Fiber-reinforced composition containing propylene random copolymer

Abstract

The present invention is directed to a fiber reinforced polypropylene composition (C) comprising a propylene random copolymer (P), a fiber (F) and an adhesion promoter (AP), as well as to an article comprising this fiber reinforced polypropylene composition (C).

Description

[Technical Field]

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

[0002] Fiber-reinforced materials are widely used in various applications, especially in engineering fields where higher stiffness, higher heat distortion temperature (HDT), 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 metallocene catalysts is a promising candidate due to additional advantages such as controlled molecular weight distribution, good comonomer incorporation, and low emissions. However, current grades have inherent drawbacks, as stiffness and HDT are often not high enough. Some specific applications, such as automotive exteriors, also require excellent impact properties.

[0003] Therefore, there is a need in the art for a fiber reinforced polypropylene material that combines good stiffness and impact properties with low emissions. Additionally, excellent flow properties are required for injection molding processes. Summary of the Invention [Problem to be solved by the invention]

[0004] It is therefore an object of the present invention to provide a high flow fiber reinforced polypropylene composition characterized by balanced stiffness and impact properties and low emissions. [Means for solving the problem]

[0005] The object is to provide a fiber-reinforced polypropylene composition (C), which, based on the total weight of the fiber-reinforced composition (C), a) 57.0 to 95.0 wt. % of a propylene random copolymer (P), wherein the comonomer is selected from ethylene and / or at least one C4 to C12 α-olefin, and the propylene random copolymer (P) is i) a melt flow rate MFR2 (230°C, 2.16 kg) determined according to ISO 1133 in the range of 45 to 150 g / 10 min; and ii) the melting temperature Tm determined according to differential scanning calorimetry (DSC) in the range of 125-150°C; A propylene random copolymer (P) having the formula: b) 5.1 to 40.0% by weight of fiber (F); c) optionally 0.1 to 5.0 wt. % of an adhesion promoter (AP); The problem is solved by a fiber reinforced polypropylene composition (C) comprising:

[0006] According to one embodiment of the present invention, the propylene random copolymer (P) has 1,2 erythro position defects in an amount of at least 0.4 mol% (mol-%). One preferred embodiment of the present invention is a fiber reinforced composition (C), which comprises, based on the total weight of the fiber reinforced composition (C): a) 57.0 to 94.9% by weight of a propylene random copolymer (P), wherein the comonomer is selected from ethylene and / or at least one C4 to C12 α-olefin, and the propylene random copolymer (P) is i) Melt flow rate MFR2 (230°C, 2.16 kg) determined according to ISO 1133 in the range of 45 to 150 g / 10 min; ii) a melting temperature Tm determined according to differential scanning calorimetry (DSC) in the range of 125-150°C, and iii) 1,2 erythro regio defects in an amount of at least 0.4 mole % A propylene random copolymer (P) having the formula: b) 5.0 to 40.0% by weight of fiber (F); c) 0.1 to 5.0 wt. % of an adhesion promoter (AP); The present invention relates to a fiber-reinforced composition (C) comprising:

[0007] According to another embodiment of the present invention, the propylene random copolymer (P) is i) a first propylene random copolymer (P1); ii) a second propylene random copolymer (P2) having a higher comonomer content than the first propylene random copolymer (P1); The weight ratio of the first propylene random copolymer (P1) to the second propylene random copolymer (P2) is in the range of 20 / 80 to 60 / 40, and the total amount of the first propylene random copolymer (P1) and the second propylene random copolymer (P2) relative to the propylene random copolymer (P) is at least 95.0% by weight.

[0008] According to a further embodiment of the present invention, the propylene random copolymer (P) has a comonomer content in the range of 1.0 to 6.0 mol %.

[0009] According to another embodiment of the present invention, the first propylene random copolymer (P1) has a comonomer content in the range of 0.4 to 2.5 mol % and the second propylene random copolymer (P2) has a comonomer content in the range of 2.8 to 7.0 mol %.

[0010] According to one embodiment of the present invention, the comonomer is at least one C4 to C12 α-olefin. It is particularly preferred that the comonomer is 1-hexene or 1-butene.

[0011] According to one embodiment of the present invention, the propylene random copolymer (P) has a xylene solubles content (XCS) determined in accordance with ISO 16152 (25°C) in the range of 3.0 to 15.0 wt% based on the total weight of the propylene random copolymer.

[0012] According to another embodiment of the present invention, the propylene random copolymer (P) is visbroken at a visbreaking ratio of at least 5.0 [final MFR2 (230°C / 2.16 kg) / initial MFR2 (230°C / 2.16 kg)], where "final MFR2 (230°C / 2.16 kg)" is the MFR2 (230°C / 2.16 kg) of the propylene random copolymer (P) after visbreaking, and "initial MFR2 (230°C / 2.16 kg)" is the MFR2 (230°C / 2.16 kg) of the propylene random copolymer (P) before visbreaking. MFR2 (230°C, 2.16 kg) is determined according to ISO 1133.

[0013] According to a further embodiment of the present invention, the propylene random copolymer (P) has a melt flow rate MFR2 (230°C, 2.16 kg), determined according to ISO 1133 before visbreaking, in the range of 0.5 to 10.0 g / 10 min.

[0014] According to another embodiment of the present invention, the fibers (F) are glass fibers (GF), preferably short glass fibers (SGF) having an average length of 2.0 to 10.0 mm and / or an average diameter of 5 to 20 μm.

[0015] According to one 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 ISO 1133 of 20.0 g / 10 min to 400 g / 10 min.

[0016] According to a further 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 8.0 to 60.0 g / 10 min.

[0017] According to another embodiment of the present invention, the propylene random copolymer (P) is obtained in the presence of a solid catalyst system (SCS) comprising a metallocene compound.

[0018] It is particularly preferred that the metallocene compound has the formula (I): R n (Cp)2MX2(I) In the above formula (I), each Cp is independently an unsubstituted or substituted and / or fused cyclopentadienyl ligand, such as a substituted or unsubstituted cyclopentadienyl, a substituted or unsubstituted indenyl or a substituted or unsubstituted fluorenyl ligand, wherein the optional one or more substituents are independently preferably selected from halogen, hydrocarbyl (e.g. C1-C20-alkyl, C2-C20-alkenyl, C2-C20-alkynyl, C3-C12-cycloalkyl, C6-C20-aryl or C7-C20-arylalkyl), C3-C12-cycloalkyl containing 1, 2, 3 or 4 heteroatoms in the ring portion, C6-C20-heteroaryl, C1-C20-haloalkyl, -SiR"3, -OSiR"3, -SR", -PR"2, OR" or -NR"2; each R" is independently hydrogen or hydrocarbyl, such as C1-C20-alkyl, C2-C20-alkenyl, C2-C20-alkynyl, C3-C12-cycloalkyl or C6-C20-aryl, or, for example in the case of -NR"2, the two substituents R" together with the nitrogen atom to which they are attached can form a ring, for example a 5- or 6-membered ring; R is a bridging group of 1 to 3 atoms, for example a bridging group of 1 to 2 C atoms and 0 to 2 heteroatoms, which heteroatoms can be, for example, Si, Ge and / or O atoms, each of the bridging atoms independently optionally carrying a substituent, for example a C-C alkyl, tri(C-C alkyl)silyl, tri(C-C alkyl)siloxy or C-C aryl substituent, or a bridging group of 1 to 3, for example 1 or 2, heteroatoms, for example silicon, germanium and / or oxygen atoms, for example each R 10are independently C1-C20-alkyl, C3-12-cycloalkyl, C6-C20-aryl or tri(C1-C20-alkyl)silyl residues, for example trimethylsilyl, -SiR 10 2, M is a group 4 transition metal, such as Zr or Hf, especially Zr; each X is independently a σ-ligand, for example H, halogen, C1-C20-alkyl, C1-C20-alkoxy, C2-C20-alkenyl, C2-C20-alkynyl, C3-C12-cycloalkyl, C6-C20-aryl, C6-C20-aryloxy, C7-C20-arylalkyl, C7-C20-arylalkenyl, -SR", -PR"3, -SiR"3, -OSiR"3, -NR"2 or -CH2-Y, where Y is C6-C20-aryl, C6-C20-heteroaryl, C1-C20-alkoxy, C6-C20-aryloxy, NR"2, -SR", -PR"3, -SiR"3 or -OSiR"3; Each of the above ring moieties can be further substituted, either alone or as part of another moiety as a substituent on Cp, X, R″ or R, for example with C1-C20-alkyl, which may contain Si and / or O atoms; n is 1 or 2.

[0019] The present invention is further directed to an article comprising a fiber-reinforced composition (C) according to any one of claims 1 to 14.

[0020] In the following, the invention will be described in more detail. DETAILED DESCRIPTION OF THE INVENTION

[0021] Fiber-reinforced composition (C) The fiber-reinforced composition (C) according to the present invention comprises a propylene random copolymer (P), fibers (F), and an adhesion promoter (AP).

[0022] In particular, the fiber-reinforced composition (C) comprises, based on the total weight of the fiber-reinforced composition (C): a) 57.0 to 95.0 wt %, preferably 60.0 to 90.0 wt %, more preferably 65.0 to 85.0 wt %, and even more preferably 70.0 to 80.0 wt % of the propylene random copolymer (P); b) 5.0 to 40.0% by weight, preferably 8.0 to 37.0% by weight, more preferably 11.0 to 32.0% by weight, and even more preferably 15.0 to 27.0% by weight of the above-mentioned fibers (F); Includes:

[0023] According to a preferred embodiment of the present invention, the fiber-reinforced composition (C) further comprises an adhesion promoter (AP).

