Fiber Reinforced Polypropylene Composition

Abstract

The present invention is directed to a fiber reinforced composition (C) comprising a heterophasic polypropylene composition (HECO), a fiber (F) and an adhesion promoter (AP), and to an article comprising this fiber reinforced composition (C).

Description

Technical Field

[0001] The present invention is directed to a fiber-reinforced composition (C) comprising a heterophasic polypropylene composition (HECO), a fiber (F) and an adhesion promoter (AP), and an article comprising this fiber-reinforced composition (C).

Background Art

[0002] Fiber-reinforced materials are widely used in various applications, especially in engineering fields where higher rigidity 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. Polypropylene can meet most of the target properties. Polypropylene prepared in the presence of a metallocene catalyst is a promising candidate due to additional advantages such as a controlled molecular weight distribution, good comonomer incorporation and low emissions. However, due to the nature of the compound, in the case of a high filling rate, the tensile strength and elongation at break are often impaired.

[0003] Therefore, in the art, there is a need for a fiber-reinforced polypropylene composition that features excellent thermal deflection properties and low emissions, while maintaining high levels of tensile strength and elongation at break.

Summary of the Invention

Problems to be Solved by the Invention

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

Means for Solving the Problems

[0005] Accordingly, the present invention provides a fiber-reinforced composition (C) which, based on the total weight of this fiber-reinforced composition (C) a) 55.0 to 95.0% by weight of a heterophasic polypropylene composition (HECO), wherein i) A matrix of a homopolymer or copolymer of propylene (PP) having at least 0.4 mol% of 1,2 erythro positional defects and a comonomer content of 8.5 mol% or less, and ii) An elastomeric ethylene copolymer (E) dispersed in the matrix to form a heterophasic polypropylene composition (HECO), and b) 5.0 to 45.0 wt% of fibers (F), and c) Optionally 0.1 to 5.0 wt% of an adhesion promoter (AP) is included, The fiber-reinforced composition (C) is directed to a fiber-reinforced composition (C) having 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.

[0006] A preferred embodiment of the present invention is a fiber-reinforced composition (C), based on the total weight of the fiber-reinforced composition (C), a) 55.0 to 95.0 wt% of a heterophasic polypropylene composition (HECO), which i) A matrix of a propylene copolymer (cPP) having at least 0.4 mol% of 1,2 erythro positional defects and a comonomer content of 8.5 mol% or less, and ii) An elastomeric ethylene copolymer (E) dispersed in the matrix to form a heterophasic polypropylene composition (HECO), and b) 5.0 to 45.0 wt% of fibers (F), and c) Optionally 0.1 to 5.0 wt% of an adhesion promoter (AP) is included, The fiber-reinforced composition (C) provides a fiber-reinforced composition (C) having 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.

[0007] According to one embodiment of the present invention, the heterophasic polypropylene composition (HECO) is based on the total weight of the heterophasic copolymer (HECO) i) The matrix is a homopolymer or copolymer of propylene (PP) of 60.0 to 95.0% by weight, and ii) an elastomeric ethylene copolymer (E) of 5.0 to 40.0% by weight is included.

[0008] According to a further embodiment of the present invention, the elastomeric ethylene copolymer (E) has an ethylene content in the range of 15.0 to 85.0% by weight based on the total weight of the elastomeric ethylene copolymer (E).

[0009] According to another embodiment of the present invention, the heterophasic polypropylene composition (HECO) has a melting temperature Tm determined according to differential scanning calorimetry (DSC) in the range of 130 to 165°C.

[0010] According to one embodiment of the present invention, the heterophasic polypropylene composition (HECO) has an intrinsic viscosity (IV) measured according to ISO1628 / 1 (at 135°C in decalin) of the soluble part (soluble fraction, SF) determined according to CRYSTEX QC in the range of 1.8 to 3.0 dl / g.

[0011] According to a further embodiment of the present invention, the fiber (F) is a glass fiber (GF), preferably i) an average length of 2.0 to 10.0 mm, and / or ii) an average diameter of 5 to 20 μm is a short glass fiber (SGF).

[0012] According to another embodiment of the present invention, the adhesion promoter (AP) is a polar modified polypropylene (PM-PP) which is a homopolymer or copolymer of propylene grafted with maleic anhydride having a melt flow rate MFR2 (230°C, 2.16 kg) determined according to ISO1133 of at least 20.0 g / 10 min.

[0013] According to the first embodiment of the present invention, the homopolymer or copolymer of propylene (PP) is a propylene homopolymer (hPP), and the elastomeric ethylene polymer (E) is a copolymer of ethylene and propylene.

[0014] According to the first embodiment of the present invention, the propylene homopolymer (hPP) has a melting temperature Tm determined according to differential scanning calorimetry (DSC) in the range of 140 to 160 °C.

[0015] According to the first embodiment of the present invention, the heterophasic polypropylene composition (HECO) has a comonomer content in the range of 2.2 to 8.7 mol%.

[0016] The heterophasic polypropylene composition (HECO) according to the first embodiment of the present invention i) a cold xylene soluble part (XCS) content determined at 25 °C according to ISO 16152 in the range of 5.0 to 35.0% by weight based on the total weight of the heterophasic polypropylene composition (HECO), and / or ii) an ethylene content of the cold xylene soluble part (XCS) fraction in the range of 20.9 to 44.7 mol%, and / or ii) a soluble part (SF) determined according to CRYSTEX QC in the range of 5.0 to 35.0% by weight based on the total weight of the heterophasic polypropylene composition (HECO), and / or iv) an ethylene content of the soluble part (SF) determined according to CRYSTEX QC in the range of 20.9 to 44.7 mol% is particularly preferably to have.

[0017] According to the first embodiment of the present invention, the heterophasic polypropylene composition (HECO) has a melt flow rate MFR2 (230 °C, 2.16 kg) determined according to ISO 1133 in the range of 20.0 to 100 g / 10 min.

[0018] According to the first embodiment of the present invention, the fiber-reinforced composition (C) has a tensile elastic modulus determined according to ISO 527-1A in the range of 3000 to 6000 MPa, and / or an elongation at break determined according to ISO 527-2 of more than 3.0%.

[0019] According to the second embodiment of the present invention, the homopolymer or copolymer of propylene (PP) is preferably a propylene copolymer (cPP) copolymer of propylene and ethylene having an ethylene content in the range of 2.2 to 8.5 mol%, and the elastomeric ethylene copolymer (E) preferably has an ethylene content in the range of 55.0 to 85.0 wt% based on the total weight of the elastomeric ethylene copolymer (E), and is a copolymer of ethylene and a C4-C 12 α-olefin, preferably 1-octene.

[0020] According to the second embodiment of the present invention, the propylene copolymer (cPP) has a melt flow rate MFR2 (230 ° C, 2.16 kg) determined according to ISO 1133 in the range of 5.0 to 20.0 g / 10 min, and / or the elastomeric ethylene copolymer (E) has a melt flow rate MFR (190 ° C, 2.16 kg) determined according to ISO 1133 in the range of 0.8 to 20.0 g / 10 min, and / or a density determined according to ISO 1183-187 in the range of 860 to 890 kg / m 3 of.

[0021] According to the second embodiment of the present invention, the fiber-reinforced composition (C) has a melt flow rate MFR2 (230 ° C, 2.16 kg) determined according to ISO 1133 in the range of 1.0 to 10.0 g / 10 min.

[0022] According to the second embodiment of the present invention, the fiber-reinforced composition (C) has a tensile elastic 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%.

[0023] According to one embodiment of the present invention, the fiber-reinforced composition (C) has a density of 20.0% by weight or less, determined according to ISO 1183-187 of over 900 kg / m 3 and further comprises a low-density polyethylene (LDPE) homopolymer or copolymer containing ethylene and optionally vinyl acetate.

[0024] According to one embodiment of the present invention, the homopolymer or copolymer of propylene (PP) is obtained in the presence of a solid catalyst system (SCS) containing a metallocene compound.

[0025] It is particularly preferred that this metallocene compound has the formula (I), [Chemical formula] In the above formula (I), each X is independently a σ-donor ligand, L is a divalent bridging group (bridge) selected from -R’2C-, -R’2C-CR’2-, -R’2Si-, -R’2Si-SiR’2-, -R’2Ge-, and each R’ is independently a hydrogen atom, or a C1-C 20 hydrocarbyl group which may contain one or more heteroatoms or fluorine atoms from groups 14 to 16 of the periodic table, or optionally, two R’ groups can combine to form a ring, each R 1 can be independently the same or different and is hydrogen, a linear or branched C1-C6-alkyl group, C 7~20 -arylalkyl, C 7~20 -alkylaryl group or C 6~20 -aryl group or OY group, where Y is a C 1~10 -hydrocarbyl group, and optionally, two adjacent R 1 groups can be part of a ring containing the phenyl carbon to which they are attached, each R 2 can be independently the same or different and is a CH2-R 8 group, where R 8 is H or a linear or branched C 1~6- an alkyl group, C 3~8 - a cycloalkyl group, C 6~10 - an aryl group, and R 3 is a linear or branched C1-C6-alkyl group, C 7~20 - arylalkyl, C 7~20 - alkylaryl group or C6-C 20 - aryl group, and R 4 is a C(R 9 )3 group, and R 9 is a linear or branched C1-C6-alkyl group, R 5 is hydrogen, or an aliphatic C1-C 20 -hydrocarbyl group which may contain one or more heteroatoms from groups 14-16 of the periodic table, R 6 is hydrogen, or an aliphatic C1-C 20 -hydrocarbyl group which may contain one or more heteroatoms from groups 14-16 of the periodic table, or R 5 and R 6 together can form a 5-membered saturated carbon ring which may be substituted by n groups R 10 , where n is 0-4, each R 10 is the same or different and is a C1-C 20 -hydrocarbyl group, or a C1-C 20 -hydrocarbyl group which may contain one or more heteroatoms belonging to groups 14-16 of the periodic table, R 7 is H, or a linear or branched C1-C6-alkyl group, or an aryl or heteroaryl group having 6-20 carbon atoms which may be substituted by 1-3 groups R 11 , each R 11 is independently the same or different and can be hydrogen, a linear or branched C1-C6-alkyl group, C 7~20 -arylalkyl, C 7~20 -alkylaryl group or C 6~20- an aryl group or an OY group, where Y is C 1~10 - a hydrocarbyl group.

[0026] The present invention is further directed to an article comprising the above fiber-reinforced composition (C).

Brief Description of the Drawings

[0027]

Figure 1

[0028] Hereinafter, the fiber-reinforced composition (C) will be described in more detail.

[0029] Fiber-reinforced composition (C) The present invention is directed to a fiber-reinforced composition (C) comprising a heterophasic polypropylene composition (HECO), a fiber (F), and an adhesion promoter (AP).

[0030] In particular, the fiber-reinforced composition (C) is, based on the total weight of the fiber-reinforced composition (C), a) 55.0 to 95.0% by weight, preferably 55.0 to 90.0% by weight, more preferably 60.0 to 85.0% by weight, even more preferably 66.0 to 82.0% by weight, for example 72.0 to 79.0% by weight of the heterophasic polypropylene composition (HECO), and b) 5.0 to 45.0% by weight, preferably 10.0 to 40.0% by weight, more preferably 12.0 to 35.0% by weight, even more preferably 14.0 to 29% by weight, for example 18.0 to 23.0% by weight of the fiber (F) and.

[0031] According to a preferred embodiment of the present invention, the fiber-reinforced composition (C) further comprises an adhesion promoter (AP).

[0032] Therefore, when the fiber-reinforced composition (C) is based on the total weight of the fiber-reinforced composition (C), a) 55.0 to 94.9% by weight, preferably 55.0 to 90.0% by weight, more preferably 60.0 to 85.0% by weight, even more preferably 66.0 to 82.0% by weight, for example 72.0 to 79.0% by weight of a heterophasic polypropylene composition (HECO), and b) 5.0 to 45.0% by weight, preferably 10.0 to 40.0% by weight, more preferably 12.0 to 35.0% by weight, even more preferably 14.0 to 29% by weight, for example 18.0 to 23.0% by weight of fibers (F), and c) 0.1 to 5.0% by weight, preferably 0.3 to 4.8% by weight, more preferably 0.5 to 4.0% by weight, even more preferably 0.8 to 3.0% by weight, for example 1.0 to 2.0% by weight of an adhesion promoter (AP) is preferably included.

[0033] The fiber-reinforced composition (C) according to the present invention may contain an additive (AD).

[0034] Therefore, the fiber-reinforced composition (C) according to the present invention, based on the total weight of the fiber-reinforced composition (C), a) 55.0 to 94.9% by weight, preferably 55.0 to 90.0% by weight, more preferably 60.0 to 85.0% by weight, even more preferably 66.0 to 82.0% by weight, for example 72.0 to 79.0% by weight of a heterophasic polypropylene composition (HECO) and b) 5.0 to 45.0% by weight, preferably 10.0 to 40.0% by weight, more preferably 12.0 to 35.0% by weight, even more preferably 14.0 to 29% by weight, for example 18.0 to 23.0% by weight of fibers (F), and c) 0.1 to 5.0% by weight, preferably 0.3 to 4.8% by weight, more preferably 0.5 to 4.0% by weight, even more preferably 0.8 to 3.0% by weight, for example 1.0 to 2.0% by weight of an adhesion promoter (AP), and d) 0.01 to 2.5% by weight of an additive (AD) is included, and more preferably consists of these. The additive (AD) is described in more detail below.

