Patent Description:
Polypropylene is a material used in a wide variety of technical fields, and reinforced polypropylenes have in particular gained relevance in fields previously exclusively relying on non-polymeric materials, in particular metals. One particular example of reinforced polypropylenes are glass fiber reinforced polypropylene composites. Such materials enable tailoring of the properties of the composites by selecting the type of polypropylene, the amount of glass fiber and sometimes by selecting the type of compatibilizer used. Accordingly, nowadays glass fiber reinforced polypropylene composites are a well-established materials for applications requiring high stiffness, heat deflection resistance and impact resistance. However, one drawback of the commercial available fiber reinforced polypropylene composites is their rather high emission caused by rather high amount of oligomers obtained as side product in the polymerization process and a possibly necessary radical-induced degradation, commonly called visbreaking, to increase the melt flow rate (MFR<NUM>) and processability. This is related to the fact that not only the end properties of the fiber reinforced polypropylene composites need to be considered, but also the manufacture of articles made therefrom in an efficient way, i.e. the flowability of the composite must be rather high.

Accordingly, there is the need for glass fiber reinforced polypropylene composites being stiff and having rather high heat deflection resistance paired with low emissions and which can be further processed with a high throughput rate.

The finding of the present invention is that the fiber reinforced polypropylene composite must comprise a metallocene catalysed polypropylene having a broad molecular weight distribution and a Ziegler-Natta catalysed heterophasic propylene copolymer. Hence it is preferred that both polymers have not been visbroken, i.e. not modified in a radical-induced process to reduce the molecular weight.

Accordingly, the present invention is directed to a fiber reinforced composite comprising.

wherein further the polypropylene (PP1) has.

Further preferred embodiments of such a composite are defined in the claims dependent on claim <NUM> and are also defined in more detail below.

The present invention is also directed to articles, preferably automotive article, comprising at least <NUM> wt. -% of the fiber reinforced composite according to the present invention.

In the following the fiber reinforced composite is defined in more detail and subsequently the components of said composite.

The present invention is directed to a fiber reinforced composite comprising a polypropylene (PP1), a heterophasic propylene copolymer (HECO), glass fibers (GF) and a compatibilizer (CA). The fiber reinforced composite is understood as known in the art. That is, the polypropylene (PP1) together with the heterophasic propylene copolymer (HECO) forms the dominant part of the continuous phase in which the glass fibers are embedded. In case the glass fibers are short glass fibers, said fibers are dispersed in the polymer mixture comprising the polypropylene (PP1) and the heterophasic propylene copolymer (HECO), wherein the polymer mixture acts as the continuous phase. The compatibilizer (CA) improves the adhesion between the polar glass fibers and the non-polar polymer mixture comprising the polypropylene (PP1) and the heterophasic propylene copolymer (HECO).

wherein the total amount of the polypropylene (PP1), the heterophasic propylene copolymer (HECO), the glass fibers (GF) and the compatibilizer (CA) in the fiber reinforced composite is at least <NUM> wt. -%, preferably at least <NUM> wt.

Beside these four components, typical additives may be present which for instance are added to enhance the lifetime of the polypropylene (PP1) and the heterophasic propylene copolymer (HECO), i.e. antioxidants (see definition of additives below).

wherein the total amount of the polypropylene (PP1), the heterophasic propylene copolymer (HECO), the glass fibers (GF) the compatibilizer (CA), and the additives (AD), in the fiber reinforced composite is at least <NUM> wt. -%, preferably in the range of <NUM> to <NUM> wt. -%, like in the range of <NUM> to <NUM> wt.

In a specific embodiment the fiber reinforced composite according to this invention preferably consists of.

As mentioned above the continuous phase of the fiber reinforced composition is mainly dominated by the polypropylene (PP1) and the heterophasic propylene copolymer (HECO). Accordingly it is preferred that the continuous phase of the fiber reinforced composition in which the glass fibers are embedded comprises at least <NUM> wt. -%, more preferably at least <NUM> wt. -% of a mixture consisting of the polypropylene (PP1) and the heterophasic propylene copolymer (HECO).

Further, due to the presence of the heterophasic propylene copolymer (HECO) the fiber reinforced composition contains an elastomeric polymer, i.e. the ethylene-propylene rubber (EPR). An elastomeric polymer is understood as a polymer which does not form a continuous phase within a (semi)crystalline polypropylene. In other words, an elastomeric polymer is dispersed in the (semi)crystalline polypropylene, i.e. forms inclusion in the (semi)crystalline polypropylene. A polymer containing an elastomeric polymer as inclusions as a second polymer phase is called heterophasic. The presence of second polymer phases or the so-called inclusions are for instance visible by high resolution microscopy, like electron microscopy or atomic force microscopy, or by dynamic mechanical thermal analysis (DMTA). Specifically in DMTA the presence of a multiphase structure can be identified by the presence of at least two distinct glass transition temperatures. Hence, the polymer phase of the fiber reinforced composition according to this invention in itself forms a system in which the polypropylene (PP1) together with the propylene homopolymer (H-PP2) form a continuous phase in which the ethylene-propylene rubber (EPR) is dispersed.

Accordingly it is preferred that the weight ratio between the mixture of the polypropylene (PP1) and the propylene homopolymer (H-PP2) acting as the matrix and the ethylene-propylene rubber (EPR) dispersed in said matrix [((PP1)+(H-PP2)/(EPR)] is in the range of <NUM>:<NUM> to <NUM>:<NUM>, more preferably in the range of <NUM>:<NUM> to <NUM>:<NUM>.

Furthermore it is preferred that the weight ratio between the polypropylene (PP1) and the propylene homopolymer (H-PP2) [(PP1)/(H-PP2)] is in the range of <NUM>:<NUM> to <NUM>:<NUM>, more preferably in the range of <NUM>:<NUM> to <NUM>:<NUM>.

Additionally it is preferred that the molecular weight of the polypropylene (PP1) and the propylene homopolymer (H-PP2) of the heterophasic propylene copolymer (HECO) are rather similar. Accordingly it is preferred that the propylene homopolymer (H-PP2) of the heterophasic propylene copolymer (HECO) has a melt flow rate MFR<NUM> (<NUM>, <NUM>) measured according to ISO <NUM> in the range of <NUM> to <NUM>/<NUM>, more preferably in the range of <NUM> to <NUM>/<NUM>, with the proviso that the melt flow ratio MFR<NUM> between the polypropylene (PP1) and the propylene homopolymer (H-PP2) of the heterophasic propylene copolymer (HECO) [MFR<NUM>(PP1)/MFR<NUM>(H-PP2)] is in the range of <NUM> to <NUM>, more preferably in the range of <NUM> to <NUM>.

Further it is preferred that the fiber reinforced composite has a melt flow rate MFR<NUM> (<NUM>, <NUM>) measured according to ISO <NUM> in the range of <NUM> to <NUM>/<NUM>, more preferably in the range of <NUM> to <NUM>/<NUM>.

The fiber reinforced composite according to this invention is especially featured by low emissions. Accordingly, it is preferred that the fiber reinforced composite has a VOC (volatile organic compounds) value determined according to VDA <NUM> October <NUM> of below <NUM>µg/g, more preferably in the range of <NUM> to below <NUM>µg/g, still more preferably in the range of <NUM> to <NUM>µg/g.

