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WO2024068576A1 - Composition de polypropylène destinée à l'isolation de câble - Google Patents

Composition de polypropylène destinée à l'isolation de câble Download PDF

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Publication number
WO2024068576A1
WO2024068576A1 PCT/EP2023/076452 EP2023076452W WO2024068576A1 WO 2024068576 A1 WO2024068576 A1 WO 2024068576A1 EP 2023076452 W EP2023076452 W EP 2023076452W WO 2024068576 A1 WO2024068576 A1 WO 2024068576A1
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WIPO (PCT)
Prior art keywords
polypropylene composition
propylene
copolymer
total amount
determined
Prior art date
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PCT/EP2023/076452
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English (en)
Inventor
Katja Klimke
Per-Ola Hagstrand
Ulf Nilsson
Thomas Gkourmpis
Lars Efraimsson
Anette Johansson
Gerhard Hubner
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Borealis GmbH
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Borealis GmbH
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Filing date
Publication date
Application filed by Borealis GmbH filed Critical Borealis GmbH
Priority to EP23776642.3A priority Critical patent/EP4594415A1/fr
Priority to CN202380067616.8A priority patent/CN119948097A/zh
Priority to KR1020257013024A priority patent/KR20250068767A/ko
Publication of WO2024068576A1 publication Critical patent/WO2024068576A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • 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
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L23/16—Ethene-propene or ethene-propene-diene copolymers
    • 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
    • C08L2205/03—Polymer mixtures characterised by other features containing three 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
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/02—Heterophasic composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)

Definitions

  • the present invention relates to a flexible polypropylene composition, an article comprising said polypropylene composition, preferably a cable comprising an insulation layer comprising said polypropylene composition and the use of said polypropylene composition as cable insulation for medium and high voltage cables.
  • PVC polyvinyl chloride
  • softeners to reach desirable softness of cables.
  • PVC polyvinyl chloride
  • a continuous conductor temperature of max. 70°C is normal.
  • PVC becomes rigid and usage temperatures below -10°C should be avoided.
  • conductor temperatures over 100°C the plasticizers migrate out and the materials lose their flexibility.
  • PVC materials can be produced for conductor temperatures of 90-105°C.
  • PVC is mainly used for the 1 kV area, as the higher permittivity and dissipation factor of the material means that the losses increase too much at higher voltages and therefore PVC cables are not normally used over 1 kV.
  • softeners have to be added to PVC in order to maintain a high level of flexibility. Insufficient amounts of softeners reduce low temperature properties of PVC significantly. From an environmental point of view, these softeners are not always regarded as problem- free, making them desirable to eliminate.
  • XLPE crosslinked ethylene polymer
  • thermoplastic material and especially thermoplastic propylene polymers as insulation material for medium, high and extra high voltage (MV, HV and EHV) cables as well as high-voltage direct current (HVDC) cables.
  • MV, HV and EHV medium, high and extra high voltage cables
  • HVDC high-voltage direct current cables
  • the propylene polymers need to show a good balance of properties as regards flexibility, mechanical properties, impact properties and electrical breakdown strength.
  • the present invention relates to a polypropylene composition
  • a polypropylene composition comprising
  • the present invention relates to an article comprising the polypropylene composition as described above or below.
  • said article is a cable comprising an insulation layer comprising the polypropylene composition as described above or below.
  • the present invention relates to the use of the polypropylene composition as described above or below as cable insulation for medium and high voltage cables.
  • a heterophasic polypropylene is a propylene-based copolymer with a semi-crystalline matrix phase, which can be a propylene homopolymer or a random copolymer of propylene and at least one alpha-olefin comonomer, and an elastomeric phase dispersed therein.
  • the elastomeric phase can be a propylene copolymer with a high amount of comonomer, which is not randomly distributed in the polymer chain but are distributed in a comonomer-rich block structure and a propylene-rich block structure.
  • a heterophasic polypropylene usually differentiates from a one-phasic propylene copolymer in that it shows two distinct glass transition temperatures Tg which are attributed to the matrix phase and the elastomeric phase.
  • a propylene homopolymer is a polymer, which essentially consists of propylene monomer units. Due to impurities especially during commercial polymerization processes a propylene homopolymer can comprise up to 0.1 mol% comonomer units, preferably up to 0.05 mol% comonomer units and most preferably up to 0.01 mol% comonomer units.
  • a propylene random copolymer is a copolymer of propylene monomer units and comonomer units in which the comonomer units are distributed randomly over the polypropylene chain.
  • a propylene random copolymer includes a fraction, which is insoluble in xylene - xylene cold insoluble (XCI) fraction - in an amount of at least 85 wt%, most preferably of at least 88 wt%, based on the total amount of propylene random copolymer. Accordingly, the propylene random copolymer does not contain an elastomeric polymer phase dispersed therein.
  • a propylene polymer comprising at least two propylene polymer fractions (components), which have been produced under different polymerization conditions resulting in different (weight average) molecular weights and/or different comonomer contents for the fractions, preferably produced by polymerizing in multiple polymerization stages with different polymerization conditions, is referred to as “multimodal”.
  • multi relates to the number of different polymer fractions the propylene polymer is consisting of.
  • a propylene polymer consisting of two fractions only is called “bimodal”
  • a propylene polymer consisting of three fractions only is called “trimodal”.
  • a unimodal propylene polymer only consists of one fraction.
  • the term “different” means that the propylene polymer fractions differ from each other in at least one property, preferably in the weight average molecular weight - which can also be measured in different melt flow rates of the fractions - or comonomer content or both.
  • Vis-breaking is a post reactor chemical process for modifying semi-crystalline polymers such as propylene polymers.
  • the propylene polymer backbone is degraded, for example by means of peroxides, such as organic peroxides, via beta scission.
  • the degradation is generally used for increasing the melt flow rate and narrowing the molecular weight distribution.
  • the present invention relates to a polypropylene composition
  • a polypropylene composition comprising
  • the polypropylene composition preferably comprises the copolymer of propylene and comonomer units selected from ethylene and alpha-olefins having from 4 to 12 carbon atoms (A) in an amount of from 80.0 to 99.0 wt.-%, preferably from 82.5 to 97.2 wt.%, most preferably from 85.0 to 95.0 wt.-% and the ethylene-butyl acrylate copolymer (B) in an amount of from 1.0 to 20.0 wt.-%, preferably from 2.5 to 17.5 wt%, most preferably from 5.0 to 15.0 wt.-%, all based on the total weight of the polypropylene composition.
