WO2015077902A1 - Composition de polypropylène à faible retrait et à propriétés mécaniques équilibrées - Google Patents

Composition de polypropylène à faible retrait et à propriétés mécaniques équilibrées Download PDF

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WO2015077902A1
WO2015077902A1 PCT/CN2013/001462 CN2013001462W WO2015077902A1 WO 2015077902 A1 WO2015077902 A1 WO 2015077902A1 CN 2013001462 W CN2013001462 W CN 2013001462W WO 2015077902 A1 WO2015077902 A1 WO 2015077902A1
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Prior art keywords
heco
propylene copolymer
heterophasic propylene
reactor
polypropylene composition
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PCT/CN2013/001462
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English (en)
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Shengquan ZHU
Zhu WANG
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Borouge Compounding Shanghai Co., Ltd.
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Priority to CN201380081112.8A priority Critical patent/CN105745269B/zh
Priority to PCT/CN2013/001462 priority patent/WO2015077902A1/fr
Publication of WO2015077902A1 publication Critical patent/WO2015077902A1/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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/30—Applications used for thermoforming
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/02—Heterophasic composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2308/00—Chemical blending or stepwise polymerisation process with the same catalyst

Definitions

  • the present invention is directed to a polyolefin composition having low shrinkage and balanced mechanical properties including high impact, strength, and stiffness.
  • High impact polystyrenes have been widely applied in the fields of household appliances, medical appliances, automotives, pipes and toys due to a favorable combination of mechanical properties including
  • high impact polystyrenes are at least gradually replaced by polypropylenes in order to lower production cost.
  • high impact polystyrenes are made from crude oil while polypropylenes can be made from cheaper sources including natural gas or shale gas.
  • polypropylenes typically offer an attractive combination of mechanical properties including high impact strength and stiffness, polypropylenes usually exhibit greater shrinkage during molding processes than high impact polystyrenes.
  • the specific finding of the present invention is to provide a polypropylene composition (PP) comprising, (a) a propylene homopolymer (homo-PP) having a melt flow rate MFR 2 (230°C, 2, 16 kg) measured
  • EEC elastomeric ethylene copolymer having a melt flow rate MFR 2 ( 190°C, 2,16 kg) measured according to ISO 1 133 in the range of from 0.5 to 50.0 g/lOmin, and
  • XCS xylene cold soluble fraction measured according to ISO 16152 (25 °C) of from 15.0 to 45.0 wt.-%, based on the total weight of the heterophasic propylene copolymer (HECO-2), and/or
  • a comonomer content preferably an ethylene content, of 10.0 to 22.0 wt.-%, based on the total weight of the heterophasic propylene copolymer (HECO-2).
  • a comonomer content preferably an ethylene content, of 25.0 to 41.0 wt.-% , and/or
  • a comonomer content preferably an ethylene content, of 30.0 to 45.0 wt.-%.
  • the polypropylene composition (PP) comprises
  • the comonomer content, preferably the ethylene content, of the xylene cold soluble (XCS) fraction of the second heterophasic propylene copolymer (HECO-2) is at least 3.0 wt-%, higher than the comonomer content, preferably the ethylene content, of the xylene cold soluble (XCS) fraction of the first heterophasic propylene copolymer (HECO-1).
  • the intrinsic viscosity of the xylene cold soluble (XCS) fraction of the second heterophasic propylene copolymer (HECO-2) is at least 0.3 dl/g, preferably at least 0.5dl/g, lower than the intrinsic viscosity (IV) of the xylene cold soluble (XCS) fraction of the first heterophasic propylene copolymer (HECO- 1 ).
  • the propylene homopolymer has a melt flow rate MFR 2 (230°C) which is at least 3.0 g 1 Omin lower than the melt flow rate MFR 2 (230°C) of the polypropylene matrix (M), i.e. the propylene homopolymer (H-PP2), of the second heterophasic propylene copolymer (HECO-2).
  • the weight ratio of the combined heterophasic propylene copolymers (HECO-1 ) and (HECO-2) to the inorganic filler (F) [HECO l+HECO-2 / F] is from 2.0 to 0.3.
  • the weight ratio of the propylene homopolymer (homo-PP) to the inorganic filler (F) [homo-PP F] is from 1.2 to 0.2.
  • the polypropylene composition (PP) is used for the production of household articles, medical articles, automotive articles, pipes and toys.
  • the polypropylene composition (PP) according to the present invention exhibits reduced shrinkage while having balanced mechanical properties including high impact strength and stiffness as well as excellent tensile strength and flexural modulus.
  • One essential component of the polypropylene composition (PP) according to the present invention is a propylene homopolymer (homo-PP).
  • the polypropylene composition (PP) comprises the propylene homopolymer (homo-PP) in an amount of from 10.0 to 30.0 wt.-%, preferably of from 15.0 to 25.0 wt.-%, and even more preferably of from 18.0 to 23.0 wt.-% based on the total weight of the polypropylene composition (PP).
  • 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, it is preferred that the propylene homopolymer (homo-PP) 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 (homo-PP) 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 13 C- NMR spectroscopy. In an especially preferred embodiment no 2,1 erythro regio-defects are detectable.
  • the propylene homopolymer preferably has a melt flow rate MFR 2 (230°C) measured according to ISO 1 133 in the range of from 20.0 to 70.0 g/l Omin, preferably in the range of from 30.0 to 60.0 g/10 min, preferably in the range of from 45.0 to 55.0 g/l Omin, like in the range of 48.0 to 52.0 g/l Omin.
  • the propylene homopolymer (homo-PP) can be chemically identical to the matrices (M) of the two essential heterophasic propylene copolymers (HECO- 1 ) and/or (HECO-2) which are described in more detail below.
  • the propylene homopolymer (homo-PP) is chemical different, prefereably different in the melt flow rate, to the matrix, i.e. to the propylene homopolymer (H-PP-1), of first heterophasic propylene copolymer (HECO-1 ), however can be chemically identical or different to the matrix, i.e. to the propylene homopolymer (H-PP-2), of second heterophasic propylene copolymer (HECO-2).
  • the propylene homopolymer (homo-PP) has a melt flow rate MFR 2 (230°C) which is higher, preferably at least 10 g/1 Omin higher, more preferably at least 20 g/lOmin higher, still more preferably 20 to 65 g/lOmin higher, yet more preferably at least 30 to 55 g/lOmin higher, than the matrix, i.e. the propylene homopolymer (H-PP-1), of first heterophasic propylene copolymer (HECO-1), and optionally said propylene homopolymer (homo-PP) has a melt flow rate MFR 2 (230°C) which is similar, e.g.
  • the propylene homopolymer has a tensile modulus measured according to ISO 527-2 of at least 1,400 MPa, more preferably of at least 1,500 MPa, like in the range of 1,500 to 1,800 MPa.
  • the propylene homopolymer (homo-PP) is known in the art and is preferably made with a Ziegler-Natta catalyst.
  • the polypropylene composition (PP) according to the present invention further comprises two specific heterophasic propylene copolymers.
  • heterophenasic indicates that an elastomeric copolymer is (finely) dispersed in a matrix.
  • the elastomeric propylene copolymer forms inclusions in the matrix.
  • the matrix contains (finely) dispersed inclusions being not part of the matrix and said inclusions contain the elastomeric propylene copolymer.
  • inclusion shall preferably indicate that the matrix and the inclusion form different phases within the heterophasic propylene copolymer, said inclusions are for instance visible by high resolution microscopy, like electron microscopy or scanning force microscopy.
  • the final composition is probably of a complex structure.
