EA040146B1 - FOAMED PRODUCT CONTAINING POLYPROPYLENE COMPOSITION AND USE OF POLYPROPYLENE COMPOSITION FOR MANUFACTURING FOAMED PRODUCT - Google Patents

Description

The present invention relates to the use of a polypropylene composition (K) comprising a heterophasic propylene copolymer (HESO1) which has an intrinsic viscosity (IV) of a xylene-soluble fraction (XF) of more than 3.5 dl/g, an inorganic filler (H) and a nucleating agent (abbreviated as 3A), which is a dicarboxylic acid and/or its salt to obtain a foamed product, as well as to a foamed product containing the specified polypropylene composition (K).

Recent requirements for polymers for the automotive industry include weight reduction while maintaining a combination of mechanical properties and surface appearance. Strict CO2 emission limits have been approved in the European Union which require vehicle manufacturers (Original Equipment Manufacturers, OEMs) to reduce emissions from the 160 g/km currently available to 120 g/km by 2012-2015 . Thus, car manufacturers are looking for ways to reduce the weight of products and comply with the requirements of the law. One approach to obtaining low density polypropylene compositions is the use of compositions containing inorganic fillers or glass fibers. However, the reduction in density by the use of polypropylene compounds reinforced with inorganic filler or glass fibers has its limitations.

Thus, the next possible step towards additional weight reduction is foaming during the injection molding step, which can produce both visible and invisible parts of cars. Foamed parts have the advantage of reduced density, but they have an unsatisfactory surface and unsatisfactory mechanical properties. Thus, most foam parts are not used in visible interior/exterior structures.

Accordingly, there is a need in the art to provide foamed articles containing an expandable polypropylene composition characterized by a combination of good mechanical characteristics combined with a flawless surface appearance.

Thus, one of the objectives of the present invention is to provide a foamed article containing a polypropylene composition having a high degree of fluidity, good dimensional stability, a good balance of mechanical properties and surface appearance, and, importantly, that the foamed articles obtained from the composition retain the existing set of characteristics.

During the development of the present invention, it has been found that from a heterophasic filled polypropylene composition comprising a high molecular weight elastomer fraction and a dicarboxylic acid nucleating agent, foamed articles having excellent mechanical properties and suitable surface appearance can be obtained.

Accordingly, the present invention relates to a foamed product containing a polypropylene composition (K) containing

a) 15.0 to 35% by weight of a heterophasic propylene copolymer (HESO1) having an intrinsic viscosity (IV) of a xylene soluble fraction (XF) of greater than 3.5 dl/g, wherein the xylene soluble fraction (XF) is determined at 25°C in accordance with ISO 16152, wherein said heterophasic propylene copolymer (HECO1) contains

i) a matrix (M1) representing a propylene polymer, and ii) an elastomeric propylene copolymer (E1) containing ethylene and/or C ₄ -C8 α-olefins as comonomer(s), where the elastomeric copolymer (E1) is dispersed in the specified matrix,

b) from 5.0 to 30.0 wt.% inorganic filler (H) and

c) from 0.001 to 2.0 wt.% nucleating agent (ZA), which is a dicarboxylic acid and/or its salt;

which also contains from 36.0 to 60.0 wt.% of a heterophasic propylene copolymer (HECO2) having an intrinsic viscosity (IV) of a xylene-soluble fraction (XF) in the range of 1.0 to 3.3 dl/g, where the soluble in xylene, the fraction (RKF) is determined at 25°C in accordance with ISO 16152, wherein said heterophasic propylene copolymer (HECO2) contains i) a matrix (M2) which is a propylene polymer and ii) an elastomeric propylene copolymer (E2) containing ethylene and/or C ₄ -C 8 α-olefins as comonomer(s), wherein the elastomeric copolymer (E2) is dispersed in said matrix.

According to one embodiment of the present invention, the comonomer content of the xylene-soluble fraction (XFR) of the heterophasic propylene copolymer (HESO1) is less than 40.0 mole%.

According to another embodiment of the present invention, the content of the comonomer in the xylene-soluble fraction (XFR) in the heterophasic propylene copolymer (HECO2) is greater than or equal to 40.0 mole%.

According to another embodiment of the present invention, the foamed article further comprises a high density polyethylene (HDPE) and/or a plastomer (PL), which is a copolymer of ethylene and a C ₄ -C ₈ α-olefin.

According to one embodiment of the present invention, the foamed product further comprises

i) from 2.0 to 10.0 wt.% high density polyethylene (HDPE), ii) from 5.0 to 15.0 wt.% plastomer (PL), which is a copolymer of ethylene and C ₄ -C ₈ αolefin , based on the total weight of the polypropylene composition (K).

According to another embodiment of the present invention, the heterophasic propylene copolymer (HECO1) has

i) melt flow index MFR ₂ (230°C), determined in accordance with ISO 1133, from 1.0 to 20.0 g/10 min, and/or ii) a comonomer content from 5.0 to 30.0 mol. %, and/or iii) the content of the xylene-soluble fraction (RKF) from 15.0 to 40.0 wt.%.

According to another embodiment of the present invention, the heterophasic propylene copolymer (HECO2) has

i) melt flow index MFR ₂ (230° C.), determined in accordance with ISO 1133, from 50 to 120 g/10 min, and/or ii) a comonomer content of 4.0 to 30.0 mol.%, and/or iii) a xylene-soluble fraction (RKF) content of 8.0 to 35.0% by weight.

Particularly preferably, the first propylene polymer (M1) and/or the second propylene polymer (M2) are propylene homopolymers.

According to one embodiment of the present invention, the first elastomeric propylene copolymer (E1) and/or the second elastomeric propylene copolymer (E2) are copolymers of propylene and ethylene.

According to another embodiment of the present invention, the foamed article has a melt flow index MFR ₂ (230°C), determined in accordance with ISO 1133, from 10.0 to 40.0 g/10 min.

According to another embodiment of the present invention, the plastomer (PL) is a copolymer of ethylene and 1-octene.

According to one embodiment of the present invention, the inorganic filler (H) is talc and/or wollastonite.

Particularly preferably, the nucleating agent (ZA) is 1,2-cyclohexanedicarboxylic acid and/or a salt thereof.

The present invention also relates to the use of the polypropylene composition (K) described above in relation to a foamed article for the manufacture of a foamed article.

The present invention also relates to a foamed product, preferably a foamed automotive part, containing the polypropylene composition (K) described above.

Below the present invention is disclosed in more detail.

Polypropylene composition (K)

According to the invention, the polypropylene composition (K) comprises a heterophasic propylene copolymer (HESO1) comprising a matrix (M1) which is a propylene polymer (PP1) and an elastomeric propylene copolymer (E1) dispersed in said matrix. Thus, the matrix (M1) contains (finely) dispersed inclusions which are not part of the matrix (M1) and said inclusions contain the elastomeric propylene copolymer (E1). The term inclusion indicates that the matrix (M1) and inclusions form different phases, described below.

In addition, according to the invention, the polypropylene composition includes an inorganic filler (H) and a nucleating agent (HA), which is a dicarboxylic acid and/or its salt.

Accordingly, the polypropylene composition (K) preferably comprises at least 15.0 wt.%, more preferably at least 20.0 wt.%, even more preferably at least 25.0 wt.% heterophasic propylene copolymer (HECO1), from 5.0 to 30.0 wt%, more preferably 8.0 to 25.0 wt%, even more preferably 12.0 to 16.0 wt% inorganic filler (H) and 0.001 to 2, 0 wt.%, more preferably from 0.01 to 1.0 wt.%, even more preferably from 0.05 to 0.1 wt.% nucleating agent (ZA), based on the total weight of the polypropylene composition (K).

According to one of the preferred embodiments of the present invention, the polypropylene composition (K) further comprises a heterophasic propylene copolymer (HESO2) which is different from a heterophasic propylene copolymer (HESO1).

Said heterophasic propylene copolymer (HESO2) includes a matrix (M2) which is a propylene polymer (PP2) and an elastomeric propylene copolymer (E2) dispersed in said matrix. Thus, the matrix (M2) contains (finely) dispersed inclusions that are not part of the matrix (M2), and these inclusions contain an elastomeric propylene copolymer (E2).

Thus, if the polypropylene composition (K) includes a heterophasic propylene copolymer (HESO2), then the polypropylene composition (K) includes a heterophasic system,

- 2 040146 comprising a matrix (M) formed by a propylene polymer (PP1) and a propylene polymer (PP2), and the first elastomeric propylene copolymer (E1) and the second elastomeric propylene copolymer (E2) are dispersed in said matrix (M). Thus, the matrix (M) contains (finely) dispersed inclusions that are not part of the matrix (M), and these inclusions contain an elastomeric propylene copolymer (E1) and an elastomeric propylene copolymer (E2).

Preferably, the polypropylene composition (K) comprises 15.0 to 35.0 wt.%, more preferably 18.0 to 30.0 wt.%, even more preferably 22.0 to 27.0 wt.% heterophasic propylene copolymer (GESO1); from 36.0 to 60.0 wt.%, more preferably from 37.0 to 53.0 wt.%, even more preferably from 38.0 to 45.0 wt.% heterophasic propylene copolymer (HECO2); from 5.0 to 30.0 wt.%, more preferably from 8.0 to 25.0 wt.%, even more preferably from 12.0 to 16.0 wt.% of inorganic filler (H) and from 0.001 to 2 0.0 wt.%, more preferably from 0.01 to 1.0 wt.%, even more preferably from 0.05 to 0.1 wt.% of the nucleating agent (ZA), based on the total weight of the polypropylene composition (K).

Preferably, the polypropylene composition (K) contains a propylene polymer (PP1) and a propylene polymer (PP2) forming a matrix (M) in a ratio of 1:1 to 3:1 and an elastomeric propylene copolymer (E1) and an elastomeric propylene copolymer (E2) in ratio from 1:1 to 3:1.

Accordingly, the polypropylene composition (K) preferably comprises 40 to 63% by weight, more preferably 46 to 60% by weight, even more preferably 50 to 53% by weight of propylene polymer (PP1); from 20 to 32 wt.%, more preferably from 23 to 30 wt.%, even more preferably from 25 to 27 wt.% propylene polymer (PP2); from 3 to 26 wt.%, more preferably from 7 to 20 wt.%, even more preferably from 13 to 17 wt.% elastomeric propylene copolymer (E1; from 2 to 14 wt.%, more preferably from 3 to 10 wt. %, even more preferably from 6 to 8 wt.% elastomeric propylene copolymer (E2), from 5.0 to 30.0 wt.%, more preferably from 8.0 to 25.0 wt.%, even more preferably from 12 0 to 16.0 wt.% inorganic filler (H) and from 0.001 to 2.0 wt.%, more preferably from 0.01 to 1.0 wt.%, even more preferably from 0.05 to 0.1 wt.% nucleating agent (ZA), based on the total weight of the polypropylene composition (K).

In addition, the polypropylene composition (K) preferably includes high density polyethylene (HDPE).

Thus, the polypropylene composition (K) preferably comprises 15.0 to 35.0 wt.%, more preferably 18.0 to 30.0 wt.%, even more preferably 22.0 to 27.0 wt.% heterophasic propylene copolymer (HESO1); from 36.0 to 60.0 wt.%, more preferably from 37.0 to 53.0 wt.%, even more preferably from 38.0 to 45.0 wt.% heterophasic propylene copolymer (HECO2); from 2.0 to 10.0 wt.%, more preferably from 3.0 to 8.0 wt.%, even more preferably from 4.0 to 6.0 wt.% high density polyethylene (HDPE); from 5.0 to 30.0 wt.%, more preferably from 8.0 to 25.0 wt.%, even more preferably from 12.0 to 16.0 wt.% of inorganic filler (H) and from 0.001 to 2 0.0 wt.%, more preferably from 0.01 to 1.0 wt.%, even more preferably from 0.05 to 0.1 wt.% of the nucleating agent (ZA), based on the total weight of the polypropylene composition (K).

Additionally or as an alternative to the preceding paragraph, the polypropylene composition (K) preferably further comprises a plastomer (PL) which is a copolymer of ethylene and a C ₄ -C ₈ α-olefin.

Accordingly, the polypropylene composition (K) preferably comprises 15.0 to 35.0 wt.%, more preferably 18.0 to 30.0 wt.%, even more preferably 22.0 to 27.0 wt.% heterophasic propylene copolymer (GESO1); from 36.0 to 60.0 wt.%, more preferably from 37.0 to 53.0 wt.%, even more preferably from 38.0 to 45.0 wt.% heterophasic propylene copolymer (HECO2); from 2.0 to 10.0 wt.%, more preferably from 3.0 to 8.0 wt.%, even more preferably from 4.0 to 6.0 wt.% high density polyethylene (HDPE); from 5.0 to 15.0 wt.%, more preferably from 6.0 to 12.0 wt.%, even more preferably from 7.0 to 10.0 wt.% of the plastomer (PL); from 5.0 to 30.0 wt.%, more preferably from 8.0 to 25.0 wt.%, even more preferably from 12.0 to 16.0 wt.% of inorganic filler (H) and from 0.001 to 2 0.0 wt.%, more preferably from 0.01 to 1.0 wt.%, even more preferably from 0.05 to 0.1 wt.% of the nucleating agent (ZA), based on the total weight of the polypropylene composition (K).

Preferably, the polypropylene composition (K) is produced by a sequential polymerization process in which at least two, for example three, reactors are connected in series. For example, said method includes the following steps:

a) polymerization of propylene and possibly ethylene in the first reactor (P1) to obtain a propylene polymer (PP1);

b) transporting the propylene polymer (PP1) to the second reactor (P2);

c) polymerizing propylene and optionally ethylene in said second reactor (P2) in the presence of said propylene polymer (PP1) to form a propylene polymer (PP2), where said propylene polymer (PP1) and said propylene polymer (PP2) form a matrix (M);

d) transfer of the matrix (M) to the third reactor (R3);

- 3 040146

e) polymerization of propylene and/or C ₄ -C ₈ α-olefin in the specified third reactor (R3) in the presence of a matrix (M) to obtain a third polymer fraction, which is an elastomeric propylene copolymer (E1);

f) transporting the matrix (M) and the elastomeric propylene copolymer (E1) to the fourth reactor (P4);

g) polymerization of propylene and/or C4-C8 α-olefin in said fourth reactor (P4) in the presence of a matrix (M) and an elastomeric propylene copolymer (E1) to obtain a fourth polymer fraction, which is an elastomeric propylene copolymer (E2), wherein said the matrix (M) and said elastomeric propylene copolymer (E1) and said propylene elastomeric copolymer (E2) form a heterophasic propylene copolymer;

h) melt blending said heterophasic propylene copolymer produced in the fourth reactor (P4) with an inorganic filler (H), a nucleating agent (HA), optionally high density polyethylene (HDPE) and optionally a plastomer (PL).

Alternatively, the polypropylene composition (K) is obtained by melt-blending a first heterophasic propylene copolymer (HESO1) comprising a matrix (M1), which is a propylene polymer (PP1), and a dispersed phase, which is an elastomeric propylene copolymer (E1), of a second heterophasic propylene copolymer copolymer (GESO2) comprising a matrix (M2), which is a propylene polymer (PP2), and a dispersed phase, which is an elastomeric propylene copolymer (E2), an inorganic filler (H), a nucleating agent (ZA), possibly a high density polyethylene (HDPE) ) and possibly a plastomer (PL). Melt blending of said first heterophasic propylene copolymer (HECO1) and said second heterophasic propylene copolymer (HECO2) results in a heterophasic system in which propylene polymer (PP1) and propylene polymer (PP2) form a matrix (M) and elastomeric propylene copolymer ( E1) and elastomeric propylene copolymer (E2) form a dispersed phase.

Particularly preferably, a polypropylene composition (K) is obtained by melt blending said first heterophasic propylene copolymer (HECO1) and said second heterophasic propylene copolymer (HECO2) with an inorganic filler (H), a nucleating agent (HA) and optionally high density polyethylene (HDPE) and/or plastomer (PL).

Preferably, the polypropylene composition (K) according to the present invention comprises only heterophasic propylene copolymer (HECO1), heterophasic propylene copolymer (HECO2), high density polyethylene (HDPE) and plastomer (PL) as polymeric components. In other words, the polypropylene composition (K) may contain additional additives, but does not contain another polymer in an amount greater than 5.0 wt.%, more preferably greater than 3.0 wt.%, for example, greater than 1.0 wt.% based on total weight of the polypropylene composition (K). One additional polymer that may be present in such low amounts is polyethylene, which is a reaction by-product obtained during the formation of the polypropylene composition (K). Accordingly, particularly preferably, the polypropylene composition (K) according to the invention contains only heterophasic propylene copolymer (HESO1), heterophasic propylene copolymer (HECO2), high density polyethylene (HDPE) and plastomer (PL) and optionally polyethylene in the amount indicated in this paragraph.

The polypropylene composition (K) according to the present invention may include additives (DOB).

Accordingly, the polypropylene composition (K) preferably comprises, more preferably consists of from 15.0 to 35.0 wt.%, more preferably from 18.0 to 30.0 wt.%, even more preferably from 22.0 to 27.0 wt.% heterophasic propylene copolymer (HESO1); from 36.0 to 60.0 wt.%, more preferably from 37.0 to 53.0 wt.%, even more preferably from 38.0 to 45.0 wt.% heterophasic propylene copolymer (HECO2); from 2.0 to 10.0 wt.%, more preferably from 3.0 to 8.0 wt.%, even more preferably from 4.0 to 6.0 wt.% high density polyethylene (HDPE); from 5.0 to 15.0 wt.%, more preferably from 6.0 to 12.0 wt.%, even more preferably from 7.0 to 10.0 wt.% of the plastomer (PL); from 5.0 to 30.0 wt.%, more preferably from 8.0 to 25.0 wt.%, even more preferably from 12.0 to 16.0 wt.% of inorganic filler (H); from 0.001 to 2.0 wt.%, more preferably from 0.01 to 1.0 wt.%, even more preferably from 0.05 to 0.1 wt.% nucleating agent (ZA) and from 0.0 to 5 0.0 wt.%, more preferably from 0.05 to 4.0 wt.%, even more preferably from 0.1 to 3.0 wt.% additives (DOB), based on the total weight of the polypropylene composition (K). Additives (DOB) are discussed in more detail below.

