High-purity recycled polypropylene material

Abstract

This disclosure relates to a polymer composition comprising at least 95% by weight of post-consumer recycled polypropylene resin based on the total weight of the polymer composition, preferably a melt-processed polymer composition, wherein the ethylene content (C2(CF)) of the crystalline fraction (CF) is The present disclosure relates to a polymer composition in which the total weight of the crystalline fraction of the polymer composition, as measured by the Crystex analysis described herein, is in the range of [C2-3.4] to [C2-0.2] wt%, preferably [C2-3.0] to [C2-0.6] wt%, more preferably [C2-2.4] to [C2-1.2] wt%, and the content of each compound selected from hexanal, limonene, benzene, styrene, and toluene in the polymer composition is below the detection limit as measured by the headspace gas chromatography / mass spectrometry (HS-GC-MS) described herein. The disclosure further relates to the use of the polymer composition in the manufacture of articles and each article.

Description

Technical Field

[0001] The present disclosure relates to a polymer composition comprising a post-consumer recycled polypropylene resin, preferably a melt-processed polymer composition. The present disclosure also relates to the use of the polymer composition, preferably the melt-processed polymer composition, in the manufacture of articles, and to each molded article.

Background Art

[0002] The problem of treating accumulated plastic waste and the corresponding environmental issues have been widely noticed by the general public and experts. Therefore, the recycling of plastic materials that can turn plastic waste into resources for new plastic products has become an important topic. Thus, in the recycling and reuse of plastic materials, it is possible to balance the environmental and economic aspects.

[0003] The recycling of plastic materials has already started in the mid-1990s by implementing a collection system, which enables more targeted collection and separation of plastic materials from other household waste, but the reuse of plastic materials from plastic waste is still limited. So-called post-consumer recycled (PCR) plastic materials usually contain mixtures of different plastics and various contaminants. Methods for further purifying post-consumer recycled (PCR) plastic materials have been developed.

[0004] Post-consumer recycled materials obtained by mechanical recycling equipment, including sorting by color and chemical structure followed by an intensive washing process, still have some drawbacks because the purification is limited to the surface of the polymer particles and substances in the bulk of the particles cannot be removed. Using extrusion and degassing / aeration, larger-sized fillers can be partially removed and volatile substances can be reduced, for example, via melt filtration. The mechanical recycling process is generally known and is described, for example, in International Publication No. 2022 / 200588 and International Publication No. 2022 / 200587.

[0005] Nevertheless, even with current advanced mechanical recycling technologies, properties such as filler content, the presence of certain metals, color, volatile substances, and odor can hinder applications requiring higher purity polymer materials.

[0006] Solvent-based recycling provides recycled polymers of higher purity. For example, International Publication 2017 / 003798 discloses a dissolution process for post-consumer polymers, which prepares polymers with relatively low contaminant content. Further solvent-based recycling processes are disclosed in International Publications 2022 / 128490 and 2022 / 128488. However, these contaminant levels are insufficient for use in all applications, and recycled polymers of even higher purity are required.

[0007] Due to the voluntary setting of sustainability targets by many companies, demand for high-quality recycled materials is very strong and on the rise. In addition, regulations aiming to incorporate a certain percentage of recycled materials into final products are planned for the future.

[0008] Therefore, there is a need for high-purity post-consumer recycled materials that can be used for a variety of applications. [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] International Publication No. 2022 / 200588 [Patent Document 2] International Publication No. 2022 / 200587 [Patent Document 3] International Publication No. 2017 / 003798 [Patent Document 4] International Publication No. 2022 / 128490 [Patent Document 5] International Publication No. 2022 / 128488 [Overview of the project] [Problems that the invention aims to solve]

[0010] The object of the present invention is to provide a polymer composition containing a high content of post-consumer recycled polypropylene resin that addresses the above-mentioned needs. [Means for solving the problem]

[0011] Accordingly, the present invention relates to a polymer composition comprising at least 95% by weight of post-consumer recycled polypropylene resin based on the total weight of the polymer composition, preferably a melt-processed polymer composition, wherein the polymer composition is The ethylene content (C2(CF)) of the crystalline fraction (CF) is, The present invention provides a composition in which the content of each compound selected from hexanal, limonene, benzene, styrene, and toluene in the polymer composition is in the range of [C2-3.4] to [C2-0.2]% by weight, preferably [C2-3.0] to [C2-0.6]% by weight, and more preferably [C2-2.4] to [C2-1.2]% by weight, relative to the total weight of the crystalline fraction of the polymer composition as measured by the Crystex analysis described herein; and the content of each compound selected from hexanal, limonene, benzene, styrene, and toluene in the polymer composition is below the detection limit as measured by the headspace gas chromatography / mass spectrometry (HS-GC-MS) described herein.

[0012] Surprisingly, it was found that the removal of impurities such as limonene and hexanal (which can cause odors) was improved by dissolving the (mechanically) pre-treated plastic feedstock in one or more organic solvents selected from hydrocarbons with boiling points between 75°C and 250°C to recover the purified polymer fraction, and then melt-processing the purified polymer fraction while further separating the solvent.

[0013] The present invention further relates to the use of polymer compositions, preferably melt-processed polymer compositions, in the manufacture of articles, and to each article. [Brief explanation of the drawing]

[0014] [Figure 1] Figure 1 shows the relationship between the ethylene content (C2) of the polypropylene resin and the ethylene content (C2(CF)) of the crystalline fraction of each resin for Examples IE1 and IE2, compared with various virgin PP resins. [Modes for carrying out the invention]

[0015] For the purposes of this specification and the following claims, the term “post-consumer waste” means material that has completed at least its first use cycle (or life cycle), i.e., material that has already served its first purpose. The term “virgin” means newly manufactured material and / or material that has not yet been recycled and is not yet used for the first time. The term “recycled” as used herein means material that has been reprocessed from “recycled waste.”

[0016] The present invention provides a polymer composition comprising a post-consumer recycled polypropylene resin, preferably a melt-processed polymer composition, wherein the content of each compound selected from hexanal, limonene, benzene, styrene, and toluene in the polymer composition is below the detection limit as measured by headspace gas chromatography / mass spectrometry (HS-GC-MS) as described herein.

[0017] Therefore, the content of the most relevant odor-activating substances in the polymer composition of the present invention, preferably the post-consumer recycled polypropylene resin of the polymer composition, and especially the melt-processed polymer composition, is very low. The content indicates the purity grade of the material. Generally, such low content can only be obtained in virgin polymers and not in recycled materials. The high purity grade of the post-consumer recycled polypropylene resin of the polymer composition of the present invention, preferably the melt-processed polymer composition, enables its use in a variety of applications. For example, it can be used in applications where contaminants may adversely affect the manufacture or handling of goods. Furthermore, because the content of contaminants is undefined, its use can also be considered in applications where recycled polymers have not yet been approved according to regulations (e.g., the food industry). Therefore, the polymer composition of the present invention, preferably the melt-processed polymer composition, enables applications in fields where the application of recycled polymers is not yet possible.

[0018] <Polymer composition> The present invention relates to polymer compositions, preferably melt-processed polymer compositions such as melt-extruded polymer compositions. The polymer compositions of the present invention, preferably melt-processed polymer compositions, consist of a post-consumer recycled polypropylene resin, preferably in essence.

[0019] The polymer composition of the present invention, preferably a melt-processed polymer composition, contains at least 95% by weight, preferably at least 97% by weight, more preferably at least 98% by weight, and even more preferably at least 99% by weight of post-consumer recycled polypropylene resin, based on the total weight of the polymer composition. In some embodiments, the polymer composition of the present invention, preferably a melt-processed polymer composition, contains post-consumer recycled polypropylene resin as a single polymer component. According to another embodiment, the polymer composition consists essentially of post-consumer recycled polypropylene resin. In this case, the post-consumer recycled polypropylene resin corresponds to all the polymer material present in the entire composition.

[0020] It is understood that additives such as polymer stabilizers may be present in the polymer composition in low concentrations, up to 5% by weight, preferably up to 3% by weight, more preferably up to 2% by weight, and even more preferably 1% by weight, based on the total weight of the polymer composition. In one aspect of this specification, the polymer composition comprises a post-consumer recycled polypropylene resin and optionally these low concentrations of polymer additives. Generally, low concentrations of additives, up to 5% by weight, do not significantly alter the properties of the polymer composition. In particular, the properties described in this disclosure are not significantly altered by the addition. This means that the described properties based on the total weight of the polymer composition would typically have similar, and possibly even identical, values ​​if measured directly on the post-consumer recycled polypropylene resin. Examples of additives include primary antioxidants, such as sterically hindered phenols (octadecyl 3-(3',5'-di-tertbutyl-4-hydroxyphenyl)propionate (e.g., Irganox 1076), 2,2'-thiodiethylenebis-(3,5-di-tertbutyl-4-hydroxyphenyl)-propionate (e.g., Irganox 1330FF), 2,5,7,8-tetramethyl-2(4',8',12'-trimethyltridecyl)chroman-6-ol (e.g., Irganox E 201), etc.), and secondary antioxidants, such as phosphite esters (e.g., Irgafos 168) or phosphonits.

[0021] Preferably, the compound content in the post-consumer recycled polypropylene resin described later is similar or at least not high in each polymer composition, preferably the melt-processed polymer composition.

[0022] Post-consumer recycled (PCR) polypropylene resin According to the present invention, post-consumer recycled (PCR) polypropylene resin means a resin containing at least one post-consumer recycled polypropylene, i.e., polypropylene obtained from post-consumer waste. Preferably, the post-consumer recycled polypropylene resin contains at least 80% by weight, preferably up to 100% by weight, for example 80-99% by weight, preferably at least 90% by weight, and more preferably at least 95% by weight, of the total weight of the post-consumer recycled polypropylene resin as measured by Fourier transform infrared (FTIR) spectroscopy, of at least one post-consumer recycled polypropylene, i.e., polypropylene obtained from post-consumer waste.

[0023] Therefore, post-consumer recycled polypropylene resin has already completed at least its first use cycle (or life cycle), meaning it has already fulfilled its initial purpose. Unlike virgin polypropylene resin, post-consumer recycled polypropylene resin is a newly produced material that has not yet been recycled. Post-consumer recycled polypropylene resin is also different from industrial waste, i.e., manufacturing scrap that does not typically reach consumers.

[0024] The polymer (i.e., polypropylene) composition of the present invention, preferably a post-consumer recycled (PCR) polypropylene resin of a melt-processed polymer composition, is preferably prepared from a plastic supply raw material comprising, preferably, at least polypropylene, plastic waste such as post-consumer waste, by a process including a mechanical recycling step and a solvent-based recycling step, preferably in combination with a melt-processing step described herein.

[0025] Generally, virgin polymer materials and mechanically recycled polymer materials can be easily distinguished based on the presence or absence of contaminants such as limonene, fatty acids, paper, and / or wood, or generally the ash content. Polypropylene can be further distinguished with respect to the origin of the material by the possible presence of non-polyolefin polymers such as polystyrene and / or polyamide. However, this post-consumer recycled resin is comparable to virgin polypropylene in many of these conventional differentiating characteristics.

[0026] The post-consumer recycled polypropylene resin of the polymer composition of the present invention preferably has an ethylene content (C2(CF)) of the crystalline fraction (CF) measured according to the Crystex analysis described herein in the range of [C2-3.4] to [C2-0.2] wt%, more preferably [C2-3.0] to [C2-0.6] wt%, and most preferably [C2-2.4] to [C2-1.2] wt% based on the total weight of the crystalline fraction of the post-consumer recycled polypropylene resin, whereby it can be distinguished from virgin polypropylene. C2 here represents the value obtained for the ethylene content of each polymer, as will be further described later.

[0027] That is, the ethylene content (C2(CF)) of the crystalline fraction (CF) is preferably in wt% based on the total weight of the crystalline fraction of the post-consumer recycled polypropylene resin, [-3.4 + C2] < C2(CF) < [-0.2 + C2], more preferably [-3.0 + C2] < C2(CF) < [-0.6 + C2], and most preferably [-2.4 + C2] < C2(CF) < [-1.2 + C2].

[0028] Similarly, the polymer composition of the present invention, preferably the melt-processed polymer composition, can be distinguished from virgin polypropylene (composition) by the ethylene content (C2(CF)) of the crystalline fraction (CF) being in the range of [C2-3.4] to [C2-0.2] wt%, more preferably [C2-3.0] to [C2-0.6] wt%, and most preferably [C2-2.4] to [C2-1.2] wt% based on the total weight of the crystalline fraction of the polymer composition.

[0029] As can be seen from Figure 1, the relationship between the ethylene content of the crystalline fraction and the ethylene content of the polymer sample differs between recycled polypropylene resin (SbR product) and virgin polypropylene resin.

[0030] The polymer compositions of the present invention, preferably melt-processed polymer compositions, can be further distinguished from mechanically regenerated polypropylene (compositions) by the gamma phase content, as measured by wide-angle X-ray scattering (WAXS). Regenerated polypropylene materials obtained by solvent-based recycling processes have generally been found to have a much lower gamma phase content in their crystalline structure (measured by WAXS) than the corresponding regenerated polypropylene materials obtained by mechanical recycling processes.

[0031] Preferably, the post-consumer recycled polypropylene resin contains at least 80% by weight, more preferably at least 85% by weight, even more preferably at least 90% by weight, and preferably up to 100% by weight of one or more propylene (co)polymer components, as measured by Fourier transform infrared (FTIR) spectroscopy based on the total weight of the post-consumer recycled polypropylene resin. The expression "propylene (co)polymer component" means propylene homopolymer component and / or propylene copolymer component.

[0032] Preferably, the polymer composition contains one or more propylene(co)polymer components in an amount of at least 80% by weight, more preferably at least 85% by weight, even more preferably at least 90% by weight, and preferably up to 100% by weight, as measured by Fourier transform infrared (FTIR) spectroscopy based on the total weight of the polymer composition.

[0033] Preferably, the polymer composition contains 0 to 1% by weight of a non-polyolefin polymer relative to the total weight of the polymer composition, as measured by Fourier transform infrared (FTIR) spectroscopy. More preferably, the polyamide (PA) and / or polystyrene (PS) polymer in the polymer composition cannot be identified by FTIR spectroscopy. Even more preferably, the PET and / or PVC in the polymer composition cannot be identified by FTIR spectroscopy. Most preferably, none of the PA, PS;PET, and PVC in the polymer composition can be identified by FTIR spectroscopy.

[0034] In particular, the post-consumer recycled polypropylene resin contains 0 to 1% by weight of a non-polyolefin polymer relative to the total weight of the post-consumer recycled polypropylene resin as measured by Fourier transform infrared (FTIR) spectroscopy. More preferably, the polyamide (PA) and / or polystyrene (PS) polymers in the post-consumer recycled polypropylene resin are not detectable by FTIR spectroscopy. Even more preferably, the PET and / or PVC in the post-consumer recycled polypropylene resin are not detectable by FTIR spectroscopy. Most preferably, none of the PA, PS;PET and PVC in the post-consumer recycled polypropylene resin are detectable by FTIR spectroscopy.

[0035] Post-consumer recycled polypropylene resin, and therefore the polymer composition, also preferably comprises a mixture such as a polymer blend of one or more propylene (co)polymer components, including a propylene homopolymer component and / or a propylene copolymer component.

[0036] A "polymer blend" means a mixture of two or more components, at least one of which is a polymer. Generally, blends can be prepared by mixing two or more components. Suitable mixing procedures are known in the art. If such a blend contains virgin material, the virgin material is preferably polypropylene containing at least 90% by weight of a reactor-produced polypropylene material and optionally polymer additives.

[0037] The term "propylene homopolymer" is quantitatively determined based on the total weight of the propylene polymer. 13 C( 1 H) This refers to a propylene polymer consisting of at least 99.0% by weight, preferably at least 99.5% by weight, and more preferably at least 99.8% by weight, of propylene monomer units, as measured by nuclear magnetic resonance (NMR) spectroscopy. In one embodiment, only propylene monomer units in a propylene homopolymer are detectable.

[0038] Propylene homopolymers can exist as isotactic, syndiotactic, and / or atactic propylene homopolymers, depending on their crystalline structure.

[0039] The term "propylene copolymer" usually refers to a propylene polymer containing propylene monomer units and other comonomer units, preferably ethylene comonomer units and / or one or more alpha-olefin comonomer units having 4 to 10 carbon atoms, most preferably ethylene comonomer units. Preferably, the content of propylene monomer units in the propylene copolymer is quantitative. 13 C( 1 Based on the total weight of the propylene copolymer measured by ¹H-NMR spectroscopy, it is at least 70% by weight, and by other methods, quantitatively... 13 C( 1 Based on the total molar content of propylene copolymer measured by ¹H-NMR spectroscopy, it is 70 mol%.

[0040] In some embodiments, the polymer composition contains less than 12% by weight, more preferably less than 10% by weight, most preferably less than 9% by weight, and typically at least 0.1% by weight of ethylene propylene rubber (EPR), based on the total weight of the polymer composition, as measured by cross-fractionation chromatography (CFC) analysis described herein.

[0041] In particular, the post-consumer recycled polypropylene resin contains less than 12% by weight, more preferably less than 10% by weight, most preferably less than 9% by weight, and usually at least 0.1% by weight of ethylene propylene rubber (EPR) based on the total weight of the post-consumer recycled polypropylene resin measured by cross-fractionation chromatography (CFC) analysis described herein.

[0042] The content of ethylene comonomer measured by an IR detector can range from 15 to 50% by weight based on the total weight of ethylene propylene rubber.

[0043] The polymer composition may further contain one or more ethylene (co)polymer components including an ethylene homopolymer component of up to 10% by weight, more preferably up to 6% by weight, most preferably up to 4% by weight based on the total weight of the polymer composition, and an ethylene copolymer component containing ethylene monomer units and one or more alpha-olefin comonomer units having 4 to 10 carbon atoms, measured by quantitative C{ 13 C{ 1 H}-NMR spectroscopy.

[0044] In particular, the post-consumer recycled polypropylene resin contains an ethylene homopolymer component of up to 10% by weight, more preferably up to 6% by weight, most preferably up to 4% by weight based on the total weight of the post-consumer recycled polypropylene resin, and an ethylene copolymer component containing ethylene monomer units and one or more alpha-olefin comonomer units having 4 to 10 carbon atoms, measured by quantitative C{ 13 C{ 1 H}-NMR spectroscopy.

