Fiber-reinforced compositions and articles containing fiber-reinforced compositions

Abstract

The present invention relates to a fiber-reinforced composition (C), which has a melt flow rate MFR2 (230°C, 2.16 kg) determined in accordance with ISO 1133 in the range of 10.0 to 100.0 g / 10 min, and which comprises, based on the total weight of the fiber-reinforced composition (C), a) 20.0 to 89.9 wt. % of a propylene random copolymer (P), the propylene random copolymer (P) being a copolymer of propylene and C4 to C12 The present invention relates to a fiber-reinforced composition (C) comprising a) a copolymer of at least one comonomer selected from α-olefins, the propylene random copolymer (P) having 1,2 erythro position defects in an amount of 0.4-1.2 mol %, b) 5.0-45.0 wt % of glass fibers (GF), c) 0.1-5.0 wt % of an adhesion promoter (AP), and d) 5.0-50.0 wt % of a heterophasic polypropylene copolymer (HECO). Furthermore, the present invention relates to an article comprising such a fiber-reinforced composition (C).

Description

[Technical Field]

[0001] The present invention relates to glass fiber reinforced polypropylene compositions and articles comprising the glass fiber reinforced polypropylene compositions. [Background technology]

[0002] Glass fiber reinforced materials are used in many technical applications. They are particularly useful in engineering fields where high stiffness, high heat distortion temperature (HDT), and good impact resistance are often required. Polypropylene is one of the most popular base polymers for preparing glass fiber reinforced materials. This is primarily due to polypropylene's versatility, low cost, and low density. One type of polypropylene used as a base polymer in glass fiber reinforced materials is polypropylene obtained in the presence of a metallocene catalyst or a single-site catalyst.

[0003] However, available polypropylenes obtained by metallocene or single-site catalysis have inherent drawbacks: their stiffness is not high enough, their HDT is low, and in some specific areas of application, such as exterior, a certain ductility may be required.

[0004] Therefore, it is desirable to have a glass fiber reinforced polypropylene composition that combines the properties of good ductility, high HDT, and good impact resistance. It is further desirable for the glass fiber reinforced polypropylene composition to have low emissions, such as low emissions of volatile organic compounds (VOCs). Furthermore, in order to process the composition by injection molding (IM), a relatively high melt flow rate (MFR) is required. Summary of the Invention [Means for solving the problem]

[0005] One aspect of the present invention provides a fiber-reinforced composition (C). The fiber-reinforced composition (C) has a melt flow rate MFR2 (230°C, 2.16 kg) determined in accordance with ISO 1133 in the range of 10.0 to 100.0 g / 10 min. The fiber-reinforced composition (C) contains, based on the total weight of the fiber-reinforced composition (C), a) 20.0 to 89.9 wt % of a propylene random copolymer (P), which is a copolymer of propylene and at least one comonomer selected from a C4 to C12 α-olefin, and which has 1,2 erythro position defects in an amount ranging from 0.4 to 1.2 mol %; b) 5.0 to 45.0 wt% glass fiber (GF); c) 0.1 to 5.0 wt. % of an adhesion promoter (AP); d) 5.0 to 50.0 wt. % heterophasic polypropylene copolymer (HECO); Includes:

[0006] It has been surprisingly found that the desired properties can be achieved by a glass fiber reinforced polypropylene composition comprising the specific high flow random copolymer described herein, glass fiber, heterophasic polypropylene copolymer, and adhesion promoter. In particular, the fiber reinforced composition of the present invention has improved HDT and ductility, high impact resistance, and stiffness. The composition of the present invention has low hydrocarbon emissions and a melt flow suitable for IM processing.

[0007] Another aspect of the present invention provides an article comprising the fiber-reinforced composition (C) according to the present invention.

[0008] Preferred embodiments of the invention are defined in the dependent claims.

[0009] According to one embodiment, the propylene random copolymer (P) has a melting temperature Tm, determined according to differential scanning calorimetry (DSC), in the range of 125 to 150°C.

[0010] According to one embodiment, the propylene random copolymer (P) has a comonomer content ranging from 2.5 to 10.0 mol %.

[0011] According to one embodiment, the propylene random copolymer (P) has 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.

[0012] According to one embodiment, the propylene random copolymer (P) is a copolymer of propylene and 1-butene.

[0013] According to one embodiment, 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) is at least 95.0% by weight based on the propylene random copolymer (P).

[0014] According to one embodiment, 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 14.0 mol%, wherein the comonomer content of the second propylene random copolymer (P2) is higher than the comonomer content of the first propylene random copolymer (P1); Includes:

[0015] According to one embodiment, the glass fibers (GF) are i) an average length of 1.0 to 10.0 mm, and / or ii) average diameter of 5 to 20 μm It has.

[0016] According to one embodiment, the adhesion promoter (AP) is preferably a polar modified propylene homopolymer or copolymer (PM-PP) comprising polar groups selected from the group consisting of acid anhydrides, carboxylic acids, carboxylic acid derivatives, primary and secondary amines, hydroxyl compounds, oxazolines and epoxides, ionic compounds, and combinations thereof.

[0017] According to one embodiment, the heterophasic polypropylene copolymer (HECO) is i) a matrix that is a propylene homopolymer (hPP); ii) an elastomeric ethylene copolymer (E) dispersed in the matrix, the elastomeric ethylene polymer (E) being a copolymer of ethylene, propylene, and optionally at least one comonomer selected from C4 to C12 α-olefins (e.g., 1-butene or 1-hexene); Includes:

[0018] According to one embodiment, the heterophasic polypropylene copolymer (HECO) is i) the ethylene content of the xylene cold solubles (XCS) fraction in the range of 20.0 to 55.0 wt. %; ii) a xylene cold solubles (XCS) content, determined at 25°C according to ISO 16152, in the range of 5.0 to 45.0 wt. %, based on the total weight of the heterophasic polypropylene copolymer (HECO); iii) Intrinsic viscosity (IV) of the XCS fractions, determined in decalin at 135°C according to DIN ISO 1628 / 1, of 1.5 to 6.0 dl / g It has one or more of the following.

[0019] According to one embodiment, the heterophasic polypropylene copolymer (HECO) has a melt flow rate MFR2 (230°C, 2.16 kg) determined according to ISO 1133 in the range of 4.0 to 50.0 g / 10 min.

[0020] According to one embodiment, the heterophasic polypropylene copolymer (HECO) has a melting temperature Tm, determined according to differential scanning calorimetry (DSC), in the range of 150-170°C.

[0021] According to one embodiment, the propylene random copolymer (P) is obtained in the presence of a solid catalyst system (SCS) comprising a metallocene compound.

[0022] According to one embodiment, the solid catalyst system (SCS) comprises: (i) A metallocene compound of formula (I), [ka] 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-, and -R'2Ge-, and each R' is independently a C1-C heteroatom which may contain one or more hydrogen atoms or fluorine atoms selected from Groups 14 to 16 of the periodic table. 20 - a hydrocarbyl group, or optionally two R' groups together form a ring; Each R 1 are independently the same or different and are 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, Y is C 1~10 -hydrocarbyl group, and optionally two adjacent R 1 groups are part of a ring that includes the phenyl carbon to which they are attached; Each R 2 are independently the same or different, and CH-R8 is a group, and 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 C(R 9 )3 groups, R 9 is a linear or branched C1-C6 alkyl group, R 5 is an aliphatic C1-C group which may contain hydrogen or one or more heteroatoms from groups 14-16 of the periodic table of the elements; 20 - is a hydrocarbyl group, R 6 is an aliphatic C1-C group which may contain hydrogen or one or more heteroatoms from groups 14-16 of the periodic table of the elements; 20 - a hydrocarbyl group, or R 5 and R 6 are taken together and form n groups R 10 and n is 0 to 4, Each R 10 are the same or different, C1 to C 20 -hydrocarbyl group, C1-C optionally containing one or more heteroatoms belonging to groups 14-16 of the periodic table 20 -hydrocarbyl group, R 7 is H or a linear or branched C1-C6 alkyl group or 1 to 3 groups R 1 is an aryl or heteroaryl group having 6 to 20 carbon atoms, optionally substituted by a metallocene compound; (ii) a cocatalyst system comprising a boron-containing cocatalyst and / or an aluminoxane cocatalyst; (iii) optionally, a silica support; Includes:

[0023] Where the term "comprising" is used in the present specification and claims, it does not exclude other unspecified elements of greater or lesser functional importance. For the purposes of the present invention, the terms "consisting essentially of" and "consisting of" are considered to be specific embodiments of the term "comprising". Hereinafter, when a group is defined as comprising at least a certain number of features or embodiments, this should also be understood to disclose a group that optionally consists essentially of or consists of these features or embodiments. Whenever the terms "including" or "having" are used, these terms are meant to be equivalent to "comprising" as defined above.