  • the matrix of the heterophasic propylene copolymer may form a continuous phase being the matrix of the composition wherein the elastomeric copolymers and optional additives form together or individually inclusions dispersed therein.
  • heterophasic propylene copolymers ensure high impact and other basic mechanical property, such as tensile strength and flexural modulus.
  • First heterophasic propylene copolymer (HECO-1) HECO-1
  • the polyolefin composition according to the present invention comprises a first heterophasic propylene copolymer (HECO-1 ) as an essential component. It is preferred that the first heterophasic propylene copolymer (HECO- 1 ) before mixed with the other components mentioned herein comprises as polymer components only the matrix polypropylene (PP-1) and dispersed therein the elastomeric propylene copolymer (E-l).
  • HECO-1 first heterophasic propylene copolymer
  • PP-1 matrix polypropylene
  • E-l elastomeric propylene copolymer
  • the first heterophasic propylene copolymer (HECO-1 ) may contain further additives but no other polymer in an amount exceeding 5 wt-%, more preferably exceeding 3 wt.-%, like exceeding 1 wt.-%, based on the total amount of the first heterophasic propylene copolymer (HECO-1 ), more preferably based on the polymers present in the first heterophasic propylene copolymer (HECO-1 ).
  • One additional polymer which may be present in such low amounts is a polyethylene which is a reaction product obtained by the preparation of the first heterophasic propylene copolymer (HECO-1).
  • a first heterophasic propylene copolymer (HECO-1 ) as defined in the instant invention contains only a polypropylene (PP-1), an elastomeric propylene copolymer (E-l) and optionally a polyethylene in amounts as mentioned in this paragraph.
  • the first heterophasic propylene copolymer has a rather low melt flow rate, i.e. has a melt flow rate MFR 2 (230 °C) in the range of 0.05 to 4.0 g/lOmin, more preferably in the range of 0.10 to 3.0 g/1 Omin, yet more preferably in the range of 0.15 to 2.0 g/10 min, still even more preferably in the range of 0.15 to 1.5 g/1 Omin.
  • the propylene content in the first heterophasic propylene copolymer (HECO-1 ) is at least 93.0 wt.- %, more preferably 93.0 to 97.5 wt-%, more preferably 93.0 to 97.0 wt-%, and even more preferably 95.0 to 96.5 wt-% based on the total amount of the first heterophasic propylene copolymer (HECO-1), more preferably based on the amount of the polymer components of the first heterophasic propylene copolymer (HECO-1 ), yet more preferably based on the amount of the polypropylene (PP-1) and the elastomeric propylene copolymer (E-l) together.
  • the remaining part constitutes the comonomers, like ethylene, as defined for the polypropylene (PP-1) being a propylene copolymer (R-PP-1 ) and the elastomeric propylene copolymer (E-l), respectively.
  • PP-1 polypropylene
  • E-l elastomeric propylene copolymer
  • the comonomer content is preferably equal or lower than 7.0 wt.-%, more preferably in the range of from 2.5 to 7.0 wt-%, yet more preferably in the range of from 3.0 to 7.0 wt-% and even more preferably in the range of from 3.5 to 5.0 wt-% based on the total weight of the heterophasic propylene copolymer (HECO-1 ), more preferably based on the amount of the polymer components of the first heterophasic propylene copolymer (HECO-1), yet more preferably based on the amount of the polypropylene (PP-1) and the elastomeric propylene copolymer (E-l ) together.
  • the matrix of the first heterophasic propylene copolymer (HECO-1) is the polypropylene (PP-1).
  • the polypropylene (PP-1) according to this invention constituting the matrix of the first heterophasic copolymer (HECO-1 ) shall have a melt flow rate MFR 2 (230 °C) in the range of from 0.05 to 4.0 g/l Omin, more preferably in the range of 0.10 to 3.0 g/l Omin, yet more preferably in the range of 0.15 to 2.0 g/10 min, still even more preferably in the range of 0.15 to 1.5 g/l Omin.
  • the polypropylene (PP-1 ) can be a propylene copolymer (R-PP-1) or a propylene homopolymer (H-PP-1), the latter is preferred.
  • the polypropylene (PP-1) has a comonomer content equal or below 7.0 wt- %, still more preferably equal or below 5.0 wt-%.
  • propylene homopolymer e.g. the expressions propylene homopolymer (H-PP-1 ),propylene homopolymer (H-PP-2) and propylene homopolymer (homo-PP) used in the instant invention relates to a polypropylene that consists substantially, i.e. of more than 99.5 wt-%, such as at least 99.6 wt-%, still more preferably of at least 99.7 wt-%, like of at least 99.8 wt-%, of propylene units. In case other monomeric units are present in minor amounts, the units are selected from ethylene and/or a C 4 to Cn a-olefin as described below. In a preferred embodiment only propylene units in the propylene homopolymer are detectable.
  • polypropylene (PP-1 ) is a propylene copolymer (R-PP-1) it comprises monomers
  • the propylene copolymer (R-PP-1) comprises, especially consists of, monomers copolymerizable with propylene from the group consisting of ethylene, 1-butene and 1-hexene. More specifically the propylene copolymer (R-PP-1) comprises - apart from propylene - units derivable from ethylene and/or 1-butene.
  • the propylene copolymer (R-PP-1 ) comprises units derivable from ethylene and propylene only.
  • the comonomer content in the propylene copolymer (R-PP-1) is preferably in the range of more than 1.0 to 9.0 wt-%, still more preferably in the range of more than 1.0 to 7.0 wt-%.
  • the polypropylene (PP-1 ) can have a xylene cold soluble content (XCS) in a broad range, i.e. up to 5.0 wt.- %.
  • the polypropylene (PP- 1 ) may have a xylene cold soluble content (XCS) in the range of 0.3 to 5.0 wt.-%, preferably in the range of 0.5 to 4.5 wt.-%, like in the range of 1.0 to 4.0 wt.-%.
  • XCS xylene cold soluble content
  • One further essential component of the first heterophasic propylene copolymer (HECO-1 ) is its elastomeric propylene copolymer (E- 1 ).
  • the elastomeric propylene copolymer (E-1 ) preferably comprises monomers copolymerizable with propylene, for example comonomers such as ethylene and/or C 4 to Cn a-olefins, in particular ethylene and/or C 4 to Cio a-olefins, e.g. 1 -butene and/or 1 -hexene.
  • the elastomeric propylene copolymer (E-1 ) comprises, especially consists of, monomers copolymerizable with propylene from the group consisting of ethylene, 1 -butene and 1-hexene.
  • the elastomeric propylene copolymer (E-1 ) comprises - apart from propylene - units derivable from ethylene and/or 1 -butene.
  • the elastomeric propylene copolymer phase (E- 1 ) comprises units derivable from ethylene and propylene only.
  • the polypropylene (PP-1 ) is a propylene copolymer (R-PP- 1 ) it is preferred that the comonomer(s) of the propylene copolymer (R-PP-1 ) and the elastomeric propylene copolymer (E- 1 ) are the same.
  • the properties of the elastomeric propylene copolymer phase (E- 1 ) are mainly influenced by the xylene cold soluble (XCS) content of the first heterophasic propylene copolymer (HECO- 1 ).
  • the xylene cold soluble (XCS) fraction of the first heterophasic propylene copolymer (HECO-1 ) is regarded as the elastomeric propylene copolymer (E- 1 ) of the first heterophasic propylene copolymer (HECO-1 ).