[0035] Therefore, the fiber-reinforced composition (C) according to the present invention, based on the total weight of the fiber-reinforced composition (C), a) 55.0 to 94.9% by weight (for example, 55.0 to 94.8% by weight), preferably 55.0 to 90.0% by weight, more preferably 60.0 to 85.0% by weight, even more preferably 66.0 to 82.0% by weight, for example 72.0 to 79.0% by weight of a heterophasic polypropylene composition (HECO), and b) 5.0 to 45.0% by weight, preferably 10.0 to 40.0% by weight, more preferably 12.0 to 35.0% by weight, even more preferably 14.0 to 29% by weight, for example 18.0 to 23.0% by weight of fibers (F), and c) 0.1 to 5.0% by weight, preferably 0.3 to 4.8% by weight, more preferably 0.5 to 4.0% by weight, even more preferably 0.8 to 3.0% by weight, for example 1.0 to 2.0% by weight of an adhesion promoter (AP), and d) 0.01 to 2.5% by weight of an additive (AD) and preferably consists of these, and components a) to d) are preferably selected so that the total is 100% by weight.

[0036] Furthermore, the fiber-reinforced composition (C) according to the present invention may further contain low-density polyethylene (LDPE).

[0037] Therefore, according to another embodiment of the present invention, the fiber-reinforced composition (C), based on the total weight of the fiber-reinforced composition (C), a) 55.0 to 94.9% by weight, preferably 55.0 to 90.0% by weight, more preferably 60.0 to 85.0% by weight, even more preferably 66.0 to 82.0% by weight, for example 72.0 to 79.0% by weight of a heterophasic polypropylene composition (HECO), and c) 5.0 to 25.0% by weight, preferably 10.0 to 22.0% by weight, more preferably 12.0 to 35.0% by weight, even more preferably 14.0 to 29% by weight, for example 18.0 to 23.0% by weight of fibers (F), and d) 0.1 to 5.0% by weight, preferably 0.3 to 4.8% by weight, more preferably 0.5 to 4.0% by weight, even more preferably 0.8 to 3.0% by weight, for example 1.0 to 2.0% by weight of an adhesion promoter (AP), and e) 0.0 to 20.0% by weight, preferably 5.0 to 18.0% by weight, more preferably 12.0 to 17.0% by weight, even more preferably 13.0 to 16.0% by weight of low density polyethylene (LDPE), and f) 0.01 to 2.5% by weight of an additive (AD) and preferably consists of these.

[0038] According to another embodiment of the present invention, the fiber-reinforced composition (C) is based on the total weight of the fiber-reinforced composition (C), a) 55.0 to 94.9% by weight (for example 55.0 to 94.8% by weight), preferably 55.0 to 90.0% by weight, more preferably 60.0 to 85.0% by weight, even more preferably 66.0 to 82.0% by weight, for example 72.0 to 79.0% by weight of a heterophasic polypropylene composition (HECO), and c) 5.0 to 25.0% by weight, preferably 10.0 to 22.0% by weight, more preferably 12.0 to 35.0% by weight, even more preferably 14.0 to 29% by weight, for example 18.0 to 23.0% by weight of fibers (F), and d) 0.1 to 5.0% by weight, preferably 0.3 to 4.8% by weight, more preferably 0.5 to 4.0% by weight, even more preferably 0.8 to 3.0% by weight, for example 1.0 to 2.0% by weight of an adhesion promoter (AP), and e) 0.0 to 20.0% by weight, preferably 5.0 to 18.0% by weight, more preferably 12.0 to 17.0% by weight, even more preferably 13.0 to 16.0% by weight of low density polyethylene (LDPE), and f) 0.01 to 2.5% by weight of an additive (AD) and preferably consists of these, and components a) to d) are selected so that the total is 100% by weight.

[0039] Preferably, the fiber-reinforced composition (C) of the present invention does not contain (a) a heterophasic polypropylene composition (HECO), an adhesion promoter (AP), and an optional additional polymer (s) different from low-density polyethylene (LDPE) in an amount exceeding 5.0% by weight, preferably exceeding 3.0% by weight, more preferably exceeding 2.5% by weight, based on the total weight of the fiber-reinforced composition (C). One additional polymer that may be present in such small amounts is polyethylene, which is a reaction by-product obtained by the preparation of the heterophasic polypropylene composition (HECO). Thus, it is specifically understood that the fiber-reinforced composition (C) contains only the heterophasic polypropylene composition (HECO), the adhesion promoter (A), the optional low-density polyethylene (LDPE), and optionally, polyethylene in the amounts mentioned in this paragraph, as polymer compounds.

[0040] 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, even more preferably in the range of 2.0 to 35.0 g / 10 min, for example, in the range of 2.5 to 29.0 g / 10 min.

[0041] According to one preferred embodiment, the fiber-reinforced composition (C) has a melt flow rate MFR2 (230 °C, 2.16 kg) determined according to ISO 1133 in the range of 1.0 to 10.0 g / 10 min (for example, 2.0 to 10.0 g / 10 min, or 2.5 to 10.0 g / 10 min). A melt flow rate in the range of 1.0 to 10.0 g / 10 min (and sub-ranges) is particularly preferred in combination with the "second embodiment of the present invention" defined herein.

[0042] With respect to mechanical properties, the fiber-reinforced composition (C) preferably has a tensile modulus determined according to ISO 527-1A of at least 2000 MPa, more preferably at least 2200 MPa, even more preferably at least 2300 MPa, for example at least 2400 MPa, and / or a tensile strength determined according to ISO 527-2 of at least 40 MPa, more preferably at least 42 MPa, even more preferably at least 45 MPa, for example at least 50 MPa.

[0043] In addition to or instead of the previous paragraph, the fiber-reinforced composition preferably has an elongation at break determined at 23 °C according to ISO 527-2 of at least 3.0%, more preferably at least 3.2%, even more preferably at least 3.4%.

[0044] The fiber-reinforced composition (C) is preferably obtained by melt-blending (melt-mixing) a heterophasic polypropylene composition (HECO), fibers (F), optionally an adhesion promoter (AP), optionally additives (AD), and optionally low-density polyethylene (LDPE).

[0045] Hereinafter, the heterophasic polypropylene composition (HECO), fibers (F), adhesion promoter (AP) and low-density polyethylene (LDPE) will be described in more detail.

[0046] Heterophasic polypropylene composition (HECO) The fiber-reinforced composition (C) of the present invention contains a heterophasic polypropylene composition (HECO).

[0047] The heterophasic polypropylene composition (HECO) according to the present invention comprises a matrix which is a homopolymer or copolymer (PP) of propylene, and an elastomeric ethylene copolymer (E) dispersed in the matrix. Thus, the matrix contains a (finely) dispersed admixture which is not part of the matrix, and this admixture contains the elastomeric copolymer (E). The term "admixture" indicates that the matrix and this admixture form different phases within the heterophasic polypropylene composition (HECO). The presence of the second phase or so-called admixture can be seen, for example, by high-resolution microscopy, such as electron microscopy or atomic force microscopy, or by dynamic mechanical thermal analysis (DMTA). Specifically, in DMTA, the presence of a multiphase structure can be identified by the presence of at least two distinguishable glass transition temperatures.

[0048] Thus, the heterophasic polypropylene composition (HECO) according to the present invention preferably (a) a (semi)crystalline homopolymer or copolymer (PP) of propylene as the matrix, and (b) an elastomeric ethylene copolymer (E) is included.

[0049] In particular, when the heterophasic polypropylene composition (HECO) is based on the total weight of the heterophasic polypropylene composition (HECO), (a) 60.0 to 95.0% by weight, more preferably 61.0 to 92.0% by weight, of a matrix which is a homopolymer or copolymer (PP) of propylene, and (b) 5.0 to 40.0% by weight, more preferably 8.0 to 39.0% by weight, of an elastomeric ethylene copolymer (E) is included, and more preferably it is preferably composed of these.

[0050] The heterophasic polypropylene composition (HECO) according to the present invention preferably has at least two distinguishable glass transition temperatures Tg(1) and Tg(2). In particular, the first glass transition temperature Tg(1) is preferably less than -15°C, more preferably less than -25°C. In addition, the second glass transition temperature Tg(2) is preferably at least -5°C, more preferably at least -4°C.

[0051] 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, even more preferably in the range of 7.0 to 87.0 g / 10 min, for example in the range of 8.0 to 80.0 g / 10 min.

[0052] Furthermore, it is preferable that the heterophasic polypropylene composition (HECO) has an intrinsic viscosity (IV) measured according to ISO 1628 / 1 (at 135°C in decalin) of the soluble fraction (SF) determined according to CRYSTEX QC in the range of 1.8 to 3.0 dl / g, more preferably in the range of 2.5 to 3.0 dl / g.

[0053] Preferably, it is desirable that the heterophasic polypropylene composition (HECO) is thermomechanically stable. Therefore, it is understood 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, even more preferably in the range of 135 to 158°C, for example in the range of 139 to 157°C.

[0054] The homopolymer or copolymer of propylene (PP) has 1,2-erythro regiodefects in an amount of at least 0.4 mol% (preferably in the range of 0.4 to 1.2 mol%). Without being bound by theory, the large amount of misinsertion of propylene in the polymer chain indicates that the homopolymer or copolymer of propylene (PP) is produced in the presence of a single-site catalyst, preferably a metallocene catalyst. For example, a homopolymer or copolymer of propylene produced in the presence of a Ziegler-Natta catalyst can have an amount of 1,2-erythro regiodefects far below 0.4 mol% and, in many cases, is known in the art to be essentially free of 1,2-erythro regiodefects.

[0055] The heterophasic polypropylene composition (HECO) contains a comonomer in addition to propylene. Preferably, the heterophasic polypropylene composition (HECO) contains ethylene and / or C4-C 12 α-olefin in addition to propylene.

[0056] Therefore, the term "copolymer of propylene" according to the present invention refers to (a) propylene, and (b) ethylene and / or C4-C 12 α-olefin and is preferably understood as a polypropylene containing units derivable from these and preferably consisting of these.

[0057] Furthermore, the term "ethylene copolymer" according to the present invention refers to (a) ethylene and (b) C3-C 12 α-olefin and is preferably understood as a polyethylene containing units derivable from these and preferably consisting of these.

[0058] Therefore, the homopolymer or copolymer of propylene (PP), i.e., the matrix of the heterophasic polypropylene composition (HECO), is a monomer copolymerizable with propylene, such as ethylene and / or C4-C12 It can contain comonomers such as α-olefins, especially ethylene and / or C4-C8 α-olefins, for example 1-butene and / or 1-hexene. The elastomeric ethylene copolymer (E) is a monomer copolymerizable with ethylene, for example C3-C 12 It can contain comonomers such as α-olefins, especially propylene, 1-butene, 1-hexene and / or 1-octene. More specifically, the heterophasic polypropylene composition (HECO) of the present invention contains units derivable from 1-butene, 1-hexene and / or 1-octene in addition to propylene and ethylene.

[0059] Therefore, the homopolymer or copolymer (PP) of propylene according to the present invention can be a propylene homopolymer or a propylene copolymer.

[0060] In particular, the homopolymer or copolymer (PP) of propylene preferably has a comonomer content, preferably an ethylene content, in the range of 8.5 mol% or less, more preferably in the range of 0.0 - 8.3 mol%, even more preferably in the range of 0.0 - 8.0 mol%, for example in the range of 0.0 - 6.0 mol%.

[0061] The elastomeric ethylene copolymer (E) according to the present invention is a monomer copolymerizable with ethylene, for example C3-C 12 It contains comonomers such as α-olefins, especially 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 - 85.0 wt%, more preferably in the range of 18.0 - 82.0 wt%, even more preferably in the range of 19.0 - 79.0 wt%, for example in the range of 20.0 - 76.0 wt% based on the total weight of the elastomeric ethylene copolymer (E).

[0062] According to the first embodiment of the present invention, the homopolymer or copolymer (PP) of propylene is preferably a propylene homopolymer (hPP).

[0063] As used herein, the expression "propylene homopolymer" relates to polypropylene consisting substantially, i.e., at least 99.0 wt%, more preferably at least 99.5 wt%, even more preferably at least 99.8 wt%, for example at least 99.9 wt%, of propylene units. In another embodiment, only propylene units are detectable, i.e., only propylene is polymerized.

[0064] Thus, according to a first embodiment of the present invention, the heterophasic polypropylene composition (HECO) is a) a matrix that is a propylene homopolymer (hPP), and b) an elastomeric ethylene copolymer (E) and includes.

[0065] The elastomeric ethylene copolymer (E) according to the first embodiment of the present invention includes a monomer copolymerizable with ethylene, such as a comonomer such as C3-C 12 α-olefin, particularly propylene, 1-butene, 1-hexene and / or 1-octene. According to the first embodiment of the present invention, it is particularly preferred that the elastomeric ethylene copolymer (E) is a copolymer of ethylene and propylene. In other words, the elastomeric ethylene copolymer (E) according to the first embodiment of the present invention includes only units derivable from ethylene and propylene.