[0024] In the following, the invention will be described in more detail. DETAILED DESCRIPTION OF THE INVENTION

[0025] Fiber-reinforced composition (C) The fiber reinforced composition (C) comprises a propylene random copolymer (P), glass fibers (GF), a heterophasic polypropylene copolymer (HECO), and an adhesion promoter (AP).

[0026] In particular, the fiber-reinforced composition (C) comprises, based on the total weight of the fiber-reinforced composition (C): a) a propylene random copolymer (P) in the range of 20.0 to 89.9 wt%, preferably 25.0 to 79.5 wt%, more preferably 30.0 to 64.0 wt%, even more preferably 35.0 to 54.0 wt%, for example 38.25 to 48.75 wt%, b) glass fiber (GF) in the range of 5.0 to 45.0 wt%, preferably 10.0 to 40.0 wt%, more preferably 15.0 to 35.0 wt%, even more preferably 15.0 to 25.0 wt%, for example 17.5 to 22.5 wt%, c) an adhesion promoter (AP) in the range of 0.1 to 5.0 wt.%, preferably 0.5 to 3.0 wt.%, more preferably 1.0 to 2.5 wt.%, even more preferably 1.0 to 2.0 wt.%, for example 1.25 to 1.75 wt.%; d) heterophasic polypropylene copolymer (HECO) in the range of 5.0 to 50.0 wt.%, preferably 10.0 to 50.0 wt.%, more preferably 20.0 to 45.0 wt.%, even more preferably 30.0 to 40.0 wt.%, for example 32.5 to 37.5 wt.%; Includes:

[0027] According to one embodiment, the fiber reinforced composition (C) comprises, based on the total weight of the fiber reinforced composition (C): a) a propylene random copolymer (P) in the range of 20.0 to 89.9 wt%, preferably 25.0 to 79.5 wt%, more preferably 30.0 to 64.0 wt%, even more preferably 35.0 to 54.0 wt%, for example 38.25 to 48.75 wt%, b) glass fiber (GF) in the range of 5.0 to 45.0 wt%, preferably 10.0 to 40.0 wt%, more preferably 15.0 to 35.0 wt%, even more preferably 15.0 to 25.0 wt%, for example 17.5 to 22.5 wt%, c) an adhesion promoter (AP) in the range of 0.1 to 5.0 wt.%, preferably 0.5 to 3.0 wt.%, more preferably 1.0 to 2.5 wt.%, even more preferably 1.0 to 2.0 wt.%, for example 1.25 to 1.75 wt.%; d) heterophasic polypropylene copolymer (HECO) in the range of 5.0 to 50.0 wt.%, preferably 10.0 to 50.0 wt.%, more preferably 20.0 to 45.0 wt.%, even more preferably 30.0 to 40.0 wt.%, for example 32.5 to 37.5 wt.%; and components a) to d) total 100% by weight, and optionally consist of them.

[0028] The fiber-reinforced composition (C) preferably comprises an additive (AD). According to one preferred embodiment, the fiber-reinforced composition (C) comprises, based on the total weight of the fiber-reinforced composition (C): a) a propylene random copolymer (P) in the range of 20.0 to 89.89 wt%, preferably 25.0 to 79.4 wt%, more preferably 30.0 to 63.9 wt%, even more preferably 35.0 to 53.5 wt%, for example 38.25 to 47.75 wt%, b) glass fiber (GF) in the range of 5.0 to 45.0 wt%, preferably 10.0 to 40.0 wt%, more preferably 15.0 to 35.0 wt%, even more preferably 15.0 to 25.0 wt%, for example 17.5 to 22.5 wt%, c) an adhesion promoter (AP) in the range of 0.1 to 5.0 wt.%, preferably 0.5 to 3.0 wt.%, more preferably 1.0 to 2.5 wt.%, even more preferably 1.0 to 2.0 wt.%, for example 1.25 to 1.75 wt.%; d) heterophasic polypropylene copolymer (HECO) in the range of 5.0 to 50.0 wt.%, preferably 10.0 to 50.0 wt.%, more preferably 20.0 to 45.0 wt.%, even more preferably 30.0 to 40.0 wt.%, for example 32.5 to 37.5 wt.%, e) an additive (AD) in the range of 0.01 to 5.0 wt%, preferably 0.1 to 4.0 wt%, more preferably 0.1 to 3.0 wt%, even more preferably 0.5 to 2.5 wt%, for example 1.0 to 2.0 wt%; Includes:

[0029] According to one preferred embodiment, the fiber-reinforced composition (C) comprises, based on the total weight of the fiber-reinforced composition (C): a) a propylene random copolymer (P) in the range of 20.0 to 89.89 wt%, preferably 25.0 to 79.4 wt%, more preferably 30.0 to 63.9 wt%, even more preferably 35.0 to 53.5 wt%, for example 38.25 to 47.75 wt%, b) glass fiber (GF) in the range of 5.0 to 45.0 wt%, preferably 10.0 to 40.0 wt%, more preferably 15.0 to 35.0 wt%, even more preferably 15.0 to 25.0 wt%, for example 17.5 to 22.5 wt%, c) an adhesion promoter (AP) in the range of 0.1 to 5.0 wt.%, preferably 0.5 to 3.0 wt.%, more preferably 1.0 to 2.5 wt.%, even more preferably 1.0 to 2.0 wt.%, for example 1.25 to 1.75 wt.%; d) heterophasic polypropylene copolymer (HECO) in the range of 5.0 to 50.0 wt.%, preferably 10.0 to 50.0 wt.%, more preferably 20.0 to 45.0 wt.%, even more preferably 30.0 to 40.0 wt.%, for example 32.5 to 37.5 wt.%, e) an additive (AD) in the range of 0.01 to 5.0 wt%, preferably 0.1 to 4.0 wt%, more preferably 0.1 to 3.0 wt%, even more preferably 0.5 to 2.5 wt%, for example 1.0 to 2.0 wt%; The total of components a) to e) is 100% by weight, and preferably consists of these.

[0030] Preferably, the fiber-reinforced composition (C) of the present invention does not contain more than 5.0 wt. %, preferably more than 3.0 wt. %, more preferably more than 2.5 wt. % of additional polymers other than the propylene random copolymer (P), the heterophasic polypropylene copolymer (HECO), and the adhesion promoter (AP), 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 from the preparation of the heterophasic polypropylene copolymer (HECO).

[0031] The fiber reinforced composition (C) has a melt flow rate MFR2 (230°C, 2.16 kg), determined in accordance with ISO 1133, in the range of 10.0 to 100.0 g / 10 min, preferably in the range of 12.0 to 80.0 g / 10 min, more preferably in the range of 14.0 to 70.0 g / 10 min, and even more preferably in the range of 15.0 to 60.0 g / 10 min.

[0032] The fiber-reinforced composition (C) has a melting temperature, determined by differential scanning calorimetry (DSC), of 155°C or less, preferably in the range of 125 to 150°C, more preferably in the range of 130 to 145°C, for example in the range of 132 to 142°C.

[0033] 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 3200 to 5200 MPa, for example in the range of 4000 to 5000 MPa. Furthermore, the fiber-reinforced composition (C) has a tensile strength, determined according to ISO 527-2, in the range of 40 to 100 MPa, preferably in the range of 50 to 90 MPa, more preferably in the range of 60 to 90 MPa, for example in the range of 70 to 80 MPa.

[0034] In addition to or instead of the preceding paragraph, the fiber-reinforced composition (C) has a viscosity of at least 30.0 kJ / m 2 , more preferably at least 35.0 kJ / m 2 , and even more preferably 40.0 kJ / m 2 , and even more preferably at least 45 kJ / m 2 , most preferably at least 50.0 kJ / m 2 It is preferred that the unnotched Charpy impact strength determined in accordance with ISO 179 1eU at 23°C is 100 kJ / m. A reasonable upper limit for the unnotched Charpy impact strength determined in accordance with ISO 179 1eU at 23°C is 100 kJ / m. 2 may be.

[0035] Furthermore, it is preferred that the fiber reinforced composition (C) has a heat distortion temperature (HDT), determined in accordance with ISO 75 A, of at least 125° C., more preferably at least 130° C., even more preferably at least 135° C., still more preferably at least 140° C., such as at least 145° C. A reasonable upper limit for the heat distortion temperature (HDT), determined in accordance with ISO 75 A, may be 160° C.

[0036] 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 45 μg / g, more preferably less than 35 μg / g, even more preferably less than 30 μg / g, still more preferably less than 25 μg / g, for example less than 15 μg / g.

[0037] Likewise, it is preferred that the fiber-reinforced composition (C) comprises a small amount of intermediate volatile compounds (FOG), measured according to VDA278, of less than 100 μg / g, more preferably less than 90 μg / g, even more preferably less than 85 μg / g, and even more preferably less than 80 μg / g.

