under the action of mechanical stress and a reagent in the form of a surfactant. The ESCR is determined in accordance with IEC 60811-406, method B. The reagent employed is 10 weight% Igepal CO 630 in water. The materials were prepared according to instructions for HDPE as follows: The materials were pressed at 165°C to a thickness of 1.75 - 2.00 mm. The notch was 0.30 - 0.40 mm deep. i) Shore D hardness
Two different Shore D hardness measurements were conducted:
Firstly, Shore D hardness is determined according to ISO 868 on moulded specimen with a thickness of 4 mm. The shore hardness is determined after 1 sec, 3 sec or 15 sec after the pressure foot is in firm contact with the test specimen. The sample is compression moulded according to ISO 17855-2 and milled into specimens of 80x10x4 mm.
Secondly, Shore D hardness is determined according to ASTM D2240-03. The same samples as for the Shore D hardness according to ISO 868 were used. j) Strain hardening (SH) modulus
The strain hardening test is a modified tensile test performed at 80 °C on a specially prepared thin sample. The Strain Hardening Modulus (MPa), <Gp>, is calculated from True Strain- True Stress curves; by using the slope of the curve in the region of True Strain, l, is between 8 and 12.
The true strain, l, is calculated from the length, 1 (mm), and the gauge length, 10 (mm), as shown by Equation 1. x = 1 +r « where D1 is the increase in the specimen length between the gauge marks, (mm). The true stress, otrue (MPa), is calculated according to formula 2, assuming conservation of volume between the gauge marks:
Figure imgf000045_0001
where sh is the engineering stress.
The Neo-Hookean constitutive model (Equation 3) is used to fit the true strain- true stress data from which <Gp> (MPa) for 8 < l < 12 is calculated.
Figure imgf000045_0002
where C is a mathematical parameter of the constitutive model describing the yield stress extrapolated to l = 0.
Initially five specimens are measured. If the variation coefficient of <Gp> is greater than 2,5 %, then two extra specimens are measured. In case straining of the test bar takes place in the clamps the test result is discarded. The PE granules of materials were compression molded in sheets of 0.30 mm thickness according to the press parameters as provided in ISO 17855-2.
After compression molding of the sheets, the sheets were annealed to remove any orientation or thermal history and maintain isotropic sheets. Annealing of the sheets was performed for 1 h in an oven at a temperature of (120 ± 2) °C followed by slowly cooling down to room temperature by switching off the temperature chamber. During this operation free movement of the sheets was allowed.
Next, the test pieces were punched from the pressed sheets. The specimen geometry of the modified ISO 37:1994 Type 3 (Figure 3) was used. The sample has a large clamping area to prevent grip slip, dimensions given in Table 1.
Table 1: Dimensions of Modified ISO 37:1994 Type 3
Figure imgf000046_0001
The punching procedure is carried out in such a way that no deformation, crazes or other irregularities are present in the test pieces. The thickness of the samples was measured at three points of the parallel area of the specimen; the lowest measured value of the thickness of these measurements was used for data treatment.
1. The following procedure is performed on a universal tensile testing machine having controlled temperature chamber and non-contact extensometer: 2. Condition the test specimens for at least 30 min in the temperature chamber at a temperature of (80 ± 1) °C prior to starting the test.
