Propylene composition for foaming having a high melt flow rate

Abstract

The present invention relates to a polypropylene composition (C), an injection-molded article and a foamed article comprising said polypropylene composition (C), and the use of said polypropylene composition (C) for the production of an injection-molded article and / or a foamed article. The polypropylene composition (C) comprises i) from 55.0 to 95.0 wt.-%, based on the total weight of the composition, of a heterophasic propylene copolymer (HECO) comprising a semi-crystalline matrix phase and an elastomeric phase dispersed in said matrix phase and a xylene cold soluble fraction (XCS) in the range of from 18.0 to 45.0 wt.-%, determined according to ISO 16152 at 23 °C, and ii) from 5.0 to 45.0 wt.-%, based on the total weight of the composition, of a propylene copolymer (PP) with at least one comonomer selected from C4-C8-alkene, wherein the polypropylene composition (C) has a melt flow rate MFR2, measured according to ISO 1333 at 230 °C and 2.16 kg, in the range of from 20.0 to 100.0 g / 10 min. 10 a random copolymer (CP) of a group of comonomers of alpha-olefins, the random copolymer (CP) being synthesized in the presence of a single-site catalyst, wherein the polypropylene composition (C) has a melt flow rate MFR2, as measured according to ISO 1333 at 230 °C and 2.16 kg, of from 20.0 to 100.0 g / 10 min.

Description

Technical Field

[0001] This invention relates to a high-flowability polypropylene composition (C) comprising a multiphase propylene copolymer (HECO) and propylene with at least one compound selected from C4-C. 10 Random copolymers (CP) of comonomers of the α-olefin group are synthesized in the presence of a single active site catalyst. The invention further relates to injection-molded articles comprising the polypropylene composition (C) and foamed articles comprising the propylene composition (C). Background Technology

[0002] Polypropylene is used in many applications and is the material of choice in many fields, such as automotive applications, because it can be customized to meet specific needs. However, the recent demand in the plastics industry is toward weight reduction.

[0003] Mature polymers used in lightweight injection molding, thin-wall injection molding, or foam injection molding applications are multiphase ethylene-propylene copolymers with high elastomer content, ranging from approximately 18 to 45% by weight, known as reactor-based thermoplastic olefin elastomers (RTPOs). These polymers are not only used directly in demanding applications such as automotive and electrical products, but also form the backbone of most advanced compounds in these and other fields. Catalysts and polymerization techniques impose constraints on RTPO design, particularly where high flowability (e.g., measured by high melt flow rate (MFR)) is required, reflecting the trend towards thinner, lighter components. The morphology of RTPOs resulting from a complex combination of design factors is readily modifiable during processing, especially in thin components. The orientation of elastomer particles often leads to anisotropy in mechanical properties and shrinkage, but can also cause surface defects and coating performance issues.

[0004] Therefore, it is of interest to stabilize the phase morphology through modifiers such as compatibilizers. EP 3 825 357 A1 discloses a polypropylene composition comprising a multiphase propylene copolymer and a copolymer of propylene with a comonomer selected from α-olefins having 4 to 10 carbon atoms, exhibiting excellent foaming properties and a good balance of mechanical properties of the foamed components. However, in the examples, the flowability of the polypropylene composition is limited to a maximum melt flow rate (MFR2) of 12 g / 10 min.

[0005] Therefore, suitable polypropylene compositions are needed that have high flowability, good mechanical properties, and low shrinkage, making them suitable for injection molding applications, especially lightweight injection molding, thin-wall injection molding, or foam injection molding applications. Summary of the Invention

[0006] This invention relates to a polypropylene composition (C), comprising:

[0007] i) a multiphase propylene copolymer (HECO) comprising a semi-crystalline matrix phase and an elastomeric phase dispersed in the matrix phase, in the range of 55.0 to 95.0% by weight based on the total weight of the composition, and xylene cold soluble fraction (XCS) determined at 23°C according to ISO 16152 in the range of 18.0 to 45.0% by weight based on the total weight of the multiphase propylene copolymer (HECO), and

[0008] ii) From 5.0 to 45.0% by weight of propylene and at least one C4-C group based on the total weight of the composition. 10 Random copolymers (CPs) of comonomers of the α-olefin group are synthesized in the presence of a single active site catalyst.

[0009] The polypropylene composition (C) therein has a melt flow rate (MFR2) of 20.0 to 100.0 g / 10 min, measured according to ISO 1333 at 230 °C and 2.16 kg.

[0010] The present invention also relates to an injection-molded article comprising a polypropylene composition (C) as described above or below.

[0011] The present invention also relates to a foamed article, preferably a foamed injection molded article, comprising a polypropylene composition (C) as described above or below.

[0012] Finally, the present invention also relates to the use of polypropylene compositions as described above or as follows for the production of injection-molded articles and / or foamed articles.

[0013] The invention is defined in more detail below.

[0014] definition

[0015] Propylene homopolymers are polymers that are essentially composed of propylene monomer units. Due to impurities, especially those from industrial polymerization processes, propylene homopolymers may contain up to 0.1 mol% comonomer units, preferably up to 0.05 mol% comonomer units, and most preferably up to 0.01 mol% comonomer units.

[0016] Propylene random copolymers are copolymers of propylene monomer units and comonomer units, preferably selected from ethylene and C4-C. 10 α-olefins, wherein comonomer units are randomly distributed along the polymer chain. Propylene random copolymers may contain comonomer units derived from one or more comonomers with different carbon atomic weights.

[0017] Multiphase polypropylene is a propylene-based copolymer having a semi-crystalline matrix phase and an elastomeric phase dispersed therein. The semi-crystalline matrix phase can be a propylene homopolymer or a random copolymer of propylene and at least one α-olefin comonomer. In the case of a random multiphase propylene copolymer, the semi-crystalline matrix phase is a random copolymer of propylene and at least one α-olefin comonomer.

[0018] The elastomeric phase can be a propylene copolymer with a large number of comonomers, which are not randomly distributed in the polymer chain but are distributed in both comonomer-rich block structures and propylene-rich block structures. Multiphase polypropylene is generally distinguished from single-phase propylene copolymers in that it exhibits two different glass transition temperatures (Tg), which are attributed to the matrix phase and the elastomeric phase.

[0019] Unless otherwise stated, the following quantities are given in weight % (wt%). Detailed Implementation

[0020] Polypropylene composition (C)

[0021] In one aspect, the present invention relates to a polypropylene composition (C) comprising:

[0022] i) a multiphase propylene copolymer (HECO) of 55.0 to 95.0% by weight based on the total weight of the composition, the multiphase propylene copolymer (HECO) comprising a semi-crystalline matrix phase and an elastomeric phase dispersed in the matrix phase, and a xylene cold soluble fraction (XCS) of 18.0 to 45.0% by weight based on the total weight of the multiphase propylene copolymer (HECO), determined at 23°C according to ISO 16152.

[0023] ii) From 5.0 to 45.0% by weight of propylene and at least one C4-C group based on the total weight of the composition. 10 Random copolymers (CPs) of comonomers of the α-olefin group are synthesized in the presence of a single active site catalyst.

[0024] The polypropylene composition (C) therein has a melt flow rate (MFR2) of 20.0 to 100.0 g / 10 min, measured according to ISO 1333 at 230 °C and 2.16 kg.

[0025] In a preferred embodiment, the polypropylene composition (C) includes

[0026] i) a multiphase propylene copolymer (HECO) of 55.0 to 95.0% by weight based on the total weight of the composition, the multiphase propylene copolymer (HECO) comprising a semi-crystalline matrix phase and an elastomeric phase dispersed in the matrix phase, and a xylene cold soluble fraction (XCS) of 18.0 to 45.0% by weight based on the total weight of the multiphase propylene copolymer (HECO), determined at 23°C according to ISO 16152.

[0027] ii) From 5.0 to 45.0% by weight of propylene and at least one C4-C group based on the total weight of the composition. 10 Random copolymers (CPs) of comonomers of the α-olefin group, synthesized in the presence of a single active site catalyst; and

[0028] iii) From 0.0 to 15.0% by weight of mineral filler (F) based on the total weight of the composition;

[0029] The polypropylene composition (C) therein has a melt flow rate (MFR2) of 20.0 to 100.0 g / 10 min, measured according to ISO 1333 at 230 °C and 2.16 kg.

[0030] In addition to the basic components as defined above, the polypropylene composition (C) of the present invention may also contain additional components. However, it is preferred that the total content of the multiphase propylene copolymer (HECO), random copolymer (CP), and optional filler (F) reaches at least 90% by weight, more preferably at least 95% by weight, based on the total weight of the polypropylene composition (C).