[0045] In some embodiments, the polymer composition comprises 0.1 to 1.0% by weight, preferably 0.2 to 0.5% by weight, of a highly crystalline fraction (HCF) ethylene polymer and / or 1.0 to 5.0% by weight, preferably 2.0 to 3.5% by weight, of a lowly crystalline fraction (LCF) ethylene polymer, as measured by cross-fractionation chromatography (CFC) analysis as described herein, based on the total weight of the polymer composition.

[0046] In particular, the post-consumer recycled polypropylene resin comprises 0.1 to 1.0% by weight, preferably 0.2 to 0.5% by weight, of high crystalline fraction (HCF) ethylene polymer and / or 1.0 to 5.0% by weight, preferably 2.0 to 3.5% by weight, of low crystalline fraction (LCF) ethylene polymer, as measured by cross-fractionation chromatography (CFC) analysis as described herein, based on the total weight of the post-consumer recycled polypropylene resin.

[0047] Since the propylene(co)polymer or ethylene(co)polymer content cannot be directly measured, the weight content is determined by the equivalent ratio from calibrations using isotactic polypropylene (iPP) homopolymer and high-density polyethylene (HDPE).

[0048] The propylene(co)polymer component is preferably highly crystalline, as defined below. However, less crystalline or amorphous copolymer components may also be present in post-consumer recycled polypropylene resins and thus in polymer compositions.

[0049] Preferably, the polymer composition contains 85-95% by weight, more preferably 87-94% by weight, and most preferably 88-93% by weight of crystalline fraction (CF) relative to the total weight of the polymer composition, as measured according to the Crystex analysis described herein.

[0050] In particular, the post-consumer recycled polypropylene resin contains 85-95% by weight, more preferably 87-94% by weight, and most preferably 88-93% by weight of the crystalline fraction (CF) relative to the total weight of the post-consumer recycled polypropylene resin, as measured according to the Crystex analysis described herein.

[0051] Low-crystallinity or amorphous copolymer components constitute the majority of the soluble fraction (SF), and they are present in amounts of preferably 5 to 15% by weight, more preferably 6 to 13% by weight, and even more preferably 7 to 12% by weight, relative to the total weight of the polymer composition as measured according to the Crystex analysis described herein. In particular, they are present in amounts of 5 to 15% by weight, more preferably 6 to 13% by weight, and even more preferably 7 to 12% by weight, relative to the total weight of the post-consumer recycled polypropylene resin as measured according to the Crystex analysis described herein.

[0052] In some embodiments, the polymer composition contains an ethylene content (C2) of 1.5 to 10.0% by weight, preferably 2.0 to 8.0% by weight, and more preferably 2.0 to 7.0% by weight, relative to the total weight of the polymer composition, as measured according to the Crystex analysis described herein.

[0053] In particular, the post-consumer recycled polypropylene resin contains an ethylene content (C2) of 1.5% to 10.0% by weight, preferably 2.0 to 8.0% by weight, and more preferably 2.0 to 7.0% by weight, relative to the total weight of the post-consumer recycled polypropylene resin, as measured according to the Crystex analysis described herein.

[0054] In some embodiments, the polymer composition contains an ethylene content (C2(CF)) of the crystalline fraction in an amount of 0.3 to 5% by weight, preferably 0.4 to 4% by weight, and more preferably 0.5 to 3% by weight, relative to the total weight of the crystalline fraction of the polymer composition, as measured according to the Crystex analysis described herein.

[0055] In particular, the post-consumer recycled polypropylene resin contains an ethylene content (C2(CF)) of the crystalline fraction in an amount of 0.3 to 5% by weight, preferably 0.4 to 4% by weight, and more preferably 0.5 to 3% by weight, relative to the total weight of the crystalline fraction of the post-consumer recycled polypropylene resin, as measured according to the Crystex analysis described herein.

[0056] In some embodiments, the polymer composition contains an ethylene content (C2(SF)) of the soluble fraction in an amount of 10 to 40% by weight, preferably 15 to 35% by weight, and more preferably 20 to 30% by weight, relative to the total weight of the soluble fraction of the polymer composition, as measured according to the Crystex analysis described herein.

[0057] In particular, the post-consumer recycled polypropylene resin contains ethylene content (C2(SF)) of the soluble fraction in an amount of 10 to 40% by weight, preferably 15 to 35% by weight, and more preferably 20 to 30% by weight, relative to the total weight of the soluble fraction of the post-consumer recycled polypropylene resin, as measured according to the Crystex analysis described herein.

[0058] In some embodiments, the polymer composition, particularly the post-consumer recycled polypropylene resin thereof, has an intrinsic viscosity (IV(SF)) of the soluble fraction in the range of 0.8 to 3.0 dl / g, preferably 0.9 to 2.5 dl / g, more preferably 1 to 2 dl / g, as measured according to the Crystex analysis described herein.

[0059] Advantageously, the polymer composition, particularly the post-consumer recycled polypropylene resin thereof, has a ratio of the molecular weight of the soluble fraction (SF) to the molecular weight of the ethylene polymer (PE): Mw(SF) / Mw(PE), which is greater than 2 and preferably less than 5, as measured by cross-fractionation chromatography (CFC) analysis as described herein. A high Mw(SF) / Mw(PE) value means that the high molecular weight ethylene polymer fraction is removed from the composition, while the high molecular weight EPR (ethylene propylene rubber) fraction is retained. Because EPR has a high intrinsic viscosity, beneficial properties are imparted to the composition.

[0060] Preferably, the (weight-average) molecular weight (Mw) of the soluble fraction (SF) of the polymer composition, particularly the post-consumer recycled polypropylene resin, as measured by cross-fractionation chromatography (CFC) analysis described herein, is in the range of 100 to 350 kg / mol, more preferably 110 to 200 kg / mol, and most preferably 120 to 180 kg / mol.

[0061] Preferably, the (weight-average) molecular weight (Mw) of the polymer composition, particularly the ethylene polymer (PE) of the post-consumer recycled polypropylene resin, as measured by cross-fractionation chromatography (CFC) analysis described herein, is in the range of 20 to 100 kg / mol, more preferably 25 to 80 kg / mol, and most preferably 30 to 60 kg / mol.

[0062] This polymer composition, and in particular its post-consumer recycled polypropylene resin, is advantageously represented by its low C2 content and high PEP / EEE ratio in the TREF fraction at 70-95°C, indicating that it is virtually polyethylene-free.

[0063] In some embodiments, the polymer composition, particularly the post-consumer recycled polypropylene resin thereof, has a low ethylene content of less than 34% by weight, preferably less than 30% by weight, more preferably less than 25% by weight, even more preferably less than 16% by weight, and preferably more than 2.5% by weight, in the fraction that elutes at 70-95°C, where high molar mass PE, EP copolymer and low molecular weight i-PP are eluted, as measured by cross-fractionation chromatography (CFC) analysis described herein.

[0064] In some embodiments, the polymer composition, particularly the post-consumer recycled polypropylene resin thereof, is quantitatively as described herein. 13 C{ 1 The ratio of comonomer sequence distributions at the triad level, PEP / EEE, measured by 1H NMR spectroscopy, is greater than 0.3, preferably greater than 0.4. EEE represents the ethylene block of the triad, and PEP represents the propylene-ethylene-propylene block.

[0065] Volatile substances and emissions In polymer compositions, preferably in melt-processed polymer compositions after pelletization, and particularly in post-consumer recycled polypropylene resins, the content of each compound selected from hexanal, limonene, benzene, styrene, and toluene is below the detection limit when measured by headspace gas chromatography / mass spectrometry (HS-GC-MS) as described herein.

[0066] Preferably, in the polymer composition of the present invention, preferably in the melt-processed polymer composition after pelletization, and especially in the post-consumer recycled polypropylene resin, the content of compounds having a boiling point of less than 250°C is very low, and more preferably, such compounds are below the detection limit when measured by the headspace gas chromatography / mass spectrometry (HS-GC-MS) method described herein.

[0067] contaminated materials The polymer composition of the present invention, preferably a melt-processed polymer composition containing post-consumer recycled polypropylene resin, preferably has a very low content of contaminants. This allows for use in a variety of applications. Preferably, the metal content of the polymer composition, and especially the post-consumer recycled polypropylene resin, is very low. For certain contaminants, the content in the polymer composition, and especially in the post-consumer recycled polypropylene resin, is lower than that in virgin polypropylene polymer. In particular, the content of metals used as co-catalysts is reduced.

[0068] The polymer composition preferably has a very low ash content, comparable to virgin polypropylene. Preferably, it also has a very low content of other contaminants. The content of contaminants for the polymer composition is described below. The content of contaminants in post-consumer recycled polypropylene resin is similarly low, i.e., it is present in the same maximum content and range in post-consumer recycled polypropylene resin.

[0069] In some embodiments, a polymer composition comprising post-consumer recycled polypropylene resin, preferably a melt-processed polymer composition, has an ash content of up to 0.07% by weight, preferably up to 0.06% by weight, and more preferably up to 0.05% by weight, relative to the total weight of the polymer composition, preferably the melt-processed polymer composition, as measured according to thermogravimetric analysis (TGA) as described herein. That is, the ash content is in the range of 0 to a maximum of 0.07% by weight, preferably 0 to a maximum of 0.06% by weight, and more preferably 0 to a maximum of 0.05% by weight, relative to the total weight of the polymer composition, preferably the melt-processed polymer composition.

[0070] In particular, the post-consumer recycled polypropylene resin has an ash content of up to 0.07% by weight, preferably up to 0.06% by weight, and more preferably up to 0.05% by weight, relative to the total weight of the post-consumer recycled polypropylene resin, preferably the melt-processed polymer composition, as measured according to the thermogravimetric analysis (TGA) described herein. That is, the ash content is in the range of 0 to 0.07% by weight, preferably 0 to 0.06% by weight, and more preferably 0 to 0.05% by weight, relative to the total weight of the post-consumer recycled polypropylene resin, preferably the melt-processed polymer composition.

[0071] Therefore, the ash content of the post-consumer recycled polypropylene resin and polymer composition is preferably very low. The ash content indicates the purity grade of the material. Generally, such low ash content can only be obtained in virgin polymers and not in recycled materials. The high purity grade of the post-consumer recycled polypropylene resin and polymer composition of the present invention enables its use in a variety of applications. For example, it can be used in applications where contaminants may adversely affect the manufacture or handling of goods. Furthermore, because the contaminant content is undefined, its use can be considered in applications where recycled polymers are not yet approved by regulations (e.g., the food industry). Therefore, the polymer composition of the present invention, preferably a melt-processed polymer composition, enables application in fields where the application of recycled polymers is not yet possible.

[0072] In some embodiments, the polymer composition, preferably a melt-processed polymer composition, has a heavy metal content (w / w) of less than 10 ppm, preferably less than 5 ppm, relative to the total weight of the polymer composition, preferably a melt-processed polymer composition, as measured by X-ray fluorescence (XRF) spectroscopy as the sum of the metal content of cadmium (Cd), chromium (Cr), mercury (Hg), and lead (Pb). In more preferred embodiments, cadmium, chromium, mercury, and / or lead are not identifiable by X-ray fluorescence (XRF) spectroscopy.

[0073] In particular, the post-consumer recycled polypropylene resin has a heavy metal content (w / w) of less than 10 ppm, preferably less than 5 ppm, relative to the total weight of the post-consumer recycled polypropylene resin, as measured by X-ray fluorescence (XRF) spectroscopy as the sum of the metal content of cadmium (Cd), chromium (Cr), mercury (Hg), and lead (Pb). In a more preferred embodiment, cadmium, chromium, mercury, and / or lead are not identifiable by X-ray fluorescence (XRF) spectroscopy.

[0074] In some embodiments, the polymer composition, preferably a melt-processed polymer composition, has a titanium (Ti) content (w / w) of less than 100 ppm, preferably less than 50 ppm, and more preferably less than 20 ppm, relative to the total weight of the polymer composition, preferably a melt-processed polymer composition, as measured by X-ray fluorescence (XRF) spectroscopy.

[0075] In particular, the post-consumer recycled polypropylene resin has a titanium (Ti) content (w / w) of less than 100 ppm, preferably less than 50 ppm, and more preferably less than 20 ppm, relative to the total weight of the post-consumer recycled polypropylene resin, as measured by X-ray fluorescence (XRF) spectroscopy.

[0076] A low titanium content indicates a low content of fillers (e.g., titanium dioxide) in the polymer composition.

[0077] In some embodiments, the polymer composition, preferably a melt-processed polymer composition, has a w / w content of at least one of aluminum (Al), calcium (Ca), or chlorine (Cl) of less than 40 ppm, preferably less than 30 ppm, and more preferably less than 20 ppm, relative to the total weight of the polymer composition, preferably a melt-processed polymer composition, as measured by X-ray fluorescence (XRF) spectroscopy.

[0078] In particular, the post-consumer recycled polypropylene resin has a w / w content of at least one of aluminum (Al), calcium (Ca), or chlorine (Cl) relative to the total weight of the post-consumer recycled polypropylene resin, as measured by X-ray fluorescence (XRF) spectroscopy, of less than 40 ppm, preferably less than 30 ppm, and more preferably less than 20 ppm.

[0079] In one embodiment, the aluminum content is less than 40 ppm, preferably less than 30 ppm, more preferably less than 20 ppm, for example, 0-40 ppm, 0-30 ppm, or 0-20 ppm, respectively. In another embodiment, the calcium content is less than 40 ppm, preferably less than 30 ppm, more preferably less than 20 ppm, for example, 0-40 ppm, 0-30 ppm, or 0-20 ppm, respectively. In yet another embodiment, the chlorine content is less than 40 ppm, preferably less than 30 ppm, more preferably less than 20 ppm, for example, 0-40 ppm, 0-30 ppm, or 0-20 ppm, respectively. In yet another embodiment, the aluminum, calcium, and chlorine content are less than 40 ppm, preferably less than 30 ppm, more preferably less than 20 ppm, for example, 0-40 ppm, 0-30 ppm, or 0-20 ppm, respectively. These content levels apply to polymer compositions, particularly post-consumer recycled polypropylene resins.

[0080] Odor The polymer composition of the present invention, preferably a melt-processed polymer composition, may be characterized by an odor grade of 3 or less (analyzed according to VDA270-B3).

[0081] color Generally, a major drawback of recycled polymers is their high coloring content, which results in a colored, or typically gray, appearance. Therefore, their use is strongly limited to products with a strong color or where appearance is not critical.

[0082] Preferably, the polymer composition of the present invention, preferably the melt-processed polymer composition, has a very low content of coloring components in the post-consumer recycled polypropylene resin.

[0083] The coloration of polymers can be represented using the L*a*b* color space defined by the International Commission on Illumination (CIE). This model represents the color opposition theory, which states that two colors cannot be red and green, or yellow and blue, at the same time. L* represents lightness, a* represents the red / green coordinate, and b* represents the yellow / blue coordinate. The deltas of L*(ΔL*), a*(Δa*), and b*(Δb*) can be positive or negative. However, the sum of the differences, delta E (ΔE, also called the Euclidean distance), is always positive.

[0084] The polymer composition, particularly its post-consumer recycled polypropylene resin, is advantageously characterized by an L* value in the CIEL*a*b* color space determined according to ISO 11664-4 being at least 75, preferably 86-97, more preferably 89-97, for example 90-97.

[0085] In some embodiments, the polymer composition is of the following formula: TIFF2026510752000002.tif11121 (The reference background value here is L ref = 96.01;a ref = -0.29;b ref (= 1.79) The color difference ΔE is less than 7.5, preferably less than 7.0, for example less than 6, and more preferably less than 5.5, compared to a reference background determined according to ISO 11664-4.

[0086] In some embodiments, the post-consumer recycled polypropylene resin has a color difference ΔE defined above, less than 6, preferably less than 5.5.

[0087] The color difference indicates the color intensity of the component, and the color of the component and the reference background (here, L ref = 96.01;a ref= -0.29; b ref It is defined as a numerical comparison with the background plate (= 1.79). It represents the difference in absolute color coordinates (CIEL*a*b* color space) and is called delta (Δ or D).

[0088] In some embodiments, the polymer composition, particularly the post-consumer recycled polypropylene resin, is described in the following CIEL*a*b* color space: -L* is 86-97, preferably 89-97, for example 90-97; -a* is between -0.5 and 0.0; -b* is between 0.0 and 10.0, preferably between 0.0 and 5.0. It holds.

[0089] In the embodiments described above, the color difference ΔE is very small, and the composition appears white. The L* value represents the lightness or brightness of the composition, and a high L* value indicates that the composition is very bright. Therefore, each polymer composition having a low color difference ΔE and / or a high L* value has a white and / or bright appearance comparable to virgin propylene polymers. Thus, they are suitable for white or light-colored articles where appearance is important.

[0090] In some embodiments, the polymer composition, particularly the post-consumer recycled polypropylene resin, has a melt flow rate MFR2 measured at 230°C under a 2.16 kg load according to ISO 1133, in the range of 10 to 40 g / 10 min, preferably 12 to 36 g / 10 min, and more preferably 15 to 30 g / 10 min.

[0091] Optical and mechanical properties The polymer composition comprising post-consumer recycled polypropylene resin of the present invention, preferably a melt-processed polymer composition, preferably has a beneficial balance of mechanical properties, particularly fracture, elongation, and impact properties, and optical properties, particularly good total light transmittance.

[0092] Therefore, the polymer composition of the present invention, preferably a melt-processed polymer composition, is preferably characterized by its good mechanical properties and permeability.

[0093] The polymer composition, particularly the post-consumer recycled polypropylene resin thereof, preferably has a total light transmittance of 60-100%, preferably 65-90%, and more preferably 70-85%, as measured according to ASTM D1003-13 for a 60 x 60 x 1 mm compression-molded plaque.

[0094] In some embodiments, the polymer composition, particularly the post-consumer recycled polypropylene resin, preferably has a tensile modulus E measured according to ISO 527-1 / -2 for a 2 mm thick compression molded specimen of tensile type 5A using a test speed of 20 mm / second, in the range of 1200 to 2000 MPa, more preferably in the range of 1300 to 1900 MPa, even more preferably in the range of 1400 to 1800 MPa, and most preferably in the range of 1500 to 1700 MPa.

[0095] In some embodiments, the polymer composition, particularly the post-consumer recycled polypropylene resin, preferably has a Charpy Notch impact strength of 2.0 to 7.0 kJ / m² at 23°C, measured according to ISO 179-1 / 1eA using an 80 × 10 × 4 mm compression-molded test specimen prepared according to EN ISO 19069-2. 2 The range is, more preferably 3.0 to 6.0 kJ / m 2 The range, more preferably 3.2 to 5.0 kJ / m 2 It is within the range.