3. Clamp the test piece on the upper side.
4. Close the temperature chamber. 5. Close the lower clamp after reaching the temperature of (80 ± 1) °C.
6. Equilibrate the sample for 1 min between the clamps, before the load is applied and measurement starts.
7. Add a pre-load of 0.5 N at a speed of 5 mm/min.
8. Extend the test specimen along its major axis at a constant traverse speed (20 mm/min) until the sample breaks.
During the test, the load sustained by the specimen is measured with a load cell of 200 N. The elongation is measured with a non-contact extensometer. k) Water content
The water content was determined as described in ISO15512:2019 Method A - Extraction with anhydrous methanol. There the test portion is extracted with anhydrous methanol and the extracted water is determined by a coulometric Karl Fischer Titrator. l) Cable extrusion
The cable extrusion is done on a Nokia-Maillefer cable line. The extruder has five temperature zones with temperatures of 170/175/180/190/190°C and the extruder head has three zones with temperatures of 210/210/210°C. The extruder screw is a barrier screw of the design Elise. The die is a semi-tube on type with 5.9 mm diameter and the outer diameter of the cable is 5 mm. The compound is extruded on a 3 mm in diameter, solid aluminum conductor to investigate the extrusion properties. Line speed is 75 m/min. The pressure at the screen and the current consumption of the extruder is recorded for each material. m) Pressure deformation
Pressure test is conducted according to EN 60811-508. An extruded cable sample is placed in an air oven at a 115 °C and subjected to a constant load applied by means of a special indentation device (with a rectangular indentation 0.7 mm wide knife) for 6 hours. The percentage of indentation is measured afterwards using a digital gauge. n) Tensile testing of cable
Tensile testing of cable is conducted according to EN60811-501. At least 24 hours later after cable extrusion, the conductor is removed and the cable is cut into specimens of 15cm’ s long. The specimens are conditioned for at least 16 hours at 23°C and 50% relative humidity before testing.
Tensile properties are measured at 23°C and 50% relative humidity with Zwick Z005, 500N load cell. Tensile testing speed is 25mm/min, grip distance is 50mm and gauge length is 20mm. o) Cable shrinkage
The shrinkage of the composition is determined with the cable samples obtained from the cable extrusion. The cables are conditioned in the constant room at least 24 hours before the cutting of the samples. The conditions in the constant room are 23 ± 2°C and 50± 5% humidity. Samples are cut to 400 mm at least 2 m away from the cable ends. They are further conditioned in the constant room for 24 hours after which they are place in an oven on a talcum bed at 100°C for 24 hours. After removal of the sample from the oven they are allowed to cool down to room temperature and then measured. The shrinkage is calculated according to formula below:
[(Leefore - LMter) / Leefore] x 100 %, wherein L is length. p) Tear resistance
Tear resistance is measured on compression moulded plaques of 1 mm thickness according to BS 6469 section 99.1. A test piece with a cut is used to measure the tear force by means of a tensile testing machine. The tear resistance is calculated by dividing the maximum force needed to tear the specimen by its thickness. q) Ash content
Thermogravimetric Analysis (TGA) experiments were performed with a Perkin Elmer TGA 8000. Approximately 10-20 mg of materials were placed in a platinum pan. The temperature was equilibrated at 50°C for 10 minutes, and afterwards raised to 950°C under nitrogen at 20°C/min. The ash content was evaluated as the weight % at 850 °C. r) Amount of Limonene This method allows nature of a raw mixed-plastic-polyethylene primary recycling blend to be determined.
Limonene quantification was carried out using solid phase microextraction (HS-SPME-GC- MS) by standard addition.
20 mg cryomilled samples were weighed into 20 mL headspace vials and after the addition of limonene in different concentrations and a glass-coated magnetic stir bar, the vial was closed with a magnetic cap lined with silicone/PTFE. Micro capillaries (10 pL) were used to add diluted limonene standards of known concentrations to the sample. Limonene was added to the samples to obtain concentration levels of 1 mg/kg, 2 mg/kg, 3 mg/kg and 4 mg/kg limonene. For quantification, ion-93 acquired in SIM mode was used. Enrichment of the volatile fraction was carried out by headspace solid phase microextraction with a 2 cm stable flex 50/30 pm DVB/C arboxen/PDMS fibre at 60°C for 20 minutes. Desorption was carried out directly in the heated injection port of a GCMS system at 270°C.
