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WO2025027124A1 - Copolymère séquencé de farnésène-styrène hydrogéné en tant que modificateur pour compositions de polypropylène - Google Patents

Copolymère séquencé de farnésène-styrène hydrogéné en tant que modificateur pour compositions de polypropylène Download PDF

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Publication number
WO2025027124A1
WO2025027124A1 PCT/EP2024/071791 EP2024071791W WO2025027124A1 WO 2025027124 A1 WO2025027124 A1 WO 2025027124A1 EP 2024071791 W EP2024071791 W EP 2024071791W WO 2025027124 A1 WO2025027124 A1 WO 2025027124A1
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range
polypropylene composition
heterophasic
determined according
iso
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Inventor
Jingbo Wang
Markus Gahleitner
Klaus Bernreitner
Pauli Leskinen
Jani Aho
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Borealis GmbH
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Borealis GmbH
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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
    • 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

Definitions

  • the present invention is directed to a heterophasic polypropylene composition
  • a heterophasic polypropylene composition comprising a heterophasic propylene -ethylene copolymer and a hydrogenated styrene famesene block copolymer
  • Polypropylenes are widely used in various applications such as for packaging and for films. Whilst one strategy for minimizing the impact of polypropylene waste is to use polypropylene compositions suitable for recycling, other strategies involve reducing the amount of polypropylene used to begin with and/or ensuring that the polypropylene articles can be reused, both of which strategies rely far less on complicated recycling infrastmcture. In order to ensure that the ‘reduce’ and ‘reuse’ principles may be applied, it is important to develop compositions having improved properties, in particular mechanical and optical properties, allowing for thinner fdms/moulded articles (helping to reduce the amount of polypropylene used) and helping the resultant articles to maintain their shape/properties in subsequent uses.
  • bio-based polymers such as those derived from plant materials
  • bio-based polymers such as those derived from plant materials
  • styrene-based elastomers like styrene-ethylene-butylene block copolymers (SEBS) may be used as modifiers to improve the properties of polypropylene compositions, with such compositions described in WO 2013/144060 Al, WO 2020/221706 Al, and WO 2020/245251 A2.
  • SEBS styrene-ethylene-butylene block copolymers
  • the present invention is thus based on the finding that hydrogenated styrene famesene block copolymers may be used as modifiers for polypropylenes, thus improving various polymer properties whilst also reducing the olefin-derived (and thus crude oil-derived) content of the resultant compositions.
  • the present invention is directed to a heterophasic polypropylene composition (PC) comprising: a) from 70.0 to 99.0 wt.-%, relative to the total weight of the heterophasic polypropylene composition (PC), of a heterophasic propylene -ethylene copolymer (HECO), having a melt flow rate (MFR2), determined according to ISO 1133 at 230 °C and 2.16 kg, in the range from 1.0 to 100 g/ 10 min, comprising: i) a crystalline matrix (M) being a propylene homo- or copolymer; and ii) an amorphous propylene-ethylene elastomer (E); and b) from 1.0 to 30.0 wt.-%, relative to the total weight of the heterophasic polypropylene composition (PC), of a hydrogenated styrene famesene block copolymer (HSFC); c) optionally, from 0.0001 to 1.0 wt
  • HECO hetero
  • the present invention is directed to articles, more preferably films or moulded articles, comprising at least 90 wt.-%, more preferably at least 95 wt.-%, most preferably at least 98 wt.-% of the heterophasic polypropylene composition (PC) of the first aspect.
  • PC heterophasic polypropylene composition
  • the present invention is directed to a use of a hydrogenated styrene famesene block copolymer (HSFC) for improving the Charpy notched impact strength (NIS(23)), determined according to ISO 179-1 eA at 23 °C on 80* 10x4 mm 3 injection- moulded specimens prepared according to ISO 19069-2, of a polypropylene composition obtained by blending a polypropylene, more preferably the heterophasic propylene-ethylene copolymer (HECO) according to the first aspect, with 1.0 to 30.0 wt.-% of the hydrogenated styrene famesene block copolymer (HSFC).
  • HECO heterophasic propylene-ethylene copolymer
  • the present invention is directed to a use of a hydrogenated styrene famesene block copolymer (HSFC) for improving the haze of a polypropylene composition obtained by blending a polypropylene, more preferably the heterophasic propylene-ethylene copolymer (HECO) according to the first aspect, with 1.0 to 30.0 wt.-% of the hydrogenated styrene famesene block copolymer (HSFC).
  • HECO heterophasic propylene-ethylene copolymer
  • the present invention is directed to a use of a hydrogenated styrene famesene block copolymer (HSFC) for improving the dart drop impact strength (DDI), determined according to ISO 7765-1 on a 50 pm blown film sample, of a polypropylene composition obtained by blending a polypropylene, more preferably the heterophasic propylene-ethylene copolymer (HECO) according to the first aspect, with 1.0 to 30.0 wt.-% of the hydrogenated styrene famesene block copolymer (HSFC).
  • HSFC hydrogenated styrene famesene block copolymer
  • a propylene homopolymer is a polymer that essentially consists of propylene monomer units. Due to impurities especially during commercial polymerization processes, a propylene homopolymer can comprise up to 0. 1 mol-% comonomer units, preferably up to 0.05 mol-% comonomer units and most preferably up to 0.01 mol-% comonomer units.
  • a propylene random copolymer is a copolymer of propylene monomer units and comonomer units, preferably selected from ethylene and C4-C8 alpha-olefins, in which the comonomer units are distributed randomly over the polymeric chain.
  • the propylene random copolymer can comprise comonomer units from one or more comonomers different in their amounts of carbon atoms.
  • Heterophasic propylene copolymers typically comprise: a) a crystalline propylene homopolymer or copolymer matrix (M); and b) an elastomeric rubber, preferably a propylene-ethylene copolymer (E).
  • said crystalline matrix phase is a random copolymer of propylene and at least one alpha-olefin comonomer.
  • the elastomeric phase can be a propylene copolymer with a high amount of comonomer that is not randomly distributed in the polymer chain but is distributed in a comonomer-rich block structure and a propylene -rich block structure.