[0031] Other typical polymer components may be, for example, additives, the selection of which is well known to those skilled in the art; and masterbatch polypropylene, used to introduce the additives into the polypropylene composition (C).

[0032] Typically, additives are selected from antioxidants, antislip agents, nucleating agents, anti-scratch agents, anti-scorching agents, metal passivators, UV stabilizers, deacidifiers, lubricants, antistatic agents, pigments, and combinations thereof. These additives are well known in the polymer industry and their use is familiar to those skilled in the art. Any additives present may be added either as a separate raw material or as a mixture with the carrier polymer (i.e., in the form of a so-called masterbatch).

[0033] Based on the total weight of the polypropylene composition (C), the amount of additives in the polypropylene composition (C) is preferably in the range of 0.0 to 10% by weight, more preferably 0.01 to 5% by weight.

[0034] In one embodiment, the polypropylene composition (C) of the present invention comprises:

[0035] i) Multiphase propylene copolymer (HECO) from 55.0 to 95.0% by weight,

[0036] ii) From 5.0 to 45.0% by weight of random copolymers (CP), and

[0037] iii) Optional mineral filler (F) ranging from 0.0 to 15.0% by weight.

[0038] The polypropylene composition (C) contains 55.0 to 95.0% by weight, more preferably 58.0 to 92.0% by weight, and most preferably 60.0 to 90.0% by weight.

[0039] The random copolymer (CP) content in the polypropylene composition (C) is 5.0 to 45.0% by weight, more preferably 8.0 to 42.0% by weight, and most preferably 10.0 to 40.0% by weight.

[0040] Therefore, it is preferred that the polypropylene composition (C) comprises:

[0041] i) Multiphase propylene copolymer (HECO) ranging from 58.0 to 92.0% by weight,

[0042] ii) From 8.0 to 42.0% by weight of random copolymers (CP), and

[0043] iii) Optional mineral filler (F) ranging from 0.0 to 15.0% by weight.

[0044] A further preferred embodiment of the polypropylene composition (C) includes:

[0045] i) Multiphase propylene copolymer (HECO) from 60.0 to 90.0% by weight,

[0046] ii) From 10.0 to 40.0% by weight of random copolymers (CP), and

[0047] iii) Optional mineral filler (F) ranging from 0.0 to 15.0% by weight.

[0048] The preparation and further processing of the polypropylene composition (C) involves blending the individual components of the polypropylene composition (C), for example, by using conventional compounding or blending equipment, such as a Banbury internal mixer, a two-roll rubber mill, a Buss-co-kneader, or a twin-screw extruder. Typical extrusion temperatures are in the range of 170 to 270°C, or more preferably in the range of 180 to 240°C.

[0049] The polypropylene composition (C) of the present invention has a melt flow rate (MFR2) measured according to ISO 1333 at 230°C and 2.16 kg, ranging from 20.0 to 100.0 g / 10 min, preferably from 22.5 to 75.0, more preferably from 25.0 to 50.0, and most preferably from 27.0 to 45.0 g / 10 min.

[0050] The polypropylene composition (C) of the present invention preferably has a tensile modulus measured according to ISO 527-1,-2 in the range of 900 to 2500 MPa, more preferably in the range of 950 to 2200 MPa, and most preferably in the range of 975 to 2000 MPa.

[0051] The polypropylene composition (C) of the present invention preferably has a flexural modulus measured according to ISO 178 in the range of 850 to 2500 MPa, more preferably in the range of 900 to 2200 MPa, and most preferably in the range of 925 to 2000 MPa.

[0052] The polypropylene composition (C) of the present invention preferably has a concentration of 7.5 to 20.0 kJ / m³. 2 Within the range, preferably between 8.0 and 18.0 kJ / m 2 Within the range, the optimal value is between 8.5 and 16.0 kJ / m³. 2 Notched impact strength of simply supported beams measured at 23°C according to ISO 179-leA within the specified range.

[0053] The polypropylene composition (C) of the present invention preferably has a melt temperature (T) measured by differential scanning calorimetry (DSC) in the range of 155 to 172°C, more preferably in the range of 158 to 170°C, and most preferably in the range of 160 to 167°C. m ).

[0054] The polypropylene composition (C) of the present invention preferably has a crystallization temperature (T) measured by differential scanning calorimetry (DSC) in the range of 116 to 136°C, more preferably in the range of 120 to 133°C, and most preferably in the range of 122 to 130°C. c ).

[0055] The polypropylene composition (C) of the present invention preferably has an elongation at break measured according to ISO 527 in the range of 20 to 500%, more preferably 22 to 450%, and most preferably 24 to 425%.

[0056] The polypropylene composition (C) of the present invention preferably has a shrinkage in flow (or shrinkage in the flow direction) of less than 1.8%, more preferably 1.7% or less, and most preferably 1.6% or less, as measured according to EN DIN ISO 294-4.

[0057] The lower limit of the shrinkage rate in the flow direction is typically 0.7%, preferably 0.9%.

[0058] The polypropylene composition (C) of the present invention preferably has less than 2.0%, more preferably 1.8% or less, and most preferably 1.7% or less of a cross-flow shrinkage (or vertical flow shrinkage, shrinkage in the cross-flow direction or shrinkage in the direction perpendicular to the flow direction) as measured according to EN DIN ISO 294-4.

[0059] The lower limit of the lateral flow shrinkage rate is typically 0.7%, preferably 0.9%.

[0060] The polypropylene composition (C) of the present invention preferably has a puncture energy in the range of 2 to 50 J, more preferably in the range of 3 to 45 J, as measured in an instrumented drop hammer impact test according to ISO 6603-2.

[0061] Therefore, the filler-free polypropylene composition (C) preferably has a puncture energy of at least 8 J, more preferably at least 10 J.

[0062] The polypropylene composition (C) of the present invention preferably has energy to max force in an instrumented drop hammer impact test, measured according to ISO 6603-2, in the range of 1 to 25 J, preferably in the range of 2 to 22 J.

[0063] Therefore, the filler-free polypropylene composition (C) preferably has an energy of at least 10 J, more preferably at least 12 J, up to the maximum force.

[0064] Multiphase propylene copolymer (HECO)

[0065] The multiphase propylene copolymer (HECO) of the present invention is preferably a copolymer of propylene and ethylene.

[0066] The semi-crystalline matrix phase can be a propylene homopolymer or a random copolymer of propylene and ethylene comonomer units.

[0067] The elastomer phase is typically a copolymer of propylene and ethylene, such as a block copolymer of propylene and ethylene.

[0068] The multiphase propylene copolymer (HECO) preferably has a content of 5.0 to 20.0% by weight, more preferably 7.0 to 17.0% by weight, and most preferably 9.0 to 15.0% by weight based on the total weight of the multiphase propylene copolymer (HECO). 13 Total ethylene content determined by C-NMR spectroscopy.

[0069] Preferably, the multiphase propylene copolymer (HECO) has a content based on the total weight of the multiphase propylene copolymer (HECO) in the range of 80.0 to 95.0% by weight, more preferably in the range of 83.0 to 93.0% by weight, and most preferably in the range of 85.0 to 91.0% by weight. 13 Total propylene content determined by C-NMR spectroscopy.

[0070] Multiphase propylene copolymer (HECO) is preferably composed of propylene and ethylene.

[0071] The multiphase propylene copolymer (HECO) of the present invention preferably has a melt flow rate MFR2 measured according to ISO 1333 at 230°C and 2.16 kg, in the range of 5.0 to 50.0 g / 10 min, more preferably in the range of 10.0 to 40.0 g / 10 min, and most preferably in the range of 12.0 to 30.0 g / 10 min.

[0072] The multiphase propylene copolymer (HECO) of the present invention has a xylene cold soluble fraction (XCS) determined according to ISO 16152 at 23°C in the range of 18.0 to 45.0% by weight, more preferably in the range of 20.0 to 42.5% by weight, most preferably in the range of 23.0 to 40.0% by weight, and for example in the range of 25.0 to 35.0% by weight, based on the total weight of the multiphase propylene copolymer (HECO).

[0073] The xylene cold soluble fraction is usually composed of most of the elastomer phase, and therefore can be regarded as a measure of the elastomer phase.

[0074] The multiphase propylene copolymer (HECO) of the present invention preferably has an intrinsic viscosity (iV) of the xylene cold soluble fraction measured according to DIN ISO 1628 / 1 (in decahydronaphthalene, at 135°C) in October 1999, in the range of 2.0 to 4.0 dl / g, more preferably in the range of 2.5 to 3.5 dl / g, most preferably in the range of 2.7 to 3.3 dl / g, for example in the range of 2.9 to 3.2 dl / g.