GCMS Parameters:
Column: 30 m HP 5 MS 0.25*0.25
Injector: Splitless with 0.75 mm SPME Liner, 270°C
Temperature program: -10°C (1 min)
MS: Single quadrupole, direct interface, 280°C interface temperature
Acquisition: SIM scan mode
Scan parameter: 20-300 amu
SIM Parameter: m/Z 93, 100 ms dwell time s) Gel content
The gel count was measured with a gel counting apparatus consisting of a measuring extruder, ME 25 / 5200 VI, 25*25D, with five temperature conditioning zones adjusted to a temperature profile of 170/180/190/190/190°C), an adapter and a slit die (with an opening of 0.5 * 150 mm). Attached to this were a chill roll unit (with a diameter of 13 cm with a temperature set of 50°C), a line camera (CCD 4096 pixel for dynamic digital processing of grey tone images) and a winding unit.
For the gel count content measurements the materials were extruded at a screw speed of 30 rounds per minute, a drawing speed of 3-3.5 m/min and a chill roll temperature of 50°C to make thin cast films with a thickness of 70 pm and a width of approximately 110 mm.
The resolution of the camera is 25 pm x 25 pm on the film.
The camera works in transmission mode with a constant grey value (auto. set. margin level = 170). The system is able to decide between 256 grey values from black = 0 to white = 256. For detecting gels, a sensitivity level dark of 25% is used.
For each material the average number of gel dots on a film surface area of 10 m2 was inspected by the line camera. The line camera was set to differentiate the gel dot size according to the following:
Gel size (the size of the longest dimension of a gel)
600 pm to 999 pm above 1000 pm
2. Materials
HE6063 is a natural bimodal high density polyethylene jacketing compound for energy and communication cables (available from Borealis AG).
HE3493-LS-H is a natural bimodal high density polyethylene compound for pipes (available from Borealis AG).
Additive package: The additive package consists of 27.3 wt% of pentaerythrityl-tetrakis(3- (3’,5’-di-tert. butyl-4-hydroxyphenyl)-propionate (CAS No. 6683-19-8), 9.1 wt% of tris (2,4- di-t-butylphenyl) phosphite (CAS No. 31570-04-4), 9.1 wt% of calcium stearate (CAS No. 1592-23-0) and 54.5 wt% of poly((6-((l,l,3,3-tetramethylbutyl)amino)-l,3,5-triazine-2,4- diyl)(2,2,6,6-tetramethyl-4-piperidyl)imino)-l,6-hexanediyl ((2,2,6,6-tetramethyl-4- piperidyl)imino)) (CAS No. 71878-19-8).
NAV 102 is a mixed-plastic-low density polyethylene (LDPE) primary recycling blend available from Ecoplast Kunststoffrecycling GmbH. Samples of NAV 102 (NAV 102-1 with the Lot No 190206-1, NAV- 102-2 with the Lot No 190611 -II and NAV 102-5 with the Lot No 200312-1) differing as to melt flow rate and also rheology were tested, the properties of these samples are shown in table A.
In the following examples also two additional samples of NAV-102 (NAV 102-3 with the Lot No 190612-1 and NAV 102-4 with the Lot No 190611-1) were used. The properties of these samples were not measured but should be similar to those of NAV 102-1, NAV 102-2 and NAV 102-5.
Table A: Properties of NAY 102
Figure imgf000052_0001
n.m = not measurable
3. Experiments a) Comparative examples:
CE1 (comparative example 1) are 100 % reactor-made HE6063 pellets.
CE2 (comparative example 2) is 100 % compounded HE6063 (blank extrusion of CE1). b) Inventive examples:
In inventive example 1 (IE1), 25 wt% HE6063 was melt mixed with 75 wt% NAV 102-2.
In inventive example 2 (IE2) 50 wt% HE6063 was melt mixed with 50 wt% NAV 102-2.
In inventive example 3 (IE3) 60 wt% HE6063 was melt mixed with 40 wt% NAV 102-2.
In inventive example 4 (IE4) 75 wt% HE6063 was melt mixed with 25 wt% NAV 102-2.
In inventive example 5 (IE5), 25 wt% HE6063 was melt mixed with 75 wt% NAV 102-3.
In inventive example 6 (IE6) 50 wt% HE6063 was melt mixed with 50 wt% NAV 102-3.
