WO2022120648A1 - Compositions de polyoléfine remplies de fibres de verre à faibles retrait et gauchissement - Google Patents

Compositions de polyoléfine remplies de fibres de verre à faibles retrait et gauchissement Download PDF

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WO2022120648A1
WO2022120648A1 PCT/CN2020/134973 CN2020134973W WO2022120648A1 WO 2022120648 A1 WO2022120648 A1 WO 2022120648A1 CN 2020134973 W CN2020134973 W CN 2020134973W WO 2022120648 A1 WO2022120648 A1 WO 2022120648A1
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range
polyolefin composition
composition
ethylene copolymer
heco
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PCT/CN2020/134973
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English (en)
Inventor
Rock ZHU
Jenny PAN
Emily QIANG
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Borouge Compounding Shanghai Co., Ltd.
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Priority to PCT/CN2020/134973 priority Critical patent/WO2022120648A1/fr
Publication of WO2022120648A1 publication Critical patent/WO2022120648A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay

Definitions

  • the present invention relates to a polyolefin composition
  • a polyolefin composition comprising a heterophasic propylene-ethylene copolymer, glass fibers, an inorganic filler, a polar-modified polypropylene and additives, as well as articles comprising said compositions.
  • Polypropylene is a material used in a wide variety of technical fields, and reinforced polypropylenes have in particular gained relevance in fields previously exclusively relying on non-polymeric materials, in particular metals.
  • reinforced polypropylenes are glass fiber reinforced polypropylenes. Such materials enable a tailoring of the properties of the composition by selecting the type of polypropylene, the amount of glass fiber and sometimes by selecting the type of coupling agent used. Furthermore, these materials are often more cost effective than alternative, highly engineered plastics. Accordingly, glass-fiber reinforced polypropylene is now a well-established material for applications requiring good mechanical properties such as high stiffness and thermal stability, for example in automotive exterior parts.
  • polypropylene compositions in automotive exterior parts are known to warp slightly after the molding process.
  • glass fiber-reinforced polypropylene compositions tend to have uneven shrinkage in different directions, since glass fibers tend to align during the injection molding process, leading to lower shrinkage in the direction of melt flow than in other directions. This uneven shrinkage leads to the warping of the articles, an outcome that it is beneficial to avoid.
  • PC polyolefin composition
  • HECO heterophasic propylene-ethylene copolymer
  • a crystalline matrix being a propylene homopolymer and having a melt flow rate (MFR 2 ) , measured according to ISO 1133 at 230 °C and 2.16 kg, of less than 80.0 g/10min;
  • heterophasic propylene-ethylene copolymer HECO has a melt flow rate (MFR 2 ) , measured according to ISO 1133 at 230 °C and 2.16 kg, in the range from 5.0 to 100.0 g/10 min;
  • the total amounts of the heterophasic propylene-ethylene copolymer (HECO) , the glass fibers (GF) , the inorganic filler (F) , the polar-modified polypropylene (PMP) and the at least one additive (A) add up to at least 90 wt. -%, more preferably at least 95 wt. -%, most preferably at least 98 wt. -%, based on the total weight of the composition.
  • heterophasic propylene-ethylene copolymer has one or more, preferably all, of the following properties:
  • a total ethylene (C2) content in the range from 5.0 to 20.0 wt. -%, preferably in the range from 6.0 to 17.0 wt. -%, most preferably in the range from 7.0 to 14.0 wt. -%;
  • XCS xylene cold solubles
  • the crystalline matrix (M) of the heterophasic propylene-ethylene copolymer (HECO) has a melt flow rate (MFR 2 ) , measured according to ISO 1133 at 230 °C and 2.16 kg, in the range from 20.0 to 79.0 g/10 min.
  • heterophasic propylene-ethylene copolymer comprises a polymeric nucleating agent, preferably a vinyl cycloalkane polymer, more preferably a vinyl cyclohexane polymer, most preferably a vinyl cyclohexane homopolymer.
  • the glass fibers (GF) are chopped glass fibers, more preferably chopped glass fibers with a nominal diameter in the range from 5 to 30 ⁇ m, preferably in the range from 7 to 20 ⁇ m, most preferably in the range from 10 to 15 ⁇ m, and/or a chop length in the range from 1.0 to 10.0 mm, more preferably in the range from 2.0 to 7.0 mm, most preferably in the range from 3.0 to 5.0 mm.
  • the inorganic filler (F) has an aspect ratio in the range from 22 to 130, preferably being selected from the group containing talc, calcium carbonate, barium sulfate, mica, kaolin, montmorillonite and mixtures thereof, most preferably the inorganic filler (F) is talc or mica.
  • the polyolefin composition has an average shrinkage, measured according to ISO 2577 on test bars having length 150 mm, width 100 mm and thickness 3.2 mm, injection molded in line with EN ISO1873-2, expressed as (SN+SP) /2, where SN is the shrinkage measured in the width direction normal to the melt flow direction and SP is the shrinkage measured in the length direction parallel to the melt flow direction, of less than 0.70%, more preferably less than 0.60%, most preferably less than or equal to 0.50%.
  • the polyolefin composition has a warpage, measured according to ISO 2577 on test bars having length 150 mm, width 100 mm and thickness 3.2 mm, injection molded in line with EN ISO1873-2, expressed as SN-SP, where SN is the shrinkage measured in the width direction normal to the melt flow direction and SP is the shrinkage measured in the length direction parallel to the melt flow direction, of less than 0.70%, more preferably less than 0.60%, most preferably less than or equal to 0.50%.
