WO2020113461A1 - Composition appropriée pour des pare-chocs - Google Patents

Composition appropriée pour des pare-chocs Download PDF

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Publication number
WO2020113461A1
WO2020113461A1 PCT/CN2018/119341 CN2018119341W WO2020113461A1 WO 2020113461 A1 WO2020113461 A1 WO 2020113461A1 CN 2018119341 W CN2018119341 W CN 2018119341W WO 2020113461 A1 WO2020113461 A1 WO 2020113461A1
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WO
WIPO (PCT)
Prior art keywords
10min
mfr
iso1133
heco
polypropylene
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PCT/CN2018/119341
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English (en)
Inventor
Ben Chen
Jenny PAN
Henry ZHOU
Shengquan ZHU
Rongcai HUANG
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Borouge Compounding Shanghai Co., Ltd.
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Application filed by Borouge Compounding Shanghai Co., Ltd. filed Critical Borouge Compounding Shanghai Co., Ltd.
Priority to CN201880099773.6A priority Critical patent/CN113166506B/zh
Priority to PCT/CN2018/119341 priority patent/WO2020113461A1/fr
Publication of WO2020113461A1 publication Critical patent/WO2020113461A1/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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/02—Heterophasic composition

Definitions

  • This invention concerns specific polypropylene compounds suitable for automotive applications, specifically bumpers.
  • PP compounds are widely used for automotive interior and exterior application such as door panel, instrument panel and bumper due to its excellent property and easy to process. Due to less petrochemical consumption and less CO 2 emission requirement, automotive OEMs require to decrease part weight to achieve the light-weight target.
  • a way to achieve light-weight target is to reduce thickness of the bumper, i.e. a thin-wall bumper.
  • a regular bumper has a thickness of 2.8mm in the market, and a thin-wall bumper requires a thickness of 2.3mm -2.5mm.
  • stiffness of PP compounds have to be improved to makeup stiffness loss due to the thickness reduction. Furthermore, the thinner the wall thickness, the faster the cooling rate and solidifying of melt is in mold tunnel. So a higher flowability of compounds is required to prepare a thin-wall bumper. Compounds flowability should be increased high enough to fill the mold completely and quickly. Unfortunately a higher flowability will go hand in hand with limited mechanical properties. Thus, for thin-wall bumpers, there is a multidimensional conflict of aims, namely having higher melt flow for adequate solidification and further high stiffness as well as high impact properties.
  • the present invention is based on the finding, an outstanding balance of stiffness, flowability and mechanical properties can be achieved by a composition obtainable by a specific blend.
  • the present invention insofar provides
  • composition comprising
  • composition whereby said composition has an MFR (ISO1133, 230°C/2.16kg) of 30 to 50 g/10min and is obtainable by extruding
  • -%additives optionally selected from the group of antioxidant, UV-stabilizer, anti-scratch agent, mold release agent, and/or acid-scaverage agent;
  • the present invention further provides a process for producing a composition having a MFR (ISO1133, 230°C/2.16kg) of 30 to 50 g/10min, the process comprising the steps of
  • -%additives optionally selected from the group of antioxidant, UV-stabilizer, anti-scratch agent, mold release agent, and/or acid-scaverage agent;
  • component f) is premixed in an amount of up to 3 wt. -%with one or more of additives g) , whereby component f) is used in the form of a powder yielding a first premixture
  • the present invention is concerned with an injection-molded article comprising, preferably consisting of the inventive composition.
  • composition comprising:
  • composition preferably has an MFR (ISO1133, 230°C/2.16kg) of 30 to 50 g/10min.
  • the present invention is concerned with the use of a composition having a MFR (ISO1133, 230°C/2.16kg) of 30 to 50 g/10min obtainable by extruding
  • -%additives optionally selected from the group of antioxidant, UV-stabilizer, anti-scratch agent, mold release agent, and/or acid-scaverage agent;
  • Heterophasic polypropylenes denote polypropylenes having more than one phase, i.e. a matrix phase and dispersed therein an elastomer phase. Multiphase nature of heterophasic polypropylenes is easily detectable for example using glass transition point analysis according to ISO6721-7.
  • An elastomer copolymer is a copolymer of ethylene having elastic properties.
  • Carrier or carrier polymer denotes the polymeric material (s) to be used for introducing the additives into the composition. It is self-explaining a carrier polymer may also be one or more of the polymeric components present, i.e. foreseen in inventive composition.
  • Inorganic filler denotes a filler with has a skeletal strucutre that does not include carbon atoms. Carbon black is not an inorganic filler.
  • a bumper is a structure attached to or integrated with the front and rear ends of a motor vehicle, to absorb impact in a minor collision and/or to optimize aerodynamics.
  • the inventive composition have a better flowability, flexural modulus and toughness which allows the provision of thin wall bumpers having a thickness of 2.5 mm or lower, preferably 2.3 mm or lower.
  • Component a) i.e. 40 to 60 wt. -%of a first heterphasic polypropylene HECO-PP1 having a MFR of 90 -120 g/10min (ISO1133, 230°C/2.16kg) mainly ensures high flowability and basic mechanical properties.
  • Optional component b) i.e. 0 to 25 wt. -%of a second heterphasic polypropylene HECO-PP2 having a MFR of 10 -30 g/10min (ISO1133, 230°C/2.16kg) moderates melt flow rate and additionally improves mechanical properties.
  • Optional component c) i.e. 0 to 11 wt. -%of a propylene homopolymer (Homo-PP) having a MFR of 1-100 g/10min (ISO1133, 230°C/2.16kg) may be added for boosting stiffness.
  • Component d) i.e. 12 to 20 wt. -%elastomer copolymer derived from of ethylene and at least one of C4 ⁇ C12 alpha olefins, having a MFR of 0.2 to 8g/10min (ISO1133, 190°C/2.16kg) improves impact of the final composition.
