Glass Fiber Composite

Abstract

A fiber-reinforced composite comprising polypropylene produced in the presence of a metallocene catalyst, a heterophasic propylene copolymer produced in the presence of a Ziegler-Natta catalyst, and glass fibers.

Description

[Technical field]

[0001] The present invention is directed to a fiber reinforced composite comprising polypropylene, a heterophasic propylene copolymer and glass fibers, and to an article comprising the fiber reinforced composite. [Background technology]

[0002] Polypropylene is a material used in a wide variety of technical fields, and reinforced polypropylene has gained particular relevance in fields that previously relied exclusively on non-polymeric materials, especially metals. One specific example of reinforced polypropylene is glass fiber reinforced polypropylene composites. Such materials make it possible to tailor the properties of the composite by choosing the type of polypropylene, the amount of glass fiber, and sometimes by choosing the type of compatibilizer used. Thus, today, glass fiber reinforced polypropylene composites are well established materials for applications requiring high stiffness, heat distortion resistance, and impact resistance. However, one disadvantage of commercially available fiber reinforced polypropylene composites is the rather high amount of oligomers obtained as by-products in the polymerization process, and the low melt flow rate (MFR 2 ) and its rather high emissions caused by radical-induced decomposition, commonly called visbreaking, which is sometimes necessary to improve processability. This is linked to the need to consider not only the final properties of the fiber-reinforced polypropylene composites, but also the efficient manufacture of moulded articles made therefrom, i.e. the flowability of the composite must be rather high. Summary of the Invention [Problem to be solved by the invention]

[0003] Thus, there is a need for glass fiber reinforced polypropylene composites that have low emissions yet are stiff, have fairly high heat distortion resistance, and can be further processed at high throughput rates. [Means for solving the problem]

[0004] The present invention is based on the finding that the fiber reinforced polypropylene composite must contain a metallocene catalyzed polypropylene having a broad molecular weight distribution and a Ziegler-Natta catalyzed heterophasic propylene copolymer, and therefore both polymers are preferably not visbroken, i.e., not modified by a radical-induced process to reduce the molecular weight.

[0005] Accordingly, the present invention provides a fiber-reinforced composite material, comprising: (a) 30 to 60% by weight of polypropylene (PP1) based on the fiber reinforced composite material; (b) 10-40 wt. % based on the fiber reinforced composite of a heterophasic propylene copolymer (HECO), the heterophasic propylene copolymer (HECO) comprising a propylene homopolymer (H-PP2) and an ethylene-propylene rubber (EPR); (c) 10 to 40% by weight of glass fiber (GF) based on the fiber-reinforced composite material; (d) 0.05 to 5.0% by weight of a compatibilizer (CA) based on the fiber-reinforced composite material; Including, the total amount of said polypropylene (PP1), said heterophasic propylene copolymer (HECO), said glass fiber (GF) and said compatibilizer (CA) in said fiber reinforced composite is at least 95 wt. %; Furthermore, the polypropylene (PP1) is (i) Melt flow rate (MFR) measured according to ISO 1133 in the range of 40.0 to 250 g / 10 min. 2 (230℃, 2.16kg), (ii) 0.5% by weight or less 13 comonomer content, determined by C-NMR spectroscopy, the comonomer, if present, being ethylene; (iii) a molecular weight distribution (MWD) as determined by gel permeation chromatography (GPC) in the range of greater than 4.5 to less than 8.5; and (iv) in the range of 0.20 to 1.00%; 13 2,1-site defects determined by C-NMR spectroscopy having Still further, the propylene homopolymer (H-PP2) of the heterophasic propylene copolymer (HECO) is (v) in the range of 0 to less than 0.10%; 13 2,1-site defects determined by C-NMR spectroscopy The present invention is directed to a fiber-reinforced composite having a

[0006] Further preferred embodiments of such a composite are defined in the claims dependent on claim 1 and are also defined in more detail below.

[0007] The present invention is also directed to an article, preferably an automotive article, comprising at least 95% by weight of the fiber reinforced composite material according to the present invention.

[0008] In the following, the fibre reinforced composite is defined in more detail, followed by the components of this composite.

[0009] Fiber Reinforced Composites The present invention is directed to a fiber reinforced composite comprising polypropylene (PP1), heterophasic propylene copolymer (HECO), glass fiber (GF) and a compatibilizer (CA). It is understood that fiber reinforced composites are known in the art. That is, polypropylene (PP1) together with heterophasic propylene copolymer (HECO) form the majority of the continuous phase in which the glass fiber is embedded. When the glass fiber is a short glass fiber, the fiber is dispersed in a polymer mixture comprising polypropylene (PP1) and heterophasic propylene copolymer (HECO), which acts as the continuous phase. The compatibilizer (CA) improves the adhesion between the polar glass fiber and the mixture of non-polar polymers comprising polypropylene (PP1) and heterophasic propylene copolymer (HECO).

[0010] Accordingly, the present invention provides a fiber-reinforced composite material, comprising: (a) 30 to 60% by weight, preferably 35 to 55% by weight, of polypropylene (PP1) based on the fiber-reinforced composite material; (b) 10-40 wt. %, preferably 20-35 wt. %, based on the fiber reinforced composite, of a heterophasic propylene copolymer (HECO), comprising a propylene homopolymer (H-PP2) and an ethylene-propylene rubber (EPR); (c) 10 to 40% by weight, preferably 15 to 30% by weight, of glass fiber (GF) based on the fiber-reinforced composite material; (d) 0.05 to 5.0% by weight, preferably 0.1 to 5.0% by weight, of a compatibilizer (CA) based on the fiber-reinforced composite material; Including, The present invention is directed to a fiber reinforced composite, in which the total amount of polypropylene (PP1), heterophasic propylene copolymer (HECO), glass fiber (GF) and compatibilizer (CA) in the fiber reinforced composite is at least 95% by weight, preferably at least 97% by weight.

[0011] Besides these four components, typical additives added to extend the life of, for example, polypropylene (PP1) and heterophasic propylene copolymers (HECO) may be present, namely antioxidants (see additives definition below).

[0012] Accordingly, the present invention provides a fiber-reinforced composite material, comprising: (a) 35 to 55% by weight of polypropylene (PP1) based on the fiber-reinforced composite material; (b) 20-35 wt. % based on the fiber reinforced composite of a heterophasic propylene copolymer (HECO), the heterophasic propylene copolymer (HECO) comprising a propylene homopolymer (H-PP2) and an ethylene-propylene rubber (EPR); (c) 15 to 30 weight percent glass fiber (GF) based on the fiber-reinforced composite material; (d) 0.1 to 5.0% by weight of a compatibilizer (CA) based on the fiber-reinforced composite; (e) 0.1 to 5.0% by weight of an additive (AD) based on the fiber-reinforced composite material; Including, The total amount of polypropylene (PP1), heterophasic propylene copolymer (HECO), glass fiber (GF), compatibilizer (CA) and additive (AD) in the fiber reinforced composite is at least 98% by weight, preferably in the range of 98-100% by weight, for example in the range of 99-100% by weight, directed to the fiber reinforced composite.

[0013] In a particular embodiment, the fiber reinforced composite according to the invention preferably comprises: (a) 35 to 55% by weight of polypropylene (PP1) based on the fiber-reinforced composite material; (b) 20-35 wt. % based on the fiber reinforced composite of a heterophasic propylene copolymer (HECO), the heterophasic propylene copolymer (HECO) comprising a propylene homopolymer (H-PP2) and an ethylene-propylene rubber (EPR); (c) 15 to 30 weight percent glass fiber (GF) based on the fiber-reinforced composite material; (d) 0.1 to 5.0% by weight of a compatibilizer (CA) based on the fiber-reinforced composite; (e) 0.1 to 5.0% by weight of an additive (AD) based on the fiber-reinforced composite material; It consists of:

[0014] As mentioned above, the continuous phase of the fiber reinforced composition is predominantly dominated by polypropylene (PP1) and heterophasic propylene copolymer (HECO). It is therefore preferred that the continuous phase of the fiber reinforced composition in which the glass fibers are embedded comprises at least 97% by weight, more preferably at least 98% by weight, of a mixture of polypropylene (PP1) and heterophasic propylene copolymer (HECO).

[0015] Furthermore, due to the presence of heterophasic propylene copolymer (HECO), the fiber reinforced composition contains an elastomeric polymer, i.e. ethylene-propylene rubber (EPR). An elastomeric polymer is understood as a polymer that does not form a continuous phase in the (semi-)crystalline polypropylene. In other words, the elastomeric polymer is dispersed in the (semi-)crystalline polypropylene, i.e. forms inclusions (mixtures) in the (semi-)crystalline polypropylene. A polymer that contains an elastomeric polymer as inclusions as a second polymer phase is called heterophasic. The presence of a second polymer phase or so-called inclusions can be seen, for example, by high-resolution microscopy, e.g. electron microscopy or atomic force microscopy, or by dynamic mechanical thermal analysis (DMTA). In particular, in DMTA, the presence of a multiphase structure can be identified by the presence of at least two distinguishable glass transition temperatures. Thus, the polymer phase of the fiber reinforced composition according to the invention itself forms a system in which the polypropylene (PP1) and the propylene homopolymer (H-PP2) form the continuous phase in which the ethylene-propylene rubber (EPR) is dispersed.

[0016] Therefore, it is preferable that the weight ratio [(PP1)+(H-PP2) / (EPR)] of the mixture of polypropylene (PP1) and propylene homopolymer (H-PP2) acting as a matrix to the ethylene-propylene rubber (EPR) dispersed in this matrix is ​​in the range of 75:25 to 95:5, more preferably in the range of 80:20 to 92:8.

[0017] Furthermore, the weight ratio of polypropylene (PP1) to propylene homopolymer (H-PP2) [(PP1) / (H-PP2)] is preferably in the range of 60:40 to 80:20, more preferably in the range of 68:32 to 77:23.

[0018] In addition, it is preferred that the molecular weights of the polypropylene (PP1) and the propylene homopolymer (H-PP2) of the heterophasic propylene copolymer (HECO) are fairly similar. Thus, the propylene homopolymer (H-PP2) of the heterophasic propylene copolymer (HECO) has a melt flow rate MFR measured according to ISO 1133 in the range of 40.0 to 250 g / 10 min, more preferably in the range of 50.0 to 150 g / 10 min. 2 (230°C, 2.16 kg), provided that the melt flow ratio MFR of polypropylene (PP1) and propylene homopolymer (H-PP2) of heterophasic propylene copolymer (HECO) 2 [MFR 2 (PP1) / MFR 2 (H-PP2)] is preferably in the range of 0.75 to 1.25, and more preferably in the range of 0.80 to 1.20.

[0019] Further, the fiber reinforced composite has a melt flow rate MFR, measured according to ISO 1133, in the range of 8.0 to 50 g / 10 min, more preferably in the range of 10 to 30 g / 10 min. 2 (230° C., 2.16 kg).

[0020] The fibre-reinforced composites according to the invention are characterised in particular by low emissions: they therefore preferably have a VOC (volatile organic compounds) value, determined according to VDA 278 October 2011, of less than 150 μg / g, more preferably in the range from 50 to less than 150 μg / g, even more preferably in the range from 60 to 100 μg / g.

[0021] It is further preferred that the fibre reinforced composite has a tensile modulus, determined on injection moulded specimens at 1 mm / min according to ISO 527-1, in the range of 3500-7000 MPa, more preferably in the range of 3800-6500 MPa, for example in the range of 4000-63000 MPa, and also that the fibre reinforced composite has an elongation at break in the same tensile test preferably above 2.0%, more preferably in the range of 2.1-10.0%, for example in the range of 2.2-8.0%.