It is further preferred that the fiber reinforced composite has a tensile modulus as determined on injection moulded specimens according to ISO <NUM>-<NUM> at <NUM>/min in the range of <NUM> to <NUM> MPa, more preferably in the range of <NUM> to <NUM> MPa, like in the range of <NUM> to <NUM> MPa. Also, the fiber reinforced composite preferably has an elongation at break in the same tensile test of more than <NUM> %, more preferably in the range of <NUM> to <NUM> %, like in the range of <NUM> to <NUM> %.

Additionally or alternatively to the requirement of the previous paragraph the fiber reinforced composite has an impact Charpy impact strength determined according to ISO <NUM>-1eU at <NUM> in the range of <NUM> to <NUM> kJ/m<NUM>, more preferably in the range of <NUM> to <NUM> kJ/m<NUM>, like in the range of <NUM> to <NUM> kJ/m<NUM>.

In a very specific embodiment the fiber reinforced composite has a heat deflection temperature HDT measured in accordance with ISO <NUM> B at a load of <NUM> MPa in the range from <NUM> to <NUM>, more preferably in the range of <NUM> to <NUM>, like in the range of <NUM> to <NUM>.

One essential component of the present invention is the polypropylene (PP1), which needs to be carefully selected to reach the desired properties. Accordingly, the polypropylene (PP1) according to this invention must have been produced with a metallocene catalyst and must have a rather broad molecular weight distribution (MWD) for such produced polypropylenes.

Accordingly, the polypropylene (PP1) has been produced in the presence of a specific metallocene catalyst as defined in more detail below. In contrast to polypropylenes produced in the presence of Ziegler-Natta catalysts, polypropylenes produced in the presence of metallocene catalysts are characterized by mis-insertions of monomer units during the polymerization process. Therefore, the polypropylene (PP1) according to this invention has a certain amount of <NUM>,<NUM>-regio defects, which indicates that it has been produced with a metallocene catalyst. That is the polypropylene (PP1) according to this invention has <NUM>,<NUM> regio-defects in the range of <NUM> to <NUM> %, more preferably in the range of <NUM> to <NUM> %, determined by <NUM>C-NMR spectroscopy.

Accordingly, the polypropylene (PP1) according to this invention has.

More preferably, the polypropylene (PP1) according to this invention has.

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

Therefore it is preferred that the polypropylene (PP1) of this invention is a propylene homopolymer (H-PP1) having.

Further the polypropylene (PP1), preferably the propylene homopolymer (H-PP1), has a rather high amount of polymer which elutes below <NUM> by Temperature Rising Elution fractionation (TREF). Accordingly, it is preferred that the the polypropylene (PP1) has a fraction which elutes below <NUM> by Temperature Rising Elution fractionation (TREF) in the range of <NUM> to <NUM> wt. -%, more preferably in the range of <NUM> to <NUM> wt.

Accordingly, it is preferred that the polypropylene (PP1) has.

Still yet more preferably the polypropylene (PP1) is a propylene homopolymer (H-PP1) having.

In addition the polypropylene (PP1) can be further defined by its melting temperature and the xylene soluble content.

Accordingly it is preferred that the polypropylene (PP1), especially the propylene homopolymer (H-PP1) has a melting temperature Tm determined by DSC according to ISO <NUM>-<NUM> (heating and cooling rate <NUM>/min) in the range of <NUM> to <NUM>.

The polypropylene (PP1) according to this invention is further preferably characterized by a very low xylene cold soluble (XCS) content, which cannot be reached by Ziegler-Natta catalysts. Thus in a preferred embodiment the polypropylene (PP1), more preferably the propylene homopolymer (H-PP1), according to this invention has a xylene cold soluble (XCS) fraction measured according to ISO <NUM> (<NUM>) in the range of <NUM> to <NUM> wt. -%, more preferably in the range of <NUM> to <NUM> wt.

As mentioned above it is preferred that the polypropylene (PP1) of this invention is produced by a specific metallocene catalyst. Accordingly, 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 the metallocene catalyst having the formula (I)
<CHM>.

In the following the term "formula (I)" stands for the metallocene catalyst as defined in the previous paragraph.

Hence it is especially preferred that the polypropylene (PP1) has.

wherein the polypropylene (PP1) is produced by polymerizing propylene and optionally ethylene in the presence of the metallocene catalyst having the formula (I) as defined above.

Still more preferably the polypropylene (PP1) is a propylene homopolymer (H-PP1) having.

wherein said propylene homopolymer (H-PP1) is produced by polymerizing propylene in the presence of the metallocene catalyst having the formula (I) as defined above.

Additionally it is preferred that the polypropylene (PP1), like the propylene homopolymer (H-PP1) has not been visbroken. Visbreaking, or controlled degradation by a radical-induced process initiated by peroxides or other radical generators, is normally used to enhance the melt flow rate and thus to lower the molecular weight and to narrow the molecular weight distribution. However degradation, i.e. vis-breaking, of a polymer is obtained by the use of peroxides. Visbreaking as well as the use of peroxides may enhance the emission values (in terms of VOC or FOG) due to undesired side reaction leading to an increased amount of oligomers. Further, the presence of peroxides may lead to an undesired discoloration of the polypropylene. In other words, whether a polypropylene has been visbroken can be identified by the decomposition products of the peroxides or other radical generators, and by discoloration of the polypropylene. In the following whenever the term "non-visbreaking" or "non-visbroken" is used it is therefore understood that the melt flow rate, the molecular weight and the molecular weight distribution of the polypropylene (PP1) has not been altered by chemical or physical treatment and further that the polypropylene (PP1) is free of decomposition products of peroxides or other radical generators. Further vis-breaking is anyway against the teaching of the present invention as it is desired that the polypropylene (PP1) of this invention has a rather broad molecular weight distribution, which is in contradiction of vis-breaking.

Accordingly it is preferred that the polypropylene (PP1) has not been visbroken and has.

More preferably the polypropylene (PP1) is a propylene homopolymer (H-PP1), wherein said propylene homopolymer (H-PP1) has not been visbroken and has.

wherein the propylene homopolymer (H-PP1) is produced by polymerizing propylene in the presence of the metallocene catalyst having the formula (I) as defined above.

In the following the polymerization of the polypropylene is described in detail.

The polypropylene (PP1) according to this invention can be produced in one reactor or in a reactor cascade of two or more reactors, preferably two reactors. As the polypropylene (PP1) according to this invention must have a broad molecular weight distribution (MWD), i.e. of at least <NUM>, it is preferred that the polypropylene (PP1) is produced in at least two reactors, in each reactor a polypropylene fraction is produced which differ considerable in the molecular weight thereby arriving at a final polypropylene (PP1) having a broader molecular weight distribution (MWD) as if the polypropylene (PP1) had only been produced in one reactor. The polymerization processes suitable for producing the polypropylene (PP1) according to this invention are known in the art. They comprise at least one polymerization stage, where polymerization is typically 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 contains at least one bulk reactor zone and optionally at least one gas phase reactor zone, each zone comprising at least one reactor and all reactors being arranged in cascade. In one particularly preferred embodiment, the polymerization process comprises at least one bulk reactor and at least one gas phase reactor arranged in that order. The process may further comprise pre- and post-reactors. Pre-reactors comprise typically pre-polymerization reactors. In this kind of processes, the use of higher polymerization temperatures is preferred in order to achieve specific properties of the polymer. Typical temperatures in these processes are <NUM> or higher, preferably <NUM> or higher. The higher polymerization temperatures as mentioned above can be applied in some or all reactors of the reactor cascade.

