heterophasic propylene-ethylene copolymer / propylene-butene random copolymer blend

Abstract

A multiphase polypropylene (PC) composition comprising: i) 40.0 to 90.0% by weight of a multiphase C3C2 copolymer (HECO), the multiphase C3C2 copolymer (HECO) having an MFR2 of 1.0 to 5.0 g / 10 min and a Tc of 149 to 160 °C. m The composition includes: 1) 60.0 to 95.0% by weight of CF content, 0.0 to 2.0% by weight of C2 (CF), 5.0 to 40.0% by weight of SF content and 18.0 to 30.0% by weight of C2 (SF); and ii) 10.0 to 60.0% by weight of C3C4 random copolymer (RACO), which has an MFR2 content of 0.5 to 15.0 g / 10 min and a C4 content of 1.0 to 10.0% by weight.

Description

Technical Field

[0001] The present invention relates to a multiphase polypropylene composition comprising a multiphase propylene-ethylene copolymer (HECO) and a propylene-butene random copolymer (RACO), a method for producing such a multiphase polypropylene composition, and a membrane comprising the multiphase polypropylene composition. Background Technology

[0002] Multiphase propylene copolymer films are widely used in various fields, such as food packaging, including packaging films and containers. These films are known for their well-balanced properties, such as strength, hardness, transparency, and impact resistance. Metallized films are also used as packaging materials, for example, in the form of layered polypropylene film / aluminum foil structures.

[0003] Although this membrane has shown to have a good balance of performance, optimizing the balance between mechanical, optical and sealing properties remains an art, requiring trade-offs in some properties in order to achieve improvements in others.

[0004] To address these issues, multilayer films combine the beneficial properties of one layer (such as mechanical or barrier properties) with those of another layer (such as sealing properties). While such multilayer films do produce a beneficial combination of properties, significant difficulties exist associated with recycling such films. Therefore, there is a need for novel multiphase polypropylene compositions with a beneficial balance of mechanical, optical, and sealing properties for use in single-layer films suitable for packaging materials and readily recyclable.

[0005] WO 2020 / 011825 A1 discloses blends of metallocene-catalyzed multiphase propylene-ethylene copolymers and Ziegler-Natta-catalyzed multiphase propylene-ethylene copolymers for use in packaging materials.

[0006] WO 2018 / 077663 A1 discloses a Ziegler-Natta catalyzed heterophase propylene-ethylene copolymer utilizing a dual nucleation strategy.

[0007] Although significant progress has been made in this field in recent years, there is still room for further development of single-layer films that are suitable for packaging materials and easy to recycle. Summary of the Invention

[0008] This invention is based on the discovery that blends of multiphase propylene-ethylene copolymers and propylene-butene random copolymers have favorable optical and sealing properties while maintaining acceptable mechanical properties.

[0009] Therefore, in a first aspect, the present invention relates to a multiphase polypropylene composition (PC) comprising:

[0010] i) 40.0 to 90.0% by weight of a multiphase propylene-ethylene copolymer (HECO) relative to the total weight of the multiphase polypropylene composition (PC), the multiphase propylene-ethylene copolymer (HECO) having a melt flow rate (MFR2) in the range of 1.0 to 5.0 g / 10 min, determined according to ISO 1133 at 230 °C under a load of 2.16 kg, and a melt temperature (T) in the range of 149 to 160 °C, determined by differential scanning calorimetry (DSC). m The multiphase propylene-ethylene copolymer (HECO) comprises:

[0011] a) is a crystalline matrix (M) of propylene homopolymer, which has a molecular weight distribution in the range of 0.05 to 1.40 mol% by quantitative analysis. 13 The defect content in the 2,1-region was determined by C-NMR spectroscopy; and

[0012] b) Amorphous propylene-ethylene elastomer (E);

[0013] The multiphase propylene-ethylene copolymer (HECO) is characterized by its soluble fraction (SF) and crystalline fraction (CF) as determined by CRYSTEX QC analysis:

[0014] i. A crystalline fraction (CF) of 60.0 to 95.0% by weight of the total weight of the multiphase propylene-ethylene copolymer (HECO), the crystalline fraction (CF) having an ethylene content (C2) (CF) determined by quantitative IR spectroscopy in the range of 0.0 to 2.0% by weight; and

[0015] ii. A soluble fraction (SF) of 5.0 to 40.0% by weight of the total weight of the multiphase propylene-ethylene copolymer (HECO), the soluble fraction (SF) having an ethylene content C2 (SF) determined by quantitative IR spectroscopy in the range of 12.0 to 40.0% by weight;

[0016] ii) 10.0 to 60.0% by weight of propylene-butene random copolymer (RACO) relative to the total weight of the multiphase polypropylene composition (PC), the propylene-butene random copolymer (RACO) having a melt flow rate (MFR2) in the range of 0.5 to 15.0 g / 10 min, determined according to ISO 1133 at 230 °C under a load of 2.16 kg, and a permeability in the range of 1.0 to 10.0% by weight. 13 1-Butene content determined by C-NMR spectroscopy;

[0017] iii) Optional nucleating agent (NU) of 0.0001 to 1.0% by weight relative to the total weight of the multiphase polypropylene composition (PC); and

[0018] iv) Optional 0.1 to 5.0% by weight of other additives (A) different from the nucleating agent (NU).

[0019] In another aspect, the present invention relates to a method for producing a multiphase polypropylene composition (PC) according to the first aspect, comprising the following steps:

[0020] a) Provides multiphase propylene-ethylene copolymer (HECO), propylene-butene random copolymer (RACO), optional nucleating agent (NU), and optional other additives (A); and

[0021] b) In an extruder, preferably a twin-screw extruder, the multiphase propylene-ethylene copolymer (HECO), propylene-butene random copolymer (RACO), optional nucleating agent (NU), and optional other additives (A) are blended and extruded at a temperature in the range of 120 to 250°C to produce a multiphase polypropylene composition (PC), preferably in granular form.

[0022] In a final aspect, the present invention relates to a film, more preferably a cast film, comprising at least 90% by weight, more preferably at least 95% by weight, and most preferably at least 98% by weight of a multiphase polypropylene composition (PC) according to the first aspect.

[0023] definition

[0024] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Although any methods and materials similar to or equivalent to those described herein may be used in practice to test the invention, preferred materials and methods are described herein. In describing and claiming protection for this invention, the following terms will be used according to the definitions stated below.

[0025] Unless otherwise expressly stated, the terms “a”, “an”, etc., are used to refer to one or more.

[0026] In the following text, unless otherwise stated, quantities are given in weight % (wt.-%).

[0027] Propylene homopolymers are polymers that consist essentially of propylene monomer units. Due to impurities, especially during commercial polymerization processes, propylene homopolymers may contain up to 0.1 mol% of comonomer units, preferably up to 0.05 mol% of comonomer units, and most preferably up to 0.01 mol% of comonomer units.

[0028] Propylene copolymers are copolymers of propylene monomer units and comonomer units, preferably selected from ethylene and C4-C8 α-olefins. Propylene random copolymers are propylene copolymers in which comonomer units are randomly distributed along the polymer chain, while propylene block copolymers comprise blocks of propylene monomer units and blocks of comonomer units. Propylene random copolymers may contain comonomer units of one or more comonomers with different carbon atomic masses.

[0029] Multiphase propylene copolymers typically contain:

[0030] a) Crystalline propylene homopolymer or copolymer matrix (M); and

[0031] b) Elastomer rubber, preferably propylene-ethylene copolymer (E).

[0032] The elastomeric phase can be a propylene copolymer with a large number of comonomers, which are not randomly distributed in the polymer chain but distributed in both comonomer-rich block structures and propylene-rich block structures. Multiphase polypropylene generally differs from single-phase propylene copolymers because it exhibits two different glass transition temperatures (Tg), which are attributed to the matrix phase and the elastomeric phase.

[0033] The invention will now be described in more detail. Detailed Implementation

[0034] Multiphase propylene-ethylene copolymer

[0035] An essential component of multiphase polypropylene (PC) compositions is multiphase propylene-ethylene copolymer (HECO).

