Polyolefin composition comprising recycled post-consumer polymer (PCR)

Abstract

In the present disclosure a polyolefin composition comprising a component I, which is a polyethylene enriched post consumer recyclate and a component II, which is a virgin derived polyolefin, having good mechanical properties such as high Environmental Stress Crack Resistance besides good processing properties and resulting in high quality applications. The polyolefin composition is advantageously used for injection moulding articles and products as caps and closures. Figure 1 shows DSC thermograms of virgin PE and PCR. The additional fraction of PP in the material from SUEZ is clearly visible.

Description

POLYOLEFIN COMPOSITION COMPRISING RECYCLED POST-CONSUMER POLYMER (PCR)FIELD OF INVENTION

[0001] The present disclosure relates to a polyolefin composition comprising a recycled polyethylene component, with high Environmental Stress Crack Resistance and a high melt flow ratio which is advantageously used for injection moulding articles and products, especially for production of caps and closure.BACKGROUND OF THE INVENTION

[0002] Polyolefins are increasingly consumed in large amounts in a wide range of applications, including packaging for food and beverages, components for the automotive industry, and a huge variety of different other articles.

[0003] The resulting amount of post-consumer waste is therefore enormous, that’s why people try to process Post-Consumer Waste (PCR) to reuse it. The plastic waste is collected, sorted by plastic type, and then mechanically crushed, washed, and melted into new plastic granules.

[0004] Polyethylene based materials are a particular problem when it comes to reuse. Considering the huge amount of waste collected, compared to the small amount of waste recycled back into the stream, there is still a great potential for reuse and mechanical recycling.

[0005] In general, these polyolefinic recyclates are commonly inhomogeneous, and are often mixed and cross contaminated with polypropylene (PP) and also nonpolyolefins, such as polyethylene terephthalate (PET), polyamide (PA), polystyrene (PS) or non-polymeric substances like wood, paper, glass or aluminum which results in worse processability, while these multicomponent cross-contaminations drastically limit final applications. Despite various closed loop processes like bottle-to-bottle or cup-to-cup recycling, all face the same challenge: efficient separation is difficult, often resulting in excessive PP in PE (or vice versa), making it very hard to achieve pure recyclate without significant effort.

[0006] WO 2021 / 074171 A1 relates to polyethylene compositions containing high levels of post-consumer recycled (PCR) material for use in caps and closures. It addresses the challenge of maintaining mechanical performance and environmental stress-crack resistance while incorporating significant PCR content. By combiningJanuary 28, 2026 1 / 27selected PCR polyethylene with a tailored polyethylene booster resin, the composition achieves improved ESCR, good processability, and a balanced property profile suitable for injection- or compression-moulded closure applications.

[0007] Furthermore, recycled polyethylene (rPE) as described e.g. in EP 4045 589 B1 has been used to produce new plastic articles in order to reduce waste and lower the demand for virgin polymers. Various types of plastics, including HDPE, LLDPE, LDPE, PP, PVC, PET, PS and PC, are commonly recycled. However, the reuse of recycled HDPE presents several challenges. One known issue addressed in this patent is the presence of undesirable odors, which may result from multiple heat histones or contamination in the recycling stream. Another challenge is achieving adequate mechanical performance, especially environmental stress crack resistance (ESCR) and impact resistance, when incorporating significant amounts of recycled HDPE. Prior art, such as described in WO 2012 / 139967 A1 and WO 2016 / 005265 A1. Therefore, recyclates are blended with virgin material, using different processes for recycling HDPE and blending the post-consumer HDPE with virgin polyethylene resins to obtain improved mechanical properties. These mentioned(?)documents describe compositions combining PCR HDPE with virgin Ziegler-Natta-catalyzed multimodal polyethylene to enhance ESCR and processing behavior.

[0008] Despite these developments, difficulties remain in producing closures and molded articles with good mechanical strength, organoleptic properties and stress-crack resistance when recycled polyethylene is incorporated at higher levels.

[0009] Comparing the properties of recycled polyolefin materials and virgin materials, the recyclate normally shows properties, which are much worse unless the amount of recycled polyolefin added is extremely low. For example, such materials often have limited impact strength and poor other mechanical properties (such as e.g., ESCR) and thus, they do not fulfil customer requirements. The use of post-consumer recyclate material PCR material may result in poor processabilityand less mechanical strength in products etc. Polyethylene grades are used in a wide range of rigid applications where a significant contribution to sustainability and low carbon solutions is desired. A particular problem in recycled polyethylene materials is that variations of the desired properties can also be observed in recycled polyethylene blendsJanuary 28, 2026 2 / 27depending on the waste origin, e.g. the ESCR (Environmental Stress Crack Resistance) suffers from inhomogeneity of the polyolefin composition.

[0010] The object of the present invention is therefore to provide a polyolefin composition comprising high amounts of recovered post consumer plastic waste and providing a polyolefin composition with good properties. Further it is an object of the invention to provide a polyolefin composition wherein at least a part of virgin polyolefin is replaced by polyolefinic material recovered from a specific source of waste plastic material, e.g. from bottle to bottle processes, offering cap to cap use, while thermomechanical properties mechanical properties, processability, high environmental stress crack resistance and impact resistance of such a polyolefin composition are suitable for caps and closure applications.SUMMARY OF THE INVENTION