Multimodal polymers can be produced according to several processes which are described, e.g. in <CIT>, <CIT>, and <CIT>.

Preferably, the process for producing the polypropylene (PP1) comprises two polymerization stages, in which in the <NUM>st polymerization stage a the slurry reactor (SR), like a loop reactor (LR), while in the <NUM>nd polymerization stage a gas phase reactor is used.

The conditions in the <NUM>st polymerization stage may be as follows:.

Subsequently, the reaction mixture from <NUM>st polymerization stage is transferred to the gas phase reactor (GPR), whereby the conditions are preferably as follows:.

The residence time can vary in both reactor zones.

In one embodiment of the process for producing the polypropylene (PP1) the residence time in the slurry reactor (SR), e.g. loop (LR), is in the range <NUM> to <NUM> hours, e.g. <NUM> to <NUM> hours and the residence time in the gas phase reactor (GPR) will generally be <NUM> to <NUM> hours, like <NUM> to <NUM> hours.

A preferred multistage process is a "loop-gas phase"-process, such as developed by Borealis (known as BORSTAR® technology) described e.g. in patent literature, such as in <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT> or in <CIT>. A further suitable slurry-gas phase process is the Spheripol® process of Basell.

As mentioned above the polypropylene (PP1) according to this invention is especially obtained in a polymerization process using a metallocene catalyst having the formula (I)
<CHM>
wherein each R' are independently the same or can be different and are hydrogen or a linear or branched C<NUM>-C<NUM> alkyl group, whereby at least on R' per phenyl group is not hydrogen,.

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

Specific preferred metallocene catalysts of the invention include:.

The most preferred catalyst is rac-anti-dimethylsilanediyl[<NUM>-methyl-<NUM>,<NUM>-bis-(<NUM>',<NUM>'-dimethylphenyl)-<NUM>,<NUM>,<NUM>,<NUM>-tetrahydros-indacen-<NUM>-yl] [<NUM>-methyl-<NUM>-(<NUM>',<NUM>'-dimethylphenyl)-<NUM>-methoxy-<NUM>-tert-butylinden-<NUM>-yl] zirconium dichloride
<CHM>.

The ligands required to form the complexes and hence catalysts of the invention can be synthesized by any process and the skilled organic chemist would be able to devise various synthetic protocols for the manufacture of the necessary ligand materials. For Example <CIT> discloses the necessary chemistry. Synthetic protocols can also generally be found in <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT> and <CIT>. Especially reference is made to <CIT> in which the most preferred catalyst of the present invention is described. The examples section also provides the skilled person with sufficient direction.

To form an active catalytic species it is normally necessary to employ a cocatalyst as is well known in the art.

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

The aluminoxane cocatalyst can be one of formula (III):
<CHM>
where n is usually from <NUM> to <NUM> and R has the meaning below.

Aluminoxanes are formed on partial hydrolysis of organoaluminum compounds, for example those of the formula AlR<NUM>, AlR<NUM>Y and Al<NUM>R<NUM>Y<NUM> where R can be, for example, C<NUM>-C<NUM> alkyl, preferably C<NUM>-C<NUM> alkyl, or C<NUM>-C<NUM> cycloalkyl, C<NUM>-C<NUM> arylalkyl or alkylaryl and/or phenyl or naphthyl, and where Y can be hydrogen, halogen, preferably chlorine or bromine, or C<NUM>-C<NUM> alkoxy, preferably methoxy or ethoxy. The resulting oxygen-containing aluminoxanes are not in general pure compounds but mixtures of oligomers of the formula (III).

The preferred aluminoxane is methylaluminoxane (MAO). Since the aluminoxanes used according to the invention as cocatalysts are not, owing to their mode of preparation, pure compounds, the molarity of aluminoxane solutions hereinafter is based on their aluminium content.

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

It will be appreciated by the skilled man that where boron based cocatalysts are employed, it is normal to pre-alkylate the complex by reaction thereof with an aluminium alkyl compound, such as TIBA. This procedure is well known and any suitable aluminium alkyl, e.g. Al(C<NUM>-C<NUM> alkyl)<NUM>. can be used. Preferred aluminium alkyl compounds are triethylaluminium, triisobutylaluminium, tri-isohexylaluminium, tri-n-octylaluminium and tri-isooctylaluminium.

Alternatively, when a borate cocatalyst is used, the metallocene catalyst complex is in its alkylated version, that is for example a dimethyl or dibenzyl metallocene catalyst complex can be used.

Boron based cocatalysts of interest include those of formula (IV).

wherein Y is the same or different and is a hydrogen atom, an alkyl group of from <NUM> to about <NUM> carbon atoms, an aryl group of from <NUM> to about <NUM> carbon atoms, alkylaryl, arylalkyl, haloalkyl or haloaryl each having from <NUM> to <NUM> carbon atoms in the alkyl radical and from <NUM>-<NUM> carbon atoms in the aryl radical or fluorine, chlorine, bromine or iodine. Preferred examples for Y are methyl, propyl, isopropyl, isobutyl or trifluoromethyl, unsaturated groups such as aryl or haloaryl like phenyl, tolyl, benzyl groups, p-fluorophenyl, <NUM>,<NUM>- difluorophenyl, pentachlorophenyl, pentafluorophenyl, <NUM>,<NUM>,<NUM>-trifluorophenyl and <NUM>,<NUM>-di(trifluoromethyl)phenyl. Preferred options are trifluoroborane, triphenylborane, tris(<NUM>-fluorophenyl)borane, tris(<NUM>,<NUM>-difluorophenyl)borane, tris(<NUM>-fluoromethylphenyl)borane, tris(<NUM>,<NUM>,<NUM>-trifluorophenyl)borane, tris(penta-fluorophenyl)borane, tris(tolyl)borane, tris(<NUM>,<NUM>-dimethyl-phenyl)borane, tris(<NUM>,<NUM>-difluorophenyl)borane and/or tris (<NUM>,<NUM>,<NUM>-trifluorophenyl) borane.

Particular preference is given to tris(pentafluorophenyl)borane.

However it is preferred that borates are used, i.e. compounds containing a borate <NUM>+ ion. Such ionic cocatalysts preferably contain a non-coordinating anion such as tetrakis(pentafluorophenyl)borate and tetraphenylborate. Suitable counterions are protonated amine or aniline derivatives such as methylammonium, anilinium, dimethylammonium, diethylammonium, N- methylanilinium, diphenylammonium, N,N-dimethylanilinium, trimethylammonium, triethylammonium, tri-n-butylammonium, methyldiphenylammonium, pyridinium, p-bromo-N,N- dimethylanilinium or p-nitro-N,N-dimethylanilinium.

Preferred ionic compounds which can be used according to the present invention include:.

Preference is given to triphenylcarbeniumtetrakis(pentafluorophenyl) borate,.

It has been surprisingly found that certain boron cocatalysts are especially preferred. Preferred borates of use in the invention therefore comprise the trityl ion. Thus the use of N,N-dimethylammonium-tetrakispentafluorophenylborate and Ph3CB(PhF5)<NUM> and analogues therefore are especially favoured.

