Fiber-reinforced polypropylene composition

Abstract

The present invention relates to a fiber reinforced composition (C) comprising a heterophasic polypropylene composition (HECO), fibers (F) and an adhesion promoter (AP) and to articles comprising said fiber reinforced composition (C).

Description

Technical Field

[0001] The present invention relates to a fiber reinforced composition (C) comprising a heterophasic polypropylene composition (HECO), fibers (F) and an adhesion promoter (AP) and to articles comprising said fiber reinforced composition (C). Background Art

[0002] Fiber-reinforced materials are widely used in various applications, particularly in engineering, where increased stiffness and good impact resistance are considered beneficial. Polypropylene is one of the most popular base polymers due to its versatility, low cost, and low density. It can meet most target properties. Polypropylene produced in the presence of metallocene catalysts is a promising candidate due to additional benefits such as controlled molecular weight distribution, good comonomer incorporation, and low emissions. However, due to the nature of the compound, tensile strength and elongation at break often suffer at high filler ratios.

[0003] Therefore, there is a need in the art for a fiber reinforced polypropylene composition characterized by excellent heat flexural properties and low emissions, while tensile strength and elongation at break are maintained at high levels. Summary of the Invention

[0004] Therefore, it is an object of the present invention to provide a fiber reinforced polypropylene composition having good mechanical properties, which fiber reinforced polypropylene composition is preferably based on a polypropylene produced in the presence of a metallocene catalyst.

[0005] Accordingly, the present invention relates to a fiber reinforced composition (C) comprising a) 55.0 to 95.0 wt.-%, based on the total weight of the fiber reinforced composition (C), of a heterophasic polypropylene composition (HECO) comprising

[0006] i) is a matrix of a propylene homo- or copolymer (PP) having an amount of 1,2 erythro regio defects of at least 0.4 mol-% and a comonomer content equal to or lower than 8.5 mol-%, and

[0007] ii) an elastomeric ethylene copolymer (E) dispersed in said matrix,

[0008] b) 5.0 to 45.0% by weight of fibers (F), and

[0009] c) optionally 0.1 to 5.0% by weight of an adhesion promoter (AP),

[0010] wherein the fiber-reinforced composition (C) has a melt flow rate MFR2 (230° C., 2.16 kg) measured according to ISO 1133 in the range of 1.0 to 60.0 g / 10 min.

[0011] A preferred embodiment of the present invention provides a fiber-reinforced composition (C) comprising, based on the total weight of the fiber-reinforced composition (C),

[0012] a) 55.0 to 95.0 wt.-% of a heterophasic polypropylene composition (HECO) comprising

[0013] i) is a matrix of a propylene copolymer (cPP) having an amount of 1,2 erythro regio defects of at least 0.4 mol-% and a comonomer content equal to or below 8.5 mol-%, and

[0014] ii) an elastomeric ethylene copolymer (E) dispersed in said matrix,

[0015] b) 5.0 to 45.0% by weight of fibers (F), and

[0016] c) optionally 0.1 to 5.0% by weight of an adhesion promoter (AP),

[0017] wherein the fiber reinforced composition (C) has a melt flow rate MFR2 (230° C., 2.16 kg) measured according to ISO 1133 in the range of 1.0 to 60.0 g / 10 min.

[0018] According to one embodiment of the present invention the heterophasic polypropylene composition (HECO) comprises based on the total weight of the heterophasic copolymer (HECO)

[0019] i) 60.0 to 95.0 wt.% of a matrix which is a propylene homopolymer or copolymer (PP), and

[0020] ii) 5.0 to 40.0 wt.% of an elastomeric ethylene copolymer (E).

[0021] According to another embodiment of the present invention the elastomeric ethylene copolymer (E) has an ethylene content in the range of 15.0 to 85.0 wt.-%, based on the total weight of the elastomeric ethylene copolymer (E).

[0022] According to another embodiment of the present invention the heterophasic polypropylene composition (HECO) has a melting temperature Tm determined according to differential scanning calorimetry (DSC) in the range of 130 to 165 °C.

[0023] According to one embodiment of the present invention the heterophasic polypropylene composition (HECO) has an intrinsic viscosity (IV) measured according to ISO 1628 / 1 (in decalin at 135 °C) of the soluble fraction (SF) determined according to CRYSTEX QC in the range of 1.8 to 3.0 dl / g.

[0024] According to another embodiment of the present invention, the fibers (F) are glass fibers (GF), preferably short glass fibers (SGF), having

[0025] i) an average length of 2.0 to 10.0 mm, and / or

[0026] ii) an average diameter of 5 to 20 μm.

[0027] According to another embodiment of the present invention, the adhesion promoter (AP) is a polar modified polypropylene (PM-PP) which is a propylene homopolymer or copolymer grafted with maleic anhydride, the polar modified polypropylene (PM-PP) having a melt flow rate MFR2 (230°C, 2.16 kg), measured according to ISO 1133, of at least 20.0 g / 10 min.

[0028] According to a first embodiment of the present invention the propylene homo- or copolymer (PP) is a propylene homopolymer (hPP) and the elastomeric ethylene polymer (E) is a copolymer of ethylene and propylene.

[0029] According to a first embodiment of the present invention the propylene homopolymer (hPP) has a melting temperature Tm determined according to differential scanning calorimetry (DSC) in the range of 140 to 160 °C.

[0030] According to a first embodiment of the present invention the heterophasic polypropylene composition (HECO) has a comonomer content in the range of 2.2 to 8.7 mol-%.

[0031] It is especially preferred that the heterophasic polypropylene composition (HECO) according to the first embodiment of the present invention has

[0032] i) a xylene cold soluble (XCS) content determined according to ISO 16152 at 25 °C in the range of 5.0 to 35.0 wt.-%, based on the total weight of the heterophasic polypropylene composition (HECO), and / or

[0033] ii) an ethylene content of the xylene cold soluble (XCS) fraction in the range of 20.9 to 44.7 mol%.

[0034] and / or

[0035] ii) a soluble fraction (SF) determined according to CRYSTEX QC in the range of 5.0 to 35.0 wt.-%, based on the total weight of the heterophasic polypropylene composition (HECO), and / or

[0036] iv) an ethylene content of the soluble fraction (SF) determined according to CRYSTEX QC in the range of 20.9 to 44.7 mol%.

[0037] According to a first embodiment of the present invention the heterophasic polypropylene composition (HECO) has a melt flow rate MFR2 (230°C, 2.16 kg) determined according to ISO 1133 in the range of 20.0 to 100 g / 10 min.

[0038] According to a first embodiment of the invention, the fiber reinforced composition (C) has a tensile modulus determined according to ISO 527-1A in the range of 3000 to 6000 MPa and / or an elongation at break determined according to ISO 527-2 of greater than 3.0%.

[0039] According to a second embodiment of the present invention, the propylene homopolymer or copolymer (PP) is a propylene copolymer (cPP), a copolymer of propylene and ethylene, preferably having an ethylene content of 2.2 to 8.5 mol%, and the elastomeric ethylene copolymer (E) is ethylene and C4 to C 12 A copolymer of an alpha-olefin, preferably 1-octene, the copolymer preferably having an ethylene content of 55.0 to 85.0 wt.-%, based on the total weight of the elastomeric ethylene copolymer (E).

[0040] According to a second embodiment of the invention the propylene copolymer (cPP) has a melt flow rate MFR2 (230°C, 2.16 kg) determined according to ISO 1133 in the range of 5.0 to 20.0 g / 10 min, and / or the elastomeric ethylene copolymer (E) has a melt flow rate MFR (190°C, 2.16 kg) determined according to ISO 1133 in the range of 0.8 to 20.0 g / 10 min, and / or in the range of 860 to 890 kg / m 3 The density is determined according to ISO 1183-187 within the range of .

[0041] According to a second embodiment of the present invention, the fiber reinforced composition (C) has a melt flow rate MFR2 (230° C., 2.16 kg), determined according to ISO 1133, in the range of 1.0 to 10.0 g / 10 min.

[0042] According to a second embodiment of the invention, the fiber reinforced composition (C) has a tensile modulus determined according to ISO 527-1A in the range of 2500 to 5500 MPa, and / or an elongation at break determined according to ISO 527-2 of greater than 10.0%.

[0043] According to one embodiment of the present invention, the fiber reinforced composition (C) further comprises up to 20.0 wt% of a low density polyethylene (LDPE) homopolymer or copolymer having a mass fraction greater than 900 kg / m 3 The density is determined according to ISO 1183-187 and comprises ethylene and optionally vinyl acetate.

[0044] According to one embodiment of the present invention the propylene homo- or copolymer (PP) is obtained in the presence of a solid catalyst system (SCS) comprising a metallocene compound.

[0045] It is particularly preferred that the metallocene compound has the formula (I)

[0046]

[0047] wherein each X is independently a σ-donor ligand,

[0048] L is a divalent bridge selected from -R'2C-, -R'2C-CR'2-, -R'2Si-, -R'2Si-SiR'2-, -R'2Ge-, wherein each R' is independently a hydrogen atom or a C1-C ... 20 - a hydrocarbon group, or optionally two R' groups together can form a ring,

[0049] Each R 1 are independently identical or can be different and are hydrogen, linear or branched C1-C6-alkyl, C 7-20 -aralkyl, C 7-20 -alkylaryl or C 6-20 -aryl or OY group, where Y is C 1-10 -hydrocarbyl, and optionally two adjacent R 1 The groups can be part of a ring containing the phenyl carbon to which they are bonded,

[0050] Each R 2 are independently the same or can be different, and are CH2-R 8 Group, where R 8 H or linear or branched C 1-6 -alkyl, C 3-8 -cycloalkyl, C 6-10 -aryl,

[0051] R 3 is a straight or branched C1-C6-alkyl, C 7-20 -aralkyl, C 7-20 -alkylaryl or C6-C 20 -aryl,

[0052] R 4 C(R 9 )3 groups, wherein R 9 is a linear or branched C1-C6-alkyl group,

[0053] R 5 is hydrogen or an aliphatic C1-C12 radical optionally containing one or more heteroatoms from Groups 14 to 16 of the Periodic Table 20 -hydrocarbon group;

[0054] R 6 is hydrogen or an aliphatic C1-C12 radical optionally containing one or more heteroatoms from Groups 14 to 16 of the Periodic Table 20 - a hydrocarbon group; or

[0055] R 5 and R 6 can together form a 5-membered saturated carbocyclic ring, which is optionally substituted by n groups R 10 substituted, n is 0 to 4;

[0056] Each R 10 Same or different, and can be C1-C 20 -hydrocarbyl, or a C1-C ... 20 -hydrocarbon group;

[0057] R 7 is H or a linear or branched C1-C6-alkyl radical or optionally substituted by 1 to 3 radicals R 11 a substituted aryl or heteroaryl group having 6 to 20 carbon atoms,

[0058] Each R 11 are independently identical or can be different and are hydrogen, linear or branched C1-C6-alkyl, C 7-20 -aralkyl, C 7-20 -alkylaryl or C 6-20 -aryl or OY group, where Y is C 1-10 -hydrocarbon group.

[0059] The present invention also relates to an article comprising the fiber-reinforced composition (C) as described above.

[0060] Hereinafter, the fiber-reinforced composition (C) is described in more detail. DETAILED DESCRIPTION

[0061] Fiber-reinforced composition (C)

[0062] The present invention relates to a fiber reinforced composition (C) comprising a heterophasic polypropylene composition (HECO), fibers (F) and an adhesion promoter (AP).

[0063] In particular, the fiber-reinforced composition (C) comprises, based on the total weight of the fiber-reinforced composition (C),

[0064] a) 55.0 to 95.0 wt.%, preferably 55.0 to 90.0 wt.%, more preferably 60.0 to 85.0 wt.%, still more preferably 66.0 to 82.0 wt.%, like 72.0 to 79.0 wt.% of the heterophasic polypropylene composition (HECO), and

[0065] b) 5.0 to 45.0 wt. %, preferably 10.0 to 40.0 wt. %, more preferably 12.0 to 35.0 wt. %, still more preferably 14.0 to 29 wt. %, such as 18.0 to 23.0 wt. % of fibers (F).

[0066] According to a preferred embodiment of the present invention, the fiber-reinforced composition (C) further comprises an adhesion promoter (AP).

[0067] Therefore, it is preferred that the fiber-reinforced composition (C) comprises, based on the total weight of the fiber-reinforced composition (C),

[0068] a) 55.0 to 94.9 wt.%, preferably 55.0 to 90.0 wt.%, more preferably 60.0 to 85.0 wt.%, still more preferably 66.0 to 82.0 wt.%, like 72.0 to 79.0 wt.% of the heterophasic polypropylene composition (HECO),

[0069] b) 5.0 to 45.0 wt. %, preferably 10.0 to 40.0 wt. %, more preferably 12.0 to 35.0 wt. %, still more preferably 14.0 to 29 wt. %, such as 18.0 to 23.0 wt. % of fibers (F), and

[0070] c) 0.1 to 5.0 wt. %, preferably 0.3 to 4.8 wt. %, more preferably 0.5 to 4.0 wt. %, still more preferably 0.8 to 3.0 wt. %, such as 1.0 to 2.0 wt. % of an adhesion promoter (AP).

[0071] The fiber-reinforced composition (C) according to the present invention may comprise additives (AD).

[0072] Therefore, it is preferred that the fiber-reinforced composition (C) according to the present invention comprises, more preferably consists of, based on the total weight of the fiber-reinforced composition (C),

[0073] a) 55.0 to 94.9 wt.%, preferably 55.0 to 90.0 wt.%, more preferably 60.0 to 85.0 wt.%, still more preferably 66.0 to 82.0 wt.%, like 72.0 to 79.0 wt.% of the heterophasic polypropylene composition (HECO),

[0074] b) 5.0 to 45.0 wt. %, preferably 10.0 to 40.0 wt. %, more preferably 12.0 to 35.0 wt. %, still more preferably 14.0 to 29 wt. %, such as 18.0 to 23.0 wt. % of fibers (F),

[0075] c) 0.1 to 5.0 wt. %, preferably 0.3 to 4.8 wt. %, more preferably 0.5 to 4.0 wt. %, still more preferably 0.8 to 3.0 wt. %, such as 1.0 to 2.0 wt. % of an adhesion promoter (AP), and

[0076] d) 0.01 to 2.5% by weight of additives (AD).

[0077] Additives (AD) are described in more detail below.

[0078] Therefore, it is preferred that the fiber reinforced composition (C) according to the present invention comprises, more preferably consists of, the following items, based on the total weight of the fiber reinforced composition (C),

[0079] a) 55.0 to 94.9 wt.-% (e.g. 55.0 to 94.8 wt.-%), preferably 55.0 to 90.0 wt.-%, more preferably 60.0 to 85.0 wt.-%, still more preferably 66.0 to 82.0 wt.-%, like 72.0 to 79.0 wt.-% of the heterophasic polypropylene composition (HECO),

[0080] b) 5.0 to 45.0 wt. %, preferably 10.0 to 40.0 wt. %, more preferably 12.0 to 35.0 wt. %, still more preferably 14.0 to 29 wt. %, such as 18.0 to 23.0 wt. % of fibers (F),

[0081] c) 0.1 to 5.0 wt. %, preferably 0.3 to 4.8 wt. %, more preferably 0.5 to 4.0 wt. %, still more preferably 0.8 to 3.0 wt. %, such as 1.0 to 2.0 wt. % of an adhesion promoter (AP), and

[0082] d) 0.01 to 2.5% by weight of additives (AD),

[0083] Components a) to d) are selected so as to add up to 100% by weight.