In inventive example 7 (IE7) 75 wt% HE6063 was melt mixed with 25 wt% NAV 102-3.
In inventive example 8 (IE8) 50 wt% HE6063 was melt mixed with 50 wt% NAV 102-4.
In inventive example 9 (IE9) 50 wt% HE6063 was melt mixed with 50 wt% NAV 102-1.
In inventive example 10 (IE10) 75 wt% HE6063 was melt mixed with 25 wt% NAV 102-1. In inventive example 11 (IE11) 49.7 wt% HE6063 was melt mixed with 50 wt% NAV 102-5 and 0.3 wt% additive package.
In inventive example 12 (IE12) 49.7 wt% HE6063 was melt mixed with 50 wt% NAV 102-5 and 0.3 wt% additive package.
In inventive example 13 (IE13) 50 wt% HE6063 was melt mixed with 40 wt% NAV 102-1 and 10 wt% HE3493-LS-H.
In inventive example 14 (IE14) 50 wt% HE6063 was melt mixed with 40 wt% NAV 102-2 and 10 wt% HE3493-LS-H.
In inventive example 15 (IE15) 40 wt% HE6063 was melt mixed with 50 wt% NAV 102-2 and 10 wt% HE3493-LS-H.
In inventive example 16 (IE16) 40 wt% HE6063 was melt mixed with 50 wt% NAV 102-3 and 10 wt% HE3493-LS-H.
In inventive example 17 (IE17) 40 wt% HE6063 was melt mixed with 50 wt% NAV 102-4 and 10 wt% HE3493-LS-H.
In inventive example 18 (IE18) 39.7 wt% HE6063 was melt mixed with 50 wt% NAV 102-5, 10 wt% HE3493-LS-H and 0.3 wt% additive package.
In inventive example 19 (IE19) 39.7 wt% HE6063 was melt mixed with 50 wt% NAV 102-5, 10 wt% HE3493-LS-H and 0.3 wt% additive package. The compositions of examples CE1, CE2, IE1-IE10 and IE13-IE17 were prepared via melt blending on a co-rotating twin screw extruder (Coperion ZSK32 Megacompounder, L/D = 48) at 150°C in the first barrel after the feeding zone and 220-230°C in all the following barrels, a screw speed of 120 rpm and a throughput rate of about 15-25 kg/h. The compositions of examples IE11, IE12, IE18 and IE19 were prepared via melt blending on a Berstoff ZE110 extruder at 200°C in the first two barrels after the feeding zone and 230°C in all the following barrels, a screw speed of 420 rpm for IE11, 280-300 rpm for IE12, IE18 and IE19 and a throughput rate of about 1.8 to 2.0 ton/h.. The polymer melt mixtures were discharged and pelletized. Mechanical properties were tested as described above. Thereby, the final MFR of the compounds is influenced by the compounding condition, e.g, the screw speed.
The properties of the compositions and cables made from these compositions are shown below in Table B for the compositions of examples CE1-CE2, IE1-IE4 and IE8, in Table C for the compositions of examples CE1-CE2 and IE5, IE6, IE7, IE9, IE10, IE11 and IE12 and in Table D for the compositions of examples CE1-CE2 and IE13, IE14, IE15, IE16, IE17, IE18 and IE 19.
For examples IE3, IE4, IE10, IE11, IE12, IE18 and IE19 the values for the LDPE content have been calculated according to the content of NAV 102 and the LDPE content of the used batch of NAV 102. For all other examples, where listed, the values for the LDPE content has been measured as described in the test method section.
