EA041396B1 - REINFORCED POLYPROPYLENE COMPOSITION - Google Patents

Description

The invention relates to a reinforced polypropylene composition containing a heterophasic polypropylene copolymer, a polar modified polypropylene and carbon fibers. Additionally, the present invention relates to an article containing a reinforced polypropylene composition.

Reinforced polymer compositions are widely used. However, in addition to the requirements for rigidity and impact resistance, low weight is also an important requirement for many automotive applications. In general, there are two possibilities to meet these requirements, namely, one is to reduce the density of the material, and the other is to increase the stiffness of the material. With regard to increasing stiffness, this can usually be achieved by adding fibers to the polymer as a reinforcing material. For example, glass fiber is widely used as a reinforcing material because of its good workability, excellent properties, and low cost. Carbon fibers are also well known as a reinforcing material due to their low density combined with high stiffness. However, the addition of fibers as a reinforcing material generally results in an overall increase in density, so that it is very difficult to obtain a sufficiently light weight material with well balanced mechanical properties.

Accordingly, there continues to be a need in the automotive industry for a composite material that meets the high demands of well balanced mechanical properties such as high stiffness and low weight impact strength.

The finding of the present invention is the use of a specific heterophasic propylene copolymer in combination with polar modified polypropylene and carbon fibers to improve the mechanical properties of the polypropylene composition.

In a first aspect, the present invention relates to a polypropylene (C) composition comprising:

(a) 55 to 95 parts by weight heterophasic propylene copolymer (HECO), wherein the heterophasic propylene copolymer (HECO) contains a polypropylene matrix (M) and an elastomeric copolymer (E) containing units derived from propylene and ethylene or C ₄ -C ₂₀ alpha-olefins or ethylene and C ₄ -C ₂₀ alpha-olefins;

(b) from 1.0 to 10 wt.h. polar modified polypropylene (PMP);

(c) 7.0 to 35 parts by weight carbon fibers (CF) based on the total weight of the parts of compounds (a), (b) and (c), while the intrinsic viscosity (IV) of the xylene cold soluble fraction (XCS) of the heterophasic propylene copolymer (HECO) is in the range of 3 .0 to 4.0 dl/g.

The polypropylene composition (C) may contain a heterophasic propylene copolymer (HECO) in an amount of at least 55 to 95 wt.% of the total weight of the polypropylene composition (C).

A heterophasic propylene copolymer (HECO) may have:

(a) MFR2 (230° C., 2.16 kg) melt flow rate, as measured according to ISO 1133, not more than 60 g/10 min.

The polypropylene composition (C) may contain polar modified polypropylene (PMP) in an amount of 1.0 to 10% by weight, preferably 2.5 to 10% by weight, based on the total weight of the polypropylene composition (C).

Polar modified polypropylene (PMP) may contain groups derived from polar groups selected from the group consisting of acid anhydrides, carboxylic acids, carboxylic acid derivatives, primary or secondary amines, hydroxyl compounds, oxazoline epoxides and ionic compounds.

Polar modified polypropylene (PMP) may be a propylene polymer grafted with maleic anhydride.

The polypropylene composition (C) may contain carbon fibers (CF) in an amount of at least 7.0 to 35% of the total weight of the polypropylene composition (C).

The heterophasic propylene copolymer (HECO) and the polar modified polypropylene (PMP) may be present in an amount of at least 57.5% by weight, preferably in an amount of at least 76% by weight, more preferably in an amount of at least 82% by weight, even more preferably in an amount of at least 89% by weight based on the total weight of the polypropylene composition (C).

Heterophasic propylene copolymer (HECO), polar modified polypropylene (PMP) and carbon fibers (CF) may be present in an amount of at least 60 wt.%, preferably in an amount of at least 81 wt.%, more preferably in an amount of at least 89 wt.%, even more preferably in an amount of at least 98 wt.% of the total weight of the polypropylene composition (C).

The polypropylene composition (C) may have:

tensile modulus, as measured according to ISO 527-2, of at least 2500 MPa; and/or (d) tensile strength to break, as measured according to ISO 527-2, of at least 25 MPa; and/or

- 1 041396 (e) Charlie cut strength, as measured according to ISO 179-1eU:2000 at 23° C., of at least 35 kJ/m ² ; and/or (f) an elongation at break, as measured according to ISO 527-2, of at least 6.0%.

(c) tensile modulus, as measured according to ISO 527-2, of at least 2500

MPa; and/or (d) tensile strength to break, as measured according to ISO 527-2, of at least 25 MPa; and/or (e) Charlie cut strength, as measured according to ISO 179-1eU:2000 at 23° C., of at least 35 kJ/m ² ; and/or (f) an elongation at break, as measured according to ISO 527-2, of at least 6.0%.

Preferably the polypropylene composition (C) does not contain any fibers other than carbon fibers (CF).

In a second aspect, the present invention relates to an article containing the polymer composition (C) according to the first aspect.

The article may be a cast article or an extruded article, preferably a cast article.

The product may be an automotive product, preferably an automotive exterior or interior product, such as technical brackets, shrouds, structural brackets, bumpers, footwell trim panels, running boards, body panels, spoilers, dashboards and interior trim products. salon.

Next, the polypropylene composition (C) and the article containing the polypropylene composition (C) will be described in more detail.

Polypropylene composition (C).

The present invention relates to a composition of polypropylene (C) containing heterophasic propylene copolymer (HECO), polar modified polypropylene (PMP) and carbon fibers (CF).

The polypropylene composition (C) may contain:

(a) heterophasic propylene copolymer (HECO) in the range of 55 to 95 parts by weight, preferably in the range of 73 to 92 parts by weight, more preferably in the range of 79 to 90 parts by weight; and/or (b) polar modified polypropylene (PMP) in the range from 1.0 to 10 parts by weight, preferably in the range from 2.5 to 10 parts by weight, more preferably in the range from 3.0 to 7, 0 wt.h., even more preferably in the range from 3.0 to 6.0 wt.h.; and/or (c) carbon fibers (CF) in the range from 2.5 to 35 wt.h., preferably in the range from 5.0 to 20 wt.h., more preferably in the range from 7.0 to 15 wt. hours;

based on the total weight of parts of heterophasic propylene copolymer (HECO), polar modified polypropylene (PMP) and carbon fibers (CF).

In one embodiment of the present invention, the polypropylene composition contains heterophasic propylene copolymer (HECO) in the range from 55 to 95 parts by weight, polar modified polypropylene (PMP) in the range from 1.0 to 10 parts by weight. and carbon fibers (CF) in the range of 2.5 to 35 parts by weight, based on the total weight of parts of heterophasic propylene copolymer (HECO), polar modified polypropylene (PMP) and carbon fibers (CF).

In one embodiment of the present invention, the polypropylene composition contains heterophasic propylene copolymer (HECO) in the range from 55 to 95 parts by weight, polar modified polypropylene (PMP) in the range from 2.5 to 10 parts by weight. and carbon fibers (CF) in the range of 2.5 to 35 parts by weight, based on the total weight of parts of heterophasic propylene copolymer (HECO), polar modified polypropylene (PMP) and carbon fibers (CF).

In one embodiment of the present invention, the polypropylene composition contains heterophasic propylene copolymer (HECO) in the range from 73 to 92 parts by weight, polar modified polypropylene (PMP) in the range from 3.0 to 7.0 parts by weight. and carbon fibers (CF) in the range of 2.5 to 35 parts by weight, based on the total weight of parts of heterophasic propylene copolymer (HECO), polar modified polypropylene (PMP) and carbon fibers (CF).

In one embodiment of the present invention, the polypropylene composition contains heterophasic propylene copolymer (HECO) in the range from 79 to 90 parts by weight, polar modified polypropylene (PMP) in the range from 3.0 to 6.0 parts by weight. and carbon fibers (CF) in the range of 5.0 to 20 parts by weight, based on the total weight of parts of heterophasic propylene copolymer (HECO), polar modified polypropylene (PMP) and carbon fibers (CF).

In one embodiment of the present invention, the polypropylene composition contains heterophasic propylene copolymer (HECO) in the range from 79 to 90 parts by weight, polar modified polypropylene (PMP) in the range from 3.0 to 6.0 parts by weight. and carbon fibers (CF) in the range from 7.0 to 15 wt.h. based on the total weight of parts of heterophasic propylene copolymer (HECO), polar modified polypropylene (PMP) and carbon fibers (CF).

- 2 041396

In one embodiment of the present invention, the polypropylene composition contains a heterophasic propylene copolymer (HECO) in the range from 55 to 95 wt.%, polar modified polypropylene (PMP) in the range from 1.0 to 10 wt.% and carbon fibers (CF) in the range from 2.5 to wt.% of the total weight of the polypropylene composition (C).

In one embodiment of the present invention, the polypropylene composition contains a heterophasic propylene copolymer (HECO) in the range from 55 to 95 wt.%, polar modified polypropylene (PMP) in the range from 2.5 to 10 wt.% and carbon fibers (CF) in the range from 2.5 to 35 wt.% of the total weight of the polypropylene composition (C).

In one embodiment of the present invention, the polypropylene composition contains heterophasic propylene copolymer (HECO) in the range from 73 to 92 wt.%, polar modified polypropylene (PMP) in the range from 3.0 to 7.0 wt.% and carbon fibers (CF) in the range from 2.5 to 35 wt.% of the total weight of the polypropylene composition (C).

In one embodiment of the present invention, the polypropylene composition contains heterophasic propylene copolymer (HECO) in the range from 79 to 90 wt.%, polar modified polypropylene (PMP) in the range from 3.0 to 6.0 wt.% and carbon fibers (CF) in the range from 5.0 to 20 wt.% of the total weight of the polypropylene composition (C).

In one embodiment of the present invention, the polypropylene composition contains heterophasic propylene copolymer (HECO) in the range from 79 to 90 wt.%, polar modified polypropylene (PMP) in the range from 3.0 to 6.0 wt.% and carbon fibers (CF) in the range from 7.0 to 15 wt.% of the total weight of the polypropylene composition (C).

It should be understood that the polypropylene composition (C) contains a heterophasic propylene copolymer (HECO) and a polar modified polypropylene (PMP) in an amount of at least 57.5 wt.%, preferably in an amount of at least 76 wt.%, more preferably in an amount of at least 82% by weight, even more preferably in an amount of at least 88% by weight, based on the total weight of the polypropylene composition (C).

Additionally, it should be understood that the composition of polypropylene (C) contains a heterophasic propylene copolymer (HECO) and polar modified polypropylene (PMP) and carbon fibers (CF) in an amount of at least 60 wt.%, preferably in an amount of at least 81 wt. %, more preferably in an amount of at least 89 wt.%, even more preferably in an amount of at least 98 wt.% of the total weight of the polypropylene composition (C).

The polypropylene composition (C) may have a melt flow rate MFR ₂ (230°C, 2.16 kg), as measured according to ISO 1133, not more than 25 g/10 min, preferably not more than 15 g/10 min, since in the range of 1.0 to 25 g/10 min, preferably in the range of 5.0 to 15 g/10 min, more preferably in the range of 7.0 to 12 g/10 min.