  • the polypropylene composition can further comprise polymeric components, which are different from the components (A) and (B), in an amount of preferably 0.0 to 10.0 wt% based on the total amount of the polypropylene composition.
  • polymeric components of the polypropylene composition consist of components (A) and (B).
  • the polypropylene composition can comprise one or more additives in an amount of from 0.0 up to 5.0 wt%, based on the total amount of the polypropylene composition.
  • the one or more additives are preferably selected from acid scavengers, antioxidants, alpha nucleating agents, beta nucleating agents, etc.
  • Such additives are commercially available and for example described in “Plastic Additives Handbook”, 6 th edition 2009 of Hans Zweifel (pages 1141 to 1190).
  • additives are added in quantities of 1 to 50000 ppm for each single component.
  • the one or more additives can be added to the polymeric components in a blending step. Thereby, the one or more additives can be added to the polymeric components in form of master batches in which one or more additives are blended with a carrier polymer in concentrated amounts. Any optional carrier polymer is calculated to the amount of additives, based on the total amount of the propylene copolymer composition.
  • the polypropylene composition preferably has a total amount of units derived from ethylene of from 10.0 to 25.0 wt%, more preferably from 12.5 to 22.5 wt% and most preferably from 15.0 to 20.0 wt%, based on the total amount of monomer units in the polypropylene composition. Further, the polypropylene composition preferably has a total amount of units derived from propylene of from 72.5 to 87.5 wt%, more preferably from 75.0 to 85.0 wt% and most preferably from 77.5 to 82.5 wt%, based on the total amount of monomer units in the polypropylene composition.
  • the polypropylene composition preferably has a total amount of units derived from butyl acrylate of from 0.1 to 10.0 wt%, more preferably from 0.5 to 7.5 wt% and most preferably from 1.0 to 5.0 wt%, based on the total amount of monomer units in the polypropylene composition.
  • the polypropylene composition preferably has a xylene cold soluble (XCS) fraction in a total amount of from 30.0 to 55.0 wt%, more preferably from 32.5 to 52.5 wt%, still more preferably from 34.0 to 50.0 wt% and most preferably from 36.0 to 47.5 wt%, based on the total weight amount of the polypropylene composition.
  • XCS xylene cold soluble
  • the xylene cold soluble (XCS) fraction preferably has a total amount of units derived from ethylene of from 25.0 to 45.0 wt%, more preferably from 27.5 to 40.0 wt% and most preferably from 30.0 to 37.5 wt%, based on the total amount of monomer units in the xylene cold soluble (XCS) fraction.
  • the xylene cold soluble (XCS) fraction preferably has a total amount of units derived from propylene of from 50.0 to 73.0 wt%, more preferably from 52.5 to 70.0 wt% and most preferably from 55.0 to 65.0 wt%, based on the total amount of monomer units in the xylene cold soluble (XCS) fraction.
  • the xylene cold soluble (XCS) fraction preferably has a total amount of units derived from butyl acrylate of from 0.5 to 12.5 wt%, more preferably from 1.0 to 10.0 wt% and most preferably from 2.0 to 7.5 wt%, based on the total amount of monomer units in the xylene cold soluble (XCS) fraction.
  • the xylene cold soluble (XCS) fraction preferably has an intrinsic viscosity of from 150 to 300 cm 3 /g, preferably from 175 to 275 cm 3 /g and most preferably from 200 to 250 cm 3 /g, measured in decalin. Additionally, the xylene cold soluble (XCS) fraction preferably has a weight average molecular weight Mw of from 150000 to 300000 g/mol, more preferably from 175000 to 275000 g/mol and most preferably from 200000 to 250000 g/mol.
  • the xylene cold soluble (XCS) fraction preferably has a polydispersity index, being the ratio of the weight average molecular weight and the number average molecular weight Mw/Mn, of from 4.5 to 13.0, preferably from 4.7 to 12.5 and most preferably from 5.0 to 12.0.
  • the polypropylene composition has a fraction insoluble in cold xylene (XCI) preferably in a total amount of from 45.0 to 70.0 wt%, more preferably from 47.5 to 67.5 wt% still more preferably from 50.0 to 66.0 wt% and most preferably from 52.5 to 64.0 wt%, based on the total weight amount of the polypropylene composition.
  • XCI fraction insoluble in cold xylene
  • the xylene cold soluble (XCS) fraction and the fraction insoluble in cold xylene (XCI) add to 100 wt% of the polypropylene composition.
  • the fraction insoluble in cold xylene (XCI) preferably has a total amount of units derived from ethylene of from 3.5 to 20.0 wt%, more preferably from 5.0 to 17.5 wt% and most preferably from 6.0 to 15.0 wt%, based on the total amount of monomer units in the fraction insoluble in cold xylene (XCI).
  • the fraction insoluble in cold xylene (XCI) preferably has a total amount of units derived from propylene of from 80.0 to 96.5 wt%, more preferably from 82.0 to 95.0 wt% and most preferably from 84.0 to 94.0 wt%, based on the total amount of monomer units in the fraction insoluble in cold xylene (XCI).
  • the fraction insoluble in cold xylene (XCI) preferably has a total amount of units derived from butyl acrylate of from 0 to 2.5 wt%, more preferably from 0 to 2.0 wt% and most preferably from 0 to 1.5 wt%, based on the total amount of monomer units in the fraction insoluble in cold xylene (XCI).
  • the fraction insoluble in cold xylene (XCI) preferably has an intrinsic viscosity of from 175 to 350 cm 3 /g, preferably from 200 to 325 cm 3 /g and most preferably from 225 to 300 cm 3 /g, measured in decalin. Additionally, the fraction insoluble in cold xylene (XCI) preferably has a weight average molecular weight Mw of from 250000 to 400000 g/mol, more preferably from 275000 to 375000 g/mol and most preferably from 300000 to 350000 g/mol.
  • the fraction insoluble in cold xylene (XCI) preferably has a polydispersity index, being the ratio of the weight average molecular weight and the number average molecular weight Mw/Mn, of from 3.0 to 9.0, preferably from 3.7 to 8.0 and most preferably from 4.0 to 7.5.
  • the ratio of the intrinsic viscosities of the XCI fraction to the XCS fraction of the polypropylene composition is preferably in the range of from 0.9 to 1.7, more preferably from 1.0 to 1.5 and most preferably from 1.0 to 1.4.