[0075] The multiphase propylene copolymer (HECO) of the present invention preferably has a content based on the total weight of xylene cold soluble fraction in the range of greater than 30.0 to 50.0% by weight, more preferably in the range of 34.0 to 48.0% by weight, most preferably in the range of 36.0 to 46.0% by weight, for example in the range of 38.0 to 44.0% by weight. 13 Ethylene content in xylene cold soluble fraction determined by C-NMR spectroscopy.

[0076] The multiphase propylene copolymer (HECO) of the present invention preferably has a concentration of 10.0 to 30.0 kJ / m³. 2 Within the range, more preferably from 12.0 to 25.0 kJ / m 2 Within the range, the optimal value is between 13.0 and 20.0 kJ / m³. 2 Notched impact strength (NIS) of simply supported beams measured at 23°C according to ISO 179-1eA within the specified range.

[0077] The multiphase propylene copolymer (HECO) of the present invention preferably has a flexural modulus measured according to ISO 178 in the range of 800 to 1500 MPa, more preferably in the range of 850 to 1300 MPa, and most preferably in the range of 900 to 1200 MPa.

[0078] According to a preferred embodiment, the multiphase propylene copolymer (HECO) of the present invention has been polymerized using a heterogeneous Ziegler-Natta catalyst system and / or has been polymerized in a multi-stage polymerization apparatus.

[0079] The multiphase propylene copolymer (HECO) described above is commercially available.

[0080] Random copolymer (CP)

[0081] The random copolymer (CP) of the present invention is synthesized in the presence of a single active site catalyst and propylene and at least one C4-C alloy. 10 Random copolymers of comonomers of the α-olefin group, preferably random copolymers of propylene and 1-butene or random copolymers of propylene and 1-hexene synthesized in the presence of a single active site catalyst.

[0082] The random copolymer (CP) preferably has a melt flow rate MFR2 measured at 230°C and 2.16 kg according to ISO 1333 in the range of 25.0 to 150.0 g / 10 min, more preferably 30.0 to 125.0 g / 10 min, even more preferably 32.5 to 100.0 g / 10 min, and most preferably 35.0 to 80.0 g / 10 min.

[0083] Melt flow rate (MFR2) can be obtained during polymerization by adjusting the flow rate of chain transfer agent such as hydrogen or by reducing the viscosity of random copolymers produced in the reactor with a melt flow rate of less than 25 g / 10 min.

[0084] The random copolymer (CP) preferably has a xylene cold soluble fraction (XCS) determined at 23°C according to ISO 16152 in the range of 0.5 to 12.5% ​​by weight, more preferably 0.7 to 11.0% by weight, even more preferably 0.8 to 10.0% by weight, and most preferably 0.9 to 9.0% by weight, based on the total weight of the random copolymer (CP).

[0085] Atactic copolymers produced by viscosity reduction cracking typically have higher levels of xylene cold soluble fraction (XCS) than atactic copolymers produced by reactors.

[0086] Random copolymers (CP) preferably have a melt temperature (Tm) measured by differential scanning calorimetry (DSC) in the range of 120 to 155°C, more preferably in the range of 128 to 148°C, and most preferably in the range of 133 to 143°C. m ).

[0087] Random copolymers (CP) preferably have a crystallization temperature (Tc) measured by differential scanning calorimetry (DSC) in the range of 80 to 120°C, more preferably in the range of 90 to 115°C, and most preferably in the range of 95 to 110°C. c ).

[0088] The random copolymer (CP) preferably has a comonomer content in the range of 1.0 to 5.0 mol% based on the molar amount of the random copolymer (CP), more preferably 1.2 to 4.5 mol%, even more preferably 1.4 to 4.0 mol%, and most preferably in the range of 1.6 to 3.5 mol%.

[0089] According to a preferred embodiment, the random copolymer (CP) of the present invention is a random copolymer of propylene and 1-hexene, comprising...

[0090] i) a first random propylene copolymer (CP-A) of propylene and 1-hexene, comprising 30 to 70% by weight, wherein the first random propylene copolymer (CP-A) has a 1-hexene content in the range of 0.05 to less than 1.9 mol%, and

[0091] ii) A second random propylene copolymer (CP-B) of 70 to 30% by weight of propylene and 1-hexene, wherein the second random propylene copolymer (CP-B) has a higher 1-hexene content than the first random propylene copolymer (CP-A).

[0092] The copolymer (CP) has a total 1-hexene content in the range of 1.5 to 3.5 mol%.

[0093] According to another preferred embodiment, the random copolymer (CP) of the present invention is a random copolymer of propylene and 1-butene, comprising...

[0094] i) 30 to 70% by weight of a propylene-1-butene copolymer (CP-A) having a 1-butene content of 0.4 to 7.7 mol%; and

[0095] (ii) 70 to 30% by weight of propylene-1-butene copolymer (CP-B) having a 1-butene content of 0.8 to 6.1 mol%;

[0096] The random copolymer (CP) has a 1-butene content of 2.0 to 4.0 mol%, and the 1-butene content of copolymers (CP-A) and (CP-B) is different.

[0097] Preparation of random copolymers (CP)

[0098] The copolymer (CP) is preferably a random copolymer of propylene, and is particularly obtainable by a process as defined in detail below, preferably by a process as defined in detail below.

[0099] The method for preparing the random copolymer (CP) present in the polypropylene composition (C) as defined above is a sequential polymerization method comprising at least two reactors connected in series, wherein the method includes the following steps:

[0100] (A) Polymerizing propylene and at least one compound selected from C4-C in the first reactor (R-1) 10 The comonomers of the α-olefin group are used to obtain the first random propylene copolymer (A). The first reactor (R-1) is a slurry reactor (SR), preferably a loop reactor (LR).

[0101] (B) The first random propylene copolymer (A) and unreacted comonomer in the first reactor (R-1) are transferred to the second reactor (R-2), which is a gas-phase reactor (GPR-1).

[0102] (C) Feed propylene and at least one compound selected from C4-C into the second reactor (R-2). 10 Comonomers of the α-olefin group,

[0103] (D) Polymerizing propylene and at least one compound selected from C4-C in the second reactor (R-2) in the presence of the first random propylene copolymer (A). 10Comonomers of the α-olefin group are used to obtain a second random propylene copolymer (B), wherein the first random propylene copolymer (A) and the second random propylene copolymer (B) form a random copolymer (CP) as defined in this invention.

[0104] The polymerization is further carried out in the first reactor (R-1) and the second reactor (R-2) in the presence of a solid catalyst system (SCS), which contains...

[0105] (i) Transition metal compounds having formula (I)

[0106] R n (Cp)2MX2(I)

[0107] Where "M" stands for zirconium (Zr) or hafnium (Hf),

[0108] Each "X" is independently a monovalent anion σ-ligand.

[0109] Each “Cp” is an independently selected cyclopentadienyl-type organic ligand composed of unsubstituted or substituted and / or fused cyclopentadienyl, substituted or unsubstituted indenyl, or substituted or unsubstituted fluorenyl groups, said organic ligand being coordinated with a transition metal (M).

[0110] “R” is a divalent bridging group that connects the organic ligand (Cp).

[0111] "n" can be 1 or 2, preferably 1, and

[0112] (ii) Optionally, a co-catalyst (Co) containing an element (E) of Group 13 of the periodic table (IUPAC), preferably a co-catalyst (Co) containing a compound of Al and / or B.

[0113] For the definitions of random copolymer (CP), first random propylene copolymer (A), and second random propylene copolymer (B), please refer to the definitions given above.

[0114] Solid catalyst systems (SCS) are defined in more detail below.

[0115] The term "sequential polymerization" refers to the production of random copolymers (CPs) in at least two reactors connected in series. More precisely, the term "sequential polymerization" in this application refers to the direct transfer of the polymer from a first reactor (R-1) with unreacted comonomers to a second reactor (R-2). Therefore, a defining aspect of this method is the preparation of random copolymers (CPs) in two distinct reactors, wherein the reactants from the first reactor (R-1) are directly transferred to the second reactor (R-2). Thus, this method comprises at least a first reactor (R-1) and a second reactor (R-2). In one specific embodiment, the method consists of two polymerization reactors (R-1) and (R-2). The term "polymerization reactor" should indicate where the primary polymerization occurs. Therefore, in the case where the method consists of two polymerization reactors, this definition does not exclude the option of including a prepolymerization step, for example, in a prepolymerization reactor. Considering the primary polymerization reactor, the term "consisting of" is merely a closed-ended expression.

