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 an article 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 an article comprising said fiber reinforced composition (C). BACKGROUND

[0002] Fiber reinforced materials are widely used in various applications, especially in the engineering field, where higher stiffness and good impact resistance are seen as benefits. Polypropylene is one of the most popular base polymers due to its versatility, low cost and low density. It can fulfill most target properties. Polypropylenes prepared in the presence of metallocene catalysts are a promising candidate material due to additional benefits such as controlled molecular weight distribution, good comonomer incorporation and low emissions. However, due to the nature of the compounds, tensile strength and elongation at break are often compromised at high filler ratios.

[0003] Therefore, there is a need in the art for a fiber reinforced polypropylene composition featuring excellent heat deflection properties and low emissions, while tensile strength and elongation at break remain at high levels. SUMMARY

[0004] It is therefore an object of the present invention to provide a fiber reinforced polypropylene composition featuring good mechanical properties, preferably based on polypropylene prepared in the presence of a metallocene catalyst.

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

[0006] i) a matrix which is a propylene homopolymer or copolymer (PP) having an amount of 1,2 erythro regiodefects of at least 0.4 mol-% and a comonomer content of equal or below 8.5 mol-%, and

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

[0008] b) 5.0 to 45.0 wt.-% of fibers (F), and

[0009] c) optionally 0.1 to 5.0 wt.-% of an adhesion promoter (AP),

[0010] wherein 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.

[0011] According to one embodiment of the present application, the heterophasic polypropylene composition (HECO) comprises

[0012] i) 60.0 to 95.0 wt.-% of a matrix which is a propylene homopolymer or copolymer (PP), and

[0013] ii) 5.0 to 40.0 wt.-% of an elastomeric ethylene copolymer (E).

[0014] According to another embodiment of the present application, 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).

[0015] According to another embodiment of the present application, 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.

[0016] According to one embodiment of the present application, the heterophasic polypropylene composition (HECO) has an intrinsic viscosity (IV) of the soluble fraction (SF) measured according to ISO 1628 / 1 (in decalin at 135 °C) in the range of 1.8 to 3.0 dl / g determined according to CRYSTEX QC.

[0017] According to another embodiment of the present application, the fibers (F) are glass fibers (GF), preferably short glass fibers (SGF), having

[0018] i) an average length of 2.0 to 10.0 mm, and / or

[0019] ii) an average diameter of 5 to 20 pm.

[0020] According to another embodiment of the present application, 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) determined according to ISO 1133 of at least 20.0 g / 10 min.

[0021] According to a first embodiment of the present application, the propylene homopolymer or copolymer (PP) is a propylene homopolymer (hPP) and the elastomeric ethylene polymer (E) is a copolymer of ethylene and propylene.

[0022] According to the first embodiment of the present application, the propylene homopolymer (hPP) has a melting temperature Tm determined according to differential scanning calorimetry (DSC) in the range of 140 to 160 °C.

[0023] According to the first embodiment of the present application, the heterophasic polypropylene composition (HECO) has a comonomer content in the range of 2.2 to 8.7 mol%.

[0024] It is especially preferred that the heterophasic polypropylene composition (HECO) according to the first embodiment of the present application has

[0025] 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

[0026] ii) an ethylene content of the xylene cold soluble (XCS) fraction in the range of 20.9 to 44.7 mol%.

[0027] and / or

[0028] 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

[0029] iv) an ethylene content of the soluble fraction (SF) determined according to CRYSTEX QC in the range of 20.9 to 44.7 mol%.

[0030] According to the first embodiment of the present application, 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.

[0031] According to the first embodiment of the present application, the fiber reinforced composition (C) has a tensile modulus determined according to ISO 527-1 A in the range of 3000 to 6000 MPa, and / or an elongation at break determined according to ISO 527-2 of more than 3.0%.

[0032] According to the second embodiment of the present application, the propylene homopolymer or copolymer (PP) is a propylene copolymer (cPP), a copolymer of propylene and ethylene, which copolymer preferably has an ethylene content of 2.2 to 8.5 mol%, the elastomeric ethylene copolymer (E) is a copolymer of ethylene and C4 to C 12 a copolymer of an alpha-olefin, preferably 1-octene, which copolymer preferably has an ethylene content of 55.0 to 85.0 wt.-%, based on the total weight of the elastomeric ethylene copolymer (E).

[0033] According to the second embodiment of the present application, 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 a density determined according to ISO 1183-187 in the range of 860 to 890 kg / m 3

[0034] According to the second embodiment of the present application, 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.

[0035] According to the second embodiment of the present application, 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 more than 10.0 %.

[0036] According to one embodiment of the present application, the fiber reinforced composition (C) further comprises up to 20.0 wt.-% of a low density polyethylene (LDPE) homo- or copolymer having a density determined according to ISO 1183-187 of more than 900 kg / m 3 and comprising ethylene and optionally vinyl acetate.

[0037] According to one embodiment of the present application, the propylene homo- or copolymer (PP) is obtained in the presence of a solid catalyst system (SCS) comprising a metallocene compound. It is especially preferred that the metallocene compound has the formula (I)

[0038]

[0039] wherein each X is independently a sigma-donor ligand,

[0040] 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 -hydrocarbyl group, or optionally two R' groups together can form a ring,

[0041] ​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,

[0042] 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,

[0043] R 3 is a straight or branched C1-C6-alkyl, C 7-20 -aralkyl, C 7-20 -alkylaryl or C6-C 20 -aryl,

[0044] R 4 C(R 9 )3 groups, wherein R 9 is a linear or branched C1-C6-alkyl group,

[0045] 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;

[0046] 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

[0047] 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;

[0048] Each R 10 Same or different, and can be C1-C 20 -hydrocarbyl, or a C1-C ... 20 -hydrocarbon group;

[0049] R 7H or linear or branched C1-C6-alkyl or optionally substituted with one to three groups R 11 substituted aryl or heteroaryl having 6 to 20 carbon atoms,

[0050] each R 11 independently the same 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 groups, wherein Y is C 1-10 - hydrocarbyl groups.

[0051] The present application also relates to an article comprising the fiber reinforced composition (C) as described above.

[0052] In the following, the fiber reinforced composition (C) is described in more detail. DETAILED DESCRIPTION

[0053] The fiber reinforced composition (C)

[0054] The present application relates to a fiber reinforced composition (C) comprising a heterophasic polypropylene composition (HECO), fibers (F) and an adhesion promoter (AP).

[0055] In particular, the fiber reinforced composition (C) comprises, based on the total weight of the fiber reinforced composition (C)

[0056] 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.-%, such as 72.0 to 79.0 wt.-% of a heterophasic polypropylene composition (HECO), and

[0057] 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).

[0058] According to a preferred embodiment of the present application, the fiber reinforced composition (C) further comprises an adhesion promoter (AP).

[0059] Therefore, it is preferred that the fiber reinforced composition (C) comprises, based on the total weight of the fiber reinforced composition (C)

[0060] 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 a heterophasic polypropylene composition (HECO),

[0061] 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.-%, like 18.0 to 23.0 wt.-% of fibers (F), and

[0062] 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.-%, like 1.0 to 2.0 wt.-% of an adhesion promoter (AP).

[0063] The fiber reinforced composition (C) according to the present application can comprise additives (AD).

[0064] It is therefore preferred that the fiber reinforced composition (C) according to the present application comprises, more preferably consists of,

[0065] 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 a heterophasic polypropylene composition (HECO),

[0066] 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.-%, like 18.0 to 23.0 wt.-% of fibers (F),

[0067] 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.-%, like 1.0 to 2.0 wt.-% of an adhesion promoter (AP), and

[0068] d) 0.01 to 2.5 wt.-% of additives (AD),

[0069] The additives (AD) are described in more detail hereinafter.

[0070] It is therefore preferred that the fiber reinforced composition (C) according to the present application comprises, more preferably consists of,

[0071] 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 a heterophasic polypropylene composition (HECO),

[0072] 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.-%, like 18.0 to 23.0 wt.-% of fibers (F),

[0073] 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.-%, like 1.0 to 2.0 wt.-% of an adhesion promoter (AP), and

[0074] d) 0.01 to 2.5 wt.-% of an additive (AD),

[0075] wherein components a) to d) are selected to add up to 100 wt.-%.

[0076] Further, the fiber reinforced composition (C) according to the present application can also comprise a low density polyethylene (LDPE).

[0077] According to another embodiment of the present application, therefore, the fiber reinforced composition (C) comprises, more preferably consists of

[0078] 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 a heterophasic polypropylene composition (HECO),

[0079] b) 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.-%, like 18.0 to 23.0 wt.-% of fibers (F),

[0080] 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.-%, like 1.0 to 2.0 wt.-% of an adhesion promoter (AP),

[0081] d) 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 a low density polyethylene (LDPE), and

[0082] e) 0.01 to 2.5 wt.-% of an additive (AD).

[0083] According to another embodiment of the present application, the fiber reinforced composition (C) comprises, preferably consists of, based on the total weight of the fiber reinforced composition (C),

[0084] 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 a heterophasic polypropylene composition (HECO),

[0085] b) 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.-%, like 18.0 to 23.0 wt.-% of fibers (F),

[0086] 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.-%, like 1.0 to 2.0 wt.-% of an adhesion promoter (AP),

[0087] d) 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 a low density polyethylene (LDPE), and

[0088] e) 0.01 to 2.5 wt.-% of an additive (AD),

[0089] wherein components a) to d) are selected to add up to 100 wt.-%.

[0090] Preferably, the fiber-reinforced composition (C) of the present application does not comprise more than 5.0 wt.-%, preferably more than 3.0 wt.-%, more preferably more than 2.5 wt.-%, based on the total weight of the fiber-reinforced composition (C), of (a) further polymers different from the heterophasic polypropylene composition (HECO), the adhesion promoter (AP) and the optional low-density polyethylene (LDPE). One additional polymer which can be present in such low amounts is polyethylene, which is a reaction by-product obtained by preparing the heterophasic polypropylene composition (HECO). It is therefore to be particularly understood that the fiber-reinforced composition (C) comprises 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 as polymeric compounds.

[0091] 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, like in the range of 2.5 to 29.0 g / 10 min.

[0092] According to one 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 10.0 to 60.0 g / 10 min, more preferably in the range of 10.0 to 40.0 g / 10 min, still more preferably in the range of 10.0 to 35.0 g / 10 min, like in the range of 10.0 to 29.0 g / 10 min (e.g. 20.0 to 29.0 g / 10 min). The melt flow rate range (and the preferred subranges) of 10.0 to 60.0 g / 10 min is particularly preferred in combination with “first embodiment of the present application” as defined herein.

[0093] With regard to mechanical properties, it is preferred that the fiber-reinforced composition (C) has a tensile modulus determined according to ISO 527-1 A of at least 2000 MPa, more preferably of at least 2200 MPa, still more preferably of at least 2300 MPa, like of at least 2400 MPa and / or a tensile strength determined according to ISO 527-2 of at least 40 MPa, more preferably of at least 42 MPa, still more preferably of at least 45 MPa, like of at least 50 MPa.

[0094] Additionally or alternatively to the previous paragraph, it is preferred that the fiber-reinforced composition has an elongation at break determined according to ISO 527-2 at 23 °C of at least 3.0 %, more preferably of at least 3.2 %, still more preferably of at least 3.4 %.

