Mixed plastic polypropylene blend

Abstract

A mixed plastic polypropylene blend containing primarily polypropylene, containing no benzene and having a distinct CIELAB color.

Description

Technical Field

[0001] The present invention typically relates to a mixed plastic polypropylene blend derived from recycled materials.

Background Art

[0002] Many attempts have been made to purify the recycling stream derived from used waste. Among these means, washing, screening (sorting), aeration, distillation, etc. may be mentioned. For example, International Publication No. 2018046578 pamphlet discloses a process for producing polyolefin recycled materials from mixed colored polyolefin waste including packaging waste, which includes cold washing the waste with water, then washing with an alkaline medium at 60°C, and then performing flake color sorting to receive a fraction rich in color-sorted (white, transparent, other colors) monopolyolefins. These fractions are then treated at 50 to 155°C. US Patent No. 5767230A describes a process that includes contacting a PCR polyolefin chip containing volatile impurities with a heating gas at an empty tower velocity (superficial velocity) sufficient to substantially reduce volatile impurities such as odor-active substances. However, until now, contamination by residual benzene has been a problem. The origin of the residual benzene in used recycled materials remains unclear, but it is an obstacle to end-use in fields such as medical packaging and food packaging. The residual amount, i.e., trace amounts of benzene, is particularly problematic because it makes odor testing by sniffing experiments impossible. Therefore, end-uses with certain requirements regarding odor are prevented. Color still remains as a problem that has not been completely addressed. Many reuse applications require materials that are close to those typically represented as white. As a further problem, known recycled materials suffer from low homogeneity as reflected by surface contamination in injection-molded products. There is a specific demand for recycled materials suitable for injection molding for dosing caps, toiletries, screw caps, caps, and closures.

Prior Art Documents

Patent Documents

[0003] Patent Document 1 Pamphlet of International Publication No. 2018 / 046578 Patent Document 2 Specification of U.S. Patent No. 5,767,230 A Summary of the Invention Problems to be Solved by the Invention

[0004] Therefore, there remains a problem of providing a more valuable polypropylene blend. Means for Solving the Problems

[0005] The present invention is a mixed plastic polypropylene blend, (i) a crystal part (crystalline fraction) (CF) content determined according to CRYSTEX QC analysis in the range of 86.0 to 94.0% by weight, and (ii) a soluble part (soluble fraction) (SF) content determined according to CRYSTEX QC analysis in the range of 6.0 to 14.0% by weight and has, (iii) the above crystal part (CF) has a propylene content (C3(CF)) determined by FT-IR spectroscopy calibrated by quantitative 13 C-NMR spectroscopy in the range of 95.0 to 99.0% by weight, preferably 96.0 to 98.0% by weight, (iv) the above crystal part (CF) has an ethylene content (C2(CF)) determined by FT-IR spectroscopy calibrated by quantitative 13 C-NMR spectroscopy in the range of 1.0 to 5.0% by weight, preferably 2.0 to 4.0% by weight, more preferably 2.5 to 3.5% by weight, (v) the above soluble part (SF) has an intrinsic viscosity (iV(SF)) in the range of 1.10 to less than 1.50 dl / g, preferably 1.25 to 1.45 dl / g, (vi) When the mixed plastic polypropylene blend has inorganic residues measured by thermogravimetric analysis (TGA) in accordance with DIN ISO 1172:1996 of 0.05 to 3.0% by weight, preferably 0.05 to 2.5% by weight, optionally 1.0 to 2.5% by weight, based on the mixed plastic polypropylene blend, (vii) When the mixed plastic polypropylene blend does not contain benzene above the detection limit of HS GC-MS 80°C / 2h, (viii) The mixed plastic polypropylene blend, · has L values of 72.0 to 97.0, preferably 80.0 to 97.0 * , · has a values of -5.0 to 0.0 * , · has b values of 0.0 to less than 22.0 * in the CIELAB color space (L * a * b * ), (ix) The mixed plastic polypropylene blend has a large amplitude oscillatory shear - non-linear factor [Large Amplitude Oscillatory Shear - Non-Linear Factor, LAOS-NLF] (190°C, 1000%) higher than 2.3,

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[0006] The present invention also relates to a pelletized mixed plastic polypropylene blend and a mixed plastic polypropylene blend bisbroken (visbroken) by a peroxide. The present invention further provides an article made from the mixed plastic polypropylene blend, as well as uses in the packaging and / or medical fields. In a still further aspect, the present invention relates to a blend of the mixed plastic polypropylene blend and at least one virgin polyolefin.

[0007] Mixed plastics are defined as the presence of small amounts of compounds not normally found in virgin polypropylene blends, such as polystyrene, polyamide, polyester, wood, paper, limonene, aldehydes, ketones, fatty acids, metals, and / or long-term degradation products of stabilizers. Virgin polypropylene blends represent blends directly derived from the manufacturing process without intermediate use. As a matter of definition, "mixed plastics" can be considered equivalent to detectable amounts of polystyrene and / or polyamide-6 and / or limonene and / or fatty acids. The mixed plastic polypropylene blend further has a broad molecular weight distribution because it is a mechanical blend of a large amount of polypropylene and some very small amounts of low-density polyethylene and linear low-density polyethylene. Those skilled in the art will understand that polypropylene from various manufacturing processes will end up in the plastic waste stream, especially when pre-sorted (classified) into plastic waste streams rich in polyolefins.

[0008] Furthermore, those skilled in the art will understand that the soluble fraction (SF) obtained by CRYSTEX QC analysis, having an intrinsic viscosity (iV(SF)) in the range of 1.10 to less than 1.50 dl / g, is typically found in materials from the recycling stream. In a preferred embodiment of the present invention, the soluble fraction (SF) obtained by CRYSTEX QC analysis has an intrinsic viscosity (iV(SF)) in the range of 1.25 to less than 1.45 dl / g.

[0009] Surprisingly, it has been found that the hybrid plastic polypropylene blend according to the present invention provides better surface properties that enable many demanding end - uses.

[0010] In a first embodiment, the amounts of the crystalline fraction (CF) and the soluble fraction (SF) in the CRYSTEX QC analysis are a crystalline fraction (CF) content of 87.0 to 90.0 wt%, and a soluble fraction (SF) content of 10.0 to 13.0 wt% which is preferably. In a second embodiment, the amounts of the crystalline fraction (CF) and the soluble fraction (SF) in the CRYSTEX QC analysis are a crystalline fraction (CF) content of 91.0 to 94.0 wt%, and a soluble fraction (SF) content of 6.0 to 9.0 wt% which is.

[0011] In the first embodiment, the hybrid plastic polypropylene blend has · an L of 85.0 to 97.0 * , · an a of - 5.0 to 0.0 * , · a b from 0.0 to less than 8.0 * in the CIELAB color space (L * a * b * ).

[0012] In the second embodiment, the hybrid plastic polypropylene blend has · an L of 72.0 to 97.0, preferably 80.0 to 97.0 * , · an a of - 5.0 to 0.0 * , · a b from 0.0 to less than 22.0, usually from more than 8.0 to less than 22.0 * in the CIELAB color space (L * a * b * ). The CIELAB color can be affected by the sorting process. The more yellowish the material is acceptable, the higher b * is.