[0116] The first reactor (R-1) is a slurry reactor (SR) and can be any continuous or simple stirred batch reactor or loop reactor operating in slurry. According to the invention, the slurry reactor (SR) is preferably a loop reactor (LR).

[0117] The second reactor (R-2) and any subsequent reactors are gas-phase reactors (GPRs). Such gas-phase reactors (GPRs) can be any mechanically mixed or fluidized bed reactor. Preferably, the gas-phase reactor (GPR) comprises a mechanically stirred fluidized bed reactor with a gas velocity of at least 0.2 m / sec. Therefore, it should be understood that the gas-phase reactor (GPR) is preferably a fluidized bed reactor with a mechanical stirrer.

[0118] The conditions in each reactor (temperature, pressure, reaction time, monomer feed) depend on the desired product, which is within the knowledge of those skilled in the art. As noted above, the first reactor (R-1) is a slurry reactor (SR), such as a loop reactor (LR), while the second reactor (R-2) is a gas-phase reactor (GPR-1). Subsequent reactors (if any) are also gas-phase reactors (GPR).

[0119] The preferred multi-stage process is the "loop-gas phase" process, such as the one developed by Borealis A / S of Denmark (called...). (Technology), for example, as described in patent documents, such as EP 0 887 379 or WO 92 / 12182.

[0120] Multimodal polymers can be produced by several methods, such as those described in WO 92 / 12182, EP 0887 379 and WO 98 / 58976. The contents of these documents are incorporated herein by reference.

[0121] Preferably, in this method for producing random copolymers (CP) as defined above, the conditions of the first reactor (R-1) in step (A), i.e., the slurry reactor (SR), such as a loop reactor (LR), can be as follows:

[0122] - The temperature is in the range of 40°C to 110°C, preferably between 60°C and 100°C, and more preferably in the range of 65°C to 90°C.

[0123] - The pressure is in the range of 20 bar to 80 bar, preferably between 40 bar and 70 bar.

[0124] - Hydrogen can be added in a manner known to the public to control molar mass.

[0125] Subsequently, the reaction mixture from step (A) is transferred to the second reactor (R-2), i.e., the gas phase reactor (GPR-1), i.e., to step (D), wherein the conditions in step (D) are preferably as follows:

[0126] - The temperature range is 50°C to 130°C, preferably between 60°C and 100°C.

[0127] - The pressure is in the range of 5 bar to 50 bar, preferably between 15 bar and 40 bar.

[0128] - Hydrogen can be added in a manner known to the public to control molar mass.

[0129] The residence times in the two reactor zones can be different.

[0130] In one embodiment of the process for producing random copolymers (CP), the residence time in a slurry reactor (SR), such as a loop reactor (LR), is in the range of 0.2 to 4.0 hours, for example, in the range of 0.3 to 1.5 hours, and the residence time in a gas phase reactor (GPR) is typically 0.2 to 6.0 hours, such as 0.5 to 4.0 hours.

[0131] If desired, polymerization can be carried out in a known manner under supercritical conditions in a first reactor (R-1), i.e., in a slurry reactor (SR), as in a loop reactor (LR).

[0132] The conditions in other gas-phase reactors (GPRs) (if present) are similar to those in the second reactor (R-2).

[0133] This method may also include prepolymerization prior to polymerization in the first reactor (R-1). Prepolymerization may be carried out in the first reactor (R-1), however, it is preferred that prepolymerization be carried out in a separate reactor (the so-called prepolymerization reactor).

[0134] The random copolymer (CP) according to the present invention is prepared in the presence of a solid catalyst system (SCS) containing a transition metal compound.

[0135] In a preferred embodiment, the transition metal compound has formula (I).

[0136] R n (Cp)2MX2(I)

[0137] Each Cp is independently an unsubstituted or substituted and / or fused cyclopentadienyl ligand, such as a substituted or unsubstituted cyclopentadienyl, a substituted or unsubstituted indenyl, or a substituted or unsubstituted fluorenyl ligand; the optional one or more substituents are preferably independently selected from halogens, hydrocarbon groups (e.g., C1-C20-alkyl, C2-C20-alkenyl, C2-C20-alkynyl, C3-C12-cycloalkyl, C6-C20-aryl, or C7-C20-aralkyl), C3-C12-cycloalkyl, C6-C20-heteroaryl, C1-C20-haloalkyl, -SiR"3, -OSiR"3, -SR", -PR"2, OR" or -NR"2, containing 1, 2, 3 or 4 heteroatoms in the ring moiety.

[0138] Each R" is independently a hydrogen or hydrocarbon group, such as C1-C20-alkyl, C2-C20-alkenyl, C2-C20-alkynyl, C3-C12-cycloalkyl, or C6-C20-aryl; or, for example, in the case of -NR"2, the two substituents R" can form a ring together with the nitrogen atom to which they are attached, such as a five-membered ring or a six-membered ring;

[0139] R is a bridge with 1-3 atoms, for example, a bridge with 1-2 C atoms and 0-2 heteroatoms, wherein the heteroatoms can be, for example, Si, Ge, and / or O atoms, and each bridge atom can independently carry a substituent, such as C1-C20-alkyl, tris(C1-C20-alkyl)silyl, tris(C1-C20-alkyl)siloxy, or C6-C20-aryl substituents; or a bridge with 1-3, for example, one or two heteroatoms, such as silicon, germanium, and / or oxygen atoms, such as –SiR. 10 2, where each R 10 Independently, it is a C1-C20-alkyl, C3-12-cycloalkyl, C6-C20-aryl, or tri(C1-C20-alkyl)silyl-residue, such as trimethylsilyl;

[0140] M is a group 4 transition metal, such as Zr or Hf, especially Zr;

[0141] Each X is independently a σ-ligand, such as H, halogen, C1-C20-alkyl, C1-C20-alkoxy, C2-C20-alkenyl, C2-C20-alkynyl, C3-C12-cycloalkyl, C6-C20-aryl, C6-C20-aryloxy, C7-C20-aralkyl, C7-C20-arylenyl, -SR", -PR"3, -SiR"3, -OSiR"3, -NR"2 or -CH2-Y, wherein Y is C6-C20-aryl, C6-C20-heteroaryl, C1-C20-alkoxy, C6-C20-aryloxy, NR"2, -SR", -PR"3, -SiR"3 or -OSiR"3;

[0142] Each of the above-mentioned ring moiety, either as a substituent of Cp, X, R" or R, or as part of another moiety, may be further substituted, for example, by being substituted with a C1-C20-alkyl group that may contain Si and / or O atoms.

[0143] n is 1 or 2.

[0144] Suitably, in each X as -CH2-Y, each Y is independently selected from C6-C20-aryl, NR"2, -SiR"3, or -OSiR"3. Most preferably, the X as -CH2-Y is benzyl. Each X other than -CH2-Y is independently a halogen, C1-C20-alkyl, C1-C20-alkoxy, C6-C20-aryl, C7-C20-arylenyl, or -NR"2 as defined above, for example -N(C1-C20-alkyl)2.

[0145] Preferably, each X is a halogen, methyl, phenyl, or -CH2-Y, and each Y is independently as defined above.

[0146] Cp is preferably cyclopentadienyl, indenyl, or fluorenyl, optionally substituted as defined above. Ideally, Cp is cyclopentadienyl or indenyl.

[0147] In a suitable subgroup of compounds of formula (I), each Cp independently carries 1, 2, 3 or 4 substituents as defined above, preferably 1, 2 or 3, for example 1 or 2 substituents, the substituents preferably selected from C1-C20-alkyl, C6-C20-aryl, C7-C20-aralkyl (where the individual aryl ring or the aryl ring as part of another part may be further substituted, as described above), -OSiR"3, wherein R" is as indicated above, preferably C1-C20-alkyl.

[0148] R is preferably a methylene, ethylene, or silyl bridge, wherein the silyl group can be substituted as defined above, for example, (dimethyl)Si=, (methylphenyl)Si=, (methylcyclohexyl)silyl=, or (trimethylsilylmethyl)Si=; n is 0 or 1. Preferably, R" is not hydrogen.

[0149] Specific subgroups include well-known Zr and Hf metallocenes having two η5-ligands bridged to a cyclopentadienyl ligand, optionally substituted with a silaneoxy or alkyl group (e.g., C1-6-alkyl) as defined above; or bridged to an indenyl ligand having two bridging links, optionally substituted with a silaneoxy or alkyl group as defined above at any ring position, such as 2-, 3-, 4-, and / or 7-. Preferred bridges are ethylene or -SiMe2.