[0096] Alternatively, or in addition, these overall performance characteristics can be expressed by their optical-mechanical capabilities: Optomechanical capability (OMA) is understood as the ratio of mechanical (especially impact and bending) behavior to optical performance, i.e., haze. The goal is to maximize mechanical properties while minimizing optical performance, such as haze. Optomechanical capability can be determined by multiplying the flexural modulus by the notched impact strength and comparing this product to the haze measured on a 1 mm plaque. This overall performance can also be expressed by process-focused optomechanical capability (pOMA).

[0097] The optical-mechanical properties of the polymer composition, particularly the post-consumer recycled polypropylene resin, may be at least 50, for example, 50 to 200.

[0098] In some embodiments, the optical-mechanical capability (pOMA) of the polymer composition, particularly the post-consumer recycled polypropylene resin, can be at least 50 or more, for example, 50 to 200.

[0099] The polymer composition of the present invention, preferably a melt-processed polymer composition, containing post-consumer recycled polypropylene resin, preferably has further mechanical properties comparable to virgin polypropylene, particularly a beneficial balance of fracture, elongation, and impact properties.

[0100] In some embodiments, the polymer composition, particularly the post-consumer recycled polypropylene resin thereof, has a tensile strength at yield (TSY) measured according to ISO 527-1 / -2 as described herein, in the range of at least 26 MPa, 28-50 MPa, preferably at least 28 MPa, and more preferably at least 30 MPa.

[0101] In some embodiments, the polymer composition, particularly the post-consumer recycled polypropylene resin, has a flexibility of more than 9, preferably more than 10, such as 9 to 15, as calculated herein.

[0102] The polymer composition comprising post-consumer recycled polypropylene resin of the present invention, preferably a melt-processed polymer composition, preferably has beneficial dynamic mechanical properties comparable to virgin polypropylene, particularly in terms of heat deflection resistance.

[0103] In some embodiments, the polymer composition, particularly the post-consumer recycled polypropylene resin, is determined by the DMTA described herein and has a thermal deflection resistance expressed as the temperature at which it reaches a storage modulus E' of 400 MPa (T(E'=400MPa)) of at least 97°C, preferably in the range of 97°C to 110°C, and more preferably in the range of 98°C to 105°C.

[0104] In some embodiments, the polymer composition, particularly the post-consumer recycled polypropylene resin, is measured at 90°C and has a storage modulus (E', 90°C) determined by the DMTA described herein in the range of 470 to 600 MPa, preferably in the range of 480 to 550 MPa.

[0105] In some embodiments, the polymer composition, particularly the post-consumer recycled polypropylene resin thereof, has a storage modulus (E', 120°C) measured with DMTA as described herein at 120°C in the range of 210 to 350 MPa, preferably in the range of 240 to 300 MPa.

[0106] A polymer composition, preferably a melt-processed polymer composition, can be provided in any of the above embodiments.

[0107] <Method for preparing post-consumer recycled (PCR) polypropylene resin> Plastic supply raw materials The post-consumer recycled polypropylene resin described herein can be obtained from a plastic supply raw material, preferably comprising plastic waste such as post-consumer waste, which contains at least polypropylene.

[0108] Plastic supply materials may include mixtures of polymers, particularly polyolefins, more specifically mixtures of polypropylene with other polyolefins and / or other polymers, such as polyethylene (PE), polystyrene (PS), polyamide (PA), polyvinyl chloride (PVC), expanded polystyrene (EPS), and / or polyethylene terephthalate (PET), additives used to formulate the plastic material, and use-related impurities derived from the lifecycle of the material and the plastic object, and / or use-related impurities derived from the waste recovery and sorting circuitry, and these compounds are collectively considered impurities. Plastic supply materials may further include other contaminants derived from other components of the original plastic object, such as paper, cardboard, wood, fibers, metal, glass, and sand.

[0109] Therefore, the plastic feed material may contain impurities. The plastic feed material may contain up to 50% by weight of impurities, preferably up to 20% by weight, more preferably up to 15% by weight, for example, 1 to 10% by weight, relative to the total weight of the plastic feed material. One specific example of impurities contained in the plastic feed material is additives. Additives used in plastics are organic or inorganic compounds such as fillers, colorants, pigments, plasticizers, property modifiers, and combustion retarders.

[0110] In particular, the plastic supply material includes polyolefins such as polypropylene (PP), polyethylene (PE), and copolymers thereof, especially mixtures of polyolefins. According to this disclosure, the plastic supply material usually contains at least 60% by weight, preferably at least 80% by weight, more preferably at least 85% by weight, for example 80-90% by weight of polyolefins, based on the total weight of the plastic supply material. The plastic supply material preferably contains at least 60% by weight, more preferably at least 80% by weight, most preferably at least 85% by weight, for example 80-90% by weight of polypropylene, based on the total weight of the plastic supply material.

[0111] Preparation process The polymer composition of the present invention, which includes post-consumer recycled (PCR) polypropylene resin, preferably a melt-processed polymer composition, can be prepared from plastic supply raw materials by a recycling process that includes the above-described solvent-based recycling (SbR) process in combination with a mechanical recycling process.

[0112] Accordingly, the present invention also relates to a polymer composition, preferably a melt-processed polymer composition, comprising a post-consumer recycled polypropylene resin as defined herein in terms of its properties, wherein the polymer composition is obtained or can be obtained from a plastic supply raw material by a recycling process comprising the following steps: M) A step of pre-treating plastic feed material by subjecting it to a mechanical recycling process which includes a sieving step, a sorting step by at least one of polymer type, polymer article form, and / or color, a shredding step, and optionally a step of washing the plastic feed material (e.g., a water washing step), and optionally a step of melting the pre-treated plastic feed material; S) A step of obtaining post-consumer recycled polypropylene resin by subjecting the pre-treated, optionally molten, plastic feed material to a solvent-based recycling process, which is preferably carried out by dissolving a plastic feed material containing polypropylene in a solvent and separating insoluble components and soluble impurities, Sa) A dissolution step comprising contacting the pre-treated plastic supply material with a dissolution solvent at a dissolution temperature of 100°C to 300°C and a dissolution pressure of 1.0 to 20.0 MPa (abs) to obtain at least one, preferably one, crude polymer solution, wherein the dissolution solvent is selected from organic solvents containing one or more hydrocarbons having a boiling point of 75°C to 250°C; Sb) Optionally, the crude polymer solution obtained from step Sa) is brought into contact with at least one adsorbent at a temperature of 100 to 300°C and a pressure of 1.0 to 20.0 MPa abs to obtain at least one purified polymer solution; and A step comprising recovering the polymer from the at least one crude polymer solution (Sc) (from the at least one purified polymer solution) to obtain at least one solvent fraction and one purified polymer fraction; and C) A step of melting and processing the post-consumer recycled polypropylene resin obtained from step S), Ca) A step of further separating the solvent from the purified polymer fraction, and Cb) A step comprising melting the purified polymer fraction to obtain the polymer composition of the present invention.

[0113] All the definitions, embodiments, and further features described above for post-consumer recycled polypropylene resins and polymer compositions of the present invention also apply similarly to post-consumer recycled polypropylene resins and polymer compositions obtained or obtainable by recycling process steps.

[0114] Throughout this disclosure, pressure is expressed in absolute pressure (abs).

[0115] Advantageously, the process includes the following steps: Ma) A process of providing a plastic supply raw material, preferably comprising plastic waste such as post-consumer waste, which includes at least polypropylene; Mb) A step of sieving the plastic supply material to produce sieved plastic waste containing polypropylene having only articles of the longest dimensions within a specified range, such as at least 30 mm to 400 mm; Md) A step of sorting the sieved plastic waste by one or more sorting systems, wherein the sieved waste polymer material is sorted by at least the type of polymer, the form of the polymer article, and / or color, thereby producing sorted polypropylene recycled material to be used in subsequent steps; Md) A step of shredding the sorted polypropylene recycled material to form a flake-like polypropylene recycled flow, thereby obtaining a pre-treated plastic feed material in which the flakes preferably have a maximum dimension of 2.5 mm to 20 mm; Sa) A dissolution step comprising contacting the pre-treated plastic supply material with a solvent to obtain at least one crude polymer solution; and thereafter S-E1) Optionally, separate the insoluble matter to obtain at least one clarified polymer solution and one insoluble fraction; Sb) A step of adsorbing the impurities by contact with an adsorbent solid to obtain at least one purified polymer solution; Sc) A step of recovering the polymer to obtain at least one solvent fraction and one purified polymer fraction; Ca) A step of further separating the solvent from the purified polymer fraction, and Cb) A step of melt-processing the purified polymer fraction, preferably by melt extrusion and / or pelletization, wherein additives are preferably added in a molten state, and a polymer composition comprising post-consumer polypropylene recycled resin is obtained by melt-processing, preferably by melt extrusion and / or pelletization.

[0116] Mechanical recycling pretreatment (M) Plastic supply materials, including at least polypropylene, are first pre-treated by a mechanical recycling process, which preferably includes the following steps: A process of providing plastic supply raw materials, preferably consisting of plastic waste such as post-consumer waste, including polypropylene; Mb) A step of sieving the plastic supply material to produce sieved plastic waste having only the longest articles within a defined range; Md) A step of sorting the sieved plastic waste by one or more sorting systems, wherein the sieved waste polymer material is sorted by at least the type of polymer, the form of the polymer article, and / or color, thereby producing sorted polypropylene recycled material to be used in subsequent steps; Md) A step of shredding the sorted polypropylene recycled material to form a flake-like polypropylene recycling stream, thereby obtaining pre-treated flake-like polypropylene recycled material in which the flakes preferably have a maximum dimension of 2.5 mm to 20 mm; Me) Optionally, washing the pre-treated flaked polypropylene recycled material once or more times with a gaseous and / or aqueous washing medium, thereby applying the principle of gravity to separate the flakes from the medium and obtain washed and pre-treated polypropylene recycled material; Mf) Optionally, a step of separating the washed and pre-treated polypropylene recycled material into a light fraction of polypropylene recycled material and a heavy fraction of polypropylene recycled material to obtain a pre-treated heavy fraction of polypropylene recycled material; and Mg) optionally, the pre-treated heavy fraction of the recycled polypropylene material, or, if step Mf) is not present, the washed and pre-purified recycled polypropylene material, is further sorted to obtain one or more target polypropylenes by removing flakes containing one or more materials other than the target polypropylene and / or flakes of undesirable colors (e.g., natural, black, etc.) using one or more optical sorters including NIR and / or optical sensors; Mh) A step of optionally melt-extruding the flake-like pre-treated polypropylene material obtained from the last step among steps Md) to Mg), optionally pelletizing it, and obtaining a pre-treated polypropylene recycled material that has been melt-extruded and optionally pelletized.

[0117] Pre-treated polypropylene recycled material that has been melt-extruded and optionally pelletized, or if step Mh) is not available, further purified and pre-treated polypropylene recycled material, or if steps Mg) and beyond are not available, pre-purified heavy fraction polypropylene recycled material, or if steps Mf) and beyond are not available, washed and pre-treated polypropylene recycled material, or if steps Me) and beyond are not available, pre-treated flake-shaped polypropylene recycled material can be used as the plastic feedstock for the solvent-based recycling process described above.

[0118] As described above, the pre-treated polypropylene recycled material is preferably supplied as a molten feed to the dissolution step Sa) of a solvent-based recycling process, so that the pre-treated polypropylene recycled material in flake or molten-extruded form, such as pellets, is melted before being supplied to the dissolution step Sa). The supply temperature of the molten polypropylene feed is preferably above the dissolution temperature in step Sa). More preferably, the temperature of the molten polypropylene feed is higher than the temperature in step Sa). The molten feed can be pressurized to match the pressure of the dissolution step, so continuous molten feeding is possible. However, batch operation is also possible but is not very desirable.

[0119] Process of sieving plastic supply raw materials (Mb) According to this disclosure, the pretreatment of the plastic feed material includes a step Mb) of sieving the plastic feed material. Sieving is performed to remove fractions that are too large and too small so that the sieved plastic recycled material has only articles with a maximum length of, for example, 400 mm. Preferably, the maximum length is 30 to 400 mm, more preferably 50 to 100 mm.

[0120] The process of sorting the sieved plastic waste (Mc) According to this disclosure, the pretreatment of plastic supply material includes a step Mc) of sorting sieved plastic waste using one or more sorting systems, wherein the sieved waste polymer material is sorted by at least one of polymer type, polymer article form, and / or color, thereby generating a pretreated polypropylene recycling stream.

[0121] A preferred sorting system includes near-infrared (NIR) and / or optical sensors to sort the sieved plastic waste by at least polymer type, polymer article form, and / or color, thereby producing sorted polypropylene recycled material to be used in step Md) and beyond. In step Mc), the sieved plastic waste is preferably sorted by at least color, and optionally also by polyolefin type and / or article form. The sorted polypropylene material is preferably rich in polypropylene content and may contain any desired mixture of polypropylene objects, which are colored and / or uncolored, and flexible and / or rigid.

[0122] As used herein, the term “form of article” refers to the shape and form of an article present in waste polymer material. Such articles may exist in the form of films, bags, and pouches, which can be considered flexible articles, and in the form of molded articles such as food containers, skincare product containers, and plastic bottles, which can be considered rigid articles. Commercial optical sorters such as Tomra Autosort, RTT Steinert Unisort, and Redwave Pellenc can separate so-called rigid articles from so-called flexible articles through the aerodynamic properties of the articles (i.e., a gas flow is normally applied to the flow, and articles that are rigid articles fall in a different arc than flexible articles), thereby converting the flow containing such articles into so-called rigid and flexible flows.

[0123] In the sorting process (Mc), materials other than polypropylene, such as polystyrene, polyamide, polyethylene, metal, paper, and wood, are preferably sorted and removed.

[0124] In the sorting process (Mc), preferably, white and natural-colored waste are sorted and removed so that only non-white and / or non-natural-colored waste, which is least desirable for direct reuse, substantially remains in one or more sorted polypropylene recycling streams. In this context, "natural" means that the object is of a natural color. This means that it does not essentially contain colorants such as pigments (such as carbon black), dyes, or inks. On the other hand, "white" means that a white pigment is present in the object.

[0125] The process of cutting the sorted polypropylene recycling stream (Md) According to this disclosure, the pretreatment of the plastic supply raw material includes step Md) shredding the sorted polypropylene recycled material to form a flake-like polypropylene recycled flow. Preferably, the flakes have a maximum dimension of 2.5 to 20 mm, more preferably 5 to 15 mm.

[0126] The generated and pre-treated flake-type recycled polypropylene material is suitable as a pre-treated plastic feedstock or for solvent-based recycling processes from step Me) onward. This selected polypropylene material includes homogeneous mixtures of colored and uncolored polypropylene articles, as well as heterogeneous mixtures of flexible and rigid polypropylene articles.

[0127] Process Me) for cleaning the recycled flow of flake-shaped polypropylene. According to this disclosure, the pretreatment of the plastic supply raw material includes a step Me) of washing the flaked polypropylene recycled material once or more times with a gaseous and / or aqueous washing medium, thereby applying the principle of gravity to separate the flakes from the medium and produce washed polypropylene recycled material and obtain a pretreated polypropylene recycled flow.

[0128] The generated, washed and pre-treated polypropylene recycled material is suitable as a pre-treated plastic feedstock or for solvent-based recycling processes from step Mf) onward.

[0129] Step Me) preferably includes the following steps: M-e1) A step of washing flake-shaped polypropylene recycled material once or more with an aqueous cleaning solution to obtain suspended polypropylene recycled material, removing the aqueous cleaning solution and optionally any material not floating on the surface of the aqueous cleaning solution from the suspended polypropylene recycled material, thereby generating a cleaned polypropylene recycled flow; and M-e2) A process to dry the washed polypropylene recycled flow to obtain dried polypropylene.

[0130] Step Mf) to separate the recycled flow of pre-treated polypropylene. According to this disclosure, the pretreatment of plastic supply material optionally includes a step Mf) of separating optionally washed and pretreated polypropylene recycled material into a light fraction polypropylene recycled stream and a heavy fraction polypropylene recycled stream. Separation is preferably carried out by a wind shifter. Separation may also be carried out based on the aerodynamic properties of the particles (e.g., flakes) (e.g., separating thin, light, flexible flakes from heavy, thick, rigid flakes). In the sorting step Mf), preferably, thin, light, flexible flakes are sorted and removed such that substantially only rigid polypropylene objects remain in the sorted polypropylene recycled stream. Preferably, the further sorted, pre-purified polypropylene recycled material contains 65 to 100% by weight of rigid polypropylene relative to the total amount of pre-purified polypropylene recycled material.

[0131] The generated and pre-treated heavy fraction polypropylene recycled material is suitable as a pre-treated plastic feedstock or for solvent-based recycling processes from step Mg) onward. This selected polypropylene material includes a mixture of colored and uncolored polypropylene articles, rich in rigid polypropylene articles.

[0132] Further sorting process (Mg) According to this disclosure, the pretreatment of the plastic supply material optionally includes a step Mg) for further sorting of heavy fraction polypropylene recycled material, or, if step Mf) is not present, a step Mg) for further sorting of the pretreated polypropylene recycled material using one or more optical sorters having NIR and / or optical sensors for sorting one or more target polypropylenes. In the sorting step Mg), preferably, flakes containing one or more materials other than the target polypropylene, and / or flakes of undesirable colors (e.g., natural, black, etc.) are removed to obtain a further purified and pretreated polypropylene recycled stream.

[0133] The resulting, further refined and pre-treated polypropylene recycled material is suitable as a pre-treated plastic feedstock or for solvent-based recycling processes from step Mh onward.

[0134] Melt extrusion process (Mh) According to this disclosure, the pretreatment of the plastic supply material includes a step Mh) of melt-extruding an optionally pretreated polypropylene material in flake form. The melt-extruded plastic supply material can optionally be pelletized. In step Mh), the melt-extruded pretreated polypropylene material is optionally provided as pellets.

[0135] Process Mh) is preferably carried out in an extruder, which may be a single-screw or twin-screw extruder, which can be fed using one or more loss-in-weight (LIW) feeders, or it may be fed using a so-called pre-processing unit (PCU) known to those skilled in the art. The dimensionless throughput Q of this extruder can be calculated by the following formula: TIFF2026510752000003.tif1295 (where tr is the extruder throughput, sd is the screw diameter, and ss is the screw speed, which is 0.75 to 0.20, preferably 0.10 to 0.15.)

[0136] The target melting temperature is 190-270°C, preferably 200-250°C, and more preferably 200-230°C.

[0137] The pre-treated polypropylene material can optionally be degassed during extrusion to remove moisture and reduce VOCs.

