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WO2025202325A1 - Composition de polypropylène pour l'isolation de câbles - Google Patents

Composition de polypropylène pour l'isolation de câbles

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Publication number
WO2025202325A1
WO2025202325A1 PCT/EP2025/058325 EP2025058325W WO2025202325A1 WO 2025202325 A1 WO2025202325 A1 WO 2025202325A1 EP 2025058325 W EP2025058325 W EP 2025058325W WO 2025202325 A1 WO2025202325 A1 WO 2025202325A1
Authority
WO
WIPO (PCT)
Prior art keywords
polypropylene composition
copolymer
determined
propylene
iso
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2025/058325
Other languages
English (en)
Inventor
Katja Klimke
Per-Ola Hagstrand
Ulf Nilsson
Thomas Gkourmpis
Lars Efraimsson
Anette Johansson
Gerhard Hubner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Borealis GmbH
Original Assignee
Borealis GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Borealis GmbH filed Critical Borealis GmbH
Publication of WO2025202325A1 publication Critical patent/WO2025202325A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • 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
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/02—Heterophasic composition

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 materials can be produced for conductor temperatures of 90-105°C. But in essence, 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 normally not used over 1 kV. In addition, softeners have to be added to PVC in order to maintain a high level of flexibility.
  • thermoplastic material and especially thermoplastic propylene polymers as insulation material for medium, high and extra high voltage (MV, HV and EHV) cables.
  • transmission system operators are expressing an increasing interest for recycling cable components at end-of-life.
  • MV medium voltage
  • HV high voltage
  • EHV extra high voltage
  • HVDC high-voltage direct current
  • the present invention relates to an article comprising the polypropylene composition as described above or below.
  • 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 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 copolymer of ethylene and polar comonomer units (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.
  • A copolymer of propylene and comonomer units selected from ethylene and alpha-olefins having from 4 to 12 carbon atoms
  • A copolymer of propylene and comonomer units selected from ethylene and alpha-olefins
  • component (A) the copolymer of propylene and comonomer units selected from ethylene and alpha-olefins having from 4 to 12 carbon atoms
  • component (B) the copolymer of ethylene and polar comonomer units
  • 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 weight 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 weight 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).
  • the polypropylene composition contains from 0 to 5.00 wt.-%, more preferably from 0 to 2.50 wt.-% of the alpha-nucleating agent, based on the total amount of the polypropylene composition.
  • the amount of pure alpha-nucleating agent in the polypropylene composition is preferably in the range of from 0 to 5000 ppm, more preferably from 0 to 4000 ppm, based on the total amount of the polypropylene composition.
  • the alpha-nucleating agent is generally not restricted.
  • the alpha-nucleating agent is preferably selected from the group consisting of
  • the alpha-nucleating agent is preferably selected from the group consisting of dibenzylidenesorbitol (e.g. 1 ,3 : 2,4 dibenzylidene sorbitol), dibenzylidenesorbitol derivative, preferably dimethyldibenzylidenesorbitol (e.g. 1 ,3 : 2,4 di(methylbenzylidene) sorbitol), or substituted nonitol-derivatives, such as 1 ,2,3-trideoxy-4,6:5,7-bis-0-[(4- propylphenyl)methylene]-nonitol, vinylcycloalkane polymer, vinylalkane polymer, and mixtures thereof.
  • dibenzylidenesorbitol e.g. 1 ,3 : 2,4 dibenzylidene sorbitol
  • dibenzylidenesorbitol derivative preferably dimethyldibenzylidenesorbitol (e.g.
  • vinylcycloalkane polymers such as e.g. vinylcyclohexane (VCH) polymers.
  • VCH vinylcyclohexane
  • BNT Borealis Nucleation Technology
  • the alpha-nucleating agent can be added to the polypropylene composition as an isolated raw material or in a mixture with a carrier polymer, i.e. in a so-called master batch.
  • the amount of the carrier polymer of the master batch thereby is calculated to the amount of the alpha-nucleating agent.
  • the polypropylene composition comprises an alpha-nucleating agent.
  • the pure amount of alpha-nucleating agent is preferably in the range of from 0.1 to 5000 ppm, more preferably from 1 to 5000 ppm.
  • the pure amount of alpha-nucleating is 0 ppm.
  • the one or more additives can be added to the polymeric components in a blending step.
  • 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 weight of the propylene copolymer composition.