  • Component e) i.e. 16 to 22 wt. -%inorganic filler, preferably talc also improves stiffness.
  • the inorganic filler is selected from glass fibers, carbon fibers, phyllosilicate, mica, wollastonite or mixtures thereof. Even more preferably the inorganic filler is selected from the group of mica, wollastonite, kaolinite, smectite, montmorillonite and talc. The most preferred inorganic filler is talc.
  • Component f) i.e. 0.5 to 2 wt-%of polypropylene homo-and/or copolymer as carrier for additives ensures good dispersion of the additives.
  • Optional components g) i.e. 0 to 3 wt. -%additives, optionally selected from the group of antioxidant, UV-stabilizer, anti-scratch agent, mold release agent, and/or acid-scaverage agent ensure long term stability.
  • Optional component h) i.e. 0 to 5 wt. -%color master batch (es) provide a good occurance.
  • the composition according to the present invention preferably has a flexural modulus (ISO178) measured on injection molded specimens of 80 x 10 x 4 mm prepared in accordance with ISO 294-1: 1996 of at least 1900 MPa, preferably 2000 MPa, more preferably 2400 MPa.
  • the adaptation of the flexural modulus may be achieved via variation of the amount of the amout of propylene homopolymer and/or the amount of talc and/or the amount of component b) , i.e. the second heterophasic polypropylene HECO-PP2.
  • the composition according to the present invention preferably is obtained by using talc in the extrusion with a B. E. T of 15 to 25 m2/g (ISO9277) , more preferably 16 to 22 m2/g (ISO9277) , and most preferably 16 to 20 m2/g (ISO9277) .
  • B. E. T 15 to 25 m2/g
  • ISO9277 more preferably 16 to 22 m2/g
  • ISO9277 most preferably 16 to 20 m2/g
  • Higher B. E. T. of talc helps to increase stiffness of the composition.
  • composition according to the present invention is preferably obtained by using talc in the extrusion with a medium diameter D50 of 3.7-11.0 micrometer, more preferably 8.0 to 11.0 micrometer (ISO13320-1) , most preferably 9.0 to 11.0 micrometer (ISO13320-1) .
  • the D95 of the talc used in the extrusion preferably is 6.8 to 36.0 micrometer (ISO13320-1) , and more preferably 31.0 to 35.0 micrometer (ISO13320-1) .
  • component c) i.e. optional propylene homopolymer Homo-PP having a MFR of 1-100 g/10min (ISO1133, 230°C/2.16kg) , preferably 2-50g/10min. more preferably 3-20g/10min., and being added for boosting stiffness is present in an amount of at least 0.5 wt.-%, more preferably of at least 1.0 wt. -%with respect to the total of the composition, especially more preferably of from 0.5 wt% to 30.0 wt%, even more preferably of from 1.0 wt%to 15.0 wt%, most preferably of from 1.0wt%to 11wt%with respect to the total weight of the composition.
  • component c) i.e. optional propylene homopolymer Homo-PP having a MFR of 1-100 g/10min (ISO1133, 230°C/2.16kg) , preferably 2-50g/10min. more preferably 3-20g/10min., and being
  • composition according to the present invention is obtained by a preferred extrusion process contributing to the excellent balance of properties, the preferred extrusion process being characterized by the following steps:
  • a carrier polymer or any of the present polymeric components in an amount of up to 3 wt. -%with respect to the total weight of the composition finally produced is premixed with one or more of additives g) , whereby the carrier polymer used is preferably present in the form of a powder yielding a first premixture,
  • composition according to the present invention is preferably obtainable by an extrusion wherein the die temperature of extruder is within the range of 190 to 230°C.
  • composition according to present invention is preferably obtainable by an extrusion wherein the srew speed is within 500 to 640 rotations per minute.
  • the composition according to the present invention is preferalby obtainable by an extrusion in a twin screw extruder having a die, wherein the barrel temperature profile increases from 100 to 220°C in a first section in the extrusion direction and optionally decreases from the maximum temperature reached at the end of the first section to a barrel temperature within the range of 190 to 210°C in a second section positioned downstream of the first section and upstream of the die.
  • the composition according to the present invention preferably includes as component d) an ethylene octene copolymer or ethylene butene copolymer, which has a density of 0.860 g/cm 3 to 0.880 g/cm 3 and/or a melt flow rate of 0.2 to 3.4 g/10min (ISO1133, 190°C/2.16kg) .
  • component d) is an ethylene octene copolymer having a density of 0.860 g/cm 3 to 0.880 g/cm 3 and a melt flow rate of 0.2 to 3.4 g/10min (ISO1133, 190°C/2.16kg) .
  • the present invention is also concerned with a process for producing a composition according to the present invention having a MFR (ISO1133, 230°C/2.16kg) of 30 to 50 g/10min. All preferred aspects and embodiments as described with relation to the composition shall also apply to the process.
  • the article particularly the automotive article and specifically an article /automotive article having a thickness of below 2.8 mm, preferably below 2.6 mm, more preferably equal or below 2.5 mm.
  • the article according to the present invention preferably is a bumper. It is particularly preferred the bumper has a thickness of 2.5 mm or less.
  • the present invention concerns the use of the composition having a MFR (ISO1133, 230°C/2.16kg) of 30 to 50 g/10min as described herein and being obtainable by extruding
  • -%additives optionally selected from the group of antioxidant, UV-stabilizer, anti-scratch agent, mold release agent, and/or acid-scaverage agent;
  • a heterophasic propylene copolymer comprises a polypropylene as a matrix and dispersed therein an elastomeric propylene copolymer (EC) .
  • the polypropylene matrix contains (finely) dispersed inclusions being not part of the matrix and said inclusions contain the elastomeric propylene copolymer.