[0138] Degassing may be performed via up to three, particularly two, degassing ports, for example, one degassing port for top degassing and one degassing port for side degassing, these ports forming part of the extruder. The pressure in the degassing ports may be in the range of 0.5 kPa to 75 kPa (abs), preferably 1 kPa to 50 kPa (abs), and more preferably 1 kPa to 10 kPa (abs), and is achieved with a suitable vacuum system including one or more vacuum pumps.

[0139] The melt-extruded and pre-treated polypropylene material can optionally be melt-filtered downstream of the extruder.

[0140] Melt filtration can be performed using a continuous melt filtration system such as a so-called laser filter manufactured by Erema, an ERF filter manufactured by Ettlinger / Maag, or a band filter manufactured by Britas. The filtration level is typically in the range of 50 to 500 μm, preferably 50 to 250 μm, and more preferably 50 to 150 μm.

[0141] Optionally, the pressure for melt filtration is provided by one or more gear melt pumps, as is well known to those skilled in the art, which enable efficient pressurization with low energy input, thereby reducing the melt temperature and the risk of polymer degradation.

[0142] The generated and melt-treated, preferably melt-extruded, and / or optionally pelletized, pre-treated polypropylene recycled material is suitable for solvent-based recycling processes.

[0143] The pre-treated polypropylene recycled material may preferably have a polypropylene content of more than 90%, preferably more than 95%, based on the total weight of the pre-treated polypropylene recycled material.

[0144] Pre-treated recycled polypropylene material may still contain up to 1.5 wt% inorganic contaminants, such as talc, chalk, TiO2, and pigments, up to about 5 wt% polyethylene, and small amounts of other polymers, such as less than 0.4 wt%, such as PA, PET, EVA, or PVC, and odor-activating substances such as limonene, n-hexanal, toluene, and other odor-activating substances.

[0145] Pre-treated recycled polypropylene material can be analyzed using an NIR flake analyzer to determine the polypropylene and contaminant content before being subjected to a solvent-based recycling process.

[0146] Solvent-based recycling process S) The post-consumer recycled polypropylene resin of this disclosure is obtained by a recycling process that includes a solvent-based recycling process S) for recycling plastic supply raw materials, including plastic waste such as post-consumer waste, which contains polypropylene, after the mechanical recycling process M) described above, by dissolving polypropylene in a solvent under specific temperature and pressure conditions, and optionally contacting the resulting polymer solution with an adsorbent solid. Typically, the dissolving solvent must be able to dissolve polyolefins, particularly polypropylene. Therefore, preferably, the dissolving solvent is a non-polar solvent or a mixture thereof. Therefore, preferably the solvent is a hydrocarbon or a mixture of hydrocarbons. More preferably, the dissolving solvent is a paraffinic solvent or a mixture of paraffinic solvents due to the paraffinic nature ('Similia similibus solventum') of polyolefins.

[0147] Preferably, a solvent-based recycling process S) for purifying pre-treated plastic feedstock includes, and preferably consists of, the following steps: Sa) A dissolution step as defined above, comprising contacting a pre-treated plastic feed material obtained from a mechanical recycling process with a solvent to obtain at least one crude polymer solution; and thereafter S-E1) Optionally, separate the insoluble matter to obtain at least one clarified polymer solution and one insoluble fraction; S-E2) Optionally, a washing step to obtain at least one rinse wastewater and one washed polymer solution by contact with a high-concentration solution; S-E3) Optionally, an extraction step to obtain at least one extracted polymer solution and one used solvent by contact with an extraction solvent; Sb) Adsorption step to adsorb the impurities by contact with an adsorbent solid to obtain at least one purified polymer solution; and finally Sc) A step of recovering the polymer (from at least one purified polymer solution) to obtain at least one solvent fraction and one purified polymer fraction.

[0148] As an example, a solvent-based recycling process S) includes the following steps: Sa) A dissolution step comprising contacting a plastic supply material with a dissolving solvent at a dissolution temperature of 100°C to 300°C and a dissolution pressure of 1.0 to 20.0 MPa (abs), wherein the dissolving solvent is selected from at least one organic solvent containing one or more hydrocarbons having a boiling point of 75°C to 250°C, and obtaining at least one crude polymer solution; Sb) An adsorption step to obtain at least one purified polymer solution by contacting the crude polymer solution obtained from step Sa) with at least one adsorbent at a temperature of 100-300°C and a pressure of 1.0-20.0 MPa (abs); and thereafter Sc) A step of recovering the polymer (from at least one purified polymer solution) to obtain at least one solvent fraction and one purified polymer fraction.

[0149] As a preferred example, a solvent-based recycling process step S) includes, and preferably consists of, the following steps: Sa) A dissolution step comprising contacting a plastic supply material with a dissolving solvent at a dissolution temperature of 100°C to 300°C and a dissolution pressure of 1.0 to 20.0 MPa (abs), wherein the dissolving solvent is selected from at least one organic solvent containing one or more hydrocarbons having a boiling point of 75°C to 250°C, and obtaining at least one crude polymer solution; S-E1) A step of separating insoluble matter to obtain at least one clarified polymer solution and one insoluble fraction; S-E2) Optionally, a washing step to obtain at least one rinse wastewater and one washed polymer solution by contact with a high-concentration solution; S-E3) Optionally, an extraction step to obtain at least one extracted polymer solution and one used solvent by contact with an extraction solvent; Sb) An adsorption step in which the clarified polymer solution obtained from step S-E1), or optionally the washed polymer solution from step S-E2), or the extracted polymer solution from step S-E3), is brought into contact with at least one adsorbent at a temperature of 100-300°C and a pressure of 1.0-20.0 MPa (abs) to obtain at least one purified polymer solution; and thereafter Sc) A step of recovering the polymer (from at least one purified polymer solution) to obtain at least one solvent fraction and one purified polymer fraction.

[0150] Melting process Sa) According to this disclosure, the process includes a dissolution step (Sa) in which a pre-treated plastic supply material is brought into contact with a dissolution solvent at a dissolution temperature of 100°C to 300°C and a dissolution pressure of 1.0 to 20.0 MPa (abs) to obtain at least one, preferably one, crude polymer solution. Specifically, this step advantageously enables the dissolution of at least a portion, preferably all, of the polymer, preferably polypropylene.

[0151] The term "dissolution" should be understood to mean any phenomenon that leads to the formation of a liquid containing a polymer dissolved in at least one polymer solution, i.e., a solvent, more specifically, a dissolving solvent. Those skilled in the art are well aware of the phenomena involved in the dissolution of polymers, which include at least mixing, dispersion, homogenization, and de-entanglement of polymer chains, particularly thermoplastic chains.

[0152] During and at the end of the dissolution process Sa), pressure and temperature conditions make it possible to maintain the dissolution solvent, preferably at least a portion and preferably all of it, in a liquid state, while at least a portion of the soluble fraction of the feedstock, particularly the target polymer, preferably the target thermoplastic, preferably the target polypropylene, and impurities, is advantageously at least partially, preferably completely dissolved. Contact between the dissolution solvent and the pre-treated plastic feedstock can be carried out in a pipeline and / or in one apparatus and / or between two apparatuses to dissolve the polymer of the pre-treated plastic feedstock in the dissolution solvent at least partially, preferably completely. Thus, process Sa) advantageously includes at least one dissolution apparatus and optionally at least one feedstock preparation apparatus, mixing apparatus and / or transfer apparatus. These apparatus and / or apparatus may be, for example, a static mixer, an extruder, a pump, a "reactor" (e.g., a stirring vessel), a countercurrent or reverse current column, or a combination of lines and apparatus. Apparatus for transferring fluids such as gases, especially liquids or solids, is well known to those skilled in the art. In non-limiting embodiments, the transfer device may include a compressor, pump, extruder, vibrating tube, endless thread, or valve. The equipment and / or apparatus may also include, or be combined with, a heating system (e.g., an oven, heat exchanger, tracing, etc.) to achieve the conditions necessary for dissolution.

[0153] In the dissolution step Sa), at least the pretreated plastic feed material is supplied, particularly in the form of one or more pretreated plastic feed material streams, and the dissolving solvent is supplied, particularly in the form of one or more dissolving solvent streams, preferably using one or more transfer devices. The pretreated plastic feed material streams may differ from the dissolving solvent streams. Some or all of the plastic feed material may also be supplied to step Sa) as a mixture with some or all of the dissolving solvent, and the remainder of the solvent and / or the remainder of the feed material may be supplied separately to step Sa) as needed. While the pretreated plastic feed material is in contact with the dissolving solvent, the dissolving solvent is preferably at least partially, preferably completely liquid, while the pretreated plastic feed material, including polymers, particularly thermoplastics, such as polyolefins, and especially polypropylene, may optionally be solid or liquid, containing suspended solid particles. The pretreated plastic feed material may optionally be injected into the dissolution apparatus as a mixture with the dissolving solvent, or as a suspension in the dissolving solvent, and the preparation and injection of the suspension may be continuous or batch.

[0154] Preferably, step Sa) comprises at least one extruder and a melting apparatus. In this case, the pre-treated plastic feed material is supplied to the extruder so that at least a portion, preferably all, of the target polymer, particularly the target polypropylene, contained in the feed material is in a molten state at the outlet of the extruder. The pre-treated plastic feed material is then injected into the melting apparatus in a state at least partially molten. The pre-treated plastic feed material in a state at least partially molten may also be fed by a viscous fluid-specific pump, commonly known as a melt pump or gear pump. The advantage of the pre-treated plastic feed material being (at least partially) molten is that the dissolution of the pre-treated plastic feed material into the solvent is faster and more uniform. In this way, the residence time in the melting process can be reduced and dissolution is promoted. The pre-treated plastic feed material in a state at least partially molten may also be filtered at the outlet of the extruder using a filter, optionally in addition to the melting pump, for the purpose of removing the coarsest particles. Generally, the mesh size of this filter is 10 microns to 1 mm, preferably 20 microns to 200 microns. Preferably, in order to promote shear between the dissolving solvent and the pre-treated plastic feed material, and thus close mixing, and to contribute to the dissolution of the polymer, particularly polypropylene, step Sa) advantageously comprises several extruders into which the dissolving solvent is injected.

[0155] The dissolution solvent used in the dissolution step (Sa) is an organic solvent or a mixture of organic solvents. Preferably, the dissolution solvent is selected from organic solvents, preferably preferentially comprising hydrocarbons having a boiling point of 75°C to 250°C, preferably 80°C to 220°C, and more preferably 80°C to 180°C. Solvents with high boiling points are advantageous in terms of energy consumption because they typically require lower process pressures. Furthermore, lower process pressures are desirable because they allow for safer process control. The boiling point of the dissolution solvent shall be understood as the boiling point of the dissolution solvent at atmospheric pressure (especially equal to 0.1 MPa). The dissolution solvent comprises or preferably comprises one or more hydrocarbons, preferably one or more alkanes, preferably containing 6 to 12 carbon atoms, very preferably 6 to 10 carbon atoms, selected from, for example, cyclohexane and heptane isomers.

[0156] In some embodiments, the dissolving solvent comprises or consists of at least one n-alkane, preferably selected from C7, C8, C9, and C10 n-alkanes or mixtures thereof. In some embodiments, the dissolving solvent comprises or consists of at least one cycloalkane, preferably selected from C6, C7, C8, C9, and C10 cycloalkanes or mixtures thereof. In some embodiments, the dissolving solvent comprises or consists of at least one isoalkane, preferably selected from C7, C8, C9, and C10 isoalkanes or mixtures thereof. In some embodiments, the dissolving solvent comprises or consists of at least one n-alkane, preferably selected from C7, C8, C9, and C10 n-alkanes and mixtures thereof, preferably at least one cycloalkane, preferably selected from C6, C7, C8, C9, and C10 cycloalkanes and mixtures thereof, and / or preferably at least one isoalkane, preferably selected from C7, C8, C9, and C10 isoalkanes and mixtures thereof.

[0157] Preferably, the dissolving solvent, which is an organic solvent, preferably a hydrocarbon, has a critical temperature of 90 to 400°C, preferably 200 to 390°C, more preferably 250 to 350°C, and a critical pressure of 1.5 to 5.0 MPa (abs), preferably 2.0 to 4.3 MPa (abs), more preferably 2.4 to 4.2 MPa (abs). According to a particular embodiment, the boiling point of the dissolving solvent is higher than 75°C, preferably 80 to 220°C, more preferably 80 to 180°C, and / or the solvent preferably comprises an alkane containing at least 7 carbon atoms. Advantageously, dissolution is carried out at a dissolution temperature of 100 to 300°C and a dissolution pressure of 1.0 to 20.0 MPa (abs). More specifically, the temperature and pressure change throughout step Sa) from ambient conditions, i.e., the temperature of the pre-treated plastic feed material at 10 to 30°C and atmospheric pressure (0.1 MPa), until the dissolution conditions, more specifically the dissolution temperature and dissolution pressure, are reached. In particular, the dissolution temperature is 100 to 300°C, preferably 150 to 250°C, and the dissolution pressure is 1.0 to 20.0 MPa (abs), preferably 1.5 to 15.0 MPa (abs), and very preferably 2.0 to 10.0 MPa (abs). Very advantageously, at the end of dissolution step Sa), the dissolved polymer flow is at the dissolution temperature and dissolution pressure. According to a particular embodiment of dissolution step Sa), the dissolution pressure is 1.5 to 2.4 MPa (abs), preferably 1.7 to 2.2 MPa (abs). In this very specific embodiment, any water that may be present in the pre-treated plastic feedstock (in the case of wet plastic feedstock) can then be evaporated and removed during and / or before dissolution, for example, by degassing through vents located on the dissolution line and / or equipment, particularly on the extruder. When this particular embodiment of dissolution step Sa) is implemented, the processing process of the plastic feedstock of the present disclosure does not include any step S-E2) of washing with a high-concentration solution, particularly an aqueous solution. In step Sa), the thermal degradation of the polymer, particularly polypropylene, can be prevented or limited by limiting the temperature to 300°C or less, preferably 250°C or less. Preferably, the melting temperature is above the melting point of the polymer, particularly thermoplastics, more specifically polypropylene, in order to promote their melting.Preferably, the temperature of the dissolution step Sa) is below the critical temperature of the dissolving solvent to prevent the formation of a supercritical phase that can hinder dissolution during the dissolution step Sa). In parallel, the dissolution pressure is greater than the saturated vapor pressure of the dissolving solvent at the dissolution temperature so that the dissolving solvent is at least partially, preferably completely, liquid at the dissolution temperature. Advantageously, the dissolution pressure is above the critical pressure of the dissolving solvent so that the recovery step Sc) can be carried out under conditions where at least a portion of the solvent is in a supercritical state, in particular without the need to significantly increase the pressure between the outlet of step Sa) and step Sc). If the dissolution pressure in step Sa) is above the critical pressure of the dissolving solvent, the dissolution temperature is below the critical temperature of the dissolving solvent so that at least a portion of the dissolving solvent remains liquid. Much advantageously, the dissolution temperature and pressure conditions achieved in step Sa) are adjusted so that the mixture (dissolving solvent + polymer of interest) is a single-phase mixture. Preferably, the weight ratio of the pre-treated plastic feed material to the dissolving solvent is 0.01 to 5.0, more preferably 0.05 to 3.0, and even more preferably 0.10 to 1.0.

[0158] Advantageously, the dissolution step Sa) is carried out with a residence time of 1 to 600 minutes, preferably 2 to 300 minutes, and more preferably 2 to 180 minutes. The residence time is understood to be the residence time at the dissolution temperature and pressure, i.e., the duration of the plastic feed material pretreated with the dissolution solvent at the dissolution temperature and pressure in step Sa). Advantageously, the dissolution solvent used in step Sa) preferably consists of a supply of fresh solvent and / or a stream of regenerated solvent obtained from a recovery step Sc). Optionally, the processing may include an intermediate adsorption step S-a') located during or directly downstream of the dissolution step Sa), which preferably includes introducing an adsorbent solid such as alumina, silica, silica-alumina, activated carbon, or decolorized earth (e.g., bleached earth) in the form of divided particles into the crude polymer solution obtained at the end of step Sa) or optionally during the dissolution step Sa). The adsorbent solid can then be removed during any intermediate purification steps, for example, any step S-E1) for separating insoluble substances and / or any washing step S-E2). This optional step S-a'), which is adsorption in the presence of the divided form of the adsorbent solid, can optimize the purification of the polymer solution.

[0159] The crude polymer solution obtained at the end of step Sa) includes at least the dissolving solvent, the polymer, and in particular the purified target polymer that the disclosure seeks to recover, dissolved in the dissolving solvent. Generally, the crude polymer solution also includes soluble impurities that are also soluble in the dissolving solvent. It may also contain insoluble impurities or compounds in suspension. The crude polymer solution obtained at the end of step Sa) may optionally include polymers other than the target polymer (i.e., other than polypropylene), for example, in molten form.

[0160] (Optional step S-E1) for separating insoluble matter) The processing process may optionally further include step S-E1) of separating insoluble substances by solid-liquid separation, which can advantageously yield at least one clarified polymer solution and one insoluble fraction. The insoluble fraction advantageously contains at least some, preferably all, of the insoluble impurities suspended in the crude polymer solution obtained particularly from step Sa).

[0161] When incorporated into the process of this disclosure, the step S-E1) for separating insoluble material is located between the dissolution step Sa) and the polymer recovery step Sc), and upstream or downstream of the adsorption step Sb), preferably upstream of the adsorption step Sb). If any step S-E1) for separating insoluble material is located downstream of the adsorption step Sb), the adsorption step Sb) corresponds to an intermediate adsorption step S-a').

[0162] Therefore, the insoluble material separation step S-E1) can remove at least some, preferably all, of the insoluble compound particles in the dissolving solvent that may be present in a suspended state in the crude polymer solution obtained from step Sa) or any step S-a') under the temperature and pressure conditions of step Sa). Insoluble impurities removed during any step S-E1) for insoluble material separation include, for example, pigments, mineral compounds, packaging residues (glass, wood, corrugated cardboard, paper, aluminum), and insoluble polymers.

[0163] When this separation process S-E1) is implemented, operational problems in downstream process steps, particularly clogging and / or erosion, can be limited, while simultaneously contributing to the purification of the plastic feed material.

[0164] When incorporated into this process, step S-E1) for separating insoluble matter is advantageously carried out at a temperature of 100-300°C, preferably 150-250°C, and at a pressure of 1.0-20.0 MPa, preferably 1.5-15.0 MPa (abs), very preferably 2.0-10.0 MPa (abs). Very advantageously, any step S-E1) for separating insoluble matter is carried out under the dissolution temperature and pressure conditions, i.e., under the outlet temperature and pressure conditions of step Sa).