[0150] The preparation of metallocenes can be carried out according to or similar methods known in the literature and are within the skill of those skilled in the art. Thus, for preparation, see, for example, EP-A-129 368, and examples of compounds in which the metal atom bears the -NR”2 ligand, see, for example, WO-A-985683 1 and WO-A-0034341. Also see, for preparation, see, for example, EP-A-260130, WO-A-9728170, WO-A-9846616, WO-A-9849208, WO-A-9912981, WO-A-9919335, WO-A-9856831, WO-A-00 34341, EP-A-423 101 and EP-A-537 130.

[0151] The complexes of the present invention are preferably asymmetric. This simply means that the two indenyl ligands forming the metallocene are different, that is, each indenyl ligand carries a set of substituents that are chemically different or located at different positions relative to the other indenyl ligand. More precisely, they are chiral, racemic-bridged bis-indenyl metallocenes. While the complexes of the present invention would ideally be in their cis configuration, they are in their trans configuration. For the purposes of the invention, racemic-trans means that the two indenyl ligands are oriented in opposite directions relative to the cyclopentadienyl-metal-cyclopentadienyl plane, while racemic-cis means that the two indenyl ligands are oriented in the same direction relative to the cyclopentadienyl-metal-cyclopentadienyl plane.

[0152] The preferred complexes of this invention have formula (II') or (II).

[0153]

[0154] in

[0155] M is Zr;

[0156] Each X is a σ ligand, preferably each X is independently a hydrogen atom, a halogen atom, a C1-C6 alkoxy group, a C1-C6 alkyl group, a phenyl group, or a benzyl group;

[0157] L is a divalent bridge selected from -R'2C-, -R'2C-CR'2, -R'2Si-, -R'2Si-SiR'2-, and -R'2Ge-, where each R' is independently a hydrogen atom, a C1-C20 alkyl group, a C3-C10 cycloalkyl group, a tris(C1-C20 alkyl)silyl group, a C6-C20 aryl group, or a C7-C20 aralkyl group.

[0158] Each R 2 Or R 2 'It is a C1-C10 alkyl group;

[0159] R 5 'Is a C1-C10 alkyl or Z'R 3 'group;

[0160] R 6 It is hydrogen or C1-C10 alkyl;

[0161] R 6 It is a C1-C10 alkyl or C6-C10 aryl;

[0162] R 7 It is hydrogen, C1-C6 alkyl or Zr 3 Group;

[0163] R 7 It is hydrogen or a C1-C10 alkyl group;

[0164] Z and Z' are independently O or S;

[0165] R 3 ' is a C1-C10 alkyl or C6-C10 aryl, which may optionally be substituted with one or more halogen groups;

[0166] R 3 It is a C1-C10 alkyl group;

[0167] Each n is independently between 0 and 4, for example, 0, 1, or 2;

[0168] Each R 1 Independently, it is a C1-C20 hydrocarbon group, such as a C1-C10 alkyl group.

[0169] The compounds particularly preferred by this invention include:

[0170] Racemic-dimethylsilylbis[2-methyl-4-(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indarsen-1-yl]zirconium dichloride

[0171] Racemic-dimethylsilylbis(2-methyl-4-phenyl-5-methoxy-6-tert-butylinden-1-yl)zirconium dichloride

[0172] Racemic-trans-Me2Si(2-Me-4-Ph-6-tBu-Ind)(2-Me-4-Ph-5-OMe-6-tBu-Ind)ZrCl2

[0173] Racemic-trans-Me2Si(2-Me-4-(p-tBuPh)-Ind)(2-Me-4-Ph-5-OMe-6-tBu-Ind)ZrCl2

[0174] Racemic-trans-Me2Si(2-Me-4-(3,5-di-tBuPh)-6-tBu-Ind)(2-Me-4-Ph-5-OMe-6-tBu-Ind)ZrCl2

[0175] Racemic-trans-Me2Si(2-Me-4-(p-tBuPh)-Ind)(2-Me-4-Ph-5-OC6F5)-6-iPr-Ind)ZrCl2

[0176] Racemic-trans-Me(CyHex)Si(2-Me-4-Ph-6-tBu-Ind)(2-Me-4-Ph-5-OMe-6-tBu-Ind)ZrCl2

[0177] Racemic-trans-Me2Si(2-Me-4-(3,5-di-tBuPh)-7-Me-Ind)(2-Me-4-Ph-5-OMe-6-tBu-Ind)ZrCl2

[0178] Racemic-trans-Me2Si(2-Me-4-(3,5-di-tBuPh)-7-OMe-Ind)(2-Me-4-Ph-5-OMe-6-tBu-Ind)ZrCl2

[0179] Racemic-trans-Me2Si(2-Me-4-(p-tBuPh)-6-tBu-Ind)(2-Me-4-Ph-5-OMe-6-tBu-Ind)ZrCl2

[0180] Racemic-trans-Me2Si(2-Me-4-(p-tBuPh)-Ind)(2-Me-4-(4-tBuPh)-5-OMe-6-tBu-Ind)ZrCl2

[0181] Racemic-trans-Me2Si(2-Me-4-(p-tBuPh)-Ind)(2-Me-4-(3,5-tBu2Ph)-5-OMe-6-tBu-Ind)ZrCl2

[0182] Racemic-trans-Me2Si(2-Me-4-(p-tBuPh)-Ind)(2-Me-4-Ph-5-OtBu-6-tBu-Ind)ZrCl2.

[0183] The most preferred metallocene complex (main catalyst) is racemic-trans-dimethylsilyl(2-methyl-4-phenyl-5-methoxy-6-tert-butyl-indenyl)(2-methyl-4-(4-tert-butylphenyl)indenyl)zirconium dichloride.

[0184] In addition to the metallocene complex (the main catalyst), the metallocene catalyst also contains a co-catalyst as defined in WO 2015 / 011135 A1. Therefore, the preferred co-catalyst is methylaluminoxane (MAO) and / or borate esters, preferably triphenylmethyl tetra(pentafluorophenyl)borate.

[0185] Particularly preferred are metallocene catalysts that are unsupported, i.e., without the use of an external support. For the preparation of such metallocene complexes, please refer again to WO 2015 / 011135 A1.

[0186] To adjust the melt flow rate (MFR2) of the random copolymer (CP), random copolymers with a low melt flow rate (MFR2) of no more than 25 g / 10 min, for example no more than 10 g / 10 min, such as no more than 7.5 g / 10 min or no more than 5.0 g / 10 min can undergo a viscosity-reducing cracking step.

[0187] Viscosity reduction cracking is a post-reactor chemical process used to modify semi-crystalline polymers, such as propylene polymers. In the viscosity reduction cracking process, the propylene polymer backbone is degraded via β-fractionation using peroxides, such as organic peroxides. This degradation is typically used to increase melt flow rate and reduce molecular weight distribution.

[0188] The viscosity reduction cracking step is preferably performed as described in WO 2013 / 092620 A1.

[0189] Mineral packing (F)

[0190] Furthermore, the polypropylene composition (C) according to the invention may contain a mineral filler (F) in an amount from 0.0 to 15.0% by weight based on the total weight of the polypropylene composition.

[0191] Preferably, the polypropylene composition (C) comprises a mineral filler (F) in an amount ranging from 2.0 to 13.0% by weight, for example from 3.0 to 12.0% by weight, based on the total weight of the polypropylene composition.

[0192] In one specific embodiment, the polypropylene composition (C) is free of mineral filler (F).

[0193] If present, the mineral filler (F) is preferably selected from the group consisting of free mica, wollastonite, kaolinite, montmorillonite, talc and mixtures thereof.

[0194] Generally, the mineral filler (F) may have a median particle size d in the range of 0.1 to 30 μm, preferably in the range of 0.2 to 25 μm, and more preferably in the range of 0.3 to 20 μm. 50 .

[0195] The preferred filler (F) is talc. Preferably, a median particle size d is used, in the range of 0.1 to 10 μm, more preferably in the range of 0.2 to 6.0 μm, and even more preferably in the range of 0.3 to 4.0 μm. 50 Talc is used as filler (F). Most preferably, talc is used as the sole mineral filler (F). Even more preferably, the talc used has a top cut particle size of 0.8 to 50 μm, preferably 1.0 to 25 μm, and most preferably 1.2 to 20 μm (according to ISO 787-7, 95% of the particles are below this size).

[0196] Products and uses

[0197] The polypropylene composition (C) of the present invention can be used to produce articles, such as molded articles, preferably injection-molded articles. Furthermore, the polypropylene composition of the present invention can be used to produce foamed articles, such as foam injection-molded articles. Even more preferably, it is used to produce automotive articles, especially automotive interior and exterior articles, such as instrument panel brackets, front-end modules, grilles, structural brackets, bumpers, side trim pieces, pedal accessories, body panels, spoilers, dashboards, interior trim pieces, etc. Preferably, the article is an automotive interior article.

