Hydrogenated styrene farnesene block copolymers as modifiers for polypropylene compositions

Abstract

A heterophasic polypropylene composition (PC) comprising: a) 70.0 to 99.0 wt% of HECO having an MFR2 of 1.0 to 100 g / 10 min, b) 1.0 to 30.0 wt% of a hydrogenated styrene-farnesene block copolymer (HSFC), c) optionally 0.0001 to 1.0 wt% of one or more nucleating agents (NU), and d) optionally 0.01 to 5.0 wt% of one or more additional additives (A) different from the one or more nucleating agents (NU).

Description

Technical Field

[0001] This invention relates to a multiphase polypropylene composition comprising a multiphase propylene-ethylene copolymer and a hydrogenated styrene-farnesene block copolymer, articles containing the multiphase polypropylene composition, and the use of the hydrogenated styrene-farnesene block copolymer as a modifier of polypropylene to improve haze, Charpy notched impact strength, and / or dart impact strength. Background Technology

[0002] Polypropylene is widely used in a variety of applications, such as packaging and films. One strategy for minimizing the impact of polypropylene waste is to use polypropylene compositions suitable for recycling, while other strategies include reducing the initial amount of polypropylene used and / or ensuring that polypropylene articles are reusable, both of which significantly reduce reliance on complex recycling infrastructure. To ensure that the principles of “reduction” and “reuse” can be implemented, it is crucial to develop compositions with improved properties, particularly mechanical and optical properties. This allows for thinner films / molded articles (which helps reduce the amount of polypropylene used) and enables the resulting articles to maintain their shape and properties in subsequent applications.

[0003] In addition, the use of bio-based polymers (such as bio-based polymers derived from plant materials) is also attractive because it avoids the depletion of oil resources and is a renewable raw material that does not increase net carbon dioxide emissions into the atmosphere.

[0004] As is well known, styrene-based elastomers, such as styrene-ethylene-butene block copolymers (SEBS), can be used as modifiers to improve the properties of polypropylene compositions, which have been described in WO2013 / 144060A1, WO2020 / 221706A1 and WO2020 / 245251A2.

[0005] Despite these promising advances, further improvements are still needed to achieve the best possible performance, and alternative modifiers derived from bio-based feedstocks are particularly attractive. Summary of the Invention

[0006] This invention is based on the discovery that hydrogenated styrene-farnesene block copolymers can be used as modifiers for polypropylene, thereby improving various properties of the polymer while reducing the content of olefin derivatives (and thus crude oil derivatives) in the resulting compositions.

[0007] In a first aspect, the present invention relates to a multiphase polypropylene composition (PC) comprising:

[0008] a) 70.0 to 99.0 wt% of a multiphase propylene-ethylene copolymer (HECO) relative to the total weight of the multiphase polypropylene composition (PC), wherein the multiphase propylene-ethylene copolymer (HECO) has a melt flow rate (MFR2) of 1.0 to 100 g / 10 min as determined according to ISO 1133 at 230 °C and 2.16 kg, the multiphase propylene-ethylene copolymer (HECO) comprising:

[0009] i) a crystalline matrix (M), wherein the crystalline matrix (M) is a propylene homopolymer or copolymer; and

[0010] ii) Amorphous propylene-ethylene elastomers (E);

[0011] b) 1.0 to 30.0 wt% hydrogenated styrene farnesene block copolymer (HSFC) relative to the total weight of the multiphase polypropylene composition (PC).

[0012] c) Optionally, 0.0001 to 1.0 wt% of one or more nucleating agents (NU) relative to the total weight of the multiphase polypropylene composition (PC); and

[0013] d) Optionally, 0.01 to 5.0 wt% of one or more other additives (A) different from the said one or more nucleating agents (NU) relative to the total weight of the multiphase polypropylene composition (PC).

[0014] In a second aspect, the present invention relates to articles, more preferably films or molded articles, comprising at least 90 wt%, more preferably at least 95 wt%, and most preferably at least 98 wt% of the multiphase polypropylene composition (PC) described in the first aspect.

[0015] In a third aspect, the present invention relates to the use of a hydrogenated styrene-farnesene block copolymer (HSFC) for improving the Charpy notched impact strength (NIS(23)) of a polypropylene composition, said Charpy notched impact strength (NIS(23)) being 80 × 10 × 4 mm prepared according to ISO 19069-2 at 23°C, according to ISO 179-1eA. 3 The polypropylene composition was obtained by blending polypropylene (more preferably, according to the first aspect, a multiphase propylene-ethylene copolymer (HECO)) with 1.0 to 30.0 wt% of hydrogenated styrene-farnesene block copolymer (HSFC) as measured on injection-molded specimens.

[0016] In a fourth aspect, the present invention relates to the use of a hydrogenated styrene-farnesene block copolymer (HSFC) for improving the haze of a polypropylene composition obtained by blending polypropylene (more preferably, a multiphase propylene-ethylene copolymer (HECO) according to the first aspect) with 1.0 to 30.0 wt% of the hydrogenated styrene-farnesene block copolymer (HSFC).

[0017] In a fifth aspect, the present invention relates to the use of a hydrogenated styrene-farnesene block copolymer (HSFC) for improving the dart impact strength (DDI) of a polypropylene composition obtained by blending polypropylene (more preferably, a multiphase propylene-ethylene copolymer (HECO) according to the first aspect) with 1.0 to 30.0 wt% of the hydrogenated styrene-farnesene block copolymer (HSFC), wherein the dart impact strength (DDI) is determined according to ISO 7765-1 on a 50 µm blown film sample.

[0018] definition

[0019] 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. While 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 in accordance with the definitions listed below.

[0020] Unless otherwise expressly stated, the terms “a”, “an”, etc., are used to refer to one or more.

[0021] Unless otherwise stated, all contents are expressed as weight percentage (wt%).

[0022] Propylene homopolymers are polymers that consist essentially of propylene monomer units. Due to the presence of impurities (especially those present 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.

[0023] Propylene random copolymers are copolymers composed of propylene monomer units and comonomer units (preferably selected from ethylene and C4-C8 α-olefins), wherein the comonomer units are randomly distributed along the polymer chain. Propylene random copolymers may contain comonomer units from one or more comonomers with different numbers of carbon atoms.

[0024] Multiphase propylene copolymers typically contain:

[0025] a) A matrix of crystalline propylene homopolymer or crystalline propylene copolymer (M); and

[0026] b) Elastomer rubber, preferably propylene-ethylene copolymer (E).

[0027] For random multiphase propylene copolymers, the crystalline matrix phase is a random copolymer of propylene and at least one α-olefin comonomer.

[0028] The elastomeric phase can be a propylene copolymer containing a large amount of comonomers, which are not randomly distributed in the polymer chain but are distributed in both comonomer-rich block structures and propylene-rich block structures. The difference between multiphase polypropylene and single-phase propylene copolymers is usually that they exhibit two different glass transition temperatures (Tg), which are attributed to the matrix phase and the elastomeric phase.

[0029] The present invention will now be described in more detail. Detailed Implementation

[0030] The first aspect of the present invention relates to a multiphase polypropylene composition (PC) comprising:

[0031] a) Multiphase propylene-ethylene copolymer (HECO);

[0032] b) Hydrogenated styrene-farnesene block copolymer (HSFC);

[0033] c) Optionally, one or more nucleating agents (NU); and

[0034] d) One or more other additives (A) that may be different from the one or more nucleating agents (NU).

[0035] Multiphase propylene-ethylene copolymer (HECO)

[0036] An essential component of the multiphase polypropylene composition (PC) is the multiphase propylene-ethylene copolymer (HECO).

[0037] The content of multiphase propylene-ethylene copolymer (HECO) is set to 70.0 to 99.0 wt%, more preferably 80.0 to 97.0 wt%, and most preferably 85.0 to 95.0 wt%, relative to the total weight of the multiphase polypropylene composition (PC).

[0038] The melt flow rate (MFR2) of the multiphase propylene-ethylene copolymer (HECO) measured according to ISO 1133 at 230 °C and 2.16 kg is 1.0 to 100 g / 10 min, more preferably 1.3 to 20 g / 10 min, and most preferably 1.5 to 5.0 g / 10 min.