[0084] Furthermore, the fiber-reinforced composition (C) according to the present invention may also comprise low-density polyethylene (LDPE).

[0085] Therefore, according to another embodiment of the present invention, the fiber reinforced composition (C) comprises, more preferably consists of, based on the total weight of the fiber reinforced composition (C)

[0086] a) 55.0 to 94.9 wt.%, preferably 55.0 to 90.0 wt.%, more preferably 60.0 to 85.0 wt.%, still more preferably 66.0 to 82.0 wt.%, like 72.0 to 79.0 wt.% of the heterophasic polypropylene composition (HECO),

[0087] c) 5.0 to 25.0 wt. %, preferably 10.0 to 22.0 wt. %, more preferably 12.0 to 35.0 wt. %, still more preferably 14.0 to 29 wt. %, such as 18.0 to 23.0 wt. % of fibers (F),

[0088] d) 0.1 to 5.0 wt. %, preferably 0.3 to 4.8 wt. %, more preferably 0.5 to 4.0 wt. %, still more preferably 0.8 to 3.0 wt. %, such as 1.0 to 2.0 wt. % of an adhesion promoter (AP),

[0089] e) 0.0 to 20.0 wt%, preferably 5.0 to 18.0 wt%, more preferably 12.0 to 17.0 wt%, still more preferably 13.0 to 16.0 wt% of low density polyethylene (LDPE), and

[0090] f) 0.01 to 2.5% by weight of additives (AD).

[0091] According to another embodiment of the present invention, the fiber reinforced composition (C) comprises, preferably consists of, based on the total weight of the fiber reinforced composition (C),

[0092] a) 55.0 to 94.9 wt.-% (e.g. 55.0 to 94.8 wt.-%), preferably 55.0 to 90.0 wt.-%, more preferably 60.0 to 85.0 wt.-%, still more preferably 66.0 to 82.0 wt.-%, like 72.0 to 79.0 wt.-% of the heterophasic polypropylene composition (HECO),

[0093] c) 5.0 to 25.0 wt. %, preferably 10.0 to 22.0 wt. %, more preferably 12.0 to 35.0 wt. %, still more preferably 14.0 to 29 wt. %, such as 18.0 to 23.0 wt. % of fibers (F),

[0094] d) 0.1 to 5.0 wt. %, preferably 0.3 to 4.8 wt. %, more preferably 0.5 to 4.0 wt. %, still more preferably 0.8 to 3.0 wt. %, such as 1.0 to 2.0 wt. % of an adhesion promoter (AP),

[0095] e) 0.0 to 20.0 wt%, preferably 5.0 to 18.0 wt%, more preferably 12.0 to 17.0 wt%, still more preferably 13.0 to 16.0 wt% of low density polyethylene (LDPE), and

[0096] f) 0.01 to 2.5% by weight of additives (AD),

[0097] Components a) to d) are selected so as to add up to 100% by weight.

[0098] Preferably, the fiber reinforced composition (C) of the present invention does not comprise (a) other polymers different from the heterophasic polypropylene composition (HECO), the adhesion promoter (AP) and the optional low density polyethylene (LDPE) in an amount of more than 5.0 wt.-%, preferably in an amount of more than 3.0 wt.-%, more preferably in an amount of more than 2.5 wt.-%, based on the total weight of the fiber reinforced composition (C). An additional polymer that may be present in such low amounts is polyethylene, which is a reaction by-product obtained by preparing the heterophasic polypropylene composition (HECO). Therefore, it is particularly understood that the fiber reinforced composition (C) comprises as polymer compounds only the heterophasic polypropylene composition (HECO), the adhesion promoter (A), the optional low density polyethylene (LDPE) and the optional polyethylene in the amounts described in this paragraph.

[0099] The fiber reinforced composition (C) has a melt flow rate MFR2 (230°C, 2.16 kg) determined according to ISO 1133 in the range of 1.0 to 60.0 g / 10 min, more preferably in the range of 1.2 to 40.0 g / 10 min, still more preferably in the range of 2.0 to 35.0 g / 10 min, such as in the range of 2.5 to 29.0 g / 10 min.

[0100] According to a preferred embodiment, the fiber-reinforced composition (C) has a melt flow rate MFR2 (230°C, 2.16 kg) determined according to ISO 1133 in the range of 1.0 to 10.0 g / 10 min (e.g. 2.0 to 10.0 g / 10 min or 2.5 to 10.0 g / 10 min). The melt flow rate range (and sub-ranges) of 1.0 to 10.0 g / 10 min is particularly preferably combined with the "second embodiment of the invention" defined herein.

[0101] With regard to mechanical properties, it is preferred that the fiber-reinforced composition (C) has a tensile modulus measured according to ISO 527-1A of at least 2000 MPa, more preferably at least 2200 MPa, still more preferably at least 2300 MPa, such as at least 2400 MPa and / or a tensile strength measured according to ISO 527-2 of at least 40 MPa, more preferably at least 42 MPa, still more preferably at least 45 MPa, such as at least 50 MPa.

[0102] Additionally or alternatively to the previous paragraph, it is preferred that the fiber reinforced composition has an elongation at break measured according to ISO 527-2 at 23° C. of at least 3.0%, more preferably at least 3.2%, still more preferably at least 3.4%.

[0103] The fiber reinforced composition (C) is preferably obtained by melt blending the heterophasic polypropylene composition (HECO), fibers (F), optional adhesion promoter (AP), optional additives (AD) and optional low density polyethylene (LDPE).

[0104] In the following the heterophasic polypropylene composition (HECO), the fibers (F), the adhesion promoter (AP) and the low density polyethylene (LDPE) will be described in more detail.

[0105] Heterophasic polypropylene composition (HECO)

[0106] The fiber reinforced composition (C) of the present invention comprises a heterophasic polypropylene composition (HECO).

[0107] Heterophasic polypropylene composition (HECO) according to the present invention comprises a matrix as a propylene homopolymer or copolymer (PP) and the elastomeric ethylene copolymer (E) dispersed therein. Therefore, the matrix contains (fine) dispersed inclusions that are not a part for the matrix, and the inclusions contain the elastomeric ethylene copolymer (E). The term inclusion represents that the matrix and inclusions form different phases in the heterophasic polypropylene composition (HECO). The presence of the second phase or so-called inclusions is for example visible by high-resolution microscopy, such as electron microscopy or atomic force microscopy, or by dynamic mechanical thermal analysis (DMTA). Particularly, in DMTA, the presence of a heterophasic structure can be identified by the presence of at least two different glass transition temperatures.

[0108] Thus, the heterophasic polypropylene composition (HECO) according to this invention preferably comprises

[0109] (a) a (semi-)crystalline propylene homopolymer or copolymer (PP) as matrix, and

[0110] (b) Elastomeric ethylene copolymer (E).

[0111] In particular it is preferred that the heterophasic polypropylene composition (HECO) comprises, more preferably consists of, based on the total weight of the heterophasic polypropylene composition (HECO),

[0112] (a) 60.0 to 95.0 wt.%, more preferably 61.0 to 92.0 wt.% of a matrix which is a propylene homo- or copolymer (PP), and

[0113] (b) 5.0 to 40.0 wt%, more preferably 8.0 to 39.0 wt% of an elastomeric ethylene copolymer (E).

[0114] It is preferred that the heterophasic polypropylene composition (HECO) according to this invention has at least two different glass transition temperatures Tg(1) and Tg(2). In particular, it is preferred that the first glass transition temperature Tg(1) is below -15°C, more preferably below -25°C. Furthermore, it is preferred that the second glass transition temperature Tg(2) is at least -5°C, more preferably at least -4°C.

[0115] Preferably, the heterophasic polypropylene composition (HECO) has a melt flow rate MFR2 (230°C, 2.16 kg) determined according to ISO 1133 in the range of 5.0 to 100 g / 10 min, more preferably in the range of 6.0 to 95.0 g / 10 min, yet more preferably in the range of 7.0 to 87.0 g / 10 min, like in the range of 8.0 to 80.0 g / 10 min.

[0116] Furthermore, it is preferred that the heterophasic polypropylene composition (HECO) has an intrinsic viscosity (IV) measured according to ISO 1628 / 1 (in decalin at 135 °C) of the soluble fraction (SF) determined according to CRYSTEX QC in the range of 1.8 to 3.0 dl / g, more preferably in the range of 2.5 to 3.0 dl / g.

[0117] Preferably, it is desired that the heterophasic polypropylene composition (HECO) is thermo-mechanically stable. Thus, it is appreciated that the heterophasic polypropylene composition (HECO) has a melting temperature Tm, determined according to differential scanning calorimetry (DSC), in the range of 130 to 165 °C, more preferably in the range of 132 to 159 °C, yet more preferably in the range of 135 to 158 °C, such as in the range of 139 to 157 °C.

[0118] The propylene homopolymer or copolymer (PP) has an amount of 1,2-erythro regio defects of at least 0.4 mol % (preferably in the range of 0.4 to 1.2 mol %). Without being bound by theory, the large amount of intercalation of propylene in the polymer chain indicates that the propylene homopolymer or copolymer (PP) is produced in the presence of a single-site catalyst, preferably a metallocene catalyst. It is known in the art that propylene homopolymers or copolymers produced, for example, in the presence of a Ziegler-Natta catalyst can have 1,2-erythro regio defects far below 0.4 mol % and are typically substantially free of 1,2-erythro regio defects.

[0119] The heterophasic polypropylene composition (HECO) comprises in addition to propylene comonomers. Preferably, the heterophasic polypropylene composition (HECO) comprises in addition to propylene ethylene and / or C4 to C 12 α-olefins.

[0120] Accordingly the term "propylene copolymer" according to this invention is understood as a polypropylene comprising, more preferably consisting of, units derived from

[0121] (a) Propylene

[0122] and

[0123] (b) ethylene and / or C4 to C 12 α-olefins.

[0124] Furthermore, the term "ethylene copolymer" according to the present invention is understood as a polyethylene derived from, more preferably consisting of, units derived from

[0125] (a) Ethylene

[0126] and

[0127] (b) C3 to C 12 α-olefins.

[0128] Thus, the propylene homo- or copolymer (PP), i.e. the matrix of the heterophasic polypropylene composition (HECO), may comprise monomers copolymerizable with propylene, e.g. comonomers such as ethylene and / or C4 to C 12 α-olefins, in particular ethylene and / or C4 to C8 α-olefins, for example 1-butene and / or 1-hexene. The elastomeric ethylene copolymer (E) may contain monomers copolymerizable with ethylene, for example comonomers such as C3 to C8 12 α-Olefins, in particular propylene, 1-butene, 1-hexene and / or 1-octene. More specifically the instant heterophasic polypropylene composition (HECO) comprises - apart from propylene and ethylene - units derivable from 1-butene, 1-hexene and / or 1-octene.

[0129] Thus the propylene homo- or copolymer (PP) according to this invention can be a propylene homo- or copolymer.

[0130] In particular it is preferred that the propylene homo- or copolymer (PP) has a comonomer content, preferably an ethylene content, equal to or lower than 8.5 mol-%, more preferably in the range of 0.0 to 8.3 mol-%, still more preferably in the range of 0.0 to 8.0 mol-%, like in the range of 0.0 to 6.0 mol-%.

[0131] The elastomeric ethylene copolymer (E) according to the present invention comprises monomers copolymerizable with ethylene, e.g. comonomers such as C3 to C 12 α-olefins, in particular propylene, 1-butene, 1-hexene and / or 1-octene. Preferably, the elastomeric ethylene copolymer (E) has an ethylene content in the range of 15.0 to 85.0 wt.-%, more preferably in the range of 18.0 to 82.0 wt.-%, still more preferably in the range of 19.0 to 79.0 wt.-%, such as in the range of 20.0 to 76.0 wt.-%, based on the total weight of the elastomeric ethylene copolymer (E).

[0132] According to the first embodiment of the present invention it is preferred that the propylene homo- or copolymer (PP) is a propylene homopolymer (hPP).

[0133] The expression "propylene homopolymer" as used herein relates to a polypropylene consisting essentially of, i.e. at least 99.0 wt.-%, more preferably at least 99.5 wt.-%, still more preferably at least 99.8 wt.-%, such as at least 99.9 wt.-% propylene units. In another embodiment, only propylene units are detectable, i.e. only propylene is polymerized.

[0134] Thus according to a first embodiment of the present invention the heterophasic polypropylene composition (HECO) comprises

[0135] a) as a matrix for propylene homopolymer (hPP), and

[0136] b) Elastomeric ethylene copolymer (E).

[0137] The elastomeric ethylene copolymer (E) according to the first embodiment of the present invention comprises monomers copolymerizable with ethylene, e.g. comonomers such as C3 to C 12 α-olefins, in particular propylene, 1-butene, 1-hexene and / or 1-octene. According to the first embodiment of the present invention, it is particularly preferred that the elastomeric ethylene copolymer (E) is a copolymer of ethylene and propylene. In other words, the elastomeric ethylene copolymer (E) according to the first embodiment of the present invention comprises units derivable only from ethylene and propylene.

[0138] Accordingly it is preferred that the heterophasic polypropylene composition (HECO) according to the first embodiment of this invention comprises units derivable from ethylene and propylene only.

[0139] Preferably, the heterophasic polypropylene composition (HECO) according to the first embodiment of this invention has a comonomer content, preferably an ethylene content, in the range of 2.2 to 8.7 mol-%, more preferably in the range of 2.7 to 5.8 mol-%, still more preferably in the range of 2.9 to 4.4 mol-%.

[0140] Furthermore, it is preferred that the heterophasic polypropylene composition (HECO) according to the first embodiment of this invention has a xylene cold soluble (XCS) content determined according to ISO 16152 at 25 °C in the range of 5.0 to 35.0 wt.-%, more preferably in the range of 7.0 to 20.0 wt.-%, yet more preferably in the range of 9.0 to 15.0 wt.-%, like in the range of 10.0 to 12.0 wt.-%, based on the total weight of the heterophasic polypropylene composition (HECO) according to the first embodiment of this invention.

[0141] Additionally or alternatively, it is preferred that the xylene cold soluble (XCS) fraction of the heterophasic polypropylene composition (HECO) according to the first embodiment of this invention has a comonomer content, preferably an ethylene content, in the range of 20.9 to 44.7 mol-%, more preferably in the range of 25.0 to 40.0 mol-%, yet more preferably in the range of 28.0 to 38.0 mol-%, like in the range of 30.0 to 34.0 mol-%.

[0142] Preferably, the heterophasic polypropylene composition (HECO) according to the first embodiment of this invention has an intrinsic viscosity (IV) measured according to ISO 1628 / 1 (in decalin at 135 °C) of the xylene cold soluble (XCS) fraction in the range of 1.8 to 3.0 dl / g, more preferably in the range of 2.2 to 2.8 dl / g, yet more preferably in the range of 2.3 to 2.7 dl / g.

[0143] Additionally or alternatively with respect to the previous paragraph, it will be appreciated that the heterophasic polypropylene composition (HECO) according to the first embodiment of this invention preferably has a soluble fraction (SF) determined according to CRYSTEXQC in the range of 5.0 to 35.0 wt.-%, more preferably in the range of 7.0 to 20.0 wt.-%, yet more preferably in the range of 9.0 to 15.0 wt.-%, like in the range of 10.0 to 12.0 wt.-%, based on the total weight of the heterophasic polypropylene composition (HECO) according to the first embodiment of this invention.

[0144] The comonomer content, preferably the ethylene content, of the soluble fraction (SF) determined according to CRYSTEX QC of the heterophasic polypropylene composition (HECO) according to the first embodiment of this invention is preferably in the range of 20.9 to 44.7 mol-%, more preferably in the range of 25.0 to 40.0 mol-%, yet more preferably in the range of 28.0 to 38.0 mol-%, like in the range of 30.0 to 34.0 mol-%.