[0024] Therefore, the fiber-reinforced composition (C) is, based on the total weight of the fiber-reinforced composition (C), a) 57.0 to 94.9 wt %, preferably 60.0 to 90.0 wt %, more preferably 65.0 to 85.0 wt %, and even more preferably 70.0 to 80.0 wt % of the propylene random copolymer (P); b) 5.0 to 40.0% by weight, preferably 8.0 to 37.0% by weight, more preferably 11.0 to 32.0% by weight, and even more preferably 15.0 to 27.0% by weight of the above-mentioned fibers (F); c) 0.1 to 5.0% by weight, preferably 0.5 to 4.0% by weight, more preferably 0.8 to 3.5% by weight, and even more preferably 1.0 to 3.0% by weight of the adhesion promoter (AP); Includes:

[0025] Furthermore, the fiber-reinforced composition (C) according to the present invention may contain an additive (AD). In one embodiment, the fiber-reinforced composition (C) contains, based on the total weight of the fiber-reinforced composition (C): a) 57.0 to 94.8% by weight, preferably 60.0 to 90.0% by weight, more preferably 65.0 to 85.0% by weight, and even more preferably 70.0 to 80.0% by weight of the propylene random copolymer (P); b) 5.0 to 40.0% by weight, preferably 8.0 to 37.0% by weight, more preferably 11.0 to 32.0% by weight, and even more preferably 15.0 to 27.0% by weight of the above-mentioned fibers (F); c) 0.1 to 5.0 wt. %, preferably 0.5 to 4.0 wt. %, more preferably 0.8 to 3.5 wt. %, and even more preferably 1.0 to 3.0 wt. % of the adhesion promoter (AP), d) 0.01 to 2.5 wt% of an additive (AD); The amount of components a) to d) is preferably selected to be 100% by weight.

[0026] Therefore, the fiber-reinforced composition (C) is, based on the total weight of the fiber-reinforced composition (C), a) 57.0 to 92.4 wt %, preferably 60.0 to 90.0 wt %, more preferably 65.0 to 85.0 wt %, and even more preferably 70.0 to 80.0 wt % of the propylene random copolymer (P); b) 5.0 to 40.0% by weight, preferably 8.0 to 37.0% by weight, more preferably 11.0 to 32.0% by weight, and even more preferably 15.0 to 27.0% by weight of the above-mentioned fibers (F); c) 0.1 to 5.0 wt. %, more preferably 1.0 to 3.0 wt. % of the adhesion promoter (AP), d) 0.01 to 2.5 wt% of an additive (AD); Preferably, the additive (AD) comprises, and more preferably consists of, the additive (AD) being described in more detail below.

[0027] Preferably, the fiber-reinforced composition (C) of the present invention does not contain (a) additional polymer(s) other than the propylene random copolymer (P) and the adhesion promoter (AP) in an amount of more than 5.0 wt. %, preferably more than 3.0 wt. %, and more preferably more than 2.5 wt. %, based on the total weight of the fiber-reinforced composition (C). One additional polymer that may be present in such a small amount is polyethylene, a reaction by-product obtained by preparing the propylene random copolymer (P). It is therefore particularly understood that the fiber-reinforced composition (C) contains only the propylene random copolymer (P), the adhesion promoter (A), and optionally, the amount of polyethylene mentioned in this paragraph as polymeric compounds.

[0028] It is particularly preferred that the fiber-reinforced composition (C) of the present invention does not contain more than 5.0 wt. %, preferably more than 3.0 wt. %, and more preferably more than 2.5 wt. % of an elastomeric polymer, based on the total weight of the fiber-reinforced composition (C). In particular, it is preferred that the fiber-reinforced composition (C) of the present invention does not contain more than 5.0 wt. %, preferably more than 3.0 wt. %, and more preferably more than 2.5 wt. % of an ethylene propylene rubber (EPR), based on the total weight of the fiber-reinforced composition (C). Therefore, it is preferred that the fiber-reinforced composition have a xylene solubles content (XCS), determined according to ISO 16152 (25°C), in the range of 3.0 to 15.0 wt. %, more preferably 3.5 to 12.0 wt. %, even more preferably 4.0 to 10.0 wt. %, for example, 4.5 to 9.5 wt. %, based on the total weight of the fiber-reinforced composition (C).

[0029] Preferably, 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 8.0 to 60.0 g / 10 min, more preferably in the range of 10.0 to 50.0 g / 10 min, even more preferably in the range of 12.0 to 40.0 g / 10 min, for example in the range of 14.0 to 30.0 g / 10 min.

[0030] Furthermore, the fiber-reinforced composition (C) preferably has a melting temperature, as determined by differential scanning calorimetry (DSC), of 155°C or less, more preferably in the range of 125 to 150°C, even more preferably in the range of 130 to 145°C, for example in the range of 132 to 140°C.

[0031] With regard to the mechanical properties, it is preferred that the fiber reinforced composition (C) has a tensile modulus determined according to ISO 527-1A in the range of 2500 to 6000 MPa, more preferably in the range of 2800 to 5500 MPa, even more preferably in the range of 3000 to 5200 MPa, for example in the range of 3200 to 5000 MPa, and / or a tensile strength determined according to ISO 527-2 in the range of 40 to 100 MPa, preferably in the range of 40 to 80 MPa, more preferably in the range of 42 to 70 MPa, even more preferably in the range of 45 to 68 MPa, for example in the range of 50 to 65 MPa.

[0032] In addition to or instead of the preceding paragraph, the fiber-reinforced composition (C) has a thermal conductivity of at least 25.0 kJ / m 2 , more preferably at least 30.0 kJ / m 2 , and even more preferably 35.0 kJ / m 2 , e.g., at least 40.0 kJ / m 2 It is preferred that the unnotched Charpy impact strength determined at 23°C in accordance with ISO 179 be 100 kJ / m. A reasonable upper limit for the unnotched Charpy impact strength determined at 23°C in accordance with ISO 179 is 100 kJ / m. 2 is.

[0033] Furthermore, it is preferred that the fiber reinforced composition (C) has a heat deflection temperature (HDT) determined in accordance with ISO 75A of at least 110° C., more preferably at least 115° C., even more preferably at least 120° C., such as at least 125° C. A reasonable upper limit for the heat deflection temperature (HDT) determined in accordance with ISO 75A is 155° C.

[0034] Furthermore, it is preferred that the fiber reinforced composition (C) comprises a low amount of volatile compounds (VOCs) determined according to VDA 278 of less than 25 μg / g, more preferably less than 20 μg / g, even more preferably less than 15 μg / g, for example less than 12 μg / g.

[0035] Likewise, it is preferred that the fiber-reinforced composition (C) comprises a small amount of intermediate volatile compounds (FOG) determined according to VDA 278 of less than 80 μg / g, more preferably less than 75 μg / g, even more preferably less than 45 μg / g, for example less than 40 μg / g.

[0036] The fiber reinforced composition (C) is preferably obtained by melt blending (melt mixing) the propylene random copolymer (P), the fibers (F), optionally an adhesion promoter (AP) and optionally an additive (AD).

[0037] The components of the fiber-reinforced composition (C) are described in more detail below.

[0038] Propylene random copolymer (P) The fiber-reinforced composition (C) of the present invention comprises a propylene random copolymer (P).

[0039] In particular, the propylene random copolymer (P) is a copolymer of propylene and ethylene and / or at least one C4-C12 α-olefin. Accordingly, the propylene random copolymer (P) comprises a monomer copolymerizable with propylene selected from ethylene and a C4-C12 α-olefin. Preferably, the comonomer is selected from ethylene and a C4-C6 α-olefin, such as 1-butene and / or 1-hexene. It is particularly preferred that the propylene random copolymer according to the present invention comprises, and more preferably consists of, propylene and a monomer copolymerizable with propylene selected from the group consisting of ethylene, 1-butene, and 1-hexene. More specifically, the propylene random copolymer (P) according to the present invention comprises, in addition to propylene, units derivable from ethylene, 1-butene, and / or 1-hexene.

[0040] According to a preferred embodiment of the present invention, the comonomer is 1-hexene. Therefore, it is particularly preferred that the propylene random copolymer (P) contains only units derivable from propylene and 1-hexene. In other words, it is preferred that only propylene and 1-hexene are polymerized.

[0041] 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 concentrations of the comonomer dyads, for example the 1-hexene dyad, obey the following relationship: [HH]<[H] 2 During the ceremony, [HH] is the mole fraction of adjacent comonomer units, e.g., adjacent 1-hexene units; [H] is the mole fraction of all comonomer units, eg, all 1-hexene units, in the polymer.

[0042] Preferably, the propylene random copolymer (P) has a comonomer content, more preferably a 1-hexene content, in the range of 1.0 to 6.0 mol%, more preferably in the range of 1.5 to 5.2 mol%, even more preferably in the range of 2.0 to 4.7 mol%, for example in the range of 2.2 to 4.2 mol%.

[0043] Furthermore, the propylene random copolymer (P) is preferably bimodal.

[0044] In particular, the propylene random copolymer (P) i) a first propylene random copolymer (P1); ii) a second propylene random copolymer (P2) having a higher comonomer content, preferably a 1-hexene content, than the first propylene random copolymer (P1); The total amount of the first propylene random copolymer (P1) and the second propylene random copolymer (P2) relative to the propylene random copolymer (P) is preferably at least 95.0% by weight, more preferably 97.0% by weight, even more preferably 99.0% by weight, for example 99.9% by weight. It is particularly preferred that this random propylene copolymer essentially consists of, and preferably consists of, the first propylene random copolymer (P1) and the second propylene random copolymer (P2).

[0045] With respect to the term "random copolymer," reference is made to the definition provided above.

[0046] Preferably, the weight ratio of the first propylene random copolymer (P1) to the second propylene random copolymer (P2) is in the range of 20 / 80 to 60 / 40, more preferably in the range of 30 / 70 to 55 / 45, even more preferably in the range of 40 / 60 to 50 / 50.

[0047] The second propylene random copolymer (P2) preferably has a higher comonomer content, such as 1-hexene content, than the first propylene random copolymer (P1). Preferably, the ratio C(P2) / C(P1) is in the range of 1.1 to 10.0, more preferably 2.0 to 7.5, and even more preferably 3.0 to 6.2, where C(P2) is the comonomer content, preferably 1-hexene content, in [mol%] of the second propylene random copolymer (P2), and C(P1) is the comonomer content, preferably 1-hexene content, in [mol%] of the first propylene random copolymer (P2).

[0048] It is especially preferred that the first propylene random copolymer (P1) has a comonomer content, preferably a 1-hexene content, in the range of 0.4 to 2.5 mol %, more preferably in the range of 0.5 to 2.0 mol %, even more preferably in the range of 0.6 to 1.6 mol %.