The polypropylene composition (C) may have a tensile modulus, as measured according to ISO 527-2, of at least 2500 MPa, preferably at least 3000 MPa, such as in the range of 2500 to 6500 MPa, preferably in the range of 3000 to 6000 MPa.

The polypropylene composition (C) may have a tensile strength to break, as measured according to ISO 527-2, of at least 25 MPa, preferably at least 30 MPa, such as in the range of 25 to 80 MPa, preferably in the range of 30 to 70 MPa.

The polypropylene composition (C) may have a Charlie cut impact strength, as measured according to ISO 179-1eU:2000, at 23°C of at least 35 kJ/m ² , preferably at least 40 kJ/m ² , such as in in the range from 35 to 80 kJ/m ² , preferably in the range from 40 to 60 kJ/m ² .

The polypropylene composition (C) may have an elongation at break, as measured according to ISO 527-2, of at least 6.0%, preferably at least 7.0%, as in the range of 6.0 to 20%, preferably ranging from 7.0 to 10%.

In one embodiment of the present invention, the polypropylene composition (C) has a melt flow rate MFR2 (230° C., 2.16 kg), as measured according to ISO 1133, ranging from 1.0 to 25 g/10 min, a tensile modulus , as measured according to ISO 527-2, ranging from 2500 to 6500 MPa, Charly impact strength, as measured according to ISO 179-1eU:2000 at 23°C, ranging from 35 to 80 kJ/m ² and elongation to break point, as measured according to ISO 527-2, ranging from 6.0 to 20%.

In one embodiment of the present invention, the polypropylene composition (C) has a melt flow rate MFR2 (230° C., 2.16 kg), as measured according to ISO 1133, ranging from 1.0 to 25 g/10 min, a tensile modulus , as measured according to ISO 527-2, ranging from 2500 to 6500 MPa, Charly impact strength, as measured according to ISO 179-1eU:2000 at 23°C, ranging from 40 to 60 kJ/m ² and elongation to break point, as measured according to ISO 527-2, ranging from 7.0 to 10%.

In one embodiment of the present invention, the polypropylene composition (C) has a melt flow rate MFR2 (230° C., 2.16 kg), as measured according to ISO 1133, ranging from 1.0 to 25 g/10 min, a tensile modulus , as measured according to ISO 527-2, ranging from 3000 to

- 3 041396

6000 MPa, Charlie cut impact strength as measured according to ISO 179-1eU:2000 at 23°C, ranging from 40 to 60 kJ/m ² and elongation at break, as measured according to ISO 527-2, within from 7.0 to 10%.

Preferably, the heterophasic propylene copolymer (HECO) is the only heterophasic propylene copolymer present in the polypropylene composition (C). In one embodiment of the present invention, the heterophasic propylene copolymer (HECO) is the only heterophasic propylene copolymer present in the polypropylene composition (C).

Preferably, the polar modified polypropylene (PMP) is the only polar modified polypropylene present in the polypropylene composition (C). In one embodiment of the present invention, the polar modified polypropylene (PMP) is the only polar modified polypropylene present in the polypropylene composition (C).

In a preferred embodiment of the present invention, the polypropylene composition (C) does not contain other polymers than heterophasic propylene copolymer (HECO) and polar modified polypropylene (PMP) in an amount exceeding 10% by weight, preferably in an amount exceeding 5% by weight, more preferably in an amount exceeding 2.5% by weight, even more preferably in an amount exceeding 0.8% by weight, based on the total weight of the polypropylene composition (C). In the case where an additional polymer is present, such polymer is a typical polymer carrier material (PCM) for additives.

Preferably heterophasic propylene copolymer (HECO) and polar modified polypropylene (PMP) are the only polymers present in the polypropylene (C) composition. In one embodiment of the present invention, heterophasic propylene copolymer (HECO) and polar modified polypropylene (PMP) are the only polymers present in the polypropylene (C) composition.

Preferably, carbon fibers (CF) are the only fibers present in the polypropylene (C) composition. In one embodiment of the present invention, the polypropylene composition (C) does not contain: fibers selected from the group consisting of glass fibers, metal fibers, mineral fibers, ceramic fibers and mixtures thereof. In one embodiment of the present invention, the polypropylene composition (C) does not contain: fibers derived from inorganic material.

Therefore, in a preferred embodiment of the present invention, the polypropylene composition (C) consists of a heterophasic propylene copolymer (HECO), polar modified polypropylene (PMP) and carbon fibers (CF). However, it should be understood that situations where additives (AD) are present are not excluded, as will be described below.

The polypropylene composition (C) can be obtained by melt blending. This method may include the steps of adding:

(a) a heterophasic propylene copolymer (HECO);

(b) polar modified polypropylene (PMP); and (c) carbon fibers (CF) into an extruder and extruding them to form said polypropylene composition (C).

The polymer composition (C) may be compounded and granulated using any of a variety of commonly known and used compounding and mixing devices and methods in the field of resin compounding. However, it is preferable to use compounding and mixing methods that do not adversely affect the spatial dimensions of the carbon fiber or the spatial dimensions of fibers other than carbon fibers.

Conventional compounding or mixing devices such as a Banbury mixer, 2-roll resin mixer, Buss mixer or twin screw extruder can be used to mix the individual components of the composition of the present invention. The polymeric materials exiting the extruder/mixer are generally in the form of granules. Further, these granules are preferably subjected to subsequent processing, for example, by injection molding, to obtain articles and products from the composition of the present invention.

Heterophasic propylene copolymer (HECO).

It should be understood that the polypropylene composition (C) must have well balanced mechanical properties, in particular high impact strength in combination with high elongation at break. In order to achieve these properties, the inclusion of a heterophasic propylene copolymer (HECO) is mandatory.

The heterophasic polypropylene (HECO) may have an MFR2 (230° C., 2.16 kg), as measured according to ISO 1133, ranging from not more than 60 g/10 min, preferably not more than 25 g/10 min, more preferably not more than than 15 g/10 min, such as in the range of 2.0 to 60 g/10 min, preferably in the range of 5.0 to 25 g/10 min, more preferably in the range of 7.0 to 14 g/10 min .

Heterophasic polypropylene (HECO) may have a total comonomer content of not more than 40

- 4 041396 mol.%, preferably not more than 30 mol.%, even more preferably not more than 25 mol.%, such as in the range from 5.0 to 40 mol.%, preferably in the range from 10 to 30 mol. %, more preferably in the range from 15 to 25 mol.%.

The heterophasic polypropylene (HECO) may have a xylene cold soluble fraction (XCS) content of not more than 55 wt.%, preferably not more than 45 wt.%, more preferably not more than 38 wt.%, such as in the range of 10 up to 55 wt.%, preferably in the range from 20 to 45 wt.%, more preferably in the range from 25 to 38 wt.% of the total mass of heterophasic polypropylene (HECO).

The heterophasic polypropylene (HECO) may have an intrinsic viscosity (IV) of the xylene cold soluble fraction (XCS) of not more than 4.0 dl/g, preferably not more than 3.5 dl/g, such as in the range of 2, 8 to 4.0 dl/g, preferably in the range of 3.0 to 3.5 dl/g.

The heterophasic polypropylene (HECO) may have a xylene cold soluble fraction (XCS) comonomer content of not more than 65 mol%, preferably not more than 60 mol%, more preferably not more than 50 mol%, such as within from 30 to 65 mol.%, preferably in the range from 35 to 60 wt.%, more preferably in the range from 45 to 50 mol.%.

The heterophasic propylene copolymer (HECO) contains, preferably consists of:

(a) polypropylene matrix (M); and (b) an elastomeric copolymer (E) containing units derived from propylene and ethylene and/or C ₄ -C ₂₀ alpha-olefin, more preferably from ethylene and/or C ₄ -C ₁₀ alpha-olefin and most preferably from ethylene , C ₄ , C ₆ and/or C ₈ alpha-olefin, eg ethylene and optionally units derived from conjugated dienes.

The heterophasic polypropylene (HECO) may have a propylene content of at least 60 mole %, preferably at least 70 mole %, such as in the range of 60 to 95 mole %, preferably in the range of 70 to 90 mole %. The rest is comonomer, i.e. C2 and/or C ₄ -C ₂₀ alpha olefin, more preferably ethylene. Therefore, the heterophasic propylene copolymer (HECO) contains comonomers, preferably ethylene and/or C ₄ -C ₁₂ α-olefin, more preferably ethylene, not more than 40 mol.%, preferably not more than 30 mol.%, such as in the range from 5.0 to 40 mol.%, preferably in the range from 10 to 30 mol.%, preferably in the range from 15 to 25 mol.%.

As described in the description of the present patent application, the heterophasic propylene copolymer (HECO) contains as polymer components only the polypropylene matrix (M) and the elastomeric copolymer (E).

In the present invention, the xylene cold insoluble (XCI) fraction of the heterophasic propylene copolymer (HECO) is the matrix (M) and optionally polyethylene, while the xylene cold soluble (XCS) fraction is the elastomeric portion of the heterophasic propylene copolymer (HECO), those. elastomeric copolymer (E).

Accordingly, the content of the matrix (M), i.e. the content of the cold xylene insoluble (XCI) fraction in the heterophasic propylene copolymer (HECO) is preferably in the range of 60 to 80 wt.%, more preferably in the range of 62 to 70 wt.% of the total mass of the heterophasic propylene copolymer (HECO ).

On the other hand, the content of the elastomeric copolymer (E), i. e. the content of the xylene cold soluble fraction (XCS) in the heterophasic propylene copolymer (HECO) is preferably in the range of 20 to 40 wt.%, more preferably 30 to 38 wt.% of the total weight of the heterophasic propylene copolymer (HECO).

The polypropylene matrix (M) may be a random propylene copolymer (RPP) or a propylene homopolymer (HPP), the latter being substantially preferred.

In the case where the polypropylene matrix (M) is a propylene homopolymer (HPP), the comonomer content of the polypropylene matrix (M) may be equal to or less than 1.0 wt.%, preferably equal to or less than 0.8 wt.%, more preferably equal to or less than 0.5 wt.%, such as not more than 0.2 wt.%, based on the total weight of the polypropylene matrix (M).

As used in the description of this patent application, the term propylene homopolymer refers to polypropylene, which essentially consists of, i. from more than 99.7 wt.%, even more preferably at least 99.8 wt.% propylene units based on the total mass of propylene homopolymer (HPP). In a preferred embodiment of the present invention, only propylene units are detected in the propylene homopolymer (HPP).

In the case where the polypropylene matrix (M) is a random propylene copolymer (RPP), it should be understood that the random propylene copolymer (RPP) contains monomers copolymerizable with propylene, for example comonomers such as ethylene and/or C4-C20alpha-olefin, in particular ethylene and/or C ₄ -C ₂₀ alpha-olefin, for example ethylene, C ₄ , C ₆ and/or C8 alpha-olefin. Preferably the random propylene copolymer (RPP) contains, essentially consists of monomers copolymerizable with propylene from the group consisting of ethylene, 1-butene and 1-hexene. In particular, the random propylene copolymer (RPP) of the present invention contains, in addition to units,

- 5 041396 derived from propylene, units derived from ethylene and/or 1-butene. In a preferred embodiment of the present invention, the random propylene copolymer (RPP) contains units derived from ethylene and propylene only.