[0036] The multiphase propylene-ethylene copolymer (HECO) is present in the multiphase polypropylene composition (PC) in an amount ranging from 40.0 to 90.0% by weight, more preferably from 42.0 to 80.0% by weight, and most preferably from 45.0 to 70.0% by weight relative to the total weight of the multiphase polypropylene composition (PC).

[0037] Multiphase propylene-ethylene copolymer (HECO) comprises:

[0038] a) is the crystalline matrix (M) of propylene homopolymer; and

[0039] b) Amorphous propylene-ethylene elastomer (E).

[0040] The multiphase propylene-ethylene copolymer (HECO) has a melt flow rate (MFR2) measured according to ISO 1133 at 230°C and 2.16 kg in the range of 1.0 to 5.0 g / 10 min, more preferably in the range of 1.1 to 3.5 g / 10 min, and most preferably in the range of 1.2 to 2.0 g / 10 min.

[0041] Multiphase propylene-ethylene copolymer (HECO) is characterized by its soluble fraction (SF) and crystalline fraction (CF) as determined by CRYSTEX QC analysis.

[0042] The multiphase propylene-ethylene copolymer (HECO) preferably has a soluble fraction (SF) content determined according to CRYSTEX QC analysis in the range of 5.0 to 40.0% by weight, more preferably in the range of 8.0 to 35.0% by weight, and most preferably in the range of 10.0 to 30.0% by weight.

[0043] The multiphase propylene-ethylene copolymer (HECO) has a crystallization fraction (CF) content determined according to CRYSTEX QC analysis in the range of 60.0 to 95.0% by weight, more preferably in the range of 65.0 to 92.0% by weight, and most preferably in the range of 70.0 to 90.0% by weight.

[0044] The soluble fraction of the multiphase propylene-ethylene copolymer (HECO), as analyzed by CRYSTEX QC, has a content in the range of 12.0 to 40.0 wt%, more preferably in the range of 14.0 to 35.0 wt%, still more preferably in the range of 16.0 to 30.0 wt%, and most preferably in the range of 18.0 to 27.0 wt%, as determined by quantitative analysis. 13 Ethylene content (C2(SF)) determined by FT-IR spectroscopy calibrated by C-NMR spectroscopy.

[0045] The crystalline fraction of the multiphase propylene-ethylene copolymer (HECO), as analyzed by CRYSTEX QC, has a content in the range of 0.0 to 2.0 wt%, more preferably in the range of 0.0 to 1.0 wt%, and most preferably in the range of 0.0 to 0.7 wt%, determined by quantitative analysis. 13 Ethylene content (C2(CF)) determined by FT-IR spectroscopy calibrated by C-NMR spectroscopy.

[0046] The soluble fraction of the multiphase propylene-ethylene copolymer (HECO) as analyzed by CRYSTEX QC preferably has an intrinsic viscosity (iV(SF)) as determined according to DIN ISO 1628 / 1 in the range of 1.00 to 4.00 dL / g, more preferably in the range of 1.20 to 3.50 dL / g, still more preferably in the range of 1.40 to 3.20 dL / g, even more preferably in the range of 1.60 to 3.00 dL / g, and most preferably in the range of 2.00 to 2.80 dL / g.

[0047] The crystalline fraction of the multiphase propylene-ethylene copolymer (HECO) as analyzed by CRYSTEX QC preferably has an intrinsic viscosity (iV(CF)) as determined according to DIN ISO 1628 / 1 in the range of 1.00 to 4.00 dL / g, more preferably in the range of 1.20 to 3.50 dL / g, still more preferably in the range of 1.40 to 3.20 dL / g, even more preferably in the range of 1.60 to 3.00 dL / g, and most preferably in the range of 2.00 to 2.80 dL / g.

[0048] The multiphase propylene-ethylene copolymer (HECO) preferably has an intrinsic viscosity (iV) measured according to DIN ISO 1628 / 1 in the range of 1.00 to 4.00 dL / g, more preferably in the range of 1.20 to 3.50 dL / g, still more preferably in the range of 1.40 to 3.20 dL / g, even more preferably in the range of 1.60 to 3.00 dL / g, and most preferably in the range of 2.00 to 2.80 dL / g.

[0049] The multiphase propylene-ethylene copolymer (HECO) preferably has a content in the range of 1.5 to 9.0% by weight, more preferably in the range of 2.0 to 8.0% by weight, and most preferably in the range of 2.3 to 7.0% by weight, according to quantitative analysis. 13 Ethylene content (C2) determined by quantitative FT-IR spectroscopy calibrated by C-NMR spectroscopy.

[0050] The multiphase propylene-ethylene copolymer (HECO) has a first melting temperature (T0) determined by differential scanning calorimetry (DSC) in the range of 149 to 160°C, more preferably in the range of 150 to 159°C, and most preferably in the range of 151 to 158°C. m ).

[0051] Enthalpy of fusion (H) associated with the first melting temperature m Preferably, it is in the range of 50 to 100 J / g, more preferably in the range of 60 to 90 J / g, and most preferably in the range of 65 to 85 J / g.

[0052] Preferably, the crystalline matrix (M) of the multiphase propylene-ethylene copolymer (HECO) has a melt flow rate (MFR2) measured according to ISO 1133 at 230°C under a load of 2.16 kg, in the range of 1.0 to 5.0 g / 10 min, more preferably in the range of 1.2 to 4.0 g / 10 min, and most preferably in the range of 1.5 to 3.5 g / 10 min.

[0053] The crystalline matrix (M) of the multiphase propylene-ethylene copolymer (HECO) has a content in the range of 0.05 to 1.40 mol%, more preferably in the range of 0.10 to 1.00 mol%, still more preferably in the range of 0.20 to 0.90 mol%, and most preferably in the range of 0.45 to 0.85 mol%, consisting of a quantitative... 13 The content of defects in the 2,1- region was determined by C-NMR spectroscopy.

[0054] The presence of defects in the 2,1-region indicates that the multiphase propylene-ethylene copolymer (HECO) has polymerized in the presence of a single active site catalyst system, rather than in the presence of a Ziegler-Natta catalyst system.

[0055] Therefore, it is also preferred that the multiphase propylene-ethylene copolymer (HECO) has been polymerized in the presence of a single active center catalyst (SSC), more preferably a metallocene catalyst.

[0056] Suitable multiphase propylene-ethylene copolymers are commercially available from one of many well-known commercial sources, or can be produced by those skilled in the art by any method known in the art. While multiphase propylene-ethylene copolymers (HECO) can be prepared by melt blending a crystalline matrix (M) and an amorphous propylene-ethylene elastomer (E), it is preferred that the crystalline matrix (M) and the amorphous propylene-ethylene elastomer (E) be prepared in the continuous steps of a sequential polymerization method, wherein the multiphase propylene-ethylene copolymer (HECO) is formed in a so-called reactor blend without mechanical blending.

[0057] propylene-butene random copolymer (RACO)

[0058] Another essential component of multiphase polypropylene (PC) compositions is propylene-butene random copolymer (RACO).

[0059] The propylene-butene random copolymer (RACO) is present in the multiphase polypropylene composition (PC) in an amount ranging from 10.0 to 60.0% by weight relative to the total weight of the multiphase polypropylene composition (PC), more preferably from 20.0 to 58.0% by weight, and most preferably from 30.0 to 55.0% by weight.

[0060] Those skilled in the art will understand that, compared to multiphase propylene-ethylene copolymer (HECO), propylene-butene random copolymer (RACO) is single-phase.

[0061] Propylene-butene random copolymer (RACO) is a random copolymer containing propylene monomer units and 1-butene comonomer units.

[0062] The propylene-butene random copolymer (RACO) has a melt flow rate (MFR2) measured according to ISO 1133 at 230°C under a load of 2.16 kg, in the range of 0.5 to 15.0 g / 10 min, more preferably in the range of 0.8 to 10.0 g / 10 min, still more preferably in the range of 1.0 to 8.0 g / 10 min, and most preferably in the range of 1.0 to 4.0 g / 10 min.