  • the polyolefin composition has a melt flow rate (MFR 2 ) , measured according to ISO 1133 at 230 °C and 2.16 kg, in the range from 5.0 to 20.0 g/10 min.
  • the present invention is further directed to an article comprising more than 75 wt. -%of the polyolefin composition (PC) according to the invention, preferably a molded article, most preferably an injection molded article.
  • PC polyolefin composition
  • heterophasic propylene-ethylene copolymer HECO
  • the main component of the polyolefin composition is the heterophasic propylene-ethylene copolymer (HECO) .
  • a heterophasic propylene copolymer comprises at least two distinct phases, namely a crystalline matrix phase (M) , which is a propylene homopolymer, and an elastomeric propylene-ethylene copolymer (EC) .
  • M crystalline matrix phase
  • EC elastomeric propylene-ethylene copolymer
  • the crystalline matrix (M) of the heterophasic propylene copolymer (HECO) of the present invention is bimodal.
  • the elastomeric propylene-ethylene copolymer (EC) is unimodal.
  • the elastomeric propylene-ethylene copolymer (EC) is bimodal.
  • the heterophasic propylene-ethylene copolymer (HECO) of the present invention has a melt flow rate (MFR 2 ) , measured according to ISO 1133 at 230°C and 2.16 kg, in the range from 5.0 to 100.0 g/10 min, more preferably in the range from 8.0 to 80.0 g/10 min, most preferably in the range from 10.0 to 50.0 g/10 min.
  • MFR 2 melt flow rate
  • the heterophasic propylene-ethylene copolymer (HECO) of the present invention has a xylene cold solubles (XCS) content in the range from 10.0 to 50.0 wt. -%, more preferably in the range from 13.0 to 40.0 wt. -%, most preferably in the range from 16.0 to 35.0 wt. -%.
  • XCS xylene cold solubles
  • heterophasic propylene-ethylene copolymer (HECO) of the present invention has an ethylene content of the xylene cold soluble fraction (C2 (XCS) ) in the range from 25.0 to 50.0 wt. -%, more preferably in the range from 30.0 to 45.0 wt. -%, most preferably in the range from 33.0 to 40.0 wt. -%.
  • C2 (XCS) xylene cold soluble fraction
  • heterophasic propylene-ethylene copolymer (HECO) of the present invention has a total ethylene (C2) content in the range from 5.0 to 20.0 wt. -%, preferably in the range from 6.0 to 17.0 wt. -%, most preferably in the range from 7.0 to 14.0 wt. -%, as determined by quantitative 13 C-NMR spectroscopy.
  • heterophasic propylene-ethylene copolymer (HECO) of the present invention has an intrinsic viscosity of the xylene cold soluble fraction (IV (XCS) ) in the range from 1.8 to 3.2 dl/g, preferably in the range from 2.0 to 3.0 dl/g, most preferably in the range from 2.3 to 2.8 dl/g.
  • the crystalline matrix (M) has a melt flow rate (MFR 2 ) , measured according to ISO 1133 at 230°C and 2.16 kg, of less than 80.0 g/10 min, more preferably in the range from 20.0 to 79.0 g/10 min, yet more preferably in the range from 30.0 to 70.0 g/10 min, most preferably in the range from 35.0 to 60.0 g/10 min.
  • MFR 2 melt flow rate
  • heterophasic propylene-ethylene copolymer (HECO) of the present invention has a flexural modulus measured according to ISO 178 in the range from 700 to 2000 MPa, more preferably from 800 to 1700 MPa, yet more preferably from 900 to 1500 MPa.
  • the heterophasic propylene-ethylene copolymer (HECO) of the present invention has a Charpy Notched Impact Strength measured according to ISO 179/1eA at +23 °C in the range from 5.0 to 100 kJ/m 2 , more preferably from 7.0 to 80 kJ/m 2 , most preferably from 8.0 to 70 kJ/m 2 .
  • the heterophasic propylene-ethylene copolymer (HECO) of the present invention has a Charpy Notched Impact Strength measured according to ISO 179/1eA at -20 °C in the range from 1.0 to 20.0 kJ/m 2 , more preferably from 2.0 to 15.0 kJ/m 2 , most preferably from 4.0 to 12.0 kJ/m 2 .
  • heterophasic propylene-ethylene copolymer (HECO) of the present invention may either be synthesized or selected from commercially available polypropylenes.
  • the heterophasic propylene-ethylene copolymer preferably comprises a polymeric nucleating agent.
  • a preferred example of such a polymeric nucleating agent is a vinyl polymer, such as a vinyl polymer derived from monomers of the formula
  • R 1 and R 2 together with the carbon atom they are attached to, form an optionally substituted saturated or unsaturated or aromatic ring or a fused ring system, wherein the ring or fused ring moiety contains four to 20 carbon atoms, preferably 5 to 12 membered saturated or unsaturated or aromatic ring or a fused ring system or independently represent a linear or branched C4-C30 alkane, C4-C20 cycloalkane or C4-C20 aromatic ring.
  • R 1 and R 2 together with the C-atom wherein they are attached to, form a five-or six-membered saturated or unsaturated or aromatic ring or independently represent a lower alkyl group comprising from 1 to 4 carbon atoms.