[0145] Preferably, the heterophasic polypropylene composition (HECO) according to the first embodiment of this invention has an intrinsic viscosity (IV) measured according to ISO 1628 / 1 (in decalin at 135 °C) of the soluble fraction (SF) determined according to CRYSTEX QC in the range of 1.8 to 3.0 dl / g, more preferably in the range of 2.2 to 2.8 dl / g, yet more preferably in the range of 2.3 to 2.7 dl / g.

[0146] It is preferred that the heterophasic polypropylene composition (HECO) according to the first embodiment of this invention has a moderate melt flow rate. Thus, the heterophasic polypropylene composition (HECO) according to the first embodiment of this invention preferably has a melt flow rate MFR2 (230°C, 2.16 kg) determined according to ISO 1133 in the range of 20.0 to 100.0 g / 10 min, more preferably in the range of 45.0 to 95.0 g / 10 min, yet more preferably in the range of 56.0 to 90.0 g / 10 min, like in the range of 70.0 to 80.0 g / 10 min.

[0147] Furthermore, it is preferred that the heterophasic polypropylene composition (HECO) according to the first embodiment of this invention has a melting temperature Tm determined according to differential scanning calorimetry (DSC) in the range of 130 to 165 °C, more preferably in the range of 135 to 160 °C, yet more preferably in the range of 145 to 159 °C, like in the range of 152 to 157 °C.

[0148] Concerning the mechanical properties, it is preferred that the heterophasic polypropylene composition (HECO) according to the first embodiment of this invention has a flexural modulus determined according to ISO 178 in the range of 500 to 2000 MPa, more preferably in the range of 800 to 1900 MPa, still more preferably in the range of 1000 to 1500 MPa, like in the range of 1100 to 1300 MPa.

[0149] Additionally or alternatively to the previous paragraph, it is preferred that the heterophasic polypropylene composition (HECO) according to the first embodiment of this invention has a 2 , more preferably at least 2.5 kJ / m2 , still more preferably at least 3.0 kJ / m 2 , such as at least 3.5kJ / m 2 Charpy notched impact strength measured at 23°C according to ISO 179 / 1eA, and / or at least 0.5 kJ / m 2 , more preferably at least 0.8 kJ / m 2 , still more preferably at least 1.3 kJ / m 2 , such as at least 1.7 kJ / m 2 Charpy notched impact strength measured at -20°C according to ISO 179 / 1eA.

[0150] Furthermore, it is preferred that the fiber reinforced composition (C) according to the first embodiment of the present invention has a tensile modulus determined according to ISO 527-1A in the range of 3000 to 6000 MPa, more preferably in the range of 3500 to 5800 MPa, still more preferably in the range of 4200 to 5300 MPa, such as in the range of 4700 to 5000 MPa.

[0151] Additionally or alternatively, it is preferred that the fiber reinforced composition (C) according to the first embodiment of the invention has an elongation at break determined according to ISO 527-2 of greater than 3.0%, more preferably greater than 3.2%, still more preferably greater than 3.3%, such as greater than 3.4%.

[0152] The heterophasic polypropylene composition (HECO) according to the first embodiment of the present invention can be further defined by its individual components, namely the matrix which is the propylene homopolymer (hPP) and the elastomeric ethylene copolymer (E) which is a copolymer of ethylene and propylene.

[0153] The matrix being a propylene homopolymer (hPP) preferably has a melt flow rate MFR2 (230°C, 2.16 kg), determined according to ISO 1133, in the range of 30.0 to 200 g / 10 min, more preferably in the range of 40.0 to 110 g / 10 min, still more preferably in the range of 60.0 to 95.0 g / 10 min, like in the range of 75.0 to 85.0 g / 10 min.

[0154] Preferably, the propylene homopolymer (hPP) has a melting temperature Tm, determined according to differential scanning calorimetry (DSC), in the range of 140 to 160 °C, more preferably in the range of 142 to 159 °C, yet more preferably in the range of 145 to 158 °C, like in the range of 147 to 157 °C.

[0155] The propylene homopolymer (hPP) has at least 0.4 mol-% of 1,2-erythro regio defects which, as outlined above, indicates that the propylene homopolymer (PP) is produced in the presence of a single-site catalyst, preferably a metallocene catalyst.

[0156] As described in more detail hereinafter, the heterophasic polypropylene composition (HECO) according to the first embodiment of the present invention is preferably obtained in a sequential process in the presence of a metallocene catalyst. Therefore, it is particularly preferred that the propylene homopolymer (hPP) and the elastomeric ethylene copolymer (E) are prepared in a sequential process in the presence of a metallocene catalyst.

[0157] Thus, it is preferred that the elastomeric ethylene copolymer (E) being a copolymer of ethylene and propylene according to the first embodiment of the invention also has an amount of 1,2 erythro regio defects of at least 0.4 mol%, preferably in the range of 0.4 to 1.2 mol%.

[0158] The heterophasic polypropylene composition (HECO) according to the first embodiment of the present invention preferably comprises

[0159] i) 60.0 to 99.0 wt.%, more preferably 75.0 to 98.0 wt.%, still more preferably 80.0 to 95.0 wt.%, like 85.0 to 90.0 wt.% of the matrix, which matrix is ​​a propylene homopolymer (hPP), and

[0160] ii) 1.0 to 40.0 wt%, more preferably 2.0 to 25.0 wt%, still more preferably 5.0 to 20.0 wt%, like 10.0 to 15.0 wt% of an elastomeric ethylene copolymer (E), which is a copolymer of ethylene and propylene.

[0161] The heterophasic polypropylene composition (HECO) according to the first embodiment of the present invention can be produced by blending, preferably melt blending, the propylene homopolymer (hPP) and the elastomeric ethylene copolymer (E) together or by producing the propylene homopolymer (hPP) and the elastomeric ethylene copolymer (E) in a sequential process, the latter being preferred.

[0162] The process for preparing the heterophasic polypropylene composition (HECO) according to the first embodiment of the present invention is preferably a sequential polymerization process comprising at least two reactors connected in series, wherein the process comprises the following steps

[0163] (A) polymerizing propylene in a first reactor (R-1) being a slurry reactor (SR), preferably a loop reactor (LR), to obtain a first fraction of propylene homopolymer (hPP) as defined in the instant invention,

[0164] (B) transferring said first fraction of propylene homopolymer (hPP) from the first reactor (R-1) to a second reactor (R-2) being a gas phase reactor (GPR-1),

[0165] (C) feeding propylene to the second reactor (R-2),

[0166] (D) polymerizing propylene in the second reactor (R-2) and in the presence of the first fraction of propylene homopolymer (hPP) to obtain a second fraction of propylene homopolymer (hPP), said first and second fractions forming the propylene homopolymer (hPP) of the present invention,

[0167] (E) transferring the propylene homopolymer (hPP) of the second reactor (R-2) into a third reactor (R-3) which is a gas phase reactor (GPR-2),

[0168] (F) propylene and selected from ethylene and C4 to C 12 A comonomer of an α-olefin, preferably ethylene, is fed to the third reactor (R-3),

[0169] (G) in the third reactor (R-3) and in the propylene homopolymer (hPP) propylene and selected from ethylene and C4 to C 12 The elastomeric ethylene copolymer (E) as defined in the instant invention is obtained by polymerization in the presence of a comonomer of an α-olefin, preferably ethylene, said propylene homopolymer (hPP) and said elastomeric ethylene copolymer (E) forming a heterophasic polypropylene composition (HECO) as defined in the instant invention, wherein further

[0170] In the first reactor (R-1), the second reactor (R-2) and the third reactor (R-3), the polymerization is carried out in the presence of a solid catalyst system (SCS).

[0171] The solid catalyst system (SCS) is defined in more detail below.

[0172] The term "sequential polymerization process" means that the heterophasic polypropylene composition (HECO) according to the first embodiment of the present invention is produced in at least two reactors connected in series. More precisely, the term "sequential polymerization process" means in this application that the polymer of the first reactor (R-1) and the unreacted monomers are directly conveyed to the second reactor (R-2). Therefore, a decisive aspect of the inventive process is that the heterophasic polypropylene composition (HECO) is produced in at least two different reactors, wherein the reaction material of the first reactor (R-1) is directly conveyed to the second reactor (R-2). Therefore, the inventive process comprises at least a first reactor (R-1) and a second reactor (R-2). In a specific embodiment, the inventive process consists of three polymerization reactors (R-1), (R-2) and (R-3). The term "polymerization reactor" should indicate that the main polymerization occurs. Therefore, in the case where the process consists of three polymerization reactors, this definition does not exclude the option of the entire process including a prepolymerization step, for example in a prepolymerization reactor. The term "consisting of..." is only a closed expression with respect to the main polymerization reactor.

[0173] The first reactor (R-1) is a slurry reactor (SR) and can be any continuous or simple batch stirred tank reactor or loop reactor operating in slurry. According to the present invention, the slurry reactor (SR) is preferably a loop reactor (LR).

[0174] The second reactor (R-2), the third reactor (R-3) and any subsequent reactors are gas phase reactors (GPR). Such gas phase reactors (GPR) can be any mechanically mixed or fluidized bed reactor. Preferably, one or more gas phase reactors (GPR) comprise a mechanically stirred fluidized bed reactor having a gas velocity of at least 0.2 m / s. Therefore, it should be understood that the gas phase reactor (GPR) is a fluidized bed type reactor preferably with a mechanical stirrer.

[0175] The conditions in each reactor (temperature, pressure, reaction time, monomer feed) depend on the desired product as known to those skilled in the art. As described above, the first reactor (R-1) is a slurry reactor (SR), such as a loop reactor (LR), while the second reactor (R-2) and the third reactor (R-3) are gas phase reactors (GPR-1) and (GPR-2). Subsequent reactors (if present) are also gas phase reactors (GPR).

[0176] A preferred multi-stage process is a "loop-gas phase" process, such as that developed by Borealis A / S of Denmark (known as technology), described, for example, in patent literature, such as EP 0 887 379 or WO 92 / 12182.

[0177] Multimodal polymers can be produced according to several processes as described, for example, in WO 92 / 12182, EP 0 887 379 and WO 98 / 58976. The contents of these documents are included herein by reference.

[0178] Preferably, in the inventive process for producing the heterophasic polypropylene composition (HECO) as defined above, the conditions for step (A) in the first reactor (R-1), i.e. the slurry reactor (SR), like the loop reactor (LR), may be the following conditions:

[0179] - a temperature in the range of 40°C to 110°C, preferably between 60°C and 100°C, more preferably in the range of 65 to 90°C,

[0180] - a pressure in the range of 20 to 80 bar, preferably between 40 and 70 bar,

[0181] Hydrogen can be added for controlling the molar mass in a manner known per se.

[0182] Subsequently, the reaction mixture from step (A) is transferred to the second reactor (R-2), i.e. the gas phase reactor (GPR-1), i.e. to step (D), wherein the conditions in step (D) are preferably the following:

[0183] - a temperature in the range of 50°C to 130°C, preferably between 60°C and 100°C,

[0184] - a pressure in the range of 5 to 50 bar, preferably between 15 and 40 bar,

[0185] Hydrogen can be added for controlling the molar mass in a manner known per se.

[0186] The residence time can be varied in the two reactor zones.

[0187] In one embodiment of the process for producing the heterophasic polypropylene composition (HECO) the residence time in the slurry reactor (SR), e.g. the loop (LR) is in the range of 0.2 to 4.0 hours, e.g. 0.3 to 1.5 hours, while the residence time in the gas phase reactor (GPR) is typically 0.2 to 6.0 hours, such as 0.5 to 4.0 hours.

[0188] If desired, the polymerization can be carried out in a known manner under supercritical conditions in the first reactor (R-1), ie in the slurry reactor (SR), such as in the loop reactor (LR).

[0189] The conditions in the third reactor (R-3), ie the second gas phase reactor (GPR-2) and any other subsequent gas phase reactors (GPR), if present, are similar to those of the second reactor (R-2).

[0190] The process of the present invention may also comprise a prepolymerization prior to the polymerization in the first reactor (R-1). The prepolymerization can be carried out in the first reactor (R-1), but preferably, the prepolymerization is carried out in a separate reactor, the so-called prepolymerization reactor.

[0191] The heterophasic polypropylene composition (HECO) according to the first embodiment of the invention is produced in the presence of a solid catalyst system (SCS) comprising a transition metal compound.

[0192] It is particularly preferred that the solid catalyst system (SCS) comprises a metallocene catalyst of a metallocene complex, a cocatalyst system comprising a boron-containing cocatalyst and / or an aluminoxane cocatalyst and a silica support.

[0193] In particular, it is preferred that the metallocene catalyst comprises

[0194] (i) Metallocene complex having the general formula (I)

[0195]

[0196] wherein each X is independently a σ-donor ligand,

[0197] L is a divalent bridge selected from -R'2C-, -R'2C-CR'2-, -R'2Si-, -R'2Si-SiR'2-, -R'2Ge-, wherein each R' is independently a hydrogen atom or a C1-C ... 20 - a hydrocarbon group, or optionally two R' groups together can form a ring,

[0198] Each R 1 are independently identical or can be different and are hydrogen, linear or branched C1-C6-alkyl, C 7-20 -aralkyl, C 7-20 -alkylaryl or C 6-20 -aryl or OY group, where Y is C 1-10 -hydrocarbyl, and optionally two adjacent R 1 The groups can be part of a ring containing the phenyl carbon to which they are bonded,

[0199] Each R 2 are independently the same or can be different, and are CH2-R 8 Group, where R 8H or linear or branched C 1-6 -alkyl, C 3-8 -cycloalkyl, C 6-10 -aryl,

[0200] R 3 is a straight or branched C1-C6-alkyl, C 7-20 -aralkyl, C 7-20 -alkylaryl or C6-C 20 -aryl,

[0201] R 4 C(R 9 )3 groups, wherein R 9 is a linear or branched C1-C6-alkyl group,

[0202] R 5 is hydrogen or an aliphatic C1-C12 radical optionally containing one or more heteroatoms from Groups 14 to 16 of the Periodic Table 20 -hydrocarbon group;

[0203] R 6 is hydrogen or an aliphatic C1-C12 radical optionally containing one or more heteroatoms from Groups 14 to 16 of the Periodic Table 20 - a hydrocarbon group; or

[0204] R 5 and R 6 can together form a 5-membered saturated carbocyclic ring, which is optionally substituted by n groups R 10 substituted, n is 0 to 4;

[0205] Each R 10 Same or different, and can be C1-C 20 -hydrocarbyl, or a C1-C ... 20 -hydrocarbon group;

[0206] R 7 is H or a linear or branched C1-C6-alkyl radical or optionally substituted by 1 to 3 radicals R 11 a substituted aryl or heteroaryl group having 6 to 20 carbon atoms,

[0207] Each R 11 are independently identical or can be different and are hydrogen, linear or branched C1-C6-alkyl, C 7-20 -aralkyl, C 7-20 -alkylaryl or C 6-20 -aryl or OY group, where Y is C 1-10 - hydrocarbon group,

[0208] (ii) a cocatalyst system comprising a boron-containing cocatalyst and / or an aluminoxane cocatalyst, and

[0209] (iii) Silica support.

