Polyolefin composition containing polypropylene polymer and recycled plastic material

Abstract

The present invention relates to a polyolefin composition comprising: a) at least one heterophasic polypropylene copolymer having a melt flow rate MFR2 (230°C, 2.16 kg, measured according to ISO 1133) of at least 40 g / 10 min, preferably at least 60 g / 10 min; b) at least one polypropylene homopolymer having a melt flow rate MFR2 (230°C, 2.16 kg, measured according to ISO 1133) of at least 400 g / 10 min; and c) a blend (A) of recycled plastic materials recovered from waste plastic materials originating from post-consumer and / or industrial waste, containing polypropylene and polyethylene in a ratio of 3:7 to 12:1 and having a melt flow rate MFR2 (230°C, 2.16 kg, measured according to ISO 1133) of at least 5 g / 10 min, characterized in that the polyolefin composition has a melt flow rate MFR2 (230°C, 2.16 kg, measured according to ISO 1133) of at least 20 g / 10 min.

Description

Technical Field

[0001] The present invention relates to a polyolefin composition comprising at least one heterophasic polypropylene copolymer, at least one polypropylene homopolymer and a recycled plastic material, an article comprising the polyolefin composition, and a method for preparing such a polyolefin composition.

Background Art

[0002] Polyolefins, particularly polyethylene and polypropylene, have come to be consumed in large quantities in a wide range of applications such as packaging of foods and other goods, fibers, automotive parts, and various manufactured articles. Comparing the large amount of waste to be recovered with the amount of waste to be recycled, it can be seen that there remains great potential for the intelligent reuse of plastic waste and the mechanical recycling of plastic waste.

[0003] One of the major trends in the field of polyolefins is the use of recycled materials derived from various sources. The flow of durable consumer goods such as yellow bags, yellow trash cans, regional collections, waste electrical and electronic equipment (WEEE), or used automobiles (ELV) contains various plastics. These materials can be processed to recover plastics such as acrylonitrile-butadiene-styrene (ABS), high impact polystyrene (HIPS), polypropylene (PP), and polyethylene (PE). Separation can utilize density separation in water, and further separation based on fluorescence, near infrared absorption, or Raman fluorescence can be performed. However, it is generally very difficult to obtain pure recycled polypropylene or pure recycled polyethylene.

[0004] Generally, the recycled amount of polypropylene available in the market is a mixture of both polypropylene (PP) and polyethylene (PE), which is particularly applicable to the flow of post - consumer waste. Further, commercially recycled products from post - consumer waste sources have conventionally been cross - contaminated with non - polyolefin materials such as polyethylene terephthalate, polyamide, polystyrene, and non - polymeric substances such as wood, paper, glass, and aluminum. Such cross - contamination severely restricts the end - uses of the recycling stream, leaving no beneficial end - uses. In particular, polyolefin recycling materials from the post - consumer waste stream are a mixture of PE and PP. The better the quality of recycled products, the more difficult they are to obtain and the higher the price.

[0005] The problem that recycled products are inferior in quality compared to virgin products can be overcome to some extent by mixing recycled products with virgin polymers.

[0006] Compositions containing virgin polymers (i.e., polymers used for the first time) and recycled mixed plastics are being studied.

[0007] EP0575465B1 targets a polymer blend composition containing (a) 30 - 70 wt% of a low - melting - point polymer comprising an ethylene / α - olefin copolymer having a density of 0.88 - 0.915 g / cm 3 , an MFR of 1.5 - 7.5 dg / min, a molecular weight distribution of 3.5 or less, a composition distribution breadth index of more than 70%, and an essentially single melting point in the range of 60°C - 115°C as measured by DSC peak Tm; and (b) 70 - 30 wt% of a propylene - based polymer having 88 - 100 mol% of propylene and 12 - 0 mol% of an α - olefin other than propylene.

[0008] US5266392A claims a polyethylene / polypropylene blend comprising: ≥50 wt% crystalline polypropylene; at least about 10 wt% linear low-density polyethylene having a density of about 0.915 to about 0.94 dispersed in the matrix of said polypropylene; α-olefin content of ~5 to ~25 mol%, melt index greater than about 50 dg / min, weight-average molecular weight of about 5000 to about 50000, and about 0.88 to about 0.90 g / cm³. 3 This includes some ethylene / α-olefin plastomer compatibilizer having a density and at least 10% X-ray crystallinity; this covers the use of plastomers as compatibilizers in very general terms, including recycling, of course. Regarding plastomers, only very low and very high densities are excluded, but pure HDPE is also excluded.

[0009] WO2015 / 169690A1 is a blend comprising (A) 75-90 wt% polypropylene and (Bl) 70-30 wt% polyethylene, with (A) 75-90 wt% polypropylene and (Bl) 55-90 wt% polypropylene having an MFR2 of 1.0-300 g / 10 min (230°C, load 2.16 kg, compliant with ISO 1133), and (B) 10-10 wt% copolymer of ethylene and propylene or C4-C10 α-olefins having a glass transition temperature Tg (measured in DMTA) lower than -25°C and an intrinsic viscosity of at least 3.0 dl / g (measured in decalin at 135°C), and heterophase polyo The present invention relates to a polypropylene-polyethylene blend comprising a compatibilizer (B) 10-25 wt% which is a refyn composition, wherein the blend has (i) a Charpy notch impact strength (measured at 23°C in accordance with ISO 179-leA) at least 2% higher than the blend without compatibilizer (B), and simultaneously (ii) a flexural modulus (measured in accordance with ISO 178) at least 3% higher than the blend without compatibilizer (B), and (iii) a thermal deformation resistance (measured with DMTA) expressed as a temperature at which the storage modulus G' reaches 40 MPa (T(G'=40MPa)) at least 4°C higher than the blend without compatibilizer (B).

[0010] EP3165473A1 relates to a polyolefin composition comprising a blend of recycled polypropylene and recycled polyethylene (A), polypropylene having an MFR of 50 g / 10 min or more, and a compatibilizer which is a heterophase polyolefin composition, wherein the entire composition has an MFR higher than 25 g / 10 min.

[0011] WO2020 / 070176A1 relates to a polyolefin composition containing recycled polyolefins and suitable for more expensive products. The composition comprises a propylene homopolymer having an MFR of at least 400 g / 10 min. [Prior art documents] [Patent Documents]

[0012] [Patent Document 1] European Patent No. 0575465 [Patent Document 2] U.S. Patent No. 5,266,392 [Patent Document 3] International Publication No. 2015 / 169690 [Patent Document 4] European Patent Application Publication No. 3165473 [Patent Document 5] International Publication No. 2020 / 070176 [Overview of the project] [Problems that the invention aims to solve]

[0013] However, known polymer compositions containing recycled materials are not suitable for the high-end market; rather, currently available recycled compositions are intended for low-end applications such as wooden boxes, flower pots, and benches. Currently available recycled compositions do not match virgin materials in terms of their mechanical properties.

[0014] To meet the demands of high-end markets, such as high-flow applications, and to compete with virgin materials, certain adjustments are necessary (especially in the non-food and non-healthcare product sectors). Currently available recycled materials primarily face problems in terms of composition (variations in PP and PE content, etc.), consistency (in terms of flow properties), property profile (poor balance of stiffness and impact), and cross-contamination (non-polyolefin components, inorganic materials such as aluminum and paper), as well as color and odor. In particular, a suitable melt flow rate is desired for high-flow applications.

[0015] Furthermore, polymer compositions containing recycled materials known from the prior art mainly consist of heterogeneous impact copolymers (or heterogeneous polypropylene copolymers) or random copolymers as virgin polymers. These polymers constitute the EPR phase. Moreover, the long-term stabilization of materials known from the prior art may not be good enough for the materials to be subjected to further reprocessing or recycling processes.

[0016] Therefore, the object of the present invention was to provide a polyolefin composition containing polyolefin material recovered from waste plastic material that does not have the drawbacks of polymer compositions of the prior art. In particular, composite solutions combining virgin materials and recycled materials are urgently needed to solve the above problems in a balanced manner and to provide advanced material products to the market. [Means for solving the problem]

[0017] This objective was addressed by providing the following polyolefin compositions: a) At least one heterogeneous polypropylene copolymer having a melt flow rate MFR2 (230°C, 2.16 kg, measured according to ISO 1133) of at least 40 g / 10 min, preferably at least 60 g / 10 min, of 20-48 wt%; b) At least one polypropylene homopolymer having a melt flow rate of at least 400 g / 10 min MFR2 (230°C, 2.16 kg, measured according to ISO 1133) of 2-30 wt%; and c) A blend (A) of recycled plastic material containing 40-60 wt% of polypropylene and polyethylene in a ratio of 3:7-12:1, which is recovered from waste plastic material derived from used waste and / or industrial waste having a melt flow rate of at least 5 g / 10 min MFR2 (230°C, 2.16 kg, measured according to ISO 1133); Includes, The polyolefin composition has a melt flow rate MFR2 (230°C, 2.16 kg, measured according to ISO 1133) of at least 20 g / 10 min, preferably at least 25 g / 10 min. [Effects of the Invention]

[0018] As will be discussed in more detail below, the melt flow rate of this polyolefin composition can cover a broad spectrum and can be adjusted according to customer needs. The melt flow rate is an important indicator for understanding the flow within the mold. Changes in the melt flow rate affect the conversion interface and the performance of the end application. By providing polyolefin compositions with different melt flow rates, customer needs can be met. [Modes for carrying out the invention]

[0019] This polyolefin composition combines a homopolymer PP material as a melt flow rate improver for recycled PP / PE materials with a virgin high-flow heterogeneous PP material as an impact booster. This allows for the use of polyolefin compositions with a high proportion of recycled materials in current applications in packaging fields such as caps, closures, and lids, particularly in thin-wall packaging.