[0013] The mixed plastic polypropylene blend according to the present invention typically has a melt flow rate (ISO 1133, 2.16 kg; 230 °C) of 2.0 to 100 g / 10 min. The melt flow rate can be affected, for example, but not limited to, by dividing the used plastic waste stream that is derived from an extended producer responsibility scheme, such as the German DSD, or sorted into multiple pre-sorted fractions from municipal solid waste and recombined from them in a suitable manner. As a further method of modifying the melt flow rate of the final mixed plastic polypropylene blend, peroxides can be introduced in the final pelletizing step. Usually, the MFR is in the range of 2.0 to 100 g / 10 min, preferably 5.0 to 80 g / 10 min, more preferably 10 to 60 g / 10 min, and most preferably 12 to 55 g / 10 min.

[0014] The MFR of the second embodiment is preferably in the range of 2.0 to 12 g / 10 min (ISO 1133, 2.16 kg; 230 °C). This MFR range particularly applies to non-bis-breaking mixed plastic polypropylene blends. Bis-breaking also allows an increase in MFR up to 30 g / 10 min for the second embodiment.

[0015] Usually, the mixed plastic polypropylene blend according to the present invention will be a recycled material.

[0016] Typically, the recycling properties can be evaluated by the presence of one or more of the following substances. a) Polystyrene, b) Polyamide-6, c) Limonene determined by using headspace solid-phase microextraction (HS-SPME-GC-MS), d) Fatty acids determined by using headspace solid-phase microextraction (HS-SPME-GC-MS).

[0017] Presence means the detectable limit. The detection limits of limonene and fatty acids in headspace solid-phase microextraction (HS-SPME-GC-MS) are less than 0.1 ppm. That is, trace amounts of these substances can easily enable confirmation of the recycling properties.

[0018] The following amounts are preferred. a) Polystyrene: 0 to 2.0% by weight, more preferably 0 to 0.5% by weight b) Polyamide-6: 0 to 1.5% by weight, more preferably 0 to 0.5% by weight c) Limonene determined by using headspace solid-phase microextraction (HS-SPME-GC-MS): 0.1 ppm to 50 ppm d) Fatty acids determined by using headspace solid-phase microextraction (HS-SPME-GC-MS): 0.1 ppm to 200 ppm, more preferably 50 ppm.

[0019] Needless to say, the amounts of a), b), c) and d) should be as small as possible. In a particularly preferred embodiment, the mixed plastic polypropylene blend does not contain polystyrene and does not contain polyamide, which means that both polymers are below the detection limit.

[0020] The mixed plastic polypropylene blend according to the present invention preferably has a soluble part (SF) obtained by CRYSTEX QC analysis, having an ethylene content (C2(SF)) determined by FT-IR spectroscopy calibrated by C-NMR spectroscopy, in the range of 12.0 to 32.0% by weight. 13 C-NMR spectroscopy calibrated by FT-IR spectroscopy determined ethylene content (C2(SF)) to have a soluble part (SF) obtained by CRYSTEX QC analysis.

[0021] In a first embodiment, the mixed plastic polypropylene blend according to the present invention preferably has a soluble part (SF) obtained by CRYSTEX QC analysis, having an ethylene content (C2(SF)) determined by FT-IR spectroscopy calibrated by C-NMR spectroscopy, in the range of 25.0 to 32.0% by weight. 13 C-NMR spectroscopy calibrated by FT-IR spectroscopy determined ethylene content (C2(SF)) to have a soluble part (SF) obtained by CRYSTEX QC analysis.

[0022] In the second embodiment, the mixed plastic polypropylene blend according to the present invention preferably has a quantitative range of 10.0 to 25.0% by weight, more preferably 12.0 to 25.0% by weight, even more preferably 12.0 to 20.0% by weight, and most preferably 14.0 to 19.0% by weight. 13 It has a soluble part (SF) obtained by CRYSTEX QC analysis and has an ethylene content (C2(SF)) determined by FT-IR spectroscopy calibrated by 13C-NMR spectroscopy.

[0023] The mixed plastic polypropylene blend according to the present invention is preferably characterized in that the odor (VDA270-B3) is 4.0 or less, preferably 3.0 or less. It should be understood that many commercial recycling grades that do not report odors are actually worse because odor tests under VDA270 are prohibited due to the presence of problematic substances.

[0024] In a further aspect, the mixed plastic polypropylene blend according to the present invention, particularly the mixed plastic polypropylene blend of the first embodiment, preferably has a large amplitude oscillatory shear - non-linear factor (LAOS-NLF) (190 °C; 1000%) greater than 2.7, more preferably greater than 3.3.

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[0025] In the second embodiment, the large amplitude oscillatory shear - non-linear factor (LAOS-NLF) (190 °C; 1000%) is simply higher than 2.3.

[0026] While not wishing to be bound by theory, the processing of the polymer is thought to contribute to the branching induced by the encapsulated contaminants (admixtures). The LAOS-NLF may be affected by selecting the feedstock such that approximately 10 wt% of the material is soft polypropylene. In this regard, "soft polypropylene" means a tensile modulus (measured as described in the experimental section) of less than 900 MPa. The incorporation of low density polyethylene and linear low density polyethylene, more precisely, the presence of a low crystalline PE fraction (LCF-PE) as observed in CFC analysis in an amount of 2.0 to 4.0 wt% also contributes to a large amplitude oscillatory shear - non-linear factor (LAOS-NLF) (190 °C; 1000%) higher than 2.3. Some regions should be understood to operate collection stations that collect highly sorted consumer plastics. Such very valuable plastic streams are commercially available and enable the upgrading of other low-quality streams (e.g., from softer polypropylene mixtures) from other waste treatment resources. A second embodiment having a higher amount of crystalline fraction (CF), namely a crystalline fraction (CF) content of 91.0 to 94.0 wt% and a soluble fraction (SF) content of 6.0 to 9.0 wt% is more restrictive, whereby the large amplitude oscillatory shear - non-linear factor (LAOS-NLF) (190 °C; 1000%) is somewhat lower. In a further aspect, the mixed plastic polypropylene blend according to the first embodiment of the present invention has a tensile modulus (ISO527-2; 23 °C at a crosshead speed of 1 mm / min) using an injection molded specimen (dogbone shape, 4 mm thickness) as described in EN ISO1873-2 of at least 1300 MPa, preferably at least 1350 MPa, most preferably at least 1390 MPa. Such a relatively high tensile modulus is due to a relatively small amount of rubbery and plastomeric materials. Usually, the tensile modulus (ISO527-2; 23 °C at a crosshead speed of 1 mm / min) of the first embodiment does not exceed 1500 MPa.

[0027] The mixed plastic polypropylene blend according to the second embodiment of the present invention has a tensile modulus (ISO527-2 at a crosshead speed of 1 mm / min; 23°C) using an injection molded test piece described in EN ISO1873-2 (dogbone shape, 4 mm thickness) of at least 1200 MPa, preferably at least 1250 MPa. Usually, the tensile modulus (ISO527-2 at a crosshead speed of 1 mm / min; 23°C) of the second embodiment does not exceed 1400 MPa.