[0039] Multiphase propylene-ethylene copolymers (HECOs) can be characterized using trichlorobenzene (TCB) as a solvent according to the CRYSTEX QC method. This method will be described in the determination method section below. The crystalline fraction (CF) contains the majority of the matrix phase and only a small portion of the elastomer phase; the soluble fraction (SF) contains the majority of the elastomer phase and only a small portion of the matrix phase. In some cases, this method yields more useful data (e.g., compared to methods based on xylene cold dissolution) because the crystalline fraction (CF) and soluble fraction (SF) more accurately correspond to the matrix phase and elastomer phase, respectively. Due to the different separation methods used in the xylene extraction method and the CRYSTEX QC method, the properties of the XCS / XCI fraction of the former and the crystalline / soluble (CF / SF) fraction of the latter are not entirely the same, meaning that the amounts and properties of the matrix phase and the elastomer phase may differ.

[0040] Multiphase propylene-ethylene copolymer (HECO) is obtained through quantitative analysis. 13 The ethylene content (C2 (total)) determined by FT-IR spectroscopy calibrated by C-NMR spectroscopy is preferably 0.3 to 8.0 wt%, more preferably 0.5 to 5.0 wt%, and most preferably 1.0 to 2.5 wt%.

[0041] The soluble fraction (SF) content of the multiphase propylene-ethylene copolymer (HECO) as determined by CRYSTEM QC analysis is preferably 5.0 to 40.0 wt%, more preferably 6.0 to 20.0 wt%, and most preferably 7.0 to 10.0 wt%.

[0042] Multiphase propylene-ethylene copolymer (HECO) was analyzed by CRYSTEX QC using quantitative methods. 13 The ethylene content (C2(SF)) of the soluble fraction determined by FT-IR spectroscopy calibrated by C-NMR spectroscopy is preferably 10.0 to 90.0 wt%, more preferably 15.0 to 50.0 wt%, and most preferably 20.0 to 30.0 wt%.

[0043] The intrinsic viscosity (iV(SF)) of the soluble fraction of the multiphase propylene-ethylene copolymer (HECO), as determined by CRYSTEX QC analysis, is preferably 1.20 to 5.00 dL / g, more preferably 1.50 to 3.50 dL / g, and most preferably 2.00 to 3.00 dL / g.

[0044] The content of crystal fraction (CF) in the multiphase propylene-ethylene copolymer (HECO) as determined by CRYSTEX QC analysis is preferably 60.0 to 95.0 wt%, more preferably 80.0 to 94.0 wt%, and most preferably 90.0 to 93.0 wt%.

[0045] Multiphase propylene-ethylene copolymer (HECO) was analyzed by CRYSTEX QC using quantitative methods. 13 The ethylene content (C2(CF)) of the crystallization fraction determined by FT-IR spectroscopy calibrated by C-NMR spectroscopy is preferably 0.0 to 5.0 wt%, more preferably 0.0 to 3.0 wt%, and most preferably 0.0 to 1.0 wt%.

[0046] The intrinsic viscosity (iV(CF)) of the crystalline fraction of the multiphase propylene-ethylene copolymer (HECO) as determined by CRYSTEX QC analysis is preferably 1.50 to 5.00 dL / g, more preferably 2.00 to 3.50 dL / g, and most preferably 2.30 to 2.80 dL / g.

[0047] The intrinsic viscosity (iV) of the multiphase propylene-ethylene copolymer (HECO) as determined by CRYSTEM QC analysis is preferably 1.50 to 5.00 dL / g, more preferably 2.00 to 3.50 dL / g, and most preferably 2.30 to 2.80 dL / g.

[0048] The melting temperature (T0) of multiphase propylene-ethylene copolymer (HECO) determined by differential scanning calorimetry (DSC) m The temperature is preferably 149 to 160 °C, more preferably 151 to 159 °C, and most preferably 153 to 158 °C.

[0049] The relevant enthalpy of fusion (Hc) of multiphase propylene-ethylene copolymer (HECO) determined by differential scanning calorimetry (DSC) m The preferred concentration is 50 to 120 J / g, more preferably 70 to 110 J / g, and most preferably 90 to 100 J / g.

[0050] The crystallization temperature (Tc) of multiphase propylene-ethylene copolymer (HECO) determined by differential scanning calorimetry (DSC) c The temperature is preferably 110 to 130 °C, more preferably 117 to 129 °C, and most preferably 124 to 128 °C.

[0051] The first glass transition temperature (T0) of multiphase propylene-ethylene copolymer (HECO) as determined according to ISO 6721-7 g1 The preferred temperature is -60 to -35 °C, more preferably -50 to -37 °C, and most preferably -45 to -40 °C.

[0052] The second glass transition temperature (T2) of multiphase propylene-ethylene copolymer (HECO) as determined according to ISO 6721-7 g2 The temperature is preferably -5 to +5 °C, more preferably -2 to +3 °C, and most preferably 0 to +2 °C.

[0053] Multiphase propylene-ethylene copolymer (HECO) comprises:

[0054] i) a crystalline matrix (M), said crystalline matrix being a propylene homopolymer or a propylene copolymer; and

[0055] ii) Amorphous propylene-ethylene elastomers (E);

[0056] The preferred crystallization matrix is ​​a homopolymer.

[0057] The melt flow rate (MFR) of the matrix component (M) was determined according to ISO 1133 at 230 °C and 2.16 kg. M The preferred concentration is 1.0 to 100 g / 10 min, more preferably 1.3 to 20 g / 10 min, and most preferably 1.5 to 5.0 g / 10 min.

[0058] The matrix component (M) of the crystallization was quantitatively determined. 13 The defect content in the 2,1-region, as determined by C-NMR spectroscopy, is preferably 0.05 to 1.20 mol%, more preferably 0.20 to 1.00 mol%, and most preferably 0.40 to 0.80 mol%. These ranges are typical for polypropylene polymerized using metallocene catalysts.

[0059] Preferably, the multiphase propylene-ethylene copolymer (HECO) is polymerized in the presence of a single-point catalyst (more preferably a metallocene catalyst).

[0060] Hydrogenated styrene-farnesene block copolymer (HSFC)

[0061] Another essential component of the multiphase polypropylene composition (PC) is hydrogenated styrene farnesene block copolymer (HSFC).

[0062] The content of hydrogenated styrene farnesene block copolymer (HSFC) is set to 1.0 to 30.0 wt%, more preferably 3.0 to 20.0 wt%, and most preferably 5.0 to 15.0 wt%, relative to the total weight of the multiphase polypropylene composition (PC).

[0063] The melt flow rate (MFR) of hydrogenated styrene-farnesene block copolymer (HSFC) was determined according to ISO 1133 at 230°C and 10 kg. 10 The preferred concentration is 1.0–1000 g / 10 min, more preferably 1.0–100 g / 10 min, and most preferably 20–100 g / 10 min.

[0064] The hydrogenated styrene farnesene block copolymer (HSFC) has a Shore A hardness of 3 to 30, more preferably 5 to 23, and most preferably 7 to 15, as determined by ISO 868.

[0065] The styrene content of the hydrogenated styrene-farnesene block copolymer (HSFC) as determined by quantitative FT-IR spectroscopy is preferably 1.0 to 35.0 wt%, more preferably 10.0 to 27.0 wt%, and most preferably 15.0 to 20.0 wt%, relative to the total weight of the HSFC.

[0066] One or more nucleating agents (NU)

[0067] Optional components of the multiphase polypropylene composition (PC) are one or more nucleating agents (NU).

[0068] In the presence of one or more nucleating agents (NU), the content of one or more nucleating agents (NU) is set to 0.0001 to 1.0 wt% relative to the total weight of the multiphase polypropylene composition (PC), more preferably 0.001 to 0.50 wt%, and most preferably 0.01 to 0.30 wt%.

[0069] In a broad sense, each nucleating agent can be any nucleating agent suitable for polypropylene nucleation. More preferably, one or more nucleating agents (NU) are α-nucleating agents.

[0070] More preferably, at least one of the one or more α-nucleating agents (NU) is a particulate α-nucleating agent, more preferably a particulate α-nucleating agent comprising a compound having a phosphate group.