  • a heterophasic polypropylene usually differentiates from a monophasic propylene copolymer in that it shows two distinct glass transition temperatures Tg which are attributed to the matrix phase and the elastomeric phase.
  • the present invention is directed to a heterophasic polypropylene composition (PC) comprising: a) a heterophasic propyl ene-ethylene copolymer (HECO); b) a hydrogenated styrene famesene block copolymer (HSFC); c) optionally one or more nucleating agents (NU); and d) optionally, one or more further additives (A) different to the one or more nucleating agents (NU).
  • PC heterophasic polypropylene composition
  • HECO heterophasic propyl ene-ethylene copolymer
  • HSFC hydrogenated styrene famesene block copolymer
  • NU optionally one or more nucleating agents
  • A optionally, one or more further additives
  • HECO Heterophasic propylene-ethylene copolymer
  • heterophasic polypropylene composition PC
  • HECO heterophasic propylene-ethylene copolymer
  • the heterophasic propylene-ethylene copolymer is provided in an amount in the range from 70.0 to 99.0 wt.-%, more preferably in the range from 80.0 to 97.0 wt.-%, most preferably in the range from 85.0 to 95.0 wt.-%, relative to the total weight of the heterophasic polypropylene composition (PC).
  • the heterophasic propylene-ethylene copolymer has a melt flow rate (MFR2), determined according to ISO 1133 at 230 °C and 2.16 kg, in the range from 1.0 to 100 g/ 10 min, more preferably in the range from 1.3 to 20 g/10 min, most preferably in the range from 1.5 to 5.0 g/10 min.
  • MFR2 melt flow rate
  • the heterophasic propylene-ethylene copolymer may be characterized according to the CRYSTEX QC method using trichlorobenzene (TCB) as a solvent. This method is described below in the determination methods section.
  • the crystalline fraction (CF) contains for the most part the matrix phase and only a small part of the elastomeric phase and the soluble fraction (SF) contains for the most part the elastomeric phase and only a small part of the matrix phase. In some cases, this method results in more useful data (than for example xylene cold soluble -based methods), since the crystalline fraction (CF) and the soluble fraction (SF) more accurately correspond to the matrix and elastomeric phases respectively.
  • the heterophasic propylene -ethylene copolymer preferably has an ethylene content (C2(total)), determined by FT-IR spectroscopy calibrated by quantitative 13 C-NMR spectroscopy, in the range from 0.3 to 8.0 wt.-%, more preferably in the range from 0.5 to 5.0 wt.-%, most preferably in the range from 1.0 to 2.5 wt.-%.
  • the heterophasic propylene -ethylene copolymer preferably has a soluble fraction (SF) content, determined according to CRYSTEX QC analysis, in the range from 5.0 to 40.0 wt.-%, more preferably in the range from 6.0 to 20.0 wt.-%, most preferably in the range from 7.0 to 10.0 wt.-%.
  • SF soluble fraction
  • the heterophasic propylene -ethylene copolymer preferably has an ethylene content of the soluble fraction (C2(SF)), according to CRYSTEX QC analysis, determined by FT-IR spectroscopy calibrated by quantitative 13 C-NMR spectroscopy, in the range from 10.0 to 90.0 wt.-%, more preferably in the range from 15.0 to 50.0 wt.-%, most preferably in the range from 20.0 to 30.0 wt.-%.
  • the heterophasic propylene -ethylene copolymer preferably has an intrinsic viscosity of the soluble fraction (iV(SF)), determined according to CRYSTEX QC analysis, in the range from 1.20 to 5.00 dL/g, more preferably in the range from 1.50 to 3.50 dL/g, most preferably in the range from 2.00 to 3.00 dL/g.
  • iV(SF) intrinsic viscosity of the soluble fraction
  • the heterophasic propylene -ethylene copolymer preferably has a crystalline fraction (CF) content, determined according to CRYSTEX QC analysis, in the range from 60.0 to 95.0 wt.-%, more preferably in the range from 80.0 to 94.0 wt.-%, most preferably in the range from 90.0 to 93.0 wt.-%.
  • CF crystalline fraction
  • the heterophasic propylene -ethylene copolymer preferably has an ethylene content of the crystalline fraction (C2(CF)), according to CRYSTEX QC analysis, determined by FT-IR spectroscopy calibrated by quantitative 13 C-NMR spectroscopy, in the range from 0.0 to 5.0 wt.-%, more preferably in the range from 0.0 to 3.0 wt.-%, most preferably in the range from 0.0 to 1.0 wt.-%.
  • the heterophasic propylene -ethylene copolymer preferably has an intrinsic viscosity of the crystalline fraction (iV(CF)), determined according to CRYSTEX QC analysis, in the range from 1.50 to 5.00 dL/g, more preferably in the range from 2.00 to 3.50 dL/g, most preferably in the range from 2.30 to 2.80 dL/g.
  • iV(CF) intrinsic viscosity of the crystalline fraction
  • the heterophasic propylene -ethylene copolymer preferably has an intrinsic viscosity (iV), determined according to CRYSTEX QC analysis, in the range from 1.50 to 5.00 dL/g, more preferably in the range from 2.00 to 3.50 dL/g, most preferably in the range from 2.30 to 2.80 dL/g.
  • iV intrinsic viscosity
  • the heterophasic propylene -ethylene copolymer preferably has a melting temperature (T m ), determined by differential scanning calorimetry (DSC), in the range from 149 to 160 °C, more preferably in the range from 151 to 159 °C, most preferably in the range from 153 to 158 °C.
  • T m melting temperature
  • DSC differential scanning calorimetry
  • the heterophasic propylene -ethylene copolymer preferably has an associated melting enthalpy (H m ), determined by differential scanning calorimetry (DSC), in the range from 50 to 120 J/g, more preferably in the range from 70 to 110 J/g, most preferably in the range from 90 to 100 J/g.
  • H m melting enthalpy
  • the heterophasic propylene -ethylene copolymer (HECO) preferably has a crystallization temperature (T c ), determined by differential scanning calorimetry (DSC), in the range from 110 to 130 °C, more preferably in the range from 117 to 129 °C, most preferably in the range from 124 to 128 °C.