  • the inclusions are for instance visible by high resolution microscopy, like electron microscopy or scanning force microscopy.
  • the matrix of the heterophasic propylene copolymer as well as the rubber phase of the heterophasic propylene copolymer may consist of a single polymer only or may be a mixture of two or more polymers each, preferably consist of a single polymer only
  • the heterophasic propylene copolymer may be produced by melt-blending and/or by reactor blending.
  • reactor-blending denotes that the individual fractions of the polymers are produced in subsequent stages, in the presence of the product of the previous stage.
  • the matrix and the disperse phase of a heterophasic polypropylene may be produced in such subsequent stages.
  • Component a) i.e. the first heterphasic polypropylene HECO-PP1 preferably is present in an amount of 40 to 55 wt. -%with respect to the total composition.
  • Heterophasic polypropylene HECO-PP1 further preferably has one or more of the following properties:
  • Component b) i.e. the second heterophasic polypropylene HECO-PP2 preferably is present in an amount of 3 to 20 wt%, more preferably 5 to 15 wt. -%with respect to the total weight of the composition.
  • Heterophasic polypropylene HECO-PP2 further preferably has one or more of the following properties:
  • HECO-PP1 and HECO-PP2 differ in at least one aspect. Preferably HECO-PP1 and HECO-PP2 will differ as to their melt flow rate.
  • MFR of HECO-PP1 (ISO1133, 230°C/2.16kg) is higher than, and preferably is at least two times MFR of HECO-PP2 (ISO1133, 230°C/2.16kg) , more preferably at least three times MFR of HECO-PP2,
  • flexural modulus of HECO-PP1 (ISO178) is higher than flexural modulus of HECO-PP2
  • xylene soluble content XCS of HECO-PP1 is lower than xylene soluble content XCS of HECO-PP2.
  • intrinsic viscosity of the xylene soluble content IV (XCS) of HECO-PP1 (decalin 135°C, DIN ISO1628/1) is lower than the intrinsic viscosity of the xylene soluble content IV (XCS) of HECO-PP2 (decalin 135°C, DIN ISO1628/1) .
  • component c) i.e. the propylene homopolymer having a MFR of 1-100 g/10min (ISO1133, 230°C/2.16kg)
  • component c) i.e. the propylene homopolymer having a MFR of 1-100 g/10min (ISO1133, 230°C/2.16kg)
  • component c) will differ from the matrix of HECO-PP1 and also will differ from the matrix of HECO-PP2 by a lower melt flow rate, which helps to increase stiffness of the composition.
  • HECO-PP1 can have a propylene homopolymer as matrix or a random propylene copolymer as matrix.
  • HECO-PP2 can have a propylene homopolymer as matrix or a random propylene copolymer as matrix.
  • a homopolymer matrix is preferred for HECO-PP1.
  • a homopolymer matrix is preferred for HECO-PP2. More preferably both matrix components of HECO-PP1 and HECO-PP2 are homopolymers. If a random propylene copolymer is used as matrix, it should preferably not have a comonomer content of above 5.0 wt. -%.
  • Component c) i.e. the propylene homopolymer preferably has a melt flow rate MFR2 (230 °C, 2.16 kg) measured according to ISO 1133 of not more than 50 g/10 min, preferably in the range of 1 to 30 g/10 min, still more preferably in the range of 2 to 15 g/10 min.
  • the melting temperature T m of Component c) i.e. the propylene homopolymer is preferably in the range of 150 to 170 °C, like in the range of 155 to 170 °C.
  • the amount of component c) i.e. the propylene homopolymer (Homo-PP) is preferably in the range of 0.5 to 30.0 wt. -%, more preferably of from 1.0 to 15.0wt. -%based on the total weight of the total composition according to the present invention.
  • propylene homopolymer as used throughout the instant invention relates to a polypropylene that consists substantially, i.e. of equal or more than 99.9 wt.-%, of propylene units. In a preferred embodiment only propylene units in the propylene homopolymer are detectable.
  • Component c) i.e. the propylene homopolymer (Homo-PP) is preferably isotactic. Accordingly, it is appreciated that the propylene homopolymer (Homo-PP) has a rather high pentad concentration, i.e. higher than 80 %, more preferably higher than 85 %, yet more preferably higher than 90 %, still more preferably higher than 92 %, still yet more preferably higher than 93 %, like higher than 95 %.
  • Color master batch (es) can be present in amounts of 0.1 to 5 wt. -%and preferably are present in amounts of 0.1 to 2.0 wt. -%most preferably 0.1 to 1.0 wt. -%.
  • Color master batch (es) allow the introduction of pigments. The most conventional and preferred pigment is carbon black.
  • the composition having a MFR (ISO1133, 230°C/2.16kg) of 30 to 45 g/10min is obtainable by extruding
  • -%additives optionally selected from the group of antioxidant, UV-stabilizer, anti-scratch agent, mold release agent, and/or acid-scaverage agent;
  • composition having a MFR (ISO1133, 230°C/2.16kg) of 30 to 45 g/10min is obtainable by extruding
  • -%additives optionally selected from the group of antioxidant, UV-stabilizer, anti-scratch agent, mold release agent, and/or acid-scaverage agent;
  • the heterophasic polypropylene (HECO-PP1) according to this invention is preferably produced in a multistage process known in the art, wherein the matrix is produced at least in one slurry reactor and subsequently the elastomeric copolymer is produced at least in one gas phase reactor.
  • the polymerization system can comprise one or more conventional stirred slurry reactors and/or one or more gas phase reactors.
  • the reactors used are selected from the group of loop and gas phase reactors and, in particular, the process employs at least one loop reactor and at least one gas phase reactor. It is also possible to use several reactors of each type, e.g. one loop and two or three gas phase reactors, or two loops and one or two gas phase reactors, in series.