[0071] Preferably, at least one of one or more α-nucleating agents (NU) comprises having the structure [(Ar 1 O)(Ar 2 O)(O=)PO] n The particulate α-nucleating agent of compound X, wherein:

[0072] Ar 1 and Ar 2 Each is independently selected from phenyl groups substituted with one or more C1 to C6 straight-chain alkyl or branched-chain alkyl groups, wherein Ar 1 and Ar 2 It can also be linked by a direct single bond, an oxygen atom, or a C1 to C6 alkylene group;

[0073] n is 1 or 2. If n=1, then X is selected from Li, Na, K and Al(OH)2. If n=2, then X is selected from Mg, Ca and Al(OH).

[0074] More preferably, at least one of the one or more α-nucleating agents (NU) is a particulate α-nucleating agent comprising a compound selected from: sodium bis(4-tert-butylphenyl) phosphate, sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate, lithium 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate and hydroxybis[2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate aluminum].

[0075] Most preferably, at least one of one or more α-nucleating agents (NU) comprises lithium 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate.

[0076] Those skilled in the art will understand that such particulate α-nucleating agents can exist as a single compound or as a particulate blend. One particulate blend containing lithium 2,2'-methylene-bis-(4,6-di-tert-butylphenyl)phosphate as the main component is ADK STAB NA-71, which is available from Adeka.

[0077] One or more other additives (A)

[0078] Another optional component of the multiphase polypropylene composition (PC) is one or more other additives (A) that are different from one or more nucleating agents (NU).

[0079] In the presence of one or more other additives (A), the content of one or more other additives (A) is set to 0.01 to 5.0 wt% relative to the total weight of the multiphase polypropylene composition (PC).

[0080] Selecting suitable additives for multiphase polypropylene (PC) compositions is common knowledge to those skilled in the art.

[0081] For example, one or more other additives (A) may be selected from antioxidants, stabilizers, fillers, colorants and antistatic agents.

[0082] Such additives are generally commercially available and are described, for example, on pages 871-873 of Hans Zweifel's Plastic Additives Handbook (5th edition, 2001).

[0083] It should be understood that, based on the total weight of the multiphase polypropylene composition (PC), the content of additive (A) includes any carrier polymer used to introduce the additive into the multiphase polypropylene composition (PC), i.e., a masterbatch carrier polymer. An example of such a carrier polymer is a polypropylene homopolymer in powder form.

[0084] Multiphase polypropylene composition (PC)

[0085] The multiphase polypropylene composition (PC) comprises, more preferably, the following:

[0086] a) 70.0 to 99.0 wt%, more preferably 80.0 to 97.0 wt%, and most preferably 85.0 to 95.0 wt%, of the multiphase polypropylene composition (PC) relative to the total weight of the composition;

[0087] b) 1.0 to 30.0 wt%, more preferably 3.0 to 20.0 wt%, and most preferably 5.0 to 15.0 wt% of hydrogenated styrene farnesene block copolymer (HSFC) relative to the total weight of the multiphase polypropylene composition (PC).

[0088] c) Optionally, relative to the total weight of the multiphase polypropylene composition (PC), one or more nucleating agents (NU) are present in amounts of 0.0001 to 1.0 wt%, more preferably 0.001 to 0.50 wt%, and most preferably 0.01 to 0.30 wt%; and

[0089] d) Optionally, 0.01 to 5.0 wt% of one or more other additives (A) different from the said one or more nucleating agents (NU) relative to the total weight of the multiphase polypropylene composition (PC).

[0090] In a broad sense, multiphase polypropylene compositions (PC) include:

[0091] a) 70.0 to 99.0 wt%, more preferably 80.0 to 97.0 wt%, and most preferably 85.0 to 95.0 wt%, of the multiphase polypropylene composition (PC) relative to the total weight of the composition.

[0092] b) 1.0 to 30.0 wt%, more preferably 3.0 to 20.0 wt%, and most preferably 5.0 to 15.0 wt% of hydrogenated styrene farnesene block copolymer (HSFC) relative to the total weight of the multiphase polypropylene composition (PC).

[0093] c) Optionally, one or more nucleating agents (NU) are present in an amount of 0.0001 to 1.0 wt%, more preferably 0.001 to 0.50 wt%, and most preferably 0.01 to 0.30 wt%, relative to the total weight of the multiphase polypropylene composition (PC); and

[0094] d) Optionally, 0.01 to 5.0 wt% of one or more other additives (A) different from the said one or more nucleating agents (NU) relative to the total weight of the multiphase polypropylene composition (PC).

[0095] In a preferred embodiment, the multiphase polypropylene composition (PC) comprises, more preferably, the following:

[0096] a) 80.0 to 97.0 wt% of multiphase propylene-ethylene copolymer (HECO) relative to the total weight of the multiphase polypropylene composition (PC);

[0097] b) 3.0 to 20.0 wt% of hydrogenated styrene farnesene block copolymer (HSFC) relative to the total weight of the multiphase polypropylene composition (PC).

[0098] c) Optionally, 0.001 to 0.50 wt% of one or more nucleating agents (NU) relative to the total weight of the multiphase polypropylene composition (PC); and

[0099] d) Optionally, 0.01 to 5.0 wt% of one or more other additives (A) different from one or more nucleating agents (NU) relative to the total weight of the multiphase polypropylene composition (PC).

[0100] In another preferred embodiment, the multiphase polypropylene composition (PC) comprises, more preferably, the following:

[0101] a) 85.0 to 95.0 wt% of multiphase propylene-ethylene copolymer (HECO) relative to the total weight of the multiphase polypropylene composition (PC);

[0102] b) 5.0 to 15.0 wt% hydrogenated styrene farnesene block copolymer (HSFC) relative to the total weight of the multiphase polypropylene composition (PC).

[0103] c) Optionally, 0.01 to 0.30 wt% of one or more nucleating agents (NU) relative to the total weight of the multiphase polypropylene composition (PC); and

[0104] d) Optionally, 0.01 to 5.0 wt% of one or more other additives (A) different from the said one or more nucleating agents (NU) relative to the total weight of the multiphase polypropylene composition (PC).

[0105] In one embodiment, the multiphase polypropylene composition (PC) comprises, more preferably, the following:

[0106] a) 70.0 to 99.0 wt%, more preferably 80.0 to 97.0 wt%, and most preferably 85.0 to 95.0 wt%, of the multiphase polypropylene composition (PC) relative to the total weight of the composition; and

[0107] b) 1.0 to 30.0 wt%, more preferably 3.0 to 20.0 wt%, and most preferably 5.0 to 15.0 wt% of hydrogenated styrene farnesene block copolymer (HSFC) relative to the total weight of the multiphase polypropylene composition (PC).

[0108] In another embodiment, the multiphase polypropylene composition (PC) comprises, more preferably, the following:

[0109] a) 70.0 to 98.9999 wt%, more preferably 80.0 to 96.999 wt%, and most preferably 85.0 to 94.99 wt%, of the multiphase polypropylene composition (PC) relative to the total weight of the composition.

[0110] b) 1.0 to 29.9999 wt%, more preferably 3.0 to 19.999 wt%, and most preferably 5.0 to 14.99 wt% of hydrogenated styrene-farnesene block copolymer (HSFC) relative to the total weight of the multiphase polypropylene composition (PC); and

[0111] c) One or more nucleating agents (NU) in an amount of 0.0001 to 1.0 wt%, more preferably 0.001 to 0.50 wt%, and most preferably 0.01 to 0.30 wt%, relative to the total weight of the multiphase polypropylene composition (PC).

[0112] In another embodiment, the multiphase polypropylene composition (PC) comprises, preferably, the following:

[0113] a) 70.0 to 98.99 wt%, more preferably 80.0 to 96.99 wt%, and most preferably 85.0 to 94.99 wt%, of the multiphase polypropylene composition (PC) relative to the total weight of the composition.

[0114] b) 1.0 to 29.9 wt%, more preferably 3.0 to 19.9 wt%, and most preferably 5.0 to 14.9 wt% of hydrogenated styrene-farnesene block copolymer (HSFC) relative to the total weight of the multiphase polypropylene composition (PC); and

[0115] c) 0.01 to 5.0 wt% of one or more other additives (A) different from one or more nucleating agents (NU) relative to the total weight of the multiphase polypropylene composition (PC).