[0063] The propylene-butene random copolymer (RACO) has a content in the range of 1.0 to 10.0% by weight, more preferably in the range of 3.0 to 9.0% by weight, and most preferably in the range of 5.0 to 8.0% by weight. 13 The 1-butene content was determined by C-NMR spectroscopy.

[0064] Preferably, the propylene-butene random copolymer (RACO) has a melting temperature (Tm) determined by differential scanning calorimetry (DSC) in the range of 120 to 145°C, more preferably in the range of 130 to 144°C, and most preferably in the range of 135 to 142°C. m ).

[0065] It is also preferred that the propylene-butene random copolymer (RACO) has a xylene cold solubles (XCS) content determined according to ISO 16152 in the range of 0.1 to 10.0% by weight, more preferably in the range of 0.3 to 5.0% by weight, and most preferably in the range of 0.5 to 4.0% by weight.

[0066] The propylene-butene random copolymer (RACO) preferably has a content in the range of 0.05 to 1.40 mol%, more preferably in the range of 0.10 to 1.00 mol%, still more preferably in the range of 0.20 to 0.90 mol%, and most preferably in the range of 0.45 to 0.85 mol%. 13 The content of defects in the 2,1- region was determined by C-NMR spectroscopy.

[0067] Therefore, it is preferred that the propylene-butene random copolymer (RACO) is polymerized in the presence of a single active center catalyst (SSC), more preferably a metallocene catalyst.

[0068] nucleating agent

[0069] An optional component of the multiphase polypropylene composition (PC) is a nucleating agent (NU).

[0070] If present, the nucleating agent (NU) is present in the multiphase polypropylene composition (PC) in an amount ranging from 0.0001 to 1.0% by weight relative to the total weight of the multiphase polypropylene composition (PC), more preferably from 0.001 to 0.50% by weight, and most preferably from 0.01 to 0.20% by weight.

[0071] The nucleating agent may be selected from any known nucleating agent in the art, including polymeric nucleating agents, benzoate nucleating agents, sorbitol-based nucleating agents, particulate nucleating agents (such as talc), and phosphate-based nucleating agents.

[0072] Additive (A)

[0073] Another optional component of the multiphase polypropylene composition (PC) is an additive (A) that is different from the nucleating agent (NU).

[0074] If present, additive (A) is present in the multiphase polypropylene composition (PC) in an amount ranging from 0.1 to 5.0% by weight relative to the total weight of the multiphase polypropylene composition (PC).

[0075] Additive (A) is preferably selected from antioxidants, UV stabilizers, anti-scratch agents, mold release agents, deacidifiers, lubricants, antistatic agents, colorants or pigments, and mixtures thereof. These additives are well known to those skilled in the art and can be selected without difficulty.

[0076] It should be understood that the amount of additive (A) given relative to the total weight of the multiphase polypropylene composition (PC) includes any carrier polymer used to introduce the additive into the multiphase polypropylene composition (PC), i.e., the masterbatch carrier polymer. An example of such a carrier polymer is a polypropylene homopolymer in powder form.

[0077] Multiphase polypropylene (PC) composition

[0078] The multiphase polypropylene (PC) composition of the present invention comprises, more preferably, the following components:

[0079] i) 40.0 to 90.0% by weight, more preferably 42.0 to 80.0% by weight, and most preferably 45.0 to 70.0% by weight of the multiphase polypropylene composition (PC);

[0080] ii) 10.0 to 60.0% by weight, more preferably 20.0 to 58.0% by weight, and most preferably 30.0 to 55.0% by weight of propylene-butene random copolymer (RACO) relative to the total weight of the multiphase polypropylene composition (PC);

[0081] iii) optionally, 0.0001 to 1.0% by weight, more preferably 0.001 to 0.50% by weight, and most preferably 0.01 to 0.20% by weight of nucleating agent relative to the total weight of the multiphase polypropylene composition (PC); and

[0082] iv) Optional 0.1 to 5.0% by weight of other additives (A) different from the nucleating agent (NU).

[0083] In the broadest sense, the multiphase polypropylene composition (PC) of the present invention comprises, more preferably, the following components:

[0084] i) 40.0 to 90.0% by weight of multiphase propylene-ethylene copolymer (HECO) relative to the total weight of the multiphase polypropylene composition (PC);

[0085] ii) 10.0 to 60.0% by weight of propylene-butene random copolymer (RACO) relative to the total weight of the multiphase polypropylene composition (PC);

[0086] iii) Optional nucleating agent (NU) of 0.0001 to 1.0% by weight relative to the total weight of the multiphase polypropylene composition (PC); and

[0087] iv) Optional 0.1 to 5.0% by weight of other additives (A) different from the nucleating agent (NU).

[0088] Preferably, the multiphase polypropylene composition (PC) of the present invention comprises the following components, more preferably composed of the following components:

[0089] i) 42.0 to 80.0% by weight of multiphase propylene-ethylene copolymer (HECO) relative to the total weight of the multiphase polypropylene composition (PC);

[0090] ii) 20.0 to 58.0% by weight of propylene-butene random copolymer (RACO) relative to the total weight of the multiphase polypropylene composition (PC);

[0091] iii) Optional nucleating agent (NU) of 0.001 to 0.50% by weight relative to the total weight of the multiphase polypropylene composition (PC); and

[0092] iv) Optional 0.1 to 5.0% by weight of other additives (A) different from the nucleating agent (NU).

[0093] Particularly preferred is that the multiphase polypropylene composition (PC) of the present invention comprises the following components, more preferably composed of the following components:

[0094] i) 45.0 to 70.0% by weight of multiphase propylene-ethylene copolymer (HECO) relative to the total weight of the multiphase polypropylene composition (PC);

[0095] ii) 30.0 to 55.0% by weight of propylene-butene random copolymer (RACO) relative to the total weight of the multiphase polypropylene composition (PC);

[0096] iii) Optional nucleating agent (NU) of 0.01 to 0.20% by weight relative to the total weight of the multiphase polypropylene composition (PC); and

[0097] iv) Optional 0.1 to 5.0% by weight of other additives (A) different from the nucleating agent (NU).

[0098] In one embodiment, the multiphase polypropylene composition (PC) comprises a multiphase polypropylene-ethylene copolymer (HECO) and a propylene-butene random copolymer (RACO), preferably consisting of a multiphase polypropylene-ethylene copolymer (HECO) and a propylene-butene random copolymer (RACO).

[0099] In an alternative embodiment, the multiphase polypropylene composition (PC) comprises a multiphase polypropylene-ethylene copolymer (HECO), a propylene-butene random copolymer (RACO), and a nucleating agent (NU), preferably consisting of a multiphase polypropylene-ethylene copolymer (HECO), a propylene-butene random copolymer (RACO), and a nucleating agent (NU).

[0100] In another embodiment, the multiphase polypropylene composition (PC) comprises a multiphase polypropylene-ethylene copolymer (HECO), a propylene-butene random copolymer (RACO), and an additive (A), preferably consisting of a multiphase polypropylene-ethylene copolymer (HECO), a propylene-butene random copolymer (RACO), and an additive (A).

[0101] In the last embodiment, the multiphase polypropylene composition (PC) comprises multiphase polypropylene-ethylene copolymer (HECO), propylene-butene random copolymer (RACO), nucleating agent (NU), and additive (A), preferably consisting of multiphase polypropylene-ethylene copolymer (HECO), propylene-butene random copolymer (RACO), nucleating agent (NU), and additive (A).

[0102] The multiphase polypropylene composition (PC) preferably has a melt flow rate (MFR2) measured according to ISO 1133 at 230°C under a load of 2.16 kg, in the range of 1.0 to 10.0 g / 10 min, more preferably in the range of 1.0 to 5.0 g / 10 min, and most preferably in the range of 1.0 to 3.0 g / 10 min.