[0038] According to one particularly preferred embodiment, the fiber-reinforced composition (C) comprises: (i) a melt flow rate MFR2 (230°C, 2.16 kg) determined in accordance with ISO 1133 in the range of 10.0 to 100.0 g / 10 min, preferably in the range of 12.0 to 80.0 g / 10 min, more preferably in the range of 14.0 to 70.0 g / 10 min, and even more preferably in the range of 15.0 to 60.0 g / 10 min; (ii) 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 3200 to 5200 MPa, for example in the range of 4000 to 5000 MPa; (iii) at least 30.0 kJ / m 2 , more preferably at least 35.0 kJ / m 2 , and even more preferably 40.0 kJ / m 2 , and even more preferably at least 45 kJ / m 2 , most preferably at least 50.0 kJ / m 2 Unnotched Charpy impact strength determined at 23°C according to ISO 179 1eU of (iv) a heat distortion temperature (HDT) determined according to ISO 75 A of at least 125°C, more preferably at least 130°C, even more preferably at least 135°C, still even more preferably at least 140°C, e.g., at least 145°C; (v) an amount of volatile compounds (VOCs) determined in accordance with VDA 278 of less than 45 μg / g, more preferably less than 35 μg / g, even more preferably less than 30 μg / g, still even more preferably less than 25 μg / g, for example less than 15 μg / g It has.

[0039] The fiber reinforced composition (C) is preferably obtained by melt blending the propylene random copolymer (P), glass fibers (GF), heterophasic polypropylene copolymer (HECO), adhesion promoter (AP) and optionally additives (AD). Such melt blending processes are well known in the art.

[0040] The components of the fiber-reinforced composition (C) are described in more detail below.

[0041] Propylene random copolymer (P) The fiber-reinforced composition (C) contains a propylene random copolymer (P), which is present in the composition (C) in an amount of 20.0 to 89.9 wt %, preferably 25.0 to 79.5 wt %, more preferably 30.0 to 64.0 wt %, even more preferably 35.0 to 54.0 wt %, for example, 38.25 to 48.75 wt %, based on the total weight of the composition (C).

[0042] The propylene random copolymer (P) is a copolymer of propylene and at least one comonomer selected from C4 to C12 α-olefins. Accordingly, the propylene random copolymer (P) comprises a monomer copolymerizable with propylene selected from C4 to C12 α-olefins. Preferably, the comonomer is selected from C4 to C6 α-olefins, such as 1-butene and / or 1-hexene. The propylene random copolymer according to one embodiment of the present invention preferably comprises, and more preferably consists of, propylene and a monomer copolymerizable with propylene selected from the group consisting of 1-butene and 1-hexene. More specifically, the propylene random copolymer (P) of the present invention comprises, in addition to propylene, units derivable from 1-butene and / or 1-hexene. Accordingly, according to one preferred embodiment, the propylene random copolymer (P) is a copolymer of propylene and at least one comonomer selected from 1-butene and 1-hexene.

[0043] According to one embodiment, the comonomer is 1-hexene. Therefore, the propylene random copolymer (P) can contain only units derived from propylene and 1-hexene. In other words, in one embodiment, only propylene and 1-hexene are polymerized.

[0044] According to one particularly preferred embodiment, the propylene random copolymer (P) is a copolymer of propylene and 1-butene.

[0045] The term "random copolymer" can 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 1-hexene and / or 1-butene dyads, obey the following relationship: [HH]<[H] 2 During the ceremony, [HH] is the mole fraction of adjacent comonomer units, such as adjacent 1-hexene and / or 1-butene units; [H] is the mole fraction of total comonomer units, eg, total 1-hexene and / or 1-butene units, in the polymer.

[0046] Preferably, the propylene random copolymer (P) has a comonomer content, such as a 1-butene content, in the range of 2.5 to 10.0 mol%, more preferably in the range of 3.0 to 8.0 mol%, even more preferably in the range of 3.5 to 7.5 mol%, still even more preferably in the range of 4.0 to 7.0 mol%, even more preferably in the range of 4.5 to 6.5 mol%, for example in the range of 5.0 to 6.0 mol%.

[0047] Furthermore, the propylene random copolymer (P) is preferably bimodal.

[0048] 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-butene content, than the first propylene random copolymer (P1); Preferably, the total amount of the first propylene random copolymer (P1) and the second propylene random copolymer (P2) based on the propylene random copolymer (P) is 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 the random propylene copolymer essentially consists of, and preferably consists of, the first propylene random copolymer (P1) and the second propylene random copolymer (P2). With regard to the term "random copolymer", reference is made to the definition provided above.

[0049] 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 70 / 30, more preferably in the range of 30 / 70 to 60 / 40, and even more preferably in the range of 45 / 55 to 55 / 45.

[0050] According to one 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); 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, more preferably 30 / 70 to 60 / 40, and even more preferably 45 / 55 to 55 / 45; The total amount of the first propylene random copolymer (P1) and the second propylene random copolymer (P2) is 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, based on the propylene random copolymer (P).

[0051] In this embodiment, the second propylene random copolymer (P2) has a higher comonomer content, for example, 1-butene 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 1.2 to 5.0, even more preferably 1.2 to 3.0, even more preferably 1.2 to 2.0, for example, 1.3 to 1.8, where C(P2) is the comonomer content, preferably 1-butene content, in [mol%] of the second propylene random copolymer (P2), and C(P1) is the comonomer content, preferably 1-butene content, in [mol%] of the first propylene random copolymer (P2).

[0052] It is preferred that the first propylene random copolymer (P1) has a comonomer content, preferably a 1-butene content, in the range of 2.0 to 6.0 mol %, more preferably in the range of 3.0 to 5.5 mol %, even more preferably in the range of 3.5 to 5.5 mol %, still more preferably in the range of 4.0 to 5.0 mol %.

[0053] The second propylene random copolymer (P2) preferably has a comonomer content, preferably a 1-butene content, in the range of 4.0 to 14.0 mol%, more preferably in the range of 5.0 to 10.0 mol%, even more preferably in the range of 5.5 to 8.0 mol%, and even more preferably in the range of 6.0 to 7.0 mol%.

[0054] According to one embodiment, 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 3.0 to 5.5 mol%, more preferably in the range of 3.5 to 5.5 mol%, even more preferably in the range of 4.0 to 5.0 mol%, ii) a second propylene random copolymer (P2) having a comonomer content in the range of 4.0 to 14.0 mol%, preferably in the range of 5.0 to 10.0 mol%, more preferably in the range of 5.5 to 8.0 mol%, even more preferably in the range of 6.0 to 7.0 mol%; wherein the comonomer content of the second propylene random copolymer (P2) is higher than the comonomer content of the first propylene random copolymer (P1).

[0055] The propylene random copolymer (P) has a 1,2 erythro regio-defect amount in the range of 0.4 to 1.2 mol %. Without being bound by theory, the large amount of misinsertion of propylene and / or polymerized comonomers, such as 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 a 1,2 erythro regio-defect amount well below 0.4 mol %, and are often substantially free of 1,2 erythro regio-defects.

[0056] Preferably, 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 g / 10 min, preferably 55.0 to 130 g / 10 min, more preferably 65.0 to 120 g / 10 min, even more preferably 70.0 to 110 g / 10 min, for example 80.0 to 100 g / 10 min. Therefore, it is preferred that the propylene random copolymer (P) according to the present invention has a fairly high melt flow rate.

[0057] In this regard, the propylene random copolymer (P) may be visbroken, however, it is preferred that the propylene random copolymer (P) is not visbroken.

[0058] The melting temperature Tm of the propylene random copolymer (P), determined according to differential scanning calorimetry (DSC), is preferably in the range of 125 to 150°C, more preferably in the range of 128 to 145°C, even more preferably in the range of 132 to 145°C, still more preferably in the range of 135 to 145°C, for example in the range of 138 to 142°C.

[0059] The propylene random copolymer (P) can be further characterized by the amount of its xylene cold solubles (XCS). According to one preferred embodiment of the present invention, the propylene random copolymer (P) has a xylene solubles (XCS) determined in accordance with ISO 16152 (25°C) in the range of 0.1 to 5.0 wt%, preferably 0.2 to 3.0 wt%, more preferably 0.3 to 2.0 wt%, for example 0.3 to 1.0 wt%, based on the total weight of the propylene random copolymer (P).

[0060] The small amount of xylene-solubles at low temperatures (XCS) also indicates that the propylene random copolymer (P) preferably does not contain elastomer (co)polymers that form inclusions as second phases to improve mechanical properties. 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).

[0061] The propylene random copolymer (P) has a glass transition temperature of greater than -30°C, for example greater than -25°C, for example greater than -20°C. The propylene random copolymer (P) preferably has a glass transition temperature of greater than -10°C, for example in the range of -5 to 0°C.