[0116] In the final embodiment, the multiphase polypropylene composition (PC) comprises, more preferably, the following:

[0117] a) 70.0 to 98.9899 wt%, more preferably 80.0 to 96.989 wt%, and most preferably 85.0 to 94.98 wt%, of the multiphase polypropylene composition (PC) relative to the total weight of the composition.

[0118] b) 1.0 to 29.9899 wt%, more preferably 3.0 to 19.989 wt%, and most preferably 5.0 to 14.89 wt% of hydrogenated styrene farnesene block copolymer (HSFC) relative to the total weight of the multiphase polypropylene composition (PC).

[0119] c) One or more nucleating agents (NUs) in an amount of 0.0001 to 1.0 wt%, more preferably 0.001 to 0.50 wt%, and most preferably 0.01 to 0.30 wt%, relative to the total weight of the multiphase polypropylene composition (PC); and

[0120] d) 0.01 to 5.0 wt% of one or more other additives (A) different from the said one or more nucleating agents (NU) relative to the total weight of the multiphase polypropylene composition (PC).

[0121] In all the above embodiments, the sum of the contents of the multiphase propylene-ethylene copolymer (HECO), the hydrogenated styrene-farnesene block copolymer (HSFC), one or more optional nucleating agents (NU), and other optional additives different from the one or more nucleating agents (NU) is preferably at least 90 wt%, more preferably at least 95 wt%, and even more preferably at least 98 wt%. Most preferably, the multiphase polypropylene composition (PC) consists of the multiphase propylene-ethylene copolymer (HECO), the hydrogenated styrene-farnesene block copolymer (HSFC), one or more optional nucleating agents (NU), and one or more optional additives different from the one or more nucleating agents (NU).

[0122] The melt flow rate (MFR2) of the multiphase polypropylene composition (PC), as determined according to ISO 1133 at 230°C and 2.16 kg, is preferably 1.0 to 100 g / 10 min, more preferably 1.3 to 20 g / 10 min, and most preferably 1.5 to 5.0 g / 10 min.

[0123] The melting temperature (Tm) of multiphase polypropylene (PC) compositions determined by differential scanning calorimetry (DSC) m The temperature is preferably 149 to 160 °C, more preferably 151 to 159 °C, and most preferably 153 to 158 °C.

[0124] The relevant enthalpy of fusion (H2) of multiphase polypropylene (PC) compositions determined by differential scanning calorimetry (DSC)m The preferred concentration is 50 to 120 J / g, more preferably 70 to 105 J / g, and most preferably 85 to 95 J / g.

[0125] The crystallization temperature (T) of multiphase polypropylene (PC) compositions determined by differential scanning calorimetry (DSC) c The temperature is preferably 110 to 130 °C, more preferably 117 to 129 °C, and most preferably 124 to 128 °C.

[0126] The first glass transition temperature (T0) of the multiphase polypropylene composition (PC) as determined according to ISO 6721-7 g1 The preferred temperature is -70 to -55 °C, more preferably -67 to -58 °C, and most preferably -64 to -61 °C.

[0127] The second glass transition temperature (T2) of the multiphase polypropylene composition (PC) as determined according to ISO 6721-7 g2 The temperature is preferably -50 to -34 °C, more preferably -46 to -36 °C, and most preferably -43 to -38 °C.

[0128] The third glass transition temperature (T3) of the multiphase polypropylene composition (PC) as determined according to ISO 6721-7 g3 The temperature is preferably -5 to +5 °C, more preferably -2 to +3 °C, and most preferably 0 to +3 °C.

[0129] The term "first glass transition temperature (T)" g1 "Second glass transition temperature (T)" g2 ")" and "Third glass transition temperature (T)" g3 The phrase "" only indicates that the glass transition temperature of the multiphase polypropylene composition should be within a given range, not that the glass transition temperature within that range must be the first / second / third highest or the first / second / third lowest glass transition temperature of the composition. Therefore, if a composition has a single glass transition temperature of 1°C, it still satisfies the "third glass transition temperature (T)" requirement even if the first and second glass transition temperatures within the aforementioned range are not present. g3 This characteristic is present. (Of course, the composition does not meet the requirements for the first glass transition temperature and the second glass transition temperature.)

[0130] The shear storage modulus (G') of the multiphase polypropylene composition (PC) as determined according to ISO 6721 is preferably 400 to 1000 MPa, more preferably 450 to 800 MPa, and most preferably 500 to 700 MPa.

[0131] Multiphase polypropylene (PC) composition prepared according to ISO 178 in accordance with ISO 19069-2, measuring 80 × 10 × 4 mm. 3 The flexural modulus measured on the injection-molded specimen is preferably 800 to 2000 MPa, more preferably 900 to 1700 MPa, and most preferably 1000 to 1500 MPa.

[0132] Multiphase polypropylene (PC) composition prepared according to ISO 179-1eA at 23°C in accordance with ISO 19069-2, measuring 80×10×4mm. 3 The Charpy notched impact strength (NIS(23)) measured on the injection-molded specimen is preferably 20 to 100 kJ / m. 2 More preferably 30 to 90 kJ / m 2 The optimal value is 50 to 80 kJ / m 2 .

[0133] The haze value of the multiphase polypropylene composition (PC) measured on a 1 mm thick plate according to ASTM D1003 is preferably 5% to 30%, more preferably 10% to 26%, and most preferably 15% to 23%.

[0134] The haze value of the multiphase polypropylene composition (PC) as measured on a 50µm blown film sample according to ASTM D1003 is preferably 0.1% to 6.0%, more preferably 1.0% to 5.0%, and most preferably 2.0% to 4.8%.

[0135] The dart impact strength (DDI) of the multiphase polypropylene composition (PC) measured on a 50µm blown film sample according to ISO 7765-1 is preferably 200g to 700g, more preferably 250g to 600g, and most preferably 300g to 500g.

[0136] The sealing initiation temperature (SIT) of the multiphase polypropylene composition (PC) determined according to the method described in the determination method is preferably 128 to 138°C, more preferably 130 to 137°C, and most preferably 132 to 136°C.

[0137] The longitudinal tensile modulus (TM-MD) of the multiphase polypropylene composition (PC) measured on a 50µm blown film sample according to ISO 527-3 is preferably 1000 to 2000 MPa, more preferably 1200 to 1800 MPa, and most preferably 1300 to 1500 MPa.

[0138] The transverse tensile modulus (TM-TD) of the multiphase polypropylene composition (PC) measured on a 50µm blown film sample according to ISO 527-3 is preferably 800 to 2000 MPa, more preferably 1000 to 1700 MPa, and most preferably 1100 to 1400 MPa.

[0139] Products

[0140] In a second aspect, the present invention relates to articles comprising at least 90 wt%, more preferably at least 95 wt%, and most preferably at least 98 wt% of the multiphase polypropylene composition (PC) described in the first aspect, more preferably films or molded articles.

[0141] In one embodiment, the article of the second aspect is a molded article.

[0142] In another embodiment, the article of the second aspect is a film, more preferably a blown film.

[0143] The haze value of the membrane in this embodiment, as measured according to ASTM D1003, is preferably 0.1% to 6.0%, more preferably 1.0% to 5.0%, and most preferably 2.0% to 4.8%.

[0144] The dart impact strength (DDI) of the membrane in this embodiment, as measured according to ISO 7765-1, is preferably 200 to 700 g, more preferably 250 to 600 g, and most preferably 300 to 500 g.

[0145] The sealing initiation temperature (SIT) of the membrane in this embodiment, as measured by the method described in the measurement method, is preferably 128 to 138°C, more preferably 130 to 137°C, and most preferably 132 to 136°C.

[0146] The longitudinal tensile modulus (TM-MD) of the membrane in this embodiment, as measured according to ISO 527-3, is preferably 1000 to 2000 MPa, more preferably 1200 to 1800 MPa, and most preferably 1300 to 1500 MPa.