Preferably, the polypropylene composition (K) has a moderate melt flow index. Thus, preferably the melt flow index MFR ₂ (230° C., 2.16 kg) of the polypropylene composition (K), determined in accordance with ISO 1133, is from 10.0 to 40.0 g/10 min, more preferably from 12 0 to 35.0 g/10 min, even more preferably 14.0 to 28.0 g/10 min, such as 14.0 to 19.0 g/10 min.

- 4 040146

In addition, the polypropylene composition (K) preferably has a sufficiently high flexural modulus, as determined on a dense (non-foamed) injection molded sample.

Accordingly, the polypropylene composition (K) preferably has a flexural modulus, determined on injection molded samples according to ISO 178, from 1000 to 3000 MPa, more preferably from 1500 to 2800 MPa, even more preferably from 2000 to 2500 MPa.

Additionally or as an alternative to the preceding paragraph, the polypropylene composition (K) preferably has a Charpy impact value determined in accordance with ISO 179/1eA at 23° C. on a dense injection molded sample of at least 10.0 kJ /m ² , more preferably at least 12.0 kJ/m ² , even more preferably at least 15.0 kJ/m ² .

Preferably, the polypropylene composition (K) has a sufficiently low density to be determined on a dense injection molded sample. In particular, the polypropylene composition (K) preferably has a density of less than 4.0 g/cm ³ , more preferably less than 2.0 g/cm ³ , even more preferably less than 1.5 g/cm ³ , for example less than 1.1 g/ ^cm3 .

Preferably, the foamed injection molded polypropylene composition (K) has a sufficiently low density. In particular, the density of the expanded polypropylene composition is preferably less than 2.0 g/cm ³ , more preferably less than 1.5 g/cm ³ , even more preferably less than 1.1 g/cm ³ , for example less than 0.9 g/cm ³ .

The heterophasic propylene copolymer (HECO1), heterophasic propylene copolymer (HECO2), high density polyethylene (HDPE), plastomer (PL), inorganic filler (H), and nucleating agent (HA) are discussed in more detail below.

Heterophasic propylene copolymer (HESO1)

The polypropylene composition (K) according to the invention comprises a heterophasic propylene copolymer (HESO1).

The heterophasic propylene copolymer (HESO1) of the present invention includes a matrix (M1) which is a propylene polymer (PP1) and an elastomeric propylene copolymer dispersed therein, which is an elastomeric propylene copolymer (E1). Thus, the matrix (M1) contains (finely) dispersed inclusions which are not part of the matrix (M1) and said inclusions contain the elastomeric propylene copolymer (E1). The term inclusion means that the matrix (M1) and the inclusions form different phases in the heterophasic propylene copolymer (HECO1). The presence of a second phase or so-called inclusions can be observed, for example, using a high-resolution microscope, such as an electron microscope or an atomic force microscope, or they can be detected using dynamic mechanical thermal analysis (DMTA). In particular, when conducting DMTA, the presence of a multiphase structure can be identified by the presence of at least two different glass transition temperatures.

Accordingly, the heterophasic propylene copolymer (HECO1) according to the present invention preferably comprises:

(a) (semi)crystalline propylene polymer (PP1) as matrix (M1) and (b) elastomeric propylene copolymer (E1).

Preferably, the mass ratio [PP1/E1] of the amount of propylene polymer (PP1) to the amount of elastomeric propylene copolymer (E1) in the heterophasic propylene copolymer (HECO1) is from 90/10 to 40/60, more preferably from 85/15 to 45/55, more preferably 83/17 to 50/50, for example 75/25 to 60/40.

Preferably, the heterophasic propylene copolymer (HESO1) according to the present invention comprises only propylene polymer (PP1) and elastomeric propylene copolymer (E1) as polymer components. In other words, the heterophasic propylene copolymer (HESO1) may contain additional additives, but does not contain another polymer in an amount greater than 5.0 wt.%, more preferably greater than 3.0 wt.%, for example, greater than 1.0 wt.% based on total weight of the heterophasic propylene copolymer (HESO1). One additional polymer that may be present in such low amounts is polyethylene, which is a by-product of the heterophasic propylene copolymer (HESO1) reaction. Accordingly, it should be especially noted that the heterophasic propylene copolymer (HECO1) according to the invention contains only propylene polymer (PP1), elastomeric propylene copolymer (E1) and possibly polyethylene in the amount indicated in this paragraph.

The heterophasic propylene copolymer (HECO1) used in the present invention has a fairly low melt flow rate. Accordingly, the heterophasic propylene copolymer (HESO1) has a melt flow index MFR ₂ (230°C) from 1.0 to 20.0 g/10 min, preferably from 3.0 to 15.0 g/10 min, more preferably from 5, 0 to 10 g/10.0 min.

Preferably, it is desirable that the heterophasic propylene copolymer (HECO1) has

- 5 040146 thermomechanical stability. Accordingly, preferably the melting point of the heterophasic propylene copolymer (HESO1) is at least 162°C, more preferably 163 to 167°C, even more preferably 163 to 165°C.

In addition to propylene, heterophasic propylene copolymer (HECO1) includes comonomers. Preferably, in addition to propylene, the heterophasic propylene copolymer (HESO1) comprises ethylene and/or C ₄ -C ₈ α-olefins. Accordingly, the term propylene copolymer according to the present invention means a polypropylene comprising, preferably consisting of, units derived from (a) propylene and (b) ethylene and/or C4-C8 α-olefins.

Thus, a heterophasic propylene copolymer (HESO1), i.e. propylene polymer (PP1) in combination with an elastomeric propylene copolymer (E1) may include monomers copolymerizable with propylene, for example comonomers such as ethylene and/or C ₄ -C ₈ α-olefins, in particular ethylene and/or C ₄ -C _6α -olefins, for example 1-butene and/or 1-hexene. Preferably, the heterophasic propylene copolymer (HECO1) according to the present invention comprises, in particular consists of, propylene copolymerizable monomers selected from the group consisting of ethylene, 1-butene and 1-hexene. In particular, in addition to propylene, the heterophasic propylene copolymer (HECO1) according to the present invention includes units that can be obtained from ethylene and/or 1-butene. In one of the preferred embodiments, the heterophasic propylene copolymer (HESO1) according to the present invention includes units that can only be obtained from ethylene and propylene. Even more preferably, the propylene polymer (PP1) as well as the elastomeric propylene copolymer (E1) constituting the heterophasic propylene copolymer (HECO1) contain the same comonomers such as ethylene.

In addition, it should be taken into account that the heterophasic propylene copolymer (HESO1) preferably has a sufficiently low total comonomer content, preferably an ethylene content. Thus, the comonomer content of the heterophasic propylene copolymer (HECO1) is preferably 5.0 to 30.0 mol%, preferably 6.0 to 18.0 mol%, more preferably 7.0 to 13.0 mol%. .%

The amount of cold xylene soluble fraction (XCF) in the heterophasic propylene copolymer (HECO1) determined according to ISO 16152 (25°C) is from 15.0 to 40.0% by weight, preferably from 17.0 to 35, 0 wt%, more preferably 20.0 to 33.0 wt%, even more preferably 23.0 to 30.0 wt%.

Additionally, it should be taken into account that the amount of cold xylene-soluble fraction (RKF) of the heterophasic propylene copolymer (HESO1) is due to its inherent viscosity. The low intrinsic viscosity (IV) value reflects the low weight average molecular weight. For the purposes of the present invention, it is preferred that, determined according to ISO 1628/1 (at 135° C. in decalin), the intrinsic viscosity (IV) of the cold xylene-soluble fraction (XFR) of the heterophasic propylene copolymer (HESO1) is greater than 3.5 dl/g . More preferably, the intrinsic viscosity (IV) of the heterophasic propylene copolymer (HESO1) is 3.5 to 9.0 dl/g, preferably 3.7 to 8.5 dl/g, more preferably 3.9 to 8, 0 dl/g.

In addition, the comonomer content, i.e. the content of ethylene in the xylene cold-soluble fraction (RCF) of the heterophasic propylene copolymer (HECO1) is preferably less than 39.0 mol.%, preferably from 20.0 to 38.0 mol.%, more preferably from 23.0 to 35.0 mole %, more preferably 25.0 to 29.0 mole % The comonomers present in the xylene cold soluble fraction (XF) are the comonomers mentioned above in the description of the propylene polymer (M1) and the elastomeric propylene copolymer (E1), respectively. In one preferred embodiment, the comonomer is ethylene alone.

The characterization of the heterophasic propylene copolymer (HECO1) may further include the characterization of its individual components, i.e. propylene polymer (PP1) and elastomeric propylene copolymer (E1).

The propylene polymer (PP1) may be a propylene copolymer or a propylene homopolymer, with propylene homopolymer being preferred.

When the propylene polymer (PP1) is a propylene copolymer, the propylene polymer (PP1) includes monomers capable of being copolymerized with propylene, for example comonomers such as ethylene and/or C ₄ -C ₈ α-olefins, in particular ethylene and /or C ₄ -C ₆ α-olefins, for example 1-butene and/or 1-hexene. Preferably, the propylene polymer (PP1) according to the present invention comprises, in particular consists of monomers capable of copolymerization with propylene selected from the group consisting of ethylene, 1-butene and 1-hexene. In particular, the propylene polymer (PP1) according to the present invention, in addition to propylene, includes units that can be obtained from ethylene and/or 1-butene. In one of the preferred embodiments, the propylene polymer (PP1) includes units that can only be obtained from ethylene and propylene.

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The melt flow index MFR2 (230°C/2.16 kg) of the propylene polymer (PP1) according to the present invention, determined in accordance with ISO 1133, is from 70 to 300 g/10 min, more preferably from 75 to 250 g/10 min , even more preferably in the range of 80 to 200 g/10 min.

As noted above, the heterophasic propylene copolymer (HESO1) has a low comonomer content. Accordingly, the content of the comonomer in the propylene polymer (PP1) is from 0.0 to 5.0 mol.%, more preferably from 0.0 to 3.0 mol.%, even more preferably from 0.0 to 1.0 mol.% . Particularly preferably, the propylene polymer (PP1) is a propylene homopolymer.

The propylene polymer (PP1) preferably comprises at least two polymer fractions, for example two or three polymer fractions, each of which is a propylene homopolymer. Even more preferably, the propylene polymer (PP1) comprises, preferably consists of, a first fraction (G-PP1a) of a propylene homopolymer and a second fraction (G-PP1b) of a propylene homopolymer.

Preferably, the first fraction (G-PP1a) of the propylene homopolymer and the second fraction (Gnn1b) of the propylene homopolymer differ in their melt flow characteristics.

Accordingly, one of the fractions (G-PP1) and (G-PP1b) of the propylene homopolymer constituting the propylene polymer (PP1) has a low melt flow index MFR2 (230° C./2.16 kg), and the other fraction has a high flow index melt MFR2 (230° C./2.16 kg), wherein the low melt flow fraction and the high melt flow fraction correspond to equation (I), more preferably equation (Ia), even more preferably equation (Ib):

MFR (high) _>

MFR (low) - ' ^U

PTR (high) ' ^- PTR (low) (la)

MFR (high) ' ^- MFR (low) where MFR (high) is the melt flow index MFR2 (230°C / 2.16 kg) (g / 10 min) of the fraction of propylene homopolymer with a higher melt flow index MFR2 (230°C /2.16 kg) and MFR (low) - melt flow index MFR2 (230°C/2.16 kg) (g/10 min) fraction of propylene homopolymer with lower melt flow index MFR2 (230°C/2.16 kg).

Preferably the first fraction (G-PP1a) of the propylene copolymer is a random copolymer fraction with a higher MFR2 (230°C/2.16 kg) and the second fraction (G-PP1b) of the propylene copolymer is a random copolymer fraction with a lower melt flow index MFR2 (230°C/2.16 kg).

Accordingly, the melt flow index MFR2 (230°C/2.16 kg) of the first fraction (G-PP1a) of the propylene homopolymer is preferably from 90 to 160 g/10 min, more preferably from 100 to 150 g/10 min, even more preferably from 120 to 140 g/10 min, and/or the melt flow index MFR2 (230°C/2.16 kg) of the second fraction (G-PP1b) of the propylene homopolymer is preferably from 10 to 39 g/10 min, more preferably from 17 to 32 g/10 min, even more preferably 22 to 27 g/10 min.

In addition, the weight ratio between the first fraction (G-PP1a) of the propylene homopolymer and the second fraction (G-PP1b) of the propylene homopolymer is preferably 20:80 to 80:20, more preferably 75:25 to 25:75, even more preferably from 55:45 to 45:55.

The heterophasic propylene copolymer (HESO1) preferably comprises 60 to 95 wt%, more preferably 70 to 90 wt%, even more preferably 72 to 87 wt% propylene polymer (PP1), based on the total weight of the heterophasic propylene copolymer ( GESO1).

Additionally, the heterophasic propylene copolymer (HESO1) preferably comprises 5 to 40 wt.%, more preferably 10 to 30 wt.%, even more preferably 13 to 28 wt.% elastomeric propylene copolymer (E1), based on the total weight of the heterophasic propylene copolymer (GESO1).

Thus, according to the invention, the heterophasic propylene copolymer (HECO1) preferably comprises, more preferably consists of from 60 to 95 wt.%, more preferably from 70 to 90 wt.%, even more preferably from 72 to 87 wt.% of propylene polymer (PP1 ) and from 5 to 40 wt.%, more preferably from 10 to 30 wt.%, even more preferably from 13 to 28 wt.% of the elastomeric propylene copolymer (E1), based on the total weight of the heterophasic propylene copolymer (HECO1).

Accordingly, the other component of the heterophasic propylene copolymer (HESO1) is an elastomeric propylene copolymer (E1) dispersed in a matrix (M1) which is a propylene polymer (PP1). Information disclosed in the description of the comonomers used

- 7 040146 to obtain the first heterophasic propylene copolymer (HESO1), also refers to the comonomers used to obtain the elastomeric propylene copolymer (E1). Accordingly, the elastomeric propylene copolymer (E1) comprises monomers capable of being copolymerized with propylene, for example comonomers such as ethylene and/or C4-C8 α-olefins, in particular ethylene and/or C ₄ -C ₆ α-olefins, for example 1-butene and/or 1-hexene. Preferably, the elastomeric propylene copolymer (E1) comprises, in particular consists of, propylene copolymerizable monomers selected from the group consisting of ethylene, 1-butene and 1-hexene. In particular, the elastomeric propylene copolymer (E1), in addition to propylene, includes units that can be obtained from ethylene and/or 1-butene. Thus, in one particularly preferred embodiment, the elastomeric propylene copolymer (E1) includes units that can only be obtained from ethylene and propylene.

The comonomer content of the elastomeric propylene copolymer (E1) is preferably 15.0 to 55.0 mol%, more preferably 20.0 to 50.0 mol%, even more preferably 25.0 to 40.0 mol%. %

The heterophasic propylene copolymer (HESO1) according to the invention may contain up to 5.0% by weight of additives such as nucleating agents and antioxidants, as well as slip and antiblock additives. Preferably the content of additives (without a-nucleating agents) is less than 3.0 wt.%, for example less than 1.0 wt.%.

According to one of the preferred embodiments of the present invention, the heterophasic propylene copolymer (HECO1) contains an α-nucleating agent.

According to the present invention, the alpha nucleating agent is not an additive (DOB).

The alpha nucleating agent 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;

(ii) dibenzylidene sorbitol (for example, 1,3:2,4-dibenzylidene sorbitol) and Cl-C ₈ -α-kyl-substituted derivatives of dibenzylidene sorbitol, such as methyldibenzylidene sorbitol, ethyldibenzylidene sorbitol, or dimethyldibenzylidene sorbitol (for example, 1,3:2,4-di(methylbenzylidene)sorbitol ), or substituted nonit derivatives such as 1,2,3-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene]nonite;

(iii) salts of diesters of phosphoric acid, for example sodium 2,2'-methylene-bis(4,6-di-tert-butylphenyl)phosphate or hydroxy-bis[2,2'-methylene-bis(4,6-di -tert-butylphenyl)phosphate]aluminum;

(iv) a vinyl cycloalkane polymer or a vinyl alkane polymer;

(v) their mixtures.

Preferably, the alpha nucleating agent included in the composition according to the invention is a vinyl cycloalkane polymer and/or a vinyl alkane polymer, more preferably a vinyl cycloalkane polymer such as a vinyl cyclohexane (VCH) polymer. A particularly preferred α-nucleating agent is a vinylcyclohexane (VCH) polymer. It should be taken into account that the amount of vinylcycloalkane, for example vinylcyclohexane (VCH) polymer and/or vinylalkane polymer, more preferably vinylcyclohexane (VCH) polymer in the composition is not more than 500 ppm, preferably not more than 200 ppm, more preferably not more than 100 ppm, for example from 0.1 to 500 ppm, preferably from 0.5 to 200 ppm, more preferably from 1 to 100 ppm. In addition, it should be taken into account that the vinyl cycloalkane polymer and/or the vinyl alkane polymer is introduced into the composition by means of BNT technology. A description of BNT technology can be found in WO 99/24478, WO 99/24479, and in particular WO 00/68315. According to this technique, a catalyst system, preferably a Ziegler-Natta procatalyst, can be modified by polymerizing a vinyl-containing compound in the presence of a catalyst system including, in particular, a special Ziegler-Natta procatalyst, an external donor, and a co-catalyst which is a vinyl-containing compound having 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 preferably used for obtaining a heterophasic composition (GEKO) contained in a modified polypropylene composition (MPP). The polymerized vinyl-containing compound serves as an alpha nucleating agent. The weight ratio of vinyl-containing 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 0.5 (1:2) to 2 (2:1). ).