  • the heterophasic propylene -ethylene copolymer (HECO) preferably has a first glass transition temperature (T g i), determined according to ISO 6721-7, in the range from -60 to - 35 °C, more preferably in the range from -50 to -37 °C, most preferably in the range from - 45 to -40 °C.
  • the heterophasic propylene -ethylene copolymer preferably has a second glass transition temperature (T g 2), determined according to ISO 6721-7, in the range from -5 to +5 °C, more preferably in the range from -2 to +3 °C, most preferably in the range from 0 to +2 °C.
  • T g 2 second glass transition temperature
  • the heterophasic propylene -ethylene copolymer comprises: i) a crystalline matrix (M) being a propylene homo- or copolymer; and ii) an amorphous propylene-ethylene elastomer (E);
  • the crystalline matrix is preferably a homopolymer.
  • the crystalline matrix component (M) preferably has a melt flow rate (MFRM), determined according to ISO 1133 at 230 °C and 2.16 kg, in the range from 1.0 to 100 g/10 min, more preferably in the range from 1.3 to 20 g/10 min, most preferably in the range from 1.5 to 5.0 g/10 min.
  • MFRM melt flow rate
  • the crystalline matrix component (M) preferably has a content of 2,1 -regiodefects as determined by quantitative 13 C-NMR spectroscopy in the range from 0.05 to 1.20 mol-%, more preferably in the range from 0.20 to 1.00 mol-%, most preferably in the range from 0.40 to 0.80 mol-%. These ranges are typical for polypropylenes polymerized using metallocene catalysts.
  • heterophasic propylene-ethylene copolymer has been polymerized in the presence of a single site catalyst, more preferably a metallocene catalyst.
  • Hydrogenated styrene farnesene block copolymer HSFC
  • a further essential component of the heterophasic polypropylene composition is the hydrogenated styrene famesene block copolymer (HSFC).
  • the hydrogenated styrene famesene block copolymer is provided in an amount in the range from 1.0 to 30.0 wt.-%, more preferably in the range from 3.0 to 20.0 wt.-%, most preferably in the range from 5.0 to 15.0 wt.-%, relative to the total weight of the heterophasic polypropylene composition (PC).
  • the hydrogenated styrene famesene block copolymer preferably has a melt flow rate (MFRio), determined according to ISO 1133 at 230 °C and 10 kg, in the range from 1.0 to 1000 g/10 min, more preferably in the range from 1.0 to 100 g/10 min, most preferably in the range from 20 to 100 g/10 min.
  • MFRio melt flow rate
  • the hydrogenated styrene famesene block copolymer preferably has a Shore A hardness, determined according to ISO 868, in the range from 3 to 30, more preferably in the range from 5 to 23, most preferably in the range from 7 to 15.
  • the hydrogenated styrene famesene block copolymer preferably has a styrene content, determined according to quantitative FT-IR spectroscopy, in the range from 1.0 to 35.0 wt.-%, relative to the total weight of the hydrogenated styrene famesene block copolymer (HSFC), more preferably in the range from 10.0 to 27.0 wt.-%, most preferably in the range from 15.0 to 20.0 wt.-%.
  • NU nucleating agents
  • An optional component of the heterophasic polypropylene composition is one or more nucleating agents (NU).
  • the one or more nucleating agents (NU) are provided in an amount in the range from 0.0001 to 1.0 wt.-%, more preferably in the range from 0.001 to 0.50 wt.-%, most preferably in the range from 0.01 to 0.30 wt.-%, relative to the total weight of the heterophasic polypropylene composition (PC).
  • each nucleating agent can be any nucleating agent suitable for the nucleation of polypropylene. It is further preferred that one or more nucleating agents (NU) are alpha-nucleating agents.
  • At least one of the one or more alpha nucleating agents is a particulate alpha nucleating agent, more preferably a particulate alpha nucleating agent that comprises a compound having a phosphate moiety.
  • At least one of the one or more alpha nucleating agents (NU) is a particulate alpha nucleating agent that comprises a compound selected from the group consisting of sodium di(4-tert-butylphenyl)phosphate, sodium 2,2’-methylene-bis-(4,6-di-tert.butylphenyl) phosphate, lithium 2,2’-methylene-bis-(4,6-di-tert.butylphenyl) phosphate, and aluminium hydroxybis[2,2’methylene-bis(4,6-di-tert-butylphenyl)phosphate].
  • At least one of the one or more alpha nucleating agents (NU) comprises lithium 2,2’-methylene-bis-(4,6-di-tert.butylphenyl) phosphate.
  • particulate alpha nucleating agents may be present either as a single compound or as a particulate blend.
  • One such particulate blend that contains lithium 2,2’-methylene-bis-(4,6-di-tert.butylphenyl) phosphate as the major component is ADK STAB NA-71, commercially available from Adeka Corp.
  • One or more further additives (A)
  • Another optional component of the heterophasic polypropylene composition (PC) is one or more further additives (A) different to the one or more nucleating agents (NU).
  • the one or more further additives (A) are provided in a total amount in the range from 0.01 to 5.0 wt.-%, relative to the total weight of the heterophasic polypropylene composition (PC).
  • the one or more further additives (A) may be selected from the group consisting of antioxidants, stabilizers, fillers, colorants, and antistatic agents.
  • An example of such a carrier polymer would be a polypropylene homopolymer in the form of powder.