[0011] This object has been solved by providinga polyolefin composition comprising,I. Component I in the range from 80 to 20 wt. %, preferably in the range from 75 to 25 wt. %, preferably in the range from 70 to 30 wt. %, preferably in the range from 60 to 40 wt. % of a polyethylene enriched blend of a post-consumer recyclate component (PCR) (based on the total weight of the polyolefin composition), comprising 85 to 100 wt. % of polyethylene and 15 to 0 wt. % of polypropylene (based on the total weight of the polyolefin composition), having a) a density in the range from 0.948 to 0.960 g / cm3, preferably in the range from 0.950 to 0.958 g / cm3, preferably in the range from 0.953 to 0.956 g / cm3(ISO 1183, at 23 °C);b) a MI2 in the range from 1.0 to 3.0 g / 10 min, preferably in the range from 1.3 to 2.5 g / 10 min, preferably in the range from 1.5 to 2.0 g / 10 min (ISO 1133, 190°C, 2.16 kg);II. component II in the range from 20 to 80 wt. %, preferably in the range from 25 to 75 wt. %, preferably in the range from 30 to 70 wt. %, preferably in the range from 40 to 60 wt. % (based on the total weight of the polyolefin composition) of at least one multimodal polyethylene, comprisinga) at least one polyethylene homopolymer,b) at least one polyethylene copolymer, formed from ethylene and at least one olefin with at least 4 and / or 6 carbon atoms used as comonomer, havingJanuary 28, 2026 3 / 27c) a density in the range of 0.948 to 0.960 g / cm3, preferably in the range of 0.950 to 0.958 g / cm3, preferably in the range of 0.952 to 0.955 g / cm3(ISO 1183); d) a melt flow rate MI2 in the range of 1.0 to 5.0 g / 10 min, preferably in the range of 1.5 to 4.0 g / 10 min, preferably in the range of 2.0 to 3.0 g / 10 min (ISO 1133, 190 °C, 2.16 kg);wherein the sum of all ingredients adds up to 100 wt. %.

[0012] The polyolefin composition comprising component I, polyethylene enriched post consumer recyclate, specifically using recyclate preferably from caps and closures, and component II, the virgin polyethylene component, derived either from Ziegler Natta catalyzed processes or by using a Hybrid catalyst, offers a significant improvement in material properties such as high environmental stress crack resistance ESCR or impact resistance. This innovative composition enhances the mechanical strength and durability of the final product, making it suitable for high-stress applications such as caps and closures. Additionally, the use of recyclate reduces the overall environmental footprint by minimizing the reliance on virgin materials and promoting the circular economy. This combination not only meets industry standards for performance but also aligns with sustainability goals, providing a competitive edge in the market.DETAILED DESCRIPTION OF THE INVENTION

[0013] This object has been solved by providinga polyolefin composition comprising,I. Component I in the range of 80 to 20 wt. % of a polyethylene enriched blend of a post consumer recyclate (PCR) (based on the total weight of the polyolefin composition), comprising 85 to 100 wt. % of polyethylene and 15 to 0 wt. % of polypropylene (based on the total weight of the polyolefin composition), having a) a density in the range from 0.948 to 0.960 g / cm3(ISO 1183, at 23 °C);b) a MI2 in the range from 1.0 to 3.0 g / 10 min (ISO 1133, 190 °C, 2.16 kg);II. component II in the range of 20 to 80 wt. % (based on the total weight of the polyolefin composition) of at least one multimodal polyethylene, comprising a) at least one polyethylene homopolymer,b) at least one polyethylene copolymer formed from ethylene and at least one olefin with at least 4 and / or 6 carbons atoms used as comonomer, havingJanuary 28, 2026 4 / 27c) a density in the range of 0.948 to 0.960 g / cm3(ISO 1183);d) a melt flow rate MI2 in the range of 1.0 to 5.0 g / 10 min (ISO 1133, 190 °C, 2.16 kg);wherein the sum of all components always adds up to 100 wt. %.

[0014] This polyolefin composition provides a blended material comprising recyclate and less virgin polyethylene, being suitable for production of caps and closures, wherein only small amounts of component I, the polyethylene enriched polyethylene has is replaced by component II, the virgin derived polyolefin material, wherein the achieved properties can be seen by the good mechanical properties. Such compositions are applicable due to high melt flow and ideal combination of density and environmental stress crack resistance for high quality injection moulding applications, especially for caps and closures. Optionally the polyolefin composition can comprise further additives.

[0015] Further, the polyolefin composition has an FNCT in the range of 3.0 to 15.0 h, preferably in the range of 4.0.0 to 13.5 h, preferably in the range of 5.0 to 12.0 h (ISO 16770, 80 °C, 4 MPa, Arkopal N100).

[0016] Further, the polyolefin composition has a Charpy in the range of 2.0 to 10.0 kJ / m2, preferably in the range of 3.5 to 8.0 kJ / m2, preferably in the range of 4.0 to 7.0 kJ / m2(ISO 179-1).

[0017] Further providing enhanced mechanical properties: The polyolefin composition comprising component I, the polyethylene enriched post consumer recyclate and component II, the virgin polyethylene can improve the impact resistance and environmental stress crack resistance of the material. This makes the caps and closures more durable and capable of withstanding repeated use and mechanical stress.

[0018] The blend is easy to process, making it easier for injection molding to obtain caps and closures. This can lead to more efficient manufacturing processes and reduced production times.

[0019] Incorporating polyethylene recyclates reduces the reliance on virgin materials, thereby decreasing the environmental impact. This approach supports sustainability initiatives and can improve the company’s environmental credentials.

[0020] The polyolefin composition, wherein component II, the polyethylene component of virgin origin is havingJanuary 28, 2026 5 / 27a) a FNCT in the range of 8.0 to 20.0 h, preferably in the range of 10.0 to 18.0 h, preferably in the range of 12.0 to 16.0 h (ISO 16770, 80 °C, 4 MPa, Arkopal N100);b) a charpy acN in the range of 2.0 to 15.0 kJ / m2, preferably in the range of 3.5 to 12.5 kJ / m2, preferably in the range of 4.0 to 11.0 kJ / m2(ISO 179-1).