  • the polypropylene composition preferably has a total amount of units derived from ethylene of from 12.5 to 25.0 wt.-%, preferably from 15.0 to 22.5 wt.-%, more preferably from 16.5 to 21 .0 wt.-%, still more preferably from 17.5 to 20.0 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 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 polar monomer comonomer units, preferably units derived from vinyl acetate (VA), of from 0.1 to 7.5 wt.-%, more preferably from 0.5 to 6.0 wt.-%, still more preferably from 0.7 to 5.0 wt.-%, even more preferably from 1 .0 to 3.0 wt.-%, based on the total amount of monomer units in the polypropylene composition.
  • VA vinyl acetate
  • the polypropylene composition preferably has a xylene cold soluble (XCS) fraction in a total amount of from 30.0 to 50.0 wt.-%, more preferably from 32.5 to 47.5 wt.-%, still more preferably from 35.0 to 45.0 wt.-% and most preferably from 37.5 to 42.5 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 polar comonomer units, preferably from vinyl acetate (VA(XCS)) 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 xylene cold soluble (XCS) fraction.
  • VA(XCS) vinyl acetate
  • the xylene cold soluble (XCS) fraction preferably has an intrinsic viscosity (IV(XCS)) of from 125 to 275 cm 3 /g, preferably from 150 to 250 cm 3 /g and most preferably from 175 to 225 cm 3 /g, measured in decalin. Additionally, the xylene cold soluble (XCS) fraction preferably has a weight average molecular weight Mw(XCS) of from 125000 to 275000 g/mol, more preferably from 150000 to 250000 g/mol and most preferably from 175000 to 230000 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(XCS), of from 4.5 to 13.0, preferably from 4.7 to 12.5 and most preferably from 5.0 to 12.0.
  • 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 propylene (C3(XCI)) 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 polar comonomer units, preferably units derived from vinyl acetate (VA(XCI)), 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 fraction insoluble in cold xylene (XCI).
  • VA(XCI) vinyl acetate
  • the fraction insoluble in cold xylene (XCI) preferably has a weight average molecular weight Mw of from 275000 to 425000 g/mol, more preferably from 300000 to 400000 g/mol and most preferably from 325000 to 375000 g/mol.
  • the ratio of the intrinsic viscosities of the XCS fraction to the XCI fraction (IV(XCS)/IV(XCI)) of the polypropylene composition is preferably in the range of from 0.4 to 1.1 , more preferably from 0.5 to 1 .0 and most preferably from 0.6 to 0.9.
  • the ratio of ethylene content of the XCS fraction to the XCI fraction (C2(XCS)/C2(XCI)) of the polypropylene composition is preferably in the range of from 2.5 to 7.5, more preferably from 3.5 to 6.5, and most preferably from 4.0 to 6.0.
  • the ratio of the content of polar comonomer units, preferably vinyl acetate content of the XCS fraction to the XCI fraction (VA(XCS)/VA(XCI)) of the polypropylene composition is preferably in the range of from 7.5 to 15.0, more preferably from 8.5 to 14:0, and most preferably from 10.0 to 13.0.
  • the ratio of weight average molecular weight of the XCI fraction to the XCS fraction (Mw(XCI)/Mw(XCS)) of the polypropylene composition is preferably in the range of from 1 .45 to 2.50, preferably from 1 .50 to 2.25, more preferably from 1 .52 to 2.00 and most preferably from 1 .55 to 1 .90.
  • the polypropylene composition preferably has a good balance of properties in regard of flexibility, mechanical properties, thermal properties and impact properties as illustrated by the following properties:
  • the polypropylene composition preferably has a melt flow rate MFR2 of from 0.7 to 4.0 g/10 min, more preferably from 1 .0 to 3.5 g/10 min, still more preferably from 1 .2 to 3.2 g/10 min and most preferably from 1 .5 to 3.0 g/10 min, determined according to ISO 1133 at 230°C and 2.16 kg.
  • 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, determined according to ISO 178 method A.
  • the polypropylene composition preferably 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 , determined according to ISO 179-1/1 eA.
  • 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 , determined according to ISO 179-1/1 eA.
  • the polypropylene composition preferably has a melting temperature Tm of from 140 to 159°C, more preferably from 143 to 157°C and most preferably from 145 to 153°C, determined by to DSC analysis according to ISO 11357.
  • 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, determined by to DSC analysis according to ISO 11357.
  • the difference of the melting temperature to the crystallization temperature Tm-Tc is preferably in the range of from 35 to 65°C, more preferably 40 to 60°C and most preferably from 45 to 55 °C.
  • 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, more preferably from - 2.5 to -12.5°C and most preferably from -4.0 to -10.0°C Still further, the polypropylene composition preferably has a glass temperature attributed to the elastomeric phase Tg (EP) of from -40.0 to -55.0°C, more preferably from -42.5 to -52.5°C and most preferably from -44.0 to -50.0°C.