[0147] The transverse tensile modulus (TM-TD) of the membrane in this embodiment, as measured according to ISO 527-3, is preferably 800 to 2000 MPa, more preferably 1000 to 1700 MPa, and most preferably 1100 to 1400 MPa.

[0148] All the alternatives provided above for the multiphase polypropylene composition (PC) of the first aspect can be applied to articles according to this aspect with the necessary modifications in detail.

[0149] use

[0150] In a third aspect, the present invention relates to the use of a hydrogenated styrene-farnesene block copolymer (HSFC) for improving the Charpy notched impact strength (NIS(23)) of a polypropylene composition, said Charpy notched impact strength NIS(23) being 80 × 10 × 4 mm prepared according to ISO 19069-2 at 23°C according to ISO 179-1eA. 3 The polypropylene composition was obtained by blending polypropylene with 1.0 to 30.0 wt% of hydrogenated styrene-farnesene block copolymer (HSFC), as measured on injection-molded specimens.

[0151] Preferably, the Charpy notched impact strength (NIS(23)) of a polypropylene composition containing 1.0 to 30.0 wt% hydrogenated styrene-farnesene block copolymer (HSFC) is at least 100% higher than that of a similar polypropylene composition not containing hydrogenated styrene-farnesene block copolymer (HSFC), more preferably at least 200% higher, and most preferably at least 300% higher.

[0152] In a fourth aspect, the present invention relates to the use of a hydrogenated styrene-farnesene block copolymer (HSFC) for improving the haze of a polypropylene composition obtained by blending polypropylene with 1.0 to 30.0 wt% of the hydrogenated styrene-farnesene block copolymer (HSFC).

[0153] In one embodiment, the use of the fourth aspect improves the haze of the polypropylene composition as measured according to ASTM D1003 on a 1 mm thick plate.

[0154] In this embodiment, it is particularly preferred that the haze value of the polypropylene composition containing 1.0 to 30.0 wt% hydrogenated styrene-farnesene block copolymer (HSFC) is at least 20% lower than that of a similar polypropylene composition not containing hydrogenated styrene-farnesene block copolymer (HSFC), more preferably at least 30% lower, and most preferably at least 40% lower.

[0155] In another embodiment, the use of the fourth aspect improves the haze of the polypropylene composition as measured on a 50µm blown film sample according to ASTM D1003.

[0156] In this embodiment, it is particularly preferred that the haze value of the polypropylene composition containing 1.0 to 30.0 wt% hydrogenated styrene-farnesene block copolymer (HSFC) is at least 10% lower than that of a similar polypropylene composition not containing hydrogenated styrene-farnesene block copolymer (HSFC), more preferably at least 20% lower, and most preferably at least 30% lower.

[0157] In a fifth aspect, the present invention relates to the use of a hydrogenated styrene-farnesene block copolymer (HSFC) for improving the dart impact strength (DDI) of a polypropylene composition prepared by blending polypropylene with 1.0 to 30.0 wt% of the hydrogenated styrene-farnesene block copolymer (HSFC), wherein the dart impact strength (DDI) is determined according to ISO 7765-1 on a 50 µm blown film sample.

[0158] Particularly preferred is that the dart impact strength (DDI) of a polypropylene composition containing 1.0 to 30.0 wt% hydrogenated styrene-farnesene block copolymer (HSFC) is at least 200% higher than that of a similar polypropylene composition not containing hydrogenated styrene-farnesene block copolymer (HSFC), more preferably at least 350% higher, and most preferably at least 500% higher.

[0159] In the applications of the third, fourth, and fifth aspects, the polypropylene is preferably a multiphase propylene-ethylene copolymer, more preferably a multiphase propylene-ethylene copolymer (HECO) of the first aspect.

[0160] Similarly, in the applications of the third, fourth and fifth aspects, the hydrogenated styrene-farnesene block copolymer (HSFC) is preferably the hydrogenated styrene-farnesene block copolymer (HSFC) of the first aspect.

[0161] The polypropylene compositions obtained in the third, fourth, and fifth aspects are preferably the multiphase polypropylene compositions (PC) of the first aspect.

[0162] All the alternatives provided above for the multiphase polypropylene composition (PC), multiphase propylene-ethylene copolymer (HECO), and hydrogenated styrene-farnesene block copolymer (HSFC) for the first aspect can be adapted to the uses of the third, fourth, and fifth aspects with the necessary modifications in detail. Example

[0163] A. Measurement Method

[0164] Unless otherwise defined, the following definitions of terms and measurement methods apply to the above general description of the invention (including the claims) and the following embodiments.

[0165] Quantitative analysis of microstructure using NMR spectroscopy

[0166] Quantitative nuclear magnetic resonance (NMR) spectroscopy has been used to quantify the comonomer content and regional defect content of polymers.

[0167] Use targeting 1 H and 13C was run on a Bruker Avance III 400 NMR spectrometer at 400.15 MHz and 100.62 MHz, respectively, and quantitative data were recorded in solution. 13 C{ 1 H⁺ NMR spectroscopy. Using… 13 The optimal 10mm extended temperature probe was used to record all spectra at 125°C, and all pneumatic devices used nitrogen. Approximately 200 mg of material was dissolved in approximately 3 ml of [unspecified solution]. 1,2 -Tetrachloroethane- d 2(TCE- d 2) Chromium acetylacetone (Cr(acac)3) was added to obtain a 65 mM relaxant solution {singh09} dissolved in the solvent. To ensure solution homogeneity, after preliminary sample preparation in a heating block, the NMR tube was further heated in a rotary furnace for at least 1 hour. After inserting the tube into the magnet, it was rotated at 10 Hz. This setup was chosen primarily for the high resolution and accurate quantification requirements of ethylene content. Standard single-pulse excitation without NOE was used, with optimized tip angle, 1 s cycle delay, and a dual-level WALTZ16 decoupling scheme {zhou07, busico07}. A total of 6144 (6 k) transient signals were acquired for each spectrum.

[0168] Using proprietary computer programs for quantitative analysis 13 C{ 1 The ¹H NMR spectra were processed, integrated, and the relevant quantitative characteristics were determined based on the integration. All chemical shifts were indirectly referenced to the central methylene group (30.00 ppm) of the ethylene block (EEE) using the chemical shift of the solvent. A similar reference method can be used even if this structural unit is not present.

[0169] The characteristic signals {wang00, cheng84, randall89} corresponding to ethylene incorporation were observed.

[0170] The comonomer fraction was determined using the method of Wang et al. {wang00} through analysis of... 13 C{ 1 Quantization is achieved by integrating multiple signals across the entire spectral region of the H spectrum. This method was chosen for its robustness and ability to handle regional defects when necessary. The integration region was slightly adjusted to improve applicability across the entire range of comonomer contents.

[0171] For systems where isolated ethylene is observed only in the PPEPP sequence, the method of Wang et al. 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 the absolute ethylene content. Using this set of sites, the corresponding integral equation becomes:

[0172]

[0173] p T = I D + I F + I D

[0174] p = (p S + p T ) / 2

[0175]

[0176] fE = e / (e + p)

[0177] The same symbols are used as in the article by Wang et al.

[0178] The molar percentage of comonomer incorporated is calculated from the mole fraction:

[0179]

[0180] The weight percentage of comonomer incorporated is calculated from the mole fraction:

[0181]

[0182] Characteristic signals {resconi00, wang00} corresponding to regional defects were observed. The presence of two methyl sites at 17.7 ppm and 17.2 ppm indicates the existence of isolated 2,1-erythromorphic regional defects, which was also confirmed by other characteristic sites. Two inequivalent Sαβ signals at 34.9 ppm and 34.7 ppm, respectively, and a T at 34.1 ppm... γγ The signal indicates the presence of a 2,1-erythroline region defect adjacent to the ethylene unit.