[0210] The term "σ-donor ligand" is well known to those skilled in the art, i.e., a group that binds to the metal via a σ bond. Thus, the anionic ligand "X" can independently be a halogen or selected from the group consisting of R', OR', SiR'3, OSiR'3, OSO2CF3, OCOR', SR', NR'2 or PR'2 groups, wherein R' is independently hydrogen, a linear or branched, cyclic or acyclic C1 to C 20 Alkyl, C2 to C 20 Alkenyl, C2 to C 20 Alkynyl, C3 to C 12 Cycloalkyl, C6 to C 20 Aryl, C7 to C 20 Aralkyl, C7 to C 20 Alkaryl, C8 to C 20 Aralkenyl, wherein the R' group may optionally contain one or more heteroatoms belonging to Groups 14 to 16. In a preferred embodiment, the anionic ligands "X" are identical and are either halogen, such as Cl, or methyl or benzyl.

[0211] Preferred monovalent anionic ligands are halogens, especially chloride (Cl).

[0212] Preferred metallocene complexes include:

[0213] rac-dimethylsilylenebis[2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride,

[0214] Racemic-trans-dimethylsilanylidene[2-methyl-4-(4′-tert-butylphenyl)-inden-1-yl][2-methyl-4-(4′-tert-butylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride,

[0215] rac-trans-dimethylsilanylidene[2-methyl-4-(4′-tert-butylphenyl)-inden-1-yl][2-methyl-4-phenyl-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride,

[0216] Racemic-trans-dimethylsilylene[2-methyl-4-(3',5'-tert-butylphenyl)-1,5,6,7-tetrahydro-sym-indacene-1-yl][2-methyl-4-(3',5'-dimethyl-phenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride,

[0217] Racemic-trans-dimethylsilylene[2-methyl-4,8-bis-(4′-tert-butylphenyl)-1,5,6,7-tetrahydro-sym-indacene-1-yl][2-methyl-4-(3′,5′-dimethyl-phenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride,

[0218] Racemic-trans-dimethylsilylene[2-methyl-4,8-bis-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-sym-indacen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride,

[0219] Racemic-trans-dimethylsilanylidene[2-methyl-4,8-bis-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-sym-indacene-1-yl][2-methyl-4-(3',5-di-tert-butyl-phenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride.

[0220] Particularly preferred is rac-trans-dimethylsilylene[2-methyl-4,8-bis-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-sym-indacen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium(II) dichloride

[0221]

[0222] The complex compound of the present invention and the ligand required for the catalyst of the present invention can be synthesized by any method, and a skilled organic chemist can design various synthesis schemes for the manufacture of necessary ligand materials. For example, WO 2007 / 116034 discloses necessary chemistry. Synthesis schemes can also be found generally in WO 2002 / 02576, WO 2011 / 135004, WO 2012 / 084961, WO 2012 / 001052, WO 2011 / 076780, WO 2015 / 158790 and WO 2018 / 122134. With particular reference to WO 2019 / 179959, the most preferred catalyst of the present invention is described.

[0223] According to the present invention, a cocatalyst system comprising a boron-containing cocatalyst and / or an aluminoxane cocatalyst is used in combination with the metallocene catalyst complex defined above.

[0224] The aluminoxane cocatalyst may be a catalyst having formula (III):

[0225]

[0226] wherein n is generally 6 to 20, and R has the following meanings.

[0227] Aluminoxanes are formed upon partial hydrolysis of organoaluminum compounds, such as those having the formula AlR3, AlR2Y, and Al2R3Y3, wherein R can be, for example, C1-C 10 Alkyl, preferably C1-C5 alkyl, or C 3-10 Cycloalkyl, C7-C 12 Aralkyl or alkaryl and / or phenyl or naphthyl, and wherein Y can be hydrogen, halogen, preferably chlorine or bromine, or C1-C 10 Alkoxy groups, preferably methoxy or ethoxy groups. The oxygen-containing aluminoxanes obtained are usually not pure compounds but mixtures of oligomers of formula (III).

[0228] The preferred aluminoxane is methylaluminoxane (MAO).Since the aluminoxanes used as cocatalysts according to the invention are not pure compounds due to the way they are prepared, the molar concentrations of the aluminoxane solutions hereinafter are based on their aluminum content.

[0229] According to the present invention, a boron-containing cocatalyst may also be used instead of the aluminoxane cocatalyst, or the aluminoxane cocatalyst may be used in combination with the boron-containing cocatalyst.

[0230] Those skilled in the art will appreciate that where a boron-based cocatalyst is used, the complex is typically pre-alkylated by reaction with an alkylaluminum compound such as TIBA. This procedure is well known and any suitable alkylaluminum may be used, for example Al(C1-C6 alkyl). Preferred alkylaluminum compounds are triethylaluminum, triisobutylaluminum, triisohexylaluminum, tri-n-octylaluminum and tri-isooctylaluminum.

[0231] Alternatively, when a borate cocatalyst is used, the metallocene catalyst complex is in its alkylated form, ie, for example, a dimethyl or dibenzyl metallocene catalyst complex may be used.

[0232] Boron-based cocatalysts of interest include those of formula (IV)

[0233] BY3(IV)

[0234] wherein Y is the same or different and is a hydrogen atom, an alkyl group having 1 to about 20 carbon atoms, an aryl group having 6 to about 15 carbon atoms, an alkaryl group, an aralkyl group, a haloalkyl group, or a haloaryl group, wherein each group has 1 to 10 carbon atoms in the alkyl group and 6 to 20 carbon atoms in the aryl group, or fluorine, chlorine, bromine, or iodine. Preferred examples of Y are methyl, propyl, isopropyl, isobutyl, or trifluoromethyl, unsaturated groups such as aryl or haloaryl groups, for example, phenyl, tolyl, benzyl, p-fluorophenyl, 3,5-difluorophenyl, pentachlorophenyl, pentafluorophenyl, 3,4,5-trifluorophenyl, and 3,5-bis(trifluoromethyl)phenyl. Preferred options are trifluoroborane, triphenylborane, tri(4-fluorophenyl)borane, tri(3,5-difluorophenyl)borane, tri(4-fluoromethylphenyl)borane, tri(2,4,6-trifluorophenyl)borane, tri(pentafluorophenyl)borane, tri(tolyl)borane, tri(3,5-dimethyl-phenyl)borane, tri(3,5-difluorophenyl)borane and / or tri(3,4,5-trifluorophenyl)borane.

[0235] Tris(pentafluorophenyl)borane is particularly preferred.

[0236] However, it is preferred to use borates, i.e. compounds containing borate ions. Such ionic co-catalysts preferably contain non-coordinating anions such as tetrakis(pentafluorophenyl)borate and tetraphenylborate. Suitable counterions are protonated amines or aniline derivatives such as methylammonium, aniline, dimethylammonium, diethylammonium, N-methylaniline, diphenylammonium, N,N-dimethylaniline, trimethylammonium, triethylammonium, tri-n-butylammonium, methyldiphenylammonium, pyridinium, p-bromo-N,N-dimethylaniline or p-nitro-N,N-dimethylaniline.

[0237] Preferred ionic compounds that can be used according to the present invention include triethylammonium tetra(phenyl)borate, tributylammonium tetra(phenyl)borate, trimethylammonium tetra(tolyl)borate, tributylammonium tetra(tolyl)borate, tributylammonium tetra(pentafluorophenyl)borate, tripropylammonium tetra(dimethylphenyl)borate, tributylammonium tetra(trifluoromethylphenyl)borate, tributylammonium tetra(4-fluorophenyl)borate, N,N-dimethylcyclohexylammonium tetra(pentafluorophenyl)borate, N,N-dimethylbenzylammonium tetra(pentafluorophenyl)borate, N,N-dimethylaniline tetra(phenyl)borate, N,N-diethylaniline tetra(pentafluorophenyl)borate, N,N-dimethylaniline tetra(pentafluorophenyl)borate, )N,N-di(propyl)ammonium borate, di(cyclohexyl)ammonium tetrakis(pentafluorophenyl)borate, triphenylphosphonium tetrakis(phenyl)borate, triethylphosphonium tetrakis(phenyl)borate, diphenylphosphonium tetrakis(phenyl)borate, tri(methylphenyl)phosphonium tetrakis(phenyl)borate, tri(dimethylphenyl)phosphonium tetrakis(phenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, or ferroceniumtetrakis(pentafluorophenyl)borate.

[0238] Preferred are triphenylcarbonium tetrakis(pentafluorophenyl)borate, N,N-dimethylcyclohexylammonium tetrakis(pentafluorophenyl)borate, or N,N-dimethylbenzylammonium tetrakis(pentafluorophenyl)borate.

[0239] Surprisingly, it has been found that certain boron cocatalysts are particularly preferred. Thus, preferred borates for use in the present invention include trityl ions. Thus, the use of N,N-dimethylammonium-tetrakispentafluorophenylborate and Ph3CB(PhF5)4 and the like are particularly preferred.

[0240] According to the present invention, preferred cocatalysts are alumoxanes, more preferably methylalumoxane, combinations of alumoxanes with alkylaluminum, boron or borate cocatalysts, and combinations of alumoxanes with boron-based cocatalysts.

[0241] Suitable amounts of promoters are well known to those skilled in the art.

[0242] The molar ratio of boron to the metal ion of the metallocene may be in the range of 0.5:1 to 10:1 mol / mol, preferably in the range of 1:1 to 10:1, especially in the range of 1:1 to 5:1 mol / mol.

[0243] The molar ratio of Al in the aluminoxane to the metal ion of the metallocene may be in the range of 1:1 to 2000:1 mol / mol, preferably in the range of 10:1 to 1000:1, and more preferably in the range of 50:1 to 500:1 mol / mol.

[0244] The catalyst can be used in supported or unsupported form, preferably in supported form. The particulate support material used is preferably an organic or inorganic material, such as silica, alumina or zirconium oxide or a mixed oxide, such as silica-alumina, in particular silica, alumina or silica-alumina. Preference is given to using a silica support. Those skilled in the art are aware of the procedures required for supporting the metallocene catalyst.

[0245] Particularly preferably, the support is a porous material so that the complex can be loaded into the pores of the support, for example using methods similar to those described in WO 94 / 14856 (Mobil), WO 95 / 12622 (Borealis) and WO 2006 / 097497.

[0246] The average particle size of the silica support can generally be from 10 to 100 μm. However, it has been shown that particular advantages can be achieved if the support has an average particle size d50 of from 15 to 80 μm, preferably from 18 to 50 μm. The average pore diameter of the silica support can be in the range of from 10 to 100 nm, with a pore volume of from 1 to 3 mL / g.

[0247] Examples of suitable support materials are silicas such as ES757 produced and sold by PQ, Sylopol 948 produced and sold by Grace or SUNSPERA DM-L-303 produced by AGC Si-Tech. The support can optionally be calcined before use in the catalyst preparation to achieve an optimal silanol group content.

[0248] The use of these vectors is well known in the art.

[0249] According to a second embodiment of the present invention the propylene homo- or copolymer (PP) as matrix of the heterophasic polypropylene composition (HECO) is a propylene copolymer (cPP).

[0250] The heterophasic polypropylene composition (HECO) according to the second embodiment of the present invention preferably has a rather low melt flow rate. Preferably, the heterophasic polypropylene composition (HECO) according to the second embodiment of the present invention has a melt flow rate MFR2 (230°C, 2.16 kg) determined according to ISO 1133 in the range of 5.0 to 20.0 g / 10 min, more preferably in the range of 6.0 to 15.0 g / 10 min.

[0251] It is preferred that the heterophasic polypropylene composition (HECO) according to the second embodiment of the present invention comprises the following based on the total weight of the heterophasic polypropylene composition (HECO):

[0252] i) 40.0 to 90.0 wt.%, more preferably 45.0 to 85.0 wt.%, still more preferably 56.0 to 74.0 wt.%, like 58.0 to 65.0 wt.% of the propylene copolymer (cPP), and

[0253] ii) 10.0 to 60.0 wt%, more preferably 15.0 to 55.0 wt%, still more preferably 26.0 to 44.0 wt%, like 35.0 to 42.0 wt% of the elastomeric ethylene copolymer (E).

[0254] The propylene copolymer (cPP) preferably comprises monomers copolymerizable with propylene, for example comonomers such as ethylene and / or C4 to C8 α-olefins, in particular ethylene and / or C4 to C6 α-olefins, for example 1-butene and / or 1-hexene. Preferably, the propylene copolymer (cPP) comprises monomers copolymerizable with propylene selected from the group consisting of ethylene, 1-butene and 1-hexene, in particular consists of monomers copolymerizable with propylene selected from the group consisting of ethylene, 1-butene and 1-hexene. More particularly, the propylene copolymer (cPP) comprises, in addition to propylene, units derived from ethylene and / or 1-butene. Thus, in a particularly preferred embodiment, the propylene copolymer (cPP) comprises units derived only from ethylene and propylene.

[0255] In particular it is preferred that the propylene copolymer (cPP) is a random propylene copolymer, like a random copolymer of propylene and ethylene.

[0256] The term "random copolymer" is preferably understood according to IUPAC (Pure Appl. Chem., Vol. 68, No. 8, pp. 1591-1595, 1996). Preferably, the molar concentration of the comonomer dyad (e.g., ethylene dyad) obeys the relationship

[0257] [HH]<[H] 2

[0258] in

[0259] [HH] is the mole fraction of adjacent comonomer units, such as adjacent ethylene units, and

[0260] [H] is the mole fraction of the total comonomer units in the polymer, such as the mole fraction of the total ethylene units.

[0261] Preferably, the propylene copolymer (cPP) has a comonomer content, like ethylene content, in the range of 2.2 to 8.5 mol-%, more preferably in the range of 2.5 to 6.0 mol-%, still more preferably in the range of 3.0 to 4.8 mol-%, like in the range of 3.5 to 4.0 mol-%.

[0262] Furthermore, it is preferred that the propylene copolymer (cPP) has a melt flow rate MFR2 (230°C, 2.16 kg) determined according to ISO 1133 in the range of 5.0 to 20.0 g / 10 min, more preferably in the range of 6.0 to 15.0 g / 10 min, yet more preferably in the range of 6.5 to 12.0 g / 10 min, like in the range of 7.0 to 10.0 g / 10 min.

[0263] The melting temperature of the propylene copolymer (cPP) is preferably in the range of 120 to 150 °C, more preferably in the range of 123 to 145 °C, still more preferably in the range of 128 to 140 °C, like in the range of 133 to 139 °C.

[0264] The process for the preparation of the propylene copolymer (cPP) is preferably a sequential polymerization process comprising at least two reactors connected in series, wherein the process comprises the following steps

[0265] (A) optionally polymerizing propylene and optionally selected from ethylene and C4 to C 12 a comonomer of an α-olefin, preferably ethylene, to obtain a first propylene copolymer fraction,

[0266] (B) transferring the first propylene copolymer fraction and unreacted comonomer from the first reactor (R-1) to a second reactor (R-2) which is a gas phase reactor (GPR-1),

[0267] (C) propylene and selected from ethylene and C4 to C 12 A comonomer of an α-olefin, preferably ethylene, is fed to the second reactor (R-2),

[0268] (D) in the second reactor (R-2) and between the first propylene copolymer fraction and a propylene copolymer selected from ethylene and C4 to C 12 The first propylene copolymer fraction and the second propylene copolymer fraction are polymerized in the presence of a comonomer of an α-olefin, preferably ethylene, to obtain a second propylene copolymer fraction, said first propylene copolymer fraction and said second propylene copolymer fraction forming a propylene copolymer (cPP) as defined in the instant invention, wherein further

[0269] In the first reactor (R-1) and the second reactor (R-2), the polymerization is carried out in the presence of a solid catalyst system (SCS).