According to the present invention, the preferred cocatalysts are alumoxanes, more preferably methylalumoxanes, combinations of alumoxanes with Al-alkyls, boron or borate cocatalysts, and combination of alumoxanes with boron-based cocatalysts.

Suitable amounts of cocatalyst will be well known to the skilled man.

The molar ratio of boron to the metal ion of the metallocene may be in the range <NUM>:<NUM> to <NUM>:<NUM> mol/mol, preferably <NUM>:<NUM> to <NUM>:<NUM>, especially <NUM>:<NUM> to <NUM>:<NUM> mol/mol.

The molar ratio of Al in the aluminoxane to the metal ion of the metallocene may be in the range <NUM>:<NUM> to <NUM>:<NUM> mol/mol, preferably <NUM>:<NUM> to <NUM>:<NUM>, and more preferably <NUM>:<NUM> to <NUM>:<NUM> mol/mol.

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 a silica support is preferred. The skilled person is aware of the procedures required to support a metallocene catalyst.

Especially preferably, the support is a porous material so that the complex may be loaded into the pores of the support, e.g. using a process analogous to those described in <CIT> (Mobil), <CIT>(Borealis) and <CIT>.

The average particle size of the silica support can be typically from <NUM> to <NUM>. However, it has turned out that special advantages can be obtained if the support has an average particle size from <NUM> to <NUM>, preferably from <NUM> to <NUM>.

The average pore size of the silica support can be in the range <NUM> to <NUM> and the pore volume from <NUM> to <NUM>/g.

Examples of suitable support materials are, for instance, ES757 produced and marketed by PQ Corporation, Sylopol <NUM> produced and marketed by Grace or SUNSPERA DM-L-<NUM> silica produced by AGC Si-Tech Co. Supports can be optionally calcined prior to the use in catalyst preparation in order to reach optimal silanol group content.

The use of these supports is routine in the art.

The second mandatory component of the fiber reinforced composition according to this invention is the heterophasic propylene copolymer (HECO).

The heterophasic propylene copolymer (HECO) according to this invention comprises a matrix being a propylene homopolymer (HPP-<NUM>) and dispersed therein an ethylene-propylene rubber (EPR). Thus the matrix contains (finely) dispersed inclusions being not part of the matrix and said inclusions contain the ethylene-propylene rubber (EPR). As mentioned above when defining the continuous phase of the fiber reinforced composite, the term "inclusion" indicates that the matrix and the inclusion form different phases within the heterophasic propylene copolymer (HECO). The presence of second phases or the so called inclusions are for instance visible by high resolution microscopy, like electron microscopy or atomic force microscopy, or by dynamic mechanical thermal analysis (DMTA). Specifically, in DMTA the presence of a multiphase structure can be identified by the presence of at least two distinct glass transition temperatures.

Accordingly, the heterophasic propylene copolymer (HECO) according to this invention comprises.

As will be explained in more detail below the heterophasic propylene copolymer (HECO) according to this invention has been produced in the presence of a Ziegler-Natta catalyst of the <NUM>th generation (cf. Accordingly in contrast to the polypropylene (PP1) which shows a considerable amount of <NUM>,<NUM> regio-defects in the polymer chain, the heterophasic propylene copolymer (HECO) shows none of the <NUM>,<NUM> regio-defects or almost none of <NUM>,<NUM> regio-defects.

Accordingly the heterophasic propylene copolymer (HECO) according to this invention comprises.

It is especially preferred that the the heterophasic propylene copolymer (HECO) according to this invention comprises.

Additionally it is preferred that, like the polypropylene (PP1), also the propylene homopolymer (H-PP2) of the heterophasic propylene copolymer (HECO) has a broad molecular weight distribution (MWD), i.e. in the range of <NUM> to below <NUM>, more preferably in the range of <NUM> to <NUM>.

Accordingly in a preferred embodiment the heterophasic propylene copolymer (HECO) according to this invention comprises.

wherein the propylene homopolymer (H-PP2) has.

To achieve further improved properties for the fiber reinforced composite according to this invention the molecular weight of the polypropylene (PP1) and of the propylene homopolymer (H-PP2) of the heterophasic propylene copolymer (HECO) must be rather similar. Thus it is preferred that the propylene homopolymer (H-PP2) of the heterophasic propylene copolymer (HECO) has a melt flow rate MFR<NUM> (<NUM>, <NUM>) measured according to ISO <NUM> in the range of <NUM> to <NUM>/<NUM>, more preferably in the range of <NUM> to <NUM>/<NUM>, with the proviso that the melt flow ratio MFR<NUM> between the polypropylene (PP1) and the propylene homopolymer (H-PP2) of the heterophasic propylene copolymer (HECO) [MFR<NUM>(PP1)/MFR<NUM>(H-PP2)] is in the range of <NUM> to <NUM>, more preferably in the range of <NUM> to <NUM>.

Thus in a specific preferred embodiment the heterophasic propylene copolymer (HECO) according to this invention comprises.

The propylene homopolymer (H-PP2) of the heterophasic propylene copolymer (HECO) can be further characterized by its high melting temperature which is typical for a propylene homopolymer obtained by <NUM>th generation Ziegler-Natta catalyst, i.e. by a melting temperature of at least <NUM>, more preferably of at least <NUM>, like in the range of <NUM> to <NUM>.

Therefore it is preferred that the heterophasic propylene copolymer (HECO) according to this invention comprises.

Additionally the heterophasic propylene copolymer (HECO) can be further defined by its elastomeric part, i.e. by the ethylene-propylene rubber (EPR). As known by the skilled person for heterophasic systems in which the matrix is a propylene homopolymer and the elastomeric part an ethylene-propylene rubber (EPR), the xylene soluble fraction (XCS) reflects the rubber, while the propylene homopolymer (H-PP2) is reflected by the xylene insoluble fraction.

Thus, it is preferred that the heterophasic propylene copolymer (HECO) according to this invention has a xylene cold soluble (XCS) content determined at <NUM> according ISO <NUM> in the range of <NUM> to <NUM> wt. -%, more preferably in the range of <NUM> to <NUM> wt.

Further it is preferred that the ethylene content of the xylene cold soluble fraction is considerably high. Thus, in a preferred embodiment the heterophasic propylene copolymer (HECO) has an ethylene content determined by <NUM>C-NMR of the xylene cold soluble (XCS) fraction in the range of <NUM> to <NUM> mol-%, more preferably in the range of <NUM> to <NUM> mol-%.

In addition, the molecular weight of the ethylene propylene rubber (EPR) of the heterophasic propylene copolymer should be preferably not 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 <NUM>/<NUM> (at <NUM> in decalin) in the range of <NUM> to <NUM> dl/g, preferably in the range of <NUM> to <NUM> dl/g.

Finally, it is preferred that the heterophasic propylene copolymer (HECO) has an ethylene content determined by <NUM>C-NMR in the range of <NUM> to <NUM> mol-%, more preferably in the range of <NUM> to <NUM> mol-% and/or a melt flow rate MFR<NUM> (<NUM>, <NUM>) measured according to ISO <NUM> in the range of <NUM> to <NUM>/<NUM>, more preferably in the range of <NUM> to <NUM>/<NUM>.

Accordingly it is in particular preferred that the heterophasic propylene copolymer (HECO) according to this invention comprises.