  • the process comprises also a prepolymerisation with the chosen catalyst system, as described in detail below, comprising the Ziegler-Natta procatalyst, the external donor and the cocatalyst.
  • the prepolymerisation is conducted as bulk slurry polymerization in liquid propylene, i.e. the liquid phase mainly comprises propylene, with minor amount of other reactants and optionally inert components dissolved therein.
  • the prepolymerisation reaction 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.
  • the pressure in the prepolymerisation reactor is not critical but must be sufficiently high to maintain the reaction mixture in liquid phase.
  • the pressure may be from 20 to 100 bar, for example 30 to 70 bar.
  • the catalyst components are preferably all introduced to the prepolymerisation step. However, where the solid catalyst component (i) and the cocatalyst (ii) can be fed separately it is possible that only a part of the cocatalyst is introduced into the prepolymerisation stage and the remaining part into subsequent polymerization stages. Also in such cases it is necessary to introduce so much cocatalyst into the prepolymerisation stage that a sufficient polymerization reaction is obtained therein. It is possible to add other components also to the prepolymerization stage. Thus, hydrogen may be added into the prepolymerization stage to control the molecular weight of the prepolymer as is known in the art. Further, antistatic additive may be used to prevent the particles from adhering to each other or to the walls of the reactor. The precise control of the prepolymerization conditions and reaction parameters is within the skill of the art.
  • a slurry reactor designates any reactor, such as a continuous or simple batch stirred tank reactor or loop reactor, operating in bulk or slurry and in which the polymer forms in particulate form.
  • Bulk means a polymerization in reaction medium that comprises at least 60 wt. -%monomer.
  • the slurry reactor comprises a bulk loop reactor.
  • Gas phase reactor means any mechanically mixed or fluid bed reactor.
  • the gas phase reactor comprises a mechanically agitated fluid bed reactor with gas velocities of at least 0.2 m/sec.
  • the particularly preferred embodiment for the preparation of the heterophasic polypropylene (HECO-PP1) of the invention comprises carrying out the polymerization in a process comprising either a combination of one loop and one or two gas phase reactors or a combination of two loops and one or two gas phase reactors.
  • a preferred multistage process is a slurry-gas phase process, such as developed by Borealis and known as the technology.
  • EP 0 887 379 A1, WO 92/12182, WO 2004/000899, WO 2004/111095, WO 99/24478, WO 99/24479 and WO 00/68315 are incorporated herein by reference.
  • a further suitable slurry-gas phase process is the process of Basell.
  • heterophasic polypropylene (HECO-PP1) according to this invention are produced by using a special Ziegler-Natta procatalyst in combination with a special external donor, as described below in detail, preferably in the or in the -PP process.
  • One preferred multistage process may therefore comprise the steps of:
  • Temperature is preferably from 40 to 110 °C, preferably between 50 and 100 °C, in particular between 60 and 90 °C, with a pressure in the range of from 20 to 80 bar, preferably 30 to 60 bar, with the option of adding hydrogen in order to control the molecular weight in a manner known per se.
  • the reaction product of the slurry polymerization which preferably is carried out in a loop reactor, is then transferred to the subsequent gas phase reactor (s) , wherein the temperature preferably is within the range of from 50 to 130 °C, more preferably 60 to 100 °C, at a pressure in the range of from 5 to 50 bar, preferably 8 to 35 bar, again with the option of adding hydrogen in order to control the molecular weight in a manner known per se.
  • the average residence time can vary in the reactor zones identified above.
  • the average residence time in the slurry reactor for example a loop reactor, is in the range of from 0.5 to 5 hours, for example 0.5 to 2 hours, while the average residence time in the gas phase reactor generally will be from 1 to 8 hours.
  • the polymerization may be effected in a known manner under supercritical conditions in the slurry, preferably loop reactor, and/or as a condensed mode in the gas phase reactor.
  • the heterophasic polypropylenes are preferably obtained by a multistage polymerization process, as described above, in the presence of a catalyst system comprising as component (i) a Ziegler-Natta procatalyst which contains a trans-esterification product of a lower alcohol and a phthalic ester.
  • the procatalyst used according to the invention is prepared by
  • R 1’ and R 2’ are independently at least a C 5 alkyl
  • dialkylphthalate of formula (I) takes place to form the internal donor
  • step d) optionally reacting the product of step c) with additional TiCl 4.
  • the procatalyst is produced as defined for example in the patent applications WO 87/07620, WO 92/19653, WO 92/19658 and EP 0 491 566. The content of these documents is herein included by reference.
  • dialkylphthalate of formula (I) selected from the group consisting of propylhexylphthalate (PrHP) , dioctylphthalate (DOP) , di-iso-decylphthalate (DIDP) , and ditridecylphthalate (DTDP) , yet more preferably the dialkylphthalate of formula (I) is a dioctylphthalate (DOP) , like di-iso-octylphthalate or diethylhexylphthalate, in particular diethylhexylphthalate,
  • R 1 and R 2 being methyl or ethyl, preferably ethyl
  • dialkylphthalat of formula (II) being the internal donor
  • the adduct of the formula MgCl 2 *nROH, wherein R is methyl or ethyl and n is 1 to 6, is in a preferred embodiment melted and then the melt is preferably injected by a gas into a cooled solvent or a cooled gas, whereby the adduct is crystallized into a morphologically advantageous form, as for example described in WO 87/07620.
  • This crystallized adduct is preferably used as the catalyst carrier and reacted to the procatalyst useful in the present invention as described in WO 92/19658 and WO 92/19653.
  • the procatalyst used according to the invention contains 2.5 wt. -%of titanium at the most, preferably 2.2%wt. -%at the most and more preferably 2.0 wt. -%at the most. Its donor content is preferably between 4 to 12 wt. -%and more preferably between 6 and 10 wt. -%.