[0022] In addition or alternatively to the requirements of the preceding paragraph, the fibre-reinforced composite material has a thermal conductivity of 30.0 to 75.0 kJ / m 2 More preferably, the range is 35.0 to 70.0 kJ / m 2 In the range of, for example, 40.0 to 65.0 kJ / m 2 The Charpy impact strength, determined at 23°C according to ISO 179-1eU, is in the range of

[0023] In a particularly specific embodiment, the fibre reinforced composite has a heat distortion temperature (HDT) measured at a load of 0.46 MPa according to ISO 75 B in the range of 146-160°C, more preferably in the range of 148-158°C, for example in the range of 150-156°C.

[0024] Polypropylene (PP1) One essential component of the present invention is the polypropylene (PP1), which must be carefully selected to achieve the desired properties. Thus, the polypropylene (PP1) of the present invention must be produced using a metallocene catalyst and must have a fairly broad molecular weight distribution (MWD) for such produced polypropylene.

[0025] Thus, the polypropylene (PP1) is produced in the presence of a specific metallocene catalyst, which is defined in more detail below. In contrast to polypropylene produced in the presence of a Ziegler-Natta catalyst, polypropylene produced in the presence of a metallocene catalyst is characterized by misinsertion of monomer units during the polymerization process. Therefore, the polypropylene (PP1) according to the present invention has a specific amount of 2,1-position defects, which indicates that the polypropylene (PP1) according to the present invention was produced using a metallocene catalyst. That is, the polypropylene (PP1) according to the present invention has a specific amount of 2,1-position defects in the range of 0.20 to 1.00%, more preferably in the range of 0.40 to 0.90%, 13 It has a 2,1 position defect as determined by C-NMR spectroscopy.

[0026] Thus, the polypropylene (PP1) according to the present invention has (i) a melt flow rate (MFR), measured according to ISO 1133, in the range of 40.0 to 250 g / 10 min, preferably in the range of 50.0 to 150 g / 10 min; 2 (230℃, 2.16kg) (ii) 0.5% by weight or less 13 a comonomer content determined by C-NMR spectroscopy, the comonomer being ethylene; and (iii) a molecular weight distribution (MWD) determined by gel permeation chromatography (GPC) in the range of from greater than 4.5 to less than 8.5, preferably in the range of from 5.5 to 8.0; (iv) in the range of 0.20 to 1.00%, more preferably in the range of 0.40 to 0.90%; 13 2,1-site defects determined by C-NMR spectroscopy has.

[0027] More preferably, the polypropylene (PP1) according to the present invention is (i) a melt flow rate (MFR), measured according to ISO 1133, in the range of 40.0 to 250 g / 10 min, preferably in the range of 50.0 to 150 g / 10 min; 2 (230℃, 2.16kg) (ii) 0.5% by weight or less 13 a comonomer content determined by C-NMR spectroscopy, the comonomer being ethylene; and (iii) a molecular weight distribution (MWD) determined by gel permeation chromatography (GPC) in the range of from greater than 4.5 to less than 8.5, preferably in the range of from 5.5 to 8.0; (iv) in the range of 0.20 to 1.00%, more preferably in the range of 0.40 to 0.90%; 13 2,1-site defects as determined by C-NMR spectroscopy; (v) the melting temperature Tm, determined by DSC (heating and cooling rate 10°C / min) according to ISO 11357-3, in the range of 150-159°C; has.

[0028] It is especially preferred that the polypropylene (PP1) is a propylene homopolymer (H-PP1).

[0029] Therefore, the polypropylene (PP1) of the present invention (i) a melt flow rate (MFR), measured according to ISO 1133, in the range of 40.0 to 250 g / 10 min, preferably in the range of 50.0 to 150 g / 10 min; 2 (230℃, 2.16kg) (ii) a molecular weight distribution (MWD) determined by gel permeation chromatography (GPC) in the range of from greater than 4.5 to less than 8.5, preferably in the range of from 5.5 to 8.0; (iii) in the range of 0.20 to 1.00%, more preferably in the range of 0.40 to 0.90%; 13 2,1-site defects determined by C-NMR spectroscopy It is preferable that the propylene homopolymer is a propylene homopolymer (H-PP1) having the formula:

[0030] Furthermore, the polypropylene (PP1), preferably the propylene homopolymer (H-PP1), has a significant amount of polymer that elutes by Temperature Rising Elution fractionation (TREF) below 100° C. It is therefore preferred that the polypropylene (PP1) has a fraction that elutes by Temperature Rising Elution fractionation (TREF) below 100° C. in the range of 12-20% by weight, more preferably in the range of 14-18% by weight.

[0031] Therefore, polypropylene (PP1) (i) a melt flow rate (MFR), measured according to ISO 1133, in the range of 40.0 to 250 g / 10 min, preferably in the range of 50.0 to 150 g / 10 min; 2 (230℃, 2.16kg) (ii) 0.5% by weight or less 13 a comonomer content determined by C-NMR spectroscopy, the comonomer being ethylene; and (iii) a molecular weight distribution (MWD) determined by gel permeation chromatography (GPC) in the range of from greater than 4.5 to less than 8.5, preferably in the range of from 5.5 to 8.0; (iv) in the range of 0.20 to 1.00%, more preferably in the range of 0.40 to 0.90%; 13 2,1-site defects as determined by C-NMR spectroscopy; (v) a fraction eluting at less than 100° C. by temperature rising elution fractionation (TREF) in the range of 12 to 20% by weight, more preferably in the range of 14 to 18% by weight; It is preferred that the compound has the formula:

[0032] Even more preferably, the polypropylene (PP1) is (i) a melt flow rate (MFR), measured according to ISO 1133, in the range of 40.0 to 250 g / 10 min, preferably in the range of 50.0 to 150 g / 10 min; 2 (230℃, 2.16kg) (ii) a molecular weight distribution (MWD) determined by gel permeation chromatography (GPC) in the range of from greater than 4.5 to less than 8.5, preferably in the range of from 5.5 to 8.0; (iii) in the range of 0.20 to 1.00%, more preferably in the range of 0.40 to 0.90%; 13 2,1-site defects as determined by C-NMR spectroscopy; (iv) A fraction eluting at less than 100°C by temperature rising elution fractionation (TREF) in the range of 12 to 20% by weight, more preferably in the range of 14 to 18% by weight. The propylene homopolymer (H-PP1) has the formula:

[0033] Additionally, polypropylene (PP1) can be further defined by its melting temperature and xylene solubles content.

[0034] It is therefore preferred that the polypropylene (PP1), in particular the propylene homopolymer (H-PP1), has a melting temperature Tm, determined by DSC (heating and cooling rate 10°C / min) according to ISO 11357-3, in the range of 150-159°C.

[0035] The polypropylene (PP1) according to the invention is further preferably characterized by a very low cold xylene solubles (XCS) content, which cannot be reached by Ziegler-Natta catalysts. Thus, in a preferred embodiment, the polypropylene (PP1) according to the invention, more preferably the propylene homopolymer (H-PP1), has a cold xylene solubles (XCS) fraction, measured according to ISO 16152 (25°C), in the range of 0.5-3.0% by weight, more preferably in the range of 0.8-2.5% by weight.

[0036] As mentioned above, it is preferred that the polypropylene (PP1) of the present invention is produced by a specific metallocene catalyst. Thus, in a preferred embodiment, the polypropylene (PP1), more preferably the propylene homopolymer (H-PP1), is produced by polymerizing propylene and optionally ethylene in the presence of a metallocene catalyst having formula (I). [ka] In the formula, each R 1 may be independently the same or different and are hydrogen or linear or branched C 1 ~C 6 alkyl group, at least one R per phenyl group 1 is not hydrogen, R' is C 1 ~C 10 Hydrocarbyl groups, preferably C 1 ~C 4 is a hydrocarbyl group, more preferably a methyl group; X is independently a hydrogen atom, a halogen atom, or C 1 ~C 6 Alkoxy group, C 1 ~C 6 It is an alkyl group, a phenyl group or a benzyl group.

[0037] Hereinafter, the term "Formula (I)" refers to the metallocene catalyst defined in the previous paragraph.

[0038] Therefore, polypropylene (PP1) (i) a melt flow rate (MFR), measured according to ISO 1133, in the range of 40.0 to 250 g / 10 min, preferably in the range of 50.0 to 150 g / 10 min; 2 (230℃, 2.16kg) (ii) 0.5% by weight or less 13 a comonomer content determined by C-NMR spectroscopy, the comonomer being ethylene; and (iii) a molecular weight distribution (MWD) determined by gel permeation chromatography (GPC) in the range of from greater than 4.5 to less than 8.5, preferably in the range of from 5.5 to 8.0; (iv) in the range of 0.20 to 1.00%, more preferably in the range of 0.40 to 0.90%; 13 2,1-site defects as determined by C-NMR spectroscopy; (v) optionally, a fraction eluting below 100° C. by temperature rising elution fractionation (TREF) in the range of 12-20 wt.%, more preferably in the range of 14-18 wt.%; and it is particularly preferred that the polypropylene (PP1) is prepared by polymerizing propylene and optionally ethylene in the presence of a metallocene catalyst having the formula (I) defined above.

[0039] Even more preferably, the polypropylene (PP1) is (i) a melt flow rate (MFR), measured according to ISO 1133, in the range of 40.0 to 250 g / 10 min, preferably in the range of 50.0 to 150 g / 10 min; 2 (230℃, 2.16kg) (ii) a molecular weight distribution (MWD) determined by gel permeation chromatography (GPC) in the range of from greater than 4.5 to less than 8.5, preferably in the range of from 5.5 to 8.0; (iii) in the range of 0.20 to 1.00%, more preferably in the range of 0.40 to 0.90%; 13 2,1-site defects as determined by C-NMR spectroscopy; (iv) optionally, a fraction eluting below 100° C. by temperature rising elution fractionation (TREF) in the range of 12-20 wt.%, more preferably in the range of 14-18 wt.%; and wherein the propylene homopolymer (H-PP1) is prepared by polymerizing propylene in the presence of a metallocene catalyst having the formula (I) defined above.

[0040] In addition, it is preferred that the polypropylene (PP1), e.g. propylene homopolymer (H-PP1), is not visbroken. Visbreaking, or controlled degradation by radical-induced processes initiated by peroxides or other radical generators, is usually used to increase the melt flow rate and thus reduce the molecular weight and narrow the molecular weight distribution. However, the degradation of the polymer, i.e. visbreaking, is obtained by the use of peroxides. Visbreaking and the use of peroxides can increase the emission values ​​(in terms of VOC or FOG) due to undesirable side reactions that lead to an increase in the amount of oligomers. Furthermore, the presence of peroxides can lead to undesirable discoloration of the polypropylene. In other words, whether a polypropylene is visbroken can be confirmed by the decomposition products of peroxides and other radical generators and the discoloration of the polypropylene. Therefore, in the following, whenever the terms "non-visbroken" or "not visbroken" are used, it is understood that the melt flow rate, molecular weight and molecular weight distribution of the polypropylene (PP1) have not been altered by chemical or physical treatment, and further that the polypropylene (PP1) does not contain decomposition products of peroxides or other radical generators. Moreover, visbreaking is in any case contrary to the teaching of the present invention, since it is desired that the polypropylene (PP1) of the present invention has a fairly broad molecular weight distribution, which is inconsistent with visbreaking.