Still more preferably the heterophasic propylene copolymer (HECO) according to this invention comprises.

Still yet more preferably the heterophasic propylene copolymer (HECO) according to this invention comprises.

Even yet more preferably the heterophasic propylene copolymer (HECO) according to this invention comprises.

As mentioned above, the heterophasic propylene copolymer (HECO) according to this invention has been produced with a <NUM>th generation Ziegler-Natta catalyst. Such catalysts are state of the art and well known to the skilled person. For instance as Ziegler-Natta catalyst the BHC01P catalyst of Borealis (prepared according to<CIT> as disclosed in <CIT>; especially with the use of dioctylphthalate as dialkylphthalate of formula (I) according to <CIT>) or the catalyst Polytrack <NUM>, commercially available from Grace. <CIT> and <CIT> can be used.

Also the polymerization conditions for the production of the heterophasic propylene copolymer (HECO) are known to the skilled person. The heterophasic propylene copolymer (HECO) is produced in two polymerization zones, in the first zone the propylene homopolymer (H-PP2) is produced while in the second polymerization zone the ethylene-propylene rubber (EPR) is obtained. Each zone may contain one or more reactors. For instance the first zone may contain just a loop reactor whereas the second zone may just contain one gas phase reactor. However it is preferred that the first zone contains a loop reactor and a gas phase reactor, while second zone contains two gas phase reactors.

Thus, the process for the preparation of the heterophasic propylene copolymer (HECO) according to the present invention is preferably a sequential polymerization process comprising at least two reactors, preferably four reactors, connected in series, wherein said process comprises the steps of.

A preferred multistage process is a "loop-gas phase"-process, such as developed by Borealis A/S, Denmark (known as BORSTAR® technology) described e.g. in patent literature, such as in <CIT> or in <CIT>.

Heterophasic polymers can be produced according to several processes which are described, e.g. in <CIT>, <CIT>, and <CIT>.

Preferably, in the instant process for producing the heterophasic propylene copolymer (HECO) as defined above the conditions for the first reactor (R-<NUM>), i.e. the slurry reactor (SR), like a loop reactor (LR), of step (A) may be as follows:.

Subsequently, the reaction mixture from step (A) is transferred to the second reactor (R-<NUM>), i.e. gas phase reactor (GPR-<NUM>), i.e. to step (D), whereby the conditions in step (D) are preferably as follows:.

In one embodiment of the process for producing the heterophasic polypropylene composition (HECO) the residence time in the slurry reactor (SR), e.g. loop (LR) is in the range <NUM> to <NUM> hours, e.g. <NUM> to <NUM> hours and the residence time in the first gas phase reactor (GPR-<NUM>) will generally be <NUM> to <NUM> hours, like <NUM> to <NUM> hours.

If desired, the polymerization may be effected in a known manner under supercritical conditions in the first reactor (R-<NUM>), i.e. in the slurry reactor (SR), like in the loop reactor (LR).

The conditions in the third reactor (R-<NUM>), i.e. the second gas phase reactor (GPR-<NUM>) and any other subsequent gas phase reactors (GPR), if present, are similar to the second reactor (R-<NUM>). Also residence times in the second and the third gas phase reactor (GPR-<NUM> and GPR-<NUM>) are in the same range or higher than in the first gas phase reactor (GPR-<NUM>).

The present process may also encompass a pre-polymerization prior to the polymerization in the first reactor (R-<NUM>). The pre-polymerization can be conducted in the first reactor (R-<NUM>), however it is preferred that the pre-polymerization takes place in a separate reactor, a so called pre-polymerization reactor.

The third mandatory component in the fiber reinforced composite are the glass fibers. The glass fibers can be any type of glass fibers like long glass fibers or short glass fibers. However it is especially preferred that the glass fibers are short glass fibers, also known as cut glass fibers or chopped glass strands.

The short glass fibers used in the fiber reinforced composite preferably have an average fiber length prior to compounding in the range of from <NUM> to <NUM>, more preferably in the range of <NUM> to <NUM>, still more preferably in the range of <NUM> to <NUM>.

It is further preferred that the short glass fibers used in the fiber reinforced composite preferably have an average diameter prior to compounding of from <NUM> to <NUM>, more preferably from <NUM> to <NUM>, still more preferably <NUM> to <NUM>.

Preferably, the short glass fibers have an aspect ratio, defined as the ratio between average fiber length and average fiber diameter, prior to compounding of <NUM> to <NUM>, preferably of <NUM> to <NUM>, more preferably <NUM> to <NUM>. The aspect ratio is the relation between average length and average diameter of the fibers.

A further component present in the fiber reinforced composite is the compatibilizer or also called coupling agent or adhesion promotor. The compatibilizer improves the adhesion between the non-polar polypropylene and the polar glass fibers.

The compatibilizer according to this invention is preferably a polar modified polypropylene. The polar modified polypropylene, like a polar modified propylene homopolymer or a polar modified copolymer, are highly compatible with the polypropylene of the fiber reinforced composite according to this invention.

In terms of structure, the polar modified polypropylenes are preferably selected from graft or block copolymers.

In this context, preference is given to polar modified polypropylenes containing groups deriving from polar compounds, in particular selected from the group consisting of acid anhydrides, carboxylic acids, carboxylic acid derivatives, primary and secondary amines, hydroxyl compounds, oxazoline and epoxides, and also ionic compounds.

Specific examples of the said polar compounds are unsaturated cyclic anhydrides and their aliphatic diesters, and the diacid derivatives. In particular, one can use maleic anhydride and compounds selected from C<NUM> to C<NUM> linear and branched dialkyl maleates, C<NUM> to C<NUM> linear and branched dialkyl fumarates, itaconic anhydride, C<NUM> to C<NUM> linear and branched itaconic acid dialkyl esters, maleic acid, fumaric acid, itaconic acid and mixtures thereof.

In a particular preferred embodiment of the present invention, the polar modified polypropylene is maleic anhydride grafted polypropylene, wherein the polypropylene is either a propylene-ethylene copolymer or a propylene homopolymer. It is especially preferred that the polar modified polypropylene is maleic anhydride grafted polypropylene, wherein the polypropylene is a propylene homopolymer.

The polar modified polypropylene, especially the maleic anhydride grafted polypropylene, can be produced in a simple manner by reactive extrusion of the polypropylene, for example with maleic anhydride in the presence of free radical generators (like organic peroxides), as disclosed for instance in <CIT>.

The amounts of groups deriving from polar compounds, like the amount of maleic anhydride, in the polar modified polypropylene, are from <NUM> to <NUM> wt. %, preferably from <NUM> to <NUM> wt. %, and more preferably from <NUM> to <NUM> wt.

Preferably the polar modified polypropylene, like the maleic anhydride grafted polypropylene, has a melt flow rate MFR<NUM> (<NUM>, <NUM>) measured according to ISO <NUM> of at least <NUM>/<NUM>, more preferably of at least <NUM>/<NUM>, yet more preferably in the range of <NUM> to <NUM>/<NUM>, still yet more preferably in the range of <NUM> to <NUM>/<NUM>.

Fiber reinforced composite according to this invention may in addition comprise additives. Typical additives are acid scavengers, antioxidants, colorants, light stabilizers, slip agents, anti-scratch agents, dispersing agents, processing aids, lubricants, pigments, e.g. carbon black, and the like.