  • Tg matrix phase
  • EP elastomeric phase
  • the polypropylene composition preferably has a shear thinning index SHI1/100 of from 5.0 to 22.5, more preferably from 7.5 to 20.0 and most preferably from 10.0 to 17.5.
  • the polypropylene composition preferably has a polydispersity index PI of from 1 .5 to 5.0 s -1 , more preferably from 2.0 to 4.5 s -1 and most preferably from 2.5 to 4.0 s’ 1 .
  • the polypropylene composition is prepared by melt blending the copolymer of propylene (A) and the copolymer of ethylene and polar comonomer units (B), the optional additional polymeric components and the optional further additives, all as described above or below.
  • the present invention relates to a polypropylene composition having
  • a xylene cold solubles (XCS) fraction content of from 30.0 to 50.0 wt.-%, preferably from 32.5 to 47.5 wt.-%, more preferably from 35.0 to 45.0 wt.-% and most preferably from 37.5 to 42.5 wt.-%, based on the total weight amount of the polypropylene composition; • said xylene cold solubles (XCS) fraction having a weight average molecular weight (Mw(XCS)) of from 150000 to 300000 g/mol, more preferably from 175000 to 275000 g/mol and most preferably from 200000 to 250000 g/mol, determined by GPC measurement;
  • Mw(XCS) weight average molecular weight
  • a fraction insoluble in cold xylene (XCI) content of from 50.0 to 70.0 wt.-%, preferably from 52.5 to 67.5 wt.-%, more preferably from 55.0 to 65.0 wt.-% and most preferably from 57.5 to 62.5 wt.-%, based on the total weight amount of the polypropylene composition; and
  • the polypropylene composition of said second aspect 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 copolymer of ethylene and polar comonomer units (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.
  • A copolymer of propylene and comonomer units selected from ethylene and alpha-olefins having from 4 to 12 carbon atoms
  • A copolymer of propylene and comonomer units selected from ethylene and alpha-olefins having
  • the copolymer of propylene and comonomer units selected from ethylene and alpha-olefins having from 4 to 12 carbon atoms (A) and the copolymer of ethylene and polar comonomer units (B) also apply to the polypropylene composition of this second aspect.
  • 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 copolymer of ethylene and polar comonomer units (B) (abbreviated “copolymer of ethylene (B)” or 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) 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) and determined by quantitative 13 C ⁇ 1 H ⁇ -NMR spectroscopy.
  • the copolymer of propylene (A) preferably has a total propylene content of from 84.0 to 90.0 wt.-%, more preferably from 85.0 to 89.0 wt.-%, most preferably from 86.0 to 88.0 wt.-%, based on the total weight of the copolymer of propylene and ethylene determined by quantitative 13 C ⁇ 1 H ⁇ -NMR spectroscopy.
  • the copolymer of propylene (A) has a melt flow rate MFR2 of from 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, determined according to ISO 1133 at 230°C and 2.16 kg.
  • the copolymer of propylene (A) is a heterophasic copolymer of propylene and ethylene.
  • the heterophasic copolymer of propylene and ethylene has a matrix phase and an elastomeric phase dispersed in said matrix phase.
  • 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.
  • 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.
  • EP elastomeric phase
  • a copolymer of propylene (A) such as a heterophasic propylene copolymer
  • the matrix phase and the elastomeric phase usually cannot exactly be divided from each other.
  • 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 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. Additionally, 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 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, determined according to ISO 178 method A.
  • the copolymer of propylene (A) preferably 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 , determined according to ISO 179-1/1 eA.
  • 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 , determined according to ISO 179-1/1 eA.
  • the copolymer of propylene (A) preferably has a melting temperature Tm of from 140 to 159°C, more preferably from 143 to 157°C and most preferably from 145 to 153°C, determined by to DSC analysis according to ISO 11357.
  • the copolymer of propylene (A) 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, determined by to DSC analysis according to ISO 11357.
  • the difference of the melting temperature to the crystallization temperature T m -T c is preferably in the range of from 20 to 65°C, more preferably 25 to 60°C and most preferably from 27 to 55°C.
  • 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 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 prepolymerization reactor.
  • the matrix phase of the heterophasic copolymer of propylene and ethylene 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 copolymer of propylene and ethylene 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
  • a further suitable slurry-gas phase process is the Spheripol® process of LyondellBasell.
  • Suitable sequential polymerization processes for polymerizing copolymer of propylene (A), preferably the heterophasic copolymer of propylene and ethylene, are e.g. disclosed in WO 2015/117948.