[0020] For the purposes of this specification and the subsequent claims, the term “recycled” is used to indicate that a material has been recovered from spent waste and / or industrial waste. That is, spent waste refers to material that has completed at least one first use cycle (or life cycle), i.e., has already served its first purpose and passed through the hands of a consumer, while industrial waste refers to manufacturing scrap that does not typically reach consumers. In the spirit of the present invention, the “recycled polymer” may also contain, based on the total weight of the recycled polymer, other components derived from the first use, up to 17 wt%, preferably up to 3 wt%, more preferably up to 1 wt%, and even more preferably up to 0.1 wt%. The types and amounts of these components affect the physical properties of the recycled polymer. The physical properties described below relate to the main components of the recycled polymer.

[0021] As further described below, other typical components derived from the first use are thermoplastic polymers such as polystyrene and PA6, talc, chalk, ink, wood, paper, limonene, and fatty acids. The content of polystyrene (PS) and polyamide 6 (PA6) in the recycled polymer can be determined by Fourier transform infrared spectroscopy (FTIR), and the content of talc, chalk, wood, and paper can be measured by thermogravimetric analysis (TGA).

[0022] The term "virgin" refers to newly manufactured, unrecycled material and / or object before its first use. If the origin of a polymer is not explicitly mentioned, the polymer is a "virgin" polymer.

[0023] The total amount of all virgin polypropylene polymers (homopolymers and heterogeneous polymers) used in this polyolefin composition may be added in the range of 22 to 73 wt%, preferably 30 to 65 wt%, and more preferably 38 to 55 wt%, based on the total weight of the polymer composition.

[0024] The amount of recycled plastic material blend (A) used in this polyolefin composition, which is recovered from waste plastic materials derived from used waste and / or industrial waste and contains polypropylene and polyethylene in a ratio of 3:7 to 12:1, can be in the range of 40 to 60 wt%, preferably 45 to 55 wt%, and more preferably 50 to 55 wt%, (based on the total weight of the polymer composition).

[0025] Further additives may be included in the polyolefin composition, and it should be understood that the total amount of all components is always 100 wt% in each of the embodiments described herein.

[0026] According to one embodiment, the polyolefin composition, a) 25-45 wt%, more preferably 28-35 wt%, of at least one heterophase polypropylene copolymer; b) 5-27 wt%, more preferably 10-25 wt%, of at least one polypropylene homopolymer; and c) A blend of recycled plastic materials containing 45-55 wt%, more preferably 50-55 wt%, of polypropylene and polyethylene (A); and Further additives It includes, and is added in such a way that the sum of all components is always 100 wt%.

[0027] In a further embodiment, the polyolefin composition is a) At least one heterogeneous polypropylene copolymer in an amount of 20-40 wt%, preferably 25-35 wt%, and more preferably 28-32 wt%; b) At least one polypropylene homopolymer in an amount of 10-30 wt%, preferably 12-27 wt%, more preferably 15-25 wt%; and c) A blend of recycled plastic material containing 40-60 wt%, preferably 50-55 wt%, of polypropylene and polyethylene (A); and Further additives It includes, and is added in such a way that the sum of all components is always 100 wt%.

[0028] The polyolefin compositions described above may have a melt flow rate MFR2 (measured at 230°C, 2.16 kg, according to ISO 1133) of at least 50 g / 10 min, preferably at least 60 g / 10 min, particularly in the range of 50 to 80 g / 10 min, preferably 55 to 75 g / 10 min, and more preferably 60 to 72 g / 10 min. Therefore, the melt flow rate of the final polyolefin composition can be adjusted depending on the ratio of different polymer components.

[0029] In a further embodiment, the polyolefin composition is a) At least one heterophase polypropylene copolymer in an amount of 35-48 wt%, preferably 40-48 wt%, more preferably 45-48 wt%; b) At least one polypropylene homopolymer in an amount of 2-10 wt%, preferably 2-5 wt%, more preferably 2-3 wt%; and c) A blend of recycled plastic material containing 40-60 wt%, preferably 50-55 wt%, of polypropylene and polyethylene (A); and Further additives It includes, and is added in such a way that the sum of all components is always 100 wt%.

[0030] The melt flow rate MFR2 (measured according to ISO 1133 at 230 °C, 2.16 kg) of such a polyolefin composition is at least 20 g / 10 min, preferably at least 25 g / 10 min, more preferably at least 30 g / 10 min, particularly in the range of 20 to 50 g / 10 min, preferably 25 to 45 g / 10 min, more preferably 27 to 42 g / 10 min.

[0031] In a further embodiment, the polyolefin composition has a tensile modulus (ISO 527-2) of at least 1200 MPa, preferably at least 1300 MPa, more preferably at least 1400 MPa, particularly in the range of 1200 to 1500 MPa, more particularly 1300 to 1400 MPa.

[0032] In yet another embodiment, the polyolefin composition has an impact strength (ISO 179, Charpy 1eA +23 °C) of at least 4 kJ / m 2 preferably at least 5 kJ / m 2 more preferably at least 6 kJ / m 2 even more preferably at least 7 kJ / m 2 particularly in the range of 4 to 8 kJ / m 2 more particularly 4.2 to 7.7 kJ / m 2 even more particularly 4.8 to 7 kJ / m 2 most particularly 5.4 to 6.6 kJ / m 2

[0033] In yet another embodiment, the polyolefin composition has a puncture energy (ISO 6603-2, 4.4 m / s, 2 mm, 23 °C) of at least 1.5 J, preferably at least 2 J, more preferably at least 3 J, even more preferably at least 4 J, particularly in the range of 1.5 to 15 J, more particularly 2 to 12 J, even more particularly 5 to 10 J.

[0034] [Heterophasic polypropylene virgin polymer] ​The heterogeneous polypropylene copolymer contains a polypropylene matrix (M) and an elastomer copolymer (E) as polymer components. The polypropylene matrix (M) is preferably a random propylene copolymer or a propylene homopolymer, with the latter being particularly preferred. The elastomer copolymer (E) contains units derived from propylene and ethylene and / or C4-C20 α-olefins, more preferably ethylene and / or C4-C10 α-olefins, most preferably ethylene, C4, C6 and / or C8 α-olefins, for example ethylene, and optionally units derived from conjugated dienes.

[0035] In one embodiment, at least one heterogeneous polypropylene polymer a) used in the polyolefin composition is selected from the group including: - At least one heterogeneous polypropylene copolymer (PPHeco-1) having a melt flow rate MFR2 (measured at 230°C, 2.16 kg, according to ISO 1133) in the range of -80 to 120 g / 10 min, preferably 90 to 110 g / 10 min, more preferably 100 g / 10 min to 105 g / 10 min; and At least one heterogeneous polypropylene copolymer (PPHeco-2) having a melt flow rate MFR2 (measured at 230°C, 2.16 kg, according to ISO 1133) in the range of -60 to 90 g / 10 min, more preferably 70 to 80 g / 10 min.

[0036] It will be understood that this polyolefin composition may contain not just one, but two heterogeneous virgin polypropylene copolymers having different melt flow rates. This allows for adjustment of the melt flow rate of the final polyolefin composition.

[0037] [Heterogeneous polypropylene copolymer (PPHeco-1)] At least one heterogeneous polypropylene copolymer (PPHeco-1) has a melt flow rate MFR2 (measured at 230°C, 2.16 kg, according to ISO 1133) in the range of 80-120 g / 10 min, preferably 90-110 g / 10 min, and more preferably 100-105 g / 10 min.

[0038] The heterogeneous propylene copolymer (PPHeco-1) of the present invention has a soluble fraction (SF) content determined by CRYSTEX analysis, which is in the range of 10.0 to 25.0 wt%, preferably 15.0 to 20.0 wt%, based on the total weight of the heterogeneous polypropylene copolymer.

[0039] The soluble fraction (SF) of heterogeneous propylene copolymer (PPHeco-1) is: 13 The ethylene content (C2(SF)) determined by quantitative FT-IR spectroscopy calibrated by 13C-NMR spectroscopy is in the range of 15.0 to 35.0 wt%, preferably 20.0 to 32.0 wt%, and more preferably 25.0 to 30.0 wt%.

[0040] The soluble fraction (SF) of the heterogeneous propylene copolymer (PPHeco-1) has an intrinsic viscosity (iV(SF)) of 4.5 dl / g or less, preferably 3.5 dl / g or less, for example in the range of 2.0 to 4.5 dl / g, preferably in the range of 2.7 to 3.5 dl / g, for example 3.0 dl / g.