[0183] Using 17.7 ppm (I e8 ) and 17.4 ppm (I e6 The average integral value of the two characteristic methyl sites at the location is used to quantify the amount of isolated 2,1-erythromorphic defects (P). 21e孤立 ):

[0184] P 21e孤立 = ( Ie6 + I e8 ) / 2

[0185] Using the methine site (I) at 34.1 ppm Tγγ To quantify the amount of defects (P) in the 2,1 region adjacent to ethylene. E21 ):

[0186] P E21 = I Tγγ

[0187] Based on the methyl region (I) between 23.0 and 19.9 ppm CH3 To quantify the total amount of propylene (P) 总 ), and corrected for sites within this region that were unrelated to propylene insertion. Methyl P generated by defects in the 2,1 region adjacent to ethylene γγ Already exists in I CH3 middle:

[0188]

[0189] Considering two propylene units in a 2,1-red regional defect, the isolated 2,1-red regional defect (P) 21e孤立 Multiply the quantity by 2.

[0190] Mole percentage of isolated 2,1-erythromorphic defects relative to all propylene:

[0191]

[0192] To quantify the molar percentage of defects in the 2,1 region adjacent to ethylene relative to all propylene:

[0193]

[0194] 2.1 The total number of defects is quantified as follows:

[0195]

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

[0196] No characteristic signal {resconi00} was observed corresponding to other types of regional defects (2,1-Su type, 3,1-Insertion type).

[0197] zhou07 Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh, D. Winniford, B., J. Mag. Reson. 187 (2007) 225

[0198] Busico, V., Carbonniere, P., Cipullo, R., Pellecchia, R., Severn, J., Talarico, G., Macromol. Rapid Commun. 2007, 28, 1128

[0199] Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253

[0200] Wang, W-J., Zhu, S., Macromolecules 33 (2000), 1157

[0201] Cheng, H. N., Macromolecules 17 (1984), 1950

[0202] Singh, G., Kothari, A., Gupta, V., Polymer Testing 28 5(2009), 475

[0203] Randall, J. Macromol. Sci., Rev. Macromol. Chem. Phys. 1989, C29, 201.

[0204] CRYSTEMQC analysis

[0205] Crystallization and soluble fractionation methods

[0206] The crystalline fraction (CF) and soluble fraction (SF) of polypropylene (PP) compositions, as well as the comonomer content and intrinsic viscosity of each fraction, were analyzed using a CRYSTEX instrument (Polymer Char, Valencia, Spain). Detailed information on the techniques and methods 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: comparison to standard separation methods, International Journal of Polymer Analysis and Characterization, 25:8, 581-596).

[0207] The crystalline and amorphous fractions were separated by a temperature cycle 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 performed using an integrated infrared detector (IR4); intrinsic viscosity (IV) was determined using an online dual-capillary viscometer.

[0208] The IR4 detector is a multi-wavelength detector capable of detecting IR absorbance in two different frequency bands (CH3 stretching vibration (centered at approximately 2960 cm⁻¹)). -1 ) and CH stretching vibration (2700-3000 cm) -1 The IR4 detector is used to determine the concentration of ethylene-propylene copolymers and the ethylene content. It employs a range of known ethylene contents from 2 wt% to 69 wt% (via...). 13 Eight EP copolymers (measured by C-NMR) were calibrated, each with various concentrations ranging from 2 to 13 mg / ml. To simultaneously obtain both concentration and ethylene content characteristics at a variety of expected polymer concentrations during Crystex analysis, the following calibration equation was used:

[0209] (Equation 1)

[0210] (Equation 2)

[0211] The constants a to e in Equation 1 and the constants a to f in Equation 2 are determined by using least squares regression analysis.

[0212] CH3 / 1000C can be converted to ethylene content (wt%) using the following formula:

[0213] (Equation 3)

[0214] XS calibration correlates the amounts of soluble fraction (SF) and crystalline fraction (CF) with the amounts of xylene cold soluble fraction (XCS) and the corresponding xylene cold insoluble fraction (XCI) determined according to the standard gravimetric method in accordance with ISO 16152. XS calibration is achieved by testing various EP copolymers with XS content ranging from 2-31 wt%. The determined XS calibration is linear.

[0215] (Equation 4)

[0216] The intrinsic viscosity (IV) of the parent EP copolymer and its soluble and crystalline fractions was determined using an online dual-capillary viscometer and correlated with the corresponding IV values ​​determined in decahydronaphthalene according to standard methods of ISO 1628-3. Calibration was performed using various EP and PP copolymers with IV values ​​of 2–4 dL / g. The obtained calibration curves were linear.

[0217] (Equation 5)

[0218] The sample to be analyzed was weighed at a concentration of 10 mg / ml to 20 mg / ml. To avoid injecting gels and / or polymers (e.g., PET and PA) that may be insoluble in trichlorobenzene (TCB) at 160°C, the weighed sample was placed in a stainless steel mesh with a MW 0.077 / D 0.05 mm.

[0219] After the sample vials are automatically filled with 1,2,4-trichlorobenzene (1,2,4-TCB) containing 250 mg / L 2,6-tert-butyl-4-methylphenol (BHT) as an antioxidant, the samples are dissolved at 160°C until complete dissolution, typically for 60 minutes, while maintaining a constant stirring speed of 400 rpm. To prevent sample degradation, the polymer solution is covered with an N2 atmosphere during the dissolution process.

[0220] A predetermined volume of sample solution is injected into a column packed with an inert support, where the sample crystallizes and the soluble fraction separates from the crystalline fraction. This process is repeated twice. During the first injection, the entire sample is measured at high temperature to determine the IV [dl / g] and C2 [wt%] of the PP composition. During the second injection, the soluble fraction (at low temperature) and the crystalline fraction (at high temperature) (wt% SF, wt% C2, IV) are measured with each crystallization cycle.

[0221] melt flow rate

[0222] Melt flow rate (MFR) was determined according to ISO 1133 and expressed in g / 10 min. MFR is an indicator of polymer flowability (and therefore processability). A higher melt flow rate generally indicates a lower polymer viscosity. The MFR2 of polypropylene was measured at 230°C and a load of 2.16 kg. The MFR of hydrogenated styrene-farnesene block copolymers... 10 The results were measured at a temperature of 230℃ and a load of 10kg.

[0223] Xylene soluble fraction at room temperature (XCS, wt%): The amount of polymer soluble in xylene is determined at 25°C according to ISO 16152 (5th edition, 2005-07-01).

[0224] Styrene content

[0225] Styrene content was determined by Fourier transform infrared spectroscopy (FTIR). Films with a thickness of 300 µm were prepared from granules by hot pressing (190 °C, 100 bar, 1 min). Two films were prepared for each sample. The prepared film samples were measured using a Perkin Elmer FTIR spectrophotometer system 2000. (The measurement was performed at 1602 cm⁻¹.) -1 The peak (phenyl absorption) at the point was integrated and evaluated using an internally established calibration curve. The arithmetic mean of the two measurements is given as the result.

[0226] Calibration: Various polypropylene compounds consisting of polypropylene (PP) and an elastomer containing styrene (with known styrene content) were prepared and measured according to the method described above.

[0227] Shore hardness (A or D) is determined according to ISO 868.

[0228] DSC analysis, melting temperature (T) m ) and heat of fusion (H f ), crystallization temperature (T) c ) and heat of crystallization (H c): Determined using a TAInstrument Q200 differential scanning calorimeter (DSC) on samples ranging from 5 to 7 mg. DSC was performed according to ISO 11357 / Part 3 / Method C2, using a heating / cooling / heating cycle at a scan rate of 10 °C / min, covering a temperature range of -30 to +225 °C. Crystallization temperature (T c ) and enthalpy of crystallization (H c The melting temperature (T) is determined during the cooling step, while it is determined during the second heating step. m ) and enthalpy of fusion (H m ).

[0229] The glass transition temperature Tg and storage modulus G' at 23 °C were determined by dynamic mechanical analysis according to ISO 6721-7. Measurements were taken between -100 °C and +150 °C at a heating rate of 2 °C / min and a frequency of 1 Hz on a compression-formed sample (40 × 10 × 1 mm). 3 The above is performed in a twisting mode.

[0230] Flexural modulus was determined according to ISO 178 Method A (three-point bending test) on an 80 mm × 10 mm × 4 mm specimen. A test speed of 2 mm / min and a span length of 16 times the thickness were used, as per the standard. The test temperature was 23 ± 2 °C. Injection molding was performed according to ISO 19069-2, with a melt temperature of 230 °C for all materials, regardless of the melt flow rate.