[0103] The multiphase polypropylene composition (PC) preferably has a content in the range of 1.0 to 5.0% by weight, more preferably in the range of 1.5 to 4.0% by weight, and most preferably in the range of 2.0 to 3.5% by weight. 13 Ethylene content (C2) determined by C-NMR spectroscopy.

[0104] The multiphase polypropylene composition (PC) preferably has a content in the range of 1.0 to 5.0 wt%, more preferably in the range of 1.5 to 4.0 wt%, and most preferably in the range of 1.8 to 3.5 wt%, by quantitative analysis. 13 The 1-butene content (C4) was determined by C-NMR spectroscopy.

[0105] The multiphase polypropylene composition (PC) preferably has a xylene cold solubles (XCS) content determined according to ISO 16152 in the range of 5.0 to 20.0% by weight, more preferably in the range of 8.0 to 19.0% by weight, and most preferably in the range of 10.0 to 18.0% by weight.

[0106] The multiphase polypropylene composition (PC) preferably has a crystallization temperature (Tc) determined by differential scanning calorimetry (DSC) in the range of 114.0 to 130.0 °C, more preferably in the range of 115.0 to 127.0 °C, and most preferably in the range of 116.0 to 125.0 °C. c ).

[0107] The multiphase polypropylene composition (PC) preferably has a first melting temperature (T0) determined by differential scanning calorimetry (DSC) in the range of 149 to 162°C, more preferably in the range of 150 to 159°C, and most preferably in the range of 151 to 156°C. m1 ).

[0108] Further preferably, the enthalpy of fusion (H) associated with the first melting temperature is... m1 The concentration is in the range of 50 to 100 J / g, more preferably in the range of 55 to 95 J / g, and most preferably in the range of 60 to 90 J / g.

[0109] This first melting temperature is considered to be associated with the crystalline matrix (M) of the multiphase propylene-ethylene copolymer (HECO).

[0110] The multiphase polypropylene composition (PC) preferably has a second melting temperature (T0) determined by differential scanning calorimetry (DSC) in the range of 125 to 145°C, more preferably in the range of 127 to 141°C, and most preferably in the range of 129 to 138°C. m2 ).

[0111] Further preferably, the enthalpy of fusion (H) associated with the second melting temperature is... m2 The concentration is in the range of 0.1 to 15.0 J / g, more preferably in the range of 0.2 to 10.0 J / g, and most preferably in the range of 0.3 to 7.0 J / g.

[0112] This second melting temperature is believed to be associated with propylene-butene random copolymer (RACO).

[0113] The multiphase polypropylene composition (PC) preferably has an 80×10×4mm diameter prepared according to ISO 19069-2 according to ISO 178, more preferably in the range of 900 to 1700 MPa, and most preferably in the range of 950 to 1500 MPa. 3 Flexural modulus measured on injection-molded specimens.

[0114] Multiphase polypropylene (PC) compositions preferably have a concentration of 8.0 to 100 kJ / m³. 2 More preferably, it is within the range of 25.0 to 85.0 kJ / m 2 Within this range, the most preferred value is between 40.0 and 70.0 kJ / m³. 2 Within the range of ISO 179-1eA, prepared at 23°C according to ISO 19069-2, 80×10×4mm. 3 Notched beam impact strength (NIS) measured on an injection-molded specimen.

[0115] It is also preferred that the multiphase polypropylene composition (PC) has a haze value measured on a 50 μm cast film sample according to ASTM D1003 in the range of 0.0 to 6.0%, more preferably in the range of 0.0 to 4.0%, and most preferably in the range of 0.0 to 3.5%.

[0116] Preferably, the 50 μm cast film sample prepared from the multiphase polypropylene composition (PC) has a longitudinal tensile modulus (TM-MD) measured at 23°C according to ISO 527-3 in the range of 500 to 1200 MPa, more preferably in the range of 550 to 1100 MPa, and most preferably in the range of 600 to 900 MPa.

[0117] It is also preferred that the 50 μm cast film sample prepared from the multiphase polypropylene composition (PC) has a transverse tensile modulus (TM-TD) measured at 23°C according to ISO 527-3 in the range of 400 to 1200 MPa, more preferably in the range of 450 to 1100 MPa, and most preferably in the range of 500 to 900 MPa.

[0118] Furthermore, it is preferred that the 50 μm cast film sample prepared from the multiphase polypropylene composition (PC) has a sealing initiation temperature (SIT) in the range of 115 to 130°C, more preferably in the range of 117 to 127°C, and most preferably in the range of 119 to 125°C.

[0119] Particularly preferred is the difference (T) between the first melting temperature and the sealing initiation temperature. m1 -SIT) in the range of 28 to 40°C, more preferably in the range of 29 to 37°C, and most preferably in the range of 30 to 35°C.

[0120] method

[0121] In another aspect, the present invention relates to a method for producing a multiphase polypropylene composition (PC) according to the first aspect, comprising the following steps:

[0122] a) Provides multiphase propylene-ethylene copolymer (HECO), propylene-butene random copolymer (RACO), optional nucleating agent (NU), and optional other additives (A); and

[0123] b) In an extruder, preferably a twin-screw extruder, the multiphase propylene-ethylene copolymer (HECO), propylene-butene random copolymer (RACO), optional nucleating agent (NU), and optional other additives (A) are blended and extruded at a temperature in the range of 120 to 250°C to produce a multiphase polypropylene composition (PC), preferably in granular form.

[0124] In particular, it is preferred to use conventional compounding or blending equipment, such as a Banbury mixer, a two-roll rubber mill, a Buss-co-kneader, or a twin-screw extruder. More preferably, mixing is completed in a co-rotating twin-screw extruder. The polymer material recovered from the extruder is typically in granular form.

[0125] All alternative positions of the multiphase polypropylene composition (PC) and its components described above can be adapted to another method with the necessary modifications.

[0126] In one embodiment, the multiphase polypropylene composition can be obtained by another method, more preferably by the other method.

[0127] Products

[0128] In a final aspect, the present invention relates to a membrane comprising at least 90% by weight, more preferably at least 95% by weight, and most preferably at least 98% by weight of a multiphase polypropylene composition (PC) according to the first aspect.

[0129] Understandably, the membrane cannot contain more than 100% by weight of a multiphase polypropylene composition (PC).

[0130] In a particularly preferred embodiment, the membrane is composed of a multiphase polypropylene composition (PC).

[0131] The film is preferably a cast film or a blown film, and most preferably a cast film.

[0132] The film (more preferably a cast film) preferably has a thickness in the range of 1.0 to 100 μm, more preferably in the range of 2.5 to 80 μm, still more preferably in the range of 5.0 to 60 μm, and most preferably in the range of 20 to 55 μm.

[0133] The film (more preferably a cast film) can be a single-layer film, or alternatively, a single layer in a multilayer film, for example, as a sealing layer. Preferably, the film (more preferably a cast film) is a single-layer film.

[0134] The film (more preferably a cast film) preferably has a longitudinal tensile modulus (TM-MD) measured at 23°C according to ISO 527-3 in the range of 500 to 1200 MPa, more preferably in the range of 550 to 1100 MPa, and most preferably in the range of 600 to 900 MPa.

[0135] The film (more preferably a cast film) preferably has a transverse tensile modulus (TM-TD) measured at 23°C according to ISO 527-3 in the range of 400 to 1200 MPa, more preferably in the range of 450 to 1100 MPa, and most preferably in the range of 500 to 900 MPa.

[0136] The film (more preferably a cast film) preferably has a haze value measured according to ASTM D1003 in the range of 0.0 to 6.0%, more preferably in the range of 0.0 to 4.0%, and most preferably in the range of 0.0 to 3.5%.

[0137] The film (more preferably a cast film) preferably has a sealing initiation temperature (SIT) in the range of 115 to 130°C, more preferably in the range of 117 to 127°C, and most preferably in the range of 119 to 125°C.

[0138] Particularly preferred is the difference (T0) between the first melting temperature of the multiphase polypropylene composition (PC) and the sealing initiation temperature of the film. m1 -SIT) in the range of 28 to 40°C, more preferably in the range of 29 to 37°C, and most preferably in the range of 30 to 35°C.