[0041] The heterogeneous propylene copolymer (PPHeco-1) is preferably, 13 The total ethylene (C2) content, as determined by quantitative FT-IR spectroscopy calibrated by 13C-NMR spectroscopy, is 1.0 to 15.0 wt%, more preferably 5 to 10.0 wt%, and most preferably 7.0 to 9.0 wt%.

[0042] Heterophase polypropylene copolymer (PPHeco-1) has a Charpy-notch impact strength (NIS) of at least 4 kJ / m², measured according to ISO 179-1eA at 23°C. 2 Preferably at least 5 kJ / m³ 2For example, 4-7 kJ / m³ 2 A range of preferably 4-6 kJ / m 2 A range, for example, 4 kJ / m 2 or 5 kJ / m 2 The heterogeneous polypropylene copolymer (PPHeco-1) may have a tensile modulus of elasticity measured according to ISO 178 of at least 1000 MPa, preferably at least 1400 MPa, for example in the range of 1000 to 2000 MPa, preferably in the range of 1300 to 1800 MPa, for example 1400 MPa or 1500 MPa.

[0043] [Heterogeneous polypropylene copolymer (PPHeco-2)] At least one heterogeneous polypropylene copolymer (PPHeco-2) has a melt flow rate MFR2 (measured at 230°C, 2.16 kg, according to ISO 1133) in the range of 60-90 g / 10 min, more preferably 70-80 g / 10 min.

[0044] The heterogeneous polypropylene copolymer (PPHeco-2) of the present invention has a soluble fraction (SF) content determined by CRYSTEX analysis, which is in the range of 10.0 to 20.0 wt%, preferably 15.0 to 18.0%, based on the total weight of the heterogeneous polypropylene copolymer.

[0045] The soluble fraction (SF) of heterogeneous polypropylene copolymer (PPHeco-2) is 13 The ethylene content (C2(SF)) determined by quantitative FT-IR spectroscopy calibrated by 13C-NMR spectroscopy is in the range of 15.0 to 35.0 wt%, preferably 20.0 to 32.0 wt%, and more preferably 25.0 to 30.0 wt%.

[0046] The soluble fraction (SF) of the heterogeneous polypropylene copolymer (PPHeco-2) has an intrinsic viscosity (iV(SF)) of 4.5 dl / g or less, preferably 3.5 dl / g or less, for example, in the range of 2.0 to 4.5 dl / g, preferably in the range of 2.5 to 3.5 dl / g, and more preferably in the range of 2.5 to 3.0 dl / g, for example, 2.6 to 2.7 dl / g.

[0047] The heterogeneous polypropylene copolymer (PPHeco-2) is preferably, 13 The total ethylene (C2) content, as determined by quantitative FT-IR spectroscopy calibrated by 13C-NMR spectroscopy, is 1.0 to 15.0 wt%, more preferably 5 to 10.0 wt%, and most preferably 6.0 to 8.0 wt%.

[0048] Heterophase polypropylene copolymer (PPHeco-2) has a Charpy notch impact strength (NIS) of at least 4 kJ / m², measured according to ISO 179-1eA at 23°C. 2 Preferably at least 5 kJ / m³ 2 For example, 4-7 kJ / m³ 2 A range of 5-6 kJ / m 2 A range, for example, 5 kJ / m 2 The heterogeneous polypropylene copolymer (PPHeco-2) may have a tensile modulus of elasticity measured according to ISO 178 of at least 1000 MPa, preferably at least 1400 MPa, for example in the range of 1000 to 2000 MPa, preferably in the range of 1300 to 1800 MPa, for example 1500 MPa.

[0049] [Polypropylene virgin homopolymer] The polypropylene homopolymer b) used as the virgin polymer in this polyolefin composition is selected from the group including the following: - At least one polypropylene homopolymer (PPH-1) having a melt flow rate MFR2 (measured at 230°C, 2.16 kg, according to ISO 1133) in the range of -600 to 1000 g / 10 min, preferably 700 to 900 g / 10 min, and more preferably 800 to 850 g / 10 min; At least one polypropylene homopolymer (PPH-2) having a melt flow rate MFR2 (measured at 230°C, 2.16 kg, according to ISO 1133) in the range of -1000 to 1500 g / 10 min, preferably 1100 to 1300 g / 10 min, and more preferably 1200 to 1250 g / 10 min; - At least one polypropylene homopolymer (PPH-3) having a melt flow rate MFR2 (measured at 230°C, 2.16 kg, according to ISO 1133) in the range of -1700 to 2300 g / 10 min, preferably 1800 to 2200 g / 10 min, more preferably 2000 to 2100 g / 10 min; - At least one polypropylene homopolymer (PPH-4) having a melt flow rate MFR2 (measured according to ISO 1133) of -400 to 500 g / 10 min, preferably in the range of 420 to 480 g / 10 min, for example, 450 g / 10 min.

[0050] It will be understood that this polyolefin composition may contain not just one, but two or more polypropylene virgin homopolymers having different melt flow rates. This allows for adjustment of the melt flow rate of the final polyolefin composition.

[0051] The properties and characteristics of various polypropylene homopolymers that can be used in this polyolefin composition are described below.

[0052] [Polypropylene homopolymer (PPH-1)] At least one polypropylene homopolymer (PPH-1) has a melt flow rate MFR2 (measured at 230°C, 2.16 kg, according to ISO 1133) in the range of 600 to 1000 g / 10 min, preferably 700 to 900 g / 10 min, and preferably 800 to 850 g / 10 min.

[0053] Polypropylene homopolymer (PPH-1) has a melting point of at least 140°C, preferably at least 150°C, preferably in the range of 150-160°C, for example, 158°C.

[0054] [Polypropylene homopolymer (PPH-2)] At least one polypropylene homopolymer (PPH-2) has a melt flow rate MFR2 (measured at 230°C, 2.16 kg, according to ISO 1133) in the range of 1000 to 1500 g / 10 min, preferably 1100 to 1300 g / 10 min, and more preferably 1200 to 1250 g / 10 min.

[0055] Polypropylene homopolymer (PPH-2) has a melting point of at least 140°C, preferably at least 150°C, preferably in the range of 150-160°C, for example, 158°C.

[0056] [Polypropylene homopolymer (PPH-3)] At least one polypropylene homopolymer (PPH-3) has a melt flow rate MFR2 (measured at 230°C, 2.16 kg, according to ISO 1133) in the range of 1700-2300 g / 10 min, preferably 1800-2200 g / 10 min, and more preferably 2000-2100 g / 10 min.

[0057] [Polypropylene homopolymer (PPH-4)] At least one polypropylene homopolymer (PPH-4) has a melt flow rate MFR2 (measured at 230°C, 2.16 kg, according to ISO 1133) in the range of 400-500 g / 10 min, preferably 420-480 g / 10 min, for example, 450 g / 10 min.

[0058] Polypropylene homopolymer (PPH-4) has a melting point of at least 145°C, preferably at least 155°C, preferably in the range of 150-170°C, for example, 161°C.

[0059] More specific embodiments of this composition will be described below.

[0060] In the first embodiment, a polyolefin composition is provided, comprising the following: a) At least one heterogeneous polypropylene copolymer (PPHeco-1) having a melt flow rate MFR2 (measured at 230°C, 2.16 kg, more preferably 100-105 g / 10 min) in the range of 80-120 g / 10 min, preferably 90-110 g / 10 min, more preferably 100-105 g / 10 min, with a melt flow rate of 20-40 wt%, preferably 25-35 wt%, more preferably 28-32 wt%; b) At least one polypropylene homopolymer (PPH-1) having a melt flow rate MFR2 (measured at 230°C, 2.16 kg, according to ISO 1133) in the range of 600-1000 g / 10 min, preferably 700-900 g / 10 min, more preferably 800-850 g / 10 min, with a melt flow rate of 10-30 wt%, preferably 12-27 wt%, more preferably 15-25 wt%; c) A blend (A) of recycled plastic material containing polypropylene and polyethylene in an amount of 40-60 wt%, preferably 50-55 wt%, and optionally further additives, which are added so that the sum of all components is always 100 wt%.

[0061] Such a first polyolefin composition may have the following characteristics: Melt flow rate MFR2 (measured at 230°C, 2.16 kg, according to ISO 1133) in the range of -50 to 80 g / 10 min, preferably 55 to 75 g / 10 min, more preferably 60 to 72 g / 10 min; Tensile modulus of elasticity in the range of -1200 to 1500 MPa, and more particularly in the range of 1300 to 1400 MPa (ISO 527-2); -4~8kJ / m 2 , especially 4.2~7.7 kJ / m³ 2 Furthermore, especially 4.8~7kJ / m³ 2 , especially 5.4~6.6 kJ / m³ 2 Impact strength in the range of (Charpy 1eA +23℃), and Puncture energy in the range of -1.5 to 15 J, more particularly 2 to 12 J, and even more particularly 5 to 10 J (ISO 6603-2, 4.4 m / s, 2 mm, 23°C).