[0095] The fiber-reinforced composition (C) is preferably obtained by melt blending the heterophasic polypropylene composition (HECO), the fibers (F), optionally the adhesion promoter (AP), optionally the additives (AD) and optionally the low density polyethylene (LDPE).

[0096] 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.

[0097] Heterophasic polypropylene composition (HECO)

[0098] The fiber-reinforced composition (C) of the present application comprises a heterophasic polypropylene composition (HECO).

[0099] The heterophasic polypropylene composition (HECO) according to the present application comprises as a matrix a propylene homopolymer or copolymer (PP) and dispersed therein an elastomeric ethylene copolymer (E). Thus, the matrix contains (finely) dispersed inclusions which are not part of the matrix, and the inclusions contain the elastomeric ethylene copolymer (E). The term inclusions indicates that the matrix and the inclusions form different phases in the heterophasic polypropylene composition (HECO). The presence of a second phase or so-called inclusions is visible, for example, by high-resolution microscopy, such as electron microscopy or atomic force microscopy, or by dynamic mechanical thermal analysis (DMTA). In particular, in DMTA, the presence of a heterophasic structure can be identified by the presence of at least two different glass transition temperatures.

[0100] Thus, the heterophasic polypropylene composition (HECO) according to the present application preferably comprises

[0101] (a) a (semi)crystalline propylene homopolymer or copolymer (PP) as a matrix, and

[0102] (b) an elastomeric ethylene copolymer (E).

[0103] 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),

[0104] (a) 60.0 to 95.0 wt.-%, more preferably 61.0 to 92.0 wt.-%, of a matrix which is a propylene homopolymer or copolymer (PP), and

[0105] (b) 5.0 to 40.0 wt.-%, more preferably 8.0 to 39.0 wt.-%, of an elastomeric ethylene copolymer (E).

[0106] It is preferred that the heterophasic polypropylene composition (HECO) according to the present application 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. Further, it is preferred that the second glass transition temperature Tg(2) is at least -5 °C, more preferably at least 0 °C.

[0107] 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, still 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.

[0108] Further, it is preferred that the heterophasic polypropylene composition (HECO) has an intrinsic viscosity (IV) of the soluble fraction (SF) measured according to ISO 1628 / 1 (in decalin at 135 °C) 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.

[0109] Preferably, it is desired that the heterophasic polypropylene composition (HECO) is thermomechanically stable. Accordingly, 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, preferably in the range of 130 to 160 °C, more preferably in the range of 130 to 159 °C, even more preferably in the range of 132 to 159 °C, still more preferably in the range of 135 to 158 °C, like in the range of 139 to 157 °C.

[0110] 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 high amount of misinsertions 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 in the presence of, for example, a Ziegler-Natta catalyst can have 1,2 erythro regio defects far below 0.4 mol-% and typically are essentially free of 1,2 erythro regio defects.

[0111] In addition to propylene, the heterophasic polypropylene composition (HECO) comprises a comonomer. Preferably, in addition to propylene, the heterophasic polypropylene composition (HECO) comprises ethylene and / or C4 to C 12α-olefins.

[0112] Thus, the term "propylene copolymer" according to the present application is understood to be a polypropylene comprising, more preferably consisting of units derived from

[0113] (a) propylene

[0114] and

[0115] (b) ethylene and / or C4 to C 12 α-olefins.

[0116] Further, the term "ethylene copolymer" according to the present application is understood to be a polyethylene comprising, more preferably consisting of units derived from

[0117] (a) ethylene

[0118] and

[0119] (b) C3 to C 12 α-olefins.

[0120] Thus, the propylene homopolymer or copolymer (PP), i.e. the matrix of the heterophasic polypropylene composition (HECO), can comprise monomers, e.g. comonomers, copolymerizable with propylene, such as ethylene and / or C4 to C 12 α-olefins, in particular ethylene and / or C4 to C8 α-olefins, e.g. 1-butene and / or 1-hexene. The elastomeric ethylene copolymer (E) can comprise monomers, e.g. comonomers, copolymerizable with ethylene, such as C3 to C 12 α-olefins, in particular propylene, 1-butene, 1-hexene and / or 1-octene. More specifically, the heterophasic polypropylene composition (HECO) of the present application comprises, in addition to propylene and ethylene, units derived from 1-butene, 1-hexene and / or 1-octene.

[0121] Thus, the propylene homopolymer or copolymer (PP) according to the present application can be a propylene homopolymer or a propylene copolymer.

[0122] In particular, it is preferred that the propylene homopolymer or copolymer (PP) has a comonomer content, preferably an ethylene content, equal to or below 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-%.

[0123] The elastomeric ethylene copolymer (E) according to the present application comprises monomers, e.g. comonomers, copolymerizable with ethylene, such as C3 to C 12a-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.-%, like in the range of 20.0 to 76.0 wt.-%, based on the total weight of the elastomeric ethylene copolymer (E).

[0124] According to the first embodiment of the present application, it is preferred that the propylene homopolymer or copolymer (PP) is a propylene homopolymer (hPP).

[0125] 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.-%, like at least 99.9 wt.-%, of propylene units. In another embodiment, only propylene units are detectable, i.e. only propylene is polymerized.

[0126] According to the first embodiment of the present application, the heterophasic polypropylene composition (HECO) comprises

[0127] a) as a matrix a propylene homopolymer (hPP), and

[0128] b) an elastomeric ethylene copolymer (E).

[0129] The elastomeric ethylene copolymer (E) according to the first embodiment of the present application comprises monomers copolymerizable with ethylene, e.g. comonomers, such as C3 to C 12 a-olefins, in particular propylene, 1-butene, 1-hexene and / or 1-octene. According to the first embodiment of the present application, 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 application comprises units derived from ethylene and propylene only.

[0130] Accordingly, it is preferred that the heterophasic polypropylene composition (HECO) according to the first embodiment of the present application comprises units derived from ethylene and propylene only.

[0131] Preferably, the heterophasic polypropylene composition (HECO) according to the first embodiment of the present application 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.-%.

[0132] Furthermore, it is preferred that the heterophasic polypropylene composition (HECO) according to the first embodiment of the present application has a xylene cold solubles (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.-%, still 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 the present application.

[0133] Additionally or alternatively, it is preferred that the xylene cold solubles (XCS) fraction of the heterophasic polypropylene composition (HECO) according to the first embodiment of the present application 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-%, still more preferably in the range of 28.0 to 38.0 mol-%, like in the range of 30.0 to 34.0 mol-%.

[0134] Preferably, the heterophasic polypropylene composition (HECO) according to the first embodiment of the present application has an intrinsic viscosity (IV) measured according to ISO 1628 / 1 (in decalin at 135 °C) of the xylene cold solubles (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, still more preferably in the range of 2.3 to 2.7 dl / g.

[0135] Additionally or alternatively to the previous paragraph, it can be appreciated that the heterophasic polypropylene composition (HECO) according to the first embodiment of the present application preferably has a soluble fraction (SF) determined according to CRYSTEX QC in the range of 5.0 to 35.0 wt.-%, more preferably in the range of 7.0 to 20.0 wt.-%, still 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 the present application.

[0136] 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 the present application is preferably in the range of 20.9 to 44.7 mol-%, more preferably in the range of 25.0 to 40.0 mol-%, still more preferably in the range of 28.0 to 38.0 mol-%, like in the range of 30.0 to 34.0 mol-%.

[0137] Preferably, the heterophasic polypropylene composition (HECO) according to the first embodiment of the present application has an intrinsic viscosity (IV) of the soluble fraction (SF) determined according to CRYSTEX QC measured according to ISO 1628 / 1 (in decaline at 135 °C) in the range of 1.8 to 3.0 dl / g, more preferably in the range of 2.2 to 2.8 dl / g, still more preferably in the range of 2.3 to 2.7 dl / g.

[0138] It is preferred that the heterophasic polypropylene composition (HECO) according to the first embodiment of the present application has a moderate melt flow rate. Thus, the heterophasic polypropylene composition (HECO) according to the first embodiment of the present application 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, still 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.

[0139] Further, it is preferred that the heterophasic polypropylene composition (HECO) according to the first embodiment of the present application has a melting temperature Tm determined according to differential scanning calorimetry (DSC) in the range of 130 to 165 °C, preferably in the range of 130 to 160 °C, more preferably in the range of 135 to 160 °C, still more preferably in the range of 145 to 159 °C, like in the range of 152 to 157 °C.

[0140] With regard to mechanical properties, it is preferred that the heterophasic polypropylene composition (HECO) according to the first embodiment of the present application 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.

[0141] Additionally or alternatively to the previous paragraph, it is preferred that the heterophasic polypropylene composition (HECO) according to the first embodiment of the present application has a Charpy notched impact strength determined according to ISO 179 / 1 eA at 23 °C of at least 1.5 kJ / m 2 , more preferably of at least 2.5 kJ / m 2 , still more preferably of at least 3.0 kJ / m 2 , like of at least 3.5 kJ / m 2 , and / or a Charpy notched impact strength determined according to ISO 179 / 1 eU at -20 °C of at least 0.5 kJ / m 2 , more preferably of at least 0.8 kJ / m 2It is still more preferred that the notched Charpy impact strength determined according to ISO 179 / 1 eA at -20 °C is at least 1.3 kJ / m 2 It is still more preferred that the notched Charpy impact strength determined according to ISO 179 / 1 eA at -20 °C is at least 1.3 kJ / m 2 It is still more preferred that the notched Charpy impact strength determined according to ISO 179 / 1 eA at -20 °C is at least 1.3 kJ / m

[0142] It is still more preferred that the notched Charpy impact strength determined according to ISO 179 / 1 eA at -20 °C is at least 1.3 kJ / m

[0143] Additionally or alternatively, it is preferred that the fiber reinforced composition (C) according to the first embodiment of the present application has an elongation at break determined according to ISO 527-2 of more than 3.0 %, more preferably more than 3.2 %, still more preferably more than 3.3 %, such as more than 3.4 %.

[0144] The heterophasic polypropylene composition (HECO) according to the first embodiment of the present application can further be defined by its individual components, i.e. the matrix is a propylene homopolymer (hPP) and the elastomeric ethylene copolymer (E) is a copolymer of ethylene and propylene.

[0145] 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, such as in the range of 75.0 to 85.0 g / 10 min.

[0146] 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, still more preferably in the range of 145 to 158 °C, such as in the range of 147 to 157 °C.

[0147] The propylene homopolymer (hPP) has at least 0.4 mole-% of 1,2 erythro regio defects, as outlined above, the 1,2 erythro regio defects indicating that the propylene homopolymer (PP) is produced in the presence of a single-site catalyst, preferably a metallocene catalyst.

[0148] As described in more detail hereinafter, the heterophasic polypropylene composition (HECO) according to the first embodiment of the present application is preferably obtained in a sequential process in the presence of a metallocene catalyst. It is thus particularly preferred that the propylene homopolymer (hPP) and the elastomeric ethylene copolymer (E) are produced in a sequential process in the presence of a metallocene catalyst.

[0149] It is thus preferred that the elastomeric ethylene copolymer (E) being a copolymer of ethylene and propylene according to the first embodiment of the present application further 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-%.

[0150] The heterophasic polypropylene composition (HECO) according to the first embodiment of the present application preferably comprises

[0151] 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 a matrix which is a propylene homopolymer (hPP), and

[0152] 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.

[0153] The heterophasic polypropylene composition (HECO) according to the first embodiment of the present application 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.