[0021] The polyolefin composition, wherein the polyethylene enriched post consumer recyclate is havinga) a FNCT in the range from 0.1 to 10.0 h, preferably in the range 0.15 to 9.5 h, preferably in the range from 0.2 to 8.5 h (ISO 16770, at 25 °C4 MPa, Arkopal N100);b) a charpy acN in the range from 1.0 to 10.0 kJ / m2, preferably in the range from 1.5 to 7.0 kJ / m2, preferably in the range from 2.5 to 5.0 kJ / m2(ISO 179-1 , 50 °C, 6MPa).

[0022] The polyolefin composition may further comprise additives. Examples of additives for use in such a composition are pigments or dyes, acid scavengers and / or UV stabilizers, primary and secondary antioxidants, antistatic agents, nucleating agents and utilization agents (such as processing aid agents). Preferred additives are, at least one antioxidant and / or at least one UV stabilizer. The amount of these additives is in the range of 0.0 to 4.0 wt. %, preferably in the range of 0.01 to 3.0 wt. %, preferably in the range of 0.01 to 2.0 wt. % based on the total weight of the polyolefin composition.

[0023] Further can be acid scavengers added, one common example is calcium stearate. While due to the recycling origin of consumer waste, the composition may comprise further organic fillers, and / or inorganic fillers, and / or additives in the range of 0.5 to 8.5 wt. %, preferably in the range of 1.0 to 5.0 wt. %, preferably in the range of 2.0 to 3.5wt. %, based on the total weight of the polyolefin composition.

[0024] The polyolefin composition, wherein the polyethylene enriched post consumer recyclate component is comprising a post consumer resin from post consumer waste, and / or a mixed plastic polyethylene recycling blend obtained from post consumer recyclate, obtainable by sorting, shredding etc. of post consumer waste, comprising polyethylene. Using sorted recyclates provided by the advantages in modem recycling technology, as they have improved the quality and consistency of recycled polyethylene, sorting has developed meaning that still contaminants are often present in the recyclate used, but the amount of polypropylene significantly has beenJanuary 28, 2026 6 / 27reduced. When blended with virgin polyethylene, the resulting material can achieve a uniform quality that meets industry standards.

[0025] The polyolefin composition is comprisinga) component I in the range of 80 to 20 wt. %, preferably in the range of 70 to 30 wt. %, preferably in the range of 60 to 40 wt. % (based on the total weight of the polyolefin composition) of the polyethylene enriched blend of the post consumer recyclate component, wherein the post consumer recyclate material is comprising polypropylene and polyethylene, in the range of 85.0 to 100 wt. % of polyethylene, preferably in the range of 90.0 to 99.0 wt. %, preferably in the range of 95.0 to 97.0 wt. % and in the range of 15.0 to 0 wt. % of polypropylene, preferably in the range of 10 to 1 wt. %, preferably in the range of 5.0 to 3.0 wt. % and is preferably derived from caps and closures, b) component II in the range of 20 to 80 wt. %, preferably 30 to 70 wt. %, more preferably 60 to 40 wt. % of the at least one bimodal polyethylene, wherein the polyethylene is obtained using a Hybrid- catalyst or Ziegler-Natta- catalyst; c) and optionally further additives, wherein the sum of all components always adds up to 100 wt. %.

[0026] Component I, the polyethylene enriched post consumer recyclate provided as colored, sorted flakes, size distribution of 13 mm at the most, preferably derived from caps and closures.

[0027] The polyolefin composition comprises component I, the polyethylene enriched blend of a post-consumer recyclate component which preferably is having food approval and is preferably derived from recycled caps and closures from beverages and consumer goods, comprising mainly polyethylene and polypropylene.

[0028] Anexample of this is Multiprop 3230 (Veolia), which is used in one of the examples mentioned.

[0029] The blend can be either recycled post-consumer waste, preferably from consumer waste such as caps and closures, derived from beverages, such as PET-bottles and the PE and PP caps. Also, the recyclate used can be derived from waste streams of recycled post-consumer waste and / or post-industrial waste.

[0030] Preferably, component I, the polyethylene enriched recycled material is obtained from recycled waste by means of plastic recycling processes known in the art. Such recyclates are commercially available, e.g. from Veolia e.g., “Multiprop 3230” (Germany),January 28, 2026 7 / 27

[0031] It is considered that the present invention could be applicable to a broad range of different polyethylene enriched recyclates used in compositions comprising recyclate and having a high content of recycled polyethylene. Such polyethylene enriched recycled material may be provided in the form of flakes or granules.

[0032] The polyolefin composition comprises as component I post consumer plastic waste and as component II virgin polyethylene, resulting in the inventive polyolefin composition suitable to be used for second life applications such as in injection moulding applications, with very good mechanical properties and also high environmental stress crack resistance. The processing and application properties of recyclates are in many cases detrimental compared to virgin plastic. It has been found that by compounding, blending mixing and extruding, the at least bimodal, and / or multimodal polyethylene as described herein can be turned into the present polyolefin composition. The composition comprises a post consumer polyethylene based composition with superior properties, which match the required key properties as required for different applications.

[0033] Component II derived from virgin sources, in the range of 20 to 80 wt. %, preferably 30 to 70 wt. %, more preferably 60 to 40 wt. % (based on the total weight of the polyolefin composition) of at least one multimodal polyethylene, derived either from a multi reactor process, or by using a single site hybrid catalyst as described in the following, comprisinga) at least one polyethylene homopolymer,b) at least one polyethylene copolymer formed from ethylene and at least one olefin with at least 4 and / or 6 carbons atoms used as comonomer, obtained from a further reactor process, wherein at least two different components are obtained, and distributed to finally obtain a multimodal polyethylene component having the following properties: such asc) a density in the range of 0.948 to 0.960 g / cm3, preferably in the range of 0.950 to 0.958 g / cm3, preferably in the range of 0.952 to 0.955 g / cm3(ISO 1183); d) a melt flow rate MI2 in the range of 1.0 to 5.0 g / 10 min, preferably in the range of 1.5 to 4.0 g / 10 min, preferably in the range of 2.0 to 3.0 g / 10 min (ISO 1133, 190 °C, 2.16 kg).