  • the polypropylene composition preferably has a melt flow rate MFR2 of 0.5 to 7.5 g/10 min, more preferably from 0.8 to 7.0 g/10 min, still more preferably from 1.0 to 6.5 g/10 min and most preferably from 1.2 to 6.0 g/10 min.
  • the polypropylene composition preferably has a flexural modulus of from 150 MPa to 350 MPa, more preferably of from 175 MPa to 335 MPa and most preferably of from 200 MPa to 315 MPa.
  • the polypropylene composition has a Charpy notched impact strength at 23°C of from 50 to 110 kJ/m 2 , more preferably from 60 to 100 kJ/m 2 and most preferably from 65 to 95 kJ/m 2 .
  • the polypropylene composition preferably has a Charpy notched impact strength at -20°C of from 4.0 to 25.0 kJ/m 2 , more preferably from 5.5 to 20.0 kJ/m 2 and most preferably from 7.0 to 15.0 kJ/m 2 .
  • the polypropylene composition has a melting temperature Tm of from 140 to 159°C, preferably from 143 to 157°C and most preferably from 145 to 153°C.
  • the polypropylene composition preferably has a crystallization temperature Tc of from 85 to 130°C, more preferably from 87 to 128°C and most preferably from 90 to 125°C.
  • the difference of the melting temperature to the crystallization temperature Tm-Tc is preferably in the range of from 20 to 65°C, preferably 25 to 60°C and most preferably from 27 to 55°C.
  • the polypropylene composition preferably has at least two glass transition temperatures.
  • Tg matrix phase
  • Tg (EP) elastomeric phase
  • the polypropylene composition preferably has a glass temperature attributed to the matrix phase Tg (matrix) in the range of from -1.0 to -15.0°C, preferably from -2.5 to -12.5°C and most preferably from -5.0 to -11 ,0°C.
  • the polypropylene composition preferably has a glass temperature attributed to the elastomeric phase Tg (EP) of from -40.0 to -55.0°C, preferably from -42.5 to -52.5°C and most preferably from -45.0 to -50.0°C.
  • Tg elastomeric phase
  • the polypropylene composition has a shear thinning index SHI1/100 of from 2.5 to 20.0, more preferably from 5.0 to 17.5 and most preferably from 7.5 to 15.0.
  • the polypropylene composition preferably has a polydispersity index PI of from 1.0 to 4.5 s' 1 , more preferably from 1.5 to 4.0 s' 1 and most preferably from 2.0 to 3.5 s' 1 .
  • the polypropylene composition is prepared by melt blending the components (A) and (B), the optional additional polymeric components and the optional further additives, all as described above or below.
  • the polypropylene composition is preferably not subjected to vis-breaking.
  • the polypropylene composition does not comprise, i.e. is free of a dielectric fluid, such as e.g. described in EP 2 739679.
  • copolymer of propylene and comonomer units selected from ethylene and alpha-olefins having from 4 to 12 carbon atoms (abbreviated “copolymer of propylene (A)” or component (A)) and the ethylene-butyl acrylate copolymer (B) (abbreviated component (B)) are described in more detail.
  • the polypropylene composition according to the invention comprises a copolymer of propylene and comonomer units selected from ethylene and alpha-olefins having from 4 to 12 carbon atoms (A) (in the following “copolymer of propylene (A)”).
  • the comonomer units are selected from ethylene and alpha-olefins having from 4 to 12 carbon atoms, such as ethylene, 1 -butene, 1 -hexene or 1 -octene.
  • the copolymer of propylene (A) can comprise one type of comonomer units or two or more types such as two types of comonomer units. It is preferred that the copolymer of propylene (A) comprises one type of comonomer units. Especially preferred is ethylene.
  • the copolymer of propylene (A) preferably has a total amount of comonomer units, preferably of ethylene, of from 10.0 to 16.0 wt%, preferably from 11.0 to 15.0 wt%, most preferably from 12.0 to 14.0 wt%, based on the total amount of monomer units in the copolymer of propylene (A).
  • the copolymer of propylene (A) is a heterophasic copolymer of propylene.
  • the heterophasic propylene copolymer has a matrix phase and an elastomeric phase dispersed in said matrix phase.
  • the matrix phase is preferably a propylene random copolymer.
  • the comonomer units of said propylene random copolymer of the matrix phase usually are the same as for the copolymer of propylene as described above. Said comonomer units preferably are selected from ethylene and alpha-olefins having from 4 to 12 carbon atoms, such as ethylene, 1 -butene, 1 -hexene or 1 -octene.
  • the propylene random copolymer of the matrix phase can comprise one type of comonomer units or two or more types such as two types of comonomer units. It is preferred that the propylene random copolymer of the matrix phase comprises one type of comonomer units. Especially preferred is ethylene.
  • Heterophasic propylene copolymers are typically characterized by comprising at least two glass transition temperatures. Said two glass transition temperatures can be attributed to the matrix phase (Tg (matrix)) and the elastomeric phase (Tg (EP)).
  • the heterophasic propylene copolymer preferably has a glass transition temperature attributed to the matrix phase Tg (matrix) in the range of from -1.0 to -15.0°C, preferably from -2.5 to -12.5°C and most preferably from -5.0 to -10.0°C.
  • the heterophasic propylene copolymer preferably has a glass transition temperature attributed to the elastomeric phase Tg (EP) in the range of from -40.0 to -55.0°C, preferably from -42.5 to -52.5°C and most preferably from -45.0 to -50.0°C.
  • Tg elastomeric phase
  • the matrix phase and the elastomeric phase usually cannot exactly be divided from each other.
  • the matrix phase and the elastomeric phase of a heterophasic polypropylene copolymer several methods are known.
  • One method is the extraction of a fraction, which contains to the most part the elastomeric phase with xylene, thus separating a xylene cold solubles (XCS) fraction from a xylene cold insoluble (XCI) fraction.
  • XCS xylene cold solubles
  • XCI xylene cold insoluble
  • the copolymer of propylene (A) preferably has a xylene cold soluble (XCS) fraction in a total amount of from 25.0 to 50.0 wt%, more preferably from 27.5 to 45.0 wt%, still more preferably from 30.0 to 42.5 wt% and most preferably from 32.5 to 40.0 wt%, based on the total weight amount of the copolymer of propylene (A).