  • the procatalyst used according to the invention has been produced by using ethanol as the alcohol and dioctylphthalate (DOP) as dialkylphthalate of formula (I) , yielding diethyl phthalate (DEP) as the internal donor compound.
  • DOP dioctylphthalate
  • DEP diethyl phthalate
  • the Ziegler-Natta procatalyst can be modified by polymerising a vinyl compound in the presence of the catalyst system, comprising the special Ziegler-Natta procatalyst, an external donor and a cocatalyst, which vinyl compound has the formula:
  • R 3 and R 4 together form a 5-or 6-membered saturated, unsaturated or aromatic ring or independently represent an alkyl group comprising 1 to 4 carbon atoms
  • the modified catalyst is used for the preparation of the heterophasic polypropylene composition according to this invention.
  • the polymerized vinyl compound can act as an alpha-nucleating agent.
  • This modification is in particular used for the preparation of the heterophasic polypropylene (H-PP1) .
  • Concerning the modification of catalyst reference is made to the international applications WO 99/24478, WO 99/24479 and particularly WO 00/68315, incorporated herein by reference with respect to the reaction conditions concerning the modification of the catalyst as well as with respect to the polymerization reaction.
  • the catalyst system used preferably comprises in addition to the special Ziegler-Natta procatalyst an organometallic cocatalyst as component (ii) . Accordingly, it is preferred to select the cocatalyst from the group consisting of trialkylaluminium, like triethylaluminium (TEA) , dialkyl aluminium chloride and alkyl aluminium sesquichloride.
  • TAA triethylaluminium
  • Component (iii) of the catalysts system used is an external donor represented by formula (IIIa) or (IIIb) .
  • Formula (IIIa) is defined by
  • R 5 represents a branched-alkyl group having 3 to 12 carbon atoms, preferably a branched-alkyl group having 3 to 6 carbon atoms, or a cyclo-alkyl having 4 to 12 carbon atoms, preferably a cyclo-alkyl having 5 to 8 carbon atoms.
  • R 5 is selected from the group consisting of iso-propyl, iso-butyl, iso-pentyl, tert. -butyl, tert. -amyl, neopentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and cycloheptyl.
  • R x and R y can be the same or different a represent a hydrocarbon group having 1 to 12 carbon atoms.
  • R x and R y are independently selected from the group consisting of linear aliphatic hydrocarbon group having 1 to 12 carbon atoms, branched aliphatic hydrocarbon group having 1 to 12 carbon atoms and cyclic aliphatic hydrocarbon group having 1 to 12 carbon atoms. It is in particular preferred that R x and R y are independently selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, octyl, decanyl, iso-propyl, iso-butyl, iso-pentyl, tert. -butyl, tert.
  • both R x and R y are the same, yet more preferably both R x and R y are an ethyl group.
  • the external donor is of formula (IIIa) , like dicyclopentyl dimethoxy silane [Si (OCH 3 ) 2 (cyclo-pentyl) 2 ] or diisopropyl dimethoxy silane [Si (OCH 3 ) 2 (CH (CH 3 ) 2 ) 2 ] .
  • the heterophasic propylene copolymer according to the present invention is preferably produced in a sequential polymerization process, i.e. in a multistage process, known in the art, as described above.
  • heterophasic propylene copolymer is produced in a sequential polymerization process comprising the steps of
  • step (d) transferring the polypropylene (PP-1) of step (c) into a third reactor (R3) ,
  • step (e) polymerizing in the third reactor (R3) and in the presence of the polypropylene (PP-1) obtained in step (c) propylene and at least one of ethylene and/or C 4 to C 12 ⁇ -olefin obtaining thereby a first elastomeric propylene copolymer fraction, the first elastomeric propylene copolymer fraction is dispersed in the polypropylene (PP-1) ,
  • step (g) polymerizing in the fourth reactor (R4) and in the presence of the mixture obtained in step (e) propylene and at least one of ethylene and/or C 4 to C 12 ⁇ -olefin obtaining thereby the second elastomeric propylene copolymer fraction, the polypropylene (PP-1) , the first elastomeric propylene copolymer fraction, and the second elastomeric propylene copolymer fraction form the heterophasic propylene copolymer (HECO-PP2) .
  • HECO-PP2 heterophasic propylene copolymer
  • the elastomeric propylene copolymer (E-1) can be also produced in one gas phase reactor, i.e. the fourth reactor (R4) is optional.
  • the second polypropylene fraction in the first reactor (R1) the second polypropylene fraction can be produced and in the second reactor (R2) the first polypropylene fraction can be obtained.
  • the elastomeric propylene copolymer phase Accordingly in the third reactor (R3) the second elastomeric propylene copolymer fraction can be produced whereas in the fourth reactor (R4) the first elastomeric propylene copolymer fraction is made.
  • the monomers are flashed out.
  • the term “sequential polymerization process” indicates that the heterophasic propylene copolymer (HECO-PP2) is produced in at least two, like three or four reactors connected in series. Accordingly the present process comprises at least a first reactor (R1) and a second reactor (R2) , more preferably a first reactor (R1) , a second reactor (R2) , a third reactor (R3) and a fourth reactor (R4) , and more preferably a first reactor (R1) , a second reactor (R2) , and a third reactor (R3) .
  • the term “polymerization reactor” shall indicate that the main polymerization takes place.
  • the process consists of four or three polymerization reactors
  • this definition does not exclude the option that the overall process comprises for instance a pre-polymerization step in a pre-polymerization reactor.
  • the term “consist of” is only a closing formulation in view of the main polymerization reactors.
  • 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 fourth reactor (R4) are preferably gas phase reactors (GPR) .