  • the heterophasic polypropylene composition (PC) comprises, more preferably consists of: a) from 70.0 to 99.0 wt.-%, more preferably from 80.0 to 97.0 wt.-%, most preferably from 85.0 to 95.0 wt.-%, relative to the total weight of the heterophasic polypropylene composition (PC), of the heterophasic propylene-ethylene copolymer (HECO); b) from 1.0 to 30.0 wt.-%, more preferably from 3.0 to 20.0 wt.-%, most preferably from 5.0 to 15.0 wt.-%, relative to the total weight of the heterophasic polypropylene composition (PC), of the hydrogenated styrene famesene block copolymer (HSFC); c) optionally, from 0.0001 to 1.0 wt.-%, more preferably in the range from 0.001 to 0.50 wt.-%, most preferably in the range from 0.01 to 0.30 wt
  • the heterophasic polypropylene composition (PC) comprises: a) from 70.0 to 99.0 wt.-%, more preferably from 80.0 to 97.0 wt.-%, most preferably from 85.0 to 95.0 wt.-%, relative to the total weight of the heterophasic polypropylene composition (PC), of the heterophasic propylene-ethylene copolymer (HECO); b) from 1.0 to 30.0 wt.-%, more preferably from 3.0 to 20.0 wt.-%, most preferably from 5.0 to 15.0 wt.-%, relative to the total weight of the heterophasic polypropylene composition (PC), of the hydrogenated styrene famesene block copolymer (HSFC); c) optionally, from 0.0001 to 1.0 wt.-%, more preferably in the range from 0.001 to 0.50 wt.-%, most preferably in the range from 0.01 to 0.30 wt.-
  • the heterophasic polypropylene composition (PC) comprises, more preferably consists of: a) from 80.0 to 97.0 wt.-%, relative to the total weight of the heterophasic polypropylene composition (PC), of the heterophasic propylene-ethylene copolymer (HECO); b) from 3.0 to 20.0 wt.-%, relative to the total weight of the heterophasic polypropylene composition (PC), of the hydrogenated styrene famesene block copolymer (HSFC); c) optionally, from 0.001 to 0.50 wt.-%, relative to the total weight of the heterophasic polypropylene composition (PC), of one or more nucleating agents (NU); and d) optionally, from 0.01 to 5.0 wt.-%, relative to the total weight of the heterophasic polypropylene composition (PC), of one or more further additives (A) different to the one or more nucleating agents (NU).
  • HECO heterophasic
  • the heterophasic polypropylene composition (PC) comprises, more preferably consists of: a) from 85.0 to 95.0 wt.-%, relative to the total weight of the heterophasic polypropylene composition (PC), of the heterophasic propylene-ethylene copolymer (HECO); b) from 5.0 to 15.0 wt.-%, relative to the total weight of the heterophasic polypropylene composition (PC), of the hydrogenated styrene famesene block copolymer (HSFC); c) optionally, from 0.01 to 0.30 wt.-%, relative to the total weight of the heterophasic polypropylene composition (PC), of one or more nucleating agents (NU); and d) optionally, from 0.01 to 5.0 wt.-%, relative to the total weight of the heterophasic polypropylene composition (PC), of one or more further additives (A) different to the one or more nucleating agents (NU).
  • HECO heterophasic poly
  • the heterophasic polypropylene composition (PC) comprises, more preferably consists of: a) from 70.0 to 99.0 wt.-%, more preferably from 80.0 to 97.0 wt.-%, most preferably from 85.0 to 95.0 wt.-%, relative to the total weight of the heterophasic polypropylene composition (PC), of the heterophasic propylene-ethylene copolymer (HECO); and b) from 1.0 to 30.0 wt.-%, more preferably from 3.0 to 20.0 wt.-%, most preferably from 5.0 to 15.0 wt.-%, relative to the total weight of the heterophasic polypropylene composition (PC), of the hydrogenated styrene famesene block copolymer (HSFC).
  • PC hydrogenated styrene famesene block copolymer
  • the heterophasic polypropylene composition (PC) comprises, more preferably consists of: a) from 70.0 to 98.9999 wt.-%, more preferably from 80.0 to 96.999 wt.-%, most preferably from 85.0 to 94.99 wt.-%, relative to the total weight of the heterophasic polypropylene composition (PC), of the heterophasic propylene -ethylene copolymer (HECO); b) from 1.0 to 29.9999 wt.-%, more preferably from 3.0 to 19.999 wt.-%, most preferably from 5.0 to 14.99 wt.-%, relative to the total weight of the heterophasic polypropylene composition (PC), of the hydrogenated styrene famesene block copolymer (HSFC); and c) from 0.0001 to 1.0 wt.-%, more preferably in the range from 0.001 to 0.50 wt.-%, most preferably in the range from 0.
  • the heterophasic polypropylene composition (PC) comprises, more preferably consists of: a) from 70.0 to 98.99 wt.-%, more preferably from 80.0 to 96.99 wt.-%, most preferably from 85.0 to 94.99 wt.-%, relative to the total weight of the heterophasic polypropylene composition (PC), of the heterophasic propylene-ethylene copolymer (HECO); b) from 1.0 to 29.9 wt.-%, more preferably from 3.0 to 19.9 wt.-%, most preferably from 5.0 to 14.9 wt.-%, relative to the total weight of the heterophasic polypropylene composition (PC), of the hydrogenated styrene famesene block copolymer (HSFC); and c) from 0.01 to 5.0 wt.-%, relative to the total weight of the heterophasic polypropylene composition (PC), of one or more further additives (A) different to
  • the heterophasic polypropylene composition (PC) comprises, more preferably consists of: a) from 70.0 to 98.9899 wt.-%, more preferably from 80.0 to 96.989 wt.-%, most preferably from 85.0 to 94.98 wt.-%, relative to the total weight of the heterophasic polypropylene composition (PC), of the heterophasic propylene-ethylene copolymer (HECO); b) from 1.0 to 29.9899 wt.-%, more preferably from 3.0 to 19.989 wt.-%, most preferably from 5.0 to 14.89 wt.-%, relative to the total weight of the heterophasic polypropylene composition (PC), of the hydrogenated styrene famesene block copolymer (HSFC); c) from 0.0001 to 1.0 wt.-%, more preferably in the range from 0.001 to 0.50 wt.-%, most preferably
  • the sum of the individual contents of the heterophasic propylene -ethylene copolymer (HECO), the hydrogenated styrene famesene block copolymer (HSFC), the optional one or more nucleating agents (NU), and the optional further additive different to the one or more nucleating agents (NU) preferably add up to at least 90 wt.-%, more preferably at least 95 wt.-%, yet more preferably at least 98 wt.-%.
  • the heterophasic polypropylene composition consists of the heterophasic propylene -ethylene copolymer (HECO), the hydrogenated styrene fame sene block copolymer (HSFC), the optional one or more nucleating agents (NU), and the optional one or more further additives different to the one or more nucleating agents (NU).
  • HECO heterophasic propylene -ethylene copolymer
  • HSFC hydrogenated styrene fame sene block copolymer
  • NU optional one or more nucleating agents
  • further additives different to the one or more nucleating agents (NU).