[0041] Therefore, polypropylene (PP1) is not visbroken. (i) a melt flow rate (MFR), measured according to ISO 1133, in the range of 40.0 to 250 g / 10 min, preferably in the range of 50.0 to 150 g / 10 min; 2 (230℃, 2.16kg) (ii) 0.5% by weight or less 13 a comonomer content determined by C-NMR spectroscopy, the comonomer being ethylene; and (iii) a molecular weight distribution (MWD) determined by gel permeation chromatography (GPC) in the range of from greater than 4.5 to less than 8.5, preferably in the range of from 5.5 to 8.0; (iv) in the range of 0.20 to 1.00%, more preferably in the range of 0.40 to 0.90%; 13 2,1-site defects as determined by C-NMR spectroscopy; (v) optionally, a fraction eluting below 100° C. by temperature rising elution fractionation (TREF) in the range of 12-20 wt.%, more preferably in the range of 14-18 wt.%; and the polypropylene (PP1) is preferably prepared by polymerizing propylene and optionally ethylene in the presence of a metallocene catalyst having the formula (I) defined above.

[0042] More preferably, the polypropylene (PP1) is a propylene homopolymer (H-PP1), which is not visbroken, (i) a melt flow rate (MFR), measured according to ISO 1133, in the range of 40.0 to 250 g / 10 min, preferably in the range of 50.0 to 150 g / 10 min; 2 (230℃, 2.16kg) (ii) a molecular weight distribution (MWD) determined by gel permeation chromatography (GPC) in the range of from greater than 4.5 to less than 8.5, preferably in the range of from 5.5 to 8.0; (iii) in the range of 0.20 to 1.00%, more preferably in the range of 0.40 to 0.90%; 13 2,1-site defects as determined by C-NMR spectroscopy; (iv) optionally, a fraction eluting below 100° C. by temperature rising elution fractionation (TREF) in the range of 12-20 wt.%, more preferably in the range of 14-18 wt.%; and the propylene homopolymer (H-PP1) is prepared by polymerizing propylene in the presence of a metallocene catalyst having the formula (I) defined above.

[0043] Below, the polymerization of polypropylene is described in detail. The polypropylene (PP1) according to the invention can be produced in one reactor or in a reactor cascade of two or more reactors, preferably two reactors. Since the polypropylene (PP1) according to the invention must have a broad molecular weight distribution (MWD), i.e. a broad molecular weight distribution (MWD) of at least 4.5, it is preferred that the polypropylene (PP1) is produced in at least two reactors, producing polypropylene fractions with significantly different molecular weights in each reactor, thereby arriving at a final polypropylene (PP1) with a broader molecular weight distribution (MWD) than if the polypropylene (PP1) was produced in only one reactor. Several polymerization processes suitable for producing the polypropylene (PP1) according to the invention are known in the prior art. They comprise at least one polymerization stage, the polymerization typically being carried out in solution, slurry, bulk or gas phase. Typically, the polymerization process comprises additional polymerization stages or reactors. In one particular embodiment, the process comprises at least one bulk reactor zone and optionally at least one gas-phase reactor zone, each zone comprising at least one reactor, all reactors being arranged in a cascade. In one particularly preferred embodiment, the polymerization process comprises at least one bulk reactor and at least one gas-phase reactor arranged next to the bulk reactor. The process may further comprise a pre-reactor and a post-reactor. The pre-reactor typically comprises a pre-polymerization reactor. In this type of process, the use of higher polymerization temperatures is preferred to achieve certain properties of the polymer. Typical temperatures in these processes are 70° C. or higher, preferably 75° C. or higher. The above-mentioned higher polymerization temperatures can be applied in some or all reactors of the reactor cascade.

[0044] Multimodal polymers can be prepared according to several processes, for example those described in WO 92 / 12182, EP 0 887 379 and WO 98 / 58976, the contents of which are incorporated herein by reference.

[0045] Preferably, the process for producing polypropylene (PP1) comprises two polymerization stages, the first polymerization stage using a slurry reactor (SR), e.g. a loop reactor (LR), whereas the second polymerization stage uses a gas phase reactor.

[0046] The conditions for the first polymerization stage may be as follows: The temperature is in the range of 70°C to 110°C, preferably 72°C to 100°C, more preferably 75°C to 90°C, the pressure is in the range of 20 bar to 80 bar, preferably 40 bar to 70 bar; Hydrogen is added in a known manner to control the molar mass; If polypropylene (PP1) contains a small amount of ethylene, ethylene is supplied.

[0047] The reaction mixture from the first polymerization stage is subsequently transferred to a gas phase reactor (GPR), where the conditions are preferably as follows: The temperature is in the range of 50°C to 130°C, preferably 60°C to 100°C, the pressure is in the range of 5 bar to 50 bar, preferably 15 bar to 40 bar; Hydrogen is added in a known manner to control the molar mass; If polypropylene (PP1) contains a small amount of ethylene, ethylene is supplied.

[0048] The residence time may be different in both reactor zones.

[0049] In one embodiment of the process for producing polypropylene (PP1), the residence time in the slurry reactor (SR), e.g., loop (LR), will be in the range of 0.2 to 2.5 hours, e.g., 0.3 to 1.5 hours, and the residence time in the gas phase reactor (GPR) will generally be 0.8 to 6.0 hours, e.g., 1.0 to 4.0 hours.

[0050] A preferred multi-stage process is the "loop gas phase" process, for example that developed by Borealis (known as BORSTAR® technology), described in patent documents such as EP 0 887 379, WO 92 / 12182, WO 2004 / 000899, WO 2004 / 111095, WO 99 / 24478, WO 99 / 24479 or WO 00 / 68315. A further suitable slurry-gas phase process is the Spheripol® process from Basell.

[0051] As mentioned above, the polypropylene (PP1) according to the invention is obtained in particular in a polymerization process using a metallocene catalyst having the formula (I), [ka] In the formula, each R 1 may be independently the same or different, and are hydrogen or linear or branched C 1 ~C 6 alkyl group, at least one R per phenyl group 1 is not hydrogen, R' is C 1 ~C 10 Hydrocarbyl groups, preferably C 1 ~C 4 is a hydrocarbyl group, more preferably a methyl group; X is independently a hydrogen atom, a halogen atom, or C 1 ~C 6 Alkoxy group, C 1 ~C 6It is an alkyl group, a phenyl group or a benzyl group.

[0052] Most preferably, X is a chlorine, benzyl or methyl group. Preferably, both X groups are the same. The most preferred options are two chlorides, two methyls or two benzyl groups, especially two chlorides.

[0053] Specific preferred metallocene catalysts of the present invention 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.

[0054] The most preferred catalyst is rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride. [ka]

[0055] The ligands required to form the complexes and thus the catalysts of the present invention can be synthesized by any process, and an organic chemist skilled in the art will be able to devise various synthesis protocols to produce the required ligand materials. For example, WO 2007 / 116034 discloses the necessary chemical reactions. Synthesis 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. In particular, reference is made to WO 2019 / 179959, in which the most preferred catalysts of the present invention are described. The Examples section also provides sufficient direction for the skilled artisan.

[0056] Cocatalyst To form an active catalytic species, it is usually necessary to employ a cocatalyst, as is well known in the art.

[0057] According to the present invention, a cocatalyst system comprising a boron-containing cocatalyst and / or an aluminoxane cocatalyst is used in combination with the metallocene catalyst complex defined above.

[0058] The aluminoxane cocatalyst can be of formula (III). [ka] In the formula, n is usually 6 to 20, and R has the following meaning.

[0059] Aluminoxanes are organoaluminum compounds, such as those of the formula AlR 3 , AlR 2 Y and Al 2 R 3 Y 3wherein R is, for example, C 1 ~C 10 -alkyl, preferably C 1 ~C 5 -alkyl, or C 3 ~C 10 -Cycloalkyl, C 7 ~C 12 -arylalkyl or C 7 ~C 12 -alkylaryl and / or phenyl or naphthyl, Y being hydrogen, halogen, preferably chlorine or bromine, or C 1 ~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).

[0060] A preferred aluminoxane is methylaluminoxane (MAO). The aluminoxanes used as cocatalysts according to the present invention are not pure compounds due to the manner of their preparation, so the molar concentrations of the aluminoxane solutions hereinafter are based on their aluminum content. According to the present invention, a boron-containing cocatalyst can also be used in place of the aluminoxane cocatalyst, or the aluminoxane cocatalyst can be used in combination with a boron-containing cocatalyst.

[0061] 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 ~C 6 Alkyl) 3 Preferred aluminum alkyl compounds are triethylaluminum, triisobutylaluminum, triisohexylaluminum, tri-n-octylaluminum and triisooctylaluminum.

[0062] Alternatively, when a borate (boron ate complex) cocatalyst is used, the metallocene catalyst complex can be an alkylated version thereof, ie, for example, a dimethyl or dibenzyl metallocene catalyst complex can be used.

[0063] Boron-based cocatalysts of interest include those of formula (IV): BY 3 (IV) In the formula, Y is the same or different and is a hydrogen atom, an alkyl group having 1 to about 20 carbon atoms, an aryl group having 6 to about 15 carbon atoms, an alkylaryl 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, unsaturated groups such as 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.

[0064] Particularly preferred is tris(pentafluorophenyl)borane.

[0065] However, it is preferred to use borate, i.e. compounds containing borate 3+ ions. 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.

[0066] Preferred ionic compounds that can be used in accordance with the present invention include the following: triethylammonium tetra(phenyl)borate, tributylammonium tetra(phenyl)borate, trimethylammonium tetra(tolyl)borate, tributylammonium tetra(tolyl)borate, tributylammonium tetra(pentafluorophenyl)borate, tripropylammonium tetra(dimethylphenyl)borate, tributylammonium tetra(trifluoromethylphenyl)borate, tributylammonium tetra(4-fluorophenyl)borate, N,N-dimethylcyclohexylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylbenzylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetra(phenyl)borate, N,N-diethylanilinium tetra(phenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-di(propyl)ammonium tetrakis(pentafluorophenyl)borate, di(cyclohexyl)ammonium tetrakis(pentafluorophenyl)borate, triphenylphosphonium tetrakis(phenyl)borate, triethylphosphonium tetrakis(phenyl)borate, diphenylphosphonium tetrakis(phenyl)borate, tri(methylphenyl)phosphonium tetrakis(phenyl)borate, tri(dimethylphenyl)phosphonium tetrakis(phenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, or Ferrocenium tetrakis(pentafluorophenyl)borate.

[0067] The preferred triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylcyclohexylammonium tetrakis(pentafluorophenyl)borate, or N,N-Dimethylbenzylammonium tetrakis(pentafluorophenyl)borate It is.

[0068] Surprisingly, it has been found that certain boron cocatalysts are particularly preferred. Thus, the preferred borates used in the present invention contain trityl ions. Thus, the use of N,N-dimethylammonium-tetrakispentafluorophenylborate and Ph3CB(PhF5)4 and analogs thereof is particularly preferred.

[0069] 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.

[0070] Suitable amounts of cocatalyst are well known to those skilled in the art. The molar ratio of boron to the metal ion of the metallocene may range from 0.5:1 to 10:1 mol / mol, preferably from 1:1 to 10:1, especially from 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.

[0071] The catalyst can be used in supported or unsupported form, preferably in supported form.The particulate support material used is preferably an organic or inorganic material, such as silica, alumina or zirconia, or a mixed oxide, such as silica-alumina, in particular silica, alumina or silica-alumina.The use of silica supports is preferred.Those skilled in the art are aware of the procedures required for supporting metallocene catalysts.

[0072] 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.

[0073] The average particle size of the silica support may typically be between 10 and 100 μm, however, it has been found that particular advantages are obtained when the support has an average particle size between 15 and 80 μm, preferably between 18 and 50 μm. The average pore size of the silica support can be in the range of 10 to 100 nm, and the pore volume can be 1 to 3 mL / g.

[0074] Examples of suitable support materials are, for example, ES757 manufactured and sold by PQ Corporation, Sylopol 948 manufactured and sold by Grace, or SUNSPERA DM-L-303 silica manufactured by AGC Si-Tech Co. The support can be optionally calcined prior to use in the catalyst preparation to obtain optimal silanol group content.