[0062] In a second embodiment, a polyolefin composition is provided, comprising the following: a) At least one heterogeneous polypropylene copolymer (PPHeco-2) having a melt flow rate MFR2 (measured at 230°C, 2.16 kg, according to ISO 1133) in the range of 60-90 g / 10 min, more preferably 70-80 g / 10 min, with a concentration of 20-40 wt%, preferably 25-35 wt%, more preferably 28-32 wt%; b) At least one polypropylene homopolymer (PPH-1) having a melt flow rate MFR2 (measured at 230°C, 2.16 kg, according to ISO 1133) in the range of 600-1000 g / 10 min, preferably 700-900 g / 10 min, more preferably 800-850 g / 10 min, with a melt flow rate of 10-30 wt%, preferably 12-27 wt%, more preferably 15-25 wt%; c) A blend (A) of recycled plastic material containing polypropylene and polyethylene in an amount of 40-60 wt%, preferably 50-55 wt%, and optionally further additives, which are added so that the sum of all components is always 100 wt%.

[0063] Such a second polyolefin composition may have the following characteristics: Melt flow rate MFR2 (measured at 230°C, 2.16 kg, according to ISO 1133) in the range of -50 to 80 g / 10 min, preferably 55 to 75 g / 10 min, more preferably 60 to 72 g / 10 min; Tensile modulus of elasticity in the range of -1200 to 1500 MPa, and more particularly in the range of 1300 to 1400 MPa (ISO 527-2); -4~8kJ / m 2 , especially 4.2~7.7 kJ / m³ 2 Furthermore, especially 4.8~7kJ / m³ 2 , especially 5.4~6.6 kJ / m³ 2 Impact strength in the range of (Charpy 1eA +23℃), and Puncture energy in the range of -1.5 to 15 J, more particularly 2 to 12 J, and even more particularly 5 to 10 J (ISO 6603-2, 4.4 m / s, 2 mm, 23°C).

[0064] In a third embodiment, a polyolefin composition is provided, comprising the following: a) At least one heterogeneous polypropylene copolymer (PPHeco-1) having a melt flow rate MFR2 (measured at 230°C, 2.16 kg, according to ISO 1133) in the range of 80-120 g / 10 min, preferably 90-110 g / 10 min, more preferably 100 n-105 g / 10 min, with a melt flow rate of 35-48 wt%, preferably 40-48 wt%, more preferably 45-48 wt%; b) At least one polypropylene homopolymer (PPH-1) having a melt flow rate MFR2 (measured at 230°C, 2.16 kg, more preferably 2 to 3 wt%) in the range of 600 to 1000 g / 10 min, preferably 700 to 900 g / 10 min, more preferably 800 to 850 g / 10 min, with a melt flow rate of 2 to 10 wt%, preferably 2 to 5 wt%, more preferably 2 to 3 wt%, and c) A blend (A) of recycled plastic materials containing 40-60 wt%, preferably 50-55 wt%, of polypropylene and polyethylene.

[0065] Such a third polyolefin composition may have the following characteristics: Melt flow rate MFR2 in the range of -25 to 50 g / 10 min, preferably 27 to 45 g / 10 min, more preferably 30 to 42 g / 10 min (measured at 230°C, 2.16 kg, according to ISO 1133); Tensile modulus of elasticity in the range of -1200 to 1500 MPa, and more particularly in the range of 1300 to 1400 MPa (ISO 527-2); -4~8kJ / m 2 , especially 4.2~7.7 kJ / m³ 2 Furthermore, especially 4.8~7kJ / m³ 2 , especially 5.4~6.6 kJ / m³ 2 Impact strength in the range of (Charpy 1eA +23℃), and Puncture energy in the range of -1.5 to 15 J, more particularly 2 to 12 J, and even more particularly 5 to 10 J (ISO 6603-2, 4.4 m / s, 2 mm, 23°C).

[0066] In a fourth embodiment, a polyolefin composition is provided, comprising the following: a) At least one heterogeneous polypropylene copolymer (PPHeco-2) having a melt flow rate MFR2 (measured at 230°C, 2.16 kg, according to ISO 1133) in the range of 60-90 g / 10 min, more preferably 70-80 g / 10 min, with a concentration of 35-48 wt%, preferably 40-48 wt%, more preferably 45-48 wt%; b) At least one polypropylene homopolymer (PPH-1) having a melt flow rate MFR2 (measured at 230°C, 2.16 kg, more preferably 2 to 3 wt%) in the range of 600 to 1000 g / 10 min, preferably 700 to 900 g / 10 min, more preferably 800 to 850 g / 10 min, with a melt flow rate of 2 to 10 wt%, preferably 2 to 5 wt%, more preferably 2 to 3 wt%, and c) A blend (A) of recycled plastic materials containing 40-60 wt%, preferably 50-55 wt%, of polypropylene and polyethylene.

[0067] Such a fourth polyolefin composition may have the following characteristics: Melt flow rate MFR2 in the range of -25 to 50 g / 10 min, preferably 27 to 45 g / 10 min, more preferably 30 to 42 g / 10 min (measured at 230°C, 2.16 kg, according to ISO 1133); Tensile modulus of elasticity in the range of -1200 to 1500 MPa, and more particularly in the range of 1300 to 1400 MPa (ISO 527-2); -4~8kJ / m 2 , especially 4.2~7.7 kJ / m³ 2 Furthermore, especially 4.8~7kJ / m³ 2 , especially 5.4~6.6 kJ / m³ 2 Impact strength in the range of (Charpy 1eA +23℃); and Puncture energy in the range of -1.5 to 15 J, more particularly 2 to 12 J, and even more particularly 5 to 10 J (ISO 6603-2, 4.4 m / s, 2 mm, 23°C).

[0068] [Blend of recycled materials (A)] Blend (A) is obtained from recycled waste streams. Blend (A) may be a combination of recycled spent waste or industrial waste, or both, such as from the automotive industry. Blend (A) is particularly preferably composed of recycled spent waste and / or industrial waste.

[0069] In one embodiment, blend (A) may be a polypropylene (PP)-rich recycled plastic material containing significantly more polypropylene than polyethylene. Recycled waste streams rich in polypropylene can be obtained, for example, from the automotive industry, and in particular, certain automotive parts such as bumpers can be a source of fairly pure polypropylene material through enhanced recycling streams and sorting. PP-rich material can be obtained by selective processing, degassing and filtration, as well as / or sorting according to type and color, such as NIR or Raman sorting and VIS sorting. It can be obtained from domestic waste streams (i.e., it is a product of domestic recycling), such as the "Yellow Bag" recycling system organized under the "Green Dot" organization, which operates in some regions of Germany.

[0070] Preferably, polypropylene-rich recycled materials are obtained from recycled waste by means of plastic recycling processes known in the art. Such PP-rich recycled products are commercially available from, for example, Corepla (Italian Consortium for the Collection, Recovery and Recycling of Packaging Plastic Waste), Resource Plastics Corp. (Brampton, ON), Kruschitz GmbH, Plastics and Recycling (AT), Vogt Plastik GmbH (DE), Mtm ​​Plastics GmbH (DE), and others. Extensive examples of polypropylene-rich recycled materials include Dipolen® PP, Purpolen® PP (Mtm Plastics GmbH), Axpoly® recycled polypropylene pellets (Axion Ltd), and polypropylene copolymers (BSP Compounds). The present invention is considered to be applicable to a wide range of recycled polypropylene materials or materials or compositions with a high recycled polypropylene content. Polypropylene-rich recycled materials may also be in the form of granules.

[0071] As described above, the polyolefin composition according to the present invention comprises a polymer blend containing a1) polypropylene and a2) polyethylene as component A); the weight ratio of a1) to a2) is 3:7 to 12:1; and the polymer blend A) is made from recycled material.

[0072] A more preferred embodiment of the present invention specifies that the ratio of polypropylene a1) to polyethylene a2) is 7:1 to 10:1, preferably 8:1 to 9.5:1.

[0073] Another preferred embodiment of the present invention specifies that the melt enthalpy of component a2) / melt enthalpy of component a1) in the polymer composition is in the range of 0.2 to 2.0, preferably in the range of 0.25 to 1.75.

[0074] According to one embodiment, the recycled plastic material blend (A) contains a relative amount of units derived from propylene in an amount of more than 50 wt%, preferably more than 53 wt%, more preferably more than 60 wt%, more preferably more than 70 wt%, more preferably more than 75 wt%, more preferably more than 80 wt%, even more preferably more than 90 wt%, and even more preferably more than 95 wt%, based on the total weight of the composition of blend A.

[0075] A more preferred embodiment of the present invention specifies that the content of polypropylene a1) in component A) is in the range of 75 to 99 wt%, preferably 83 to 95 wt%, based on the total weight of component A). The content of polypropylene a1) in component A) can be determined by FTIR spectroscopy, as described in the experimental section. More preferably, component a1) contains more than 95 wt%, preferably 96 to 99.9 wt%, of isotactic polypropylene, and most preferably consists of isotactic polypropylene.