  • XCS xylene cold soluble
  • the xylene cold soluble (XCS) fraction preferably has an amount of comonomer units, preferably of ethylene, of from 23.0 to 35.0 wt%, more preferably from 23.5 to 32.5 wt% and most preferably from 24.0 wt% to 30.0 wt%, based on the total amount of monomer units in the xylene cold soluble (XCS) fraction.
  • the xylene cold soluble (XCS) fraction preferably has an intrinsic viscosity of from 150 to 350 cm 3 /g, preferably from 200 to 325 cm 3 /g and most preferably from 225 to 300 cm 3 /g, measured in decalin.
  • the xylene cold soluble (XCS) fraction preferably has a weight average molecular weight Mw of from 185000 to 350000 g/mol, more preferably from 200000 to 325000 g/mol and most preferably from 210000 to 315000 g/mol.
  • the xylene cold soluble (XCS) fraction preferably has a polydispersity index, being the ratio of the weight average molecular weight and the number average molecular weight Mw/Mn, of from 3.5 to 8.5, preferably from 3.7 to 8.0 and most preferably from 4.0 to 7.5.
  • the copolymer of propylene (A) has a fraction insoluble in cold xylene (XCI) preferably in a total amount of from 50.0 to 75.0 wt%, more preferably from 55.0 to 72.5 wt%, still more preferably from 57.5 to 70.0 wt% and most preferably from 60.0 to 67.5 wt%, based on the total weight amount of the copolymer of propylene (A).
  • XCI fraction insoluble in cold xylene
  • the fraction insoluble in cold xylene (XCI) preferably has an amount of comonomer units, preferably of ethylene, of from 3.0 to 9.0 wt%, preferably from 4.0 to 8.5 wt% and most preferably from 4.5 to 7.5 wt%, based on the total amount of monomer units in the fraction insoluble in cold xylene (XCI).
  • the fraction insoluble in cold xylene (XCI) preferably has an intrinsic viscosity of from 185 to 350 cm 3 /g, preferably from 220 to 325 cm 3 /g and most preferably from 210 to 300 cm 3 /g, measured in decalin.
  • the fraction insoluble in cold xylene (XCI) preferably has a weight average molecular weight Mw of from 225000 to 450000 g/mol, more preferably from 240000 to 425000 g/mol and most preferably from 260000 to 400000 g/mol.
  • the fraction insoluble in cold xylene (XCI) preferably has a polydispersity index, being the ratio of the weight average molecular weight and the number average molecular weight Mw/Mn, of from 3.5 to 7.5, preferably from 3.7 to 7.0 and most preferably from 4.0 to 6.5.
  • the ratio of the intrinsic viscosities of the XCI fraction to the XCS fraction of the copolymer of propylene is preferably in the range of from 0.9 to 1.5, more preferably from 1.0 to 1.4 and most preferably from 1.0 to 1.3.
  • the copolymer of propylene (A) preferably has a melt flow rate MFR2 of 0.5 to 2.5 g/10 min, preferably from 0.8 to 2.3 g/10 min, still more preferably from 1.0 to 2.0 g/10 min and most preferably from 1.2 to 1.7 g/10 min.
  • the copolymer of propylene (A) preferably has a flexural modulus of from 130 MPa to 400 MPa, more preferably of from 150 MPa to 390 MPa and most preferably of from 175 MPa to 380 MPa.
  • the copolymer of propylene (A) has a Charpy notched impact strength at 23°C of from 50 to 110 kJ/m 2 , more preferably from 65 to 100 kJ/m 2 and most preferably from 75 to 95 kJ/m 2 .
  • the copolymer of propylene (A) preferably has a Charpy notched impact strength at -20°C of from 5.0 to 10.0 kJ/m 2 , more preferably from 5.5 to 9.0 kJ/m 2 and most preferably from 6.0 to 8.0 kJ/m 2 .
  • the copolymer of propylene (A) has a melting temperature Tm of from 140 to 159°C, preferably from 143 to 157°C and most preferably from 145 to 153°C.
  • the copolymer of propylene (A) has a crystallization temperature Tc of from 85 to 130°C, preferably from 87 to 128°C and most preferably from 90 to 125°C.
  • the difference of the melting temperature to the crystallization temperature Tm-Tc is preferably in the range of from 20 to 65°C, preferably 25 to 60°C and most preferably from 27 to 55°C.
  • the copolymer of propylene (A) has an intrinsic viscosity of from 185 to 350 cm 3 /g, preferably from 200 to 325 cm 3 /g and most preferably from 210 to 300 cm 3 /g, measured in decalin.
  • the copolymer of propylene (A) can be polymerized in a sequential multistage polymerization process, i.e. in a polymerization process in which two or more polymerization reactors are connected in series.
  • a sequential multistage polymerization process i.e. in a polymerization process in which two or more polymerization reactors are connected in series.
  • two or more, more preferably three or more, such as three or four, polymerization reactors are connected in series.
  • the term “polymerization reactor” shall indicate that the main polymerization takes place. Thus in case the process consists of four polymerization reactors, this definition does not exclude the option that the overall process comprises for instance a pre-polymerization step in a pre-polymerization reactor.
  • the matrix phase of the heterophasic propylene copolymer is polymerized in first polymerization reactor for producing a unimodal matrix phase or in the first and second polymerization reactor for producing a multimodal matrix phase.
  • the elastomeric phase of the heterophasic propylene copolymer is preferably polymerized in the subsequent one or two polymerization reactor(s) in the presence of the matrix phase for producing a unimodal elastomeric phase or a multimodal elastomeric phase.
  • the polymerization reactors are selected from slurry phase reactors, such as loop reactors and/or gas phase reactors such as fluidized bed reactors, more preferably from loop reactors and fluidized bed reactors.
  • a preferred sequential multistage polymerization process is a “loop-gas phase”-process, such as developed by Borealis A/S, Denmark (known as BORSTAR® technology) described e.g. in patent literature, such as in EP 0 887 379, WO 92/12182 WO 2004/000899, WO 2004/111095, WO 99/24478, WO 99/24479 or in WO 00/68315.
  • a further suitable slurry-gas phase process is the Spheripol® process of LyondellBasell.
  • Suitable sequential polymerization processes for polymerizing the copolymer of propylene (A), preferably the heterophasic propylene copolymer, are e.g. disclosed in EP 1 681 315 A1 or WO 2013/092620 A1.