[0231] Notched impact strength (NIS)

[0232] Charpy notched impact strength (NIS) was determined according to ISO 179 1eA at +23°C or -20°C, using an 80×10×4mm sample prepared according to ISO 19069-2. 3 For the injection-molded strip test specimens, the melt temperature of all materials was 230℃, regardless of the material melt flow rate.

[0233] Tensile modulus (longitudinal and transverse) was determined according to ISO 527-3 at 23°C on a 50 μm thick single-layer blown film produced as shown below. The test was performed at a crosshead speed of 1 mm / min.

[0234] Haze is produced according to ASTM D1003 as shown below, with a thickness of 50 μm, in blown film (haze (film)) or according to ISO 19069-2, in injection molding, with dimensions of 60×60×1 mm. 3 The measurement was performed on a haze plate (haze plate).

[0235] Dart Impact Intensity (DDI)

[0236] ISO 7765-1:1988 / Method A

[0237] The test method involves determining the energy that causes membrane failure under specified impact conditions from a free-falling dart from a designated height, such energy causing 50% of the test specimens to fail (step method A). A uniform mass increment of the impactor is used during testing, and after each specimen is tested, the impactor weight is reduced or increased by a uniform increment based on the observed results (failure or non-failure) on the specimen.

[0238] Standard conditions:

[0239] Adjustment time: >96 hours

[0240] Test temperature: 23℃

[0241] Darthead material: phenolic resin

[0242] Dart diameter: 38mm

[0243] Drop height: 660mm

[0244] result:

[0245] • Impact failure mass [g]

[0246] •Minimum thickness [mm]

[0247] • Maximum thickness [mm]

[0248] According to ISO 7765-1:1988 / Method A, the membrane having the indicated thickness and produced according to the following "Examples" is tested and reported in grams (g).

[0249] The DDI per unit thickness (in g / μm) is calculated by dividing the DDI (in g) by the film thickness (in μm).

[0250] Sealing Intake Test (SIT)

[0251] This method is used to determine the sealing window (sealing temperature range) of a membrane. The procedure is similar to a hot-tack test and is performed on the same machine. Unlike hot-tack, the determined sealing range corresponds to the strength of the seal after cooling (with a 30-second delay). The conditions used are as follows:

[0252] • Sealing time (1 second)

[0253] • Sealing pressure (0.4 N / mm) 2 )

[0254] • Delay time (30s)

[0255] • Clamp separation speed (42mm / s)

[0256] Sealing range = (Sealing start temperature to sealing end temperature)

[0257] The test results provide a quantitative and useful indication of the membrane's sealing strength and indicate the optimal sealing temperature range.

[0258] The lower limit (Seal Initiation Temperature - SIT) is the seal temperature at which an average seal force of 5 N is measured. The upper limit (Seal End Temperature - SET) is determined as the first seal temperature at which at least two specimens exhibit a burn-through failure mode. The maximum seal force corresponds to the highest seal force measured.

[0259] The temperature interval is set to a default of 5°C, but can be reduced to 1°C when the curve shows a sharp increase or decrease in force between two temperature gradients. This is done to display a better curve profile.

[0260] Unlike ASTM F1921-12, the test parameters for sealing time, sealing pressure, delay time, and clamp separation speed were modified. The force / temperature profile was measured continuously until thermal failure of the membrane occurred. In addition to the failure mode assessments described in the standard, other failure modes were used.

[0261] 2. Example

[0262] The catalytic system for the polymerization of multiphase propylene-ethylene copolymer (HECO) corresponds to ICS4 of WO2020 / 239598A1, which contains the metallocene compound racemic-trans-dimethylsilanediyl[2-methyl-4,8-bis(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indeno-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylindeno-1-yl]zirconium dichloride.

[0263] Table 1: Polymerization conditions for multiphase propylene-ethylene copolymer (HECO)

[0264]

[0265] The content of 2,1- region defects in the HECO crystal matrix is ​​0.69 mol.

[0266] In a Coperion ZSK 47 co-rotating twin-screw extruder, HECO was compounded with the following at 220°C: 0.05 wt% pentaerythritol tetra(3-(3',5'-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox 1010 from BASF, Germany; CAS No.: 6683-19-8); 0.05 wt% tris(2,4-di-tert-butylphenyl) phosphite (Irgafos 168 from BASF, Germany; CAS No.: 31570-04-4); 0.03 wt% synthetic hydrotalcite (Hycite 713 from BASF, Germany; CAS No.: 11097-59-9); and 0.10 wt% nucleating agent (ADKStab NA-71 from Adeka, Germany; CAS No. (Main Component): 85209-93-4).

[0267] In addition to HECO mentioned above, the following commercially available components were also used:

[0268] HSFC, hydrogenated styrene-farnesene block copolymer, was commercially available from Kuraray Europe (Germany) under the trade name SEPTONSF902, with an MFR of 10 (230℃, 10kg) 55g / 10min, styrene content 18 wt%, Shore A hardness 8.

[0269] SEBS, a styrene-ethylene-butene triblock copolymer, was commercially available from Kraton (USA) under the trade name G1645MO. Its MFR2 (230°C, 2.16 kg) is 2.0–4.5 g / 10 min, its styrene content is 11.5–13.5 wt%, and its Shore A hardness is 35.

[0270] The compositions of the present invention and the comparative compositions were prepared by compounding in a Coperion ZSK 18 co-rotating twin-screw extruder at 210°C and a rate of 7 kg / h, according to the formulations shown in Table 2.

[0271] The properties of the resulting compositions listed in Table 2 were measured directly on samples prepared from the compositions (selecting appropriate samples according to the above-described determination methods) or on 50 µm blown films (film thickness 50 µm, air blowing ratio 1:2.5, 6.1 m / min) prepared on the Collin blown film laboratory production line.

[0272] Table 2: Formulations and properties of the compositions of the present invention and comparative compositions

[0273]

[0274] As shown in Table 2, compared to polypropylene alone, the addition of HSFC to polypropylene (i.e., HECO) resulted in a decrease in haze (sheet and film) and an increase in Charpy impact strength (+23°C) and dart impact strength. While similar effects were achieved using SEBS modifiers, HSFC modifiers were significantly more effective than SEBS modifiers in most cases, with IE2 exhibiting a significantly lower haze (sheet) value than CE2 (despite using a smaller amount of modifier). Furthermore, while both SEBS and HSFC reduced flexural modulus (composition) and tensile modulus (film, longitudinal MD, and transverse TD), the reduction was smaller with HSFC modifiers compared to SEBS modifiers. This indicates that IE1 exhibited superior stiffness and impact strength compared to CE2, a particularly significant effect as increased stiffness is typically accompanied by a decrease in impact strength (and vice versa). Additionally, it is noteworthy that HSFC-modified compositions are suitable for both film and molded article production.

[0275] These effects allow for the production of thinner packaging, helping to reduce the amount of plastic waste generated. Furthermore, due to the high bio-based content of HSFCs, the resulting compositions and packaging materials have a lower total content of olefin derivatives, which further benefits environmental protection.

Claims

1. A multiphase polypropylene composition (PC), said multiphase polypropylene composition (PC) comprising: a) 70.0 to 99.0 wt% of a multiphase propylene-ethylene copolymer (HECO) relative to the total weight of the multiphase polypropylene composition (PC), wherein the multiphase propylene-ethylene copolymer (HECO) has a melt flow rate (MFR2) of 1.0 to 100 g / 10 min as determined according to ISO 1133 at 230 °C and 2.16 kg. The multiphase propylene-ethylene copolymer (HECO) comprises: i) a crystalline matrix (M), wherein the crystalline matrix (M) is a propylene homopolymer or a propylene copolymer; and ii) Amorphous propylene-ethylene elastomers (E); as well as b) 1.0 to 30.0 wt% hydrogenated styrene farnesene block copolymer (HSFC) relative to the total weight of the multiphase polypropylene composition (PC). c) Optionally, 0.0001 to 1.0 wt% of one or more nucleating agents (NU) relative to the total weight of the multiphase polypropylene composition (PC); and d) Optionally, 0.01 to 5.0 wt% of one or more other additives (A) different from the said one or more nucleating agents (NU) relative to the total weight of the multiphase polypropylene composition (PC).

