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 fibre reinforced polypropylene composites. Such materials enable tailoring of the properties of the composites by selecting the type of polypropylene, the amount of glass fibre and sometimes by selecting the type of compatibilizer used. Accordingly, nowadays glass fibre reinforced polypropylene composites are a well-established material for applications requiring high stiffness, heat deflection resistance and impact resistance (examples include automotive components with a load-bearing function in the engine compartment, support parts for polymer body panels, washing machine and dishwasher components). However, one drawback of the commercially available fibre reinforced polypropylene composites is their rather high emission caused by rather high amount of oligomers obtained as side product in the polymerization process.

<CIT> describes a fiber reinforced composition comprising a heterophasic propylene copolymer, a propylene homopolymer and/or a propylene copolymer, and fibers, wherein the propylene copolymer comprises not more than <NUM> wt% C2 to C10 α-olefins other than propylene, the propylene homopolymer and the propylene copolymer having a melt flow rate MFR<NUM> (<NUM>) of at least <NUM>/<NUM>, and the composition has a melt flow rate MFR<NUM> (<NUM>) of at least <NUM>/<NUM>.

<CIT> describes long-fiber-reinforced polypropylene particles having a good opening property during molding. The obtained molded body exhibits an excellent appearance and has high mechanical strength. The particles contain a polypropylene, which is at least one type of polymer selected from propylene homopolymers and propylene-α-olefin random copolymers, and which is produced by using a metallocene catalyst, and a modified polypropylene based resin modified with an unsaturated carboxylic acid or a derivative thereof.

Accordingly, there is the need of glass fibre reinforced polypropylene composites being stiff and having rather high heat deflection resistance paired with low emissions.

The finding of the present invention is that the fibre reinforced polypropylene composite must comprise a polypropylene having low molecular weight distribution and rather high melting temperature. Preferably, the polypropylene has 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 polypropylene composite comprising.

The present invention is especially directed to a fiber reinforced polypropylene composite consists of.

Preferred embodiments of the fiber reinforced composite are defined in the dependent claims of the invention.

The present invention is further directed to a process for the manufacture of the fiber reinforced composite as defined in the present invention comprising the steps of adding.

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

Preferably the polypropylene according to this invention is obtained by polymerizing propylene and optionally ethylene, more preferably only propylene, in the presence of the metallocene catalyst having the formula (I)
<CHM>.

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.

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

In the following, the invention is described in more detail.

The present invention is directed to a fiber reinforced composite comprising a polypropylene, short glass fibers and a compatibilizer. The fiber reinforced composite is understood as known in the art. That is, the polypropylene forms the continuous phase in which the short glass fibers are embedded. Since the glass fibers are short glass fibers, said fibers are dispersed in the polypropylene wherein the polypropylene acts as the continuous phase. The compatibilizer improves the adhesion between the non-polar polypropylene and the polar glass fibers.

Beside the three components typical additives may be present which for instance are added to enhance the lifetime of the polypropylene, i.e. antioxidants (see definition of additives below).

Thus in a preferred embodiment the fiber reinforced composite according to this invention preferably comprises.

The fiber reinforced composition preferably does not contain an elastomeric polymer. An elastomeric polymer is understood as a polymer which does not form a continuous phase within the polypropylene. In other words, an elastomeric polymer is dispersed in the polypropylene, i.e. forms inclusion in the polypropylene. A polymer containing an elastomeric polymer as inclusions as a second phase would by contrast be called heterophasic and is preferably not part of the present invention. 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.

Therefore, in a specific embodiment the fiber reinforced composite according to this invention preferably consists of.

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 <NUM>µg/g, still more preferably in the range of <NUM> to <NUM>µg/g.

Additionally or alternatively to the requirement of the previous paragraph, the fiber reinforced composite has FOG (low volatility or condensable organic compounds) value determined according to VDA <NUM> October <NUM> of below <NUM>µg/g, more preferably in the range of <NUM> to <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 molded 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 extension 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>.

The essential component of the present invention is the polypropylene, which needs to be carefully selected to reach the desired properties. Accordingly, the polypropylene according to this invention needs a specific melting temperature and a rather narrow molecular weight distribution (MWD).

Further, the polypropylene according to this invention 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 misinsertions of monomer units during the polymerization process. Therefore, the polypropylene according to this invention has a certain amount of <NUM>,<NUM>-regio defects. That is the polypropylene 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 according to this invention has.