  • the copolymer of propylene (A), preferably the heterophasic propylene copolymer can be polymerized in the presence of a Ziegler-Natta catalyst or a single site catalyst.
  • Suitable Ziegler-Natta catalysts are e.g. disclosed in US 5,234,879, WO 92/19653, WO 92/19658, WO 99/33843, WO 03/000754, WO 03/000757, WO 2013/092620 A1 or WO 2015/091839.
  • Suitable single site catalysts are e.g. disclosed in WO 2006/097497, WO 2011/076780 or WO 2013/007650.
  • the copolymer of propylene (A) is preferably not subjected to a visbreaking step as e.g. described in WO 2013/092620 A1.
  • Heterophasic propylene copolymer resins suitable as copolymer of propylene (A) are also commercially available. These resins are usually already additivated with stabilizer packages. Thus, when using commercially available resins as copolymer of propylene the addition of additives as described above might have to be adjusted to the already present additives.
  • the polypropylene composition according to the invention comprises an ethylene-butyl acrylate copolymer (B).
  • B ethylene-butyl acrylate copolymer
  • an ethylene-butyl acrylate copolymer contains ethylene monomers and butyl acrylate comonomers. No further comonomers may be present.
  • the ethylene-butyl acrylate copolymer (B) has a butyl acrylate content, determined according to FT-IR, in the range from 15.0 to 40.0 wt%. More preferably, the ethylene-butyl acrylate copolymer (B) has a butyl acrylate content, determined according to FT-IR, in the range from 20.0 to 35.0 wt%, most preferably in the range from 25.0 to 30.0 wt%.
  • the ethylene-butyl acrylate copolymer (B) preferably has a density of from 900 to 950 kg/m 3 , more preferably from 910 to 945 kg/m 3 , most preferably from 920 to 940 kg/m 3 , determined according to ISO 1183.
  • the ethylene-butyl acrylate copolymer (B) preferably has a melt flow rate MFR2 of from 1.0 to 20.0 g/10 min, preferably from 2.0 to 15.0 g/10 min, most preferably from 3.0 to 10.0 g/10 min, determined according to ISO 1133 at 190°C and 2.16 kg.
  • the ethylene-butyl acrylate copolymer (B) preferably has a melting temperature Tm of from 60 to 110°C, preferably from 70 to 100°C, most preferably from 80 to 95°C, determined by differential scanning calorimetry.
  • the ethylene-butyl acrylate copolymer (B) can be produced in a high pressure polymerization process by means of free radical polymerization.
  • Ethylene-butyl acrylate copolymer resins suitable as ethylene-butyl acrylate copolymer (B) are also commercially available. These resins are usually already additivated with stabilizer packages. Thus, when using commercially available resins as ethylene-butyl acrylate copolymer (B) the addition of additives as described above might have to be adjusted to the already present additives.
  • polymerisation methods well known to the skilled person may be used. It is within the scope of the invention for a multimodal, e.g. at least bimodal, polymers to be produced by blending each of the components in-situ during the polymerisation process thereof (so called in-situ process) or, alternatively, by blending mechanically two or more separately produced components in a manner known in the art.
  • a multimodal, e.g. at least bimodal, polymers to be produced by blending each of the components in-situ during the polymerisation process thereof (so called in-situ process) or, alternatively, by blending mechanically two or more separately produced components in a manner known in the art.
  • the present invention further relates to an article comprising the polypropylene composition as defined above or below.
  • the article is preferably a cable comprising an insulation layer comprising the polypropylene composition as described above or below.
  • the cable usually comprises of at least one conductor and at least one insulation layer comprising the polypropylene composition as described above or below.
  • the term "conductor” means herein above and below that the conductor comprises one or more wires.
  • the wire can be for any use and be e.g. optical, telecommunication or electrical wire.
  • the cable may comprise one or more such conductors.
  • the conductor is an electrical conductor and comprises one or more metal wires.
  • the cable is preferably a power cable.
  • a power cable is defined to be a cable transferring energy operating at any voltage, typically operating at voltages higher than 1 kV.
  • the voltage applied to the power cable can be alternating (AC), direct (DC), or transient (impulse).
  • the polypropylene composition of the invention is very suitable for power cables, especially for power cables operating at voltages 6 kV to 36 kV (medium voltage (MV) cables) and at voltages higher than 36 kV, known as high voltage (HV) cables and extra high voltage (EHV) cables, which EHV cables operate, as well known, at very high voltages.
  • MV medium voltage
  • HV high voltage
  • EHV extra high voltage
  • the cable system typically either consists of one conductor and one insulation layer comprising the polypropylene composition as described above or below, or of one conductor, one insulation layer comprising the polypropylene composition as described above or below and an additional jacketing layer, or of one conductor, one semiconductive layer and one insulation layer comprising the polypropylene composition as described above or below.
  • the cable system typically consists of one conductor, one inner semiconductive layer, one insulation layer comprising the polypropylene composition as described above or below and one outer semiconductive layer, optionally covered by an additionally jacketing layer.
  • the semiconductive layers mentioned preferably comprise, more preferably consist of a thermoplastic polyolefin composition, preferably a polyethylene composition or a polypropylene composition, containing a sufficient amount of electrically conducting solid fillers preferably carbon black.
  • the thermoplastic polyolefin composition of the semiconductive layer(s) is a polypropylene composition, more preferably a polypropylene composition comprising a heterophasic propylene copolymer as polymeric component.
  • the thermoplastic polyolefin composition of the at least one semiconductive layer, preferably both semiconductive layers of the cable comprise the same copolymer of propylene as the insulation layer, i.e. the copolymer of propylene as described above or below.
  • the cable comprising an insulation layer comprising the polypropylene composition according to the invention as described above shows AC electrical breakdown strength in form of Weibull alpha-value and Weibull beta-value.
  • the cable preferably has a Weibull alpha-value of from 35.0 to 65.0 kV/mm, preferably from 40.0 to 65.0 kV/mm and most preferably from 44.0 to 65.0 kV/mm, when measured on a 10 kV cable.
  • the cable preferably has a Weibull beta-value of from 15.0 to 250.0, preferably from 20.0 to 250.0, most preferably from 22.0 to 250.0, when measured on a 10 kV cable.
  • the insulation layer comprising the polypropylene composition according to the invention can be used for medium and high voltage cables.