  • the heterophasic polypropylene composition preferably has a melt flow rate (MFR2), determined according to ISO 1133 at 230 °C and 2.16 kg, in the range from 1.0 to 100 g/ 10 min, more preferably in the range from 1.3 to 20 g/10 min, most preferably in the range from 1.5 to 5.0 g/10 min.
  • MFR2 melt flow rate
  • the heterophasic polypropylene composition (PC) preferably has a melting temperature (T m ), determined by differential scanning calorimetry (DSC), in the range from 149 to 160 °C, more preferably in the range from 151 to 159 °C, most preferably in the range from 153 to 158 °C.
  • the heterophasic polypropylene composition (PC) preferably has an associated melting enthalpy (H m ), determined by differential scanning calorimetry (DSC), in the range from 50 to 120 J/g, more preferably in the range from 70 to 105 J/g, most preferably in the range from 85 to 95 J/g.
  • the heterophasic polypropylene composition preferably has a crystallization temperature (T c ), determined by differential scanning calorimetry (DSC), in the range from 110 to 130 °C, more preferably in the range from 117 to 129 °C, most preferably in the range from 124 to 128 °C.
  • T c crystallization temperature
  • the heterophasic polypropylene composition (PC) preferably has a first glass transition temperature (T g i), determined according to ISO 6721 -7, in the range from -70 to -55 °C, more preferably in the range from -67 to -58 °C, most preferably in the range from -64 to -61 °C.
  • T g i first glass transition temperature
  • the heterophasic polypropylene composition (PC) preferably has a second glass transition temperature (T g 2), determined according to ISO 6721 -7, in the range from -50 to -34 °C, more preferably in the range from -46 to -36 °C, most preferably in the range from -43 to -38 °C.
  • T g 2 second glass transition temperature
  • the heterophasic polypropylene composition preferably has a third glass transition temperature (T g s), determined according to ISO 6721 -7, in the range from -5 to +5 °C, more preferably in the range from -2 to +3 °C, most preferably in the range from 0 to +3 °C.
  • T g s third glass transition temperature
  • first glass transition temperature (T g i)”, “second glass transition temperature (T g2 )”, and “third glass transition temperature (Tgs)” merely mean that the heterophasic polypropylene composition has to have a glass transition temperature in the given range, not that the glass transition temperature in that range has to be the first/second/third highest or first/second/third lowest glass transition temperature of the composition.
  • first glass transition temperature (T g i) the glass transition temperature in that range has to be the first/second/third highest or first/second/third lowest glass transition temperature of the composition.
  • the heterophasic polypropylene composition preferably has a shear storage modulus (G’), determined according to ISO 6721, in the range from 400 to 1000 MPa, more preferably in the range from 450 to 800 MPa, most preferably in the range from 500 to700 MPa.
  • G shear storage modulus
  • the heterophasic polypropylene composition preferably has a flexural modulus, determined according to ISO 178 on 80x 10x4 mm 3 injection-moulded specimens prepared according to ISO 19069-2, in the range from 800 to 2000 MPa, more preferably in the range from 900 to 1700 MPa, most preferably in the range from 1000 to 1500 MPa.
  • the heterophasic polypropylene composition preferably has a Charpy Notched Impact Strength (NIS(23)) measured according to ISO 179-1 eA at 23 °C on 80x 10x4 mm 3 injection-moulded specimens prepared according to ISO 19069-2, in the range from 20 to 100 kJ/m 2 , more preferably in the range from 30 to 90 kJ/m 2 , most preferably in the range from 50 to 80 kJ/m 2 .
  • NIS(23) Charpy Notched Impact Strength
  • the heterophasic polypropylene composition (PC) preferably has a haze value, determined according to ASTM D 1003 on a plaque with a thickness of 1 mm, in the range from 5 to 30%, more preferably in the range from 10 to 26%, most preferably in the range from 15 to 23%.
  • the heterophasic polypropylene composition (PC) preferably has a haze value, determined according to ASTM D 1003 on a 50 pm blown film sample, in the range from 0.1 to 6.0%, more preferably in the range from 1.0 to 5.0%, most preferably in the range from 2.0 to 4.8%.
  • the heterophasic polypropylene composition preferably has a dart drop impact strength (DDI), measured according to ISO 7765-1 on a 50 pm blown film sample, in the range from 200 to 700 g, more preferably in the range from 250 to 600 g, most preferably in the range from 300 to 500 g.
  • DMI dart drop impact strength
  • the heterophasic polypropylene composition preferably has a sealing initiation temperature (SIT), determined according to the method as described in the determination methods, in the range from 128 to 138 °C, more preferably in the range from 130 to 137 °C, most preferably in the range from 132 to 136 °C.
  • SIT sealing initiation temperature
  • the heterophasic polypropylene composition preferably has a tensile modulus in the machine direction (TM-MD), determined according to ISO 527-3on a 50 pm blown fdm sample, in the range in the range from 1000 to 2000 MPa, more preferably in the range from 1200 to 1800 MPa, most preferably in the range from 1300 to 1500 MPa.
  • TM-MD machine direction
  • the heterophasic polypropylene composition preferably has a tensile modulus in the transverse direction (TM-TD), determined according to ISO 527-3on a 50 pm blown fdm sample, in the range in the range from 800 to 2000 MPa, more preferably in the range from 1000 to 1700 MPa, most preferably in the range from 1100 to 1400 MPa.
  • TM-TD tensile modulus in the transverse direction
  • the present invention is directed to articles, more preferably films or moulded articles, comprising at least 90 wt.-%, more preferably at least 95 wt.-%, most preferably at least 98 wt.-% of the heterophasic polypropylene composition (PC) of the first aspect.
  • PC heterophasic polypropylene composition
  • the article of the second aspect is a moulded article.
  • the article of the second aspect is a film, more preferably a blown film.
  • the film of this embodiment preferably has a haze value, determined according to ASTM D 1003, in the range from 0.1 to 6.0%, more preferably in the range from 1.0 to 5.0%, most preferably in the range from 2.0 to 4.8%.