  • the copolymer of propylene (A), preferably the heterophasic copolymer of propylene and ethylene can be polymerized in the presence of a Ziegler-Natta catalyst.
  • Suitable Ziegler-Natta catalysts are e.g. disclosed in WO 2015/117948.
  • 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 and ethylene are also commercially available. These resins are usually already additivated with stabilizer packages. Thus, when using commercially available resins as copolymer of propylene (A) 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 a copolymer of ethylene and polar comonomer units (B).
  • copolymer of ethylene and polar comonomer units contains ethylene monomer units and polar comonomer units. No further comonomer units may be present.
  • the polar comonomer units are preferably selected from the group of carboxyl acid esters with unsaturated carboxylic acid or the group of carboxyl acid esters with an unsaturated alcohol, preferably the group of carboxyl acid esters with an unsaturated alcohol.
  • Suitable examples for the group of carboxyl acid esters with unsaturated carboxylic acid are C1-C6-acrylates and C1-C6-alkyl methacrylates, more preferably methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate and butyl methacrylate.
  • Suitable examples for the group of group of carboxyl acid esters with an unsaturated alcohol are vinyl esters of C1 to C10 carboxylic acids, preferably vinyl esters of C1 to C6 carboxylic acids. Especially preferred is vinyl acetate.
  • the copolymer of ethylene (B) is an ethylene vinyl acetate copolymer.
  • the copolymer of ethylene (B) preferably has a polar comonomer content, more preferably a vinyl acetate content, determined by 1 H NMR spectroscopy, of from 10.0 to 40.0 wt.-%, more preferably from 12.0 to 35.0 wt.-%, still more preferably from 14.0 to 30.0 wt.-%, based on the on the total amount of monomer units in the copolymer of ethylene (B).
  • the copolymer of ethylene (B) has a melt flow rate MFR2 of from more than 20 to 1000 g/10 min, preferably from 30 to 800 g/10 min, more preferably from 100 to 750 g/10 min, still more preferably from 200 to 700 g/10 min, even more preferably from 300 to 650 g/10 min, and most preferably from 400 to 600 g/10 min, determined according to ISO 1133 at 190°C and 2.16 kg.
  • the copolymer of ethylene (B) preferably has a melting temperature Tm of from 95.0 to 115.0 °C, more preferably from 97.5 to 112.5°C, still more preferably from 100.0 to 110.0°C, determined by to DSC analysis according to ISO 11357.
  • the copolymer of ethylene (B) preferably has a crystallization temperature Tc of from 55.0 to 75.0°C, more preferably from 57.5 to 72.5°C, still more preferably from 60.0 to 70.0°C, determined by to DSC analysis according to ISO 11357.
  • the copolymer of ethylene (B) preferably has a difference of the melting temperature to the crystallization temperature Tm-Tc in the range of from 30 to 55°C, more preferably 33 to 50°C and still more preferably from 35 to 45°C.
  • the copolymer of ethylene (B) has a weight average molecular weight Mw of from 10,000 to 50,000 g/mol, more preferably from 15,000 to 40,000 g/mol, still more preferably from 20,000 to 30,000 g/mol, determined by GPC.
  • the copolymer of ethylene is the copolymer of ethylene and polar comonomer units (B) is a copolymer of ethylene and vinyl acetate (EVA), which has a melt flow rate MFR2 of from 200 to 1000 g/10 min, preferably 300 to 800 g/10 min, more preferably 350 to 750 g/ 10 min, and most preferably 400 to 600 g/10 min, determined according to ISO 1133 at 190°C and 2.16 kg.
  • EVA ethylene and vinyl acetate
  • VA vinyl acetate
  • the copolymer of ethylene (B) can be produced in a high pressure polymerization process by means of free radical polymerization.
  • Ethylene-polar comonomer copolymer resins suitable as copolymer of ethylene (B) are also commercially available. These resins are usually already additivated with stabilizer packages. Thus, when using commercially available resins as copolymer of ethylene(B) the addition of additives as described above might have to be adjusted to the already present additives.
  • 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.
  • 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.
  • the terms have well known meanings and indicate the operating level of such cables.
  • 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 article is preferably a cable comprising a semiconductive layer comprising a semiconductive composition, which comprises the polypropylene composition as described above or below.
  • the cable comprises an inner semiconductive layer and/or an outer semiconductive layer comprising a semiconductive composition, which comprises the polypropylene composition as described above or below.
  • the semiconductive layer preferably the inner semiconductive layer and/or an outer semiconductive layer preferably comprises from 90 to 100 wt.-%, preferably from 95 to 100 wt.-%, still more preferably from 99 to 100 wt.-%, based on the total weight of the semiconductive layer, most preferably consists of the semiconductive composition.