  • the present invention relates to the use of the polypropylene composition as described above or below as cable insulation for medium and high voltage cables.
  • Said medium and high voltage cables preferably meet all properties requirements as described for the cables above and below.
  • the polypropylene composition shows a good balance of properties regarding high flexibility, a good mechanical strength, good impact properties and high crystallization and melting temperature which allow the use as cable insulation e.g. for medium and high voltage cables at high operation temperatures.
  • the flexibility and the impact properties can be further improved whereby the high crystallization and melting temperature are maintained.
  • the polypropylene composition can be easily compounded to prepare the insulation layer without need of increasing the melt flow rate via visbreaking the composition or the copolymer of propylene (A).
  • Cables comprising an insulation layer comprising the inventive polypropylene composition surprisingly show good AC breakdown strength in form of Weibull alpha-value and Weibull beta-value.
  • the addition of the ethylene-butyl acrylate copolymer (B) to the polypropylene composition further improves the AC breakdown strength compared to polypropylene compositions which only include the copolymer of propylene (A) as polymeric compound.
  • the good AC breakdown strength in form of Weibull alpha-value and Weibull beta-value can be obtained without addition of a dielectric fluid such as e.g. described in EP 2 739 679.
  • the melt flow rate is the quantity of polymer in grams which the test apparatus standardized to ISO 1133 or ASTM D1238 extrudes within 10 minutes at a certain temperature under a certain load.
  • melt flow rate MFR2 of propylene based polymers and the polypropylene composition is measured at 230°C with a load of 2.16 kg according to ISO 1133.
  • melt flow rate MFR2 of the ethylene based polymers and polyethylene compositions is measured at 190°C with a load of 2.16 kg according to ISO 1133.
  • the melt flow rate can also be measured according to ASTM D 1238. b) Density
  • Density is measured according to ISO 1183. Sample preparation is done by compression moulding in accordance with ISO 17855-2.
  • the density can also be measured according to ASTM D 792. c) Comonomer content Method I (HECOs)
  • 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. This approach allowed comparable referencing even when this structural unit was not present. Characteristic signals corresponding to the incorporation of ethylene were observed ⁇ 7 ⁇ .
  • the comonomer fraction was quantified using the method of Wang et. al. ⁇ 6 ⁇ through integration of multiple signals across the whole spectral region in the 13 C ⁇ 1 H ⁇ spectra. This method was chosen for its robust nature and ability to account for the presence of regiodefects when needed. Integral regions were slightly adjusted to increase applicability across the whole range of encountered comonomer contents.
  • Quantitative 1 H NMR spectra recorded in solution-state using a Bruker Avance III 400 NMR spectrometer operating at 400.15 and 100.62 MHz for 1 H and 13 C respectively. All spectra were recorded using a 13 C optimised 10 mm selective excitation probehead at 125°C using nitrogen gas for all pneumatics. Approximately 200 mg of material was dissolved in 7,2- tetrachloroethane-cfe (TCE-cfe), using approximately 3 mg of BHT (CAS 128-37-0) as stabiliser.
  • TCE-cfe 7,2- tetrachloroethane-cfe
  • Standard single-pulse excitation was employed utilising a 30-degree pulse, a relaxation delay of 3 s and 10 Hz sample rotation. 64 transients were acquired per spectra using 4 dummy scans. A total of 32k data points were collected per FID with a dwell time of 60 ps, which corresponded to a spectral window of approx. 20 ppm. The FID was then zero filled to 64k data points and an exponential window function applied with 0.3 Hz line-broadening.
  • Quantitative 1 H NMR spectra were processed, integrated and quantitative properties determined. All chemical shifts were internally referenced to the residual protonated solvent signal at 5.95 ppm.
  • BA butylacrylate
  • the butylacrylate content in mole percent was calculated as:
  • the butylacrylate content in weight percent was calculated as:
  • BA [wt%] 100 * ( fBA * 128.17) I (fBA * 128.17) + ((1- fBA) * 28.05))
  • 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.
  • Standard single-pulse excitation was employed without NOE, using an optimised tip angle, 1 s recycle delay and a bi-level WALTZ16 decoupling scheme as described in Z. Zhou, R. Kuemmerle, X. Qiu, D. Redwine, R. Cong, A. Taha, D. Baugh, B. Winniford, J. Mag. Reson. 187 (2007) 225 and V. Busico, P. Carbonniere, R. Cipullo, C. Pellecchia, J. Severn, G. Talarico, Macromol. Rapid Commun. 2007, 28, 1128. 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. 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.
  • the comonomer fraction was quantified using a comparable triad approach as reported by L. Abis, Mackromol. Chem. 187, 1877-1886 (1986) for ZN C2C3 copolymers.
  • C2 content only the total amount resulting from both C2C3, EBA copolymer and additional blend component containing C2 can be quantified by use of the methylene sequence at 30.0 ppm. assignment table 13 C NMR spectra triad equations
  • Film samples of the polymers were prepared for the FTIR measurement: 0.5 to 0.7 mm thickness was used for ethylene butyl acrylate >6 wt.-% butylacrylate content and 0.05 to 0.12 mm thickness was used for ethylene butyl acrylate ⁇ 6 wt.-% butylacrylate content.
  • the maximum absorbance for the peak for the butyl acrylate >6 wt.- % at 3450 cm-1 was subtracted with the absorbance value for the base line at 3510 cm-1 (Abutylacrylate - A3510).
  • the maximum absorbance peak for the polyethylene peak at 2020 cm-1 was subtracted with the absorbance value for the base line at 2120 cm-1 (A2020 -A2120).
  • the ratio between (Abutylacrylate-A3510) and (A2020-A2120) was then calculated in the conventional manner, which is well documented in the literature.
  • DSC Differential scanning calorimetry
  • Tm melting temperature
  • Tc crystallization temperature
  • Crystallization temperature and heat of crystallization are determined from the cooling step, while melting temperature and heat of fusion (Hf) are determined from the second heating step.
  • the quantity of xylene soluble matter in polypropylene is determined according to the ISO16152 (first edition; 2005-07-01).