[0034] Due to the extraordinary good properties of component II, the virgin polyethylene component as it combines both properties in a unique combination andJanuary 28, 2026 8 / 27is therefore very suitable for compounding with component I, the polyethylene enriched post consumer recyclate, it can be used for compounding of the virgin polyethylene component into the recyclate and obtain polyolefin composition which have good properties regarding processability and mechanical properties.

[0035] Compounding refers per definition to a process of combining different materials or substances to create a new mixture or substances with specific properties or characteristics that may not be achievable individually. This process is used in various applications to enhance the performance of the materials.

[0036] An important feature of polyolefin composition and also of polyethylene components of recycled origin and multimodal virgin component is the environmental stress cracking resistance (ESCR, which can be measured by a full notched creep test ), which defines the formation of cracks in a material caused by relatively low tensile stress and environmental conditions, and is given in the number of hours that 50 % of the specimens tested exhibit stress cracks. The ESCR in polyethylene depends strongly on molecular weight, molecular weight distribution, chain branching (measured indirectly by density), and ESCR testing conditions (i.e., reagent concentration, temperature, stress). In general, resistance to slow crack growth (ESCR) decreases as the amount of crystallinity increases in a material.

[0037] In an embodiment the polyolefin composition is having an environmental stress crack resistance (ESCR) is in the range from 5 to 15 h, preferably in the range from 6 to 14 h, most preferably in the range from 7 to 13h (ISO 16770, 6 MPa, Arkopal N100, 50°C).

[0038] The polyolefin composition comprising component II from post-consumer waste, and / or a mixed plastic polyethylene recycling blend obtained from post consumer recyclate, obtainable by sorting, washing, steaming, shredding, extrusion etc. of post consumer polyethylene comprising waste.

[0039] Selection of components of polyethylene comprising one or more different polyethylene post consumer resins. Post consumer blends are derived from all different post consumer materials, and also comprising post industrial polyethylene based waste.

[0040] The polyolefin composition comprises component I, which is a polyethylene enriched post consumer recyclate from post consumer waste shredded into pieces such that their final size, measured at the maximum length of the pieces, is 10 mm or greater, preferably derived from caps and closures.January 28, 2026 9 / 27

[0041] Component I is a post-consumer resin that preferably originated from a specific collection of domestic or household waste. Preferably, polyethylene post-consumer resin. In a preferred embodiment, component A is or comprises a regrind from postconsumer sorted caps. However, polyethylene post consumer recyclate, enriched in polyethylene, often contains low amounts of polypropylene having comparable features, may be used.

[0042] The amount of polypropylene present in component I is in the range of 15 to 0 wt. %, preferably in the range of 7.0 to 5.0 wt. %, preferably in the range of 5.0 wt. % to 3.0 wt. %.

[0043] Leaving a certain amount of polypropylene in polyethylene in general significantly enhanced cost reduction as a polyethylene enriched recyclate does not necessarily need to be 100% pure without any contaminants. Using a recycled polyethylene - polypropylene blend can therefore reduce material costs, as recycled PP is generally less expensive than virgin materials. This cost-saving can be significant, especially in large-scale production.

[0044] The polyolefin composition, comprising as component I a polyethylene of virgin origin, obtainable using a Ziegler Natta catalyst or Hybrid catalyst, being a bimodal, preferably a multimodal polyethylene, wherein the polyethylene is homopolymer and / or copolymer or mixture thereof, the copolymer comprising ethylene and one or more alpha-olefin co-monomers selected from the group comprising C3 to C20 alpha-olefins; with preference, the co-monomer is 1 -hexene, 1- butene or 1-octen.

[0045] The polyolefin composition according to any of the preceding claims, characterized in that polyethylene is at least a bimodal, preferably multimodal polyethylene obtained by a process using a preferably a hybrid catalyst system, obtainable by a process described herein.

[0046] Surprisingly, it has been found that the resulting polyolefin composition may comprise a content of recycled material of at least 20 wt.% but can be used in the manufacture of caps or closures as it shows a desired balance of mechanical properties comprising stiffness and environmental stress crack resistance (ESCR), and good processing properties. In addition, the composition of polyethylene shows good processability performances as it can be injected at a pressure of less than 1450 bar, preferably of less than 1400 bar during the manufacture of caps or closures. The inventive polyolefin composition is remarkable as it provides a process and aJanuary 28, 2026 10 / 27composition comprising a high content of recycled material but can be used to produce caps or closures with high stiffness and processability but enhanced ESCR

[0047] The polyolefin composition is obtained by different steps, providing the steps of blending, mixing and extruding using optionally a twin screw extruder for blending of component I and component II and optionally pelletizing the obtained polyolefin composition.

[0048] The step of blending of the components can be carried out according to any blending method known from the art and in any combinations thereof in different variations. This can be, for instance, dry blending, wet blending or melt blending. The blending conditions depend upon the blending technique and the kind and ratio of the recycled polyethylene involved.

[0049] Preferably, the polyolefin composition further comprises at least one ultraviolet absorber selected from the group of hydroxyphenyl benzotriazoles; with preference, in an amount of at least 500 ppm based on the total weight of the polyolefin composition of polyethylene and / or in an amount of at most 4000 ppm based on the total weight of the polyolefin composition, preferably in an amount of at most 2000 ppm based on the total weight of the polyolefin composition. Especially when post consumer polyethylene enriched recycled material is blended with polyethylene of virgin origin, the absorption of UV light accelerates degradation of polyethylene, therefore for protection ultraviolet absorber should be added.