[0076] Furthermore, blend (A) may have a relative amount of ethylene-derived units of less than 47 wt%, more preferably less than 40 wt%, more preferably less than 30 wt%, more preferably less than 20 wt%, and most preferably less than 10 wt%. Typically, the relative amount of ethylene-derived units is greater than 5 wt% of the total weight of blend (A). The ethylene present is understood to be preferably ethylene derived from polyethylene and ethylene-containing copolymers.

[0077] In another preferred embodiment of the present invention, the content of polyethylene a2) in component A) is in the range of 1 to 25 wt%, preferably 5 to 20 wt%, and more preferably 7 to 17 wt%, based on the total weight of component A). The content of polyethylene a2) in component A) can be determined by FTIR spectroscopy, as described in the experimental section. Furthermore, preferably, component a2) consists of a polyethylene-ethylene-containing copolymer.

[0078] The polyethylene fraction of the recycled material may include recycled high-density polyethylene (rHDPE), recycled medium-density polyethylene (rMDPE), recycled low-density polyethylene (rLDPE), linear low-density polyethylene (LLDPE), and mixtures thereof. In one embodiment, the recycled material may be 0.8 g / cm³. 3 More preferably 0.9 g / cm³ 3 More preferably 0.91 g / cm³ 3 This is a high-density PE with an average density of over 100%.

[0079] Furthermore, the polyethylene fraction of the recycled material may also contain a plastomer. A plastomer is a polymer material that combines rubber-like properties with the processability of plastic. An important plastomer is ethylene-α-olefin copolymer.

[0080] Ethylene-based plastomers are preferably copolymers of ethylene and C4-C8 α-olefins. Suitable C4-C8 α-olefins include 1-butene, 1-hexene, and 1-octene, preferably 1-butene or 1-octene, more preferably 1-octene. Preferably, copolymers of ethylene and 1-octene are used. Such ethylene-based plastomers are commercially available, i.e., from Borealis AG (AT) under the trade name Queo, from DOW Chemical Corp (USA) under the trade names Engage or Affinity, or from Mitsui under the trade name Tafmer. Alternatively, ethylene-based plastomers can be prepared by known processes in a one- or two-step polymerization process including solution polymerization, slurry polymerization, gas-phase polymerization, or a combination thereof, in the presence of a suitable catalyst known to those skilled in the art, such as a vanadium oxide catalyst or a single-site catalyst, e.g., a metallocene catalyst or a geometrically constrained catalyst. Ethylene plastomers may already be present in the spent and / or industrial waste used in the manufacture of blend (A). Alternatively, ethylene plastomers may be added to the spent and / or industrial waste during the waste plastic recycling process in which blend (A) is manufactured.

[0081] Another preferred embodiment of the present invention specifies that component A) contains a thermoplastic polymer different from a1) and a2) in less than 5 wt%, preferably less than 3 wt%, more preferably 0.01 to 2 wt%, more preferably less than 4.0 wt% PA6 and less than 5 wt% polystyrene, based on the total weight of component A), and even more preferably component A) contains 0.5 to 3 wt% polystyrene.

[0082] According to yet another preferred embodiment of the present invention, component A) contains less than 5 wt%, preferably less than 4 wt%, and more preferably 0.01 to 4 wt%, of talc based on the total weight of component A).

[0083] In another preferred embodiment of the present invention, component A) contains less than 4 wt%, preferably less than 3 wt%, and more preferably 0.01 to 2 wt%, of chalk based on the total weight of component A).

[0084] According to another preferred embodiment of the present invention, component A) contains less than 1 wt%, preferably less than 0.5 wt%, and more preferably 0.01 to 1 wt%, of paper based on the total weight of component A).

[0085] A further preferred embodiment of the present invention specifies that component A) contains less than 1 wt%, preferably less than 0.5 wt%, and more preferably 0.01 to 1 wt%, of wood based on the total weight of component A).

[0086] In another preferred embodiment of the present invention, component A) contains less than 1 wt%, preferably less than 0.5 wt%, and more preferably 0.01 to 1 wt%, of metal based on the total weight of component A).

[0087] According to the present invention, blend (A) has a limonene content of 0.1 ppm to 100 ppm, more preferably 1 ppm to 50 ppm, and most preferably 2 ppm to 35 ppm, as determined by solid-phase microextraction (HS-SPME-GC-MS). Limonene is conventionally found in recycled polyolefin materials and originates from packaging applications such as cosmetics, detergents, shampoos, and similar products. Therefore, blend (A) contains limonene if it includes materials derived from such types of household waste.

[0088] Fatty acid content is yet another indicator of the recycled origin of blend (A). However, certain processing in the recycling process may reduce the fatty acid content to below the detection limit. According to the present invention, blend (A) preferably has a fatty acid content of 1 ppm to 200 ppm, preferably 1 ppm to 150 ppm, more preferably 2 ppm to 100 ppm, and most preferably 3 ppm to 80 ppm, as determined by solid-phase microextraction (HS-SPME-GC-MS).

[0089] In a preferred embodiment, blend (A) comprises (i) less than 5 wt%, preferably less than 1.5 wt%, of polystyrene; and / or (ii) less than 3.5 wt%, preferably less than 1 wt%, of talc; and / or (iii) less than 1.0 wt%, preferably less than 0.5 wt%, of polyamide.

[0090] Because it is derived from recycled materials, blend (A) may also contain organic fillers and / or inorganic fillers and / or additives in an amount of up to 10 wt%, preferably 3 wt%, relative to the weight of blend (A).

[0091] Therefore, in one embodiment of the polyolefin composition, the blend (A) of recycled plastic materials comprises: A-1) Polypropylene content of 50-99 wt%, A-2) Polyethylene content of 1-40 wt%, A-3) 0-5.0 wt% polystyrene and / or copolymer such as ABS, A-4) 0-3.0 wt% stabilizer, A-5) 0-4.0 wt% polyamide-6, A-6) 0-3.0 wt% talc, A-7) 0-3.0 wt% chalk, A-8) Paper with a concentration of 0-1.0 wt%, A-9) 0-1.0 wt% wood, A-10) 0~0.5 wt% of metal, A-11) Limonene determined by solid-phase microextraction (HS-SPME-GC-MS) at concentrations of 0.1 ppm to 100 ppm, and A-12) Total fatty acid content determined using solid-phase microextraction (HS-SPME-GC-MS) at concentrations of 0-200 ppm. Here, all quantities are given relative to the total weight of blend (A).

[0092] As described above, blend (A) may include one or more additional ingredients selected from the following: Based on the total weight of blend (A), A-4) A maximum of 3.0 wt% of stabilizer, preferably a maximum of 2.0 wt% of stabilizer. A-5) Up to 4.0 wt% polyamide-6, preferably up to 2.0 wt% polyamide-6. A-6) A maximum of 3.0 wt% talc, preferably a maximum of 1.0 wt% talc. A-7) Chalk up to 3.0 wt%, preferably up to 1.0 wt%, A-8) Paper with a maximum of 1.0 wt%, preferably paper with a maximum of 0.5 wt%, A-9) Wood up to 1.0 wt%, preferably up to 0.5 wt%, and A-10) A maximum of 0.5 wt% of metal, preferably a maximum of 0.1 wt% of metal.

[0093] In one embodiment, the recycled plastic material blend (A) may have a melt flow rate of 4 to 20 g / 10 min, preferably 5 to 15 g / 10 min, and more preferably 6 to 12 g / 10 min (ISO 1133, 2.16 kg, 230°C).

[0094] According to another embodiment, the recycled plastic material blend (A) may have a melt flow rate MFR2 (ISO1133, 230°C, 2.16 kg) in the range of 16 to 50 g / 10 min, preferably in the range of 18 to 22 g / 10 min.

[0095] In a more preferred embodiment of the present invention, the Charpy-notch impact strength of blend A), measured at 23°C according to ISO 179-1eA, is 3.0 kJ / m 2 More preferably 4.0~7.0 kJ / m 2 The range is, more preferably 5.0 to 6.0 kJ / m 2 It is within the range of [the specified range].

[0096] A more preferred embodiment of the present invention specifies that the tensile modulus of blend A), as measured according to ISO 527-2, is in the range of 800 to 1500 MPa, preferably in the range of 1100 to 1400 MPa.

[0097] This polyolefin composition preferably does not contain glass fibers and / or chalk (except for small amounts that may be present in the recycled material of Blend A).

[0098] However, additional additives may be added.

[0099] [Additives] In one embodiment, the polyolefin composition may include at least one dosing agent for receiving filler / pigment during extrusion. The at least one coupling agent has a melt flow rate MFR2 of 1 to 5 g / 10 min, preferably 2 to 3 g / 10 min, and a density of 800 to 100 kg / m³. 3 Preferably 900-950 kg / m 3 The polymer may be a polypropylene homopolymer. Such polymers are commercially available, for example, under the trade name HC001A-B1 from Borealis AG. The amount of the agent in the polyolefin composition may be 1 to 2 wt%, for example, 1.2 to 1.4 wt%.

