Dual nucleation for high flow impact copolymers

Abstract

The present invention relates to a high flowability ethylene-propylene copolymer composition having an improved balance of properties in terms of mechanical properties and impact resistance. The ethylene-propylene copolymer composition has a melt flow rate MFR greater than 10 g / 10 min and contains (A) 97.00-99.45 wt% of an ethylene-propylene impact copolymer, (B) 0.05-0.50 wt% of an alpha-nucleating agent of formula (I) of the specification, and (C) 0.50-2.00 wt% of a mineral alpha-nucleating agent, wherein the median particle size is 10 m or less. The impact copolymer comprises a1) 75 to 88 wt% of a crystalline polypropylene homopolymer fraction (CF) having an intrinsic viscosity in the range of 0.7 to 2.6 dl / g; and a2) 12 to 25 wt% of an amorphous ethylene-propylene copolymer fraction (SF) having an intrinsic viscosity in the range of 1.5 to 4.5 dl / g and an ethylene content in the range of 25.0 to 55.0 wt%.

Description

Technical Field

[0001] This invention relates to a high-flowability ethylene-propylene copolymer composition that offers an improved balance of mechanical and impact resistance properties. The invention also relates to the use of this composition. Background Technology

[0002] Multiphase ethylene-propylene copolymers (also known as ethylene-propylene impact copolymers, or simply multiphase copolymers HECO) are widely used in the packaging industry due to their excellent combination of stiffness and impact resistance. Applications of multiphase copolymers can be found in many aspects of daily life. One of the main application areas for such copolymers is injection molding of thin-walled articles. Typical examples include plastic cups, buckets, and small containers primarily used for food and non-food packaging. For suitability for thin-walled injection molding applications, polypropylene should exhibit excellent processing properties / flowability, typically manifested by a high melt flow rate (MFR), i.e., a low average molecular weight. Nevertheless, in the polymer and packaging industries, considering mechanical properties, especially the amount of impurities, there remains a desire to improve the availability of multiphase copolymer compositions with high melt flow rates (MFRs).

[0003] However, existing technologies have several limitations.

[0004] Therefore, there is a need in the art for ethylene-propylene copolymer compositions with a high melt flow rate (MFR) greater than 10 g / 10 min, suitable for injection molding and thin-walled article production, which exhibit an improved balance of mechanical and impact properties, such as high flexural modulus and impact strength, and high processability, such as high melt flow rate. Summary of the Invention

[0005] It has been surprisingly found that the interaction of a specific ethylene-propylene impact copolymer with 75-88 wt% crystalline portion (CF) and 12-25 wt% amorphous portion (SF, sometimes also called soluble portion) with a combination of two specific α-nucleating agents results in an excellent balance between mechanical properties, impact resistance and processability.

[0006] This invention relates to an ethylene-propylene copolymer composition comprising 97.00-99.45 wt% (relative to 100% of the ethylene-propylene copolymer composition) of an ethylene-propylene impact copolymer, said ethylene-propylene impact copolymer comprising 75-88 wt% of a crystalline polypropylene homopolymer portion (CF) and 12-25 wt% of an amorphous ethylene-propylene copolymer portion (SF), both determined according to CRYSTEX QC analysis; 0.05-0.50 wt% of an α-nucleating agent selected from the group consisting of salts of formula (I); and 0.50-2.00 wt% of a mineral α-nucleating agent, wherein the median particle size (D50, measured according to ISO 13317-3 sedimentation method) is 10 μm or less. The melt flow rate (MFR2 according to ISO 1133, at 230 °C and 2.16 kg load) of the composition is greater than 10 g / 10 min. The intrinsic viscosity IV of the crystalline portion (CF) is... CF (Measured in decahydronaphthalene at 135 °C according to ISO 1628 / 1) Intrinsic viscosity IV of the amorphous fraction (SF) is in the range of 0.7 to 2.6 dl / g. SF (Measured in decahydronaphthalene at 135 °C according to ISO 1628 / 1) Ethylene content C2 in the range of 1.5 to 4.5 dl / g. SF (through quantitative methods) 13 (FT-IR spectroscopy measurements calibrated by C-NMR spectroscopy) in the range of 25.0 to 55.0 wt%.

[0007] Formula (I):

[0008] Ra n M m X o

[0009] In formula (I), M is independently a metal cation, X is independently an anion, and Ra is independently an organic anion of formula (II):

[0010] Equation (II)

[0011] In formula (II), R is independently an aliphatic hydrocarbon group, k is independently in the range of 1 to 3, n is in the range of 1 to 4, m is 1 or 2, and o is chosen to make the total charge of the salt of formula (I) 0.

[0012] The inventors unexpectedly discovered that the synergistic interaction between the two specific α-nucleating agents as defined above and the specific impact copolymers as defined above produces excellent properties, particularly a favorable balance between processing properties, mechanical properties and impact resistance.

[0013] Furthermore, the present invention relates to molded articles comprising the compositions of the present invention, and the use of the compositions of the present invention in the preparation of molded articles.

[0014] definition

[0015] Unless otherwise stated, the following quantities are expressed as a weight percentage (wt.-%).

[0016] The term "comprising" (and the terms "containing," "including," or "having") used in this invention does not exclude other components. For the purposes of this invention, the term "composed of" is considered to be the same as the term "comprising" (and the terms "containing," "including," or "having"), unless otherwise expressly defined. Similarly, if a group is defined below as including at least a certain number of embodiments, this should also be understood as disclosing a group that preferably consists only of those embodiments, unless otherwise expressly defined. Unless otherwise expressly described, the description of this invention should be understood to mean that one or more of any described preferred embodiments of the invention can be combined with features (or sub-features) of the invention and / or other embodiments described in its most general features.

[0017] In addition, when referring to a singular noun, use the indefinite or definite article, such as “a”, “an”, or “the”, unless otherwise specified, this includes the plural form of the noun. Detailed Implementation

[0018] Ethylene-propylene copolymer composition

[0019] This invention relates to an ethylene-propylene copolymer composition. The melt flow rate (MFR) of the ethylene-propylene copolymer composition (also known as MFR2, measured at 230 °C, 2.16 kg, ISO 1133) is greater than 10 g / 10 min. The ethylene-propylene copolymer composition comprises (A) 97.00-99.45 wt% of an ethylene-propylene impact copolymer, (B) 0.05-0.50 wt% of an α-nucleating agent selected from the group consisting of salts of formula (I) below, and (C) 0.50-2.00 wt% of a mineral α-nucleating agent, wherein the particle size is 10 µm or less. The percentages are given relative to 100 wt% of the whole composition. The composition may contain other components within the above-mentioned limits, preferably consisting of components (A), (B), and (C) and optional additives (i.e., additives may be present or absent).

[0020] Ethylene-propylene impact copolymers comprise a1) a crystalline moiety (CF) and a1) an amorphous moiety (SF). The crystalline moiety (CF) and the amorphous moiety (SF) can be characterized by CRYSTEX QC analysis. In CRYSTEX QC analysis, the crystalline moiety (CF) and the amorphous (soluble) moiety (SF) are obtained and can be quantified and analyzed based on the monomer and comonomer content and intrinsic viscosity (IV). Ethylene-propylene impact copolymers are multiphase copolymers, preferably Ziegler-Natta catalyzed multiphase copolymers. Multiphase propylene copolymers typically comprise:

[0021] a) A crystalline propylene homopolymer or copolymer matrix (M); and

[0022] b) Elastomer rubber, preferably propylene-ethylene elastomer (E).

[0023] In the case of random multiphase propylene copolymers, the crystalline matrix phase is a random copolymer of propylene and at least one α-olefin comonomer. The elastomeric phase can be a propylene copolymer with a high comonomer content, where the comonomer is not randomly distributed in the polymer chain, but rather distributed in comonomer-rich block structures and propylene-rich block structures. Multiphase polypropylene generally differs from single-phase propylene copolymers because it exhibits at least two different glass transition temperatures T0. g This is attributed to the matrix phase and the elastomer phase.

[0024] Specifically, the ethylene-propylene impact copolymer is preferably a heterogeneous copolymer polymerized using a heterogeneous Ziegler-Natta catalyst system. The distinction between Ziegler-Natta catalyzed copolymers and mono-site catalyzed copolymers is known in the art and can be based, for example, on analysis of catalyst residues and / or comonomer distribution in the copolymer. For example, the absence of 2,1-region defects is a key indicator that the propylene polymer has been polymerized in the presence of a Ziegler-Natta catalyst. Therefore, the Ziegler-Natta catalyzed (polypropylene) (co)polymer or (co)polymer portion is preferably substantially free of (less than 0.10 mol%, preferably 0.05 mol% or less, even more preferably 0.02 mol% or less) by […]. 13 2,1-Region defects as determined by C-NMR spectroscopy. Intrinsic viscosity IV of the crystalline fraction (CF). CF The intrinsic viscosity IV of the amorphous fraction (SF) is in the range of 0.7 to 2.6 dl / g. SF The ethylene content (C2) ranges from 1.5 to 4.5 dl / g. SF Within the range of 25.0 to 55.0 wt%.

[0025] Within the scope of the independent claims, the composition preferably further comprises up to 2.45 wt%, more preferably 0.01 to 2.45 wt%, of an additive. Any known additive may be used. The additive may be added as a separate substance (raw material) or in the form of a premix, commonly referred to as a masterbatch, in which case the additive may also comprise a small amount of isotactic polypropylene homopolymer. The amount is not more than 2.00 wt%, typically in the range of 0.00 to 1.50 wt%. The additive is preferably selected from the group consisting of antioxidants, UV stabilizers, antistatic agents, acid scavengers, and slip agents. More preferably, no other nucleating agents should be present. Preferably, at least an antioxidant is present as an additive.

[0026] The composition preferably has a strength of 9900 or higher, more preferably between 10000 and 16000 (MPa). * kJ / m 2 Mechanical performance parameters MPP1 (NIS23) within the range of ]) * FM), which is defined as NIS23 (Charpy notched impact strength at 23 °C according to ISO 179 1eA) [kJ / m 2 The product of the flexural modulus (according to ISO 178) [MPa].

[0027] The composition preferably has mechanical property parameters MPP2(NIS23) in the range of 6500 to 12000, more preferably 6700 to 10000. * FM / MD (shrinkage rate), which is defined as NIS23 [kJ / m 2 The product of the flexural modulus [MPa] and the MD shrinkage rate (longitudinal shrinkage rate; as defined below) [%].

[0028] The composition preferably has an MFR in the range of 11 to 100 g / 10 min, more preferably in the range of 12 to 90 g / 10 min.

[0029] The composition preferably has a crystallization temperature Tc in the range of 125 to 135°C, more preferably in the range of 128 to 132°C (determined by differential scanning calorimetry according to ISO 11357).

[0030] The composition preferably has a flexural modulus in the range of 1400 to 1750 MPa, more preferably in the range of 1450 to 1700 MPa (according to ISO 178).

[0031] The composition preferably has a concentration of 5.5 kJ / m³. 2 Or higher, more preferably between 6.0 and 15.0 kJ / m 2 For example, 6.5 to 12.5 kJ / m2 NIS23 within the range (Charpy notched impact strength at 23 °C according to ISO 179 1eA).

[0032] The composition preferably has a concentration of 2.5 kJ / m³. 2 Or higher, more preferably between 2.8 and 7.0 kJ / m 2 For example, 2.9 to 6.5 kJ / m 2 NIS-20°C range (Charpy notched impact strength at -20°C according to ISO 179 1eA).