[0154] The process for producing a heterophasic polypropylene composition (HECO) according to the first embodiment of the present application is preferably a sequential polymerization process comprising at least two reactors connected in series, wherein the process comprises the following steps

[0155] (A) polymerizing propylene in a first reactor (R-1 ) being a slurry reactor (SR), preferably a loop reactor (LR), obtaining a first fraction of a propylene homopolymer (hPP) as defined in the present application,

[0156] (B) transferring the first fraction of the propylene homopolymer (hPP) of the first reactor (R-1 ) to a second reactor (R-2) being a gas phase reactor (GPR-1 ),

[0157] (C) feeding propylene to the second reactor (R-2),

[0158] (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,

[0159] (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),

[0160] (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),

[0161] (G) polymerizing propylene and a copolymer selected from ethylene and C4 to C 12 ] a-olefin, preferably ethylene, to obtain an elastomeric ethylene copolymer (E) as defined herein, said propylene homopolymer (hPP) and said elastomeric ethylene copolymer (E) forming a heterophasic polypropylene composition (HECO) as defined herein, wherein further

[0162] 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).

[0163] The solid catalyst system (SCS) is defined in more detail below.

[0164] The term "sequential polymerization process" means that the heterophasic polypropylene composition (HECO) according to the first embodiment of the present application is produced in at least two reactors connected in series. More precisely, the term "sequential polymerization process" means in the present application that the polymer of the first reactor (R-1) is directly transferred to the second reactor (R-2) with unreacted monomers. Thus, 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 transferred to the second reactor (R-2). Thus, the inventive process comprises at least a first reactor (R-1) and a second reactor (R-2). In a particular embodiment, the inventive process consists of three polymerization reactors (R-1), (R-2) and (R-3). The term "polymerization reactor" shall mean that the main polymerization takes place. Thus, in case the process consists of three polymerization reactors, this definition does not exclude the option that the whole process comprises a prepolymerization step in e.g. a prepolymerization reactor. The term "consists of" is only a closed expression with respect to the main polymerization reactors.

[0165] The first reactor (R-1) is a slurry reactor (SR) and can be any continuous or simply batch stirred tank reactor or loop reactor operated in slurry. According to the present application, the slurry reactor (SR) is preferably a loop reactor (LR).

[0166] The second reactor (R-2), the third reactor (R-3) and any subsequent reactor is a gas phase reactor (GPR). Such a gas phase reactor (GPR) can be any mechanically mixed or fluid bed reactor. Preferably, the gas phase reactor(s) (GPR) comprises a mechanically agitated fluid bed reactor with gas velocities of at least 0.2 m / s. Thus, it is appreciated that the gas phase reactor (GPR) is a fluid bed type reactor with preferably a mechanical stirrer.

[0167] The conditions in each reactor (temperature, pressure, reaction time, monomer feed) depend on the desired product as known to the skilled person. As mentioned above, the first reactor (R-1) is a slurry reactor (SR), like 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). The subsequent reactors, if present, are also gas phase reactors (GPR).

[0168] A preferred multi-stage process is a "loop-gas phase" process, such as the process developed by Borealis A / S, Denmark (known as BORSTAR® technology), described for example in the patent literature, such as in EP 0 887 379 or WO 92 / 12182. The BORSTAR® technology) described for example in the patent literature, such as in EP 0 887 379 or WO 92 / 12182.

[0169] The multimodal polymers can be produced according to several methods as described for example in WO 92 / 12182, EP 0 887 379 and WO 98 / 58976. The content of these documents is included herein by reference.

[0170] Preferably, in the process of the present application for producing a heterophasic polypropylene composition (HECO) as defined above, the conditions for the first reactor (R-1), i.e. the slurry reactor (SR), such as a loop reactor (LR), of step (A) can be the following conditions:

[0171] - the temperature is 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,

[0172] - the pressure is in the range of 20 bar to 80 bar, preferably between 40 bar and 70 bar,

[0173] - hydrogen can be added for controlling the molar mass in a manner known per se.

[0174] 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 conditions:

[0175] - the temperature is in the range of 50 °C to 130 °C, preferably between 60 °C and 100 °C,

[0176] - the pressure is in the range of 5 bar to 50 bar, preferably between 15 bar and 40 bar,

[0177] - hydrogen can be added for controlling the molar mass in a manner known per se.

[0178] The residence time can vary in the two reactor zones.

[0179] In one embodiment of the process for producing a heterophasic polypropylene composition (HECO), the residence time in the slurry reactor (SR), such as a loop (LR), is in the range of 0.2 to 4.0 hours, for example 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.

[0180] If desired, the polymerization can be carried out in the first reactor (R-1), i.e. in the slurry reactor (SR), such as in the loop reactor (LR), under supercritical conditions in a known manner.

[0181] The conditions in the third reactor (R-3), i.e. the second gas phase reactor (GPR-2) and any further subsequent gas phase reactor (GPR) if present, are similar to the second reactor (R-2).

[0182] The process according to the present application can 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.

[0183] The heterophasic polypropylene composition (HECO) according to the first embodiment of the present application according to the present application is prepared in the presence of a solid catalyst system (SCS) comprising a transition metal compound.

[0184] It is particularly preferred that the solid catalyst system (SCS) comprises a metallocene catalyst comprising a metallocene complex, a cocatalyst system comprising a boron containing cocatalyst and / or an aluminoxane cocatalyst and a silica support. In particular, it is preferred that the metallocene catalyst comprises

[0185] (i) a metallocene complex having the general formula (I)

[0186]

[0187] wherein each X is independently a sigma-donor ligand,

[0188] 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 hydrocarbyl group, or optionally two R' groups together can form a ring,

[0189] each R 1 are independently the same or can be different and are a hydrogen, a linear or branched C1-C6-alkyl group, a C 7-20 - an aralkyl group, a C 7-20 - an alkylaryl group or a C 6-20 - an aryl group or an OY group, wherein Y is a C 1-10 - a hydrocarbyl group, and optionally two adjacent R 1 groups together can be part of a ring comprising the phenyl carbon to which they are bound,

[0190] each R 2 are independently the same or can be different and are a CH2-R 8 group, wherein R 8 is H, or a linear or branched C 1-6- alkyl, C 3-8 - cycloalkyl, C 6-10 - aryl,

[0191] R 3 is a linear or branched C1-C6-alkyl, C 7-20 - aralkyl, C 7-20 - alkylaryl or C6-C 20 - aryl,

[0192] R 4 is a C(R 9 )3 group, wherein R 9 is a linear or branched C1-C6-alkyl,

[0193] R 5 is hydrogen or an aliphatic C1-C 20 -hydrocarbyl group optionally containing one or more heteroatoms belonging to group 14 of the periodic table of elements;

[0194] R 6 is hydrogen or an aliphatic C1-C 20 -hydrocarbyl group optionally containing one or more heteroatoms belonging to group 14 of the periodic table of elements; or

[0195] R 5 and R 6 together can form a 5-membered saturated carbocyclic ring, which is optionally substituted by n groups R 10 , n being 0 to 4;

[0196] each R 10 is the same or different and can be a C1-C 20 -hydrocarbyl group, or a C1-C 20 -hydrocarbyl group optionally containing one or more heteroatoms belonging to group 14 of the periodic table of elements;

[0197] R 7 is H or a linear or branched C1-C6-alkyl or an aryl or heteroaryl group having 6 to 20 carbon atoms, which is optionally substituted by 1 to 3 groups R 11 , and

[0198] each R 11 is independently the same or can be different and is hydrogen, a linear or branched C1-C6-alkyl, C 7-20 - aralkyl, C 7-20 - alkylaryl or C 6-20 - aryl or an OY group, wherein Y is a C 1-10 -hydrocarbyl group.

[0199] (ii) a cocatalyst system comprising a boron-containing cocatalyst and / or an aluminoxane cocatalyst, and

[0200] (iii) a silica support.

[0201] The term "σ-donor ligand" is well known to the person skilled in the art, i.e. a group which 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'2or PR'2groups, wherein R' is independently hydrogen, linear or branched, cyclic or acyclic, C1to C20alkyl, C2to C20alkenyl, C2to C20alkynyl, C6to C20cycloalkyl, C7to C20aralkyl, C8to C20alkaryl, C7to C20aralkenyl, C7to C20aralkynyl, wherein the R' groups can optionally contain one or more heteroatoms belonging to groups 14 to 16. In a preferred embodiment, the anionic ligand "X" is identical and is either a halogen, such as Cl, or a methyl or benzyl group. 20 alkyl, C2to C 20 alkenyl, C2to C 20 alkynyl, C3to C 12 cycloalkyl, C6to C 20 aryl, C7to C 20 aralkyl, C7to C 20 alkaryl, C8to C 20 aralkenyl, wherein the R' groups can optionally contain one or more heteroatoms belonging to groups 14 to 16. In a preferred embodiment, the anionic ligand "X" is identical and is either a halogen, such as Cl, or a methyl or benzyl group.

[0202] A preferred monovalent anionic ligand is a halogen, in particular chlorine (Cl).

[0203] Preferred metallocene complexes include:

[0204] rac-dimethylsilanediylbis[2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert- butylinden-1-yl]zirconium dichloride,

[0205] rac-trans-dimethylsilanediyl[2-methyl-4-(4'-tert-butylphenyl)-inden-1-yl][2-methyl-4- (4'-tert-butylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride,

[0206] rac-trans-dimethylsilanediyl[2-methyl-4-(4'-tert-butylphenyl)-inden-1-yl][2-methyl-4- (4'-tert-butylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride,

[0207] rac-trans-dimethylsilanediyl[2-methyl-4-(4'-tert-butylphenyl)-inden-1-yl][2-methyl-4- (4'-tert-butylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride,

[0208] rac-trans-dimethylsilylene[2-methyl-4,8-bis-(4'-tert-butylphenyl)-1,5,6,7- tetrahydro-s-indacen-1-yl][2-methyl-4-(3',5'-dimethyl-phenyl)-5-methoxy-6-tert- butyl-inden-1-yl]zirconium dichloride,

[0209] rac-trans-dimethylsilylene[2-methyl-4,8-bis-(3',5'-dimethylphenyl)-1,5,6,7- tetrahydro-s-indacen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert- butyl-inden-1-yl]zirconium dichloride,

[0210] rac-trans-dimethylsilylene[2-methyl-4,8-bis-(3',5'-dimethylphenyl)-1,5,6,7- tetrahydro-s-indacen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert- butyl-inden-1-yl]zirconium dichloride.

[0211] Especially preferred is rac-trans-dimethylsilylene[2-methyl-4,8-bis-(3',5'- dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)- 5-methoxy-6-tert-butyl-inden-1-yl]zirconium dichloride (II)

[0212]

[0213] The ligands required to form the complexes of the application and thus the catalysts of the application can be synthesized by any method and the skilled organic chemist will be able to devise various synthetic schemes for the manufacture of the necessary ligand materials. For example, WO 2007 / 116034 discloses the necessary chemistry. Synthetic schemes can also generally be found in WO 2002 / 02576, WO 2011 / 135004, WO 2012 / 084961, WO 2012 / 001052, WO 2011 / 076780, WO 2015 / 158790 and WO 2018 / 122134. Reference is made in particular to WO 2019 / 179959 in which the most preferred catalysts of the application are described.

[0214] According to the application, a cocatalyst system comprising a boron containing cocatalyst and / or an aluminoxane cocatalyst is used in combination with the metallocene catalyst complex defined above.