[0050] The polyethylene component of virgin origin is obtainable by a polymerization process comprising the steps ofa) polymerizing the ethylene monomer andb) optionally one or more alpha olefin co-monomers,c) in the presence of a hybrid catalyst system, prepared comprising the following steps:i. provision of a mixture of at least two different organic transition metal compounds, at least one hydrolyzed organo- aluminum compound and a solvent andii. impregnation of a dry porous support component with the mixture of a total volume of the mixture being from 0.6 to 1.5 times the total pore volume of the support component.

[0051] Use of polyolefin composition preferably for injection moulding and compression moulding applications.January 28, 2026 11 / 27

[0052] Use of polyolefin composition, for manufacturing of a cap or closure, having high environmental crack resistance and stiffness, which can be provided by the polyolefin composition.

[0053] An article comprising the polyolefin composition according to any of the preceding claims, characterized in that the article is processed via injection moulding, preferably wherein the article is used for caps and closures.

[0054] ESCR of production of caps and closure is a key to demanding applications, apart from excellent processability. A narrow molar mass distribution is favorable for injection moulding processing but unfavorable for getting a higher ESCR performance. Polyethylene combines both properties in a unique combination and is therefore very suitable for blending with recycled HDPE. The used virgin resin for preparing the blends shows a higher flow melt rate, typical for injection moulding applications, in contrast to the blend composition as described in WO 2021 / 074171.

[0055] The present disclosure is also concerned with maximizing the loading of recycled material (with loadings of up to 85 wt. % of recyclate) in the composition and with the use of a combination of specific blends of component II to improve the ESCR properties.

[0056] The inhomogeneity of the post consumer recyclate can often be easily detected by means of DSC reflecting different melting points and enthalpies of blend ingredients. Figure 1 shows DSC thermograms of virgin PE and PCR. The additional fraction of PP in the material from SUEZ is clearly visible.

[0057] The underlying problem to be solved is the use of a “Hybrid” catalyst with two components in a single reactor. Hybrid Catalysts have been found to deliver an excellent combination of high Charpy and ESCR properties in combination with extraordinary high melt index enabling significant lowering of processing temperatures, saving cost, time and energy when the polyethylene is processed via injection molding or compression molding which is unprecedented so far in known polyethylene world. Regarding the data, the contribution of polyethylene of virgin origin for the technical effect is clearly shown that the hybrid grades perform much better with respect to Charpy and FNCT at the same density and even significantly higher MFR (2.16 kg).

[0058] Furthermore, component I obtainable by using the inventive hybrid catalyst, is also a much desired blending component to improve recyclate processing andJanuary 28, 2026 12 / 27application properties. As the properties like the melt index of component II are so high, the loading of the inventive polyethylene with less processable recyclate is much higher.

[0059] These hybrid catalysts introduce an “in-reactor” blend with excellent homogeneity, high ESCR and Charpy properties, as they move polyethylene processes to a new level in product properties. By modifying the catalyst composition it is possible to tune the polymer structure, the type and the reaction conditions, besides resulting in high processability, as the use of two active sites on the catalyst it combines e.g. good ESCR performance with high impact strength at low temperatures, while the obtained polyethylene gain excellent processability from the 1st active component of the hybrid catalyst and mechanical properties from the 2nd active component: Resulting in a completely new approach of designing and adjusting desired properties in polyethylene synthesis.CATALYST PREPARATION

[0060] The preparation of the catalyst system to obtain polyethylene (B) is described in the following in more detail, comprising the following steps:

[0061] A) provision of a mixture of at least two different organic transition metal compounds, at least one hydrolyzed organoaluminum compound and a solvent and

[0062] B) impregnation of a dry porous support component with the mixture from step A), with the total volume of the mixture being from 0.6 to 1.5 times the total pore volume of the support component.

[0063] Furthermore, we have found a catalyst system for the polymerization of olefins which has an angle of repose determined in accordance with ISO 4324 is not more than 48° and comprises at least two different organic transition metal compounds and at least one hydrolyzed organoaluminum compound.

[0064] In addition, we have found the use of the catalyst system for the polymerization or copolymerization of olefins and a process for preparing polyolefins by polymerization or copolymerization of olefins in the presence of the catalyst system.

[0065] Possible organic transition metal compounds are in principle all compounds of the transition metals of groups 3 to 12 of the Periodic Table or the lanthanides which contain organic groups and preferably form catalysts which are active in olefin polymerization after reaction with the hydrolyzed organo-aluminum compound. These are usually compounds in which at least one monodentate or polydentate ligand is bound via a sigma or pi bond to the central atom. Possible ligands include both ligands January 28, 2026 13 / 27containing cyclopentadienyl radicals and ligands which are free of cyclopentadienyl radicals. A large number of such compounds which are suitable for olefin polymerization are described in Chem. Rev. 2000, Vol. 100, No. 4. Multinuclear cyclopentadienyl complexes are also suitable for olefin polymerization. Organic transition metal compounds containing only halogens and / or alkoxides are less well suited.Catalyst preparation is described in detail in EP1740626, where either catalyst (Example 1 or Comparative Example 1) yields polyethylene suitable for use as component II in the described polyolefin composition.

[0066] Example 1

[0067] A mixture of 632 mg (1.042 mmol) of 2,6-diacetylpyridinebis(2,4-dichloro-6-methylphenylanil)iron dichloride, 4.38 g (8.903 mmol) of bis(n-butylcyclopentadienyl)hafnium dichloride and 188 ml, of MAO (4.75 M in toluene, 895 mmol) was stirred at room temperature for 30 minutes and subsequently added to 147.9 g of the pretreated support material while stirring and the mixture was stirred at room temperature for a further 2 hours ((Fe+Hf):AI=1 :90). The ratio of the total volume of the added solution to the pore volume of the support was 0.84. The solid was dried under reduced pressure until it was free flowing. This gave 310.4 g of catalyst which still contained 34% by weight of solvent (based on the total weight and calculated assuming complete application of all components to the support).