[0066] Thus, the heterophasic polypropylene composition (HECO) according to the first embodiment of the present invention preferably includes only units derivable from ethylene and propylene.

[0067] Preferably, the heterophasic polypropylene composition (HECO) according to the first embodiment of the present invention has a comonomer content, preferably an ethylene content, in the range of 2.2 to 8.7 mol%, more preferably in the range of 2.7 to 5.8 mol%, even more preferably in the range of 2.9 to 4.4 mol%.

[0068] Furthermore, the heterophasic polypropylene composition (HECO) according to the first embodiment of the present invention preferably has a cold xylene soluble fraction (XCS) content determined at 25 °C in accordance with ISO 16152 in the range of 5.0 to 35.0% by weight, more preferably in the range of 7.0 to 20.0% by weight, even more preferably in the range of 9.0 to 15.0% by weight, for example in the range of 10.0 to 12.0% by weight, based on the total weight of the heterophasic polypropylene composition (HECO) according to the first embodiment of the present invention.

[0069] Additionally or alternatively, the cold xylene soluble fraction (XCS) of the heterophasic polypropylene composition (HECO) according to the first embodiment of the present invention preferably 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%, even more preferably in the range of 28.0 to 38.0 mol%, for example in the range of 30.0 to 34.0 mol%.

[0070] Preferably, the heterophasic polypropylene composition (HECO) according to the first embodiment of the present invention has an intrinsic viscosity (IV) measured in accordance with ISO 1628 / 1 (135 °C in decalin) of the cold xylene soluble fraction (XCS) in the range of 1.8 to 3.0 dl / g, more preferably in the range of 2.2 to 2.8 dl / g, even more preferably in the range of 2.3 to 2.7 dl / g.

[0071] In addition to or instead of the paragraphs above, it is understood that the heterophasic polypropylene composition (HECO) according to the first embodiment of the present invention preferably has a soluble fraction (SF) determined in accordance with CRYSTEX QC in the range of 5.0 to 35.0% by weight, more preferably in the range of 7.0 to 20.0% by weight, even more preferably in the range of 9.0 to 15.0% by weight, for example in the range of 10.0 to 12.0% by weight, based on the total weight of the heterophasic polypropylene composition (HECO) according to the first embodiment of the present invention.

[0072] 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 invention is preferably in the range of 20.9 to 44.7 mol%, more preferably in the range of 25.0 to 40.0 mol%, even more preferably in the range of 28.0 to 38.0 mol%, for example in the range of 30.0 to 34.0 mol%.

[0073] Preferably, the heterophasic polypropylene composition (HECO) according to the first embodiment of the present invention has an intrinsic viscosity (IV) measured according to ISO1628 / 1 (135 °C in decalin) of the soluble fraction (SF) determined according to CRYSTEX QC in the range of 1.8 to 3.0 dl / g, more preferably in the range of 2.2 to 2.8 dl / g, even more preferably in the range of 2.3 to 2.7 dl / g.

[0074] The heterophasic polypropylene composition (HECO) according to the first embodiment of the present invention preferably has a medium melt flow rate. Therefore, the heterophasic polypropylene composition (HECO) according to the first embodiment of the present invention preferably has a melt flow rate MFR2 (230 °C, 2.16 kg) determined according to ISO1133 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, even more preferably in the range of 56.0 to 90.0 g / 10 min, for example in the range of 70.0 to 80.0 g / 10 min.

[0075] Furthermore, the heterophasic polypropylene composition (HECO) according to the first embodiment of the present invention has a melting temperature Tm determined according to differential scanning calorimetry (DSC) in the range of 130 to 165 °C, more preferably in the range of 135 to 160 °C, even more preferably in the range of 145 to 159 °C, for example in the range of 152 to 157 °C.

[0076] Regarding the mechanical properties, the heterophasic polypropylene composition (HECO) according to the first embodiment of the present invention preferably 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, even more preferably in the range of 1000 to 1500 MPa, for example in the range of 1100 to 1300 MPa.

[0077] In addition to or instead of the previous paragraph, the heterophasic polypropylene composition (HECO) according to the first embodiment of the present invention has a notched Charpy impact strength determined at 23 °C according to ISO 179 / 1eA of at least 1.5 kJ / m 2 , more preferably at least 2.5 kJ / m 2 , even more preferably at least 3.0 kJ / m 2 , for example at least 3.5 kJ / m 2 , and / or a notched Charpy impact strength determined at -20 °C according to ISO 179 / 1eA of at least 0.5 kJ / m 2 , more preferably at least 0.8 kJ / m 2 , even more preferably at least 1.3 kJ / m 2 , for example at least 1.7 kJ / m 2 .

[0078] Furthermore, the fiber-reinforced composition (C) according to the first embodiment of the present invention preferably has a tensile modulus determined according to ISO 527-1A in the range of 3000 to 6000 MPa, more preferably in the range of 3500 to 5800 MPa, even more preferably in the range of 4200 to 5300 MPa, for example in the range of 4700 to 5000 MPa.

[0079] Additionally or alternatively, the fiber-reinforced composition (C) according to the first embodiment of the present invention preferably has an elongation at break determined according to ISO 527-2 of more than 3.0%, more preferably more than 3.2%, even more preferably more than 3.3%, for example more than 3.4%.

[0080] The heterophasic polypropylene composition (HECO) according to the first embodiment of the present invention can be further defined by its individual components, namely, the matrix which is a propylene homopolymer (hPP) and the elastomeric ethylene copolymer (E) which is a copolymer of ethylene and propylene.

[0081] The matrix which is 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, even more preferably in the range of 60.0 to 95.0 g / 10 min, for example in the range of 75.0 to 85.0 g / 10 min.

[0082] 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, even more preferably in the range of 145 to 158 °C, for example in the range of 147 to 157 °C.

[0083] The propylene homopolymer (hPP) has 1,2 erythro regiodefects in an amount of at least 0.4 mol%, which, as outlined above, indicates that this propylene homopolymer (PP) is produced in the presence of a single-site catalyst, preferably a metallocene catalyst.

[0084] As described in more detail below, the heterophasic polypropylene composition (HECO) according to the first embodiment of the present invention is preferably obtained in a sequential (continuous) process in the presence of a metallocene catalyst. Therefore, it is particularly preferred that the propylene homopolymer (hPP) and the elastomeric ethylene copolymer (E) are prepared in a sequential process in the presence of a metallocene catalyst.

[0085] Therefore, the elastomeric ethylene copolymer (E) according to the first embodiment of the present invention, which is a copolymer of ethylene and propylene, also preferably has 1,2 erythro positional defects in an amount of at least 0.4 mol% (preferably in the range of 0.4 to 1.2 mol%).

[0086] The heterophasic polypropylene composition (HECO) according to the first embodiment of the present invention preferably comprises i) a matrix of a propylene homopolymer (hPP) in an amount of 60.0 to 99.0% by weight, more preferably 75.0 to 98.0% by weight, even more preferably 80.0 to 95.0% by weight, for example 85.0 to 90.0% by weight, ii) an elastomeric ethylene copolymer (E) which is a copolymer of ethylene and propylene in an amount of 1.0 to 40.0% by weight, more preferably 2.0 to 25.0% by weight, even more preferably 5.0 to 20.0% by weight, for example 10.0 to 15.0% by weight and.

[0087] The heterophasic polypropylene composition (HECO) according to the first embodiment of the present invention can be prepared by blending both the propylene homopolymer (hPP) and the elastomeric ethylene copolymer (E), preferably by melt blending, or by producing the propylene homopolymer (hPP) and the elastomeric ethylene copolymer (E) in a sequential process, with the latter being preferred.

[0088] The process for preparing the heterophasic polypropylene composition (HECO) according to the first embodiment of the present invention is preferably a sequential polymerization process comprising at least two reactors connected in series, and this process (A) polymerizing propylene in a first reactor (R-1), preferably a loop reactor (LR), which is a slurry reactor (SR), to obtain a first fraction of the propylene homopolymer (hPP) defined in the present invention; (B) transferring the first fraction of the propylene homopolymer (hPP) from the first reactor (R-1) to a second reactor (R-2), which is a gas phase reactor (GPR-1); (C) Supplying propylene to the second reactor (R-2); (D) Polymerizing propylene in the second reactor (R-2) in the presence of a first fraction of propylene homopolymer (hPP) to obtain a second fraction of propylene homopolymer (hPP), wherein these first and second fractions are steps of forming the propylene homopolymer (hPP) of the present invention; (E) Transferring the propylene homopolymer (hPP) from the second reactor (R-2) to a third reactor (R-3) which is a gas-phase reactor (GPR-2); (F) Supplying propylene, and a comonomer selected from ethylene and C4-C 12 α-olefins, preferably ethylene, to the third reactor (R-3); (G) Polymerizing propylene, and a comonomer selected from ethylene and C4-C 12 α-olefins, preferably ethylene, in the presence of the propylene homopolymer (hPP) in the third reactor (R-3) to obtain the elastomeric ethylene copolymer (E) defined in the present invention, wherein the propylene homopolymer (hPP) and the elastomeric ethylene copolymer (E) are steps of forming the heterophasic polypropylene composition (HECO) defined in the present invention; comprising, further, In the first reactor (R-1), the second reactor (R-2) and the third reactor (R-3), the polymerization occurs in the presence of a solid catalyst system (SCS).

[0089] The solid catalyst system (SCS) is defined in more detail below.

[0090] The term "sequential polymerization process" means that the heterophasic polypropylene composition (HECO) according to the first embodiment of the present invention is produced in at least two reactors connected in series. More precisely, the term "sequential polymerization process" indicates in the present application that the polymer of the first reactor (R-1) is directly conveyed to the second reactor (R-2) together with the unreacted monomers. Therefore, a decisive aspect of the process is the preparation of the heterophasic polypropylene composition (HECO) in at least two different reactors, and the reaction materials of the first reactor (R-1) are directly conveyed to the second reactor (R-2). Therefore, the process includes at least the first reactor (R-1) and the second reactor (R-2). In one particular embodiment, the process consists of three polymerization reactors (R-1), (R-2) and (R-3). The term "polymerization reactor" shall indicate that the main polymerization takes place therein. Therefore, when the process consists of three polymerization reactors, this definition does not exclude the option that the whole process includes, for example, a prepolymerization (preliminary polymerization, prepolymerization) step in a prepolymerization reactor. The term "consists of (...)" is only a closing formulation considering the main polymerization reactor.

[0091] The first reactor (R-1) is a slurry reactor (SR) and can be any continuous or simply stirred batch tank reactor or loop reactor operating in slurry. According to the present invention, the slurry reactor (SR) is preferably a loop reactor (LR).

[0092] The second reactor (R-2), the third reactor (R-3) and any subsequent reactors are gas-phase reactors (GPR). Such gas-phase reactors (GPR) can be any mechanically mixed reactor or fluidized bed reactor. Preferably, the gas-phase reactor (GPR) includes a mechanically stirred fluidized bed reactor having a gas velocity of at least 0.2 m / s. Therefore, it is understood that the gas-phase reactor (GPR) is preferably a fluidized bed reactor equipped with a mechanical stirrer.

[0093] The conditions (temperature, pressure, reaction time, monomer feed) in each reactor depend on the desired product and are within the knowledge of a person skilled in the art. As already shown above, the first reactor (R-1) is a slurry reactor (SR), for example a loop reactor (LR), while the second reactor (R-2) and the third reactor (R-3) are gas phase reactors (GPR-1) and (GPR-2). Subsequent reactors, if present, are also gas phase reactors (GPR).

[0094] A preferred multi-stage process is a "loop-gas phase" process such as that developed by Borealis A / S, Denmark (known as the BORSTAR® technology) and described in patent documents such as European Patent Application Publication No. 0887379 or International Publication No. 92 / 12182 pamphlet etc.

[0095] Multimodal (multiphasic) polymers can be produced according to several processes described, for example, in International Publication No. 92 / 12182 pamphlet, European Patent Application Publication No. 0887379, and International Publication No. 98 / 58976 pamphlet. The content of these documents is hereby incorporated by reference into this specification.

[0096] Preferably, in the process for producing the heterophasic polypropylene composition (HECO) defined above, the conditions for the first reactor (R-1) in step (A), i.e., the slurry reactor (SR), for example the loop reactor (LR), may be as follows. · 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, · The pressure is in the range of 20 bar to 80 bar, preferably between 40 bar and 70 bar, · Hydrogen can be added to control the molar mass by methods known per se.

[0097] 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., step (D), and the conditions in step (D) at this time are preferably as follows. · The temperature is in the range of 50 °C to 130 °C, preferably between 60 °C and 100 °C, · The pressure is in the range of 5 bar to 50 bar, preferably between 15 bar and 40 bar, · Hydrogen can be added to control the molar mass by a method known per se.

[0098] The residence time may be different in both reactor zones.

[0099] In one embodiment of the process for producing a heterophasic polypropylene composition (HECO), the residence time in the slurry reactor (SR), for example a loop (LR), is in the range of 0.2 to 4.0 hours, for example 0.3 to 1.5 hours, and the residence time in the gas-phase reactor (GPR) is generally 0.2 to 6.0 hours, for example 0.5 to 4.0 hours.