  • the amount of the elastomeric propylene copolymer (E- 1 ), i.e. of the xylene cold soluble (XCS) fraction, of the first heterophasic propylene copolymer (HECO- 1 ) preferably is in the range of from 8.0 to 20.0 wt-%, more preferably in the range of from 10.0 to 18.0 wt-% and even more preferably in the range of from 1 1.0 to 15.0 wt-%. These values are based on the first heterophasic propylene copolymer (HECO-1) and not on the total polypropylene composition (PP).
  • the elastomeric propylene copolymer (E-l) has a balanced weight average molecular weight. Accordingly the intrinsic viscosity must be carefully chosen.
  • the elastomeric propylene copolymer phase (E-l), i.e. the xylene cold soluble fraction (XCS) of the first heterophasic propylene copolymer (HECO-1) has an intrinsic viscosity (IV) determined according to DIN ISO 1628/1 (in decaline at 135 °C) in the range of from 2.5 to 5.0 dl/g, more preferably in the range of from equal or more than 2.8 to 4.5 dl/g, and still even more preferably in the range of equal or more than from 3.0 to 4.0 dl/g, like in the range of 3.3 to 3.8 dl/g.
  • the comonomer content, preferably the ethylene content, within the elastomeric propylene copolymer phase (E-l) shall be preferably also in a specific range. Accordingly in a preferred embodiment the comonomer content, more preferably ethylene content, of the elastomeric propylene copolymer (E-l ), i.e. of the xylene cold soluble fraction (XCS) of the first heterophasic propylene copolymer (HECO-1), is in the range of from 25.0 to 41.0 wt-%, still more preferably in the range of from 28.0 to 38.0 wt-%, yet more preferably in the range of from 30.0 to 38.0 wt-%.
  • XCS xylene cold soluble fraction
  • the propylene content of the elastomeric propylene copolymer (E-l), i.e. of the xylene cold soluble fraction (XCS) of the first heterophasic propylene copolymer (HECO-1 ), is preferably in the range of from 59.0 to 75.0 wt -%, still more preferably in the range of 62.0 to 72.0 wt-%, yet more preferably in the range of from 62.0 to 70.0 wt-%.
  • the first heterophasic polypropylene (HECO-1) as well its individual components (matrix and elastomeric copolymer) can be produced by blending different polymer types, i.e. of different molecular weight and/or comonomer content.
  • the first heterophasic polypropylene (HECO- 1 ) as well its individual components (matrix and elastomeric copolymer) are produced in a sequential step process, using reactors in serial configuration and operating at different reaction conditions. As a consequence, each fraction prepared in a specific reactor will have its own molecular weight distribution and/or comonomer content distribution.
  • the first heterophasic propylene copolymer (HECO-1) according to this invention is commercially available. Accordingly a skilled person in the art is in a position to produce a first heterophasic propylene copolymer (HECO-1) as defined herein.
  • the first heterophasic propylene copolymer (HECO-1) is preferably produced in a sequential polymerization process, i.e. in a multistage process, known in the art, wherein the polypropylene (PP-1 ) is produced at least in one slurry reactor, preferably in a slurry reactor and optionally in a subsequent gas phase reactor, and subsequently the elastomeric propylene copolymer (E-l ) is produced at least in one, i.e. one or two, gas phase reactor(s).
  • PP-1 polypropylene
  • E-l elastomeric propylene copolymer
  • the first heterophasic propylene copolymer (HECO-1 ) 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 i2 a-olefin obtaining thereby a first elastomeric propylene copolymer fraction, the first elastomeric propylene copolymer fraction is dispersed in the polypropylene (PP-1 ),
  • the polypropylene (PP-1), the first elastomeric propylene copolymer fraction, and the second elastomeric propylene copolymer fraction form the heterophasic propylene copolymer (HECO-1 ).
  • the elastomeric propylene copolymer (E) 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 (Rl) 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 first heterophasic propylene copolymer (HECO-1) is produced in at least two, like three or four reactors connected in series. Accordingly the present process comprises at least a first reactor (Rl ) and a second reactor (R2), more preferably a first reactor (Rl), a second reactor (R2), a third reactor (R3) and a fourth reactor (R4).
  • the term “polymerization reactor” shall indicate that the main polymerization takes place. Thus in case the process consists of four polymerization reactors, this definition does not exclude the option that the overall process comprises for instance a pre- polymerization step in a pre-polymerization reactor.
  • the term “consist of is only a closing formulation in view of the main polymerization reactors.
  • the first reactor (Rl ) 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).
  • 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 (Rl) is a slurry reactor (SR), like a loop reactor (LR), whereas the second reactor (R2), the third reactor (R3) and the fourth reactor (R4) are gas phase reactors (GPR).
  • SR slurry reactor
  • GPR-1 first gas phase reactor
  • GPR-2 second gas phase reactor
  • GPR-3 third gas phase reactor
  • the third gas phase reactor (GPR-3) is optional, i.e. three reactors (LR, GPR-1 , GPR-2) are used.
  • a preferred multistage process is a "loop-gas phase"-process, such as developed by Borealis A/S, Denmark
  • a further suitable slurry-gas phase process is the Spheripol ® process of Basell.
  • the conditions for the first reactor (Rl), 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 1 10 °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, hydrogen can be added for controlling the molar mass in a manner known per se.
  • 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,
  • hydrogen can be added for controlling the molar mass in a manner known per se.
  • 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 (Rl), 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).
  • the process comprises also a prepolymerization with the catalyst system, as described in detail below, comprising a Ziegler-Natta procatalyst, an external donor and optionally a cocatalyst.
  • the catalyst system as described in detail below, comprising a Ziegler-Natta procatalyst, an external donor and optionally a cocatalyst.
  • the prepolymerization 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 prepolymerization reaction is typically conducted at a temperature of 10 to 60 °C, preferably from 15 to 50 °C, and more preferably from 20 to 45 °C.
  • the pressure in the prepolymerization 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 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
  • prepolymerization 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 first heterophasic propylene copolymer (HECO-1) 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.
  • the procatalyst used according to the invention for preparing the first heterophasic propylene copolymer (HECO-1 ) is prepared by
  • R 1 and R 2 are independently at least a C 5 alkyl
  • step c) optionally reacting the product of step c) with additional T1CI4
  • 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.
  • the adduct which is first melted and then spray crystallized or emulsion solidified, is used as catalyst carrier.
  • 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
  • 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 catalyst used according to the invention is the catalyst as described in the example section; especially with the use of dioctylphthalate as dialkylphthalate of formula (I).
  • the catalyst system used preferably comprises in addition to the special Ziegler-Natta procatalyst an organometallic cocatalyst as component (ii).
  • the cocatalyst from the group consisting of trialkylaluminium, like triethylaluminium (TEA), dialkyl aluminium chloride and alkyl aluminium sesquichloride.
  • TAA triethylaluminium
  • dialkyl aluminium chloride dialkyl aluminium chloride
  • alkyl aluminium sesquichloride alkyl aluminium sesquichloride
  • Component (iii) of the catalysts system used is an external donor represented by formula (Ilia) or (Illb).
  • Formula (Ilia) 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.
  • Formula (Illb) is defined by Si(OCH 2 CH 3 ) 3 (NR x R y ) (Illb)
  • R x and R y can be the same or different, representing 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.
  • 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.-amyl, neopentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and cycloheptyl.
  • 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 (Ilia), like dicyclopentyl dimethoxy silane
  • the external donor of formula (Illb) is diethylaminotriethoxysilane.
  • 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 (component (i)), an external donor (component (iii) and optionally a cocatalyst (component (iii)), which vinyl compound has the formula:
  • R 3 and R 4 together form a 5- or 6-membered saturated, unsaturated or aromatic ring or
  • the modified catalyst is used for the preparation of the heterophasic propylene copolymer according to this invention.