[0028] Surprisingly, the mixed plastic polypropylene blend according to the first embodiment of the present invention provides exceptional time stability with respect to the melt flow rate, η (eta) (2.7 kPa) and η (300 rad / s). Even more surprisingly, a very high melt strength was observed. Even more surprisingly, it has been found that the mixed plastic polypropylene blend according to the present invention has very good homogeneity. For example, different (selected) pellets of one batch, when analyzed separately, showed essentially the same melt flow rate, η (2.7 kPa) and η (300 rad / s) values. This is an exceptional finding since substantial variations are expected in recycled materials.

[0029] The mixed plastic polypropylene blend according to the second embodiment has been found to have excellent processability, as reflected by a shear thinning factor (STF) which is a ratio of η0.05 to η300 greater than 13.0.

[0030] The notched Charpy impact strength (uninstrumented, ISO179-1 at +23°C) of the mixed plastic polypropylene blend according to the present invention is preferably higher than 4.0 kJ / m 2 and more preferably higher than 4.5 kJ / m 2 The notched Charpy impact strength (uninstrumented, ISO179-1 at +23°C) of the mixed plastic polypropylene blend according to the second embodiment is preferably higher than 6.0 kJ / m 2 and more preferably higher than 8.0 kJ / m2 Higher, most preferably 8.3 kJ / m 2 Higher than that.

[0031] In a particularly preferred embodiment, the mixed plastic polypropylene blend according to the present invention has a notched Charpy impact strength (NIS) (1eA) (uninstrumented, ISO 179-1 at +23 °C) according to ISO 179-1eA at +23 °C for an 80×10×4 mm injection-molded test specimen prepared according to EN ISO 1873-2 of at least 8.0 kJ / m 2 , preferably 8.3 kJ / m 2 and, with respect thereto, further, the soluble fraction (SF) obtained by CRYSTEX QC analysis has an ethylene content (C2(SF)) determined by FT-IR spectroscopy calibrated by 13C-NMR spectroscopy in the range of 12.0 to 20.0 wt%, more preferably still, the mixed plastic polypropylene blend 13 has, · an L of 72.0 to 97.0, preferably 80.0 to 97.0 * , · an a of -5.0 to 0.0 * , · a b of 0.0 to less than 22.0 * in the CIELAB color space (L * a * b).

[0032] In this particularly preferred aspect of the second embodiment, the crystalline fraction (CF) content determined according to CRYSTEX QC analysis is preferably in the range of 91.0 to 94.0 wt%, and the soluble fraction (SF) content determined according to CRYSTEX QC analysis is preferably in the range of 6.0 to 9.0 wt%.

[0033] The present invention, i.e., the mixed plastic polypropylene blend according to the first and second embodiments, preferably exists in the form of pellets. Pelletization contributes to a small amount of volatile substances.

[0034] In one embodiment, the hybrid plastic polypropylene blend according to the present invention is bisbroken by one or more peroxides. The hybrid plastic polypropylene blend can be subjected to visbreaking like any other virgin polypropylene blend. When the hybrid plastic polypropylene blend according to the present invention is subjected to visbreaking, the degradation products of the visbreaking process may be found in the resulting blend. It should be understood that the degradation products of the visbreaking process (as commonly used in the art for virgin materials) are not considered impurities. Visbreaking can be carried out in the first and second embodiments.

[0035] In a further aspect, the present invention relates to a molded article made from the hybrid plastic polypropylene blend described herein. This applies to the first and second embodiments.

[0036] In yet a further aspect, the present invention relates to a blend containing the hybrid plastic polypropylene blend described herein and at least one virgin polyolefin. Again, this applies to the first and second embodiments. For example, the virgin polypropylene homopolymer contained in heterophasic polypropylene can be replaced by the hybrid plastic polypropylene blend described herein.

[0037] The present invention also relates to the use of the hybrid plastic polypropylene blend according to the present invention, i.e., the first and second embodiments, in the packaging and / or medical fields.

Brief Description of the Drawings

[0038]

Figure 1

Modes for Carrying Out the Invention

[0039] The process for providing a mixed plastic polypropylene blend according to the present invention is very stringent. This process includes the following a) providing used plastic waste; b) sorting articles made of polystyrene, polyamide, polyethylene, metal, paper, wood, and other non-polypropylene materials, thereby providing a used plastic material; c) sorting colored articles, thereby providing a used plastic material including mainly white bottles, mainly white yogurt cups, mainly white cans, mainly colorless panels, mainly colorless parts, etc.; d) grinding the selected used plastic material that is mainly white or colorless, washing it in an aqueous solution containing various detergents, then drying it, windsifting it, and screening it; e) subjecting the pretreated used plastic material to further sorting to remove non-polyolefins and colored portions to obtain an intermediate; f) a quality control step of subjecting the intermediate from step e) to Cross Fractionation Chromatography to determine the low crystalline polyethylene fraction (LCF-PE) in the CFC and double-checking whether the amount falls within the range of 2.0 to 4.0% by weight; g) discarding the intermediate that does not have a low crystalline polyethylene fraction in the range of 2.8 to 4.2% by weight; h) extruding the above material to obtain the polypropylene blend according to the present invention in the form of pellets; i) an optional venting step, which is preferably carried out at such a temperature by preheating the used plastic material to a temperature in the range of 100 to 130°C using an air stream having a temperature of at least 100°C; and includes.

[0040] Several possible feedstocks from separate collection systems (e.g., from extended producer responsibility schemes) and especially from urban waste collection systems are commercially available, enabling the provision of used plastic waste. Depending on the quality of the sorting plants where consumers participate and are involved, the purity of these feedstocks varies, which is usually indicated by the collection system. It is further possible to screen the intermediate after step b) for the presence of clearly very old ("ancient") mainly colorless / original (colored) plastic articles. Discoloration (e.g., significant yellowing) and / or significant scratches of mainly colorless / original plastic articles enable sorting. Such steps can remove so-called substances of very high concern. These substances such as Pb, Hg, polybrominated diphenyl ethers, etc. have been prohibited for quite some time but still exist in the real world. This is because consumers tend to store plastic articles, for example in the form of plastic toys, for many years and finally discard them into the collection system. The additional screening step can be assisted by the analytical control of the above substances of very high concern.

[0041] Odour control and assessment can be achieved by several methods. An overview is provided inter alia by Demets, Ruben et al., "Development and application of an analytical method to quantify odour removal in plastic waste recycling processes", Resources, Conservation and Recycling 161 (2020): 104907. This document is incorporated herein by reference.

Examples

[0042] Experiment The following examples are included to demonstrate specific aspects and embodiments of the invention as recited in the claims. However, it should be understood by those skilled in the art that the following description is merely illustrative and should in no way be construed as limiting the invention.