Such nucleating agents are commercially available and are discussed in, for example, Plastic Additives Handbook, 5th ed., 2001, Hans Zweifel (pp. 967-990).

A heterophasic propylene copolymer (HESO1) can be obtained by mixing a propylene polymer (PP1) and an elastomeric propylene copolymer (E1). However, the heterophasic propylene copolymer (HESO1) is preferably produced in a sequential process using reactors connected in series operating under different reaction conditions. As a consequence, each fraction produced in a particular reactor may have its own molecular weight distribution and/or comonomer content distribution.

Accordingly, preferably, a heterophasic propylene copolymer (HECO1) is produced by a sequential polymerization process comprising the following steps:

(a) polymerization of propylene and optionally at least one of the following: ethylene and/or C ₄ -C ₁₂ α-olefin in the first reactor (P1), resulting in the production of the first polypropylene fraction of the propylene polymer (PP1), and preferably said the first polypropylene fraction is a propylene homopolymer;

(b) transporting the first polypropylene fraction to the second reactor (P2);

(c) polymerizing propylene and optionally at least one of the following: ethylene and/or C ₄ -C ₁₂ α-olefin in the second reactor (P2), in the presence of said first polypropylene fraction, to obtain a second polypropylene fraction, and preferably said the second polypropylene fraction is a second propylene homopolymer, said first polypropylene fraction and said second polypropylene fraction forming a propylene polymer (PP1), i. heterophasic propylene copolymer matrix (HESO1);

(d) transporting the propylene polymer (PP1) obtained in step (c) to the third reactor (P3);

(e) polymerization of propylene and ethylene in the third reactor (P3), in the presence of the propylene polymer (PP1) obtained in step (c), to obtain the first fraction of the propylene copolymer, which is a component of the elastomeric propylene copolymer (E1), dispersed in the propylene polymer ( PP1);

(f) transporting the propylene polymer (PP1) and the first fraction of the propylene copolymer, which is a component of the elastomeric propylene copolymer (E1), to the fourth reactor (P4);

(g) polymerizing propylene and ethylene in a fourth reactor (P4), in the presence of a propylene polymer (PP1) and a first propylene copolymer fraction, which is a component of an elastomeric propylene copolymer (E1), to obtain a second propylene copolymer fraction, which is a component of an elastomeric propylene copolymer (E1 ) dispersed in a propylene polymer (PP1), where the propylene polymer (PP1) and the elastomeric propylene copolymer (E1) form a heterophasic propylene copolymer (HECO1).

Of course, in the first reactor (P1) the second polypropylene fraction can be obtained, and in the second reactor (P2) the first polypropylene fraction can be obtained. The same applies to the elastomeric propylene copolymer phases.

Preferably, in the area between the second reactor (P2) and the third reactor (P3), the monomers are flashed.

The term sequential polymerization process indicates that the heterophasic propylene copolymer (HECO1) is produced in at least two, eg three or four, reactors connected in series. Accordingly, the process according to the invention comprises at least a first reactor (P1) and a second reactor (P2), more preferably a first reactor (P1), a second reactor (P2), a third reactor (P3) and a fourth reactor (P4). The term polymerization reactor indicates that the main polymerization is taking place. Thus, if the process consists of four polymerization reactors, this definition does not exclude that the entire process includes, for example, a prepolymerization step in the prepolymerization reactor. The term consists of is a limiting wording only when describing basic polymerization reactors.

The first reactor (P1) is preferably a slurry reactor (SR) which can be any continuous reactor or a simple stirred batch reactor or loop reactor in which the reaction is carried out in bulk or in slurry. Bulk polymerization means polymerization in a reaction medium which includes at least 60% by weight of monomer.

According to the present invention, the slurry reactor (SR) is preferably a loop reactor (LR) (for carrying out the reaction in bulk).

The second reactor (P2) may be a slurry reactor, for example a loop reactor such as the first reactor, or alternatively a gas phase reactor (GFR).

The third reactor (P3) and the fourth reactor (P4) are preferably gas phase reactors (GFR).

Gas phase reactors (GFRs) can be any mechanically stirred or fluidized bed reactors. Preferably gas phase reactors (GFRs) include mechanically agitated fluidized bed reactors in which gas velocities reach at least 0.2 m/s. Thus, preferably the gas phase reactor is a fluidized bed reactor, preferably equipped with a mechanical stirrer.

Thus, in one of the preferred embodiments, the first reactor (P1) is a slurry reactor (SR), such as a loop reactor (LR), while the second reactor (P2), the third reactor (P3) and the fourth reactor (P4) are gas-phase reactors (GFR). Accordingly, at least four, preferably four, polymerization reactors are used in the process according to the invention, namely a slurry reactor (SR) such as a loop reactor (LR), a first gas phase reactor (GFR-1), a second gas phase reactor (GFR -2) and a third gas-phase reactor (GFR-3) connected in series. If necessary, a prepolymerization reactor is placed before the slurry reactor (SR).

In another preferred embodiment, the first reactor (P1) and the second reactor (P2) are slurry reactors (SR) such as loop reactors (LR) and the third reactor (P3) and fourth reactor (P4) are gas phase reactors (GFR) . Accordingly, at least three, preferably three, polymerization reactors are used in the process according to the invention, namely two slurry reactors (SR), such as two loop reactors (LR), and two gas phase reactors (GFR-1) and (GFR-2) connected in series. If necessary, a pre-polymerization reactor is placed before the first slurry reactor (SR).

The preferred multi-stage process is the loop gas phase process such as developed by Borealis A/S, Denmark, known as the BORSTAR® technology, disclosed for example in patent literature such as EP 0887379, WO 92/12182, WO 2004/000899, WO 2004 /111095, WO 99/24478, WO 99/24479 or WO 00/68315.

Another suitable slurry gas phase process is the Spheripol® process developed by Basell.

Preferably, in the process disclosed above for the production of a heterophasic propylene copolymer (HECO1) according to the invention in the first reactor (P1), i.e. in a slurry reactor (SR) such as a loop reactor (LR) of step (a), the following conditions can be created:

temperature 50°C to 110°C, preferably 60°C to 100°C, more preferably 68 to 95°C, pressure 20 bar to 80 bar (2 to 8x106 Pa), preferably 40 bar to 70 bar (4 to 7x106 Pa), hydrogen can be added to adjust the molar mass by methods known in the art.

The reaction mixture obtained in step (a) is then transferred to the second reactor (P2), i.e. into a gas-phase reactor (GFR-1), i.e. to step (c), and step (c) is preferably carried out under the following conditions:

temperature 50°C to 130°C, preferably 60°C to 100°C, pressure 5 bar to 50 bar (0.5 to 5x106 Pa), preferably 15 bar to 35 bar (1.5 to 3.5x106 Pa), hydrogen can be added to adjust the molar mass by methods known in the art.

The residence time in the zones of the three reactors may be different.

In one of the embodiments of the method for producing polypropylene, the residence time in the reactor in which the reaction proceeds in bulk, for example in a loop (loop reactor), is from 0.1 to 2.5 hours, for example from 0.15 to 1.5 hours, and the residence time in the gas phase reactor is typically 0.2 to 6.0 hours, such as 0.5 to 4.0 hours.

The reaction mixture obtained in step (c) is then transferred to the third reactor (P3), i.e. gas-phase reactor (GFR-2), and possibly into the fourth reactor (P4), i.e. gas-phase reactor (GFR-3). The conditions and residence times in the reactors (P3) and/or (P4) are preferably identical to the conditions and residence times in the reactor (P2) indicated in the preceding paragraphs.

If necessary, in the first reactor (P1), i.e. in a slurry reactor (SR), such as a loop reactor (LR), and/or in a condensed mode in gas phase reactors (GFR), the polymerization can be carried out in a known manner under supercritical conditions.

Preferably, the process also includes prepolymerization in the presence of a catalyst system, discussed in more detail below, including a Ziegler-Natta procalyst, an external donor, and optionally a co-catalyst.

In one preferred embodiment, the prepolymerization is carried out as bulk slurry polymerization in liquid propylene, i. the liquid phase mainly comprises propylene with a small amount of other reactants and possibly inert components dissolved in propylene.

The prepolymerization reaction is usually carried out at a temperature of 10 to 60°C, preferably 15 to 50°C, and more preferably 20 to 45°C.

The choice of pressure in the prepolymerization reactor is not critical, but the pressure must be high enough to maintain the reaction mixture in the liquid phase. Thus, the pressure may be from 20 to 100 bar (0.2 to 1 x 10 ⁷ Pa), for example 30 to 70 bar (3 to 7 x 10 6 Pa).

All catalyst components are preferably introduced during the prepolymerization step. However, if the solid component (i) of the catalyst and the co-catalyst (ii) can be supplied separately, it is possible that only a part of the co-catalyst is introduced during the pre-polymerization step, and the remainder is introduced during the subsequent polymerization steps. In addition, in such cases, it is necessary to introduce an amount of cocatalyst into the prepolymerization stage,

- 10 040146 which is sufficient to carry out the polymerization reaction at this stage.

Other components may also be added during the prepolymerization step. Thus, as is known in the art, hydrogen can be added to control the molecular weight of the prepolymer during the prepolymerization step. In addition, an antistatic additive can be used to prevent the particles from sticking together or sticking to the walls of the reactor.

Precise control of prepolymerization conditions and reaction parameters is known in the art.

According to the invention, a heterophasic propylene copolymer (HESO1) is produced by the multi-stage polymerization process discussed above in the presence of a catalyst system comprising as component (i) a Ziegler-Natta procalyst, which contains a transesterification product of a lower alcohol and a phthalic acid ester.

The procatalyst used according to the invention to obtain a heterophasic composition (HESO1) is obtained by

a) reacting the spray-crystallized or emulsion-hardened adduct of MgCl2 and C ₁ -C ₂ alcohol with TiCl ₄ ;

b) reacting the product obtained in step a) with a dialkyl phthalate having the formula (I) O

D) where R ¹ and R ² independently represent at least C ₅ alkyl, under conditions in which the trans-esterification reaction proceeding between said C1-C2 alcohol and said dialkyl phthalate having formula (I) leads to the formation of an internal donor ;

c) washing the product obtained in step b), or

d) possibly reacting the product obtained in step c) with additional TiCl ₄ .

The procatalyst is prepared as described, for example, in WO 87'/07620, WO 92/19653, WO 92/19658 and EP 0491566. The contents of these documents are hereby incorporated by reference.

First, an adduct of MgCl ₂ and C ₁ -C ₂ alcohol is prepared having the formula MgCl ₂ -nROH, where R is methyl or ethyl and n is 1 to 6. Ethanol is preferably used as the alcohol.

The adduct, which is first melted and then crystallized by spraying or emulsion curing, is used as a catalyst carrier.

In the next step, the spray-crystallized or emulsion-hardened adduct having the formula MgCl ₂ -nROH, where R is methyl or ethyl, preferably ethyl, and n is from 1 to 6, is contacted with TiCl ₄ , resulting in the formation of a titanated support , after which the following steps are performed:

adding to said titanated support (i) a dialkyl phthalate having the formula (I) in which R ¹ and R ² are independently at least C ₅ alkyl, for example at least C 8 alkyl, or preferably (ii) a dialkyl phthalate having the formula ( I) wherein R ¹ and R ² are the same and are at least C ₅ alkyl, such as at least C 8 alkyl, or more preferably (iii) a dialkyl phthalate having formula (I) which is selected from the group consisting of propylhexyl phthalate (PrHF), dioctyl phthalate (DOP), di-isodecyl phthalate (DIDP) and ditridecyl phthalate (DTDP), more preferably a dialkyl phthalate having formula (I), which is dioctyl phthalate (DOP), such as di-isooctyl phthalate or diethylhexyl phthalate, in particular diethylhexyl phthalate , to obtain a first product, subjecting said first product to conditions suitable for trans-esterification, i. e. temperature exceeding 100°C, preferably between 100 and 150°C, more preferably between 130 and 150°C, resulting in trans-esterification of said methanol or ethanol of said ester groups of said dialkyl phthalate having formula (I) to form preferably at least 80 mol%, more preferably 90 mol%, most preferably 95 mol% of a dialkyl phthalate having formula (II)

O where R ¹ and R ² are methyl or ethyl, preferably ethyl, a dialkyl phthalate having

- 11 040146 formula (II), is an internal donor, and the extraction of the specified trans-esterification product, which is the composition of pronatalistic (component (i)).

In one preferred embodiment, the adduct having the formula MgCl2-nROH, where R is methyl or ethyl and n is 1 to 6, is melted, whereupon the melt is preferably introduced by gas into the cooled solvent or cooled gas, whereby the adduct crystallizes in a morphologically preferred form, such as described in WO 87/07620.

The resulting crystallized adduct is preferably used as a catalyst carrier and reacted with a procatalyst used according to the present invention as described in WO 92/19658 and WO 92/19653.

After removal of the catalyst residue by extraction, an adduct of the titanated support and an internal donor is obtained, in which the alcohol group of the ester is replaced.

In the event that a sufficient amount of titanium remains on the carrier, it will act as the active element of the pronatalistic agent.

Otherwise, after the treatment described above, the titanization is repeated to create a sufficient concentration of titanium and thus sufficient activity.

Preferably, the procatalyst used according to the invention contains no more than 2.5 wt.% titanium, preferably no more than 2.2 wt.% and more preferably no more than 2.0 wt.%. Its donor content is preferably 4 to 12% by weight, and more preferably 6 to 10% by weight.

More preferably, the procatalyst used according to the invention is prepared using ethanol as the alcohol and dioctyl phthalate (DOP) as the dialkyl phthalate having formula (I), resulting in diethyl phthalate (DEP), which is an internal donor.

Even more preferably, the catalyst used according to the invention is the catalyst discussed in the Examples section; in particular when using dioctyl phthalate as the dialkyl phthalate having the formula (I).

Used, along with a special Ziegler-Natta procatalyst, to obtain a heterophasic composition (GEKO) according to the invention, the catalyst system preferably includes an organometallic cocatalyst as component (ii).

Accordingly, the co-catalyst is preferably selected from the group consisting of trialkylaluminum, eg triethylaluminum (TEA), dialkylaluminum chloride and alkylaluminum sesquichloride.

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

where R ⁵ represents a branched alkyl group containing from 3 to 12 carbon atoms, preferably a branched alkyl group containing from 3 to 6 carbon atoms, or a cycloalkyl containing from 4 to 12 carbon atoms, preferably a cycloalkyl containing from 5 to 8 atoms carbon.

In particular, R ⁵ is preferably selected from the group consisting of isopropyl, isobutyl, isopentyl, t-butyl, t-amyl, neopentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and cycloheptyl.

Formula (IIIb) is shown below:

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

R ^x and R ^y are independently selected from the group consisting of a linear aliphatic hydrocarbon group containing 1 to 12 carbon atoms, a branched aliphatic hydrocarbon group containing 1 to 12 carbon atoms, and a cyclic aliphatic hydrocarbon group containing 1 to 12 carbon atoms. carbon. In particular, R ^x and R ^y are preferably independently selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, octyl, decanyl, isopropyl, isobutyl, isopentyl, t-butyl, t-amyl, neopentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and cycloheptyl.

More preferably R ^x and R ^y are the same, even more preferably R ^x and R ^y are ethyl groups.

More preferably, the external donor has the formula (IIIa), for example, is dicyclopentyldimethoxysilane [Si(OCH ₃ ) ₂ (cyclopentyl) ₂ ], diisopropyldimethoxysilane [Si(OCH ₃ ) ₂ (CH(CH ₃ ) ₂ ) ₂ ].

Most preferably, the external donor is dicyclopentyldimethoxysilane [Si(OCH ₃ ) ₂ (cyclopentyl) ₂ ] (donor D).

In another embodiment, the Ziegler-Natta procatalyst can be modified by polymerizing a vinyl-containing compound in the presence of a catalyst system comprising a custom Ziegler-Natta procatalyst (component (i)), an external donor (component (iii)) and optionally a co-catalyst

- 12 040146 (component (iii)), where the vinyl-containing compound has the formula:

where R ³ and R ⁴ together form a 5- or 6-membered saturated, unsaturated or aromatic cycle, or independently represent an alkyl group containing from 1 to 4 carbon atoms, and the modified catalyst is used to obtain a heterophasic composition (HEKO) according to the present invention. The polymerized vinyl-containing compound may serve as an azo-forming agent.

Information on the modification of the catalyst is found in WO 99/24478, WO 99/24479, and in particular WO 00/68315, which are incorporated into the present description by reference in so far as the reaction conditions used to modify the catalyst, as well as in the part regarding the polymerization reaction.

Heterophasic propylene copolymer (HESO2)

According to one of the preferred embodiments of the present invention, the polypropylene composition (K) further comprises a heterophasic propylene copolymer (HESO2) which is different from a heterophasic propylene copolymer (HESO1).

The heterophasic propylene copolymer (HECO2) of the present invention includes a matrix (M2) which is a propylene polymer (PP2) and an elastomeric propylene copolymer dispersed therein which is an elastomeric propylene copolymer (E2). Thus, the matrix (M2) contains (finely) dispersed inclusions that are not part of the matrix (M2), and these inclusions contain an elastomeric propylene copolymer (E2). The explanation of the inclusion term is given above.