  • Tg Glass transition temperature Tg was determined by dynamic mechanical analysis (DMTA) according to ISO 6721-7. The measurements were done in torsion mode on compression moulded samples (40x10x1 mm3) between -100°C and +150°C with a heating rate of 2°C/min and a frequency of 1 Hz. Tg was determined from the curve of the loss angle (tan(b)). g) Intrinsic viscosity (IV)
  • the reduced viscosity (also known as viscosity number), r
  • Relative viscosities of a diluted polymer solution with concentration of 1 mg/ml and of the pure solvent are determined in an automated capillary viscometer (Lauda PVS1) equipped with 4 Ubbelohde capillaries placed in a thermostatic bath filled with silicone oil. The bath temperature is maintained at 135 °C. The sample is dissolved with constant stirring until complete dissolution is achieved (typically within 90 min).
  • the efflux time of the polymer solution as well as of the pure solvent are measured several times until three consecutive readings do not differ for more than 0.2s (standard deviation).
  • the relative viscosity of the polymer solution is determined as the ratio of averaged efflux times in seconds obtained for both, polymer solution and solvent: [dimensionless]
  • the column set was calibrated using universal calibration (according to ISO 16014-2:2003) with 19 narrow MWD polystyrene (PS) standards in the range of 0.5 kg/mol to 11 500 kg/mol.
  • PS polystyrene
  • the PS standards were dissolved at 160°C for 15 min or alternatively at room temperatures at a concentration of 0.2 mg/ml for molecular weight higher and equal 899 kg/mol and at a concentration of 1 mg/ml for molecular weight below 899 kg/mol.
  • the conversion of the polystyrene peak molecular weight to polyethylene molecular weights is accomplished by using the Mark Houwink equation and the following Mark Houwink constants:
  • a third order polynomial fit was used to fit the calibration data.
  • the flexural modulus was determined acc. to ISO 178 method A (3-point bending test) on 80 mm x 10 mm x 4 mm specimens. Following the standard, a test speed of 2 mm/min and a span length of 16 times the thickness was used. The testing temperature was 23 ⁇ 2° C. Injection moulding was carried out according to ISO 19069-2 using a melt temperature of 230°C for all materials irrespective of material melt flow rate. j) Charpy notched impact strength
  • the Charpy notched impact strength was determined acc. to ISO 179-1/1 eA on notched 80 mm x 10 mm x 4 mm specimens (specimens were prepared according to ISO 179-1/1eA). Testing temperatures were 23 ⁇ 2° C or -20 ⁇ 2° C. Injection moulding was carried out acc. to ISO 19069-2 using a melt temperature of 230°C for all materials irrespective of material melt flow rate. k) 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, q*, the dynamic shear viscosity, r , the out- of-phase component of the complex shear viscosity q” and the loss tangent, tan 6 which can be expressed as follows:
  • Shear Thinning Index which correlates with MWD and is independent of Mw
  • the SH I(2/IOO> is defined by the value of the complex viscosity, in Pa- s, determined for a value of G* equal to 1 kPa, divided by the value of the complex viscosity, in Pa- s, determined for a value of G* equal to 100 kPa.
  • q*3oorad/s (eta*3oorad/ s or eta 3 oo) is used as abbreviation for the complex viscosity at the frequency of 300 rad/s and q*o.osrad/s (eta*o.osrad/s or etao.os) is used as abbreviation for the complex viscosity at the frequency of 0.05 rad/s.
  • the polydispersity index, PI is defined by equation 10.
  • CO C OP 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.
  • AC electric breakdown strength ACBD
  • the calculation of the Weibull parameters of the data set of six breakdown values follows the least squares regression procedure as described in I EC 62539 (2007).
  • the Weibull alpha parameter in this document refers to the scale parameter of the Weibull distribution, i.e. the voltage for which the failure probability is 0.632.
  • the Weibull beta value refers to the shape parameter.
  • Catalyst The catalyst used in the polymerization process for the heterophasic propylene copolymer powder A1 was a Ziegler-Natta catalyst, which is described in patent publications EP491566, EP591224 and EP586390. As co-catalyst triethyl-aluminium (TEAL) and as donor dicyclo pentyl dimethoxy silane (D-donor) was used. • Polymerization of the heterophasic propylene copolymer powder
  • Heterophasic propylene copolymer powder A1 was produced in a BorstarTM plant in the presence of the above described polymerization catalyst using one liquid-phase loop reactor and two gas phase reactors connected in series under conditions as shown in Table 1.
  • the first reaction zone was a loop reactor and the second and third reaction zones were gas phase reactors.
  • the matrix phase was polymerized in the loop and first gas phase reactor and the elastomeric phase was polymerized in the second gas phase reactor.
  • the catalyst as described above was fed into a prepolymerization reactor which precedes the first reaction zone.
  • Table 1 Polymerization conditions of the heterophasic propylene copolymer powder: b) Preparation of the polypropylene compositions
  • heterophasic propylene copolymer powder A1 from the polymerization reaction was compounded in a twin screw extruder together with different stabilizer packages to obtain the polypropylene compositions of reference examples RE1 and RE2.
  • RE2 alpha-nucleating agent was added to the powder and the composition was vis-broken to a melt flow rate MFR 2 (230°C, 2.16 kg) of 3.9 g/10 min as disclosed in the example section of WO 2017/198633.
  • the polypropylene compositions RE1 and RE2 show the properties as listed below in Table 3.
  • the compounded pellets of reference example RE1 were compounded in a second compounding step in a Buss 100 MDK L/D 11D co-kneader together with different additives.
  • An overview of the production of the polypropylene compositions CE1 and IE1 are shown in Table 4.
  • the properties of CE1 and IE1 are shown in Table 5.
  • Table 4 Compounding of IE1-IE3 and CE1 in a Buss 100 MDK L/D 11 D co-kneader:
  • Stabiliser onepack 1 consists of 21.8 wt% Pentaerythrityl-tetrakis(3-(3’,5’-di-tert. butyl-4- hydroxyphenyl)-propionate (CAS-No. 6683-19-8), 43.6 wt% Tris (2,4-di-t-butylphenyl) phosphite (CAS-No. 31570-04-4) and 34.6 wt% Calcium stearate (CAS-No. 1592-23-0), all commercially available from a variety of companies.
  • Stabiliser onepack 2 consists of 29 wt% Pentaerythrityl-tetrakis(3-(3’,5’-di-tert. butyl-4- hydroxyphenyl)-propionate (CAS-No. 6683-19-8), 58 wt% Tris (2,4-di-t-butylphenyl) phosphite (CAS-No. 31570-04-4) and 13 wt% Magnesium Oxide (CAS-No. 1309-48-4), all commercially available from a variety of companies.