[0043] Test Method a) CRYSTEX Determination of the crystalline and soluble fractions and their respective properties (IV and ethylene content) The crystalline (CF) and soluble (SF) fractions of the polypropylene (PP) composition, as well as the comonomer content and intrinsic viscosity of each fraction, were analyzed using a CRYSTEX apparatus, Polymer Char (Valencia, Spain). Details of the technique and method can be found in the literature (Ljiljana Jeremic, Andreas Albrecht, Martina Sandholzer, and 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). The crystalline and amorphous fractions were separated by a temperature cycle of dissolution at 160 °C, crystallization at 40 °C, and redissolution in 1,2,4-trichlorobenzene at 160 °C. Quantification of SF and CF and determination of the ethylene content (C2) were achieved by an integrated infrared detector (IR4), and an on-line two-capillary viscometer was used for the determination of the intrinsic viscosity (IV).

[0044] The IR4 detector has two different bands (CH3 stretching vibrations (at about 2960 cm which are useful for the determination of the concentration and ethylene content in ethylene-propylene copolymers)-1 centered) and CH stretching vibration (2700 - 3000 cm -1 )) is a multi - wavelength detector that measures IR absorbance. The IR4 detector is calibrated at various concentrations in the range of 2 wt% to 69 wt% of known ethylene content ( 13 measured by C - NMR) using a series of eight EP copolymers. For the various polymer concentrations expected during Crystex analysis, since both characteristics, concentration and ethylene content, are encountered simultaneously, the following calibration equations are applied.

[0045] Conc = a + b×Abs(CH)+c×(Abs(CH)) 2 +d×Abs(CH3)+e×(Abs(CH3) 2 +f×Abs(CH)×Abs(CH3) (Equation 1) CH3 / 1000C = a + b×Abs(CH)+c×Abs(CH3)+d×(Abs(CH3) / Abs(CH))+e×(Abs(CH3) / Abs(CH)) 2 (Equation 2)

[0046] The constants a - e in Equation 1 and the constants a - f in Equation 2 were determined using least - squares regression analysis. CH3 / 1000C is converted to ethylene content (wt%) using the following relationship. wt% (ethylene in EP copolymer)=100 - CH3 / 1000TC×0.3 (Equation 3) The amounts of the soluble fraction (SF) and the crystalline fraction (CF) are correlated, by XS calibration, to the amounts of the "cold xylene soluble fraction" (XCS) and the cold xylene insoluble fraction (XCI), respectively, and determined according to the standard gravimetric method according to ISO16152. The XS calibration is achieved by testing various EP copolymers having XS contents in the range of 2 - 31 wt%. The determined XS calibration is linear. wt% XS = 1.01×wt% SF (Equation 4)

[0047] The intrinsic viscosity (IV) of the parent EP copolymer and its soluble and crystalline parts was determined using an online two-capillary viscometer and correlated with the corresponding IV determined by standard methods in decalin according to ISO 1628-3. Calibration was achieved using various EPPP copolymers with IV = 2 - 4 dL / g. The determined calibration curve is linear. IV (dL / g) = a × Vsp / c (Equation 5)

[0048] The sample to be analyzed is weighed at a concentration of 10 mg / ml to 20 mg / ml. To avoid the injection of gels and / or polymers that may not dissolve in TCB at 160 °C, such as PET and PA, the weighed sample is filled into a stainless-steel mesh MW0.077 / D0.05 mm. 1,2,4-TCB containing 250 mg / l 2,6-tert-butyl-4-methylphenol (BHT) as an antioxidant was automatically filled into a vial, and then the sample was dissolved at 160 °C for usually 60 minutes with continuous stirring at 400 rpm until complete dissolution was achieved. To avoid deterioration of the sample, during dissolution, the polymer solution is covered with an N2 atmosphere. A sample solution of a specified volume is injected into a column filled with an inert carrier where crystallization of the sample and separation of the soluble part from the crystalline part take place. This process is repeated twice. During the first injection, the entire sample is measured at a high temperature to determine the IV [dl / g] and C2 [wt%] of the PP composition. During the second injection, the soluble part (at low temperature) and the crystalline part (at high temperature) are measured (wt% SF, wt% C2, IV) in a crystallization cycle.

[0049] b) Quantification of microstructure by NMR spectroscopy (calibration only) Quantitative nuclear magnetic resonance (NMR) spectroscopy was used for calibration.

[0050] Quantitative 13C{1H} NMR spectra were recorded in solution using a Bruker Avance Neo 400 NMR spectrometer operating at 400.15 and 100.62 MHz for 1H and 13C, respectively. All spectra were recorded using a 10 mm extended temperature probe head optimized for 13C at 125 °C and nitrogen gas for all air pressures. Approximately 200 mg of the material was dissolved in approximately 3 ml of 1,2-tetrachloroethane-d2 (TCE-d2) together with approximately 3 mg of BHT (2,6-di-tert-butyl-4-methylphenol, CAS 128-37-0) and chromium(III) acetylacetonate (Cr(acac)3) giving a 60 mM solution of the relaxant in the solvent as described by G. Singh, A. Kothari, V. Gupta, Polymer Testing 2009, 28(5), 475.

[0051] To ensure a homogeneous solution, after the initial sample preparation in a heat block, the NMR tube was further heated in a rotary oven for at least 1 h. After insertion into the magnet, the tube was rotated at 10 Hz. This setting was chosen mainly for the high resolution and quantitativeness required for the accurate quantification of the ethylene content. A standard single pulse excitation without NOE was employed using an optimized tip angle, a recycle delay of 1 s, and a bilinear WALTZ16 decoupling scheme (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.

[0052] The quantitative 13C{1H} NMR spectra were processed, integrated, and the relevant quantitative characteristics were determined from the integral values. All chemical shifts were indirectly referenced to the central methylene group of the ethylene block (EEE) at 30.00 ppm using the chemical shift of the solvent. This approach enabled comparable referencing even in the absence of this structural unit.

[0053] Characteristic signals corresponding to the incorporation of ethylene were observed (as described in Cheng, H.N., Macromolecules 1984, 17, 1950), and the comonomer fraction was calculated as the fraction of ethylene in the polymer relative to all monomers in the polymer. fE = (E / (P + E))

[0054] The comonomer fraction was quantified through the integration of multiple signals over the entire spectral region of the 13C{1H} spectrum using the method of W-J. Wang and S. Zhu, Macromolecules 2000, 33, 1157. The integration regions were slightly adjusted to enhance applicability over the full range of the facing comonomer content.

[0055] The comonomer incorporation in mole percent was calculated from the mole fraction. E [mol%] = 100 × fE The comonomer incorporation in weight percent was calculated from the mole fraction. E [wt%] = 100 × (fE × 28.06) / ((fE × 28.06) + ((1 - fE) × 42.08))

[0056] c) The tensile modulus and tensile break strain were measured according to ISO 527-2 (crosshead speed = 1 mm / min; test speed 50 mm / min, 23 °C) using injection-molded test specimens (dog-bone shape, thickness 4 mm) described in EN ISO 1873-2. The measurements were carried out after a conditioning time of 96 hours (h) for the test specimens.

[0057] d) The impact strength was determined as the notched Charpy impact strength (1eA) (non-instrumented, ISO 179-1 at +23°C) in accordance with ISO 179-1eA at +23°C on injection-molded test specimens measuring 80×10×4 mm prepared in accordance with EN ISO 1873-2.