[0100] In another embodiment, the polyolefin composition may contain at least one impact modifier. The impact modifier may be a plastomer and / or elastomer. Suitable elastomers may be ethylene / propylene copolymers (C2 / C3 or C3 / C2 elastomers) having different C2 / C3 ratios, ethylene / butene copolymers (C2 / C4 elastomers), ethylene / octen copolymers (C2 / C8 elastomers), grafted ethylene elastomers (such as MAH grafted ethylene elastomers), or C2 / C3 and C2 / C4 block copolymers, particularly ethylene-based 1-octen elastomers. Ethylene-based 1-octen elastomers may be 0.5-8 g / 10 min MFR (190°C, 2.16 kg), 866-904 kg / m² 3 It may have a density of . Such compounds are commercially available, for example, under the trade name Queo 6800.

[0101] Other additives for use in the composition include pigments or dyes (e.g., carbon black), stabilizers (antioxidants), acid fasteners and / or UV stabilizers, antistatic agents, nucleating agents and utilization agents (such as processing aids). Preferred additives are carbon black, at least one antioxidant and / or at least one UV stabilizer.

[0102] Generally, the amount of these additives is in the range of 0 to 5.0 wt%, preferably 0.01 to 3.0 wt%, and more preferably 0.01 to 2.0 wt%, based on the total weight of the composition.

[0103] Examples of antioxidants commonly used in this technical field include sterically hindered phenols (such as CAS number 6683-19-8, also marketed by BASF as Irganox 1010 FF (trademark)), phosphorus-based antioxidants (such as CAS number 31570-04-4, also marketed by Clariant as Hostanox PAR 24 (FF) (trademark) or by BASF as Irgafos 168 (FF) (trademark)), sulfur-based antioxidants (such as CAS number 693-36-7, also marketed by BASF as Irganox PS-802 FL (trademark)), nitrogen-based antioxidants (such as 4,4'-bis(1,1'-dimethylbenzyl)diphenylamine), or antioxidant blends. Preferred antioxidants may be tris(2,4-di-t-butylphenyl) phosphite and / or octadecyl 3-(3',5'-di-t-butyl-4-hydroxyphenyl)propionate.

[0104] Acid fasteners are also commonly known in the art. Examples include calcium stearate, sodium stearate, zinc stearate, magnesium oxide and zinc oxide, synthetic hydrotalcite (e.g., SHT, CAS number 11097-59-9), lactates and lactylates, as well as calcium stearate (CAS number 1592-23-0) and zinc stearate (CAS number 557-05-1).

[0105] Common anti-blocking agents include natural silica, such as diatomaceous earth (CAS number 60676-86-0 (SuperfFloss (trademark)), CAS number 60676-86-0 (SuperFloss E (trademark)) or CAS number 60676-86-0 (Celite)). 499 (trademark); Synthetic silica (CAS numbers 7631-86-9, 7631-86-9, 7631-86-9, 7631-86-9, 7631-86-9, 7631-86-9, CAS number 112926-00-8, 7631-86-9, or CAS number 7631-86-9, etc.); Silicates (e.g., aluminum silicate (kaolin) (CAS number 1318-74-7), sodium aluminum silicate (CAS number 1344-00-9), calcined kaolin (CAS number 92704-41-1), aluminum silicate (CAS number 1327-36-2), or calcium silicate (CAS number 1344-95-2); Synthetic zeolites (e.g., sodium calcium aluminosilicate hydrate) This is aluminosilicatehydrate (CAS number 1344-01-0), or sodium calcium aluminosilicate hydrate (CAS number 1344-01-0).

[0106] Examples of UV-blocking agents include bis(2,2,6,6-tetramethyl-4-piperidyl)-sebacate (CAS No. 52829-07-9, Tinuvin 770) and 2-hydroxy-4-n-octoxy-benzophenone (CAS No. 1843-05-6, Chimassorb 81). Preferred UV stabilizers are low molecular weight and / or high molecular weight UV stabilizers, such as n-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, 2,2,6,6-tetramethyl-4-piperidinol, and higher fatty acids (mainly stearic acid) and / or mixtures of poly((6-morpholino-s-triazine-2,4-diyl)(1,2,2,6,6-pentamethyl-4-piperidyl)imino)hexameta-ylene(1,2,2,6,6-pentamethyl-4-piperidyl)imino)).

[0107] Alpha-nucleating agents such as sodium benzoate (CAS No. 532-32-1) and 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol (CAS No. 135861-56-2, Millad 3988). Suitable antistatic agents include, for example, glycerol esters (CAS No. 97593-29-8), ethoxylated amines (CAS No. 71786-60-2 or 61791-31-9), or ethoxylated amides (CAS No. 204-393-1). Typically, these additives are added in amounts of 100 to 2,000 ppm for each individual component of the polymer.

[0108] The present invention is also understood to relate to a method for preparing a polyolefin composition as defined herein. The method is - A step of providing a required amount of a mixture of (A) the at least one polypropylene homopolymer (b) and the at least one heterogeneous polypropylene copolymer (a) and the blend of the recycled plastic material (A); - A step of melting the mixture in an extruder; and -Optionally, a step to pelletize the obtained polyolefin composition. Includes.

[0109] For the purposes of the present invention, mixing and melting can be carried out using any suitable melting and mixing means known in the art.

[0110] However, the melting and mixing steps are preferably carried out in a mixer and / or blender, a high-shear or low-shear mixer, a high-speed blender, or a twin-screw extruder. Most preferably, the melting and mixing steps are carried out in a twin-screw extruder, such as a co-rotating twin-screw extruder. Such twin-screw extruders are well known in the art, and those skilled in the art will adapt the melting and mixing conditions (e.g., melting temperature, screw speed, etc.) according to the process equipment.

[0111] The polyolefin composition according to the present invention can be used in a wide range of applications, such as the manufacture of caps, closures, lids, and thin-walled packaging. [Examples]

[0112] [Experimental item] The following examples are included to illustrate specific aspects and embodiments of the invention as described in the claims. However, those skilled in the art should understand that the following description is merely illustrative and should not be construed as limiting the invention in any way.

[0113] [Test Method] The following definitions of terms and determination methods apply to the above general description of the present invention and to the following examples, unless otherwise defined.

[0114] a) Amount of iPP, polystyrene, ethylene (and ethylene-containing copolymer) content, and amount of polyamide-6 and polystyrene (and containing copolymer) To establish different calibration curves, different standards of iPP and HDPE, and iPP, PS, and PA6 were blended. To quantify the foreign polymer content, IR spectra were recorded in the solid state using a Bruker Vertex 70 FTIR spectrometer. Films were fabricated using a compression molding machine at 190°C with a clamping force of 4–6 MPa. The film thickness for the iPP and HDPE calibration standards was 300 μm, while film thicknesses of 50–100 μm were used for the quantification of iPP, PS, and PA6. Spectral range: 4000–400 cm⁻¹ -1 Aperture: 6mm, spectral resolution: 2cm -1 Standard transmission FTIR spectroscopy was performed using 16 background scans, 16 spectral scans, an interferogram zero-filling factor of 32, and Norton-Beer strong apodization.

[0115] iPP 1167cm -1The absorption of the band is measured, and the iPP content is quantified according to the calibration curve (absorption / thickness (cm) vs. iPP content (weight %)). 1601cm -1 (PS) and 3300cm -1 The absorption of the (PA6) band is measured, and the PS and PA6 content is quantified according to the calibration curve (absorption / thickness (cm) vs. PS and PA content (wt%)). The polyethylene and ethylene-containing copolymer content is obtained by subtracting (iPP + PS + PA6) from 100, taking into account the content of non-polymeric impurities determined by the method described below. The analysis is performed as a double test.

[0116] b) The amounts of talc and chalk were measured by thermogravimetric analysis (TGA). The experiment was performed using a Perkin Elmer TGA 8000. Approximately 10–20 mg of the material was placed in a platinum pan. The temperature was equilibrated at 50°C for 10 minutes, and then raised to 950°C under nitrogen at a heating rate of 20°C / min. The weight loss (WCO2) between approximately 550°C and 700°C was attributed to CO2 generated from CaCO3, and therefore the chalk content was evaluated as follows: Chalk content = 100 / 44 × WCO2

[0117] Subsequently, the temperature was lowered to 300°C at a cooling rate of 20°C / min. Then, the gas was switched to oxygen, and the temperature was raised again to 900°C. The weight loss in this process was allocated to carbon black (Wcb). Once the carbon black and chalk content was known, the ash content excluding chalk and carbon black was calculated as follows: Ash content = (ash content remaining) -56 / 44 x WCO2 - Wcb

[0118] Here, the ash content is expressed as a weight percentage measured at 900°C during the first process, which was carried out under nitrogen. The ash content is estimated to be the same as the talc content of the recycled material investigated.

[0119] c) Amount of paper and wood Paper and wood were identified by conventional laboratory methods, including milling, flotation, microscopy, and thermogravimetric analysis (TGA) or flotation techniques.

[0120] d) The amount of metal was determined by X-ray fluorescence (XRF).

[0121] e) The amount of limonene was determined by solid-phase microextraction (HS-SPME-GC-MS). Further details for specific samples are provided below.

[0122] f) The amount of total fatty acids was determined by solid-phase microextraction (HS-SPME-GC-MS). Further details for specific samples are provided below.