[0049] The second propylene random copolymer (P2) preferably has a comonomer content, preferably a 1-hexene content, in the range of 2.8 to 7.0 mol %, more preferably in the range of 3.0 to 6.0 mol %, even more preferably in the range of 3.2 to 5.0 mol %.

[0050] Preferably, the propylene random copolymer (P) has at least 0.4 mol %, more preferably 0.4 to 1.2 mol %, of 1,2 erythro regio defects. Without being bound by theory, the large amount of misinsertion of propylene and / or 1-hexene and / or 1-butene within the polymer chain indicates that the propylene random copolymer (P) is produced in the presence of a single-site catalyst, preferably a metallocene catalyst. It is known in the art that propylene random copolymers produced in the presence of a Ziegler-Natta catalyst can have 1,2 erythro regio defects in amounts far less than 0.4 mol %, and in many cases are essentially free of 1,2 erythro regio defects.

[0051] Furthermore, the propylene random copolymer (P) according to the present invention preferably has a fairly high melt flow rate, i.e., a melt flow rate MFR2 (230°C, 2.16 kg) determined in accordance with ISO 1133 in the range of 45.0 to 150 g / 10 min, preferably 50.0 to 130 g / 10 min, more preferably 55.0 to 110 g / 10 min, and even more preferably 60.0 to 100 g / 10 min.

[0052] In this respect, the propylene random copolymer (P) is preferably visbroken.

[0053] By visbreaking the propylene random copolymer (P) thermally or with peroxide under more controlled conditions, the molar mass distribution (MWD) becomes narrower because long molecular chains are more easily decomposed or cleaved, decreasing the molar mass M, and the MFR2 increases corresponding to the decrease in molar mass M. The MFR2 increases with an increase in the amount of peroxide used. Unless otherwise specified, throughout the present invention, the melt flow rate MFR2 (230°C / 2.16 kg) of the propylene random copolymer (P) is preferably the melt flow rate (230°C / 2.16 kg) after visbreaking.

[0054] Preferred mixing devices suitable for visbreaking are discontinuous and continuous kneaders, twin-screw and single-screw extruders equipped with special mixing sections, and co-kneaders.

[0055] Visbreaking may be carried out in any known manner, for example by using a peroxide visbreaking agent. Typical visbreaking agents are 2,5-dimethyl-2,5-bis(tert-butyl-peroxy)hexane (DHBP) (e.g., sold under the trade names Luperox 101 and Trigonox 101), 2,5-dimethyl-2,5-bis(tert-butyl-peroxy)hexyne-3 (DYBP) (e.g., sold under the trade names Luperox 130 and Trigonox 145), dicumyl peroxide (DCUP) (e.g., sold under the trade names Luperox DC and Perkadox BC), di-tert-butyl-peroxide (DTBP) (e.g., sold under the trade names Trigonox B and Luperox Di), tert-butyl-cumyl-peroxide (BCUP) (e.g., sold under the trade names Trigonox T and Luperox 801), and bis(tert-butylperoxy-isopropyl)benzene (DIPP) (e.g., sold under the trade names Perkadox (Commercially available peroxides are commercially available under the trade names 14S and Luperox DC). The appropriate amount of peroxide to be used according to the present invention is known in principle to those skilled in the art and can be easily calculated based on the amount of propylene random copolymer (P) to be visbroken, the MFR2 (230°C / 2.16 kg) value of the propylene random copolymer (P) to be visbroken, and the desired target MFR2 (230°C / 2.16 kg) of the resulting product. Thus, a typical amount of peroxide visbreaking agent is 0.005 to 0.7% by weight, more preferably 0.01 to 0.4% by weight, based on the amount of polypropylene used.

[0056] Typically, visbreaking according to the invention is carried out in an extruder, which results in an increase in melt flow rate under appropriate conditions. During visbreaking, the higher molar mass chains of the starting material are broken statistically more frequently than the lower molar mass molecules, resulting in an overall decrease in average molecular weight and an increase in melt flow rate, as described above.

[0057] Therefore, the melt flow rate MFR2(initial) (230°C / 2.16 kg) of the propylene random copolymer (P), i.e., the melt flow rate before visbreaking, is much lower, such as in the range of 0.5 to 10.0 g / 10 min. For example, the melt flow rate MFR2(initial) (230°C / 2.16 kg) of the propylene random copolymer (P) before visbreaking is in the range of 0.8 to 8.0 g / 10 min, for example, in the range of 1.0 to 6.0 g / 10 min.

[0058] In one embodiment of the present invention, the propylene random copolymer (P) has been visbroken at a visbreaking ratio [final MFR2 (230°C / 2.16 kg) / initial MFR2 (230°C / 2.16 kg)] of at least 5.0, where "final MFR2 (230°C / 2.16 kg)" is the MFR2 (230°C / 2.16 kg) of the propylene random copolymer (P) after visbreaking, and "initial MFR2 (230°C / 2.16 kg)" is the MFR2 (230°C / 2.16 kg) of the propylene random copolymer (P) before visbreaking. Preferably, the propylene random copolymer (P) is visbroken at a visbreaking ratio [final MFR2 (230°C / 2.16 kg) / initial MFR2 (230°C / 2.16 kg)] of 5.0 to 100, where "final MFR2 (230°C / 2.16 kg)" is the MFR2 (230°C / 2.16 kg) of the propylene homopolymer after visbreaking, and "initial MFR2 (230°C / 2.16 kg)" is the MFR2 (230°C / 2.16 kg) of the propylene homopolymer before visbreaking. More preferably, the propylene random copolymer (P) is visbroken at a visbreaking ratio [final MFR2 (230°C / 2.16 kg) / initial MFR2 (230°C / 2.16 kg)] of 10 to 80, even more preferably 20 to 70, wherein "final MFR2 (230°C / 2.16 kg)" is the MFR2 (230°C / 2.16 kg) of the propylene random copolymer (P) after visbreaking, and "initial MFR2 (230°C / 2.16 kg)" is the MFR2 (230°C / 2.16 kg) of the propylene random copolymer (P) before visbreaking.

[0059] The melting temperature Tm of the propylene random copolymer (P), determined according to differential scanning calorimetry (DSC), is in the range of 125 to 150°C, preferably in the range of 128 to 145°C, more preferably in the range of 130 to 142°C, and even more preferably in the range of 132 to 140°C.

[0060] The propylene random copolymer (P) is further characterized by the amount of xylene cold solubles (XCS). The propylene random copolymer (P) preferably has a xylene solubles content (XCS) determined according to ISO 16152 (25°C) in the range of 3.0 to 15.0 wt%, more preferably 3.5 to 12.0 wt%, even more preferably 4.0 to 10.0 wt%, for example, 5.0 to 9.0 wt%. According to another preferred embodiment, the propylene random copolymer (P) has a xylene solubles content (XCS) determined according to ISO 16152 (25°C) in the range of 0.1 to 15.0 wt%, more preferably 0.1 to 12.0 wt%, even more preferably 0.1 to 10.0 wt%, for example, 0.1 to 9.0 wt%.

[0061] The low amount of xylene cold solubles (XCS) also indicates that the propylene random copolymer (P) preferably does not contain elastomer (co)polymers that form inclusions as a second phase to improve mechanical properties. Polymers containing elastomer (co)polymers as second-phase inserts are, in contrast, called heterophasic and are preferably not part of the present invention. The presence of second phases or so-called inclusions 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 distinct glass transition temperatures.

[0062] Therefore, the propylene random copolymer (P) according to the present invention preferably does not have a glass transition temperature below -30°C, preferably below -25°C, more preferably below -20°C.

[0063] According to another preferred embodiment of the present invention, the comonomer of the propylene random copolymer is 1-butene. Therefore, it is particularly preferred that the propylene random copolymer (P) contains only units derivable from propylene and 1-butene. In other words, it is preferred that only propylene and 1-butene are polymerized.

[0064] In another preferred embodiment, the propylene random copolymer (P) has a 1-butene content in the range of 1.0 to 6.0 mol%, more preferably in the range of 1.5 to 5.2 mol%, even more preferably in the range of 2.0 to 5.2 mol%, for example in the range of 3.5 to 5.0 mol%. In another preferred embodiment, the comonomer of the propylene random copolymer is 1-butene, and the propylene random copolymer (P) has a 1-butene content in the range of 1.0 to 6.0 mol%, more preferably in the range of 1.5 to 5.2 mol%, even more preferably in the range of 2.0 to 5.2 mol%, for example in the range of 3.5 to 5.0 mol%.

[0065] According to another preferred embodiment of the present invention, the comonomer of the propylene random copolymer is 1-butene and the propylene random copolymer (P) is i) a first propylene random copolymer (P1) having a comonomer content in the range of 2.0 to 6.0 mol%, preferably in the range of 2.5 to 5.5 mol%, more preferably in the range of 3.0 to 5.0 mol% (for example, 4.0 to 4.5 mol%); ii) a second propylene random copolymer (P2) having a comonomer content in the range of 4.0 to 10.0 mol%, preferably in the range of 5.0 to 9.0 mol%, more preferably in the range of 5.5 to 8.0 mol% (for example, 6.0 to 7.0 mol%); Includes:

[0066] According to another preferred embodiment of the present invention, the comonomer of the propylene random copolymer is 1-butene, and the propylene random copolymer (P) has a xylene solubles content (XCS) determined in accordance with ISO 16152 (25°C) in the range of 0.1 to 5.0 wt %, preferably in the range of 0.2 to 3.0 wt %, and more preferably in the range of 0.3 to 2.0 wt %, based on the total weight of the propylene random copolymer (P).

[0067] According to another preferred embodiment of the present invention, the comonomer of the propylene random copolymer is 1-butene, and the propylene random copolymer (P) has a melt flow rate MFR2 (230°C, 2.16 kg) determined in accordance with ISO 1133 in the range of 45.0 to 150.0 g / 10 min, preferably in the range of 50.0 to 130.0 g / 10 min, more preferably in the range of 55.0 to 110.0 g / 10 min, and even more preferably in the range of 60.0 to 100.0 g / 10 min. The propylene random copolymer (P) can be obtained, and is preferably obtained, in particular by the process defined in detail below.