[0068] Comparative example C1

[0069] A mixture of 3.2 mg (56.44 pmol) of 2,6-diacetylpyridinebis(2,4-dichloro-6-methylphenylanil)iron dichloride and 1.07 ml of MAO (4.75 M in toluene, 5.07 mmol) in a further 10 ml of toluene was stirred at room temperature for 30 minutes and subsequently added to 8.6 g of the pretreated support material while stirring and the mixture was stirred at room temperature for a further 2 hours. The ratio of the total volume of the added solution to the pore volume of the support was 0.85. The solid was dried under reduced pressure until it was free-flowing and the calculated residual moisture content of solvent was less than 5%. A mixture of 241.6 mg (491.13 pmol) of bis(n-butylcyclopentadienyl)hafnium dichloride and 9.3 ml of MAO (4.75 M in toluene, 44.21 mmol) in a further 1.7 ml of toluene, which had been stirred at room temperature for 30 min beforehand, was added to the solid obtained in this way and the mixture was subsequently stirred at room temperature for a further two hours. The ratio of the total volume of the added solution to the pore volume of the support was 0.85. TheJanuary 28, 2026 14 / 27solid was dried under reduced pressure until it was free-flowing and the calculated residual moisture content of solvent was less than 5%. ((Fe+Hf):AI=1 :90). This gave 12 g of catalyst which still contained 2.3% by weight of solvent (based on the total weight and calculated assuming complete application of all components to the support).

[0070] Polymerisation:

[0071] Prod. Productivity of the catalyst in g of polymer obtained per g of catalyst used per hour total-CH3 is the amount of CH3-groups per 1000C including end groups.

[0072] Bis(n-butylcyclopentadienyl)hafnium dichloride is commercially available from Crompton Ltd. A. Preparation of the individual catalyst components.

[0073] 2,6-Bis[1-(2-tert.butylphenylimino)ethyl]pyridine was prepared as in example 6 of WO 98 / 27124 and 2,6-Bis[1-(2-tert.butylphenylimino)ethyl]pyridine iron(ll) dichloride was prepared as in example 15 of WO 98 / 27124.2, 6-Bis[1 -(2,4,6-trimethylphenylimino)ethyl]pyridine was prepared as in example 1 of WO 98 / 27124 and reacted in an analogous manner with iron(ll) chloride to give 2,6-Bis[, 1 -(2,4,6-trimethylphenylimino)ethyl]pyridine iron(ll) dichloride, as likewise disclosed in WO 98 / 27124. 2,6-Bis[1-(2,4-dichloro-6-methylphenylimino)ethyl]pyridine iron(ll)dichloride was prepared according to the method of Qian et al., Organometallics 2003, 22, 4312-4321. Here, 65.6 g of 2,6-diacetylpyridine (0.4 mol), 170 g of 2,4-dichloro-6-methylaniline (0.483 mol), 32 g of silica gel type 135 and 160 g of molecular sieves (4A) were stirred in 1500 ml of toluene at 800 C for 5 hours and a further 32 g of silica gel type 135 and 160 g of molecular sieves (4A) were subsequently added. The mixture was stirred at 80 °C for a further 8 h, the insoluble solid was filtered off and washed twice with toluene. The solvent was distilled off from the filtrate obtained in this way, the residue was admixed with 200 ml of methanol and subsequently stirred at 55°C for 1 hour. The suspension formed in this way was filtered and the solid obtained was washed with methanol and freed of the solvent. This gave 95 g of 2,6-Bis[1 -(2,4,6-trimethylphenylimino)ethyl]pyridine in 47% yield. The reaction with iron(ll) chloride was carried out as described by Qian et al., Organometallics 2003, 22, 4312-4321.

[0074] 2,6-Bis[1-(4,6-Dimethyl-2-chloro-phenylimino) ethyl]pyridine iron(ll) dichloride was prepared in analogy to 2,6-Bis[1-(2,4-dichloro-6-methylphenylimino)ethyl]pyridine iron(ll) dichloride as described above.

[0075] B) Preparation of the mixed catalyst systems employed for synthesis of the polyethylene a):

[0076] Example 1January 28, 2026 15 / 27

[0077] a) Support pretreatment

[0078] XPO-2107, a spray-dried silica gel from Grace, was calcinated at 600 °C for 6 hours and subsequently 252.2 g of the dried silica gel admixed with 164.5 ml of MAO (4.75 M in Toluol, 0.78 mol). The mixture was stirred for one hour, filtered, the solid washed with toluene and then died under reduced pressure, b) Preparation of the mixed catalyst systems

[0079] A mixture of 1.48 g (2.45 mmol) of 2,6-Bis[1-(2,4-dichloro-6-methylphenylimino)ethyl]pyridine iron(ll) dichloride, 3.61 g (7.34 mmol) of bis(n-butylcyclopentadienyl)hafnium dichloride and 159.6 ml of MAO (4.75 M in toluene, 0.76 mol) was stirred at room temperature for 1 h and subsequently added while stirring to a suspension of 237.1 g of the pretreated support material a) in 800 ml of toluene. The mixture was stirred at room temperature for a further 3 hours, the resulting solid filtered off and washed with toluene. The solid was dried under reduced pressure until it was free-flowing. This gave 256.7 g of catalyst.

[0080] Example 2a)

[0081] Support pretreatment

[0082] XPO-2107, a spray-dried silica gel from Grace, was calcinated at 600 °C for 6 h.

[0083] b) Preparation of the mixed catalyst systems

[0084] A mixture of 5.35 g (9.69 mmol) of 2,6-Bis[1-(2-tert.butylphenylimino)ethyl]pyridine iron(ll) dichloride, 7.49 g (15.22 mmol) of bis(n-butylcyclopentadienyl)hafnium dichloride and 472 ml of MAO (4.75 M in toluene, 2.24 mol) was stirred at room temperature for 30 minutes and subsequently added while stirring to a suspension of 276.8 g of the pretreated support material a) during the course of 45 min ((Fe+Hf):AI=1 :90). The solid was dried under reduced pressure until it was free-flowing. This gave 609 g of catalyst which still contained 31.5 % by weight of solvent (based on the total weight and calculated on the basis of complete application of all components to the support).