  • Such 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 a loop reactor (LR)
  • the second reactor (R2) , the third reactor (R3) and the fourth reactor (R4) are gas phase reactors (GPR)
  • GPR gas phase reactors
  • at least three, preferably three polymerization reactors namely a slurry reactor (SR) , like a loop reactor (LR) , a first gas phase reactor (GPR-1) , and a second gas phase reactor (GPR-2) connected in series are used. If needed prior to the slurry reactor (SR) a pre-polymerization reactor is placed.
  • step (a) the conditions for the first reactor (R1) , i.e. the slurry reactor (SR) , like a loop reactor (LR) , of step (a) may be as follows:
  • the temperature is within the range of 50 °C to 110 °C, preferably between 60 °C and 100 °C, more preferably between 68 and 95 °C,
  • the pressure is within the range of 20 bar to 80 bar, preferably between 40 bar to 70 bar,
  • step (c) the reaction mixture from step (a) is transferred to the second reactor (R2) , i.e. gas phase reactor (GPR-1) , i.e. to step (c) , whereby the conditions in step (c) 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 condition in the third reactor (R3) and the fourth reactor (R4) preferably in the second gas phase reactor (GPR-2) and third gas phase reactor (GPR-3) , is similar to the second reactor (R2) .
  • the residence time can vary in the three reactor zones.
  • the residence time in bulk reactor e.g. loop is in the range 0.1 to 2.5 hours, e.g. 0.15 to 1.5 hours and the residence time in gas phase reactor will generally be 0.2 to 6.0 hours, like 0.5 to 4.0 hours.
  • 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 reactors (GPR) .
  • R1 first reactor
  • SR slurry reactor
  • LR loop reactor
  • GPR gas phase reactors
  • the process comprises also a prepolymerization with the catalyst system, as described in detail above, comprising a Ziegler-Natta procatalyst, an external donor and optionally a cocatalyst.
  • a Ziegler-Natta procatalyst for example, a Ziegler-Natta procatalyst, an external donor and optionally a cocatalyst.
  • the catalyst components are preferably all introduced to the prepolymerization step.
  • the solid catalyst component (i) and the cocatalyst (ii) can be fed separately it is possible that only a part of the cocatalyst is introduced into the prepolymerization stage and the remaining part into subsequent polymerization stages. Also in such cases it is necessary to introduce so much cocatalyst into the prepolymerization stage that a sufficient polymerization reaction is obtained therein. It is possible to add other components also to the prepolymerization stage.
  • hydrogen may be added into the prepolymerization stage to control the molecular weight of the prepolymer as is known in the art.
  • antistatic additive may be used to prevent the particles from adhering to each other or to the walls of the reactor.
  • heterophasic propylene copolymer (HECO-PP2) is obtained by a multistage polymerization process, as described above, in the presence of a catalyst system comprising as component (i) a Ziegler-Natta procatalyst which contains a trans-esterification product of a lower alcohol and a phthalic ester.
  • heterophasic propylene copolymer (HECO-PP2) is ⁇ -nucleated.
  • the ⁇ -nucleation is not effected by a vinylcycloalkane polymer or a vinylalkane polymer as indicated above, the following ⁇ -nucleating agents may be present
  • salts of monocarboxylic acids and polycarboxylic acids e.g. sodium benzoate or aluminum tert-butylbenzoate, and
  • dibenzylidenesorbitol e.g. 1, 3 : 2, 4 dibenzylidenesorbitol
  • C 1 -C 8 -alkyl-substituted dibenzylidenesorbitol derivatives such as methyldibenzylidenesorbitol, ethyldibenzylidenesorbitol or dimethyldibenzylidenesorbitol (e.g.
  • salts of diesters of phosphoric acid e.g. sodium 2, 2'-methylenebis (4, 6, -di-tert-butylphenyl) phosphate or aluminium-hydroxy-bis [2, 2'-methylene-bis (4, 6-di-t-butylphenyl) phosphate]
  • diesters of phosphoric acid e.g. sodium 2, 2'-methylenebis (4, 6, -di-tert-butylphenyl) phosphate or aluminium-hydroxy-bis [2, 2'-methylene-bis (4, 6-di-t-butylphenyl) phosphate]
  • Component d) i.e. 12 to 20 wt. -%of elastomer copolymer derived from of ethylene and at least one of C4 ⁇ C12 alpha olefins (EEC) , having a MFR of 0.2 to 8g/10min (ISO1133, 190°C/2.16kg) shall be described in more detail in the following.
  • the comonomers present in the elastomeric copolymer (EEC) are C 4 to C 12 ⁇ -olefins, like 1-butene, 1-hexene and 1-octene, the latter especially preferred.
  • the elastomeric copolymer (EEC) is an ethylene-1-butane copolymer, or ethylene-1-octene copolymer with the amounts given in this paragraph.
  • the amount of elastomeric copolymer (EEC) in the final composition is rather moderate. Accordingly, it is preferred that the elastomeric copolymer is preferably present in the total composition according to the present invention in an amount of between 10.0 and 25wt%, preferably 13.0 and 19.0 wt. -%, more preferably in an amount between 14.0 and 18.0 wt. -%, based on the total weight of the total polypropylene composition according to the present invention.
  • the elastomeric copolymer (EEC) is known in the art and belongs in a preferred embodiment to the Queo and Engage products well known in the art.
  • the elastomeric copolymer (EEC) usually will be preent in dispersed form in the matrix, i.e. in the polypropylene (PP) homo-or random copolymers of the heterophasic propylene copolymers (HECOs) , by compounding.
  • PP polypropylene
  • HECOs heterophasic propylene copolymers
  • the composition according to the present invention comprises inorganic filler.