[0165] When incorporated into this process, step S-E1) for separating insoluble matter is preferably supplied with a crude polymer solution obtained from step Sa) or a crude polymer solution obtained from an optional intermediate adsorption step S-a'). According to another embodiment, any step S-E1) may be supplied with a washed polymer solution obtained from an optional washing step S-E2).

[0166] When incorporated into this process, step S-E1) may advantageously include at least one solid-liquid separation apparatus, such as a separation flask, decanter, centrifugal decanter, centrifuge, filter, sand filter, vortex separator, electrostatic separator, or triboelectric separator, preferably a portion including a decanter, filter, sand filter and / or electrostatic separator. Removal of the insoluble fraction can be easily carried out by apparatus for transferring and / or removing trace amounts of solvent that may be present in the insoluble fraction, such as a conveyor, vibrating tube, endless screw, extruder or peeler. Therefore, step S-E1) may include apparatus for transferring and / or removing trace amounts of solvent to remove the insoluble fraction.

[0167] According to a particular embodiment of any step S-E1), the step S-E1) for separating insoluble matter comprises at least two, and usually fewer than five, solid-liquid separation devices in series and / or parallel. The presence of at least two solid-liquid separation devices in series can improve the removal of insoluble matter, while the presence of devices in parallel can manage the maintenance of the devices and / or the work of removing blockages.

[0168] Certain insoluble compounds, in particular pigments and inorganic fillers that were conventionally added during polymer formulation, can be introduced in the form of particles smaller than 1 μm. This is the case, for example, for titanium dioxide, calcium carbonate, and carbon black. According to a particular embodiment of any step S-E1), the step S-E1) for separating insoluble substances advantageously comprises an electrostatic separator, which can efficiently remove at least some, preferably all, of the insoluble particles smaller than 1 μm. According to another particular embodiment of any step S-E1), the step S-E1) for separating insoluble substances comprises a sand filter for removing particles of different sizes, in particular particles smaller than 1 μm.

[0169] Depending on the properties of the raw materials supplied, the polymer solution, preferably a crude polymer solution, supplied to step S-E1) may optionally include a second liquid phase, for example, consisting of a molten polymer. According to another specific embodiment of any step S-E1), step S-E1) advantageously includes equipment for separating this second liquid phase, preferably by at least one three-phase separator.

[0170] Adsorption process Sb) The processing steps according to this disclosure optionally include an adsorption step Sb) to obtain at least one purified polymer solution. The purified polymer solution obtained at the end of step Sb) advantageously contains the polymer to be recovered by this disclosure in a purified dissolved state in a dissolving solvent.

[0171] The adsorption step Sb) is advantageously carried out downstream of the dissolution step Sa) and upstream of the polymer recovery step Sc). The adsorption step Sb) is preferably carried out upstream or downstream of an additional purification step. For example, it can be carried out upstream of any step S-E1) and / or S-E2), and in particular corresponding to any intermediate adsorption step S-a'). It can also be carried out upstream or downstream of any extraction step S-E3), for example. Thus, the adsorption step Sb) is carried out by contacting the polymer solution to be supplied to step Sb), in particular the crude polymer solution obtained from step Sa), the clarified polymer solution obtained from any step S-E1), or the washed polymer solution obtained from any step S-E2), or otherwise the extracted polymer solution obtained from any step S-E3), with one or more adsorbents.

[0172] The adsorption step Sb) advantageously comprises an adsorption section operated in the presence of at least one adsorbent, which is preferably solid and in particular in the form of a fixed bed, a jet bed (or slurry, i.e., in the form of particles introduced into the flow to be purified and accompanied by this flow), or a boiling bed, preferably in the form of a fixed bed or a jet bed. The adsorbent used in step Sb) is preferably alumina, silica, silica-alumina, activated carbon, decolorized earth, or a mixture thereof, preferably in the form of activated carbon, decolorized earth, or a mixture thereof, preferably in the form of a fixed bed or a jet bed, and the circulation of the flow may be upward or downward.

[0173] Advantageously, the adsorption step Sb) is carried out at a temperature of 100 to 300°C, preferably 150 to 250°C, and a pressure of 1.0 to 20.0 MPa (abs), preferably 1.5 to 15.0 MPa (abs), and very preferably 2.0 to 10.0 MPa (abs). Very advantageously, the adsorption step Sb) is carried out under the dissolution temperature and pressure conditions, i.e., at the dissolution temperature and pressure achieved in step Sa). Preferably, in step Sb), the space velocity (or HSV) per hour, which corresponds to the ratio of the volumetric flow rate of the polymer solution supplied to step Sb) to the volume of the adsorbent, is 0.05 to 10 h -1Preferably 0.1 to 5.0 hours -1 That is the case.

[0174] The adsorption portion of step Sb) may, according to another embodiment, consist of adding adsorbent particles to a polymer solution, particularly a crude polymer solution, the particles being separated from the polymer solution via a step of removing the adsorbent particles located downstream of the adsorption portion. The removal of the adsorbent particles may, advantageously, correspond to a step S-E1) or a washing step S-E2) for separating insoluble substances. Such implementation of adsorption step Sb) that performs solid / liquid separation following the introduction of adsorbent particles may, advantageously, correspond to any intermediate adsorption step S-a') described herein.

[0175] Polymer recovery process (Sc) According to this disclosure, the process includes a polymer recovery step Sc) to obtain at least one solvent fraction and one purified polymer fraction to obtain a polymer composition comprising a post-consumer polypropylene recycled resin. The polymer recovery step Sc) advantageously comprises at least one solvent recovery unit, preferably 1 to 6 solvent recovery units, more preferably 2, 3, 4 or 5 solvent recovery units. The polymer recovery step Sc) is supplied with a purified polymer solution or optionally an extracted polymer solution.

[0176] Accordingly, the polymer recovery step Sc) is directed at first separating, at least partially, preferably primarily, the polymer solution supplied to step Sc), i.e., the purified polymer solution or optionally the extracted polymer solution, in order to recover, at least partially, preferably primarily, and more preferably completely, the polymer free from the dissolving solvent and other solvents that may still be present in the polymer solution supplied to step Sc) used in this process, such as the extraction solvent. The term “primarily” should be understood to mean at least 50% by weight, preferably at least 70% by weight, more preferably at least 90% by weight, and very preferably at least 95% by weight, relative to the weight of the solvent contained in the polymer solution supplied to step Sc), particularly the dissolving solvent and optionally the extraction solvent contained in the purified polymer solution or optionally the extracted polymer solution supplied to step Sc). Any method known to those skilled in the art for separating the solvent from the polymer may be employed, in particular any method that allows for a phase change of the polymer or the solvent. The solvent can be separated, for example, by evaporation and / or flash defloration, stripping, segregation, density difference and in particular by decantation or centrifugation. In a preferred embodiment, the polymer is recovered in at least one solvent recovery section, particularly two, three, or four solvent recovery sections, by evaporation and / or flash defoliation at a temperature in the range of 100 to 300°C, preferably 110 to 275°C, more preferably 150 to 250°C, and a pressure in the range of 10 Pa to 4 MPa (abs), preferably 0.1 kPa to 4 MPa (abs), particularly 0.1 kPa to 2 MPa (abs).In a specific embodiment, the polymer recovery step Sc) comprises three or four solvent recovery sections for flash defoliation, wherein the first flash defoliation is carried out at a temperature in the range of 110 to 275°C and a pressure in the range of 0.8 kPa to 2 MPa (abs), particularly 0.1 MPa to 2 MPa (abs), the final defoliation (i.e., the third or fourth flash defoliation, respectively) is carried out at a temperature in the range of 110 to 275°C and a pressure in the range of 0.1 kPa to 1 MPa (abs), particularly 0.1 kPa to 0.1 MPa (abs), and the intermediate flash defoliation is carried out at a temperature in the range of 110 to 275°C and at a pressure between the first and last flash defoliation such that the pressure decreases from the first to the last flash defoliation. To protect the recycled polypropylene resin from thermal degradation, a heat stabilizer (e.g., Irganox 1076 and / or Irgafos 168) may be advantageously added to the purified polymer solution obtained from step Sb) before separating the solvent from the solution in step Sc).

[0177] The resulting purified polymer fraction corresponds to a concentrated polymer solution or a solid purified polymer.

[0178] According to certain embodiments of the present disclosure, in order to improve polymer purification efficiency, at least a portion of the purified polymer fraction obtained at the end of step Sc) can be recycled to the dissolution step Sa) and undergo the processing cycle again.

[0179] After solvent separation in step Sc), the solvent content is typically less than 5% by weight, preferably less than 2% by weight, and more preferably less than 1% by weight, relative to the total weight of the purified polymer fraction.

[0180] Melting process C) The purified polymer fraction containing post-consumer polypropylene recycled resin obtained from step Sc) of the solvent-based recycling process is processed in the following steps: Ca) Preferably, a step of further separating the solvent from the purified polymer fraction by evaporation of the solvent (referred to herein as degassing) and / or flash defoliation; Cb) A step of melt-processing a purified polymer fraction, preferably by melt extrusion and / or pelletization, preferably further including a step of adding additives, to form a melt-processed, preferably melt-extruded and / or pelletized, recycled polypropylene product; Cc) Optionally, a process of aerating a recycled polypropylene product to remove volatile organic compounds, thereby producing an aerated, melt-processed, preferably melt-extruded and / or pelletized, recycled polypropylene product. This process yields a polymer composition, namely a polymer composition comprising the post-consumer recycled polypropylene resin of the present disclosure.

[0181] Steps to further separate the solvent from the purified polymer fraction (Ca) According to this disclosure, the process further comprises, preferably, a step of separating the solvent from the purified polymer fraction by evaporation and / or defloration of the solvent, in a manner known to those skilled in the art. The solvent content after solvent separation is typically less than 2,000 ppm, preferably less than 1,000 ppm, and more preferably less than 500 ppm, relative to the total weight of the purified polymer fraction.

[0182] This step, which involves further separating (degassing) the solvent from the purified polymer fraction, facilitates the removal of high-boiling-point residual contaminants such as limonene, n-hexanal, toluene, and other odor-active substances.

[0183] The step of further separating the solvent from the purified polymer fraction (Ca) can be performed simultaneously with the step of melting the purified polymer fraction (Cb). Therefore, the further separation of the solvent from the purified polymer fraction can be performed during the melting process of the purified polymer fraction.

[0184] In a preferred embodiment, the step of further separating the solvent from the purified polymer fraction is carried out during the melting process of the purified polymer fraction in an extruder having a degassing port (described further below), the extrusion being carried out preferably at a temperature in the range of 220 to 280°C, preferably 240 to 270°C, and at a pressure in the degassing port in the range of 0.5 kPa to 0.1 MPa (abs), preferably 1 kPa to 50 kPa (abs), more preferably 1 kPa to 10 kPa (abs).

[0185] Typically, the solvent content of the degassed, melt-extruded, and purified polymer fraction can be in the range of 100 to 500 ppm, for example, 300 to 500 ppm, based on the total weight of the purified polymer fraction.

[0186] Process Cb) to melt and process the purified polymer fraction According to the present disclosure, the process comprises a step of melt-processing, preferably by melt extrusion and / or pelletizing, a purified polymer fraction, and preferably a step of adding additives, to form a melt-processed, preferably melt-extruded and / or pelletized, recycled polypropylene product comprising the post-consumer recycled polypropylene resin of the present disclosure as the melt-processed polymer composition of the present disclosure. Any additives may be added in a molten state or in a solid state melting in the polymer molten material, preferably in a molten state.

[0187] Step Cb is preferably carried out in a single-screw or twin-screw extruder combined with a suitable pelletizing system. The extruder can be designed to degas (as disclosed above) and optionally mix with additives such as polymer stabilizers. The screw speed of the extruder may be in the range of 50 to 500 rpm. The dimensionless throughput Q of the extruder may be in the range of 0.02 to 0.15, preferably 0.03 to 0.12, more preferably 0.03 to 0.10. The target melting temperature of the purified polymer fraction is typically in the range of 190 to 280°C, preferably 220 to 280°C, more preferably 240 to 270°C.

[0188] In embodiments in which the purified polymer fraction is melt-extruded, the extruder may be equipped with up to four, for example, two or three, upper and / or side degassing ports. The absolute pressure at the degassing ports may be in the range of 0.5 kPa to 0.1 MPa (abs), preferably 1 kPa to 50 kPa (abs), more preferably 1 kPa to 10 kPa (abs), which can be achieved using a suitable vacuum system, for example, one or more vacuum pumps.

[0189] The degassing process can be improved by adding 0.01 to 1% by weight of a stripping agent, such as alcohol (e.g., ethanol or isopropanol), supercritical carbon dioxide, water, or a combination thereof, based on the weight of the purified polymer fraction. The stripping agent is preferably water. The stripping agent can be injected into the extruder under pressure using a suitable pump. In embodiments where the extruder has three degassing ports, a stripping agent such as water, in the range of 0.01 to 1% by weight based on the weight of the purified polymer fraction, is preferably added to the second and third degassing ports, respectively.

[0190] The process of pelletizing a molten polymer composition can be carried out using a suitable pelletizing system well known to those skilled in the art, such as a water pelletizing system, a strand pelletizing system, or a watering pelletizing system. Optionally, a gear melt pump can be used to overcome the pressure loss in the pelletizer die plate, preventing excessive energy input due to pressurization by the extruder, thus preventing the associated increase in melt temperature and the risk of polymer degradation. This may be particularly advantageous in high-power lines where large die plates result in large pressure losses (e.g., >30 bar). The gear melt pump can also prevent reverse filling into the extruder screw or overflow into the degassing port, which could lead to insufficient degassing or, in the worst case, line shutdown.

[0191] Process Cc) for aeration of recycled polypropylene products According to this disclosure, the process may include a step of aerating a recycled polypropylene product to remove residual volatile organic compounds, thereby producing an aerated, melt-processed, preferably melt-extruded and / or pelletized, recycled polypropylene product comprising the post-consumer recycled polypropylene resin of this disclosure as the polymer composition of this disclosure. Aeration can be carried out by heating the recycled polypropylene product to a temperature above 100°C, for example, in the range of 110 to 130°C.

[0192] The solvent content after aeration is typically less than 300 ppm by weight, preferably less than 200 ppm by weight, and more preferably less than 100 ppm by weight. Generally, the solvent content after aeration may be in the range of 20 to 100 ppm by weight, based on the total weight of the recycled polypropylene product.

[0193] According to this disclosure, a polymer composition comprising at least 95% by weight of post-consumer recycled polypropylene resin, based on the total weight of the polymer composition, can be prepared by a process comprising the following steps: M) A step of pre-treating plastic feed material, comprising subjecting the plastic feed material to a mechanical recycling process including a sieving step, a sorting step by at least one of polymer type, polymer article form, and / or color, a shredding step, and optionally a step of washing the plastic feed material (e.g., a water washing step), and optionally a step of melting the pre-treated plastic feed material; S) A step of subjecting the pre-treated plastic supply material, which includes polypropylene, to a solvent-based recycling process, wherein the pre-treated plastic supply material is dissolved in a solvent and insoluble components and soluble impurities are separated, in order to obtain the post-consumer recycled polypropylene resin, Sa) A dissolution step of contacting the pre-treated plastic supply material with a dissolution solvent at a dissolution temperature of 100°C to 300°C and a dissolution pressure in the range of 1.0 to 20.0 MPa (abs) to obtain at least one, preferably one, crude polymer solution, wherein the dissolution solvent is selected from organic solvents containing one or more hydrocarbons having a boiling point of 75°C to 250°C; Sb) optionally, the crude polymer solution obtained from step Sa) is adsorbed by contacting it with at least one adsorbent at a temperature of 100 to 300°C and a pressure of 1.0 to 20.0 MPa (abs) to obtain at least one purified polymer solution; and A step comprising: recovering the polymer and recovering the polymer by evaporating and / or flash defoliating the polymer in at least one solvent fraction and one purified polymer fraction in at least one solvent recovery section, particularly two or three solvent recovery sections, at a temperature in the range of 100 to 300°C, preferably 110 to 275°C, and a pressure in the range of 10 Pa to 4 MPa (abs), preferably 0.1 MPa (abs) to 4 MPa (abs), particularly 0.1 kPa to 2 MPa (abs), thereby obtaining at least one solvent fraction and one purified polymer fraction; and C) A process of melting the post-consumer recycled polypropylene resin obtained from step S), wherein step C) Ca) A step of further separating the solvent from the purified polymer fraction, and Cb) A step of melting the purified polymer fraction, The step of further separating the solvent from the purified polymer fraction is performed while the purified polymer fraction is melt-processed in an extruder having a degassing port at a temperature in the range of 220 to 280°C, preferably 240 to 270°C, and at a pressure in the degassing port in the range of 0.5 kPa to 0.1 MPa (abs), preferably 1 kPa to 50 kPa (abs), more preferably 1 kPa to 10 kPa (abs), to obtain the polymer composition.

[0194] Use and articles This disclosure also relates to the use of polymer compositions, preferably melt-processed polymer compositions, comprising post-consumer recycled polypropylene resin of any of the embodiments described above in the manufacture of articles.

[0195] This disclosure also relates to the use of polymer compositions, preferably melt-processed polymer compositions, comprising post-consumer recycled polypropylene resin of any of the embodiments described above in packaging applications.

[0196] This disclosure further relates to articles comprising a polymer composition comprising a post-consumer recycled polypropylene resin of any of the embodiments described above, preferably a melt-processed polymer composition.

[0197] The articles are preferably selected from the group consisting of caps, closures, bottles, containers, automotive articles, and the like.

[0198] The article contains, based on the total weight of the article, more than 20% by weight, preferably more than 30% by weight, most preferably more than 40% by weight of a polymer composition, preferably further comprising post-consumer recycled polypropylene resin.

[0199] Further additives can be added to the polymer composition for the preparation of articles. In particular, additives common in the preparation process of polypropylene, such as modifiers, stabilizers, antistatic agents, lubricants, nucleating agents, foaming nucleating agents, acid scavengers, UV stabilizers, slip agents, and pigments, as well as fillers and reinforcing agents, can be added. The post-consumer recycled polypropylene resin or polymer composition of this disclosure, preferably a melt-processed polymer composition, preferably contains no additives or only small amounts of additives. Such additives are generally found in virgin polymers and recycled polypropylene from the preparation process of prior-use articles. The advantage is that additives can be selectively added based on the intended use of the post-consumer recycled polypropylene resin or polymer composition, preferably a melt-processed polymer composition. [Examples]

[0200] <Measurement method> The following definitions of terms and measurement methods apply to the above general description and the following examples of this disclosure unless otherwise specified. Unless otherwise indicated, measurements of the experimental portions were performed on the recycled resin, i.e., the polymer composition, after melt processing.