  • the semiconductive composition preferably comprises at least 52.0 wt.-%, preferably from 55.0 to 90.0 wt.-%, more preferably from 60.0 to 85.0 wt.-%, most preferably from 65.0 to 80.0 wt.-% of the polypropylene composition and from 5.0 to 40.0 wt.-%, preferably from 10.0 to 38.0 wt.-%, more preferably from 15.0 to 35.0 wt.-%, most preferably from 20.0 to 33.0 wt.-% of carbon black, all based on the total weight amount of the semiconductive composition.
  • the semiconductuve composition can further comprise a polyolefin functionalized with a mono- or polycarboxylic acid compound or a derivative of a mono- or polycarboxylic acid compound.
  • Said functionalized polyolefin is preferably present in an amount of not more than 5.0 wt.-%, preferably from 0.05 to 2.5 wt.-%, more preferably from 0.1 to 1 .0 wt.-%, most preferably from 0.2 to 0.8 wt.-%, based on the total weight amount of the semiconductive composition.
  • any carbon black which is electrically conductive can be used.
  • the carbon black will be a speciality carbon black or a P-type black.
  • suitable carbon blacks include furnace blacks.
  • the carbon black may have a nitrogen adsorption surface area (NSA) of 5 to 400 m 2 /g, for example of 10 to 300 m 2 /g, e.g. of 30 to 200 m 2 /g, when determined according to ASTM D6556-19.
  • NSA nitrogen adsorption surface area
  • the carbon black may have one or more of the following properties: i) a primary particle size of at least 5 nm, for example 5 to 30 nm, preferably 10 to 20 nm which is defined as the average particle diameter according to ASTM D3849-14, ii) iodine adsorption number of at least 10 mg/g, for example 10 to 300 mg/g, preferably 30 to 250 mg/g, more preferably 30 to 200 mg/g, such as 30 to 60 mg/g, or 80 to 140 mg/g, when determined according to ASTM D-1510-19; and/or iii) oil absorption number (OAN) of at least 30 ml/100g, for example 30 to 140 ml/100g, preferably 50 to 130 ml/100g, more preferably 70 to 130 ml/100g, when measured according to ASTM D 2414-19.
  • OAN oil absorption number
  • furnace blacks have a primary particle size of 28 nm or less.
  • Particularly suitable furnace blacks of this category may have an iodine adsorption number between 60 and 300 mg/g. It is further suitable that the oil absorption number (of this category) is between 50 and 225 ml/100g, for example between 50 and 200 ml/100g.
  • suitable carbon blacks can be made by any other process or can be further treated.
  • Suitable carbon blacks for semiconductive cable layers are suitably characterized by their cleanliness. Therefore, suitable carbon blacks have an ashcontent of less than 0.2wt% measured according to ASTM D1506, a 325 mesh sieve residue of less than 30 ppm according to ASTM D1514 and have less than 3 wt.-%, preferably less than 1 wt.-% total sulphur according to ASTMD1619.
  • Furnace carbon black is a generally acknowledged term for the well-known carbon black type that is produced in a furnace-type reactor. As examples of carbon blacks, the preparation process thereof and the reactors, reference can be made to i.a.
  • “Functionalized with a mono- or polycarboxylic acid compound or a derivative of a mono- or polycarboxylic acid compound” or shortly “functionalized” means herein generally that the polymer is functionalized with carbonyl containing groups originating from said mono- or polycarboxylic acid group or a derivative thereof.
  • the carbonyl containing compound used for the functionalization is typically unsaturated. Such compound contains preferably at least one ethylenic unsaturation and at least one carbonyl group.
  • Such carbonyl containing groups can be incorporated to a polymer by grafting a compound bearing said carbonyl containing group(s) or by copolymerising a monomer with a comonomer(s) bearing such carbonyl containing group(s).
  • the functionalized carbonyl containing compound of functionalized polyolefin is understood not to mean any polar comonomer(s), e.g. an acrylate, a methacrylate or an acetate comonomer.
  • the functionalized polyolefin is different from the copolymer of propylene (A) and the copolymer of ethylene (B).
  • the functionalized polyolefins suitable for the present invention are well known and are commercially available or can be produced according to the known processes described in the chemical literature.
  • Preferable polycarboxylic acid compounds for functionalization are unsaturated dicarboxylic acids or derivatives thereof. More preferable carbonyl containing compounds for the functionalization are derivatives of unsaturated mono- or polycarboxylic acid compounds, more preferably derivatives of unsaturated dicarboxylic acids.