[0075] The use of these carriers is routine in the art.

[0076] Heterophasic Polypropylene Composition (HECO) The second essential component of the fiber reinforced composition according to the present invention is a heterophasic propylene copolymer (HECO).

[0077] The heterophasic polypropylene copolymer (HECO) according to the invention comprises a matrix which is a propylene homopolymer (HPP-2) and an ethylene-propylene rubber (EPR) dispersed in the matrix. The matrix therefore contains (finely) dispersed inclusions which are not part of the matrix, and which contain ethylene-propylene rubber (EPR). As stated above, when defining the continuous phase of the fiber reinforced composite, the term "inclusions" indicates that the matrix and the inclusions form different phases within the heterophasic propylene copolymer (HECO). 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). In particular, in DMTA, the presence of a multiphase structure can be identified by the presence of at least two distinguishable glass transition temperatures.

[0078] Thus, the heterophasic propylene copolymer (HECO) according to the present invention has (a) propylene homopolymer (H-PP2); (b) Ethylene-propylene rubber (EPR) and Includes.

[0079] As will be explained in more detail below, the heterophasic propylene copolymer (HECO) according to the present invention is produced in the presence of a fourth generation Ziegler-Natta catalyst (see Nello Pasquini, Polypropylene Handbook, 2nd Edition, pages 17 and 18). Thus, in contrast to polypropylene (PP1), which exhibits a significant amount of 2,1 defects in the polymer chain, the heterophasic propylene copolymer (HECO) exhibits no or very few 2,1 defects.

[0080] Thus, the heterophasic propylene copolymer (HECO) according to the present invention has (a) in the range of 0 to less than 0.10%; 13 Propylene homopolymer (H-PP2) with 2,1 positional defects determined by C-NMR spectroscopy; (b) Ethylene-propylene rubber (EPR) and Includes.

[0081] The heterophasic propylene copolymer (HECO) according to the present invention is (a) 2,1 position defect 13 propylene homopolymer (H-PP2) which is not detectable by C-NMR spectroscopy; (b) Ethylene-propylene rubber (EPR) and It is particularly preferred that the compound comprises:

[0082] In addition, like polypropylene (PP1), the propylene homopolymer (H-PP2) of the heterophasic propylene copolymer (HECO) also preferably has a broad molecular weight distribution (MWD), i.e., in the range of 5.0 to less than 10.0, more preferably in the range of 6.0 to 9.0.

[0083] Thus, in a preferred embodiment, the heterophasic propylene copolymer (HECO) according to the present invention comprises (a) propylene homopolymer (H-PP2); (b) Ethylene-propylene rubber (EPR) and Propylene homopolymer (H-PP2) is (i) Within the range of 0 to less than 0.10% 13 The 2,1 positional defect is determined by C-NMR spectroscopy, and preferably the 2,1 positional defect is 13 Not detectable by C-NMR spectroscopy (ii) It has a molecular weight distribution (MWD) in the range of 5.0 to less than 10.0, preferably in the range of 6.0 to 9.0.

[0084] In order to achieve further improved properties for the fiber reinforced composite according to the invention, the molecular weight of the polypropylene (PP1) and the molecular weight of the propylene homopolymer (H-PP2) of the heterophasic propylene copolymer (HECO) should be quite similar. Therefore, it is necessary that the propylene homopolymer (H-PP2) of the heterophasic propylene copolymer (HECO) has a melt flow rate MFR measured according to ISO 1133 in the range of 40.0 to 250 g / 10 min, more preferably in the range of 50.0 to 150 g / 10 min. 2 (230°C, 2.16 kg), provided that the melt flow ratio MFR of polypropylene (PP1) and propylene homopolymer (H-PP2) of heterophasic propylene copolymer (HECO) 2 [MFR 2 (PP1) / MFR 2 (H-PP2)] is preferably in the range of 0.75 to 1.25, and more preferably in the range of 0.80 to 1.20.

[0085] Thus, in a particular preferred embodiment, the heterophasic propylene copolymer (HECO) according to the present invention comprises (a) propylene homopolymer (H-PP2); (b) Ethylene-propylene rubber (EPR) and Propylene homopolymer (H-PP2) is (i) Within the range of 0 to less than 0.10% 13 The 2,1 positional defect is determined by C-NMR spectroscopy, and preferably the 2,1 positional defect is 13 Not detectable by C-NMR spectroscopy (ii) having a molecular weight distribution (MWD) in the range of 5.0 to less than 10.0, preferably in the range of 6.0 to 9.0; (iii) a melt flow rate MFR, measured according to ISO 1133, in the range of 40.0 to 250 g / 10 min, more preferably in the range of 50.0 to 150 g / 10 min; 2 (230°C, 2.16 kg), provided that the melt flow ratio MFR of polypropylene (PP1) and propylene homopolymer (H-PP2) of heterophasic propylene copolymer (HECO) 2 [MFR 2 (PP1) / MFR 2 (H-PP2)] is in the range of 0.75 to 1.25, more preferably in the range of 0.80 to 1.20.

[0086] The propylene homopolymer (H-PP2) of the heterophasic propylene copolymer (HECO) can be further characterized by its high melting temperature, which is typical for propylene homopolymers obtained with 4th generation Ziegler-Natta catalysts, i.e., at least 160°C, more preferably at least 163°C, e.g., in the range of 163-167°C.

[0087] Therefore, the heterophasic propylene copolymer (HECO) according to the present invention (a) propylene homopolymer (H-PP2); (b) Ethylene-propylene rubber (EPR) and The propylene homopolymer (H-PP2) is (i) having a melting temperature, as determined by differential scanning calorimetry (DSC), of at least 160°C, more preferably at least 163°C, for example in the range of 163 to 167°C; (ii) In the range of 0 to less than 0.10% 13 The 2,1 positional defect is determined by C-NMR spectroscopy, and preferably the 2,1 positional defect is 13 Not detectable by C-NMR spectroscopy (iii) having a molecular weight distribution (MWD) in the range of 5.0 to less than 10.0, preferably in the range of 6.0 to 9.0; (iv) optionally a melt flow rate MFR, measured according to ISO 1133, in the range of 40.0 to 250 g / 10 min, more preferably in the range of 50.0 to 150 g / 10 min; 2 (230°C, 2.16 kg), provided that the melt flow ratio MFR of polypropylene (PP1) and propylene homopolymer (H-PP2) of heterophasic propylene copolymer (HECO) 2 [MFR 2 (PP1) / MFR 2 (H-PP2)] is in the range of 0.75 to 1.25, more preferably in the range of 0.80 to 1.20. It is preferred.

[0088] In addition, the heterophasic propylene copolymer (HECO) can be further defined by its elastomeric portion, i.e., ethylene-propylene rubber (EPR). As known to those skilled in the art for heterophasic systems where the matrix is ​​propylene homopolymer and the elastomeric portion is ethylene-propylene rubber (EPR), the xylene soluble fraction (XCS) reflects the rubber, whereas the propylene homopolymer (H-PP2) is reflected by the xylene insoluble fraction.

[0089] Therefore, the heterophasic propylene copolymer (HECO) according to the present invention preferably has a xylene cold solubles (XCS) content, determined at 25° C. according to ISO 16152, in the range of 22 to 45% by weight, more preferably in the range of 25 to 40% by weight.

[0090] Furthermore, it is preferred that the ethylene content of the cold xylene soluble fraction is fairly high. Thus, in a preferred embodiment, the heterophasic propylene copolymer (HECO) has an ethylene content in the range of 40-60 mol %, more preferably in the range of 48-58 mol %, of the cold xylene soluble (XCS) fraction. 13 The ethylene content was determined by C-NMR.

[0091] In addition, the molecular weight of the ethylene propylene rubber (EPR) of the heterophasic propylene copolymer should preferably not be too low.Thus, it is preferred that the xylene cold soluble (XCS) fraction of the heterophasic propylene copolymer (HECO) has an intrinsic viscosity (IV) measured according to ISO 1628 / 1 (135°C in decalin) in the range of 2.0-5.0 dl / g, preferably in the range of 2.0-3.5 dl / g.

[0092] Finally, the heterophasic propylene copolymer (HECO) is present in the range of 15 to 33 mol %, more preferably in the range of 20 to 30 mol %. 13 Ethylene content determined by C-NMR and / or melt flow rate MFR measured according to ISO 1133 in the range of 10 to 50 g / 10 min, more preferably in the range of 15 to 40 g / 10 min. 2 (230° C., 2.16 kg).

[0093] Thus, the heterophasic propylene copolymer (HECO) according to the present invention (a) propylene homopolymer (H-PP2); (b) Ethylene-propylene rubber (EPR) and wherein the heterophasic propylene copolymer (HECO) has a xylene cold solubles (XCS) content, determined at 25°C according to ISO 16152, in the range of 22 to 45 wt.%, more preferably in the range of 25 to 40 wt.%, Furthermore, the propylene homopolymer (H-PP2) of the heterophasic propylene copolymer (HECO) is (i) Within the range of 0 to less than 0.10% 13 The 2,1 positional defect is determined by C-NMR spectroscopy, and preferably the 2,1 positional defect is 13 Not detectable by C-NMR spectroscopy (ii) having a molecular weight distribution (MWD) in the range of 5.0 to less than 10.0, preferably in the range of 6.0 to 9.0; (iii) optionally a melt flow rate MFR, measured according to ISO 1133, in the range of 40.0 to 250 g / 10 min, more preferably in the range of 50.0 to 150 g / 10 min;2 (230°C, 2.16 kg), provided that the melt flow ratio MFR of polypropylene (PP1) and propylene homopolymer (H-PP2) of heterophasic propylene copolymer (HECO) 2 [MFR 2 (PP1) / MFR 2 (H-PP2)] is in the range of 0.75 to 1.25, more preferably in the range of 0.80 to 1.20. It is particularly preferred.

[0094] Even more preferably, the heterophasic propylene copolymer (HECO) according to the present invention has (a) propylene homopolymer (H-PP2); (b) Ethylene-propylene rubber (EPR) and wherein the heterophasic propylene copolymer (HECO) has a xylene cold solubles (XCS) content, determined at 25°C according to ISO 16152, in the range of 22 to 45 wt.%, preferably in the range of 25 to 40 wt.%, Furthermore, the cold xylene soluble (XCS) fraction of heterophasic propylene copolymer (HECO) (i) in the range of 40 to 60 mol%, more preferably in the range of 48 to 58 mol%, 13 Ethylene content determined by C-NMR having Furthermore, the propylene homopolymer (H-PP2) of the heterophasic propylene copolymer (HECO) is (i) Within the range of 0 to less than 0.10% 13 The 2,1 positional defect is determined by C-NMR spectroscopy, and preferably the 2,1 positional defect is 13 Not detectable by C-NMR spectroscopy (ii) having a molecular weight distribution (MWD) in the range of 5.0 to less than 10.0, preferably in the range of 6.0 to 9.0; (iii) optionally a melt flow rate MFR, measured according to ISO 1133, in the range of 40.0 to 250 g / 10 min, more preferably in the range of 50.0 to 150 g / 10 min; 2(230°C, 2.16 kg), provided that the melt flow ratio MFR of polypropylene (PP1) and propylene homopolymer (H-PP2) of heterophasic propylene copolymer (HECO) 2 [MFR 2 (PP1) / MFR 2 (H-PP2)] is in the range of 0.75 to 1.25, more preferably in the range of 0.80 to 1.20.