Such additives are commercially available and for example described in "<NPL>).

Additives are frequently provided in form of a masterbatch. A masterbatch is a composition in which an additive or an additive mixture in rather high amount is dispersed in a polymer. Accordingly, the term "additive" according to the present invention also includes carrier materials, in particular polymeric carrier materials, in which the "active additive" or "active additive mixture" is dispersed.

The reinforced fiber composite is produced as well known in the art. Accordingly the fiber reinforced composite is manufactured by a processes comprising the steps of adding.

to an extruder and extruding the same by obtaining said fiber reinforced composite.

For the extruding, i.e. melt blending, the individual components of the composite a conventional compounding or blending apparatus, e.g. a Banbury mixer, a <NUM>-roll rubber mill, Buss-co-kneader or a twin screw extruder may be used. The fiber reinforced composite recovered from the extruder/mixer is usually in the form of granules. These granules are then preferably further processed, e.g. by injection moulding to generate articles and products of the inventive composite.

It is especially preferred that the fiber reinforced composite according to the present invention is prepared by melt blending the individual components in an extruder, preferably a twin screw extruder.

In particular, it is preferred that the fiber reinforced composite according to the present invention is obtained by a process comprising the steps of.

The present invention is further directed to an article, preferably an automotive article, comprising at least <NUM> wt. -%, more preferably at least <NUM> wt. -%, yet more preferably consist, of the fiber reinforced composite according to the present invention.

Especially preferred embodiments are as follows:
One embodiment provides a fiber reinforced composite comprising.

In one embodiment, the fiber reinforced composite has a melt flow rate MFR<NUM> (<NUM>, <NUM>) measured according to ISO <NUM> in the range of <NUM> to <NUM>/<NUM>.

In one embodiment, the glass fibers are embedded in a continuous phase, said continuous phase comprises at least <NUM> wt. -% of a mixture consisting of the polypropylene (PP1) and the heterophasic propylene copolymer (HECO).

In one embodiment, the propylene homopolymer (H-PP2) of the heterophasic propylene copolymer (HECO) has a melt flow rate MFR<NUM> (<NUM>, <NUM>) measured according to ISO <NUM> in the range of <NUM> to <NUM>/<NUM> with the proviso that the melt flow ratio MFR<NUM> between the polypropylene (PP1) and the propylene homopolymer (H-PP2) of the heterophasic propylene copolymer (HECO) [MFR<NUM>(PP1)/MFR<NUM>(H-PP2)] is in the range of <NUM> to <NUM>.

In one embodiment, the weight ratio between the mixture of the polypropylene (PP1) and the propylene homopolymer (H-PP2) and the ethylene-propylene rubber (EPR) [((PP1)+(H-PP2)/(EPR)] is in the range of <NUM>:<NUM> to <NUM>:<NUM>.

In one embodiment, the weight ratio between the polypropylene (PP1) and the propylene homopolymer (H-PP2) of the heterophasic propylene copolymer (HECO) [(PP1)/(H-PP2)] is in the range of <NUM>:<NUM> to <NUM>:<NUM>.

In one embodiment, 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 more than <NUM> to below <NUM>.

In one embodiment, 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 <NUM>.

In one embodiment, the heterophasic propylene copolymer (HECO) has a melt flow rate MFR<NUM> (<NUM>, <NUM>) measured according to ISO <NUM> in the range of <NUM> to <NUM>/<NUM>.

In one embodiment, the heterophasic propylene copolymer (HECO) has a xylene cold soluble (XCS) content determined at <NUM> according ISO <NUM> in the range of <NUM> to <NUM> wt.

In one embodiment, the heterophasic propylene copolymer (HECO) has an ethylene content determined by <NUM>C-NMR of the xylene cold soluble (XCS) fraction in the range of <NUM> to <NUM> mol-%.

In one embodiment, the heterophasic propylene copolymer (HECO) has an ethylene content in the range of <NUM> to <NUM> mol-%.

In one embodiment, the xylene cold soluble (XCS) fraction of the heterophasic propylene copolymer (HECO) has an intrinsic viscosity (IV) measured according to ISO <NUM>/<NUM> (at <NUM> in decalin) in the range of <NUM> to <NUM> dl/g.

In one embodiment, the heterophasic propylene copolymer (HECO) is non-visbroken.

In one embodiment, the polypropylene (PP1) has a fraction which elutes below <NUM> by Temperature Rising Elution fractionation (TREF) in the range of <NUM> to <NUM> wt.

In one embodiment, the polypropylene (PP1) is a propylene homopolymer.

In one embodiment, the polypropylene (PP1) is non-visbroken.

In one embodiment, the polypropylene (PP1) has a melting temperature Tm determined according to differential scanning calorimetry (DSC) in the range of <NUM> to <NUM>.

In one embodiment, the polypropylene (PP1) has a xylene cold soluble (XCS) content determined at <NUM> according ISO <NUM> in the range of <NUM> to <NUM> wt.

In one embodiment, the polypropylene (PP1) is produced by polymerizing propylene and optionally ethylene in the presence of the metallocene catalyst having the formula (I)
<CHM>.

In one embodiment, the glass fibers (GF) are short glass fibers, and optionally the glass fibers (GF) have an average fiber length of <NUM> to <NUM> prior to compounding and optionally an average diameter of <NUM> to <NUM>.

In one embodiment, the compatibilizer (CA) is a polar modified polypropylene, preferably is a maleic anhydride grafted polypropylene, and optionally the maleic anhydride grafted polypropylene has a maleic anhydride content of <NUM> to <NUM> wt. -% and preferably a melt flow rate MFR<NUM> (<NUM>, <NUM>) measured according to ISO <NUM> of at least <NUM>/<NUM>, more preferably in the range of <NUM> to <NUM>/<NUM>.

In one embodiment, the fiber reinforced composite consists of.

The invention is now described by way of examples.

The following definitions of terms and determination methods apply for the above general description of the invention including the claims as well as to the below examples unless otherwise defined.

Quantitative nuclear-magnetic resonance (NMR) spectroscopy was used to quantify the isotacticity and regio-regularity of the ethylene-propylene copolymer.

Quantitative <NUM>C{<NUM>H} NMR spectra were recorded in the solution-state using a Bruker Advance III <NUM> NMR spectrometer operating at <NUM> and <NUM> for <NUM>H and <NUM>C respectively. All spectra were recorded using a <NUM>C optimised <NUM> extended temperature probehead at <NUM> using nitrogen gas for all pneumatics.

Approximately <NUM> of material was dissolved in <NUM>,<NUM>-tetrachloroethane-dz (TCE-d<NUM>). To ensure a homogenous solution, after initial sample preparation in a heat block, the NMR tube was further heated in a rotatary oven for at least <NUM> hour. Upon insertion into the magnet the tube was spun at <NUM>. This setup was chosen primarily for the high resolution needed for tacticity distribution quantification (<NPL>; <NPL>). Standard single-pulse excitation was employed utilising the NOE and bi-level WALTZ16 decoupling scheme (<NPL>; <NPL>). A total of <NUM> (<NUM>) transients were acquired per spectra.

Quantitative <NUM>C{<NUM>H} NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals using proprietary computer programs.

All chemical shifts are internally referenced to the methyl isotactic pentad (mmmm) at <NUM> ppm.