Accordingly, the heterophasic propylene copolymer (HECO2) of the present invention preferably includes (a) a (semi)crystalline propylene polymer (PP2) as a matrix (M2) and (b) an elastomeric propylene copolymer (E2).

Preferably, the weight ratio (PP2/E2) of the amount of propylene polymer (PP2) to the amount of elastomeric propylene copolymer (E2) in the heterophasic propylene copolymer (HECO2) is from 90/10 to 40/60, more preferably from 85/15 to 45/55, more preferably 83/17 to 50/50, for example 82/18 to 60/40.

Preferably, the heterophasic propylene copolymer (HECO2) according to the present invention comprises only propylene polymer (PP2) and elastomeric propylene copolymer (E2) as polymer components. In other words, the heterophasic propylene copolymer (HECO2) may contain additional additives, but does not contain another polymer in an amount greater than 5.0 wt.%, more preferably greater than 3.0 wt.%, for example, greater than 1.0 wt.%, based on from the total mass of heterophasic propylene copolymer (HESO2).

One additional polymer that may be present in such low amounts is polyethylene, which is a by-product of the heterophasic propylene copolymer (HECO2) reaction. Accordingly, it should be especially noted that the heterophasic propylene copolymer (HECO2) according to the invention contains only propylene polymer (PP2), elastomeric propylene copolymer (E2) and optionally polyethylene in the amount indicated in this paragraph.

The heterophasic propylene copolymer (HECO2) used in the present invention has a rather low melt flow index. Accordingly, the heterophasic propylene copolymer (HECO2) has a melt flow index MFR2 (230° C.) of 50 to 120 g/10 min, preferably 60 to 110 g/10 min, more preferably 65 to 91 g/10 min.

Preferably, it is desirable that the heterophasic propylene copolymer (HECO2) has thermomechanical stability. Suitably, the melting point of the heterophasic propylene copolymer (HECO2) is preferably at least 160°C, more preferably 160 to 167°C, even more preferably 162 to 165°C.

In addition to propylene, heterophasic propylene copolymer (HECO2) also includes comonomers. Preferably, in addition to propylene, the heterophasic propylene copolymer (HESO2) comprises ethylene and/or C ₄ -C ₈ α-olefins. Accordingly, the term propylene copolymer according to the present invention means a polypropylene comprising, preferably consisting of, units derived from (a) propylene and (b) ethylene and/or C ₄ -C ₈ α-olefins.

Thus, a heterophasic propylene copolymer (HECO2), i.e. propylene polymer (PP2) in combination with an elastomeric propylene copolymer (E2), may include monomers copolymerizable with propylene, for example comonomers such as ethylene and/or C ₄ -C ₈ α-olefins, in particular ethylene and/or C ₄ -C _6α -olefins, for example 1-butene and/or 1-hexene. Preferably, the heterophasic propylene copolymer (HECO2) according to the present invention comprises, in particular consists of, propylene copolymerizable monomers selected from the group,

- 13 040146 consisting of ethylene, 1-butene and 1-hexene. In particular, in addition to propylene, the heterophasic propylene copolymer (HECO2) according to the present invention includes units that can be obtained from ethylene and/or 1-butene. In one preferred embodiment, the heterophasic propylene copolymer (HECO2) according to the present invention includes units that can only be obtained from ethylene and propylene. Even more preferably, the propylene polymer (PP2) as well as the elastomeric propylene copolymer (E2) constituting the heterophasic propylene copolymer (HECO2) contain the same comonomers such as ethylene.

In addition, it should be taken into account that the heterophasic propylene copolymer (HECO2) preferably has a sufficiently low total comonomer content, preferably an ethylene content. Thus, the comonomer content of the heterophasic propylene copolymer (HECO2) is preferably 4.0 to 30.0 mol%, preferably 6.0 to 18.0 mol%, more preferably 10.0 to 13.0 mol%. .%

The amount of cold xylene soluble fraction (XCF) in the heterophasic propylene copolymer (HESO2) determined according to ISO 16152 (25°C) is from 8.0 to 35.0% by weight, preferably from 11.0 to 30, 0 wt.%, more preferably from 12.0 to 25.0 wt.%, even more preferably from 13.0 to 22.0 wt.%.

Additionally, it should be taken into account that the amount of the cold xylene-soluble fraction (RKF) of the heterophasic propylene copolymer (HESO2) is determined by its inherent viscosity. The low intrinsic viscosity (IV) value reflects the low weight average molecular weight. For the purposes of the present invention, it is preferable that, determined in accordance with ISO 1628/1 (at 135° C. in decalin), the intrinsic viscosity (IV) of the xylene cold-soluble fraction (RKF) of the heterophasic propylene copolymer (HESO2) is from 1.0 to 3, 3 dl/g, preferably 1.5 to 3.2 dl/g, more preferably 1.7 to 3.0 dl/g.

In addition, the comonomer content, i.e. the content of ethylene in the xylene cold-soluble fraction (XCF) of the heterophasic propylene copolymer (HECO2) is preferably greater than or equal to 40 mol.%, preferably 40 to 55 mol.%, more preferably 42 to 50 mol.%, more preferably 43 to 46 mole % The comonomers present in the cold xylene soluble fraction (XCF) are the comonomers described above for propylene polymer (PP2) and elastomeric propylene copolymer (E2), respectively. In one preferred embodiment, the comonomer is ethylene alone.

The characterization of the heterophasic propylene copolymer (HECO2) may further include the characterization of its individual components, i. propylene polymer (PP2) and elastomeric propylene copolymer (E2).

The propylene polymer (PP2) may be a propylene copolymer or a propylene homopolymer, with propylene homopolymer being preferred.

When the propylene polymer (PP2) is a propylene copolymer, the propylene polymer (PP2) includes monomers capable of being copolymerized with propylene, for example comonomers such as ethylene and/or C4-C8 α-olefins, in particular ethylene and/or C4-C6 α-olefins, for example 1-butene and/or 1-hexene. Preferably, the propylene polymer (PP2) according to the present invention comprises, in particular consists of monomers capable of copolymerization with propylene, selected from the group consisting of ethylene, 1-butene and 1-hexene. In particular, the propylene polymer (PP2) according to the present invention, in addition to propylene, includes units that can be obtained from ethylene and/or 1-butene. In one of the preferred embodiments, the propylene polymer (PP2) includes units that can only be obtained from ethylene and propylene.

The melt flow index MFR ₂ (230°C/2.16 kg) of the propylene polymer (PP2) according to the present invention, determined in accordance with ISO 1133, is from 120 to 500 g/10 min, more preferably from 130 to 200 g/10 min, even more preferably 140 to 170 g/10 min.

As noted above, the heterophasic propylene copolymer (HESO2) has a low comonomer content. Accordingly, the content of the comonomer in the propylene polymer (PP2) is from 0.0 to 5.0 mol.%, more preferably from 0.0 to 3.0 mol.%, even more preferably from 0.0 to 1.0 mol.% Particularly preferably, the propylene polymer (PP2) is a propylene homopolymer.

The heterophasic propylene copolymer (HECO2) preferably comprises 60 to 95 wt%, more preferably 60 to 90 wt%, even more preferably 65 to 87 wt% propylene polymer (PP2), based on the total weight of the heterophasic propylene copolymer ( GESO2).

Additionally, the heterophasic propylene copolymer (HECO2) preferably comprises 5 to 40 wt%, more preferably 10 to 40 wt%, even more preferably 13 to 35 wt% elastomeric propylene copolymer (E2), based on the total weight of the heterophasic propylene copolymer (GESO2).

Thus, according to the invention, the heterophasic propylene copolymer (HECO2) preferably comprises, more preferably consists of 60 to 95% by weight, preferably 60 to 90% by weight, more preferably 65.0 to 87.0% by weight of propylene polymer (PP2) and from 5 to 40 wt.%, preferably from 10 to 40 wt.%, more preferably from 13.0 to 35.0 wt.% of the elastomeric propylene copolymer (E2), based on the total mass of the heterophasic propylene copolymer (GESO2).

Accordingly, the other component of the heterophasic propylene copolymer (HECO2) is an elastomeric propylene copolymer (E2) dispersed in a matrix (M2) which is a propylene polymer (PP2). The information disclosed in the description of the comonomers used to make the heterophasic propylene copolymer (HECO2) also applies to the comonomers used to make the elastomeric propylene copolymer (E2). Accordingly, the elastomeric propylene copolymer (E2) comprises monomers capable of being copolymerized with propylene, for example comonomers such as ethylene and/or C4-C8 α-olefins, in particular ethylene and/or C ₄ -C ₆ α-olefins, for example 1-butene and/ or 1-hexene. Preferably, the elastomeric propylene copolymer (E2) comprises, in particular consists of, propylene copolymerizable monomers selected from the group consisting of ethylene, 1-butene and 1-hexene. In particular, the elastomeric propylene copolymer (E2), in addition to propylene, includes units that can be obtained from ethylene and/or 1-butene. Thus, in one particularly preferred embodiment, the elastomeric propylene copolymer (E2) includes units that can only be obtained from ethylene and propylene.

The comonomer content of the elastomeric propylene copolymer (E2) is preferably 35.0 to 70.0 mol%, more preferably 37.0 to 60.0 mol%, even more preferably 40.0 to 50.0 mol%. %

The heterophasic propylene copolymer (HECO2) according to the invention may contain up to 5.0% by weight of additives such as nucleating agents and antioxidants, as well as friction reducing and antiblocking additives. Preferably, the content of additives (without α nucleating agents) is less than 3.0 wt.%, for example, less than 1.0 wt.%.

According to a preferred embodiment of the present invention, the heterophasic propylene copolymer (HECO2) contains an α-nucleating agent.

According to the present invention, the alpha nucleating agent is not an additive (DOB).

The alpha nucleating agent 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;

(ii) dibenzylidene sorbitol (for example, 1,3:2,4-dibenzylidene sorbitol) and C ₁ -C ₈ -αkyl-substituted derivatives of dibenzylidene sorbitol, such as methyldibenzylidene sorbitol, ethyldibenzylidene sorbitol or dimethyldibenzylidene sorbitol (for example, 1,3:2,4-di(methylbenzylidene) sorbitol), or substituted nonit derivatives such as 1,2,3-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene]-nonit;

(iii) salts of diesters of phosphoric acid, for example, sodium 2,2'-methylene-bis(4,6-di-tert-butylphenyl)phosphate or hydroxy-bis[2,2'-methylene-bis(4,6-di- tert-butylphenyl)phosphate]aluminum;

(iv) a vinyl cycloalkane polymer or a vinyl alkane polymer;

(v) their mixtures.

Preferably, the alpha nucleating agent included in the composition according to the invention is a vinyl cycloalkane polymer and/or a vinyl alkane polymer, more preferably a vinyl cycloalkane polymer such as a vinyl cyclohexane (VCH) polymer. A particularly preferred α-nucleating agent is a vinylcyclohexane (VCH) polymer. It should be taken into account that the amount of vinylcycloalkane, for example vinylcyclohexane (VCH), polymer and/or vinylalkane polymer, more preferably vinylcyclohexane (VCH) polymer, in the composition is not more than 500 ppm, preferably not more than 200 ppm, more preferably not more than 100 ppm, for example from 0.1 to 500 ppm, preferably from 0.5 to 200 ppm, more preferably from 1 to 100 ppm. In addition, it should be taken into account that the vinyl cycloalkane polymer and/or the vinyl alkane polymer is introduced into the composition by means of BNT technology. A description of BNT technology can be found in 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 polymerizing a vinyl-containing compound in the presence of a catalyst system including, in particular, a special Ziegler-Natta procatalyst, an external donor, and a co-catalyst, which is a vinyl-containing compound having the formula:

where R ³ and R ⁴ together form a 5- or 6-membered saturated, unsaturated or aromatic cycle or independently represent an alkyl group containing from 1 to 4 carbon atoms, and the modified catalyst is preferably used to obtain a heterophasic composition (GEKO) contained in modified polypropylene composition (mPP). The polymerized vinyl-containing compound serves as an alpha nucleating agent. The weight ratio of vinyl-containing 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 0.5 (1:2) to 2 (2:1). ).

Such nucleating agents are commercially available and are discussed, for example, in the Plastic Additives Handbook, 5th ed., 2001, Hans Zweifel (pp. 967-990).

A heterophasic propylene copolymer (HESO2) can be obtained by mixing a propylene polymer (PP2) and an elastomeric propylene copolymer (E2). Preferably, however, the heterophasic propylene copolymer (HECO2) is produced in a sequential process using reactors connected in series operating under different reaction conditions. As a consequence, each fraction obtained in a particular reactor may have its own molecular weight distribution and/or distribution of comonomer content.

The heterophasic propylene copolymer (HECO2) according to the present invention is preferably produced by a sequential polymerization process, i.e. in a multi-stage process known in the art, in which the propylene polymer (PP2) is produced in at least one slurry reactor, preferably in the slurry reactor and possibly in a gas phase reactor located downstream, and then the elastomeric propylene copolymer (E2) is produced at least in one, i.e. in one or two gas-phase reactors.

Accordingly, the heterophasic propylene copolymer (HECO2) is preferably produced by a sequential polymerization process comprising the following steps:

(a) polymerizing propylene and optionally at least one of the following: ethylene and/or C ₄ -C ₁₂ α-olefin in the first reactor (P1), obtaining the first polypropylene fraction of the propylene polymer (PP2), and preferably said first polypropylene the fraction is a propylene homopolymer;

(b) optionally transporting the first polypropylene fraction to a second reactor (P2);

(c) polymerizing propylene and optionally at least one of the following: ethylene and/or C ₄ -C ₁₂ α-olefin in the second reactor (P2) in the presence of said first polypropylene fraction, resulting in a second polypropylene fraction, where said second polypropylene fraction is preferably a second propylene homopolymer, and said polypropylene first polypropylene fraction and said second polypropylene fraction form a propylene polymer (PP2), i.e. heterophasic propylene copolymer matrix (HESO2);

(d) transporting the propylene polymer (PP2) obtained in step (c) to the third reactor (P3), (e) polymerizing propylene and ethylene in the third reactor (P3), in the presence of the propylene polymer (PP2) obtained in step ( c) to obtain an elastomeric propylene copolymer (E2) dispersed in a propylene polymer (PP2), wherein the propylene polymer (PP2) and the elastomeric propylene copolymer (E2) form a heterophasic propylene copolymer (HECO2).

Of course, in the first reactor (P1) the second polypropylene fraction can be obtained and in the second reactor (P2) the first polypropylene fraction can be obtained. The same applies to the elastomeric propylene copolymer phases.

Preferably, in the area between the second reactor (P2) and the third reactor (P3), the monomers are flashed.

The term sequential polymerization process indicates that the heterophasic propylene copolymer (HECO2) is produced in at least two, eg three or four, reactors connected in series. Accordingly, the process according to the invention comprises at least a first reactor (P1) and a second reactor (P2), more preferably a first reactor (P1), a second reactor (P2) and a third reactor (P3). The term polymerization reactor is defined above.

The first reactor (P1) is preferably a slurry reactor (SR) which can be any continuous reactor or a simple stirred batch reactor or loop reactor in which the reaction is carried out in bulk or in slurry. Bulk polymerization means polymerization in a reaction medium which includes at least 60% by weight of monomer.

According to the present invention, the slurry reactor (SR) is preferably a loop reactor (LR) (for carrying out the reaction in bulk).

The second reactor (P2) may be a slurry reactor, for example a loop reactor such as the first reactor, or alternatively a gas phase reactor (GFR).

The third reactor (P3) is preferably a gas phase reactor (GFR).

Gas phase reactors (GFRs) can be any mechanically stirred or fluidized bed reactors. Preferably gas phase reactors (GFRs) include mechanically agitated fluidized bed reactors in which gas velocities reach at least 0.2 m/s. Thus, preferably the gas phase reactor is a fluidized bed reactor, preferably equipped with a mechanical stirrer.

Thus, in one preferred embodiment, the first reactor (P1) is a slurry reactor (SR) such as a loop reactor (LR), while the second reactor (P2) and the third reactor (P3) are gas phase reactors (GFR) . Accordingly, at least three, preferably three, polymerization reactors are used in the process according to the invention, namely

- 16 040146 slurry reactor (SR), such as a loop reactor (LR), a first gas phase reactor (GFR-1) and a second gas phase reactor (GFR-2), connected in series. If necessary, a prepolymerization reactor is placed before the slurry reactor (SR).

In another preferred embodiment, the first reactor (P1) and the second reactor (P2) are slurry reactors (SR), such as loop reactors (LR), while the third reactor (P3) is a gas phase reactor (GFR). Accordingly, at least three, preferably three, polymerization reactors are used in the process according to the invention, namely two slurry reactors (SR), for example two loop reactors (LR), and a gas phase reactor (GFR-1) connected in series. If necessary, a pre-polymerization reactor is placed before the first slurry reactor (SR).

The preferred multi-stage process is the loop-gas-phase process such as the technology developed by Borealis A/S, Denmark (known as the BORSTAR® technology) discussed for example in patent literature such as EP 0887379, WO 92/12182, WO 2004/000899 , WO 2004/111095, WO 99/24478, WO 99/24479 or WO 00/68315.

Another suitable slurry gas phase process is the Spheripol® process developed by Basell.

Preferably, in the process disclosed above for the production of a heterophasic propylene copolymer (HECO2) according to the invention in the first reactor (P1), i.e. in a slurry reactor (SR) such as a loop reactor (LR) of step (a), the following conditions can be created: temperature from 50°C to 110°C, preferably from 60°C to 100°C, more preferably from 68 to 95°C, pressure 20 bar to 80 bar (2 to 8x106 Pa), preferably 40 bar to 70 bar (4 to 7x106 Pa), hydrogen can be added to adjust the molar mass by methods known in the art.