[0139] The film according to the invention is well-suited for a variety of packaging applications or the production of packaging articles, with a preference for applications related to food packaging.

[0140] Packaging articles containing multiphase polypropylene (PC) compositions include, for example, bags, pouches, packaging films, or finishing films.

[0141] Example

[0142] 1. Measurement Method

[0143] Unless otherwise defined, the following definitions of terms and methods of measurement apply to the above general description of the invention, including the claims, and the following embodiments.

[0144] Quantitative analysis of microstructure using NMR spectroscopy

[0145] Quantitative nuclear magnetic resonance (NMR) spectroscopy is used to quantify the comonomer content of polymers.

[0146] Use for 1 H and 13 Quantitative recordings were performed in the molten state using a Bruker Avance III 500 NMR spectrometer operating at 500.13 and 125.76 MHz, respectively. 13 C{ 1 ¹H NMR spectroscopy. Nitrogen gas was used for all pneumatic devices at 180°C. 13 All spectra were recorded using a C-optimized 7mm magic angle rotation (MAS) probe. Approximately 200 mg of material was loaded into a 7mm outer diameter zirconia MAS rotor and rotated at 4 kHz. This setup was chosen primarily for the high sensitivity required for rapid identification and accurate quantification {klimke06, parkinson07, castignolles09}. Standard single-pulse excitation was employed with a short 3s cycle delay using NOE {pollard04, klimke06} and the RS-HEPT decoupling scheme {fillip05, griffin07}. A total of 1024 (1k) transient signals were acquired for each spectrum.

[0147] Quantitative 13 C{ 1The ¹H NMR spectra were processed, integrated, and the relevant quantitative properties were determined from the integration. All chemical shifts were internally referenced at 21.85 ppm for the methyl isotactic pentatonic group (mmmm).

[0148] The characteristic signal {brandolini01} corresponding to the incorporation of 1-butene was observed, and the content of the comonomer was quantified.

[0149] The amount of isolated 1-butene incorporated into the PBP sequence was quantified using the integral at the αB2 site at 43.6 ppm and taking into account the number of reporter sites for each comonomer.

[0150] B = I αB2 / 2

[0151] The amount of 1-butene sequentially incorporated into the PBBP sequence was quantified by integrating the ααB2B2 site at 40.5 ppm and taking into account the number of reporter sites for each comonomer:

[0152] BB = 2 * I ααB2B2

[0153] In the presence of BB, the B value must be corrected for the effect of αB2 sites generated by BB:

[0154] B = (I αB2 / 2)-BB / 2

[0155] The total 1-butene content is calculated based on the sum of isolated and continuously incorporated 1-butene:

[0156] B 总 =B+BB

[0157] The characteristic signal {brandolini01} corresponding to the incorporation of ethylene was observed, and the content of comonomers was quantified.

[0158] The amount of isolated ethylene incorporated into the PEP sequence was quantified by integrating the Sββ site at 24.3 ppm and taking into account the number of reporter sites for each comonomer.

[0159] E = I Sββ

[0160] If a characteristic signal corresponding to ethylene continuously incorporated into the PEE sequence is observed, quantification is performed using the Sβδ site at 27.0 ppm:

[0161] EE = I Sβδ

[0162] Characteristic signals {resconi00} corresponding to regional defects were observed. The presence of isolated 2,1-erythromeric regional defects was indicated by the presence of two methyl sites at 17.7 and 17.2 ppm, by the presence of a methylene site at 42.4 ppm, and confirmed by other characteristic sites. The presence of 2,1-regional defects adjacent to ethylene units was indicated by two inequivalent Sαβ signals at 34.8 ppm and 34.4 ppm, respectively, and by Tγγ at 33.7 ppm.

[0163] The amount of isolated 2,1-Erythian region defects (P) 21e孤立的 Using the integral of the methylene site at 42.4 ppm (I) e9 To quantify:

[0164] P 21e孤立的 =I e9

[0165] If present, use the methine site at 33.7 ppm (I Tγγ To quantify the amount of defects (P) in the 2,1 region adjacent to ethylene. E21 ):

[0166] P E21 =I Tγγ

[0167] Then, the total ethylene content is calculated based on the sum of isolated, continuously incorporated ethylene and ethylene adjacent to defects in region 2,1:

[0168] E 总 =E + EE + P E21

[0169] The amount of propylene was quantified based on the Sαα methylene site at 46.7 ppm, including all additional propylene units not covered by Sαα, such as factor 3*P. 21e孤立的 Three missing propylene units from isolated 2,1-erythroid region defects were considered:

[0170] P 总 =I Sαα +3*P 21e孤立的 +B+0.5*BB+E+0.5*EE+2*P E21

[0171] Then, the total mole fraction of 1-butene and ethylene in the polymer is calculated as follows:

[0172] fB = B 总 / (E 总 +P 总 +B 总 )

[0173] fE=E 总 / (E 总 +P 总 +B 总 )

[0174] The molar percentage of comonomer incorporated is calculated from the molar fraction:

[0175] B[moles%] = 100 * fB

[0176] E[mol%] = 100 * fE

[0177] Calculate the weight percentage of comonomer incorporated from the mole fraction:

[0178] B[weight%] = 100*(fB*56.11) / ((fE*28.05)+(fB*56.11)+((1-(fE+fB))*42.08))

[0179] E[weight%] = 100 * (fE * 28.05) / ((fE * 28.05) + (fB * 56.11) + ((1 - (fE + fB)) * 42.08))

[0180] The molar percentage of isolated 2,1-erythroide region defects relative to all propylene was quantified:

[0181] [21e] mole% = 100*P 21e孤立的 / P 总

[0182] The molar percentage of defects in the 2,1 region adjacent to ethylene was quantified relative to all propylene:

[0183] [E21] mole% = 100 * P E21 / P 总

[0184] The total quantity of defects 2.1 is as follows:

[0185]

[21] mole% = [21e] + [E21]

[0186] No characteristic signal {resconi00} was observed corresponding to other types of regional defects (2,1-Su-type, 3,1-insertion).

[0187] References (as mentioned above):

[0188] klimke06 Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, H.W., Wilhelm, M., Macromol. Chem. Phys. 2006; 207: 382.

[0189] parkinson07 Parkinson, M., Klimke, K., Spiess, H.W., Wilhelm, M., Macromol. Chem. Phys. 2007; 208: 2128.

[0190] pollard04 Pollard, M., Klimke, K., Graf, R., Spiess, H.W., Wilhelm, M., Sperber, O., Piel, C., Kaminsky, W., Macromolecules 2004; 37: 813.

[0191] filip05 Filip, X., Tripon, C., Filip, C., J. Mag. Resn. 2005, 176, 239

[0192] griffin07 Griffin, J.M., Tripon, C., Samoson, A., Filip, C., and Brown, S.P., Mag. Res. in Chem. 2007 45, S1, S198.

[0193] castignolles09 Castignolles, P., Graf, R., Parkinson, M., Wilhelm, M., Gaborieau, M., Polymer 50(2009)2373.

[0194] resconi00 Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253.

[0195] brandolini01 A.J. Brandolini, D.D. Hills, “NMR spectra of polymers and polymer additives”, Marcel Deker Inc., 2000

[0196] Crystex analysis

[0197] Methods for crystallization and soluble fractionation

[0198] Polymer Char (Valencia, Spain) analyzed the crystalline fraction (CF) and soluble fraction (SF) of polypropylene (PP) compositions, along with the comonomer content and intrinsic viscosity of the corresponding fractions, using a CRYSTEX instrument. Details of this technique and method can be found in the literature (Ljiljana Jeremic, Andreas Albrecht, Martina Sandholzer & Markus Gahleitner (2020) Rapid characterization of high-impact ethylene-propylene copolymer composition by crystallization extraction separation: comparability to standard separation methods, International Journal of Polymer Analysis and Characterization, 25:8, pp. 581-596).