  • the polymerized vinyl compound can act as an a-nucleating agent.
  • the first heterophasic propylene copolymer (HECO-1 ) is -nucleated.
  • the -nucleation is not effected by a vinylcycloalkane polymer or a vinylalkane polymer as indicated above, the following a-nucleating agents may be present (i) salts of monocarboxylic acids and polycarboxylic acids, e.g. sodium benzoate or aluminum tert- butylbenzoate, and
  • dibenzylidenesorbitol e.g. 1,3 : 2,4 dibenzylidenesorbitol
  • dibenzylidenesorbitol derivatives such as methyldibenzylidenesorbitol, ethyldibenzylidenesorbitol or dimethyldibenzylidenesorbitol (e.g. 1 ,3 : 2,4 di(methylbenzylidene) sorbitol), or substituted nonitol-derivatives, such as l ,2,3,-trideoxy-4,6:5,7-bis-0-[(4-propylphenyl)methylene]-nonitol, and
  • salts of diesters of phosphoric acid e.g. sodium 2,2'-methylenebis (4, 6,-di-tert-butylphenyl)
  • the polyolefin composition according to the present invention further comprises a second heterophasic propylene copolymer (HECO-2) as an essential component.
  • HECO-2 heterophasic propylene copolymer
  • the second heterophasic propylene copolymer (HECO-2) typically has a higher melt flow rate MFR 2 than the first heterophasic propylene copolymer (HECO-1 ). Furthermore, the intrinsic viscosity (IV) of the xylene cold soluble (XCS) fraction of the second heterophasic propylene copolymer (HECO-2) is preferably lower than in the xylene cold soluble (XCS) fraction of the first heterophasic propylene copolymer (HECO-1). Hence it is preferred that
  • the melt flow rate MFR 2 (230°C) of the first heterophasic propylene copolymer (HECO-1) is at least 5 g/l Omin, more preferably at least 8 g/l Omin yet more preferably at least 10 g/l Omin, lower than the melt flow rate MFR 2 (230°C) of the second heterophasic propylene copolymer (HECO-2);
  • the intrinsic viscosity (IV) of the xylene cold soluble (XCS) fraction of the first heterophasic propylene copolymer (HECO-1 ) is at least 0.3 dl/g, more preferably at least 0.5 dl/g, still more preferably 0.5 to 1.8 dl/, like 0.8 to 1.5 dl/g, higher than the melt flow rate MFR 2 (230°C) of the second heterophasic propylene copolymer (HECO-2)
  • the comonomer content, like ethylene content, of the first heterophasic propylene copolymer (HECO-1) is at least 2.0 wt.-%, more preferably at least 5.0 wt.-%, yet more preferably in the range of 2.0 to 18.0 wt.-%, like 5.0 to 15.0 wt.-%, like 5.0 to 10.0wt%, lower than the comonomer content, like ethylene content, of the second heterophasic prop
  • the second heterophasic propylene copolymer (HECO-2) before mixed with the other components mentioned herein comprises as polymer components only the matrix polypropylene (PP-2) and dispersed therein the elastomeric propylene copolymer (E-2).
  • the second heterophasic propylene copolymer (HECO-2) may contain further additives but no other polymer in an amount exceeding 5 wt-%, more preferably exceeding 3 wt.-%, like exceeding 1 wt.-%, based on the total amount of the second heterophasic propylene copolymer (HECO-2), more preferably based on the polymers present in the second heterophasic propylene copolymer (HECO-2).
  • One additional polymer which may be present in such low amounts is a polyethylene which is a reaction product obtained by the preparation of the second heterophasic propylene copolymer (HECO-2).
  • a second heterophasic propylene copolymer (HECO-2) as defined in the instant invention contains only a polypropylene (PP-2), an elastomeric propylene copolymer (E-2) and optionally a polyethylene in amounts as mentioned in this paragraph.
  • the second heterophasic propylene copolymer has a melt flow rate MFR2 (230°C) measured according to ISO 1 133 in the range of from 7.0 to 19 g/l Omin, more preferably in the range of 8.0 to 15.0 g/l Omin, still more preferably in the range of from 9.0 to 14.0 g/lOmin, and even more preferably in the range of from 10.0 to 12.0 g/l Omin.
  • the propylene content in the second heterophasic propylene copolymer (HECO-2) is preferably in the range 78.0 to 92.0 wt-%, more preferably in the range of 80.0 to 91.0 wt-%, yet more preferably in the range of 82.0 to 90.0 wt-% and even more preferably 85.0 to 89.0 wt-% based on the total weight of the second heterophasic propylene copolymer (HECO-2), more preferably based on the amount of the polymer components of the second heterophasic propylene copolymer (HECO-2), yet more preferably based on the amount of the polypropylene (PP-2) and the elastomeric propylene copolymer (E-2) together.
  • the remaining part constitutes the comonomers, like ethylene, as defined for the polypropylene (PP-2) being a propylene copolymer (R-PP-2) and the elastomeric propylene copolymer (E-2), respectively.
  • PP-2 polypropylene
  • R-PP-2 propylene copolymer
  • E-2 elastomeric propylene copolymer
  • the comonomer content is preferably in the range of 8.0 to 22.0 wt.-%, more preferably in the range of 9.0 to 20.0 wt-%, yet more preferably in the range of 10.0 to 18.0 wt-% and even more preferably in the range of 1 1.0 to 15.0 wt-% based on the total weight of the second heterophasic propylene copolymer (HECO-2), more preferably based on the amount of the polymer components of the second heterophasic propylene copolymer (HECO-2), yet more preferably based on the amount of the polypropylene (PP-2) and the elastomeric propylene copolymer (E-2) together.
  • the matrix of the second heterophasic propylene copolymer (HECO-2) is the polypropylene (PP-2).
  • the polypropylene (PP-2) according to this invention constituting the matrix of the second heterophasic copolymer (HECO-2) shall have a melt flow rate MFR 2 (230 °C) in the range of from 40.0 to 80.0 g/lOmin, more preferably in the range of 45.0 to 70.0 g/lOmin, yet more preferably in the range of 50.0 to 65.0 g/10 min, still even more preferably in the range of 50.0 to 60.0 g/l Omin.
  • the polypropylene (PP-2) can be a propylene copolymer (R-PP-2) or a propylene homopolymer (H-PP-2), the latter is preferred.
  • the polypropylene (PP-2) has a comonomer content equal or below 7.0 wt- %, more preferably equal or below 4.0 wt-%, still more preferably equal or below 1.0 wt-%.
  • the polypropylene (PP-2) is a propylene copolymer (R-PP-2) it comprises monomers
  • the propylene copolymer (R-PP-2) comprises, especially consists of, monomers copolymerizable with propylene from the group consisting of ethylene, 1-butene and 1 -hexene. More specifically the propylene copolymer (R-PP-2) comprises - apart from propylene - units derivable from ethylene and/or 1-butene.
  • the propylene copolymer (R-PP-2) comprises units derivable from ethylene and propylene only.
  • the comonomer content in the propylene copolymer (R-PP-2) is preferably in the range of more than 1.0 to 7.0 wt-%, still more preferably in the range of more than 1.0 to 4.0 wt-%.
  • the polypropylene (PP-2) can have a xylene cold soluble content (XCS) in a broad range, i.e. up to 5.0 wt.- %>.
  • the polypropylene (PP-2) may have a xylene cold soluble content (XCS) in the range of 0.3 to 5.0 wt.-%, preferably in the range of 0.5 to 4.5 wt.-%, like in the range of 1.0 to 4.0 wt.-%.