The examples according to the invention show an improved balance of properties especially in regard of ESCR, SH index and Shore D hardness while maintaining good tensile properties and impact properties. Additionally, the example according to the invention show a surprisingly low gel content due to the use of NAV 102 recycling blends, which themselves have a low gel content indicating a high purity. It is believed that especially the surprisingly high ESCR values result from said high purity indicated in the low gel contents. The > in the ESCR data means that the measurement is still running. Table B: Properties of CE1-CE2, IE1-IE4 and IE8
Figure imgf000055_0001
Figure imgf000056_0001
Table C: Properties of CE1, CE2 and IE5, IE6, IE7, IE9, IE10, IE11 and IE12
Figure imgf000057_0001
Figure imgf000058_0001
Table D: Properties of CE1, CE2 and IE13, IE14, IE15, IE16, IE17, IE18 and IE19
Figure imgf000059_0001
Figure imgf000060_0001

Claims

Claims
1. A mixed-plastic-polyethylene composition comprising a total amount of ethylene units (C2 units) of from 90.00 to 99.00 wt%, and a total amount of continuous units having 3 carbon atoms corresponding to polypropylene (continuous C3 units) of from 0.10 to 5.00 wt%, with the total amounts of C2 units and continuous C3 units being based on the total weight amount of monomer units in the composition and measured according to quantitative 13C{ 1H} NMR measurement, and wherein the composition has a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 2.0 g/10 min; and a density of from 930 kg/m3 to 955 kg/m3, preferably from 932 to 953 kg/m3.
2. The mixed-plastic polyethylene composition according to claim 1 comprising one or more in any combination of, more preferably all of: a total amount of units having 3 carbon atoms as isolated peaks in the NMR spectrum (isolated C3 units) of from 0 wt% to 0.50 wt%, more preferably from 0 wt% to 0.40 wt%, still more preferably from 0 wt% to 0.30 wt%; a total amount of units having 4 carbon atoms (C4 units) of from 0.20 wt% to 4.00 wt%, more preferably from 0.30 wt% to 3.50 wt%, still more preferably from 0.50 wt% to 3.00 wt%; a total amount of units having 6 carbon atoms (C6 units) of from 0.20 wt% to 5.00 wt%, more preferably from 0.30 wt% to 4.00 wt%, still more preferably from 0.50 wt% to 3.50 wt%; a total amount of units having 7 carbon atoms (C7 units) of from 0 wt% to 0.80 wt%, more preferably from 0 wt% to 0.70 wt%, still more preferably from 0 wt% to 0.65 wt%; a LDPE content of from 5.00 to 50.00 wt%, more preferably from 8.00 wt% to 48.00 wt%, still more preferably from 10.00 wt% to 46.00 wt% and most preferably from 11.50 wt% to 45.00 wt%, wherein the total amounts of isolated C3 units, C4 units, C6 units, C7 units and LDPE content are based on the total weight amount of monomer units in the composition and are measured or calculated according to quantitative 13C{ 1H} NMR measurement.
3. The mixed-plastic polyethylene composition according to claim 1 or 2 obtainable by blending and extruding components comprising
10 to 85 wt.-%, based on the overall weight of the composition, of a mixed- plastic-polyethylene primary recycling blend (A) wherein at least 90 wt.-%, preferably at least 95 wt.-%, more preferably 100 wt.-% of the mixed-plastic-polyethylene primary blend (A) originates from post-consumer waste and/or post-industrial waste; and wherein the mixed- plastic-polyethylene primary blend (A) has a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 1.2 g/10 min, preferably from 0.3 to 1.1 g/10 min, a density of from 910 to 945 kg/m3, preferably from 915 to 942 kg/m3, most preferably from 920 to 940 kg/m3, a total amount of ethylene units (C2 units) of from 80.00 to 96.00 wt%, and a total amount of continuous units having 3 carbon atoms corresponding to polypropylene (continuous C3 units) of from 0.20 to 6.50 wt%; with the total amounts of C2 units and continuous C3 units being based on the total weight amount of monomer units in the mixed-plastic-polyethylene primary blend (A) and measured according to quantitative 13C{ 1H} NMR measurement
15 to 90 wt.-%, based on the overall weight of the composition, of a secondary blend (B) of virgin high-density polyethylene (HDPE), wherein the secondary blend (B) has ethylene monomer units and comonomer units derived from olefins having from 3 to 6 carbon atoms, a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 1.2 g/10 min, preferably from 0.3 to 0.7 g/10 min; a density of from 940 to 970 kg/m3, a polydispersity index PI of from 1.0 to 2.8 s 1 as obtained from rheological measurement.