  • Preferred vinyl compounds for the preparation of a polymeric nucleating agent to be used in accordance with the present invention are in particular vinyl cycloalkanes, in particular vinyl cyclohexane (VCH) , vinyl cyclopentane, and vinyl-2-methyl cyclohexane, 3-methyl-1-butene, 3-ethyl-1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene or mixtures thereof.
  • the vinyl polymer is a vinyl cycloalkane polymer, preferably selected from vinyl cyclohexane (VCH) , vinyl cyclopentane and vinyl-2-methyl cyclohexane, with vinyl cyclohexane polymer being a particularly preferred embodiment.
  • VCH vinyl cyclohexane
  • vinyl cyclopentane vinyl cyclopentane
  • vinyl-2-methyl cyclohexane vinyl cyclohexane
  • the vinyl polymer of the polymeric nucleating agent is a homopolymer, most preferably a vinyl cyclohexane homopolymer.
  • the glass fibers (GF) are The glass fibers (GF)
  • PC polyolefin composition
  • GF glass fibers
  • the glass fibers are preferably provided in the form of chopped glass fibers.
  • the chopped glass fibers have a nominal diameter in the range from 5 to 30 ⁇ m, preferably in the range from 7 to 20 ⁇ m, most preferably in the range from 10 to 15 ⁇ m.
  • the chopped glass fibers have a chop length in the range from 1.0 to 10.0 mm, more preferably in the range from 2.0 to 7.0 mm, most preferably in the range from 3.0 to 5.0 mm.
  • the inorganic filler (F) is the inorganic filler (F)
  • PC polyolefin composition
  • F inorganic filler
  • the inorganic filler is selected from the group containing talc, calcium carbonate, barium sulfate, mica, kaolin and montmorillonite and mixtures thereof.
  • the inorganic filler (F) is talc or mica.
  • the inorganic filler (F) according to the present invention is provided in flaked form, having an aspect ratio in the range from 20 to 150, more preferably in the range from 21 to 140, most preferably in the range from 22 to 130.
  • the aspect ratio of the inorganic filler is defined as the ratio of the particle diameter, as measured by laser diffraction, to the particle thickness, as measured by scanning electron microscope.
  • the inorganic filler (F) has an average particle size (diameter d 50 ) in the range from 1.0 to 30 ⁇ m, more preferably in the range from 3.0 to 20.0 ⁇ m, most preferably in the range from 5.0 to 15.0 ⁇ m.
  • the inorganic filler (F) has an average particle size (diameter d 95 ) in the range from 5.0 to 50.0 ⁇ m, more preferably in the range from 10.0 to 45.0 ⁇ m, most preferably in the range from 15.0 to 40.0 ⁇ m.
  • PC polyolefin composition
  • PMP polar-modified polypropylene
  • the polar-modified polypropylene (PMP) is used as a compatibilizer in the composition, which further helps to disperse the glass fibers within the polyolefin composition (PC) .
  • the polar-modified polypropyplene (PMP) has a content of polar groups content in the range from 0.5 to 3.0 wt. -%, more preferably in the range from 0.7 to 2.5 wt. -%, most preferably in the range from 0.8 to 2.0 wt. -%.
  • the polar-modified polypropylene (PMP) has a melt flow rate (MFR 2 ) , measured according to ISO 1133 at 230°C and 2.16 kg, in the range from 30.0 to 150.0 g/10 min, more preferably in the range from 40.0 to 120.0 g/10 min, most preferably in the range from 50.0 to 100.0 g/10 min.
  • MFR 2 melt flow rate
  • the polar-modified polypropylene is a maleic anhydride-modified polypropylene.
  • Suitable commercially available polar-modified polypropylenes include CMG5701, available from Fine-Blend Compatibilizer Jiangsu Co., Ltd. (China) .
  • the polyolefin composition (PC) of the present invention may contain additives (A) in an amount of from 0.1 to 5.0 wt. -%.
  • additives (A) in an amount of from 0.1 to 5.0 wt. -%.
  • the skilled practitioner would be able to select suitable additives that are well known in the art.
  • the additives (A) are preferably selected from antioxidants, UV-stabilisers, anti-scratch agents, mold release agents, acid scavengers, lubricants, anti-static agents, colorant or pigment, and mixtures thereof.
  • the content of additives (A) given with respect to the total weight of the polyolefin composition (PC) , includes any carrier polymers used to introduce the additives to said polyolefin composition (PC) , i.e. masterbatch carrier polymers.
  • An example of such a carrier polymer would be a polypropylene homopolymer in the form of powder.
  • the polyolefin composition of the present invention comprises several essential components, including the heterophasic propylene-ethylene copolymer (HECO) , the glass fibers (GF) , the inorganic filler (F) , the polar-modified polypropylene (PMP) and the at least one additive (A) .
  • HECO heterophasic propylene-ethylene copolymer
  • GF glass fibers
  • F inorganic filler
  • PMP polar-modified polypropylene
  • A at least one additive
  • the polyolefin comprises:
  • the polyolefin composition (PC) of the present invention can comprise further components, in addition to the essential components as defined above.
  • the total amounts of the heterophasic propylene-ethylene copolymer (HECO) , the glass fibers (GF) , the inorganic filler (F) , the polar-modified polypropylene (PMP) and the at least one additive (A) must add up to at least 90 wt. -%, more preferably at least 95 wt. -%, most preferably at least 98 wt. -%, based on the total weight of the composition.