[0198] Therefore, in another aspect, the present invention relates to injection-molded articles comprising a polypropylene composition as defined herein.

[0199] In another respect, the present invention relates to foamed articles comprising polypropylene compositions as defined herein, preferably foamed injection molded articles.

[0200] In another aspect, the present invention relates to the use of polypropylene compositions as defined herein for the production of injection-molded articles and / or foamed articles.

[0201] All preferred embodiments described for the polypropylene composition (C), multiphase propylene copolymer (HECO), and random copolymer (CP), as well as optional mineral filler (F), are also applicable to the articles and uses of the present invention described herein.

[0202] The present invention will now be illustrated by the embodiments provided below. The experimental data and embodiments shown below are to be understood by those skilled in the art as illustrative and do not further limit the invention.

[0203] Example

[0204] 1. Measurement Method

[0205] MFR2 (230℃) is measured according to ISO 1133 (230℃, 2.16kg load).

[0206] Xylene cold solubles (XCS, wt%) were determined at 25°C according to ISO 16152; First Edition; 1 July 2005.

[0207] Quantitative analysis of ethylene content in microstructure-HECO using NMR spectroscopy

[0208] Quantitative nuclear magnetic resonance (NMR) spectroscopy was used to quantify the comonomer content of the polymer. (This is relevant to the following sentence about NMR spectroscopy and its application.) 1 H and 13 A Bruker Advance III 400 NMR spectrometer, operating at 400.15 MHz and 100.62 MHz respectively, recorded quantitative data in solution. 13 C{ 1 ¹H NMR spectroscopy. Nitrogen gas was used for all pneumatic devices at 125°C. 13All spectra were recorded using a C-optimized 10mm extended temperature probe. Approximately 200 mg of material was dissolved together with chromium acetylacetone (Cr(acac)3) in 3 mL of 1,2-tetrachloroethane-d2 (TCE-d2) to obtain a 65 mM solution of the relaxant in the solvent (Singh, G., Kothari, A., Gupta, V., Polymer Testing 28 5 (2009), 475). To ensure a homogeneous solution, the NMR tube was further heated in a rotary oven for at least 1 hour after the initial sample preparation in the heating block. After insertion into the magnet, the tube was rotated at 10 Hz. This setting was chosen primarily for high resolution and was quantitatively necessary for accurate ethylene content quantification. A standard single-pulse excitation without NOE was employed, using an optimized sharp angle, a 1-second cyclic delay, and a dual-layer WALTZ16 decoupling 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). A total of 6144 (6 k) transient signals were acquired for each spectrum.

[0209] Quantitative analysis was performed using a dedicated computer program. 13 C{ 1 The ¹H NMR spectra were processed, integrated, and the relevant quantitative properties were determined from the integration. All chemical shifts were indirectly referenced to the central methylene group of the ethylene block (EEE) at 30.00 ppm using the chemical shifts of the solvent. This method allows for comparable references even if the structural unit is not present. Characteristic signals corresponding to the incorporation of ethylene can be observed (Cheng, HN, Macromolecules 17 (1984), 1950).

[0210] Because characteristic signals corresponding to 2,1-erythro-type region defects have been observed (as described in L. Resconi, L. Cavallo, A. Fait, F. Piemontesi, Chem. Rev. 2000, 100(4), 1253, and in Cheng, HN, Macromolecules 1984, 17, 1950, and in WJ. Wang and S. Zhu, Macromolecules 2000, 33, 1157), corrections are needed for the effect of region defects on defined properties. No characteristic signals corresponding to other types of region defects have been observed.

[0211] Using the method of Wang et al. (Wang, WJ., Zhu, S., Macromolecules 33 (2000), 1157), by finding in 13 C{ 1 The fraction of comonomers is quantified by integrating multiple signals across the entire spectral region of the H spectrum. This method was chosen because of its robustness and ability to indicate the presence of regional defects when needed. The integration region was slightly adjusted to improve applicability across the entire range of comonomer contents encountered.

[0212] For systems where only isolated ethylene is observed in the PPEPP sequence, the method of Wang et al. is modified to reduce the influence of non-zero integrals from sites that are known to be absent. This method reduces the overestimation of ethylene content in such systems and is achieved by reducing the number of sites used to determine the absolute ethylene content to the following:

[0213] E=0.5(Sββ+Sβγ+Sβδ+0.5(Sαβ+Sαγ))

[0214] By using this set of sites, the corresponding integral equation becomes:

[0215] E = 0.5(I H +I G +0.5(I C +I D ))

[0216] The same notation used is employed in the article by Wang et al. (Wang, WJ., Zhu, S., Macromolecules 33 (2000), 1157). The equation for absolute propylene content has not been modified.

[0217] Calculate the molar percentage of comonomer incorporated from the molar fraction:

[0218] E[mol%] = 100 * fE

[0219] Calculate the weight percentage of comonomer incorporated using mole fraction:

[0220] E[weight%]=100*(fE*28.06) / ((fE*28.06)+((1-fE)*42.08))

[0221] The distribution of comonomer sequences at the ternary group level was determined using the analytical method of Kakugo et al. (Kakugo, M., Naito, Y., Mizunuma, K., Miyatake, T. Macromolecules 15 (1982) 1150). This method was chosen because of its robustness and because the integration region was slightly adjusted to increase applicability to a wider range of comonomer contents.

[0222] 1-Hexene comonomer content of propylene-1-hexene copolymer (CP)

[0223] Use for 1 H and 13 Quantitative recordings were performed in the molten state using a Bruker Avance III 500 NMR spectrometer operating at 500.13 and 125.76 MHz, respectively. 13 C{ 1 ¹H NMR spectroscopy. Nitrogen gas was used for all pneumatic devices at 180°C. 13All spectra were recorded using a C-optimized 7mm magic angle rotation (MAS) probe. Approximately 200 mg of material was loaded into a 7mm outer diameter zirconia MAS rotor and rotated at 4 kHz. This setup was chosen primarily for the high sensitivity required for rapid identification and accurate quantification (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). Standard single-pulse excitation was employed, utilizing NOE (Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, HW, Wilhelm, M., Macromol. Chem. Phys. 2006; 207:382., Pollard, M., Klimke, K., Graf, R., Spiess, HW, Wilhelm, M., Sperber, O., Piel, C., Kaminsky, W., Macromolecules 2004; 37:813.) and RS-HEPT decoupling scheme (Filip, X., Tripon, C., Filip, C., J. Mag. Resn. 2005, 176, 239., Griffin, JM, Tripon, C., Samoson, A., Filip, C. and Brown, SP, Mag. Resn.) with a short cyclic delay of 3 s. (Chem. 2007 45, S1, S198). A total of 16384 (16k) transient signals were acquired for each spectrum.

[0224] Quantitative 13 C{ 1 The ¹H NMR spectra were processed, integrated, and the quantitative properties were determined from the integration. All chemical shifts were internally referenced at 21.85 ppm for the isotactic pentamematic methyl group (mmmm).

[0225] Characteristic signals corresponding to the incorporation of 1-hexene were observed, and the content of comonomers was quantified as follows.

[0226] The amount of 1-hexene incorporated into the isolated PHP sequence was quantified by integrating the αB4 site at 44.2 ppm and taking into account the number of reporter sites for each comonomer:

[0227] H=IαB4 / 2

[0228] The amount of 1-hexene incorporated into the PHHP bicontinuous sequence was quantified by integrating the ααB4 site at 41.7 ppm and taking into account the number of reporter sites for each comonomer:

[0229] HH=2*IααB4

[0230] When bicontinuous incorporation is observed, the amount of 1-hexene incorporated into the isolated PHP sequence needs to be compensated for due to the overlap of signals αB4 and αB4B4 at 44.4 ppm.

[0231] H = (IαB4 – 2 * IααB4) / 2

[0232] The total 1-hexene content is calculated based on the sum of isolated and continuous 1-hexene incorporations:

[0233] H 总 =H+HH

[0234] When no sites indicating continuous incorporation are observed, the total 1-hexene comonomer content is calculated solely from this amount:

[0235] H 总 =H

[0236] Characteristic signals of the indicator region 2,1-Erythian defects were observed (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253).

[0237] The presence of 2,1-erythromorphic defects was indicated by the presence of Pαβ(21e8) and Pαγ(21e6) methyl sites at 17.7 and 17.2 ppm, and confirmed by other characteristic signals.