[0215] The aluminoxane cocatalyst can be one having the formula (III):

[0216]

[0217] wherein n is typically from 6 to 20 and R has the following meanings.

[0218] Aluminium alkoxides are formed upon partial hydrolysis of organoaluminium compounds, such as those having the formula AIR3, AIR2Y and AI2R3Y3, wherein R can be, for example, Ci-C 10 alkyl, preferably Ci-C5alkyl, or C 3-10 cycloalkyl, C7-C 12 aralkyl or alkylaryl and / or phenyl or naphthyl, and wherein Y can be hydrogen, halogen, preferably chlorine or bromine, or Ci-C 10 alkoxy, preferably methoxy or ethoxy. The resulting oxygen-containing aluminoxane is not typically a pure compound, but rather a mixture of oligomers of the formula (III).

[0219] A preferred aluminoxane is methylaluminoxane (MAO). Since the aluminoxanes used as cocatalysts according to the present application are not pure compounds due to their mode of preparation, the molar concentrations of the aluminoxane solutions in the following are based on their aluminium content.

[0220] According to the present application, boron-containing cocatalysts can also be used instead of aluminoxane cocatalysts, or aluminoxane cocatalysts can be used in combination with boron-containing cocatalysts.

[0221] The skilled person will appreciate that in the case of the use of boron-based cocatalysts, the complex is typically pre-alkylated by its reaction with an alkylaluminium compound, such as TIBA. This procedure is well known and any suitable alkylaluminium can be used, for example AI(Ci-C6alkyl)3. Preferred alkylaluminium compounds are triethylaluminium, triisobutylaluminium, triisohexylaluminium, tri-n-octylaluminium and tri-iso-octylaluminium.

[0222] Optionally, when borate cocatalysts are used, the metallocene catalyst complex is in its alkylated form, i.e. for example a dimethyl or dibenzyl metallocene catalyst complex can be used.

[0223] Boron-based cocatalysts of interest include those of the formula (IV)

[0224] BY3(IV)

[0225] 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 alkylaryl, arylalkyl, haloalkyl or haloaryl group, wherein the alkyl group has 1 to 10 carbon atoms and the aryl group has 6 to 20 carbon atoms in each group, or fluorine, chlorine, bromine or iodine. Preferred embodiments of Y are methyl, propyl, isopropyl, isobutyl or trifluoromethyl, unsaturated groups such as aryl or haloaryl groups, like phenyl, tolyl, benzyl, p-fluorophenyl, 3,5-difluorophenyl, pentachlorophenyl, pentafluorophenyl, 3,4,5-trifluorophenyl and 3,5-di(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.

[0226] Particularly preferred is tri(pentafluorophenyl)borane.

[0227] However, it is preferred to use borates, i.e. compounds containing the borate 3+ ion. Such ionic co-catalysts preferably contain a non-coordinating anion, such as tetra(pentafluorophenyl)borate and tetraphenylborate. Suitable counterions are protonated amines or aniline derivatives, such as methylammonium, aniline, dimethylammonium, diethylammonium, N-methylanilinium, diphenylammonium, N,N-dimethylanilinium, trimethylammonium, triethylammonium, tri(n-butyl)ammonium, methyldiphenylammonium, pyridinium, p-bromo-N,N-dimethylanilinium or p-nitro-N,N-dimethylanilinium.

[0228] Preferred ionic compounds which can be used according to the present application include: triethylammonium tetra(phenyl)borate, tributylammonium tetra(phenyl)borate, trimethylammonium tetra(methylphenyl)borate, tributylammonium tetra(methylphenyl)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-dimethylanilinium tetra(phenyl)borate, N,N-diethylanilinium tetra(phenyl)borate, N,N-dimethylanilinium tetra(pentafluorophenyl)borate, N,N-di(propyl)ammonium tetra(pentafluorophenyl)borate, dicyclohexylammonium tetra(pentafluorophenyl)borate, triphenylphosphonium tetra(phenyl)borate, triethylphosphonium tetra(phenyl)borate, diphenylphosphonium tetra(phenyl)borate, tri(methylphenyl)phosphonium tetra(phenyl)borate, tri(dimethylphenyl)phosphonium tetra(phenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, or ferrocenium tetrakis(pentafluorophenyl)borate.

[0229] Preferred is triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylcyclohexylammonium tetra(pentafluorophenyl)borate, or N,N-dimethylbenzylammonium tetra(pentafluorophenyl)borate.

[0230] Surprisingly, it was found that certain boron co-catalysts are especially preferred. Thus, preferred borate salts for use in the present application include the triphenylmethyl ion. Thus, it is especially preferred to use N,N-dimethylammonium-tetra-pentafluorophenylborate and Ph3CB(PhF5)4 and the like.

[0231] According to the present application, preferred co-catalysts are aluminoxanes, more preferably methylaluminoxane, combinations of aluminoxanes with alkylaluminum, boron or borate co-catalysts, and combinations of aluminoxanes with boron-based co-catalysts.

[0232] Suitable amounts of co-catalysts are well known to the person skilled in the art.

[0233] The molar ratio of boron to the metal ion of the metallocene can be in the range of 0.5:1 to 10:1 mol / mol, preferably in the range of 1 :1 to 10:1, in particular in the range of 1 :1 to 5:1 mol / mol.

[0234] The molar ratio of Al in aluminoxane to the metal ion of the metallocene can range from 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.

[0235] 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 zirconia or mixed oxides, such as silica-alumina, in particular silica, alumina or silica-alumina. Preferably, a silica support is used. The person skilled in the art knows the procedures required for supporting the metallocene catalyst.

[0236] Especially preferably, the support is a porous material, so that the complex can be loaded into the pores of the support, for example using a method similar to that described in WO 94 / 14856 (Mobil), WO 95 / 12622 (Borealis) and WO 2006 / 097497.

[0237] The average particle size of the silica support can generally be in the range of 10 to 100 pm. However, it has proven to be of particular advantage if the support has an average particle size dso of 15 to 80 pm, preferably 18 to 50 pm. The average pore diameter of the silica support can be in the range of 10 to 100 nm, with a pore volume of 1 to 3 mL / g.

[0238] Examples of suitable support materials are, for example, ES757 produced and marketed by PQ Corporation, Sylopol 948 produced and marketed by Grace or SUNSPERA DM-L-303 silica produced by AGC Si-Tech Corporation. The support can optionally be calcined prior to use for catalyst preparation in order to achieve an optimal silanol group content.

[0239] The use of these supports is well known in the art.

[0240] According to the second embodiment of the present application, the propylene homo- or copolymer (PP) as matrix of the heterophasic polypropylene composition (HECO) is a propylene copolymer (cPP).

[0241] The heterophasic polypropylene composition (HECO) according to the second embodiment of the present application preferably has a rather low melt flow rate. Preferably, the melt flow rate MFR2 (230 °C, 2.16 kg) determined according to ISO 1133 of the heterophasic polypropylene composition (HECO) according to the second embodiment of the present application is 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.

[0242] It is preferred that the heterophasic polypropylene composition (HECO) according to the second embodiment of the present application comprises based on the total weight of the heterophasic polypropylene composition (HECO)

[0243] 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 a propylene copolymer (cPP), and

[0244] 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 an elastomeric ethylene copolymer (E).

[0245] The propylene copolymer (cPP) preferably comprises monomers copolymerizable with propylene, e.g. comonomers, such as ethylene and / or C4to C8a-olefins, in particular ethylene and / or C4to C6a-olefins, e.g. 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 specifically, the propylene copolymer (cPP) comprises units derived from ethylene and / or 1 -butene in addition to propylene. Thus, in an especially preferred embodiment, the propylene copolymer (cPP) comprises units derived from ethylene and propylene only.

[0246] In particular, it is preferred that the propylene copolymer (cPP) is a random propylene copolymer, like a random copolymer of propylene and ethylene.

[0247] The term “random copolymer” is to be understood preferably according to IUPAC (Pure Appl. Chem., Vol. 68, No. 8, pp. 1591-1595, 1996). Preferably, the molar concentration of copolymerized monomer dyads, like ethylene dyads, obeys the following relationship

[0248] [HH]<[H] 2

[0249] wherein

[0250] [HH] is the mole fraction of adjacent copolymerized monomer units, like adjacent ethylene units, and

[0251] [H] is the mole fraction of total copolymerized monomer units in the polymer, like the mole fraction of total ethylene units.

[0252] Preferably, the propylene copolymer (cPP) has a comonomer content, like an 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-%.

[0253] Further, 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, still 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.

[0254] 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.

[0255] The process for preparing the propylene copolymer (cPP) is preferably a sequential polymerization process comprising at least two reactors connected in series, wherein the process comprises the steps of

[0256] (A) polymerizing in a first reactor (R-1) being a slurry reactor (SR), preferably a loop reactor (LR), propylene and optionally a comonomer selected from the group consisting of ethylene and C4 to C 12 a comonomer of an alpha-olefin, preferably ethylene, obtaining a first propylene copolymer fraction,

[0257] (B) transferring the first propylene copolymer fraction and unreacted comonomer of the first reactor (R-1) into a second reactor (R-2) being a gas phase reactor (GPR-1),

[0258] (C) feeding propylene and a comonomer selected from the group consisting of ethylene and C4 to C 12 an alpha-olefin, preferably ethylene, into the second reactor (R-2),

[0259] (D) polymerizing in the second reactor (R-2) and in the presence of the first propylene copolymer fraction and a comonomer selected from the group consisting of ethylene and C4 to C 12 an alpha-olefin, preferably ethylene, obtaining a second propylene copolymer fraction, the first propylene copolymer fraction and the second propylene copolymer fraction forming the propylene copolymer (cPP) as defined in the present invention, wherein further

[0260] 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).

[0261] It is preferred that the solid catalyst system (SCS) comprises a metallocene catalyst of formula (I) and a cocatalyst as described with respect to the heterophasic polypropylene composition (HECO) according to the first embodiment of the present application.

[0262] It is therefore preferred that the solid catalyst system (SCS) described above including all preferred embodiments is applied to the preparation of the propylene copolymer (cPP).

[0263] With respect to the term "sequential polymerization process", reference is made to the definition provided above.

[0264] If applied, the first reactor (R-1) is a slurry reactor (SR) and can be any continuous or simple batch stirred tank reactor or loop reactor operated in slurry. According to the present application, the slurry reactor (SR) is preferably a loop reactor (LR).

[0265] 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 fluid bed reactors. Preferably, the gas phase reactor(s) (GPR) comprise(s) a mechanically agitated fluid bed reactor with gas velocities of at least 0.2 m / s. Thus, it should be understood that the gas phase reactor (GPR) is a fluid bed type reactor preferably with a mechanical stirrer.

[0266] The conditions in each reactor (temperature, pressure, reaction time, monomer feed) depend on the desired product as known to the skilled person. 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) is a gas phase reactor (GPR-1). The subsequent reactors, if present, are also gas phase reactors (GPR).

[0267] A preferred multi-stage process is a "loop-gas phase" process, such as the process developed by Borealis A / S, Denmark (known as BORSTAR® technology), described for example in the patent literature, such as in EP 0 887 379 or WO 92 / 12182.

[0268] The multimodal polymers can be produced according to several methods described for example in WO 92 / 12182, EP 0 887 379 and WO 98 / 58976. The content of these documents is included herein by reference.