The reaction mixture obtained in step (a) is then transferred to the second reactor (P2), i.e. into a gas-phase reactor (GFR-1), i.e. to step (c), and step (c) is preferably carried out under the following conditions:

temperature 50°C to 130°C, preferably 60°C to 100°C, pressure 5 bar to 50 bar (0.5 to 5x106 Pa), preferably 15 bar to 35 bar (1.5 to 3.5x106 Pa), hydrogen can be added to adjust the molar mass by methods known in the art.

The conditions in the third reactor (P3), which is preferably the second gas phase reactor (GFR-2), are similar to those in the second reactor (P2).

The residence time in the zones of the three reactors may be different.

In one of the embodiments of the method for producing polypropylene, the residence time in the reactor in which the reaction proceeds in bulk, for example, in a loop (loop reactor), is from 0.1 to 2.5 hours, for example from 0.15 to 1.5 hours, and the residence time in the gas phase reactor is typically 0.2 to 6.0 hours, such as 0.5 to 4.0 hours.

If necessary, in the first reactor (P1), i.e. in a slurry reactor (SR), such as a loop reactor (LR), and/or in a condensed mode in gas phase reactors (GFR), the polymerization can be carried out in a known manner under supercritical conditions.

Preferably, the process also includes prepolymerization in the presence of a catalyst system, discussed in more detail below, including a Ziegler-Natta procalyst, an external donor, and optionally a co-catalyst.

In one of the preferred embodiments, the prepolymerization is carried out as a bulk slurry polymerization in liquid propylene, i. e. the liquid phase mainly includes propylene with a small amount of other reagents and, possibly, inert components dissolved in propylene.

The prepolymerization reaction is generally carried out at a temperature of 10 to 60°C, preferably 15 to 50°C, and more preferably 20 to 45°C.

The choice of pressure in the prepolymerization reactor is not critical, but the pressure must be high enough to maintain the reaction mixture in the liquid phase. Thus, the pressure may be from 20 to 100 bar (0.2 to 1 x 10 ⁷ Pa), for example 30 to 70 bar (3 to 7 x 10 6 Pa).

All catalyst components are preferably introduced during the prepolymerization step. However, if the solid catalyst component (i) and the cocatalyst (ii) can be supplied separately, it is possible that only a part of the cocatalyst is introduced in the prepolymerization step and the remainder is introduced in the subsequent polymerization steps. In addition, in such cases, it is necessary to introduce an amount of co-catalyst into the pre-polymerization step that is sufficient to carry out the polymerization reaction.

Other components may also be added during the prepolymerization step. Thus, as is known in the art, hydrogen can be added in the prepolymerization step to control the molecular weight of the prepolymer. In addition, an antistatic additive can be used to prevent the particles from sticking together or sticking to the walls of the reactor.

- 17 040146

Precise control of prepolymerization conditions and reaction parameters is known in the art.

According to the invention, a heterophasic propylene copolymer (HECO2) is produced by the multi-stage polymerization process discussed above in the presence of a catalyst system comprising as component (i) a Ziegler-Natta procatalyst which contains a transesterification product of a lower alcohol and a phthalic acid ester.

In selecting the preferred catalyst system, mention may be made of the catalyst disclosed above in the description of the heterophasic propylene copolymer (HECO1).

According to another preferred embodiment, a Ziegler-Natta catalyst suitable for the production of a heterophasic propylene copolymer (HECO2) comprises a high yield Ziegler-Natta catalyst that includes an internal donor as a component that can be used at high polymerization temperatures of 80° C. or more. As an internal donor (IDD), a high yield Ziegler-Natta catalyst may include succinate, diester, phthalate, etc. or mixtures thereof, and be, for example, a commercially available catalyst available from LyondellBasell under the tradename Avant ZN. Examples of Avant ZN series catalysts are Avant ZN 126 and Avant ZN 168. Avant ZN 126 is a Ziegler-Natta catalyst containing 3.5% by weight titanium and a diester compound as internal electron donor; this catalyst is supplied by LyondellBasell. Avant ZN 168 is a Ziegler-Natta catalyst containing 2.6 wt% titanium and succinate as an internal electron donor; this catalyst is supplied by Lyondell Basell. Another example of an Avant ZN series catalyst is the ZN180M catalyst supplied by LyondellBasell.

In another embodiment, the Ziegler-Natta procatalyst suitable for the preparation of the second heterophasic propylene copolymer (HECO2) may also be modified by polymerization of a vinyl-containing compound in the presence of the catalyst system discussed above.

Plastomer (PL)

According to one of the preferred embodiments of the present invention, the polypropylene composition (K) further comprises a plastomer (PL), which is a copolymer of ethylene and a C4-C8 α-olefin.

The plastomer (PL) may be any elastomeric polyolefin, provided that it is chemically different from the elastomeric propylene copolymers (E1) and (E2) defined herein. More preferably the plastomer (PL) is a very low density polyolefin, even more preferably a very low density polyolefin polymerized in the presence of a single site catalyst, preferably a metallocene catalyst. Typically, a plastomer (PL) is an ethylene copolymer.

The density of the plastomer (PL) is less than 0.900 g/cm ³ . More preferably, the plastomer density (PL) is less than or equal to 0.890 g/cm ³ , even more preferably 0.845 to 0.890 g/cm ³ .

Preferably, the melt flow index MFR ₂ (190° C., 2.16 kg) of the plastomer (PL) is less than 50 g/10 min, more preferably 10.0 to 40 g/10 min, even more preferably 15.0 to 35 g/10 min, e.g. 25.0 to 33.0 g/10 min.

Preferably the plastomer (PL) includes units derived from ethylene and C ₄ -C ₂₀ α-olefin.

The plastomer (PL) comprises, preferably consists of, units that can be derived from (i) ethylene and (ii) at least another C ₄ -C ₂₀ α-olefin such as a C ₄ -C ₁₀ α-olefin, more preferably from units that can be derived from (i) ethylene and (ii) at least another α-olefin selected from the group consisting of 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene. Particularly preferably, the plastomer (PL) comprises at least units that can be derived from (i) ethylene and (ii) 1-butene or 1-octene. Particularly preferably, the plastomer (PL) is a copolymer of ethylene and 1-octene.

In one particularly preferred embodiment, the plastomer (PL) consists of units that can be derived from ethylene and 1-octene.

The content of comonomer, for example the content of C ₄ -C ₂₀ α-olefin, in the plastomer (PL) is from 3.0 to 25.0 mol.%, more preferably from 4.0 to 20.0 mol.%, even more preferably from 5.0 to 15.0 mol%, e.g. 6.0 to 10.0 mol%

In one preferred embodiment, the plastomer (PL) is produced in the presence of at least one metallocene catalyst. The plastomer (PL) can also be made in the presence of more than one metallocene catalyst, or it can be a mixture of elastomers made in the presence of different metallocene catalysts. In some embodiments, the plastomer (PL) is essentially a linear ethylene polymer (SNEP). SNAP-type polymers and other plastomers (PL) produced using metallocene catalysts are known in the art, such as those described in US 5,272,236. These polymers are also commercially available, such as Queo™ plastomers supplied by Borealis, supplied by Dow Chemical Co., or EXACT™ polymers supplied

- 18 040146

Exxon or TAFMER™ polymers supplied by Mitsui.

High density polyethylene (HDPE)

According to one preferred embodiment of the present invention, the polypropylene composition (K) further comprises high density polyethylene (HDPE).

The expression high density polyethylene used in the description of the present invention refers to a polyethylene obtained in the presence of a Ziegler-Natta catalyst or a metallocene catalyst, which is essentially, i. more than 99.70 mol.%, even more preferably at least 99.80 mol.% consists of units of ethylene. In one preferred embodiment, only ethylene units can be detected in high density polyethylene (HDPE).

The density of high density polyethylene (HDPE) is at least 0.800 g/cm ³ . More preferably, the density of high density polyethylene (HDPE) is from 0.830 to 0.970 g/cm ³ , even more preferably from 0.900 to 0.965 g/cm ³ , for example from 0.940 to 0.960 g/cm ³ .

Particularly preferably, the weight average molecular weight Mw of the high density polyethylene (HDPE) is 60 to 85 kg/mol, preferably 65 to 85 kg/mol, even more preferably 70 to 80 kg/mol.

In addition, high density polyethylene (HDPE) preferably has a sufficiently broad molecular weight distribution (Mw/Mn). Accordingly, the molecular weight distribution (Mw/Mn) of high density polyethylene (HDPE) is preferably 6.0 to 8.0, more preferably 6.5 to 7.5, such as 6.5 to 7.0.

In addition, high density polyethylene (HDPE) preferably has a sufficiently low melt flow index. Accordingly, the melt flow index MFR (190°C, 2.16 kg) of high density polyethylene (HDPE), determined in accordance with ISO 1133, is preferably from 0.1 to 15.0 g/10 min, more preferably from 1.0 up to 10.0 g/10 min, even more preferably 2.0 to 4.0 g/10 min at 190°C.

Preferably, the high density polyethylene (HDPE) of the present invention is a high density polyethylene known in the art. In particular, the high density polyethylene (HDPE) is preferably the commercially available MB7541 ethylene homopolymer from Borealis AG.

Germinating agent (NA)

The polypropylene composition (K) according to the present invention further comprises a nucleating agent (HA) which is a dicarboxylic acid and/or a salt thereof.

Accordingly, said nucleating agent (NA) is preferably an aliphatic or aromatic compound containing two carboxylic acid functional groups in the form of free acids or in the form of acids partially or completely neutralized with alkali or alkaline earth metal cations. In particular, the functional groups of the carboxylic acid of the nucleating agent (NA) according to the present invention may be free acids or acids partially or completely neutralized with sodium, lithium, potassium, calcium, barium, magnesium, strontium cations or mixtures of these cations. Preferably all cations are alkaline earth metal cations. Particularly preferably, the alkaline earth metal cation is a calcium cation.

Preferably, said nucleating agent (NA) is an aliphatic compound containing two carboxylic acid functional groups in the form of free acids or acids partially or completely neutralized with alkali or alkaline earth metal cations. In particular, the nucleating agent (NA) may be a linear or cyclic aliphatic compound. Accordingly, the nucleating agent (NA) is selected from the group consisting of oxalic acid, malonic acid, succinic acid, malic acid, citric acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,1- cyclobutanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid and/or salts thereof.

Particularly preferably, the nucleating agent (NA) is a cyclic aliphatic compound containing two acid functional groups in the form of free acids or acids partially or completely neutralized with alkali or alkaline earth metal cations. Suitably, the nucleating agent (3A) is selected from the group consisting of 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, and/or salts thereof.

Particularly preferably, the nucleating agent (ZA) is 1,2-cyclohexanedicarboxylic acid. Particularly preferably, the nucleating agent (HA) is a composition comprising 1,2-cyclohexanedicarboxylic acid and its calcium salt.

The present invention also relates to the use of a nucleating agent (HA), which is a dicarboxylic acid and/or a salt thereof, to reduce banding of the polypropylene composition (K) discussed above.

According to the present invention, the nucleating agent (NA) does not belong to the class of fillers (H) and additives (DOB).

- 19 040146

Inorganic filler (N)

Another requirement for the composition according to the present invention is the presence of an inorganic filler (H).

Preferably the inorganic filler (H) is a mineral filler. According to the invention, the inorganic filler (H) is a phyllosilicate, mica or wollastonite. A more preferred inorganic filler (H) is selected from the group consisting of mica, wollastonite, kaolinite, smectite, montmorillonite and talc.

The most preferred inorganic fillers (H) are talc and/or wollastonite. Particularly preferably, the inorganic filler (H) is talc.

Preferably, the average particle size (D ₅₀ ) of the filler particles (H) is from 0.8 to 20 μm and the upper threshold particle size (D ₉₅ ) is from 10 to 20 μm; preferably the average particle size (D ₅₀ ) is 5.0 to 8.0 µm and the upper threshold particle size (D ₉₅ ) is 12 to 17 µm, more preferably the average particle size (D ₅₀ ) is 5.5 to 7 .8 µm and the upper threshold size (D ₉₅ ) of the particles is from 13 to 16.5 µm.

According to the present invention, the filler (H) does not belong to the class of α-nucleating agents and additives (DOB).

The filler (H) is a product known in the art and commercially available.

Additives (DOB)

In addition to a heterophasic propylene copolymer (HESO1), a heterophasic propylene copolymer (HESO2), an inorganic filler (H), possibly a plastomer (PL) and possibly a high density polyethylene (HDPE), the composition (K) according to the invention may include additives (DOB). Typical additives are acid scavengers, antioxidants, colorants, light stabilizers, plasticizers, slip agents, extreme pressure agents, dispersants, processing aids, lubricants, pigments, and the like. As stated above, the nucleating agent (NA) and inorganic filler (H) are not additives (DOB).

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

In addition, the term additives (DOB) according to the present invention also includes carrier materials, in particular polymeric carrier materials.

Polymer carrier material

Preferably the composition (K) according to the invention does not include any other polymer or polymers other than the heterophasic propylene copolymers (HESO1) and (HESO2), plastomer (PL) and high density polyethylene (HDPE), in an amount exceeding 15% by weight, preferably in an amount greater than 10 wt.%, more preferably in an amount greater than 9 wt.%, based on the weight of the composition (K). The amount of any polymer which is an additive carrier material (DOB) is not included in the amount of the polymer compounds referred to in the present invention, but is included in the amount of the respective additive.

The additive carrier polymeric material (DOB) is a carrier polymer that ensures uniform distribution of the additive in the composition (K) according to the invention. The choice of polymer carrier material is not limited to a particular polymer. The polymeric carrier material may be an ethylene homopolymer, an ethylene copolymer derived from ethylene and an α-olefin comonomer such as a C ₃ -C ₈ α-olefin comonomer, a propylene homopolymer and/or a propylene copolymer derived from propylene and an α-olefin comonomer such as ethylene and/or C4-C8 α-olefin comonomer.

Product

The composition according to the present invention is preferably used to obtain articles, more preferably foamed articles. Even more preferably, it is used in automotive parts, in particular passenger car interiors and exteriors such as bumpers, side panels, treads, body panels, spoilers, instrument panels, interior panels and the like.

The present invention also relates to products, more preferably foamed products, comprising, preferably comprising at least 60 wt.%, more preferably at least 80 wt.%, even more preferably at least 95 wt.% of the composition according to the invention, for example consisting from the given composition. Accordingly, the invention mainly relates to parts of automotive parts, in particular interior and exterior parts of passenger cars, such as bumpers, side panels, treads, body panels, spoilers, instrument panels, interior panels and the like, which include, preferably include at least at least 60 wt.%, more preferably at least 80 wt.%, even more preferably at least 95 wt.%, for example consist of a composition according to the invention.

Application

The present invention also relates to the use of the composition according to the invention for the preparation of the foamed article described above.

The present invention is described in more detail below with the help of the following examples.

Examples 1. Measurement methods.

Unless otherwise indicated, the following definitions of terms and descriptions of methods refer to the above general description of the invention, as well as to the examples below.

Calculation of the comonomer content in the first elastomeric propylene copolymer fraction, i.e. polymer fraction of heterophasic propylene copolymer (HESO1) obtained in the third reactor (P3):

C(PP) - w(nni2)xC(Iini2) w(nil3) = C(PPZ) where w(PP12) is the mass fraction (wt.%) of the first and second propylene polymer fractions, polymer obtained in the first and second reactors (P1 + P2), w(PP3) - mass fraction (in wt.%) of the first fraction of the elastomeric propylene copolymer, i.e. polymer obtained in the third reactor (P3),

C(PP12) - comonomer content (in mol.%) in the first and second fractions of the propylene polymer, i.e. polymer obtained in the first and second reactors (P1 + P2),

C(PP) - comonomer content (in mol.%) in the first and second fractions of the propylene polymer and in the first fraction of the elastomeric propylene copolymer, i.e. polymer obtained in the first, second and third reactors (P1 + P2 + P3),

C(PP2) - calculated comonomer content (in mol.%) in the first fraction of the elastomeric propylene copolymer, i.e. polymer obtained in the third reactor (P3).

Calculation of the comonomer content in the second fraction of the elastomeric propylene copolymer, i.e. polymer fraction of heterophasic propylene copolymer (HESO1) obtained in the fourth reactor (P3):

С(PP) - w(nni23)xC(nni23) _ _w( < _nn4 ) - С(PP4) , i.e. polymer obtained in the first, second and third reactors (P1+P2+P3), w(PP4) is the mass fraction (in wt.%) of the second fraction of the elastomeric propylene copolymer, i.e. polymer obtained in the fourth reactor (P4),

C(PP123) - comonomer content (in mol.%) in the first and second fractions of the propylene polymer and the first fraction of the elastomeric propylene copolymer, i.e. polymer obtained in the first, second and third reactors (P1 + P2 + P3),

C(PP) - comonomer content (in mol.%) in the first and second fractions of the propylene polymer and the first and second fractions of the elastomeric propylene copolymer, i.e. polymer obtained in the first, second and third reactors (P1 + P2 + P3),

C(PP4) - calculated comonomer content (in mol.%) in the second fraction of the elastomeric propylene copolymer, i.e. polymer obtained in the fourth reactor (P4).