It should be understood that the random propylene copolymer (RPP) preferably has a comonomer content in the range of 0.3 to 1.0 wt.%, more preferably in the range of 0.3 to 0.8 wt.%, even more preferably in the range of 0.3 to 0.7% by weight based on the total weight of the random propylene copolymer (RPP).

As used in the description of this patent application, the term random indicates that the comonomers of the random propylene copolymer (RPP) are randomly distributed in units derived from propylene. As used in the description of this patent application, the term random is preferably understood according to IUPAC (Glossary of basic terms in polymer science; IUPAC recommendations 1996).

As will be described below, heterophasic propylene copolymer (HECO) along with its individual components (matrix and elastomeric copolymer) can be obtained by blending different types of polymers. Preferably, however, the heterophasic propylene copolymer (HECO) along with its individual components (matrix and elastomeric copolymer) is produced using a sequential polymerization process using reactors in serial configuration and operating under different reaction conditions.

Additionally, it should be understood that the polypropylene matrix (M) of the heterophasic propylene copolymer (HECO) has a moderate melt flow rate MFR2 as defined according to ISO1133 at a load of 2.16 kg and at a temperature of 230°C. As stated above, the melt flow rate of MFR2 (230°C, 2.16 kg), as measured according to ISO1133, polypropylene matrix (M) is equal to the melt flow rate of MFR2 cold xylene insoluble fraction (XCI), heterophasic propylene copolymer (HECO) . Therefore, the xylene cold insoluble (XCI) fraction of the heterophasic propylene copolymer (HECO) is preferred, i.e. the polypropylene matrix (M) has a melt flow rate MFR2 (230° C., 2.16 kg), as measured according to ISO1133, in the range of 20.0 to 150.0 g/10 min, more preferably in the range of 25.0 to 110 g/10 min, even more preferably in the range of 30.0 to 100 g/10 min, and even more preferably 35.0 to 90 g/10 min.

Preferably the polypropylene matrix (M) is isotactic. Accordingly, it should be understood that the polypropylene matrix (M) has a rather high concentration of pentads, i.e. higher than 80%, preferably higher than 85%, more preferably higher than 90%, even more preferably higher than 92%, and even more preferably higher than 93%, such as higher than 95%.

The second component of the heterophasic propylene copolymer (HECO) is an elastomeric copolymer (E).

The elastomeric copolymer (E) contains, preferably consists of units derived from (i) propylene and (ii) ethylene, and/or at least another C ₄ -C ₂₀ α-olefin, such as C ₄ -C ₁₀ α -olefin, more preferably the units are derived from (i) propylene and (ii) ethylene, and at least another α-olefin selected from the group consisting of 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene. The elastomeric copolymer (E) may additionally contain units derived from non-conjugated dienes, however, it is preferred that the elastomeric copolymer (E) consists of units derived only from (i) propylene and (ii) ethylene, and/or C ₄ -C _2O α-olefins. Suitable non-conjugated dienes (dienes without conjugated double bonds), if used, include straight and branched acyclic dienes such as 1,4-hexadiene, 1,5-hexadiene, 1,6-octadiene, 5-methyl-1,4hexadiene, 3,7-dimethyl-1,6-octadiene, 3,7-dimethyl-1,7-octadiene and mixtures of dihydromyrcene and dihydroocymene isomers, and single ring acyclic dienes such as 1,4-cyclohexadiene, 1,5-cyclooctadiene , 1,5-cyclododecadiene, 4-vinylcyclohexene, 1-allyl-4-isopropylidenecyclohexane, 3-allyl-cyclopentene, 4-cyclohexene and 1-isopropenyl-4-(4-butenyl)cyclohexane.

In the present invention, the content of units derived from propylene in the elastomeric copolymer (E) is commensurate with the content of propylene determined in the xylene cold soluble fraction (XCS). Accordingly, the propylene determined in the xylene cold soluble fraction (XCS) is in the range from 50.0 to 75.0 wt.%, more preferably from 55.0 to 70.0 wt.%, and even more preferably from 58 0 to 67.0 wt.% of the total mass of the fraction soluble in cold xylene (XCS). Therefore, in a specific embodiment of the present invention, the elastomeric copolymer (E), i. cold xylene soluble fraction (XCS) contains 25.0 to 50.0 wt.%, preferably 30.0 to 45.0 wt.%, more preferably 33.0 to 42.0 wt.% units derived from ethylene and/or at least another C-Cf α-olefin. Preferably, the elastomeric copolymer (E) is ethylene-propylene-diene monomer non-conjugated rubber (EPDM) and/or ethylene-propylene rubber (EPR), the latter being substantially preferred, with a content of propylene and/or ethylene as indicated in this paragraph.

The polypropylene composition (C) preferably contains an alpha-nucleating agent. Even more preferably, the present invention is free of beta-nucleating agents. Nucleating agent

- 6 041396 is preferably selected from the group consisting of:

(i) salts of monocarboxylic acids and polycarboxylic acids, for example sodium benzoate or aluminum t-butyl benzoate; and (ii) dibenzylidene sorbitol (eg 1.3:2.4 dibenzylidene sorbitol) and C ₁ -C ₈ -alkyl-substituted dibenzylidene sorbitol derivatives such as methyldibenzylidene sorbitol, ethyldibenzylidene sorbitol or dimethyldibenzylidene sorbitol (eg 1.3:2.4 di(methylbenzylidene) sorbitol ), or nonit-substituted derivatives such as 1,2,3,-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene]nonite; and (iii) salts of diesters of phosphoric acid, for example sodium 2,2'-methylenebis (4,6,-di-tert-butylphenyl) phosphate or aluminum hydroxy-bis[2,2'-methylene-bis(4,6- di-1-butylphenyl)phosphate]; and (iv) a vinyl cycloalkane polymer and a vinyl alkane polymer (as described in more detail below); and (v) mixtures thereof.

Such additives and nucleating agents are generally commercially available and are described in, for example, Plastic Additives Handbook, 5th edition, 2001 of Hans Zweifel.

Most preferably, the alpha-nucleating agent is part of the heterophasic propylene copolymer (HECO) and hence the polypropylene composition (C). Accordingly, the content of the alpha-nucleating agent in the heterophasic propylene copolymer (HECO) is preferably up to 5.0% by weight based on the total weight of the heterophasic propylene copolymer (HECO). In a preferred embodiment of the present invention, the heterophasic propylene copolymer (HECO) contains not more than 3000 ppm, more preferably from 1 to 2000 ppm of an alpha-nucleating agent, in particular selected from the group consisting of dibenzylidene sorbitol (for example, 1.3: 2,4 dibenzylidene sorbitol), dibenzylidene sorbitol derivatives, preferably dimethyldibenzylidene sorbitol (e.g. 1,3:2,4 di(methylbenzylidene) sorbitol), or nonit-substituted derivatives such as 1,2,3-trideoxy-4,6:5,7- bis-O-[(4-propylphenyl)methylene]nonite, vinylcycloalkane polymer, vinylalkanopolymer, and mixtures thereof.

In a preferred embodiment of the present invention, the heterophasic propylene copolymer (HECO) and hence the polypropylene composition (C) contains a vinyl cycloalkane such as vinyl cyclohexane (VCH) polymer and/or a vinyl alkane polymer such as an alpha nucleating agent. Preferably, in this embodiment of the present invention, the heterophasic propylene copolymer (HECO) contains a vinylcycloalkane, such as vinylcyclohexane (VCH), polymer and/or a vinylalkane polymer, preferably vinylcyclohexane (VCH). Preferably, the vinylcycloalkane polymer is a vinylcyclohexane (VCH) polymer which is incorporated into a heterophasic propylene copolymer (HECO) and hence into a polypropylene (C) composition using BNT technology. More preferably, in this preferred embodiment of the present invention, the amount of vinylcycloalkane such as vinylcyclohexane (VCH) polymer and/or vinylalkane polymer, more preferably vinylcyclohexane (VCH) polymer in the heterophasic propylene copolymer (HECO) is not more than 500 ppm, more preferably 1 to 200 ppm, most preferably 5 to 100 ppm, and the amount of vinylcycloalkane such as vinylcyclohexane (VCH) polymer and/or vinylalkane polymer, more preferably vinylcyclohexane (VCH) polymer in the heterophasic propylene copolymer (HECO ) is not more than 500 ppm, more preferably 1 to 200 ppm, most preferably 5 to 100 ppm. Accordingly, therefore, preferably the polypropylene composition (C) contains no more than 500 ppm, more preferably 0.1 to 200 ppm, most preferably 0.2 to 100 ppm of vinylcycloalkane, such as vinylcyclohexane (VCH), polymer.

With regard to BNT technology, reference is made to international patent applications WO 99/24478, WO 99/24479 and in particular WO 00/68315. According to this technology, a catalyst system, preferably a Ziegler-Natta procatalyst, can be modified by polymerization with a vinyl compound in the presence of a catalyst system containing, in particular, a specific Ziegler-Natta procatalyst, an external donor and a co-catalyst, where the vinyl compound has the formula:

CH ₂ =CH-CHR ³ R ⁴ where R ³ and R ⁴ together form a 5- or 6-membered saturated, unsaturated or aromatic ring, or independently represent an alkyl group containing from 1 to 4 carbon atoms, and the modified catalyst is used for obtaining heterophasic polypropylene according to the present invention, i.e. heterophasic propylene copolymer (HECO). A polymerized vinyl compound may be used as the alpha nucleating agent. The weight ratio of vinyl compound to solid catalyst component in the catalyst modification step is preferably up to 5 (5:1), more preferably up to 3 (3:1), such as in the range of 0.5 (1:2) to 2 ( 2:1). The most preferred vinyl compound is vinylcyclohexane (VCH).

The nucleating agent can be introduced as a masterbatch. In this case, the masterbatch contains

7 041396 a nucleating agent which is preferably a polymeric nucleating agent, more preferably an alpha nucleating agent, most preferably a vinylcycloalkane such as a vinylcyclohexane (VCH) polymer and/or a vinylalkane polymer, preferably a vinylcyclohexane (VCH) polymer, as above or below, in an amount of not more than 500 ppm, more preferably from 1 to 200 ppm, and even more preferably from 5 to 100 ppm, based on the total weight of the masterbatch. In this embodiment of the present invention, more preferably, said masterbatch is present in an amount of no more than 10.0 wt.%, more preferably no more than 5.0 wt.%, and most preferably no more than 3.5 wt.% of the total amount of heterophasic propylene copolymer (HECO). Most preferably, the masterbatch contains, preferably consists of, a polymer that has undergone nucleation using BNT technology.