[0269] ​With regard to the conditions and residence times of the first reactor (R-1), i.e. the slurry reactor (SR), such as loop reactor (LR), and the second reactor (R-2), i.e. the gas phase reactor (GPR), reference is made to the conditions defined above with regard to the heterophasic polypropylene composition (HECO) according to the first embodiment of the present application. This applies accordingly to the optional application of a prepolymerization step.

[0270] The elastomeric ethylene copolymer (E) according to the second embodiment of the present application can comprise monomers, e.g. comonomers, copolymerizable with ethylene, such as C3 to C12 12 alpha-olefins, 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 present application comprises units derived from 1-butene, 1-hexene and / or 1-octene in addition to ethylene.

[0271] It is especially preferred that the elastomeric ethylene copolymer (E) according to the second embodiment of the present application is a copolymer of ethylene and 1-octene.

[0272] Preferably, the elastomeric ethylene copolymer (E) according to the second embodiment of the present application is a very low density polyethylene, more preferably a very low density polyethylene polymerized using single-site catalysis.

[0273] The elastomeric ethylene copolymer (E) according to the second embodiment of the present application has a density determined according to ISO 1183-187 in the range of 860 to 890 kg / m3, more preferably in the range of 865 to 885 kg / m3, still more preferably in the range of 870 to 884 kg / m3, like in the range of 879 to 883 kg / m3. 3 3 3 3

[0274] Preferably, the elastomeric ethylene copolymer (E) according to the second embodiment of the present application 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.

[0275] ​​​​The ethylene content of the elastomeric ethylene copolymer (E) according to the second embodiment of the present application 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).

[0276] Further, it is preferred that the elastomeric ethylene copolymer (E) according to the second embodiment of the present application has a melting temperature Tm determined according to differential scanning calorimetry (DSC) of below 100 °C, more preferably in the range of 50 °C to 90 °C, still more preferably in the range of 55 °C to 85 °C.

[0277] Additionally or alternatively to the previous paragraph, it is preferred that the elastomeric ethylene copolymer (E) according to the second embodiment of the present application has a glass transition temperature in the range of 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.

[0278] In a preferred embodiment, the elastomeric ethylene copolymer (E) according to the second embodiment of the present application is prepared with at least one single-site catalyst. The elastomeric ethylene copolymer (E) according to the second embodiment of the present application 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 application is a substantially linear ethylene polymer (SLEP). SLEPs 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 Queo TM Plastomer, ENGAGE available from The Dow Chemical Company TM Plastomer resin, EXACT from Exxon TM Polymer or TAFMER from Mitsui TM Polymer, Lucene polymer from LG, Fortify polymer from Sabic or Solumer polymer from SK Chemicals.

[0279] The heterophasic polypropylene composition (HECO) according to the second embodiment of the present application can further comprise a low density polyethylene (LDPE).

[0280] 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, like in the range of 2.5 to 3.5 g / 10 min.

[0281] Further, it is preferred that the low density polyethylene (LDPE) has a density determined according to ISO 1183-187 of more than 900 kg / m3, preferably in the range of 920 to 960 kg / m3, more preferably in the range of 925 to 955 kg / m3, still more preferably in the range of 930 to 950 kg / m3, like in the range of 935 to 945 kg / m3. 3 3 3

[0282] Further, 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, olefinically 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. It is especially preferred that the polar comonomer is vinyl acetate.

[0283] Further, 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.-%, like 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.

[0284] The low density polyethylene (LDPE) is preferably produced by free-radically initiated high pressure polymerization.

[0285] Preferably, the low density polyethylene (LDPE) is a copolymer known in the art. It is especially preferred that the low density polyethylene (LDPE) is a commercially available copolymer of ethylene and Borealis' vinyl acetate OE5328I.

[0286] ​​​The heterophasic polypropylene composition (HECO) according to the second embodiment of the present application is preferably obtained by melt blending a propylene copolymer (cPP), an elastomeric ethylene copolymer (E) and optionally a low density polyethylene (LDPE).

[0287] The fiber reinforced composition (C) according to the second embodiment of the present application 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, like in the range of 2.5 to 3.8 g / 10 min.

[0288] Further, it is preferred that the fiber reinforced composition (C) according to the second embodiment of the present application has a tensile modulus determined according to ISO 527-1 A 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, like in the range of 2650 to 2800 MPa.

[0289] Additionally or alternatively, it is preferred that the fiber reinforced composition (C) according to the second embodiment of the present application has an elongation at break determined according to ISO 527-2 of more than 10.0 %, more preferably of more than 10.3 %, still more preferably of more than 10.8 %, like equal to or more than 11.0 %.

[0290] Fibers (F)

[0291] The essential component of the fiber reinforced composition (C) of the present application is the fibers (F).

[0292] Preferably, the fibers (F) are selected from the group consisting of glass fibers, carbon fibers, polymeric fibers, metal fibers, mineral fibers, ceramic fibers and mixtures thereof. More preferably, the fibers (F) are glass fibers and / or carbon fibers.

[0293] It is especially preferred that the fibers (F) are glass fibers (GF). Preferably, the glass fibers (GF) are chopped glass fibers, also referred to as short glass fibers (SGF) or chopped strands, and / or long glass fibers (LGF), preferably long glass fibers (LGF) obtained from glass rovings.

[0294] It is particularly preferred that the fibers (F) are short glass fibers (GF).

[0295] The cut or short glass fibers (SGF) for 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, like in the range of 3.0 to 7.0 mm.

[0296] The cut or short glass fibers (SGF) for the fiber reinforced composition (C) preferably have an average diameter of 5 to 20 pm, more preferably of 6 to 18 pm, still more preferably of 8 to 16 pm.

[0297] Preferably, the short glass fibers (SGF) have an aspect ratio of 125 to 650, preferably of 150 to 500, more preferably of 200 to 450. The aspect ratio is the relationship between the average length and the average diameter of the fibers.

[0298] adhesion promoter (AP)

[0299] According to the present application, the fiber reinforced polypropylene composition (C) can 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).

[0300] The adhesion promoter (AP) is designated as a polar modified polypropylene (PM-PP) homo- or copolymer.

[0301] The polar modified polypropylene (PM-PP) homo- or copolymer comprises a low molecular weight compound with a reactive polar group. Most preferred are modified polypropylene homo- and copolymers, like copolymers of propylene and ethylene or with other a-olefins (e.g. C4 to C 10 a-olefins), as they are highly compatible with the propylene homo- or copolymer (PP) of the fiber reinforced polypropylene composition (C) of the present application.

[0302] In terms of structure, the polar modified polypropylene (PM-PP) homo- or copolymer is preferably selected from the group consisting of grafted homo- or copolymers.

[0303] Herein, it is preferred that the polar modified polypropylene (PM-PP) homo- or copolymer contains 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.

[0304] Specific examples of the polar compound are unsaturated cyclic anhydrides and their aliphatic diester and diacid derivatives. In particular, maleic anhydride and a compound selected from the group consisting of Ci to Cio linear and branched dialkyl maleate, Ci to Cio linear and branched dialkyl fumarate, itaconic anhydride, Ci to Cio linear and branched dialkyl itaconate, acrylic acid, maleic acid, fumaric acid, itaconic acid and mixtures thereof can be used.

[0305] It is particularly preferred to use a polypropylene homopolymer or copolymer grafted with maleic anhydride or acrylic acid as the polar modified polypropylene (PM-PP) homopolymer or copolymer, i.e. the adhesion promoter (AP).

[0306] The modified polymer, i.e. the adhesion promoter, can be produced in a simple manner by reactive extrusion of the polymer, for example together with maleic anhydride or acrylic acid in the presence of a free-radical generator, such as an organic peroxide, as disclosed for example in US 4,506,056, US 4,753,997 or EP 1 805 238.

[0307] The preferred amount of groups derived from the polar compound in the polar modified polypropylene (PM-PP) homopolymer or copolymer, i.e. the adhesion promoter (AP), is in the range of 0.5 to 5.0 wt.-%. For example, the amount can be in the range of 0.5 wt.-% to 4.5 wt.-%, preferably in the range of 0.5 wt.-% to 4.0 wt.-%, more preferably in the range of 0.5 wt.-% to 3.5 wt.-%.

[0308] The preferred value of the melt flow rate MFR2(230 °C) of the polar modified polypropylene (PM-PP) homopolymer or copolymer, i.e. the adhesion promoter (AP), is at least 20.0 to 400 g / 10 min. It is particularly preferred that the polar modified polypropylene (PM-PP) homopolymer or copolymer has 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.

[0309] In a preferred embodiment of the present application, 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).

[0310] additive (AD)

[0311] In addition to the heterophasic polypropylene composition (HECO), the fibres (F) and the adhesion promoter (AP), the fibre-reinforced composition (C) according to the present application can comprise additives (AD). Typical additives are acid scavengers, antioxidants, colorants, light stabilizers, plasticizers, slip agents, scratch resistant agents, dispersants, processing aids, lubricants, pigments and the like.

[0312] Such additives are commercially available, for example as described in the “Plastic Additives Handbook”, 6thEdition, 2009 by Hans Zweifel, pages 1141 to 1190.

[0313] Furthermore, the term “additives (AD)” according to the present application also includes carrier materials, in particular polymeric carrier materials.

[0314] Polymeric carrier materials

[0315] Preferably, the fibre-reinforced composition (C) according to the present application does not comprise (a) further 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 fibre-reinforced composition (C). Any polymer which is a carrier material of an additive (AD) is not counted as amount of the polymer compounds indicated in the present application, but as amount of the respective additive.

[0316] The polymeric carrier material of the additives (AD) is a carrier polymer to ensure a homogeneous distribution in the fibre-reinforced polypropylene composition (C) according to the present application. The polymeric carrier material is not limited to a specific polymer. The polymeric carrier material can be an ethylene homopolymer, an ethylene copolymer obtained from ethylene and an alpha-olefin comonomer such as a C3 to C8 alpha-olefin comonomer, a propylene homopolymer and / or a propylene copolymer obtained from propylene and an alpha-olefin comonomer such as ethylene and / or a C4 to C8 alpha-olefin comonomer. Preferably, the polymeric carrier material does not contain monomeric units derived from styrene or derivatives thereof.

[0317] Articles

[0318] The present application also relates to articles, such as injection moulded articles, comprising the fibre-reinforced composition (C) as defined above. The present application in particular relates to articles, such as injection moulded articles, 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 the fibre-reinforced polypropylene composition (C) as defined above. In an especially preferred embodiment, the present application relates to articles, such as injection moulded articles, consisting of the fibre-reinforced composition (C) as defined above.

[0319] Preferably, the article is an automotive article, such as an injection molded automotive article.

[0320] Further embodiments

[0321] [1] Fibre-reinforced composition (C) comprising, based on the total weight of the fibre-reinforced composition (C)

[0322] a) 55.0 to 94.9 wt.-% of a heterophasic polypropylene composition (HECO) comprising

[0323] i) a matrix which is a propylene homopolymer 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 below 8.5 mol-%, and

[0324] ii) an elastomeric ethylene copolymer (E) dispersed in the matrix,

[0325] b) 5.0 to 45.0 wt.-% of fibres (F), and

[0326] c) optionally 0.1 to 5.0 wt.-% of an adhesion promoter (AP),

[0327] wherein the fibre-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.

[0328] [2] Fibre-reinforced composition (C) according to embodiment [1], wherein the heterophasic polypropylene composition (HECO) comprises, based on the total weight of the heterophasic copolymer (HECO)

[0329] i) 60.0 to 95.0 wt.-% of a matrix which is a propylene homopolymer or copolymer (PP), and

[0330] ii) 5.0 to 40.0 wt.-% of an elastomeric ethylene copolymer (E).