[0201] Meltflow rate The melt flow rate (MFR) was measured according to ISO 1133, with units of g / 10min. MFR is an indicator of polymer fluidity and therefore processability. A higher melt flow rate indicates lower polymer viscosity. Here, MFR2 was measured at a temperature of 230°C under a load of 2.16 kg.

[0202] 13 Ethylene content and triad distribution of propylene by 13C-NMR The ethylene content of the polymer was quantified using quantitative nuclear magnetic resonance (NMR) spectroscopy.

[0203] quantitative 13 C{ 1 The H}NMR spectrum is, 1 H and 13 The spectra were recorded in solution using a Bruker Avance Neo 400 NMR spectrometer operating at 400.15 and 100.62 MHz for C, respectively. All spectra were recorded in solution. 13 Using a 10mm extended temperature probe head optimized for C, recordings were made at 125°C using nitrogen gas in all pneumatic systems. Approximately 200 mg of the substance was used. Approximately 3 mg of BHT (2,6-di-tert-butyl-4-methylphenol CAS 128-37-0) and chromium(III)-acetylacetonate (Cr(acac)3) were dissolved in approximately 3 ml of 1,2-tetrachloroethane-d2 (TCE-d2) to obtain a 60 mM solvent solution of the mitigating agent as described in G. Singh, A. Kothari, V. Gupta, Polymer Testing 2009, 28(5), 475.

[0204] To ensure a homogeneous solution, after initial sample preparation on a heat block, the NMR tube was further heated in a rotary oven for at least 1 hour. The tube was then inserted into a magnet and rotated at 10 Hz. This setup was chosen primarily for the high resolution and accurate quantification of ethylene content required. Standard single-pulse excitation without NOE was used with an optimized tip angle, a 1-second recycle delay, and bilevel WALTZ16 decoupling method, as described in Z. Zhou, R. Kuemmerle, X. Qiu, D. Redwine, R. Cong, A. Taha, D. Baugh, B. Winniford, J. Mag. Reson. 187 (2007) 225 and V. Busico, P. Carbonniere, R. Cipullo, C. Pellecchia, J. Severn, G. Talarico, Macromol. Rapid Commun. 2007, 28, 1128. A total of 6144 (6k) transient signals were acquired per spectrum.

[0205] quantitative 13 C{ 1 The 1H NMR spectra were processed and integrated, and relevant quantitative properties were determined from the integrated values. All chemical shifts were indirectly referenced to the central methylene group of 30.00 ppm ethylene block (EEE) using the chemical shift of the solvent. This method allowed for comparative reference even when this structural unit was not present.

[0206] A characteristic signal corresponding to the introduction of ethylene was observed (as described in Cheng, HN, Macromolecules 1984, 17, 1950), and the comonomer fraction was calculated as the fraction of ethylene in the polymer relative to the total monomers in the polymer: TIFF2026510752000004.tif1255

[0207] The comonomer fraction was determined using the method described by WJ. Wang and S. Zhu, Macromolecules 2000 33 1157. 13 C{ 1 Quantification was performed by integrating multiple signals across the entire spectral range of the H} spectrum. The integration region was slightly adjusted to enhance applicability across the entire range of encountered comonomer content.

[0208] The molar percentage of comonomer introduction was calculated from the mole fraction: TIFF2026510752000005.tif1255

[0209] The weight percentage of comonomer introduction was calculated from the mole fraction: TIFF2026510752000006.tif11134

[0210] The triad-level comonomer sequence distribution, representing the amounts of EEE, EEP, PEP, PPP, EPP, and EPE, was obtained using the method described in Kakugo, M., Naito, Y., Mizunuma, K., Miyatake, T. Macromolecules 15 (1982) 1150 under predetermined conditions. 13 It was determined by integrating multiple signals across the entire spectral region of the C{1H} spectrum.

[0211] Crystex analysis: crystalline fraction (CF) and soluble fraction (SF) The crystalline fraction (CF) and soluble fraction (SF) of PCR polypropylene resin, as well as the ethylene content and intrinsic viscosity of each fraction, were analyzed using a CRYSTEX instrument at Polymer Char (Valencia, Spain) according to ISO 16152-2022-Method 2. Details of the method and techniques can be found in the literature (Ljiljana Jeremic, Andreas Albrecht, Martina Sandholzer & Markus Gahleitner (2020) Rapid characterization of high-impact ethylene-propylene copolymer composition by crystallization extraction separation: comparability to standard separation methods, International Journal of Polymer Analysis and Characterization, 25:8, 581-596).

[0212] The crystalline and amorphous fractions are separated through a temperature cycle involving dissolution at 160°C, crystallization at 40°C, and redissolution in 1,2,4-trichlorobenzene at 160°C. Quantification of SF and CF, as well as measurement of ethylene content (C2), are performed using an integrated infrared detector (IR4), while an online two-capillary viscometer is used to measure intrinsic viscosity (IV).

[0213] The IR4 detector uses two different frequency bands (CH3 stretching oscillation (approximately 2960 cm)). -1 (centered around) and CH expansion vibration (2700~3000cm -1 This multi-wavelength detector is useful for measuring the concentration and ethylene content in ethylene-propylene copolymers by measuring IR absorbance in ) ). The IR4 detector is useful for measuring ethylene content in the range of 2 wt% to 69 wt% ( 13The analysis was calibrated using eight EP copolymers (each with varying concentrations ranging from 2 mg / ml to 13 mg / ml, measured by 13C-NMR). To accommodate the characteristics of both concentration and ethylene content for the various polymer concentrations expected during Crystex analysis, the following calibration formulas were applied: TIFF2026510752000007.tif36154

[0214] The constants a to e in Equation 1 and a to f in Equation 2 were determined using least squares regression analysis.

[0215] CH3 / 1000C is converted to ethylene content (by weight) using the following relationship: TIFF2026510752000008.tif9122

[0216] The intrinsic viscosity (IV) of PCR polypropylene resin and its soluble and crystalline fractions was measured using an online two-capillary viscometer and correlated with the corresponding IV' measured by standard method in decalin according to ISO 1628-3. Calibration was performed on various EP-PP copolymers with IV = 2–4 dL / g. The determined calibration curve is linear: TIFF2026510752000009.tif1146

[0217] The samples to be analyzed were weighed at concentrations of 10 mg / ml to 20 mg / ml. To avoid the possibility of injecting gels or polymers that do not dissolve in TCB at 160°C, such as PET and PA, the weighed samples were packed into a stainless steel mesh with a mass of 0.077 mm and a density of 0.05 mm.

[0218] After automatically filling the vial with 1,2,4-TCB containing 250 mg / l of 2,6-tert-butyl-4-methylphenol (BHT) as an antioxidant, the sample is dissolved at 160°C for 60 minutes, usually with constant stirring at 400 rpm, until completely dissolved. To prevent sample degradation, the polymer solution is covered with an N2 atmosphere during dissolution.

[0219] A specified volume of sample solution is injected into a column packed with an inert support, where crystallization of the sample and separation of the soluble fraction from the crystalline portion occur. 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 using the crystallization cycle (wt%SF, wt%CF, wt%C2, wt%C2(SF), wt%C2(CF), IV(SF), IV(CF)), where wt%CF is calculated as follows: TIFF2026510752000010.tif1466

[0220] Cross-fraction chromatography The chemical composition distribution and molecular weight distribution at a given elution temperature (polymer crystallinity in solution), as well as the corresponding average molecular weights (Mn, Mw, Mv), were determined by fully automated cross-fractionation chromatography (CFC) as described in Ortin A., Monrabal B., Sancho-Tello J., Macromol.Symp., 2007, 257, 13-28.

[0221] Cross-fractional chromatography (TREF x SEC) was performed using a CFC (PolymerChar, Valencia, Spain). The concentration was monitored using a 4-frequency IR5 infrared detector (PolymerChar, Valencia, Spain). The polymer was dissolved at a concentration of approximately 1 mg / ml at 160°C for 150 minutes.

[0222] To avoid the possibility of injecting gels or polymers that do not dissolve in 160°C TCB, such as PET and PA, the weighed samples were packed into a stainless steel mesh with a mass of 0.077 mm and a diameter of 0.05 mm.

[0223] When the sample was completely dissolved, a 0.5 ml aliquot was loaded onto the TREF column and stabilized at 110 °C for a while. The polymer was crystallized by applying a constant cooling rate of 0.1 °C / min until 30 °C. Discontinuous elution was performed using the following temperature steps: (35, 40, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 103, 106, 109, 112, 115, 117, 119, 121, 123, 125, 127, 130, 135, and 140 °C).

[0224] In the GPC analysis, which is the second dimension, three PL Olexis columns and one Olexis Guard column manufactured by Agilent (Church Stretton, UK) were used as the stationary phase. As the eluent, 1,2,4-trichlorobenzene (TCB, stabilized with 250 mg / L 2,6-di-tert-butyl-4-methyl-phenol) was applied at a constant flow rate of 1 mL / min at 150 °C. The column set was calibrated with at least 15 narrow MWD polystyrene (PS) standards in the range of 0.5 kg / mol to 11,500 kg / mol using universal calibration (conforming to ISO 16014-2:2003). The molecular weight of PS was converted to the equivalent molecular weight of PP using the following Mark Houwink constants. TIFF2026510752000011.tif2396

[0225] The calibration data was fitted using a third-order polynomial fit. The data processing was performed using PolymerChar software equipped with a CFC device.

[0226] a) Calculation of the relative fraction (weight %) of isotactic PP in a specific molecular weight and elution temperature region To calculate the relative fraction (weight %) of isotactic PP at a certain molecular weight and elution temperature, first, the amount (weight %) of isotactic PP needs to be calculated from the CFC contour plot: TIFF2026510752000012.tif13127 Here, EPR is the fraction of the soluble fraction (SF) in TCB at 35 °C obtained by CFC analysis that has a molar mass exceeding logM of 3.5. TIFF2026510752000013.tif16106 (where Hj is the height of the signal and j represents the logM value).

[0227] Since the TREF profile slightly depends on the low molecular weight part, the molecular weight of the low molecular weight limit depends on the elution temperature (T el ). This low molecular weight limit was determined using the following equation: TIFF2026510752000014.tif14116

[0228] Taking this into account, the PE fraction is calculated in the following way: TIFF2026510752000015.tif18107 Here, H ij is the two-dimensional differential distribution at the corresponding elution temperature (T el )i and logM value j obtained with the corresponding data processing software.

[0229] The high crystalline PE fraction (HCF-PE) is defined as the part of the PE fraction that elutes at 90 °C to 100 °C. TIFF2026510752000016.tif14113 (where H ij is the height of the signal, i is the elution temperature, and j represents the logM value.)

[0230] This fraction mainly contains homopolymer PE and copolymers of PE, and the amount of comonomer is very small, less than about 3 SCB / 1000 TC (L. Wild, T.R. Ryle, D.C. Knoblauch, I.R. Peat, J. Polym. Sci, Polym. Phys. 20, (1982), 441 - 455).

[0231] Here, the low crystalline PE fraction (LCF-PE) is defined as the part of the PE fraction that elutes at 35 °C to 89 °C. TIFF2026510752000017.tif15101 (in the formula, H ij (where i represents signal height, i represents elution temperature, and j represents logM value.)

[0232] This fraction mainly contains copolymer fractions of HDPE and LLDPE obtained with a Zn catalyst, or LLDPE obtained with an SS catalyst, but also contains LDPE because these types of polymers co-elute with an equivalent amount of SCB / 1000TC.

[0233] b) Calculation of Mw(PE) (50~95℃) and Mw(SF) The calculation for Mw(PE)(50~95℃) is performed using the following formula: TIFF2026510752000018.tif1497(here, w i is the weight fraction of the TREF fraction at temperature i, and M wi This represents the weight-average molecular weight of the fraction determined by CFC analysis. Fractions of less than 0.5% by weight are ignored in the calculation. Here, Mw(SF) is the Mw value of the 35°C TREF fraction measured by CFC analysis.

[0234] c) Calibration of the IR5 detector to measure the number of short-chain branches per 1000 total carbon atoms (SCB / 1000TC) The IR5 detector provides various detector signals, which are expressed as concentration signals (2800 cm⁻¹). -1 ~3000cm -1 A broad spectral band covering the spectral region of methyl (CH3) (2959 cm⁻¹). -1 A narrowband filter with a width centered on (2928cm²), and methylene (CH2) (2928cm²). -1(centered around ). The ratio of the detection signals for methyl and methylene correlates with the total amount of methyl (CH3) per 1000 carbon atoms (CH3 / 1000TC) (A. Ortin, B. Monrabal, J. Montesinos, P. del Hierro, Macromol. Symp. 2009, 282, 65-70). CH3 / 1000TC can be measured using an IR5 detector by calibrating the CH3 / CH2 ratio against the nominal CH3 / 1000TC content. Linear fitting was used for this purpose.

[0235] The branching degrees of all calibration set samples are described in K. Klimke, M. Parkinson, C. Piel, W. Kaminsky, HW Spiess, M. Wilhelm, Macromol. Chem. and Phys., 2006, 207, 382; M. Parkinson, K. Klimke, HW Spiess, M. Wilhelm, Macromol. Chem. and Phys., 2007, 208, 2128. 13 The results were measured by 13C-molten state NMR. The calibration set used in this method included 17 different single-site catalyzed short-chain branched polyethylenes, as well as Ziegler-Natta catalyzed fractions of polyethylene-cobutene, polyethylene-cohexene, and polyethylene-cooctene, covering branching levels of up to 80 methyl groups per 1000 carbon atoms (CH3 / 1000C).

[0236] d) Calculation of SCB / 1000TC for the TREF fraction at 70-95℃ The following formula is used to calculate the SCB / 1000TC content of the TREF fraction (70-95°C): TIFF2026510752000019.tif14112(here, w i This is the weight fraction of the TREF fraction at temperature i, and is SCB / 1000TC. iThis represents the corresponding short-chain branching amount per 1000 total carbon atoms in the corresponding TREF fraction, as analyzed by CFC analysis combined with a composition detector. Since the majority of comonomers in polypropylene compounds are ethylene, the corresponding C2 content (by weight) can be calculated using the following method: Fractions less than 0.5% by weight are ignored in the calculation.

[0237] Basic references: Zhang, Macromol Symp. 282 (2009), 111-127 W. Yau, D. Gillespie, Polymer 42 (2001) 8947-8958 Monrabal, in “Encyclopedia of Analytical Chemistry”, RA Meyers, Ed., John Wiley & Sons Ltd., 2000 Nakano, Y. Goto, J. Appl. Polym. Sci. (1981), 26, 4217 W. Yau, Macromol. Symp. 2007, 257, 29-45 Faldi, JBP Soares, Polymer 42 (2001) 3057-3066 Ortin, B. Monrabal, J, Sancho-Tello, Macromol. Symp. 257 (2007), 13‐28

[0238] Measurement of the amounts of "iPP", "PVC", "PA", "PET", and "PS" using transmission infrared spectroscopy. The components and their amounts in recycled polymer resins are measured using FTIR spectroscopy: Sample preparation: All calibration samples and samples to be analyzed were prepared in the same manner on a molten press plate.

[0239] Approximately 2 - 3 g of the compound to be analyzed was melted at 190 °C. Then, a pressure of 60 - 80 bar was applied for 20 seconds using a hydraulic heating press. Next, to control the form of the compound, the sample was cooled to room temperature in 40 seconds using a cold press at the same pressure. The thickness of the plate was controlled using a metal calibration frame plate with dimensions of 2.5 cm × 2.5 cm and a thickness of 100 - 200 μm (depending on the MFR of the sample). The thickness of each plate was measured before FTIR measurement. All plates had a thickness of 100 - 200 μm.

[0240] To control the plate surface and prevent interference during measurement, all plates were sandwiched between two sheets of double-sided silicone release paper and pressed.

[0241] In the case of powder samples or non-uniform compounds, the pressurization process may be repeated three times to enhance uniformity by pressurization and cutting under the same conditions as described above.

[0242] Spectrometer: A standard transmission FTIR spectrometer such as a Bruker Vertex 70 FTIR spectrometer was used with the following setup: · Spectral range: 4000 - 400 cm -1 · Aperture: 6 mm · Spectral resolution: 2 cm -1 · Background scan: 16 times, spectral scan: 16 times · Interferogram zero filling factor: 32 · Strong apodization using the Norton Beer function The spectra were recorded and analyzed using Bruker Opus software.

[0243] Calibration sample: Since FTIR is a secondary analysis method, several calibration standard samples were formulated to cover the target analysis range: · For polyamide (PA), 0.2 wt% - 2.5 wt% · For polystyrene (PS), 0.1 wt% - 5 wt% • For polyethylene terephthalate (PET), 0.2% to 2.5% by weight • For polyvinyl chloride (PVC), 0.1% to 4% by weight

[0244] The following commercially available materials were used in the formulation: Borealis HC600TF as iPP, Borealis FB3450 as HDPE, RAMAPET N1 S (Indorama polymer) as PET, Ultramid® B36LN (BASF) as polyamide 6, Styrolution PS 486N (Ineos) as high-impact polystyrene (HIPS), and Inovin PVC 263B (powder form) as PVC.

[0245] To prevent deterioration, all ingredients are manufactured on a small scale using a Haake mixer at temperatures below 265°C for less than 10 minutes.

[0246] To minimize degradation, add additional antioxidants such as Irgafos 168 (3000 ppm).

[0247] calibration: The calibration principle for FTIR is the same for all components. The value obtained by dividing the intensity of a specific FTIR band by the plate thickness is the same as the value obtained on the same plate. 1 H or 13 The amount of components measured by 13C solution state NMR correlates with the amount of components measured by 13C solution state NMR.

[0248] Each specific FTIR absorption band is selected because its intensity increases with component concentration and it is separated from other peaks, regardless of the composition of the calibration material and the actual sample.

[0249] This methodology is described in Signoret et al. “Alterations of plastic spectra in MIR and the potential impacts on identification towards recycling”, Resources, conservation and Recycling journal, 2020, volume 161, article 104980.