  • Preferred carbonyl containing compounds for functionalization are anhydrides of a mono- or polycarboxylic acid, which are also referred as "acid anhydrides” or “anhydrides”.
  • the acid anhydrides can be linear or cyclic.
  • the functionalized polyolefin is an acid anhydride functionalized polyolefin, more preferably a maleic anhydride (MAH) functionalized polyolefin.
  • the functionalized polyolefin is obtainable by grafting maleic anhydride to a polyolefin (also referred herein shortly as MAH grafted polyolefin or MAH-g-polyolefin).
  • Preferred polyolefin for functionalized polyolefin is a functionalized polypropylene or polyethylene. Both polyolefin types are well known in the field.
  • the functionalized polyolefin is a functionalized polyethylene
  • it is preferably selected from a polyethylene produced in a low pressure process using a coordination catalyst or a polyethylene produced in a high pressure (HP) polymerization process and which bears said carbonyl containing groups. Both meanings are well known in the field.
  • the MFR (190°C, 2.16 kg) of the functionalized polyethylene is preferably of above 0.05 g/10 min, preferably from 0.1 to 200 g/20 min, preferably from 0.80 to 100 g/10 min, more preferably from 1.0 to 50.0 g/10 min.
  • the functionalized polyolefin is a functionalized polyethylene produced in a low pressure process using a coordination catalyst, then it is preferably selected from copolymers of ethylene with one or more comonomer(s), preferably alpha-olefin(s).
  • Such polyethylene copolymers have preferably a density of from 850 to 950 kg/m 3 , preferably from 900 to 945 kg/m 3 , preferably from 910 to 940 kg/m 3 .
  • Such functionalized polyethylene copolymer is preferably a functionalized linear low density polyethylene copolymers (LLDPE) which preferably has a density from 915 to 930 kg/m 3 .
  • LLDPE linear low density polyethylene copolymers
  • Preferable LLDPE as functionalized polyolefin is MAH functionalized LLDPE, preferably MAH-g- LLDPE.
  • the functionalized polyolefin is a functionalized polyethylene produced in a HP process
  • the polyethylene is preferably produced by radical polymerization in a HP process in the presence of an initiator(s).
  • the HP reactor can be e.g. a well known tubular or autoclave reactor or a mixture thereof, preferably a tubular reactor.
  • the high pressure (HP) polymerization and the adjustment of process conditions for further tailoring the other properties of the polyolefin depending on the desired end application are well known and described in the literature, and can readily be used by a skilled person.
  • Suitable polymerization temperatures range up to 400 °C, preferably from 80 to 350°C and pressure from 70 MPa, preferably 100 to 400 MPa, more preferably from 100 to 350 MPa.
  • Such functionalized polyethylene produced in a HP process is preferably a low density polyethylene (LDPE) which is functionalized and preferably has a density of from 900 to 950 kg/m 3 , preferably from 910 to 940 kg/m 3 , preferably from 915 to 930 kg/m 3 . More preferably, the functionalized LDPE polymer is selected from a LDPE homopolymer or a LDPE copolymer of ethylene with one or more comonomers (referred herein also as functionalized polar LDPE copolymer), which bears said carbonyl containing groups.
  • LDPE low density polyethylene
  • Suitable comonomers for functionalized LDPE copolymer are selected from olefins, preferably alpha-olefins, or polar comonomers, or any mixtures thereof. As said above such polar comonomers may additionally be present and are differentiated from the carbonyl containing compounds used for the functionalization.
  • Functionalized LDPE copolymer of ethylene with polar comonomer may optionally comprise other comonomer(s), such as alpha-olefin(s).
  • Polar comonomer is preferably selected from a comonomer containing hydroxyl group(s), alkoxy group(s), carbonyl group(s), carboxyl group(s), ether group(s) or ester group(s), or a mixture thereof, more preferably from a comonomer(s) containing carboxyl and/or ester group(s), still more preferably, the polar comonomer(s) is selected from the group of acrylate(s), methacrylate(s) acrylic acids, methacrylic acids or acetate(s), or any mixtures thereof.
  • the polar comonomer(s) for the functionalized polar LDPE copolymer is more preferably selected from the group of alkyl acrylates, alkyl methacrylates, acrylic acids, methacrylic acids or vinyl acetate, or a mixture thereof. It is further preferred that the comonomers are selected from C1- to C6- alkyl acrylates, C1- to C6 -alkyl methacrylates, acrylic acids, methacrylic acids and vinyl acetate, more preferred from C1- to C4- alkyl acrylate such as methyl, ethyl, propyl or butyl acrylate, or vinyl acetate, or any mixture thereof.