  • the inorganic filler (F) is present in the polypropylene composition (PP) in amounts of 10 to 30 wt. -%, more preferably in the range of from 15.0 to 25.0 wt. -%, and even more preferably in the range of from 16 to 22 wt. -%, even more preferably in the range of from 17 to 22 wt. %, based on the total weight of the composition according to the present invention.
  • the inorganic filler is mica, wollastonite, kaolinite, smectite, calcium carbonate, montmorillonite, talc, phyllosilicate or a mixture thereof.
  • the most preferred inorganic filler is talc.
  • the inorganic filler preferably has a median particle size d 50 calculated from the particle size distribution in mass percent and measured by laser diffraction in the range of 0.2 to 20.0 ⁇ m, more preferably in the range of 0.3 to 15.0 ⁇ m, still more preferably in the range of 3.0 to 12.0 ⁇ m.
  • the inorganic filler has a specific surface area BET in the range from 1.0 to 50.0 m 2 /g, more preferably in the range from 5.0 to 40.0 m 2 /g, still more preferably in the range from 15.0 to 22.0 m 2 /g and most preferably in the range of 15.0 to 20.0 m 2 /g.
  • composition according to the present invention is a propylene homopolymer (Homo-PP) .
  • the propylene homopolymer (Homo-PP) is added to the composition according to the present invention to improve the stiffness.
  • the polypropylene composition (PP) comprises the propylene homopolymer (Homo-PP) in an amount of from 0.5 to 30.0 wt. -%, preferably of from 1.0 to 15.0 wt. -%, and even more preferably of from 1.0 to 11.0 wt. -%based on the total weight of the total composition according to the present invention.
  • the propylene homopolymer is not a heterophasic polymer, i.e. a system comprising a crystalline matrix phase in which an elastomeric phase is dispersed. Accordingly, the propylene homopolymer (Homo-PP) as such is monophasic, i.e. in DMTA no multiphase structure can be identified as there exists just one glass transition temperature.
  • the propylene homopolymer (Homo-PP) preferably has a melting temperature of more than 155°C, i.e. of more than 155 to 169 °C, more preferably of at least 158°C, i.e. in the range of from 158 to 168 °C, still more preferably in the range of from 162 to 168°C.
  • a further characteristic of the propylene homopolymer is the low amount of misinsertions of propylene within the polymer chain, which indicates that the propylene homopolymer (Homo-PP) is produced in the presence of a Ziegler-Natta catalyst.
  • the propylene homopolymer is preferably featured by low amount of 2, 1 erythro regio-defects, i.e. of equal or below 0.4 mol. -%, more preferably of equal or below than 0.2 mol. -%, like of not more than 0.1 mol. -%, determined by 13C-NMR spectroscopy. In an especially preferred embodiment no 2, 1 erythro regio-defects are detectable.
  • the propylene homopolymer preferably has a melt flow rate MFR2 (230°C) measured according to ISO 1133 in the range of from 2.0 to 30.0 g/10min, preferably in the range of from 2.0 to 20.0 g/10 min.
  • the propylene homopolymer can be chemically identical to the matrix (M) of one of the heterophasic propylene copolymers (HECO-PP1 or HECO-PP2) .
  • the propylene homopolymer (homo-PP) is chemical different, preferably different in the melt flow rate, to the matrix, i.e. to the propylene homopolymer (PP-1) , of the matrix phasees of any one of both heterophasic propylene copolymers (HECO-PP1 and HECO-PP2)
  • the propylene homopolymer has a melt flow rate MFR 2 (230°C) which is lower, preferably at least 5 g/10min lower, more preferably at least 8 g/10min lower, even more preferably 5 to 50 g/10min lower, yet more preferably 8 to 20 g/10min lower, than the matrix, i.e. the propylene homopolymer , of any one of both heterophasic propylene copolymers (HECO-PP1 and HECO-PP2) , which helps to increase stiffness of the composition.
  • MFR 2 230°C
  • Preparation of propylene homopolymers is known in the art. Preferably Ziegler-Natta catalysts are used.
  • Charpy notched impact strength was determined according to ISO 179 /1eA at 23 °C and at 0 °C by using injection moulded test specimens as described in EN ISO 1873-2 (80 x 10 x 4 mm) .
  • Flexural Modulus The flexural modulus was determined in 3-point-bending according to ISO 178 on injection molded specimens of 80 x 10 x 4 mm prepared in accordance with ISO 294-1: 1996.
  • melt flow rates were measured with a load of 2.16 kg (MFR 2 ) , at 230 °C or 190°C as set forth in ISO 1133.
  • Intrinsic viscosity was measured according to DIN ISO 1628/1, October 1999 (in Decalin at 135 °C) .
  • Density was measured according to ISO 1183-187. Sample preparation was done by compression moulding in accordance with ISO 1872-2: 2007.
  • B.E. T was measured according to ISO9277.
  • Brunauer–Emmett–Teller (B.E. T) applies adsorption evaluation for analysis of the surface.
  • Quantitative nuclear-magnetic resonance (NMR) spectroscopy was used to quantify the comonomer content and comonomer sequence distribution of the polymers.
  • Quantitative 13 C ⁇ 1 H ⁇ NMR spectra were recorded in the solution-state using a Bruker Advance III 400 NMR spectrometer operating at 400.15 and 100.62 MHz for 1 H and 13 C respectively. All spectra were recorded using a 13 C optimised 10 mm extended temperature probehead at 125°C using nitrogen gas for all pneumatics.
  • the comonomer fraction was quantified using the method of Wang et. al. (Wang, W-J., Zhu, S., Macromolecules 33 (2000) , 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 comonomer sequence distribution at the triad level was determined using the analysis method of Kakugo et al. (Kakugo, M., Naito, Y., Mizunuma, K., Miyatake, T. Macromolecules 15 (1982) 1150) . This method was chosen for its robust nature and integration regions slightly adjusted to increase applicability to a wider range of comonomer contents.