[0085] Example 3

[0086] Support pretreatment and preparation of the mixed catalyst systems were done essentially as described in example 1, except that 2,6-Bis[1-(4,6-Dimethyl-2-chloro-phenylimino) ethyljpyridine iron(ll) dichloride was employed instead as the iron catalyst complex.

[0087] C. Polymerization of the catalystJanuary 28, 2026 16 / 27

[0088] The polymerization was always carried out in a fluidized-bed reactor having a diameter of 0.5 m. The reaction temperature was in the range of 94 to 1050 °C, the output in the range of 3.1 to 3.8 kg / h, ethylene was dosed at 3.0 to 5.0 kg / h and 1-hexene at 50 to 100 g / h, hydrogen gas was metered at 0.5 to 1.5 l / h. The pressure in the reactor was 20 bar.0.1 g of tri-isobutylaluminium per hour were metered in in each case, except for comparative examples where hydrogen was metered at about 3 to 4 l / h. More detailed information on representative individual synthetic polymerization protocols is published in WO 2005 / 103095. Catalysts were the catalysts from at least one of examples 1-3. Post-reactor granulation took place in a twin screw extruder, having a gear-pump operated discharger unit. The polyethylene product had specifications commensurate with the claims and description.EXAMPLES

[0089] The recyclate polyethylene PCR1 Multiprop 3230 is commercially available and sold by Veolia, it contains polyethylene enriched blend of a post-consumer recyclates made susbstancially from PE . The properties of the recyclate are reported in Table 3.

[0090] PCR2 is a recyclate polyethylene component commercially available from Suez, and available under the name Nextpro 480103, which is commercially available and sold by Veolia, it contains polyethylene enriched blend of a post-consumer recyclate, from bottle caps.

[0091] The FNCT (full notched creep test) as a tool for measuring the ESCR (environmental stress crack resistance) is carried out on notched PE specimens immersed in a defined wetting agent (e.g., 2% Arkopal N100, Dehyton, or equivalent surfactant) according to ISO16770. The specimen is exposed to a constant tensile load corresponding to 6 MPa at a test temperature of 50 °C.

[0092] The density of the polyethylene material is determined in accordance with IS0 1183-1, most commonly by the immersion method (method A) at 23 °C. The density is then calculated from buoyancy according to the ISO procedure. The result is reported in g / cm3with the test temperature explicitly stated.January 28, 2026 17 / 27

[0093] The melt index (Ml or MFR) is determined according to ISO 1133-1 using a capillary extrusion rheometer under defined temperature and load conditions. A polymer sample is heated to 190 °C, and the mass of material extruded through a standard die over 10 minutes is measured. The result is expressed in g / 10min and reported for the specific load condition (e.g., 2.16 kg, 5.0 kg, 21.6 kg).

[0094] Impact strength is determined using standardized pendulum impact methods, most commonly Charpy (IS0 179) or tensile-impact (ISO 8256). In this test, a conditioned specimen is mounted in the impact device and struck by a pendulum hammer. The energy absorbed during fracture is recorded and expressed as the impact strength in kJ / m2. The test temperature (e.g. 23 °C or -30 °C) is always specified, since impact resistance decreases significantly at lower temperatures.

[0095] Intrinsic viscosity (I.V.) is determined according to ISO 1628-1 and ISO 1628-3, by dissolving the polymer in decalin at 135 °C and measuring the flow time of the solution through a capillary viscometer. The intrinsic viscosity is calculated from the relative viscosity values using the ISO-defined procedures and is expressed in dl / g.

[0096] Thermal properties are determined by Differential Scanning Calorimetry (DSC) according to ISO 11357-1 / -2, using the second heating scan (after an initial heating and controlled cooling cycle) to obtain stable values independent of the specimen’s prior thermal history.

[0097] Differential Scanning Calorimetry (DSC) is performed in accordance with ISO 11357-1 and IS011357-2 on polymer specimens to determine melting and crystallization behavior. A first heating run is conducted to erase the thermal history of the material, followed by a controlled cooling run and preferably a second heating run, which is used for reporting the characteristic thermal transitions (e.g., melting temperature, crystallization temperature, and heat of fusion). The second heating is preferred because it provides more stable, reproducible thermograms with reduced variations, as the influence of prior processing or storage history has been removed. Differential Scanning Calorimetry (DSC) is especially valuable for the analysis of recycled materials, as it facilitates the identification and qualitative assessment of impurities and the overall composition of recyclates. Unlike virgin grades, which are manufactured directly from the reactor and are inherently free from contamination byJanuary 28, 2026 18 / 27other plastics or polyolefins, recyclates may contain a range of foreign polymer fractions. DSC is therefore an important tool for distinguishing recyclates from virgin grades, as it can detect the presence of non-target materials that are absent in pure, unblended polymers.