[0058] e) Inorganic residue: TGA in accordance with DIN ISO 1172:1996 using a Perkin Elmer TGA8000. Approximately 10 - 20 mg of the material was placed in a platinum pan. The temperature was equilibrated at 50°C for 10 minutes and then raised to 950°C under nitrogen at a heating rate of 20°C / min. The ash content was evaluated as the weight % at 850°C.

[0059] f) MFR: The melt flow rate was measured under a load of 230°C and 2.16 kg (MFR2). The melt flow rate is the amount of polymer in grams extruded within 10 minutes at a temperature of 230°C under a load of 2.16 kg by a test apparatus standardized to ISO 1133.

[0060] g) Amount of metal Determined by X-ray fluorescence (XRF).

[0061] h) Amount of paper, wood (for reference purposes only) Paper and wood can be determined by conventional laboratory methods including grinding, flotation, microscopic observation, and thermogravimetric analysis (TGA).

[0062] i) Benzene content By HS GC-MS at 80°C / 2h as described below. Static headspace analysis The parameters of the applied static headspace gas chromatography - mass spectrometry (HS / GC / MS) method are described here.

[0063] 4.000 ± 0.100 g of the sample was weighed into a 20 ml HS vial and sealed with a PTFE cap.

[0064] The mass spectrometer was operated in scan mode, and the total ion chromatogram (TIC) was recorded for each analysis. More detailed information on applicable method parameters and data evaluation is shown below.

[0065] · HS parameters (Agilent G1888 headspace sampler) Vial equilibration time: 120 minutes Oven temperature: 80 °C Loop temperature: 205 °C Transfer line temperature: 210 °C Low oscillation · GC parameters (Agilent 7890A GC system) Column: ZB-WAX 7HG-G007-22 (30 m × 250 μm × 1 μm) Carrier gas: Helium 5.0 Flow rate: 2 ml / min Split: 5:1 GC oven program: 35 °C, 0.1 minute To 250 °C at 10 °C / min 1 minute at 250 °C · MS parameters (Agilent 5975C inert XL MSD) Acquisition mode: Scan Scan parameters: Low mass: 20 High mass: 200 Threshold: 10 · Software / Data evaluation MSD ChemStation E.02.02.1431 MassHunter GC / MS Acquisition B.07.05.2479 AMDIS GC / MS Analysis version 2.71 NIST Mass Spectral Library version 2.0 g · AMDIS deconvolution parameters Minimum match factor: 80 Threshold: Low Scan direction: High to Low Data file format: Agilent files Instrument type: Quadrupole Component width: 20 Adjacent peak subtraction: Two(2) Resolution: High Sensitivity: Very high Shape requirements: Medium Solvent tailing: 44 m / z Column bleed: 207 m / z Min.model peaks: 2 Min.S / N: 10 Min.certain peaks: 0.5

[0066] Data evaluation The TIC data was further deconvoluted using AMDIS software (refer to the above parameters) and compared with a custom target library based on the mass spectrum library (NIST). This custom target library contained the respective mass spectra of the selected substances (e.g., benzene). If the recognized peaks showed a minimum match factor of 80 and were confirmed as a match by an experienced mass spectrometry personnel, the substance was recognized as "tentatively identified". In this study, the description "below the limit of detection (<LOD)" refers to the condition where either the match factor is less than 80 (AMDIS) or the peak itself is not even recognized. The results refer only to the measured sample, the measurement time, and the parameters applied.

[0067] j) CIELAB color space (L * a * b * ) CIE L measured in accordance with DIN EN ISO11664-4 * a * b * In the uniform color space, the color coordinates are as follows: L * - lightness coordinate; a * - red / green coordinate, +a * indicates red, -a * indicates green; b * - yellow / blue coordinate, +b * indicates yellow, -b * indicates blue. L * 、a * 、and b * The coordinate axes of define the three-dimensional CIE color space. Standard Konica Minolta Colorimeter CM-3700A.

[0068] k) Odor VDA270-B3 VDA270 is the determination of the odor characteristics of trim materials in automobiles. In this study, the odor is determined according to Variant B3 of VDA270 (2018). The odor of each sample is evaluated by each assessor according to the VDA270 scale after lifting the lid of the bottle as low as possible. The six - step scale consists of the following grades: Grade 1: Not perceivable, Grade 2: Perceivable but not unpleasant, Grade 3: Clearly perceivable but not unpleasant, Grade 4: Unpleasant, Grade 5: Strongly unpleasant, Grade 6: Unacceptable. The assessors should remain quiet during the evaluation and are not allowed to bias each other by discussing individual results during the test. The assessors are also not allowed to adjust their evaluations after testing another sample. For statistical reasons (and as accepted by VDA270), the assessors are forced to use the entire process in the evaluation. Therefore, the odor grade is rounded to an integer based on the average of all individual evaluations.

[0069] l) Limonene detection The quantification of limonene can be performed using headspace solid - phase microextraction (HS - SPME - GC - MS) by standard addition. Weigh 50 mg of the ground sample into a 20 mL headspace vial, add different concentrations of limonene and a glass - coated magnetic stir bar, and then close the vial with a magnetic cap lined with silicone / PTFE. Using a microcapillary (10 pL), add a diluted limonene standard of known concentration to the sample. Additions of 0 ng, 2 ng, 20 ng, and 100 ng are equivalent to 0 mg / kg, 0.1 mg / kg, 1 mg / kg, and 5 mg / kg of limonene, and in addition, standard amounts of 6.6 mg / kg, 11 mg / kg, and 16.5 mg / kg of limonene are used in combination with some of the samples tested in this application. Ion 93 obtained in SIM mode is used for quantification. The concentration of the volatile fraction is carried out by headspace solid - phase microextraction using a 2 cm StableFlex 50 / 30 μm DVB / Carboxen / PDMS fiber at 60 °C for 20 minutes. Desorption is carried out directly at 270 °C in the heated injection port of the GCMS system. GCMS parameters: Column: 30 m HP 5 MS 0.25×0.25 Injector: Splitless, 0.75 mm SPME liner, 270 °C Temperature program: -10 °C (1 min) Carrier gas: Helium 5.0, 31 cm / sec linear velocity, constant flow MS: Single quadrupole type, direct interface, 280 °C interface temperature Acquisition: SIM scan mode Scan parameters: 20 - 300 amu SIM parameters: m / Z 93, 100 ms dwell time

[0070] m) Fatty acid detection Quantification of fatty acids is performed using headspace solid-phase microextraction (HS-SPME-GC-MS) with standard addition. Weigh 50 mg of the pulverized sample in a 20 mL headspace vial, add different concentrations of limonene and a glass-coated magnetic stir bar, and then close the vial with a magnetic cap lined with silicone / PTFE. Using a 10 μL microcapillary, add known concentrations of a diluted free fatty acid mixture (acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, and octanoic acid) standards to the sample at three different levels. Additions of 0 ng, 50 ng, 100 ng, and 500 ng are equivalent to 0 mg / kg, 1 mg / kg, 2 mg / kg, and 10 mg / kg of each individual acid. For quantification, ion 60 obtained in SIM mode is used for all acids except propionic acid, and for propionic acid, ion 74 is used. GCMS parameters: Column: 20 m ZB Wax plus 0.25×0.25 Injector: Split 5:1 at 250 °C with a glass-lined split liner Temperature program: 40 °C (1 min), 6 °C / min to 120 °C, 15 °C to 245 °C (5 min) Carrier: Helium 5.0, 40 cm / sec linear velocity, constant flow MS: Single quadrupole type, direct interface, 220 °C interface temperature Acquisition: SIM Scan Mode Scan Parameters: 46 - 250 amu, 6.6 scans / second SIM Parameters: m / z 60, 74, 6.6 scans / second

[0071] n) Presence of polyamide - 6 and polystyrene By FTIR spectroscopy, at 1601 cm -1 (PS) and at 3300 cm -1 (PA6) the absorption of the bands is used.