4. The mixed-plastic polyethylene composition according to claim 3 having a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 1.0 g/lOmin and being obtainable by blending and extruding components comprising
10 to 83 wt.-%, based on the overall weight of the composition, of the mixed- plastic-polyethylene primary recycling blend (A);
16 to 80 wt.-%, based on the overall weight of the composition, of a secondary blend (B) of virgin high-density polyethylene (HDPE); and 1 to 20 wt.-%, based on the overall weight of the composition, of a tertiary blend (C) of virgin high-density polyethylene (HDPE), the blend (C) having ethylene monomer units and comonomer units derived from olefins having from 3 to 6 carbon atoms, a melt flow rate (ISO 1133, 5 kg, 190 °C) of from 0.01 to 0.5 g/lOmin, and a density of from 945 to 970 kg/m3.
5. A mixed-plastic-polyethylene composition having a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 2.0 g/lOmin; and a density of from 930 kg/m3 to 955 kg/m3, preferably from 932 to 953 kg/m3; obtainable by blending and extruding components comprising
10 to 85 wt.-%, based on the overall weight of the composition, of a mixed- plastic-polyethylene primary recycling blend (A), wherein at least 90 wt.-%, preferably at least 95 wt.-%, more preferably 100 wt.- % of the mixed-plastic-polyethylene primary blend (A) originates from post consumer waste and/or post-industrial waste having a limonene content of from 2 to 500 mg/kg; and wherein the mixed-plastic-polyethylene primary blend (A) has a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 1.2 g/lOmin, preferably from 0.3 to 1.1 g/lOmin , a density of from 910 to 945 kg/m3, preferably from 915 to 942 kg/m3, most preferably from 920 to 940 kg/m3 a total amount of ethylene units (C2 units) of from 80.00 to 96.00 wt%, and with the total amount of C2 units being based on the total weight amount of monomer units in the mixed-plastic-polyethylene primary blend (A) and measured according to quantitative 13C{ 1H} NMR measurement,
15 to 90 wt.-%, based on the overall weight of the composition, of a secondary blend (B) of virgin high-density polyethylene (HDPE), wherein the secondary blend (B) has ethylene monomer units and comonomer units derived from olefins having from 3 to 6 carbon atoms, a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 1.2 g/10 min, preferably from 0.3 to 0.7 g/10 min; a density of from 940 to 970 kg/m3, a polydispersity index PI of from 1.0 to 2.8 s 1 as obtained from rheological measurement, and
- preferably a limonene content below 2 ppm.
6. The mixed-plastic-polyethylene composition according to claim 5, having a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 1.0 g/lOmin and being obtainable by blending and extruding components comprising
10 to 83 wt.-%, based on the overall weight of the composition, of the mixed- plastic-polyethylene primary recycling blend (A);
16 to 80 wt.-%, based on the overall weight of the composition, of a secondary blend (B) of virgin high-density polyethylene (HDPE); and 1 to 20 wt.-%, based on the overall weight of the composition, of a tertiary blend (C) of virgin high-density polyethylene (HDPE), the blend (C) having ethylene monomer units and comonomer units derived from olefins having from 3 to 6 carbon atoms, a melt flow rate (ISO 1133, 5 kg, 190 °C) of from 0.01 to 0.5 g/lOmin, and a density of from 945 to 970 kg/m3, and - preferably a limonene content below 2 ppm.
7. The mixed-plastic-polyethylene composition according to any one of the preceding claims, wherein the composition has a Large Amplitude Oscillatory Shear Non Linear Factor at a strain of 1000%, LAOSNLF (1000%), of from 1.900 to 4.000, more preferably from 2.000 to 3.500, still more preferably from 2.100 to 3.000 and most preferably from 2.125 to 2.850.