[0100] If desired, the above polymerization may be carried out in a known manner under supercritical conditions in the first reactor (R-1), i.e., in the slurry reactor (SR), for example in a loop reactor (LR).

[0101] The conditions in the third reactor (R-3), i.e., the second gas-phase reactor (GPR-2), and any other subsequent gas-phase reactors (GPR) present, are the same as those in the second reactor (R-2).

[0102] The process may also include prepolymerization before the polymerization in the first reactor (R-1). This prepolymerization can be carried out in the first reactor (R-1), however, it is preferably carried out in a separate reactor, a so-called prepolymerization reactor.

[0103] The heterophasic polypropylene composition (HECO) according to the first embodiment of the present invention according to the present invention is prepared in the presence of a solid catalyst system (SCS) containing a transition metal compound.

[0104] It is particularly preferred that the solid catalyst system (SCS) is a metallocene catalyst containing a metallocene complex, a boron-containing cocatalyst and / or an aluminoxane cocatalyst, and a silica support.

[0105] In particular, this metallocene catalyst is (i) a metallocene complex of general formula (I),

Chemical formula

[0106] The term "σ-donor ligand" is well understood by those skilled in the art and is a group bonded to a metal via a σ-bond. Thus, the anionic ligand "X" can independently be a halogen or can alternatively be selected from the group consisting of R', OR', SiR'3, OSiR'3, OSO2CF3, OCOR', SR', NR'2 or PR'2 groups, where R' is independently hydrogen, linear or branched, cyclic or acyclic, C1-C 20 alkyl, C2-C 20 alkenyl, C2-C 20 alkynyl, C3-C 12 cycloalkyl, C6-C 20 aryl, C7-C 20 arylalkyl, C7-C 20 alkylaryl, C8-C 20 arylalkenyl, and the R' groups can optionally contain one or more heteroatoms belonging to groups 14-16. In a preferred embodiment, the anionic ligand "X" is the same and is either a halogen, such as Cl, or either methyl or benzyl.

[0107] A preferred monovalent anionic ligand is a halogen, especially chlorine (Cl).

[0108] Preferred metallocene complexes include rac-dimethylsilanediylbis[2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride, rac-anti-dimethylsilanediyl[2-methyl-4-(4'-tert-butylphenyl)-inden-1-yl][2-methyl-4-(4'-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride, rac-anti-dimethylsilanediyl[2-methyl-4-(4'-tert-butylphenyl)-inden-1-yl][2-methyl-4-phenyl-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride, rac-anti-dimethylsilanediyl[2-methyl-4-(3',5'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride, rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride, rac-anti-dimethylsilanediyl[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-butylindene-1-yl]zirconium dichloride, rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3',5'-5-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride are exemplified.

[0109] Particularly preferred is rac-anti-dimethylsilanediyl[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-butylindene-1-yl]zirconium dichloride (II).

Chem.

[0110] The above complex, and thus the ligand necessary to form the catalyst of the present invention, can be synthesized by any process, and an organic chemist skilled in the art would be able to devise various synthetic protocols for producing the necessary ligand materials. For example, WO 2007 / 116034 discloses the necessary chemical reactions. Synthetic protocols 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. In particular, reference is made to WO 2019 / 179959, which describes the most preferred catalyst of the present invention.

[0111] According to the present invention, a cocatalyst system comprising a boron-containing cocatalyst and / or an aluminoxane cocatalyst is used in combination with the metallocene catalyst complex defined above.

[0112] The aluminoxane cocatalyst can be of the formula (III).

Chem.

[0113] Aluminoxane is formed by the partial hydrolysis of an organoaluminum compound, for example a compound of the formula AlR3, AlR2Y and Al2R3Y3, in which R is, for example, C1-C 10 -alkyl, preferably C1-C5-alkyl, or C3-C 10 -cycloalkyl, C7-C 12 -arylalkyl or C7-C 12 -alkylaryl, and / or can be phenyl or naphthyl, and Y can be hydrogen, halogen, preferably chlorine or bromine, or C1-C 10 -alkoxy, preferably methoxy or ethoxy. The resulting oxygen-containing aluminoxane is generally not a pure compound but a mixture of oligomers of the formula (III).

[0114] A preferred aluminoxane is methylaluminoxane (MAO). Since the aluminoxane used as a cocatalyst according to the present invention is not a pure compound due to the mode of its preparation, the molar concentration of the subsequent aluminoxane solution is based on its aluminum content.

[0115] According to the present invention, a boron-containing cocatalyst can also be used instead of the aluminoxane cocatalyst, or the aluminoxane cocatalyst can be used in combination with a boron-containing cocatalyst.

[0116] It will be understood by those skilled in the art that when a boron-based cocatalyst is used, the complex is usually pre-alkylated by reaction with an aluminum alkyl compound such as TIBA. This procedure is well known and any suitable aluminum alkyl, for example Al(C1-C6 alkyl)3, can be used. Preferred aluminum alkyl compounds are triethylaluminum, triisobutylaluminum, triisohexylaluminum, tri-n-octylaluminum and triisooctylaluminum.

[0117] Alternatively, when a borate (boron-art complex) cocatalyst is used, the metallocene catalyst complex is its alkylated version, i.e., for example, a dimethyl or dibenzyl metallocene catalyst complex can be used.

[0118] The boron-based cocatalyst to be noted includes the boron-based cocatalyst of formula (IV). BY3(IV) In formula (IV), 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 having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical, respectively, or fluorine, chlorine, bromine or iodine. Preferred examples of Y are methyl, propyl, isopropyl, isobutyl or trifluoromethyl, unsaturated groups such as aryl or haloaryl, for example phenyl, tolyl, benzyl group, p-fluorophenyl, 3,5-difluorophenyl, pentachlorophenyl, pentafluorophenyl, 3,4,5-trifluorophenyl and 3,5-di(trifluoromethyl)phenyl. Preferred options are borane trifluoride, triphenylborane, tris(4-fluorophenyl)borane, tris(3,5-difluorophenyl)borane, tris(4-fluoromethylphenyl)borane, tris(2,4,6-trifluorophenyl)borane, tris(pentafluorophenyl)borane, tris(tolyl)borane, tris(3,5-dimethyl-phenyl)borane, tris(3,5-difluorophenyl)borane and / or tris(3,4,5-trifluorophenyl)borane.

[0119] Particularly preferred is tris(pentafluorophenyl)borane.

[0120] However, it is preferable to use a borate, i.e., a compound containing borate 3+ ions. Such an ionic cocatalyst preferably contains a non-coordinating anion such as tetrakis(pentafluorophenyl)borate and tetraphenylborate. Suitable counterions are protonated amines or aniline derivatives such as methylammonium, anilinium, dimethylammonium, diethylammonium, N-methylanilinium, diphenylammonium, N,N-dimethylanilinium, trimethylammonium, triethylammonium, tri-n-butylammonium, methyldiphenylammonium, pyridinium, p-bromo-N,N-dimethylanilinium or p-nitro-N,N-dimethylanilinium.

[0121] Preferred ionic compounds that can be used according to the present invention include the following. Triethylammonium tetra(phenyl)borate, Tributylammonium tetra(phenyl)borate, Trimethylammonium tetra(tolyl)borate, Tributylammonium tetra(tolyl)borate, Tributylammonium tetra(pentafluorophenyl)borate, Tripropylammonium tetra(dimethylphenyl)borate, Tributylammonium tetra(trifluoromethylphenyl)borate, Tributylammonium tetra(4-fluorophenyl)borate, N,N-Dimethylcyclohexylammonium tetrakis(pentafluorophenyl)borate, N,N-Dimethylbenzylammonium tetrakis(pentafluorophenyl)borate, N,N-Dimethylanilinium tetra(phenyl)borate, N,N-Diethylanilinium tetra(phenyl)borate, N,N-Dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N - Di(propyl)ammonium tetrakis(pentafluorophenyl)borate, Di(cyclohexyl)ammonium tetrakis(pentafluorophenyl)borate, Triphenylphosphonium tetrakis(phenyl)borate, Triethylphosphonium tetrakis(phenyl)borate, Diphenylphosphonium tetrakis(phenyl)borate, Tri(methylphenyl)phosphonium tetrakis(phenyl)borate, Tri(dimethylphenyl)phosphonium tetrakis(phenyl)borate, Triphenylcarbenium tetrakis(pentafluorophenyl)borate, or Ferrocenium tetrakis(pentafluorophenyl)borate).

[0122] Preferably, Triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N - Dimethylcyclohexylammonium tetrakis(pentafluorophenyl)borate, or N,N - Dimethylbenzylammonium tetrakis(pentafluorophenyl)borate is.

[0123] Surprisingly, certain boron cocatalysts have been found to be particularly preferred. Therefore, preferred borates used in the present invention contain trityl ions. Accordingly, the use of N,N - dimethylammonium - tetrakispentafluorophenylborate and Ph3CB(PhF5)4 and their analogs is particularly preferred.

[0124] According to the present invention, preferred cocatalysts are aluminoxanes, more preferably methylaluminoxane, combinations of aluminoxanes and Al alkyls, boron or borate cocatalysts, and combinations of aluminoxanes and boron - based cocatalysts.

[0125] The appropriate amount of the cocatalyst is well known to those skilled in the art. The molar ratio of boron to the metal ion of the metallocene may be in the range of 0.5:1 to 10:1 mol / mol, preferably 1:1 to 10:1, particularly 1:1 to 5:1 mol / mol. The molar ratio of Al in the aluminoxane to the metal ion of the metallocene may be in the range of 1:1 to 2000:1 mol / mol, preferably 10:1 to 1000:1, more preferably 50:1 to 500:1 mol / mol.

[0126] The catalyst can be used in a supported form or an unsupported form, preferably in a supported form. The particulate carrier material used is preferably an organic material or an inorganic material, such as silica, alumina or zirconia, or a mixed oxide, such as silica-alumina, particularly silica, alumina or silica-alumina. The use of a silica carrier is preferred. Those skilled in the art know the procedures necessary for supporting the metallocene catalyst.

[0127] Particularly preferably, the carrier is a porous material, and as a result, the complex may be loaded into the pores of the carrier using a process similar to those described in, for example, WO 94 / 14856 (Mobil), WO 95 / 12622 (Borealis) and WO 2006 / 097497.

[0128] The average particle size (average grain diameter) of the silica carrier can typically be 10 to 100 μm. However, it has been found that special advantages can be obtained when the carrier has a median particle size d50 of 15 to 80 μm, preferably 18 to 50 μm. The average pore diameter of the silica carrier can be in the range of 10 to 100 nm, and the pore volume can be 1 to 3 mL / g.

[0129] Examples of suitable carrier materials are, for example, ES757 manufactured and sold by PQ Corporation, Sylopol 948 manufactured and sold by Grace, or SUNSPERA DM-L-303 silica manufactured by AGC Si-Tech Co. The carrier can be optionally calcined before use in catalyst preparation to reach an optimal silanol group content.

[0130] The use of these carriers is well known in the art.

[0131] According to a second embodiment of the present invention, the homopolymer or copolymer (PP) of propylene that is the matrix of the heterophasic polypropylene composition (HECO) is a propylene copolymer (cPP).

[0132] The heterophasic polypropylene composition (HECO) according to the second embodiment of the present invention 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 invention 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.

[0133] The heterophasic polypropylene composition (HECO) according to the second embodiment of the present invention is based on the total weight of the heterophasic polypropylene composition (HECO), i) 40.0 to 90.0 wt%, more preferably 45.0 to 85.0 wt%, even more preferably 56.0 to 74.0 wt%, for example 58.0 to 65.0 wt% of a propylene copolymer (cPP), and ii) 10.0 to 60.0 wt%, more preferably 15.0 to 55.0 wt%, even more preferably 26.0 to 44.0 wt%, for example 35.0 to 42.0 wt% of an elastomeric ethylene copolymer (E) and preferably contains.

[0134] The propylene copolymer (cPP) preferably contains comonomers copolymerizable with propylene, such as ethylene and / or C4-C8 α-olefins, particularly ethylene and / or C4-C6 α-olefins, such as comonomers like 1-butene and / or 1-hexene. Preferably, the propylene copolymer (cPP) contains comonomers copolymerizable with propylene from the group consisting of ethylene, 1-butene, and 1-hexene, and especially consists of these. More specifically, the propylene copolymer (cPP) contains units derivable from ethylene and / or 1-butene in addition to propylene. Therefore, in a particularly preferred embodiment, the propylene copolymer (cPP) contains only units derivable from ethylene and propylene.

[0135] In particular, the propylene copolymer (cPP) is preferably a random propylene copolymer, such as a random copolymer of propylene and ethylene.

[0136] The term "random copolymer" should preferably be understood according to IUPAC (Pure Appl. Chem., Vol. 68, No. 8, pp. 1591-1595, 1996). Preferably, the molar concentration of comonomer dyads, such as ethylene dyads, follows the following relationship. [HH]<[H] 2 wherein [HH] is the mole fraction of adjacent comonomer units, such as adjacent ethylene units, [H] is the mole fraction of all comonomer units in the polymer, such as all ethylene units.