  • the heterophasic propylene-ethylene copolymer is present in the polyolefin composition (PC) in an amount of from 40.0 to 75.0 wt. -%more preferably in an amount of from 50.0 to 72.0 wt. -%, most preferably in an amount from 55.0 to 70.0 wt. -%, based on the total weight of the composition.
  • the glass fibers (GF) are present in the polyolefin composition (PC) in an amount of from 10.0 to 35.0 wt. -%more preferably in an amount of from 15.0 to 30.0 wt. -%, most preferably in an amount from 17.0 to 25.0 wt. -%, based on the total weight of the composition.
  • the inorganic filler (F) is present in the polyolefin composition (PC) in an amount of from 5.0 to 25.0 wt. -%more preferably in an amount of from 8.0 to 22.0 wt. -%, most preferably in an amount from 10.0 to 20.0 wt. -%, based on the total weight of the composition.
  • the polar-modified polypropylene (PMP) is present in the polyolefin composition (PC) in an amount of from 0.2 to 2.0 wt. -%more preferably in an amount of from 0.4 to 1.5 wt. -%, most preferably in an amount from 0.5 to 1.0 wt. -%, based on the total weight of the composition.
  • the polyolefin composition (PC) comprises, preferably consists of:
  • the polyolefin composition comprises, preferably consists of:
  • the polyolefin composition comprises, preferably consists of:
  • the polyolefin composition has a melt flow rate (MFR 2 ) , measured according to ISO 1133 at 230 °C and 2.16 kg, in the range from 5.0 to 20.0 g/10 min, more preferably in the range from 6.0 to 15.0 g/10 min, most preferably in the range from 7.0 to 10.0 g/10 min.
  • MFR 2 melt flow rate
  • the polyolefin composition according to the present invention requires beneficial mechanical properties such as stiffness and impact strength, in addition to minimal shrinkage and warpage.
  • the polyolefin composition (PC) has a flexural modulus measured according to ISO 178 of at least 4000 MPa, more preferably of at least 4300 MPa, most preferably of at least 4500 MPa.
  • the flexural modulus will not typically exceed 8000 MPa
  • the polyolefin composition has a tensile modulus measured according to ISO 527 of at least 4000 MPa, more preferably of at least 4200 MPa, most preferably of at least 4400 MPa.
  • the tensile modulus will not typically exceed 8000 MPa
  • the polyolefin composition (PC) has a Charpy notched impact strength measured according to ISO 179/1eA at +23°C of at least 8.0 kJ/m 2 , more preferably of at least 8.5 kJ/m 2 , most preferably of at least 9.0 kJ/m 2 .
  • the Charpy notched impact strength will not typically exceed 20.0 kJ/m 2 .
  • the polyolefin composition has a Charpy unnotched impact strength measured according to ISO 179/1eA at +23°C of at least 30.0 kJ/m 2 , more preferably of at least 35.0 kJ/m 2 , most preferably of at least 38.0 kJ/m 2 .
  • the Charpy unnotched impact strength will not typically exceed 80.0 kJ/m 2 .
  • the polyolefin composition has an average shrinkage, measured according to ISO 2577 on test bars having length 150 mm, width 100 mm and thickness 3.2 mm, injection molded in line with EN ISO1873-2, expressed as (SN+SP) /2, where SN is the shrinkage measured in the width direction normal to the melt flow direction and SP is the shrinkage measured in the length direction parallel to the melt flow direction, of less than 0.70%, more preferably less than 0.60%, most preferably less than or equal to 0.50%.
  • the polyolefin composition has a warpage, measured according to ISO 2577 on test bars having length 150 mm, width 100 mm and thickness 3.2 mm, injection molded in line with EN ISO1873-2, expressed as SN-SP, where SN is the shrinkage measured in the width direction normal to the melt flow direction and SP is the shrinkage measured in the length direction parallel to the melt flow direction, of less than 0.70%, more preferably less than 0.60%, most preferably less than or equal to 0.50%.
  • heterophasic propylene-ethylene copolymer (HECO) comprised in the composition according to this invention is preferably produced in a sequential polymerization process in the presence of a Ziegler-Natta catalyst, more preferably in the presence of a catalyst (system) as defined below.
  • the heterophasic propylene-ethylene copolymer is reactor made, preferably has been produced in a sequential polymerization process, wherein the crystalline matrix (M) has been produced in at least one reactor, preferably in two reactors, and subsequently the elastomeric propylene-ethylene copolymer (EC) has been produced in at least one further reactor, preferably in either one or two further reactors, wherein, if two reactors have been used, a first elastomeric propylene-ethylene copolymer fraction (EC1) has been produced in one of the two further reactors and the second elastomeric propylene-ethylene copolymer fraction (EC2) has been produced in the other one of the two further reactors.
  • the first elastomeric propylene-ethylene copolymer fraction (EC1) is produced first and subsequently the second elastomeric propylene-ethylene copolymer fraction (EC2) is produced.
  • polymerization reactor shall indicate that the main polymerization takes place. Thus in case the process consists of four polymerization reactors, this definition does not exclude the option that the overall process comprises for instance a pre-polymerization step in a pre-polymerization reactor.
  • consist of is only a closing formulation in view of the main polymerization reactors, i.e. does not exclude prepolymerisation reactors prior to said main polymerization reactors.