Characteristic signals corresponding to regio defects (<NPL>; <NPL>; <NPL>) or comonomer were observed.

The tacticity distribution was quantified through integration of the methyl region between <NUM>-<NUM> ppm correcting for any sites not related to the stereo sequences of interest (<NPL>; <NPL>).

Specifically the influence of regio-defects and comonomer on the quantification of the tacticity distribution was corrected for by subtraction of representative regio-defect and comonomer integrals from the specific integral regions of the stereo sequences.

The isotacticity was determined at the pentad level and reported as the percentage of isotactic pentad (mmmm) sequences with respect to all pentad sequences: <MAT>.

The presence of <NUM>,<NUM> erythro regio-defects was indicated by the presence of the two methyl sites at <NUM> and <NUM> ppm and confirmed by other characteristic sites. Characteristic signals corresponding to other types of regio-defects were not observed (<NPL>).

The amount of <NUM>,<NUM> erythro regio-defects was quantified using the average integral of the two characteristic methyl sites at <NUM> and <NUM> ppm: <MAT>.

The total amount of propene was quantified as the sum of primary inserted propene and all other present regio-defects: <MAT>.

The mole percent of <NUM>,<NUM> erythro regio-defects was quantified with respect to all propene: <MAT>.

The melt flow rate (MFR) is determined according to ISO <NUM> and is indicated in g/<NUM>. The MFR is an indication of the flowability, and hence the processability, of the polymer. The higher the melt flow rate, the lower the viscosity of the polymer. The MFR<NUM> of the polypropylene is determined at a temperature of <NUM> and a load of <NUM>.

Calculation of melt flow rate MFR<NUM> (<NUM>) of the polypropylene produced in the <NUM>st gas phase reactor (GPR1): <MAT> wherein.

Molar mass averages (Mz, Mw and Mn) and molecular weight distribution (MWD), i.e. Mw/Mn, were determined by Gel Permeation Chromatography (GPC) according to ISO <NUM>-<NUM>:<NUM> and ASTM D <NUM>-<NUM> using the following formulas: <MAT> <MAT> <MAT> where Ai and Mi are the chromatographic peak slice area and polyolefin molecular weight (MW).

A PolymerChar GPC instrument, equipped with infrared (IR) detector was used with <NUM> × Olexis and 1x Olexis Guard columns from Polymer Laboratories and <NUM>,<NUM>,<NUM>-trichlorobenzene (TCB, stabilized with <NUM>/l <NUM>,<NUM>-Di-tert-butyl-<NUM>-methyl-phenol) as solvent at <NUM> and at a constant flow rate of <NUM>/min. <NUM>µL of sample solution were injected per analysis. The column set was calibrated using universal calibration (according to ISO <NUM>-<NUM>:<NUM>) with at least <NUM> narrow MWD polystyrene (PS) standards in the range of <NUM>/mol to <NUM>/mol. Mark Houwink constants used for PS, PE and PP are as described per ASTM D <NUM>-<NUM>. All samples were prepared by dissolving <NUM> to <NUM> of polymer in <NUM> (at <NUM>) of stabilized TCB (same as mobile phase) for <NUM> hours for PP or <NUM> hours for PE at <NUM> under continuous gentle shaking in the autosampler of the GPC instrument.

The chemical composition distribution was determined by analytical Temperature Rising Elution fractionation as described by <NPL>.

The separation of the polymer in TREF is according to their crystallinity in solution. The TREF profiles were generated using a CRYSTAF-TREF <NUM>+ instrument manufactured by PolymerChar S. (Valencia, Spain).

The polymer sample was dissolved in <NUM> ,<NUM>,<NUM>-trichlorobenzene (TCB, stabilized with <NUM>/L <NUM>,<NUM>-Di tert butyl-<NUM>-methyl-phenol) at a concentration between <NUM> and <NUM>/ml at <NUM> for <NUM> and <NUM> of the sample solution was injected into the column (<NUM> inner diameter, <NUM> length, filled with inert e.g. glass beads). The column oven was then rapidly cooled to <NUM> and held at <NUM> for <NUM> for stabilization purpose and it was later slowly cooled to <NUM> under a constant cooling rate (<NUM>/min). The polymer was subsequently eluted from the column with <NUM> ,<NUM>,<NUM>-trichlorobenzene (stabilized with <NUM>/L <NUM>,<NUM>-Di tert butyl-<NUM>-methyl-phenol) at a flow rate of <NUM> mlJmin at <NUM> for a period of <NUM> followed by a temperature increase from <NUM> to <NUM> at a constant heating rate of <NUM>/ram with a flow rate of <NUM>/min. The concentration of the polymer during elution was recorded by an infrared detector (measuring the C-H absorption at <NUM> micrometer wavelength). The detector response was plotted as a function of the temperature.

The normalized concentration plot was presented as fractogram together with the cumulative concentration signal normalized to <NUM>.

The high crystalline fraction (HCF) is the amount in wt. -% of the polymer fraction which elutes at <NUM> and above elution temperature.

The low crystalline fraction (LCF) is than the amount in wt. -% of the polymer fraction which elutes between <NUM> and below <NUM>.

The amount of the polymer soluble in xylene was determined at <NUM> according to ISO <NUM>; 5th edition; <NUM>-<NUM>-<NUM>.

Intrinsic viscosity: The intrinsic viscosity (IV) was measured according to DIN ISO <NUM>/<NUM>, October <NUM>, in Decalin at <NUM>.

DSC analysis, melting temperature (Tm) and melting enthalpy (Hm), crystallization temperature (Tc) and crystallization enthalpy (Hc): measured with a TA Instrument Q200 differential scanning calorimetry (DSC) on <NUM> to <NUM> samples. DSC was run according to ISO <NUM> / part <NUM> /method C2 in a heat / cool / heat cycle with a scan rate of <NUM>/min in the temperature range of -<NUM> to +<NUM>. Crystallization temperature (Tc) and crystallization enthalpy (Hc) were determined from the cooling step, while the melting temperature (Tm) and the melting enthalpy (Hm) were determined from the second heating step.

Spiral flow length: This method specifies a principle to test, by use of injection moulding, the flowability of a plastic material taking into consideration the cooling effect of the mould. Plastic is melted down and plasticized by a screw in a warm cylinder. Melted plastic is injected by the screw function as a piston, into a cavity with a certain speed and pressure. The cavity is shaped as a spiral with a divided scale for length measurement printed in the steel. That gives the possibility to read the flow length directly on the injection moulded test spiral specimen.

Spiral Test was carried out using an Engel ES <NUM>/<NUM> HL injection moulding apparatus with a spiral mould and pressure of <NUM> bar.

The spiral flow length can be determined immediately after the injection operation.

The Flexural Modulus was determined according to ISO <NUM> method A (<NUM>-point bending test) on <NUM>×<NUM>×<NUM><NUM> specimens. Following the standard, a test speed of <NUM>/min and a span length of <NUM> times the thickness was used. The testing temperature was <NUM>±<NUM>° C. Injection moulding was carried out according to ISO <NUM>-<NUM> using a melt temperature of <NUM> for all materials irrespective of material melt flow rate.

Tensile modulus, tensile strength and elongation at break are measured according to ISO <NUM>-<NUM> using injection moulded specimens as described in EN ISO <NUM>-<NUM> (<NUM> B dog bone shape, <NUM> thickness).