  • XCS xylene cold soluble content
  • XCS xylene cold soluble
  • the elastomeric propylene copolymer (E-2) preferably comprises monomers copolymerizable with propylene, for example comonomers such as ethylene and/or C 4 to C12 a-olefins, in particular ethylene and/or C 4 to Cio a-olefins, e.g. 1-butene and/or 1-hexene.
  • the elastomeric propylene copolymer (E-2) comprises, especially consists of, monomers copolymerizable with propylene from the group consisting of ethylene, 1 -butene and 1-hexene. More specifically the elastomeric propylene copolymer (E-2) comprises - apart from propylene - units derivable from ethylene and/or 1-butene.
  • the elastomeric propylene copolymer phase (E-2) comprises units derivable from ethylene and propylene only.
  • polypropylene (PP-2) is a propylene copolymer (R-PP-2) it is preferred that the comonomer(s) of the propylene copolymer (R-PP-2) and the elastomeric propylene copolymer (E-2) are the same.
  • the properties of the elastomeric propylene copolymer phase (E-2) are mainly influenced by the xylene cold soluble (XCS) content of the second heterophasic propylene copolymer (HECO-2).
  • the xylene cold soluble (XCS) fraction of the second heterophasic propylene copolymer (HECO-2) is regarded as the elastomeric propylene copolymer (E-2) of the second heterophasic propylene copolymer (HECO-2).
  • HECO-2 xylene cold soluble (XCS) fraction
  • HECO-2 xylene cold soluble (XCS) fraction
  • XCS xylene cold soluble
  • HECO-2 xylene cold soluble (XCS) fraction
  • HECO-2 xylene cold soluble (XCS) fraction
  • the elastomeric propylene copolymer (E-2) has a balanced weight average molecular weight. Accordingly the intrinsic viscosity must be carefully chosen.
  • the elastomeric propylene copolymer phase (E-2), i.e. the xylene cold soluble fraction (XCS) of the second heterophasic propylene copolymer (HECO-2), has an intrinsic viscosity (IV) determined according to DIN ISO 1628/1 (in decaline at 135 °C) in the range of from 2.0 to 4.0 dl/g, more preferably in the range of from equal or more than 2.0 to 3.5 dl/g, and still even more preferably in the range of equal or more than from 2.0 to 3.0 dl/g, like in the range of 2.1 to 2.8 dl/g.
  • the comonomer content, preferably the ethylene content, within the elastomeric propylene copolymer phase (E-2) shall be preferably also in a specific range. Accordingly in a preferred embodiment the comonomer content, more preferably ethylene content, of the elastomeric propylene copolymer (E-2), i.e. of the xylene cold soluble fraction (XCS) of the second heterophasic propylene copolymer (HECO-2), is in the range of from 28.0 to 50.0 wt-%, still more preferably in the range of from 32.0 to 45.0 wt-%, yet more preferably in the range of from 35.0 to 42.0 wt-%.
  • XCS xylene cold soluble fraction
  • the propylene content of the elastomeric propylene copolymer (E-2), i.e. of the xylene cold soluble fraction (XCS) of the second heterophasic propylene copolymer (HECO-2), is preferably in the range of from 50.0 to 72.0 wt -%, still more preferably in the range of 55.0 to 68.0 wt-%, yet more preferably in the range of from 58.0 to 65.0 wt-%.
  • the second heterophasic polypropylene (HECO-2) as well its individual components can be produced by blending different polymer types, i.e. of different molecular weight and/or comonomer content.
  • the second heterophasic polypropylene (HECO-2) as well its individual components are produced in a sequential step process, using reactors in serial configuration and operating at different reaction conditions. As a consequence, each fraction prepared in a specific reactor will have its own molecular weight distribution and/or comonomer content distribution.
  • the second heterophasic propylene copolymer comprises an a-nucleating agent.
  • the present invention is free of ⁇ -nucleating agents.
  • the a-nucleating agent is preferably selected from the group consisting of
  • salts of monocarboxylic acids and polycarboxylic acids e.g. sodium benzoate or aluminum tert- butylbenzoate, and
  • dibenzylidenesorbitol e.g. 1 ,3 : 2,4 dibenzylidenesorbitol
  • dibenzylidenesorbitol derivatives such as methyldibenzylidenesorbitol, ethyldibenzylidenesorbitol or dimethyldibenzylidenesorbitol (e.g. 1 ,3 : 2,4 di(methylbenzylidene) sorbitol), or substituted nonitol-derivatives, such as l,2,3,-trideoxy-4,6:5,7-bis-0-[(4-propylphenyl)methylene]-nonitol, and
  • salts of diesters of phosphoric acid e.g. sodium 2,2'-methylenebis (4, 6,-di-tert-butylphenyl)
  • the second heterophasic propylene copolymer (HECO-2) contains up to 5 wt.-% of the a- nucleating agent.
  • the second heterophasic propylene copolymer (HECO-2) contains not more than 200 ppm, more preferably of 1 to 200 ppm, more preferably of 5 to 100 ppm of a a- nucleating agent, in particular selected from the group consisting of dibenzylidenesorbitol (e.g. 1 ,3 : 2,4 dibenzylidene sorbitol), dibenzylidenesorbitol derivative, preferably dimethyldibenzylidenesorbitol (e.g.
  • nonitol-derivatives such as l,2,3,-trideoxy-4,6:5,7-bis-0- [(4-propylphenyl)methylene]-nonitol, vinylcycloalkane polymer, vinylalkane polymer, and mixtures thereof.
  • the second heterophasic propylene copolymer contains a
  • the second heterophasic propylene copolymer (HECO-2) contains a vinylcycloalkane, like vinylcyclohexane (VCH), polymer and/or vinylalkane polymer.
  • the vinylcycloalkane is vinylcyclohexane (VCH) polymer introduced into the second heterophasic propylene copolymer (HECO-2) by the BNT technology.
  • the second heterophasic propylene copolymer (HECO-2) according to this invention is commercially available. Accordingly a skilled person in the art is in a position to produce a second heterophasic propylene copolymer (HECO-2) as defined herein.
  • the second heterophasic propylene copolymer (HECO-2) is preferably obtained by a specific process.
  • the second heterophasic propylene copolymer (HECO-2) is preferably obtained by a sequential polymerization process in the first reactor ( 1 st R') and optionally in a second reactor (2 nd R') the propylene homopolymer (H-PP2) is produced, whereas in the third reactor (3 rd R') and optionally in a fourth reactor (4 th R') the elastomeric propylene copolymer (E2) of the second heterophasic propylene copolymer (HECO-2) is obtained.
  • the term "sequential polymerization process" indicates that the second heterophasic propylene copolymer (HECO-2) is produced in at least two reactors, preferably in three or four reactors, connected in series.
  • the present process comprises at least a first reactor (1 st R'), an optional second reactor (2 nd R'), a third reactor (3 rd R') and optional a fourth reactor (4 th R')
  • polymerization reactor shall indicate that the main polymerization takes place.
  • 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 matrix (M2) i.e.
  • the propylene homopolymer (H-PP2) is produced.
  • a propylene homopolymer fraction (H-PP2a) and (H-PP2b) is produced which may differ or be the same in the melt flow rate as indicated above.
  • the first propylene homopolymer fraction (H-PP2a) is produced in the first reactor (1 st R') whereas the second propylene homopolymer fraction (H-PP2b) is produced in the second reactor (2 nd R').
  • the weight ratio between the first propylene homopolymer fraction (H-PP2a) and second propylene homopolymer fraction (H-PP2b) is 20/80 to 80/20, more preferably 30/70 to 70/30, yet more preferably 40/60 to 65/35.