[0098] In the context of polyolefin recyclates, DSC is further employed to identify and distinguish different polymeric components within the material. Since each polymer (e.g., HDPE, LDPE, PP) exhibits characteristic melting transitions, multiple melting peaks, shifts in melting temperatures, or abnormal peak shapes are indicative of foreign polymer fractions or contaminants. The technique is therefore particularly suitable for qualitatively and semi-quantitatively assessing the possible presence and proportion of non-target materials in recycled polyolefin streams. This includes evaluating the purity of recyclates, detecting incompatible or non miscible blends, and monitoring batch-to-batch variability.January 28, 2026 19 / 27Table 1: Components and compositions of inventionTable 2: Summary of physical and application properties of components and inventive polyolefin composition.January 28, 2026 20 / 27Table 3: Specification Multiprop von Veolia.>< < >< &January 28, 2026 21 / 27

Claims

CLAIMS1. A polyolefin composition comprising,III. Component I in the range of 80 to 20 wt. % of a polyethylene enriched blend of a post consumer recyclate (PCR) (based on the total weight of the polyolefin composition), comprising 85 to 100 wt. % of polyethylene and 15 to 0 wt. % of polypropylene (based on the total weight of the polyolefin composition), having c) a density in the range from 0.948 to 0.960 g / cm3(ISO 1183, at 23 °C);d) a MI2 in the range from 1.0 to 3.0 g / 10 min (ISO 1133, 190 °C, 2.16 kg);IV. component II in the range of 20 to 80 wt. % (based on the total weight of the polyolefin composition) of at least one multimodal polyethylene, comprising e) at least one polyethylene homopolymer,f) at least one polyethylene copolymer formed from ethylene and at least one olefin with at least 4 and / or 6 carbons atoms used as comonomer, having g) a density in the range of 0.948 to 0.960 g / cm3(ISO 1183);h) a melt flow rate MI2 in the range of 1.0 to 5.0 g / 10 min (ISO 1133, 190 °C, 2.16 kg);wherein the sum of all components always adds up to 100 wt. %.

2. The polyolefin composition, according to claim 1 , wherein the polyethylene component II of virgin origin, is havinga) a FNCT in the range of 8.0 to 20.0 h (measured at 50 °C, at 6 MPa according to ISO 16770),b) a charpy in the range of 2.0 to 15.0 kJ / m2(measured at RT, according to ISO 179-19).

3. The polyolefin composition, according to any of the preceding claims, wherein the polyethylene enriched post consumer recyclate (component II) is havingc) a Charpy in the range from 2.0 to 15.0 kJ / m2(measured at RT, according to ISO 179-21);d) a FNCT in the range from 8.0 to 20 h (measured at, 50 °C, 6 MPa, according to ISO 16770).

4. The polyolefin composition, according to claim 1, comprisingJanuary 28, 2026 23 / 27a) Component I in the range of 80 to 20 wt. % (component I) (based on the total weight of the polyolefin composition) of the polyethylene enriched blend of the post consumer recyclate component, wherein the post consumer recyclate material is comprising polypropylene and polyethylene, in a range from 85.0 to 100 wt. % of polyethylene and in a range 15.0 to 0 wt. % of polypropylene, and is preferably derived from caps and closures, b) Component II in the range of 20 to 80 wt. % of the at least one bimodal polyethylene, wherein the polyethylene is obtained using a Hybrid- catalyst or Ziegler- Natta- catalyst;c) wherein the sum of all components always adds up to 100 wt. %.

5. The polyolefin composition, according to any of the preceding claims, wherein component I is comprising an amount of polypropylene in an amount in the range of 15 to 0 wt. %.

6. The polyolefin composition, according to any one of the preceding claims, having an impact strength (according to ISO 179-1 , at 23 °C) is in the range from 4.0 to 20.0 kJ / m2, preferably in the range from 5.0 to 18.0 kJ / m2, preferably in the range from 6.0 to 15.0 kJ / m2, and an impact strength (ISO 179-1, at 0 °C) in the range from 1.0 to 20.0 kJ / m27. The polyolefin composition, according to any of the preceding claims, wherein component I is comprising a post consumer waste, and / or a mixed plastic polyethylene recycling blend obtained from post consumer recyclate, obtainable by sorting, shredding etc. of post consumer waste, comprising polyethylene.

8. The polyolefin composition, according to any of the preceding claims, characterized in that, component I comprises preferably PCR having food approval, more preferably comprising preferablya regrind from bottle's caps and closures, comprising polyethylene and polypropylene.

9. The polyolefin composition, according any of the preceding claims, characterized in that, component I comprises a polyethylene based recyclate plasticJanuary 28, 2026 24 / 27from post consumer waste shredded into pieces such that their final size, measured at the maximum length of the pieces, is 10 mm or greater.

10. The polyolefin composition, according to any of the preceding claims, characterized in that component II is a polyethylene of virgin origin, obtainable using a Ziegler Natta catalyst or a Hybrid catalyst, being a multimodal homopolymer and / or copolymer or mixture thereof, the copolymer comprising ethylene and one or more alpha-olefin co-monomers selected from the group comprising C3 to C20 alpha-olefins; with preference, the co-monomer is 1 -hexene, 1- buten or 1-octen.

11. Use of a polyolefin composition, according to any one of the preceding claims, for manufacturing of a cap or closure.

12. Process for producing the polyolefin composition according to any one of the preceding claims, wherein the process comprises the steps of providing a mixture ofa) Component I in the range of 80 to 20 wt. % of a polyethylene enriched blend of a post consumer recyclate (based on the total weight of the polyolefin composition) of the polyethylene enriched blend of recycled plastic material, comprising 85 to 100 wt. % of polyethylene and 15 to 0 wt. % of propylene (based on the total weight of the polyolefin composition),b) Component II and in the range of 20 to 80 wt. % of at least one multimodal polyethylene, comprisingi. at least one polyethylene homopolymer, at least one polyethylene copolymer formed from ethylene and at least one olefin with at least 4 and / or 6 carbon atoms used as comonomer, (based on the total weight of the polyolefin composition)ii. and optionally further additivesa. melting the mixture in an extruder, andb. optionally pelletizing the obtained polyolefin composition.January 28, 2026 25 / 2713. The polyolefin composition according to any of the preceding claims, characterized in that, the polyolefin composition is obtained by providing the steps of blending, mixing and extruding using optionally a twin screw extruder, for the blending of component I and component II, and optionally pelletizing the obtained polyolefin composition.

14. An article comprising the polyolefin composition, according to any one of the preceding claims, in particular cap and closure.January 28, 2026 26 / 27

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