[0033] The composition preferably has a heat distortion temperature (HDT; measured according to ISO 75 B, under low load, on an 80x10x4 mm³ specimen) in the range of 95 to 115°C, more preferably 97 to 112°C, for example 98 to 110°C.

[0034] The composition preferably has a longitudinal shrinkage rate (MD shrinkage rate; as defined below) of 1.75% or less, preferably in the range of 0.90% to 1.70%.

[0035] ethylene-propylene impact copolymer

[0036] Next, the ethylene-propylene impact copolymer contained in the composition of the present invention will be described.

[0037] The ethylene-propylene impact copolymer comprises 75-88 wt% crystalline polypropylene homopolymer (CF) and 12-25 wt% amorphous ethylene-propylene copolymer (SF). The intrinsic viscosity IV of the crystalline portion (CF) is... CF The intrinsic viscosity IV of the amorphous fraction (SF) is in the range of 0.7 to 2.6 dl / g. S The ethylene content (C2) ranges from 1.5 to 4.5 dl / g. SF The content is in the range of 25.0 to 55.0 wt%. This impact copolymer has been shown to achieve good interaction with the nucleation system defined in the claims.

[0038] Preferably, the ethylene-propylene impact copolymer comprises 77–86 wt% of a crystalline polypropylene homopolymer portion (CF) and 14–23 wt% of an amorphous ethylene-propylene copolymer portion (SF). More preferably, the ethylene-propylene impact copolymer comprises 79–85 wt% of a crystalline polypropylene homopolymer portion (CF) and 15–21 wt% of an amorphous ethylene-propylene copolymer portion (SF).

[0039] The ethylene-propylene impact copolymer preferably has a xylene cold soluble content of 12 to 30 wt%, more preferably 14 to 25 wt%, for example 15 to 22 wt% (XCS, according to ISO 16152 at 25 °C).

[0040] The ethylene-propylene impact copolymer preferably has a total C2 content of 4.2 to 11.2 wt%, more preferably 5.0 to 10.5 wt%, for example, in the range of 5.5 to 10.0 wt%. EP ), which is quantified 13 FT-IR spectroscopy measurements calibrated by C-NMR spectroscopy.

[0041] The ethylene-propylene impact copolymer preferably has a C2 content (C2-XCS) in the cold soluble fraction of xylene in the range of 30 to 50 wt%, more preferably 32 to 47 wt%, for example 35 to 45 wt%, which is determined by quantitative analysis. 13 FT-IR spectroscopy measurements calibrated by C-NMR spectroscopy.

[0042] The ethylene-propylene impact copolymer preferably has an intrinsic viscosity IV in the range of 0.8 to 3.0 dl / g, more preferably 1.0 to 2.8 dl / g, for example, 1.2 to 2.6 dl / g. EP .

[0043] The ethylene-propylene impact copolymer preferably has an MFR greater than 10 g / 10 min, more preferably in the range of 11 to 100 g / 10 min, and even more preferably in the range of 12 to 90 g / 10 min (according to ISO 1133 at 230 °C and 2.16 kg load).

[0044] The ethylene-propylene impact copolymer preferably has a melting temperature Tm in the range of 160 to 170°C, more preferably in the range of 162 to 168°C (determined by differential scanning calorimetry according to ISO 11357).

[0045] The ethylene content (C2) of the crystalline polypropylene homopolymer portion (CF) of the ethylene-propylene impact copolymer. CF Preferably, it is in the range of 0.3 to 2.5 wt%, more preferably 0.5 to 2.2 wt%, for example, in the range of 0.7 to 2.0 wt%. The intrinsic viscosity IV of the crystalline portion (CF) CF Preferably, it is in the range of 0.8 to 2.5 dl / g, more preferably in the range of 0.9 to 2.3 dl / g.

[0046] The ethylene content (C2) of the amorphous ethylene-propylene copolymer portion (SF) of the ethylene-propylene impact copolymer. SFPreferably, the content is in the range of 30.0 to 50.0 wt%, more preferably in the range of 33.0 to 47.0 wt%. The amorphous portion (SF) preferably has an intrinsic viscosity IV in the range of 1.7 to 4.0 dl / g, more preferably in the range of 1.9 to 3.5 dl / g. SF .

[0047] The ratio of the intrinsic viscosity of the amorphous ethylene-propylene copolymer portion (SF) to the intrinsic viscosity of the crystalline polypropylene homopolymer portion (CF) (IV) SF / IV CF The value is preferably in the range of 0.9 to 3.5, more preferably in the range of 1.0 to 3.0, for example in the range of 1.1 to 2.8.

[0048] nucleating agent

[0049] The nucleating agents (forming nucleation systems) of the present invention will now be described. The present invention is based on the advantageous interaction between two specific particulate nucleating agents and the high-flowability impact copolymers defined herein. While the specific interactions achieved by this combination are not fully understood, it has been found that this combination provides significant improvements. The term “particulate nucleating agent” refers to a nucleating agent that neither melts nor dissolves in the polypropylene copolymer within the temperature range used for processing, for example, between the melting point and 300 °C. For details, see M. Gahleitner, C. Grein, S. Kheirandish & J. Wolfschwenger, “Nucleation of Polypropylene Homo- and Copolymers”, Intern. Polym. Proc. 26 (2011) 2-20).

[0050] The composition of the present invention contains 0.05-0.50 wt% of an α-nucleating agent (also referred to as the "first nucleating agent") selected from the group consisting of salts of formula (I) and 0.50-2.00 wt% of a mineral α-nucleating agent (also referred to as the "second nucleating agent"). The composition may contain other nucleating agents as long as they do not impart the properties of the composition, but preferably only these two nucleating agents are contained.

[0051] The mineral α-nucleating agent (second nucleating agent) preferably has a median particle size D50 in the range of 0.5 to 10.0 µm, more preferably in the range of 1.0 to 9.5 µm, and even more preferably in the range of 1.5 to 9.0 µm, for example in the range of 2.0 to 8.5 µm or in the range of 2.2 to 8.0 µm. The mineral α-nucleating agent can be selected, for example, from the group consisting of talc, silica, calcite, and rutile. Talc has been found to be particularly suitable as the mineral nucleating agent of the present invention, and therefore is preferred.

[0052] The content of the second nucleating agent in the composition of the present invention is preferably 0.55-1.95 wt%.

[0053] The first nucleating agent is at least one compound selected from the group consisting of organometallic salts represented by formula (I) (preferably exactly one compound):

[0054] Ra n M m X o Formula (I)

[0055] In formula (I), M is independently a metal cation, X is independently an anion, and Ra is independently an organic anion of formula (II):

[0056] Equation (II)

[0057] Where R is independently an aliphatic hydrocarbon group, k is independently in the range of 1 to 3, n is in the range of 1 to 4, m is 1 or 2, and o is selected such that the total charge of the salt of formula (I) is 0. k, m, n, and o are preferably integers (or 0 in the case of o). In this context, the term "independently" means that if multiple groups / ions are present, these groups / ions are independently selected from the list above. Preferably, the independently selected groups / ions are the same, i.e., formula (I) refers to a single compound. Furthermore, the term "o is selected such that the total charge of the salt of formula (I) is 0" means that the valences of the ions in formula (I) are matched, i.e., Ra is -1, M is positive, and X is negative. For example, when using "Na + When "M" is used and m=1, o must be 0 (n must be 1). When using "Ca" 2+ When "M" is used, if m=1, o must be 0 when n=2, and o must be 1 when n=1 and X is a monovalent anion, such as "OH-". When using "Al"... 3+ When X is a monovalent anion, such as "OH-", and m=1 and n=2, o is 1.

[0058] The salt of formula (I) contains the organic anion Ra, and is therefore a salt of an aromatic carboxylic acid (aromatic carboxylate). As shown in formula (II), the position of R can be freely chosen, but is preferably at the meta (3,5) position and / or the para (4) position, preferably at least the para position.

[0059] In formula (I), M is independently an alkali metal cation, an alkaline earth metal cation, a boron cation or an aluminum cation, preferably an alkali metal cation or an aluminum cation.

[0060] In formula (I), m is 1 or 2, preferably 1. o is preferably 0, 1 or 2, more preferably 0 or 1. X is preferably an inorganic anion independently, more preferably a monovalent inorganic anion. X is preferably selected from Cl. - OH - SH - HSO3 - HSO4 - NO3 - NO2 - SO4 2- PO4 3- CO3 2- or CN - The group consisting of OH is preferred. - SH - Or NO3 - More preferably OH - And o is preferably 1.

[0061] In formula (II), R is preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 4 to 5 carbon atoms. Preferably, at least one R is provided at the para position (relative to the carboxylic acid group). Preferably, R is an acyclic (open-chain) aliphatic hydrocarbon group. R is preferably a straight-chain or branched alkyl group, preferably branched alkyl, more preferably selected from isopropyl, isobutyl, sec-butyl, tert-butyl, and neopentyl. R is particularly preferably tert-butyl.

[0062] In formula (II), k is 1 or 2, more preferably 1. In a preferred embodiment, R is tert-butyl, R is at the para position, and k is 1. In formula (I), n is preferably 1, 2, or 3, more preferably 1 or 2, and even more preferably 2. Preferably, M is an alkali metal cation or an aluminum cation, n is 1 or 2, m is 1, o is 0 or 1, and X is OH. - Or NO3 - R is tert-butyl, isobutyl, or neopentyl. Formula (I) is preferably represented by (Ra)2(OH)Al.

[0063] The content of the first nucleating agent in the composition of the present invention is preferably 0.08-0.40 wt%.

[0064] Impact copolymer production method

[0065] Impact copolymers can be prepared through a series of reactions to produce in-reactor blends of polymers that effectively generate multiphase components comprising crystalline and amorphous portions. Polymerization in the presence of a Ziegler-Natta catalyst is particularly preferred, as this facilitates the advantageous tuning of the properties of the impact copolymers.

[0066] A preferred multi-stage method for producing impact copolymers is the "loop-gas phase" method, such as the one developed by Borealis A / S in Denmark (called BORSTAR® technology), described in, for example, patent documents such as EP 0887 379, WO 92 / 12182, WO 2004 / 000899, WO 2004 / 111095, WO 99 / 24478, WO 99 / 24479, or WO00 / 68315. Another suitable slurry-gas phase process is the Spheripol® process from Basel.

[0067] Ethylene-propylene impact copolymers are preferably produced by a method comprising the following steps:

[0068] a) In a first polymerization reactor, propylene is polymerized in the presence of a Ziegler-Natta catalyst system to produce a first propylene polymer fraction;

[0069] b) Transferring the polymerization mixture, which includes the Ziegler-Natta catalyst system and the first propylene polymer portion, from the first polymerization reactor to the second polymerization reactor;

[0070] c) In a second polymerization reactor, propylene is polymerized in the presence of a Ziegler-Natta catalyst system to produce a second propylene polymer fraction;

[0071] d) Transfer the polymerization mixture, which includes the Ziegler-Natta catalyst system and the first and second propylene polymer portions, from the second polymerization reactor to the third polymerization reactor;

[0072] e) In a third polymerization reactor, propylene and ethylene are polymerized in the presence of a Ziegler-Natta catalyst system to produce a propylene-ethylene copolymer portion;

[0073] f) Remove from the third polymerization reactor a polymerization mixture comprising the Ziegler-Natta type catalyst system, the first and second propylene polymer portions, and the third propylene-ethylene copolymer portion; and

[0074] g) Obtain a polymer composition comprising the first and second propylene polymer portions and the third propylene-ethylene copolymer portion.

[0075] The method is optionally performed after the pre-polymerization step.

[0076] The first polymerization reactor is preferably a slurry-phase reactor, such as a loop reactor, with a liquid bulk loop reactor being the most suitable.