  • the matrix (M2) i.e. the propylene homopolymer (H-PP2), of the second heterophasic propylene copolymer (HECO-2), is obtained.
  • This matrix (M2) is subsequently transferred into the third reactor (3 rd R') and optional fourth reactor (4 th R') in which the elastomeric propylene copolymer (E2) is produced and thus the second heterophasic propylene copolymer (HECO-2) of the instant invention is obtained.
  • the first reactor (1 st R') 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 (2 nd R'), the third reactor (3 rd R') and fourth reactor (4 th R') are preferably gas phase reactors (GPR).
  • GPR gas phase reactors
  • Such gas phase reactors (GPR) can be any mechanically mixed or fluid bed reactors.
  • the gas phase reactors 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 (1 st R') is a slurry reactor (SR), like loop reactor (LR), whereas the second reactor (2 nd R'), the third reactor (3 rd R') and the optional fourth reactor (4 th R') are gas phase reactors (GPR).
  • SR slurry reactor
  • GPR gas phase reactor
  • at least two, preferably at least two or three 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 optionally a 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
  • WO 92/12182 WO 2004/000899, WO 2004/1 1 1095, WO 99/24478, WO 99/24479 or in WO 00/68315.
  • a further suitable slurry-gas phase process is the Spheripol ® process of Basell.
  • the conditions for the first reactor (1 st R'), i.e. the slurry reactor (SR), like a loop reactor (LR), may be as follows:
  • the temperature is within the range of 40 °C to 1 10 °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, hydrogen can be added for controlling the molar mass in a manner known per se.
  • the reaction mixture from the first reactor (1 st R') is transferred to the second reactor (2 nd R'), i.e. 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,
  • hydrogen can be added for controlling the molar mass in a manner known per se.
  • the condition in the third reactor (3 rd R') and the fourth reactor (4 th R'), preferably in the second gas phase reactor (GPR-2) and third gas phase reactor (GPR-3), are similar to the second reactor (2 nd R').
  • the residence time can vary in the three or four reactor zones.
  • the residence time the first reactor (1 st R'), i.e. the slurry reactor (SR), like a loop reactor (LR), is in the range 0.2 to 4 hours, e.g. 0.3 to 1.5 hours and the residence time in the gas phase reactors 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 (1 st R'), 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).
  • the process comprises also a prepolymerization with the catalyst system, as mentioned below, comprising a Ziegler-Natta procatalyst, an external donor and optionally a cocatalyst.
  • the catalyst system as mentioned below, comprising a Ziegler-Natta procatalyst, an external donor and optionally a cocatalyst.
  • the prepolymerization 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 prepolymerization 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 prepolymerization 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 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
  • prepolymerization 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.
  • the second heterophasic propylene copolymer (HECO-2) is obtained by a sequential polymerization process, as described above, in the presence of a catalyst system comprising a Ziegler-Natta catalyst and optionally an external donor, preferably a catalyst system comprising three components, namely as component (i) a Ziegler-Natta procatalyst, and optionally as component (ii) an organometallic cocatalyst and as component (iii) an external donor represented by formula (Ilia) or (Illb), preferably represented by formula (Ilia), as described above in accordance with the preparation of the first heterophasic propylene copolymer (HECO-1 ).
  • the external donor is of formula (Ilia), like dicyclopentyl dimethoxy silane
  • EEC Elastomeric ethylene copolymer
  • a further essential component of the present polypropylene composition (PP) is an elastomeric ethylene copolymer (EEC).
  • the elastomeric ethylene copolymer (EEC) is added to the polypropylene composition (PP) according to the present invention for improving toughness and reducing shrinkage.
  • the elastomeric ethylene copolymer is an ethylene copolymer comprising ethylene monomer units and comonomer units selected from C3 to C 2 o a-olefins, preferably propene, 1 -butene, 1-hexene and 1-octene, or C 5 to C 2 o ⁇ , ⁇ -alkadienes, preferably 1,7-octadiene.
  • the comonomer is selected from 1 -butene, 1-hexene, and 1 - octene, wherein 1-octene is most preferred as the comonomer.
  • the elastomeric ethylene copolymer may contain between 55.0 to 85.0 wt.-% ethylene, preferably 60.0 to 80.0 wt.-% ethylene, and more preferably 65.0 to 75.0 wt.-% ethylene, based on the total amount of the elastomeric polyolefin copolymer. The remaining part to 100 wt.-% constitute the comonomer units.
  • the elastomeric ethylene copolymer (EEC) has a melt flow rate MFR 2 (190 °C) measured according to ISO 1 133 in the range of from 0.5 to 50.0 g/l Omin. More preferably, the elastomeric ethylene copolymer (POC) has a melt flow rate MFR 2 (190 °C) in the range of from 20.0 to 40.0 g/lOmin, more preferably in the range of from 25.0 to 35.0 g/lOmin, and most preferably in the range of from 28.0 to 32.0 g/10min.
  • the elastomeric ethylene copolymer (EEC) has preferably a density of below 920 kg/m 3 , more preferably of below 900 kg/m 3 , still more preferably in the range of from 800 to 920 kg/m 3 , yet more preferably in the range of from 850 to 900 kg/m 3 and most preferably in the range of from 860 to 890 kg/m 3 .
  • the elastomeric ethylene copolymer (EEC) is known in the art and belongs in a preferred embodiment to the Exact or Engage series, respectively.
  • One important aspect of the present invention is that the amount of elastomeric ethylene copolymer (EEC) in the polypropylene composition (PP) is rather low.
  • the elastomeric ethylene copolymer is present in the polypropylene composition (PP) according to the present invention in an amount of between 1.0 and 10.0 wt.-%, preferably in an amount between 3.0 and 10.0 wt.-%, more preferably in an amount between 5.0 and 9.0 wt.-% based on the total weight of the polypropylene composition (PP).
  • the polypropylene composition (PP) according to the present invention comprises inorganic filler (F).
  • the inorganic filler (F) is present in the polypropylene composition (PP) in amounts of up to 50 wt.-%. It is preferred that the amount of inorganic filler (F) is in the range of from 25.0 to 48.0 wt.-%, more preferably in the range of from 30.0 to 45.0 wt.-%, and even more preferably in the range of from 35.0 to 40.0 wt.-% based on the total weight of the polypropylene composition (PP).
  • the inorganic filler (F) is mica, wollastonite, kaolinite, smectite, calcium carbonate,
  • the most preferred inorganic filler (F) is talc.
  • the inorganic filler (F) 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 ⁇ , more preferably in the range of 0.3 to 15.0 ⁇ , still more preferably in the range of 0.4 to 10.0 ⁇ .
  • the most preferred median particle size d 50 is in the range of 0.60 to 7.0 ⁇ , including the most appropriate median particle size d 50 of 2.40 ⁇ .
  • the mineral filler (F) preferably has a cutoff particle size d 95 calculated from the particle size distribution in mass percent and measured by laser diffraction of equal or below 20 ⁇ , more preferably of equal or below 15 ⁇ , and even more preferably of equal or below 10 ⁇ .
  • the inorganic filler (F) 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 10.0 to 30.0 m 2 /g and even more preferably in the range of 10.0 to 20.0 m 2 /g. It is preferred that the inorganic filler (F) is present in a specific weight ratio relative to the combined first and second heterophasic propylene copolymer (HECO-1 ) and (HECO-2) in the polypropylene composition (PP).
  • HECO-1 first and second heterophasic propylene copolymer
  • PP polypropylene composition
  • the weight ratio of the combined heterophasic propylene copolymers (HECO-1 ) and (HECO-2) to the inorganic filler (F) [HECOl+HECO-2 / F] is from 2.8 to 0.3.