[0331] [3] Fibre-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).

[0332] [4] Fibre-reinforced composition (C) according to any one 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.

[0333] [5] The fiber-reinforced composition (C) according to any one of embodiments [1] to [4], wherein the heterophasic polypropylene composition (HECO) has an intrinsic viscosity (IV) of the soluble fraction (SF) measured according to ISO 1628 / 1 (in decalin at 135 °C) in the range of 1.8 to 3.0 dl / g, determined according to CRYSTEX QC.

[0334] [6] The fiber-reinforced composition (C) according to any one of embodiments [1] to [5], wherein the fibers (F) are glass fibers (GF), preferably short glass fibers (SGF), having

[0335] i) an average length of 2.0 to 10.0 mm, and / or

[0336] ii) an average diameter of 5 to 20 pm.

[0337] [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 homo- or copolymer grafted with maleic anhydride, the polar modified polypropylene (PM-PP) having a melt flow rate MFR (230 °C, 2.16 kg) of at least 20.0 g / 10 min to 400 g / 10 min, determined according to ISO 1133.

[0338] [8] The fiber-reinforced composition (C) according to any one of embodiments [1] to [7], wherein

[0339] i) the propylene homo- or copolymer (PP) is a propylene homopolymer (hPP), and

[0340] ii) the elastic ethylene polymer (E) is a copolymer of ethylene and propylene.

[0341] [9] The fiber-reinforced composition (C) according to embodiment [8], wherein the propylene homopolymer (hPP) has a melting temperature Tm in the range of 140 to 160 °C, determined according to differential scanning calorimetry (DSC).

[0342]

[10] The 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

[0343] ii) a melt flow rate MFR2 (230 °C, 2.16 kg) in the range of 20.0 to 100 g / 10 min, determined according to ISO 1133.

[0344]

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

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

[0345] 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

[0346] ii) an ethylene content of the xylene cold soluble (XCS) fraction in the range of 20.9 to 44.7 mol.-%.

[0347] and / or

[0348] 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

[0349] iv) an ethylene content of the soluble fraction (SF) determined according to CRYSTEX QC in the range of 20.9 to 44.7 mol.-%.

[0350]

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

[11] , having

[0351] i) a tensile modulus determined according to ISO 527-1A in the range of 3000 to 6000 MPa, and / or

[0352] ii) an elongation at break determined according to ISO 527-2 of more than 3.0%.

[0353]

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

[0354] i) the propylene homopolymer or copolymer (PP) is a propylene copolymer (cPP), a copolymer of propylene and ethylene, the copolymer having an ethylene content of 2.2 to 8.5 mol.-%, and

[0355] ii) the elastomeric ethylene copolymer (E) is a copolymer of ethylene and C4 to C 12 an alpha-olefin, preferably 1-octene, the copolymer having an ethylene content of 55.0 to 85.0 wt.-%, based on the total weight of the elastomeric ethylene copolymer (E).

[0356]

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

[13] , wherein

[0357] 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

[0358] ii) the elastomeric ethylene copolymer (E) has a melt flow rate MFR2(190 °C, 2.16 kg) determined according to ISO 1133 in the range of 0.8 to 20.0 g / 10 min, and / or a density determined according to ISO 1183-187 in the range of 860 to 890 kg / m 3

[0359] and / or

[0360] iii) 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.

[0361]

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

[13] or

[14] , having

[0362] i) a tensile modulus determined according to ISO 527-1A in the range of 2500 to 5500 MPa, and / or

[0363] ii) an elongation at break determined according to ISO 527-2 of more than 10.0 %.

[0364]

[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) homo- or copolymer having a density determined according to ISO 1183-187 of more than 900 kg / m 3 and comprising ethylene and optionally vinyl acetate.

[0365]

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

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

[0366]

[0367] wherein each X is independently a sigma-donor ligand,

[0368] ​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-C6-alkyl group optionally containing one or more heteroatoms from groups 14 to 16 of the periodic table or a fluorine atom, 20 - a hydrocarbyl group, or optionally two R' groups together can form a ring,

[0369] each R 1 is independently the same or can be different and is a hydrogen, a linear or branched C1-C6-alkyl group, a C 7-20 - aralkyl, C 7-20 - alkylaryl or C 6-20 - aryl or OY group, wherein Y is C 1-10 - a hydrocarbyl group, and optionally two adjacent R 1 groups together can be part of a ring comprising the phenyl carbon to which they are bonded,

[0370] each R 2 is independently the same or can be different and is a CH2-R 8 group, wherein R 8 is H or a linear or branched C 1-6 - alkyl group, C 3-8 - cycloalkyl group, C 6-10 - aryl group,

[0371] R 3 is a linear or branched C1-C6-alkyl group, C 7-20 - aralkyl, C 7-20 - alkylaryl or C6-C 20 - aryl group,

[0372] R 4 is a C(R 9 )3 group, wherein R 9 is a linear or branched C1-C6-alkyl group,

[0373] R 5 is a hydrogen or an aliphatic C1-C6-alkyl group optionally containing one or more heteroatoms from groups 14 to 16 of the periodic table; 20 - a hydrocarbyl group;

[0374] R 6 is a hydrogen or an aliphatic C1-C6-alkyl group optionally containing one or more heteroatoms from groups 14 to 16 of the periodic table; 20 - a hydrocarbyl group; or

[0375] R 5 and R 6 together can form a 5-membered saturated carbon ring, which is optionally substituted by n groups R 10 , n being from 0 to 4;

[0376] each R 10 are identical or different and can be C1-C 20 - a hydrocarbon group, or a C1-C 20 - a hydrocarbon group;

[0377] R 7 H or linear or branched C1-C6-alkyl, optionally substituted with 1 to 3 groups R 11 substituted aryl or heteroaryl having 6 to 20 carbon atoms,

[0378] 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 groups, wherein Y is C 1-10 - a hydrocarbon group.

[0379]

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

[17] .

[0380] The application will now be described in more detail by means of the examples provided hereinafter.

[0381] Examples

[0382] A. Measurement methods

[0383] The following definitions of terms and determination methods apply to the above general description of the application as well as to the below examples unless otherwise defined.

[0384] Melt flow rate

[0385] The melt flow rate (MFR) is determined according to ISO 1133 and is expressed in g / 10 min. The MFR is an indication of the flowability of the polymer and thus of its processability. The higher the MFR, 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.

[0386] Melting temperature T m and crystallization temperature T c The measurements are carried out with a Mettler TA820 differential scanning calorimeter (DSC) on 5 to 7 mg samples. The DSC is run according to ISO 11357 / part 3 / method C2 in a heat / cool / heat cycle with a scan rate of 10 °C / min in the temperature range of -30 to +225 °C. The crystallization temperature is determined from the cooling step, while the melting temperature is determined from the second heating step.

[0387] All mechanical measurements were performed after a 96 h sample conditioning time at 23 °C at 50 % relative humidity.

[0388] By 13 Quantitative C-NMR spectroscopy for the quantification of the microstructure of the PP matrix

[0389] Quantitative nuclear magnetic resonance (NMR) spectroscopy was employed to quantify the stereoregularity and regioregularity of the crystalline matrix of the polymers.

[0390] Quantitative 1 H and 13 C NMR spectra were recorded in solution state on a Bruker Advance III 400 NMR spectrometer operating at 400.15 and 100.62 MHz for 13 C, 1 H} respectively. All spectra were recorded at 125 °C using a 13C-optimised 10 mm extended temperature probehead, with nitrogen gas being used for all pneumatic devices.

[0391] For propylene homopolymers, about 200 mg of material was dissolved in 1,2-tetrachloroethane-d2(TCE-d2). To ensure homogeneity of the solution, after the initial sample preparation in the heating block, the NMR tube was further heated in a rotating oven for at least 1 hour. After insertion into the magnet, the tube was spun at 10 Hz. This setting was chosen mainly for the high resolution required for the stereoregularity distribution quantification (Busico, V., Cipullo, R., Prog. Polym. Sci. 26 (2001) 443; Busico, V.; Cipullo, R., Monaco, G., Vacatello, M., Segre, A. L., Macromolecules 30 (1997) 6251). Standard single-pulse excitation was employed, using NOE and bi-level WALTZ16 decoupling (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) transients were acquired for each spectrum.

[0392] The quantitative 13 C{1 H}NMR spectra were processed, integrated and the relevant quantitative properties were determined from the integrals. 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 related to the stereosequence of interest (Busico, V., Cipullo, R., Prog. Polym. Sci. 26 (2001) 443; Busico, V., Cipullo, R., Monaco, G., Vacatello, M., Segre, A. L., Macromoleucles 30 (1997) 6251).

[0393] In particular, the effect of regio defects and comonomer integrations on the quantification of the tacticity distribution was corrected by subtracting representative regio defects and comonomer integrations from the specific integral region of the stereosequence. The isotacticity was determined at the pentad level and reported as the percentage of isotactic pentad (mmmm) sequences over all pentad sequences:

[0394] [mmmm] % = 100 * (mmmm / sum of all pentads).

[0395] The presence of 2,1-erythro regio defects was indicated by the presence of two methyl sites at 17.7 and 17.2 ppm and confirmed by other characteristic sites.

[0396] Characteristic signals corresponding to other types of regio defects were not observed (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253). The average integration of the two characteristic methyl sites at 17.7 and 17.2 ppm was used to quantify the amount of 2,1-erythro regio defects:

[0397] P 21e = (I e6 + I e8 ) / 2.

[0398] The number of 1,2 primary inserted propylene was quantified based on the methyl region and corrected for sites contained within this region that are not related to primary insertion and primary insertion sites not contained within this region:

[0399] P 12 = I CH3 + P 12e

[0400] The total amount of propene is quantified as the sum of the primary inserted propene and all other regio defects present:

[0401] P 总 =P 12 +P 21e

[0402] The mole percentage of 2,1-erythro regio defects relative to all propylene was quantified:

[0403] [21e] mol% = 100*(P 21e / P 总 )

[0404] Determination of C2 and C3 content in PP copolymers

[0405] 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 13A 10 mm extended temperature probe was used for the C-optimization at 125 °C. About 200 mg of material was dissolved in 3 ml of 1,2-tetrachloroethane-d2 (TCE-d2) with chromium(III) acetylacetonate (Cr(acac)3) to obtain a 65 mM solution of the relaxant in the solvent (Singh, G., Kothari, A., Gupta, V., Polymer Testing 28 5 (2009), 475). To ensure a homogeneous solution, the NMR tube was further heated in a rotating oven for at least 1 h after initial sample preparation in the heating block. After insertion of the magnet, the tube was spun at 10 Hz. This setting was chosen mainly for the high resolution and accurate ethylene content quantification which quantitatively requires this setting. Standard single pulse excitation without NOE was employed using an optimized tip angle, a recycle delay of 1 s and a two-step 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 acquired per spectrum.

[0406] The quantitative 13 C{ 1 H} NMR spectra were processed, integrated and the relevant quantitative properties were determined from the integrals. 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. This approach allows a comparable reference even if this structural unit is not present. Characteristic signals corresponding to the incorporation of ethylene were observed (Cheng, H. N., Macromolecules 17 (1984), 1950).