[0077] While there are no particular limitations on the reaction conditions, the operating temperature in the first polymerization reactor (preferably a loop reactor) is preferably in the range of 62 to 85 °C, more preferably in the range of 65 to 82 °C, and even more preferably in the range of 67 to 80 °C. Typically, the pressure in the first polymerization reactor, preferably a loop reactor, is in the range of 20 to 80 bar, preferably 30 to 70 bar, for example, in the range of 35 to 65 bar (absolute pressure).

[0078] The propylene homopolymer is preferably produced in a first polymerization reactor, and more preferably in a loop reactor. Therefore, the first propylene polymer portion is preferably the propylene homopolymer portion.

[0079] Hydrogen is typically added in the first polymerization reactor to control the molecular weight, thereby controlling the melt flow rate MFR2.

[0080] Preferably, the hydrogen-to-propylene ratio (H2 / C3 ratio) in the first polypropylene reactor, more preferably a loop reactor, is in the range of 1.5 to 20.0 mol / kmol, more preferably 2.0 to 15.0 mol / kmol. Preferably, the melt flow rate MFR2 (230 °C, 2.16 kg, ISO 1133) of the first propylene polymer portion is in the range of 10 to 200 g / 10 min, more preferably 15 to 180 g / 10 min, more preferably 18 to 150 g / 10 min.

[0081] The second polymerization reactor can be a liquid bulk loop reactor or a gas-phase reactor, preferably a gas-phase reactor. The second polymerization reactor is preferably a (first) gas-phase reactor, such as a first fluidized bed gas-phase reactor.

[0082] Preferably, the operating temperature in the second polymerization reactor and the first gas-phase reactor is in the range of 60 to 95 °C, more preferably in the range of 65 to 85 °C.

[0083] Typically, the pressure in the second polymerization reactor, preferably in the first gas-phase reactor, is in the range of 5 to 50 bar, preferably 15 to 40 bar.

[0084] The propylene homopolymer is preferably produced in a second polymerization reactor, and more preferably in a first gas-phase reactor. Therefore, the second propylene polymer portion is preferably the propylene homopolymer portion.

[0085] Hydrogen is preferably added in the second polymerization reactor to control the molecular weight, thereby controlling the melt flow rate MFR2.

[0086] Preferably, in the second polypropylene reactor, the ratio of hydrogen to propylene (H2 / C3 ratio) in the first gas phase reactor is in the range of 20 to 200 mol / kmol, more preferably in the range of 30 to 150 mol / kmol.

[0087] Preferably, the melt flow rate MFR2 (230 °C, 2.16 kg, ISO 1133) of the combined first and second propylene polymer portions is in the range of 10 to 200 g / 10 min, more preferably in the range of 12 to 150 g / 10 min, and more preferably in the range of 15 to 120 g / 10 min. Further preferably, the amount of the portion of the combined first and second propylene polymer portions soluble in cold xylene (XCS) at 25 °C is no more than 3.5 wt%, preferably in the range of 0.1 to 3.0 wt%, based on the total weight of the combined first and second propylene polymer portions.

[0088] The third polymerization reactor is preferably a (second) gas phase reactor, such as a second fluidized bed gas phase reactor.

[0089] Preferably, the operating temperature in the third polymerization reactor, and more preferably in the second gas-phase reactor, is in the range of 65 to 85 °C, more preferably in the range of 68 to 82 °C. Typically, the operating temperature in the third polymerization reactor is lower than that in the second polymerization reactor.

[0090] Typically, the pressure in the third polymerization reactor, preferably in the second gas-phase reactor, is in the range of 5 to 50 bar, preferably 15 to 40 bar.

[0091] In the third polymerization reactor, the propylene-ethylene copolymer is preferably produced in the second gas-phase reactor. Therefore, the third propylene polymer portion is the propylene-ethylene copolymer portion.

[0092] In the third polymerization reactor, the ratio of ethylene to propylene (C2 / C3 ratio) in the second gas-phase reactor is preferably in the range of 100 to 800 mol / kmol, more preferably in the range of 200 to 600 mol / kmol.

[0093] Hydrogen is preferably added in the second polymerization reactor to control the molecular weight, thereby controlling the melt flow rate MFR2.

[0094] Preferably, in the third polymerization reactor, the ratio of hydrogen to ethylene (H2 / C2 ratio) in the second gas-phase reactor is in the range of 100 mol / kmol to 400 mol / kmol, more preferably in the range of 150 to 300 mol / kmol.

[0095] The preparation of the first, second, and third propylene polymer portions may include prepolymerization in a prepolymerization reactor upstream of the first polymerization reactor, in addition to the (major) polymerization stages in at least three prior polymerizations.

[0096] Polypropylene is preferably produced in the prepolymerization reactor. Prepolymerization is preferably carried out in the presence of a Ziegler-Natta catalyst system. According to this embodiment, the Ziegler-Natta catalyst system is introduced into the prepolymerization step. However, this does not preclude the option of adding an additional co-catalyst at a later stage, such as during polymerization, for example, in the first reactor. In one embodiment, if prepolymerization is carried out, all components of the Ziegler-Natta type catalyst are added only to the prepolymerization reactor.

[0097] The prepolymerization reaction is typically carried out at a temperature of 0 to 60°C, preferably 15 to 50°C, and more preferably 20 to 45°C.

[0098] The pressure in the prepolymerization reactor is not critical, but it must be high enough to keep the reaction mixture in the liquid phase. Therefore, the pressure can be 20 to 100 bar, for example, 30 to 70 bar.

[0099] In a preferred embodiment, the prepolymerization is carried out in liquid propylene by bulk slurry polymerization, i.e., the liquid phase mainly comprises propylene, wherein an inert component is optionally dissolved.

[0100] Other components may also be added during the prepolymerization stage. Therefore, as is known in the art, hydrogen can be added during the prepolymerization stage to control the molecular weight of polypropylene. Furthermore, antistatic additives can be used to prevent particles from adhering to each other or to the reactor wall.

[0101] Precise control of prepolymerization conditions and reaction parameters is within the scope of those skilled in the art.

[0102] Due to the aforementioned process conditions in prepolymerization, it is preferable to obtain a mixture of Ziegler-Natta catalyst system and polypropylene produced in the prepolymerization reactor. Preferably, a single Ziegler-Natta catalyst is (finely) dispersed in the polypropylene. In other words, the unit catalyst particles introduced into the prepolymerization reactor are broken into smaller fragments, which are uniformly distributed in the grown polypropylene. The size of the introduced unit catalyst particles and the size of the resulting fragments are not substantially related to the present invention and the knowledge of those skilled in the art.

[0103] As described above, if prepolymerization is used, after the prepolymerization, the mixture of unit point catalyst and polypropylene produced in the prepolymerization reactor is transferred to the first polymerization reactor.

[0104] Without using prepolymerization, propylene and other components, such as the Ziegler-Natta catalyst system, are directly introduced into the first polymerization reactor. The residence time of the polymerization mixture at different polymerization stages can be adjusted to obtain the amounts of the first, second, and third polymer fractions in the impact copolymer.

[0105] Preferably, the first propylene polymer portion is present in an amount of 30 to 60 wt%, more preferably 35 to 55 wt%, based on the total weight of the combined first, second, and third propylene polymer portions. The amount of polypropylene produced in the prepolymer reactor (if present) is typically included in the amount of the first propylene polymer portion.

[0106] Preferably, the second propylene polymer portion is present in an amount of 25 to 50 wt%, more preferably 30 to 45 wt%, based on the total weight of the combined first, second, and third propylene polymer portions.

[0107] Preferably, the third propylene polymer portion is present in an amount of 10 to 30 wt%, more preferably 12 to 25 wt%, based on the total weight of the combined first, second and third propylene polymer portions.

[0108] The Ziegler-Natta catalyst system preferably comprises (a) a Ziegler-Natta catalyst (ZN-C) containing a compound of a Group 4 to 6 transition metal (according to IUPAC) (TC), a Group 2 metal compound (MC) and an internal donor (ID); (b) a co-catalyst (Co) and (c) an optional external donor (ED).

[0109] The catalyst used in this invention is a solid Ziegler-Natta catalyst (ZN-C) comprising a compound (TC) of a Group 4 to 6 (IUPAC) transition metal, such as titanium, a Group 2 metal compound (MC), such as magnesium, and an internal donor (ID), preferably a non-phthalic acid compound, more preferably a non-phthalic acid ester, and even more preferably a diester of a non-phthalic acid dicarboxylic acid, described in more detail below. Therefore, the catalyst is preferably completely free of (undesirable) phthalic acid compounds. Furthermore, the solid catalyst is preferably free of any external support material, such as silica or MgCl2, but the catalyst is self-supported. Self-supported catalysts are not necessarily free of magnesium halides, as these are formed during the reaction between the magnesium compound and TiCl4; however, the presence of magnesium halides as an external support medium is preferably excluded.

[0110] The Ziegler-Natta catalyst (ZN-C) can be further defined by the obtained method. Therefore, the Ziegler-Natta catalyst (ZN-C) is preferably obtained by a method including the following steps:

[0111] a)

[0112] a1) Provides a solution of at least one Group 2 metal alkoxy compound (Ax) optionally in an organic liquid reaction medium, said Ax being a reaction product of a Group 2 metal compound (MC) and an alcohol (A), said alcohol (A) comprising at least one ether moiety in addition to the hydroxyl moiety; or

[0113] a2) Provide a solution of at least one Group 2 metal alkoxy compound (Ax') optionally in an organic liquid reaction medium, said Ax' being a reaction product of a mixture of a Group 2 metal compound (MC) and an alcohol (A) and a monohydric alcohol (B) of formula ROH; or

[0114] a3) Provides a solution of a mixture of a Group 2 alkoxy compound (Ax) and a Group 2 metal alkoxy compound (Bx) optionally in an organic liquid reaction medium, wherein Bx is a reaction product of a Group 2 metal compound (MC) and a monohydric alcohol (B); and

[0115] b) Add the solution from step a) to a compound (TC) of at least one group 4 to 6 transition metal, and

[0116] c) Obtain solid catalyst component particles

[0117] And the addition of a preferred non-phthalic acid internal electron donor (ID) in any (arbitrary) step prior to step c).

[0118] Preferably, the internal donor (ID) or its precursor is added to the solution in step a).

[0119] Based on the steps described above, the Ziegler-Natta catalyst (ZN-C) can be obtained by precipitation or emulsion (liquid / liquid two-phase system)-curing method, depending on the physical conditions, particularly the temperatures used in steps b) and c). In both methods (precipitation or emulsion curing), the chemical properties of the catalyst are identical.

[0120] In the precipitation method, the solution of step a) is combined with at least one transition metal compound (TC) from step b), and the entire reaction mixture is maintained at at least 50 °C, more preferably in the temperature range of 55 to 110 °C, and even more preferably in the temperature range of 70 to 100 °C, to ensure that the catalyst component is completely precipitated in the form of solid particles (step c).

[0121] In the emulsion-curing method, in step b), the solution from step a) is typically added to at least one transition metal compound (TC) at a low temperature, for example, -10 to below 50°C, preferably -5 to 30°C. During emulsion stirring, the temperature is typically maintained at -10 to below 40°C, preferably -5 to 30°C. Droplets of the emulsion dispersion form an active catalyst composition. The droplets are appropriately cured (step c) by heating the emulsion to a temperature of 70 to 150°C, preferably 80 to 110°C. The present invention preferably uses catalysts prepared by the emulsion-curing method.

[0122] In a preferred embodiment of step a), a solution of a2) or a3) is used, i.e., a solution of (Ax') or a mixture of (Ax) and (Bx). Preferably, the Group 2 metal (MC) is magnesium.