Calculation of the cold xylene soluble (XXL) fraction content of the elastomeric propylene copolymer, i.e. polymer fraction of heterophasic propylene copolymer (HESO1) obtained in the third and fourth reactors (P3+R4):

RK (GEKO) - sh (PP12) xRK (PP12) _

- RK(E) where w(PP12) is the mass fraction (in wt.%) of the first and second fractions of the propylene polymer, i.e. polymer obtained in the first and second reactors (P1 + P2), w(E) is the mass fraction (in wt.%) of the elastomeric propylene copolymer fraction, i.e. polymer obtained in the third and fourth reactors (P3+R4),

RK(PP12) - the content of the cold xylene (RKF) soluble substance (in wt.%) of the first and second fractions of the propylene polymer, i.e. polymer obtained in the first and second reactors (P1 + P2),

RK(GEKO) - content of cold xylene soluble (RKF) substance (in wt.%) of the first and second fractions of the propylene polymer and the fraction of the elastomeric propylene copolymer, i.e. polymer obtained in the first, second, third and fourth reactors (P1+P2+P3+R4),

RK(E) - calculated content of soluble in cold xylene (RKF) substance (in wt.%)

- 21 040146 elastomeric propylene copolymer fractions, i.e. polymer obtained in the third and fourth reactors (P3+R4).

Calculation of the cold xylene soluble (XXL) content of the first fraction of the elastomeric propylene copolymer, i.e. polymer fraction of heterophasic propylene copolymer (HESO1) obtained in the third reactor (P3):

RK(PP) - νν(ΠΠ12)χ RK(PP12) --- ----------- = RK(PPZ) w(PPZ) ^{1 7} where w(PP12) - mass fraction (in wt .%) of the first and second fractions of the propylene polymer, i.e. polymer obtained in the first and second reactors (P1 + P2), w(PP3) - mass fraction (in wt.%) of the first fraction of the elastomeric propylene copolymer, i.e. polymer obtained in the third reactor (P3),

RK(PP12) - the content of the cold xylene (RKF) soluble substance (in wt.%) of the first and second fractions of the elastomeric propylene polymer, i.e. polymer obtained in the first and second reactors (P1 + P2),

RK(PP) is the content of cold xylene soluble (RKF) substance (in wt.%) of the first and second fractions of the propylene polymer and the first fraction of the elastomeric propylene copolymer, i.e. polymer obtained in the first, second and third reactors (P1 + P2 + P3),

RK(PP3) - calculated content of cold xylene soluble (Xylene) substance (in wt.%) of the first fraction of the elastomeric propylene copolymer, i.e. polymer obtained in the third reactor (P3).

Calculation of the cold xylene soluble (XXL) content of the second fraction of the elastomeric propylene copolymer, i.e. polymer fraction obtained in the fourth reactor (P4):

PK(PP) - w(nill23)x PK(PP123) w(ni!4) = PK(PP4) where w(PP123) - mass fraction (in wt.%) of the first and second fractions of the propylene polymer and the first fraction of the elastomeric propylene copolymer, i.e. polymer obtained in the first, second and third reactors (P1 + P2 + P3), w(PP4) is the mass fraction (in wt.%) of the second fraction of the propylene copolymer, i.e. polymer obtained in the fourth reactor (P4),

RK(PP123) - content of cold xylene soluble (RKF) substance (in wt.%) in the first and second fractions of the propylene polymer and the first fraction of the elastomeric propylene copolymer, i.e. polymer obtained in the first, second and third reactors (P1 + P2 + P3),

RK(PP) - content of cold xylene soluble (RKF) substance (in wt.%) in the first and second fractions of the propylene polymer and the first and second fractions of the elastomeric propylene copolymer, i.e. polymer obtained in the first, second and third reactors (P1+P2+P3+R4),

RK(PP4) - calculated content of soluble in cold xylene (RKF) substance (in wt.%) in the second fraction of the elastomeric propylene copolymer, i.e. polymer obtained in the fourth reactor (P4).

Calculation of the melt flow index MFR ₂ (230°C) of the second fraction of the propylene polymer, i.e. polymer fraction of a heterophasic propylene copolymer (HESO1) obtained in the second reactor (P2):

log(nTP(nn)-w(nni)rfO0(nPT(nni))

MFR(PP2)=10 IPP2) where w(PP1) is the mass fraction (in wt.%) of the first fraction of the propylene polymer, i.e. polymer obtained in the first reactor (P1), w(PP2) - mass fraction (in wt.%) of the second fraction of the propylene polymer, i.e. polymer obtained in the second reactor (P2),

MFR(PP) - melt flow index MFR ₂ (230°C) (g/10 min) of the first fraction of the propylene polymer, i.e. polymer obtained in the first reactor (P1),

MFR(PP) - melt flow index MFR2 (230°C) (g/10 min) of the first and second fractions of the propylene polymer, i.e. polymer obtained in the first and second reactors (P1+P2),

MFR(PP2) is the calculated melt flow rate of GTGR2 (230°C) (g/10 min) of the first fraction of the propylene polymer, i.e. polymer obtained in the second reactor (P2).

Calculation of the intrinsic viscosity of the xylene-soluble substance of the first fraction of the elastomeric propylene copolymer, i.e. polymer fraction of heterophasic propylene copolymer (HESO1) obtained in the third reactor (P3):

ΧΒ(ΠΠ) - RKF(PP12)х XV(PP12)

RKF(PPZ) = XV(PPZ) where

RKF(PP12) - the proportion of the xylene-soluble substance (in wt.%) of the first and second fractions of the propylene polymer, i.e. polymer obtained in the first and second reactors (P1 + P2),

RKF(PP3) is the fraction of xylene-soluble substance (in wt.%) of the first fraction of the elastomeric propylene copolymer, i.e. polymer obtained in the third reactor (P3),

IV(PP12) is the intrinsic viscosity (dl/g) of the xylene-soluble fraction of the first and second fractions of the propylene polymer, i.e. polymer obtained in the first and second reactors (P1 + P2),

IV(IP) is the intrinsic viscosity (dL/g) of the xylene-soluble fraction of the first and second propylene polymer fractions and the first elastomeric propylene copolymer fraction, i.e. polymer obtained in the first, second and third reactors (P1 + P2 + P3),

IV(IP3) is the calculated intrinsic viscosity (dl/g) of the xylene-soluble fraction of the first fraction of the elastomeric propylene copolymer, i.e. polymer obtained in the third reactor (P3).

Calculation of the intrinsic viscosity of the xylene-soluble fraction of the second fraction of the elastomeric propylene copolymer, i.e. polymer fraction of heterophasic propylene copolymer (HESO1) obtained in the fourth reactor (P4):

XV(PP) - RKF(PP123)xXV(PP123)

RKF(PP4) = XV(PP4) where

RKF(PP123) is the proportion of xylene-soluble substance (in wt.%) of the first and second fractions of the propylene polymer and the first fraction of the elastomeric propylene copolymer, i.e. polymer obtained in the first, second and third reactors (P1 + P2 + P3),

RKF(PP4) is the proportion of xylene-soluble substance (in wt.%) of the second fraction of the elastomeric propylene copolymer, i.e. polymer obtained in the fourth reactor (P4),

IV(PP123) is the intrinsic viscosity (dL/g) of the xylene-soluble fraction of the first and second propylene polymer fractions and the first elastomeric propylene copolymer fraction, i.e. polymer obtained in the first, second and third reactors (P1 + P2 + P3),

IV(IP) is the intrinsic viscosity (dl/g) of the xylene-soluble fraction of the first and second propylene polymer fractions and the first and second elastomeric propylene copolymer fractions, i.e. polymer obtained in the first, second, third and fourth reactors (P1+P2+P3+R4),

IV(IP4) is the calculated intrinsic viscosity (dl/g) of the xylene-soluble fraction of the second fraction of the elastomeric propylene copolymer, i.e. polymer obtained in the fourth reactor (P4).

Calculation of the comonomer content of the elastomeric propylene copolymer fraction, i.e. polymer fraction of a heterophasic propylene copolymer (HESO1) obtained in the third and fourth reactors (P3+R4):

C(GESO) - w(PP12)xC(PP12) w(3) where w(PP12) is the mass fraction (in wt.%) of the first and second fractions of the propylene polymer, i.e. polymer obtained in the first and second reactors (P1 + P2), w(E) is the mass fraction (in wt.%) of the elastomeric propylene copolymer fraction, i.e. polymer obtained in the third and fourth reactors (P3+R4),

C(PP12) - comonomer content (mol.%) in the first and second fractions of the propylene polymer, i.e. in the polymer obtained in the first and second reactors (P1 + P2),

C(GEKO) - comonomer content (mol.%) in the first and second fractions of the propylene polymer and in the elastomeric propylene copolymer, i.e. in the polymer obtained in the first, second, third and fourth reactors (P1+P2+P3+R4),

C(E) - calculated comonomer content (mol.%) in the elastomeric propylene copolymer fraction, i.e. in the polymer obtained in the third and fourth reactors (P3+R4).

Calculation of the comonomer content in the elastomeric copolymer fraction, i.e. in the polymer fraction of heterophasic propylene copolymer (HESO2) obtained in the third reactor (P3):

C(PP) - w(nni2)xC(nni2) w(nil3) where w(PP12) is the mass fraction (wt.%) of the first and second propylene polymer fractions, i.e. polymer obtained in the first and second reactors (P1 + P2), w(nn3) is the mass fraction (in wt.%) of the elastomeric propylene copolymer fraction, i.e. polymer obtained in the third reactor (P3),

C(PP12) - comonomer content (in mol.%) in the first and second fractions of the propylene polymer,

those. polymer obtained in the first and second reactors (P1 + P2),

C(PP) is the comonomer content (in mol %) of the first propylene polymer fraction, the second propylene polymer fraction and the propylene elastomeric copolymer fraction, i.e. in the polymer obtained in the first, second and third reactors (P1 + P2 + P3),

C(PP3) - calculated comonomer content (in mol.%) in the elastomeric propylene copolymer fraction, i.e. polymer obtained in the third reactor (P3).

Calculation of cold xylene soluble (XXL) content in elastomeric propylene copolymer fraction, i.e. in the polymer fraction of heterophasic propylene copolymer (HESO2) obtained in the third reactor (P3):

PK(GEKO) - w(nni2)xPK(nni2) w(3) where w(PP12) is the mass fraction (in wt.%) of the first and second propylene polymer fractions, i.e. polymer obtained in the first and second reactors (P1 + P2), w(E) is the mass fraction (in wt.%) of the elastomeric propylene copolymer fraction, i.e. polymer obtained in the third reactor (P3),

RK(PP12) is the content of cold xylene (RKF) soluble substance (in wt.%) in the first and second fractions of the propylene polymer, i.e. in the polymer obtained in the first and second reactors (P1 + P2),

RK(GEKO) is the content of cold xylene soluble (RKF) substance (wt %) in the first propylene polymer fraction, the second propylene polymer fraction and the elastomeric propylene copolymer fraction, i.e. in the polymer obtained in the first, second and third reactors (P1 + P2 + P3),

RK(E) - calculated content of soluble in cold xylene (RKF) substance (in wt.%) in the elastomeric propylene copolymer fraction, i.e. in the polymer obtained in the second and third reactors (P2+P3).

Calculation of the melt flow index MFR ₂ (230° C.) of the elastomeric propylene copolymer fraction, i.e. polymer fraction of heterophasic propylene copolymer (HESO2) obtained in the third reactor (P3):

10g(nTP(nn)-w(nni2)xl0g(nPT(nni2))

MFR(PP)=10 ^w < ⁿⁿ³ ) where w(PP12) is the mass fraction (wt.%) of the first and second propylene polymer fractions, i.e. polymer obtained in the first and second reactors (P1 + P2), w(PP3) - mass fraction (in wt.%) of the elastomeric propylene copolymer fraction, i.e. polymer obtained in the third reactor (P3),

MFR(PP12) - melt flow index MFR2 (230°C) (g/10 min) of the first and second propylene fractions, i.e. polymer obtained in the first and second reactors (P1 + P2),

MFI(PP) - MFR2 melt flow rate (230°C) (g/10 min) of the first and second fractions of the propylene polymer and the elastomeric propylene copolymer fraction, i.e. polymer obtained in the first, second and third reactors (P1 + P2 + P3),

MFR(PP3) is the calculated MFR ₂ of the melt flow (230° C.) (g/10 min) of the elastomeric propylene copolymer fraction, i.e. polymer obtained in the third reactor (P3).

Calculation of the comonomer content of the elastomeric propylene copolymer fraction, i.e. in the polymer fraction of heterophasic propylene copolymer (HESO2) obtained in the third reactor (P3):

C(HESO) - w(Iin)xC(nn) where w(PP) is the mass fraction (in wt.%) of the first and second fractions of the propylene polymer, i.e. of the polymer obtained in the first and second reactors (P1 + P2), w(E) is the mass fraction (in wt.%) of the elastomeric propylene copolymer, i.e. polymer obtained in the third reactor (P3),

C(PP) - comonomer content (mol.%) in the first and second fractions of the propylene polymer, i.e.

- 24 040146 in the polymer obtained in the first and second reactors (P1 + P2),

C(GEKO) - comonomer content (mol.%) in the propylene copolymer, i.e. comonomer content (mol.%) in the polymer obtained after polymerization in the third reactor (P3),

C(E) - calculated comonomer content (mol.%) in the elastomeric propylene copolymer fraction, i.e. in the polymer obtained in the third reactor (P3).

MFR ₂ (230° C.) is determined according to ISO 1133 (230° C., load 2.16 kg).

MFR ₂ (190° C.) is determined according to ISO 1133 (190° C., load 2.16 kg).

Quantification of the microstructure using NMR spectroscopy

Quantitative nuclear magnetic resonance (NMR) spectroscopy was used to quantify comonomer content and comonomer distribution sequence in polymers. Quantitative ^13C (1H) NMR spectra were recorded in solutions using a Broker Advance III 400 NMR spectrometer at 400.15 and 100.62 MHz for 1H and ^13C spectra, respectively. All spectra were recorded using a 10 mm ¹³ ° C. measuring head adapted for a wide temperature range at 125° C. with nitrogen gas applied to all pneumatic devices. Approximately 200 mg of material was dissolved in 3 ml of 1,2-tetrachloroethane-d ₂ (TCE-d ₂ ) containing chromium-(III)acetylacetonate (Cr(acac) ₃ ) to give a 65 mM solution of the relaxation agent in a solvent (Singh, G ., Kothari, A., Gupta, V., Polymer Testing 28 5 (2009), 475). To obtain a homogeneous solution, after the initial preparation of the sample in a thermostat, the NMR tube was additionally heated in a rotary furnace for at least 1 hour. After being placed in a magnet, the tube was rotated at a frequency of 10 Hz. This mode was chosen mainly to achieve high resolution and allows quantitative and accurate determination of the ethylene content. Standard single-pulse excitation without nuclear Overhauser effect was applied using an optimized cone angle, a recovery latency of 1 s, and a WALTZ16 two-level splitting scheme (Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh, D. Winniford, B., J. Mag. Reson 187 (2007) 225 Busico, V., Carbonniere, P., Cipullo, R., Pellecchia, R., Severn, J. , Talarico, G., Macromol Rapid Commun. 2007, 28, 1128). In total, 6144 (6k) transitions were collected for one spectrum. Quantitative ^13C (1H) NMR spectra were processed, integrated, and the required quantitative parameters were determined from the integrals using proprietary computer programs. All chemical shifts were indirectly mapped to the central methylene group of the ethylene block (EEE) (where E is ethylene) in the 3000 ppm region. (ppm) using solvent chemical shift. This approach made it possible to carry out a comparative assignment even in the absence of this structural link. Characteristic signals corresponding to ethylene incorporation have been described in Cheng, HN, Macromolecules 17 (1984), 1950.

All chemical shifts of polypropylene homopolymers were correlated with an internal standard, isotactic pentad (mmmm) of methyl at 21.85 ppm.

Characteristic signals corresponding to regiodefects were 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) or a comonomer.

The distribution of tacticity was quantified by integrating the methyl region in the range of 23.6-19.7 ppm, adjusting for any regions that were not related to the stereosequences of interest (Busico, V., Cipullo, R., Prog. Polym. Sci. 26 (2001) 443; Busico, V., Cipullo, R., Monaco, G., Vacatello, M., Segre, A.L., Macromoleucles 30 (1997) 6251).

In particular, the influence of regiodefects and comonomer on the quantification of the distribution of tacticity is corrected by subtracting the integrals of the corresponding regiodefect and comonomer from specific areas of stereosequence integration.

Isotacticity was determined at the pentad level and expressed as a percentage of isotactic pentad sequences (mmmm) of all pentad sequences:

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

The presence of 2,1-erythroregiodefects was indicated by the presence of two metallic areas in the areas of 17.7 and 17.2 ppm, which was confirmed by other characteristic areas.

Characteristic signals corresponding to other types of regiodefects were not observed (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253).

The number of 2,1-erythroregiodefects was estimated by the value of the average integral of two characteristic metallic areas in the areas of 17.7 and 17.2 ppm:

Pile - (1e6 + 1e8) / 2

The amount of initially included 1,2-propene was determined based on the data of the methyl region, corrected for the areas included in this area that are not related to the primary inclusion, and for the areas of primary inclusion excluded from this area:

P12 - 1sNZ + P12e

The total amount of propene was determined as the sum of the initially included propene and all other regiodefects present:

- 25 040146

Ptot - P12 + Plie

The molar percentage of 2,1-erythroregiodefects was determined from the ratio to the total amount of propene:

[21е] % mol. \u003d 100 * (P ₂ 1e / Rtot)

In the spectra of the copolymers, characteristic signals were observed corresponding to the incorporation of ethylene (Cheng, H. N., Macromolecules 17 (1984), 1950).

In the presence of observed regiodefects (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) corrections were required to account for the effect of such defects on comonomer content.

The amount of the comonomer fraction was determined by the method of Wang et al. (Wang, WJ., Zhu, S., Macromolecules 33 (2000), 1157) involving the integration of multiple signals over the entire spectral region of ^{the 13} C (1H) spectra. This method was chosen because of its reliability and ability to take into account the presence of regiodefects, if necessary. The regions of integration were slightly adjusted to increase the applicability of the method over the entire range of comonomer contents obtained.