[0062] The propylene random copolymer (P) may be, and preferably is, obtainable by a process defined in detail below.

[0063] 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 (e.g., two reactors in series), which process comprises: (A) polymerizing propylene and a comonomer selected from C4 to C12 α-olefins, preferably 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 comonomer from the first reactor (R-1) to a second reactor (R-2), which is a gas phase reactor (GPR-1); (C) supplying a comonomer selected from propylene and a C4 to C12 α-olefin, preferably 1-butene, to the second reactor (R-2); (D) a step of polymerizing propylene and a comonomer selected from C4 to C12 α-olefins, preferably 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 In the first reactor (R-1) and the second reactor (R-2), the polymerization is preferably carried out in the presence of a solid catalyst system (SCS), which solid catalyst system (SCS) comprises: (i) a transition metal compound of formula (I), R n (Cp)2MX2(I) During the ceremony, "M" is a Group 4 transition metal, such as 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; Includes:

[0064] 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.

[0065] A solid catalyst system (SCS) is defined in more detail below.

[0066] 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 transferring 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 method described herein, the comonomer conversion rate can be increased, and therefore, a better incorporation into the polymer chain can be achieved, which leads to a higher comonomer content and reduced stickiness problems.

[0067] 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.

[0068] The first reactor (R-1) is a slurry reactor (SR), and in particular can be any continuous or simply stirred batch tank reactor or loop reactor operating on a slurry. The slurry reactor (SR) is preferably a loop reactor (LR).

[0069] 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.

[0070] 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).

[0071] 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.

[0072] 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.

[0073] 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.

[0074] 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.

[0075] The residence time may be different in both reactor zones.

[0076] 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 or 0.2 to 1.0 hours, and the residence time in the gas phase reactor (GPR) is generally 0.2 to 6.0 hours, e.g., 0.2 to 4.0 hours or 0.2 to 1.0 hours.

[0077] 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).

[0078] The conditions in the other gas phase reactor (GPR), if present, are similar to those in the second reactor (R-2).

[0079] 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.

[0080] The propylene random copolymer (P) as defined herein is preferably prepared in the presence of a solid catalyst system (SCS), which solid catalyst system (SCS) comprises: (i) a transition metal compound of formula (I), R n (Cp)2MX2(I) During the ceremony, "M" is a Group 4 transition metal, such as 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; Includes:

[0081] The propylene random copolymer (P) defined herein is preferably prepared in the presence of a solid catalyst system (SCS) comprising a metallocene compound. A "metallocene compound" in the sense of the present invention can be understood in a broad sense as a compound comprising a metal, preferably a transition metal, bonded to two cyclopentadienyl-containing and / or cyclopentadienyl anion-containing ligands.

[0082] According to one embodiment, the metallocene compound comprises titanium, zirconium or hafnium, preferably zirconium or hafnium, more preferably zirconium.

[0083] Preferably, the solid catalyst system (SCS) comprises: (i) A metallocene compound of formula (I), [ka] 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-, and -R'2Ge-, and each R' is independently a C1-C heteroatom which may contain one or more hydrogen atoms or fluorine atoms selected from Groups 14 to 16 of the periodic table. 20 - a hydrocarbyl group, or optionally two R' groups together form a ring; Each R 1 are independently the same or different and are 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, Y is C 1~10 -hydrocarbyl group, and optionally two adjacent R 1 groups are part of a ring that includes the phenyl carbon to which they are attached; Each R 2 are independently the same or different, and CH-R 8 is a group, and 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 C(R 9 )3 groups, R 9 is a linear or branched C1-C6 alkyl group, R 5 is an aliphatic C1-C group which may contain hydrogen or one or more heteroatoms from groups 14-16 of the periodic table of the elements; 20 - is a hydrocarbyl group, R 6is an aliphatic C1-C group which may contain hydrogen or one or more heteroatoms from groups 14-16 of the periodic table of the elements; 20 - a hydrocarbyl group, or R 5 and R 6 are taken together and form n groups R 10 and n is 0 to 4, Each R 10 are the same or different, C1 to C 20 -hydrocarbyl group, C1-C optionally containing one or more heteroatoms belonging to groups 14-16 of the periodic table 20 -hydrocarbyl group, R 7 is H or a linear or branched C1-C6 alkyl group or 1 to 3 groups R 1 is an aryl or heteroaryl group having 6 to 20 carbon atoms, optionally substituted by a metallocene compound; (ii) a cocatalyst system comprising a boron-containing cocatalyst and / or an aluminoxane cocatalyst; (iii) optionally, a silica support; Includes:

[0084] Each X is independently a σ-donor ligand, and therefore each X may be the same or different, and is preferably a hydrogen atom, a halogen atom, a linear or branched, cyclic or acyclic C 1~20 - an alkyl group or an alkoxy group, C 6~20 -aryl group, C 7~20 -alkylaryl group or C 7~20 -arylalkyl groups, which may contain one or more heteroatoms from groups 14 to 16 of the periodic table. 1~20 The "hydrocarbyl group" is C 1~20 -Alkyl, C 2~20 -Alkenyl, C 2~20 -alkynyl, C 3~20 -cycloalkyl, C 3~20 -cycloalkenyl, C 6~20 -aryl group, C7~20 -alkylaryl group or C 7~20 -arylalkyl groups, or of course mixed forms of these groups, such as alkyl-substituted cycloalkyl. Linear and branched hydrocarbyl groups cannot contain cyclic units. Aliphatic hydrocarbyl groups cannot contain aryl rings.

[0085] Unless otherwise stated, preferred C 1~20 The hydrocarbyl group is C 1~20 Alkyl, C 4~20 Cycloalkyl, C 5~20 Cycloalkyl-alkyl groups, C 7~20 Alkylaryl group, C 7~20 Aryl alkyl group or C 6~20 Aryl groups, especially C 1~10 Alkyl group, C 6~10 Aryl group or C 7~12 Aryl alkyl groups, such as C 1~8 The most particularly preferred hydrocarbyl groups are methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C 5~6 -cycloalkyl, cyclohexylmethyl, phenyl or benzyl. The term "halo", when referring to the definition of the complex, includes fluoro, chloro, bromo and iodo groups, especially chloro or fluoro groups.

[0086] Any group containing "one or more heteroatoms belonging to Groups 14-16 of the Periodic Table of the Elements" preferably means O, S or N. The N group may be present as -NH- or -NR"- where R" is C1-C10 alkyl. For example, 1 to 4 heteroatoms may be present. The group containing one or more heteroatoms belonging to Groups 14-16 of the Periodic Table of the Elements may be an alkoxy group, e.g., C1-C 10 -alkoxy groups.

[0087] Preferred complexes for the preparation of propylene random copolymers are described, for example, in WO 2019179959.

[0088] A more preferred metallocene compound is of formula (II): [ka] In the formula, each R 1 are independently the same or different and are hydrogen or a linear or branched C1-C6 alkyl group, and there is at least one R per phenyl group. 1 is not hydrogen, R' is C 1~10 Hydrocarbyl groups, preferably C 1~4 a hydrocarbyl group, more preferably a methyl group; X independently represents a hydrogen atom, a halogen atom, or C 1~6 Alkoxy group, C 1~6 It is an alkyl group, a phenyl group or a benzyl group. Most preferably, X is a chlorine, benzyl or methyl group. Preferably, both X groups are the same. The most preferred options are two chlorides (chlorines), two methyls or two benzyl groups, especially two chlorides.

[0089] Specific preferred metallocene compounds include: 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'-dimethyl-phenyl)-5-methoxy-6-tert-butylinden-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-butylinden-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'-di-tert-butyl-phenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride or their corresponding zirconium dimethyl analogues Examples include:

[0090] The ligands required to form the complex, and thus the catalyst, can be synthesized by any process, and an organic chemist skilled in the art would be able to devise various synthetic protocols to produce the necessary ligand materials. For example, WO 2007 / 116034 discloses the necessary chemical reactions. Synthetic protocols can also be found generally in WO 2002 / 02576, WO 2011 / 135004, WO 2012 / 084961, WO 2012 / 001052, WO 2011 / 076780, WO 2015 / 158790, and WO 2018 / 122134. The Examples section also provides sufficient guidance to those skilled in the art.

[0091] Cocatalyst To form the active catalytic species, it is usually necessary to use a cocatalyst, as is well known in the art. Cocatalyst systems including boron-containing cocatalysts and / or aluminoxane cocatalysts can be used in combination with the metallocene compounds defined above.