[0123] g) The melt flow rate was measured as indicated under a load of 2.16 kg (MFR2) at 230°C or 190°C. The melt flow rate is the amount (g) of polymer extruded within 10 minutes by a test apparatus conforming to ISO 1133 under a load of 2.16 kg at a temperature of 230°C (or 190°C).

[0124] h) Tensile modulus, tensile strength, tensile fracture strain, tensile strain at tensile strength, tensile fracture stress Measurements were taken after the test specimens had been conditioned for 96 hours (23°C, 50% relative humidity).

[0125] The tensile modulus was measured using injection-molded test specimens (dogbone shape, 4 mm thick) as described in EN ISO 1873-2, according to ISO 527-2 (crosshead speed = 1 mm / min, 23°C).

[0126] Tensile strength and tensile fracture strain were measured using injection-molded specimens (dogbone shape, 4 mm thick) as described in EN ISO 1873-2, according to ISO 527-2 (crosshead speed = 50 mm / min, 23°C).

[0127] Tensile strain for tensile strength was determined according to ISO 527-2, using injection-molded test specimens (dogbone shape, 4 mm thick) as described in EN ISO 1873-2, with an elongation rate of 50 mm / min until the specimen fractured.

[0128] Tensile fracture stress was determined for samples prepared from tablet-formed plaques with a sample thickness of 4 mm, according to ISO 527-2 (crosshead speed = 50 mm / min).

[0129] i) Impact strength was determined as Charpy impact strength for 80 × 10 × 4 mm injection-molded test specimens prepared according to EN ISO 1873-2, at +23°C (with notch) according to ISO 179-1 / 1eA, or at +23°C (without notch) according to ISO 179-1 / 1eU. According to this standard, the sample was tested after 96 hours.

[0130] j) Puncture energy was measured according to ISO 6603-2, 4.4 m / s, 2 mm, 23°C.

[0131] k) Cold xylene soluble content (XCS) is measured at 25°C according to ISO 16152; first edition; 2005-07-01.

[0132] l)Crystex analysis Crystalline fractionation method and soluble fractionation method The crystalline (CF) and soluble (SF) fractions of polypropylene (PP) compositions, as well as the comonomer content and intrinsic viscosity of each fraction, were analyzed using CRYSTEX QC by Polymer Char (Valencia, Spain). The crystalline and amorphous fractions were separated through a temperature cycle involving dissolution at 160°C, crystallization at 40°C, and redissolution in 1,2,4-trichlorobenzene (1,2,4-TCB) at 160°C. The quantification of SF and CF, and the determination of the ethylene content (C2) of the parent EP copolymer and its soluble and crystalline fractions, were performed using an infrared detector (IR4) and an online two-capillary viscometer used for determining the intrinsic viscosity (iV). The IR4 detector is a multi-wavelength detector that detects IR absorption in two different bands (CH3 and CH2) to determine the concentration and ethylene content of the ethylene-propylene copolymer. The IR4 detector detects known ethylene content in the range of 2 wt% to 69 wt% ( 13 Calibration is performed using eight EP copolymer series with varying concentrations of each EP copolymer, ranging from 2 to 13 mg / ml, as determined by 13C-NMR spectroscopy.

[0133] The amounts of soluble fraction (SF) and crystalline fraction (CF) are correlated with the amount of "cold xylene soluble content" (XCS) and each cold xylene insoluble content (XCI) fraction, determined by the standard gravimetric method in accordance with ISO 16152 through XS calibration. XS calibration is achieved by testing various EP copolymers with XS content ranging from 2 to 31 wt%.

[0134] The intrinsic viscosities (iV) of the parent EP copolymer and its soluble and crystalline fractions are determined using an online two-capillary viscometer, and they correlate with the corresponding iVs determined by the standard method in decalin according to ISO 1628. Calibration is achieved using various EP-PP copolymers with iVs of 2–4 dL / g.

[0135] The PP composition to be analyzed is weighed to a concentration of 10 mg / ml to 20 mg / ml. 1,2,4-TCB containing 250 mg / l of 2,6-tert-butyl-4-methylphenol (BHT) as an antioxidant is automatically filled into a vial, and then dissolved at 160°C for 60 minutes under constant stirring at 800 rpm until completely dissolved.

[0136] A fixed amount of sample solution is injected into a column packed with an inert support, and the sample is crystallized and the soluble fraction is separated from the crystalline portion. 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 (low temperature) and crystalline fraction (high temperature) are measured as a result of the crystallization cycle (wt% SF, wt% C2, iV). EP stands for ethylene propylene copolymer. PP stands for polypropylene.

[0137] m) Intrinsic viscosity is measured in accordance with DIN ISO 162811, October 1999 (in decalin, 135°C).

[0138] n) Heating aging experiment Store at 120°C for 300 hours: Six tensile rods were placed in a circulating air oven. Each tensile rod conformed to the ISO 527-2 1A test specimen shape. These tensile rods were stored on a metal grid in a Heraeus NTU75 / 125 circulating air oven and conditioned at 120°C for 300 hours. After the conditioning period, the specimens were retrieved and conditioned again in a controlled environment of 23°C / 50% (relative humidity).

[0139] Store at 150°C for 75 hours: Six tensile rods were placed in a circulating air oven. Each tensile rod conformed to the ISO 527-2 1A test specimen shape. These tensile rods were stored on a metal grid in a Votsch HeatEvent 60 / 60 circulating air oven and conditioned at 150°C for 75 hours. After the conditioning period, the specimens were retrieved and conditioned again in a controlled environment of 23°C / 50% (relative humidity).

[0140] Tables 1 and 2 below summarize several examples (Comparative Example - CE; Invention - IE).

[0141] Blends A1 to A4 of various recycled materials were used. These blends are characterized by the following properties:

[0142] Blend A-1: Total C2 content: 8-10 wt%, C2(CF) content: 7-8 wt%, C2(SF) content: 28-30 wt%, MFR2: 10-16 g / 10 min, Tensile modulus: 1100-1350 MPa, Impact strength (Charpy test 23°C): 4-7 kJ / m 2

[0143] Blend A-2: Total C2 content: 9-21 wt%, C2(CF) content: 16-19 wt%, C2(SF) content: 32-35 wt%, MFR2: 15-25 g / 10 min, Tensile modulus: 1150-1350 MPa, Impact strength (Charpy test 23°C): 4-7 kJ / m 2

[0144] Blend A-3: Total C2 content: 9-21 wt%, C2(CF) content: 7-20 wt%, C2(SF) content: 32-35 wt%, MFR2: 10-40 g / 10 min, Tensile modulus: 1100-1450 MPa, Impact strength (Charpy test 23°C): 5-7 kJ / m 2

[0145] Blend A-4: Total C2 content: 9-21 wt%, C2(CF) content: 7-20 wt%, C2(SF) content: 32-35 wt%, MFR2: 10-40 g / 10 min, Tensile modulus: 1100-1450 MPa, Impact strength (Charpy test 23°C): 5-7 kJ / m 2

[0146] Table 1 shows polyolefin compositions containing the following: a) (IE2, IE5) One heterophase polypropylene copolymer (PPHeco-1, MFR2: 100g / 10 min, T C =112.3℃), one polypropylene homopolymer (PPH-1, MFR2: 800g / 10min, T C (=112.3℃), and recycled material blend A) (Blend A-1, MFR2: 10~16g / 10min, T C (=112.3℃), b) (IE4) One heterophase polypropylene copolymer (PPHeco-1, MFR2: 100g / 10 min, T C =112.3℃), one polypropylene homopolymer (PPH-1, MFR2: 800g / 10min, T C (=112.3℃), and recycled material blend A) (Blend A-2, MFR2: 15~25g / 10min, T C (=112.3℃), c) (IE1) One heterogeneous polypropylene copolymer (PPHeco-2, MFR2: 70g / 10 min, T C =112.3℃), one polypropylene homopolymer (PPH-1, MFR2: 800g / 10min, T C (=112.3℃), and recycled material blend A) (Blend A-1, MFR2: 10~16g / 10min, T C =112.3℃), and d) (IE3) One heterophase polypropylene copolymer (PPHeco-2, MFR2: 70g / 10 min, T C =112.3℃), one polypropylene homopolymer (PPH-1, MFR2: 800g / 10min, T C(=112.3℃), and recycled material blend A) (Blend A-2, MFR2: 15~25g / 10min, T C =112.3℃), and further additives, e) (IE6) One heterophase polypropylene copolymer (PPHeco-1, MFR2: 100g / 10 min, T C =112.3℃), one polypropylene homopolymer (PPH-1, MFR2: 800g / 10min, T C =112.3℃), and recycled material blend A) (Blend A-3, MFR2: 10~40g / 10min), and f) (IE7) One heterophase polypropylene copolymer (PPHeco-1, MFR2: 100g / 10 min, T C =112.3℃), one polypropylene homopolymer (PPH-1, MFR2: 800g / 10min, T C (=112.3℃), and recycled material blend A) (Blend A-4, MFR2: 10~40g / 10min).