  • [HECOl+HECO-2 / F] is from 1.2 to 0.9, and even more preferably from 1.8 to 0.6.
  • the weight ratio of propylene homopolymer (homo-PP) to the inorganic filler (F) [homo-PP/F] is from 1.2 to 0.2.
  • the weight ratio of polypropylene homopolymer (homo-PP) to the inorganic filler (F) [homo-PP/F] is from 0.9 to 0.3, and more preferably from 0.7 to 0.4.
  • the inorganic filler (F) has a surface area measured according to the commonly known BET method with N 2 gas as analysis adsorptive of less than 22 m 2 /g, more preferably of less than 20 m 2 /g, yet more preferably of less than 18 m /g.
  • Inorganic fillers (F) fulfilling these requirements are preferably anisotropic mineral fillers (F), like talc, mica and wollastonite.
  • the polypropylene composition (PP) may further (optionally) comprise at least one typical additive selected from the group consisting of acid scavengers, antioxidants, colorants, pigments, light stabilizers, UV-stabilizers, slip agents, anti-scratch agents, dispersing agents, carriers and colorants.
  • the amount of these additives shall not exceed 10.0 wt.-%, preferably not more than 7.0 wt.-%, and most preferably not more than 5.0 wt.-% based on the total weight of the polypropylene composition (PP), within the instant polypropylene composition (PP).
  • the instant polypropylene composition (PP) contains preferably an a-nucleating agent. Even more preferred the present invention is free of ⁇ -nucleating agents.
  • the nucleating agent is understood as a nucleating agent different to the inorganic filler (F). Accordingly, the nucleating agent is preferably selected from the group consisting of (i) salts of monocarboxylic acids and polycarboxylic acids, e.g. sodium benzoate or aluminum tert- butylbenzoate, and
  • dibenzylidenesorbitol e.g. 1 ,3 : 2,4 dibenzylidenesorbitol
  • dibenzylidenesorbitol derivatives such as methyldibenzylidenesorbitol, ethyldibenzylidenesorbitol or dimethyldibenzylidenesorbitol (e.g. 1 ,3 : 2,4 di(methylbenzylidene) sorbitol), or substituted nonitol-derivatives, such as l ,2,3,-trideoxy-4,6:5,7-bis-0-[(4-propylphenyl)methylene]-nonitol, and
  • salts of diesters of phosphoric acid e.g. sodium 2,2'-methylenebis (4, 6,-di-tert-butylphenyl)
  • the a-nucleating agent is part of the first and/or second heterophasic propylene copolymer (HECO-1 ) and (HECO-2) thus of the polypropylene composition (PP).
  • the ⁇ -nucleating agent content of the two essential heterophasic propylene copolymers (HECO-1 ) and (HECO-2) and thus of the polypropylene composition (PP) is preferably up to 5.0 wt.-%.
  • the two essential heterophasic propylene copolymers (HECO- 1 ) and (HECO-2) and thus the polypropylene composition (PP) contain(s) not more than 3,000 ppm, more preferably of 1 to 2,000 ppm of a ⁇ -nucleating agent, in particular selected from the group consisting of dibenzylidenesorbitol (e.g. 1 ,3 : 2,4 dibenzylidene sorbitol), dibenzylidenesorbitol derivative, preferably dimethyldibenzylidenesorbitol (e.g. 1 ,3 : 2,4
  • di(methylbenzylidene) sorbitol) or substituted nonitol-derivatives, such as l ,2,3,-trideoxy-4,6:5,7-bis-0-[(4- propylphenyl)methylene]-nonitol, vinylcycloalkane polymer, vinylalkane polymer, and mixtures thereof.
  • nonitol-derivatives such as l ,2,3,-trideoxy-4,6:5,7-bis-0-[(4- propylphenyl)methylene]-nonitol, vinylcycloalkane polymer, vinylalkane polymer, and mixtures thereof.
  • the two essential heterophasic propylene copolymers (HECO-1 ) and (HECO-2) and thus the polypropylene composition (PP) contains a vinylcycloalkane, like vinylcyclohexane (VCH), polymer and/or vinylalkane polymer, as the ⁇ -nucleating agent.
  • the two essential heterophasic propylene copolymers (HECO-1) and (HECO-2) contain a vinylcycloalkane, like vinylcyclohexane (VCH), polymer and/or vinylalkane polymer, preferably vinylcyclohexane (VCH).
  • the vinylcycloalkane is vinylcyclohexane (VCH) polymer which is optionally introduced into at least one of the two essential heterophasic propylene copolymers (HECO-1 ) and (HECO-2) and thus into the polypropylene composition (PP) by the BNT technology.
  • VCH vinylcyclohexane
  • the amount of vinylcycloalkane, like vinylcyclohexane (VCH), polymer and/or vinylalkane polymer, more preferably of vinylcyclohexane (VCH) polymer, in the two essential heterophasic propylene copolymers (HECO-1 ) and (HECO-2) is not more than 500 ppm, more preferably of 0.5 to 200 ppm, most preferably 1 to 100 ppm,. Accordingly it is thus preferred that the polypropylene composition (PP) contains not more than 500 ppm, more preferably of 0.1 to 200 ppm, most preferably 0.2 to 100 ppm, of vinylcyclohexane (VCH) polymer.
  • a catalyst system preferably a Ziegler-Natta procatalyst
  • a vinyl compound in the presence of the catalyst system, comprising in particular 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
  • the modified catalyst is used for the preparation of the heterophasic polypropylene according to this invention, i.e. of the heterophasic propylene copolymers (HECO-1 ) and (HECO-2).
  • the polymerized vinyl compound acts as an a-nucleating agent.
  • the weight ratio of vinyl compound to solid catalyst component in the modification step of the catalyst is preferably of up to 5 (5: 1), preferably up to 3 (3: 1 ) most preferably from 0.5 ( 1 :2) to 2 (2: 1).
  • the most preferred vinyl compound is vinylcyclohexane (VCH).
  • the polypropylene composition (PP) of the present invention is preferably used for the production of articles in the field of household appliances, medical appliances, automotive articles, particularly moulded automotive articles or automotive injection moulded articles, pipes and toys. Even more preferred is the use for the production of household appliances, like base or housing of air conditioner, refrigerator, etc.
  • NMR nuclear-magnetic resonance
  • Quantitative 1 C ⁇ 'H ⁇ NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals using proprietary computer programs.
  • the tacticity distribution was quantified through integration of the methyl region between 23.6-19.7 ppm correcting for any sites not related to the stereo sequences of interest (Busico, V., Cipullo, R., Prog. Polym. Sci. 26 (2001) 443; Busico, V., Cipullo, R., Monaco, G., Vacatello, M., Segre, A.L., Macromolecules 30 (1997) 6251).
  • the isotacticity was determined at the pentad level and reported as the percentage of isotactic pentad
  • the amount of 2,1 erythro regio-defects was quantified using the average integral of the two characteristic methyl sites at 17.7 and 17.2 ppm:
  • the amount of 1 ,2 primary inserted propene was quantified based on the methyl region with correction undertaken for sites included in this region not related to primary insertion and for primary insertion sites excluded from this region:
  • the total amount of propene was quantified as the sum of primary inserted propene and all other present regio-defects:
  • the comonomer fraction was quantified using the method of W-J. Wang and S. Zhu, Macromolecules 2000, 33 1 157 , through integration of multiple signals across the whole spectral region in the 13 C ⁇ '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 mole fraction.