To investigate systems in which only isolated ethylene was observed in PPEPP sequences, the method of Wang et al. was modified to reduce the effect of non-zero integrals at sites known to be absent. This approach reduces the overestimated ethylene content in such systems and involves reducing the number of centers used to determine the absolute ethylene content to the following expression:

Е = 0.5(δββ + δβγ + δβδ + 0.5(δαβ + δαγ))

Using this set of centers, the corresponding integral equation becomes:

Ε = 0.5(Ι _Η +Ig + 0.5(I _c + Id)) as indicated by Wang et al. (Wang, WJ., Zhu, S., Macromolecules 33 (2000), 1157). The equations used to estimate the absolute propylene content were not changed.

The molar percentage of included comonomer was calculated from the mole fraction:

E [mol %] = 100 * fE

The mass percentage of included comonomer was calculated from the mole fraction:

E [wt %] = 100 * (fE * 28.06) / ((fE * 28.06) + ((1 - fE) * 42.08))

The distribution of comonomer sequences at the triad level was determined by the analytical method proposed by Kakugo et al. (Kakugo, M., Naito, Y., Mizunuma, K., Miyatake, T. Macromolecules 15 (1982) 1150). This method was chosen for its robustness, and the integration regions were adjusted slightly to increase the applicability of the method to a wider range of comonomer contents.

Quantitative determination of comonomer content in plastomer (PL) by NMR spectroscopy

Quantitative nuclear magnetic resonance (NMR) spectroscopy was used to determine the comonomer content of polymers.

Quantitative ^13C (1H) NMR spectra were recorded in the molten state using a Broker Advance III 400 NMR spectrometer at 500.13 and 125.76 MHz for 1H and ^13C spectra, respectively. All spectra were recorded using an optimized ¹³ ° C. 7 mm measuring head with magic angle (MA) rotation of the sample at 150° C., supplying nitrogen gas to all pneumatic devices. Approximately 200 mg of the material was packed into a magic angle rotor made of zirconium oxide having an outer diameter of 7 mm and rotated at 4 kHz. This mode was chosen mainly to achieve the high sensitivity required for rapid identification and accurate quantitation (Klimke, K., Parkinson, M., Piel, C, Kaminsky, W., Spiess, HW, Wilhelm, M., Macromol. Chem. Phys. 2006; 207:382; Parkinson, M., Klimke, K., Spiess, HW, Wilhelm, M., Macromol. Chem. Phys. 2007; 208:2128; Castignolles, P., Graf, R. , Parkinson, M., Wilhelm, M., Gaborieau, M., Polymer 50 (2009) 2373; NMR Spectroscopy of Polymers: Innovative Strategies for Complex Macromolecules, Chapter 24, 401 (2011)). A standard single-pulse excitation with a nuclear Overhauser effect with a short recovery time of 3 s was used (Pollard, M., Klimke, K., Graf, R., Spiess, HW, Wilhelm, M., Sperber, O., Piel, C , Kaminsky, W., Macromolecules 2004; 37:813; Klimke, K., Parkinson, M., Piel, C, Kaminsky, W., Spiess, HW, Wilhelm, M., Macromol. Chem. Phys. 2006; 207 :382), and RS-HEPT splitting scheme (multipulse Khan method with rotor synchronization) (Filip, X., Tripon, C, Filip, C, J. Mag. Resn. 2005, 176, 239.; Griffin, JM, Tripon , C, Samoson, A., Filip, C, and Brown, SP, Mag. Res. in Chem. 2007 45, SI, p 198). In total, 1024 (1k) transitions were collected in one spectrum. This mode was chosen because of its high sensitivity to low comonomer levels.

Quantitative ¹³ C (1H) NMR spectra were processed, integrated, and quantitative parameters were determined using automated programs for spectral analysis adapted to specific needs. All chemical shifts were correlated with the internal standard, which was the signal of the main mass of methylene groups (8+) in the region of 30.00 ppm. (J. Randall, Macromol. Sci., Rev. Macromol.

Chem. Phys. 1989, C29, 201).

The content of octene in the copolymer of ethylene and octene

Characteristic signals corresponding to 1-octene incorporation have been observed (J. Randall, Macromol. Sci., Rev. Macromol. Chem. Phys. 1989, C29, 201.; Liu, W., Rinaldi, P., Mcintosh, L., Quirk , P., Macromolecules 2001, 34, 4757; Qiu, X., Redwine, D., Gobbi, G., Nuamthanom, A., Rinaldi, P., Macromolecules 2007, 40, 6879), and the content of each of the comonomers was calculated as a ratio to the content of all other monomers present in the polymer.

Characteristic signals were observed, which are the results of localized incorporation of 1-octene, i.e. comonomer sequences EEOEE. Localized 1-octene incorporation was quantified by the integral of the signal in the region of 38.37 ppm. This integral was assigned to the unresolved signals corresponding to the sections *B6 and *B6B6 of the localized (EEOOEE) and localized double non-continuous (EEEOEE) sequence of 1-octene, respectively. To compensate for the effect of two sections *ВВ6В6, the integral of the section ВВВ6В6 in the region of 24.7 ppm was used:

O \u003d 1 * vb + * rvbvb - 2 * ΙββΒ6Β6

Characteristic signals resulting from continuous embedding of 1-octene were also observed, i.e. EEOOEE comonomer sequences. This continuous incorporation of 1-octene was quantified by the value of the integral of the signal in the region of 40.57 ppm, correlated with the aaB6B6 regions, which correspond to the number of detected regions per comonomer:

OO = 2*ΙααΒ6Β6

Characteristic signals resulting from localized non-continuous incorporation of 1-octene were also observed, i.e. sequences of EEEOEEE comonomers. This localized non-continuous incorporation of 1-octene was quantified by the value of the signal integral in the 24.7 ppm region, correlated with eeB6B6 regions, which correspond to the number of detected regions per comonomer:

OO - 2*ΙββΒ6Β6

Also observed characteristic signals resulting from localized triple continuous incorporation of 1-octene, ie. sequences of EEOOOEE comonomers. This localized triple continuous incorporation of 1-octene was quantified by the value of the signal integral in the region of 41.2 ppm, correlated with the aaYB6B6B6 regions, which correspond to the number of identified regions per comonomer:

000 = 3/2 * ΙααγΒ6Β6Β6

Since no other signals indicating the presence of other comonomer sequences were observed, the total content of 1-octene comonomer was calculated only based on the number of localized (EEOOEE), localized double contiguous (EEOOEE), localized non-continuous (EEOOEE) and localized triple contiguous (EEOOOEE) sequences. 1-octene comonomer:

General ^- O + 00 + OEO + LLC

Observed characteristic signals of saturated end groups. The number of saturated end groups was determined from the average value of the integrals of the two resolved signals in the regions of 22.84 and 32.23 ppm. Signal integral at 22.84 ppm corresponded to unresolved signals corresponding to the 2B6 and 2S regions of the 1-octene and the saturated end of the chain, respectively. Signal integral at 32.23 ppm corresponded to unresolved signals corresponding to the 3B6 and 3S regions of the 1-octene and to the saturated end of the chain, respectively. To compensate for the influence of sections 2B6 and 3B6 of 1-octene on the total content of 1-octene, the following equation was used:

S = (1/2)*(I2S+2B6 + bs+ZBb - 2*Tot)

The content of ethylene comonomer was quantified by the integral of the main mass of methylene groups (main part) in the region of 30.00 ppm. This integral included the γ and 4B6 portions of the 1-octene signals, as well as the δ+ portions. The total content of ethylene comonomer was calculated based on the value of the integral of the main signals, taking into account the detected 1-octene sequences and end groups:

E _general = (1/2) * [ 1base. + 2*0 + 1*00 + 3*0E0 + 0*000 + 3*S]

It should be noted that in the integral of the main signals it is not required to take into account the presence of localized sequences (EEOOOEE) of the triple insertion 1-octene, since the number of ethylene units located outside the upper and lower limits of the integral is equal.

- 27 040146

The total mole fraction of 1-octene in the polymer was calculated as follows:

Yu \u003d (General / (Etotal + General)

The total amount of 1-octene comonomer incorporated (mol %) was calculated from the mole fraction according to the standard equation:

O [% mol.] \u003d 100 * Yu

The percentage mole fraction of incorporated ethylene was calculated by the formula:

E[mol %] = 100 - O[mol %]

Butene content of ethylene-butene copolymer Characteristic signals corresponding to 1-butene incorporation were observed (J. Randall, Macromol. Sci., Rev. Macromol. Chem. Phys. 1989, C29, 201), and the content of each of the comonomers was calculated as a ratio to the content of all other monomers present in the polymer.

Characteristic signals were observed resulting from localized incorporation of 1-butene, i.e. EEBEE comonomer sequences.

Localized incorporation of 1-butene was quantified by the value of the signal integral in the region of 39 ppm, correlated with *B2 sites, which correspond to the number of detected sites per comonomer:

B - 1 * B2

Observed characteristic signals resulting from double continuous incorporation of 1-butene, ie. EEBBEE comonomer sequences. The continuous double incorporation of 1butene was quantified by the value of the integral of the signal in the region of 39.4 ppm, correlated with the aaB2B2 sites, which correspond to the number of detected sites per comonomer:

BB = 2 * ΙααΒ2Β2

Also observed characteristic signals resulting from non-continuous incorporation of 1-butene, ie. sequences of EEBEEE comonomers. The non-continuous incorporation of 1-butene was quantified by the value of the integral of the signal in the region of 24.7 ppm, correlated with the sites of bbB2B2, which correspond to the number of detected sites per comonomer:

BEV = 2 * ΙββΒ2Β2

Due to the overlap of *B2 and *B2B2 regions of localized (EEBEEE) and non-continuously embedded (EEBEVEE) 1-butene, respectively, the total amount of embedded localized 1-butene is adjusted according to the amount of non-continuously embedded 1-butene:

B \u003d 1 * B2 - 2 * ΙββΒ2Β2

Characteristic signals were observed resulting from triple continuous incorporation of 1-butene, i.e. EEBBBEE comonomer sequences. The continuous triple incorporation of 1butene was quantified by the value of the integral of the signal in the region of 40.4 ppm, correlated with the ayB2B2B2 sites, which correspond to the number of identified sites per comonomer:

BBB = 3 * ΙααγΒ2Β2Β2

Because other signals indicating the presence of other comonomer sequences, i.e. at the start of butene chain alignment was not observed, the total content of 1-butene comonomer was calculated only on the basis of the amount of localized (EEBEE), double contiguous (EEBEE), non-continuous (EEBEEE) and triple contiguous (EEBBEE) sequences of 1-butene comonomer:

In _about general ^- B + BB + BEB + BBB

Observed characteristic signals of saturated end groups. The content of saturated end groups was quantitatively determined from the average value of the signal integrals in the regions of 22.84 and 32.23 ppm, assigned to the 2s and 3s regions, respectively:

S = (1/2)*(I _2S + bs)

The relative content of ethylene was quantitatively determined from the value of the integral of the signals of the main mass of methylene (δ+) at 30.00 ppm:

E = (1/2)*Ι _δ+

The total content of ethylene comonomer was calculated based on the value of the integral of the signals of the bulk of the methylene groups, taking into account the ethylene units present in other detected comonomer sequences or end groups:

Etotal \u003d E + (5/2) * B + (7/2) * BB + (9/2) * BEB + (9/2) * BBB + (3/2) * S

The total mole fraction of 1-butene in the polymer was calculated as follows:

- 28 040146

The total amount of 1-butene comonomer incorporated (mol %) was calculated from the mole fraction in the usual way:

B [mol %] = 100 * £B

The percentage mole fraction of ethylene incorporated was calculated using the formula: E[mol %] = 100 - B[mol %] in combination with 3xOlexis and 1xOlexis Guard columns supplied by Polymer Laboratories, using 1,2,4-trichlorobenzene as solvent ( TCB stabilized by adding 250 mg/l 2,6di-tert-butyl-4-methylphenol) at 160°C and a constant flow rate of 1 ml/min. For analysis, 200 μl of the sample solution was injected. The column set was universally calibrated (according to ISO 16014-2:2003) with at least 15 Narrow Molecular Weight Distribution (MWD) polystyrene (PS) standards from 0.5 kg/mol to 11500 kg/mol. As stated in ASTM D 6474-99, for PS, PE, and PP, Mark Howwink's constants were used. All samples were prepared by dissolving 5.0-9.0 mg of polymer in 8 ml (at 160°C) of stabilized TCB (the same as the mobile phase) for 2.5 h for 1111 samples or 3 h for PE samples at maximum temperature of 160°C with continuous gentle shaking in the automatic sampler of the GPC instrument.

Melting point and degree of crystallinity

DSC analysis: melting point (T _m ) and crystallization temperature (Tc) were determined using a TA Instrument Q2000 differential scanning calorimeter (DSC) using samples weighing 5 to 7 mg. DSC analysis was performed in accordance with ISO 11357/part 3/method C2 in a heat-cool-heat cycle at a scan rate of 10°C/min over a temperature range of -30 to +230°C. The crystallization temperature was determined in the cooling step, and the melting point was determined in the heating step.

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

Density was determined according to ISO 1183-187. Samples were obtained either by pressing according to ISO 1872-2:2007 or 10x10x2 mm samples were cut from injection molded foam parts.

Xylene Soluble Fraction (RKF, wt %): Cold Xylene Soluble (Xylene Soluble) content was determined at 25° C. according to ISO 16152, first edition; 2005-07-01. The part that remains insoluble is the xylene cold insoluble fraction (CIC).

Flexural Modulus: The flexural modulus was determined in a three-point bend test according to ISO 178 using 80x10x4 mm injection molded bars at 23°C according to EN ISO 1873-2.

Determination of Charly impact strength: Charly impact strength (Charly IM) was determined according to ISO 179 2C/DIN 53453 at 23°C and -20°C, using as samples 80x10x4 mm rods obtained by injection molding in accordance with with ISO 294-1:1996.

Coefficient of linear thermal expansion: The coefficient of linear thermal expansion (CLTE) was determined in accordance with ISO 1 1359-2: 1999 using 10 mm length specimens cut from the same injection molded specimens used to determine the flexural modulus . The measurements were carried out at a temperature of -30 to +80°C, at a heating rate of 1°C/min.

Appearance of the surface of dense and foamed products

The tendency to form flow traces was determined by the method described below.

This method is described in detail in WO 2010/149529, the contents of which are incorporated herein by reference.

The optical measurement system described in Sybille Frank et al., PPS 25 Intern was used to characterize the surface quality. Conf. Polym. Proc. Soc 2009 or Proceedings of the SPIE, vol. 6831, pp. 68130T-68130T-868130T-68130T-8 (2008). This method has two aspects.

1. Image registration.

The principle on which the measurement system is based is to illuminate the plates with a certain light source (LED indicator) in a closed room and record the image using a system equipped with a CCD camera.

The scheme of the device is shown in Fig. 1.

2. Image analysis.

The sample is brightly illuminated from one side, and part of the light reflected upwards is deflected by two mirrors onto a CCD sensor. The grayscale image thus obtained is analyzed for banding. From the resulting grayscale deviations, the mean square error (MSE _avg ) or the maximum root mean square error (MSE _max ) was calculated, from which the quality/homogeneity of the surface was quantified; the higher the SPC value, the

- 29 040146 more pronounced is the surface defect. The UPC _mean and UPC _max are not compared. Generally, for the same material, the tendency to form flow marks increases as the casting speed increases.

The SKPavg values were determined on dense injection-molded 440x148x2.8 mm plates made from G1 grain size material. The plates were made by injection molding with different fill times of 1, 5, 3 and 6 s, respectively.

Additional terms.

Melt temperature: 240°C.

Mold temperature: 30°C.

Dynamic pressure: hydraulic, 10 bar (106 Pa).

SCPmax values were determined on dense and foamed injection-molded 210x148x2 mm lamellae produced in a one-point gating system of material with a G2 grain size different from G1. The plates were made by injection molding with a filling period of 0.8 seconds. The chemical blowing agent used was Hydrocerol ITP 825 from Clariant having a decomposition temperature of 200°C. The blowing agent was added during the conversion step as a masterbatch containing 40% citric acid active [www.clariant.com].

The cellular structure of the foamed products was determined by optical microscopy on a section of a foamed plate obtained by injection molding.

The maximum force at break was determined on plates measuring 148x148x2 mm in a shock load test in accordance with ISO 6603-2. The test was carried out at room temperature using a lubricated striker with a diameter of 20 mm and an impact velocity of 10 mm/s. The maximum force at break was defined as the maximum peak on the stress-strain curve obtained during the test.

Compression tests were carried out on 10x10x2 mm plates at room temperature according to ISO 604:2002. The tests were carried out on a Zwick Z010U device at a test speed of 0.87 mm/min and room temperature. The compression force was determined at a deformation of 1 mm. Thus, the compression force was determined as the ratio of the force at break at a deformation of 1 mm to the area of the sample at the beginning of the experiment.

Puncture resistance was determined in an impact test according to ISO 6603-2 on injection-molded 60x60x1 mm plates at a test speed of 2.2 m/s, on which a lubricated striker with a diameter of 20 mm was lowered. The reduced puncture resistance is obtained by integrating the area under the fracture work curve determined at (60x60x2 mm).

The compressive strength at break was determined on 10x10x3 mm plates at room temperature according to ISO 604:2002. The tests were carried out on a Zwick Z010U device at a test speed of 0.87 mm/min at room temperature. The compression force was determined at a deformation of 1 mm. Thus, the compression force was determined as the ratio of the force at break at a deformation of 1 mm to the area of the sample at the beginning of the experiment.