[0092] The aluminoxane cocatalyst can be of formula (III): [ka] (III) In the formula, n is usually 6 to 20, and R has the following meaning. Aluminoxanes are formed by partial hydrolysis of organoaluminum compounds, such as compounds of formula AlR3, AlR2Y and Al2R3Y3, where R is, for example, C1-C 10 -alkyl, preferably C1-C5-alkyl, or C 3~10 -Cycloalkyl, C7-C 12 -arylalkyl or C7-C 12 -alkylaryl, and / or phenyl or naphthyl, and Y is hydrogen, halogen, preferably chlorine or bromine, or C1-C 10 -alkoxy, preferably methoxy or ethoxy. The oxygen-containing aluminoxanes obtained are generally not pure compounds but are mixtures of oligomers of formula (III). A preferred aluminoxane is methylaluminoxane (MAO). Because the aluminoxanes described herein as cocatalysts are not pure compounds due to the manner of their preparation, the molarity of the aluminoxane solutions hereinafter is based on their aluminum content.

[0093] A boron-containing cocatalyst can be used in place of the aluminoxane cocatalyst, or the aluminoxane cocatalyst can be used in combination with the boron-containing cocatalyst.

[0094] Those skilled in the art will appreciate that when a boron-based cocatalyst is used, it is common for the complex to be pre-alkylated by reaction with an aluminum alkyl compound such as TIBA. This procedure is well known and can be carried out with any suitable aluminum alkyl, e.g., Al(C 1~6 The preferred aluminum alkyl compounds are triethylaluminum, triisobutylaluminum, triisohexylaluminum, tri-n-octylaluminum and triisooctylaluminum.

[0095] Alternatively, when a borate (boron ate complex) cocatalyst is used, the metallocene compound can be an alkylated version thereof, ie, for example, a dimethyl or dibenzyl metallocene compound can be used. Boron-based cocatalysts of interest include those of formula (IV): BY3(IV) In formula (IV), Y may be 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 having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical, an arylalkyl, a haloalkyl, or a haloaryl, or a fluorine, chlorine, bromine, or iodine. Preferred examples of Y are methyl, propyl, isopropyl, isobutyl, or trifluoromethyl, an unsaturated group such as an aryl or haloaryl, for example, phenyl, tolyl, benzyl, p-fluorophenyl, 3,5-difluorophenyl, pentachlorophenyl, pentafluorophenyl, 3,4,5-trifluorophenyl, and 3,5-di(trifluoromethyl)phenyl. Preferred choices are trifluoroborane, 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. Particularly preferred is tris(pentafluorophenyl)borane.

[0096] However, it is preferred to use borate, i.e., a compound containing a borate 3+ ion. Such ionic cocatalysts preferably contain non-coordinating anions such as tetrakis(pentafluorophenyl)borate and tetraphenylborate. Suitable counterions are protonated amine 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. Preferred ionic compounds that can be used 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). The preferred triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylcyclohexylammonium tetrakis(pentafluorophenyl)borate, or N,N-Dimethylbenzylammonium tetrakis(pentafluorophenyl)borate is.

[0097] Certain boron cocatalysts are particularly preferred. Preferred borates contain the trityl ion. Thus, the use of N,N-dimethylammonium-tetrakispentafluorophenylborate and PhCB(PhF) and its analogs is particularly preferred.

[0098] In accordance with the present invention, preferred cocatalysts are alumoxanes, more preferably methylalumoxanes, combinations of alumoxanes with Al alkyls, boron or borate cocatalysts, and combinations of alumoxanes with boron-based cocatalysts.

[0099] Suitable amounts of cocatalyst are well known to those skilled in the art. The molar ratio of boron to 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, especially 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.

[0100] The catalyst can be used in a supported or unsupported form, preferably in a supported form. The particulate support material used is preferably an organic or inorganic material, such as silica, alumina or zirconia, or a mixed oxide, such as silica-alumina, in particular silica, alumina or silica-alumina. The use of a silica support is preferred. Those skilled in the art are aware of the procedures required to support metallocene catalysts.

[0101] Especially preferably, the support is a porous material so that the complex may be loaded into the pores of the support using processes similar to those described, for example, in WO 94 / 14856 (Mobil), WO 95 / 12622 (Borealis) and WO 2006 / 097497.

[0102] Glass fiber (GF) The fiber-reinforced composition (C) contains glass fibers (GF), which are present in the fiber-reinforced composition (C) in an amount ranging from 5.0 to 45.0 wt %, preferably from 10.0 to 40.0 wt %, more preferably from 15.0 to 35.0 wt %, even more preferably from 15.0 to 25.0 wt %, for example, from 17.5 to 22.5 wt %, based on the total weight of the composition (C).

[0103] The glass fibers (GF) may be short glass fibers (SGF), such as chopped glass fibers or chopped strands, and / or long glass fibers (LGF), such as long glass fibers (LGF) obtained from glass roving.

[0104] The fibers (F) are preferably short glass fibers (SGF). According to one embodiment, the glass fibers (GF) are short glass fibers (SGF) having an average length of 1.0 to 10.0 mm, preferably in the range of 1.0 to 8.0 mm, more preferably in the range of 1.5 to 7.0 mm, and even more preferably in the range of 2.0 to 6.0 mm.

[0105] According to one embodiment, the glass fibers (GF) have an average length in the range of 1.0 to 10.0 mm, preferably in the range of 1.0 to 8.0 mm, more preferably in the range of 1.5 to 7.0 mm, and even more preferably in the range of 2.0 to 6.0 mm.

[0106] According to one embodiment, the fiber-reinforced composition (C) comprises glass fibers (GF) having an average length of 1.0 to 10.0 mm, preferably in the range of 1.0 to 8.0 mm, more preferably in the range of 1.5 to 7.0 mm, and even more preferably in the range of 2.0 to 6.0 mm, which are obtained by melt-kneading the glass fibers (GF) with a random propylene copolymer (P), a heterophasic polypropylene copolymer (HECO), and an adhesion promoter (AD), as well as optional additives (AD).

[0107] The glass fibers (GF), preferably short glass fibers (SGF), may have an average diameter of 5 to 20 μm, more preferably 6 to 18 μm, and even more preferably 8 to 16 μm.

[0108] Preferably, the glass fibers (GF), more preferably 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.

[0109] According to one embodiment, the glass fibers (GF) have (i) an average length in the range of 1.0 to 10.0 mm, preferably in the range of 1.0 to 8.0 mm, more preferably in the range of 1.5 to 7.0 mm, and even more preferably in the range of 2.0 to 6.0 mm, and (ii) an average diameter in the range of 5 to 20 μm, more preferably in the range of 6 to 18 μm, and even more preferably in the range of 8 to 16 μm.

[0110] Adhesion promoter (AP) The fiber reinforced polypropylene composition (C) further comprises an adhesion promoter (AP), which is present in the fiber reinforced composition (C) in an amount ranging from 0.1 to 5.0 wt. %, preferably from 0.5 to 3.0 wt. %, more preferably from 1.0 to 2.5 wt. %, even more preferably from 1.0 to 2.0 wt. %, for example from 1.25 to 1.75 wt. %, based on the total weight of the composition (C).

[0111] The adhesion promoter (AP) is preferably a polar-modified polypropylene homopolymer or copolymer (PM-PP). The polar-modified polypropylene homopolymer or copolymer (PM-PP) preferably comprises a low molecular weight compound having a reactive polar group. Modified propylene homopolymers and copolymers, such as propylene and ethylene or other α-olefins, such as C4-C6. 10 Copolymers with α-olefins are most preferred because they are highly compatible with the propylene homopolymer or copolymer (P) of the fiber reinforced polypropylene composition (C) of the present invention.

[0112] In terms of structure, the polar-modified propylene homopolymer or copolymer (PM-PP) is preferably selected from grafted propylene homopolymers or copolymers, and in this regard, polar-modified propylene homopolymers or copolymers (PM-PP) containing polar groups selected from the group consisting of acid anhydrides, carboxylic acids, carboxylic acid derivatives, primary and secondary amines, hydroxyl compounds, oxazolines and epoxides, ionic compounds, and combinations thereof are preferred.

[0113] Thus, according to one embodiment, the adhesion promoter (AP) is a polar modified propylene homopolymer or copolymer (PM-PP) comprising polar groups selected from the group consisting of acid anhydrides, carboxylic acids, carboxylic acid derivatives, primary and secondary amines, hydroxyl compounds, oxazolines and epoxides, ionic compounds, and combinations thereof.

[0114] Specific examples of the polar compounds include unsaturated cyclic anhydrides and their aliphatic diesters and dibasic acid derivatives. In particular, maleic anhydride and maleic acid C1-C 10 Linear and branched dialkyl fumarates C1-C 10 Linear and branched dialkyl, itaconic anhydride, itaconic acid C1-C 10 Compounds selected from linear and branched dialkyl esters, acrylic acid, maleic acid, fumaric acid, itaconic acid and mixtures thereof can be used.