[0123] The alkoxymagnesium compounds (Ax), (Ax'), and (Bx) can be prepared in situ in the first step of the catalyst preparation method, namely step a), by reacting a magnesium compound with an alcohol as described above, or the alkoxymagnesium compounds can be prepared separately, or they can even be commercially available as ready-made alkoxymagnesium compounds and used as is in the catalyst preparation process of the present invention.

[0124] An exemplary example of alcohol (A) is a monoether of a diol (ethylene glycol monoether). Preferred alcohol (A) is a C2 to C4 diol monoether, wherein the ether moiety comprises 2 to 18 carbon atoms, preferably 4 to 12 carbon atoms. Preferred examples are 2-(2-ethylhexyloxy)ethanol, 2-butoxyethanol, 2-hexyloxyethanol, and 1,3-propanediol monobutyl ether, 3-butoxy-2-propanol, wherein 2-(2-ethylhexyloxy)ethanol, 1,3-propanediol monobutyl ether, and 3-butoxy-2-propanol are particularly preferred.

[0125] An exemplary monohydric alcohol (B) has the formula ROH, where R is a straight-chain or branched C6-C group. 10 Alkyl group. The most preferred monohydric alcohol is 2-ethyl-1-hexanol or octanol.

[0126] It is preferred to use a mixture of Mg alkoxy compounds (Ax) and (Bx) or a mixture of alcohols (A) and (B) respectively, and to use a molar ratio of Bx:Ax or B:A of 8:1 to 2:1, more preferably 5:1 to 3:1.

[0127] Magnesium alkoxy compounds can be the reaction products of alcohols as described above with magnesium compounds selected from dialkyl magnesium, alkylmagnesium alkoxides, magnesium dialkoxides, alkoxy magnesium halides, and alkyl magnesium halides. The alkyl group can be similar or different C1-C. 20 Alkyl groups, preferably C2-C 10 Alkyl groups. Typical alkylalkoxy magnesium compounds used are ethylbutoxide magnesium, butylpentoxide magnesium, octylbutoxide magnesium, and octyloctanoxide magnesium. Preferably, dialkyl magnesium is used. Most preferably, butyloctyl magnesium or butylethyl magnesium.

[0128] Besides alcohols (A) and (B), magnesium compounds can also react with formula R″(OH). sThe polyol (C) is reacted to obtain the alkyl magnesium alkoxide compound. If used, the preferred polyol is one in which R” is a straight-chain, cyclic, or branched C2 to C3 group. 10 Hydrocarbon group, where s is an integer from 2 to 6.

[0129] Therefore, the alkoxymagnesium compound in step a) is selected from the group consisting of: dialkyl magnesium alcohols, diaryloxy magnesium alcohols, alkoxy magnesium halides, aryloxy magnesium halides, alkylalkyl magnesium alcohols, arylalkyl magnesium alcohols, and alkylaryl magnesium alcohols. Alternatively, a mixture of dihalides and dialkyl magnesium alcohols may be used.

[0130] The solvent used to prepare this catalyst may be selected from aromatic and aliphatic straight-chain, branched, and cyclic hydrocarbons, or mixtures thereof, having 5 to 20 carbon atoms, more preferably 5 to 12 carbon atoms. Suitable solvents include benzene, toluene, cumene, xylene, pentane, hexane, heptane, octane, and nonane. Hexane and pentane are particularly preferred.

[0131] Mg compounds are typically supplied as solutions of 10 to 50 wt% in the aforementioned solvents. Typical commercially available magnesium compounds, particularly dialkyl magnesium solutions, are 20-40 wt% solutions in toluene or heptane.

[0132] The reaction to prepare alkoxymagnesium compounds can be carried out at temperatures ranging from 40°C to 70°C. The optimal temperature is selected based on the Mg compound and alcohol used.

[0133] Transition metal compounds from groups 4 to 6 are preferably titanium compounds, with titanium halides, such as TiCl4, being the most preferred.

[0134] The internal donor (ID) used in the preparation of the catalyst used in this invention is preferably selected from (di) esters, 1,3-diethers, derivatives thereof, and mixtures thereof of non-phthalic acid carboxylic acids (or dicarboxylic acids). Particularly preferred donors are diesters of monounsaturated dicarboxylic acids, particularly esters belonging to the group comprising malonic acid esters, maleic acid esters, succinic acid esters, citrate esters, glutaric acid esters, cyclohexene-1,2-dicarboxylic acid esters, and benzoic acid esters, and any derivatives thereof and / or mixtures thereof. Preferred examples are, for example, substituted maleic acid esters and citrate esters, with citrate esters being most preferred.

[0135] In emulsion processes, a two-phase liquid-liquid system can be formed by simple stirring and optionally by adding (other) solvents and additives, such as turbulence minimizing agents (TMAs) and / or emulsifiers and / or emulsion stabilizers, such as surfactants, which are used in a manner known in the art to promote emulsion formation and / or stabilization. Preferably, the surfactant is an acrylic or methacrylic acid polymer. Particularly preferred are linear C... 12 To C 20(Meth)acrylates, such as polyhexadecyl methacrylate and polyoctadecyl methacrylate and mixtures thereof. If a turbulence minimizing agent (TMA) is used, it is preferably an α-olefin polymer selected from α-olefin monomers having 6 to 20 carbon atoms, such as polyoctene, polynonene, polydecene, polyundecene, or polydodecene or mixtures thereof. Polydecene is most preferred.

[0136] The solid particulate product obtained by precipitation or emulsion solidification can be washed with aromatic and / or aliphatic hydrocarbons, preferably with toluene, heptane, or pentane, at least once, preferably at least twice, and most preferably at least three times. The catalyst can be further dried, for example by evaporation or rinsing with nitrogen, or it can be slurried into an oily liquid without any drying step.

[0137] The resulting Ziegler-Natta catalyst is ideally in particulate form, with an average particle size typically ranging from 5 to 200 µm, preferably from 10 to 100 µm. The particles are preferably dense, have low porosity, and a surface area of ​​less than 20 g / m². 2 More preferably, below 10 g / m 2 Typically, based on the catalyst composition, the amount of Ti is 1 to 6 wt%, the amount of Mg is 10 to 20 wt%, and the amount of the donor is 10 to 40 wt%.

[0138] Detailed descriptions of catalyst preparation are disclosed in WO 2012 / 007430, EP 2610271, EP 261027 and EP2610272, which are incorporated herein by reference.

[0139] Ziegler-Natta catalysts (ZN-C) are preferably used in combination with alkylaluminum co-catalysts and optional external donors.

[0140] As another component in this polymerization process, an external donor (ED) is preferably present. Suitable external donors (EDs) include certain silanes, ethers, esters, amines, ketones, heterocyclic compounds, and mixtures thereof. Silanes are particularly preferred. Silanes with the following general formula are most preferred.

[0141] R a p R b q Si(OR c ) (4-p-q)

[0142] Where R a R b and R c This indicates a hydrocarbon group, particularly an alkyl or cycloalkyl group, where p and q are numbers from 0 to 3, and their sum p + q is equal to or less than 3. R a R b and Rc They can be chosen independently of each other and can be the same or different. Specific examples of such silanes are (tert-butyl)2Si(OCH3)2, (cyclohexyl)(methyl)Si(OCH3)2, (phenyl)2Si(OCH3)2, and (cyclopentyl)2Si(OCH3)2 or the general formula.

[0143] Si(OCH2CH3)3(NR 3 R 4 )

[0144] Where R 3 and R 4 They can be the same or different, and 'a' represents a hydrocarbon group with 1 to 12 carbon atoms.

[0145] R 3 and R 4 Independently selected from the group consisting of: straight-chain aliphatic hydrocarbon groups having 1 to 12 carbon atoms, branched aliphatic hydrocarbon groups having 1 to 12 carbon atoms, and cyclic aliphatic hydrocarbon groups having 1 to 12 carbon atoms. Particularly preferred is R. 3 and R 4 Independently selected from methyl, ethyl, n-propyl, n-butyl, octyl, decyl, isopropyl, isobutyl, isopentyl, tert-butyl, tert-pentyl, neopentyl, cyclopentyl, cyclohexyl, methylcyclopentyl, and cycloheptyl. More preferably, R 3 and R 4 They are all the same, and even better R 3 and R 4 Both are ethyl.

[0146] Particularly preferred external donors (EDs) are dicyclopentyldimethoxysilane donors (D-donors) or cyclohexylmethyldimethoxysilane donors (C-donors). In addition to the Ziegler-Natta catalyst (ZN-C) and optional external donors (EDs), co-catalysts may also be used. The co-catalyst is preferably a compound of Group 13 of the periodic table (IUPAC) (e.g., organoaluminum), such as an aluminum compound, such as an alkylaluminum, aluminum halide, or alkylaluminum halide compound. Thus, in one specific embodiment, the co-catalyst (Co) is a trialkylaluminum, such as triethylaluminum (TEAL), dialkylaluminum chloride, or alkylaluminum dichloride, or mixtures thereof. In one specific embodiment, the co-catalyst (Co) is triethylaluminum (TEAL).

[0147] Preferably, the ratio between the co-catalyst (Co) and the external donor (ED) [Co / ED] and / or the ratio between the co-catalyst (Co) and the transition metal (TM) [Co / TM] should be adjusted within a certain range. More specifically,

[0148] (a) The molar ratio of the co-catalyst (Co) to the external donor (ED) [Co / ED] should preferably be in the range of 5 to 45, more preferably in the range of 5 to 35, and even more preferably in the range of 5 to 25;

[0149] and optional

[0150] (b) The molar ratio of the co-catalyst (Co) to the titanium compound (TC) [Co / TC] should preferably be in the range of 80 to 500, more preferably in the range of 100 to 350, and even more preferably in the range of 120 to 300.

[0151] When using the Ziegler-Natta catalyst system in a multi-reactor arrangement as described above, if any subsequent reactor is used, it is preferable to feed at least a portion, preferably all, of the ZN-C into the first polymerization reactor and transfer it together with the polymer (slurry) obtained in the first polymerization reactor to the subsequent reactor. If the method further includes a prepolymerization step, it is preferable to add at least a portion, preferably all, of the Ziegler-Natta catalyst (ZN-C) to the prepolymerization reactor. Subsequently, the prepolymerization product containing the Ziegler-Natta catalyst (ZN-C) is transferred to the first polymerization reactor. The co-catalyst and external donor (if present) are preferably fed together with the ZN-C.

[0152] Preferred catalyst systems (and methods for preparing such catalyst systems) for the preparation of the impact copolymers of the present invention are described in EP4141068 A1, which are incorporated herein by reference.

[0153] Use of the composition, molded article and article

[0154] The present invention also relates to the use of the compositions of the present invention in the preparation of products or articles, particularly molded articles or articles, and articles prepared using the compositions.

[0155] More particularly, the present invention relates to a molded product comprising 50 to 100 wt% of the ethylene-propylene copolymer composition of the present invention, preferably comprising 60 to 100 wt%, more preferably comprising 70 to 100 wt%, such as 80 to 100 wt%, 90 to 100 wt%, 95 to 100 wt%, 98 to 100 wt%, or 98 to 99 wt% of the ethylene-propylene copolymer composition.

[0156] This invention also relates to the use of the ethylene-propylene copolymer composition of this invention in the preparation of molded products (such as packaging articles, automotive exterior parts, automotive interior parts, or housings for electrical or electronic devices) and / or in the preparation of injection-molded articles with an average wall thickness of 2 mm or less. The injection-molded articles can be thin-walled packaging articles, such as cups, trays, buckets, or lids. The injection-molded articles can have a wall thickness in the range of 0.1 to 2.0 mm, for example, in the range of 0.2 to 2.0 mm.