[0199] The crystalline and amorphous fractions were separated by temperature cycling of dissolution at 160 °C, crystallization at 40 °C, and redissolution in 1,2,4-trichlorobenzene at 160 °C. Quantification of SF and CF, as well as determination of ethylene content (C2), were achieved using an integrated infrared detector (IR4), and intrinsic viscosity (IV) was determined using an online 2-capillary viscometer.

[0200] The IR4 detector operates in two different wavelength bands (CH3 stretching vibration, centered at approximately 2960 cm⁻¹). -1 (at the location) and CH stretching vibration (2700 to 3000 cm) -1 A multi-wavelength detector is used to measure IR absorbance at two different wavelengths. The IR absorbance at these two different wavelengths is used to determine the concentration and ethylene content in ethylene-propylene copolymers. The IR4 detector is calibrated with a series of eight EP copolymers having known ethylene contents ranging from 2% to 69% by weight (via...). 13 (Determined by C-NMR spectroscopy), and each EP copolymer had multiple concentrations between 2 and 13 mg / ml. To simultaneously capture both characteristics of the various polymer concentrations expected during Crystex analysis—concentration and ethylene content—the following calibration equation was applied:

[0201] Concentration = a + b * absorbance (CH) + c * (absorbance (CH))² + d * absorbance (CH3) + e * (absorbance (CH3)² + f * absorbance (CH) * absorbance (CH3) (Equation 1)

[0202] CH3 / 1000C=a+b*absorbance(CH)+c*absorbance(CH3)+d*(absorbance(CH3) / absorbance(CH))+e*(absorbance(CH3) / absorbance(CH))2 (Equation 2)

[0203] The constants a to e in equation 1 and the constants a to f in equation 2 are determined using least squares regression analysis.

[0204] Use the following relationship to convert CH3 / 1000C to ethylene content in weight percent:

[0205] Weight % (ethylene in EP copolymer) = 100 - CH3 / 1000TC * 0.3 (Equation 3)

[0206] The amounts of soluble fraction (SF) and crystalline fraction (CF) were correlated, via XS calibration, with the amounts of "cold soluble xylene" (XCS) and cold insoluble xylene (XCI) fractions determined according to standard gravimetric analysis in accordance with ISO 16152. XS calibration was achieved by testing various EP copolymers with XS contents ranging from 2% to 31% by weight. The determined XS calibration was linear.

[0207] Weight % XS = 1.01 * Weight % SF (Equation 4)

[0208] The intrinsic viscosity (IV) of the parent EP copolymer and its soluble and crystalline fractions was determined using an online 2-capillary viscometer and correlated with the corresponding IV determined according to ISO 1628-3 in decahydronaphthalene by a standard method. Calibration was performed using various EP-PP copolymers with IV values ​​ranging from 2 to 4 dL / g. The determined calibration curves were linear.

[0209] IV(dL / g)=a*Vsp / c (Equation 5)

[0210] Weigh out the sample to be analyzed at a concentration of 10 mg / ml to 20 mg / ml. To avoid injecting possible gels and / or polymers, such as PET and PA, that are insoluble in TCB at 160°C, load the weighed sample into a stainless steel mesh MW 0.077 / D 0.05 mm.

[0211] After autofilling vials with 1,2,4-TCB containing 250 mg / L of 2,6-tert-butyl-4-methylphenol (BHT) as an antioxidant, the sample was dissolved at 160 °C until complete dissolution, typically for 60 min, with continuous stirring at 400 rpm. To prevent sample degradation, the polymer solution was covered with an N2 atmosphere during the dissolution process.

[0212] A defined volume of sample solution was injected into a column packed with an inert support, where crystallization and separation of the soluble fraction from the crystalline fraction were performed. This process was repeated twice. During the first injection, the entire sample was measured at high temperature, and the IV [dl / g] and C2 [wt%] of the PP composition were determined. During the second injection, the soluble fraction (at low temperature) and the crystalline fraction (CF) (at high temperature) were measured using a crystallization cycle (wt% SF, wt% C2, IV).

[0213] Intrinsic viscosity

[0214] Intrinsic viscosity (iV) was measured at 135°C in decahydronaphthalene according to DIN ISO 1628 / 1, October 1999.

[0215] melt flow rate

[0216] Melt flow rate (MFR) is determined according to ISO 1133 and expressed in g / 10 min. MFR indicates the flowability of a polymer and therefore its processability. A higher melt flow rate generally indicates a lower polymer viscosity. The MFR2 for polypropylene was determined at 230°C and a load of 2.16 kg.

[0217] Xylene-soluble fraction at room temperature (XCS, wt%)

[0218] The amount of polymer soluble in xylene was determined at 25°C according to ISO 16152; 5th edition; 2005-07-01.

[0219] DSC analysis, melting temperature (T) m ) and heat of fusion (H f ), crystallization temperature (T) c ) and heat of crystallization (H c )

[0220] These properties were measured using a TA Instrument Q200 differential scanning calorimeter (DSC) on samples ranging from 5 to 7 mg. The DSC was operated according to ISO 11357 / Part 3 / Method C2 with heating / cooling / heating cycles at a temperature range of -30 to +225 °C and a scan rate of 10 °C / min. Crystallization temperature (T c ) and crystallization enthalpy (Hc The melting temperature (T) is determined by the cooling step, while the melting temperature (T) is determined by the cooling step. m ) and enthalpy of fusion (H m The result was determined by the second heating step.

[0221] Flexural modulus

[0222] The flexural modulus is determined according to ISO 178 Method A (3-point bending test) at a depth of 80mm × 10mm × 4mm (i.e., 80 × 10 × 4mm). 3 The measurements were taken on the specimen. According to the standard, a test speed of 2 mm / min and a span length of 16 times the thickness were used. The test temperature was 23 ± 2 °C. Injection molding was performed according to ISO 19069-2, and a melt temperature of 230 °C was used for all materials, regardless of the material melt flow rate.

[0223] Notched impact strength (NIS)

[0224] The notched impact strength (NIS) of a simply supported beam is determined according to ISO 179 1eA at +23°C or -20°C using an 80×10×4mm beam prepared according to ISO 19069-2. 3 The measurements were taken from injection-molded test bar specimens, and a melting temperature of 230°C was used for all materials, regardless of the material melt flow rate.

[0225] Haze

[0226] The haze was measured according to ASTM D1003-00 on a cast film with a thickness of 50 μm, which was produced on a single-layer cast film production line with a melting temperature of 220°C and a cooling roll temperature of 20°C, as described below.

[0227] tensile modulus

[0228] The tensile modulus in both the longitudinal (MD) and transverse (TD) directions was determined according to ISO 527-3 at 23°C on a 50 μm thick cast film produced on a single-layer cast film production line with a melt temperature of 220°C and a cooling roll temperature of 20°C, as described below. Tests were conducted at a crosshead speed of 1 mm / min until the yield strength and at a crosshead speed of 10 mm / min until the specimen broke.

[0229] Sealing start temperature (SIT)

[0230] This method is used to determine the sealing window (sealing temperature range) of a membrane. The procedure is similar to hot viscous measurement, but compared to hot viscous measurement, the sealing range applies to the strength of the seal (or closure) after cooling (with a delay time of 30 seconds).

[0231] Sealing range = (Sealing start temperature to sealing end temperature)

[0232] The test results provide users with a quantitative and useful indication of the strength of the sealing film and show the temperature range for optimal sealing.

[0233] The temperature interval is set to 5°C by default, but when the curve shows a sharp increase or decrease in force between two temperature steps, the temperature interval can be reduced to 1°C to represent a better curve profile.

[0234] Unlike ASTM F1921-12, the test parameters for sealing pressure, cooling time, and test speed were modified. The force / temperature profile was continued until membrane thermal failure. In addition to the failure mode assessments described in the standard, other failure modes were used.

[0235] To characterize the material, the measured values ​​of the sealing range start temperature (SIT), the temperature at maximum force (MAX), and the sealing range end temperature (SET) were also determined.