2. The multiphase polypropylene composition (PC) according to claim 1, wherein, The hydrogenated styrene-farnesene block copolymer (HSFC) has one or more of the following properties, preferably all of them: i) Melt flow rate (MFR) measured according to ISO 1133 at 230°C and 10 kg. 10 The concentration ranges from 1.0 to 1000 g / 10 min. ii) The Shore A hardness, as determined by ISO 868, is 3 to 30; and iii) The styrene content, determined by quantitative FT-IR spectroscopy, is 1.0 to 35.0 wt% relative to the total weight of the hydrogenated styrene farnesene block copolymer (HSFC).

3. The multiphase polypropylene composition (PC) according to any one of the preceding claims, wherein, The crystalline matrix (M) of the multiphase propylene-ethylene copolymer (HECO) is a propylene homopolymer, and / or the multiphase propylene-ethylene copolymer (HECO) is obtained by quantitative analysis. 13 The defect content in the 2,1- region, as determined by C-NMR spectroscopy, ranged from 0.05 to 1.20 mol.

4. The multiphase polypropylene composition (PC) according to any one of the preceding claims, wherein, The multiphase propylene-ethylene copolymer (HECO) has one or more of the following characteristics, preferably all of them: i) Based on the total weight of the multiphase propylene-ethylene copolymer (HECO), the soluble fraction (SF) content, determined by CRYSTEX QC analysis, is 5.0 to 40.0 wt%; based on the total weight of the multiphase propylene-ethylene copolymer (HECO), the crystalline fraction (CF) content, determined by CRYSTEX QC analysis, is 60.0 to 99.0 wt%. ii) Based on quantitative 13 The ethylene content (C2 (total)) determined by quantitative FT-IR spectroscopy calibrated by C-NMR spectroscopy ranged from 0.3 to 8.0 wt%; iii) Based on the quantitative method 13 The ethylene content (C2(SF)) of the CRYSTEX QC soluble fraction determined by quantitative FT-IR spectroscopy calibrated by C-NMR spectroscopy ranged from 10.0 to 90.0 wt% iv) Based on quantitative methods 13 The ethylene content (C2(CF)) of the CRYSTEX QC crystal fraction determined by quantitative FT-IR spectroscopy calibrated by C-NMR spectroscopy ranged from 0.0 to 5.0 wt%. v) The intrinsic viscosity (iV(SF)) of the CRYSTEX QC soluble fraction, as determined by CRYSTEX QC analysis, is 1.20 to 5.00 dL / g; as well as vi) The intrinsic viscosity (iV(CF)) of the CRYSTEX QC crystal fraction, as determined by CRYSTEX QC analysis, is 1.50 to 5.00 dL / g.

5. The multiphase polypropylene composition (PC) according to any one of the preceding claims, wherein, The multiphase propylene-ethylene copolymer (HECO) has one or more of the following characteristics, preferably all of them: i) Melting temperature (T) determined by differential scanning calorimetry (DSC) m The temperature ranges from 149 to 160 degrees Celsius. as well as ii) Crystallization temperature (T) determined by differential scanning calorimetry (DSC) c The temperature ranges from 110 to 130 ℃.

6. The multiphase polypropylene composition (PC) according to any one of the preceding claims, wherein, The multiphase polypropylene composition (PC) comprises, more preferably, the following: a) 80.0 to 97.0 wt%, more preferably 85.0 to 95.0 wt%, of the multiphase polypropylene composition (PC) relative to the total weight of the composition; b) 3.0 to 20.0 wt%, more preferably 5.0 to 15.0 wt%, of hydrogenated styrene farnesene block copolymer (HSFC) relative to the total weight of the multiphase polypropylene composition (PC). c) Optionally, 0.0001 to 1.0 wt% of one or more nucleating agents (NU) relative to the total weight of the multiphase polypropylene composition (PC); and d) Optionally, 0.01 to 5.0 wt% of one or more other additives (A) different from one or more nucleating agents (NU) relative to the total weight of the multiphase polypropylene composition (PC).

7. The multiphase polypropylene composition (PC) according to any one of the preceding claims, wherein, The multiphase polypropylene composition (PC) has a melt flow rate (MFR2) of 1.0 to 100 g / 10 min as determined by ISO 1133 at 230 °C and 2.16 kg.

8. The multiphase polypropylene composition (PC) according to any one of the preceding claims, wherein, The first glass transition temperature (T0) of the multiphase polypropylene composition (PC) as determined according to ISO 6721-7 g1 The temperature ranges from -70 to -55 ℃.

9. The multiphase polypropylene composition (PC) according to any one of the preceding claims, wherein, The multiphase polypropylene composition (PC) has one or more of the following characteristics, preferably all of them: i) Melting temperature (T) determined by differential scanning calorimetry (DSC) m The temperature ranges from 149 to 160 degrees Celsius. ii) Crystallization temperature (T) determined by differential scanning calorimetry (DSC) c The temperature ranges from 110 to 130 °C. iii) The second glass transition temperature (T) as determined according to ISO 6721-7 g2 The temperature ranges from -50 to -34°C; and iv) The third glass transition temperature (T) as determined according to ISO 6721-7 g3 The temperature ranges from -5 to +5 ℃.

10. The multiphase polypropylene composition (PC) according to any one of the preceding claims, wherein, The multiphase polypropylene composition (PC) has one or more of the following characteristics, preferably all of them: i) According to ASTM D1003, the haze value measured on a 1 mm thick plate is 5% to 30%; ii) According to ISO 178, 80×10×4mm [materials] prepared according to ISO 19069-2 3 The flexural modulus measured on the injection-molded specimens ranged from 800 to 2000 MPa; and iii) According to ISO 179-1 eA, at 23°C, in a sample of 80×10×4mm prepared according to ISO 19069-2 3 The Charpy notched impact strength (NIS(23)) measured on the injection-molded specimens ranged from 20 to 100 kJ / m. 2 .

11. The multiphase polypropylene composition (PC) according to any one of the preceding claims, wherein, The multiphase polypropylene composition (PC) has one or more of the following characteristics, preferably all of them: i) The haze value measured on a 50µm blown film sample is 0.1% to 6.0% according to ASTM D1003; ii) The dart impact strength (DDI) measured on a 50µm blown film sample, according to ISO 7765-1, is 200 to 700 g; as well as iii) The seal initiation temperature (SIT) determined according to the method described in the determination method is 128°C to 138°C.

12. An article, more preferably a film or molded article, comprising at least 90 wt%, more preferably at least 95 wt%, and most preferably at least 98 wt% of the multiphase polypropylene composition (PC) of any one of the preceding claims.

13. Use of hydrogenated styrene-farnesene block copolymer (HSFC) for improving the Charpy notched impact strength (NIS(23)) of polypropylene compositions, wherein, The Charpy notched impact strength is determined according to ISO 179-1 eA at 23°C, on an 80×10×4mm sample prepared according to ISO 19069-2. 3 The polypropylene composition was obtained by blending polypropylene, more preferably the multiphase propylene-ethylene copolymer (HECO) as described in any one of claims 1 to 5, with 1.0 to 30.0 wt% of hydrogenated styrene-farnesene block copolymer (HSFC), as determined on injection-molded specimens.

14. Use of hydrogenated styrene-farnesene block copolymer (HSFC) for improving the haze of polypropylene compositions, wherein, The polypropylene composition is obtained by blending polypropylene, more preferably the multiphase propylene-ethylene copolymer (HECO) as described in any one of claims 1 to 5, with 1.0 to 30.0 wt% of hydrogenated styrene-farnesene block copolymer (HSFC).

15. Use of hydrogenated styrene-farnesene block copolymer (HSFC) for improving the dart impact strength (DDI) of polypropylene compositions, wherein, The polypropylene composition is obtained by blending polypropylene, more preferably the multiphase propylene-ethylene copolymer (HECO) as described in any one of claims 1 to 5, with 1.0 to 30.0 wt% of hydrogenated styrene-farnesene block copolymer (HSFC), wherein the dart impact strength is determined according to ISO 7765-1 on a 50 µm blown film sample.

Images