More preferably, the polypropylene according to this invention has.

It is especially preferred that the polypropylene is monophasic, i.e. does not comprise polymer components which are not miscible with each other as it is the case for heterophasic propylene copolymers. As stated above, in contrast to monophasic systems heterophasic systems comprise a continuous polymer phase, like a polypropylene, in which a further non-miscible polymer, like an elastomeric polymer, is dispersed as inclusions. Said polypropylene systems containing a polypropylene matrix and inclusions as a second polymer phase would by contrast be called heterophasic and is preferably not part of the present invention. 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.

Therefore, the polypropylene according to this invention is preferably a monophasic polypropylene having a.

Yet more preferably the polypropylene according to this invention is a monophasic polypropylene having a.

It is especially preferred that the monophasic polypropylene is a propylene homopolymer. A propylene homopolymer cannot be per definition heterophasic as it just contains polymer chains of propylene. In other words, a propylene homopolymer according to this invention is always a monophasic polymer.

Therefore, it is preferred that the monophasic polypropylene of this invention is a propylene homopolymer having.

Still more preferably the monophasic polypropylene is a propylene homopolymer having.

As mentioned above, it is especially preferred that the monophasic polypropylene is a propylene homopolymer. Accordingly, the monophasic polypropylene being a propylene homopolymer has.

The polypropylene 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, more preferably the monophasic polypropylene, 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. -%, like in the range of <NUM> to <NUM> wt.

Still more preferably, the propylene homopolymer has.

In a very preferred embodiment the present invention is directed to a propylene homopolymer having.

Accordingly, it is in particular preferred that the propylene homopolymer has.

In addition, it is preferred that the polypropylene of the present invention has a certain molecular weight. Accordingly, it is preferred that the polypropylene according to this invention has a melt flow rate MFR<NUM> (<NUM>, <NUM>) measured according to ISO <NUM> in the range of <NUM> to <NUM>/<NUM>, preferably in the range of <NUM> to <NUM>/<NUM>, more preferably in the range of <NUM> to <NUM>/<NUM>.

It is therefore preferred that the polypropylene, more preferably the monophasic polypropylene, has.

In a specific embodiment, the polypropylene, preferably the monophasic polypropylene, according to this invention has.

As mentioned above, it is especially preferred that the monophasic polypropylene is a propylene homopolymer. Accordingly, it is preferred that the monophasic polypropylene being a propylene homopolymer has.

As mentioned above it is preferred that the polypropylene of this invention is produced by a specific metallocene catalyst. Accordingly, in a preferred embodiment the polypropylene, more preferably the monophasic polypropylene 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, more preferably the monophasic polypropylene, has.

wherein the polypropylene, more preferably the monophasic polypropylene, 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, preferably the monophasic polypropylene, according to this invention has.

In a specific preferred embodiment, the monophasic polypropylene is a propylene homopolymer. Accordingly, it is preferred that the propylene homopolymer has.

wherein the propylene homopolymer 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 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. visbreaking, 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 has not been altered by chemical or physical treatment and further that the polypropylene is free of decomposition products of peroxides or other radical generators.

Accordingly, it is preferred that the polypropylene has not been visbroken and has.

wherein optionally the polypropylene 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 of the previous paragraph is a non-visbroken monophasic polypropylene.

Still yet more preferably the monophasic polypropylene according to this invention is a non-visbroken monophasic polypropylene having.

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

More preferably the monophasic polypropylene according to this invention is a non-visbroken propylene homopolymer. Accordingly, it is preferred that the non-visbroken propylene homopolymer according to this invention has.

wherein optionally the non-visbroken propylene homopolymer was 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 according to this invention can be produced in one reactor or in a reactor cascade of two or more reactors, preferably two reactors. The polymerization processes suitable for producing the polypropylene according to this invention are known in the state of 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 optionally at least one gas phase reactor arranged in that order. The process may further comprise pre- and post-reactors. Pre-reactors comprise typically prepolymerization 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.

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 according to this invention is especially obtained in a polymerization process using a metallocene catalyst having the formula (I)
<CHM>.

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 synthesised 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>), <CIT>) 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 composition in the fiber reinforced composite are the short glass fibers. The short glass fibers are also known as cut glass fibers or chopped glass strands.