8. The mixed-plastic-polyethylene composition according to any one of the preceding claims, wherein the composition has an impact strength at 23 °C (according to ISO 179-1 eA) of from 10 to 27 kJ/m2 and/or an impact strength at 0 °C (according to ISO 179-1 eA) of from 5.0 to 12.0 kJ/m2.
9. The mixed-plastic-polyethylene composition according to any one of the preceding claims, wherein the composition has a strain hardening modulus (SH modulus) of from 15.0 to 30.0 MPa and/or an ESCR (Bell test failure time) of more than 1000 hours.
10. The mixed-plastic-polyethylene composition according to any one of the preceding claims having a gel content for gels with a size of from above 600 m to 1000 pm of from 25 to 250 gels/m2 and/or a gel content for gels with a size of from above 1000 pm of not more than 35 gels/m2.
11. The mixed-plastic-polyethylene composition according to any one of the preceding claims, wherein the composition has a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.2 to 1.8 g/lOmin, and/or a melt flow rate (ISO 1133, 5 kg, 190 °C) of from 1.2 to 5.0 g/lOmin, and/or a melt flow rate (ISO 1133, 21 kg, 190 °C) of from 18 to 70 g/lOmin.
12. The mixed-plastic-polyethylene composition according to any one of the preceding claims, wherein the composition has a shear thinning index SHIp o) of from 15 to 40, and/or a complex viscosity at 0.05 rad/s etao.os rad/s of from 10000 to 38000 Pa-s, and/or a complex viscosity at 300 rad/s eta3oo rad/s of from 550 to 850 Pa-s, and/or a polydispersity index PI of from 1.0 to 3.5 s 1.
13. The mixed-plastic-polyethylene composition according to any one of the preceding claims, wherein the composition has a Shore D hardness, measured according to ISO 868 with a measuring time of 1 s, Shore D Is, of from 55.0 to 70.0, and/or a Shore D hardness, measured according to ISO 868 with a measuring time of 3 s, Shore D 3s, of from 52.0 to 68.0, and/or a Shore D hardness, measured according to ISO 868 with a measuring time of 15 s, Shore D 15s, of from 50.0 to 67.0.
14. The mixed-plastic-polyethylene composition according to any one of the preceding claims, wherein the composition has a tensile strain at break, measured according to ISO 527-2 on compression moulded test specimens of type 5A, of from 650% to 900%; and/or a tensile stress at break, measured according to ISO 527-2 on compression moulded test specimens of type 5 A, of from 18 MPa to 35 MPa; and/or a tensile strain at break, measured according to ISO 527-2 on compression moulded test specimens of type 5A after ageing, of from 700% to 950%, more preferably from 750% to 930%; and/or a tensile stress at break, measured according to ISO 527-2 on compression moulded test specimens of type 5 A after ageing, of from 16 MPa to 33 MPa, more preferably from 18 MPa to 28 MPa.
15. The mixed-plastic-polyethylene composition according to any one of the preceding claims, wherein the composition has a pressure deformation of not more than 15% and/or a water content of not more than 250 ppm.
16. An article comprising the mixed-plastic-polyethylene composition according to any one of the preceding claims, preferably wherein the article is a cable comprising at least one layer comprising the mixed-plastic-polyethylene composition according to any one of the preceding claims, more preferably wherein the article is a cable comprising a jacketing layer comprising the mixed-plastic-polyethylene composition according to any one of the preceding claims.
17. The article according to claim 16 being a cable, wherein the cable has one or more of the following properties: a cable shrinkage of not more than 2.0 %. a tensile strain at break, measured according to EN60811-501 on cable specimen, of from 480% to 870%; and/or a tensile stress at break, measured according to EN60811-501 on cable specimen, of from 16 MPa to 35 MPa.