  • the film of this embodiment preferably has a dart drop impact strength (DDI), measured according to ISO 7765-1, in the range from 200 to 700 g, more preferably in the range from 250 to 600 g, most preferably in the range from 300 to 500 g.
  • DMI dart drop impact strength
  • the film of this embodiment preferably has a sealing initiation temperature (SIT), determined according to the method as described in the determination methods, in the range from 128 to 138 °C, more preferably in the range from 130 to 137 °C, most preferably in the range from 132 to 136 °C.
  • SIT sealing initiation temperature
  • the film of this embodiment preferably has a tensile modulus in the machine direction (TM- MD), determined according to ISO 527-3, in the range in the range from 1000 to 2000 MPa, more preferably in the range from 1200 to 1800 MPa, most preferably in the range from 1300 to 1500 MPa.
  • TM- MD machine direction
  • the film of this embodiment preferably has a tensile modulus in the transverse direction (TM-TD), determined according to ISO 527-3, in the range in the range from 800 to 2000 MPa, more preferably in the range from 1000 to 1700 MPa, most preferably in the range from 1100 to 1400 MPa.
  • TM-TD transverse direction
  • the present invention is directed to a use of a hydrogenated styrene famesene block copolymer (HSFC) for improving the Charpy notched impact strength (NIS(23)), determined according to ISO 179-1 eA at 23 °C on 80* 10x4 mm 3 injection- moulded specimens prepared according to ISO 19069-2, of a polypropylene composition obtained by blending a polypropylene with 1.0 to 30.0 wt.-% of the hydrogenated styrene famesene block copolymer (HSFC).
  • HSFC hydrogenated styrene famesene block copolymer
  • the Charpy notched impact strength (NIS(23)) of the polypropylene composition comprising 1.0 to 30.0 wt.-% of the hydrogenated styrene famesene block copolymer (HSFC) is at least 100% higher, more preferably at least 200% higher, most preferably at least 300% higher than an analogous polypropylene composition without the hydrogenated styrene famesene block copolymer (HSFC).
  • the present invention is directed to a use of a hydrogenated styrene famesene block copolymer (HSFC) for improving the haze of a polypropylene composition obtained by blending a polypropylene with 1.0 to 30.0 wt.-% of the hydrogenated styrene famesene block copolymer (HSFC).
  • HSFC hydrogenated styrene famesene block copolymer
  • the use of the fourth aspect improves the haze of the polypropylene composition, as determined according to ASTM D 1003 on a plaque with a thickness of 1 mm.
  • the haze value of the polypropylene composition comprising 1.0 to 30.0 wt.-% of the hydrogenated styrene famesene block copolymer (HSFC) is at least 20% lower, more preferably at least 30% lower, most preferably at least 40% lower than an analogous polypropylene composition without the hydrogenated styrene famesene block copolymer (HSFC).
  • the use of the fourth aspect improved the haze of the polypropylene composition, as determined according to ASTM D 1003 on a 50 pm blown film sample.
  • the haze value of the polypropylene composition comprising 1.0 to 30.0 wt.-% of the hydrogenated styrene famesene block copolymer (HSFC) is at least 10% lower, more preferably at least 20% lower, most preferably at least 30% lower than an analogous polypropylene composition without the hydrogenated styrene famesene block copolymer (HSFC).
  • the present invention is directed to a use of a hydrogenated styrene famesene block copolymer (HSFC) for improving the dart drop impact strength (DDI), determined according to ISO 7765-1 on a 50 pm blown film sample, of a polypropylene composition obtained by blending a polypropylene with 1.0 to 30.0 wt.-% of the hydrogenated styrene famesene block copolymer (HSFC).
  • HSFC hydrogenated styrene famesene block copolymer
  • the dart drop impact strength (DDI) of the polypropylene composition comprising 1.0 to 30.0 wt.-% of the hydrogenated styrene famesene block copolymer (HSFC) is at least 200% higher, more preferably at least 350% higher, most preferably at least 500% higher than an analogous polypropylene composition without the hydrogenated styrene famesene block copolymer (HSFC).
  • the polypropylene is preferably a heterophasic propylene -ethylene copolymer, more preferably the heterophasic propyleneethylene copolymer (HECO) of the first aspect.
  • HECO heterophasic propyleneethylene copolymer
  • the hydrogenated styrene famesene block copolymer is preferably the hydrogenated styrene famesene block copolymer (HSFC) of the first aspect.
  • the resultant polypropylene composition of each of the third, fourth and fifth aspects is preferably the heterophasic polypropylene composition (PC) of the first aspect.
  • NMR nuclear-magnetic resonance
  • the NMR tube was further heated in a rotatary oven for at least 1 hour. Upon insertion into the magnet the tube was spun at 10 Hz.
  • This setup was chosen primarily for the high resolution and quantitatively needed for accurate ethylene content quantification. Standard single-pulse excitation was employed without NOE, using an optimised tip angle, 1 s recycle delay and a bi-level WALTZ 16 decoupling scheme ⁇ zhou07,busico07 ⁇ . A total of 6144 (6k) transients were acquired per spectra.
  • Quantitative 13 C ⁇ ’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.
  • EEE ethylene block
  • Characteristic signals corresponding to the incorporation of ethylene were observed ⁇ wangOO, cheng84, randall89 ⁇ .
  • the comonomer fraction was quantified using the method of Wang et. al. ⁇ wangOO ⁇ through integration of multiple signals across the whole spectral region in the 3 C ⁇ ' 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.
  • Characteristic signals corresponding to regiodefects were observed ⁇ resconiOO, wangOO ⁇ .
  • the presence of isolated 2,1-erythro regiodefects was indicated by the presence of the two methyl sites at 17.7 and 17.2 ppm and confirmed by other characteristic sites.
  • the presence of 2,1 regiodefect adjacent an ethylene unit was indicated by the two inequivalent Sa signals at 34.9 ppm and 34.7 ppm respectively and the Tyy at 34.1 ppm.
  • the amount of isolated 2,1-erythro regiodefects was quantified using the average integral of the two characteristic methyl sites at 17.7 (I e s) and 17.4 (I e e) ppm respectively:
  • the amount of 2, 1 regiodefect adjacent to ethylene (PE2I) was quantified using the methine site at 34.1 ppm (I Tyy ):
  • PE21 IT-H
  • the total amount of propene (Ptotai) was quantified based on the methyl region (ICHS) between 23.0 and 19.9 ppm with correction undertaken for sites included in this region not related to propene insertion.