[0137] Preferably, the propylene copolymer (cPP) has a comonomer content, such as 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%, even more preferably in the range of 3.0 to 4.8 mol%, for example in the range of 3.5 to 4.0 mol%.

[0138] Furthermore, the propylene copolymer (cPP) preferably 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, even more preferably in the range of 6.5 to 12.0 g / 10 min, for example in the range of 7.0 to 10.0 g / 10 min.

[0139] 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, even more preferably in the range of 128 to 140 °C, for example in the range of 133 to 139 °C.

[0140] The process for the preparation of the propylene copolymer (cPP) is preferably a sequential polymerization process comprising at least two reactors connected in series, and this process (A) Optionally, in a first reactor (R-1), which is a slurry reactor (SR), preferably a loop reactor (LR), propylene, and optionally ethylene and C4 - C 12 α-olefins, preferably a comonomer selected from ethylene, are polymerized to obtain a first propylene copolymer fraction; (B) Transferring the first propylene copolymer fraction and unreacted comonomer from the first reactor (R-1) to a second reactor (R-2), which is a gas phase reactor (GPR-1); (C) Supplying propylene, and ethylene and C4 - C 12 α-olefins, preferably a comonomer selected from ethylene, to the second reactor (R-2); (D) Polymerizing ethylene and C4 - C 12 α-olefins, preferably a comonomer selected from ethylene, in the presence of the first propylene copolymer fraction in the second reactor (R-2) to obtain a second propylene copolymer fraction, wherein the first propylene copolymer fraction and the second propylene copolymer fraction form the propylene copolymer (cPP) as defined in the present invention; and further In the first reactor (R-1) and the second reactor (R-2), the polymerization occurs in the presence of a solid catalyst system (SCS).

[0141] This solid catalyst system (SCS) preferably contains the metallocene catalyst of formula (I) and a cocatalyst as described for the heterogeneous polypropylene composition (HECO) according to the first embodiment of the present invention, and they are referred to.

[0142] Therefore, it is preferred that the above solid catalyst system (SCS) including all preferred embodiments is applied to the preparation of propylene copolymer (cPP).

[0143] Regarding the term "sequential polymerization process", the definition provided above is referred to.

[0144] The first reactor (R-1), when applied, is a slurry reactor (SR), and can be any continuous or simple stirred batch tank reactor or loop reactor operating in slurry. According to the present invention, the slurry reactor (SR) is preferably a loop reactor (LR).

[0145] The second reactor (R-2) and any subsequent reactors are gas phase reactors (GPR). Such gas phase reactors (GPR) can be any mechanical mixing reactor or fluidized bed reactor. Preferably, the gas phase reactor (GPR) includes a mechanically stirred fluidized bed reactor having a gas velocity of at least 0.2 m / sec. Therefore, it is understood that the gas phase reactor (GPR) is preferably a fluidized bed type reactor equipped with a mechanical stirrer.

[0146] The conditions (temperature, pressure, reaction time, monomer supply) in each reactor depend on the desired product, which is within the knowledge of those skilled in the art. As already shown 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). Subsequent reactors, if present, are also gas phase reactors (GPR).

[0147] Preferred multistage processes are "loop-gas phase" processes such as those developed by Borealis A / S, Denmark (known as the BORSTAR® technology), and are described in patent documents such as European Patent Application Publication No. 0887379 or International Publication No. 92 / 12182 pamphlet.

[0148] Multimodal polymers can be produced according to several processes described in, for example, International Publication No. 92 / 12182 pamphlet, European Patent Application Publication No. 0887379, and International Publication No. 98 / 58976 pamphlet. The contents of these documents are incorporated herein by reference.

[0149] Regarding the conditions for the first reactor (R-1), i.e., the slurry reactor (SR), such as a loop reactor (LR), and the second reactor (R-2), i.e., the gas-phase reactor (GPR), and the residence time, the conditions defined above for the heterophasic polypropylene composition (HECO) according to the first embodiment of the present invention are referred to. Thus, this applies to the optional application of the prepolymerization step.

[0150] The elastomeric ethylene copolymer (E) according to the second embodiment of the present invention can include monomers copolymerizable with ethylene, such as C3 - C 12 α-olefins, particularly comonomers such as propylene, 1-butene, 1-hexene, and / or 1-octene. More specifically, the elastomeric ethylene copolymer (E) according to the second embodiment of the present invention includes units derivable from 1-butene, 1-hexene, and / or 1-octene in addition to ethylene.

[0151] It is particularly preferred that the elastomeric ethylene copolymer (E) according to the second embodiment of the present invention is a copolymer of ethylene and 1-octene.

[0152] Preferably, the elastomeric ethylene copolymer (E) according to the second embodiment of the present invention is ultra-low density polyethylene, more preferably ultra-low density polyethylene polymerized using a single-site catalyst reaction.

[0153] The elastomeric ethylene copolymer (E) according to the second embodiment of the present invention has a density determined according to ISO 1183-187 in the range of 860 to 890 kg / m 3 Preferably, the density of the elastomeric ethylene copolymer (E) according to the second embodiment of the present invention determined according to ISO 1183-187 is in the range of 865 to 885 kg / m 3 more preferably in the range of 870 to 884 kg / m 3 for example, in the range of 879 to 883 kg / m 3 in the range.

[0154] Preferably, the elastomeric ethylene copolymer (E) according to the second embodiment of the present invention has a melt flow rate MFR (190 °C, 2.16 kg) determined according to ISO 1133 in the range of 0.8 to 20.0 g / 10 min, more preferably in the range of 0.9 to 10.0 g / 10 min, even more preferably in the range of 1.0 to 5.0 g / 10 min, for example, in the range of 1.0 to 2.0 g / 10.0 min.

[0155] The ethylene content of the elastomeric ethylene copolymer (E) according to the second embodiment of the present invention is in the range of 55.0 to 85.0% by weight, preferably in the range of 65.0 to 80.0% by weight, more preferably in the range of 70.0 to 78.0% by weight, based on the total weight of the elastomeric ethylene copolymer (E).

[0156] In addition, the elastomeric ethylene copolymer (E) according to the second embodiment of the present invention preferably has a melting temperature Tm determined according to differential scanning calorimetry (DSC) in the range of less than 100 °C, more preferably in the range of 50 °C to 90 °C, even more preferably in the range of 55 °C to 85 °C.

[0157] Instead of or in addition to the previous paragraph, the elastomeric ethylene copolymer (E) according to the second embodiment of the present invention preferably has a glass transition temperature of less than -25°C, more preferably in the range of -65°C to -30°C, and even more preferably in the range of -60°C to -35°C.

[0158] In one preferred embodiment, the elastomeric ethylene copolymer (E) according to the second embodiment of the present invention is prepared using at least one single-site catalyst. The elastomeric ethylene copolymer (E) according to the second embodiment of the present invention may be prepared using a plurality of single-site catalysts, or may be a blend of a plurality of elastomeric copolymers prepared using different single-site catalysts. In some embodiments, the elastomeric ethylene copolymer (E) according to the second embodiment of the present invention is a substantially linear ethylene polymer (SLEP). Elastomeric ethylene copolymers by SLEP and other single-site catalysts are known in the art, for example, according to U.S. Patent No. 5,272,236. These resins are also commercially available, for example, as Queo (trademark) plastomers available from Borealis, ENGAGE (trademark) plastomer resins available from Dow Chemical Co., EXACT (trademark) polymers available from Exxon, or TAFMER (trademark) polymers available from Mitsui Chemicals, Lucene polymers available from LG, Fortify polymers available from Sabic, or Solumer polymers available from SK Chemicals.

[0159] The heterophasic polypropylene composition (HECO) according to the second embodiment of the present invention may further contain low-density polyethylene (LDPE).

[0160] 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, even more preferably in the range of 1.0 to 7.0 g / 10 min, for example in the range of 2.5 to 3.5 g / 10 min.

[0161] In addition, the low-density polyethylene (LDPE) is 900 kg / m 3 Preferably, it is in the range of 920 to 960 kg / m 3 More preferably, it has a density determined according to ISO 1183-187 in the range of 925 to 955 kg / m 3 Preferably, it has a density determined according to ISO 1183-187 in the range of 925 to 955 kg / m.

[0162] Furthermore, the low-density polyethylene (LDPE) is preferably 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)acrylate 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 particularly preferred that the polar comonomer is vinyl acetate.

[0163] Furthermore, the low-density polyethylene (LDPE) preferably has a comonomer content, preferably a vinyl acetate content, in the range of 10.0 to 40.0% by weight, more preferably in the range of 15.0 to 35.0% by weight, even more preferably in the range of 20.0 to 33.0% by weight, for example in the range of 25.0 to 30.0% by weight, 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 units and vinyl acetate units.

[0164] Low-density polyethylene (LDPE) is preferably produced by high-pressure polymerization with free radical initiation.

[0165] Preferably, low-density polyethylene (LDPE) is a copolymer known in the art. It is particularly preferred that the low-density polyethylene (LDPE) is a commercially available copolymer of ethylene and vinyl acetate from Borealis, OE5328I.

[0166] The heterophasic polypropylene composition (HECO) according to the second embodiment of the present invention is preferably obtained by melt blending a propylene copolymer (cPP), an elastomeric ethylene copolymer (E) and optionally low-density polyethylene (LDPE).

[0167] The fiber-reinforced composition (C) according to the second embodiment of the present invention preferably has a melt flow rate MFR2 (230 °C, 2.16 kg) determined according to ISO 1133 in the range of 1.0 to 10.0 g / 10 min, more preferably in the range of 1.5 to 6.0 g / 10 min, even more preferably in the range of 2.0 to 4.5 g / 10 min, for example in the range of 2.5 to 3.8 g / 10 min.

[0168] Furthermore, it is preferred that the fiber-reinforced composition (C) according to the second embodiment of the present invention has a tensile modulus determined according to ISO 527-1A in the range of 2500 to 5500 MPa, more preferably in the range of 2550 to 4200 MPa, even more preferably in the range of 2600 to 3500 MPa, for example in the range of 2650 to 2800 MPa.

[0169] Additionally or alternatively, it is preferred that the fiber-reinforced composition (C) according to the second embodiment of the present invention has an elongation at break determined according to ISO 527-2 of more than 10.0%, more preferably more than 10.3%, even more preferably more than 10.8%, for example 11.0% or more.

[0170] Fiber (F) The essential component of the fiber-reinforced composition (C) is the fiber (F).

[0171] Preferably, the fiber (F) is selected from the group consisting of glass fiber, carbon fiber, polymer fiber, metal fiber, mineral fiber, ceramic fiber, and mixtures thereof. More preferably, the fiber (F) is glass fiber and / or carbon fiber.

[0172] It is particularly preferable that the fiber (F) is glass fiber (GF). Preferably, the glass fiber (GF) is short glass fiber (SGF) or chopped strand, which is also known as chopped glass fiber, and / or long glass fiber (LGF), preferably long glass fiber (LGF) obtained from glass rovings.

[0173] It is particularly preferable that the fiber (F) is short glass fiber (GF).

[0174] The chopped glass fiber or short glass fiber (SGF) used in the fiber-reinforced composition (C) preferably has 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, even more preferably in the range of 2.5 to 8.0 mm, for example, in the range of 3.0 to 7.0 mm.

[0175] The chopped glass fiber or short glass fiber (SGF) used in the fiber-reinforced composition (C) preferably has an average diameter of 5 to 20 μm, more preferably 6 to 18 μm, even more preferably 8 to 16 μm.

[0176] Preferably, the short glass fiber (SGF) has an aspect ratio of 125 to 650, preferably 150 to 500, more preferably 200 to 450. The aspect ratio is the relationship between the average length and the average diameter of the fiber.

[0177] Adhesion promoter (AP) According to the present invention, the fiber-reinforced polypropylene composition (C) may further contain an adhesion promoter (AP). When the fiber (F) is glass fiber and / or carbon fiber, it is preferable that the fiber-reinforced polypropylene composition (C) contains an adhesion promoter (AP).

[0178] The adhesion promoter (AP) is specified as a polar-modified polypropylene (PM-PP) homopolymer or copolymer.

[0179] The polar-modified polypropylene (PM-PP) homopolymer or copolymer contains a low molecular weight compound having a reactive polar group. Modified polypropylene homopolymers and copolymers, such as propylene and ethylene or other α-olefins, such as C4~C 10 Copolymers with α-olefins are most preferred because they are highly compatible with the homopolymer or copolymer (PP) of propylene in the fiber-reinforced polypropylene composition (C) of the present invention.

[0180] Regarding the structure, the polar-modified polypropylene (PM-PP) homopolymer or copolymer is preferably selected from graft homopolymers or copolymers.

[0181] In this regard, polar-modified polypropylene (PM-PP) homopolymers or copolymers containing polar compounds, particularly polar compounds selected from the group consisting of acid anhydrides, carboxylic acids, carboxylic acid derivatives, primary and secondary amines, hydroxyl compounds, oxazolines, and epoxides, and groups derived from ionic compounds are preferred.

[0182] Specific examples of the above polar compounds are unsaturated cyclic anhydrides and their aliphatic diesters, dibasic acid derivatives. In particular, maleic anhydride, and maleic acid C1~C 10 linear and branched dialkyl, fumaric acid C1~C 10 linear and branched dialkyl, itaconic anhydride, itaconic acid C1~C 10Compounds selected from linear and branched dialkyl esters, acrylic acid, maleic acid, fumaric acid, itaconic acid and mixtures thereof can be used.