[0068] The process for the preparation of the propylene random copolymer (P) is preferably a sequential polymerization process comprising at least two reactors connected in series, which process comprises: (A) polymerizing propylene and a comonomer selected from ethylene and C4 to C12 α-olefins, preferably 1-hexene or 1-butene, in a first reactor (R-1), which is a slurry reactor (SR), preferably a loop reactor (LR), to obtain a first propylene random copolymer (P1) as defined in the present invention; (B) transferring the first propylene random copolymer (P1) and unreacted comonomers from the first reactor (R-1) to a second reactor (R-2) which is a gas phase reactor (GPR-1); (C) supplying propylene and a comonomer selected from ethylene and a C4 to C12 α-olefin, preferably 1-hexene or 1-butene, to the second reactor (R-2); (D) a step of polymerizing propylene and a comonomer selected from ethylene and C4 to C12 α-olefins, preferably 1-hexene or 1-butene, in the presence of the first propylene random copolymer (P1) in the second reactor (R-2) to obtain a second propylene random copolymer (P2) defined in the present invention, wherein the first propylene random copolymer (P1) and the second propylene random copolymer (P2) form the propylene random copolymer (P) defined in the present invention; and further comprising: in the first reactor (R-1) and the second reactor (R-2), the polymerization comprises: (i) a transition metal compound of formula (I), R n (Cp)2MX2(I) In the above formula (I), "M" is zirconium (Zr) or hafnium (Hf), each "X" is independently a monovalent anionic σ-ligand; each "Cp" is independently a cyclopentadienyl-type organic ligand selected from the group consisting of unsubstituted or substituted and / or fused cyclopentadienyl, substituted or unsubstituted indenyl, or substituted or unsubstituted fluorenyl, which organic ligand coordinates to a transition metal (M); "R" is a divalent bridging group that links the organic ligands (Cp), "n" is 1 or 2, preferably 1 a transition metal compound; (ii) optionally a co-catalyst (Co) comprising an element (E) from group 13 of the periodic table (IUPAC), preferably a co-catalyst (Co) comprising a compound of Al and / or B; This occurs in the presence of a solid catalyst system (SCS) containing

[0069] Regarding the definitions of the propylene random copolymer (P), the first random propylene copolymer (P1) and the second random propylene copolymer (P2), reference is made to the definitions given above.

[0070] A solid catalyst system (SCS) is defined in more detail below.

[0071] The use of a solid catalyst system (SCS) in a sequential polymerization process makes it possible to produce the above-defined propylene random copolymer (P). In particular, by preparing a propylene copolymer, i.e., a first random propylene copolymer (P1), in a first reactor (R-1) and transporting this propylene copolymer, and in particular unreacted comonomer, to a second reactor (R-2), it is possible to produce a copolymer (P) with a high comonomer content in a sequential polymerization process. Usually, the preparation of a propylene copolymer with a high comonomer content in a sequential polymerization process leads to fouling, or in severe cases, to blockage of the transfer line, usually because unreacted comonomer condenses in the transfer line. However, using the new method, the comonomer conversion rate is increased, and therefore, better incorporation into the polymer chain is achieved, which leads to a higher comonomer content and reduced stickiness problems.

[0072] The term "sequential polymerization process" means that the propylene random copolymer (P) is produced in at least two reactors connected in series. More precisely, the term "sequential polymerization process" in the present application indicates that the polymer from the first reactor (R-1) is directly transferred to the second reactor (R-2) together with unreacted comonomers. Thus, the crucial aspect of the process is the preparation of the propylene random copolymer (P) in two different reactors, and the reactants from the first reactor (R-1) are directly transferred to the second reactor (R-2). Thus, the process comprises at least a first reactor (R-1) and a second reactor (R-2). In one particular embodiment, the process consists of two polymerization reactors (R-1) and (R-2). The term "polymerization reactor" is intended to indicate that the main polymerization takes place therein. Thus, if the process consists of two polymerization reactors, this definition does not exclude the option that the overall process also comprises a prepolymerization (prepolymerization, prepolymerization) step, for example in a prepolymerization reactor. The term "consists of" is merely a closing formulation taking into account the main polymerization reactor.

[0073] 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 on a slurry. According to the present invention, the slurry reactor (SR) is preferably a loop reactor (LR).

[0074] The second reactor (R-2) 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) comprises a mechanically agitated fluidized bed reactor having a gas velocity of at least 0.2 m / sec. It is therefore understood that the gas phase reactor (GPR) is preferably a fluidized bed type reactor equipped with a mechanical agitator.

[0075] The conditions in each reactor (temperature, pressure, reaction time, monomer feed) depend on the desired product and are within the knowledge of those skilled in the art. As already indicated above, the first reactor (R-1) is a slurry reactor (SR), e.g., 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).

[0076] A preferred multi-stage process is a "loop-gas phase" process such as that developed by Borealis A / S, Denmark (known as BORSTAR® technology) and described in patent literature such as, for example, EP 0 887 379 or WO 92 / 12182.

[0077] Multimodal polymers can be produced according to several processes described, for example, in WO 92 / 12182, EP 0 887 379, and WO 98 / 58976, the contents of which are incorporated herein by reference.

[0078] Preferably, in the process for producing the propylene random copolymer (P) defined above, the conditions for the first reactor (R-1) of 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 between 65°C and 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 in a manner known per se.

[0079] 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), wherein the conditions in step (D) 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 in a manner known per se.

[0080] The residence time may be different in both reactor zones.

[0081] In one embodiment of the process for producing the propylene random copolymer (P), the residence time in the slurry reactor (SR), e.g., loop (LR), is in the range of 0.2 to 4.0 hours, e.g., 0.3 to 1.5 hours, and the residence time in the gas phase reactor (GPR) is generally 0.2 to 6.0 hours, e.g., 0.5 to 4.0 hours.

[0082] If desired, the polymerization may be carried out in a known manner under supercritical conditions in a first reactor (R-1), i.e. in a slurry reactor (SR), for example in a loop reactor (LR).

[0083] The conditions in the other gas phase reactor (GPR), if present, are similar to those in the second reactor (R-2).

[0084] The process may also include a prepolymerization prior to the polymerization in the first reactor (R-1). This prepolymerization can be carried out in the first reactor (R-1), however, it is preferred that the prepolymerization is carried out in a separate reactor, the so-called prepolymerization reactor.

[0085] The propylene random copolymer (P) according to the present invention is prepared in the presence of a solid catalyst system (SCS) containing a transition metal compound.

[0086] The transition metal compound has the formula (I): R n (Cp)2MX2(I) In the above formula (I), each Cp is independently an unsubstituted or substituted and / or fused cyclopentadienyl ligand, such as a substituted or unsubstituted cyclopentadienyl, a substituted or unsubstituted indenyl or a substituted or unsubstituted fluorenyl ligand, wherein the optional one or more substituents are independently preferably selected from halogen, hydrocarbyl (e.g. C1-C20-alkyl, C2-C20-alkenyl, C2-C20-alkynyl, C3-C12-cycloalkyl, C6-C20-aryl or C7-C20-arylalkyl), C3-C12-cycloalkyl containing 1, 2, 3 or 4 heteroatoms in the ring portion, C6-C20-heteroaryl, C1-C20-haloalkyl, -SiR"3, -OSiR"3, -SR", -PR"2, OR" or -NR"2; each R" is independently hydrogen or hydrocarbyl, such as C1-C20-alkyl, C2-C20-alkenyl, C2-C20-alkynyl, C3-C12-cycloalkyl or C6-C20-aryl, or, for example in the case of -NR"2, the two substituents R" together with the nitrogen atom to which they are attached can form a ring, for example a 5- or 6-membered ring; R is a bridging group of 1 to 3 atoms, for example a bridging group of 1 to 2 C atoms and 0 to 2 heteroatoms, which heteroatoms can be, for example, Si, Ge and / or O atoms, each of the bridging atoms independently optionally carrying a substituent, for example a C-C alkyl, tri(C-C alkyl)silyl, tri(C-C alkyl)siloxy or C-C aryl substituent, or a bridging group of 1 to 3, for example 1 or 2, heteroatoms, for example silicon, germanium and / or oxygen atoms, for example each R 10 are independently C1-C20-alkyl, C3-12-cycloalkyl, C6-C20-aryl or tri(C1-C20-alkyl)silyl residues, for example trimethylsilyl, -SiR 10 2, M is a group 4 transition metal, such as Zr or Hf, especially Zr; each X is independently a σ-ligand, for example H, halogen, C1-C20-alkyl, C1-C20-alkoxy, C2-C20-alkenyl, C2-C20-alkynyl, C3-C12-cycloalkyl, C6-C20-aryl, C6-C20-aryloxy, C7-C20-arylalkyl, C7-C20-arylalkenyl, -SR", -PR"3, -SiR"3, -OSiR"3, -NR"2 or -CH2-Y, where Y is C6-C20-aryl, C6-C20-heteroaryl, C1-C20-alkoxy, C6-C20-aryloxy, NR"2, -SR", -PR"3, -SiR"3 or -OSiR"3; Each of the above ring moieties can be further substituted, either alone or as part of another moiety as a substituent on Cp, X, R″ or R, for example with C1-C20-alkyl, which may contain Si and / or O atoms; n is 1 or 2.

[0087] Suitably, when each X is -CH2-Y, each Y is independently selected from C6-C20-aryl, NR"2, -SiR"3 or -OSiR"3. Most preferably, X as -CH2-Y is benzyl. Each X other than CH2-Y is independently halogen, C1-C20-alkyl, C1-C20-alkoxy, C6-C20-aryl, C7-C20-arylalkenyl or -NR"2 as defined above, for example -N(C1-C20-alkyl)2.

[0088] Preferably, each X is halogen, methyl, phenyl or -CH2-Y, where each Y is independently as defined above.

[0089] Cp is preferably cyclopentadienyl, indenyl or fluorenyl, optionally substituted as defined above. Ideally, Cp is cyclopentadienyl or indenyl.