  • the methyl group P prop resulting from 2,1 regiodefect adjacent to ethylene was already present in ICHS: Ptotai IcH3 + 2 * ?21e isolated
  • the isolated 2, 1-erythro regiodefects (P2ie isolated) was multiplied by 2 to take into account the two (2) propene units in the 2, 1-erythro regiodefects.
  • the total amount of 2,1 defects was quantified as following:
  • the IR4 detector was a multiple wavelength detector measuring IR absorbance at two different bands (CH 3 stretching vibration (centred at app. 2960 cm 1 ) and the CH stretching vibration (2700-3000 cm 1 ) that serve for the determination of the concentration and the Ethylene content in Ethylene -Propylene copolymers.
  • the IR4 detector was calibrated with series of 8 EP copolymers with known Ethylene content in the range of 2 wt.-% to 69 wt.-% (determined by 13 C-NMR) and each at various concentrations, in the range of 2 and 13mg/ml. To encounter for both features, concentration and ethylene content at the same time for various polymer concentrations expected during Crystex analyses the following calibration equations were applied:
  • the CHs/lOOOC was converted to the ethylene content in wt.-% using following relationship:
  • the samples to be analyzed were weighed out in concentrations of lOmg/ml to 20mg/ml. To avoid injecting possible gels and/or polymers which do not dissolve in TCB at 160 °C, like PET and PA, the weighed out sample was packed into a stainless steel mesh MW 0, 077/D 0,05mmm.
  • the melt flow rate was determined according to ISO 1133 and was indicated in g/10 min.
  • the MFR is an indication of the flowability, and hence the processability, of the polymer. The higher the melt flow rate, the lower the viscosity of the polymer.
  • the MFR2 of polypropylene was determined at a temperature of 230 °C and a load of 2.16 kg.
  • the MFR10 of the hydrogenated styrene famesene block copolymer was determined at a temperature of 230 °C and a load of 10 kg.
  • the xylene soluble fraction at room temperature (XCS, wt.-%): The amount of the polymer soluble in xylene was determined at 25 °C according to ISO 16152; 5 th edition; 2005-07-01.
  • the styrene content was measured by Fourier transform infrared spectroscopy (FTIR).
  • FTIR Fourier transform infrared spectroscopy
  • a thin film of 300 pm thickness was prepared from pelletized material by hot-pressing (190 °C, 100 bar, 1 minute). Per sample, two films were prepared. The so prepared film-samples were measured by a Perkin Elmer IR-Spectrophotometer System 2000FTIR. The peak at 1602 cm' 1 (Phenyl-Absorption) was integrated and evaluated by using an internally established calibration curve. The arithmetic mean of two measurements was given as result.
  • Shore hardness was determined according to ISO 868.
  • DSC was run according to ISO 11357 / part 3 /method C2 in a heat / cool / heat cycle with a scan rate of 10 °C/min in the temperature range of -30 to +225 °C.
  • Crystallization temperature (T c ) and crystallization enthalpy (H c ) were determined from the cooling step, while melting temperature (T m ) and melting enthalpy (H m ) were determined from the second heating step.
  • the glass transition temperature Tg and storage modulus G’ at 23 °C were determined by dynamic mechanical analysis according to ISO 6721-7. The measurements were done in torsion mode on compression moulded samples (40x10x1 mm 3 ) between -100 °C and +150 °C with a heating rate of 2 °C/min and frequency of 1 Hz.
  • the Flexural Modulus was determined according 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.
  • the Charpy notched impact strength (NIS) was measured according to ISO 179 leA at +23 °C or -20 °C, using injection moulded bar test specimens of 80x 10x4 mm 3 prepared in accordance with ISO 19069-2 using a melt temperature of 230 °C for all materials irrespective of material melt flow rate.
  • Tensile modulus in machine and transverse direction were determined according to ISO 527-3 at 23°C on monolayer blown films with a thickness of 50 qm produced as indicated below. Testing was performed at a cross head speed of 1 mm/min. Haze was determined according to ASTM D 1003 on blown films with a thickness of 50 gm produced as indicated below (haze(film)) or on plaques with dimensions 60 x 60 x 1 mm 3 produced by injection moulding in line with ISO 19069-2 (haze(plaque)).
  • This test method covers the determination of the energy that causes films to fail under specified conditions of impact of a free-falling dart from a specified height that would result in failure of 50 % of the specimens tested (Staircase method A).
  • a uniform missile mass increment was employed during the test and the missile weight was decreased or increased by the uniform increment after test of each specimen, depending upon the result (failure or no failure) observed for the specimen.
  • DDI per unit thickness was calculated by dividing DDI (in gram) to the thickness of film (in micron)
  • sealing window sealing temperature range
  • the procedure is similar to Hot-Tack test and was conducted in the same machine.
  • the sealing range determined corresponds to the strength of the seal after it had cooled down (a delay time of 30 s).
  • the conditions used were as follows: • Sealing time (I s)
  • Sealing range (Seal initiation temperature until seal end temperature)
  • the determined results provide a quantitatively useful indication of the sealing strength of the fdms and indicate the temperature range for optimal sealing.
  • the lower limit (Sealing Initiation Temperature - SIT) is the sealing temperature at which a sealing average force of 5 N is measured.
  • the upper limit (Sealing End Temperature - SET) is identified as the first sealing temperature where at least two specimens showed a bum- through failure mode.
  • the maximum sealing force corresponds to the highest measured sealing force.
  • the temperature interval was set by default to 5 °C, but can be reduced to 1 °C when the curve shows a sharp increase or decrease in the force values between two temperature steps. This was done in order to represent a better curve profile.
  • the catalyst system used for polymerization of the heterophasic propylene-ethylene copolymer corresponds to ICS4 of WO 2020/239598 Al, which contains the metallocene compound rac-anti-dimethylsilanediyl[2-methyl-4,8-bis(3’,5’-dimethyl phenyl)- 1 ,5,6,7-tetrahydro-s-indacen-l-yl][2-methyl-4-(3’,5’-dimethylphenyl)-5-methoxy-6-tert- butylinden- 1 -yl] zirconium dichloride .