[0250] The wavelengths for each calibration band are as follows: • PA is 3300cm -1 • PS is 1601cm -1 • For PET, 1410cm -1 • For PVC, 615cm -1 • Regarding iPP: 1167cm -1

[0251] For each polymer component i, a linear calibration curve (based on the linearity of the Beer-Lambert law) is constructed. Typical linear correlations used in such calibration curves are shown below: TIFF2026510752000021.tif1134(here, x i This is the fraction (by weight) of polymer component i; E i This is the absorbance intensity (absorbance unit (au)) in a specific band associated with polymer component i. These specific bands are 3300 cm⁻¹ for PA. -1 PS is 1601cm -1 PET is 1410cm -1 For PVC, 615cm -1 Regarding iPP, it is 1167cm -1 and; d is the thickness of the sample plate; Ai and Bi are the two correlation coefficients determined for each calibration curve.

[0252] For each calibration standard material, if available, 1 H or 13 The amount of each component is measured using either 13C solution-state NMR as the primary method (except for PA). The NMR measurement is performed using the exact same FTIR plate used to create the FTIR calibration curve.

[0253] ash Thermogravimetric analysis (TGA) experiments were performed using a Perkin Elmer TGA 8000 according to ISO 11358-1 (2014). Approximately 10-20 mg of the substance was placed in a platinum dish. The temperature was equilibrated at 50°C for 10 minutes, and then the temperature was increased to 950°C under nitrogen at a heating rate of 20°C / min. Ash content was evaluated as weight % at 850°C based on the total weight of the starting material used. For reference, ash content was also measured using the oven method according to ISO 3451-1 (1997), and comparable results were obtained.

[0254] Metal and chlorine content The metal and chlorine content was measured by X-ray fluorescence (XRF) spectroscopy. The instrument used for XRF analysis was a Zetium (2.4kW) wavelength dispersive spectrometer manufactured by Malvern Panalytical. The instrument was calibrated with a set of polyolefin-based standards manufactured by Malvern Panalytical. Using this method, the quantitative content of F, Na, Mg, Al, Si, P, S, Ca, Ti, Zn, Cr, Cd, Hg, Pb, As, Ni, Cu, Ba, Br, Cl, Sb, and Sn in the polyolefin matrix was measured within the specified ranges of these standards. The analysis was performed under vacuum on plaques with a diameter of 40 mm and a thickness of 2 mm.

[0255] CIE L*a*b* color space values ​​and color difference analysis Color values ​​and color differences were measured according to ISO 11664-4.

[0256] In the CIE L*a*b* unified color space, color coordinates are as follows: L* is the lightness coordinate, a* is the red / green coordinate (+a* represents red, -a* represents green), and b* is the yellow / blue coordinate (+b* represents yellow, -b* represents blue). The L*, a*, and b* coordinate axes define the three-dimensional CIE color space. A standard Konica / Minolta CM-3700 A colorimeter was used for the measurements.

[0257] Approximately 20g of freeze-dried and pulverized PP powder was placed in a sample cuvette to prevent air bubbles before measurement.

[0258] Colors of IE and CE samples, as well as the reference background color (here, L ref =96.01;a ref =-0.29;b ref A background plate with a colorimetric value of 1.79 was measured, and each measurement was saved. The color difference (Euclidean distance ΔE) between the sample and the reference background was calculated using the obtained colorimetric values ​​and the following formula: TIFF2026510752000022.tif9124

[0259] Headspace gas chromatography / mass spectrometry (HS-GC-MS) The quantification of selected marker substances is based on the static headspace (HS) method. This analysis uses a combination of an HS sampler, gas chromatograph (GC), and mass spectrometer (MS) for screening purposes.

[0260] Samples were delivered to the laboratory in sealed aluminum-coated polyethylene (PE) bags. Prior to analysis, the samples were freeze-dried and ground, and 2,000 ± 0.100 g was weighed into 20 ml HS vials, which were then sealed tightly. Duplicate measurements were performed for all samples.

[0261] HS / GC / MS parameters • HS parameters (Agilent G1888 headspace sampler) Vial equilibration time: 120 minutes (sample), 5 minutes (standard) Oven temperature: 100°C (sample), 200°C (standard) Loop temperature: 110°C (sample), 205°C (standard) Transfer line temperature: 120°C (sample), 210°C (standard) low vibration • GC parameters (Agilent 7890 A GC system) Column: ZB-WAX 7HG-G007-22 (30m × 250μm × 1μm) Carrier gas: Helium 5.0 Flow rate: 2ml / min Allocation: 10:1 GC Oven Program: 35°C for 0.1 minutes 10°C / min up to 250°C 250℃ for 1 minute • MS parameters (Agilent 5975 C inert XL MSD) Acquisition mode: Scanning Scanning parameters: Low mass: 20 High mass: 200 Threshold: 10 • Software / Data Evaluation MSD ChemStation E.02.1431 MassHunter GC / MS Acquisition B.07.05.2479 AMDIS GC / MS Analysis Version 2.71 NIST / EPA / NIH Mass Spectral Library (2011 version) NIST Mass Spectral Search Program Version 2.0g AMDIS deconvolution parameters Minimum match factor: 80 Threshold: Low Scanning direction: High to low Data file format: Agilent file Device type: Quadrupole Component width: 20 Adjacent peak subtraction: 2 Resolution: high Sensitivity: Very high Shape requirement: Medium Solvent tailing: 44 m / z Column bleed: 207 m / z Minimum model peak: 2 Minimum S / N: 10 Minimum specific peak: 0.5 · MSD ChemStation integration parameters Integrator: ChemStation Initial area reject: 0 Initial peak width: 0.005 (for limonene and acetaldehyde) 0.200 (for acetic acid) Shoulder detection: Off Initial threshold: 8.0 (for limonene and acetaldehyde) 10.5 (for acetic acid)

[0262] In this study, the description of "below the limit of detection (<LOD)" means that the peak itself is not even recognized, or the match factor is less than 80 (AMDIS), or the signal / noise ratio of the peak in the sample run (Pk-pk S / N = corrected signal / Pk-pk noise, MSD ChemStation signal-to-noise report) is less than 3. The results refer only to the measured samples, measurement times, and applied parameters.

[0263] Standard solution Standard substances containing defined marker substances were prepared (see Table A) for reliable identification and comparison with the (lowest) values of the odor detection threshold (ODT). Methanol was used as the solvent for standard substance 1 and 2-butanol for standard substance 2.

[0264] For HS / GC / MS analysis, 5 μl of each standard substance was injected into a separate 20 ml HS vial, sealed, and measured.

[0265] Assuming that all standard substances were completely vaporized, the concentrations of each analyte in the HS CG were estimated as shown in Table A. TIFF2026510752000023.tif37166

[0266] Data Evaluation Concentration C of the analyte in HS G is the amount of substance m G and effective HS volume V G The calculation takes this into consideration. TIFF2026510752000024.tif1666

[0267] The peak area of ​​each analyte can be obtained by integrating the extracted ion chromatogram (EIC). The corresponding target ions are shown in Table A. The (minimum) theoretical peak area of ​​the ODT is reflected by the following: TIFF2026510752000025.tif25112

[0268] To estimate the odor relationship of the analyte in the above HS of a polymer sample, the peak area of ​​the analyte (sample) is compared with the theoretical peak area (ODT).

[0269] Furthermore, an odor activity factor was introduced. This factor is the ratio of the actual peak area of ​​the analyte (sample) to the theoretical peak area at the lowest ODT as found in reference [1]. A value greater than 1 indicates the relationship between the analyte and odor at a given HS temperature. TIFF2026510752000026.tif16106

[0270] The Odor VDA270-B3 VDA 270 is designed to measure the odor characteristics of automotive trim materials and components that come into contact with the air introduced into the vehicle's interior.

[0271] This sensory evaluation requires a trained and selected panel of odor assessors. Typically, three testers are used. If individual results differ by more than two points in a single test, or in the case of approval testing, at least five testers are required, and double judgment is also necessary. The room in which the sensory evaluation is conducted must be free of any noticeable odors. Furthermore, strong odors such as cigarette smoke, perfume, or food smells must not cause assessors to be biased towards one another.

[0272] The samples arrive sealed in aluminum-coated polyethylene bags. Upon arrival in the laboratory, they are stored open for one week at 23°C (±2°C), protected from direct sunlight and secondary contamination. Each assessor weighs 20g (±2g) of the sample into a 1-liter wide-mouthed bottle and seals it immediately after weighing.

[0273] The wide-mouthed bottle is heated at 80°C (±2°C) for 2 hours (±10 minutes). Then, the wide-mouthed bottle is cooled to 60°C (±5°C) before the sensory panel is instructed to begin the odor assessment.

[0274] The odor of each sample is assessed by each evaluator according to the VDA270 rating scale after slightly lifting the bottle cap.

[0275] The six-level rating scale consists of the following grades: Grade 1: Imperceptible, Grade 2: Perceptible, but not bothersome. Grade 3: Clearly perceptible, but not bothersome. Grade 4: I'm interested Grade 5: Very concerning Grade 6: Unacceptable

[0276] During the assessment, assessors must maintain composure and discuss individual results during the test, ensuring that no bias is allowed between them. Furthermore, adjusting evaluations after testing other samples is also prohibited.

[0277] For statistical reasons (and as VDA270 acknowledges), assessors are compelled to use integer scales for evaluation. As a result, odor ratings are rounded to the nearest integer based on the average of all individual assessments.

[0278] Charpy-Notch impact strength (NIS) The notched Charpy impact strength was measured at 23°C according to ISO 179-1 / 1eA. Compression-molded specimens with a thickness of 4 mm were prepared from pellets in accordance with EN ISO 19069-2. The plaques were then processed into 80*10*4 mm (Type B) specimens. The notch tip radius was 0.25 mm, and the span used for testing was 62 mm. Nine to ten specimens were tested, and the average value was reported.

[0279] Optical properties Haze and total light transmittance were measured according to ASTM D1003-13. (Method A - Haze meter) Gloss is measured at 20°, 60°, and 85° according to ISO 2813.

[0280] The material was compression-molded to form a 1mm thick plaque, which was then die-cut into 60×60×1mm test pieces for testing in accordance with EN ISO 19069-2 using an ISO D1 mold.

[0281] Optomechanical capability (OMA) and process-focused optomechanical capability (pOMA) The optical-mechanical capability is determined according to the following formula: TIFF2026510752000027.tif1989

[0282] Therefore, the process-focused optic-mechanical capability: pOMA can be determined as given by the following equation: TIFF2026510752000028.tif1882

[0283] Measurement of dynamic mechanical properties - tensile stress In dynamic mechanical thermal analysis (DMTA) in tensile mode, a constant load is applied to the sample along with a sinusoidal tensile strain. When subjected to sufficiently low strain, the material response remains within a linear viscoelastic region that is independent of the strain amplitude.

[0284] The tensile storage modulus E'(1) and the tensile loss modulus E''(2) can be calculated from the following formulas: TIFF2026510752000029.tif2773(in the formula, ΔF A This is the measured amplitude of the dynamic force, in units of Newtons. S A This is the measured amplitude of dynamic displacement, in meters. L a This is the distance between the clamps, and the unit is meters. b is the width of the test specimen, and its unit is meters. d is the thickness of the test specimen, and its unit is meters. δ is the measured phase angle, in degrees.

[0285] The so-called damping coefficient is determined as shown in the following formula. TIFF2026510752000030.tif1334

[0286] The characterization of the dynamic mechanical properties was performed in accordance with ISO standards 6721-1, 6721-4, and 6721-11. Measurements were performed using a strain / stress-controlled dynamic mechanical analyzer, "Netzsch DMA 242E Artemis," equipped with a tensile sample holder for rectangular specimen shapes. Measurements were performed on rectangular specimens cut from compression-molded plates manufactured with a "Collin 400 P / M" thermopress. The plates were melted at 200°C and annealed for 300 seconds at a pressure of 5 bar, then compressed at 25 bar for 300 seconds, and cooled to room temperature at a pressure of 50 bar and a cooling rate of 15 K / min. Compression-molded plates with a shape of 100 × 100 × 0.1 mm were prepared and stored for a minimum resting time of 96 hours after compression molding. Rectangular specimens were prepared using a laboratory cutter to have dimensions of 20 mm × 4 mm × 0.1 mm (length × width × thickness), and the specimens were clamped. The free tensile length, measured at room temperature with a caliper to an accuracy of 0.05 mm, was approximately 12 mm. The width and thickness were measured with an accuracy of 0.001 mm using a suitable length gauge. Dynamic mechanical thermal analysis was performed in an inert atmosphere, using liquid nitrogen for cooling, within a temperature range of -80°C to +150°C, with a heating rate of 2 K / min, a frequency of 1 Hz, strain-stress control mode, a maximum applied dynamic stress of 7.0 MPa, a static load of 0.20 MPa, and a maximum strain of 0.20%. The specimen was clamped using a torque of 2.5 cNm applied to the screw. Adjustment at the starting temperature of -80°C was performed in an isothermal interval of 15 minutes. Evaluation was performed using the software "Proteus Thermal Analysis - Version 6.1.0", examining the temperatures at which E' and E' were 400 MPa at 90°C and 120°C. Furthermore, tanδ-(glass transition T) was investigated. g The peak temperatures of the E'' function and the E'' function are determined in the range of -80°C to 160°C using a heating rate of 2 K / min and a frequency of 1 Hz.

[0287] T g The glass transition temperature was determined from the loss angle (tan(δ)) curve.

[0288] References [1] “Dynamic mechanical analysis: a practical introduction” Kevin P. Menard 2008 by Taylor & Francis Group, LLC, Dynamic Testing and Instrumentation, 71-76, 2008

[0289] Tensile properties Tensile properties were measured at 23°C, with the tensile modulus (E), yield elongation (EAY), and tensile strength at the yield point (TSY). After 96 hours of conditioning, the sample was compressed into a 2mm thick 5A tensile test specimen according to EN ISO 19069-2, in accordance with ISO 527-1 / -2, and measured under the following conditions: Preload: 1N; Preload speed: 0.5mm / min; Test speed for elastic modulus: 0.5mm / min; Test speed: 20.0mm / min; εx for determining σs: 100%; Gripping distance: 50mm; Gauge length: 20mm; Elastic modulus: Secant method, starting elastic modulus 0.05%, ending elastic modulus 0.25%.

[0290] flexibility The flexibility value is calculated according to the following formula: TIFF2026510752000031.tif1066 Here, EAY is the yield point elongation (in %), TSY is the tensile strength at the yield point (in MPa), and E is the tensile modulus (in MPa). EAY, TSY, and E are measured at 23°C according to ISO 527.

[0291] Wide-angle X-ray scattering (WAXS) The crystallinity of iPP samples was investigated by WAXS measurements in reflection mode using a Bruker Discover D8 diffractometer equipped with a 2D GADDS detector and a CuKα X-ray detector with a Ni filter. Three measurements were performed for each sample, and the corresponding results were averaged. The amorphous halo obtained from the atactic-PP sample (D. Tranchida, L. Resconi L., Influence of 2,1-erythro regiodefects on the crystallization behavior of isotactic polypropylene, Polymer Crystallization 1 (2018) e10022) was appropriately scaled and subtracted, and the crystallinity index (XC) was quantified according to the following formula: TIFF2026510752000032.tif1633(here, A tot This is the area under the total pattern, A C (This is the area after subtracting the amorphous halo.)

[0292] Furthermore, following Turner-Jones et al. (AT Jones, JM Aizlewood, D. Beckett, Crystalline forms of isotactic polypropylene, Makromol. Chem.: Macromol. Chem. Phys. 75 (1964) 134-158), the relative content of β-modification was calculated from the intensity of specific reflections after subtracting amorphous halos: TIFF2026510752000033.tif21114 (Here, the degree of γ modification was calculated from the intensity of a specific reflection after subtracting the amorphous halo using the method developed by Pae (Pae KD, J.Polym.Sci., Part A, γ-αSolid-solid transition of isotactic polypropylene, 6, (1968) 657-663): TIFF2026510752000034.tif1866

[0293] experiment Two embodiments of the invention (IE1 and IE2) and several comparative examples ("CE") were prepared.

[0294] CE1, CE2, CE3, CE5, and CE8 were manufactured using post-consumer packaging waste as raw materials. Of these, the raw materials for CE1 mainly consisted of flexible polyolefin articles such as films and carrier bags, while the raw materials for CE2, CE3, CE5, and CE8 mainly consisted of rigid PP articles such as bottles, cups, and trays. CE1, CE2, CE3, CE5, and CE8 were obtained through a recycling process that included the following steps: A process of sieving plastic raw materials to produce sieved plastic waste containing only items with a maximum length of 400 mm; A process of sorting and removing articles manufactured from polystyrene, polyamide, polyethylene, metal, paper, and wood from the aforementioned supply raw materials, thereby providing post-consumer plastic materials, wherein CE1, CE2, and CE5 are obtained as light-color fractions by color sorting, which involves sorting and removing natural color (e.g., CE5), white products (e.g., CE2), and light-color fractions (e.g., CE1), and the materials that are not sorted and removed remain as post-consumer polypropylene recycled materials (e.g., CE3A and CE3B) having a specified mixed color; The process involves: subjecting the selected post-consumer plastic material having the specified color to wet grinding to form flake-like post-consumer plastic material with a maximum length of 20 mm; washing in an aqueous solution using thermal energy to reach a temperature in the range of 35°C to 95°C; applying a residence time in the range of 1 to 20 minutes under alkaline conditions containing various cleaning agents by adding NaOH at a concentration of 1.5 to 2% by weight; drying to a final moisture content of less than 2% by weight; performing air separation and screening to separate specific polymer materials to be recycled other than polypropylene, and narrowing the flake group to a size range optimal for optical sorting by sieving fractions of <2.5 mm; subjecting the thus pre-treated post-consumer plastic material to further sorting to remove non-polyolefin portions and specific colored portions to obtain a purified polypropylene polyolefin recycled stream; and applying a melt screen size in the range of 90 to 110 μm to melt extrude and melt filter the material to obtain a pellet-like polypropylene blend as an extruded and pelletized recycled polypropylene product.

[0295] CE3A and CE3B were prepared from different raw material lots.

[0296] The extruded and pelletized recycled polypropylene products CE1, CE2, CE3A, CE3B, CE5, and CE8 all had a polypropylene content of approximately 95% by weight (see Table 1 below). 1500 ppm of Irganox 1010 and 1500 ppm of Irgafos 168 were also added to each comparative sample CE1, CE2, CE3A, CE3B, CE5, and CE8 during extrusion.

[0297] These mechanically recycled polypropylene products can be further processed in solvent-based recycling processes as described herein.

[0298] CE5B is a "high purity" reference from mechanical recycling of polymer pellets prepared from CE5, which are dried at 120°C for 4 hours.

[0299] CE4 is the commercially available heterogeneous propylene copolymer composition "BE170CF" obtained from Borealis AG, Austria.