[0090] In a suitable sub-group of compounds of formula (I), each Cp independently carries 1, 2, 3 or 4 substituents as defined above, preferably 1, 2 or 3 substituents, for example 1 or 2 substituents, which are preferably selected from C1-C20-alkyl, C6-C20-aryl, C7-C20-arylalkyl (in which the aryl ring, alone or as part of a further moiety, may be further substituted as indicated above), -OSiR"3, where R" is as defined above, preferably C1-C20-alkyl.

[0091] R is preferably a methylene, ethylene or silyl bridging group, where silyl can be substituted as defined above, for example (dimethyl)Si=, (methylphenyl)Si=, (methylcyclohexyl)silyl= or (trimethylsilylmethyl)Si=, and n is 0 or 1. Preferably, R″ is other than hydrogen.

[0092] A particular subgroup includes the well-known metallocenes of Zr and Hf having two bridged η-ligands, such as cyclopentadienyl ligands optionally substituted with siloxy or alkyl (e.g., C1-6-alkyl) as defined above, or two bridged indenyl ligands optionally substituted on any of the ring moieties, e.g., in positions 2, 3, 4, and / or 7, with siloxy or alkyl as defined above. Preferred bridging groups are ethylene or -SiMe2.

[0093] The preparation of metallocenes can be carried out according to or analogously to methods known from the literature and is within the skill of a person skilled in the art. For the preparation, reference is therefore made to EP-A-129368, and for examples of compounds in which the metal atom carries an -NR" ligand, reference is made, inter alia, to WO-A-9856831 and WO-A-0034341. For the preparation, reference is also made, for example, to EP-A-260130, WO-A-9728170, WO-A-9846616, WO-A-9849208, WO-A-9912981, WO-A-9919335, WO-A-9856831, WO-A-0034341, EP-A-423101 and EP-A-537130.

[0094] The complexes of the present invention are preferably asymmetric. This simply means that the two indenyl ligands forming the metallocene are different, i.e., each indenyl ligand has a set of substituents that are chemically different or located at different positions relative to the other indenyl ligand. More precisely, they are chiral racemic bridged bisindenyl metallocenes. The complexes of the present invention may ideally be in the syn configuration, but they are in the anti configuration. For the purposes of the present invention, racemic anti means that the two indenyl ligands are oriented in opposite directions relative to the cyclopentadienyl-metal-cyclopentadienyl plane, while racemic syn means that the two indenyl ligands are oriented in the same direction relative to the cyclopentadienyl-metal-cyclopentadienyl plane.

[0095] Preferred complexes of the present invention are of formula (II') or (II) [ka] In the above formulas (II') and (II), M is Zr; each X is a σ (sigma) ligand, preferably each X is independently a hydrogen atom, a halogen atom, a C1-C6 alkoxy group, a C1-C6 alkyl, a phenyl, or a benzyl group; L is a divalent bridging group selected from -R'2C-, -R'2C-CR'2, -R'2Si-, -R'2Si-SiR'2-, and -R'2Ge-, and each R' is independently a hydrogen atom, a C1-C20 alkyl, a C3-C10 cycloalkyl, a tri(C1-C20 alkyl)silyl, a C6-C20 aryl, or a C7-C20 arylalkyl; Each R 2 or R 2 ' is a C1-C10 alkyl group, R 5 ' is a C1-C10 alkyl group or Z'R 3 'Based on R 6 is hydrogen or a C1-C10 alkyl group, R 6 ' is a C1 to C10 alkyl group or a C6 to C10 aryl group, R 7 is hydrogen, a C1-C6 alkyl group, or ZR 3 It is the basis, R 7 ' is hydrogen or a C1-C10 alkyl group, Z and Z′ are independently O or S; R 3 ' is a C1-C10 alkyl group or a C6-C10 aryl group optionally substituted with one or more halogen groups, R 3 is a C1-C10 alkyl group, each n is independently 0 to 4, for example, 0, 1, or 2; Each R 1 are independently a C1 to C20 hydrocarbyl group, for example a C1 to C10 alkyl group.

[0096] Particularly preferred compounds of the present invention include: rac-Dimethylsilanediylbis[2-methyl-4-(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-l-yl]zirconium dichloride rac-Dimethylsilanediylbis(2-methyl-4-phenyl-5-methoxy-6-tert-butylinden-l-yl)zirconium dichloride rac-anti-Me2Si(2-Me-4-Ph-6-tBu-Ind)(2-Me-4-Ph-5-OMe-6-tBu-Ind)ZrCl2 rac-anti-Me2Si(2-Me-4-(p-tBuPh)-Ind)(2-Me-4-Ph-5-OMe-6-tBu-Ind)ZrCl2 rac-anti-Me2Si(2-Me-4-(3,5-di-tBuPh)-6-tBu-Ind)(2-Me-4-Ph-5-OMe-6-tBu-Ind)ZrCl2 rac-anti-Me2Si(2-Me-4-(p-tBuPh)-Ind)(2-Me-4-Ph-5-OC6F5)-6-iPr-Ind)ZrCl2 rac-anti-Me(CyHex)Si(2-Me-4-Ph-6-tBu-Ind)(2-Me-4-Ph-5-OMe-6-tBu-Ind)ZrCl2 rac-anti-Me2Si(2-Me-4-(3,5-di-tBuPh)-7-Me-Ind)(2-Me-4-Ph-5-OMe-6-tBu-Ind)ZrCl2 rac-anti-Me2Si(2-Me-4-(3,5-di-tBuPh)-7-OMe-Ind)(2-Me-4-Ph-5-OMe-6-tBu-Ind)ZrCl2 rac-anti-Me2Si(2-Me-4-(p-tBuPh)-6-tBu-Ind)(2-Me-4-Ph-5-OMe-6-tBu-Ind)ZrCl2 rac-anti-Me2Si(2-Me-4-(p-tBuPh)-Ind)(2-Me-4-(4-tBuPh)-5-OMe-6-tBu-Ind)ZrCl2 rac-anti-Me2Si(2-Me-4-(p-tBuPh)-Ind)(2-Me-4-(3,5-tBu2Ph)-5-OMe-6-tBu-Ind)ZrCl2 rac-anti-Me2Si(2-Me-4-(p-tBuPh)-Ind)(2-Me-4-Ph-5-OtBu-6-tBu-Ind)ZrCl2 Examples include:

[0097] The most preferred metallocene complex (catalyst precursor (precatalyst)) is rac-anti-dimethylsilanediyl(2-methyl-4-phenyl-5-methoxy-6-tert-butyl-indenyl)(2-methyl-4-(4-tert-butylphenyl)indenyl)zirconium dichloride.

[0098] Besides the metallocene complex (catalyst precursor), the metallocene catalyst further comprises a co-catalyst as defined in WO 2015 / 011135 A1. Accordingly, preferred co-catalysts are methylaluminoxane (MAO) and / or a borate, preferably trityltetrakis(pentafluorophenyl)borate.

[0099] It is particularly preferred that the metallocene catalyst is unsupported, i.e., no external support is used. With regard to the preparation of such metallocene complexes, reference is again made to WO 2015 / 011135 A1.

[0100] Fiber (F) The essential component of the fiber-reinforced composition (C) is the fiber (F).

[0101] Preferably, the fibers (F) are selected from the group consisting of glass fibers, carbon fibers, polymer fibers, metal fibers, mineral fibers, ceramic fibers, and mixtures thereof. More preferably, the fibers (F) are glass fibers and / or carbon fibers.

[0102] It is particularly preferred that the fibers (F) are glass fibers (GF). Preferably, the glass fibers (GF) are chopped glass fibers, also known as short glass fibers (SGF) or chopped strands, and / or long glass fibers (LGF), preferably long glass fibers (LGF) obtained from glass roving.

[0103] It is particularly preferred that the fibers (F) are short glass fibers (SGF).

[0104] The chopped glass fibers or short glass fibers (SGF) used in the fiber-reinforced composition (C) preferably have an average length in the range of 2.0 to 10.0 mm, more preferably in the range of 2.3 to 9.0 mm, 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.

[0105] The chopped glass fibers or short glass fibers (SGF) used in the fiber-reinforced composition (C) preferably have an average diameter of 5 to 20 μm, more preferably 6 to 18 μm, and even more preferably 8 to 16 μm.

[0106] Preferably, the short glass fibers (SGF) have an aspect ratio of 125 to 650, preferably 150 to 500, more preferably 200 to 450. The aspect ratio is the relationship between the average length and the average diameter of the fibers.

[0107] Adhesion promoter (AP) According to the present invention, the fiber-reinforced polypropylene composition (C) may further comprise an adhesion promoter (AP). When the fibers (F) are glass fibers and / or carbon fibers, it is preferred that the fiber-reinforced polypropylene composition (C) comprises an adhesion promoter (AP).

[0108] The adhesion promoter (AP) is identified as a polar modified polypropylene (PM-PP) homopolymer or copolymer.

[0109] Polar-modified polypropylene (PM-PP) homopolymers or copolymers contain low molecular weight compounds having reactive polar groups. Modified polypropylene homopolymers and copolymers, such as copolymers of propylene and ethylene or other α-olefins, such as C4 to C10 α-olefins, are most preferred because they are highly compatible with the propylene polymer (P) of the fiber-reinforced polypropylene composition (C) of the present invention.

[0110] In terms of structure, the polar modified polypropylene (PM-PP) homopolymer or copolymer is preferably selected from graft homopolymers or copolymers.

[0111] In this regard, polar modified polypropylene (PM-PP) homopolymers or copolymers containing groups derived from polar compounds, in particular 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 ionic compounds, are preferred.

[0112] Specific examples of the polar compound include unsaturated cyclic anhydrides and their aliphatic diesters, dibasic acid derivatives, etc. In particular, compounds selected from maleic anhydride, C1-C10 linear and branched dialkyl maleates, C1-C10 linear and branched dialkyl fumarates, itaconic anhydride, C1-C10 linear and branched dialkyl itaconic acid esters, acrylic acid, maleic acid, fumaric acid, itaconic acid, and mixtures thereof can be used.

[0113] Particular preference is given to using homopolymers or copolymers of polypropylene grafted with maleic anhydride or acrylic acid as polar modified polypropylene (PM-PP) homopolymers or copolymers, ie adhesion promoters (AP).