  • Table 1 Polymerization conditions of the heterophasic propylene -ethylene copolymer
  • the crystalline matrix of the HECO has a content of 2,1 -regiodefects of 0.69 mol-%.
  • HECO was compounded in a co-rotating twin-screw extruder Coperion ZSK 47 at 220 °C with 0.05 wt.-% of pentaerythrityl-tetrakis(3-(3’,5’-di-tert. butyl-4-hydroxyphenyl)-propionate (available as Irganox 1010 from BASF AG, Germany; CAS-no.
  • 0.05 wt.-% oftris (2,4-di-t-butylphenyl) phosphite available as Irgafos 168 from BASF AG, Germany; CAS- no. 31570-04-4); 0.03 wt.-% of synthetic hydrotalcite (available as Hycite 713 from BASF AG, Germany; CAS-no. 11097-59-9); and 0.10 wt.-% of a nucleating agent (available as ADK Stab NA-71 from Adeka Corporation, Germany; CAS-no (of main component) 85209-93-4).
  • HSFC a hydrogenated styrene famesene block copolymer, commercially available under the tradename SEPTON SF902 from Kuraray Europe (DE), having an MFRio (230 °C, 10 kg) of 55 g/10 min, a styrene content of 18 wt.-% and a Shore A hardness of 8.
  • SEBS a styrene-ethylene-butylene triblock copolymer, commercially available under the tradename G1645MO from Kraton (USA), having an MFR 2 (230 °C, 2.16 kg) in the range from 2.0 to 4.5 g/10 min, a styrene content in the range from 11.5 to 13.5 wt.- % and a Shore A hardness of 35.
  • inventive and comparative compositions were prepared according to the recipes indicated in Table 2 by compounding in a co-rotating twin-screw extruder Coperion ZSK 18 at 210 °C at a rate of 7 kg/h.
  • compositions were either measured directly on specimens prepared from the composition (as appropriate for the given determination method provided above) or on a 50 pm blown film prepared on a Collin blown film lab line, with a film thickness of 50 pm, a blow up ratio of 1:2.5, and a take off speed of 6.1 m/min.
  • Table 2 Recipes and properties of inventive and comparative compositions were either measured directly on specimens prepared from the composition (as appropriate for the given determination method provided above) or on a 50 pm blown film prepared on a Collin blown film lab line, with a film thickness of 50 pm, a blow up ratio of 1:2.5, and a take off speed of 6.1 m/min.
  • the SEBS and the HSFC lower the Flexural Modulus (of the composition) and the Tensile Modulus (of the films both in MD and TD)
  • the reduction is less severe for the HSFC modifier, relative to the SEBS modifier, meaning that both the stiffness and the impact strength is better for IE1 than CE2, which is a particularly notable effect, given that an improvement in stiffness is usually accompanied by a drop in impact strength (and vice versa).
  • the HSFC-modified compositions are suitable both for producing films and moulded articles.

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Abstract

L'invention concerne une composition de polypropylène hétérophasique (PC) comprenant : a) de 70,0 à 99,0 % en poids d'un HECO, ayant un MFR2 de 1,0 à 100 g/10 min, b) de 1,0 à 30,0 % en poids, d'un copolymère séquencé de farnésène-styrène hydrogéné (HSFC) ; c) éventuellement, de 0,0001 à 1,0 % en poids d'un ou de plusieurs agents de nucléation (NU) ; et d) éventuellement, de 0,01 à 5,0 % en poids d'un ou de plusieurs autres additifs (A) différents du ou des agents de nucléation (NU).
PCT/EP2024/071791 2023-08-01 2024-08-01 Copolymère séquencé de farnésène-styrène hydrogéné en tant que modificateur pour compositions de polypropylène Pending WO2025027124A1 (fr)

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Citations (7)

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Publication number Priority date Publication date Assignee Title
WO2013144060A1 (fr) 2012-03-29 2013-10-03 Borealis Ag Polypropylène souple à propriétés optiques améliorées
EP2980153A1 (fr) * 2013-09-30 2016-02-03 Kuraray Co., Ltd. Composition élastomère thermoplastique et corps moulé
WO2020221706A1 (fr) 2019-04-29 2020-11-05 Borealis Ag Composition de polypropylène souple à comportement optique amélioré
WO2020239598A1 (fr) 2019-05-29 2020-12-03 Borealis Ag Préparation améliorée d'un système de catalyseur
WO2020245251A2 (fr) 2019-06-05 2020-12-10 Borealis Ag Film en polypropylène multicouche
EP4055103A1 (fr) * 2019-11-06 2022-09-14 Borealis AG Composition de copolymère d'éthylène-propylène hétérophasique présentant un équilibre souhaitable de propriétés mécaniques
EP4194503A1 (fr) * 2021-12-13 2023-06-14 Borealis AG Mélange de copolymère hétérophasique aléatoire de propylène-éthylène/copolymère propylène-butylène

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Publication number Priority date Publication date Assignee Title
WO2013144060A1 (fr) 2012-03-29 2013-10-03 Borealis Ag Polypropylène souple à propriétés optiques améliorées
EP2980153A1 (fr) * 2013-09-30 2016-02-03 Kuraray Co., Ltd. Composition élastomère thermoplastique et corps moulé
WO2020221706A1 (fr) 2019-04-29 2020-11-05 Borealis Ag Composition de polypropylène souple à comportement optique amélioré
WO2020239598A1 (fr) 2019-05-29 2020-12-03 Borealis Ag Préparation améliorée d'un système de catalyseur
WO2020245251A2 (fr) 2019-06-05 2020-12-10 Borealis Ag Film en polypropylène multicouche
EP4055103A1 (fr) * 2019-11-06 2022-09-14 Borealis AG Composition de copolymère d'éthylène-propylène hétérophasique présentant un équilibre souhaitable de propriétés mécaniques
EP4194503A1 (fr) * 2021-12-13 2023-06-14 Borealis AG Mélange de copolymère hétérophasique aléatoire de propylène-éthylène/copolymère propylène-butylène

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