[0300] CE6 is a commercially available random propylene copolymer composition "RD204CF" obtained from Borealis AG, Austria.

[0301] CE7 is the commercially available random propylene copolymer composition "RD734MO" obtained from Borealis AG, Austria.

[0302] Example IE1 of the present invention was prepared from mechanically regenerated CE3A (in flake form), and Example IE2 of the present invention was prepared from mechanically regenerated CE3B (in flake form), both using the same solvent-based recycling process.

[0303] (Example 1 of the invention) A pre-purified feedstock (CE3A) containing 95% by weight of polypropylene (PP) was introduced in flake form into an extruder heated to 200°C. At the extruder outlet, the feedstock was at least partially molten (i.e., at least substantially all of the polyolefin material was molten) and was mixed with n-heptane preheated to 200°C in a solvent:feedstock weight ratio of 5:1. The mixture containing the solvent and feedstock was introduced into a stirred reactor heated to 200°C and maintained at 2.0 MPa (abs) for a residence time of 1 hour. A highly homogeneous polymer solution was thus obtained.

[0304] The polymer solution is continuously withdrawn from the agitated reactor and introduced into a static sedimentation chamber. Sedimentation is carried out at 200°C and 2.0 MPa.

[0305] The clarified polymer solution is continuously withdrawn from the settler and passed through two series filters maintained at 200°C (in this order) with cutting diameters of 10 μm and 1 μm, respectively.

[0306] At the outlet of the series filter, the pre-purified polymer solution was then passed through an adsorption section containing an activated carbon particle bed. This adsorption process was carried out at 200°C and 2.0 MPa, with the weight content of the activated carbon particles equivalent to 6.3% of the weight of the pre-purified polymer solution.

[0307] Next, the purified solution at the outlet of the adsorption section was subjected to solvent-polymer separation by vaporizing n-heptane to obtain post-consumer recycled polypropylene resin, and composition IE1 was prepared by extrusion as described later. Solvent-polymer separation was performed in a flash defoliation section operating at an inlet temperature of 180°C and a pressure of 0.14 MPa.

[0308] (Example 2 of the invention) A pre-purified raw material (CE3B) containing 95% by weight of polypropylene (PP) was introduced in flake form into an extruder heated to 200°C. At the extruder outlet, the feed material was at least partially molten (i.e., at least substantially all of the polyolefin material was molten) and was mixed with n-heptane preheated to 200°C in a solvent:feed material weight ratio of 5:1. The mixture containing the solvent and feed material was introduced into a stirred reactor heated to 200°C and maintained at 2.0 MPa (abs) for a residence time of 1 hour. A highly homogeneous polymer solution was thus obtained.

[0309] The polymer solution is continuously withdrawn from the agitated reactor and introduced into a static sedimentation chamber. Sedimentation is carried out at 200°C and 2.0 MPa.

[0310] The clarified polymer solution is continuously withdrawn from the settler and passed through two series filters maintained at 200°C (in this order) with cutting diameters of 10 μm and 1 μm, respectively.

[0311] At the outlet of the series filter, the pre-purified polymer solution was then passed through an adsorption section containing an activated carbon particle bed. This adsorption process was carried out at 200°C and 2.0 MPa, with the weight content of the activated carbon particles equivalent to 3.2% of the weight of the pre-purified polymer solution.

[0312] Next, the purified solution at the outlet of the adsorption section was subjected to solvent-polymer separation by vaporizing n-heptane to obtain post-consumer recycled polypropylene resin, and composition IE2 was prepared by extrusion as described later. Solvent-polymer separation was performed in a flash defoliation section operating at an inlet temperature of 180°C and a pressure of 0.14 MPa.

[0313] To mimic the solvent removal efficiency of a defoliation and / or degassing extruder, both IE1 and IE2 were freeze-ground to powder and dried overnight at 90°C for approximately 16 hours using a vacuum of approximately 10 mbar abs (1 kPa abs). Pellets were produced from the freeze-ground and dried polymer powder using a small-scale extruder due to the small amount of freeze-ground powder. The small-scale extruder is a 16 mm screw diameter machine with no degassing option. The extruder was operated at a rotation speed of 200 rpm and a throughput of 1 kg / h. Stabilizers Irganox 1010 and Irgafos 168 were added at 1500 ppm each. Thus, the IE1 and IE2 pellets (melt-processed polymer compositions) contained at least 99 wt% post-consumer recycled polypropylene resin and approximately 0.3 wt% additives, based on the total weight of the polymer composition. The pelletized samples were analyzed without further stirring or defoliation. The properties of the PCR polypropylene samples are shown in Table 1 below.

[0314] [Table 1-1]

[0315] [Table 1-2]

[0316] The following abbreviations are used in all tables in this specification: nd = Undeterminable, i.e., below the detection limit and / or below the quantification limit. nm = Not measured LOQ=Limit of Quantification LOD = Detection Limit

[0317] Table 1 shows the general properties of the present invention examples (IE1, IE2) compared to other recycled polypropylene samples (i.e., CE1-CE3) and virgin polypropylene (CE4).

[0318] [Table 2]

[0319] Table 2 shows that the contaminant content is significantly reduced in the examples of the present invention (IE1, IE2) compared to other recycled polypropylene samples (i.e., CE1-CE3). Some contaminants are present at lower concentrations than in virgin polypropylene (i.e., CE4).

[0320] [Table 3]

[0321] The Level of Distance (LOD) was estimated by setting the signal-to-noise threshold to 3, multiplying it by the concentration of the standard substance, and dividing by the signal-to-noise level of the corresponding standard substance analysis. TIFF2026510752000039.tif1792

[0322] Table 3 shows that, compared to other recycled polypropylene samples (CE3A, CE3B, CE5B), the amount of emissions from the present invention examples (IE1, IE2) is significantly reduced, both in resin powder form and in pelletized, melt-treated form.

[0323] [Table 4]

[0324] Table 4 shows that in the examples of the present invention (IE1, IE2), the coloration is significantly reduced compared to the recycled polypropylene sample and CE3A, and is comparable to CE2 and CE5, which have been selected and removed from all colors except white and natural, respectively.

[0325] [Table 5]

[0326] Table 5 shows the general properties of the present invention examples (IE1, IE2) compared to other recycled polypropylene samples (i.e., CE1-CE3A) and virgin polypropylene (CE4).

[0327] [Table 6]

[0328] As can be seen from the data in Table 6, the optical properties (IE2) of the present invention are similar to those of virgin polymers (CE4) of a similar composition, compared to other recycled materials (CE3B) of a similar composition, while being similar to CE5, which requires the selection and removal of all non-natural colors. Despite the high haze, surprisingly high total light transmittance can be obtained for IE2.

[0329] [Table 7]

[0330] As can be seen from the data in Table 7, the flexibility parameter indicates that the mechanical properties of SbR materials IE1 and IE2 are improved (57-62% increase) compared to mechanically regenerated reference CE3A and CE3B, respectively. This parameter is similar to that obtained with reference CE4 of virgin heterogeneous PP, indicating that this material is virgin-like in this respect.

[0331] [Table 8]

[0332] As can be seen from the data in Table 8, the composition provided by the present invention (IE2) has similar values ​​for E' (120°C) and T (E' = 400 MPa), suggesting dimensional stability at high temperatures similar to that of virgin polymers (CE4) compared to other recycled materials (CE3B).

[0333] The pellets of IE1, IE2, and CE8 were analyzed by WAXS to determine their crystallinity (X c The content of the (β phase) and (γ phase) of the crystal structure (the remaining phase being the (α phase)) was measured.

[0334] Melting temperature of the sample (T m ) and crystallization temperature (T c The values ​​were measured using DSC (10K / min).

[0335] [Table 9]

[0336] As can be seen from Table 9, samples IE1 and IE2 each have significantly less gamma phase (Kγ) than the mechanically processed comparison sample CE8.

[0337] Sample CE8 was found to have an ash content of 0.07 wt% (ISO3451-1), an MFR of 14 g / 10 min (230℃ / 2.16 kg), a C2 content of 4.2 wt% (Crystex), and a C2(CF) content of 3.9 wt% (Crystex).

Claims

1. A polymer composition comprising at least 95% by weight of post-consumer recycled polypropylene resin, based on the total weight of the polymer composition, preferably a melt-processed polymer composition, wherein the polymer composition is The ethylene content (C2(CF)) of the crystalline fraction (CF) is in the range of [C2-3.4] to [C2-0.2] wt%, preferably [C2-3.0] to [C2-0.6] wt%, more preferably [C2-2.4] to [C2-1.2] wt%, relative to the total weight of the crystalline fraction of the polymer composition as measured by the Crystex analysis described herein; and A composition in which the content of each compound selected from hexanal, limonene, benzene, styrene, and toluene in the polymer composition is below the detection limit measured by the headspace gas chromatography / mass spectrometry (HS-GC-MS) method described herein.

2. The polymer composition according to claim 1, wherein the polymer composition is obtained or can be obtained from plastic supply raw materials by a recycling process comprising the following steps: M) Pre-treating the plastic feed material by subjecting it to a mechanical recycling process that includes a sieving step, a sorting step by at least one of polymer type, polymer article form, and / or color, a shredding step, and optionally a washing step (e.g., a water washing step) of the plastic feed material to obtain a pre-treated plastic feed material; S) A step of obtaining post-consumer recycled polypropylene resin by subjecting the pre-treated plastic supply material, which is obtained by dissolving the plastic supply material containing polypropylene in a solvent and separating insoluble components from soluble impurities, to a solvent-based recycling process, S-a) A dissolution step of contacting the pre-treated plastic supply material with a dissolution solvent at a dissolution temperature of 100°C to 300°C and a dissolution pressure of 1.0 to 20.0 MPa (abs) to obtain at least one, preferably one, crude polymer solution, wherein the dissolution solvent is selected from organic solvents containing one or more hydrocarbons having a boiling point of 75°C to 250°C, and a step of obtaining at least one crude polymer solution; S-b) Optionally, the crude polymer solution obtained from step S-a) is adsorbed by contacting it with at least one adsorbent at a temperature of 100 to 300°C and a pressure of 1.0 to 20.0 MPa (abs) to obtain at least one purified polymer solution; and S-c) A step of recovering the polymer to obtain at least one solvent fraction and one purified polymer fraction; and C) A step of melting and processing the post-consumer recycled polypropylene resin obtained from step S), C-a) A step of further separating the solvent from the purified polymer fraction, and C-b) A step comprising melting the purified polymer fraction to obtain the polymer composition.

3. The polymer composition according to claim 1 or 2, wherein the content of a compound having a boiling point of less than 250°C in the polymer composition is below the detection limit when measured by the headspace gas chromatography / mass spectrometry (HS-GC-MS) method described herein.

4. The polymer composition is the polymer composition according to any one of claims 1 to 3, wherein the ratio of the molecular weight of the soluble fraction (SF) to the molecular weight of the ethylene polymer (PE), as measured by cross-fractionation chromatography (CFC) analysis described herein, Mw(SF) / Mw(PE), is greater than 2.

5. The polymer composition according to any one of claims 1 to 4, wherein the ethylene content (C2) in the fraction that elutes at 70 to 95°C in temperature-increasing elution fractionation (TREF), as measured by cross-fractional chromatography (CFC) analysis as described herein, is less than 34% by weight.

6. The polymer composition is quantitative as described herein. １３ C { １ The polymer composition according to any one of claims 1 to 5, wherein the ratio PEP / EE of the comonomer sequence distribution at the triad level, as measured by 1H NMR spectroscopy, is greater than 0.3, preferably greater than 0.

4.

7. The polymer composition according to any one of claims 1 to 6, wherein the ethylene propylene rubber content, as measured by cross-fractionation chromatography (CFC) analysis described herein, is less than 12% by weight, more preferably less than 10% by weight, and typically at least 0.1% by weight, relative to the total weight of the polymer composition.

8. A polymer composition according to any one of claims 1 to 7, having at least one of the following features: The ash content (w / w) measured according to the thermogravimetric analysis (TGA) described herein is a maximum of 0.07% by weight relative to the total weight of the polymer composition; and / or The heavy metal content (w / w), as measured by the X-ray fluorescence (XRF) spectroscopy described herein as the sum of the metal content of cadmium, chromium, mercury, and lead, is less than 10 ppm relative to the total weight of the polymer composition; and / or The titanium content (w / w) as measured by the X-ray fluorescence (XRF) spectroscopy described herein is less than 100 ppm, preferably less than 50 ppm, more preferably less than 20 ppm, relative to the total weight of the polymer composition; and / or The content (w / w) of at least one of aluminum, calcium, or chlorine, as measured by the X-ray fluorescence (XRF) spectroscopy described herein, is less than 40 ppm relative to the total weight of the polymer composition.

9. A polymer composition according to any one of claims 1 to 8, having at least one of the following features: The L* value in the CIEL*a*b* color space, measured according to ISO 11664-4, is at least 75, preferably 86-97, more preferably 89-97; and / or Measured according to ISO 11664-4, using the following formula: (Here, the baseline background value is as follows: L) ｒｅｆ = 96.01; a ｒｅｆ = -0.29; b ｒｅｆ = 1.79) The color difference ΔE calculated using is less than 7.5 compared to the reference background; and / or In the CIEL*a*b* color space measured according to ISO 11664-4 -L* is 86 to 97, preferably 89 to 97; -a* is between -0.5 and 0.0; -b* is 0.0 to 10.0, preferably 0.0 to 5.

0.

10. The polymer composition according to any one of claims 1 to 9, wherein the post-consumer recycled polypropylene resin has at least one of the following characteristics: The L* value in the CIEL*a*b* color space, measured according to ISO 11664-4, is at least 75, preferably 86-97, more preferably 89-97; and / or Measured according to ISO 11664-4, using the following formula: (Here, the baseline background value is as follows: L) ｒｅｆ = 96.01; a ｒｅｆ = -0.29; b ｒｅｆ = 1.79) The color difference ΔE calculated using is less than 6 compared to the reference background; and / or In the CIEL*a*b* color space measured according to ISO 11664-4, -L* is 86 to 97, preferably 90 to 97; -a* is between -0.5 and 0.0; -b* is 0.0 to 10.0, preferably 0.0 to 5.

0.

11. A polymer composition according to any one of claims 1 to 10, having at least one of the following features: For a 60 × 60 × 1 mm compression-molded plaque, the total light transmittance measured according to ASTM D1003-13 is in the range of 60 to 100%, preferably 65 to 90%, more preferably 70 to 85%; and / or For a 2 mm thick tensile type 5A test specimen described herein, the tensile modulus E measured according to ISO 527-1 / -2 is in the range of 1200 to 2000 MPa, more preferably in the range of 1300 to 1900 MPa, even more preferably in the range of 1400 to 1800 MPa, and most preferably in the range of 1500 to 1700 MPa; and / or The Charpy notch impact strength at 23°C measured in accordance with ISO 179-1 / 1eA using 80×10×4 mm compression-molded test specimens prepared in accordance with EN ISO 19069-2 is in the range of 2.0 to 7.0 kJ / m ２ , more preferably in the range of 3.0 to 6.0 kJ / m ２ , even more preferably in the range of 3.2 to 5.0 kJ / m ２ ; and / or The optical mechanical capability, or optical mechanical capability focused on a process, as measured as defined herein, is at least 50; and / or The thermal deflection, measured in DMTA according to ISO 6721-7 and expressed as the temperature at which the storage modulus E' of 400 MPa is reached (T(E'=400 MPa)), is at least 97°C, preferably in the range of 97°C to 110°C, more preferably in the range of 98°C to 105°C; and / or The storage modulus (E', 90°C), measured at 90°C and determined by the DMTA described herein, is in the range of 470 to 600 MPa, preferably 480 to 550 MPa; and / or The storage modulus (E', 120°C) measured with the DMTA described herein at 120°C is in the range of 210 to 350 MPa, preferably in the range of 240 to 300 MPa.

12. A polymer composition according to any one of claims 1 to 11, having at least one of the following features: The tensile strength at the yield point (TSY), as measured according to ISO 527-1 / 2 as defined herein, is at least 26 MPa, particularly in the range of 28 to 50 MPa, preferably at least 28 MPa, more preferably at least 30 MPa; and / or The flexibility calculated as defined herein is greater than 9, preferably greater than 10, for example, 9 to 15.

13. The polymer composition according to any one of claims 1 to 12, wherein the polymer composition does not contain at least one of polyamide and / or polystyrene polymer and / or PET and / or PVC when measured by FTIR spectroscopy.

14. A polymer composition according to any one of claims 1 to 13, having at least one of the following features: The crystalline fraction content (CF), as measured according to the Crystex analysis described herein, is 85 to 95% by weight, preferably 87 to 94% by weight, more preferably 88 to 93% by weight, relative to the total weight of the polymer composition; and / or The soluble fraction content (SF), as measured according to the Crystex analysis described herein, is 5 to 15% by weight, preferably 6 to 13% by weight, more preferably 7 to 12% by weight, relative to the total weight of the polymer composition; and / or The total ethylene content (C2), as measured according to the Crystex analysis described herein, is 1.5 to 10.0% by weight, preferably 2.0 to 8.0% by weight, and more preferably 2.0 to 7.0% by weight, relative to the total weight of the polymer composition.

15. A polymer composition according to any one of claims 1 to 14, having at least one of the following features: Melt flow rate (MFR) measured at a load of 2.16 kg and 230°C according to ISO 1133. ２ However, the range is 10 to 40 g / 10 min, preferably 12 to 36 g / 10 min, more preferably 15 to 30 g / 10 min, and / or The intrinsic viscosity (IV(SF)) of the soluble fraction, as measured according to the Crystex analysis described herein, is 0.8 to 3.0 dl / g, preferably 0.9 to 2.5 dl / g, and more preferably 1 to 2 dl / g.

16. The polymer composition according to any one of claims 1 to 15, wherein the post-consumer recycled polypropylene resin comprises at least 80% by weight, for example 80 to 99% by weight, preferably at least 90% by weight, and more preferably at least 95% by weight, of the total weight of the post-consumer recycled polypropylene resin as measured by the Fourier transform infrared (FTIR) spectroscopy described herein, of at least one post-consumer recycled polypropylene.

17. The polymer composition according to any one of claims 1 to 16, comprising at least 97% by weight, preferably at least 98% by weight, and more preferably at least 99% by weight of post-consumer recycled polypropylene resin, based on the total weight of the polymer composition.

18. Use of a polymer composition according to any one of claims 1 to 17, preferably a melt-processed polymer composition, in the manufacture of an article.

19. An article comprising a polymer composition according to any one of claims 1 to 17, preferably a melt-processed polymer composition.

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