18. A process for preparing the mixed-plastic-polyethylene composition according to any one of claims 1 to 15, comprising the steps of: a) providing a mixed-plastic-polyethylene primary recycling blend (A) in an amount of 10 to 85 wt.-% based on the overall weight of the composition, wherein at least 90 wt.-%, preferably at least 95 wt.-%, more preferably 100 wt.-% of the mixed-plastic-polyethylene primary blend (A) originates from post-consumer waste and/or post-industrial waste wherein the mixed-plastic-polyethylene primary blend (A) has a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 1.2 g/lOmin, preferably from 0.3 to 1.1 g/lOmin, a density of from 910 to 945 kg/m3, preferably from 915 to 942 kg/m3, most preferably from 920 to 940 kg/m3, a total amount of ethylene units (C2 units) of from 80.00 to 96.00 wt%, and a total amount of continuous units having 3 carbon atoms corresponding to polypropylene (continuous C3 units) of from 0.20 to 6.50 wt%; with the total amounts of C2 units and continuous C3 units being based on the total weight amount of monomer units in the mixed-plastic-polyethylene primary recycling blend (A) and measured according to quantitative 13C{ 1H} NMR measurement, b) providing a secondary blend (B) of virgin high-density polyethylene (HDPE) in an amount of 15 to 90 wt.-% based on the overall weight of the composition, wherein the secondary blend (B) has ethylene monomer units and comonomer units derived from olefins having from 3 to 6 carbon atoms, a melt flow rate (ISO 1133, 2.16 kg, 190 °C) of from 0.1 to 1.2 g/10 min, preferably from 0.3 to 0.7 g/10 min; a density of from 940 to 970 kg/m3, a polydispersity index PI of from 1.0 to 2.8 s 1 as obtained from rheological measurement, c) melting and mixing the blend of the mixed-plastic-polyethylene primary blend (A) and the secondary blend (B) in an extruder, optionally a twin screw extruder, and d) optionally pelletizing the obtained mixed-plastic-polyethylene composition.
19. The process according to claim 18, comprising the steps of: a) providing the mixed-plastic-polyethylene primary recycling blend (A) in an amount of 10 to 83 wt.-% based on the overall weight of the composition; b) providing the secondary blend (B) of virgin high-density polyethylene (HDPE) in an amount of 16 to 80 wt.-% based on the overall weight of the composition; c) providing a tertiary blend (C) of virgin high-density polyethylene (HDPE) in an amount of 1 to 20 wt.-% based on the overall weight of the composition, wherein the tertiary blend (C) has ethylene monomer units and comonomer units derived from olefins having from 3 to 6 carbon atoms, a melt flow rate (ISO 1133, 5 kg, 190 °C) of from 0.01 to 0.5 g/lOmin, and a density of from 945 to 970 kg/m3, d) melting and mixing the blend of mixed-plastic-polyethylene primary blend (A), the secondary blend (B) and the tertiary blend (C) in an extruder, optionally a twin screw extruder, and e) optionally pelletizing the obtained mixed-plastic-polyethylene composition.
20. Use of a mixed-plastic-polyethylene composition according to any one of claims 1 to 15 for producing a cable layer, preferably a cable jacketing layer, having an ESCR (Bell test failure time) of more than 1000 hours and/or a strain hardening modulus (SH modulus) of from 15.0 to 30.0 MPa.
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WO2024133086A1 (en) 2022-12-19 2024-06-27 Basell Polyolefine Gmbh Process for producing a blended low density polyethylene composition comprising recycled polymer compositions
WO2024137484A1 (en) * 2022-12-21 2024-06-27 Equistar Chemicals, Lp Blend of ldpe and post-consumer recyclate content with reduced film defects
WO2024153753A1 (en) 2023-01-18 2024-07-25 Borealis Ag Recyclate polyethylene composition with improved mechanical and optical properties

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EP4077531A1 (en) 2022-10-26
US20230114045A1 (en) 2023-04-13
CN114829481A (en) 2022-07-29
CN114829481B (en) 2023-12-08
TW202126754A (en) 2021-07-16
KR20220117909A (en) 2022-08-24
TWI763170B (en) 2022-05-01

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