The short glass fibers used in the fiber reinforced composite have an average fiber length in the range of from <NUM> to <NUM>, preferably in the range of <NUM> to <NUM>, 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 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, 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 competibilizer or also called coupling agent or adhesion promotor. As mentioned above 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 anydride, 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, and the like.

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

Additives are typically 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 process for producing the reinforced fiber composite.

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

to an extruder and extruding the same by obtaining said fiber reinforced composite, wherein preferably the polypropylene has been produced by polymerizing propylene and optionally ethylene in the presence of the metallocene catalyst having the formula (I), preferably having the formula (II).

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 molding 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.

wherein preferably the polypropylene has been produced by polymerizing propylene and optionally ethylene in the presence of the metallocene catalyst having the formula (I), preferably having the formula (II).

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 are automotive articles are dashboards and dashboard supports, bumper supports, load-bearing components of doors and tailgates, under-the-hood components like ventilators and battery carriers, and underbody protection elements.

Based on the information provided above the present invention is especially directed to the following embodiments.

Thus, in a preferred embodiment the fiber reinforced composite according to this invention comprises.

In another preferred embodiment the fiber reinforced composite according to this invention comprises.

In still yet another preferred embodiment the fiber reinforced composite according to this invention preferably comprises.

In the following, the present invention is described by way of examples.

The melt flow rate (MFR<NUM>) is determined according to ISO <NUM> and is indicated in g/<NUM>. The MFR<NUM> of polypropylene is determined at a temperature of <NUM> and under a load of <NUM>.

The Heat deflection temperature B (HDT B) was determined according to ISO <NUM> B at <NUM> MPa using 80x10x4 mm<NUM> test bars injection molded in line with EN ISO <NUM>-<NUM>.

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

The melting temperature Tm is determined by differential scanning calorimetry (DSC) according to ISO <NUM>-<NUM> with a TA-Instruments <NUM> Dual-Cell with RSC refrigeration apparatus and data station. A heating and cooling rate of <NUM>/min is applied in a heat/cool/heat cycle between +<NUM> and +<NUM>. The crystallization temperature (Tc) is determined from the cooling step while melting temperature (Tm) and melting enthalpy (Hm) are being determined in the second heating step.

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

The Charpy impact strength was measured according to ISO <NUM>1eU at +<NUM> using injection molded bar test specimens of 80x10x4 mm<NUM> prepared in accordance with EN ISO <NUM>-<NUM>.

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 optimized <NUM> extended temperature probehead at <NUM> using nitrogen gas for all pneumatics. Approximately <NUM> of material was dissolved in <NUM> of <NUM>,<NUM>-tetrachloroethane-d<NUM> (TCE-d<NUM>) along with chromium-(lll)-acetylacetonate (Cr(acac)<NUM>) resulting in a <NUM> solution of relaxation agent in solvent (<NPL>). 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 and quantitatively needed for accurate ethylene content quantification. Standard single-pulse excitation was employed without NOE, using an optimised tip angle, <NUM> recycle delay and a 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 were indirectly referenced to the central methylene group of the ethylene block (EEE) at <NUM> ppm using the chemical shift of the solvent. This approach allowed comparable referencing even when this structural unit was not present. Characteristic signals corresponding to the incorporation of ethylene were observed <NPL>).

With characteristic signals corresponding to <NUM>,<NUM> erythro regio defects observed (as described in <NPL>, in <NPL>, and in <NPL>) the correction for the influence of the regio defects on determined properties was required. Characteristic signals corresponding to other types of regio defects were not observed.

Number average molecular weight (Mn), weight average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) were determined by Gel Permeation Chromatography (GPC) according to ISO <NUM>-<NUM>:<NUM> and ASTM D <NUM>-<NUM>. A PolymerChar GPC instrument, equipped with infrared (IR) detector was used with <NUM> x 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>,<NUM>/mol to <NUM><NUM>/mol. Mark Houwink constants for PS, PE and PP used are as described per ASTM D <NUM>-<NUM>. All samples were prepared by dissolving <NUM> - <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 max. <NUM> under continuous gentle shaking in the autosampler of the GPC instrument.

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.

Fogging was measured according to DIN <NUM>:<NUM>-<NUM>, method B (gravimetric method) on compression-moulded specimens (diameter <NUM> +/- <NUM>, thickness < <NUM>) cut out from an injection-moulded plate. With this method, the mass of fogging condensate on aluminium foil in mg is determined by means of weighing of the foil before and after the fogging test. The term "fogging" refers to a fraction of volatile substances condensed on glass parts as e.g. the windscreen of a vehicle.