  • said process comprises the steps of
  • step (d1) transferring the crystalline matrix (M) of step (c1) into a third reactor (R3) ,
  • step (e1) polymerizing propylene and ethylene in the third reactor (R3) in the presence of the crystalline matrix (M) obtained in step (c1) , obtaining thereby the first elastomeric propylene-ethylene copolymer fraction (EC1) , said crystalline matrix (M) and said first elastomeric propylene-ethylene copolymer fraction (EC1) forming a mixture (M1) ,
  • the mixture (M1) represents the heterophasic propylene-ethylene copolymer (HECO) and the xylene cold soluble (XCS) content thereof is regarded as the elastomeric propylene-ethylene copolymer (EC) .
  • the xylene cold soluble (XCS) of said mixture (M1) is regarded as the first elastomeric propylene-ethylene copolymer fraction (EC1)
  • the first elastomeric propylene-ethylene copolymer fraction (EC1) and the second elastomeric propylene-ethylene copolymer fraction (EC2) constitute the total xylene cold soluble (XCS) of the heterophasic propylene-ethylene copolymer (HECO) .
  • heterophasic propylene copolymer HECO
  • crystalline matrix M
  • first propylene homopolymer h-PP1
  • second propylene homopolymer h-PP2
  • first elastomeric propylene-ethylene copolymer fraction EC1
  • second elastomeric propylene-ethylene copolymer fraction EC2
  • the first reactor (R1) is preferably a slurry reactor (SR) and can be any continuous or simple stirred batch tank reactor or loop reactor operating in bulk or slurry.
  • Bulk means a polymerization in a reaction medium that comprises of at least 60 % (w/w) monomer.
  • the slurry reactor (SR) is preferably a (bulk) loop reactor (LR) .
  • the second reactor (R2) , the third reactor (R3) and the optional fourth reactor (R4) are preferably gas phase reactors (GPR) .
  • gas phase reactors (GPR) can be any mechanically mixed or fluid bed reactors.
  • the gas phase reactors (GPR) comprise a mechanically agitated fluid bed reactor with gas velocities of at least 0.2 m/sec.
  • the gas phase reactor is a fluidized bed type reactor preferably with a mechanical stirrer.
  • the first reactor (R1) is a slurry reactor (SR) , like loop reactor (LR)
  • the second reactor (R2) , the third reactor (R3) and the optional fourth reactor (R4) are gas phase reactors (GPR)
  • at least four, preferably four polymerization reactors namely a slurry reactor (SR) , like loop reactor (LR) , a first gas phase reactor (GPR-1) , a second gas phase reactor (GPR-2) and an optional third gas phase reactor (GPR-3) connected in series are used. If needed prior to the slurry reactor (SR) a pre-polymerization reactor is placed.
  • a preferred multistage process is a “loop-gas phase” -process, such as developed by Borealis A/S, Denmark (known as technology) described e.g. in patent literature, such as in EP 0 887 379, WO 92/12182 WO 2004/000899, WO 2004/111095, WO 99/24478, WO 99/24479 or in WO 00/68315.
  • a further suitable slurry-gas phase process is the process of Basell described e.g. in figure 20 of the paper by Galli and Vecello, Prog. Polym. Sci. 26 (2001) 1287-1336.
  • step (a1) the conditions for the first reactor (R1) , i.e. the slurry reactor (SR) , like a loop reactor (LR) , of step (a1) may be as follows:
  • the temperature is within the range of 40 °C to 110 °C, preferably between 60 °C and 100 °C, like 68 to 95 °C,
  • the pressure is within the range of 20 bar to 80 bar, preferably between 40 bar to 70 bar,
  • reaction mixture from step (a1) containing preferably the first propylene copolymer fraction (PP1) is transferred to the second reactor (R2) , i.e. the first gas phase reactor (GPR-1) , whereby the conditions are preferably as follows:
  • the temperature is within the range of 50 °C to 130 °C, preferably between 60 °C and 100 °C,
  • the pressure is within the range of 5 bar to 50 bar, preferably between 15 bar to 35 bar,
  • the polymerization may be effected in a known manner under supercritical conditions in the first reactor (R1) , i.e. in the slurry reactor (SR) , like in the loop reactor (LR) , and/or as a condensed mode in the gas phase reactor (GPR-1) .
  • R1 first reactor
  • SR slurry reactor
  • LR loop reactor
  • GPR-1 gas phase reactor
  • gas phase reactors GPR-2 and optional GPR-3 of steps (e1) and (g1) are preferably also operated within the above conditions, preferably with the exception that in gas phase reactors GPR-2 and optional GPR-3
  • the pressure is within the range of 5 bar to 50 bar, preferably between 10 bar to 30 bar.
  • the residence time can vary in the above different reactors.
  • the residence time the first reactor (R1) i.e. the slurry reactor (SR) , like a loop reactor (LR)
  • the residence time in the gas phase reactors (GPR1, GPR2 and optional GPR3) will generally be 0.2 to 6.0 hours, like 0.5 to 4.0 hours.
  • a well-known prepolymerization step may precede before the actual polymerization in the reactors R1 to R3 or R4.
  • the prepolymerisation step is typically conducted at a temperature of 0 to 50 °C, preferably from 10 to 45 °C, and more preferably from 15 to 40 °C.