[0183] It is particularly preferred to use a homopolymer or copolymer of polypropylene grafted with maleic anhydride or acrylic acid as a polar modified polypropylene (PM-PP) homopolymer or copolymer, i.e., an adhesion promoter (AP).

[0184] The above-mentioned modified polymer, i.e., the adhesion promoter, can be produced in a simple manner by reactive extrusion of the above polymer with, for example, maleic anhydride or acrylic acid in the presence of a free radical generator (such as an organic peroxide), as disclosed in, for example, U.S. Patent No. 4,506,056, U.S. Patent No. 4,753,997 or European Patent Application Publication No. 1805238.

[0185] The preferred amount of the group derived from the polar compound in the polar modified polypropylene (PM-PP) homopolymer or copolymer, i.e., the adhesion promoter (AP), is 0.5 to 5.0% by weight. For example, this amount may be in the range of 0.5% to 4.5% by weight, preferably in the range of 0.5% to 4.0% by weight, more preferably in the range of 0.5% to 3.5% by weight.

[0186] For the polar modified polypropylene (PM-PP) homopolymer or copolymer, i.e., the adhesion promoter (AP), the preferred value of the melt flow rate MFR2 (230 °C) 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.

[0187] In one preferred embodiment of the present invention, the adhesion promoter (AP) is maleic anhydride-modified polypropylene homo / copolymer and / or acrylic acid-modified polypropylene homo / copolymer. Preferably, the adhesion promoter (AP) is maleic anhydride-modified polypropylene homopolymer and / or acrylic acid-modified polypropylene homopolymer, preferably maleic anhydride-modified polypropylene homopolymer. For example, suitable polar-modified polypropylene (PM-PP) homopolymers or copolymers include, for example, polypropylene homopolymer grafted with maleic anhydride (PP-g-MAH) and polypropylene homopolymer grafted with acrylic acid (PP-g-AA).

[0188] Additive (AD) In addition to the heterophasic polypropylene composition (HECO), the fiber (F) and the adhesion promoter (AP), the fiber-reinforced composition (C) of the present invention may contain an additive (AD). Typical additives include acid scavengers, antioxidants, colorants, light stabilizers, plasticizers, slip agents, anti-scratch agents, dispersants, processing aids, lubricants, pigments, and the like.

[0189] Such additives are commercially available and are described, for example, in "Plastic Additives Handbook" by Hans Zweifel, 6th Edition, 2009 (pages 1141-1190).

[0190] Furthermore, the term "additive (AD)" according to the present invention also includes carrier materials, particularly polymer carrier materials.

[0191] Polymer carrier material Preferably, the fiber-reinforced polypropylene composition (C) of the present invention does not contain any additional polymer(s) (if more than one kind is possible) different from the components of the heterophasic polypropylene composition (HECO) and the adhesion promoter (AP) in an amount exceeding 15% by weight, preferably exceeding 10% by weight, more preferably exceeding 9% by weight, based on the weight of the fiber-reinforced polypropylene composition (C). Any polymer that is a carrier material for the additive (AD) is counted in the amount of each additive, rather than in the amount of the polymer compound as shown in the present invention.

[0192] The polymer carrier material of the additive (AD) is a carrier polymer for ensuring uniform distribution in the fiber-reinforced polypropylene composition (C) of the present invention. This polymer carrier material is not limited to a specific polymer. The polymer carrier material may be an ethylene homopolymer, an ethylene copolymer obtained from an α-olefin comonomer such as ethylene and a C3 - C8 α-olefin comonomer, a propylene homopolymer, and / or a propylene copolymer obtained from propylene and an α-olefin comonomer such as ethylene and / or a C4 - C8 α-olefin comonomer. It is preferred that the polymer carrier material does not contain monomer units derivable from styrene or its derivatives.

[0193] Article The present invention also relates to an article, such as an injection-molded article, containing the fiber-reinforced composition (C) defined above. In particular, the present invention relates to an article, such as an injection-molded article, containing at least 60% by weight, more preferably at least 80% by weight, even more preferably at least 90% by weight, for example at least 95% by weight or at least 99% by weight of the fiber-reinforced polypropylene composition (C) defined above. In a particularly preferred embodiment, the present invention relates to an article, such as an injection-molded article, consisting of the fiber-reinforced composition (C) defined above.

[0194] Preferably, the article is an automotive article, such as an injection-molded automotive article.

[0195] Further embodiments [1] A fiber-reinforced composition (C), based on the total weight of this fiber-reinforced composition (C), a) 55.0 to 94.9% by weight of i) A matrix that is a homopolymer or copolymer (PP) of propylene having at least 0.4 mol% of 1,2 erythro positional defects and a comonomer content of 8.5 mol% or less, and ii) An elastomeric ethylene copolymer (E) dispersed in the above matrix A heterophasic polypropylene composition (HECO) containing b) 5.0 to 45.0% by weight of fibers (F), and c) Optionally, 0.1 to 5.0% by weight of an adhesion promoter (AP) and The above 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, the fiber-reinforced composition (C).

[0196] [2] The above heterophasic polypropylene composition (HECO) is based on the total weight of this heterophasic copolymer (HECO), i) 60.0 to 95.0% by weight of the above matrix that is the homopolymer or copolymer (PP) of propylene, and ii) 5.0 to 40.0% by weight of the above elastomeric ethylene copolymer (E), The fiber-reinforced composition (C) according to Embodiment [1] containing

[0197] [3] The above elastomeric ethylene copolymer (E) has an ethylene content in the range of 15.0 to 85.0% by weight based on the total weight of this elastomeric ethylene copolymer (E), the fiber-reinforced composition (C) according to Embodiment [1] or Embodiment [2].

[0198] [4] The above heterophasic polypropylene composition (HECO) has a melting temperature Tm determined according to differential scanning calorimetry (DSC) in the range of 130 to 165 °C, and / or, the fiber-reinforced composition (C) according to any one of Embodiments [1] to [3].

[0199] [5] The above-mentioned heterophasic polypropylene composition (HECO) is the fiber-reinforced composition (C) according to any one of Embodiments [1] to [4], which has an intrinsic viscosity (IV) measured according to ISO1628 / 1 (at 135 °C in decalin) of the soluble part (SF) determined according to CRYSTEX QC in the range of 1.8 to 3.0 dl / g.

[0200] [6] The above-mentioned fiber (F) is a glass fiber (GF), preferably i) having an average length in the range of 2.0 to 10.0 mm, and / or ii) having an average diameter in the range of 5 to 20 μm is the fiber-reinforced composition (C) according to any one of Embodiments [1] to [5], which is a short glass fiber (SGF). [7] The above-mentioned adhesion promoter (AP) is a polar modified polypropylene (PM-PP), which is a homopolymer or copolymer of propylene grafted with maleic anhydride and has a melt flow rate MFR (230 °C, 2.16 kg) determined according to ISO1133 of at least 20.0 g / 10 min to 400 g / 10 min. It is the fiber-reinforced composition (C) according to any one of Embodiments [1] to [6].

[0201] [8] i) The above-mentioned homopolymer or copolymer of propylene (PP) is a propylene homopolymer (hPP), ii) The above-mentioned elastomeric ethylene polymer (E) is a copolymer of ethylene and propylene is the fiber-reinforced composition (C) according to any one of Embodiments [1] to [7].

[0202] [9] The above-mentioned propylene homopolymer (hPP) has a melting temperature Tm determined according to differential scanning calorimetry (DSC) in the range of 140 to 160 °C, which is the fiber-reinforced composition (C) described in Embodiment [8].

[0203]

[10] The above-mentioned heterophasic polypropylene composition (HECO) is i) A comonomer content in the range of 2.2 to 8.7 mol%, and / or ii) A melt flow rate MFR2 (230 °C, 2.16 kg) determined according to ISO 1133 in the range of 20.0 to 100 g / 10 min The fiber-reinforced composition (C) according to Embodiment [8] or Embodiment [9] having

[0204]

[11] The above-mentioned heterophasic polypropylene composition (HECO) is i) A cold xylene soluble part (XCS) content determined at 25 °C according to ISO 16152 in the range of 5.0 to 35.0 wt% based on the total weight of the above-mentioned heterophasic polypropylene composition (HECO), and / or ii) An ethylene content of the cold xylene soluble part (XCS) fraction in the range of 20.9 to 44.7 mol% and / or ii) A soluble part (SF) determined according to CRYSTEX QC in the range of 5.0 to 35.0 wt% based on the total weight of the above-mentioned heterophasic polypropylene composition (HECO), and / or iv) An ethylene content of the soluble part (SF) determined according to CRYSTEX QC in the range of 20.9 to 44.7 mol% The fiber-reinforced composition (C) according to any one of Embodiments [8] to

[10] having

[0205]

[12] i) A tensile modulus determined according to ISO 527-1A in the range of 3000 to 6000 MPa, and / or ii) An elongation at break determined according to ISO 527-2 greater than 3.0% The fiber-reinforced composition (C) according to any one of Embodiments [8] to

[11] having

[0206]

[13] i) The above-mentioned homopolymer or copolymer of propylene (PP) is a propylene copolymer (cPP) copolymer of propylene and ethylene having an ethylene content of 2.2 to 8.5 mol%, ii) The above elastomeric ethylene copolymer (E) is ethylene having an ethylene content of 55.0 to 85.0% by weight based on the total weight of the elastomeric ethylene copolymer (E) and C4 to C 12 α-olefin, preferably a copolymer with 1-octene The fiber-reinforced composition (C) according to any one of Embodiments [1] to [7].

[0207]

[14] i) The above propylene copolymer (cPP) has a melt flow rate MFR2 (230 ° C, 2.16 kg) determined according to ISO1133 in the range of 5.0 to 20.0 g / 10 min, and / or ii) The above elastomeric ethylene copolymer (E) has a melt flow rate MFR (190 ° C, 2.16 kg) determined according to ISO1133 in the range of 0.8 to 20.0 g / 10 min and / or a density determined according to ISO1183-187 in the range of 860 to 890 kg / m 3 and / or iii) The above fiber-reinforced composition (C) has a melt flow rate MFR2 (230 ° C, 2.16 kg) determined according to ISO1133 in the range of 1.0 to 10.0 g / 10 min The fiber-reinforced composition (C) according to Embodiment

[13] .

[0208]

[15] i) A tensile modulus determined according to ISO527-1A in the range of 2500 to 5500 MPa, and / or ii) An elongation at break determined according to ISO527-2 of more than 10.0% The fiber-reinforced composition (C) according to Embodiment

[13] or

[14] having the above properties.

[0209]

[16] Up to 20.0% by weight, having a density determined according to ISO1183-187 of more than 900 kg / m 3 The fiber-reinforced composition (C) according to any one of Embodiments [1] to

[15] , further comprising a low-density polyethylene (LDPE) homopolymer or copolymer containing ethylene and optionally vinyl acetate.

[0210]

[17] The homopolymer or copolymer of propylene (PP) is preferably obtained in the presence of a solid catalyst system (SCS) containing a metallocene complex having the formula (I). [Chemical formula] In the above formula (I), each X is independently a σ-donor ligand. L is a divalent bridging group selected from -R’2C-, -R’2C-CR’2-, -R’2Si-, -R’2Si-SiR’2-, -R’2Ge-, and each R’ is independently a hydrogen atom, or a C1-C 20 -hydrocarbyl group which may contain one or more heteroatoms or fluorine atoms from Groups 14 to 16 of the periodic table, or optionally, two R’ groups can combine to form a ring. Each R 1 can be independently the same or different, and is hydrogen, a linear or branched C1-C6-alkyl group, C 7~20 -arylalkyl, C 7~20 -alkylaryl group or C 6~20 -aryl group or OY group, where Y is a C 1~10 -hydrocarbyl group, and optionally, two adjacent R 1 groups can be part of a ring containing the phenyl carbon to which they are attached. Each R 2 can be independently the same or different, and is a CH2-R 8 group, where R 8 is H or a linear or branched C 1~6 -alkyl group, C 3~8 -cycloalkyl group, C 6~10 -aryl group. R 3 is a linear or branched C1-C6-alkyl group, C 7~20 -arylalkyl, C 7~20 -alkylaryl group or C6-C 20 -aryl group. R 4 is a C(R 9 )3 group, where R9 is a linear or branched C1-C6-alkyl group, R 5 is hydrogen, or an aliphatic C1-C 20 -hydrocarbyl group which may contain one or more heteroatoms from groups 14-16 of the periodic table, R 6 is hydrogen, or an aliphatic C1-C 20 -hydrocarbyl group which may contain one or more heteroatoms from groups 14-16 of the periodic table, or R 5 and R 6 together can form a 5-membered saturated carbon ring which may be substituted by n groups R 10 , where n is 0-4, each R 10 is the same or different and is a C1-C 20 -hydrocarbyl group, or a C1-C 20 -hydrocarbyl group which may contain one or more heteroatoms belonging to groups 14-16 of the periodic table, R 7 is H, or a linear or branched C1-C6-alkyl group, or an aryl or heteroaryl group having 6-20 carbon atoms which may be substituted by 1-3 groups R 11 , each R 11 is independently the same or can be different and is hydrogen, a linear or branched C1-C6-alkyl group, C 7~20 -arylalkyl, C 7~20 -alkylaryl group or C 6~20 -aryl group or an OY group, where Y is a C 1~10 -hydrocarbyl group The fiber-reinforced composition (C) according to any one of embodiments [1] to

[16] .