The Charpy unnotched impact strength was measured according to ISO <NUM>1eU at +<NUM> using injection moulded bar test specimens of <NUM>×<NUM>×<NUM><NUM> prepared in the same way as for flexural modulus.

The HDT was determined on injection moulded test specimens of <NUM>×<NUM>×<NUM><NUM> prepared in the same way as for flexural modulus. The test was performed on flatwise supported specimens according to ISO <NUM>, condition A, with a nominal surface stress of <NUM> MPa.

VOC values and FOG values were measured according to VDA <NUM> (October <NUM>; Thermal Desorption Analysis of Organic Emissions for the Characterization of Non-Metallic Materials for Automobiles, VDA Verband der Automobilindustrie) after sample preparation of injection moulding plaques according to EN ISO <NUM>-<NUM>:<NUM>. These plaques were packed in aluminium-composite foils immediately after production and the foils were sealed. According to the VDA <NUM> October <NUM> the VOC value is defined as "the total of the readily volatile to medium volatile substances. It is calculated as toluene equivalent. The method described in this recommendation allows substances in the boiling / elution range up to n-pentacosane (C<NUM>) to be determined and analyzed.

The FOG value is defined as "the total of substances with low volatility, which elute from the retention time of n-tetradecane (inclusive)". It is calculated as hexadecane equivalent. Substances in the boiling range of n-alkanes "C<NUM>" to "C<NUM>" are determined and analysed.

The average fiber diameter is determined according to ISO <NUM>:<NUM>(E), Method B, microscope magnification of <NUM>.

The following metallocene complex has been used as described in <CIT>:
<CHM>.

A steel reactor equipped with a mechanical stirrer and a filter net was flushed with nitrogen and the reactor temperature was set to <NUM>. Next silica grade DM-L-<NUM> from AGC Si-Tech Co, pre-calcined at <NUM> (<NUM>) was added from a feeding drum followed by careful pressuring and depressurising with nitrogen using manual valves. Then toluene (<NUM>) was added. The mixture was stirred for <NUM>. Next <NUM> wt. % solution of MAO in toluene (<NUM>) from Lanxess was added via feed line on the top of the reactor within <NUM>. The reaction mixture was then heated up to <NUM> and stirred at <NUM> for additional two hours. The slurry was allowed to settle and the mother liquor was filtered off. The catalyst was washed twice with toluene (<NUM>) at <NUM>, following by settling and filtration. The reactor was cooled off to <NUM> and the solid was washed with heptane (<NUM>). Finally MAO treated SiOz was dried at <NUM> under nitrogen flow for <NUM> hours and then for <NUM> hours under vacuum (-<NUM> barg) with stirring. MAO treated support was collected as a free-flowing white powder found to contain <NUM>% Al by weight.

% MAO in toluene (<NUM>) was added into a steel nitrogen blanked reactor via a burette at <NUM>. Toluene (<NUM>) was then added under stirring. The metallocene complex as described above (<NUM>) was added from a metal cylinder followed by flushing with <NUM> toluene. The mixture was stirred for <NUM> minutes at <NUM>. Trityl tetrakis(pentafluorophenyl) borate (<NUM>) was then added from a metal cylinder followed by a flush with <NUM> of toluene. The mixture was stirred for <NUM> at room temperature. The resulting solution was added to a stirred cake of MAO-silica support prepared as described above over <NUM> hour. The cake was allowed to stay for <NUM> hours, followed by drying under N<NUM> flow at <NUM> for <NUM> and additionally for <NUM> under vacuum (-<NUM> barg) under stirring stirring.

Dried catalyst was sampled in the form of pink free flowing powder containing <NUM>% Al and <NUM>% Zr.

A Ziegler-Natta catalyst system has been used.

Mg alkoxide solution was prepared by adding, with stirring (<NUM> rpm), into <NUM> of a <NUM> wt-% solution in toluene of butyl ethyl magnesium (Mg(Bu)(Et)), a mixture of <NUM> of <NUM>-ethylhexanol and <NUM> of butoxypropanol in a <NUM> I stainless steel reactor. During the addition the reactor contents were maintained below <NUM>. After addition was completed, mixing (<NUM> rpm) of the reaction mixture was continued at <NUM> for <NUM> minutes. After cooling to room temperature <NUM> of the donor bis(<NUM>-ethylhexyl)citraconate was added to the Mg-alkoxide solution keeping temperature below <NUM>. Mixing was continued for <NUM> minutes under stirring (<NUM> rpm).

<NUM> of TiCl<NUM> and <NUM> of toluene were added into a <NUM> I stainless steel reactor. Under <NUM> rpm mixing and keeping the temperature at <NUM>, <NUM> of the prepared Mg alkoxy compound was added during <NUM> hours. <NUM> I of Viscoplex® <NUM>-<NUM> and <NUM> of heptane were added and after <NUM> hour mixing at <NUM> the temperature of the formed emulsion was raised to <NUM> within <NUM> hour. After <NUM> minutes mixing was stopped catalyst droplets were solidified and the formed catalyst particles were allowed to settle. After settling (<NUM> hour), the supernatant liquid was siphoned away. Then the catalyst particles were washed with <NUM> of toluene at <NUM> for <NUM> minutes followed by two heptane washes (<NUM>, <NUM>). During the first heptane wash the temperature was decreased to <NUM> and during the second wash to room temperature.

The thus obtained catalyst was used along with triethyl-aluminium (TEAL) as co-catalyst and dicyclo pentyl dimethoxy silane (D-donor) as donor. The ratio used was:.

Claim 1:
Fiber reinforced composite comprising
(a) <NUM> to <NUM> wt.-%, based on the fiber reinforced composite, of a polypropylene (PP1),
(b) <NUM> to <NUM> wt.-%, based on the fiber reinforced composite, of a heterophasic propylene copolymer (HECO), wherein said heterophasic propylene copolymer (HECO) comprises a propylene homopolymer (H-PP2) and an ethylene-propylene rubber (EPR),
(c) <NUM> to <NUM> wt.-%, based on the fiber reinforced composite, of glass fibers (GF), and
(d) <NUM> to <NUM> wt.-%, based on the fiber reinforced composite, of a compatibilizer (CA),
the total amount of the polypropylene (PP1), the heterophasic propylene copolymer (HECO), the glass fibers (GF) and the compatibilizer (CA) in the fiber reinforced composite being at least <NUM> wt.-%,
wherein further the polypropylene (PP1) has
(i) a melt flow rate MFR<NUM> (<NUM>, <NUM>) measured according to ISO <NUM> in the range of <NUM> to <NUM>/<NUM>,
(ii) a comonomer content determined by <NUM>C-NMR spectroscopy of not more than <NUM> wt.-%, the comonomer if present being ethylene,
(iii) a molecular weight distribution (MWD) determined by gel permeation chromatography (GPC) in the range of more than <NUM> to below <NUM>, and
(iv) <NUM>,<NUM> regio-defects determined by <NUM>C-NMR spectroscopy in the range of <NUM> to <NUM> %,
wherein still further the propylene homopolymer (H-PP2) of the heterophasic propylene copolymer (HECO) has
(v) <NUM>,<NUM> regio-defects determined by <NUM>C-NMR spectroscopy in the range of <NUM> to below <NUM> %.