The heterophasic propylene copolymer (HECO) of the present invention is preferably produced using a sequential polymerization process, i.e. multi-stage method known from the technical field to which the present invention relates, where the appropriate matrix, i. a polypropylene matrix (M) is obtained using at least one slurry reactor and optionally at least one gas phase reactor, preferably one slurry reactor and one gas phase reactor, after which an elastomeric copolymer (E) is obtained using at least one gas phase reactor, preferably two gas phase reactors.

Namely, a heterophasic propylene copolymer (HECO) is obtained by obtaining a polypropylene matrix (M) using at least one reactor system, said system contains at least one reactor, by moving said polypropylene matrix (M) into a subsequent reactor system, said system contains at least one reactor where, in the presence of a polypropylene matrix (M), an elastomeric propylene copolymer (E) is obtained.

Therefore, each of the polymerization systems may comprise one or more conventional stirred slurry reactors and/or one or more gas phase reactors. Preferably the reactors used are selected from the group of loop and gas phase reactors and in particular at least one loop reactor and at least one gas phase reactor are used in the process. It is also possible to use several reactors of each type, for example one loop and two or three gas phase reactors, or two loop and one or two gas phase reactors, in series.

Preferably, the heterophasic propylene copolymer (HECO) process also comprises a prepolymerization with a selected catalyst system, as detailed below, comprising a Ziegler-Natta procatalyst, an external donor, and a cocatalyst.

In a preferred embodiment of the present invention, the prepolymerization is carried out as a bulk slurry polymerization in liquid propylene, i. the liquid phase mainly contains propylene with minor amounts of other reactants and optionally inert components dissolved therein.

Generally, the prepolymerization reaction is carried out at a temperature of 0 to 50°C, preferably 10 to 45°C, and more preferably 15 to 40°C.

The pressure in the prepolymerization reactor is not critical, but must be high enough to keep the reaction mixture in the liquid phase. Therefore, the pressure may be from 20 to 100 bar, for example 30 to 70 bar.

Preferably, all catalytic components are introduced at the prepolymerization stage. However, if the solid catalyst component (i) and the cocatalyst (ii) are supplied separately, it is possible to introduce only a part of the cocatalyst in the prepolymerization stage, and the rest is introduced in the subsequent polymerization stages. Also in such cases, it is necessary to introduce an amount of co-catalyst in the prepolymerization stage that is sufficient to carry out the polymerization reaction.

Other components can also be added at the prepolymerization stage. Therefore, hydrogen can be added to control the molar mass in the prepolymerization step using a method known in the art. Additionally, antistatic additives may be added to prevent the particles from adhering to each other or to the walls of the reactor.

Precise control of prepolymerization conditions and reaction parameters is within the skill of the art to which the present invention pertains.

A slurry reactor is any continuous or simple stirred batch reactor or loop reactor for bulk or slurry polymerization. Used in the description of the present patent application, the term polymerization in mass means polymerization in the reaction medium, including at least 60.0 wt.% monomer. In the present invention, the slurry reactor is preferably a circulating

- 8 041396 reactor for bulk polymerization.

As used in the description of this patent application, the term gas phase reactor refers to any mechanically stirred or fluidized bed reactor. Preferably, the gas phase reactor comprises a mechanically agitated fluidized bed reactor with a gas flow rate of at least 0.2 m/s.

As such, a preferred embodiment of the heterophasic propylene copolymer (HECO) of the present invention comprises carrying out the polymerization in a process comprising either a combination of one loop and one or two or three gas phase reactors, or a combination of two loop and one or two gas phase reactors.

A preferred multi-stage process is the slurry gas phase process such as developed by Borealis and known as Borstar® technology. Reference is made in this regard to EP 0887379 A1, WO 92/12182, WO 2004/000899, WO 2004/111095, WO 99/24478, WO 99/24479 and WO 00/68315. Links are entered in the description in full.

An additional suitable slurry gas phase process is the Spheripol® Basell process.

Preferably the heterophasic propylene copolymer (HECO) of the present invention is produced using a special Ziegler-Natta procatalyst in combination with a special external donor as detailed below, preferably using the Spheripol® process or the Borstar®-PP process.

Therefore, one of the preferred multi-stage processes may include the steps of obtaining a polypropylene matrix (M-1) in the presence of a selected catalyst system, such as, for example, described in detail below, containing a special Ziegler-Natta procatalyst (i), an external donor (iii) and a co-catalyst ( ii) in a slurry reactor such as a loop reactor;

transferring the product obtained in the slurry reactor, such as a loop reactor, to the first gas phase reactor;

obtaining a second part of the polypropylene matrix (M-2) in the presence of the first part of the polypropylene matrix (M-1) and in the presence of a catalyst system obtained from a slurry reactor, such as a loop reactor, to obtain a polypropylene matrix (M);

transferring the product obtained in the reactor from the first gas phase reactor to the second gas phase reactor, obtaining the first part of the elastomeric copolymer (E-1) in the presence of a polypropylene matrix (M) and a catalyst system obtained in the first gas phase reactor;

transferring the product obtained in the reactor from the second gas phase reactor to the third gas phase reactor, obtaining the second part of the elastomeric copolymer (E-2) in the presence of the polypropylene matrix (M), the first part of the elastomeric copolymer (E-1) and the catalytic system obtained in the second gas phase reactor , to obtain a heterophasic propylene copolymer (HECO);

recovery of heterophasic propylene copolymer (HECO).

As stated above, for the preferred slurry gas phase process, the following basic information on process conditions is given.

The temperature is preferably from 40 to 110°C, more preferably from 50 to 100°C, in particular from 60 to 90°C under pressure in the range from 5 to 80 bar, preferably from 10 to 60 bar with the optional addition of hydrogen to control molecular mass using the known method per se.

The reaction product of the slurry polymerization, which is preferably carried out in a loop reactor, is then transferred to the next gas phase reactor, where the temperature is from 50 to 130° C., more preferably from 60 to 100° C. under a pressure in the range from 5 to 50 bar, preferably from 8 up to 35 bar with the optional addition of hydrogen for molecular weight control using the known method per se.

If required, the polymerization can be carried out in a known manner under supercritical conditions in a slurry reactor such as a loop reactor and/or by condensation in a gas phase reactor.

According to the present invention, heterophasic polypropylene is obtained preferably using a multi-stage polymerization process as mentioned above, in the presence of a catalyst system containing as component (i) a Ziegler-Natta procatalyst containing a transesterification product of a lower alcohol and a phthalic ether.

The procatalyst used in the present invention is obtained:

a) reacting the spray adduct in crystallized or hardened emulsion form of MgCl ₂ and C1-C ₂ alcohol with TiCl ₄ ;

b) reacting the product from step a) with a dialkyl phthalate of formula (I)

- 9 041396

where R ¹ ' and R ² ' represent independently at least C5-alkyl, under conditions under which transesterification occurs between the specified C ₁ -C ₂ -alcohol and the specified dialkyl phthalate with formula (III) with the formation of an internal donor, c) washing the product steps b) and d) optionally reaction of the product of step c) with additional TiCl ₄ . The procatalyst is prepared as described, for example, in patent applications WO 87/07620, WO 92/19653, WO 92/19658 and EP 0491566, EP 591224 and EP 586390. The content of these documents is introduced here by reference in its entirety.

First, an adduct of MgCl ₂ and a C1-C ₂ alcohol is prepared with the formula MgCl ₂ *nROH, where R is methyl or ethyl and n is 1-6. The preferred alcohol used is ethanol.

The catalyst carrier used is an adduct which is first melted and then pulverized in crystallized or hardened emulsion form.

In the next step, the spray adduct in crystallized or hardened emulsion form with the formula MgCl ₂ *nROH, where R is methyl or ethyl, preferably ethyl, and n is 1-6, is contacted with TiCl ₄ to form a titanized carrier, followed by addition steps into the specified titanized carrier:

(i) a dialkyl phthalate of formula (III) with R ¹ ' and R ² ' independently representing at least C ₅ -alkyl, such as at least C ₅ -alkyl, or preferably (ii) a dialkyl phthalate of formula (III) with R ¹ ' and R ² ' independently representing at least C ₅ -alkyl, such as at least C ₅ -alkyl, or more preferably (iii) a dialkyl phthalate of formula (I) selected from the group consisting of propylhexyl phthalate (PrHP), di(ethylhexyl) phthalate (DOP), di-iso-decyl phthalate (DIDP) and ditridecyl phthalate (DTDP), even more preferably a dialkyl phthalate of formula (I) representing di(ethylhexyl) phthalate (DOP) or diisooctyl phthalate, in particular diethylhexyl phthalate, to obtain of the first product, subjecting said first product to suitable transesterification conditions, i.e. to a temperature above 100° C., preferably from 100 to 150° C., more preferably from 130 to 150° C., such that said methanol or ethanol is transesterified with said ether groups of said dialkyl phthalate of formula (I) to obtain preferably at least 80 mol%, more preferably at least 90 mol%, most preferably at least 95 mol% of the dialkyl phthalate of formula (II)

ABOUT

R1 (R)

R2

O where R ¹ and R ² is methyl or ethyl, preferably ethyl, the dialkyl phthalate of formula (IV) is an internal donor and the yield of said interesterified product as a precatalytic composition (component (i)).

The adduct having the formula MgCl ₂ *nROH where R is methyl or ethyl and n is 1-6 is melted in a preferred embodiment of the present invention and then the melt is preferably gas injected into the cooled diluent or cooled gas, thus crystallizing the adduct into a morphologically preferred form, such as described in WO 87/07620.

This crystallized adduct is preferably used as a catalyst support and is reacted with the procatalyst used in the present invention as described in WO 92/19658 and WO 92/19653.

Since the catalyst residue is removed by extraction, an adduct of the titanized support and an internal donor is obtained in which the group derived from the polyhydric alcohol ester is changed.

In the case of a sufficient amount, the titanium remains on the support and will act as the active element of the procatalyst.

Otherwise, the titanization is repeated after the above treatment to ensure sufficient titanium concentration and hence activity.

Preferably, the procatalyst used in the present invention contains at most 2.5 wt.% titanium, preferably at most 2.2 wt.%, and more preferably at most 2.0 wt.%. Preferably, the donor content is 4 to 12% by weight and more preferably 6 to 10% by weight.

More preferably, the procatalyst used in the present invention is prepared by using ethanol as the alcohol and di(ethylhexyl)phthalate (DOP) as the dialkyl phthalate of formula (I), yielding diethyl phthalate (DEP) as the internal donor compound.

In another embodiment of the present invention, the Ziegler-Natta procatalyst can be modified by polymerization with a vinyl compound in the presence of a catalyst system containing a special Ziegler-Natta procatalyst, an external donor, and a co-catalyst, where the vinyl compound has the formula

where R ³ and R ⁴ together form a 5- or 6-membered saturated, unsaturated or aromatic ring, or independently represent an alkyl group containing 1-4 carbon atoms, and a modified catalyst used to prepare the heterophasic polypropylene copolymer composition of the present invention. The polymerized vinyl compound can act as an α-nucleating agent. This modification, in particular, is used to obtain heterophasic polypropylene (HECO).