[0236] Standard conditions:

[0237] Adjustment time: >96h

[0238] Jaw sealing dimensions: 50×5mm

[0239] Sealing opening shape: flat

[0240] Sealing coating: Niptef

[0241] Sealing temperature: ambient temperature -240℃

[0242] Sealing temperature interval: 5℃

[0243] Sealing time: 1s

[0244] Delay time: 30s

[0245] Sealing pressure: 0.4 N / mm 2 (PE); 0.67 N / mm² (PP)

[0246] Fixture separation rate: 42mm / s

[0247] Sealing starting force: 5N

[0248] Sample width: 25mm

[0249] result:

[0250] The output of this method is a sealing curve.

[0251] The lower limit (seal initiation temperature - SIT) is the minimum sealing temperature at which a sealing force of at least 5 N is achieved.

[0252] 2. Example

[0253] 2.1 Synthesis of multiphase propylene-ethylene copolymer (HECO)

[0254] The catalyst used in the multiphase copolymers (HECO1 and HECO2) of the present invention is trans-dimethylsilyl[2-methyl-4,8-bis(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-symmetric-indarsen-1-yl][2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride, as disclosed as ICS3 in WO 2020 / 239598 A1.

[0255] Preparation of MAO-silica carrier

[0256] The steel reactor, equipped with a mechanical stirrer and filter, was flushed with nitrogen, and the reactor temperature was set to 20°C. Next, 5.0 kg of pre-calcined silica (DM-L-303) from AGC Si-Tech, calcined at 600°C, was added to the feed tank, followed by careful pressurization and depressurization with nitrogen using a manual valve. Then, 22 kg of toluene was added. The mixture was stirred for 15 min. Next, a 30% by weight solution (9.0 kg) of MAO from Lanxess in toluene was added through the feed line at the top of the reactor over 70 min. The reaction mixture was then heated to 90°C and stirred at 90°C for another two hours. The slurry was allowed to settle, and the mother liquor was filtered off. The catalyst was washed twice with toluene (22 kg) at 90°C, followed by settling and filtration. The reactor was cooled to 60°C, and the solids were washed with heptane (22.2 kg). Finally, the MAO-treated SiO2 was dried at 60°C under a nitrogen atmosphere for 2 hours, and then dried under vacuum (-0.5 bar, gauge pressure) with stirring for 5 hours. The MAO-treated support was collected as a free-flowing white powder, which was found to contain 12.2% Al by weight.

[0257] Catalyst preparation

[0258] At 20°C, 30% by weight of MAO (0.7 kg) in toluene was added via burette into a nitrogen-covered steel reactor. Then, toluene (5.4 kg) was added with stirring. The catalyst (93 g) as described above was added from a metal container, followed by rinsing with 1 kg of toluene. The mixture was stirred at 20°C for 60 minutes. Then, triphenylmethyl tetratetra(pentafluorophenyl)borate (91 g) was added from a metal container, followed by rinsing with 1 kg of toluene. The mixture was stirred at room temperature for 1 hour. The resulting solution was added over 1 hour to a stirred cake of MAO-silica support prepared as described above. The cake was left to stand for 12 hours, then dried at 60°C under a nitrogen stream for 2 hours, and further dried under vacuum (-0.5 bar, gauge pressure) with stirring for an additional 5 hours. The dried catalyst was sampled as a pink, free-flowing powder containing 13.9% Al and 0.11% Zr.

[0259] For the polymerization process of HECO3, the inventive embodiment for WO 2016 / 066446 A1 is used and prepolymerized with vinylcyclohexane to achieve a Ziegler-Natta type catalyst with poly(vinylcyclohexane) nucleation.

[0260] For the polymerization process of HECO4, the same catalyst is used, except that prepolymerization with vinylcyclohexane is not performed (i.e., only the catalyst used in the inventive examples of WO 2016 / 066446 A1 is used).

[0261] Nucleation via prepolymerization with vinylcyclohexane is described in detail in EP 2 960 256 B1 and EP 2 960 279 B1. Dicyclopentyldimethoxysilane (donor D) is used as an external donor, and triethylaluminum (TEAL) is used as a cocatalyst for both HECO3 and HECO4.

[0262] Subsequent aggregation is performed under the following conditions:

[0263] Table 1 Polymerization conditions for HECO

[0264]

[0265] Multiphase propylene-ethylene copolymers were compounded in a Coperion ZSK 47 twin-screw extruder at 220°C.

[0266] HECO1 and HECO2 are each blended with 2000 ppm of Irganox 225 (a 1:1 blend of pentaerythritol tetrakis(3-(3',5'-di-tert-butyl-4-hydroxytolyl)propionate and tris(2,4-di-tert-butylphenyl) phosphite) supplied by BASF AG, Germany, and 1000 ppm of calcium stearate supplied by Croda, UK.

[0267] HECO3 was blended with 1250 ppm of calcium cis-1,2-cyclohexanedicarboxylate (HyperformHPN-20E supplied by Milliken, USA), 2000 ppm of Irganox 225 (a 1:1 blend of pentaerythritol tetrakis(3-(3',5'-di-tert-butyl-4-hydroxytolyl)propionate and tris(2,4-di-tert-butylphenyl) phosphite supplied by BASF AG, Germany) and 1000 ppm of calcium stearate supplied by Croda, UK.

[0268] HECO4 was blended with 2000 ppm of Irganox 225 (a 1:1 blend of pentaerythritol tetrakis(3-(3',5'-di-tert-butyl-4-hydroxytolyl)propionate and tris(2,4-di-tert-butylphenyl) phosphite) supplied by BASF AG, Germany, 1000 ppm of calcium stearate supplied by Croda, UK, and Trigonox 101, a viscosity-reducing cracking agent supplied by Nouryon, Germany, which has the effect of reducing polymer viscosity and cracking to an MFR2 of 1.30 g / 10 min.

[0269] The performance of the pellets given in Table 1 was measured on pellets that included additives and post-vis-break (for HECO4).

[0270] 2.2 Synthesis of propylene-butene random copolymer (RACO)

[0271] The catalyst used in the polymerization process of propylene-butene random copolymer composition (RACO) is prepared as follows:

[0272] Metallocene MC1 (racemic-trans-dimethylsilyl(2-methyl-4-phenyl-5-methoxy-6-tert-butyl-indenyl)(2-methyl-4-(4-tert-butylphenyl)indenyl)zirconium dichloride) has been synthesized as described in WO 2013 / 007650.

[0273] According to Catalyst 3 of WO 2015 / 11135, a catalyst was prepared using a catalyst system of metallocene MC1, MAO, and triphenylmethyl tetra(pentafluorophenyl)borate, under the condition that the surfactant was 2,3,3,3-tetrafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)-1-propanol.

[0274] Table 2 Polymerization conditions for RACO

[0275]

[0276] 2.3 Blending of Embodiments and Comparative Examples of the Invention

[0277] The multiphase polypropylene composition of the present invention and the comparative composition CE1 were compounded in a Coperion ZSK 47 co-rotating twin-screw extruder at 220°C according to the formulations in Table 3. CE2 and CE3 were used without any further compounding steps.

[0278] The properties of the resulting compositions are also given in Table 3.

[0279] NU is ADK STAB NA-71 supplied by ADEKA Polymer Additives Europe, Germany. A is a combination of 1500 ppm Irganox B215 (a 1:2 blend of pentaerythritol tetrakis(3-(3',5'-di-tert-butyl-4-hydroxytolyl)propionate and tris(2,4-di-tert-butylphenyl) phosphite) supplied by BASF AG, Germany, and 500 ppm of synthetic hydrotalcite Hycite 713 supplied by BASF AG, Germany.

[0280] The 50μm cast film was produced on Collin's laboratory-scale cast film production line at a melting temperature of 250°C and a cooling temperature of 60°C. The output rate was 8 kg / h.

[0281] Table 3 Formulations and properties of the multiphase polypropylene compositions of the present invention and comparative multiphase polypropylene compositions.