  • the amount of the polar comonomer in the functionalized LDPE copolymer is preferably from 5 to 50 wt% based on the total amount of the composition, more preferred up to 30 wt%, most preferred up to 25 wt%.
  • Functionalized LDPE homopolymer or LDPE copolymer is preferably selected from a MAH functionalized LDPE homopolymer, a MAH functionalized LDPE copolymer which is preferably selected from a MAH functionalized ethylene methyl acrylate (EMA), a MAH functionalized ethylene ethyl acrylate (EEA), a MAH functionalized ethylene butyl acrylate (EBA) or MAH functionalized ethyl vinyl acrylate (EVA), more preferably from MAH-g-LDPE homopolymer or MAH-g-LDPE copolymer, more preferably from MAH-g-EMA, MAH-g-EEA, MAH-g-EBA or MAH-g-EVA
  • the functionalized polyolefin is a functionalized polypropylene
  • it is preferably selected from homopolymers of propylene, random copolymers of propylene or a heterophasic copolymer of propylene, which have the same meaning and properties as given above under the general description for the copolymer of propylene (A) and which bear said carbonyl containing groups.
  • Preferred polypropylene is homopolymer or a random copolymer of propylene.
  • the maleic anhydride functionalized, preferably grafted, polyolefin is maleic anhydride functionalized, preferably grafted, polypropylene (MAH-g-PP) or maleic anhydride functionalized, preferably grafted, polyethylene (MAH-g-PE).
  • Preferred polyolefin for the functionalized polyolefin is a functionalized polypropylene as defined above.
  • Such polypropylene (PP) for the functionalized polyolefin is preferably a maleic anhydride functionalized PP, more preferably MAH-g-PP.
  • the functionalized polyolefin more preferably the MAH functionalized PP, more preferably MAH-g-PP, has an MFR2 (230°C, 2.16 kg) of from 0.5 to 500 g/10 min, preferably from 1 .0 to 500 g/10 min.
  • the cable comprising a 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 75.0 kV/mm, preferably from 37.5 to 75.0 kV/mm and most preferably from 40.0 to 75.0 kV/mm, when measured on a 10 kV cable in agreement with CENELEC HD 605 5.4.15.3.4 for 6/10 kV cables.
  • the cable preferably has a Weibull beta-value of from 10.0 to 250.0, preferably from 12.5 to 250.0, most preferably from 15.0 to 250.0, when measured on a 10 kV cable in agreement with CENELEC HD 605 5.4.15.3.4 for 6/10 kV cables.
  • the insulation layer comprising the polypropylene composition according to the invention can be used for medium and high voltage cables.
  • the semiconductive 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 and/or as semiconductive layer 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 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 alphavalue and Weibull beta-value.
  • the addition of the copolymer of ethylene (B) to the polypropylene composition further improves the AC breakdown strength in form of higher Weibull alpha values and Weibull beta values 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.
  • 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.
  • TCE-c 7,2-tetrachloroethane-c/2
  • BHT 2,6-di-tert-butyl-4-methylphenol CAS 128-37-0
  • Cr(acac)3 chromium-(lll)-acetylacetonate
  • the NMR tube was further heated in a rotatory oven until full dissolving of sample.
  • 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, spectral window of approx. 20 ppm and 0.3 Hz line-broadening applied.
  • 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. Characteristic signals corresponding to vinylacetate and aliphatic bulk were observed (A.J. Brandolini, D.D. Hills, “NMR spectra of polymers and polymer additives”, Marcel Deker Inc., 2000) and contents calculated.
  • the vinylacetate (VA) incorporation was quantified using the integral of the signal at 4.9 ppm assigned to the brVA sites, accounting for the number of reporting nuclei per comonomer in various sequences and compensating for a signal from BHT resonating at similar chemical shift:
  • VA IbrVA - BHT
  • the vinylacetate content in mole percent was calculated as:
  • VA [mol%] 100 * fVA
  • the vinylacetate content in weight percent was calculated as:
  • VA [wt%] 100 * ( fVA * 86.09) / ((fVA * 86.09) + ((1- fVA) * 28.05)) Quantification of the total C2 and C3 content in composites
  • the NMR tube was further heated in a rotatory until full dissolving of sample. Upon insertion into the magnet the tube was spun at 10 Hz.