  • Alpha-nucleation via BNT was achieved by adding 2 wt% of a propylene homopolymer with an MFR 2 (230°C) of 8.0 g/10 min and a melting temperature of 162 °C, which is produced with a Ziegler-Natta type catalyst in the Borealis nucleation technology (BNT), comprising a polymeric a-nucleating agent, and is distributed by Borealis AG (Austria).
  • BNT Borealis nucleation technology
  • EBA is an ethylene-butyl acrylate copolymer produced as follows:
  • Fresh ethylene and recycled ethylene and comonomer butyl acrylate was compressed to reach an initial reactor pressure of 2500 bars in two parallel streams to supply the front and the side of a split feed 2 zone reactor with a varying L/D between around 17300 to 30400.
  • Comonomer was added in amounts to reach 27 wt.-% in the final polymer.
  • An MFR2 of the final polymer of 4.5 g/10 min was maintained.
  • the front stream was heated to 160°C in a preheating section before entering the front zone of the reactor and the side stream was cooled and entered at the side of the reactor.
  • EBA has a melt flow rate MFR 5 (190°C, 2.16 kg) of 4.5 g/10 min, a butyl acrylate content of 27.0 wt%, a density of 927 kg/m 3 , and a melting temperature Tm of 92 °C.
  • inventive composition IE1 shows improved flexibility and impact properties in addition to comparable crystallization and melting temperature compared to the comparative composition CE1.
  • 10 kV test cables were produced on a Maillefer pilot cable line of catenary continuous vulcanizing (CCV) type.
  • CCV catenary continuous vulcanizing
  • the conductors of the cable cores had a cross section being 50 mm 2 of stranded aluminium and had a cross section of 50 mm 2 .
  • the inner semiconductive layer was produced from semiconductive composition SC2 as described below and had a thickness of 1.0 mm.
  • the insulation layer was produced from the above described compositions CE1 and IE1, and had a thickness of 3.4 mm.
  • the outer semiconductive layer was produced from semiconductive compositions SC1 as described below and had a thickness of 1.0 mm.
  • the cables i.e. cable cores, were produced by extrusion via a triple head.
  • the insulation extruder had size 100 mm, the extruder for conductor screen (inner semiconductive layer) 45 mm, and the extruder for insulation screen (outer semiconductive layer) 60 mm.
  • the line speed was 6.0 m/min.
  • the vulcanisation tube had a total length of 52.5 meter consisting of a curing section followed by a cooling section.
  • the curing section was filled with N2 at 10 bar but not heated.
  • the 33- meter-long cooling section was filled with 20-25°C water.
  • the pilot cables were then subjected to AC breakdown testing.
  • Semiconductive layer 1 was prepared from ready-to-use semiconductive composition Borlink LE7710, which is a non-crosslinkable polyethylene based composition comprising carbon black, commercially available from Borealis AG.
  • Semiconductive layer 2 was prepared from 66.5 wt% of the polypropylene based composition of RE2 with 33.0 wt% of carbon black Printex Alpha, commercially available from Orion Engineered Carbons GmbH and 0.5 maleic anhydride functionalized polypropylene Exxelor PO1020, commercially available from Exxon Mobil.
  • Table 6 shows the electric properties of the 10 kV cables of examples C1 and C2 in which the inventive insulation layer IE1 is compared to comparative insulation layer CE1.
  • the cables comprising the inventive insulation layer IE1 shows an increased Weibull-alpha value and Weibull-beta value compared to the cable comprising the accordant comparative insulation layer CE1.

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Abstract

La présente invention concerne une composition de polypropylène comprenant (A) de 80,0 à 99,0 % en poids, de préférence de 82,5 à 97,2 % en poids, idéalement de 85,0 à 95,0 % en poids d'un copolymère de propylène et d'unités comonomères choisies parmi l'éthylène et les alpha-oléfines ayant de 4 à 12 atomes de carbone ayant une quantité totale d'unités comonomères de 10,0 à 16,0 % en poids, de préférence de 11,0 à 15,0 % en poids, idéalement de 12,0 à 14,0 % en poids, sur la base de la quantité totale d'unités monomères du copolymère de propylène (A) ; un indice de fluidité MFR2 de 0,5 à 2,5 g/10 min, de préférence de 0,8 à 2,3 g/10 min, encore plus préférablement de 1,0 à 2,0 g/10 min et idéalement de 1,2 à 1,7 g/10 min ; une fraction soluble dans le xylène froid (XCS) en une quantité totale de 25,0 à 50,0 % en poids, de préférence de 27,5 à 45,0 % en poids, plus préférablement de 30,0 à 42,5 % en poids et idéalement de 32,5 à 40,0 % en poids, sur la base de la quantité totale en poids du copolymère de propylène (A) ; et (B) de 1,0 à 20,0 % en poids, de préférence de 2,5 à 17,5 % en poids, idéalement de 5,0 à 15,0 % en poids d'un copolymère d'éthylène-acrylate de butyle ayant une teneur en acrylate de butyle, déterminée par FT-IR, dans la plage de 15,0 à 40,0 % en poids, un article comprenant ladite composition de polypropylène, de préférence un câble comprenant une couche d'isolation comprenant ladite composition de polypropylène et l'utilisation de ladite composition de polypropylène en tant qu'isolation de câble pour des câbles à moyenne et haute tension.
PCT/EP2023/076452 2022-09-28 2023-09-26 Composition de polypropylène destinée à l'isolation de câble Ceased WO2024068576A1 (fr)

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Citations (24)

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EP0491566A2 (fr) 1990-12-19 1992-06-24 Borealis A/S Procédé de modification de catalyseurs de polymérisation d'oléfines
WO1992012182A1 (fr) 1990-12-28 1992-07-23 Neste Oy Procede de production de polyethylene en plusieurs etapes
WO1992019653A1 (fr) 1991-05-09 1992-11-12 Neste Oy Procatalyseur pour la polymerisation d'olefines contenant un produit de transesterification entre un alcool inferieur et un ester d'acide phtalique
WO1992019658A1 (fr) 1991-05-09 1992-11-12 Neste Oy Polyolefine a gros grains, production de cette polyolefine et procatalyseur contenant un produit de transesterification entre un alcool inferieur et du dioctylphtalate utilise a cet effet
US5234879A (en) 1990-12-19 1993-08-10 Neste Oy Method for the modification of catalysts intended for the polymerization of olefins
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