[0095] Even more preferably, the heterophasic propylene copolymer (HECO) according to the present invention has (a) propylene homopolymer (H-PP2); (b) Ethylene-propylene rubber (EPR) and wherein the heterophasic propylene copolymer (HECO) has a xylene cold solubles (XCS) content, determined at 25°C according to ISO 16152, in the range of 22 to 45 wt.%, preferably in the range of 25 to 40 wt.%, Furthermore, the cold xylene soluble (XCS) fraction of heterophasic propylene copolymer (HECO) (i) in the range of 40 to 60 mol%, more preferably in the range of 48 to 58 mol%, 13 the ethylene content determined by C-NMR, and (ii) an intrinsic viscosity (IV) measured according to ISO 1628 / 1 (135° C. in decalin) in the range of 2.0 to 5.0 dl / g, preferably in the range of 2.0 to 3.5 dl / g; having Furthermore, the propylene homopolymer (H-PP2) of the heterophasic propylene copolymer (HECO) is (i) having a melting temperature, as determined by differential scanning calorimetry (DSC), of at least 160° C., more preferably at least 163° C.; (ii) In the range of 0 to less than 0.10% 13 The 2,1 positional defect is determined by C-NMR spectroscopy, and preferably the 2,1 positional defect is 13 Not detectable by C-NMR spectroscopy (iii) having a molecular weight distribution (MWD) in the range of 5.0 to less than 10.0, preferably in the range of 6.0 to 9.0; (iv) optionally a melt flow rate MFR, measured according to ISO 1133, in the range of 40.0 to 250 g / 10 min, more preferably in the range of 50.0 to 150 g / 10 min; 2 (230°C, 2.16 kg), provided that the melt flow ratio MFR of polypropylene (PP1) and propylene homopolymer (H-PP2) of heterophasic propylene copolymer (HECO) 2 [MFR 2 (PP1) / MFR 2 (H-PP2)] is in the range of 0.75 to 1.25, more preferably in the range of 0.80 to 1.20.

[0096] Even more preferably, the heterophasic propylene copolymer (HECO) according to the present invention has (a) propylene homopolymer (H-PP2); (b) Ethylene-propylene rubber (EPR) and and the heterophasic propylene copolymer (HECO) comprises (i) in the range of 15 to 33 mol%, more preferably in the range of 20 to 30 mol%, 13 Ethylene content determined by C-NMR, (ii) a melt flow rate MFR, measured according to ISO 1133, in the range of 10 to 50 g / 10 min, more preferably in the range of 15 to 40 g / 10 min; 2 (230℃, 2.16kg) having Further, the heterophasic propylene copolymer (HECO) has a xylene cold solubles (XCS) content, determined at 25°C according to ISO 16152, in the range of 22 to 45 wt.%, preferably in the range of 25 to 40 wt.%, Still further, the xylene cold soluble (XCS) fraction of the heterophasic propylene copolymer (HECO) can be (i) in the range of 40 to 60 mol%, more preferably in the range of 48 to 58 mol%, 13 the ethylene content determined by C-NMR, and (ii) an intrinsic viscosity (IV) measured according to ISO 1628 / 1 (135° C. in decalin) in the range of 2.0 to 5.0 dl / g, preferably in the range of 2.0 to 3.5 dl / g; having Still further, the propylene homopolymer (H-PP2) of the heterophasic propylene copolymer (HECO) is (i) having a melting temperature, as determined by differential scanning calorimetry (DSC), of at least 160° C., more preferably at least 163° C.; (ii) In the range of 0 to less than 0.10% 13 The 2,1 positional defect is determined by C-NMR spectroscopy, and preferably the 2,1 positional defect is 13 Not detectable by C-NMR spectroscopy (iii) having a molecular weight distribution (MWD) in the range of 5.0 to less than 10.0, preferably in the range of 6.0 to 9.0; (iv) optionally a melt flow rate MFR, measured according to ISO 1133, in the range of 40.0 to 250 g / 10 min, more preferably in the range of 50.0 to 150 g / 10 min; 2 (230°C, 2.16 kg), provided that the melt flow ratio MFR of polypropylene (PP1) and propylene homopolymer (H-PP2) of heterophasic propylene copolymer (HECO) 2 [MFR 2 (PP1) / MFR 2 (H-PP2)] is in the range of 0.75 to 1.25, more preferably in the range of 0.80 to 1.20.

[0097] As mentioned above, the heterophasic propylene copolymer (HECO) according to the present invention is produced using a fourth generation Ziegler-Natta catalyst. Such catalysts are prior art and well known to those skilled in the art. For example, as Ziegler-Natta catalyst, it is possible to use the BHC01P catalyst from Borealis (prepared according to WO 92 / 19653, as disclosed in WO 99 / 24479; in particular using dioctyl phthalate as the dialkyl phthalate of formula (I) according to WO 92 / 19658) or the catalyst Polytrack 8502 commercially available from Grace (WO 92 / 19658 and WO 92 / 19653).

[0098] The polymerization conditions for the production of heterophasic propylene copolymers (HECO) are also known to those skilled in the art. Heterophasic propylene copolymers (HECO) are produced in two polymerization zones, in the first zone propylene homopolymer (H-PP2) is produced and in the second polymerization zone ethylene-propylene rubber (EPR) is obtained. Each zone may contain one or more reactors. For example, the first zone may contain only a loop reactor and the second zone only one gas-phase reactor. However, it is preferred that the first zone contains a loop reactor and a gas-phase reactor and the second zone contains two gas-phase reactors.

[0099] Thus, the process for the preparation of heterophasic propylene copolymers (HECO) according to the present invention is preferably a sequential polymerization process comprising at least two reactors, preferably four reactors, connected in series, which process comprises: (A) polymerizing propylene in a first reactor (R-1), which is a slurry reactor (SR), preferably a loop reactor (LR), to obtain a first fraction of propylene homopolymer (H-PP2) as defined in the present invention; (B) transferring the first fraction of said propylene homopolymer (H-PP2) from the first reactor (R-1) to a second reactor (R-2), which is a gas phase reactor (GPR-1); (C) supplying propylene to the second reactor (R-2); (D) polymerizing propylene in the presence of the first fraction of propylene homopolymer (H-PP2) in the second reactor (R-2) to obtain a second fraction of propylene homopolymer (H-PP2), wherein the first and second fractions form a propylene homopolymer (H-PP2) of a heterophasic propylene copolymer (HECO); (E) transferring the propylene homopolymer (H-PP2) in the second reactor (R-2) to a third reactor (R-3), which is a gas phase reactor (GPR-2); (F) supplying propylene and ethylene to the third reactor (R-3); (G) polymerizing propylene and ethylene in the presence of the propylene homopolymer (H-PP2) in the third reactor (R-3) to obtain a first fraction of ethylene-propylene rubber (EPR); (H) transferring the mixture of the propylene homopolymer (H-PP2) and the first fraction of ethylene-propylene rubber (EPR) from the third reactor (R-3) to a fourth reactor (R-4), which is a gas phase reactor (GPR-3); (I) supplying propylene and ethylene to the fourth reactor (R-4); (J) polymerizing propylene and ethylene in the fourth reactor (R-4) in the presence of the mixture from the third reactor (R-3) to obtain a second fraction of ethylene-propylene rubber (EPR); wherein the first fraction and the second fraction of the ethylene-propylene rubber (EPR) form an ethylene-propylene rubber (EPR); The propylene homopolymer (H-PP2) and the ethylene-propylene rubber (EPR) form a heterophasic propylene copolymer (HECO), In the first reactor (R-1), the second reactor (R-2), the third reactor (R-3) and the fourth reactor (R-4), polymerization takes place in the presence of a fourth generation Ziegler-Natta catalyst.

[0100] 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.

[0101] Heterophasic polymers can be prepared according to several processes, for example those described in WO 92 / 12182, EP 0 887 379 and WO 98 / 58976, the contents of which are hereby incorporated by reference.

[0102] Preferably, in the process for producing a heterophasic propylene copolymer (HECO) as defined above, the conditions for the first reactor (R-1) of step (A), i.e. the slurry reactor (SR), e.g. the loop reactor (LR), may be as follows: the temperature is in the range of 40°C to 110°C, preferably between 60°C and 100°C, more preferably in the range of 65°C to 90°C, the pressure is in the range of 20 bar to 80 bar, preferably between 40 bar and 70 bar; Hydrogen can be added to control the molar mass in a known manner.

[0103] 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 known manner.

[0104] The residence time may be different in both reactor zones.

[0105] In one embodiment of the process for the production of the heterophasic polypropylene composition (HECO), the residence time in the slurry reactor (SR), e.g., loop (LR), is in the range of 0.2-2.5 hours, e.g., 0.3-1.5 hours, and the residence time in the first gas phase reactor (GPR-1) is generally 0.2-4.0 hours, e.g., 0.5-3.0 hours.

[0106] If desired, the polymerization may be carried out in a known manner under supercritical conditions in a first reactor (R-1), ie in a slurry reactor (SR), for example in a loop reactor (LR).

[0107] The conditions in the third reactor (R-3), i.e. the second gas phase reactor (GPR-2), and any other subsequent gas phase reactors (GPRs), if present, are similar to those in the second reactor (R-2). The residence times in the second and third gas phase reactors (GPR-2 and GPR-3) are also in the same range as or higher than those in the first gas phase reactor (GPR-1).

[0108] The process may also include a pre-polymerization prior to the polymerization in the first reactor (R-1). This pre-polymerization can take place in the first reactor (R-1), however, it is preferred that the pre-polymerization takes place in a separate reactor, the so-called pre-polymerization reactor.

[0109] Glass fiber The third essential component in the fiber reinforced composite is glass fiber. The glass fiber can be any type of glass fiber, such as long glass fiber or short glass fiber. However, it is particularly preferred that the glass fiber is short glass fiber, also known as cut glass fiber or chopped glass strand.

[0110] The short glass fibers used in the fiber reinforced composite material preferably have an average fiber length in the range of 2.0 to 10.0 mm, more preferably in the range of 2.0 to 8.0 mm, and even more preferably in the range of 2.0 to 5.0 mm, before compounding.

[0111] It is further preferred that the short glass fibres used in the fibre reinforced composite have an average diameter, prior to compounding, of preferably 5 to 20 µm, more preferably 8 to 18 µm, even more preferably 8 to 15 µm.

[0112] Preferably, the short glass fibers have, prior to compounding, an aspect ratio, defined as the ratio between the average fiber length and the average fiber diameter, of 150 to 600, preferably 200 to 500, more preferably 250 to 400. The aspect ratio is the relationship between the average length and the average diameter of the fibers.

[0113] Compatibilizer A further component present in the fibre reinforced composite is a compatibilizer, also called a coupling agent or adhesion promoter, which improves the adhesion between the non-polar polypropylene and the polar glass fibres.

[0114] The compatibilizer according to the present invention is preferably a polar modified polypropylene. Polar modified polypropylene, such as a polar modified propylene homopolymer or a polar modified copolymer, is highly compatible with the polypropylene of the fiber reinforced composite according to the present invention.

[0115] In terms of structure, the polar modified polypropylene is preferably selected from graft copolymers or block copolymers.

[0116] In this context, polar modified polypropylenes containing groups derived from polar compounds, in particular polar compounds selected from the group consisting of acid anhydrides, carboxylic acids, carboxylic acid derivatives, primary and secondary amines, hydroxyl compounds, oxazolines and epoxides, as well as ionic compounds, are preferred.

[0117] Specific examples of the polar compounds are unsaturated cyclic anhydrides and their aliphatic diesters and dibasic acid derivatives. In particular, maleic anhydride and maleic acid C 1 ~C 10 Linear and branched dialkyl fumarate C 1 ~C 10 Linear and branched dialkyl, itaconic anhydride, itaconic acid C 1 ~C 10 Compounds selected from linear and branched dialkyl esters, maleic acid, fumaric acid, itaconic acid and mixtures thereof can be used.