[0072] o) Determination of contamination on the small plate The small plate (plaque) is injection - molded with dimensions of 150×80×2 mm. Then, high - resolution images (photos) are taken on five small plates (placed close to each other). Then, the images are analyzed by software that enables automatic counting of the number of visual defects (by the naked eye) due to contamination.

[0073] p) Dynamic shear measurement (η(2.7 kPa) and η(300 rad / s)) The characterization of the polymer melt by dynamic shear measurement is in accordance with ISO standards 6721 - 1 and 6721 - 10. The measurements were carried out on an Anton Paar MCR501 stress - controlled rotational rheometer equipped with a 25 - mm parallel - plate configuration. The measurements were performed using a nitrogen atmosphere, setting the strain within the linear viscoelastic region and using a compression - molded plate. The oscillatory shear tests were carried out at 230 °C with a frequency range of 0.01 - 600 rad / s and a gap set at 1.3 mm.

[0074] In the dynamic shear experiment, the probe is subjected to uniform deformation with a sinusoidally varying shear strain or shear stress (in the modes of controlling strain and stress respectively). In the controlled - strain experiment, the probe is subjected to a sinusoidal strain that can be expressed by the following formula. γ(t)=γ0sin(ωt) (1) If the applied strain is within the range of the linear viscoelastic region, the resulting sinusoidal stress response can be given by the following formula. σ(t)=σ0sin(ωt + δ) (2) In the above formula, σ0 and γ0 are the stress amplitude and strain amplitude, respectively, ω is the angular frequency, δ is the phase difference (loss angle between the applied strain and the stress response), t is time.

[0075] The dynamic test results are typically several different rheological functions, namely the shear storage modulus G’, the shear loss modulus G”, the complex shear modulus G * , the complex shear viscosity η * , the dynamic shear viscosity η’, the out-of-phase component η” of the complex shear viscosity, and the loss tangent tanδ, and the above rheological functions can be expressed as follows.

[0076]

Number

[0077] η(x kPa) is determined according to Equation 9. η(x kPa) = (G * = x kPa) corresponding η * [Pa·s] (9)

[0078] For example, η(2.7 kPa) is determined by the value of the complex viscosity determined for the value of the complex modulus equal to 2.7 kPa. η(x rad / s) is determined according to Equation 10. η(x rad / s) = (ω = x rad / s) corresponding η * [Pa·s] (10) For example, η(300 rad / s) is determined by the value of the complex viscosity determined by the frequency sweep at 300 rad / s.

[0079] q) The shear thinning fluidization coefficient (STF) is defined as follows.

Number

[0080] References: [1] “Rheological characterization of polyethylene fractions”, Heino, E.L., Lehtinen, A., Tanner J., Seppala, J., Neste Oy, Porvoo, Finland, Theor. Appl. Rheol., Proc. Int. Congr. Rheol, 11th (1992), 1, 360 - 362 [2] “The influence of molecular structure on some rheological properties of polyethylene”, Heino, E.L., Borealis Polymers Oy, Porvoo, Finland, Annual Transactions of the Nordic Rheology Society, 1995.) [3] Definition of terms relating to the non - ultimate mechanical properties of polymers, Pure & Appl. Chem., Vol. 70, No. 3, pp. 701 - 754, 1998.

[0081] r) Large amplitude oscillatory shear (LAOS) The examination of the non-linear viscoelastic behavior under shear flow was carried out by means of large amplitude oscillatory shear. This method requires the application of a sinusoidal strain amplitude γ0 at a given angular frequency ω for a given time t. If the applied sinusoidal strain is high enough, a non-linear response is generated. In this case, the stress σ is a function of the applied strain amplitude, time and angular frequency. Under these conditions, the non-linear stress response is still a periodic function. However, it can no longer be represented by a single harmonic sinusoid. The stress [0-0] resulting from the non-linear viscoelastic response can be represented by a Fourier series containing harmonic contributions. σ(t, ω, γ0) = γ0.Σ n [G’ n (ω, γ0).sin(nωt) + G” n (ω, γ0).cos(nωt)] (1) In the above equation, σ is the stress response, t is the time, ω is the frequency, γ0 is the strain amplitude, n is the harmonic number, G’ n is the elastic Fourier coefficient of the nth order, G” n is the viscous Fourier coefficient of the nth order.

[0082] The non-linear viscoelastic response was analyzed by applying large amplitude oscillatory shear (LAOS). The time sweep measurements were carried out with an RPA2000 rheometer manufactured by Alpha Technologies, connected to a standard double cone die. During the measurement process, the test chamber was sealed and a pressure of about 6 MPa was applied. The LAOS test was carried out by applying a temperature of 190 °C, an angular frequency of 0.628 rad / s and a strain of 1000%. To ensure reaching steady state conditions, the non-linear response was determined only after at least 20 cycles per measurement were completed. The large amplitude oscillatory shear non-linear factor (LAOS_NLF) is

Equation

[0083] [1] J.M. Dealy, K.F. Wissbrun, Melt Rheology and Its Role in Plastics Processing: Theory and Applications, edited by Van Nostrand Reinhold, New York (1990) [2] S. Filipe, Non-Linear Rheology of Polymer Melts, AIP Conference Proceedings 1152, pp. 168 - 174 (2009) [3] M. Wilhelm, Macromol. Mat. Eng. 287, 83 - 105 (2002) [4] S. Filipe, K. Hofstadler, K. Klimke, A.T. Tran, Non-Linear Rheological Parameters for Characterisation of Molecular Structural Properties in Polyolefins, Proceedings of Annual European Rheology Conference, 135 (2010) [5] S. Filipe, K. Klimke, A.T. Tran, J. Reussner, Proceedings of Novel Non-Linear Rheological Parameters for Molecular Structural Characterisation of Polyolefins, Novel Trends in Rheology IV, Zlin, Czech Republic (2011) [6] K. Klimke, S. Filipe, A. T. Tran, Non-linear rheological parameters for characterization of molecular structural properties in polyolefins, Proceedings of European Polymer Conference, Granada, Spain (2011)

[0084] s) Cross fractionation chromatography The chemical composition distribution, as well as the molecular weight distribution at specific elution temperatures and the corresponding molecular weight averages (Mn, Mw and Mv) (degree of polymer crystallinity in solution) were determined by fully automated cross fractionation chromatography (CFC) as described by Ortin A., Monrabal B., Sancho-Tello J., Macromol. Symp., 2007, 257, 13 - 28.