[0238] The total amount of secondary (2,1-erythro)-intercalated propylene was quantified based on the αα21e9 methylene site at 42.4 ppm:

[0239] P21=Iαα21e9

[0240] The total amount of primary (1,2) inserted propylene was quantified based on the major Sαα methylene site at 46.7 ppm and the relative amounts of 2,1-erythro, αB4, and ααB4B4 methylene units of propylene that were not calculated (note that H and HH calculate the number of hexene monomers per sequence, not the sequence number):

[0241] P12 = I S αα+2*P21+H+HH / 2

[0242] The total amount of propylene was quantified as the sum of primary (1,2) and secondary (2,1-erythro) propylene inserts:

[0243] P 总 =P12+P21=I S αα+3*Iαα21e9+(IαB4–2*IααB4) / 2+IααB4

[0244] This simplifies to

[0245] P 总 =I S αα+3*Iαα21e9+0.5*IαB4

[0246] The total mole fraction of 1-hexene in the polymer is then calculated as follows:

[0247] fH = H 总 / (H 总 +P 总 )

[0248] The complete integral equation for the mole fraction of 1-hexene in the polymer is:

[0249] fH=(((IαB4–2*IααB4) / 2)+(2*IααB4)) / ((I S αα+3*Iαα21e9+0.5*αB4)+((IαB4–2*IααB4) / 2)+(2*IααB4))

[0250] This simplifies to:

[0251] fH=(IαB4 / 2+IααB4) / (I S αα+3*Iαα21e9+IαB4+IααB4)

[0252] The total amount of 1-hexene monomer incorporated in mole percentage is calculated from mole fraction in the usual manner:

[0253] H[molar%] = 100 * fH

[0254] The total amount of 1-hexene monomer incorporated, by weight percentage, is calculated from mole fraction in a standard manner:

[0255] H[weight%] = 100 * (fH * 84.16) / ((fH * 84.16) + ((1 - fH) * 42.08))

[0256] 1-Butene comonomer content of propylene-1-butene copolymer (CP)

[0257] Use for 1 H and 13 Quantitative recordings were performed in the molten state using a Bruker Avance III 500 NMR spectrometer operating at 500.13 and 125.76 MHz, respectively. 13 C{ 1 ¹H NMR spectroscopy. Nitrogen gas was used for all pneumatic devices at 180°C. 13 All spectra were recorded using a C-optimized 7mm magic angle rotation (MAS) probe. Approximately 200 mg of material was loaded into a 7mm outer diameter zirconia MAS rotor and rotated at 4 kHz. This setup was chosen primarily for the high sensitivity required for rapid identification and accurate quantification. Standard single-pulse excitation was employed, utilizing NOE with short cyclic delays and RS-HEPT decoupling schemes. A total of 1024 (1k) transient signals were acquired per spectrum using a 3s cyclic delay.

[0258] Quantitative 13 C{ 1 The ¹H NMR spectra were processed, integrated, and the relevant quantitative properties were determined from the integration. All chemical shifts were internally referenced at 21.85 ppm for the methyl isotactic pentamematic group (mmmm){randall89}.

[0259] Basic comonomer content method for spectroscopic analysis:

[0260] The characteristic signal {randall89} corresponding to the incorporation of 1-butene was observed, and the comonomer content was quantified as follows.

[0261] The amount of 1-butene incorporated into the isolated PPBPP sequence was quantified by integrating the αB2 site at 43.6 ppm and taking into account the number of reporter sites for each comonomer:

[0262] B = I α / 2

[0263] The amount of 1-butene incorporated into the PPBBPP bicontinuous sequence was quantified by integrating the ααB2B2 site at 40.5 ppm and taking into account the number of reporter sites for each comonomer:

[0264] BB = 2 * I αα

[0265] When bicontinuous incorporation is observed, the amount of 1-butene incorporated into the isolated PPBPP sequence needs to be compensated for due to the overlap of signals αB2 and αB2B2 at 43.9 ppm.

[0266] B = (I α –2*I αα ) / 2

[0267] The total 1-butene content is calculated based on the sum of isolated and continuous 1-butene incorporations:

[0268] B 总 =B+BB

[0269] The amount of propylene was quantified based on the major Sαα-methylene site at 46.7 ppm and the relative amounts of αB2 and αB2B2-methylene units of propylene that were not calculated (note that B and BB calculate the number of butene monomers per sequence, not the sequence number):

[0270] P 总 =I Sαα +B+BB / 2

[0271] The total mole fraction of 1-butene in the polymer is then calculated as follows:

[0272] fB = B 总 / (B 总 +P 总 )

[0273] The complete integral equation for the mole fraction of 1-butene in the polymer is:

[0274] fB=(((I α –2*I αα ) / 2)+(2*I αα )) / (I Sαα +((I α –2*I αα ) / 2)+((2*I αα ) / 2))+((I α –2*I αα ) / 2)+(2*I αα ))

[0275] This simplifies to:

[0276] fB=(Iα / 2+I αα ) / (I Sαα +I α +I αα )

[0277] The total amount of 1-butene incorporated, expressed as a mole percentage, is calculated from the mole fraction in the usual manner:

[0278] B[moles%] = 100 * fB

[0279] The total amount of 1-butene incorporated, expressed as a weight percentage, is calculated from mole fraction in a standard manner:

[0280] B[weight%] = 100*(fB*56.11) / ((fB*56.11)+((1-fB)*42.08))

[0281] Tensile modulus and elongation at break were determined according to ISO 527-2 (crosshead speed = 1 mm / min; test speed at 23°C = 50 mm / min) using dog bone-shaped specimens fabricated from injection-molded or foam-injection-molded templates as described below.

[0282] Flexural modulus according to ISO 178 for 80×10×2 or 3mm produced from injection-molded or foam-molded templates as described below. 3 The injection-molded specimens were tested using a 3-point bending method.

[0283] Notched impact strength of simply supported beams, according to ISO 179-1eA, at 23°C, for 80×10×2 or 3mm beams machined from injection-molded or foam-molded templates as described below. 3 The injection-molded samples were tested.

[0284] The puncture energy and maximum force energy were measured using an instrumented drop hammer impact test according to ISO 6603-2 on specimens manufactured from injection-molded or foam-molded templates with dimensions of 148×148×2 or 3 mm. 3 The sample was used for testing. The test was conducted at room temperature using a lubricated tip with a diameter of 20 mm and an impact velocity of 10 mm / s.

[0285] Particle size d 50 and top cut d 95 Calculated based on particle size distribution [mass percentage] determined by gravity liquid sedimentation according to ISO 13317-3 (Sedigraph).

[0286] DSC analysis, melting temperature (T) m ) and crystallization temperature (T) c ):

[0287] Samples ranging from 5 to 7 mg were measured using a TA Instrument Q2000 differential scanning calorimeter (DSC). The DSC was operated according to ISO 11357 / Part 3 / Method C2 in a heating / cooling / heating cycle at a scan rate of 10 °C / min over a temperature range of -30 °C to +225 °C. Crystallization temperature and heat of crystallization (Hc) were determined by the cooling step, while melting temperature and heat of fusion (Hf) were determined by the second heating step.

[0288] Shrinkage rate:

[0289] Shrinkage in the flow direction and transverse flow direction is measured according to EN DIN ISO 294-4 at 60×60×2mm. 3 The measurements were taken on injection-molded samples. These samples were molded on Engel Emotion 310 / 55 at a melt temperature of 230°C, with all other parameters conforming to ISO 294-1. Shrinkage in the flow direction and transverse flow direction relative to the original mold dimensions was measured after 96 hours at 23°C.

[0290] 2. Example

[0291] Catalyst preparation

[0292] The catalyst used in these embodiments was prepared as described in detail in WO 2015 / 011135 A1 (metallocene complex MC1 reacts with methylaluminoxane (MAO) and borate ester to produce catalyst 3 as described in WO 2015 / 011135 A1), under the condition that the surfactant is 2,3,3,3-tetrafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)-1-propanol. The metallocene complex (MC1 in WO 2015 / 011135A1) was prepared as described in WO 2013 / 007650 A1 (metallocene E2 in WO 2013 / 007650 A1).

[0293] Preparation of random copolymers (CP)

[0294] Random copolymers 1-5 (CP1 to CP5) were prepared in the Borstar PP pilot plant via a sequential process including a loop reactor and a gas-phase reactor. The reaction conditions are summarized in Table 1.

[0295] The random copolymer CP2 produced by the reactor has been subjected to viscous cracking as disclosed in the Examples section of WO 2017 / 198633.

[0296] Table 2 describes the formulations used for mixing comparative examples and embodiments of the present invention, while Tables 3 and 4 contain the performance of comparative examples and embodiments of the present invention.