[0157] For example, a molded product can be an injection-molded product or a fiber-reinforced composite material. In this regard, the term "product" (and similar "articles of manufacture") should include both final products (e.g., for sale) and intermediate products (e.g., for further processing).

[0158] Molded products can be automotive parts containing ethylene-propylene copolymer compositions.

[0159] Molded products can also be packaging articles, preferably thin-walled packaging articles, such as plastic cups, buckets and small containers, including their lids, for example intended for food packaging, which contain ethylene-propylene copolymer compositions.

[0160] In one embodiment, the composition of the molded product may contain fibers, such as glass fibers or carbon fibers, preferably in an amount of 0 wt% (no fibers present) to 50 wt% (relative to a total of 100 wt% of the molded product). Where fibers are present in the composition of the molded product, the amount of fibers is more preferably in the range of 5 to 40 wt%, based on the composition of the molded product.

[0161] The molded product contains 50 to 100 wt% of the copolymer composition of the present invention. Therefore, the total fiber content is at most 50 wt%.

[0162] Generally and particularly, the present invention relates to one or more of the following:

[0163] 1. An ethylene-propylene copolymer composition comprising:

[0164] A) 97.00-99.45 wt% of ethylene-propylene impact copolymer, comprising:

[0165] a1) The intrinsic viscosity IV of the 75-88 wt% crystalline polypropylene homopolymer fraction (CF, determined by CRYSTEX QC analysis) relative to 100 wt% ethylene-propylene impact copolymer. CF (Measured in decahydronaphthalene at 135 °C according to ISO 1628 / 1) in the range of 0.7 to 2.6 dl / g, and

[0166] a2) Relative to 100 wt% ethylene-propylene impact copolymer, the intrinsic viscosity IV of the 12-25 wt% amorphous ethylene-propylene copolymer fraction (SF, determined by CRYSTEX QC analysis) is... SF (Measured in decahydronaphthalene at 135 °C according to ISO 1628 / 1) Ethylene content C2 in the range of 1.5 to 4.5 dl / g. SF (through quantitative methods) 13 (FT-IR spectroscopy measurements calibrated by C-NMR spectroscopy) within the range of 25.0 to 55.0 wt%.

[0167] B) 0.05-0.50 wt% of α-nucleating agent, selected from the group consisting of salts of formula (I):

[0168] Ra n M m X o Formula (I)

[0169] Where M is an independent metal cation, X is an independent anion, and Ra is an organic anion of formula (II):

[0170] Equation (II)

[0171] Where R is an aliphatic hydrocarbon group, k is in the range of 1 to 3, n is in the range of 1 to 4, m is 1 or 2, and o is chosen to make the total charge of the salt of formula (I) 0, and

[0172] C) 0.50-2.00 wt% of mineral α-nucleating agent, wherein the average particle size D50 (according to ISO 13317-3, Sedigraph method) is less than 10 µm.

[0173] The composition has an MFR (according to ISO 1133 at 230 °C and 2.16 kg load) greater than 10 g / 10 min.

[0174] 2. The ethylene-propylene copolymer composition according to Project 1, wherein the median particle size D50 of the mineral α-nucleating agent is in the range of 0.5 to 10.0 µm, preferably in the range of 1.0 to 9.5 µm, for example, in the range of 1.5 to 9.0 µm, 2.0 to 8.5 µm or 2.2 to 8.0 µm.

[0175] 3. The ethylene-propylene copolymer composition according to item 1 or 2, wherein the mineral α-nucleating agent is talc.

[0176] 4. An ethylene-propylene copolymer composition according to any one of items 1 to 3, further comprising up to 2.45 wt%, preferably 0.01 to 2.45 wt%, of an additive, said additive preferably selected from the group consisting of antioxidants, UV stabilizers, antistatic agents, acid scavengers and slip agents.

[0177] 5. An ethylene-propylene copolymer composition according to any one of items 1 to 4, wherein the composition has a mechanical property parameter MPP1 in the range of 9900 or higher, more preferably in the range of 10000 to 16000, defined as NIS23 (Charpy notched impact strength, according to ISO 179 1eA at 23 °C) [kJ / m]. 2 The product of the flexural modulus (according to ISO 178) [MPa].

[0178] 6. An ethylene-propylene copolymer composition according to any one of items 1 to 5, wherein the composition has a mechanical property parameter MPP2 in the range of 6500 to 12000, preferably 6700 to 10000, defined as NIS23 [kJ / m]. 2 The product of the flexural modulus [MPa] and the MD shrinkage rate (longitudinal shrinkage rate; as defined below) [%].

[0179] 7. An ethylene-propylene copolymer composition according to any one of items 1 to 6, wherein the composition has an MFR in the range of 11 to 100 g / 10 min, preferably in the range of 12 to 90 g / 10 min.

[0180] 8. An ethylene-propylene copolymer composition according to any one of items 1 to 7, wherein the composition has a crystallization temperature Tc in the range of 125 to 135°C, preferably in the range of 128 to 132°C (determined according to ISO 11357 based on differential scanning calorimetry DSC).

[0181] 9. An ethylene-propylene copolymer composition according to any one of items 1 to 8, wherein the flexural modulus (according to ISO 178) of the composition is in the range of 1400 to 1750 MPa, preferably in the range of 1450 to 1700 MPa.

[0182] 10. An ethylene-propylene copolymer composition according to any one of items 1 to 9, wherein the composition has a content of 5.5 kJ / m 2 Or higher, preferably between 6.0 and 15.0 kJ / m 2 Within the range, for example, from 6.5 to 12.5 kJ / m 2 NIS23 (Charpy notched impact strength, according to ISO 179 1eA at 23 °C) within the range.

[0183] 11. An ethylene-propylene copolymer composition according to any one of items 1 to 9, wherein the composition has a concentration of 2.5 kJ / m² or higher, preferably between 2.8 and 7.0 kJ / m². 2 Within the range, for example, from 2.9 to 6.5 kJ / m 2 NIS-20°C (Charpy notched impact strength, according to ISO 179 1eA at -20°C).

[0184] 12. An ethylene-propylene copolymer composition according to any one of items 1 to 11, wherein the composition has a heat distortion temperature (HDT; according to ISO 75 B, under low load, measured on an 80x10x4 mm³ specimen) in the range of 95 to 115°C, preferably in the range of 97 to 112°C, for example in the range of 98 to 110°C.

[0185] 13. An ethylene-propylene copolymer composition according to any one of items 1 to 12, wherein the composition has a longitudinal shrinkage rate (MD shrinkage rate; measured as defined in the specification) of 1.75% or less, preferably in the range of 0.90% to 1.70%.

[0186] 14. An ethylene-propylene copolymer composition according to any one of items 1 to 13, wherein the ethylene-propylene impact copolymer comprises a1) 77-86 wt%, preferably 79-85 wt%, of a crystalline polypropylene homopolymer portion (CF) and a2) 14-23 wt%, preferably 15-21 wt%, of an amorphous ethylene-propylene copolymer portion (SF).

[0187] 15. An ethylene-propylene copolymer composition according to any one of items 1 to 14, wherein the ethylene-propylene impact copolymer has a xylene cold soluble content of 12 to 30 wt%, preferably 14 to 25 wt%, for example 15 to 22 wt% (XCS, according to ISO 16152 at 25°C).

[0188] 16. An ethylene-propylene copolymer composition according to any one of items 1 to 15, wherein the ethylene-propylene impact copolymer has a C2 content in the range of 4.2 to 11.2 wt%, preferably 5.0 to 10.5 wt%, for example 5.5 to 10.0 wt%, which is determined by quantitative analysis. 13 FT-IR spectroscopy measurements calibrated by C-NMR spectroscopy.

[0189] 17. An ethylene-propylene copolymer composition according to any one of items 1 to 16, wherein the ethylene-propylene impact copolymer has a C2 content (C2-XCS) of 30 to 50 wt%, preferably 32 to 47 wt%, for example 35 to 45 wt%, in the xylene cold-soluble fraction, which is determined by quantitative analysis. 13FT-IR spectroscopy measurements calibrated by C-NMR spectroscopy.

[0190] 18. An ethylene-propylene copolymer composition according to any one of items 1 to 17, wherein the ethylene-propylene impact copolymer has an intrinsic viscosity IV in the range of 0.8 to 3.0 dl / g, preferably 1.0 to 2.8 dl / g, for example 1.2 to 2.6 dl / g. EP .

[0191] 19. An ethylene-propylene copolymer composition according to any one of items 1 to 18, wherein the ethylene-propylene impact copolymer has an MFR greater than 10 g / 10 min, preferably in the range of 11 to 100 g / 10 min, and more preferably in the range of 12 to 90 g / 10 min (according to ISO 1133 at 230 °C and 2.16 kg load).

[0192] 20. An ethylene-propylene copolymer composition according to any one of items 1 to 19, wherein the ethylene-propylene impact copolymer has a melting temperature Tm in the range of 160 to 170°C, preferably 162 to 168°C (determined by differential scanning calorimetry according to ISO 11357).

[0193] 21. An ethylene-propylene copolymer composition according to any one of items 1 to 20, wherein the crystalline polypropylene homopolymer portion (CF) has an ethylene content (C2) in the range of 0.3 to 2.5 wt%, preferably 0.5 to 2.2 wt%, for example 0.7 to 2.0 wt%. CF .

[0194] 22. An ethylene-propylene copolymer composition according to any one of items 1 to 21, wherein the amorphous ethylene-propylene copolymer portion (SF) has an ethylene content (C2) in the range of 30.0 to 50.0 wt%, preferably 33.0 to 47.0 wt%. SF .

[0195] 23. An ethylene-propylene copolymer composition according to any one of items 1 to 22, wherein the crystalline polypropylene homopolymer portion (CF) has an intrinsic viscosity IV in the range of 0.8 to 2.5 dl / g, preferably 0.9 to 2.3 dl / g. CF .

[0196] 24. An ethylene-propylene copolymer composition according to any one of items 1 to 23, wherein the amorphous ethylene-propylene copolymer portion (SF) has an intrinsic viscosity IV in the range of 1.7 to 4.0 dl / g, preferably 1.9 to 3.5 dl / g. SF .

[0197] 25. For any ethylene-propylene copolymer composition according to any one of items 1 to 24, the ratio (IV) of the intrinsic viscosity of the amorphous ethylene-propylene copolymer portion (SF) to the intrinsic viscosity of the crystalline polypropylene homopolymer portion (CF) is... SF / IV CF The value is in the range of 0.9 to 3.5, preferably 1.0 to 3.0, for example, 1.1 to 2.8.

[0198] 26. An ethylene-propylene copolymer composition according to any one of items 1 to 25, wherein, in formula (I), M is independently an alkali metal cation, an alkaline earth metal cation, a boron cation or an aluminum cation, preferably an alkali metal cation or an aluminum cation.

[0199] 27. An ethylene-propylene copolymer composition according to any one of items 1 to 26, wherein, in formula (I), m is 1.

[0200] 28. An ethylene-propylene copolymer composition according to any one of items 1 to 27, wherein, in formula (I), o is 0, 1 or 2, preferably 0 or 1.

[0201] 29. An ethylene-propylene copolymer composition according to any one of items 1 to 28, wherein, in formula (I), o is 1 or 2, preferably 1, and X is independently an inorganic anion, preferably a monovalent inorganic anion.