[0270] It is preferred that the solid catalyst system (SCS) comprises the metallocene catalyst of formula (I) and a cocatalyst as described with reference to the heterophasic polypropylene composition (HECO) according to the first embodiment of the present invention.

[0271] Accordingly it is preferred that the above described solid catalyst system (SCS) including all preferred embodiments is applied for the preparation of the propylene copolymer (cPP).

[0272] With regard to the term "sequential polymerization method", reference is made to the definition provided above.

[0273] If applicable, the first reactor (R-1) is a slurry reactor (SR) and can be any continuous or simple batch stirred tank reactor or loop reactor operating in slurry. According to the present invention, the slurry reactor (SR) is preferably a loop reactor (LR).

[0274] The second reactor (R-2) and any subsequent reactors are gas phase reactors (GPR). Such gas phase reactors (GPR) can be any mechanically mixed or fluidized bed reactor. Preferably, one or more gas phase reactors (GPR) comprise a mechanically stirred fluidized bed reactor having a gas velocity of at least 0.2 m / s. Therefore, it should be understood that the gas phase reactor (GPR) is a fluidized bed type reactor preferably with a mechanical stirrer.

[0275] The conditions in each reactor (temperature, pressure, reaction time, monomer feed) depend on the desired product as known to those skilled in the art. As described above, the first reactor (R-1) is a slurry reactor (SR), such as a loop reactor (LR), and the second reactor (R-2) is a gas phase reactor (GPR-1). Subsequent reactors (if present) are also gas phase reactors (GPR).

[0276] A preferred multi-stage process is a "loop-gas phase" process, such as that developed by Borealis A / S of Denmark (known as technology), described, for example, in patent literature, such as EP 0 887 379 or WO 92 / 12182.

[0277] Multimodal polymers can be produced according to several processes as described, for example, in WO 92 / 12182, EP 0 887 379 and WO 98 / 58976. The contents of these documents are included herein by reference.

[0278] With regard to the conditions in the first reactor (R-1), i.e. the slurry reactor (SR), e.g. the loop reactor (LR), and the second reactor (R-2), i.e. the gas phase reactor (GPR), as well as the residence times, reference is made to the conditions defined above for the heterophasic polypropylene composition (HECO) according to the first embodiment of the invention. This applies correspondingly to the optional use of a prepolymerization step.

[0279] The elastomeric ethylene copolymer (E) according to the second embodiment of the invention may comprise monomers copolymerizable with ethylene, e.g. comonomers such as C3 to C 12 α-Olfins, in particular propylene, 1-butene, 1-hexene and / or 1-octene. More specifically, the elastomeric ethylene copolymer (E) according to the second embodiment of the invention comprises, apart from ethylene, units derivable from 1-butene, 1-hexene and / or 1-octene.

[0280] It is especially preferred that the elastomeric ethylene copolymer (E) according to the second embodiment of the present invention is a copolymer of ethylene and 1-octene.

[0281] Preferably, the elastomeric ethylene copolymer (E) according to the second embodiment of the present invention is a very low density polyethylene, more preferably a very low density polyethylene polymerised using single site catalysis.

[0282] The elastomeric ethylene copolymer (E) according to the second embodiment of the present invention has a 3 Preferably, the elastomeric ethylene copolymer (E) according to the second embodiment of the present invention has a density measured according to ISO 1183-187 in the range of 865 to 885 kg / m 3 in the range of 870 to 884 kg / m 3 In the range of 879 to 883 kg / m 3 within the range.

[0283] Preferably, the elastomeric ethylene copolymer (E) according to the second embodiment of the invention has a melt flow rate MFR (190°C, 2.16 kg) determined according to ISO 1133 in the range of 0.8 to 20.0 g / 10 min, more preferably in the range of 0.9 to 10.0 g / 10 min, still more preferably in the range of 1.0 to 5.0 g / 10 min, like in the range of 1.0 to 2.0 g / 10 min.

[0284] The ethylene content of the elastomeric ethylene copolymer (E) according to the second embodiment of the invention is in the range of 55.0 to 85.0 wt.-%, preferably in the range of 65.0 to 80.0 wt.-%, more preferably in the range of 70.0 to 78.0 wt.-%, based on the total weight of the elastomeric ethylene copolymer (E).

[0285] Furthermore, it is preferred that the elastomeric ethylene copolymer (E) according to the second embodiment of the invention has a melting temperature Tm, measured according to differential scanning calorimetry (DSC), lower than 100°C, more preferably in the range of 50 to 90°C, still more preferably in the range of 55 to 85°C.

[0286] Additionally or alternatively to the previous paragraph, it is preferred that the elastomeric ethylene copolymer (E) according to the second embodiment of the present invention has a glass transition temperature below -25°C, more preferably in the range of -65°C to -30°C, still more preferably in the range of -60°C to -35°C.

[0287] In a preferred embodiment, the elastomeric ethylene copolymer (E) according to the second embodiment of the present invention is prepared with at least one single-site catalyst. The elastomeric ethylene copolymer (E) according to the second embodiment of the present invention can also be prepared with more than one single-site catalyst, or can be a blend of multiple elastomeric copolymers prepared with different single-site catalysts. In some embodiments, the elastomeric ethylene copolymer (E) according to the second embodiment of the present invention is a substantially linear ethylene polymer (SLEP). SLEP and other single-site catalyzed elastomeric ethylene copolymers are known in the art, for example, US 5,272,236. These resins are also commercially available, for example, Queopolymer, available from Borealis. TM Plastomers, ENGAGE available from The Dow Chemical Company TM Plastomer resin, EXACT from Exxon TM Polymer or TAFMER from Mitsui TM polymers, Lucene polymers from LG, Fortify polymers from Sabic, or Solumer polymers from SK Chemicals.

[0288] The heterophasic polypropylene composition (HECO) according to the second embodiment of the present invention may further comprise a low density polyethylene (LDPE).

[0289] Preferably, the low density polyethylene (LDPE) has a melt flow rate MFR (190°C, 2.16 kg) determined according to ISO 1133 in the range of 0.5 to 5.0 g / 10 min, more preferably in the range of 0.8 to 10.0 g / 10 min, still more preferably in the range of 1.0 to 7.0 g / 10 min, such as in the range of 2.5 to 3.5 g / 10 min.

[0290] Furthermore, it is preferred that the low density polyethylene (LDPE) has a density greater than 900 kg / m 3 , preferably between 920 and 960 kg / m 3 in the range of 925 to 955 kg / m 3 The density is determined according to ISO 1183-187 within the range of .

[0291] Furthermore, it is preferred that the low-density polyethylene (LDPE) is a copolymer of ethylene and a polar comonomer copolymerizable with ethylene. Examples of polar comonomers are vinyl carboxylates selected from the group consisting of vinyl acetate and vinyl pivalate, (meth)acrylates (such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and hydroxyethyl (meth)acrylate), ethylenically unsaturated carboxylic acids (such as (meth)acrylic acid, maleic acid, and fumaric acid), (meth)acrylic acid derivatives (such as (meth)acrylonitrile and (meth)acrylamide), and vinyl ethers (such as vinyl methyl ether and vinyl phenyl ether). Preferably, the polar comonomer is a vinyl carboxylate. Particularly preferably, the polar comonomer is vinyl acetate.

[0292] Furthermore, it is preferred that the low density polyethylene (LDPE) has a comonomer content, preferably a vinyl acetate content, in the range of 10.0 to 40.0 wt.-%, more preferably in the range of 15.0 to 35.0 wt.-%, still more preferably in the range of 20.0 to 33.0 wt.-%, such as in the range of 25.0 to 30.0 wt.-%, based on the total weight of the low density polyethylene (LDPE). It is particularly preferred that the low density polyethylene (LDPE) consists only of ethylene and vinyl acetate units.

[0293] Low density polyethylene (LDPE) is preferably produced by free radical initiated high pressure polymerisation.

[0294] Preferably, the low density polyethylene (LDPE) is a copolymer known in the art. Particularly preferably, the low density polyethylene (LDPE) is a commercially available copolymer of ethylene and vinyl acetate OE5328I from Borealis.

[0295] The heterophasic polypropylene composition (HECO) according to the second embodiment of the present invention is preferably obtained by melt blending the propylene copolymer (cPP), the elastomeric ethylene copolymer (E) and optionally a low density polyethylene (LDPE).

[0296] The fiber-reinforced composition (C) according to the second embodiment of the invention preferably has a melt flow rate MFR2 (230° C., 2.16 kg) determined according to ISO 1133 in the range of 1.0 to 10.0 g / 10 min, more preferably in the range of 1.5 to 6.0 g / 10 min, still more preferably in the range of 2.0 to 4.5 g / 10 min, such as in the range of 2.5 to 3.8 g / 10 min.

[0297] Furthermore, it is preferred that the fiber reinforced composition (C) according to the second embodiment of the present invention has a tensile modulus determined according to ISO 527-1A in the range of 2500 to 5500 MPa, more preferably in the range of 2550 to 4200 MPa, still more preferably in the range of 2600 to 3500 MPa, such as in the range of 2650 to 2800 MPa.

[0298] Additionally or alternatively, it is preferred that the fiber reinforced composition (C) according to the second embodiment of the invention has an elongation at break measured according to ISO 527-2 of greater than 10.0%, more preferably greater than 10.3%, still more preferably greater than 10.8%, such as equal to or greater than 11.0%.

[0299] Fiber (F)

[0300] An essential component of the fiber-reinforced composition (C) of the present invention is the fiber (F).

[0301] Preferably, the fibers (F) are selected from the group consisting of glass fibers, carbon fibers, polymer fibers, metal fibers, mineral fibers, ceramic fibers, and mixtures thereof. More preferably, the fibers (F) are glass fibers and / or carbon fibers.

[0302] It is particularly preferred that the fibers (F) are glass fibers (GF). Preferably, the glass fibers (GF) are cut glass fibers, also known as short glass fibers (SGF) or chopped strands, and / or long glass fibers (LGF), preferably long glass fibers (LGF) obtained from glass roving.

[0303] It is particularly preferred that the fibers (F) are short glass fibers (GF).

[0304] The chopped or short glass fibers (SGF) used in the fiber-reinforced composition (C) preferably have an average length in the range of 2.0 to 10.0 mm, more preferably in the range of 2.3 to 9.0 mm, still more preferably in the range of 2.5 to 8.0 mm, such as in the range of 3.0 to 7.0 mm.

[0305] The chopped or short glass fibers (SGF) used in the fiber-reinforced composition (C) preferably have an average diameter of 5 to 20 μm, more preferably 6 to 18 μm, still more preferably 8 to 16 μm.

[0306] Preferably, the short glass fibers (SGF) have an aspect ratio of 125 to 650, preferably 150 to 500, more preferably 200 to 450. The aspect ratio is the relationship between the average length and the average diameter of a fiber.

[0307] Adhesion Promoter (AP)

[0308] According to the present invention, the fiber reinforced polypropylene composition (C) may further comprise an adhesion promoter (AP). In case the fibers (F) are glass fibers and / or carbon fibers, it is preferred that the fiber reinforced polypropylene composition (C) comprises an adhesion promoter (AP).

[0309] The adhesion promoter (AP) is designated as a polar modified polypropylene (PM-PP) homopolymer or copolymer.

[0310] Polar modified polypropylene (PM-PP) homopolymers or copolymers contain low molecular weight compounds with reactive polar groups. Most preferred are modified polypropylene homopolymers and copolymers such as propylene and ethylene or other α-olefins (e.g. C4 to C 10 Preferably, copolymers of propylene homo- or copolymers (PP) of the fiber reinforced polypropylene composition (C) are used as they are highly compatible with the propylene homo- or copolymer (PP) of the fiber reinforced polypropylene composition (C) of the present invention.

[0311] In terms of structure the polar modified polypropylene (PM-PP) homopolymer or copolymer is preferably selected from grafted homopolymers or copolymers.

[0312] In this context, preference is given to polar-modified polypropylene (PM-PP) homo- or copolymers containing groups derived from polar compounds, in particular selected from the group consisting of anhydrides, carboxylic acids, carboxylic acid derivatives, primary and secondary amines, hydroxyl compounds, oxazolines and epoxides, and ionic compounds.

[0313] Specific examples of the polar compound are unsaturated cyclic anhydrides and aliphatic diesters and diacid derivatives thereof. In particular, maleic anhydride and a compound selected from C1 to C10 linear and branched dialkyl maleates, C1 to C10 linear and branched dialkyl fumarates, itaconic anhydride, C1 to C10 linear and branched dialkyl itaconic acid esters, acrylic acid, maleic acid, fumaric acid, itaconic acid, and mixtures thereof can be used.

[0314] Particular preference is given to using polypropylene homo- or copolymers grafted with maleic anhydride or acrylic acid as polar-modified polypropylene (PM-PP) homo- or copolymers, ie adhesion promoters (AP).

[0315] Modified polymers, i.e. adhesion promoters, can be produced in a simple manner by reactive extrusion of polymers, for example with maleic anhydride or acrylic acid in the presence of free radical generators such as organic peroxides, as disclosed, for example, in US Pat. No. 4,506,056, US Pat. No. 4,753,997 or EP 1 805 238.

[0316] The preferred amount of groups derived from polar compounds in the polar-modified polypropylene (PM-PP) homopolymer or copolymer (i.e., adhesion promoter (AP)) is 0.5 to 5.0 wt. %. For example, the amount may be in the range of 0.5 to 4.5 wt. %, preferably in the range of 0.5 to 4.0 wt. %, more preferably in the range of 0.5 to 3.5 wt. %.

[0317] Preferred values ​​for the melt flow rate MFR2 (230°C) of the polar-modified polypropylene (PM-PP) homopolymer or copolymer, i.e. the adhesion promoter (AP), are at least 20.0 to 400 g / 10 min. Particularly preferred are polar-modified polypropylene (PM-PP) homopolymer or copolymers having a melt flow rate MFR2 (230°C) in the range of 40.0 to 300 g / 10 min, more preferably in the range of 50.0 to 250 g / 10 min.

[0318] In a preferred embodiment of the present invention, the adhesion promoter (AP) is a maleic anhydride-modified polypropylene homopolymer or copolymer and / or an acrylic acid-modified polypropylene homopolymer or copolymer. Preferably, the adhesion promoter (AP) is a maleic anhydride-modified polypropylene homopolymer and / or an acrylic acid-modified polypropylene homopolymer, preferably a maleic anhydride-modified polypropylene homopolymer. For example, suitable polar-modified polypropylene (PM-PP) homopolymers or copolymers include, for example, polypropylene homopolymers grafted with maleic anhydride (PP-g-MAH) and polypropylene homopolymers grafted with acrylic acid (PP-g-AA).

[0319] Additives (AD)

[0320] In addition to the heterophasic polypropylene composition (HECO), the fibers (F) and the adhesion promoter (AP), the fiber-reinforced composition (C) of the present invention may comprise additives (AD). Typical additives are acid scavengers, antioxidants, colorants, light stabilizers, plasticizers, slip agents, anti-scratch agents, dispersants, processing aids, lubricants, pigments, etc.

[0321] Such additives are commercially available and are described, for example, in the “Plastic Additives Handbook” by Hans Zweifel, 6th edition, 2009 (pp. 1141 to 1190).

[0322] Furthermore, the term "additive (AD)" according to the present invention also comprises support materials, in particular polymeric support materials.

[0323] Polymer carrier materials

[0324] Preferably, the fiber reinforced composition (C) of the present invention does not comprise (a) other polymers different from the heterophasic polypropylene composition (HECO) and the adhesion promoter (AP) in an amount of more than 15 wt.-%, preferably in an amount of more than 10 wt.-%, more preferably in an amount of more than 9 wt.-%, based on the total weight of the fiber reinforced composition (C). Any polymer serving as a carrier material for the additive (AD) is not counted towards the amount of polymer compound indicated in the present invention, but rather towards the amount of the respective additive.