The modification of the control catalyst is carried out as described in international patent applications WO 99/24478, WO 99/24479, and in particular WO 00/68315, introduced here by reference in relation to the reaction conditions related to the modification of the catalyst, along with those related to polymerization reactions.

The catalyst system used to produce the heterophasic polypropylene of the present invention preferably contains, in addition to the Ziegler-Natta procatalyst, an organometallic cocatalyst as component (ii).

Accordingly, it is preferable to select a cocatalyst from the group consisting of trialkylaluminum such as triethylaluminum (TEA), triisobutylaluminum, dialkylaluminum chloride and alkylaluminum sesquichloride.

Component (iii) of the catalytic system used is an external donor represented by formula (IIIa) or (IIIb). Formula (IIIa):

where R ⁵ is a branched alkyl group with 3 to 12 carbon atoms, preferably a branched alkyl group having 3 to 6 carbon atoms, or a cycloalkyl having 4 to 12 carbon atoms, preferably a cycloalkyl having 5 to 8 carbon atoms.

It is substantially preferred that R ⁵ be selected from the group consisting of isopropyl, isobutyl, isopentyl, tert-butyl, tertamyl, neopentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and cycloheptyl.

Formula (IIIb):

where R ^x and R ^y may be the same or different and represent a hydrocarbon group with from 1 to 12 carbon atoms.

R ^x and R ^y may be independently selected from the group consisting of a linear aliphatic hydrocarbon group of 1 to 12 carbon atoms, a branched aliphatic hydrocarbon group of 1 to 12 carbon atoms, and a cyclic aliphatic hydrocarbon group of 1 to 12 carbon atoms. It is substantially preferred that R ^x and R ^y are independently selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, octyl, decanyl, isopropyl, isobutyl, isopentyl, t-butyl, t-tamyl, neopentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and cycloheptyl.

More preferably both R ^x and R ^y are the same, even more preferably both R ^x and R ^y are an ethyl group.

More preferably, the external donor of formula (Vb) is diethylaminotriethoxysilane.

Most preferably, the external donor is that of formula (IIIa), such as dicyclopentyldimethoxysilane [Si(OCH ₃ ) ₂ (cyclopentyl) ₂ ] or diisopropyl dimethoxy silane [Si(OCH ₃ ) ₂ (CH(CH ₃ ) ₂ ) ₂ ], preferably dicyclopentyldimethoxysilane [Si(OCH ₃ ) ₂ (cyclopentyl) ₂ ].

The polypropylene composition (C) may contain a heterophasic propylene copolymer (HECO) in an amount of from 55 to 95 parts by weight, preferably in an amount of from 73 to 92 parts by weight, more preferably in an amount of from 79 to 90 parts by weight, where parts by weight represent parts by total weight of parts of heterophasic propylene copolymer (HECO), polar modified polypropylene (PMP), and carbon fibers (CF).

In one embodiment of the present invention, the polypropylene composition (C) contains a heterophasic propylene copolymer (HECO) in an amount of from 55 to 95 parts by weight, where parts by weight represent parts by total weight of parts of heterophasic propylene copolymer (HECO), polar modified polypropylene ( PMP) and carbon fibers (CF).

In one embodiment of the present invention, the polypropylene composition (C) contains a heterophasic propylene copolymer (HECO) in an amount of from 79 to 90 parts by weight, where parts by weight represent parts by total weight of parts of the heterophasic propylene copolymer (HECO), polar modified polypropylene ( PMP) and carbon fibers (CF).

- 11 041396

The polypropylene composition may contain a heterophasic propylene copolymer (HECO) in an amount of at least 55 wt.%, preferably at least 73 wt.%, more preferably at least 79 wt.%, as in the range from 55 to 95 wt.% , preferably in the range from 73 to 92 wt.%, more preferably in the range from 79 to 90 wt.% of the total weight of the polypropylene composition (C).

In one embodiment of the present invention, the polypropylene composition (C) contains a heterophasic propylene copolymer (HECO) in an amount of from 55 to 95 wt.% of the total weight of the polypropylene composition (C).

In one embodiment of the present invention, the polypropylene composition (C) contains a heterophasic propylene copolymer (HECO) in an amount of from 79 to 90 wt.h. based on the total weight of the polypropylene composition (C).

Polar modified polypropylene (PMP).

In order to more easily achieve a more uniform dispersion of carbon fibers (CF) in polymeric components that act as a matrix for carbon fibers (CF) in the polypropylene composition (C), polar modified polypropylene (PMP) is used as a binding agent.

Polar modified polypropylene (PMP) is preferably a polypropylene containing polar groups.

In the following, polypropylene will be described in more detail, which will then be modified to polar modified polypropylene (PMP).

The polypropylene is preferably a propylene homopolymer or a random propylene copolymer such as a copolymer of (i) propylene and (ii) ethylene and/or C ₄ -C ₁₂ α-olefins, preferably (i) propylene and (ii) an α-olefin selected from the group , consisting of ethylene, 1-butene, 1-hexene, 1-octene and mixtures thereof, preferably only ethylene.

In one embodiment of the present invention, the polar modified polypropylene (PMP) is a modified random propylene copolymer, wherein said random propylene copolymer contains ethylene as the only comonomer unit.

With respect to the term random propylene copolymer used in the description of this patent application, reference is made to the above information regarding the description of heterophasic propylene copolymer (HECO).

Preferably, the units derived from propylene constitute the bulk of the random propylene copolymer, i. e. at least 90.0 wt.%, more preferably in the range from 92.0 to 99.5 wt.%, even more preferably from 92.5 to 98.0 wt.%, and even more preferably from 93.0 to 96 0 wt% based on the total weight of the random propylene copolymer. Accordingly, the number of units derived from ethylene and/or C ₄ -C ₁₂ a-olefins, preferably derived from ethylene, in the random propylene copolymer is at most 10 wt.%, more preferably in the range from 0.5 to 8.0 wt. %, even more preferably in the range from 2.0 to 7.5 wt.% and even more preferably in the range from 4.0 to 7.0 wt.%, based on the total mass of the random propylene copolymer.

As such, it should be understood that the random propylene copolymer contains only units derived from propylene and ethylene. The amounts of comonomer given in this paragraph preferably refer to a random propylene copolymer which is not modified.

It should be understood that the random propylene copolymer, i. unmodified random propylene copolymer has a melting point Tm in the range of 125 to 140°C, more preferably in the range of 128 to 138°C and most preferably in the range of 131 to 136°C. The melting point given in this paragraph is the melting point of the unmodified random propylene copolymer.

It should be understood that the random propylene copolymer, i. unmodified random propylene copolymer, has a melt flow rate MFR2 (230°C), as measured according to ISO 1133, in the range of 1 to 30 g/10 min, preferably in the range of 1 to 20 g/10 min, more preferably in the range from 1 to 10 g/10 min and most preferably in the range from 2 to 6 g/10 min.

It should be understood that polar modified polypropylene (PMP) contains groups derived from polar groups. In this context, preference is given to modified polypropylene (PMP) containing groups derived 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, as well as ionic compounds.

Specific examples of said polar compounds are unsaturated cyclic anhydrides and their aliphatic diesters and diacid derivatives. In particular, maleic anhydride and compounds selected from Ο ₁ -Ο ₁₀ linear and branched dialkyl maleicates, Ci-Ci linear and branched dialkyl fumarates, itaconic anhydride, СрСш linear and branched esters of itaconic acid and dialkyl, maleic acid, fumaric acid, itaconic acid and mixtures thereof.

Regarding the structure, the polar modified polypropylene (PMP) is preferably selected from graph or block copolymers, preferably the above polypropylene, such as the above random propylene copolymer.

Preferably polar modified polypropylene (PMP), i.e. the binder is a polypropylene such as a random propylene copolymer. As mentioned above in the part of polar modified propylene (PMP) as a coupling agent grafted with such a polar group.

As such, preference is given to using a polypropylene such as a random propylene copolymer as described above in the Polar Modified Propylene (PMP) section grafted with maleic anhydride as the Polar Modified Polypropylene (PMP), i.e. bonding agent.

In one embodiment of the present invention, the polar modified polypropylene (PMP) is a random copolymer of propylene, as defined above, grafted with maleic anhydride. Therefore, in one particular preferred embodiment of the present invention, the polar modified polypropylene (PMP) is a random propylene-ethylene copolymer grafted with maleic anhydride, more preferably in which the ethylene content of the total amount of random propylene-ethylene copolymer is in the range from 2.0 to 7 .5 wt.%, more preferably in the range from 4.0 to 7.0 wt.%.

It should be understood that in order to achieve a desired dispersion of carbon fibers (CF) in polymer components, ensuring that the polymer composition (C) provides well-balanced mechanical properties, in particular high impact strength in combination with high elongation at break at low density, polar modified polypropylene (PMP) contains a number of groups derived from polar groups that is higher than that typically used in polar modified polypropylenes considered for the role of polypropylenes.

The polar modified polypropylene (PMP) may contain groups derived from polar groups in the range of 0.5 to 5.0% by weight, preferably in the range of 1.0 to 4.0% by weight, more preferably in the range of 1, 5 to 3.0 wt.%, even more preferably in the range from 1.7 to 2.3 wt.% of the total weight of the polar modified polypropylene (PMP).

Polar modified polypropylene (PMP) may have a melt space velocity MVI (170° C.; 1.2 kg) as measured according to ISO 1133 in the range of 20 to 150 cm ³ /10 min, preferably in the range of 40 to 100 cm ³ /10 min.

In one embodiment of the present invention, the polar modified polypropylene (PMP) is a random propylene-ethylene copolymer grafted with maleic anhydride, with an ethylene content of the total amount of random propylene-ethylene copolymer ranging from 2.0 to 7.5 wt.%, with groups obtained from polar groups, ranging from 0.5 to 5.0 wt.% and volume flow rate of the melt MVI (170°C; 1.2 kg), as measured according to ISO 1133, ranging from 20 to 150 cm ³ /10 min.

In one embodiment of the present invention, the polar modified polypropylene (PMP) is a random propylene-ethylene copolymer grafted with maleic anhydride, with an ethylene content of the total amount of random propylene-ethylene copolymer ranging from 2.0 to 3.0 wt.%, with groups obtained from polar groups, ranging from 1.5 to 3.0 wt.% and volume flow rate of the melt MVI (170°C; 1.2 kg), as measured according to ISO 1133, ranging from 40 to 100 cm ³ /10 min.

In one embodiment of the present invention, the polar modified polypropylene (PMP) is a random propylene-ethylene copolymer grafted with maleic anhydride, with an ethylene content of the total amount of random propylene-ethylene copolymer ranging from 2.0 to 2.8 wt.%, with groups, obtained from polar groups, ranging from 1.7 to 2.3 wt.% and volume flow rate of the melt MVI (170°C; 1.2 kg), as measured according to ISO 1133, ranging from 40 to 100 cm ³ / 10 min.

Additionally or alternatively, it should be understood that polar modified polypropylene (PMP) preferably has a melting point Tm in the range of 120 to 150°C, more preferably in the range of 125 to 145°C and most preferably in the range of 130 to 140° WITH.