[0407] The method of Wang et al. (Wang, W-J., Zhu, S., Macromolecules 33 (2000), 1157) was used to determine the relative amount of the ethylene content by 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:

[0408] E=0.5(Sββ+Sβγ+Sβδ+0.5(Sαβ+Sαγ))

[0409] By using this set of sites, the corresponding integral equation becomes:

[0410] E=0.5(I H +I G +0.5(I C +I D ))

[0411] 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.

[0412] Calculate the mole percentage of comonomer incorporation from the mole fraction:

[0413] E [mol %] = 100 * fE

[0414] Calculate the weight percent of comonomer incorporation from the mole fraction:

[0415] E[weight%]=100*(fE*28.06) / ((fE*28.06)+((1-fE)*42.08)).

[0416] 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 -1spectrometry. The absorbance is measured as the height of the peak by choosing either the so-called short baseline or the long baseline or both. The short baseline is drawn through the lowest points between about 1410 and 1320 cm -1 , the long baseline is drawn between about 1410 and 1220 cm -1 . Special calibration is required for each baseline type. Furthermore, the comonomer content of the unknown sample needs to be within the range of the comonomer content of the calibration samples.

[0417] The glass transition temperature Tg is determined by dynamic mechanical analysis according to ISO 6721-7. The measurement is performed in torsion mode on compression molded samples (40 x 10 x 1 mm 3 ) between -100 °C and +150 °C with a heating rate of 2 °C / min and a frequency of 1 Hz.

[0418] The density is measured according to ISO 1183-187. The sample preparation is done by compression molding according to ISO 1872-2:2007.

[0419] Xylene cold soluble fraction (XCS)

[0420] The xylene cold soluble fraction at room temperature (XCS, wt.-%) is determined according to ISO 16152; 5th Edition; 2005-07-01 at 25 °C.

[0421] Flexural modulus: The flexural modulus is determined according to ISO 178 in 3-point bending on injection molded test specimens of 80 x 10 x 4 mm prepared according to ISO 294-1 :1996.

[0422] Charpy notched impact strength is measured according to ISO 179-1 / 1 eA at +23 °C using injection molded test specimens (80 x 10 x 4 mm) prepared according to EN ISO 1873-2.

[0423] Tensile properties are determined on 4 mm thick injection molded dog-bone test specimens prepared according to EN ISO 1873-2. The tensile modulus is determined according to ISO 527-1A at a strain rate of 1 mm / min and 23 °C, the tensile strength and elongation at break (strain) are determined according to ISO 527-2 at a strain rate of 50 mm / min and 23 °C.

[0424] Crystex analysis

[0425] Crystallization and soluble fraction method

[0426] The polypropylene (PP) compositions were analyzed by CRYSTEX QC, Polymer Char (Valencia, Spain) for the crystalline fraction (CF) and the soluble fraction (SF) and the comonomer content and intrinsic viscosity of each fraction.

[0427] In Figure 1 a a schematic representation of the CRYSTEX QC instrument is shown. As Figure 1 b shown, the crystalline fraction and the amorphous fraction were separated by temperature cycling of dissolution at 160 °C, crystallization at 40 °C and redissolution at 160 °C in 1,2,4-trichlorobenzene (1,2,4-TCB). Quantification of the SF and CF and determination of the ethylene content (C2) of the parent EP copolymer and its soluble and crystalline fractions were achieved by an infrared detector (IR4) and the intrinsic viscosity (iV) was determined using an online 2-capillary viscometer.

[0428] The IR4 detector is a multi-wavelength detector that detects the IR absorbance at two different wavebands (CH3 and CH2) that are used to determine the concentration and the ethylene content in ethylene-propylene copolymers. The IR4 detector is calibrated with a series of 8 EP copolymers with known ethylene content (determined by 13 C-NMR spectroscopy) in the range of 2 to 69 wt% and each used EP copolymer for calibration has multiple concentrations between 2 and 13 mg / ml.

[0429] The amount of the soluble fraction (SF) and the crystalline fraction (CF) were related to the amount of “xylene cold solubles” (XCS) and xylene cold insoluble (XCI) fraction determined according to ISO 16152 following the standard gravimetric method, respectively, by XS calibration. XS calibration was achieved by testing various EP copolymers with XS content in the range of 2 to 31 wt%.

[0430] 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 standard method according to ISO 1628 in decalin. Calibration was achieved using various EP PP copolymers with iV = 2 to 4 dl / g.

[0431] A sample of the PP composition to be analyzed was weighed out at a concentration of 10 to 20 mg / ml. After automatic filling of the vial with 1,2,4-TCB containing 250 mg / l of 2,6-tert-butyl-4-methylphenol (BHT) as antioxidant, the sample was dissolved at 160 °C until complete dissolution, usually for 60 min, and stirring was continued at 800 rpm.

[0432] AsFigure 1 As shown in a and 1 b, a defined volume of sample solution is injected into a column filled with inert carrier, where crystallization of the sample and separation of the soluble fraction from the crystalline part takes place. This process is repeated twice. During the first injection, the whole sample is measured at high temperature, determining 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 using the crystallization period (wt% SF, wt% C2, iV).

[0433] EP denotes ethylene propylene copolymer.

[0434] PP denotes polypropylene.

[0435] Figure 1 (a): Schematic of the CRYSTEX QC instrument

[0436] Figure 1 (b): Elution of an EP copolymer sample in a TREF column (column filled with inert material (e.g. glass beads)) and obtaining of the soluble fraction and the crystalline fraction (see Del Hierro, P.; Ortin, A.; Monrabal, B.; ‘Soluble Fraction Analysis in polypropylene).

[0437] Intrinsic viscosity: Intrinsic viscosity (IV) is measured according to DIN ISO 1628 / 1, October 1999, in decalin at 135 °C.

[0438] VOC / Fog emissions are measured according to VDA 278:2002 on injection molded test specimens and on granular compounds. Volatile organic compounds are measured in toluene equivalents per gram. Fogging is measured in hexadecane equivalents per gram.

[0439] Measurements are performed using TDSA provided 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 pm 5% phenyl-methyl-siloxane coating.

[0440] The VOC analysis was performed according to the apparatus 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 cold trap was purged with a flow mode split of 1 :30 at temperatures ranging from -150 °C to +280 °C with a heating rate of 12 K / s and a final time of 5 min. The following GC settings were used for analysis: isothermal at 40 °C for 2 min, heating to 92 °C at 3 K / min, then to 160 °C at 5 K / min, then to 280 °C at 10 K / min, isothermal for 10 min; flow rate 1.3 ml / min.

[0441] The fog analysis was performed according to the apparatus settings 1 listed in the standard, using the following main parameters: flow mode splitless, rate 60 K / min; final temperature 120 °C; final time 60 min. The cold trap was purged with a flow mode split of 1 :30 at temperatures ranging from -150 °C to +280 °C with a heating rate of 12 K / s. The following GC settings were used for analysis: isothermal at 50 °C for 2 min, heating to 160 °C at 25 K / min, then to 280 °C at 10 K / min, isothermal for 30 min; flow rate 1.3 ml / min.

[0442] B. Examples

[0443] 1. Catalyst synthesis

[0444] The catalyst used was trans-dimethylsilylenyl[2-methyl-4,8-di(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 as disclosed in WO 2020 / 239602 A1 as ICS3.

[0445] Preparation of MAO-silica support

[0446] A steel reactor equipped with a mechanical stirrer and a filter screen was flushed with nitrogen and the reactor temperature was set to 20°C. Then 5.0 kg of a silica of the brand DM-L-303 from AGC Si-Tech, pre-calcined at 600°C, was added from a feed tank, after which the reactor was carefully pressurized and depressurized with nitrogen using a hand valve. Then 22 kg of toluene was added. The mixture was stirred for 15 min. Then 9.0 kg of a 30 wt% solution of MAO in toluene from Lanxess was added via the feed line at the top of the reactor within 70 min. Then the reaction mixture was heated to 90°C and stirred for another two hours at 90°C. 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 solid was washed with heptane (22.2 kg). Finally, the MAO-treated Si02was dried at 60° under a stream of nitrogen for 2 hours and then under stirring in vacuum (-0.5 bar, g) for 5 hours. The MAO-treated support was collected as a free-flowing white powder which was found to contain 12.2% of aluminium by weight.

[0447] Catalyst preparation

[0448] A steel reactor was flushed with nitrogen and the reactor temperature was set to 20°C. Then 5.0 kg of a silica of the brand DM-L-303 from AGC Si-Tech, pre-calcined at 600°C, was added from a feed tank, after which the reactor was carefully pressurized and depressurized with nitrogen using a hand valve. Then 22 kg of toluene was added. The mixture was stirred for 15 min. Then 9.0 kg of a 30 wt% solution of MAO in toluene from Lanxess was added via the feed line at the top of the reactor within 70 min. Then the reaction mixture was heated to 90°C and stirred for another two hours at 90°C. 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 solid was washed with heptane (22.2 kg). Finally, the MAO-treated Si02was dried at 60° under a stream of nitrogen for 2 hours and then under stirring in vacuum (-0.5 bar, g) for 5 hours. The MAO-treated support was collected as a free-flowing white powder which was found to contain 12.2% of aluminium by weight.

[0449] 2. Preparation of the reactor-intrinsic heterophasic polypropylene composition (HECO1) and propylene copolymer (cPP)

[0450] The reactor-intrinsic heterophasic polypropylene composition (HECO1) and propylene copolymer (cPP) were prepared in a sequential process comprising a loop reactor and one or two gas phase reactors in the presence of the catalyst described above. The reaction conditions and properties of the final polymers are summarized in Table 1 and Table 2.

[0451] Table 1 : Preparation of the reactor-intrinsic heterophasic polypropylene composition (HECO1) and propylene copolymer (cPP)

[0452] HECO1 cPP Pre-polymerization 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 Residence time [h] 0.36 0.32 Loop (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 MFR2 [g / 10 min] 81.9 2.1 C2 [mol%] 0.0 3.0 Residence time [h] 0.29 0.39

[0453] Table 1 : (continued)

[0454] HECO1 cPP Split ratio [wt%] 57 58 XCS [wt%] 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 Residence time [h] Split ratio [wt%] 32 42 C2 (total) [mol%] 0.0 2.4 XCS [wt%] 0.75 0.5 MFR [g / 10 min] 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 [wt%] 11 - MFR [g / 10 min] 87.5 -

[0455] Table 2: Properties of the reactor-heterophasic polypropylene composition (HECO1 ) and the propylene copolymer (cPP) after pelletization

[0456] HECO1 cPP MFR [g / 10 min] 76.2 8.3 XCS [wt%] 11.2 0.47 C2 [mol%] 2.5 3.6 C2 (XCS) [mol%] 32.5 n.d. IV (XCS) [dl / g] 2.6 n.d. Tm [℃] 157 137 Tc [℃] 121 100 1,2e [mol%] 0.7 0.8 SF [wt%] 10.6 0.5 C2 (SF) [mol%] 31.3 n.d. C2 (CF) [mol%] 0.0 IV [dl / g] 1.26 2.05 IV (SF) [dl / g] 2.51 n.d. IV (CF) [dl / g] 1.11 n.d. IV (SF) / IV (CF) [-] 2.26 n.d. Flexural modulus [MPa] 1257 760 Charpy notched impact strength (23 °C) [kJ / m 2 ]]]> 3.85 9.65 Charpy notched impact strength (-20 °C) [kJ / m 2 ]]]> 1.96 n.d. Tg (1) [℃] -45 - Tg (2) [℃] 0 -4

[0457] 3. Production of a fiber reinforced composition (C) with HECO1

[0458] The fiber reinforced composition (C) was obtained by melt blending the reactor-heterophasic polypropylene composition (HECO1 ) with glass fibers (GF), adhesion promoter (AP) and additives (AD) in a co-rotating twin-screw extruder. The composition and properties of the inventive examples and comparative examples are summarized in Table 3.