  • heterophasic propylene copolymer HECO
  • process according to the present invention includes the following process steps:
  • a vinyl compound as defined above preferably vinyl cyclohexane (VCH)
  • VCH vinyl cyclohexane
  • the weight ratio (g) of the polymer of the vinyl compound to the solid catalyst system is up to 5 (5: 1) , preferably up to 3 (3: 1) most preferably is from 0.5 (1: 2) to 2 (2: 1)
  • the obtained modified catalyst system is fed to polymerization step (a1) of the process for producing the heterophasic propylene copolymer (HECO) .
  • the used catalyst is preferably a Ziegler-Natta catalyst system and even more preferred a modified Ziegler Natta catalyst system as defined in more detail below.
  • Such a Ziegler-Natta catalyst system typically comprises a solid catalyst component, preferably a solid transition metal component, and a cocatalyst, and optionally an external donor.
  • the solid catalyst component comprises most preferably a magnesium halide, a titanium halide and an internal electron donor.
  • Such catalysts are well known in the art. Examples of such solid catalyst components are disclosed, among others, in WO 87/07620, WO 92/21705, WO 93/11165, WO 93/11166, WO 93/19100, WO 97/36939, WO 98/12234, WO 99/33842.
  • Suitable electron donors are, among others, esters of carboxylic acids, like phthalates, citraconates, and succinates. Also oxygen-or nitrogen-containing silicon compounds may be used. Examples of suitable compounds are shown in WO 92/19659, WO 92/19653, WO 92/19658, US 4,347,160, US 4,382,019, US 4,435,550, US 4,465,782, US 4,473,660, US 4,530,912 and US 4,560,671.
  • said solid catalyst components are preferably used in combination with well known external electron donors, including without limiting to, ethers, ketones, amines, alcohols, phenols, phosphines and silanes, for example organosilane compounds containing Si-OCOR, Si-OR, or Si-NR 2 bonds, having silicon as the central atom, and R is an alkyl, alkenyl, aryl, arylalkyl or cycloalkyl with 1-20 carbon atoms; and well known cocatalysts, which preferably comprise an aluminium alkyl compound as known in the art, to polymerise the propylene copolymer.
  • well known external electron donors including without limiting to, ethers, ketones, amines, alcohols, phenols, phosphines and silanes, for example organosilane compounds containing Si-OCOR, Si-OR, or Si-NR 2 bonds, having silicon as the central atom, and R is an alkyl, alkenyl,
  • the amount of nucleating agent present in the heterophasic propylene copolymer (HECO) is preferably not more than 500 ppm, more preferably is 0.025 to 200 ppm, still more preferably is 1 to 100 ppm, and most preferably is 5 to 100 ppm, based on the heterophasic propylene copolymer (HECO) and the nucleating agent, preferably based on the total weight of the heterophasic propylene copolymer (HECO) including all additives.
  • the present invention is additionally directed to a process for the preparation of the polyolefin composition (PC) of the present invention, comprising the steps of:
  • HECO heterophasic propylene-ethylene copolymer
  • a conventional compounding or blending apparatus e.g. a Banbury mixer, a 2-roll rubber mill, Buss-co-kneader or a twin-screw extruder. More preferably, mixing is accomplished in a co-rotating twin-screw extruder.
  • the polymer materials recovered from the extruder are usually in the form of pellets. These pellets are then preferably further processed, e.g. by injection molding or compression molding to generate articles and products of the inventive polyolefin composition (PC) .
  • PC polyolefin composition
  • the present invention also relates to articles comprising the polyolefin composition (PC) of the invention.
  • the article of the invention comprises more than 75 wt. -%of the polyolefin composition (PC) , more preferably more than 85 wt. -%, yet more preferably more than 90 wt. -%, most preferably more than 95 wt. -%of the of the polyolefin composition (PC) .
  • polyolefin composition (PC) is the only polyolefin component in the article.
  • the article is preferably a molded article, most preferably an injection molded article or a foam injection molded article.
  • the article is an automotive exterior part, most preferably an underbody shield, roof window structure, or lamp housing.
  • Density is measured according to ISO 1183-187. Sample preparation is done by compression molding in accordance with ISO 1872-2: 2007
  • MFR 2 The melt flow rate (MFR) is determined according to ISO 1133 and is 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 MFR 2 of polypropylene is determined at a temperature of 230 °C and a load of 2.16 kg.
  • NMR nuclear-magnetic resonance
  • the NMR tube was further heated in a rotatory oven for at least 1 hour. Upon insertion into the magnet the tube was spun at 10 Hz.
  • This setup was chosen primarily for the high resolution and quantitatively needed for accurate ethylene content quantification. Standard single-pulse excitation was employed without NOE, using an optimised tip angle, 1 s recycle delay and a bi-level WALTZ16 decoupling scheme as described in Z. Zhou, R. Kuemmerle, X. Qiu, D. Redwine, R. Cong, A. Taha, D. Baugh, B. Winniford, J. Mag. Reson. 187 (2007) 225 and V. Busico, P.
  • the comonomer fraction was quantified using the method of W-J. Wang and S. Zhu, Macromolecules 2000, 33 1157, 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 regio-defects when needed. Integral regions were slightly adjusted to increase applicability across the whole range of encountered comonomer contents.
  • the mole percent comonomer incorporation was calculated from the mole fraction.
  • the weight percent comonomer incorporation was calculated from the weight fraction.