Polar modified polypropylene (PMP) can be obtained using a simple two-stage grafting process, including a solid stage as the first stage and a melt stage as the second stage. Such process steps are well known in the art to which the present invention pertains.

- 13 041396

Polar modified polypropylene (PMP) is known in the art to which the present invention pertains and is commercially available. A suitable example is SCONA TSPP

10213GB BYK.

The polypropylene composition (C) may contain polar modified polypropylene (PMP) in the range from 1.0 to 10 parts by weight, preferably in the range from 2.5 to 10 parts by weight, more preferably in the range from 3.0 to 7 0 parts by weight, more preferably in the range of 3.0 to 6.0 parts by weight, based on the total weight of parts of heterophasic propylene copolymer (HECO), polar modified polypropylene (PMP) and carbon fibers (CF).

In one embodiment of the present invention, the polypropylene composition (C) contains polar modified polypropylene (PMP) in the range from 1.0 to 10 wt.h. based on the total weight of parts of heterophasic propylene copolymer (HECO), polar modified polypropylene (PMP) and carbon fibers (CF).

In one embodiment of the present invention, the polypropylene composition (C) contains polar modified polypropylene (PMP) in the range from 2.5 to 10 wt.h. based on the total weight of parts of heterophasic propylene copolymer (HECO), polar modified polypropylene (PMP) and carbon fibers (CF).

In one embodiment of the present invention, the polypropylene composition (C) contains polar modified polypropylene (PMP) in the range from 3.0 to 6.0 wt.h. based on the total weight of parts of heterophasic propylene copolymer (HECO), polar modified polypropylene (PMP) and carbon fibers (CF).

The polypropylene composition may contain polar modified polypropylene (PMP) in an amount of at least 1.0 wt.%, preferably at least 2.5 wt.%, more preferably at least 3.0 wt.%, such as an amount in the range from 1.0 to 10 wt.%, preferably in the range from 2.5 to 10 wt.%, more preferably in the range from 3.0 to 7.0 wt.% of the total weight of the polypropylene composition (C).

In one embodiment of the present invention, the polypropylene composition (C) contains polar modified polypropylene (PMP) in the range from 1.0 to 10 wt.% of the total weight of the polypropylene composition (C).

In one embodiment of the present invention, the polypropylene composition (C) contains polar modified polypropylene (PMP) in the range from 2.5 to 10 wt.% of the total weight of the polypropylene composition (C).

In one embodiment of the present invention, the polypropylene composition (C) contains polar modified polypropylene (PMP) in the range from 3.0 to 6.0 wt.h. based on the total weight of the polypropylene composition (C).

Preferably, the polar modified polypropylene (PMP) is the only polar modified polypropylene present in the polypropylene composition (C). In one embodiment of the present invention, the polar modified polypropylene (PMP) is the only polar modified polypropylene present in the polypropylene composition (C).

Carbon fibers (CF).

It should be understood that the polypropylene composition (C) must have well balanced mechanical properties, in particular high impact strength in combination with high elongation at break. To achieve these properties, the inclusion of carbon fibers (CF) is a must.

The carbon fibers (CF) may have an average diameter in the range of 2 to 30 dm, preferably in the range of 3 to 25 dm, more preferably in the range of 5 to 20 dm.

Carbon fibers (CF) may have a density in the range of 1.0 to 2.5 g/cm ³ , preferably in the range of 1.5 to 2.3 g/cm ³ , more preferably in the range of 1.7 to 2, 0 g/ ^cm3 .

It should be noted that carbon is not considered as a polymeric material. Additionally, carbon fibers (CF) are not considered to be covered by the term additives (AD), as described in more detail below.

The carbon fibers (CF) may be in the form of a non-woven fabric. The non-woven fabric preferably contains at least 50 wt.% carbon fibers (CF), more preferably at least 65 wt.% carbon fibers, even more preferably at least 75 wt.% carbon fibers (CF), and most preferably at least 80 wt.% of the total weight of the non-woven fabric.

The nonwoven fabric of the present invention may contain polymeric compounds such as sizing agents and/or sewing threads. It should be understood that sizing agents and/or sewing threads are not contained in an amount exceeding 10 wt.%, preferably 7.5 wt.% even more preferably 3 wt.% of the total weight of carbon fiber (CF). Sizing agents and/or sewing threads are considered to be within the scope of the term carbon fiber (CF) and are not an additional polymeric compound.

- 14 041396

When present, the amount of sewing thread is normally in the range of 0.25 to wt.%, preferably in the range of 0.5 to 7.5 wt.%, and most preferably in the range of 1.0 to 3.0 wt.% of the total weight of the nonwoven fabric. Suitable sewing threads are, for example, polyester fibres. As stated above, sewing threads are considered to be covered by the term carbon fiber (CF) and are not an additional polymeric compound.

When present, the amount of sizing agent is generally in the range of 0.25 to 15% by weight, preferably 0.5 to 10% by weight, more preferably 1.0 to 7.5% by weight. from the total mass of carbon fibers (CF). Suitable sizing agents are, for example, epoxy resins, ether polymer modified epoxy resins, polyurethane, aminosilane grafted polypropylene. As stated above, sizing agents are considered to be covered by the term carbon fiber (CF) and are not an additional polymer compound.

It should be understood that the nonwoven web may be a recyclable material, which may contain additional compounds in addition to carbon fibers, such as minor amounts of glass fibers, depending on the first application. These additional connections are considered as covered by the term carbon fiber (CF) are not an additional connection, in particular are not additional polymeric compounds and/or fiber compounds.

It should be understood that these additional compounds, such as glass fibers, are not contained in an amount exceeding 10 wt.%, preferably 5 wt.%, even more preferably 3 wt.% of the total weight of carbon fiber (CF). In one embodiment of the present invention, the carbon fiber (CF) does not contain glass fiber in an amount greater than 5 wt.% of the total weight of carbon fiber (CF). In one embodiment of the present invention, the carbon fiber (CF) does not contain glass fibers.

In the case where the carbon fibers (CF) are in the form of a non-woven fabric, the non-woven fabric is preferably in the form of a strip.

As a rule, the strip width is not more than 300 mm. Preferably the strip has a width of 10 to 300 mm, preferably a width of 25 to 250 mm and most preferably a width of 40 to 200 mm. Additionally or alternatively, the strip preferably has a length of at least 50 cm, more preferably at least 150 cm, and most preferably at least 250 cm.

The strip may be in the form of a roll. Therefore, the length is essentially not limited. However, the length is not substantially limited, i. e. the strip may represent the so-called endless strip.

The average weight of the nonwoven fabric is preferably in the range of 100 to 1000 g/m ² , more preferably in the range of 150 to 800 g/m ² , and most preferably in the range of 250 to 650 g/m ² .

The nonwoven fabric is further characterized by a constant weight per unit area. Therefore, the difference in weight between two parts of the nonwoven fabric having the same area, expressed as the quotient of the part having a higher mass to the part having a lower mass, is preferably within 10%, more preferably within 5%.

The preparation of a carbon fiber (CF) nonwoven web, such as rovings, or recyclable material, which may be in the form of a spun web, is well known in the art to which the present invention pertains. A suitable method is, for example, needle-punched.

Preferably, the nonwoven fabric is based on the formulation shown in Table 1. 2 in the form of a non-woven web, preferably needle-punched.

The polypropylene composition (C) may contain carbon fibers (CF) in an amount of 2.5 to 35 parts by weight, preferably in an amount of 5.0 to 20 parts by weight, more preferably in the range of 7.0 to 15 parts by weight. .h., even more preferably in the range from 8.5 to 12.5 wt.h., where parts by weight represent the total weight of parts of heterophasic propylene copolymer (HECO), polar modified polypropylene (PMP) and carbon fibers (CF) .

In one embodiment of the present invention, the composition of polypropylene (C) contains carbon fibers (CF) in the range from 2.5 to 35 parts by weight, where parts by weight are based on the total weight of parts of heterophasic propylene copolymer (HECO), polar modified polypropylene ( PMP) and carbon fibers (CF).

In one embodiment of the present invention, the composition of polypropylene (C) contains carbon fibers (CF) in the range from 8.5 to 12.5 parts by weight, where parts by weight represent the total weight of parts of heterophasic propylene copolymer (HECO), polar modified polypropylene (PMP) and carbon fibers (CF).

The polypropylene composition may contain carbon fibers (CF) in an amount of at least 2.5 wt.%, preferably at least 5.0 wt.%, more preferably at least

- 15 041396

7.0 wt.%, even more preferably at least 8.5 wt.%, since the amount is in the range from 2.5 to 35 wt.%, preferably in the range from 5.0 to 20 wt.%, even more preferably within

7.0 to 15.0 wt.% and even more preferably in the range from 8.5 to 12.5 wt.% of the total weight of the polypropylene (C) composition.

In one embodiment of the present invention, the polypropylene composition (C) contains carbon fibers (CF) in the range from 2.5 to 35 wt.% of the total weight of the polypropylene composition (C).

In one embodiment of the present invention, the polypropylene composition (C) contains carbon fibers (CF) in the range from 8.5 to 12.5 wt.h. based on the total weight of the polypropylene composition (C).

Preferably, carbon fibers (CF) are the only fibers present in the polypropylene (C) composition.

In one embodiment of the present invention, the polypropylene composition (C) does not contain fibers selected from the group consisting of glass fibers, metal fibers, mineral fibers, ceramic fibers and mixtures thereof.

In one embodiment of the present invention, the polypropylene composition (C) does not contain fibers derived from inorganic material.

Additives (AD).

In addition to heterophasic propylene copolymer (HECO), polar modified polypropylene (PMP) and carbon fibers (CF), the polypropylene composition (C) may contain additives (AD).

Typical additives are acid scavengers, antioxidants, colorants, light stabilizers, plasticizers, slip agents, scratch resistance agents, dispersants, processing aids, lubricants, pigments, and the like.

Such additives are commercially available and are described in, for example, Plastic Additives Handbook, 6th edition 2009 of Hans Zweifel (pp. 1141-1190).

As indicated above, the term additives (AD) used in the description of this patent application does not include fibers such as carbon fibers, glass fibers, metal fibers, mineral fibers and ceramic fibers. In other words, carbon fibers (CF) are not considered as an additive.

However, as used in the description of this patent application, the term additives (AD) also includes carrier materials, in particular polymeric carrier materials (PCM).

The polypropylene composition (C) may contain additives (AD) in an amount of up to 10 wt.%, preferably in the range from 0.01 to 10 wt.%, more preferably in the range from 0.05 to 5 wt.%, even more preferably in the range from 0.1 to 2.5 wt.% of the total weight of the polypropylene composition (C).

The polypropylene composition (C) may contain additives selected from antioxidants, acid scavengers, anti-scratch agents, release agents, lubricants, UV stabilizers, and mixtures thereof.