[0118] In certain preferred embodiments of the present invention, the polar modified polypropylene is maleic anhydride grafted polypropylene, which is either a propylene-ethylene copolymer or a propylene homopolymer. It is especially preferred that the polar modified polypropylene is maleic anhydride grafted polypropylene, which is a propylene homopolymer.

[0119] Polar modified polypropylene, especially maleic anhydride grafted polypropylene, can be prepared in a simple manner, for example by reactive extrusion of polypropylene with maleic anhydride in the presence of a free radical generator, such as an organic peroxide, as disclosed, for example, in EP-A-0 572 028.

[0120] The amount of groups derived from polar compounds in the polar modified polypropylene, for example the amount of maleic anhydride, is 0.1 to 5.0% by weight, preferably 0.5 to 4.0% by weight, more preferably 0.5 to 3.0% by weight.

[0121] Preferably, the polar modified polypropylene, such as maleic anhydride grafted polypropylene, has a melt flow rate MFR measured according to ISO 1133 of at least 50 g / 10 min, more preferably at least 80 g / 10 min, even more preferably in the range of 50 to 500 g / 10 min, and even more preferably in the range of 70 to 250 g / 10 min. 2(190°C, 2.16 kg).

[0122] Additives The fiber reinforced composite of the present invention may further comprise additives, typical additives being acid scavengers, antioxidants, colorants, light stabilizers, slip agents, anti-scratch agents, dispersants, processing aids, lubricants, pigments such as carbon black, etc.

[0123] Such additives are commercially available and are described, for example, in "Plastic Additives Handbook" by Hans Zweifel, 6th Edition, 2009 (pp. 1141-1190).

[0124] Additives are often provided in the form of a masterbatch, which is a composition in which an additive or an additive mixture is dispersed in a polymer in a significant amount. The term "additive" according to the present invention therefore also includes a carrier material, in particular a polymeric carrier material, in which an "active additive" or an "active additive mixture" is dispersed.

[0125] Manufacturing process for reinforced fiber composite materials The reinforced fiber composites are manufactured as is well known in the art. Thus, the fiber reinforced composites include: (a) Polypropylene (PP1), (b) heterophasic propylene copolymer (HECO); (c) glass fiber, (d) a compatibilizer, and (e) Optionally, additives and extruding them to obtain the fiber-reinforced composite material.

[0126] Conventional compounding or blending equipment may be used to extrude, i.e. melt blend, the individual components of the composite, such as a Banbury mixer, a two-roll rubber mill, a Buss-co-kneader or a twin screw extruder. The fiber reinforced composite material recovered from the extruder / mixer is usually in the form of granules. These granules are then preferably further processed, for example by injection molding, to produce the composite articles and products of the invention.

[0127] It is particularly preferred that the fibre reinforced composites according to the invention are prepared by melt blending the individual components in an extruder, preferably a twin screw extruder.

[0128] In particular, the fiber reinforced composite material according to the present invention is (a) feeding polypropylene (PP1), heterophasic propylene copolymer (HECO), compatibilizer (CA), and optionally additives (AD) into an extruder, preferably a twin screw extruder; (b) melt-kneading the composition obtained in step (a) at a temperature of 200 to 270°C; (c) feeding short glass fibers (GF) into an extruder, preferably a twin screw extruder, containing the composition obtained in step (b); (d) melt-kneading the composition obtained in step (c) at a temperature of 200 to 270°C to obtain the fiber-reinforced composite material; It is preferably obtained by a process comprising:

[0129] Goods The present invention further relates to an article, preferably an automotive article, comprising at least 95% by weight, more preferably at least 98% by weight, of the fiber reinforced composite according to the present invention, even more preferably consisting of the fiber reinforced composite according to the present invention.

[0130] Particularly preferred embodiments Particularly preferred embodiments are as follows: [1] A fiber-reinforced composite material, (a) 30 to 60% by weight of polypropylene (PP1) based on the fiber reinforced composite material; (b) 10-40 wt. % based on the fiber reinforced composite of a heterophasic propylene copolymer (HECO), the heterophasic propylene copolymer (HECO) comprising a propylene homopolymer (H-PP2) and an ethylene-propylene rubber (EPR); (c) 10 to 40% by weight of glass fiber (GF) based on the fiber-reinforced composite material; (d) 0.05 to 5.0% by weight of a compatibilizer (CA) based on the fiber-reinforced composite material; Including, the total amount of said polypropylene (PP1), said heterophasic propylene copolymer (HECO), said glass fiber (GF) and said compatibilizer (CA) in said fiber reinforced composite is at least 95 wt. %; Furthermore, the polypropylene (PP1) is (i) Melt flow rate (MFR) measured according to ISO 1133 in the range of 40.0 to 250 g / 10 min. 2 (230℃, 2.16kg), (ii) 0.5% by weight or less 13 a comonomer content determined by C-NMR spectroscopy, the comonomer being ethylene; and (iii) a molecular weight distribution (MWD) as determined by gel permeation chromatography (GPC) in the range of greater than 4.5 to less than 8.5; and (iv) in the range of 0.20 to 1.00%; 13 2,1-site defects determined by C-NMR spectroscopy having Still further, the propylene homopolymer (H-PP2) of the heterophasic propylene copolymer (HECO) is (v) in the range of 0 to less than 0.10%; 13 2,1-site defects determined by C-NMR spectroscopy A fiber-reinforced composite material having the above structure.

[0131] [2] The fiber-reinforced composite has a melt flow rate (MFR), measured according to ISO 1133, in the range of 8.0 to 50 g / 10 min. 2 (230°C, 2.16 kg).

[0132] [3] The fiber-reinforced composite of embodiment [1] or embodiment [2], wherein the glass fibers are embedded in a continuous phase, the continuous phase comprising at least 98% by weight of a mixture of the polypropylene (PP1) and the heterophasic propylene copolymer (HECO).

[0133] [4] The propylene homopolymer (H-PP2) of the heterophasic propylene copolymer (HECO) has a melt flow rate MFR measured according to ISO 1133 in the range of 40.0 to 250 g / 10 min. 2 (230°C, 2.16 kg), provided that the melt flow ratio MFR of the polypropylene (PP1) and the propylene homopolymer (H-PP2) of the heterophasic propylene copolymer (HECO) 2 [MFR 2 (PP1) / MFR 2 The fiber-reinforced composite material according to any one of embodiments [1] to [3], wherein (H-PP2)] is in the range of 0.80 to 1.20.

[0134] [5] The fiber-reinforced composite material according to any one of embodiments [1] to [4], wherein the weight ratio of the mixture of the polypropylene (PP1) and the propylene homopolymer (H-PP2) to the ethylene-propylene rubber (EPR) [((PP1)+(H-PP2) / (EPR)] is in the range of 75:25 to 95:5.

[0135] [6] The fiber-reinforced composite material according to any one of the embodiments [1] to [5], wherein the weight ratio of the polypropylene (PP1) to the propylene homopolymer (H-PP2) of the heterophasic propylene copolymer (HECO) [(PP1) / (H-PP2)] is in the range of 60:40 to 80:20.

[0136] [7] The fiber-reinforced composite according to any one of embodiments [1] to [6], wherein the propylene homopolymer (H-PP2) of the heterophasic propylene copolymer (HECO) has a molecular weight distribution (MWD) determined by gel permeation chromatography (GPC) in the range of from greater than 5.0 to less than 10.0.

[0137] [8] The fiber-reinforced composite according to any one of embodiments [1] to [7], wherein the propylene homopolymer (H-PP2) of the heterophasic propylene copolymer (HECO) has a melting temperature, Tm, determined according to differential scanning calorimetry (DSC), of at least 160°C.

[0138] [9] The heterophasic propylene copolymer (HECO) has a melt flow rate (MFR), measured according to ISO 1133, in the range of 10 to 50 g / 10 min. 2 The fiber-reinforced composite material according to any one of embodiments [1] to [8], having a compressive strength of 100% (230° C., 2.16 kg).

[0139]

[10] The fiber-reinforced composite according to any one of embodiments [1] to [9], wherein the heterophasic propylene copolymer (HECO) has a xylene cold solubles (XCS) content, determined at 25°C according to ISO 16152, in the range of 22 to 45 wt.%.

[0140]

[11] The heterophasic propylene copolymer (HECO) has a xylene cold soluble (XCS) fraction in the range of 40-60 mol %. 13 The fiber-reinforced composite of any one of embodiments [1] to

[10] , having an ethylene content determined by C-NMR.

[0141]

[12] The fiber-reinforced composite according to any one of embodiments [1] to

[11] , wherein the heterophasic propylene copolymer (HECO) has an ethylene content in the range of 15 to 33 mol %.

[0142]

[13] The fiber-reinforced composite according to any one of embodiments [1] to

[12] , wherein the xylene cold soluble (XCS) fraction of the heterophasic propylene copolymer (HECO) has an intrinsic viscosity (IV) measured according to ISO 1628 / 1 (135°C in decalin) in the range of 2.0 to 5.0 dl / g.

[0143]

[14] The fiber-reinforced composite of any one of embodiments [1] to

[13] , wherein the heterophasic propylene copolymer (HECO) is not visbroken.

[0144]

[15] The fiber-reinforced composite material according to any one of embodiments [1] to

[14] , wherein the polypropylene (PP1) has a fraction that elutes at less than 100°C by temperature rising elution fractionation (TREF) in the range of 12 to 20% by weight.

[0145]

[16] The fiber-reinforced composite material according to any one of embodiments [1] to

[15] , wherein the polypropylene (PP1) is a propylene homopolymer.

[0146]

[17] The fiber-reinforced composite material according to any one of embodiments [1] to

[16] , wherein the polypropylene (PP1) is not visbroken.

[0147]

[18] The fiber-reinforced composite according to any one of embodiments [1] to

[18] , wherein the polypropylene (PP1) has a melting temperature, Tm, determined by differential scanning calorimetry (DSC), in the range of 150 to 159 °C.

[0148]

[19] The fiber-reinforced composite of any one of embodiments [1] to

[19] , wherein the polypropylene (PP1) has a xylene cold solubles (XCS) content, determined at 25°C according to ISO 16152, in the range of 0.8 to 2.5 wt.%.

[0149]

[20] The polypropylene (PP1) is prepared by polymerizing propylene and optionally ethylene in the presence of a metallocene catalyst having formula (I): [ka] In the formula, each R1 may be independently the same or different and is hydrogen or a linear or branched C 1 ~C 6 alkyl group, at least one R per phenyl group 1 is not hydrogen, R' is C 1 ~C 10 Hydrocarbyl groups, preferably C 1 ~C 4 is a hydrocarbyl group, more preferably a methyl group; X is independently a hydrogen atom, a halogen atom, or C 1 ~C 6 Alkoxy group, C 1 ~C 6 is an alkyl group, a phenyl group, or a benzyl group. A fiber-reinforced composite material according to any one of embodiments [1] to

[19] .

[0150]

[21] The fiber-reinforced composite material according to any one of embodiments [1] to

[20] , wherein the glass fibers (GF) are short glass fibers.

[0151]

[22] The fiber-reinforced composite of embodiment

[21] , wherein the glass fibers (GF) have an average fiber length of 2.0 to 10.0 mm and, optionally, an average diameter of 5 to 20 μm prior to compounding.

[0152]

[23] The fiber-reinforced composite material according to any one of embodiments [1] to

[22] , wherein the compatibilizer (CA) is a polar modified polypropylene, preferably a maleic anhydride grafted polypropylene.

[0153]

[24] The maleic anhydride grafted polypropylene has a maleic anhydride content of 0.1 to 5.0 wt. % and preferably has a melt flow rate MFR, measured according to ISO 1133, of at least 70 g / 10 min, more preferably in the range of 80 to 250 g / 10 min. 2 The fiber-reinforced composite of embodiment

[23] having a compressive strength of 190° C., 2.16 kg.