[0114] The modified polymers, i.e., adhesion promoters, can be prepared in a simple manner by reactive extrusion of the polymers with, for example, maleic anhydride or acrylic acid in the presence of a free radical generator (such as an organic peroxide), as disclosed, for example, in U.S. Pat. No. 4,506,056, U.S. Pat. No. 4,753,997 or EP-A-1 805 238.

[0115] The preferred amount of groups derived from polar compounds 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 0.5 to 4.0% by weight, and more preferably 0.5 to 3.5% by weight.

[0116] For the polar modified polypropylene (PM-PP) homopolymer or copolymer, i.e., for the adhesion promoter (AP), the melt flow rate MFR2(230°C) is preferably 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 50.0 to 250 g / 10 min.

[0117] In one preferred embodiment of the present invention, the adhesion promoter (AP) is a maleic anhydride-modified polypropylene homo / copolymer and / or an acrylic acid-modified polypropylene homo / copolymer. Preferably, the adhesion promoter (AP) is a maleic anhydride-modified polypropylene homopolymer and / or an acrylic acid-modified polypropylene homopolymer, preferably a maleic anhydride-modified polypropylene homopolymer. For example, suitable polar-modified polypropylene (PM-PP) homopolymers or copolymers include, for example, a polypropylene homopolymer grafted with maleic anhydride (PP-g-MAH) and a polypropylene homopolymer grafted with acrylic acid (PP-g-AA).

[0118] According to another preferred embodiment of the invention, the adhesion promoter (AP) is the above-mentioned propylene random copolymer (P) grafted with maleic anhydride.

[0119] Additives (AD) In addition to the propylene random copolymer (P), the fiber (F) and the adhesion promoter (AP), the fiber reinforced composition (C) of the present invention may also contain additives (AD). Typical additives are acid scavengers, antioxidants, colorants, light stabilizers, plasticizers, slip agents, anti-scratch agents, dispersants, processing aids, lubricants, pigments, etc.

[0120] Such additives are commercially available and are described, for example, in Hans Zweifel's "Plastic Additives Handbook", 6th edition, 2009 (pp. 1141-1190).

[0121] Furthermore, the term "additive (AD)" according to the present invention also includes carrier materials, in particular polymeric carrier materials.

[0122] Polymeric Carrier Materials Preferably, the fiber reinforced polypropylene composition (C) of the present invention does not contain (a) additional polymer(s) other than the propylene random copolymer (P) and the adhesion promoter (AP) in an amount of more than 5.0 wt.%, preferably more than 3.0 wt.%, more preferably more than 2.0 wt.%, based on the weight of the fiber reinforced polypropylene composition (C). Any polymer that is a carrier material for an additive (AD) is counted in the amount of the respective additive, not in the amount of the polymer compound as indicated in the present invention.

[0123] The polymeric carrier material for the additive (AD) is a carrier polymer to ensure uniform distribution in the fiber-reinforced polypropylene composition (C) of the present invention. This polymeric carrier material is not limited to a specific polymer. The polymeric carrier material may be an ethylene homopolymer, an ethylene copolymer obtained from ethylene and an α-olefin comonomer such as 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 polymeric carrier material does not contain monomer units derivable from styrene or its derivatives.

[0124] Goods The present invention also relates to an article, such as an injection-molded article, comprising the above-defined fiber-reinforced composition (C). The present invention particularly relates to an article, such as an injection-molded article, comprising 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 above-defined fiber-reinforced polypropylene composition (C). In a particularly preferred embodiment, the present invention relates to an article, such as an injection-molded article, consisting of the above-defined fiber-reinforced composition (C).

[0125] Preferably, the article is an automotive article, such as an injection molded automotive article.

[0126] Further embodiments [1] A fiber-reinforced composition (C), based on the total weight of the fiber-reinforced composition (C): a) 57.0 to 95.0 wt. % of a propylene random copolymer (P), wherein the comonomer is selected from ethylene and / or at least one C4 to C12 α-olefin, and the propylene random copolymer (P) is i) a melt flow rate MFR2 (230°C, 2.16 kg) determined according to ISO 1133 in the range of 45 to 150 g / 10 min; and ii) the melting temperature Tm determined according to differential scanning calorimetry (DSC) in the range of 125-150°C; A propylene random copolymer (P) having the formula: b) 5.0 to 40.0% by weight of fiber (F); c) optionally 0.1 to 5.0 wt. % of an adhesion promoter (AP); A fiber-reinforced composition (C) comprising:

[0127] [2] The fiber-reinforced composition (C) according to [1], wherein the propylene random copolymer (P) has 1,2 erythro position defects in an amount of at least 0.4 mol %.

[0128] [3] The propylene random copolymer (P) is i) a first propylene random copolymer (P1); ii) a second propylene random copolymer (P2) having a higher comonomer content than the first propylene random copolymer (P1); wherein the weight ratio of the first propylene random copolymer (P1) to the second propylene random copolymer (P2) is in the range of 20 / 80 to 60 / 40, and the total amount of the first propylene random copolymer (P1) and the second propylene random copolymer (P2) relative to the propylene random copolymer (P) is at least 95.0% by weight. The fiber-reinforced composition (C) according to [1] or [2].

[0129] [4] The fiber-reinforced composition (C) according to any one of [1] to [3], wherein the propylene random copolymer (P) has a comonomer content in the range of 1.0 to 6.0 mol %.

[0130] [5] i) the first propylene random copolymer (P1) has a comonomer content in the range of 0.4 to 2.5 mol%, ii) the second propylene random copolymer (P2) has a comonomer content in the range of 2.8 to 7.0 mol %; The fiber-reinforced composition (C) according to any one of [1] to [4].

[0131] [6] The fiber-reinforced composition (C) according to any one of [1] to [5], wherein the comonomer is 1-hexene.

[0132] [7] The fiber-reinforced composition (C) according to any one of [1] to [6], wherein the propylene random copolymer (P) has a xylene solubles content (XCS) determined in accordance with ISO 16152 (25°C) in the range of 3.0 to 15.0 wt% based on the total weight of the propylene random copolymer (P).

[0133] [8] The fiber-reinforced composition (C) according to any one of [1] to [6], wherein the propylene random copolymer (P) is visbroken at a visbreaking ratio of at least 5.0 [final MFR2 (230°C / 2.16 kg) / initial MFR2 (230°C / 2.16 kg)], wherein "final MFR2 (230°C / 2.16 kg)" is the MFR2 (230°C / 2.16 kg) of the propylene random copolymer (P) after visbreaking, and "initial MFR2 (230°C / 2.16 kg)" is the MFR2 (230°C / 2.16 kg) of the propylene random copolymer (P) before visbreaking.

[0134] [9] The fiber-reinforced composition (C) according to [8], wherein the propylene random copolymer (P) has a melt flow rate MFR2 (230°C, 2.16 kg) determined in accordance with ISO 1133 before visbreaking in the range of 0.5 to 10.0 g / 10 min.

[0135]

[10] The fiber (F) is a glass fiber (GF), preferably i) an average length of 2.0 to 10.0 mm, and / or ii) average diameter of 5 to 20 μm The fiber-reinforced composition (C) according to any one of [1] to [9] is short glass fiber (SGF) having the following formula:

[0136]

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

[10] , wherein 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 MFR2 (230°C, 2.16 kg) of 20.0 g / 10 min to 400 g / 10 min, determined in accordance with ISO 1133.

[0137]

[12] A fiber-reinforced composition (C) according to any one of [1] to

[11] , having a melt flow rate MFR2 (230°C, 2.16 kg) determined in accordance with ISO 1133 in the range of 8.0 to 60.0 g / 10 min.

[0138]

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

[12] , wherein the propylene random copolymer (P) is obtained in the presence of a solid catalyst system (SCS) containing a metallocene compound.

[0139]

[14] The metallocene compound has the formula (I): R n (Cp)2MX2(I) In the above formula (I), each Cp is independently an unsubstituted or substituted and / or fused cyclopentadienyl ligand, such as a substituted or unsubstituted cyclopentadienyl, a substituted or unsubstituted indenyl or a substituted or unsubstituted fluorenyl ligand, wherein the optional one or more substituents are independently preferably selected from halogen, hydrocarbyl (e.g. C1-C20-alkyl, C2-C20-alkenyl, C2-C20-alkynyl, C3-C12-cycloalkyl, C6-C20-aryl or C7-C20-arylalkyl), C3-C12-cycloalkyl containing 1, 2, 3 or 4 heteroatoms in the ring portion, C6-C20-heteroaryl, C1-C20-haloalkyl, -SiR"3, -OSiR"3, -SR", -PR"2, OR" or -NR"2; each R" is independently hydrogen or hydrocarbyl, such as C1-C20-alkyl, C2-C20-alkenyl, C2-C20-alkynyl, C3-C12-cycloalkyl or C6-C20-aryl, or, for example in the case of -NR"2, the two substituents R" together with the nitrogen atom to which they are attached can form a ring, for example a 5- or 6-membered ring; R is a bridging group of 1 to 3 atoms, for example a bridging group of 1 to 2 C atoms and 0 to 2 heteroatoms, which heteroatoms can be, for example, Si, Ge and / or O atoms, each of said bridging atoms independently being a bridging group optionally carrying a substituent, for example a C-C alkyl, tri(C-C alkyl)silyl, tri(C-C alkyl)siloxy or C-C aryl substituent, or a bridging group of 1 to 3, for example 1 or 2, heteroatoms, such as silicon, germanium and / or oxygen atoms, for example each R 10 are independently C1-C20-alkyl, C3-12-cycloalkyl, C6-C20-aryl or tri(C1-C20-alkyl)silyl residues, for example trimethylsilyl, -SiR 10 2, M is a group 4 transition metal, such as Zr or Hf, especially Zr; each X is independently a σ-ligand, for example H, halogen, C1-C20-alkyl, C1-C20-alkoxy, C2-C20-alkenyl, C2-C20-alkynyl, C3-C12-cycloalkyl, C6-C20-aryl, C6-C20-aryloxy, C7-C20-arylalkyl, C7-C20-arylalkenyl, -SR", -PR"3, -SiR"3, -OSiR"3, -NR"2 or -CH2-Y, where Y is C6-C20-aryl, C6-C20-heteroaryl, C1-C20-alkoxy, C6-C20-aryloxy, NR"2, -SR", -PR"3, -SiR"3 or -OSiR"3; Each of the above ring moieties can be further substituted, either alone or as part of another moiety as a substituent on Cp, X, R″ or R, for example with C1-C20-alkyl, which may contain Si and / or O atoms; n is 1 or 2 The fiber-reinforced composition (C) according to claim

[13] .