Examples 2. Preparation of a catalyst for GESO1a and GESO2a.

First, 0.1 mol of MgCl ₂ -3EtOH was suspended under an inert atmosphere in 250 ml of decane in a reactor at atmospheric pressure. The solution was cooled to a temperature of -15°and added 300 ml of cold TiCl ₄ maintaining the specified temperature. 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 slurry was left 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 separated from the liquid by filtration and washed six times with 300 ml of heptane at 80°C. The solid catalyst component was then separated by filtration and dried. The catalyst and the general method for its preparation are described, for example, in EP 491566, EP 591224 and EP 586390.

The catalyst was further modified (VCH catalyst modification). Into a 125 ml stainless steel reactor under an inert atmosphere at room temperature were placed 15 x 35 ml of mineral oil (Paraffinum Liquidum PL68), then 0.82 g of triethylaluminum (TEAL) and 0.33 g of dicyclopentyldimethoxysilane (donor D) were added. After 10 minutes, 5.0 g of the catalyst prepared as above (Ti content 1.4 wt%) was added, and after another 20 minutes, 5.0 g of vinylcyclohexane (VCH) was added. The temperature was raised to 60° C. over 30 minutes and maintained at this temperature for 20 hours. Finally, the temperature was lowered to 20° C. and the concentration of unreacted WCH in the oil/catalyst mixture was determined to be 200 ppm wt.

Obtaining a catalyst for HECOL

The catalyst for the preparation of HECO1b was prepared similarly to the catalyst for GECO1a and HECO2a, except that diethylaminotriethoxysilane (U donor) was used instead of dicyclopentyldimethoxysilane.

- 30 040146

Obtaining a catalyst for HESO2b

The catalyst for the production of HECO2b is the commercially available ZN180M catalyst from Lyondell Basell, which was used in combination with dicyclopentyldimethoxysilane as a donor (Donor D).

The ratio of the amount of aluminum to the amount of the donor, the ratio of the amount of aluminum to the amount of titanium and polymerization conditions are presented in table. 1.

Table 1. Preparation of TECO1a, TECO1b, GECO2a and GECO2b

GESO1a

GESOL

GESO2a

GECO2b

Prepolymerization

TEAL/Ti

[mol/mol]

200

205

200

220

TEAL/donor

[mol/mol]

Temperature

Time of stay

loop reactor

Temperature

Performance ratio

5.01

0.26

0.09

0.17

0.08

H2/S3 ratio

[mol/kmol]

- 31 040146

Ratio С2/СЗ [mol/kmol] 0 0 0 0 PTR ₂ [g/10 min] 160 120 162 160 RKF [wt%] 2.1 2.2 2.0 2.0 Content C2 [mol %] 0 0 0 0 GFR 1 Temperature [°C] 80 85 95 80 Pressure [kPa] 2400 2500 1500 2200 Performance ratio [%] 40 36 45 34 H2/S3 ratio [mol/kmol] 45 204 84 175 Ratio С2/СЗ [mol/kmol] 0 0 0 0 PTR ₂ [g/10 min] 55 120 159 160 RKF [wt%] 2.0 2.0 2.9 13.0 XV (RKF) [dl/g] on the. on the. on the. on the. С2 (RKF) [mol %] on the. on the. on the. on the. Content C2 [mol %] 0 0 0 0 GFR 2 Temperature G°C1 67 75 85 80 Pressure [kPa] 2100 2000 1400 2190 Performance ratio [%] 15 22 21 14 Ratio С2/СЗ [mol/kmol] 242 701 600 550 H2/C2 ratio [mol/kmol] 23 85 170 250 PTR ₂ [g/10 min] 20 40 66 95 RKF [wt%] 18 18 20 15 XV (RKF) [dl/g] on the. on the. 2.9 2.3 С2 (RKF) [mol %] on the. 10.8 53 20 Content C2 [mol %] 10 18 AND GFRR Temperature [°C] 67 85 Pressure bar 1500 1400 Performance ratio [%] 10 13

- 32 040146

Ratio С2/СЗ [mol/kmol] 250 699 H2/C2 ratio [mol/kmol] 22 129 PTR ₂ [g/10 min] 5 24 RKF [wt%] 25 29 XV (RKF) [dl/g] 6.3 3.2 С2 (RKF) [mol %] 25.7 56 Content C2 [mol %] AND 2 20

C2 - ethylene

H2/C3 ratio=hydrogen/propylene ratio

C2/C3 ratio=ethylene/propylene ratio

H2/C2 ratio=hydrogen/ethylene ratio

GFR 1/2/3 - 1st/2nd/3rd gas-phase reactor n.a. - not analyzed

For the main polymerization, a Borstar PP pilot plant was used, which included a tank-type prepolymerization reactor equipped with a stirrer, a bulk liquid loop reactor, and one, two, or three gas phase reactors (GFR1 - GFR3). The resulting polymer powders were mixed in a Coperion ZSK 57 extruder equipped with two co-rotating screws at 220° C. with an addition of 0.2 wt.%. Irganox B225 (1:1 blend of Irganox 1010 (mixture of pentaerythryl-tetrakis(3-(3',5'-di-tert-butyl-4hydroxytoluyl)-propionate and tris(2,4-di-tert-5-butylphenyl)phosphate )phosphite) from BASF AG, Germany) and 0.05 wt.% calcium stearate.

Receiving composition (K)

Examples 1 and 2 according to the invention.

GESO1a, GESO2a, GESO2b, PL and HDPE were melt blended in an extruder equipped with two co-rotating screws in the amount shown in Table 1. 2 with the addition of 0.1 wt.%. Songnox 1010FF (pentaerythryl-tetrakis(3-(3',5'-di-tert-butyl-4-hydroxyphenyl)), 0.07 wt% Kinox-68 G (tris(2,4-di-tert-butylphenyl) )phosphite) from HPL Additives, 0.16 wt.% light stabilizers based on sterically shielded amines, which were added at a mixing ratio of 1:1 to a mixture based on Sabostab UV119 (1,3,5-triazine-2,4,6 -triamine) and Hilite 77(G) (bis-(2,2,6,6-tetramethyl-4piperidyl)sebacate), 0.1 wt.% 1,2-cyclohexanedicarboxylic acid and Ca-salt from Miliken, 0.1 wt.% erucamide (13-docosenamide) and 1.47 wt.% polypropylene homopolymer HC001A-B1 The molten polymer mixture was discharged and granulated.

Comparative Examples 1 and 2.

GESO1a and GESO2a and possibly PL and HDPE were melt blended in an extruder equipped with two co-rotating screws in the amount shown in Table 1. 2 with the addition of 0.1 wt.%. Songnox 1010FF (pentaerythryl-tetrakis(3-(3',5'-di-tert-butyl-4-hydroxyphenyl)), 0.07 wt% Kinox-68 G (tris(2,4-di-tert-butylphenyl) )phosphite) from HPL Additives, 0.16 wt.% light stabilizers based on sterically shielded amines, which were added at a mixing ratio of 1:1 to a mixture based on Sabostab UV119 (1,3,5-triazine-2,4,6 -triamine and Hilite 77(G) (bis-(2,2,6,6-tetramethyl-4piperidyl)sebacate), 0.1 wt.% NA11UH (2,2'-methylene-bis-(4,6-di -tert-butylphenyl)phosphate sodium), 0.1 wt.% erucamide (13-docosenamide) and 1.47 wt.% polypropylene homopolymer HC001A-B1. The molten polymer mixture was discharged and granulated.

Comparative example 3.

FECO1b, GESO2b, PL and HDPE were melt blended in an extruder equipped with two co-rotating screws in the amount shown in Table 1. 2 with the addition of 0.1 wt.%. Songnox 1010FF (pentaerythryl-tetrakis(3-(3',5'-di-tert-butyl-4-hydroxyphenyl)), 0.07 wt% Kinox-68 G (tris(2,4-di-tert-butylphenyl) )phosphite) from HPL Additives, 0.16 wt.% light stabilizers based on sterically shielded amines, which were added at a mixing ratio of 1:1 to a mixture based on Sabostab UV119 (1,3,5-triazine-2,4,6 -triamine) and Hilite 77(G) (bis-(2,2,6,6-tetramethyl-4piperidyl)sebacate), 0.1 wt.% 1,2-cyclohexanedicarboxylic acid and Ca-salt from Miliken, 0.1 wt.% erucamide (13-docosenamide) and 1.47 wt.% polypropylene homopolymer HC001A-B1 The molten polymer mixture was discharged and granulated.

- 33 040146

Table 2. Composite Properties of Comparative Examples (Ex) and Inventive Examples (Ex) Obtained from Tests on Dense and Chemically Foamed 2mm Injection Molded Plates

Ex 1 Ex 2 Ref.1 ref.2 Ref.3 GESO1a [wt%] 26.50 26.50 26.50 25.50 GESOL [wt%] 26.5 GESO2a [wt%] 38.11 42.50 56.50 GECO2b [wt%] 38.11 37.62 PL [wt%] 8.00 8.00 8.00 8.00 HDPE1 [wt%] 5.00 5.00 5.00 HDPE2 [wt%] 5.00 Talc1 [wt%] 14.50 Talc2 [wt%] 14.50 14.50 14.50 14.50 FOR 1 [wt%] 0.10 0.10 FOR 2 [wt%] 0.10 0.10 0.10 Pigments [wt%] 5.89 5.89 1.50 1.50 6.38 Additives [wt%] 1.90 1.90 1.90 1.90 1.90 Properties of dense products, thickness 2 mm PTR [g/10 min] 18 16 20 27 32 IPT, maximum energy [J] 21 22 on the. on the. 21 Modulus of elasticity in bending [MPa] 2030 2007 1886 2505 2072 CLTE (-30/80 °C) [-] 87 92 on the. on the. on the. Charly impact strength, +23°С [kJ / m ² ] 15 19 14 6 10 Compression force at break [MPa] 84 92 69 85 78 SCPavg, 1.5 s, G3 [-] 25 40 45 on the. 25 Density [g/ ^cm3 ] 1.03 1.03 1.04 1.04 1.04 Foam properties, thickness 3 mm Cell size [µm] 50 50 60 60 70 CLTE (-30/80 °C) [-] 95 102 on the. on the. on the. Compression force at break [MPa] 56 35 thirty 55 33 SCPmax, 0.8 s, G2 [-] on the. on the. 43 43 on the. SKPmax, 1.5 s, G3 [-] 40 40 50 on the. 120 Density [g/ ^cm3 ] 0.85 0.85 0.89 0.89 0.89

on the. - not analyzed

PL is an ethylene-octene copolymer Queo8230 from Borealis having a density of 0.880 g/cm ³ , an MFI ₂ melt flow rate (190° C.) of 30.0 g/10 min and a 1-octene content of 7.0 mole %

HDPE1 - high density polyethylene MB7541 from Borealis

HDPE2 - high density polyethylene MG9601 from Borealis

Talc 1 - Jetfine 3CA talc from Luzenac

Talc 2 - HAR T84 talc from Luzenac

3A1 - 2,2'-methylene-bis-(4,6-di-tert-butylphenyl)sodium phosphate

3A2 - 1,2-cyclohexanedicarboxylic acid and Ca-salt supplied by Miliken

The pigments are a masterbatch consisting of 70 wt.% low density polyethylene (LDPE) and 30 wt.% carbon black, where the MFR (190°C/21.6 kg) of the mixture is 15 g/10 min.

The supplements are a masterbatch containing Songnox 1010FF (pentaerythryltetrakis(3-(3',5'-di-tert-butyl-4-hydroxyphenyl)), Kinox-68 G (tris(2,4-di-tert-butylphenyl) Phosphite) from HPL Additives, sterically shielded amine light stabilizers added in a 1:1 mix to Sabostab UV119 (1,3,5-triazine-2,4,6-triamine), Hilite 77( G) (bis-(2,2,6,6-tetramethyl-4-piperidyl)sebacate), (13-docosenamide) erucamide and HC001A-B1 polypropylene homopolymer described above.

Claims (14)

CLAIM 1. A foamed product containing a polypropylene composition (K) containing: a) 15.0 to 35% by weight of a heterophasic propylene copolymer (HESO1) having an intrinsic viscosity (IV) of a xylene soluble fraction (XF) of greater than 3.5 dl/g, wherein the xylene soluble fraction (XF) is determined at 25°C in accordance with ISO 16152, wherein said heterophasic propylene copolymer (HECO1) contains: i) a matrix (M1) representing a propylene polymer, and ii) an elastomeric propylene copolymer (E1) containing ethylene and/or C ₄ -C ₈ α-olefins as comonomer(s), where the elastomeric copolymer (E1) is dispersed in specified matrix; b) from 5.0 to 30.0 wt.% inorganic filler (H) and c) from 0.001 to 2.0 wt.% nucleating agent (ZA), which is a dicarboxylic acid and/or its salt; which also contains from 36.0 to 60.0 wt.% of a heterophasic propylene copolymer (HECO2) having an intrinsic viscosity (IV) of a xylene-soluble fraction (XF) in the range of 1.0 to 3.3 dl/g, where the soluble in xylene, the fraction (RKF) is determined at 25°C in accordance with ISO 16152, and said heterophasic propylene copolymer (HESO2) contains: i) a matrix (M2) representing a propylene polymer, and ii) an elastomeric propylene copolymer (E2) containing ethylene and/or C ₄ -C ₈ α-olefins as comonomer(s), where the elastomeric copolymer (E2) is dispersed in specified matrix. 2. Foamed product according to claim 1, in which the content of the comonomer in the xylene-soluble fraction (RKF) in the heterophasic propylene copolymer (HESO1) is less than 40.0 mol.%, and the xylene-soluble fraction (RKF) is determined at 25°C in accordance with ISO 16152. 3. Foamed product according to claim 1 or 2, in which the heterophasic propylene copolymer (HECO2) has a comonomer content in xylene-soluble fraction (RKF) that is greater than or equal to 40.0 mol.%, and the xylene-soluble fraction (RKF) determined at 25°C in accordance with ISO 16152. 4. A foamed article according to any one of the preceding claims further comprising a high density polyethylene (HDPE) and/or a plastomer (PL) which is a copolymer of ethylene and a C4-C8 α-olefin. 5. Foamed product according to any one of claims 1 to 3, further comprising: i) from 2.0 to 10.0 wt.% of high density polyethylene (HDPE), ii) from 5.0 to 15.0 wt.% of a plastomer (PL), which is a copolymer of ethylene and C4-C8 αolefin, based on from the total mass of the polypropylene composition (K). 6. A foamed article according to any one of the preceding claims, wherein the heterophasic propylene copolymer (HECO1) has: i) melt flow index MFR2 (230° C.) determined in accordance with ISO 1133 from 1.0 to 20.0 g/10 min, ii) comonomer content from 5.0 to 30.0 mole %, iii) the content of xylene-soluble fraction (RKF) from 15.0 to 40.0 wt.%. 7. A foamed product according to any one of the preceding claims, wherein the heterophasic propylene copolymer (HECO2) has: i) melt flow index MFR ₂ (230°C), determined in accordance with ISO 1133, from 50 to 120 g/10 min, ii) comonomer content from 4.0 to 30.0 mol.%, iii) content of soluble in xylene fraction (RKF) from 8.0 to 35.0 wt.%. 8. A foamed article according to any one of the preceding claims, wherein the propylene polymer (M1) and/or the propylene polymer (M2) are propylene homopolymers. 9. A foamed article according to any one of the preceding claims, wherein the elastomeric propylene copolymer (E1) and/or the elastomeric propylene copolymer (E2) are copolymers of propylene and ethylene. 10. A foamed product according to any one of the preceding claims, having a melt flow index MFR ₂ (230°C), determined in accordance with ISO 1133, from 10.0 to 40.0 g/10 min. - 35 040146 11. Foamed product according to claim 4 or 5, wherein the plastomer (PL) is a copolymer of ethylene and 1-octene. 12. A foamed article according to any one of the preceding claims, wherein the inorganic filler (H) is talc and/or wollastonite. 13. A foamed article according to any one of the preceding claims, wherein the nucleating agent (HA) is 1,2-cyclohexanedicarboxylic acid and/or a salt thereof. 14. The use of a polypropylene composition (K) for the manufacture of a foamed product according to any one of claims 1 to 13, where the polypropylene composition (K) contains a) from 15.0 to 35 wt.% of a heterophasic propylene copolymer (HESO1) having an intrinsic viscosity (IV) of a xylene-soluble fraction (RKF) of more than 3.5 dl/g, where the xylene-soluble fraction (RKF) is determined at 25°C in accordance with ISO 16152, wherein said heterophasic propylene copolymer (HECO1) contains: i) a matrix (Ml) representing a propylene polymer, and ii) an elastomeric propylene copolymer (E1) containing ethylene and/or C |-C ₈ α-olefins as comonomer(s), where the elastomeric copolymer (E1) is dispersed in specified matrix; b) from 5.0 to 30.0 wt.% inorganic filler (H); c) from 0.001 to 2.0 wt.% nucleating agent (ZA), which is a dicarboxylic acid and/or its salt; which also contains from 36.0 to 60.0 wt.% of a heterophasic propylene copolymer (HECO2) having an intrinsic viscosity (IV) of a xylene-soluble fraction (XF) from 1.0 to 3.3 dl/g, where xylene-soluble fraction (RKF) is determined at 25°C in accordance with ISO 16152, and said heterophasic propylene copolymer (HESO2) contains: i) a matrix (M2) representing a propylene polymer, and ii) an elastomeric propylene copolymer (E2) containing ethylene and/or C |-C ₈ α-olefins as comonomer(s), where the elastomeric copolymer (E2) is dispersed in specified matrix. Eurasian Patent Organization, EAPO