[0154]

[25] The fiber-reinforced composite material comprises: (a) 35 to 55% by weight of the polypropylene (PP1) based on the fiber reinforced composite material; (b) 20-35 wt. % of said heterophasic propylene copolymer (HECO) based on said fiber reinforced composite; (c) 15 to 30% by weight of glass fiber (GF) based on the fiber-reinforced composite material; (d) 0.5 to 5.0% by weight of the compatibilizer (CA) based on the fiber reinforced composite material; (e) 0.1 to 5.0% by weight of an additive based on the fiber-reinforced composite material; A fiber-reinforced composite material according to any one of embodiments [1] to

[24] , comprising:

[0155] The present invention will now be described with reference to examples. EXAMPLES

[0156] A. Determination method The following definitions and methods of determination of terms apply to the above summary of the invention and the following examples, including the claims, unless otherwise defined.

[0157] Quantifying microstructure by NMR spectroscopy Quantitative nuclear magnetic resonance (NMR) spectroscopy was used to quantify the isotacticity and regioregularity of ethylene-propylene copolymers. quantitative 13 C{ 1 The H} NMR spectrum is 1 H and 13All 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 A 10 mm extended temperature probe head optimized for C was used and all pressures were recorded using nitrogen gas. Approximately 200 mg of material was dissolved in 1,2-tetrachloroethane-d 2 (TCE-d 2 ) in 1000 cc of ... Standard single-pulse excitation was employed using NOE and bilevel WALTZ16 decoupling schemes (Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh, D.; Winniford, B., J. Mag. Reson. 187 (2007) 225; Busico, V., Carbonniere, P., Cipullo, R., Pellecchia, R., Severn, J., Talarico, G., Macromol. Rapid Commun. 2007, 28, 11289). A total of 8192 (8k) transients were acquired per spectrum. quantitative 13 C{ 1 H} NMR spectra were processed and integrated using a proprietary computer program, and relevant quantitative properties were derived from the integrals. All chemical shifts are internally referenced to the methyl isotactic pentad (mmmm) at 21.85 ppm. Characteristic signals corresponding to regio-defects (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253; Wang, WJ., Zhu, S., Macromolecules 33(2000), 1157; Cheng, HN, Macromolecules 17(1984), 1950) or comonomers were observed. The tacticity distribution was quantified by integrating the methyl region from 23.6 to 19.7 ppm, correcting for any sites not related to the three-dimensional sequence of interest (Busico, V., Cipullo, R., Prog. Polym. Sci. 26 (2001) 443; Busico, V., Cipullo, R., Monaco, G., Vacatello, M., Segre, AL, Macromolecules 30 (1997) 6251). Specifically, the effects of regio-defects and comonomers on the quantification of tacticity distribution were corrected by subtracting the integrals of representative regio-defects and comonomers from the specific integral regions of the conformation. Isotacticity was determined at the pentad level and reported as the percentage of isotactic pentad (mmmm) sequences relative to total pentad sequences. [mmmm]%=100×(mmmm / sum of all pentads) The presence of the 2,1-erythro regiodefect was indicated by the presence of two methyl sites at 17.7 and 17.2 ppm and confirmed by other characteristic sites. No characteristic signals corresponding to other types of regiodefects were observed (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253). The amount of 2,1 erythro regiodefects was quantified using the average integrals of two characteristic methyl sites at 17.7 and 17.2 ppm. P 21e =(I e6 +I e8 ) / 2 The amount of 1,2 primary insertions was quantified based on the methyl tract, with corrections for sites included in this tract but not involved in the primary insertion, and for primary insertion sites excluded from this tract. P 12 =I CH3 +P 12e The total amount of propene was quantified as the sum of the primary intercalated propene and all other positional defects present. P 全 =P 12 +P 21e The mole percent of 2,1 erythro regiodefects was quantified relative to total propene. [21e] mol% = 100 × (P 21e / P 全 ) 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 in which 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(S ββ +S βγ +S βδ +0.5(S αβ +S αγ )) This was achieved by reducing With this set of sites, the corresponding integral equation can be written, using the same notation as used in Wang et al. (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. Comonomer incorporation in mole percent was calculated from the mole fraction. E [mol%] = 100 × f E 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))

[0158] Melt Flow Rate Melt flow rate (MFR) is determined according to ISO 1133 and is given in g / 10 min. MFR is an indicator of the flowability and therefore processability of a polymer. The higher the melt flow rate, the lower the viscosity of the polymer. MFR of polypropylene 2 is determined at a temperature of 230°C and a load of 2.16 kg.

[0159] Melt flow rate MFR of polypropylene produced in the first gas phase reactor (GPR1) 2 (230℃) calculation:

number

[0160] Molar mass (ethylene-propylene copolymer) The molar mass averages (Mz, Mw and Mn) and the molecular weight distributions (MWD), i.e. Mw / Mn, were determined by gel permeation chromatography (GPC) according to ISO 16014-4:2003 and ASTM D 6474-99 using the following equation:

number

[0161] TREF method Chemical composition distribution was determined by analytical temperature rising elution fractionation as described by Soares, JBP, Fractionation, Encyclopedia Of Polymer Science and Technology, John Wiley & Sons, New York, pp. 75-131, Vol. 10, 2001. The separation of polymers in the TREF follows the crystallinity of the polymers in solution. TREF profiles were generated using a CRYSTAF-TREF 200+ instrument from PolymerChar SA (Valencia, Spain). The polymer sample was dissolved in 1,2,4-trichlorobenzene (TCB, stabilized with 250 mg / L 2,6-di-tert-butyl-4-methyl-phenol) at a concentration of 1.5-2.0 mg / ml at 150 °C for 180 min, and 1.8 mL of the sample solution was injected into a column (8 mm inner diameter, 15 cm long, packed with inert, e.g., glass beads). The column oven was then rapidly cooled to 110 °C and held at 110 °C for 30 min for stabilization purposes, which was then slowly cooled to 35 °C at a constant cooling rate (0.1 °C / min). The polymer was then eluted from the column with 1,2,4-trichlorobenzene (stabilized with 250 mg / L 2,6-di-tert-butyl-4-methyl-phenol) at a flow rate of 0.5 ml / min for 10 min at 35° C., followed by increasing the temperature from 35° C. to 135° C. at a constant heating rate of 0.5° C. / min at a flow rate of 0.5 ml / min. The concentration of the polymer during elution was recorded by an infrared detector (measuring CH absorption at 3.5 micrometer wavelength). The detector response was plotted as a function of temperature. Normalized concentration plots were presented as fractograms with the cumulative concentration signal normalized to 100. Definition of High Crystalline Fraction (HCF) and Low Crystalline Fraction (LCF): The high crystalline fraction (HCF) is the amount (unit: weight %) of the polymer fraction that elutes at an elution temperature of 100° C. or higher. The low crystalline fraction (LCF) is the amount (unit: weight %) of the polymer fraction that elutes at 35 to less than 100°C.

[0162] Xylene soluble fraction at room temperature (XCS, wt%): The amount of polymer soluble in xylene was determined at 25° C. according to ISO 16152; 5th edition; 2005-07-01.

[0163] Intrinsic Viscosity: The intrinsic viscosity (IV) was determined in decalin at 135° C. according to DIN ISO 1628 / 1, October 1999.

[0164] DSC analysis, melting temperature (T m ) and enthalpy of fusion (H m), crystallization temperature (T c ) and crystallization enthalpy (H c ): Measured on 5-7 mg samples using a TA Instrument Q200 Differential Scanning Calorimetry (DSC). DSC was performed in a heat / cool / heat cycle 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. Crystallization temperature (T c ) and crystallization enthalpy (H c ) is determined from the cooling process, and the melting temperature (T m ) and enthalpy of fusion (H m ) was determined from the second heating step.

[0165] Spiral Flow Length Spiral flow length: This method defines the principle of testing the flowability of plastic materials by using injection molding, taking into account the cooling effect of the mold. The plastic is melted and plasticized by a screw in a heated cylinder. The molten plastic is injected at a certain speed and pressure by the screw, which acts as a piston, into a cavity. This cavity is molded as a spiral with a graduation scale for length measurement printed on the steel. This gives the possibility to read the flow length directly on an injection molded test spiral sample. Spiral testing was performed using an Engel ES 1050 / 250 HL injection molding machine using a spiral mold and 1400 bar pressure. Screw diameter: 55mm Specification: Injection pressure: 1400bar Tool form: circular, helical; length 1545 mm; profile: trapeze, thickness 2.1 mm; cross-sectional area 20.16 mm 2 Prechamber and die temperature: 230°C Zone 2 / Zone 3 / Zone 4 / Zone 5 / Zone 6 Temperature: 230℃ / 230℃ / 220℃ / 220℃ / 200℃ Injection cycle: Injection time including hold: 6 seconds Cooling time: 10 seconds Screw speed: 50mm / sec Tool temperature (mold temperature): 40℃ The spiral flow length can be determined immediately after the injection operation.

[0166] Flexural modulus Flexural modulus: 80 x 10 x 4 mm 3 The specimens were determined according to ISO 178 Method A (three-point bending test). According to the standard, a test speed of 2 mm / min and a support distance of 16 times the thickness were used. The test temperature was 23 ± 2°C. Injection molding was performed according to ISO 19069-2 using a melt temperature of 200°C for all materials regardless of the melt flow rate of the material.

[0167] Tensile modulus, tensile strength and elongation at break Tensile modulus, tensile strength and elongation at break were measured according to ISO 527-2 using injection moulded test specimens (1 B dogbone shape, 4 mm thickness) as described in EN ISO 1873-2.

[0168] Unnotched Charpy impact strength The unnotched Charpy impact strength was measured using 80 x 10 x 4 mm specimens prepared in the same manner as for the flexural modulus. 3 The measurements were carried out at +23°C according to ISO 179 1eU using injection moulded bar specimens of 0.02 mm.

[0169] Heat Distortion Temperature (HDT): HDT was measured using a 80×10×4 mm sample prepared in the same manner as for the bending modulus. 3 The strength was determined on injection molded specimens. Tests were performed on flat supported specimens according to ISO 75, condition A, with a nominal surface stress of 1.80 MPa.

[0170] VOCs and FOGs The VOC and FOG values ​​were determined according to VDA278 (October 2011; Thermal Desorption Analysis of Organic Emissions for the Characterization of Non-Metallic Materials for Automobiles, VDA Verband der Automobilindustrie) after sample preparation of injection-molded plates according to EN ISO19069-2:2016. The plates were packed in aluminum composite foil immediately after production and the foil was sealed. According to VDA278 October 2011, the VOC value is "the sum of readily volatile to moderately volatile substances. It is calculated as toluene equivalent. The method described in this recommendation is to determine the amount of n-pentacosane (C 25 ) to determine and analyze substances with a boiling / elution range up to 1000 nm. The FOG value is defined as the sum of the less volatile substances eluting from the retention time of n-tetradecane (including this). It is calculated as the hexadecane equivalent. 14 " ~ "C 32 " boiling point range substances are determined and analyzed.

[0171] Average Fiber Diameter The average fiber diameter is determined according to ISO 1888:2006(E), method B, microscope magnification 1000.