[0325] The polymer carrier material of the additive (AD) is a carrier polymer to ensure uniform distribution in the fiber-reinforced polypropylene composition (C) of the present invention. The polymer carrier material is not limited to a specific polymer. The polymer carrier material can be an ethylene homopolymer, an ethylene copolymer obtained by ethylene and an α-olefin comonomer (such as a C3 to C8 α-olefin comonomer), a propylene homopolymer and / or a propylene copolymer obtained by propylene and an α-olefin comonomer (such as ethylene and / or a C4 to C8 α-olefin comonomer). Preferably, the polymer carrier material does not contain monomer units derived from styrene or its derivatives.

[0326] Products

[0327] The present invention also relates to an article, such as an injection molded article, comprising a fiber-reinforced composition (C) as defined above. The present invention particularly relates to an article, such as an injection molded article, comprising at least 60 wt.%, more preferably at least 80 wt.%, still more preferably at least 90 wt.%, such as at least 95 wt.% or at least 99 wt.% of a fiber-reinforced polypropylene composition (C) as defined above. In a particularly preferred embodiment, the present invention relates to an article, such as an injection molded article, consisting of a fiber-reinforced composition (C) as defined above.

[0328] Preferably, the article is an automotive article, such as an injection molded automotive article.

[0329] Further implementation plans

[0330] [1] A fiber-reinforced composition (C) comprising, based on the total weight of the fiber-reinforced composition (C),

[0331] a) 55.0 to 94.9 wt.-% of a heterophasic polypropylene composition (HECO) comprising

[0332] i) is a matrix of a propylene homo- or copolymer (PP) having an amount of 1,2 erythro regio defects of at least 0.4 mol-% and a comonomer content equal to or lower than 8.5 mol-%, and

[0333] ii) an elastomeric ethylene copolymer (E) dispersed in the matrix,

[0334] b) 5.0 to 45.0% by weight of fibers (F), and

[0335] c) optionally 0.1 to 5.0% by weight of an adhesion promoter (AP),

[0336] wherein the fiber-reinforced composition (C) has a melt flow rate MFR2 (230° C., 2.16 kg) measured according to ISO 1133 in the range of 1.0 to 60.0 g / 10 min.

[0337] [2] The fiber reinforced composition (C) according to embodiment [1], wherein the heterophasic polypropylene composition (HECO) comprises, based on the total weight of the heterophasic copolymer (HECO),

[0338] i) 60.0 to 95.0 wt.% of a matrix which is a propylene homopolymer or copolymer (PP), and

[0339] ii) 5.0 to 40.0 wt.% of an elastomeric ethylene copolymer (E).

[0340] [3] The fiber-reinforced composition (C) according to embodiment [1] or [2], wherein the elastomeric ethylene copolymer (E) has an ethylene content in the range of 15.0 to 85.0 wt.-%, based on the total weight of the elastomeric ethylene copolymer (E).

[0341] [4] The fiber reinforced composition (C) according to any of embodiments [1] to [3], wherein the heterophasic polypropylene composition (HECO) has a melting temperature Tm determined according to differential scanning calorimetry (DSC) in the range of 130 to 165 °C, and / or

[0342] [5] The fiber reinforced composition (C) according to any of embodiments [1] to [4], wherein the heterophasic polypropylene composition (HECO) has an intrinsic viscosity (IV) measured according to ISO 1628 / 1 (in decalin at 135 °C) of the soluble fraction (SF) determined according to CRYSTEX QC in the range of 1.8 to 3.0 dl / g.

[0343] [6] The fiber-reinforced composition (C) according to any one of embodiments [1] to [5], wherein the fiber (F) is a glass fiber (GF), preferably a short glass fiber (SGF), having

[0344] i) an average length of 2.0 to 10.0 mm, and / or

[0345] ii) an average diameter of 5 to 20 μm.

[0346] [7] The fiber-reinforced composition (C) according to any one of embodiments [1] to [6], wherein the adhesion promoter (AP) is a polar modified polypropylene (PM-PP) which is a propylene homopolymer or copolymer grafted with maleic anhydride, and has a melt flow rate MFR (230°C, 2.16 kg) measured according to ISO 1133 of at least 20.0 g / 10 min to 400 g / 10 min.

[0347] [8] The fiber-reinforced composition (C) according to any one of embodiments [1] to [7], wherein

[0348] i) the propylene homopolymer or copolymer (PP) is a propylene homopolymer (hPP), and

[0349] ii) Elastomeric ethylene polymer (E) is a copolymer of ethylene and propylene.

[0350] [9] The fiber-reinforced composition (C) according to embodiment [8], wherein the propylene homopolymer (hPP) has a melting temperature Tm, determined according to differential scanning calorimetry (DSC), in the range of 140 to 160°C.

[0351]

[10] Fiber reinforced composition (C) according to embodiment [8] or [9], wherein the heterophasic polypropylene composition (HECO) has i) a comonomer content in the range of 2.2 to 8.7 mol%, and / or

[0352] ii) a melt flow rate MFR2 (230° C., 2.16 kg), determined according to ISO 1133, in the range of 20.0 to 100 g / 10 min.

[0353]

[11] The fiber reinforced composition (C) according to any of embodiments [8] to

[10] , wherein the heterophasic polypropylene composition (HECO) has

[0354] i) a xylene cold soluble (XCS) content determined according to ISO 16152 at 25 °C in the range of 5.0 to 35.0 wt.-%, based on the total weight of the heterophasic polypropylene composition (HECO), and / or

[0355] ii) an ethylene content of the xylene cold soluble (XCS) fraction in the range of 20.9 to 44.7 mol%.

[0356] and / or

[0357] ii) a soluble fraction (SF) determined according to CRYSTEX QC in the range of 5.0 to 35.0 wt.-%, based on the total weight of the heterophasic polypropylene composition (HECO), and / or

[0358] iv) an ethylene content of the soluble fraction (SF) determined according to CRYSTEX QC in the range of 20.9 to 44.7 mol%.

[0359]

[12] The fiber-reinforced composition (C) according to any one of embodiments [8] to

[11] , having

[0360] i) a tensile modulus in the range of 3000 to 6000 MPa, determined according to ISO 527-1A, and / or

[0361] ii) an elongation at break determined according to ISO 527-2 of greater than 3.0%.

[0362]

[13] The fiber-reinforced composition (C) according to any one of embodiments [1] to [7], wherein

[0363] i) the propylene homopolymer or copolymer (PP) is a propylene copolymer (cPP), a copolymer of propylene and ethylene, which copolymer has an ethylene content of 2.2 to 8.5 mol%, and

[0364] ii) Elastomeric ethylene copolymer (E) is ethylene and C4 to C 12 A copolymer of an alpha-olefin, preferably 1-octene, having an ethylene content of from 55.0 to 85.0 wt.-%, based on the total weight of the elastomeric ethylene copolymer (E).

[0365]

[14] The fiber-reinforced composition (C) according to embodiment

[13] , wherein

[0366] i) the propylene copolymer (cPP) has a melt flow rate MFR2 (230°C, 2.16 kg), determined according to ISO 1133, in the range of 5.0 to 20.0 g / 10 min, and / or

[0367] ii) the elastomeric ethylene copolymer (E) has a melt flow rate MFR (190°C, 2.16 kg) determined according to ISO 1133 in the range of 0.8 to 20.0 g / 10 min, and / or in the range of 860 to 890 kg / m 3 Density determined according to ISO 1183-187 within the range

[0368] and / or

[0369] iii) The fiber-reinforced composition (C) has a melt flow rate MFR2 (230° C., 2.16 kg), measured according to ISO 1133, in the range of 1.0 to 10.0 g / 10 min.

[0370]

[15] The fiber-reinforced composition (C) according to embodiment

[13] or

[14] , having

[0371] i) a tensile modulus in the range of 2500 to 5500 MPa, determined according to ISO 527-1A, and / or

[0372] ii) an elongation at break determined according to ISO 527-2 of greater than 10.0%.

[0373]

[16] The fiber-reinforced composition (C) according to any one of embodiments [1] to

[15] , further comprising up to 20.0 wt.% of a low-density polyethylene (LDPE) homopolymer or copolymer having a mass fraction greater than 900 kg / m 3 The density is determined according to ISO 1183-187 and comprises ethylene and optionally vinyl acetate.

[0374]

[17] The fiber reinforced composition (C) according to any one of embodiments [1] to

[16] , wherein the propylene homopolymer or copolymer (PP) is obtained in the presence of a solid catalyst system (SCS) comprising a metallocene complex, preferably having formula (I)

[0375]

[0376] wherein each X is independently a σ-donor ligand,

[0377] L is a divalent bridge selected from -R'2C-, -R'2C-CR'2-, -R'2Si-, -R'2Si-SiR'2-, -R'2Ge-, wherein each R' is independently a hydrogen atom or a C1-C ... 20 - a hydrocarbon group, or optionally two R' groups together can form a ring,

[0378] Each R 1 are independently identical or can be different and are hydrogen, linear or branched C1-C6-alkyl, C 7-20 -aralkyl, C 7-20 -alkylaryl or C 6-20 -aryl or OY group, where Y is C 1-10 -hydrocarbyl, and optionally two adjacent R 1 The groups can be part of a ring containing the phenyl carbon to which they are bonded,

[0379] Each R 2 are independently the same or can be different, and are CH2-R 8 Group, where R 8 H or linear or branched C 1-6 -alkyl, C 3-8 -cycloalkyl, C 6-10 -aryl,

[0380] R 3 is a straight or branched C1-C6-alkyl, C 7-20 -aralkyl, C 7-20 -alkylaryl or C6-C 20 -aryl,

[0381] R 4 C(R 9 )3 groups, wherein R 9 is a linear or branched C1-C6-alkyl group,

[0382] R 5 is hydrogen or an aliphatic C1-C12 radical optionally containing one or more heteroatoms from Groups 14 to 16 of the Periodic Table 20 -hydrocarbon group;

[0383] R 6 is hydrogen or an aliphatic C1-C12 radical optionally containing one or more heteroatoms from Groups 14 to 16 of the Periodic Table 20 - a hydrocarbon group; or

[0384] R 5 and R 6 can together form a 5-membered saturated carbocyclic ring, which is optionally substituted by n groups R 10 substituted, n is 0 to 4;

[0385] Each R 10 Same or different, and can be C1-C 20 -hydrocarbyl, or a C1-C ... 20 -hydrocarbon group;

[0386] R 7 is H or a linear or branched C1-C6-alkyl radical or optionally substituted by 1 to 3 radicals R 11 a substituted aryl or heteroaryl group having 6 to 20 carbon atoms,

[0387] Each R 11 are independently identical or can be different and are hydrogen, linear or branched C1-C6-alkyl, C 7-20 -aralkyl, C 7-20 -alkylaryl or C 6-20 -aryl or OY group, where Y is C 1-10 -hydrocarbon group.

[0388]

[18] An article comprising the fiber-reinforced composition (C) according to any one of embodiments [1] to

[17] .

[0389] The present invention will now be described in more detail by way of the examples provided below.

[0390] Example

[0391] A. Measurement Method

[0392] Unless defined otherwise, the following definitions of terms and assay methods apply to the above general description of the invention as well as to the following examples.

[0393] Melt flow rate

[0394] The melt flow rate (MFR) is determined according to ISO 1133 and expressed in g / 10 min. The MFR indicates the flowability, and therefore the processability, of a polymer. The higher the melt flow rate, the lower the viscosity of the polymer. The MFR2 of polypropylene is determined at a temperature of 230°C or 190°C and a load of 2.16 kg.

[0395] Melting temperature T m and crystallization temperature T c Measurements were performed on 5 to 7 mg samples using a Mettler TA820 Differential Scanning Calorimeter (DSC). The DSC was operated according to ISO 11357 / Part 3 / Method C2 in a heating / cooling / heating cycle at a scan rate of 10°C / min over a temperature range of -30 to +225°C. The crystallization temperature was determined from the cooling step, while the melting temperature was determined from the second heating step.

[0396] All mechanical measurements were carried out after a specimen conditioning time of 96 h (at 23° C. and 50% relative humidity).

[0397] pass 13 Quantitative analysis of the PP matrix microstructure by C-NMR spectroscopy

[0398] Quantitative nuclear magnetic resonance (NMR) spectroscopy is used to quantify the stereoregularity (tacticity) and regioregularity of the crystalline matrix of the polymer.

[0399] Use for 1 H and 13 Quantitative NMR spectra were recorded in solution on a Bruker Advance III 400 NMR spectrometer operating at 400.15 and 100.62 MHz, respectively. 13 C{ 1 H} NMR Spectra. All spectra were recorded at 125°C using a 13C-optimized 10 mm extended temperature probe head, using nitrogen for all pneumatics.

[0400] For propylene homopolymers, approximately 200 mg of material was dissolved in 1,2-tetrachloroethane-d2 (TCE-d2). To ensure solution homogeneity, the NMR tube was further heated in a rotary oven for at least 1 hour after initial sample preparation in a heating block. After insertion into the magnet, the tube was rotated at 10 Hz. This setting was chosen primarily for the high resolution required for quantification of the tacticity distribution (Busico, V., Cipullo, R., Prog. Polym. Sci. 26 (2001) 443; Busico, V.; Cipullo, R., Monaco, G., Vacatello, M., Segre, AL, Macromolecules 30 (1997) 6251). Standard single-pulse excitation was employed, using NOE and a two-stage WALTZ16 decoupling scheme (Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh, D. Winniford, B., J. Mag. Reson. 187 (2007) 225; Busico, V., Carbonniere, P., Cipullo, R., Pellecchia, R., Severn, J., Talarico, G., Macromol. Rapid Commun. 2007, 28, 11289). A total of 8192 (8k) transient signals were collected for each spectrum.

[0401] Quantification was performed using a proprietary computer program 13 C{1 H} NMR spectra were processed, integrated, and the relevant quantitative properties were determined from the integration. For propylene homopolymers, all chemical shifts were internally referenced to the methyl isotactic pentad (mmmm) at 21.85 ppm. The tacticity distribution was quantified by integrating the methyl region between 23.6 and 19.7 ppm, correcting for any sites not associated with the stereo sequence of interest (Busico, V., Cipullo, R., Prog. Polym. Sci. 26 (2001) 443; Busico, V., Cipullo, R., Monaco, G., Vacatello, M., Segre, AL, Macromoleucles 30 (1997) 6251).

[0402] Specifically, the quantitative effects of regio defects and comonomers on the tacticity distribution are corrected by subtracting representative regio defect and comonomer integrals from a specific integrated region of the stereo sequence. Isotacticity is determined at the pentad level and reported as the percentage of isotactic pentad (mmmm) sequences over all pentad sequences:

[0403] [mmmm]% = 100*(mmmm / sum of all pentads).

[0404] The presence of 2,1-erythro regiodefects is indicated by the presence of two methyl sites at 17.7 and 17.2 ppm and confirmed by other characteristic sites.

[0405] No characteristic signals corresponding to other types of regional defects were observed (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253). The amount of 2,1-erythro regional defects was quantified using the average integral of the two characteristic methyl sites at 17.7 and 17.2 ppm:

[0406] P 21e =(I e6 +I e8 ) / 2.