[0202] 30. An ethylene-propylene copolymer composition according to any one of items 1 to 29, wherein, in formula (I), X is selected from Cl - OH - SH - HSO3 - HSO4 - NO3 - NO2 - SO4 2- PO4 3- CO3 2- or CN - The group consisting of OH is preferred. - SH - Or NO3 - More preferably OH - o is preferably 1 or 2, more preferably 1.

[0203] 31. An ethylene-propylene copolymer composition according to any one of items 1 to 30, wherein, in formula (II), R is independently an aliphatic hydrocarbon group having 1 to 8 carbon atoms, preferably 2 to 6 carbon atoms, more preferably 4 to 5 carbon atoms.

[0204] 32. An ethylene-propylene copolymer composition according to any one of items 1 to 31, wherein, in formula (II), at least one R is provided at the para position.

[0205] 33. An ethylene-propylene copolymer composition according to any one of items 1 to 32, wherein, in formula (II), R is independently an acyclic (open-chain) aliphatic hydrocarbon group.

[0206] 34. An ethylene-propylene copolymer composition according to any one of items 1 to 33, wherein, in formula (II), R is independently a straight-chain or branched alkyl group, preferably a branched alkyl group, more preferably a group consisting of isopropyl, isobutyl, sec-butyl, tert-butyl and neopentyl, preferably tert-butyl.

[0207] 35. An ethylene-propylene copolymer composition according to any one of items 1 to 34, wherein R in formula (II) is tert-butyl.

[0208] 36. An ethylene-propylene copolymer composition according to any one of items 1 to 35, wherein, in formula (II), k is 1 or 2, preferably 1.

[0209] 37. An ethylene-propylene copolymer composition according to any one of items 1 to 36, wherein in formula (I), n is 1, 2 or 3, preferably 1 or 2, more preferably 2.

[0210] 38. An ethylene-propylene copolymer composition according to any one of items 1 to 37, wherein M is an alkali metal cation or an alumina cation, n is 1 or 2, m is 1, o is 0 or 1, and X is OH. - Or NO3 - R is tert-butyl, isobutyl or neopentyl.

[0211] 39. An ethylene-propylene copolymer composition according to any one of items 1 to 38, wherein formula (I) is represented by (Ra)2(OH)Al.

[0212] 40. An ethylene-propylene copolymer composition according to any one of items 1 to 39, wherein the ethylene-propylene impact copolymer is produced by a method comprising the following steps:

[0213] a) In a first polymerization reactor, propylene is polymerized in the presence of a Ziegler-Natta catalyst system to produce a first propylene polymer fraction;

[0214] b) Transferring the polymerization mixture, which includes the Ziegler-Natta catalyst system and the first propylene polymer portion, from the first polymerization reactor to the second polymerization reactor;

[0215] c) In a second polymerization reactor, propylene is polymerized in the presence of a Ziegler-Natta catalyst system to produce a second propylene polymer fraction;

[0216] d) Transfer the polymerization mixture, which includes the Ziegler-Natta catalyst system and the first and second propylene polymer portions, from the second polymerization reactor to the third polymerization reactor;

[0217] e) In a third polymerization reactor, propylene and ethylene are polymerized in the presence of a Ziegler-Natta catalyst system to produce a propylene-ethylene copolymer portion;

[0218] f) Remove from the third polymerization reactor a polymerization mixture comprising the Ziegler-Natta type catalyst system, the first and second propylene polymer portions, and the third propylene-ethylene copolymer portion; and

[0219] g) Obtain a polymer composition comprising the first and second propylene polymer portions and the third propylene-ethylene copolymer portion.

[0220] The method is optionally performed prior to the pre-polymerization step.

[0221] 41. The ethylene-propylene copolymer composition according to item 40, wherein the first polymerization reactor is a liquid bulk loop reactor.

[0222] 42. The ethylene-propylene copolymer composition according to item 40 or 41, wherein the second polymerization reactor is a liquid bulk loop reactor or a gas phase reactor, preferably a gas phase reactor.

[0223] 43. An ethylene-propylene copolymer composition according to any one of items 40 to 42, wherein the third polymerization reactor is a gas-phase reactor.

[0224] 44. An ethylene-propylene copolymer composition according to any one of items 1 to 43, comprising 0.55–1.95 wt% of a mineral α-nucleating agent.

[0225] 45. An ethylene-propylene copolymer composition according to any one of items 1 to 44, comprising 0.08–0.40 wt% of an α-nucleating agent selected from the group consisting of salts of formula (I).

[0226] 46. ​​A molded product comprising 50 to 100 wt% of an ethylene-propylene copolymer composition according to any one of items 1 to 45.

[0227] 47. The molded product according to item 46, comprising 60 to 100 wt%, preferably 70 to 100 wt%, such as 80 to 100 wt%, 90 to 100 wt%, 95 to 100 wt%, 98 to 100 wt%, or 98 to 99 wt% of an ethylene-propylene copolymer composition.

[0228] 48. Use of the ethylene-propylene copolymer composition according to any one of items 1 to 45 for the preparation of molded products such as packaging articles, automotive exterior parts, automotive interior parts or housings of electrical or electronic equipment.

[0229] 49. Use of the ethylene-propylene copolymer composition according to any one of items 1 to 45 for the preparation of injection molded articles with an average wall thickness of 2 mm or less.

[0230] 50. As per the application of item 49, the injection-molded articles are thin-walled packaging articles, such as cups, trays, buckets or lids.

[0231] 51. As per the application of item 49 or 50, wherein the injection-molded article has a wall thickness in the range of 0.1 to 2.0 mm, for example 0.2 to 2.0 mm.

[0232] Test methods

[0233] The following describes methods for measuring the properties of the compositions, copolymers, and products of the present invention, as well as the methods used in the embodiments of the invention. Unless otherwise explicitly stated, if a determination method (measurement method) is described in the context of (only) one product or material, or if no specific product / material is mentioned, it is understood that the same method can be used to measure the same properties of another product / material. This also applies to all measurement methods disclosed herein.

[0234] MFR (MFR2) was measured according to ISO 1133 at 230°C and a load of 2.16 kg.

[0235] According to ISO 178, in 80 x 10 x 4 mm 3 The flexural modulus was determined in three-point bending on an injection-molded specimen (80 mm x 10 mm x 4 mm) using a melt temperature of 200 °C, according to EN ISO 1873-2.

[0236] According to ISO 179-1 eA, injection molded 80 x 10 x 4 mm steel according to EN ISO 1873-2 was performed at 23°C and -20°C respectively. 3 Charpy notched impact strength (NIS23 and NIS-20) was measured on injection-molded specimens.

[0237] The heat distortion temperature (HDT) was determined according to ISO 75 B (low load), which is based on EN ISO 1873-2 for 80 x 10 x 4 mm. 3 The measurements were taken on the injection-molded sample.

[0238] Intrinsic viscosity IV of impact copolymer EPThe intrinsic viscosity of the crystalline and amorphous fractions was determined at 135 °C according to ISO 1628 / 1.

[0239] The median particle size (D50) of the mineral α-nucleating agent was measured according to ISO 13317-3 (Sedigraph method).

[0240] The xylene cold solubles (XCS) fraction was determined at 25°C according to the standard gravimetric method of ISO 16152.

[0241] -MD shrinkage rate

[0242] The longitudinal (molding direction) shrinkage rate was determined on a 60x60x2 mm³ injection molded sheet according to EN ISO 1873-2. The shrinkage rate measurement was based on ISO 294-4, which defines the MD shrinkage rate as the post-molding shrinkage rate along the flow (injection) direction after 96 hours.

[0243] -DSC analysis

[0244] Melting temperature (Tm) and crystallization temperature (Tc) were measured by DSC analysis according to ISO 11357. Specifically, DSC measurements were performed on 5 to 7 mg samples using a TA Instruments Q2000 differential scanning calorimeter (DSC). DSC was run in heating / cooling / heating cycles at a scan rate of 10 °C / min within a temperature range of -30 °C to +225 °C, according to ISO 11357 / Part 3 / Method C2. The crystallization temperature (Tc) was determined by the cooling step, while the melting temperature (Tm) was determined by the second heating step.

[0245] - CRYSTEX QC

[0246] The crystalline (CF) and amorphous (SF) fractions of the impact copolymer, as well as the comonomer content and intrinsic viscosity of each fraction, were analyzed using a CRYSTEX Polymer Char instrument (Valencia, Spain). Detailed information on this technique and method can be found in the literature (Ljiljana Jeremie, Andreas Albrecht, Martina Sandholzer & Markus Gahleitner (2020) “Rapid characterization of high-impact ethylene-propylene copolymer composition by crystallization extraction separation: comparison to standard separation methods”, International Journal of Polymer Analysis and Characterization, 25:8, 581-596).

[0247] The crystalline and amorphous fractions were separated by a temperature cycle of dissolution at 160 °C, crystallization at 40 °C, and redissolution at 160 °C in 1,2,4-trichlorobenzene (TCB). Quantification of SF and CF and determination of ethylene content (C2) were achieved using an integrated infrared detector (IR4), and an online dual-capillary viscometer was used to determine the intrinsic viscosity (IV). The IR4 detector is a multi-wavelength detector that measures two different wavelengths (CH3 stretching vibrations centered at ~2960 cm⁻¹). -1 ) and CH stretching vibration (2700-3000 cm) -1 The infrared absorbance of the IR4 detector was used to determine the concentration and ethylene content in ethylene-propylene (EP) copolymers. The IR4 detector was calibrated with a series of eight EP copolymers, with known ethylene contents ranging from 2 wt% to 69 wt% (via...). 13 (C-NMR determination), the concentration of each copolymer ranged from 2 to 13 mg / ml. To simultaneously meet the two characteristics expected during Crystex analysis—concentration and ethylene content—the following calibration equation was applied:

[0248] Cone = a + b*Abs(CH) + c*(Abs(CH)) 2 + d*Abs(CH3) + e*(Abs(CH3) 2 + f'*Abs(CH)*Abs(CH3) (Equation 1)

[0249] CH3 / 1000C = a + b*Abs(CH) + c*Abs(CH3) + d*(Abs(CH3) / Abs(CH)) + e*(Abs(CH3) / Abs(CH)) 2 (Equation 2)

[0250] The constants a to f in equation 1 and the constants a to e in equation 2 are determined by using least squares regression analysis.

[0251] Use the following relationship to convert CH3 / 1000C to ethylene content, in wt%:

[0252] wt% (ethylene in copolymer) = 100 - CH3 / 1000TC * 0.3 (Equation 3)

[0253] The amounts of the amorphous fraction (SF) and crystalline fraction (CF) were correlated, respectively, with the amounts of xylene cold-soluble (XCS) and xylene cold-insoluble (XCI) fractions as determined by the standard gravimetric method according to ISO 16152 via XS calibration. XS calibration was performed by testing various copolymers with XCS contents ranging from 2–31 wt%. The determined XS calibration was linear.

[0254] wt% XCS = 1.01 * wt% SF (Equation 4)

[0255] The intrinsic viscosity (IV) of the copolymers and their amorphous and crystalline portions was determined using an online dual-capillary viscometer and correlated with the corresponding IV determined in decahydronaphthalene according to a standard method in ISO 1628-1. Calibration was performed using various ethylene-propylene copolymers with IVs in the range of 2 to 4 dL / g. The determined calibration curves were linear.

[0256] IV(dL / g) = a*Vsp / c (Equation 5)

[0257] Weigh the sample to be analyzed at a concentration of 10 mg / ml to 20 mg / ml. To avoid injection of possible gels and / or polymers (which will not dissolve in TCB at 160°C), place the weighed sample into a stainless steel sieve with a MW of 0.077 mm and a D of 0.05 mm.