[0172] B. Preparation of the Polymer Composition a) Preparation of single-site catalyst system Catalysts for the invention examples Catalyst Complex The following metallocene complexes were used as described in WO 2019 / 179959: [ka]

[0173] Preparation of MAO-silica support A steel reactor equipped with a mechanical stirrer and a filter net was flushed with nitrogen and the reactor temperature was set at 20°C. Then, silica grade DM-L-303 from AGC Si-Tech Co (5.0 kg), pre-calcined at 600°C, was added from a feed drum, followed by careful pressurization and depressurization with nitrogen using a manual valve. Then, toluene (22 kg) was added. The mixture was stirred for 15 minutes. Then, a 30 wt% solution of MAO in toluene from Lanxess (9.0 kg) was added within 70 minutes via a feed line at the top of the reactor. The reaction mixture was then heated to 90°C and stirred at 90°C for another 2 hours. The slurry was allowed to settle and the mother liquor was filtered off. The catalyst was washed twice with toluene (22 kg) at 90°C, followed by settling and filtration. The reactor was cooled to 60°C and the solid was washed with heptane (22.2 kg). Finally, the MAO-treated SiO 2 The MAO-treated support was dried under a nitrogen stream at 60° C. for 2 hours with stirring, then under vacuum (approximately 0.5 barg) for 5 hours. The MAO-treated support was collected as a free-flowing white powder. The support was found to contain 12.2 wt % Al.

[0174] Preparation of single-site catalytic systems (SSCS) 0.7 kg of 30 wt% MAO in toluene was added to a steel nitrogen-blanked reactor via a burette at 20° C. Toluene (5.4 kg) was then added with stirring. The above metallocene complex (93 g) was added from a metal cylinder followed by flushing with 1 kg of toluene. The mixture was stirred at 20° C. for 60 minutes. Trityl tetrakis(pentafluorophenyl)borate (91 g) was then added from a metal cylinder followed by flushing with 1 kg of toluene. The mixture was stirred for 1 hour at room temperature. The resulting solution was added over 1 hour to the stirred cake of MAO-silica support prepared above. The cake was allowed to stand for 12 hours, after which N was added with stirring. 2It was dried under reflux at 60° C. for 2 hours and under vacuum (−0.5 barg) for a further 5 hours. The dried catalyst was sampled in the form of a pink free-flowing powder containing 13.9% Al and 0.11% Zr.

[0175] b) Preparation of Ziegler-Natta catalyst system A Ziegler-Natta catalyst system is used. Chemicals used: Butylethylmagnesium (Mg(Bu)(Et), BEM) 20% solution in toluene provided by Chemtura 2-Ethylhexanol provided by Amphochem; 3-Butoxy-2-propanol (DOWANOL™ PnB) provided by Dow; Bis(2-ethylhexyl)citraconate provided by SynphaBase TiCl provided by Millenium Chemicals 4 , Toluene provided by Aspokem Viscoplex® 1-254 provided by Evonik; Heptane provided by Chevron.

[0176] Preparation of Mg alkoxy compounds The Mg-alkoxide solution was prepared in a 20 L stainless steel reactor by adding a mixture of 4.7 kg 2-ethylhexanol and 1.2 kg butoxypropanol to 11 kg of a 20 wt % solution of butylethylmagnesium (Mg(Bu)(Et)) in toluene with stirring (70 rpm). The reactor contents were maintained below 45° C. during the addition. After the addition was complete, mixing (70 rpm) of the reaction mixture was continued at 60° C. for 30 minutes. After cooling to room temperature, 2.3 kg of the donor, bis(2-ethylhexyl)citraconate, was added to the above Mg-alkoxide solution while maintaining the temperature below 25° C. Mixing was continued for 15 minutes with stirring (70 rpm).

[0177] Preparation of solid catalyst component ZNCS 20.3 kg of TiCl 4 and 1.1 kg toluene were added to a 20 L stainless steel reactor. 14.5 kg of the prepared Mg alkoxy compound were added over 1.5 hours while mixing at 350 rpm and keeping the temperature at 0° C. 1.7 L Viscoplex® 1-254 and 7.5 kg heptane were added and after mixing at 0° C. for 1 hour the temperature of the formed emulsion was raised to 90° C. within 1 hour. After 30 minutes the mixing was stopped, the catalyst droplets were allowed to solidify and the formed catalyst particles were allowed to settle. After settling (1 hour) the supernatant liquid was siphoned off. The catalyst particles were then washed with 45 kg toluene at 90° C. for 20 minutes followed by two washes with heptane (30 kg, 15 minutes). During the first heptane wash the temperature was lowered to 50° C. and during the second wash it was lowered to room temperature. The catalyst thus obtained was used together with triethylaluminum (TEAL) as cocatalyst and dicyclopentyldimethoxysilane (D donor) as donor in the following ratios: TEAL / Ti: 230 mol / mol, TEAL / donor: 40 mol / mol.

[0178] [Table 1]

[0179] [Table 2(1)] [Table 2(2)]

[0180] [Table 3]

[0181] "AO" is a mixture of the highly hindered phenol, pentaerythrityl-tetrakis(3-(3',5'-di-tert-butyl-4-hydroxyphenyl)-propionate (CAS number 6683-19-8, commercially available as Irganox 1010 from BASF SE, Germany), and the phosphorus antioxidant tris(2,4-di-t-butylphenyl)phosphite (CAS number 31570-04-4, commercially available as Irgafos 168 from BASF SE, Germany), in a weight ratio of 1:1; "GF" is Nippon Electric Glass's commercially available product ECS 03 T-480H with a fiber diameter of 10.5 μm and a strand length of 3 mm; "AP" is adhesion promoter SCONA TPPP 8112 GA by Scona, which is a maleic anhydride functionalized polypropylene with a maleic anhydride content of 1.4 wt.% and a MFR (190° C., 2.16 kg) of about 80 g / 10 min; "CB" is the commercially available carbon black masterbatch "Plasblak PPP6331" from Cabot Corporation, Germany. "HPP" is a polymer with a melt flow rate of 2.7g / 10min, used as a carrier material for additives. 2 The copolymer is a commercially available propylene homopolymer HC001 from Borealis AG having the formula:

Claims

1. A fiber-reinforced composite material, (a) 30 to 60% by weight of polypropylene (PP1), based on the fiber reinforced composite; (b) 10-40 wt. % based on the fiber reinforced composite of a heterophasic propylene copolymer (HECO), the heterophasic propylene copolymer (HECO) comprising a propylene homopolymer (H-PP2) and an ethylene-propylene rubber (EPR); (c) 10 to 40 wt. % glass fiber (GF) based on the fiber reinforced composite material; (d) 0.05 to 5.0 wt. % of a compatibilizer (CA), based on the fiber-reinforced composite; Including, the total amount of said polypropylene (PP1), said heterophasic propylene copolymer (HECO), said glass fiber (GF) and said compatibilizer (CA) in said fiber reinforced composite is at least 95 wt. %; Furthermore, the polypropylene (PP1) is (i) a melt flow rate MFR measured according to ISO 1133 in the range of 40.0 to 250 g / 10 min; ２ (230℃, 2.16kg), (ii) 0.5% by weight or less, １３ comonomer content as determined by C-NMR spectroscopy, the comonomer, if present, being ethylene; and (iii) a molecular weight distribution (MWD), as determined by gel permeation chromatography (GPC), in the range of from greater than 4.5 to less than 8.5; and (iv) in the range of 0.20 to 1.00%; １３ 2,1-site defects determined by C-NMR spectroscopy having Still further, the propylene homopolymer (H-PP2) of the heterophasic propylene copolymer (HECO) comprises (v) in the range of 0 to less than 0.10%; １３ 2,1-site defects determined by C-NMR spectroscopy A fiber-reinforced composite material having the above structure.

2. 2. The fiber reinforced composite of claim 1, wherein the glass fibers are embedded in a continuous phase, the continuous phase comprising at least 98% by weight of a mixture of the polypropylene (PP1) and the heterophasic propylene copolymer (HECO).

3. The propylene homopolymer (H-PP2) of the heterophasic propylene copolymer (HECO) has a melt flow rate MFR, measured according to ISO 1133, in the range of 40.0 to 250 g / 10 min. ２ (230° C., 2.16 kg), provided that the melt flow ratio MFR of the polypropylene (PP1) and the propylene homopolymer (H-PP2) of the heterophasic propylene copolymer (HECO) is ２ [M.F.R. ２ (PP1) / MFR ２ The fiber-reinforced composite material according to claim 1 or claim 2, wherein (H-PP2)] is in the range of 0.80 to 1.

20.

4. The weight ratio of the mixture of the polypropylene (PP1) and the propylene homopolymer (H-PP2) to the ethylene-propylene rubber (EPR) [(PP1) + (H-PP2) / (EPR)] is in the range of 75:25 to 95:

5. The fiber reinforced composite material according to any one of claims 1 to 3.

5. The fiber reinforced composite material according to any one of claims 1 to 4, wherein the weight ratio of the polypropylene (PP1) to the propylene homopolymer (H-PP2) of the heterophasic propylene copolymer (HECO) [(PP1) / (H-PP2)] is in the range of 60:40 to 80:

20.

6. 6. The fiber reinforced composite according to any one of claims 1 to 5, wherein the propylene homopolymer (H-PP2) of the heterophasic propylene copolymer (HECO) has a molecular weight distribution (MWD) determined by gel permeation chromatography (GPC) in the range of from greater than 5.0 to less than 10.

0.

7. The heterophasic propylene copolymer (HECO) has a melt flow rate MFR measured according to ISO 1133 in the range of 10 to 50 g / 10 min. ２ (230°C, 2.16 kg) and in the range of 15 to 33 mol% １３ 7. The fiber reinforced composite of claim 1, having an ethylene content determined by C-NMR spectroscopy.

8. The heterophasic propylene copolymer (HECO) has a cold xylene soluble (XCS) content, determined at 25°C according to ISO 16152, ranging from 22 to 45 wt.%, and the heterophasic propylene copolymer (HECO) has a cold xylene soluble (XCS) fraction, determined at 25°C according to ISO 16152, ranging from 40 to 60 mol.%. １３ 8. The fiber reinforced composite of claim 1, having an ethylene content determined by C-NMR.

9. 9. The fiber reinforced composite according to any one of claims 1 to 8, wherein the xylene cold soluble (XCS) fraction of the heterophasic propylene copolymer (HECO) has an intrinsic viscosity (IV) measured according to ISO 1628 / 1 (135°C in decalin) in the range of 2.0 to 5.0 dl / g.

10. The polypropylene (PP1) has a fraction eluted at less than 100 ° C. by temperature rising elution fractionation (TREF) in the range of 12 to 20 wt. %. The fiber reinforced composite material according to any one of claims 1 to 9.

11. The fiber reinforced composite material according to any one of claims 1 to 10, wherein the polypropylene (PP1) is a propylene homopolymer.

12. The glass fibers (GF) are short glass fibers, and optionally the short glass fibers (GF) have an average fiber length of 2.0 to 10.0 mm before compounding. The fiber reinforced composite material according to any one of claims 1 to 11.

13. A fibre reinforced composite according to any one of claims 1 to 12, wherein the compatibiliser (CA) is a polar modified polypropylene, preferably a maleic anhydride grafted polypropylene.

14. The maleic anhydride grafted polypropylene has a maleic anhydride content of 0.1 to 5.0 wt. % and preferably has a melt flow rate MFR measured according to ISO 1133 of 70 to 250 g / 10 min. ２ (190°C, 2.16 kg).

15. (a) 35 to 55% by weight of said polypropylene (PP1), based on said fiber reinforced composite; (b) 20-35 wt. % of said heterophasic propylene copolymer (HECO), based on said fiber reinforced composite; (c) 15 to 30 wt. % glass fiber (GF) based on the fiber reinforced composite material; (d) 0.5 to 5.0 wt. % of said compatibilizer (CA), based on said fiber reinforced composite; (e) 0.1 to 5.0 wt. % of an additive based on the fiber-reinforced composite material; The fiber-reinforced composite material according to any one of claims 1 to 14, comprising:

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