[0140]

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

[14] .

[0141] The present invention will now be described in further detail by the examples provided below. [Example]

[0142] A.Measurement method The following definitions of terms and methods of determination apply to the above summary of the invention and the following examples, unless otherwise defined.

[0143] Comonomer content of 1-hexene for propylene-1-hexene copolymer (P) quantitative 13 C{ 1 The {H} NMR spectrum is 1 H and 13 All spectra were recorded in the melt using a Bruker Avance III 500 NMR spectrometer operating at 500.13 MHz and 125.76 MHz for C, respectively. 13All air pressures were recorded using nitrogen gas using a 7 mm magic angle spinning (MAS) probe head optimized for C. Approximately 200 mg of material was loaded into a 7 mm outer diameter zirconia MAS rotor and spun at 4 kHz. This setup was chosen primarily due to the high sensitivity required for rapid identification and accurate quantification (Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, HW, Wilhelm, M., Macromol. Chem. Phys. 2006;207:382.; Parkinson, M., Klimke, K., Spiess, HW, Wilhelm, M., Macromol. Chem. Phys. 2007;208:2128.; Castignolles, P., Graf, R., Parkinson, M., Wilhelm, M., Gaborieau, M., Polymer 50 (2009) 2373). NOE with a short recycle delay of 3 s (Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, HW, Wilhelm, M., Macromol. Chem. Phys. 2006;207:382; Pollard, M., Klimke, K., Graf, R., Spiess, HW, Wilhelm, M., Sperber, O., Piel, C., Kaminsky, W., Macromol. Chem. Phys. 2004;37:813.) and RS-HEPT decoupling scheme (Filip, X., Tripon, C., Filip, C., J. Mag. Resn. 2005, 176, 239.; Griffin, J. M., Tripon, C., Samoson, A., Filip, C., and Brown, S. P., Mag. Res. in Standard single-pulse excitation was employed using a 16kJ / s pulse (Chem. 2007 45, S1, S198). A total of 16384 (16k) transients were acquired per spectrum. quantitative 13 C{ 1 H} NMR spectra were processed and integrated, and relevant quantitative properties were determined from the integrals. All chemical shifts were internally referenced to the methyl isotactic pentad (mmmm) at 21.85 ppm. A characteristic signal corresponding to 1-hexene incorporation was observed and the comonomer content was quantified as follows. The amount of 1-hexene incorporated in isolated sequences of PHP was quantified using the integral value of the αB4 site at 44.2 ppm and taking into account the number of reported sites per comonomer. H=IαB4 / 2 The amount of 1-hexene incorporated in two consecutive sequences of PHHP was quantified using the integral value of ααB4 sites of 41.7 ppm and taking into account the number of reported sites per comonomer. HH=2×IααB4 When two consecutive incorporations were observed, the amount of 1-hexene incorporated in the isolated sequence of PHP needed to be corrected due to the overlap of the αB4 and αB4B4 signals at 44.4 ppm. H=(IαB4-2×IααB4) / 2 The total 1-hexene content was calculated based on the sum of isolated and consecutively incorporated 1-hexene. Htotal=H+HH If no sites of continuous incorporation were observed, the total 1-hexene comonomer content was calculated based on this amount alone. Htotal=H A characteristic signal indicating a 2,1-erythro defect was observed (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253). The presence of 2,1-erythro regiodefects was indicated by the presence of methyl moieties at Pαβ (21e8) and Pαγ (21e6) at 17.7 ppm and 17.2 ppm, and confirmed by other characteristic signals. The total amount of secondary (2,1-erythro) inserted propene was quantified based on the αα21e9 methylene moiety at 42.4 ppm. P21=Iαα21e9 The total amount of primary (1,2) inserted propene was quantified based on the predominant Sαα methylene site at 46.7 ppm and corrected for the relative amounts of 2,1-erythro, αB4 methylene units, and ααB4B4 methylene units of propene that were not taken into account (note that the H and HH counts of hexene monomers per sequence are not the number of sequences). P12=I S αα+2×P21+H+HH / 2 The total amount of propene was quantified as the sum of primary (1,2) and secondary (2,1-erythro) inserted propene. Ptotal=P12+P21=I S αα+3×Iαα21e9+(IαB4-2×IααB4) / 2+IααB4 This becomes simple as follows: Ptotal=I S αα+3×Iαα21e9+0.5×IαB4 The total mole fraction of 1-hexene in the polymer was then calculated as follows: fH=Htotal / (Htotal+Ptotal) The complete integral equation for the mole fraction of 1-hexene in the polymer is: fH=(((IαB4-2×IααB4) / 2)+(2×IααB4)) / ((I S αα+3×Iαα21e9+0.5×IαB4)+((IαB4-2×IααB4) / 2)+(2×IααB4)) This becomes simple as follows: fH=(IααB4 / 2+IααB4) / (I S αα+3×Iαα21e9+IαB4+IααB4) Total comonomer incorporation of 1-hexene in mole percent was calculated in the usual manner from the mole fractions above. H [mol%] = 100 × fH The total comonomer incorporation of 1-hexene in weight percent was calculated in the standard manner from the mole fractions above. H[weight%]=100×(fH×84.16) / ((fH×84.16)+((1-fH)×42.08))

[0144] Calculation of the comonomer content of the second propylene random copolymer (P2)

number

[0145] Comonomer content of 1-butene for propylene-1-butene copolymer (P) quantitative 13 C{ 1 {H} NMR spectra were recorded, processed and referenced as described above. A characteristic signal corresponding to the incorporation of 1-butene was observed and the comonomer content was quantified as follows: The amount of 1-butene incorporated in isolated sequences of PPBPP was quantified using the integral value of the αB2 site of 43.6 ppm and considering the number of reported sites per comonomer. B=Iα / 2 The amount of 1-butene incorporated in two consecutive sequences of PPBBPP was quantified using the integral value of ααB2B2 sites of 40.5 ppm and taking into account the number of reported sites per comonomer. BB=2×Iαα When two consecutive incorporations were observed, the amount of 1-butene incorporated in the isolated sequence of PPBPP needed to be corrected due to the overlap of the αB2 and αB2B2 signals at 43.9 ppm. B=(Iα-2×Iαα) / 2 The total 1-butene content was calculated based on the sum of isolated and sequentially incorporated 1-butene. B total =B+BB The amount of propene was quantified based on the predominant Sαα methylene site at 46.7 ppm and corrected for the relative amounts of αB2 methylene units and ααB2B2 methylene units of propene that are not taken into account (note that the B and BB counts of butane monomer per sequence are not the number of sequences). P total =I S αα+B+BB / 2 If characteristic signals corresponding to regio-defects (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253) were observed, a correction for misinserted propylene units was used for Ptotal. When 2,1-erythro misinsertion is present, the 9th carbon (S 21e9 ) (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253) was chosen for correction. In this case, P total =I S αα+B+BB / 2+3×I(S 21e9 ) The total mole fraction of 1-butene in the polymer was then calculated as follows: fB=(B total / (B total +P total ) Total comonomer incorporation of 1-butene in mole percent was calculated in the usual manner from the mole fractions above. B [mol%] = 100 × fB Total comonomer incorporation of 1-butene in weight percent was calculated in the standard manner from the above mole fractions. B[weight%]=100×(fB×56.11) / ((fB×56.11)+((1-fB)×42.08))

[0146] Melt Flow Rate (MFR) The melt flow rate MFR2 was measured using a 2.16 kg load at 230°C for propylene copolymers and a 2.16 kg load at 190°C for ethylene copolymers. The melt flow rate is the amount of polymer in grams extruded under a 2.16 kg load at 230°C and 190°C, respectively, within 10 minutes using a test apparatus standardized to ISO 1133.

[0147] Cold xylene solubles (XCS, wt%): The cold xylene solubles (XCS) content was determined at 25°C according to ISO 16152; 1st edition; 2005-07-01.

[0148] Melting temperature T m、 Crystallization temperature T c was measured using a Mettler TA820 differential scanning calorimetry (DSC) on 5-7 mg samples. DSC was performed in heat / cool / heat cycles at a scan rate of 10 °C / min in the temperature range of -30 to +225 °C according to ISO 11357 / Part 3 / Method C2. The crystallization temperature was determined from the cooling step, whereas the melting temperature was determined from the second heating step. All mechanical measurements were performed after a 96-hour conditioning period of the specimens (23°C, 50% relative humidity).

[0149] The glass transition temperature Tg was determined by dynamic mechanical analysis according to ISO 6721-7. The measurements were carried out on compression-molded samples (40 × 10 × 1 mm 3) was performed in torsional mode at a heating rate of 2°C / min between -100°C and +150°C and a frequency of 1 Hz.

[0150] The unnotched Charpy impact strength was determined at 23°C according to ISO 179-1 / 1eU by using injection-molded test specimens (80 x 10 x 4 mm) prepared according to EN ISO 1873-2.

[0151] Tensile properties were determined on 4 mm thick injection-molded dogbone specimens prepared according to EN ISO 1873-2. Tensile modulus was determined according to ISO 527-1A at a strain rate of 1 mm / min and 23°C, and tensile strength and elongation at break (strain) were determined according to ISO 527-2 at a strain rate of 50 mm / min and 23°C.

[0152] Heat deflection temperature (HDT) HDT is 80 x 10 x 4 mm prepared according to ISO1873-2 3 The test was performed on flat-supported specimens according to ISO 75, condition A, at a nominal surface stress of 1.80 MPa.