[0407] The number of 1,2 primary insertion propenes was quantified based on the methyl region and corrected for sites not involved in the primary insertion and for primary insertion sites not included in the region:

[0408] P 12 =I CH3 +P 12e

[0409] The total amount of propene is quantified as the sum of the primary inserted propene and all other regio defects present:

[0410] P 总 =P 12 +P 21e

[0411] The mole percentage of 2,1-erythro regio defects relative to all propylene was quantified:

[0412] [21e] mol% = 100*(P 21e / P 总 )

[0413] Determination of C2 and C3 content in PP copolymers

[0414] Quantitative nuclear magnetic resonance (NMR) spectroscopy was used to quantify the comonomer content and comonomer sequence distribution of the polymers. 1 H and 13 Quantitative measurements were recorded in solution on a Bruker Avance III 400 NMR spectrometer operating at 400.15 and 100.62 MHz, respectively. 13 C{ 1 H} NMR spectroscopy. Nitrogen was used for all pneumatics and all spectra were 13C optimized 10mm extended temperature probe was recorded at 125 ° C. About 200 mg of material was dissolved in 3 ml of 1,2-tetrachloroethane-d2 (TCE-d2) along with chromium (III) acetylacetonate (Cr (acac) 3) to give a 65 mM solution of the relaxation agent in the solvent (Singh, G., Kothari, A., Gupta, V., Polymer Testing 28 5 (2009), 475). To ensure a homogeneous solution, after initial sample preparation in a heating block, the NMR tube was further heated in a rotary oven for at least 1 hour. After insertion of the magnet, the tube was rotated at 10 Hz. This setting was selected primarily for high resolution and accurate ethylene content quantification and quantitatively required. Standard single-pulse excitation without NOE was used, with an optimized tip cone angle, a 1 s recycle delay, and a two-stage WALTZ16 decoupling scheme (Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh, D. Winniford, B., J. Mag. Reson. 187 (2007) 225; Busico, V., Carbonniere, P., Cipullo, R., Pellecchia, R., Severn, J., Talarico, G., Macromol. Rapid Commun. 2007, 28, 1128). A total of 6144 (6k) transients were collected for each spectrum.

[0415] Quantification was performed using a proprietary computer program 13 C{ 1 H} NMR spectra were processed, integrated and the relevant quantitative properties were determined by integration. Using the chemical shift of the solvent, all chemical shifts were indirectly referenced to the central methylene group of the ethylene block (EEE) at 30.00 ppm. Even if this structural unit does not exist, this method also allows for comparable references. Characteristic signals corresponding to the incorporation of ethylene were observed (Cheng, HN, Macromolecules 17 (1984), 1950).

[0416] Using the method of Wang et al. (Wang, WJ., Zhu, S., Macromolecules 33 (2000), 1157), the 13 C{ 1The comonomer fraction is quantified by integrating multiple signals over the entire spectral region in the H} spectrum. This method was chosen for its robustness and ability to account for the presence of regio defects when needed. The integration region was slightly adjusted to improve applicability over the entire range of comonomer contents encountered. For systems where only isolated ethylene was observed in the PPEPP sequence, the method of Wang et al. was modified to reduce the impact of nonzero integrals at sites known to be absent. This approach reduces the overestimation of ethylene content in such systems and is achieved by reducing the number of sites used to determine the absolute ethylene content to:

[0417] E=0.5(Sββ+Sβγ+Sβδ+0.5(Sαβ+Sαγ))

[0418] By using this set of sites, the corresponding integral equation becomes:

[0419] E=0.5(I H +I G +0.5(I C +I D ))

[0420] The same symbols used in the article by Wang et al. are used (Wang, WJ., Zhu, S., Macromolecules 33 (2000), 1157). The equations for absolute propylene content are not modified.

[0421] Calculate the mole percentage of comonomer incorporation from the mole fraction:

[0422] E [mol %] = 100 * fE

[0423] Calculate the weight percent of comonomer incorporation from the mole fraction:

[0424] E[weight%]=100*(fE*28.06) / ((fE*28.06)+((1-fE)*42.08)).

[0425] The comonomer content of ethylene / 1-octene copolymers was determined using a Nicolet Magna 550 IR spectrometer and Nicolet Omnic FTIR software. 13 Fourier transform infrared spectroscopy (FTIR) calibrated with C-NMR was measured in a known manner. Films with a thickness of approximately 250 μm were compression molded from the samples. Similar films were made from calibration samples with known comonomer content. The comonomer content was determined by the wavelength range of 1430 to 1100 cm -1The absorbance is measured as the peak height by selecting the so-called short baseline, the long baseline, or both. The short baseline is drawn through the lowest point at approximately 1410 to 1320 cm -1 , the long baseline is drawn at about 1410 and 1220 cm -1 A specific calibration is required for each baseline type. In addition, the comonomer content of the unknown samples needs to be within the comonomer content range of the calibration samples.

[0426] The glass transition temperature Tg was determined by dynamic mechanical analysis according to ISO 6721-7. Compression molded specimens (40×10×1 mm2) were heated between −100°C and +150°C at a heating rate of 2°C / min and a frequency of 1 Hz. 3 ) are measured in torsion mode.

[0427] Density was measured according to ISO 1183-187. Sample preparation was performed by compression molding according to ISO 1872-2:2007.

[0428] Xylene Cold Solubles (XCS)

[0429] The xylene cold soluble fraction at room temperature (XCS, wt. %) is determined according to ISO 16152; 5th edition; 2005-07-01 at 25°C.

[0430] Flexural modulus: Flexural modulus is determined in 3-point bending according to ISO 178 on injection-molded test specimens of 80 x 10 x 4 mm prepared according to ISO 294-1:1996.

[0431] Charpy notched impact strength is measured according to ISO 179-1 / 1eA at +23°C using injection moulded test specimens (80 x 10 x 4 mm) prepared according to EN ISO 1873-2.

[0432] Tensile properties were measured on 4 mm thick injection molded dog-bone specimens prepared according to EN ISO 1873-2. Tensile modulus was measured according to ISO 527-1A at a strain rate of 1 mm / min and 23°C, and tensile strength and elongation at break (strain) were measured according to ISO 527-2 at a strain rate of 50 mm / min and 23°C.

[0433] Crystex analysis

[0434] Crystallization and soluble fraction methods

[0435] The crystalline fraction (CF) and soluble fraction (SF) of the polypropylene (PP) composition as well as the comonomer content and intrinsic viscosity of each fraction were analyzed by CRYSTEX QC, Polymer Char (Valencia, Spain).

[0436] exist Figure 1 A schematic diagram of the CRYSTEX QC instrument is shown in a. Figure 1 As shown in Figure 2b, the crystalline and amorphous fractions were separated by temperature cycling of dissolution at 160°C, crystallization at 40°C, and redissolution in 1,2,4-trichlorobenzene (1,2,4-TCB) at 160°C. Quantification of SF and CF, as well as determination of the ethylene content (C2) of the parent EP copolymer and its soluble and crystalline fractions, was achieved using an infrared detector (IR4), and the intrinsic viscosity (iV) was measured using an online 2-capillary viscometer.

[0437] The IR4 detector is a multi-wavelength detector that detects IR absorbance at two different bands (CH3 and CH2) that are used to determine the concentration and ethylene content in ethylene-propylene copolymers. The IR4 detector is calibrated with a series of eight EP copolymers with known ethylene contents ranging from 2 wt% to 69 wt% (measured by 13 C-NMR spectroscopy), and each of the EP copolymers used for calibration had various concentrations between 2 and 13 mg / ml.

[0438] The amounts of the soluble fraction (SF) and the crystalline fraction (CF) are related by means of XS calibration to the amount of "xylene cold solubles" (XCS) and the xylene cold insoluble (XCI) fraction, respectively, determined according to the standard gravimetric method according to ISO 16152. The XS calibration was achieved by testing various EP copolymers having an XS content in the range of 2 to 31 wt%.

[0439] The intrinsic viscosity (iV) of the parent EP copolymer and its soluble and crystalline fractions was determined using an online 2-capillary viscometer and related to the corresponding iV determined by the standard method in decalin according to ISO 1628. Calibration was achieved using various EP PP copolymers with iV = 2 to 4 dl / g.

[0440] A sample of the PP composition to be analyzed was weighed out at a concentration of 10 to 20 mg / ml. After automatically filling the vial with 1,2,4-TCB containing 250 mg / l of 2,6-tert-butyl-4-methylphenol (BHT) as an antioxidant, the sample was dissolved at 160°C until completely dissolved, typically for 60 minutes, with constant stirring at 800 rpm.

[0441] like Figure 1 As shown in Figures 1a and 1b, a defined volume of sample solution is injected into a column filled with an inert carrier, where crystallization of the sample and separation of the soluble fraction from the crystalline portion occur. This process is repeated twice. During the first injection, the entire sample is measured at high temperature to determine the IV (dl / g) and C2 (wt%) of the PP composition. During the second injection, the soluble fraction (at low temperature) and the crystalline fraction (CF) (at high temperature) are measured during the crystallization cycle (wt% SF, wt% C2, IV).

[0442] EP stands for ethylene propylene copolymer.

[0443] PP stands for polypropylene.

[0444] Figure 1 (a) Schematic diagram of the CRYSTEX QC instrument

[0445] Figure 1 (b): Elution of the EP copolymer sample in a TREF column (a column packed with an inert material such as glass beads) and obtaining a soluble fraction and a crystalline fraction (see Del Hierro, P.; Ortin, A.; Monrabal, B.; 'Soluble Fraction Analysis in polypropylene').

[0446] Intrinsic viscosity: The intrinsic viscosity (IV) is measured according to DIN ISO 1628 / 1, October 1999, in decalin at 135°C.

[0447] VOC / Fog emissions are measured according to VDA 278:2002 on injection molded specimens and pelletized compounds. Volatile organic compounds are measured in toluene equivalents per gram. Fogging is measured in hexadecane equivalents per gram.

[0448] The measurements were performed using a TDSA supplied by Gerstel, using Helium 5.0 as carrier gas and a column HP Ultra 2 of 50 m length, 0.32 mm diameter and 0.52 μm with a 5% phenyl-methyl-siloxane coating.

[0449] VOC analysis was performed according to the instrument settings 1 listed in the standard using the following main parameters: flow mode splitless, final temperature 90°C; final time 30 min, rate 60 K / min. The cooling trap was purged with a flow mode split ratio of 1:30 over a temperature range of -150°C to +280°C at a heating rate of 12 K / s and a final time of 5 min. The following GC settings were used for the analysis: isothermal at 40°C for 2 min, heating to 92°C at 3 K / min, then heating to 160°C at 5 K / min, then heating to 280°C at 10 K / min, isothermal for 10 min; flow rate 1.3 ml / min.

[0450] Fog analysis was performed according to the instrument settings listed in the standard, using the following key parameters: splitless flow mode at 60 K / min; final temperature 120°C; and final time 60 min. The cold trap was purged with a flow mode split ratio of 1:30 over a temperature range of -150°C to +280°C, and a heating rate of 12 K / s. The following GC settings were used for the analysis: isothermal at 50°C for 2 min, heating at 25 K / min to 160°C, then heating at 10 K / min to 280°C, and isothermal for 30 min; flow rate 1.3 ml / min.

[0451] B. Examples

[0452] 1. Catalyst Synthesis

[0453] The catalyst used is trans-dimethylsilylene[2-methyl-4,8-bis(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-sym-indacene-1-yl][2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride as disclosed as ICS3 in WO 2020 / 239602 A1.

[0454] Preparation of MAO-silica support

[0455] A steel reactor equipped with a mechanical stirrer and filter was flushed with nitrogen and the reactor temperature was set to 20°C. Silica (5.0 kg) of AGC Si-Tech's DM-L-303 grade, pre-calcined at 600°C, was then added from the feed drum, followed by careful nitrogen pressure increase and reduction using a manual valve. Toluene (22 kg) was then added. The mixture was stirred for 15 minutes. A 30% by weight solution of MAO in toluene (9.0 kg) from Lanxess was then added over 70 minutes through the feed line at the top of the reactor. The reaction mixture was then heated to 90°C and stirred at 90°C for an additional two hours. The slurry was allowed to settle and the mother liquor was filtered off. The catalyst was washed twice with toluene (22 kg) at 90°C, followed by settling and filtration. The reactor was cooled to 60°C and the solids were washed with heptane (22.2 kg). Finally, the MAO-treated SiO2 was dried at 60° under a nitrogen stream for 2 hours and then dried with stirring under vacuum (-0.5 bar, gauge) for 5 hours. The MAO-treated support was collected as a free-flowing white powder, which was found to contain 12.2% aluminum (by weight).

[0456] Catalyst preparation

[0457] At 20° C., 30 wt % MAO in toluene (0.7 kg) was added via a burette to a nitrogen-sealed steel reactor. Toluene (5.4 kg) was then added with stirring. The catalyst described above (93 g) was added from a metal cylinder, followed by a rinse with 1 kg of toluene. The mixture was stirred at 20° C. for 60 minutes. Trityl tetrakis(pentafluorophenyl)borate (91 g) was then added from a metal cylinder, followed by a rinse with 1 kg of toluene. The mixture was stirred at room temperature for 1 hour. The resulting solution was added over 1 hour to a stirred cake of the MAO-silica support prepared above. The cake was allowed to stand for 12 hours, then dried at 60° C. under a stream of N 2 for 2 hours and dried under vacuum (−0.5 bar, gauge) with stirring for an additional 5 hours. The dried catalyst was sampled as a pink, free-flowing powder containing 13.9% Al and 0.11% Zr.

[0458] 2. Preparation of the heterophasic polypropylene composition (HECO1) and the propylene copolymer (cPP) in the reactor

[0459] The in-reactor heterophasic polypropylene composition (HECO1) and the propylene copolymer (cPP) were produced in a sequential process comprising a loop reactor and one or two gas phase reactors in the presence of the catalysts described above. The reaction conditions and properties of the final polymers are summarized in Tables 1 and 2.

[0460] Table 1: Preparation of in-reactor heterophasic polypropylene composition (HECO1) and propylene copolymer (cPP)

[0461] HECO1 cPP Prepolymerization temperature [℃] 18 20 pressure [kPa] 4977 4973 Catalyst feed [g / h] 2.4 1.4 TEAL / C3 [g / t] 0.0 3.1 Feed H2 / C3 ratio [mol / kmol] 0.05 0.05 Dwell time [h] 0.36 0.32 Ring pipe (R1) temperature [℃] 70 70 pressure [kPa] 4867 4860 H2 / C3 ratio [mol / kmol] 0.43 0.14 C2 / C3 ratio [mol / kmol] 1.23 30.08 <![CDATA[MFR2]]> [g / 10min] 81.9 2.1 C2 [mol%] 0.0 3.0 Dwell time [h] 0.29 0.39

[0462] Table 1: (Continued)

[0463] HECO1 cPP Split ratio [weight%] 57 58 XCS [weight%] 0.6 0.7 GPR(R2) temperature [℃] 80 80 pressure [kPa] 2500 2500 H2 / C3 ratio [mol / kmol] 3.6 1.6 C2 / C3 ratio [mol / kmol] 0.0 85.5 Dwell time [h] Split ratio [weight%] 32 42 C2(total) [mol%] 0.0 2.4 XCS [weight%] 0.75 0.5 MFR [g / 10min] 101 2.3 GPR(R3) temperature [℃] 70 - pressure [kPa] 2500 - H2 / C3 ratio [mol / kmol] 2.1 - C2 / C3 ratio [mol / kmol] 822 - Split ratio [weight%] 11 - MFR [g / 10min] 87.5 -

[0464] Table 2: Properties of the in-reactor heterophasic polypropylene composition (HECO1) and the propylene copolymer (cPP) after pelletization

[0465] HECO1 cPP MFR [g / 10min] 76.2 8.3 XCS [weight%] 11.2 0.47 C2 [mol%] 2.5 3.6 C2(XCS) [mol%] 32.5 nd IV(XCS) [dl / g] 2.6 nd Tm [℃] 157 137 Tc [℃] 121 100 1,2e [mol%] 0.7 0.8 SF [weight%] 10.6 0.5 C2(SF) [mol%] 31.3 nd C2(CF) [mol%] 0.0 IV [dl / g] 1.26 2.05 IV(SF) [dl / g] 2.51 nd IV(CF) [dl / g] 1.11 nd IV(SF) / IV(CF) [-] 2.26 nd flexural modulus [MPa] 1257 760 Charpy notched impact strength (23℃) <![CDATA[[kJ / m 2 ]]]> 3.85 9.65 Charpy notched impact strength (-20℃) <![CDATA[[kJ / m 2 ]]]> 1.96 nd Tg(1) [℃] -45 - Tg(2) [℃] 0 -4

[0466] 3. Preparation of fiber-reinforced composition using HECO1 (C)

[0467] The fiber reinforced composition (C) was obtained by melt blending the in-reactor heterophasic polypropylene composition (HECO1) with glass fibers (GF), adhesion promoter (AP) and additives (AD) in a co-rotating twin-screw extruder. The compositions and properties of the inventive examples and comparative examples are summarized in Table 3.