[0147] Table 2 shows one heterogeneous polypropylene copolymer (PPHeco-2, MFR2: 70g / 10min, T C =112.3℃) and one polypropylene homopolymer (PPH-1, MFR2: 800g / 10min, T C =112.3℃) and recycled material blend A) (A-1, MFR2: 6~12g / 10min, T C The properties of polyolefin compositions (IE8~IE10) containing (=112.3℃) and further additives are shown.

[0148] The following additives were used: Antioxidants: AO1 (Irganox 1010FF), AO2 (ARENOX DS), AO3 (IRGAFOS 168FF), AO4; Pigments: CB (Plasblak PE6121, commercially available from CAbot); AO501GRA / SONGNOX 21B FF and dosing agents HC001A-B1, FK1820.

[0149] [Table 1]

[0150] Table 1: Polyolefin compositions (Comparative Examples CE1-4) containing heteromorphic polypropylene copolymer PPHeco-1 with an MFR2 of 100 g / 1 / 10 or heteromorphic polypropylene copolymer PPHeco-2 with an MFR2 of 70 g / 1 / 10, mixed with recycled material blend A-1 (MFR2: 10-16 g / 10 min) or blend A-2 (MFR2: 15-25 g / 10 min), and heteromorphic polypropylene copolymer PPHeco-2 with an MFR2 of 100 g / 1 / 10, mixed with recycled material blend A-1 (MFR2: 10-16 g / 10 min) or blend A-2 (MFR2: 15-25 g / 10 min) and further additives, with an MFR2 of 100 g / 1 / 10 Properties of polyolefin compositions according to the present invention (Examples IE1-5), comprising one heterophase polypropylene copolymer PPHeco-2 with an MFR2 of 70 g / 10 and one polypropylene homopolymer (PPH-1, MFR2: 800 g / 10 min), and polyolefin compositions (Examples IE6-7), comprising one heterophase polypropylene copolymer PPHeco-1 with an MFR2 of 100 g / 10 min and one polypropylene homopolymer (PPH-1, MFR2: 800 g / 10 min), mixed with recycled material blend A-3 (MFR2: 10-40 g / 10 min) or blend A-4 (MFR2: 10-40 g / 10 min).

[0151] As can be seen from Table 1, the melt flow rates of the heterogeneous copolymer-homopolymer-recycled compositions according to Examples IE1-7 of the present invention are higher than those of the heterogeneous copolymer-recycled compositions CE1-4. At the same time, the tensile modulus, impact strength, and puncture energy are equivalent. For IE2 and IE3, the same thermal aging exposure as for CE2 and CE4 is achieved.

[0152] Therefore, the properties of the heterogeneous copolymer-homopolymer-recycled composition according to the present invention are characterized by a melt flow rate that enables good processing and a tensile modulus that indicates it is a stable material.

[0153] [Table 2]

[0154] Table 2: Blends of recycled materials, including Dipolen PP (MFR2: 6-12 g / 10 min blend A-1), or blends of recycled materials, including Dipolen PP (MFR2: 6-12 g / 10 min blend A-1), and one heterogeneous polypropylene copolymer (PPHeco-2, MFR2: 70 g / 10 min, T C The properties of the polyolefin composition according to the present invention (Examples IE8-10), which comprises a polyolefin composition containing (Comparative Examples CE5-6) with a temperature of 112.3℃, and a blend of recycled materials, Dipolen PP (Blend A-1) (MFR2: 6-12 g / 10 min), mixed with one heterogeneous polypropylene copolymer PPHeco-2 and one polypropylene homopolymer (MFR2: 70 g / 10 min PPH-1).

[0155] Table 2 shows that the melt flow rate of the heterogeneous copolymer-homopolymer-recycled compositions according to the present invention examples IE8-10 is higher than that of the recycled product (CE-5). Furthermore, in the present invention examples IE8-10, which use homopolymers, the impact strength is increased compared to CE6, which does not use homopolymers, while simultaneously obtaining equivalent tensile strength.

Claims

1. a) Melt flow rate MFR of 20-45 wt% at least 40 g / 10 min ２ At least one heterogeneous polypropylene copolymer having (230°C, 2.16 kg, measured according to ISO 1133); b) Melt flow rate MFR of 10-30 wt% at least 400 g / 10 min ２ At least one polypropylene homopolymer having (230°C, 2.16 kg, measured according to ISO 1133); and c) A blend (A) of recycled plastic material containing 40-60 wt% of polypropylene and polyethylene in a ratio of 3:7-12:1, with a melt flow rate of at least 5 g / 10 min MFR ２ A blend of recycled plastic materials (A) recovered from waste plastic materials derived from used waste and / or industrial waste, having the following characteristics: (230°C, 2.16 kg, measured according to ISO 1133) Includes, A melt flow rate of at least 50 g / 10 min MFR ２ A polyolefin composition characterized by having (measured at 230°C, 2.16 kg, according to ISO 1133).

2. a) 25-45 wt% of at least one heterophase polypropylene copolymer; b) 10 to 25 wt% of at least one polypropylene homopolymer; and c) A blend of recycled plastic materials containing 50-55 wt% polypropylene and polyethylene (A) The polyolefin composition according to claim 1, comprising, wherein the total amount of all components is always 100 wt%.

3. a) 20-40 wt% of at least one heterophase polypropylene copolymer; b) 12-27 wt% of at least one polypropylene homopolymer; and c) A blend of recycled plastic materials containing 50-55 wt% polypropylene and polyethylene (A) The polyolefin composition according to claim 1, comprising, wherein the total amount of all components is always 100 wt%.

4. Melt flow rate MFR of at least 60 g / 10 min ２ The polyolefin composition according to claim 3, characterized by (measured at 230°C, 2.16 kg, according to ISO 1133).

5. The polyolefin composition according to claim 3, characterized by a melt flow rate MFR 2 in the range of 50 to 80 g / 10 min (measured at 230°C, 2.16 kg, according to ISO 1133).

6. A polyolefin composition according to any one of claims 1 to 5, characterized by a tensile modulus of at least 1200 MPa (ISO 527-2).

7. The polyolefin composition according to any one of claims 1 to 6, characterized by a tensile modulus in the range of 1200 to 1500 MPa (ISO 527-2).

8. A polyolefin composition according to any one of claims 1 to 7, characterized by an impact strength of at least 4 kJ / m² (ISO 179, Charpy 1eA + 23°C).

9. The polyolefin composition according to any one of claims 1 to 8, characterized by an impact strength in the range of 4 to 8 kJ / m² (ISO 179, Charpy 1eA + 23°C).

10. A polyolefin composition according to any one of claims 1 to 9, characterized by a puncture energy of at least 1.5 J (ISO 6603-2, 4.4 m / s, 2 mm, 23°C).

11. The polyolefin composition according to any one of claims 1 to 10, characterized by a puncture energy in the range of 1.5 to 15 J (ISO 6603-2, 4.4 m / s, 2 mm, 23°C).

12. The polyolefin composition according to any one of claims 1 to 11, characterized in that the at least one heterogeneous polypropylene copolymer a) is selected from the group consisting of the following: Melt flow rate MFR in the range of -80 to 120 g / 10 min ２ At least one heterogeneous polypropylene copolymer (PPHeco-1) having (measured at 230°C, 2.16 kg, according to ISO 1133); Melt flow rate MFR in the range of -60 to 90 g / 10 min ２ At least one heterogeneous polypropylene copolymer (PPHeco-2) having (230°C, 2.16 kg, measured according to ISO 1133); or These mixtures.

13. The polyolefin composition according to any one of claims 1 to 12, characterized in that the at least one polypropylene homopolymer b) is selected from the group consisting of the following: Melt flow rate (MFR) in the range of -600 to 1000 g / 10 min ２ At least one polypropylene homopolymer (PPH-1) having (measured at 230°C, 2.16 kg, according to ISO 1133); - A melt flow rate MFR in the range of -1000 to 1500 g / 10 min ２ having at least one polypropylene homopolymer (PPH-2) measured in accordance with ISO 1133 at 230 °C and 2.16 kg; Melt flow rate (MFR) in the range of -1700 to 2300 g / 10 min ２ At least one polypropylene homopolymer (PPH-3) having (measured at 230°C, 2.16 kg, according to ISO 1133); Melt flow rate (MFR) in the range of -400 to 500 g / 10 min ２ At least one polypropylene homopolymer (PPH-4) having (measured at 230°C, 2.16 kg, according to ISO 1133).

14. The polyolefin composition according to any one of claims 1 to 13, characterized in that the blend (A) of recycled plastic materials contains a relative amount of units derived from propylene exceeding 50 wt% with respect to the total weight of the blend (A).

15. The polyolefin composition according to any one of claims 1 to 14, characterized in that the blend (A) of recycled plastic materials contains a relative amount of units derived from ethylene of less than 47 wt% with respect to the total weight of the blend (A).

16. A method for producing the polyolefin composition according to any one of claims 1 to 15, comprising the following steps: - A step of providing a required amount of a mixture of the at least one polypropylene homopolymer (b) and the at least one heterogeneous polypropylene copolymer (a) and the blend (A) of the recycled plastic material; and - A step of melting the mixture in an extruder.

17. An article comprising the polyolefin composition according to any one of claims 1 to 15, which is a cap, closure, lid, or thin-walled packaging.

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