[0153] VOC / Fog emissions were measured according to VDA278:2002 on injection molded specimens and granulated formulations. Volatile organic compounds were measured in toluene equivalents / gram. Fogging was measured in hexadecane equivalents / gram. Measurements were carried out with a TDSA supplied by Gerstel using a column HP Ultra 2 with a length of 50 m, a diameter of 0.32 mm and a 0.52 μm coating of 5% phenyl-methyl-siloxane, using helium 5.0 as carrier gas. VOC analysis was performed according to the device settings listed in the standard, using the following main parameters: flow mode splitless, final temperature 90°C, final time 30 min, rate 60 K / min. The cold trap was purged in flow mode split 1:30, with a heating rate of 12 K / s and a final time of 5 min, in the temperature range from -150°C to +280°C. The following GC settings were used for the analysis: isothermal at 40°C for 2 min, 3 K / min to 92°C, then 5 K / min to 160°C, then 10 K / min to 280°C, isothermal for 10 min, flow rate 1.3 ml / min. Fog analysis was performed according to the device settings listed in the standard, using the following main parameters: flow mode splitless, rate 60 K / min; final temperature 120 °C; final time 60 min. The cold trap was purged in the temperature range from -150 °C to +280 °C with a heating rate of 12 K / s and flow mode split 1:30. The following GC settings were used for the analysis: isothermal at 50 °C for 2 min, heated at 25 K / min to 160 °C, then heated at 10 K / min to 280 °C, isothermal for 30 min, flow rate 1.3 ml / min.

[0154] 2. Working Example Catalyst preparation Metallocene (MC1) (rac-anti-dimethylsilanediyl(2-methyl-4-phenyl-5-methoxy-6-tert-butyl-indenyl)(2-methyl-4-(4-tert-butylphenyl)indenyl)zirconium dichloride) was synthesized as described in WO 2013 / 007650. The catalyst was prepared according to Catalyst 3 in WO 2015 / 11135 using metallocene MC1 and a catalyst system of MAO and trityl tetrakis(pentafluorophenyl)borate, except that the surfactant was 2,3,3,3-tetrafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)-1-propanol. Random propylene copolymers PI and P-II were prepared using this catalyst.

[0155] Preparation of random propylene copolymer (PI) Random propylene copolymers (PI) were prepared in a sequential (continuous) process involving a loop reactor and a gas-phase reactor. The reaction conditions are summarized in Table 1.

[0156] [Table 1]

[0157] The resulting copolymer was then visbroken at 210-230°C in a co-rotating twin-screw extruder using a masterbatch (POX) of 5% by weight of 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane with polypropylene. The resulting modified propylene random copolymer (mP-1) had a melt flow rate (MFR2) of 79 g / 10 min (230°C, 2.16 kg). This means that the visbreaking ratio was 52.7.

[0158] Preparation of random propylene copolymer (P-II) The random propylene copolymer (P-II) was prepared in a sequential process including a loop reactor and a gas-phase reactor. The reaction conditions are summarized in Table 2.

[0159] [Table 2]

[0160] The resulting copolymer was compounded without visbreaking using a basic antioxidant combination for stabilization.

[0161] P-II is a C3C4 random copolymer with a melt flow rate of 94 g / 10 min (MFR2, 230°C, 2.16 kg), a C4 comonomer content of 5.5 mol%, and no nucleating agent. P-II has a melting temperature (Tm) determined by differential scanning calorimetry (DSC) of 140°C and a crystallization temperature (Tc) determined by differential scanning calorimetry (DSC) of 105°C.

[0162] Preparation of fiber-reinforced composition (C) The fiber-reinforced composition (C) was obtained by melt-blending the modified propylene random copolymer (mP-I) or propylene random copolymer (P-II) with glass fiber (GF), adhesion promoter (AP), and additive (AD) in a co-rotating twin-screw extruder. The compositions and properties of the inventive and comparative examples are summarized in Table 3.

[0163] [Table 3]

[0164] hP is a melt flow rate (MFR2) of 75 g / 10 min (230°C) and 905 kg / m 3 The commercial propylene homopolymer HJ120UB from Borealis AG, prepared using a Ziegler-Natta catalyst, has a density determined in accordance with ISO 1183-187 and a glass transition temperature Tg of +2°C. The GF is a commercial product ECS 03 T-480H from Nippon Electric Glass Co., Ltd., with a filament diameter of 10.5 μm and a strand length of 3 mm. AP1 is the adhesion promoter SCONA TPPP 8112 GA from Scona, a maleic anhydride functionalized polypropylene with a maleic anhydride content of 1.4 wt. % and a MFR (190°C, 2.16 kg) of more than 80 g / 10 min, corresponding to a MFR2 (230°C, 2.16 kg) of approximately 50 g / 10 min. AP2 is a MAH graft copolymer of propylene and 1-hexene obtained by grafting the above propylene random copolymer (P) with 0.7% by weight of maleic anhydride in the presence of 1000 ppm of POX in a co-rotating twin-screw extruder. AP2 has a melt flow rate MFR2 (230°C, 2.16 kg) of 72 g / 10 min. AD1 contains 8.0 wt% tris(2,4-di-t-butylphenyl)phosphite (Kinox-68-G from HPL Additives), 8.0 wt% pentaerythrityl-tetrakis(3-(3',5'-di-tert-butyl-4-hydroxyphenyl)-propionate (Irganox 1010FF from BASF), 20.0 wt% carbon black from Borealis (39.5 wt% masterbatch), and 64.0 wt% 905 kg / m 3 The masterbatch consisted of propylene homopolymer HC001A by Borealis having a density determined in accordance with ISO 1183-187 and an MFR (230°C, 2.16 kg) of 3.2 g / 10 min. AD2 contains 14.3 wt.% tris(2,4-di-tert.-butylphenyl)phosphite (Kinox-68-G from HPL Additives), 14.3 wt.% pentaerythrityl-tetrakis(3-(3',5'-di-tert.butyl-4-hydroxyphenyl)-propionate (Irganox 1010FF from BASF), 35.7 wt.% carbon black from Borealis (39.5 wt.% masterbatch), and 35.7 wt.% 905 kg / m 3 The masterbatch consisted of propylene homopolymer HC001A by Borealis having a density determined in accordance with ISO 1183-187 and an MFR (230°C, 2.16 kg) of 3.2 g / 10 min.

Claims

1. A fiber-reinforced composition (C), based on the total weight of the fiber-reinforced composition (C): a) 57.0 to 94.9% by weight of a propylene random copolymer (P), the comonomer being selected from at least one C4 to C12 α-olefin, said propylene random copolymer (P) being i) Melt flow rate MFR determined according to ISO 1133 in the range of 45 to 150 g / 10 min ２ (230℃, 2.16kg), ii) a melting temperature Tm determined according to differential scanning calorimetry (DSC) in the range of 125-150°C, and iii) 1,2 erythro site defects in an amount ranging from 0.4 to 1.2 mol % A propylene random copolymer (P) having the formula: b) 5.0 to 40.0% by weight of fibers (F); c) 0.1 to 5.0 wt. % of an adhesion promoter (AP); A fiber-reinforced composition (C).

2. The propylene random copolymer (P) is i) a first propylene random copolymer (P1); ii) a second propylene random copolymer (P2) having a higher comonomer content than said first propylene random copolymer (P1); The fiber reinforced composition (C) according to claim 1, comprising: a weight ratio of the first propylene random copolymer (P1) to the second propylene random copolymer (P2) in the range of 20 / 80 to 60 / 40; and a total amount of the first propylene random copolymer (P1) and the second propylene random copolymer (P2) relative to the propylene random copolymer (P) is at least 95.0% by weight.

3. The fiber-reinforced composition (C) according to claim 1 or 2, wherein the propylene random copolymer (P) has a comonomer content in the range of 1.0 to 6.0 mol %.

4. The fiber-reinforced composition (C) according to any one of claims 1 to 3, wherein the comonomer is 1-hexene.

5. i) said first propylene random copolymer (P1) has a comonomer content in the range of 0.4 to 2.5 mol %; ii) said second propylene random copolymer (P2) has a comonomer content in the range of 2.8 to 7.0 mol %; The fiber-reinforced composition (C) according to claim 2.

6. The propylene random copolymer (P) has a xylene solubles content (XCS) determined according to ISO 16152 (25 ° C.) in the range of 3.0 to 15.0 wt % based on the total weight of the propylene random copolymer (P). The fiber reinforced composition (C) according to any one of claims 1 to 5.

7. The fiber-reinforced composition (C) according to any one of claims 1 to 3, wherein the comonomer is 1-butene.

8. The propylene random copolymer (P) is i) a first propylene random copolymer (P1) having a comonomer content in the range of 2.0 to 6.0 mol %; ii) a second propylene random copolymer (P2) having a comonomer content in the range of 4.0 to 10.0 mol %; Including, The fiber reinforced composition (C) according to claim 7, wherein the second propylene random copolymer (P2) has a higher comonomer content than the first propylene random copolymer (P1), the weight ratio of the first propylene random copolymer (P1) to the second propylene random copolymer (P2) is in the range of 20 / 80 to 60 / 40, and the total amount of the first propylene random copolymer (P1) and the second propylene random copolymer (P2) relative to the propylene random copolymer (P) is at least 95.0% by weight.

9. The propylene random copolymer (P) has a xylene solubles content (XCS) determined according to ISO 16152 (25 ° C.) in the range of 0.1 to 5.0 wt % based on the total weight of the propylene random copolymer (P). The fiber reinforced composition (C) according to claim 7 or claim 8.

10. The fiber-reinforced composition (C) according to any one of claims 1 to 9, wherein the fiber (F) is a glass fiber (GF).

11. The adhesion promoter (AP) has a melt flow rate MFR, determined according to ISO 1133, of 20.0 g / 10 min to 400 g / 10 min. ２ The fiber-reinforced composition (C) according to any one of claims 1 to 10, which is a polar modified polypropylene (PM-PP) which is a homopolymer or copolymer of propylene grafted with maleic anhydride having a viscosity of 100°C, 2.16 kg.

12. Melt flow rate MFR determined according to ISO 1133 ranging from 8.0 to 60.0 g / 10 min ２ The fiber-reinforced composition (C) according to any one of claims 1 to 11, having a compressive strength of 1 / 2 at 230°C and 2.16 kg.

13. An article comprising a fiber-reinforced composition (C) according to any one of claims 1 to 12.

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