[0468] Table 3: Composition and properties of the present invention and comparative examples

[0469] IE1 CE1 CE2 HECO1 [weight%] 77.1 98.6 HECO1a [weight%] 49.1 hP [weight%] 28.0 GF [weight%] 20.0 20.0 AP [weight%] 1.5 1.5 AD1 [weight%] 1.4 1.4 1.4 MFR [g / 10min] 27 19 76 Tensile modulus [MPa] 4936 4993 1298 tensile strength [MPa] 80.3 77.9 26.3 Elongation at break [％] 3.6 3.5 10.5 VOC μg / g 26 143 32 fog μg / g 92 479 104

[0470] HECO1a is a commercial heterophasic propylene copolymer EF015AE from Borealis AG produced with a Ziegler-Natta catalyst and having a xylene cold soluble content of 29.0 wt.-%, an ethylene content of 11.1 mol-% and an intrinsic viscosity of the xylene soluble fraction of 2.7 dl / g.

[0471] hP is a commercial propylene homopolymer HJ120UB from Borealis AG produced with a Ziegler-Natta catalyst, having a melt flow rate MFR2 (230°C) of 75 g / 10 min, a 3 density and a glass transition temperature Tg of +2°C.

[0472] GF is a commercial product ECS 03T-480H of Nippon Electric Glass Co., Ltd., which has a filament diameter of 10.5 μm and a filament bundle length of 3 mm.

[0473] AP is Scona's adhesion promoter SCONA TPPP 8112GA, which is a polypropylene functionalized with maleic anhydride and has a maleic anhydride content of 1.4 wt% and an MFR (190° C., 2.16 kg) above 80 g / 10 min.

[0474] AD1 is a masterbatch consisting of 14.0 wt% of tris(2,4-di-tert-butylphenyl)phosphite (Kinox-68-G from HPLAdditives), 14.0 wt% of pentaerythritol tetrakis(3-(3',5'-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox 1010FF from BASF), 36.0 wt% of carbon black from Borealis (50 wt% masterbatch) and 36.0 wt% of propylene homopolymer HC001A from Borealis, which has a mass fraction of 905 kg / m 3 density, MFR of 3.2 g / 10 min (230°C, 2.16 kg).

[0475] 4. Preparation of compounded heterophasic polypropylene composition (HECO2)

[0476] Preparation of fiber-reinforced composition using HECO2 (C)

[0477] The propylene copolymer (cPP) was melt blended with the elastomeric ethylene copolymer (E), glass fiber (GF), adhesion promoter (AP), optional low density polyethylene (LDPE) and additives (AD) in a co-rotating twin-screw extruder. The compositions and properties of the inventive and comparative examples are summarized in Table 4.

[0478] Table 4: Composition of Examples of the Invention and Comparative Examples

[0479] IE2 IE3 CE3 CE4 cPP [weight%] 47 47 cPPa [weight%] 47 cPPb [weight%] 78.45 E [weight%] 30 15 30 LDPE [weight%] 15 GF [weight%] 20 20 20 20 AP [weight%] 1.5 1.5 1.5 1.0 AD2 [weight%] 1.5 1.5 1.5 AD3 [weight%] 0.55 MFR [g / 10min] 2.8 3.6 2.8 4.0 Tensile modulus [MPa] 2671 2758 2437 3807 tensile strength [MPa] 45.7 46.5 42.6 64.4 Elongation at break [％] 11.6 11.0 10.2 5.6 VOC μg / g 35 42 nd 28 Fog μg / g 103 106 nd 74

[0480] cPPa is a commercial propylene ethylene random copolymer RD208CF from Borealis AG prepared with a Ziegler-Natta catalyst, having an ethylene content of 7.3 mol%, a melt flow rate MFR2 (230° C., 2.16 kg) measured according to ISO 1133 of 8.0 g / 10 min, and a melting temperature Tm of 140° C.

[0481] cPPb is a metallocene propylene ethylene random copolymer according to Example IE1 of WO 2015 / 121160 A1 having an ethylene content of 4.1 mol % and a melt flow rate MFR2 (230° C., 2.16 kg) determined according to ISO 1133 of 4.0 g / 10 min.

[0482] E is a commercial copolymer of ethylene and 1-octene Queo 8201 from Borealis AG having a melt flow rate (190° C., 2.16 kg) determined according to ISO 1133 of 1.1 g / 10 min, a melting temperature Tm of 72° C., a glass transition temperature Tg of −52° C., a viscosity of 882 kg / m 3 The density is 1.5 and the ethylene content is 75.5 wt%.

[0483] LDPE was a commercial copolymer of ethylene and vinyl acetate OE5328 from Borealis AG having a melt flow rate (190° C., 2.16 kg) of 3.0 g / 10 min, measured according to ISO 1133, 950 kg / m 3 and a vinyl acetate content of 28.0 wt%.

[0484] AD2 is a masterbatch consisting of 20.0 wt% erucamide (Fine Organics' Finawax-E), 6.6 wt% tris(2,4-di-tert-butylphenyl)phosphite (BASF's Irgafox 168), 6.6 wt% pentaerythritol tetrakis(3-(3',5'-di-tert-butyl-4-hydroxyphenyl)propionate (BASF's Irganox 1010FF), 33.3 wt% carbon black (50 wt% masterbatch) from Borealis, and 33.3 wt% propylene homopolymer HC001A from Borealis, having a mass fraction of 905 kg / m 3 The density and MFR of 3.2 g / 10 min (230° C., 2.16 kg) were obtained.

[0485] AD3 is a masterbatch composed of 18.18 wt% tris(2,4-di-tert-butylphenyl)phosphite (Irgafox 168 from BASF), 36.36 wt% pentaerythritol tetrakis(3-(3′,5′-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox 1010FF from BASF), and 45.45 wt% distearate thiodipropionate (Irganox PS-802FL from BASF).

Claims

1. A fiber-reinforced composition (C), comprising: a) 55.0 to 95.0 wt.-% of a heterophasic polypropylene composition (HECO) comprising i) is a matrix of a propylene copolymer (cPP) having an amount of 1,2 erythro regio defects of at least 0.4 mol-% and a comonomer content equal to or below 8.5 mol-%, and ii) an elastomeric ethylene copolymer (E) dispersed in said matrix, b) 5.0 to 45.0% by weight of fibers (F), and c) optionally 0.1 to 5.0% by weight of an adhesion promoter (AP), wherein the fiber reinforced composition (C) has a melt flow rate MFR2, measured according to ISO 1133 at a temperature of 230° C. under a load of 2.16 kg, in the range of 1.0 to 60.0 g / 10 min.

2. The fiber-reinforced composition (C) according to claim 1, comprising: a) 55.0 to 94.9 wt.-% of the heterophasic polypropylene composition (HECO), b) 5.0 to 45.0% by weight of said fibers (F), and c) Optionally 0.1 to 5.0 wt. % of said adhesion promoter (AP).

3. Fiber reinforced composition (C) according to claim 1 or 2, wherein the heterophasic polypropylene composition (HECO) comprises: i) 40.0 to 90.0 wt.-% of said propylene copolymer (cPP), and ii) 10.0 to 60.0 wt.% of said elastomeric ethylene copolymer (E).

4. The fiber reinforced composition (C) according to claim 1 or 2, wherein the elastomeric ethylene copolymer (E) has an ethylene content in the range of 55.0 to 85.0 wt.-%, based on the total weight of the elastomeric ethylene copolymer (E).

5. The fiber reinforced composition (C) according to claim 1 or 2, wherein the propylene copolymer (cPP) is a copolymer of propylene and ethylene. 6 . The fiber-reinforced composition (C) according to claim 5 , wherein the copolymer of propylene and ethylene is a random copolymer of propylene and ethylene.

7. Fiber reinforced composition (C) according to claim 1 or 2, wherein the propylene copolymer (cPP) has a comonomer content in the range of 2.2 to 8.5 mol-%.

8. The fiber-reinforced composition (C) according to claim 1 or 2, wherein the elastomeric ethylene copolymer (E) is a copolymer of ethylene and 1-octene.

9. The fiber-reinforced composition (C) according to claim 1 or 2, wherein the fiber (F) is glass fiber (GF).

10. The fiber-reinforced composition (C) according to claim 9, wherein the glass fiber (GF) is a short glass fiber (SGF) having i) an average length of 2.0 to 10.0 mm, and / or ii) an average diameter of 5 to 20 μm.

11. The fiber-reinforced composition (C) according to claim 1 or 2, wherein the adhesion promoter (AP) is a polar modified polypropylene (PM-PP), which is a propylene homopolymer or copolymer grafted with maleic anhydride, and has a melt flow rate MFR, measured according to ISO 1133 at a temperature of 230° C. under a load of 2.16 kg, of at least 20.0 g / 10 min to 400 g / 10 min.

12. The fiber-reinforced composition (C) according to claim 1 or 2, wherein i) the propylene copolymer (cPP) is a copolymer of propylene and ethylene having an ethylene content of 2.2 to 8.5 mol%, and ii) the elastomeric ethylene copolymer (E) is ethylene and C4 to C 12 A copolymer of α-olefins having an ethylene content of from 55.0 to 85.0 wt.-%, based on the total weight of the elastomeric ethylene copolymer (E).

13. The fiber-reinforced composition (C) according to claim 12, wherein the C4 to C 12 The α-olefin is 1-octene.

14. Fiber reinforced composition (C) according to claim 1 or 2, wherein the propylene copolymer (cPP) has a melt flow rate MFR2, measured according to ISO 1133 at a temperature of 230°C under a load of 2.16 kg, in the range of 5.0 to 20.0 g / 10 min.

15. The fiber reinforced composition (C) according to claim 1 or 2, wherein the elastomeric ethylene copolymer (E) has a melt flow rate MFR, measured according to ISO 1133 at a temperature of 190°C under a load of 2.16 kg, in the range of 0.8 to 20.0 g / 10 min.

16. The fiber reinforced composition (C) according to claim 1 or 2, wherein the elastomeric ethylene copolymer (E) has a mass fraction of 860 to 890 kg / m 3 The density is determined according to ISO 1183-187 within the range of .

17. The fiber-reinforced composition (C) according to claim 1 or 2, wherein the fiber-reinforced composition (C) has a melt flow rate MFR2, measured according to ISO 1133 at a temperature of 230°C under a load of 2.16 kg, in the range of 1.0 to 10.0 g / mol.

18. The fiber-reinforced composition (C) according to claim 1 or 2, wherein the fiber-reinforced composition (C) has a tensile modulus determined according to ISO 527-1A in the range of 2500 to 5500 MPa.

19. The fiber-reinforced composition (C) according to claim 1 or 2, wherein the fiber-reinforced composition (C) has an elongation at break determined according to ISO 527-2 of greater than 10.0%.

20. The fiber-reinforced composition (C) according to claim 1 or 2, wherein the fiber-reinforced composition (C) further comprises low-density polyethylene (LDPE).

21. The fiber reinforced composition (C) according to claim 20, wherein the low density polyethylene (LDPE) has a melt flow rate MFR measured according to ISO 1133 at a temperature of 190°C under a load of 2.16 kg in the range of 0.5 to 5.0 g / 10 min.

22. The fiber-reinforced composition (C) according to claim 1 or 2, wherein the fiber-reinforced composition (C) further comprises up to 20.0 wt.% of a low-density polyethylene (LDPE) homopolymer or copolymer having a mass fraction greater than 900 kg / m 3 The density is determined according to ISO 1183-187 and comprises ethylene and optionally vinyl acetate.

23. Fiber reinforced composition (C) according to claim 1 or 2, wherein the propylene copolymer (cPP) is obtained in the presence of a solid catalyst system (SCS) comprising a metallocene complex having formula (I) wherein each X is independently a σ-donor ligand, L is a divalent bridge selected from -R'2C-, -R'2C-CR'2-, -R'2Si-, -R'2Si-SiR'2-, -R'2Ge-, wherein each R' is independently a hydrogen atom or a C1-C ... 20 - a hydrocarbon group, or optionally two R' groups together can form a ring, Each R 1 are independently identical or can be different and are hydrogen, linear or branched C1-C6-alkyl, C 7-20 -aralkyl, C 7-20 -alkylaryl or C 6-20 -aryl or OY group, where Y is C 1-10 -hydrocarbyl, and optionally two adjacent R 1 The groups can be part of a ring containing the phenyl carbon to which they are bonded, Each R 2 are independently the same or can be different, and are CH2-R 8 Group, where R 8 H or linear or branched C 1-6 -alkyl, C 3-8 -cycloalkyl, C 6-10 -aryl, R 3 is a straight or branched C1-C6-alkyl, C 7-20 -aralkyl, C 7-20 -alkylaryl or C6-C 20 -aryl, R 4 C(R 9 )3 groups, wherein R 9 is a linear or branched C1-C6-alkyl group, R 5 is hydrogen or an aliphatic C1-C ... 20 -hydrocarbon group; R 6 is hydrogen or an aliphatic C1-C12 radical optionally containing one or more heteroatoms from Groups 14 to 16 of the Periodic Table 20 - a hydrocarbon group; or R 5 and R 6 can together form a 5-membered saturated carbocyclic ring, which is optionally substituted by n groups R 10 substituted, n is 0 to 4; Each R 10 Same or different, and can be C1-C 20 -hydrocarbyl, or a C1-C ... 20 -hydrocarbon group; R 7 is H or a linear or branched C1-C6-alkyl radical or optionally substituted by 1 to 3 radicals R 11 a substituted aryl or heteroaryl group having 6 to 20 carbon atoms, Each R 11 are independently identical or can be different and are hydrogen, linear or branched C1-C6-alkyl, C 7-20 -aralkyl, C 7-20 -alkylaryl or C 6-20 -aryl or OY group, where Y is C 1-10 -hydrocarbon group.

24. The fiber reinforced composition (C) according to claim 1 or 2, wherein the propylene copolymer (cPP) has a comonomer content equal to or lower than 4.8 mol-% and a melt flow rate MFR2, measured according to ISO 1133 at a temperature of 230 °C under a load of 2.16 kg, in the range of 5.0 to 20.0 g / 10 min.

25. The fiber reinforced composition (C) according to claim 24, wherein the elastomeric ethylene copolymer has a 3 density.

26. An article comprising the fiber-reinforced composition (C) according to any one of claims 1 to 25.

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