  • T m Melting temperature: measured with a TA Instrument Q2000 differential scanning calorimetry (DSC) on 5 to 7 mg samples. DSC is run according to ISO 1 1357 / part 3 /method C2 in a heat / cool / heat cycle with a scan rate of 10 °C/min in the temperature range of -30 to +225°C. Melting temperature is determined from the second heating step.
  • DSC differential scanning calorimetry
  • Density is measured according to ISO 1 183- 1 - method A (2004). Sample preparation is done by compression moulding in accordance with ISO 1872-2:2007.
  • MFR 2 (230°C) is measured according to ISO 1 133 (230°C, 2.16 kg load).
  • MFR 2 (190°C) is measured according to ISO 1 133 (190°C, 2.16 kg load).
  • Xylene cold solubles (XCS, wt.-%): Content of xylene cold solubles (XCS) is determined at 25 °C according ISO 16152; first edition; 2005-07-01 Intrinsic viscosity is measured according to DIN ISO 1628/1, October 1999 (in Decalin at 135 °C).
  • Flexural Modulus and flexural strength were 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.
  • the izod notched impact strength is measured according to ISO 180 / 1A at 23 °C by using injection moulded test specimens as described in EN ISO 1873-2 (80 x 10 x 4 mm).
  • Median particle size d 50 and Cutoff particle size d 95 (Laser diffraction) is calculated from the particle size distribution [mass percent] as determined by laser diffraction (Mastersizer) according to ISO 13320-1. Specific surface area is determined as the BET surface according to DIN 66131/2.
  • An oblong sheet for test is prepared by injection-moulding in an injection machine, model "Engel 120" of Engel Austria GmbH, Austria.
  • a mold is attached to the injection machine, having an inner oblong cavity with a size of 150mm*90mm*3mm.
  • the injection machine has four heating zones, wherein temperature of the four zones is respectively 195°C, 200°C, 190°C and 180°C. Temperature of the mold is 40°C.
  • Raw materials for producing the sheet are fed into extruder of the injection machine, melt in the four heating zones, and are injected at a speed of 10-15mm/s into the mold.
  • a pressure of 25 bar is applied and held for 20 seconds to the melt flowing into the mold.
  • a sheet is formed and cooled in the mold for 35 seconds, and to open the mold and to remove the oblong sheet from the inner cavity of the mold. Then, the obtained sheet is conditioned at 23 ⁇ 2°C and a humidity of 50% for 48 hours before the test.
  • Moulding shrinkage is the difference in dimensions between a dry test sheet specimen and the mould cavity in which it was moulded, both the mould and the test specimen being at room temperature when measured. It is expressed as a percentage (%) of the mold cavity dimension concerned.
  • S L is the moulding shrinkage parallel to the melt flow direction, which is determined at the mid-point of the length of the test specimen.
  • Lo is the length, in millimetres, across the centre of the cavity
  • L is the corresponding length, in millimetres, of the test specimen.
  • S w is the moulding shrinkage normal to the flow direction, which is determined at the mid-point of the width of the test specimen.
  • W 0 is the width, in millimetres, across the centre of the cavity
  • W is the corresponding width, in millimetres, of the test specimen.
  • the present invention is illustrated by the following examples.
  • the hetrophasic propylene copolymers HECOl and HECO 2-1, and HECO 2-2 were used for the inventive examples, which were prepared with one slurry loop reactor and two/three gas phase reactors by the known Borstar® technology, as disclosed in EP 0,887,379 A l .
  • the catalyst used in the polymerization processes for HECO-1 , HECO-2-1 and HECO-2-2 has been produced by the publically known method as follows: First, 0.1 mol of MgCl 2 3 EtOH was suspended under inert conditions in 250 ml of decane in a reactor at atmospheric pressure. The solution was cooled to the temperature of -15°C and 300 ml of cold TiCl 4 was added while maintaining the temperature at said level. Then, the temperature of the slurry was increased slowly to 20 °C. At this temperature, 0.02 mol of dioctylphthalate (DOP) was added to the slurry. After the addition of the phthalate, the temperature was raised to 135 °C during 90 minutes and the slurry was allowed to stand for 60 minutes.
  • DOP dioctylphthalate
  • HECO-1 As donor for the preparation of HECO-1 , HECO-2-1 , and HECO-2-2, dicyclo pentyl dimethoxy silane (D- donor) was used. The aluminium to donor ratio is indicated in table 1.
  • Table la Preparation and Properties of HECO 1 and HECO 2 (Loop/GPRl )
  • Homo-PP are the following commercially available propylene homopolymers:
  • EEC is the commercial ethylene/octylene copolymer "Engage 8407” of Dow Elastomes having MFR 2 of 30 g/1 Omin (190°C/2.16 kg) and a density of 0.870 g/cm 3 .
  • Fill is the commercial talc-based mineral filler "HTP 2" of IMI Fabi Corporation (Italy) having d 50 of 2.40 ⁇ , d 95 of 8.4 ⁇ and a surface area "BET" of 8 g/m 2 .
  • the inventive compositions of IE 1 to IE 10 based on the recipes as summarized in Table 2 are prepared by using a Coperion STS-35 twin-screw extruder (available from Coperion (Nanjing) Corporation, China) with a diameter of 35 mm.
  • the twin-screw extruder runs at an average screw speed of 500 rpm with a temperature profile of zones from 180-230 °C. It has a L/D of 44.
  • the temperature of each zone, throughput and the screw speed of the extruder for preparing the inventive compositions of IE1 to IE10 are listed in Table 3.
  • each zone including zones 1 to 1 1 , zone 1 is feed port of the extruder with Room Temperature
  • throughput and screw speed of the extruder are initiative parameters, and are set on control panel of the extruder.
  • Melt temperature (temperature of the melt in the die) and torque of the extruder are passive parameters shown on control panel of the extruder.
  • a vacuum bump is located in zone 9 and generates a vacuum of -0.06 MPa inside the extruder.
  • Table 3a Extruder conditions of the inventive compositions of IE 1 to IE6
  • the comparative polymer is a high impact polystyrene (HIPS) grafted with polybutyl rubber, prepared by polymerizing styrene and grafting with polybutyl rubber simultaneously.
  • HIPS high impact polystyrene
  • Table 4a Properties of inventive compositions of IE1 to IE5
  • the inventive composition IE1 to IE 10 shows comparative shrinkage and impact, better stiffness (modulus and strength), meanwhile having much lower cost in the material and preparation.

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Abstract

La présente invention concerne une composition de polypropylène comprenant un homopolymère de propylène, deux copolymères de propylène hétérophasiques, un copolymère d'éthylène élastomère et une charge inorganique, qui présente une retrait réduit et des propriétés mécaniques équilibrées.
PCT/CN2013/001462 2013-11-29 2013-11-29 Composition de polypropylène à faible retrait et à propriétés mécaniques équilibrées WO2015077902A1 (fr)

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CN108137889A (zh) * 2015-10-06 2018-06-08 博里利斯股份公司 用于汽车应用的聚丙烯组合物
CN108137887A (zh) * 2015-10-23 2018-06-08 博里利斯股份公司 多相组合物
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CN107722448A (zh) * 2016-08-11 2018-02-23 株式会社瑞延理化 利用天然纤维的汽车内饰材料用复合组合物
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US11912849B2 (en) 2017-12-05 2024-02-27 Borealis Ag Fiber reinforced polypropylene composition
US11945926B2 (en) 2018-05-16 2024-04-02 Abu Dhabi Polymers Co. Ltd (Borouge) Llc. Foamed polypropylene composition
WO2023017805A1 (fr) * 2021-08-11 2023-02-16 サンアロマー株式会社 Composition de polypropylène et article moulé par injection

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