[0115] The polar-modified propylene homo- or copolymer (PM-PP) may contain polar groups in an amount of 0.5 to 5.0 wt % based on the total weight of the homo- or copolymer (PM-PP). For example, this amount may be in the range of 0.5 to 4.5 wt %, preferably 0.5 to 4.0 wt %, and more preferably 0.5 to 3.5 wt %.

[0116] Particularly preferred are polar-modified propylene homopolymers or copolymers (PM-PP) which are propylene homopolymers or copolymers grafted with maleic anhydride or acrylic acid, which can be produced in a simple manner by reactive extrusion of the polymer with 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.

[0117] The melt flow rate MFR2 (230°C, 2.16 kg) of the adhesion promoter (AP), preferably the polar modified propylene homopolymer or copolymer (PM-PP), is preferably 20.0 to 400 g / 10 min. It is particularly preferred that the adhesion promoter (AP), preferably the polar modified propylene homopolymer or copolymer (PM-PP), has a melt flow rate MFR2 (230°C) in the range of 30.0 to 300 g / 10 min, more preferably 40.0 to 250 g / 10 min, for example 40.0 to 100 g / 10 min.

[0118] In one preferred embodiment of the present invention, the adhesion promoter (AP) is a maleic anhydride-modified polypropylene homopolymer or copolymer and / or an acrylic acid-modified polypropylene homopolymer or copolymer. Preferably, the adhesion promoter (AP) is a maleic anhydride-modified polypropylene homopolymer and / or an acrylic acid-modified polypropylene homopolymer, preferably a maleic anhydride-modified polypropylene homopolymer. For example, suitable polar-modified polypropylene (PM-PP) homopolymers or copolymers include, for example, maleic anhydride-grafted polypropylene homopolymer (PP-g-MAH) and acrylic acid-grafted polypropylene homopolymer (PP-g-AA).

[0119] According to one preferred embodiment, the adhesion promoter (AP) is a polar-modified propylene homopolymer or copolymer (PM-PP), which is a propylene homopolymer or copolymer grafted with maleic anhydride, and the adhesion promoter (AP) has a melt flow rate MFR2 (230°C, 2.16 kg) determined in accordance with ISO 1133 of 20.0 g / 10 min to 400 g / 10 min.

[0120] According to another preferred embodiment of the invention, the adhesion promoter (AP) is the above-mentioned propylene random copolymer (P) grafted with maleic anhydride.

[0121] Heterophasic Polypropylene Copolymer (HECO) The fiber reinforced composition (C) further comprises a heterophasic polypropylene copolymer (HECO), which is present in the fiber reinforced composition (C) in an amount ranging from 5.0 to 50.0 wt.%, preferably from 10.0 to 50.0 wt.%, more preferably from 20.0 to 45.0 wt.%, even more preferably from 30.0 to 40.0 wt.%, for example from 32.5 to 37.5 wt.%, based on the total weight of the composition (C).

[0122] The heterophasic polypropylene copolymer (HECO) is preferably i) a matrix that is a propylene homopolymer (hPP); ii) an elastomeric ethylene copolymer (E) dispersed in the matrix, the elastomeric ethylene polymer (E) being a copolymer of ethylene, propylene, and optionally at least one comonomer selected from C4 to C12 α-olefins (e.g., 1-butene or 1-hexene); Includes:

[0123] According to one embodiment, the heterophasic polypropylene copolymer (HECO) is i) a matrix that is a propylene homopolymer (hPP); ii) an elastomeric ethylene copolymer (E) dispersed in the matrix, the elastomeric ethylene polymer (E) being a copolymer of ethylene and propylene; and Includes:

[0124] According to one embodiment, the heterophasic polypropylene copolymer (HECO) is i) a matrix that is a propylene homopolymer (hPP); ii) an elastomeric ethylene copolymer (E) dispersed in the matrix, the elastomeric ethylene polymer (E) being a copolymer of ethylene, propylene, and at least one comonomer selected from C4 to C12 α-olefins, preferably 1-butene or 1-hexene; Includes:

[0125] When the optional at least one comonomer selected from a C4 to C12 α-olefin is present in the elastomeric ethylene polymer (E), the at least one comonomer selected from a C4 to C12 α-olefin is preferably present in the elastomeric ethylene polymer (E) in a minor amount, meaning that the at least one comonomer selected from a C4 to C12 α-olefin is present in an amount by weight less than the weight of ethylene in the elastomeric ethylene polymer (E). For example, the at least one comonomer selected from a C4 to C12 α-olefin may be present in an amount less than 10.0 wt. %, preferably less than 5.0 wt. %, based on the total weight of the elastomeric ethylene polymer (E).

[0126] The expression "propylene homopolymer (hPP)" can be understood as a polypropylene that preferably consists essentially of propylene units, i.e., at least 99.0% by weight, more preferably at least 99.5% by weight, even more preferably at least 99.8% by weight, for example at least 99.9% by weight, of propylene units. In another embodiment, only propylene units are detectable, i.e., only propylene is polymerized.

[0127] The heterophasic polypropylene copolymer (HECO) preferably has a xylene cold solubles (XCS) content, determined at 25°C according to ISO 16152, in the range of 5.0 to 45.0 wt%, more preferably 10.0 to 42.5 wt%, even more preferably 15.0 to 40.0 wt%, still more preferably 20.0 to 40.0 wt%, for example 25.0 to 35.0 wt%, based on the total weight of the heterophasic polypropylene copolymer (HECO).

[0128] The heterophasic polypropylene copolymer (HECO) preferably has an ethylene content of the xylene cold solubles (XCS) fraction in the range of 20.0 to 55.0 wt%, more preferably in the range of 22.5 to 50.0 wt%, even more preferably in the range of 25.0 to 45.0 wt%, still even more preferably in the range of 27.5 to 40.0 wt%, for example in the range of 30.0 to 35.0 wt%.

[0129] The heterophasic polypropylene copolymer (HECO) preferably has an intrinsic viscosity (IV) of the XCS fraction, determined in decalin at 135°C according to DIN ISO 1628 / 1, of 1.5 to 6.0 dl / g, more preferably 1.5 to 5.0 dl / g, even more preferably 1.5 to 3.0 dl / g, and even more preferably 2.0 to 2.5 dl / g.

[0130] According to one preferred embodiment of the present invention, the heterophasic polypropylene copolymer (HECO) is i) an ethylene content of the xylene cold solubles (XCS) fraction in the range of 20.0 to 55.0 wt%, more preferably in the range of 22.5 to 50.0 wt%, even more preferably in the range of 25.0 to 45.0 wt%, still even more preferably in the range of 27.5 to 40.0 wt%, for example in the range of 30.0 to 35.0 wt%; ii) a xylene cold solubles (XCS) content, determined at 25°C according to ISO 16152, in the range of 5.0 to 45.0 wt.%, more preferably 10.0 to 42.5 wt.%, even more preferably 15.0 to 40.0 wt.%, still more preferably 20.0 to 40.0 wt.%, for example 25.0 to 35.0 wt.%, based on the total weight of the heterophasic polypropylene copolymer (HECO); iii) an intrinsic viscosity (IV) of the XCS fraction, determined in decalin at 135°C according to DIN ISO 1628 / 1, of 1.5 to 6.0 dl / g, more preferably 1.5 to 5.0 dl / g, even more preferably 1.5 to 3.0 dl / g, and even more preferably 2.0 to 2.5 dl / g It has.

[0131] The heterophasic polypropylene copolymer (HECO) preferably has a melt flow rate MFR2 (230°C, 2.16 kg), determined according to ISO 1133, in the range of 4.0 to 50.0 g / 10 min, more preferably in the range of 8.0 to 40.0 g / 10 min, even more preferably in the range of 12.0 to 30 g / 10 min, and even more preferably in the range of 15.0 to 25.0 g / 10 min, for example in the range of 15.0 to 20.0 g / 10 min.

[0132] It is further preferred that the heterophasic polypropylene copolymer (HECO) has a melting temperature Tm, determined according to differential scanning calorimetry (DSC), in the range of 150-170°C.

[0133] The heterophasic polypropylene copolymer (HECO) is preferably produced in a multi-stage process known in the art, in which a propylene homopolymer (hPP) matrix is ​​produced in at least one slurry reactor, and then an elastomeric ethylene copolymer (E) is produced in at least one gas-phase reactor. See, for example, the process for preparing heterophasic polypropylene copolymer (HECO) described in WO 2013 / 149915 A1.

[0134] The heterophasic polypropylene copolymer (HECO) is preferably obtained using a heterogeneous catalyst system comprising (i) a magnesium-containing support (e.g., MgCl) and (ii) a titanium compound (e.g., TiCl). Preferably, the heterophasic polypropylene copolymer (HECO) is obtained using a heterogeneous Ziegler-Natta catalyst. Such catalysts are well known in the art.