  • w (PP1) is the weight fraction [in wt. -%] of the first elastomeric propylene-ethylene copolymer fraction (EC1) , e.g. the xylene cold soluble (XCS) fraction after the third reactor (e.g. product of the third reactor comprising the matrix (M) and the first elastomeric fraction) ;
  • w (PP2) is the weight fraction [in wt. -%] of the second elastomeric propylene-ethylene copolymer fraction (EC2) , e.g. of the amount of xylene cold soluble fraction (XCS) produced in the fourth reactor (e.g. the second elastomeric fraction produced in the fourth reactor) ;
  • C (PP1) is the comonomer content [in wt-%] of the first elastomeric propylene-ethylene copolymer fraction (EC1) , e.g. of the xylene cold soluble (XCS) fraction produced in the third reactor (e.g. product of the third reactor comprising the matrix (M) and the first elastomeric fraction) ;
  • C (PP) is the comonomer content [in wt-%] of the xylene soluble fraction of the final heterophasic propylene copolymer (HECO) ,
  • C (PP2) is the calculated comonomer content [in wt-%] of the second elastomeric propylene-ethylene copolymer fraction (EC2) .
  • FT-IR standards are prepared by blending a PP homopolymer with different amounts of MAH to create a calibration curve (absorption/thickness in cm versus MAH content in weight %) .
  • the MAH content is determined in the solid-state by IR spectroscopy using a Bruker Vertex 70 FTIR spectrometer on 25x25 mm square films of 100 ⁇ m thickness (with an accuracy of ⁇ 1 ⁇ m) prepared by compression molding at 190 °C with 4 -6 mPa clamping force.
  • Standard transmission FTIR spectroscopy is employed using a spectral range of 4000-400 cm -1 , an aperture of 6 mm, a spectral resolution of 2 cm -1 , 16 background scans, 16 spectrum scans, an interferogram zero filling factor of 32 and Norton Beer strong apodisation.
  • the xylene soluble fraction (XCS) at room temperature (XCS, wt. -%) : The amount of the polymer soluble in xylene is determined at 25 °C according to ISO 16152; first edition; 2005-07-01. The remaining part is the xylene cold insoluble (XCU) fraction.
  • the intrinsic viscosity (IV) is measured according to ISO 1628-1 (at 135 °C in decalin) .
  • Charpy impact test The Charpy notched and unnotched impact strength (NIS and UIS) were measured according to ISO 179-1 eA at +23 °C and -20 °C, using injection-molded bar test specimens of 80x10x4 mm 3 prepared in accordance with ISO 1873-2: 2007.
  • Flexural Modulus and strength The flexural modulus and strength were determined in 3-point-bending at 23°C according to ISO 178 on 80x10x4 mm 3 test bars injection molded in line with EN ISO 1873-2.
  • Shrinkage is measured according to ISO 2577 on 150x100x3.2 mm 3 test bars, injection molded in line with EN ISO1873-2, wherein the longest dimension, i.e. the length (L, 150 mm) is parallel to the melt flow direction during molding whilst the width (W, 100 mm) is normal to the melt flow direction.
  • the thickness is 3.2mm.
  • Average shrinkage of the bar is represented by (SP+SN) /2.
  • Warpage is indicated by shrinkage difference between SN and SP, i.e. SN-SP.
  • Average particle size (diameter) d 50 and top cut d 95 were calculated from the particle size distribution [mass percent] as determined by laser diffraction method, using Laser Mastersizer, according to ISO 13320-1.
  • the d 50 is defined as the median diameter, whilst d 95 is the diameter at the 95 th percentile, as observed from the particle size distribution.
  • the aspect ratio of the filler is defined as the ratio of the diameter (i.e. average particle size d 50 , as determined above) to the thickness, which is measured by scanning electron microscopy.
  • the catalyst used in the polymerizations was a Ziegler-Natta catalyst from Borealis having Ti-content of 1.9 wt-% (as described in EP 591 224) .
  • the catalyst was prepolymerized with vinyl-cyclohexane (VCH) as described in EP 1 028 984 and EP 1 183 307.
  • VCH vinyl-cyclohexane
  • the ratio of VCH to catalyst of 1: 1 was used in the preparation, thus the final Poly-VCH content was less than 100 ppm.
  • the catalyst described above was fed into prepolymerization reactor together with propylene and small amount of hydrogen (2.5 g/h) and ethylene (330 g/h) .
  • Triethylaluminium as a cocatalyst and dicyclopentyldimethoxysilane as a donor was used.
  • the aluminium to donor ratio was 7.5 mol/mol and aluminium to titanium ratio was 300 mol/mol.
  • Reactor was operated at a temperature of 30 °C and a pressure of 55 barg.
  • the subsequent polymerization has been effected under the following conditions.
  • the propylene compositions of Inventive examples IE1 to IE5 and comparative examples CE1 to CE4 were prepared based on the recipes indicated in Table 2 by compounding in a co-rotating twin-screw extruder under the conditions described in Table 3.
  • the extruder has 11 heating zones.
  • h-PP propylene homopolymer with a trade name of HD601CF, commercially available from Borouge Sales &Marketing (Shanghai) . Co. Ltd., Shanghai, China, having an MFR 2 (230 °C, 2.16 kg) of 8.0 g/10 min, h-PP is not nucleated with pVCH.