[0211]

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

[17] .

[0212] The present invention will now be described in more detail by way of the following examples provided hereinafter.

Example

[0213] A. Measurement method The following definitions and determination methods of terms apply to the above general description of the present invention and the following examples unless otherwise defined.

[0214] Melt flow rate The melt flow rate (MFR) is determined in accordance with ISO 1133 and expressed in g / 10 min. MFR is an indicator of the fluidity of the polymer and thus its processability. The higher the melt flow rate, the lower the viscosity of the polymer. MFR2 of polypropylene is determined under a temperature of 230 °C or 190 °C and a load of 2.16 kg.

[0215] Melting temperature T m and crystallization temperature T c were measured using a Mettler TA820 differential scanning calorimetry (DSC) for a 5 - 7 mg sample. DSC was performed in a heating / cooling / heating cycle at a scanning rate of 10 °C / min in the temperature range of - 30 to + 225 °C in accordance with ISO 11357 / Part 3 / Method C2. The crystallization temperature was determined from the cooling process, while the melting temperature was determined from the second heating process. All mechanical measurements were carried out after a conditioning time of 96 hours (23 °C, 50% relative humidity) of the test specimens.

[0216] 13 Quantification of the PP matrix microstructure by C - NMR spectroscopy Quantitative nuclear magnetic resonance (NMR) spectroscopy was used to quantify the stereoregularity (tacticity) and regioregularity of the crystalline matrix of the polymer. Quantitative 13 C{ 1 H} NMR spectra were 1 H and 13For C, it was recorded in solution state using a Bruker Advance III 400 NMR spectrometer operating at 400.15 MHz and 100.62 MHz, respectively. All spectra were recorded using nitrogen gas for all pressures with a 10 mm extended temperature probe head optimized for 13 C. For the propylene homopolymer, approximately 200 mg of the material was dissolved in 1,2 - tetrachloroethane - d2 (TCE - d2). To ensure a homogeneous solution, after the initial sample preparation in a heat block, the NMR tube was further heated in a rotary oven for at least 1 hour. After insertion into the magnet, the tube was rotated at 10 Hz. This setting was chosen mainly for the high resolution required for the quantification of the tacticity distribution (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 the NOE and the bilinear WALTZ16 decoupling scheme (Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh, D.; Winniford, B., J. Mag. Reson. 187 (2007) 225; Busico, V., Carbonniere, P., Cipullo, R., Pellecchia, R., Severn, J., Talarico, G., Macromol. Rapid Commun. 2007, 28, 11289). A total of 8192 (8k) transient signals were acquired per spectrum. Quantitative 13 C{ 1The 1H NMR spectra were processed, integrated using a proprietary computer program, and the relevant quantitative characteristics were determined from the integration values. For propylene homopolymers, all chemical shifts are referenced to the methyl isotactic pentad (mmmm) at 21.85 ppm. The tacticity distribution was quantified by integrating the methyl region from 23.6 to 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., Macromolecules 30 (1997) 6251). Specifically, the effects of positional defects and comonomers on the quantification of the tacticity distribution were corrected by subtracting the integration values of representative positional defects and comonomers from specific integration regions of the stereosequence. Isotacticity was determined at the pentad level and reported as the percentage of isotactic pentad (mmmm) sequences relative to the sum of all pentad sequences. [mmmm]% = 100 × (mmmm / sum of all pentads) The presence of 2,1 erythro positional defects was indicated by the presence of two methyl sites at 17.7 and 17.2 ppm and confirmed by other characteristic sites. No characteristic signals corresponding to other types of positional defects were observed (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253). The amount of 2,1 erythro positional defects was quantified using the average integration values of the two characteristic methyl sites at 17.7 and 17.2 ppm. P 21e = (I e6 + I e8 ) / 2 The amount of 1,2 primary insertion propene was quantified based on the methyl region. Corrections were made for sites included in this region that are not related to primary insertion and for primary insertion sites excluded from this region. P 12 = I CH3 + P12e The total amount of propene was quantified as the sum of the primary inserted propene and all other existing positional defects present. P total =P 12 +P 21e The mole percent of 2,1 erythro positional defects was quantified relative to the total propene. [21e] mole % = 100 × (P 21e / P total )

[0217] Determination of C2 and C3 Content in PP Copolymers Quantitative nuclear magnetic resonance (NMR) spectroscopy was used to quantify the comonomer content and comonomer sequence distribution of the polymer. Quantitative 13 C{ 1 H} NMR spectra were 1 recorded in solution using a Bruker Advance III 400 NMR spectrometer operating at 400.15 MHz for H and 100.62 MHz for 13 C, respectively. All spectra were recorded at 125 °C 13A 10 mm extended temperature probe head optimized for C was used and recordings were made using nitrogen gas for all pressures. Approximately 200 mg of material was dissolved in 3 ml of 1,2-tetrachloroethane-d2 (TCE-d2) together with chromium(III) acetylacetonate (Cr(acac)3) giving 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, after the initial sample preparation in a heat block, the NMR tube was further heated in a rotary oven for at least 1 hour. After insertion into the magnet, the tube was rotated at 10 Hz. This setting was chosen mainly because of the high resolution and quantitative nature required for the accurate quantification of the ethylene content. A standard single pulse excitation without NOE was employed using an optimized tip angle, a recycle delay of 1 s and a bilinear 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) transient signals were acquired per spectrum.

[0218] Quantitative 13 C{ 1The 1H NMR spectra were processed using a proprietary computer program, integrated, and the relevant quantitative characteristics were determined from the integral values. All chemical shifts were indirectly referenced to the methylene group at the center of the ethylene block (EEE) at 30.00 ppm using the chemical shift of the solvent. This approach enabled comparable referencing even in the absence of this structural unit. Characteristic signals corresponding to the incorporation of ethylene were observed (Cheng, H.N., Macromolecules 17 (1984), 1950).

[0219] The comonomer fraction was 13 C{ 1 quantified using the method of Wang et al. (Wang, W-J., Zhu, S., Macromolecules 33 (2000) 1157) by integrating multiple signals over the entire spectral region of the 13C{1H} spectrum. This method was chosen for its robustness and the ability to account for the presence of positional defects if necessary. The integration regions were slightly adjusted to enhance their applicability over the entire range of the facing comonomer content. For systems where only isolated ethylene in the PPEPP sequence was observed, the method of Wang et al. was modified to reduce the effect of non-zero integrals at sites known to be absent. This approach reduced the overestimation of the ethylene content for such systems, which was achieved by reducing the number of sites used to determine the absolute ethylene content to E = 0.5(Sββ + Sβγ + Sβδ + 0.5(Sαβ + Sαγ)) by subtraction.

[0220] The use of this set of sites resulted in the corresponding integral equation being written in the same notation as used in the paper of Wang et al. (Wang, W-J., Zhu, S., Macromolecules 33 (2000), 1157) as E = 0.5(I H + I G + 0.5(I C + I D )) The equation used for the absolute propylene content was not modified. The equation used for the absolute propylene content was not modified.

[0221] The comonomer incorporation in mole percent was calculated from the mole fraction. E [mol%] = 100 × fE

[0222] The comonomer incorporation in weight percent was calculated from the mole fraction. E [wt%] = 100 × (fE × 28.06) / ((fE × 28.06) + ((1 - fE) × 42.08))

[0223] The comonomer content in the ethylene / 1-octene copolymer was 13 calibrated using C-NMR and measured in a known manner based on Fourier transform infrared spectroscopy (FTIR) using a Nicolet Magna 550 IR spectrometer together with Nicolet Omnic FTIR software. A film having a thickness of about 250 μm was compression molded from the sample. Similar films were made from calibration samples having known contents of comonomer. The comonomer content was determined from the spectrum in the wavenumber range of 1430 - 1100 cm -1 . The absorbance was measured as the peak height by selecting either the so-called short baseline or long baseline or both. The short baseline was drawn through the lowest point to about 1410 - 1320 cm -1 , and the long baseline was drawn between about 1410 - 1220 cm -1 . Calibration needs to be performed individually for each type of baseline. Also, the comonomer content of the unknown sample needs to be within the range of the comonomer content of the calibration sample.

[0224] The glass transition temperature Tg was determined by dynamic mechanical analysis according to ISO6721-7. The measurement was carried out in torsion mode at a heating rate of 2 °C / min and a frequency of 1 Hz between -100 °C and +150 °C for a compression molded sample (40 × 10 × 1 mm 3 ).

[0225] The density was measured in accordance with ISO 1183-187. The sample preparation was carried out by compression molding in accordance with ISO 1872-2:2007.

[0226] Cold xylene soluble part (XCS) The cold xylene soluble fraction (XCS, wt%) at room temperature was determined at 25 °C in accordance with ISO 16152; 5th edition; 2005-07-01.

[0227] Flexural modulus: The flexural modulus was determined by three-point bending in accordance with ISO 178 on injection molded test specimens (80×10×4 mm) prepared in accordance with ISO 294-1:1996.

[0228] The notched Charpy impact strength was determined at 23 °C in accordance with ISO 179-1 / 1eA by using injection molded test specimens (80×10×4 mm) prepared in accordance with EN ISO 1873-2.

[0229] The tensile properties were determined on injection molded dog-bone test specimens with a thickness of 4 mm prepared in accordance with EN ISO 1873-2. The tensile modulus was determined in accordance with ISO 527-1A at a strain rate of 1 mm / min and 23 °C, and the tensile strength and elongation at break (strain) were determined in accordance with ISO 527-2 at a strain rate of 50 mm / min and 23 °C.

[0230] Crystex analysis Method by crystalline part and soluble part The crystalline fraction (CF) and soluble fraction (SF) of the polypropylene (PP) composition, as well as the comonomer content and intrinsic viscosity of each fraction, were analyzed by CRYSTEX QC, Polymer Char (Valencia, Spain). A schematic diagram of the CRYSTEX QC machine is shown in Fig. 1a. The crystalline and amorphous parts are separated by a temperature cycle of melting at 160 °C, crystallization at 40 °C, and re-dissolution in 1,2,4-trichlorobenzene (1,2,4-TCB) at 160 °C, as shown in Fig. 1b. The quantification of SF and CF, and the determination of the ethylene content (C2) of the parent EP copolymer and its soluble and crystalline parts are achieved by an infrared detector (IR4) and an on-line dual capillary viscometer used for the determination of the intrinsic viscosity (iV). The IR4 detector is a multi-wavelength detector that detects the IR absorbance at two different bands (CH3 and CH2) for determining the concentration and ethylene content in ethylene-propylene copolymers. The IR4 detector is calibrated using a series of eight EP copolymers with known ethylene contents ( 13 determined by C-NMR spectroscopy) in the range of 2 wt% to 69 wt%, and using various concentrations from 2 to 13 mg / ml for each of the used EP copolymers used for calibration. The amounts of the soluble fraction (SF) and the crystalline fraction (CF) are correlated with the amounts of the "cold xylene soluble fraction" (XCS) and the cold xylene insoluble fraction (XCI), respectively, by XS calibration and determined according to the standard gravimetric method according to ISO16152. The XS calibration is achieved by testing various EP copolymers with XS contents in the range of 2 to 31 wt%. The intrinsic viscosity (iV) of the parent EP copolymer and its soluble and crystalline parts is determined using an on-line dual capillary viscometer and correlated with the corresponding iV' determined by the standard method in decalin according to ISO1628. The calibration is achieved using various EPPP copolymers with iV = 2 to 4 dL / g. Samples of the PP composition to be analyzed are weighed at a concentration of 10 mg / ml to 20 mg / ml. After automatically filling a vial with 1,2,4-TCB containing 250 mg / l of 2,6-tert-butyl-4-methylphenol (BHT) as an antioxidant, the sample is dissolved at 160 °C for usually 60 minutes with continuous stirring at 800 rpm until complete dissolution is achieved. As shown in FIGS. 1a and 1b, a sample solution of a specified volume is injected into a column filled with an inert carrier where crystallization of the sample and separation of the soluble part from the crystalline part are carried out. This process is repeated twice. During the first injection, the entire sample is measured at a high temperature to determine the iV [dl / g] and C2 [wt%] of the PP composition. During the second injection, the soluble part (at a low temperature) and the crystalline part (at a high temperature) are measured in the crystallization cycle (wt% SF, wt% C2, iV). EP means ethylene propylene copolymer. PP means polypropylene.

[0231] FIG. 1(a): Schematic diagram of the CRYSTEX QC instrument. FIG. 1(b): Elution of the EP copolymer sample and the obtained soluble and crystalline parts in a TREF column (a column filled with an inert material, e.g., glass beads) (see Del Hierro, P.; Ortin, A.; Monrabal, B.; "Soluble Fraction Analysis in polypropylene").

[0232] Intrinsic viscosity: The intrinsic viscosity (IV) was measured at 135 °C in decalin according to DIN ISO 1628 / 1, October 1999.