Additives (AD) may be included in the polypropylene composition (C) as a separate ingredient. Alternatively, additives (AD) may be included in the polypropylene composition (C) along with at least one other component. For example, additives (AD) can be added to polymer composition (C) along with heterophasic propylene copolymer (HECO), polar modified polypropylene (PMP) and/or carbon fibers (CF), preferably in the form of a masterbatch (MB). Therefore, the terms heterophasic propylene copolymer (HECO), polar modified polypropylene (PMP) and carbon fibers (CF) used in the description of this patent application may refer to a composition including additives (AD). Additives other than polymeric carrier materials (PCM) are normally added to the polypropylene composition (C) along with polymeric carrier materials (PCM) in the form of a masterbatch (MB).

Therefore, the composition of polypropylene (C), consisting of a heterophasic propylene copolymer (HECO), polar modified polypropylene (PMP) and carbon fibers (CF), may also contain additives (AD).

Polymer carrier material (PCM).

As stated above, in a preferred embodiment of the present invention, the polypropylene composition (C) does not contain other polymers than heterophasic propylene copolymer (HECO) and polar modified polypropylene (PMP) in an amount exceeding 10 wt.%, preferably in an amount exceeding 5 wt. %, more preferably in an amount exceeding 2.5 wt.%, even more preferably in an amount exceeding 0.8 wt.%, based on the total weight of the polypropylene composition (C). In the case where an additional polymer is present, such polymer is a typical polymer carrier material (PCM) for additives.

The polymeric carrier material (PCM) is a polymeric carrier to ensure uniform distribution in the composition (C) of the present invention. Polymer material - 16 041396 carrier (PCM) is not limited to a specific polymer. The polymeric carrier material (PCM) may be an ethylene homopolymer, an ethylene copolymer derived from ethylene and an α-olefin comonomer such as an ΟΛΑ α-olefin comonomer, a propylene homopolymer and/or a propylene copolymer derived from propylene and an α-olefin comonomer such as as ethylene and/or comonomer C _G C8 of the α-olefin.

As a rule, the polymer carrier material (PCM) as such does not improve the properties of the described polypropylene composition (C).

Product.

Additionally, the present invention relates to an article containing a composition of polypropylene (C).

The product may contain a polypropylene composition in an amount of at least 80 wt.%, such as 80 to 99.9 wt.%, preferably in an amount of at least 90 wt.%, such as from 90 to 99.9 wt.%, more preferably in an amount of at least 95 wt.%, such as from 95 to 99.9 wt.%.

The product may be a cast product or an extruded product, preferably the product is a molded product such as an injection molded product or an injection molded product.

In a preferred embodiment of the present invention, the product is an automotive product, in particular an automotive exterior or interior product, such as technical brackets, shrouds, structural brackets, bumpers, footwell trim panels, running boards, body panels, spoilers, instrument clusters. panels, products for interior trim and the like.

Examples

1. Definitions/Measurement methods.

For the above description of the present invention, unless expressly stated otherwise, the following definitions of terms and methods of measurement apply along with the examples below.

Quantitative analysis of the polymer microstructure using NMR spectroscopy.

Quantitative nuclear magnetic resonance (NMR) spectroscopy was used to evaluate the isotacticity and regioregularity of polypropylene homopolymers.

^13C {1H}NMR quantitation was recorded in solution using a Bruker Advance III 400 NMR spectrometer operating at frequencies ranging from 400.15 to 100.62 MHz for 1H and ^13C , respectively. The entire spectrum was recorded using ^{a 13°} C. optimized 10 mm linear transducer over an extended temperature range at 125° C. using nitrogen gas throughout the pneumatics.

For propylene homopolymers, about 200 mg of material was dissolved in 3 ml of 1,2-tetrachloroethane-d ₂ (TCE-d ₂ ). To ensure the homogeneity of the solution after obtaining the initial sample in the thermoblock, the NMR ampoule was additionally heated in a rotary hearth furnace for at least 1 hour. When mounted in a magnet, the ampoule was subjected to 10 Hz. This scheme was chosen primarily because of the need for high resolution quantitation to accurately quantify the regularity of the molecular structure (Busico, V., Cipullo, R., Prog. Polym. Sci. 26 (2001) 443; Busico, V.; Cipullo, R., Monaco, G., Vacatello, M., Segre, AL, Macromolecules 30 (1997) 6251). Created a standard single-pulse excitation without NOE at an optimized tilt angle with a 1-second recycle delay and a two-level WALTZ 16 decoupling circuit (Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh, D. Winniford, B., J. Mag. Reson 187 (2007) 225 Busico, V., Carbonniere, P., Cipullo, R., Pellecchia, R., Severn, J. , Talarico, G., Macromol Rapid Commun. 2007, 28, 11289). In total, the spectrum required 8192 (8k) pulses.

Conducted a quantitative analysis based on ¹³ C{1H}NMR spectrum with a certain average value and determined the corresponding quantitative values using the integral using special computer programs.

For propylene homopolymers, all chemical shifts essentially indicate a methyl isotactic pentad (mmmm) at 21.85 ppm.

Signals corresponding to regiodefects or comonomers have been observed (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253; Wang, W-J., Zhu, S., Macromolecules 33 (2000), 1157; Cheng, H. N., Macromolecules 17 (1984), 1950).

The regularity of the distribution of the molecular structure is quantified by integration of the methyl region within 23.6-19.7 ppm, corrected for any regions not associated with the stereosequence of interest (Busico, V., Cipullo, R., Prog. Polym. Sci. 26 (2001) 443; Busico, V., Cipullo, R., Monaco, G., Vacatello, M., Segre, A.L., Macromolecules 30 (1997) 6251).

In particular, the effect of regiodefects and comonomer on the quantitative analysis of the regularity of the distribution of molecular structure is corrected by subtracting the integrals of the representative regiodefect and comonomer from the specific region of the stereosequence integral.

Isotacticity was determined by the level of pentads and indicated as the percentage of sequences of isotactic pentads (mmm) of the sequences of all pentads:

[mmmm] % = 100 * (mmmm / sum of all pentads).

The presence of 2.1 erythroregiodefects is indicated by the presence of two metal patches at 17.7 and 17.2 ppm and is confirmed by other characteristic patches. No characteristic signals corresponding to other types of regiodefects were observed (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253).

A quantitative analysis of 2.1 erythroregiodefects was performed using the average integral of two characteristic methyl sites of 17.7 and 17.2 ppm:

P21e ⁼ (Ie6 + Ies) / 2

Quantitative analysis of 1,2 initially inserted propene is carried out based on the methyl region, corrected for the neglected sites included in this region, not associated with the primary insertion, and the primary insertion sites excluded from this region:

P12 \u003d 1cNC + P12e

The total amount of propene is quantified as the sum of the initially inserted propene and all other regiodefects present:

Рtotal = Р12 + ₽21e

Total - general / general.

The molar percentage of 2.1 erythrioregio defects is quantified from the total propene content:

[21e] mol.% = 100 * (P ₂ i _e / Ptotal).

The characteristic signals corresponding to the introduction of ethylene were observed (as indicated in Cheng, H.N., Macromolecules 1984, 17, 1950) and the comonomer fraction was calculated as the fraction of ethylene in the polymer relative to all monomers in the polymer.

The comonomer fraction was quantified using the WJ method. Wang and S. Zhu, Macromolecules 2000, 33 1157 by integrating multiple signals across the ¹³ C{1H} spectral region. This method was chosen for its accuracy, reliability and ability to explain the presence of regiodefects, if necessary. The integral regions were slightly adjusted to improve applicability to a wide range of comonomer content.

The mole percentage of comonomer introduced was calculated from the molar fraction.

The weight percentage of comonomer introduced was calculated from the molar fraction.

Cold xylene soluble fraction (XCS) was determined at 25 °C according to ISO 16152; first edition; 2005-07-01.

Intrinsic viscosity was measured according to DIN ISO 1628/1, October 1999 (in decalin at 135°C).

Tensile modulus was measured according to ISO 527-2 (crawl speed = 1 mm/min; 23° C.) using injection molded specimens as described in EN ISO 1873-2 (dog bone shape, 4 mm thick).

Tensile strength to break; Elongation at break is measured according to ISO 5272 (slider speed = 50 mm/min; 23° C.) using injection molded specimens as described in EN ISO 1873-2 (dog bone shape, 4 mm thick).

Charlie notched impact strength is determined according to ISO 179 1eU at 23° C. using an 80 x 10 x 4 mm ³ injection molded test piece prepared according to EN ISO 1873-2.

The average fiber diameter is determined according to ISO 1888:2006(E), Method B, microscope resolution 1000.

The melt flow rate (MFR2) is measured according to ISO 1133 at a given temperature and load.

The melt volume flow rate (MVI) is measured according to ISO 1133 at a given temperature and load.

Density is measured according to ISO 1183-187. Samples are obtained by compression molding according to ISO 1872-2:2007.

Differential scanning calorimetry (DSC analysis), when using differential scanning calorimetry (DSC) measured the melting point (T _{m ), and the enthalpy of melting (H m )} , the crystallization temperature (T _c ), the enthalpy of crystallization (H _c ), used the device TA Installment Q200 using 5 to 7 mg samples. DSC was performed according to ISO 11357/part 3 /method C2 in a heat/cool/heat cycle at a scan rate of 10°C/min at a temperature ranging from -30 to +225°C. The crystallization temperature and the enthalpy of crystallization (H _c ) were determined from the cooling step, while the melting point (Tm) and the enthalpy of melting (H _m ) were determined from the second heating step.

2. Examples.

The present invention is illustrated by the following non-limiting examples.

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Preparation of heterophasic propylene copolymer (HECO).

Obtaining a catalyst.

First, 0.1 mol MgCl2 x 3 EtOH was suspended under inert conditions in 250 ml decalin in a reactor at atmospheric pressure. The solution was cooled to a temperature of -15°and added with stirring 300 ml of cold TiCl ₄ while maintaining the temperature at the specified level. Then the temperature of the suspension was slowly raised to 20°C. At this temperature, 0.02 mol of dioctyl phthalate (DOP) was added to the suspension. After adding the phthalate, the temperature was raised to 135° C. over 90 minutes and the suspension was allowed to stand for 60 minutes. Then another 300 ml of TiCl ₄ was added and the temperature was maintained at 135° C. for 120 minutes. After that, the catalyst was filtered from the liquid and washed six times with 300 ml of heptane at a temperature of 80°C. The solid catalyst component was then filtered off and dried.

The catalyst and the concept of its production are generally described, for example, in patent publications WO 87/07620, WO 92/19653, WO 92/19658 and EP 0 491 566, EP 591224 and EP 586390.

The catalyst was further modified by prepolymerization (VCH catalyst modification).

35 ml of mineral oil (Paraffinum Liquidum PL68) was added to a 125 ml stainless steel reactor followed by 0.82 g of triethylaluminum (TEAL) and 0.33 g of dicyclopentyldimethoxysilane (donor D) under inert conditions at room temperature. After 10 minutes, 5.0 g of the catalyst obtained in 1a (Ti content 1.4 wt.%) and after an additional 20 min added 5.0 g of vinylcyclohexane (VCH)). The temperature was raised to 60° C. over 30 minutes and maintained for 20 hours. Finally, the temperature was lowered to 20° C. and the concentration of unreacted VCH in the oil/catalyst mixture was analyzed and found to be 200 ppm by weight. Di(cyclopentyl)dimethoxysilane (donor D) was used as an external donor.