[0135] Additives (AD) The fiber-reinforced composition (C) may contain an additive (AD), which may be present in the fiber-reinforced composition (C) in an amount in the range of 0.01 to 5.0 wt %, preferably in the range of 0.1 to 4.0 wt %, more preferably in the range of 0.1 to 3.0 wt %, even more preferably in the range of 0.5 to 2.5 wt %, for example in the range of 1.0 to 2.0 wt %, based on the total weight of the composition (C).

[0136] Typical additives are acid scavengers, antioxidants, colorants, light stabilizers, plasticizers, slip agents, anti-scuff agents, dispersants, processing aids, lubricants, pigments, etc. Such additives are commercially available and are described, for example, in Hans Zweifel's "Plastic Additives Handbook", 6th Edition, 2009 (pp. 1141-1190).

[0137] Furthermore, the term "additive (AD)" according to the present invention also includes carrier materials, in particular polymeric carrier materials, which may be part of an additive masterbatch.

[0138] Preferably, the fiber reinforced polypropylene composition (C) of the present invention does not comprise further polymer(s) other than the propylene random copolymer (P), the heterophasic polypropylene copolymer (HECO) 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.

[0139] 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.

[0140] Goods The present invention also relates to an article, such as an injection molded article, comprising the fiber-reinforced composition (C) defined above.

[0141] The present invention relates in particular 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, such as 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).

[0142] Preferably, the article is an automotive article, such as an injection molded automotive article.

[0143] In the following, the present invention will be described by means of specific examples, which should not be construed as limiting the present invention in any way. [Example]

[0144] 1.Measurement method The following definitions of terms and methods of determination apply to the above general description of the invention and the following examples, unless otherwise defined.

[0145] Comonomer content of 1-butene for propylene 1-butene 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 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 taking into account 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, compensating for the relative amounts of αB2 and ααB2B2 methylene units of propene, which are not taken into account (note that B and BB count the number of butane monomers per sequence, not the number of sequences). P total =ISαα+B+BB / 2 If there is a characteristic signal corresponding to the observed positional defect (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253), the compensation of the misinserted propylene unit can be performed by P total was used. In the presence of 2,1-erythro misinsertion, the ninth carbon (S 21e9) was selected for compensation. P total =ISαα+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 ) The total comonomer incorporation of 1-butene in mole percent was calculated from the mole fractions in the usual way. B [mol%] = 100 × fB Total comonomer incorporation of 1-butene in weight percent was calculated from the mole fractions in the standard manner. B[weight%]=100×(fB×56.11) / ((fB×56.11)+((1-fB)×42.08))

[0146] Calculation of the comonomer content of the second propylene random copolymer (P2)

number

[0147] Ethylene content in C2C3 RACO and C2C3 HECO Quantitative nuclear magnetic resonance (NMR) spectroscopy was used to quantify the comonomer content of the polymers. 13 C{ 1 The {H} NMR spectrum 1 H and 13 All spectra were recorded in solution using a Bruker Advance III 400 NMR spectrometer operating at 400.15 MHz and 100.62 MHz for C, respectively. 13 All air pressures were recorded using nitrogen gas with a 10 mm extended temperature probe head optimized for 1000 Hz. Approximately 200 mg of material was dissolved in 3 ml of 1,2-tetrachloroethane-d2 (TCE-d2) with chromium(III) acetylacetonate (Cr(acac)3) to give a 65 mM solution of the relaxation agent in the solvent (Singh, G., Kothari, A., Gupta, V., Polymer Testing 28 5 (2009), 475). To ensure a homogeneous solution, the NMR tube was further heated in a rotary oven for at least 1 h after initial sample preparation in a heat block. After insertion into the magnet, the tube was spun at 10 Hz. This setup was chosen primarily due to the high resolution and quantitative nature required for accurate ethylene content determination. Standard single-pulse excitation without NOE was employed using an optimized tip angle, a 1 s repetition time, and a bilevel WALTZ16 decoupling scheme (Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh, D.; Winniford, B., J. Mag. Reson. 187 (2007) 225; Busico, V., Carbonniere, P., Cipullo, R., Pellecchia, R., Severn, J., Talarico, G., Macromol. Rapid Commun. 2007, 28, 1128). A total of 6144 (6k) transients were acquired per spectrum. quantitative13 C{ 1 The {H} NMR spectra were processed and integrated using a proprietary computer program, and relevant quantitative properties were determined from the integrals. All chemical shifts were indirectly referenced to the central methylene group of the ethylene block (EEE) at 30.00 ppm using the chemical shift of the solvent. This approach allowed for comparable referencing even in the absence of this structural unit. Characteristic signals corresponding to the incorporation of ethylene were observed (Cheng, HN, Macromolecules 17 (1984), 1950). If a characteristic signal corresponding to the 2,1-erythro regiodefect was observed, correction for the effect of the regiodefect on the determined properties was necessary (as described in L. Resconi, L. Cavallo, A. Fait, F. Piemontesi, Chem. Rev. 2000, 100(4), 1253; Cheng, H.N., Macromolecules 1984, 17, 1950; and W.J. Wang and S. Zhu, Macromolecules 2000, 33, 1157). No characteristic signals corresponding to other types of regiodefects were observed. The comonomer fraction is 13 C{ 1 Quantification was performed using the method of Wang et al. (Wang, WJ., Zhu, S., Macromolecules 33 (2000) 1157) by integration of multiple signals over the entire spectral range of the {H} spectrum. This method was chosen for its robustness and ability to take into account the presence of positional defects, if necessary. The integration range was slightly adjusted to increase applicability over the full range of comonomer contents encountered. For systems where only isolated ethylene in the PPEPP sequence is observed, the method of Wang et al. was modified to reduce the effect of non-zero integrals of sites known to be absent. This approach reduces the overestimation of ethylene content for such systems, which reduces the number of sites used to determine absolute ethylene content. E=0.5(Sββ+Sβγ+Sβδ+0.5(Sαβ+Sαγ)) This was achieved by reducing it to Using this set of sites, the corresponding integral equation can be written, using the same notation as used in Wang et al.'s paper (Wang, WJ., Zhu, S., Macromolecules 33 (2000), 1157): E=0.5(I H +I G +0.5(I C +I D )) The equation used for absolute propylene content was not modified. The equation used for absolute propylene content was not modified. The mole percent comonomer incorporation was calculated from the mole fraction. E [mol%] = 100 × fE Comonomer incorporation in weight percent was calculated from the mole fraction. E[weight%]=100×(f E ×28.06) / ((f E ×28.06)+((1-f E )×42.08)) Comonomer sequence distribution at the triad level was determined using the analytical method of Kakugo et al. (Kakugo, M., Naito, Y., Mizunuma, K., Miyatake, T. Macromolecules 15 (1982) 1150.) This method was chosen because of its robustness and the integral region, which was slightly adjusted to enhance applicability to a wider range of comonomer contents.

[0148] Melt Flow Rate (MFR) The melt flow rate MFR2 was measured in accordance with ISO 1133 using a load of 2.16 kg at 230°C for propylene copolymers and a load of 2.16 kg at 190°C for ethylene copolymers. The melt flow rate is the amount of polymer in grams that can be extruded in 10 minutes under a load of 2.16 kg at temperatures of 230°C and 190°C, respectively, using a test apparatus standardized to ISO 1133.

[0149] 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.

[0150] 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).

[0151] 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.

[0152] 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.

[0153] Tensile properties were determined on 4 mm thick injection-molded dog-bone 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.

[0154] Heat distortion temperature (HDT) HDT is 80 x 10 x 4 mm prepared according to ISO1873-2 3The test was performed on flat-supported specimens according to ISO 75, condition A, at a nominal surface stress of 1.80 MPa. VOC / Fog emissions were measured according to VDA278:2002 on injection molded specimens and granulated compounds. 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 the temperature range from -150°C to +280°C with a heating rate of 12 K / s and a final time of 5 min, flow mode split 1:30. 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 a 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, and isothermal for 30 min; flow rate 1.3 ml / min.

[0155] 2. Working Example Catalyst preparation Metallocene compound (MC-2) (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-butylinden-1-yl]zirconium dichloride) was synthesized as described for MC-2 in WO 2019 / 179959. [ka] A catalyst was prepared using metallocene MC-2 and a catalyst system of MAO and trityl tetrakis(pentafluorophenyl)borate according to the process for preparing a metallocene catalyst described in the Examples of WO 2021 / 233771. This catalyst was used to prepare a random propylene copolymer P.

[0156] Preparation of random propylene copolymer (P) Random propylene copolymers (P) were prepared in a sequential process involving a loop reactor and a gas-phase reactor. The reaction conditions are summarized in Table 1.

[0157] [Table 1]

[0158] The resulting copolymer was compounded without visbreaking using a basic antioxidant combination for stabilization. Copolymer P 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 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.