The average fibre 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 SiO<NUM> 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 under 2a) (<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 silution was added to a a stirred cake of MAO-silica support prepared as described above over <NUM> hour. The cake was allowed to stay for <NUM> hours, folled by drying under N<NUM> flow at <NUM> for <NUM> and additionaly 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 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 (<NUM> rpm) for <NUM>. Next <NUM> wt% solution of MAO in toluene (<NUM>) from Lanxess was added via <NUM> 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 MAO treated silica support 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 SiO2 was dried at <NUM> for <NUM> under nitrogen flow <NUM>/h, pressure <NUM> barg and then for <NUM> hours under vacuum (-<NUM> barg) with stirring at <NUM> rpm. MAO treated support was collected as a free-flowing white powder found to contain <NUM>% Al by weight.

In a nitrogen filled glovebox, a solution of MAO <NUM> (<NUM>% wt in toluene, AXION <NUM> CA Lanxess) in dry toluene (<NUM>) was added to an aliquot of metallocene complex as described above under 2b) (<NUM>, <NUM>µmol). The mixture was stirred for <NUM> minutes at room temperature. Next, the solution was slowly added to <NUM> of MAO treated silica prepared as described above, which was placed in a glass flask. The mixture was allowed to stay overnight, washed with <NUM> of toluene and was then subjected to vacuum drying for <NUM> hour to yield pink free-flowing powder to yield <NUM> of the catalyst as pink free flowing powder. The catalyst system <NUM> has an Al content of <NUM> wt%, a Zr content of <NUM> wt% and a molar Al/Zr ratio of <NUM> mol/mol.

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> 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> 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> 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:.

The inventive examples IE1 and IE2 and comparative examples CE1 and CE2 were prepared by compounding on a co-rotating twin-screw extruder (ZSK <NUM> from Coperion) with a mixing screw typical for glass fiber compounds and an L/D ratio of <NUM>. The following process parameters were used:.

The polypropylene and the additives different from the short glass fibers were fed to the extruder and melt-kneaded in the <NUM>nd barrel. A first kneading zone for mixing the polypropylene and the additives is located between the <NUM>rd and <NUM>th barrel. The short glass fibers were added in the <NUM>th barrel using a side feeder. A second kneading zone for glass fibre dispersion is located between the <NUM>th and <NUM>th barrel.

The composites and their properties are summarized in Table <NUM>.

As glass fibers the commercial product ECS03T-<NUM> of Nippon Electric Glass having an average fiber length of <NUM> and an average diameter of <NUM>.

The following combination of additives was used in compounding: <NUM> wt% of Tris (<NUM>,<NUM>-di-t-butylphenyl) phosphite (<NPL>, commercially available as Irgafos <NUM> from BASF AF, Germany), <NUM> wt% of Pentaerythrityl-tetrakis(<NUM>-(<NUM>',<NUM>'-di-tert. butyl-<NUM>-hydroxyphenyl)-propionate (<NPL>, commercially available as Irganox <NUM> from BASF AG, Germany) and <NUM> wt% of the carbon black masterbatch "Plasblak PPP6331" of Cabot Corporation, Germany.

Claim 1:
Fiber reinforced composite comprising
(a) <NUM> to <NUM> wt.-%, based on the fiber reinforced composite, of a polypropylene,
(b) <NUM> to <NUM> wt.-%, based on the fiber reinforced composite, of short glass fibers, having an average fiber length of <NUM> to <NUM> and
(c) <NUM> to <NUM> wt.-%, based on the fiber reinforced composite, of a compatibilizer,
wherein further
the total amount of the polypropylene, the short glass fibers and the compatibilizer in the fiber reinforced composite is at least <NUM> wt.-%,
wherein still further
the polypropylene has
(i) 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>,
(ii) a comonomer content determined by <NUM>C-NMR spectroscopy of not more than <NUM> wt.-%, the comonomer being ethylene,
(iii) a molecular weight distribution (MWD) determined by gel permeation chromatography (GPC) in the range of <NUM> to below <NUM>, and
(iv) <NUM>,<NUM> regio-defects determined by <NUM>C-NMR spectroscopy in the range of <NUM> to <NUM> %.