  • Standard single-pulse excitation was employed without NOE, using an 90° tip angle, 10 s recycle delay and a waltz64 decoupling scheme. A total of 1024 (1 k) 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, EVA 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
  • the total amount of C2 and C3 is quantified by introducing the calculated values for vinylacetate (VA) from 1 H NMR results: wt% C2 total 100 wt% C3 total 100 d) Differential scanning calorimetry (DSC) analysis, melting temperature (Tm) and crystallization temperature (Tc): measured with a TA Instrument Q2000 differential scanning calorimetry (DSC) on 5 to 7 mg samples. DSC is run according to ISO 11357 in a heat I cool /heat cycle with a scan rate of 10°C/min in the temperature range of -30°C to +225°C.
  • 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.
  • 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 freguency of 1 Hz. Tg was determined from the curve of the loss angle (tan(b)). f) Xylene cold solubles (XCS) content
  • the guantity of xylene soluble matter in polypropylene is determined according to the ISO16152 (first edition; 2005-07-01).
  • the reduced viscosity (also known as viscosity number), q r ed, and intrinsic viscosity, IV, are determined according to ISO 1628-3: “Determination of the viscosity of polymers in dilute solution using capillary viscometers”.
  • 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: r ⁇ ⁇ ⁇ ⁇ q [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 egual 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 eguation 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
  • the resulting sinusoidal stress response can be given by a 0 and Yo are the stress and strain amplitudes, respectively a) is the angular freguency
  • 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, q', the out-of-phase component of the complex shear viscosity q” and the loss tangent, tan 5 which can be expressed as follows:
  • Shear Thinning Index which correlates with MWD and is independent of Mw
  • the SHI(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.
  • the polydispersity index, PI is defined by equation 10.
  • 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 IEC 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.
  • 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.
  • TEAL triethyl-aluminium
  • D-donor donor dicyclo pentyl dimethoxy silane
  • 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.
  • heterophasic propylene copolymer powder A from the polymerization reaction was compounded in a twin screw extruder together with different stabilizer packages to obtain the polypropylene composition of reference example RE1 .
  • the polypropylene composition RE1 shows 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 11 D 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 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-f- 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.
  • EVA is an ethylene-vinyl acetate copolymer produced as follows:
  • EVA has a melt flow rate MFR 2 (190°C, 2.16 kg) of 500 g/10 min, a vinyl acetate content of 15.0 wt.-%, a melting temperature Tm of 104.6 °C, a crystallization temperature Tc of 63.7°C, a weight average molecular weight Mw of 24,000 g/mol, a number average molecular weight Mn of 6,000 g/mol and a PDI (Mw/Mn) of 4.1.
  • 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 composition for 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.
  • composition for semiconductive layer 2 was prepared from 66.5 wt% of the polypropylene based composition of RE1 with 33.0 wt% of carbon black Printex Alpha, commercially available from Orion Engineered Carbons GmbH and 0.5 maleic anhydride functionalized polypropylene Exxelor P01020, commercially available from Exxon Mobil.
  • Table 6 shows the electric properties of the 10 kV cables of examples C1 and C2 in which the composition for inventive insulation layer IE1 is compared to that for comparative insulation layer CE1.
  • the cable comprising the inventive insulation layer IE1 shows an increased Weibull-alpha value and an increased Weibull-beta value compared to the cable comprising the accordant comparative insulation layer CE1 .

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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

La présente invention concerne une composition de polypropylène comprenant (A) de 80,0 à 99,0 % en poids, par rapport au poids total de la composition de polypropylène, d'un copolymère de propylène et des motifs de comonomère choisis parmi l'éthylène et les alpha-oléfines ayant de 4 à 12 atomes de carbone avec une teneur totale en comonomère de 10,0 à 16,0 % en poids, par rapport au poids total du copolymère de propylène (A) et déterminée par mesure quantitative RMN 13C{1H} ; un indice de fluidité à chaud (MFR2) de 0,5 à 2,5 g/10 min, déterminé selon la norme ISO 1133 à 230 °C et 2,16 kg ; (B) 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, de préférence encore de 30,0 à 42,5 % en poids et idéalement de 32,5 à 40,0 % en poids, sur par rapport à la quantité en poids totale du copolymère de propylène (A) et déterminée selon la norme ISO 16152 ; et de 1,0 à 20,0 % en poids, par rapport au poids total de la composition de polypropylène, d'un copolymère d'éthylène et d'unités de comonomère polaires ayant un indice de fluidité à chaud (MFR2) de plus de 20 à 1000 g/10 min, déterminé selon la norme ISO 1133 à 190° C et 2,16 kg, 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 câbles pour des câbles moyenne et haute tension.
PCT/EP2025/058325 2024-03-28 2025-03-26 Composition de polypropylène pour l'isolation de câbles Pending WO2025202325A1 (fr)

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