[0085] Cross fractionation chromatography (TREF×SEC) was carried out using a CFC apparatus (PolymerChar, Valencia, Spain). The concentration was monitored using a 4-band IR5 infrared detector (PolymerChar, Valencia, Spain). The polymer was dissolved at 160 °C for 150 minutes at a concentration of approximately 1 mg / ml.

[0086] To avoid injection of gels and polymers that may not dissolve in TCB at 160 °C, such as PET and PA, the weighed sample was filled into a stainless steel mesh with MW0.077 / D0.05 mm.

[0087] Once the sample was completely dissolved, a 0.5 ml aliquot was loaded onto a TREF column and stabilized at 110 °C for a while. The polymer was crystallized and precipitated to a temperature of 30 °C by applying a constant cooling rate of 0.1 °C / min. The discontinuous elution process was carried out 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).

[0088] In the second dimension, GPC analysis, three PL Olexis columns and one Olexis Guard column from Agilent (Church Stretton, UK) were used as the stationary phase. 1,2,4-Trichlorobenzene (TCB, stabilized with 250 mg / L 2,6-di-tert-butyl-4-methyl-phenol) was applied as the eluent at a constant flow rate of 1 mL / min at 150 °C. This column set was calibrated using universal calibration (in accordance with ISO 16014-2:2003) with at least 15 narrow MWD polystyrene (PS) standards in the range of 0.5 kg / mol to 11500 kg / mol. The PS molecular weight was converted to PP molecular weight equivalent using the following Mark Houwink constants. K PS = 19×10 -3 mL / g, α PS = 0.655 K PP = 19×10 -3 mL / g, α PP = 0.725

[0089] The calibration data was fitted using a cubic polynomial fitting. The data processing was carried out using the software provided by PolymerChar together with the CFC device.

[0090] Calculation of the specific molecular weight of iso-PP in weight % and the relative fraction in the elution temperature region In the first step, in order to calculate the specific molecular weight of iso-PP in weight percentage and the relative fraction in the elution temperature range, it is necessary to calculate the amount of iso-PP in weight percentage from the CFC contour map. IsoPP (wt%) = 100 - EPR fraction - PE fraction Equation (1) In the above equation, EPR is the fraction having a molar mass higher than 3.5 logM of the soluble part (SF) in TCB at 35 °C obtained by CFC analysis.

Number

[0091] Due to the slight dependence of the TREF profile on the low MW part, the molecular weight limit of the low MW limit depends on the elution temperature (T el ). The low MW limit was determined using the following equation. Low MW limit (for PE fraction) = 0.0185 × T el + 3.1538 Taking this into account, the PE fraction is calculated using the following approach.

Number

[0092] The highly crystalline PE fraction (HCF-PE) is defined as the part of the PE fraction that elutes at 90 °C to 100 °C.

Number

[0093] This fraction mainly contains homopolymer PE and PE copolymers with a very small amount of comonomer less than about 3 SCB / 1000 TCB (L. Wild, T. R. Ryle, D. C. Knoblauch, I. R. Peat, J. Polym. Sci, Polym. Phys. 20 (1982), 441-455).

[0094] Here, the low-crystalline PE fraction (LCF-PE) is defined as the portion of the PE fraction that elutes at 35°C to 89°C.

Number

[0095] This fraction mainly includes copolymer fractions from HDPE and LLDPE obtained by ZN catalysts, or LLDPE from SS catalysts, but also includes LDPE. This is because polymers of this type co-elute due to similar amounts of SCB / 1000TC. Basic references: Zhang, Macromol Symp. 282 (2009), 111 - 127. W.Yau, D.Gillespie, Polymer 42 (2001) 8947 - 8958. Monrabal, "Encyclopedia of Analytical Chemistry", edited by R.A.Meyers, John Wiley & Sons Ltd., 2000. Nakano, Y.Goto, J.Appl.Polym.Sci. (1981), 26, 4217. W.Yau, Macromol.Symp. 2007, 257, 29 - 45. Faldi, J.B.P.Soares, Polymer 42 (2001) 3057 - 3066. Ortin, B.Monrabal, J,Sancho-Tello, Macromol.Symp. 257 (2007), 13 - 28. Li Pi Shan, D.Gillespie, L.Hazlitt, Ecorep 2005. Lyon (Lyon).

[0096] Examples The used plastic waste was roughly sorted with respect to the polymer properties and color. In a further step, the white and colorless parts were selected. The selected parts were crushed, washed in an aqueous solution containing various detergents, subsequently dried, and screened. This pretreated used plastic material was further sorted, thereby reducing the colored parts. In a further quality control step, this intermediate was subjected to cross-fractionation chromatography (an automated instrument combining TREF and CPC; available from Polymer Char; see above for details). All intermediates having a low-crystallinity PE fraction (LCF-PE) outside the range of 2.8 to 4.2 wt% were discarded and returned to the incoming waste. After extrusion into pellets, the pellets were subjected to aeration (aeration was carried out only with IE3; aeration conditions: air at 120 °C, preheated substrate).

[0097] For Example IE4, the same process was followed. However, after roughly sorting with respect to the polymer properties and color, the used plastic waste was screened with respect to mainly colorless / original plastic articles that were visibly very old ("aged"), recognizable by discoloration (e.g., significant yellowing) and / or significant scratches of the plastic articles. Such visibly very old ("aged") mainly colorless / original plastic articles were sorted, thereby excluding, according to strict standards, i.e., in case of doubt, the articles in question. This was done to exclude the incorporation of polybrominated diphenyl ethers, which have been banned in many countries for more than about 10 years. The intermediate was also screened with respect to highly suspect substances. It was found that partial warping was not required.

[0098] All examples were subjected to CRYSTEX QC analysis.

[0099]

Table 1(1)

Table 1(2)

Table 1(3)

Table 1(4)

[0100] It can be seen that the prior art is enriched by the recycling composition of the present invention. The recycling composition of the present invention showed only minor drawbacks with respect to impact when compared to the virgin composition and the virgin bis-broken composition. Furthermore, the processability reflected by the high LAOS-NLF was actually good for IE2 and IE3. The VOC (VDA) was surprisingly good for IE3 and IE4. Comparative example CE3 was a virgin random heterophasic polypropylene copolymer. Therefore, the tensile modulus was relatively high in terms of the total amount of ethylene (reflected by the amounts of C2(CF) and C2(SF) as well as CF and SF). However, this was not a recycled material, and the processability reflected by the LAOS-NLF was relatively poor with a Charpy NIS of 7.1 kJ / m 2 of the Charpy NIS. Comparative example CE4 was a virgin random copolymer that had been subjected to bis-breaking (in order to adapt the melt flow rate to a value approximately the same as that of IE4). CE4 was significantly less rigid compared to CE3 and had a Charpy NIS of 7.6 kJ / m 2 of the Charpy NIS. Inventive example IE4 had slightly higher rigidity than CE3 and at the same time had the best overall Charpy NIS of 8.5 kJ / m 2 of the Charpy NIS. All of inventive examples IE1 to IE3 had significantly high rigidity and at the same time had only the drawback of a medium Charpy NIS.

[0101] The above examples were subjected to an evaluation of surface defects in injection-molded test articles. The best commercially available grades (CE1 and CE2) were compared. The results are shown in Figure 1.