[0258] After filling the vial with TCB containing 250 mg / L 2,6-tert-butyl-4-methylphenol (BHT) as an antioxidant, dissolve the sample at 160 °C until completely dissolved, typically for 60 min, with constant stirring at 400 rpm. To prevent sample degradation, cover the polymer solution with a nitrogen atmosphere during dissolution.

[0259] A predetermined volume of sample solution was injected into a column packed with an inert support, where crystallization and separation of the soluble and crystalline fractions were carried out. This process was repeated twice. During the first injection, the entire sample was measured at high temperature to determine the IV [dl / g] and C2 [wt%] of the composition. During the second injection, the soluble fraction (low temperature) and the crystalline fraction (high temperature) during the crystallization cycle were measured (wt% SF, wt% C2, IV).

[0260] According to ISO 16152, the content (wt%) of xylene cold solubles (XCS) at 25°C is determined.

[0261] Intrinsic viscosity in decahydronaphthalene was measured at 135°C according to DIN ISO 1628 / 1.

[0262] -Quantitative analysis of microstructure using NMR spectroscopy -Ethylene content

[0263] Quantitative nuclear magnetic resonance (NMR) spectroscopy was used to quantify the comonomer content of the polymer. A Bruker AvanceIII 400 NMR spectrometer was used for [specific measurements / analyses]. 1 H and 13 C was operated at 400.15 and 100.62 MHz, and quantification was recorded in solution. 13 C{ 1 H}NMR spectroscopy ( 13 C measurement, 1 H-decoupling). All spectra are used. 13Recordings were performed at 125 °C using a C-optimized 10 mm extended temperature probe, with all pneumatic setups using nitrogen. Approximately 200 mg of material was dissolved with chromium acetylacetone (Cr(acac)2; relaxant) in 3 ml of fully deuterated 1,2-tetrachloroethane (TCE-d2) to obtain a 65 mM relaxant solution in 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 initial sample preparation in a heat block. The tube was rotated at 10 Hz while inserted into the magnet. This setup was chosen primarily for the quantification required for high resolution and accurate ethylene content determination. Standard single-pulse excitation without NOE was used, with optimized flip angle, 1 s relaxation delay, and a two-stage WALTZ 16 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.RapidCommun.2007, 28, 1128). A total of 6144 (6 k) transients were obtained for each spectrum. Quantitative 13C{1H} NMR spectra were processed, integrated, and the relevant quantitative characteristics were determined from the integration. Using the chemical shifts of the solvent, all chemical shifts are indirectly referenced to the central methylene group of the ethylene block (EEE) at 30.00 ppm. This method allows for comparable references even in the absence of such a structural unit. Characteristic signals corresponding to ethylene incorporation were observed (Cheng, H. N., Macromolecules 17 (1984), 1950).

[0264] Characteristic signals corresponding to 2,1-erythro-type regional defects were observed (as described in L. Resconi, L. Cavallo, A. Fait, F. Piemontesi, Chem. Rev. 2000, 100 (4), 1253; Cheng, HN, Macromolecules 1984, 17, 1950; and WJ. Wang and S. Zhu, Macromolecules 2000, 331157), requiring correction for the influence of regional defects on the determined properties. No characteristic signals corresponding to other types of regional defects were observed.

[0265] The comonomer fraction was determined using the method described by Wang et al. (Wang, W-J., Zhu, S., Macromolecules 33(2000), 1157). 13 Quantification was performed by integrating multiple signals across the entire spectral region of the C{1H} spectrum. This method was chosen because of its robustness and ability to account for regional defects when needed. The integration region was slightly adjusted empirically to improve applicability across the entire comonomer content range.

[0266] For systems where only isolated ethylene is observed in the PPEPP sequence, Wang et al.'s method was modified to reduce the influence of non-zero integrals from sites known to be absent. This method reduces the overestimation of ethylene content in such systems by reducing the number of sites used to determine absolute ethylene content to:

[0267] E = 0.5 (Sββ + Sβγ + Sβδ + 0.5 (Sαβ + Sαγ))

[0268] By using this set of sites and employing the same notation as in Wang et al.'s article (Wang, WJ., Zhu, S., Macromolecules 33 (2000), 1157), the corresponding integral equation becomes:

[0269] E = 0.5 (I H + I G + 0.5 (I C + I D ))

[0270] The equation used to calculate the absolute propylene content remains unchanged. The molar percentage of comonomer incorporation is calculated using the mole fraction (fE):

[0271] E [mol%] = 100 * fE

[0272] The weight percentage of comonomer incorporated is calculated as a mole fraction (fE):

[0273] E [wt%] = 100 * (fE * 28.06) / ((fE * 28.06) + ((1 - fE) * 42.08))

[0274] 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 a slight adjustment was made to the integration region to improve applicability to a wider range of comonomer contents.

[0275] Example

[0276] The following examples illustrate certain aspects and embodiments of the invention as described in the claims. However, those skilled in the art will understand that the following description is merely illustrative and should not be construed as limiting the invention in any way. However, values ​​disclosed in the examples, such as properties and conditions, may be combined with the scope disclosed in a more general context (e.g., the claims or the general description) to give new (more limited or different) scopes without any limitation.

[0277] Preparation of impact copolymers

[0278] The ethylene-propylene impact copolymers of Examples IE1, IE2, and IE3 and Comparative Example CE1 of this invention were prepared in a Borstar PP pilot plant using a sequential process including a prepolymerization reactor, a loop reactor, and two gas-phase reactors. The reaction conditions are summarized in Table 1.

[0279] The properties of the impact copolymers and intermediate polymers are also listed in Table 1.

[0280] Table 1:

[0281] Polymer 1 Polymer 2 catalyst ZN1 ZN1 Donor (ED) D-donor D-donor Prepolymerization Co / ED mol / mol 20 8 Co / Ti mol / mol 250 166 temperature ℃ 26 30 Duration of stay min 20 20 Ring pipe temperature ℃ 70 80 Distribution ratio wt% 48 40 Feed H2 / C3 mol / kmol 3.95 11.5 MFR g / 10 min 21 103 GPR1 temperature ℃ 70 80 Distribution ratio wt% 35 40 H2 / C3 mol / kmol 40.2 105 MFR g / 10 min 21 88 MFR(GPR1) g / 10 min 21 75 XCS wt% 2.0 2.2 GPR2 temperature ℃ 70 75 C2 / C3 mol / kmol 440 445 H2 / C2 mol / kmol 220 160 Distribution ratio wt% 17 20 Impact copolymer XCS wt% 17.0 19.2 C2 (Total) wt% 7.5 8.2 C2(XCS) wt% 38.4 42.1 IV(XCS) dl / g 2.2 3.2 MFR g / 10 min 13 40 Tm ℃ 165 165 Tc ℃ 120 124 Crystex SF wt% 16.3 19.0 CF wt% 83.7 81.0 C2 wt% 7.5 8.2 C2(SF) wt% 39.1 42.6 C2(CF) wt% 1.5 1.8 IV dl / g 2.2 1.6 IV(SF) dl / g 2.5 3.1 IV(CF) dl / g 1.9 1.2 IV(SF) / IV(CF) - 1.3 2.6

[0282] Unless otherwise explained, the abbreviations used in Table 1 are as follows:

[0283] - ZN1: Emulsion-type Ziegler-Natta catalyst, the same catalyst used in the polymerization of the inventive embodiment of WO 2017 / 148970 A1, except that 15.0 g of vinylcyclohexane (VCH) is added in the modification step instead of 5.0 g used in WO 2017 / 148970 A1.

[0284] - D-donor: Dicyclopentyldimethoxysilane as an external donor (ED)

[0285] - Co / ED: The ratio between the co-catalyst (triethylaluminum; TEAL) and the external donor.

[0286] - Co / Ti: The ratio of co-catalyst to titanium

[0287] - Distribution ratio: Polymer fraction (wt%) of the final polymer from each reactor stage

[0288] - MFR(GPR1): The (calculated) MFR of the polymer fraction produced in GPR1.

[0289] Examples 1 and 2

[0290] To produce the ethylene-propylene copolymer compositions of Examples 1 and 2, polymers 1 and 2 listed in Table 1 above were mixed with antioxidant Irganox® B215 FF (antioxidant Irgafos® 168 (tris(2,4-di-tert-butylphenyl) phosphite, CAS No.: 31570-04-4) and Irganox® 1010 (pentaerythritol tetratetra[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate], CAS No.: 6683-19-8), a first (mineral) nucleating agent, and a second (salt) nucleating agent, as shown in Table 2 below.

[0291] Comparative Examples 1 to 4

[0292] Compositions according to Comparative Examples 1 to 4 were prepared in the same manner as in Examples 1 and 2 using the components and mixing amounts shown in Table 2 below.

[0293] Table 2:

[0294] Ex1 Ex2 CEx.1 CEx.2 CEx.3 CEx.4 Polymer 1 wt% 99.15 99.15 Polymer 2 wt% 97.95 97.95 94.95 PPH *1 wt% 99.15 talc (D50: 6.0 µm) wt% 0.70 1.90 0.70 1.90 0.70 5.00 Salt 1 *2 wt% 0.10 0.10 0.10 HPN-68 *3 wt% 0.10 0.10 antioxidants Irganox® wt% 0.05 0.05 0.05 0.05 0.05 0.05 Tm DSC ℃ 167 166 167 166 166 166 Tc DSC ℃ 130 131 131 133 128 127 MFR 230℃ / 2.16kg g / 10 min 13 40 13 40 8 37 Flexural modulus ISO178 MPa 1498 1575 1383 1503 2106 1453 NIS 23℃ ISO1791eA kJ / m² 7.7 6.6 7.1 6.5 2.7 4.5 NIS -20℃ ISO1791eA kJ / m² 3.9 3.0 3.5 2.8 nd 1.9 HDT ISO75B ℃ 100 102 94 100 113 96 Shrinkage rate MD *4 % 1.35 1.47 1.56 1.61 1.79 nd MPP - 11535 10395 9819 9770 5686 6539 MPP2 - 8544 7071 6294 6068 3177 nd

[0295] *1: PPH is a polypropylene homopolymer available from Borealis AG in Austria (density: 910 kg / m³). 3 , MFR230℃ / 2.16 kg:8.0 g / 10 min; IV:2.0 dl / g)

[0296] *2: Salt 1: Salt of formula (I), M=Al 3+ X=OH - n=2, m=1, o=1, Ra is the same for both, k=1, R = tert-butyl (para).

[0297] *3: Hyperform® HPN-68L (disodium bicyclo[2.2.1]heptane-2,3-dicarboxylate) manufactured by Milliken

[0298] *4: Shrinkage Rate MD: Longitudinal Shrinkage Rate

[0299] nd: Not measured

[0300] As can be seen from Table 2, the embodiments of the present invention that combine specific impact copolymers with nucleating agent systems containing mineral α nucleating agents and salts of formula (I) provide superior performance compared to Comparative Examples 1 and 2, which use dual nucleating agent systems not defined in this invention; Comparative Example 4, which uses a single (mineral) nucleating agent system; and Comparative Example 3, which uses the nucleating agent system (IE1) of Example 1 of the present invention but combined with a propylene homopolymer. The correlation between flexural modulus and NIS23 is further shown in... Figure 1 The explanation is as follows.

[0301] In particular, in addition to low MD shrinkage and high total flexural modulus, the compositions of the present invention exhibit a very good balance between mechanical properties and processability (mainly MFR), as shown in MPP and MPP2.