Getting HESO.

HECO is produced using a slurry and a plurality of gas phase reactors connected in series. The applied conditions and the properties of the obtained products are briefly described in table. 1.

___________________

Prepolymerization TEAL/Ti [mol/mol] 220 TEAL/Do [mol/mol] 7.3 Temperature [°C] thirty Time of stay M 0.08 circulation Temperature [°C] 72 Split flow (Split) [%] 35 H2/C3 [mol/kmol] 15 С2/С3 [mol/kmol] 0 MFR2 [g/10 minutes] 55 XCS [wt%] 2.0 since ₂ [mol.%] 0 1st GPR Temperature [°C] 80 Pressure [kPa] 2231 Split flow (Split) [%] thirty H2/C3 [mol/kmol] 150 С2/С3 [mol/kmol] 0 MFR2 [g/10 minutes] 55 XCS [wt%] 2.0 since ₂ [mol.%] 0 2nd GPR Temperature [°C] 70 Pressure [kPa] 2291 Split flow (Split) [%] 19 С2/С3 [mol/kmol] 584

- 19 041396

H2/C2 [mol/kmol] 117 MFR2 [g/10 minutes] AND XCS [wt%] 18 IV (XCS) [dl/g] nd C ₂ (XCS) [mol.%] nd since ₂ [mol.%] 18 Ziy GPR Temperature [°C] 85 Pressure bar 1421 Stream splitting (Split) [%] 16 С2/С3 [mol/kmol] 585 H2/C2 [mol/kmol] 93 MFR2 [g/10 minutes] AND XCS [wt%] 32 IV (XCS) [dl/g] 3.1 C ₂ (XCS) [mol.%] 48 c ₂ [mol.%] 19

C 2 - ethylene content

H2/C3 - hydrogen / propylene ratio

C2/C3 - ethylene / propylene ratio

H2/C2 - hydrogen / ethylene ratio

1st 2nd ZyORK - 1st 2nd Zy gas-phase reactor

Circulation-circulation reactor

TEAL/Ti -TEAL/Ti ratio TEAL/Do -teal/donor ratio mfr ₂ - melt flow rate XCS -fraction soluble in cold xylene _C2 (XCS) -content of ethylene in the fraction soluble in cold xylene IV (XCS) intrinsic viscosity of the fraction soluble in cold

xylene

Naturally, the properties of the products obtained in individual reactors are determined not from the homogenized material, but from samples from the reactor (local samples). The properties of the final polymer are determined from the homogenized material.

Inventive Example IE1 and Comparative Examples CE1 and CE2 are melt blended using a twin screw extruder such as a Coperion STS-35 twin screw extruder from Coperion (Nanjing) Corporation, China. The average screw speed of the twin screw extruder was 400 rpm, the temperature profile of the zones was from 180 to 250°C.

The example of the present invention IE1 and comparative examples CE1 and CE 2 are based on the formulation, a brief description of which is given in table. 2.

Table 2. Formulation for obtaining compositions according to the invention and comparative compositions

Example CE1 CE2 IEI RRN-1 [mass %]* 78.85 74.85 Elastomer [mass %]* 10 10 NOT WITH [mass %]* 84.85 RMR [mass %]* 5.0 5.0 5.0 CF [mass %]* 6.0 10.0 10.0

* the rest up to 100 wt.% - additives in their usual dosage, including polymeric carrier material, antioxidants, and UV stabilizers, such as pentaerythrityl-tetrakis(3-(3',5'-ditert.butyl-4-hydroxyphenyl)propionate in the form commercial antioxidant Irganox 1010 BASF, Germany, CAS-no. -4.

PPH-1 is a commercial product of HF955MO Borealis AG which is a propylene homopolymer with an MFR2 (230° C., 2.16 kg) melt flow rate of 20 g/10 min and a density of 908 kg/m ³ . Homo-

Claims (21)

HF955MO propylene polymer is α-nucleated with polyvinyl cyclohexane. The elastomer is a commercial product Queo8201 from Borealis AG which is an ethylene/1-octene copolymer with an MFR ₂ (190° C., 2.16 kg) melt flow rate of 1.1 g/10 min and a density of 883 kg/m ³ . PMP is a commercial product of SCONA TSPP10213GB from Co. Ltd, Germany, which is a maleic anhydride-functionalized polypropylene with an MVR (170° C., 1.2 kg) of 40 to 100 cm ³ /10 min and a maleic anhydride content of 2.0 wt.%. CF is a commercial RECATEX C90 product from SGL Carbon SE which is a nonwoven fabric containing 90% by weight carbon fiber with a density as defined according to ISO 10119:2002 of 1.8 g/m ³ and a tensile strength to break as defined according to ISO 10618:2004 4400. The properties of the example of the present invention IE1 and Comparative examples CE 1 and CE 2 are briefly described in Table 3. Table 3. Formulation for obtaining compositions according to the invention and comparative compositions Example CE1 CE2 IEI Tensile modulus (TM) [MPa] 3839 5631 3555 Tensile strength to break (TS) [MPa] 52 66 44 Extension to breaking point (TEV) [%] 5.6 4.4 8.7 Charpy cut strength (IS) [kJ/ ^m2 ] 31 32 47 Melt flow rate (MFR ₂ ) [g/10 minutes] 14.0 12.9 10.0 *of the total weight of the composition. CLAIM 1. Composition of polypropylene (C), containing: (a) 55 to 95 parts by weight heterophasic propylene copolymer (HECO), wherein the heterophasic propylene copolymer (HECO) contains a polypropylene matrix (M) and an elastomeric copolymer (E) containing units derived from propylene and ethylene or C ₄ -C ₂₀ alpha-olefins or ethylene and C ₄ -C ₂₀ alpha-olefins; (b) from 1.0 to 10 wt.h. polar modified polypropylene (PMP); (c) 7.0 to 35 parts by weight carbon fibers (CF) based on the total weight of the parts of compounds (a), (b) and (c), while the intrinsic viscosity (IV) of the xylene cold soluble fraction (XCS) of the heterophasic propylene copolymer (HECO) is in the range of 3 .0 to 4.0 dl/g. 2. The polypropylene composition (C) according to claim 1, where the polypropylene composition (C) contains a heterophasic propylene copolymer (HECO) in an amount of from 55 to 95 wt.% of the total weight of the polypropylene composition (C). 3. The polypropylene composition (C) according to any one of the preceding claims, wherein the heterophasic propylene copolymer (HECO) has a melt flow rate MFR2 (230° C., 2.16 kg) as measured according to ISO 1133 of not more than 60 g/10 min. . 4. The polypropylene composition (C) according to any one of the preceding claims, wherein the heterophasic propylene copolymer (HECO) has an ethylene or C ₄ -C ₂₀ alpha olefin or ethylene and C ₄ -C _2O alpha olefin content of not more than 35 mole %. . 5. The polypropylene composition (C) according to any one of the preceding claims, wherein the heterophasic propylene copolymer (HECO) has a cold xylene soluble fraction (XCS) content of not more than 55% by weight based on the total weight of the heterophasic propylene copolymer (HECO). - 21 041396 6. The polypropylene composition (C) according to any of the preceding claims, wherein the heterophasic propylene copolymer (HECO) has an intrinsic viscosity (IV) of the cold xylene soluble fraction (XCS) of the heterophasic propylene copolymer (HECO) in the range of 3.0 to 3 .5 dl/g. 7. The polypropylene composition (C) according to any one of the preceding claims, wherein the heterophasic propylene copolymer (HECO) has a comonomer content of cold xylene soluble fraction (XCS), heterophasic propylene copolymer (HECO) of not more than 65 mole %. 8. The composition of polypropylene (C) according to any of the preceding paragraphs, where the composition of polypropylene (C) contains polar modified polypropylene (PMP) in an amount of from 1.0 to 10 wt.%, preferably from 2.5 to 10 wt.% of the total the weight of the polypropylene composition (C). 9. The polypropylene composition (C) according to any one of the preceding claims, wherein the polar modified polypropylene (PMP) contains groups derived from polar groups selected from the group consisting of acid anhydrides, carboxylic acids, carboxylic acid derivatives, primary and secondary amines, hydroxyl compounds, oxazolines, epoxides and ionic compounds. 10. The polypropylene composition (C) according to any one of the preceding claims, wherein the polar modified polypropylene (PMP) is a propylene polymer grafted with maleic anhydride. 11. The polypropylene (C) composition according to any one of the preceding claims, wherein the polypropylene (C) composition contains carbon fibers (CF) in an amount of 7.0 to 35 wt.% of the total weight of the polypropylene (C) composition. 12. The polypropylene composition (C) according to any one of the preceding claims, wherein the heterophasic propylene copolymer (HECO) and the polar modified polypropylene (PMP) are present in an amount of at least 57.5% by weight, preferably in an amount of at least 76% by weight. , more preferably in an amount of at least 82 wt.%, even more preferably in an amount of at least 89 wt.% of the total weight of the polypropylene composition (C). 13. The polypropylene composition (C) according to any one of the preceding claims, wherein the heterophasic propylene copolymer (HECO), polar modified polypropylene (PMP) and carbon fibers (CF) are present in an amount of at least 60% by weight, preferably in an amount of at least 81 wt.%, more preferably in an amount of at least 89 wt.%, even more preferably in an amount of at least 98 wt.% of the total weight of the polypropylene composition (C). 14. A polypropylene composition (C) according to any one of the preceding claims, wherein the polypropylene composition (C) has a tensile modulus, as measured according to ISO 527-2, of at least 2500 MPa. 15. A polypropylene composition (C) according to any of the preceding claims, wherein the polypropylene composition (C) has a tensile strength to break, as measured according to ISO 527-2, of at least 25 MPa. 16. A polypropylene composition (C) according to any one of the preceding claims, wherein the polypropylene composition (C) has a Charlie cut strength, as measured according to ISO 179-leU:2000 at 23° C., of at least 35 kJ/m ² . 17. A polypropylene composition (C) according to any one of the preceding claims, wherein the polypropylene composition (C) has an elongation at break, as measured according to ISO 527-2, of at least 6.0%. 18. The polypropylene composition (C) according to any one of the preceding claims, wherein the polypropylene composition (C) does not contain any fibers other than carbon fibers (CF). 19. The polypropylene composition (C) according to any one of the preceding claims, wherein the polypropylene composition (C) does not contain any other polymers besides heterophasic propylene copolymer (HECO) and polar modified polypropylene (PMP). 20. An article containing the polymer composition (C) according to any of the preceding claims 1 to 13, wherein the article is a molded article or an extruded article. 21. The article of claim 20, wherein the article is an automotive article, preferably an automotive exterior or interior article, such as technical brackets, shrouds, structural brackets, bumpers, footwell trim panels, running boards, body panels, spoilers , instrument panels, and interior trim products. Eurasian Patent Organization, EAPO Russia, 109012, Moscow, Maly Cherkassky per., 2