[0282]

[0283] n / m = Unmeasurable

[0284] As can be seen from the data in Table 3, the composition of the present invention, which is a combination of multiphase propylene-ethylene copolymer (HECO) and propylene-butene random copolymer (RACO), exhibits very advantageous properties, especially when forming a cast film.

[0285] The haze value of the cast film is much lower than that of the comparative example (even without the use of a nucleating agent – ​​see IE3), which represents the typical level used in the art for this purpose. Furthermore, embodiments of the invention generally exhibit lower SIT, meaning there is a favorable high Tm-SIT gap. This is particularly useful when seeking to seal with the film of the invention but also to avoid film degradation / deformation due to proximity to the melting temperature.

[0286] In summary, the compositions of the present invention have improved optical / sealing properties when used in membranes, while maintaining useful mechanical properties.

Claims

1. A multiphase polypropylene composition (PC), comprising: i) 40.0 to 90.0% by weight of a multiphase propylene-ethylene copolymer (HECO) relative to the total weight of the multiphase polypropylene composition (PC), said multiphase propylene-ethylene copolymer (HECO) having a melt flow rate (MFR2) in the range of 1.0 to 5.0 g / 10 min, determined according to ISO 1133 at 230 °C under a load of 2.16 kg, and a melt temperature (T) in the range of 149 to 160 °C, determined by differential scanning calorimetry (DSC). m The multiphase propylene-ethylene copolymer (HECO) comprises: a) A crystalline matrix (M) of propylene homopolymer, said crystalline matrix (M) having a molecular weight distribution in the range of 0.05 to 1.40 mol% by quantitative analysis. 13 The defect content in the 2,1-region was determined by C-NMR spectroscopy; and b) Amorphous propylene-ethylene elastomer (E); The multiphase propylene-ethylene copolymer (HECO) is characterized by its soluble fraction (SF) and crystalline fraction (CF) as determined by CRYSTEX QC analysis: i. A crystalline fraction (CF) of 60.0 to 95.0% by weight of the total weight of the multiphase propylene-ethylene copolymer (HECO), said crystalline fraction (CF) having an ethylene content (C2) determined by quantitative IR spectroscopy in the range of 0.0 to 2.0% by weight; and ii. A soluble fraction (SF) of 5.0 to 40.0% by weight of the total weight of the multiphase propylene-ethylene copolymer (HECO), the soluble fraction (SF) having an ethylene content C2 (SF) determined by quantitative IR spectroscopy in the range of 12.0 to 40.0% by weight. ii) 10.0 to 60.0% by weight of propylene-butene random copolymer (RACO) relative to the total weight of the multiphase polypropylene composition (PC), said propylene-butene random copolymer (RACO) having a melt flow rate (MFR2) in the range of 0.5 to 15.0 g / 10 min, determined according to ISO 1133 at 230 °C under a load of 2.16 kg, and a permeability in the range of 1.0 to 10.0% by weight. 13 1-Butene content determined by C-NMR spectroscopy; iii) optionally, 0.0001 to 1.0% by weight of nucleating agent (NU) relative to the total weight of the multiphase polypropylene composition (PC); and iv) Optional 0.1 to 5.0% by weight of other additives (A) different from the nucleating agent (NU).

2. The multiphase polypropylene composition (PC) according to claim 1, wherein the soluble fraction (SF) of the multiphase propylene-ethylene copolymer (HECO) as analyzed according to CRYSTEX QC has an intrinsic viscosity (iV(SF)) in the range of 1.00 to 4.00 dL / g, as determined according to DIN ISO 1628 / 1, October 1999, in decahydronaphthalene at 135°C, and / or The crystalline fraction (CF) of the multiphase propylene-ethylene copolymer (HECO) analyzed according to CRYSTEX QC has an intrinsic viscosity (iV(CF)) in the range of 1.00 to 4.00 dL / g, as determined in DIN ISO 1628 / 1, October 1999, at 135°C in decahydronaphthalene.

3. The multiphase polypropylene composition (PC) according to claim 1, wherein the multiphase propylene-ethylene copolymer (HECO) has a content in the range of 1.5 to 9.0% by weight, determined by quantitative analysis. 13 Ethylene content (C2) determined by quantitative FT-IR spectroscopy calibrated by C-NMR spectroscopy.

4. The multiphase polypropylene composition (PC) according to claim 1, wherein the propylene-butene random copolymer (RACO) has a melting temperature (T0) determined by differential scanning calorimetry (DSC) in the range of 120 to 145°C. m ), and / or by quantitative means in the range of 0.05 to 1.40 mol%. 13 The content of defects in the 2,1- region was determined by C-NMR spectroscopy.

5. The multiphase polypropylene composition (PC) according to claim 1, wherein the propylene-butene random copolymer (RACO) has a xylene cold solubles (XCS) content in the range of 0.1 to 10.0% by weight, as determined according to ISO 16152.

6. The multiphase polypropylene composition (PC) according to claim 1, having a melt flow rate (MFR2) in the range of 1.0 to 10.0 g / 10 min, determined according to ISO 1133 at 230 °C under a load of 2.16 kg.

7. The multiphase polypropylene composition (PC) according to claim 1, having a content in the range of 1.0 to 5.0% by weight, obtained by quantitative analysis. 13 Ethylene content (C2) determined by C-NMR spectroscopy, and / or The quantitative range is from 1.0% to 5.0% by weight. 13 The 1-butene content (C4) was determined by C-NMR spectroscopy.

8. The multiphase polypropylene composition (PC) according to claim 1, having a xylene cold solubles (XCS) content in the range of 5.0 to 20.0% by weight, as determined according to ISO 16152.

9. The multiphase polypropylene composition (PC) according to claim 1, having a crystallization temperature (Tc) determined by differential scanning calorimetry (DSC) in the range of 114.0 to 130.0 °C. c ).

10. The multiphase polypropylene composition (PC) according to claim 1, having a first melting temperature (T0) determined by differential scanning calorimetry (DSC) in the range of 149 to 162°C. m1 ).

11. The multiphase polypropylene composition (PC) according to claim 10, having a second melting temperature (T0) determined by differential scanning calorimetry (DSC) in the range of 125 to 145°C. m2 ).

12. The multiphase polypropylene composition (PC) according to claim 1, having a seal initiation temperature (SIT) measured on a 50 μm cast film sample in the range of 115 to 130 °C.

13. The multiphase polypropylene composition (PC) according to claim 12, wherein the difference between the first melting temperature of the multiphase polypropylene composition (PC) determined by differential scanning calorimetry (DSC) and the sealing initiation temperature (SIT) is in the range of 28 to 40°C.

14. The multiphase polypropylene composition (PC) according to claim 1, having any one of the following properties: a) 80×10×4 mm steel prepared according to ISO 19069-2, within the range of 850 to 2000 MPa. 3 Flexural modulus measured on injection-molded specimens; and b) Between 8.0 and 100 kJ / m 2 Within the range of ISO 179-1 eA, prepared at 23°C according to ISO 19069-2, 80×10×4 mm 3 Notched beam impact strength (NIS) measured on an injection-molded specimen.

15. The multiphase polypropylene composition (PC) according to claim 1, having a haze value in the range of 0.0 to 6.0% as measured according to ASTM D1003 on a 50 μm cast film produced from said multiphase polypropylene composition (PC).

16. A method for producing the multiphase polypropylene composition (PC) according to claim 1, comprising the following steps: a) Provide the multiphase propylene-ethylene copolymer (HECO) according to claim 1, the propylene-butene random copolymer (RACO) according to claim 1, an optional nucleating agent (NU), and optional other additives (A); and b) The multiphase propylene-ethylene copolymer (HECO), the propylene-butene random copolymer (RACO), the optional nucleating agent (NU), and the optional other additives (A) are blended and extruded in an extruder at a temperature in the range of 120 to 250°C to produce the multiphase polypropylene composition (PC).

17. A membrane comprising at least 90% by weight of a multiphase polypropylene composition (PC) according to any one of claims 1 to 15.

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