[0233] VOC / Fog emission was measured according to VDA 278:2002 for injection molded test pieces and granulated formulations. Volatile organic compounds are measured in toluene equivalents / gram. Fogging is measured in hexadecane equivalents / gram. The measurements were carried out using TDSA supplied by Gerstel, using helium 5.0 as the carrier gas, a column HP Ultra 2 with a length of 50 m, a diameter of 0.32 mm and a coating of 0.52 μm of 5% phenyl-methyl-siloxane. The VOC analysis was performed in accordance with Device Setting 1 listed in the above specifications using the following main parameters: Flow mode splitless, final temperature 90 °C; final time 30 minutes, rate 60 K / min. The cold trap was purged in the temperature range of -150 °C to +280 °C at a heating rate of 12 K / sec and a final time of 5 minutes in flow mode split 1:30. The following GC settings were used for the analysis: Isothermal at 40 °C for 2 minutes, heated 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 minutes; flow rate 1.3 ml / min. The fog analysis was performed in accordance with Device Setting 1 listed in the above specifications using the following main parameters: Flow mode splitless, rate 60 K / min; final temperature 120 °C; final time 60 minutes. The cold trap was purged in the temperature range of -150 °C to +280 °C at a heating rate of 12 K / sec in flow mode split 1:30. The following GC settings were used for the analysis: Isothermal at 50 °C for 2 minutes, heated to 160 °C at 25 K / min, then to 280 °C at 10 K / min, isothermal for 30 minutes; flow rate 1.3 ml / min.

[0234] B. Examples 1. Catalyst synthesis The catalyst used was anti-dimethylsilanediyl[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-butylindene-1-yl]zirconium dichloride disclosed in WO 2020 / 239602A1 pamphlet as ICS3.

[0235] Preparation of MAO-silica support Nitrogen was passed through a steel reactor equipped with a mechanical stirrer and a filter net, and the reactor temperature was set to 20 °C. Next, silica grade DM-L-303 (5.0 kg) manufactured by AGC Si-Tech Co., which had been pre-fired at 600 °C, was added from the supply drum, and then carefully pressurized and depressurized with nitrogen using a manual valve. Then, toluene (22 kg) was added. The mixture was stirred for 15 minutes. Next, a 30 wt% solution of MAO in toluene (9.0 kg) from Lanxess was added within 70 minutes via the supply line at the top of the reactor. Then, the reaction mixture was heated to 90 °C and stirred at 90 °C for an additional 2 hours. The slurry was allowed to settle, and the mother liquor was filtered off. The catalyst was washed twice with toluene (22 kg) at 90 °C, then allowed to settle and filtered. The reactor was cooled to 60 °C, and the solid was washed with heptane (22.2 kg). Finally, the MAO-treated SiO2 was dried with stirring under a nitrogen stream at 60 °C for 2 hours and then under vacuum (-0.5 barg) for 5 hours. The MAO-treated support was collected as a free-flowing white powder. It was found that this support contained 12.2 wt% Al.

[0236] Catalyst Preparation 30 wt% MAO in toluene (0.7 kg) was added to a steel nitrogen blank reactor at 20 °C via a burette. Then, toluene (5.4 kg) was added with stirring. The catalyst (93 g) cited above was added from a metal cylinder and then flushed with 1 kg of toluene. This mixture was stirred at 20 °C for 60 minutes. Next, trityltetrakis(pentafluorophenyl)borate (91 g) was added from a metal cylinder and then flushed with 1 kg of toluene. This mixture was stirred at room temperature for 1 hour. The resulting solution was added to the stirred cake of the MAO-silica support prepared as described above over 1 hour. After the cake was allowed to stand for 12 hours, it was dried with stirring under a N2 stream at 60 °C for 2 hours and then under vacuum (-0.5 barg) for an additional 5 hours. The dried catalyst was sampled in the form of a pink free-flowing powder containing 13.9% Al and 0.11% Zr.

[0237] 2. Preparation of Heterophasic Polypropylene Composition (HECO1) and Propylene Copolymer (cPP) in the Reactor The heterophasic polypropylene composition (HECO1) and propylene copolymer (cPP) in the reactor were prepared in a sequential process including a loop reactor and one or two gas-phase reactors in the presence of the above catalyst. The reaction conditions and the properties of the final polymer are summarized in Tables 1 and 2.

[0238] [Table 1]

[0239] [Table 2]

[0240] 3. Preparation of Fiber-Reinforced Composition (C) Containing HECO1 The fiber-reinforced composition (C) was obtained by melt-blending the heterophasic polypropylene composition (HECO1) in the reactor with glass fiber (GF), adhesion promoter (AP) and additive (AD) in a co-rotating twin-screw extruder. The compositions and properties of the inventive examples and comparative examples are summarized in Table 3.

[0241] [Table 3]

[0242] HECO1a is a commercially available heterophasic propylene copolymer EF015AE from Borealis AG, prepared using a Ziegler-Natta catalyst, having a cold xylene-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. hP is a commercially available propylene homopolymer HJ120UB from Borealis AG, prepared using a Ziegler-Natta catalyst, having a melt flow rate MFR2 (230 °C) of 75 g / 10 min, a density of 905 kg / m 3 and a glass transition temperature Tg of +2 °C. GF is the commercially available product ECS 03 T-480H of Nippon Electric Glass Co., Ltd., having a filament diameter of 10.5 μm and a strand length of 3 mm. AP is the adhesion promoter SCONA TPPP 8112 GA by Scona, and is polypropylene functionalized with maleic anhydride having a maleic anhydride content of 1.4% by weight and an MFR (190 °C, 2.16 kg) exceeding 80 g / 10 min. AD1 is 14.0% by weight of tris(2,4-di-t-butylphenyl) phosphite (Kinox-68-G by HPL Additives), 14.0% by weight of pentaerythrityl-tetrakis(3-(3’,5’-di-tert-butyl-4-hydroxyphenyl)-propionate (Irganox 1010FF by BASF), 36.0% by weight of carbon black (50% by weight masterbatch) by Borealis, and 36.0% by weight of a masterbatch composed of propylene homopolymer HC001A by Borealis having a density of 905 kg / m 3 and an MFR (230 °C, 2.16 kg) of 3.2 g / 10 min.

[0243] 4. Preparation of the blended heterophasic polypropylene composition (HECO2) Preparation of the fiber-reinforced composition (C) containing HECO2 The propylene copolymer (cPP) was melt-blended with an elastomeric ethylene copolymer (E), glass fiber (GF), adhesion promoter (AP), optionally low density polyethylene (LDPE) and additive (AD) in a co-rotating twin-screw extruder. The compositions and properties of the inventive examples and comparative examples are summarized in Table 4.

[0244]

Table 4

[0245] cPPa is a commercially available propylene-ethylene random copolymer RD208CF from Borealis AG, prepared using a Ziegler-Natta catalyst, having an ethylene content of 7.3 mol%, a melt flow rate MFR2 (230 °C, 2.16 kg) determined according to ISO 1133 of 8.0 g / 10 min, and a melting temperature Tm of 140 °C. cPPb is a metallocene propylene-ethylene random copolymer according to Example IE1 of WO 2015 / 121160 A1, having an ethylene content of 4.1 mol% and a melt flow rate MFR2 (230 °C, 2.16 kg) determined according to ISO 1133 of 4.0 g / 10 min. E is a commercially available copolymer Queo 8201 of ethylene and 1-octene from Borealis AG, having a melt flow rate (190 °C, 2.16 kg) determined according to ISO 1133 of 1.1 g / 10 min, a melting temperature Tm of 72 °C, a glass transition temperature Tg of -52 °C, a density of 882 kg / m 3 and an ethylene content of 75.5 wt%. LDPE is a commercially available copolymer OE5328 of ethylene and vinyl acetate from Borealis AG, having a melt flow rate (190 °C, 2.16 kg) determined according to ISO 1133 of 3.0 g / 10 min, a density of 950 kg / m 3 and a vinyl acetate content of 28.0 wt%. AD2 is 20.0 wt% erucic acid amide (Finawax-E by Fine Organics), 6.6 wt% tris(2,4-di-tert-butylphenyl) phosphite (Irgafox 168 by BASF), 6.6 wt% pentaerythrityl-tetrakis(3-(3’,5’-di-tert-butyl-4-hydroxyphenyl)-propionate (Irganox 1010FF by BASF), 33.3 wt% carbon black (50 wt% masterbatch) by Borealis, and 33.3 wt% of, 905 kg / m 3It is a masterbatch made of propylene homopolymer HC001A by Borealis having a density of AD3 is a masterbatch consisting of 18.18 wt% of tris(2,4-di-tert-butylphenyl) phosphite (Irgafox 168 by BASF), 36.36 wt% of pentaerythrityl-tetrakis(3-(3’,5’-di-tert-butyl-4-hydroxyphenyl)-propionate (Irganox 1010FF by BASF) and 45.45 wt% of distearyl-thio-propionate (Irganox PS-802 FL by BASF).

Claims

1. A fiber-reinforced composition (C), based on the total weight of the fiber-reinforced composition (C), a) 55.0 to 95.0% by weight of a heterophasic polypropylene composition (HECO), wherein i) 1,2-erythro positional defects in an amount in the range of 0.4 to 1.2 mol%, a comonomer content of 4.8 mol% or less, and a melt flow rate MFR determined according to ISO 1133 in the range of 5.0 to 20.0 g / 10 min ２ a matrix which is a propylene copolymer (cPP) having ２ (230 °C, 2.16 kg), and ii) an elastomeric ethylene copolymer (E) dispersed in the matrix The heterophasic polypropylene composition (HECO) containing, and the elastomeric ethylene copolymer (E) has a density determined according to ISO 1183-187 in the range of 879 to 890 kg / m³, b) 5.0 to 45.0% by weight of fibers (F), and c) Optionally, 0.1 to 5.0% by weight of an adhesion promoter (AP) and containing The fiber-reinforced composition (C) has a melt flow rate MFR determined in accordance with ISO 1133 in the range of 1.0 to 60.0 g / 10 min ２ (230 °C, 2.16 kg), and is a fiber-reinforced composition (C).

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

3. The heterophasic polypropylene composition (HECO) is based on the total weight of the heterophasic copolymer (HECO), i) 40.0 to 90.0% by weight of the propylene copolymer (cPP), and ii) 10.0 to 60.0% by weight of the elastomeric ethylene copolymer (E) The fiber-reinforced composition (C) according to claim 1 or claim 2, comprising.

4. The elastomeric ethylene copolymer (E) has an ethylene content in the range of 55.0 to 85.0% by weight based on the total weight of the elastomeric ethylene copolymer (E). The fiber-reinforced composition (C) according to any one of claims 1 to 3.

5. The propylene copolymer (cPP) is a copolymer of propylene and ethylene. The fiber-reinforced composition (C) according to any one of claims 1 to 4.

6. The propylene copolymer (cPP) has a comonomer content in the range of 3.0 to 4.8 mol%. The fiber-reinforced composition (C) according to any one of claims 1 to 5.

7. The elastomeric ethylene copolymer (E) is a copolymer of ethylene and 1-octene. The fiber-reinforced composition (C) according to any one of claims 1 to 6.

8. The fiber (F) is a glass fiber (GF). The fiber-reinforced composition (C) according to any one of claims 1 to 7.

9. The adhesion promoter (AP) is a polar-modified polypropylene (PM-PP) which is a homopolymer or copolymer of propylene grafted with maleic anhydride and has a melt flow rate MFR (230 °C, 2.16 kg) determined according to ISO 1133 of at least 20.0 g / 10 min to 400 g / 10 min. The fiber-reinforced composition (C) according to any one of claims 1 to 8.

10. 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. The fiber-reinforced composition (C) according to any one of claims 1 to 9.

11. The elastomeric ethylene copolymer (E) has a density determined in accordance with ISO 1183-187 in the range of 879 to 883 kg / m ３ The fiber-reinforced composition (C) according to any one of claims 1 to 10, having a density determined in accordance with ISO 1183-187 in the range of ３ .

12. The fiber-reinforced composition (C) has a melt flow rate MFR determined according to ISO 1133 in the range of 1.0 to 10.0 g / 10 min ２ The fiber-reinforced composition (C) according to any one of claims 1 to 11, having ２ (230 °C, 2.16 kg).

13. The fiber-reinforced composition (C) according to any one of claims 1 to 12, having a tensile modulus determined according to ISO 527-1A in the range of 2500 to 5500 MPa.

14. The fiber-reinforced composition (C) according to any one of claims 1 to 13, having an elongation at break determined according to ISO 527-2 of more than 10.0%.

15. The fiber-reinforced composition (C) according to any one of claims 1 to 14, further comprising low-density polyethylene (LDPE).

16. 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. The fiber-reinforced composition (C) according to claim 15.

17. Up to 20.0% by weight, having a density determined according to ISO 1183-187 of over 900 kg / m ３ The fiber-reinforced composition (C) according to any one of claims 1 to 16, further comprising a low-density polyethylene (LDPE) homopolymer or copolymer containing ethylene and optionally vinyl acetate.

18. An article comprising the fiber-reinforced composition (C) according to any one of claims 1 to 17.

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