[0159] Preparation of fiber-reinforced composition (C) The fiber-reinforced composition (C) was obtained by melt blending the propylene random copolymer (P) with glass fiber (GF), heterophasic propylene copolymer (HECO), 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 2.

[0160] [Table 2]

[0161] P is the C3C4 random copolymer described above in Table 1. PA is a Ziegler-Natta catalyst-based, high-flow C2C3 random copolymer produced by visbreaking reactor-grade C2C3 copolymer to a MFR (230°C; 2.16 kg) of 75 g / 10 min. It has a melting temperature (Tm) of 145°C. It has no detectable 1,2-erythro regio-defects, i.e., 0 mol% 1,2-erythro regio-defects. Pb is a metallocene-catalyzed C3C4 random copolymer with a MFR of 21 g / 10 min (230°C; 2.16 kg), a C4 comonomer content of 4.3 mol%, 2000 ppm nucleating agent, and 2 wt% propylene homopolymer (HF955MO, available from Borealis). It has a melting temperature, Tm, of 146°C and a crystallization temperature, Tc, of 118°C. The amount of 1,2-erythro regiodefects is approximately 0.9 mol%. HECO is a commercial product EF015AE from Borealis, which is a Ziegler-Natta based in-reactor heterophasic propylene copolymer (rTPO) with a MFR of 18 g / 10 min (230 °C; 2.16 kg), an XCS content of 31.5 wt%, a C2(XCS) of 44.8 wt%, and an iV(XCS) of 2.3 dl / g. It has a melting temperature, Tm, of 165 °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. AP is 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. AD1 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. AD2 was prepared by mixing 10.0 wt.% tris(2,4-di-t-butylphenyl)phosphite (Kinox-68-G from HPL Additives), 10.0 wt.% pentaerythrityl-tetrakis(3-(3',5'-di-tert-butyl-4-hydroxyphenyl)-propionate (Irganox 1010FF from BASF), 25.0 wt.% carbon black from Borealis (39.5 wt.% masterbatch), and 55.0 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.

Claims

1. 1. A fiber-reinforced composition comprising: The fiber reinforced composition has a melt flow rate MFR, determined in accordance with ISO 1133, in the range of 10.0 to 100.0 g / 10 min. ２ (230°C, 2.16 kg), The fiber-reinforced composition comprises, based on the total weight of the fiber-reinforced composition: a) 20.0 to 89.9 wt % of a propylene random copolymer (P), which is a copolymer of propylene and at least one comonomer selected from a C4 to C12 α-olefin, and which has 1,2 erythro position defects in an amount ranging from 0.4 to 1.2 mol %; b) 5.0 to 45.0 wt. % glass fiber (GF); c) 0.1 to 5.0 wt. % of an adhesion promoter (AP); d) 5.0 to 50.0 wt. % of heterophasic polypropylene copolymer (HECO); 1. A fiber-reinforced composition comprising:

2. The propylene random copolymer (P) has a melt flow rate MFR, determined in accordance with ISO 1133, in the range of 45 to 150 g / 10 min. ２ 10. The fiber reinforced composition of claim 1 having a viscosity of 230°C, 2.16 kg.

3. 3. The fiber reinforced composition according to claim 1 or claim 2, wherein the propylene random copolymer (P) has a melting temperature Tm, determined according to differential scanning calorimetry (DSC), in the range of 125 to 150°C.

4. The fiber-reinforced composition according to claim 1 or claim 2, wherein the propylene random copolymer (P) has a comonomer content in the range of 2.5 to 10.0 mol %.

5. 3. The fiber-reinforced composition according to claim 1, wherein the propylene random copolymer (P) is a copolymer of propylene and 1-butene.

6. The propylene random copolymer (P) is i) a first propylene random copolymer (P1); and ii) a second propylene random copolymer (P2) having a higher comonomer content than said 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) is at least 95.0% by weight based on the propylene random copolymer (P). The fiber-reinforced composition according to claim 1 or claim 2.

7. 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 14.0 mol%, wherein the comonomer content of the second propylene random copolymer (P2) is different from the comonomer content of the first propylene random copolymer (P1); The fiber-reinforced composition of claim 1 or claim 2, comprising:

8. The glass fiber (GF) is i) an average length of 1.0 to 10.0 mm, and / or ii) average diameter of 5 to 20 μm The fiber-reinforced composition of claim 1 or claim 2, wherein

9. 3. A fiber reinforced composition according to claim 1 or claim 2, wherein the adhesion promoter (AP) is a polar modified propylene homopolymer or copolymer (PM-PP).

10. The heterophasic polypropylene copolymer (HECO) is i) a matrix which is a propylene homopolymer (hPP); ii) an elastomeric ethylene copolymer (E) dispersed in said matrix, said elastomeric ethylene polymer (E) being a copolymer of ethylene, propylene, and optionally at least one comonomer selected from a C4 to C12 α-olefin; and The fiber-reinforced composition of claim 1 or claim 2, comprising:

11. The heterophasic polypropylene copolymer (HECO) is i) an ethylene content of the xylene cold solubles (XCS) fraction in the range of 20.0 to 55.0 wt.%; ii) a xylene cold solubles (XCS) content, determined at 25°C according to ISO 16152, in the range of 5.0 to 45.0 wt.%, based on the total weight of said heterophasic polypropylene copolymer (HECO); iii) an intrinsic viscosity (IV) of the XCS fraction, determined in decalin at 135°C according to DIN ISO 1628 / 1, of 1.5 to 6.0 dl / g; 3. The fiber-reinforced composition of claim 1 or claim 2, comprising one or more of:

12. The heterophasic polypropylene copolymer (HECO) is (i) a melt flow rate MFR determined in accordance with ISO 1133 in the range of 4.0 to 50.0 g / 10 min; ２ (230°C, 2.16 kg), and (ii) a melting temperature Tm determined according to differential scanning calorimetry (DSC) in the range of 150-170°C; 3. The fiber-reinforced composition of claim 1 or claim 2, comprising one or more of:

13. 3. The fiber-reinforced composition according to claim 1 or claim 2, wherein the propylene random copolymer (P) is obtained in the presence of a solid catalyst system (SCS) comprising a metallocene compound.

14. The solid catalyst system (SCS) comprises: (i) A metallocene compound of formula (I), 【Chemistry 1】 each X is independently a σ-donor ligand; L is -R' ２ C-, -R' ２ C-CR' ２ -, -R' ２ Si—, —R′ ２ Si—SiR′ ２ -, -R' ２ Ge-, wherein each R' is independently a hydrogen atom, or one or more heteroatoms of Groups 14 to 16 of the Periodic Table, or a fluorine atom; １ ~C ２０ - a hydrocarbyl group, or optionally two R' groups together form a ring; Each R １ are independently the same or different and are hydrogen, linear or branched C １ ~C ６ - alkyl group, C ７～２０ -arylalkyl, C ７～２０ - alkylaryl group or C ６～２０ -aryl group or OY group, Y is C １～１０ -hydrocarbyl group, optionally two adjacent R １ groups are part of a ring that includes the phenyl carbon to which they are attached; Each R ２ are independently the same or different, CH ２ -R ８ is a group, and R ８ is H or a linear or branched C １～６ - alkyl group, C ３～８ -cycloalkyl group, C ６～１０ - an aryl group, R ３ is a linear or branched C １ ~C ６ - alkyl group, C ７～２０ -arylalkyl, C ７～２０ - alkylaryl group or C ６ ~C ２０ - an aryl group, R ４ is C(R ９ ) ３ is a group, and R ９ is a linear or branched C １ ~C ６ - is an alkyl group, R ５ is an aliphatic C which may contain hydrogen or one or more heteroatoms from groups 14 to 16 of the periodic table of the elements; １ ~C ２０ is a hydrocarbyl group, R ６ is an aliphatic C which may contain hydrogen or one or more heteroatoms from groups 14 to 16 of the periodic table of the elements; １ ~C ２０ - a hydrocarbyl group, or R ５ and R ６ together form n groups R １０ wherein n is 0 to 4, and Each R １０ are the same or different, C １ ~C ２０ -hydrocarbyl group, optionally containing one or more heteroatoms belonging to groups 14 to 16 of the periodic table １ ~C ２０ - may be a hydrocarbyl group, R ７ is H or a linear or branched C １ ~C ６ - an alkyl group or 1 to 3 groups R １ is an aryl or heteroaryl group having 6 to 20 carbon atoms, optionally substituted by a metallocene compound; (ii) a cocatalyst system comprising a boron-containing cocatalyst and / or an aluminoxane cocatalyst; and (iii) optionally, a silica support; 14. The fiber reinforced composition of claim 13 comprising:

15. An article comprising the fiber-reinforced composition of claim 1 or claim 2.

Images