  • ISO13320-1 was used (laser diffraction method) .
  • the xylene cold soluble fraction (XCS) is determined at 23 °C according to ISO 6427.
  • heterophasic propylene copolymer (HECO-1) used for inventive examples Ex. 1-3 was prepared with one slurry loop reactor and two gas phase reactors by the known technology, as disclosed in EP 0 887 379 A1.
  • Heterophasic propylene copolymer (HECO-PP2) used for the inventive examples was prepared with one slurry loop reactor and two gas phase reactors by the known technology, as disclosed in EP 0 887 379 A1.
  • the catalyst used in the polymerization process of the HECO-PP2 has been produced as follows:
  • the catalyst was filtered from the liquid and washed six times with 300 ml heptane at 80 °C. Then, the solid catalyst component was filtered and dried.
  • Catalyst and its preparation concept is described e.g. in patent publications EP491566, EP591224 or EP586390.
  • the catalyst was prepolymerized with vinyl cyclohexane in an amount to achieve a concentration of 200 ppm poly (vinyl cyclohexane) (PVCH) in the final polymer (see EP 1183307 A1) .
  • PVCH poly (vinyl cyclohexane)
  • TEAL triethyl-aluminium
  • D-donor donor dicyclo pentyl dimethoxy silane
  • Loop HECO-PP2 TEAL/Ti [mol/mol] 177 TEAL/D donor [mol/mol] 10.3 Temperature [°C] 80 Pressure [bar] 55 H 2 /C 3 ratio [mol/kmol] 36 MFR 2 (230 °C) [g/10 min] 40 XCS [wt. -%] 1.5 Split [wt. -%] 46 GPR 1 Temperature [°C] 95 Pressure [kPa] 24 H 2 /C 3 ratio [mol/kmol] 230 MFR 2 (230 °C) [g/10 min] 40 XCS [wt. -%] 1.4 Split [wt.
  • Irganox 1076 antioxidant Octadecyl 3- (3’, 5’-di-tert. butyl-4-hydroxyphenyl) propionate, commercially available from BASF, T m 50°C;
  • Irgafos 168 antioxidant Tris (2, 4-di-t-butylphenyl) phosphite, commercially available from BASF, T m 182°C; Rikemal AS-105 mold release agent: distilled monoglycerides, commercially available from Rikevita Co. Ltd. (Japan)
  • a twin screw extruder was used.
  • the additive mixture was premixed with polypropylene powder.
  • the additive mixture comprises antioxidant agent, mold release agent, acid scaverage agent and color master batch.
  • the resulting premixture was fed into feeder 3 being a side feeder of the twin-screw extruder.
  • Heco-PP, homoPP, and POE were fed into the main feeder 1 of the twin-screw extruder.
  • Talc was fed via side feeder 2. All feed materials were heated and mixed homogeneously via extrusion at a temperature of 100-250°C.
  • Table 3 provides an overview.
  • examples Ex. 1 to 3 have very good stiffness and still acceptable impact strength. Examples Ex 1 to 3 are allowed for ultrathin bumpers.
  • Examples Ex. 2 and 3 showed a balance of an even further improved stiffness and impact and easily allowed for preparation of bumpers having a thickness of 2.3 mm only.
  • Bumpers are made by injection molding.

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Abstract

Composition comprenant a) 40 à 70 % en poids, de préférence 40 à 60 % en poids d'un premier polypropylène hétérophasique HECO-PP1 présentant un indice de fluidité à chaud variant de 90 à 120 g/10 min (ISO1133, 230 °C/2,16 kg), d) 10 à 30 % en poids, de préférence 12 à 20 % en poids d'un copolymère élastomère dérivé de l'éthylène et d'au moins une alpha-oléfine en C4 à C12, présentant un indice de fluidité à chaud variant de 0,2 à 8 g/10 min (ISO1133, 190 °C/2,16 kg) et e) 10 à 30 % en poids, de préférence 16 à 22 % en poids d'une charge inorganique, de préférence du talc, ladite composition présentant, de préférence, un indice de fluidité à chaud (ISO1133, 230 °C/2,16 kg) variant de 30 à 50 g/10 min.
PCT/CN2018/119341 2018-12-05 2018-12-05 Composition appropriée pour des pare-chocs WO2020113461A1 (fr)

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CN104837904A (zh) * 2012-11-30 2015-08-12 博禄塑料（上海）有限公司 虎皮纹得以减轻或消除的且保留优异力学性能的聚丙烯组合物
CN105745269A (zh) * 2013-11-29 2016-07-06 博禄塑料（上海）有限公司 具有低收缩率和平衡的机械性能的聚丙烯组合物
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
CN106661290A (zh) * 2014-04-25 2017-05-10 博禄塑料（上海）有限公司 具有高流动性和平衡机械性能的聚丙烯组合物
CN107922692A (zh) * 2015-09-11 2018-04-17 博禄塑料（上海）有限公司 聚丙烯组合物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103080212A (zh) * 2010-08-27 2013-05-01 北欧化工公司 具有出色的断裂伸长性的刚性聚丙烯组合物
CN104837904A (zh) * 2012-11-30 2015-08-12 博禄塑料（上海）有限公司 虎皮纹得以减轻或消除的且保留优异力学性能的聚丙烯组合物
CN105745269A (zh) * 2013-11-29 2016-07-06 博禄塑料（上海）有限公司 具有低收缩率和平衡的机械性能的聚丙烯组合物
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
CN106661290A (zh) * 2014-04-25 2017-05-10 博禄塑料（上海）有限公司 具有高流动性和平衡机械性能的聚丙烯组合物
CN107922692A (zh) * 2015-09-11 2018-04-17 博禄塑料（上海）有限公司 聚丙烯组合物

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