[0302] This invention relates to a high-flow-rate ethylene-propylene copolymer composition that offers an improved balance of mechanical and impact resistance properties. The ethylene-propylene copolymer composition has a melt flow rate (MFR) greater than 10 g / 10 min and contains (A) 97.00-99.45 wt% of an ethylene-propylene impact copolymer, (B) 0.05-0.50 wt% of an α-nucleating agent of formula (I) as specified in the invention, and (C) 0.50-2.00 wt% of a mineral α-nucleating agent with a median particle size of 10 µm or less. The impact copolymer comprises a1) 75-88 wt% of a crystalline polypropylene homopolymer portion (CF) with an intrinsic viscosity in the range of 0.7 to 2.6 dl / g; and a2) 12-25 wt% of an amorphous ethylene-propylene copolymer portion (SF) having an intrinsic viscosity in the range of 1.5 to 4.5 dl / g and an ethylene content in the range of 25.0 to 55.0 wt%.

Claims

1. An ethylene-propylene copolymer composition comprising: A) 97.00-99.45 wt% of ethylene-propylene impact copolymer, comprising: a1) Relative to 100 wt% ethylene-propylene impact copolymer, 75-88 wt%, preferably 77-86 wt%, for example 79-85 wt% crystalline polypropylene homopolymer fraction (CF, determined by CRYSTEX QC analysis), its intrinsic viscosity IV CF (Measured in decahydronaphthalene at 135°C according to ISO 1628 / 1) in the range of 0.7 to 2.6 dl / g, preferably 0.8 to 2.5 dl / g, for example 0.9 to 2.3 dl / g, and a2) Relative to 100 wt% of the ethylene-propylene impact copolymer, 12-25 wt%, preferably 14-23 wt%, for example 15-21 wt% of the amorphous ethylene-propylene copolymer fraction (SF, determined by CRYSTEX QC analysis), its intrinsic viscosity IV SF (Measured in decahydronaphthalene at 135°C according to ISO 1628 / 1) The ethylene content C2 is in the range of 1.5 to 4.5 dl / g, preferably in the range of 1.7 to 4.0 dl / g, for example in the range of 1.9 to 3.5 dl / g. SF (through quantitative methods) 13 (FT-IR spectroscopy determination calibrated by C-NMR spectroscopy) is in the range of 25.0 to 55.0 wt%, preferably in the range of 30.0 to 50.0 wt%, for example in the range of 33.0 to 47.0 wt%. B) 0.05-0.50 wt%, preferably 0.08-0.40 wt%, of an α-nucleating agent selected from the group consisting of salts of formula (I): Ra n M m X o Formula (I) Where M is independently a metal cation, X is independently an anion, and Ra is independently an organic anion of formula (II): Equation (II) Where R is independently an aliphatic hydrocarbon group, k is independently in the range of 1 to 3, n is in the range of 1 to 4, m is 1 or 2, and o is chosen to make the total charge of the salt of formula (I) 0, and C) 0.50-2.00 wt%, preferably 0.55-1.95 wt%, of a mineral α-nucleating agent, wherein the central particle size D50 (according to ISO 13317-3, Sedigraph method) is less than 10 µm, preferably in the range of 0.5 to 10.0 µm, more preferably in the range of 1.0 to 9.5 µm, for example, in the range of 1.5 to 9.0 µm, 2.0 to 8.5 µm, or 2.2 to 8.0 µm. The composition has an MFR (according to ISO 1133 at 230°C and 2.16 kg load) greater than 10 g / 10 min, preferably 11-100 g / 10 min, for example 12-90 g / 10 min.

2. The ethylene-propylene copolymer composition according to claim 1, wherein the mineral α-nucleating agent is talc.

3. The ethylene-propylene copolymer composition according to claim 1 or 2, wherein the ethylene-propylene impact copolymer has a total C2 content in the range of 4.2 to 11.2 wt%, preferably in the range of 5.0 to 10.5 wt%, for example in the range of 5.5 to 10.0 wt%, which is determined by quantitative analysis. 13 FT-IR spectroscopy measurements calibrated by C-NMR spectroscopy.

4. The ethylene-propylene copolymer composition according to any one of claims 1 to 3, wherein the ethylene-propylene impact copolymer has a melting temperature Tm (determined by differential scanning calorimetry according to ISO 11357) in the range of 160 to 170°C, preferably in the range of 162 to 168°C.

5. The ethylene-propylene copolymer composition according to any one of claims 1 to 4, wherein the crystalline polypropylene homopolymer portion (CF) has an ethylene content (C2) in the range of 0.3 to 2.5 wt%, preferably in the range of 0.5 to 2.2 wt%, for example in the range of 0.7 to 2.0 wt%. CF .

6. The ethylene-propylene copolymer composition according to any one of claims 1 to 5, wherein the ethylene-propylene impact copolymer has an intrinsic viscosity IV in the range of 0.8 to 3.0 dl / g, preferably in the range of 1.0 to 2.8 dl / g, for example in the range of 1.2 to 2.6 dl / g. EP .

7. The ethylene-propylene copolymer composition according to any one of claims 1 to 6, wherein the intrinsic viscosity of the amorphous ethylene-propylene copolymer portion (SF) to the intrinsic viscosity of the crystalline polypropylene homopolymer portion (CF) is (IV) SF / IV CF The value is in the range of 0.9 to 3.5, preferably in the range of 1.0 to 3.0, for example in the range of 1.1 to 2.

8.

8. The ethylene-propylene copolymer composition according to any one of claims 1 to 7, wherein the composition has a crystallization temperature Tc in the range of 125 to 135°C, preferably in the range of 128 to 132°C (determined by differential scanning calorimetry according to ISO 11357).

9. The ethylene-propylene copolymer composition according to any one of claims 1 to 8, wherein the composition has one or more, preferably all of the following properties: i. The flexural modulus is in the range of 1400 to 1750 MPa, preferably in the range of 1450 to 1700 MPa (according to ISO 178). ii5.5 kJ / m 2 Or higher, preferably between 6.0 and 15.0 kJ / m 2 Within the range, for example, from 6.5 to 12.5 kJ / m 2 NIS23 (Charpy notched impact strength, according to ISO 179 1eA at 23°C) within the range. iii2.5 kJ / m 2 Or higher, preferably between 2.8 and 7.0 kJ / m 2 Within the range, for example, from 2.9 to 6.5 kJ / m 2 NIS-20°C (Charpy notched impact strength, according to ISO 179 1eA at -20°C). iv The heat distortion temperature (HDT; measured according to ISO 75 B, under low load, on an 80x10x4 mm³ specimen) is in the range of 95 to 115 °C, preferably in the range of 97 to 112 °C, for example in the range of 98 to 110 °C. The longitudinal shrinkage rate (MD shrinkage rate; measured as defined in the specification) is 1.75% or less, preferably in the range of 0.90% to 1.70%. The mechanical property parameter MPP1 is preferably in the range of 10,000 to 16,000, and is defined as NIS23 (Charpy notched impact strength, according to ISO 179 1eA at 23°C) [kJ / m]. 2 The product of the flexural modulus (according to ISO 178) [MPa], vii. The mechanical property parameter MPP2 is defined as NIS23 [kJ / m] in the range of 6500 to 12000, preferably in the range of 6700 to 10000. 2 The product of the flexural modulus [MPa] and the MD shrinkage rate (longitudinal shrinkage rate; measured as defined in the instruction manual) [%] is calculated by dividing the product of the MD shrinkage rate and the flexural modulus [MPa]. viii is the xylene cold soluble content (XCS, according to ISO 16152 at 25°C) in the range of 12 to 30 wt%, preferably in the range of 14 to 25 wt%, for example in the range of 15 to 22 wt%. The C2 content (C2-XCS) in the cold soluble fraction of xylene is in the range of 30 to 50 wt%, preferably in the range of 32 to 47 wt%, for example in the range of 35 to 45 wt%, which is determined by quantitative analysis. 13 FT-IR spectroscopy measurements calibrated by C-NMR spectroscopy The intrinsic viscosity IV is in the range of 0.8 to 3.0 dl / g, preferably in the range of 1.0 to 2.8 dl / g, for example in the range of 1.2 to 2.6 dl / g. EP .

10. The ethylene-propylene copolymer composition according to any one of claims 1 to 9, wherein, In formula (I), M is independently an alkali metal cation, an alkaline earth metal cation, a boron cation or an aluminum cation, preferably an alkali metal cation or an aluminum cation.

11. The ethylene-propylene copolymer composition according to any one of claims 1 to 10, wherein, In formulas (I) and (II), m is 1 or 2, preferably 1; o is 0, 1, or 2, preferably 0 or 1; X is independently an inorganic anion, preferably a monovalent inorganic anion, more preferably free from Cl. - OH - SH - HSO3 - HSO4 - NO3 - NO2 - SO4 2- PO4 3- CO3 2- or CN - The following groups are preferred, especially those with OH groups. - SH - Or NO3 - More preferably OH - R is independently an aliphatic hydrocarbon group having 1 to 8 carbon atoms, preferably 2 to 6 carbon atoms, more preferably 4 to 5 carbon atoms, more preferably an acyclic (open-chain) aliphatic hydrocarbon group, even more preferably a straight-chain or branched alkyl group, preferably a branched alkyl group, more preferably selected from the group consisting of isopropyl, isobutyl, sec-butyl, tert-butyl and neopentyl, preferably tert-butyl, k is 1 or 2, preferably 1, n is 1, 2 or 3, preferably 1 or 2, more preferably 2.

12. The ethylene-propylene copolymer composition according to any one of claims 1 to 11, further comprising up to 2.45 wt%, preferably 0.01 to 2.45 wt%, of an additive, said additive preferably selected from the group consisting of antioxidants, UV stabilizers, antistatic agents, acid scavengers, and slip agents.

13. The ethylene-propylene copolymer composition according to any one of claims 1 to 12, produced by a method comprising the following steps: a) In a first polymerization reactor, propylene is polymerized in the presence of a Ziegler-Natta catalyst system to produce a first propylene polymer fraction; b) Transferring the polymerization mixture, which includes the Ziegler-Natta catalyst system and the first propylene polymer portion, from the first polymerization reactor to the second polymerization reactor; c) In a second polymerization reactor, propylene is polymerized in the presence of a Ziegler-Natta catalyst system to produce a second propylene polymer fraction; d) Transfer the polymerization mixture, which includes the Ziegler-Natta catalyst system and the first and second propylene polymer portions, from the second polymerization reactor to the third polymerization reactor; e) In a third polymerization reactor, propylene and ethylene are polymerized in the presence of a Ziegler-Natta catalyst system to produce a propylene-ethylene copolymer portion; f) Remove from the third polymerization reactor a polymerization mixture comprising the Ziegler-Natta type catalyst system, the first and second propylene polymer portions, and the third propylene-ethylene copolymer portion; and g) Obtain a polymer composition comprising the first and second propylene polymer portions and the third propylene-ethylene copolymer portion. Optionally, the method includes a pre-polymerization step prior to step a.

14. A molded product comprising 50 to 100 wt% of the ethylene-propylene copolymer composition according to any one of claims 1 to 13, preferably comprising 60 to 100 wt%, more preferably 70 to 100 wt%, such as 80 to 100 wt%, 90 to 100 wt%, 95 to 100 wt%, 98 to 100 wt%, or 98 to 99 wt% of the ethylene-propylene copolymer composition.

15. The ethylene-propylene copolymer composition according to any one of claims 1 to 13 is used for the preparation of molded products, such as packaging articles, automotive exterior parts, automotive interior parts, or electrical or electronic equipment housings, and / or for the preparation of injection-molded articles with an average wall thickness of 2 mm or less, preferably thin-walled packaging articles, such as cups, trays, buckets, or lids.

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