[0459] Table 3: Composition and properties of the inventive examples and comparative examples

[0460] IE1 CE1 CE2 HECO1 [wt%] 77.1 98.6 HECO1a [wt%] 49.1 hP [wt%] 28.0 GF [wt%] 20.0 20.0 AP [wt%] 1.5 1.5 AD1 [wt%] 1.4 1.4 1.4 MFR [g / 10 min] 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 pg / g 26 143 32 Fog pg / g 92 479 104

[0461] HECO1 a is a heterophasic propylene copolymer EF015AE commercially available from Borealis AG, produced with a Ziegler-Natta catalyst, 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.

[0462] hP is a propylene homopolymer HJ120UB commercially available from Borealis AG, produced with a Ziegler-Natta catalyst, having a melt flow rate MFR2 (230 °C) of 75 g / 10 min, a density of 905 kg / m3and a glass transition temperature Tg of +2 °C. 3

[0463] GF is a product ECS 03T-480H of Nippon Electric Glass Co., Ltd., having a filament diameter of 10.5 pm and a strand length of 3 mm.

[0464] AP is an adhesion promoter SCONA TPPP 8112GA of Scona, which is a polypropylene functionalized with maleic anhydride, and having a maleic anhydride content of 1.4 wt.-% and a MFR (190 °C, 2.16 kg) of higher than 80 g / 10 min.

[0465] ​AD1 is a masterbatch consisting of 14.0 wt% tris(2,4-di-tert-butylphenyl) phosphite (HPL Additives' Kinox-68-G), 14.0 wt% pentaerythritol tetrakis(3-(3',5'-di-tert-butyl-4- hydroxyphenyl)propionate (BASF's Irganox 1010FF), 36.0 wt% carbon black of Borealis (50 wt% masterbatch) and 36.0 wt% propylene homopolymer HC001A of Borealis having a density of 905 kg / m 3 , a MFR (230°C, 2.16 kg) of 3.2 g / 10 min.

[0466] 4. Preparation of the compounded heterophasic polypropylene composition (HECO2)

[0467] Preparation of the fiber reinforced composition (C) with HECO2

[0468] A propylene copolymer (cPP) is melt blended with an elastomeric ethylene copolymer (E), glass fibers (GF), an adhesion promoter (AP), optionally a low density polyethylene (LDPE) and additives (AD) in a co-rotating twin-screw extruder. The composition and properties of the inventive examples and comparative examples are summarized in Table 4.

[0469] Table 4: Composition of the inventive examples and comparative examples

[0470] IE2 IE3 CE3 CE4 cPP [wt%] 47 47 cPPa [wt%] 47 cPPb [wt%] 78.45 E [wt%] 30 15 30 LDPE [wt%] 15 GF [wt%] 20 20 20 20 AP [wt%] 1.5 1.5 1.5 1.0 AD2 [wt%] 1.5 1.5 1.5 AD3 [wt%] 0.55 MFR [g / 10 min] 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 pg / g 35 42 n.d. 28 Fog pg / g 103 106 n.d. 74

[0471] cPPa is a commercially available propylene ethylene random copolymer RD208CF of 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) of 8.0 g / 10 min determined according to ISO 1133, a melting temperature Tm of 140°C.

[0472] 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) of 4.0 g / 10 min determined according to ISO 1133.

[0473] E is a commercially available copolymer of ethylene and 1-octene Queo 8201 of Borealis AG having a melt flow rate (190°C, 2.16 kg) of 1.1 g / 10 min determined according to ISO 1133, a melting temperature Tm of 72°C, a glass transition temperature Tg of -52°C, a density of 882 kg / m 3 and an ethylene content of 75.5 wt%.

[0474] LDPE is a commercially available copolymer of ethylene and vinyl acetate OE5328 by Borealis AG having a melt flow rate of 3.0 g / 10 min (190 °C, 2.16 kg) determined according to ISO 1133, a density of 950 kg / m 3 and a vinyl acetate content of 28.0 wt.-%.

[0475] AD2 is a masterbatch consisting of 20.0 wt.-% erucamide (Finawax-E by Fine Organics), 6.6 wt.-% tris(2,4-di-tert-butylphenyl) phosphite (Irgafox 168 by BASF), 6.6 wt.-% pentaerythritol tetrakis(3-(3',5'-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox 1010 FF by BASF), 33.3 wt.-% carbon black by Borealis (50 wt.-% masterbatch) and 33.3 wt.-% propylene homopolymer HC001 A by Borealis having a density of 905 kg / m 3 and a MFR (230 °C, 2.16 kg) of 3.2 g / 10 min.

[0476] AD3 is a masterbatch consisting of 18.18 wt.-% tris(2,4-di-tert-butylphenyl) phosphite (Irgafox 168 by BASF), 36.36 wt.-% pentaerythritol tetrakis(3-(3',5'-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox 1010 FF by BASF) and 45.45 wt.-% distearyl thiodipropionate (Irganox PS-802 FL by BASF).

Claims

1. A fiber reinforced composition (C) comprising, based on the total weight of the fiber reinforced composition (C) a) 55.0 to 95.0 wt.-% of a heterophasic polypropylene composition (HECO), the heterophasic polypropylene composition (HECO) comprising i) a matrix which is a propylene homopolymer (hPP) having an amount of 1,2 erythro regio defects of at least 0.4 mol-%, and ii) an elastomeric ethylene copolymer (E) dispersed in the matrix, b) 5.0 to 45.0 wt.-% of fibers (F), and c) optionally 0.1 to 5.0 wt.-% of an adhesion promoter (AP), wherein the fiber reinforced composition (C) has a melt flow rate MFR2 determined according to ISO 1133 at 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, based on the total weight of the fiber reinforced composition (C) a) 55.0 to 94.9 wt.-% of the heterophasic polypropylene composition (HECO), b) 5.0 to 45.0 wt.-% of the fibers (F), and c) optionally 0.1 to 5.0 wt.-% of the adhesion promoter (AP).

3. The fiber reinforced composition (C) according to claim 1 or 2, wherein the heterophasic polypropylene composition (HECO) comprises, based on the total weight of the heterophasic polypropylene composition (HECO) i) 60.0 to 95.0 wt.-% of the matrix which is the propylene homopolymer (hPP), and ii) 5.0 to 40.0 wt.-% of the 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 15.0 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 heterophasic polypropylene composition (HECO) has a melting temperature Tm determined according to differential scanning calorimetry (DSC) in the range of 130 to 165 °C.

6. The fiber reinforced composition (C) according to claim 1 or 2, wherein the heterophasic polypropylene composition (HECO) has a soluble fraction (SF) determined according to CRYSTEX QC a intrinsic viscosity (IV) measured according to ISO 1628 / 1 in decalin at 135 °C in the range of 1.8 to 3.0 dl / g.

7. The fiber reinforced composition (C) according to claim 1 or 2, wherein the fibers (F) are glass fibers (GF).

8. The fiber reinforced composition (C) according to claim 7, wherein the glass fibers (GF) are short glass fibers (SGF) having i) an average length of 2.0 to 10.0 mm, and / or ii) an average diameter of 5 to 20 pm.

9. 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 homo- or copolymer grafted with maleic anhydride, the polar modified polypropylene (PM-PP) having a melt flow rate MFR determined according to ISO 1133 at 230 °C under a load of 2.16 kg of at least 20.0 g / 10 min to 400 g / 10 min.

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

11. The fiber reinforced composition (C) according to claim 10, 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.

12. The fiber reinforced composition (C) according to claim 10, wherein the heterophasic polypropylene composition (HECO) has a comonomer content in the range of 2.2 to 8.7 mol%.

13. The fiber reinforced composition (C) according to claim 10, wherein the heterophasic polypropylene composition (HECO) has a melt flow rate MFR2 determined according to ISO 1133 at 230 °C under a load of 2.16 kg in the range of 20.0 to 100 g / 10 min.

14. The fiber reinforced composition (C) according to claim 10, wherein the heterophasic polypropylene composition (HECO) has 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).

15. The fiber reinforced composition (C) according to claim 10, wherein the heterophasic polypropylene composition (HECO) has an ethylene content of the xylene cold soluble (XCS) fraction in the range of 20.9 to 44.7 mol%.

16. The fiber reinforced composition (C) according to claim 10, wherein the heterophasic polypropylene composition (HECO) has 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).

17. The fiber reinforced composition (C) according to claim 10, wherein the heterophasic polypropylene composition (HECO) has an ethylene content of the soluble fraction (SF) determined according to CRYSTEX QC in the range of 20.9 to 44.7 mol%.

18. The fiber reinforced composition (C) according to claim 10, wherein the fiber reinforced composition (C) has a tensile modulus determined according to ISO 527-1 A in the range of 3000 to 6000 MPa.

19. The fiber reinforced composition (C) according to claim 10, wherein the fiber reinforced composition (C) has an elongation at break determined according to ISO 527-2 of more than 3.0 %.

20. 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) homo- or copolymer having a density determined according to ISO 1183-187 of more than 900 kg / m 3 and comprising ethylene and optionally ethylene vinyl acetate.

21. The fiber reinforced composition (C) according to claim 1 or 2, wherein the propylene homopolymer (hPP) is obtained in the presence of a solid catalyst system (SCS) comprising a metallocene complex.

22. The fiber reinforced composition (C) according to claim 21, wherein the metallocene complex has the formula (I) wherein each X is independently a sigma-donor ligand, Formula (I) 23. An article comprising the fiber reinforced composition (C) according to any one of claims 1 to 22. 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-C10hydrocarbon group optionally containing one or more heteroatoms from groups 14-16 of the periodic table or fluorine atoms, 20 - a hydrocarbon group, or optionally two R' groups together can form a ring, each R 1 independently the same 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 groups, wherein Y is C 1-10 - hydrocarbyl, and optionally two adjacent R 1 groups can be part of the ring comprising the phenyl carbon to which they are bonded, each R 2 independently the same or can be different and is CH2-R 8 group, wherein R 8 is H or linear or branched C 1-6 -alkyl, C 3-8 -cycloalkyl, C 6-10 -aryl, R 3 linear or branched C1-C6-alkyl, C 7-20 - aralkyl, C 7-20 - alkylaryl or C6-C 20 - aryl, R 4 is a C(R 9 )3group, wherein R 9 is a linear or branched C1-C6-alkyl group, R 5 is hydrogen or an aliphatic C1-C20 hydrocarbon group optionally containing one or more heteroatoms from groups 14 to 16 of the periodic table; 20 - a hydrocarbon group; R 6 is hydrogen or an aliphatic C1-C20 hydrocarbon group 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 are capable of forming, together with the carbon atom to which they are attached, a 5-membered saturated carbocyclic ring, which is optionally substituted with n groups R 10 , n being from 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 is independently the same or can be different and is hydrogen, linear or branched C1-C6-alkyl, C 11 independently the same or can be different and is hydrogen, linear or branched C1-C6-alkyl, C 7-20 - aralkyl, C 7-20 - alkaryl or C 6-20 - aryl or OY group, wherein Y is C 1-10 - hydrocarbyl. ​

Images