[0297] Table 1: Preparation of polypropylene composition (C)

[0298]

[0299]

[0300] In order to produce the polypropylene compositions of Examples IE1 to IE4 and Comparative Examples CE1 to CE9 of the present invention, random copolymers CP1 to CP4 were compounded with multiphase propylene copolymer HECO, additives and optional talc, as listed in Table 2 below.

[0301] Table 2: Formulations for Comparative Examples and Embodiments of the Invention

[0302] HECO 100 67 67 67 87 67 67 62 67 87 CP1 100 30 25 CP2 100 30 10 CP3 30 CP4 30 CP5 30 10 CP6 30 talc 10 Irganox B 215 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 CaSt 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 carbon black 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 PP1 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2

[0303] HECO is a commercial multiphase propylene copolymer EG066AI from Borealis AG, Austria, with an MFR (230°C / 2.16 kg) of 22 g / 10 min, an XCS content of 29 wt%, and a total ethylene content of 13.5 wt%. The XCS fraction of HECO has an intrinsic viscosity of 3.1 dl / g and an ethylene content of 40 wt%.

[0304] CP6 is a commercial C3 / C2 copolymer RJ377MO from Borealis AG of Austria, with a melt flow rate of 45 g / 10 min, a xylene-soluble content of 7.0 wt%, an ethylene content of 4.0 wt%, and a melting point of 150 °C.

[0305] Talc is the median particle size d 50 With a particle size of 1.8 μm and a top cut particle size d 95 The 6.2μm Steamic T1CA is available from Imerys in France.

[0306] Irganox B215 is a synergistic blend of stabilizers Irgafos 168 (tris(2,4-di-tert-butylphenyl) phosphite, CAS-No. 31570-04-4) and Irganox 1010 (pentaerythritol tetrakis[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate, CAS-No. 6683-19-8), and is commercially available from BASF SE.

[0307] CaSt is calcium stearate, CAS-No. 1592-23-0, and is available from Faci.

[0308] The carbon black is "Plasblak PP6331", a commercial carbon black masterbatch from Cabot Corporation in Germany.

[0309] PP1 is a polypropylene homopolymer, HC001A-B1, produced by Borealis AG in Austria, used as a masterbatch carrier polymer. Its MFR (230℃ / 2.16kg) is approximately 2 g / 10 min and T... m The temperature is 160℃.

[0310] The performance of Examples IE1 to IE4 and CE1 to CE8 is shown in Table 3 below.

[0311] As can be seen from Examples IE1 to IE4 and CE8, in order to increase the melt flow rate of the polypropylene composition to 20 g / 10 min or higher (MFR2), mechanical properties must be sacrificed to some extent. However, when using propylene-1-butene random copolymers (IE1 and IE2) or propylene-1-hexene random copolymers (IE3 and IE4), the balance of mechanical properties is better than when using propylene-ethylene random copolymers (CE8).

[0312] Compared to polypropylene compositions with lower melt flow rates, the embodiments of the present invention exhibit considerably lower flow direction shrinkage and transverse flow shrinkage.

[0313] Table 3: Comparative Examples and Performance of Embodiments of the Invention

[0314]

Claims

1. A polypropylene composition (C), comprising: i) a multiphase propylene copolymer (HECO) of 55.0 to 95.0% by weight based on the total weight of the polypropylene composition, comprising a semi-crystalline matrix phase and an elastomeric phase dispersed in the semi-crystalline matrix phase, and a xylene cold soluble fraction (XCS) of 18.0 to 45.0% by weight based on the total weight of the multiphase propylene copolymer (HECO), determined at 23°C according to ISO 16152. ii) From 5.0 to 45.0% by weight of propylene and at least one C4-C based on the total weight of the polypropylene composition. 10 Random copolymers (CPs) of comonomers of the α-olefin group, said random copolymers (CPs) being synthesized in the presence of a single active site catalyst and having a melt flow rate (MFR2) in the range of 25.0 to 150.0 g / 10 min, measured at 230 °C and 2.16 kg according to ISO 1333. The polypropylene composition (C) therein has a melt flow rate (MFR2) of 20.0 to 100.0 g / 10 min, measured according to ISO 1333 at 230 °C and 2.16 kg.

2. The polypropylene composition (C) according to claim 1, wherein the polypropylene composition further comprises: iii) Mineral filler (F) of 0.0 to 15.0% by weight based on the total weight of the polypropylene composition.

3. The polypropylene composition (C) according to claim 1 or 2, wherein the random copolymer (CP) has a comonomer content of from 1.0 to 5.0 mol% based on the molar amount of the random copolymer (CP).

4. The polypropylene composition (C) according to claim 1 or 2, wherein the random copolymer (CP) has a xylene cold soluble fraction (XCS) determined at 23°C according to ISO 16152 in the range of 0.5 to 12.5% ​​by weight based on the total weight of the random copolymer (CP).

5. The polypropylene composition (C) according to claim 1 or 2, wherein the random copolymer (CP) has a melting temperature (T0) measured by differential scanning calorimetry (DSC) in the range of 120 to 155°C. m ).

6. The polypropylene composition (C) according to claim 1 or 2, wherein the random copolymer (CP) has a crystallization temperature (Tc) measured by differential scanning calorimetry (DSC) in the range of 80 to 120°C. c ).

7. The polypropylene composition (C) according to claim 1 or 2, wherein the random copolymer (CP) is a copolymer of propylene and 1-butene or a copolymer of propylene and 1-hexene.

8. The polypropylene composition (C) according to claim 1 or 2, wherein the multiphase propylene copolymer (HECO) has: • The percentage of the total weight of the multiphase propylene copolymer (HECO) in the range of 5.0 to 20.0% by weight. 13 Ethylene content determined by C-NMR spectroscopy, and / or • Melt flow rate MFR2, measured according to ISO 1333 at 230°C and 2.16 kg, in the range of 5.0 to 50.0 g / 10 min. • The intrinsic viscosity (iV) of the xylene cold soluble fraction, measured at 135°C according to DIN ISO 1628 / 1 (October 1999) in decahydronaphthalene, in the range of 2.0 to 4.0 dl / g, and / or • Based on the total weight of the xylene cold soluble fraction, the percentage of the total weight in the range of 30.0 to 50.0% by weight. 13 The ethylene content of the xylene cold soluble fraction determined by C-NMR spectroscopy, and / or • In the range of 10.0 to 30.0 kJ / m 2 Notched impact strength (NIS) of simply supported beams measured at 23°C according to ISO 179-1eA within the specified range, and / or • Flexural modulus measured according to ISO 178 in the range of 800 to 1500 MPa.

9. The polypropylene composition (C) according to claim 2, wherein the mineral filler (F) is selected from the group consisting of mica, wollastonite, kaolinite, montmorillonite, montmorillonite, talc, and mixtures thereof.

10. The polypropylene composition (C) according to claim 9, wherein the mineral filler (F) is talc.

11. The polypropylene composition (C) according to claim 2, wherein the mineral filler (F) has a median particle size d in the range of 0.1 to 30 μm. 50 .

12. The polypropylene composition (C) according to claim 1 or 2, wherein the polypropylene composition (C) comprises: • Tensile modulus measured according to ISO 527-1,-2 in the range of 900 to 2500 MPa, and / or • Flexural modulus measured according to ISO 178 in the range of 850 to 2500 MPa, and / or • From 7.5 to 20.0 kJ / m 2 Notched impact strength of simply supported beams measured at 23°C according to ISO 179-1eA within the specified range; and / or • Melting temperature (T) measured by differential scanning calorimetry (DSC) in the range of 155 to 172 °C m ), and / or • Crystallization temperature (T) measured by differential scanning calorimetry (DSC) in the range of 116 to 136 °C c ), and / or • Elongation at break, measured according to ISO 527, in the range of 20% to 500%, and / or • Flow direction shrinkage less than 1.8% as measured according to EN DIN ISO 294-4, and / or • Less than 2.0% of the transverse flow shrinkage as measured according to EN DIN ISO 294-4, and / or • Puncture energy measured in an instrumented drop hammer impact test according to ISO 6603-2 in the range of 2 to 50 J, and / or • Energy of the maximum force measured in an instrumented drop hammer impact test in the range of 1 to 25 J according to ISO 6603-2.

13. An injection-molded article comprising the polypropylene composition (C) according to any one of claims 1 to 12.

14. A foamed article comprising the polypropylene composition according to any one of claims 1 to 12.

15. A foamed injection molded article comprising a polypropylene composition according to any one of claims 1 to 12.

16. Use of the polypropylene composition according to any one of claims 1 to 12 in the production of injection-molded articles and / or foamed articles.

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