  • Talc1 Talc with a trade name of Luzenac HAR T84 commercially available from Imerys Co. Ltd (France) , with median diameter d 50 of 10.5 ⁇ m, diameter d 95 of 34.2 ⁇ m and an aspect ratio of 125;
  • Talc2 Talc with a trade name of Hyst-D575L commercially available from Suteng Houying Group (Liaoning, China) , with median diameter d 50 of 7.2 ⁇ m, diameter d 95 of 25.5 ⁇ m and an aspect ratio of 25;
  • GF chopped strand glass fibers with a trade name of CS 248A-13P, available from Owens Corning Composites (China) , having nominal diameter of 13 ⁇ m and a chop length of 4.5 mm.
  • a an additive masterbatch consisting of 0.5 wt. -%of a carrier propylene homopolymer with a trade name of PP-H GD 225, available from Hongji petrochemical (China) , having an MFR 2 (230 °C, 2.16 kg) of 27 g/10 min, 0.5 wt. -%of a carbon black pigment, 0.4 wt. -%of octadecyl-3- [3’, 5’-di-tert-butyl-4-hydroxyphenyl] propionate] , commercially available as Irganox 1076, CAS-no. 2082-79-3, available from BASF SE (Germany) , 0.4 wt.
  • CE2 has lower shrinkage than CE1, demonstrating that HECOs are superior to propylene homopolymers in this regard.
  • the same can be seen by comparing CE4 and CE3. In both instances the warpage is, however, unaffected by the choice of base polymer.
  • talc in a flaked form having an aspect ratio in the claimed range has a beneficial effect on both the warpage and the shrinkage, as can be seen from comparing IE1 and IE2 with CE2. Furthermore the effect is more pronounced for the talc having the larger aspect ratio (c. f. IE1 with F1 (aspect ratio (125) and IE2 with F2 (aspect ratio 25) ) .
  • Comparison of IE3, IE4 and IE5 demonstrates that shrinkage and warpage decrease when the amount of talc with a high aspect ratio is increased from 10 to 15 to 20.
  • the stiffness (flexural modulus and tensile modulus) of these compositions also increases with higher talc content.

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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de polyoléfine (PC) comprenant : a) de 40,0 à 75,0 % en poids d'un copolymère de propylène-éthylène hétérophasique (HECO), comprenant : i) une matrice cristalline (M) étant un homopolymère de propylène et ayant un indice de fluidité à chaud MFR 2 inférieur à 80,0 g/10 min; et ii) un copolymère de propylène-éthylène élastomère (EC), le copolymère de propylène-éthylène hétérophasique (HECO) ayant un MFR 2 dans la plage de 5,0 à 100,0 g/10 min; b) de 10,0 à 35,0 % en poids de fibres de verre (GF); c) de 5,0 à 25,0 % en poids d'une charge inorganique (F) sous forme de flocons, ayant un rapport d'aspect dans la plage de 20 à 150; d) de 0,2 à 2,0 % en poids de polypropylène modifié polaire (PMP); et e) de 0,1 à 5,0 % en poids d'au moins un additif (A), les quantités totales de HECO, de GF, de F, de PMP et de A atteignant au moins 90 % en poids.
PCT/CN2020/134973 2020-12-09 2020-12-09 Compositions de polyoléfine remplies de fibres de verre à faibles retrait et gauchissement WO2022120648A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1479765A (zh) * 2000-12-22 2004-03-03 三星综合化学株式会社 具有耐热性,高刚性和低翘曲性的聚丙烯树脂组合物
US20140336327A1 (en) * 2013-05-08 2014-11-13 Equistar Chemicals, Lp Polyolefin masterbatch based on grafted polypropylene and metallocene catalyzed polypropylene
CN105829437A (zh) * 2013-12-20 2016-08-03 博禄塑料（上海）有限公司 具有低线性热膨胀系数和高尺寸稳定性的聚丙烯组合物
CN107108996A (zh) * 2014-12-02 2017-08-29 Sabic环球技术有限责任公司 包含多相丙烯共聚物的组合物
CN108368314A (zh) * 2015-12-23 2018-08-03 博里利斯股份公司 轻量纤维增强聚丙烯组合物
CN109890848A (zh) * 2016-11-11 2019-06-14 巴塞尔聚烯烃意大利有限公司 含有玻璃纤维填料的聚丙烯组合物
CN111471241A (zh) * 2019-01-24 2020-07-31 Sabic环球技术有限责任公司 具有改进的落锤冲击抗性的天线壳体

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1479765A (zh) * 2000-12-22 2004-03-03 三星综合化学株式会社 具有耐热性,高刚性和低翘曲性的聚丙烯树脂组合物
US20140336327A1 (en) * 2013-05-08 2014-11-13 Equistar Chemicals, Lp Polyolefin masterbatch based on grafted polypropylene and metallocene catalyzed polypropylene
CN105829437A (zh) * 2013-12-20 2016-08-03 博禄塑料（上海）有限公司 具有低线性热膨胀系数和高尺寸稳定性的聚丙烯组合物
CN107108996A (zh) * 2014-12-02 2017-08-29 Sabic环球技术有限责任公司 包含多相丙烯共聚物的组合物
CN108368314A (zh) * 2015-12-23 2018-08-03 博里利斯股份公司 轻量纤维增强聚丙烯组合物
CN109890848A (zh) * 2016-11-11 2019-06-14 巴塞尔聚烯烃意大利有限公司 含有玻璃纤维填料的聚丙烯组合物
CN111471241A (zh) * 2019-01-24 2020-07-31 Sabic环球技术有限责任公司 具有改进的落锤冲击抗性的天线壳体

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