[0102] CE1: 920 kg / m 3A PP off-white product from Van Werven having a density of and an MFR (230°C / 2.16 kg) of 24 g / 10 min.

[0103] CE2: Morssinkhof-Rymoplast supplies regrinds (ground recycled materials) and regranulates (pelletized recycled materials) of the name MOPRYLENE® having a density of 921 kg / m 3 and an MFR (230°C / 2.16 kg) of 27 g / 10 min.

[0104] Figure 1 shows the results of the defect evaluation. It can be seen that the mixed plastic polypropylene blend of the present invention resulted in the fewest number of defects and their even distribution.

[0105] CE3 is a random heterophasic copolymer that does not contain slip additives and antiblocking additives. It has a random copolymer PP matrix and C3C2 rubber.

[0106] CE3 was produced in a Borstar polypropylene plant having a configuration of a prepolymerization reactor (prepolymerization reactor, prepolymerizer), one slurry loop reactor, a first gas phase reactor, and a second gas phase reactor. The loop reactor and the first gas phase reactor were used to produce the matrix, and the second gas phase reactor was for the rubber phase. The chemical composition of the reactants in each reactor was adjusted to achieve the desired polymer design.

[0107] CE4 is a random copolymer produced in a Borstar polypropylene plant having a configuration of a prepolymerization reactor, one slurry loop reactor, and one gas phase reactor.

[0108] [Table 2]

[0109] After blending, the melt flow rate of the random copolymer CE4 was modified by bis-breaking during the compounding process in a twin-screw extruder at 200 - 230 °C using an appropriate amount of Luperox 101 (2,5-dimethyl-2,5-di(tert-butylperoxy)hexane) to achieve the target MFR2 of 8.0 g / 10 min. During the above compounding process, 1000 ppm of Irganox B215 (pentaerythrityl-tetrakis(3-(3’,5’-di-tert-butyl-4-hydroxyphenyl)-propionate, CAS No. 6683-19-8 and a 1:2 mixture of tris(2,4-di-t-butylphenyl)phosphite, CAS No. 31570-04-4, commercially available from BASF SE (BASF), Germany) and 150 ppm of magnesium oxide (CAS No. 1309-48-4) as an acid scavenger were added during the compounding process.

[0110] The catalysts used in the polymerization processes of CE3 and CE4 were prepared as follows. Chemicals used: 20% toluene solution of butylethylmagnesium (Mg(Bu)(Et), BEM) provided by Chemtura 2-ethylhexanol provided by Amphochem 3-butoxy-2-propanol-(DOWANOL™ PnB) provided by Dow Bis(2-ethylhexyl) citraconate provided by SynphaBase TiCl4 provided by Millenium Chemicals Toluene provided by Aspokem Viscoplex® 1-254 provided by Evonik Heptane provided by Chevron

[0111] Preparation of Mg alkoxy compound The Mg alkoxide solution was prepared by adding a mixture of 4.7 kg of 2-ethylhexanol and 1.2 kg of butoxypropanol to 11 kg of a toluene solution of 20 wt% butylethylmagnesium (Mg(Bu)(Et)) in a 20 L stainless steel reactor while stirring (70 rpm). During the addition, the contents of the reactor were maintained below 45 °C. After the addition was complete, the mixing (70 rpm) of the reaction mixture was continued at 60 °C for 30 minutes. After cooling to room temperature, 2.3 kg of the donor, bis(2-ethylhexyl) citraconate, was added to the Mg alkoxide solution while maintaining the temperature below 25 °C. Mixing was continued for 15 minutes while stirring (70 rpm).

[0112] Preparation of solid catalyst component 20.3 kg of TiCl4 and 1.1 kg of toluene were added to a 20 L stainless steel reactor. While mixing at 350 rpm and maintaining the temperature at 0 °C, 14.5 kg of the prepared Mg alkoxy compound was added over 1.5 hours. 1.7 L of Viscoplex® 1-254 and 7.5 kg of heptane were added and mixed at 0 °C for 1 hour, then the temperature of the formed emulsion was raised to 90 °C within 1 hour. After stopping the mixing for 30 minutes, the catalyst droplets were solidified and the formed catalyst particles were sedimented. After sedimentation (1 hour), the supernatant was siphoned off. Then the catalyst particles were washed with 45 kg of toluene at 90 °C for 20 minutes, followed by two washes with heptane (30 kg, 15 minutes). The temperature was lowered to 50 °C during the first heptane wash and to room temperature during the second wash.

[0113] Alternatively, for the polymerization of random copolymers (Comparative CE3, CE4), a Ziegler Natta catalyst without phthalate ester prepared as described as a "reference catalyst" in the example section of WO 2020 / 064673A1 pamphlet is used.

[0114] The catalyst thus obtained was used together with triethylaluminum (TEAL) as a cocatalyst and dicyclopentyldimethoxysilane (D-donor) as a donor. IE4 was further evaluated regarding Substances of Very High Concern (SVHC). The results are shown in Table 2 below.

[0115]

Table 3

[0116] RoHS - Restriction of Hazardous Substances in Electrical and Electronic Equipment RL - Reporting Limit (Test data is shown if it is ≧ RL. RL is not a regulatory limit)

[0117] Method for SVHC (in accordance with REACH Regulation 1907 / 2006 / EU) All analyses were performed by SGS. The in-organization methods at SGS are CTS-HL-114-1 and CTS-HL-234-5, which are analyzed by ICP-OES, UV-VIS, GC-MS, HPLC-DAD / MS and colorimetry

[0118] Determination of cadmium by ICP-OES, in accordance with IEC62321-5:2013-6 Determination of lead by ICP-OES, in accordance with IEC62321-5:2013-6 Determination of mercury by CV-AAS, in accordance with IEC62321-4:2013-6 Determination of chromium by ICP-OES, in accordance with IEC62321-5:2013-6

[0119] Determination of chromium(VI), in accordance with IEC62321, -> for non-metallic samples: Determination by ion chromatography, in accordance with IEC62321-7-2:2017-03 Note: The concentration of Cr(VI) in the corrosion inhibitor may vary depending on the storage time and conditions.

[0120] Determination of PBB / PBDE (flame retardants) by GC / MS, in accordance with IEC62321-6:2015-6 Note: According to the IEC, the tests for PBB / PBDE are only intended for polymers.

[0121] Plasticizers DEHP, DBP; BBP, DIBP and extended list according to REACH (IEC62321-8:2017, GC-MS)

[0122] Determination of phthalic acid esters by GC / MS after extraction with THF, in accordance with IEC62321-8:2017-3; Method not under validation Note: According to the IEC, the tests for phthalic acid esters are only intended for polymers.

[0123] CE3 is a bimodal virgin random polypropylene evaluated for comparison purposes. It can be seen that the virgin random polypropylene may be replaced by the blend of the present invention which has surprising benefits with respect to impact.

[0124] As a further application example, injection molded buckets were manufactured with standard process settings. It was found that the surface quality was as good as that of equivalent virgin materials. The thickness distribution and mechanical properties were also excellent.

Claims

1. A mixed plastic polypropylene blend, (i) a crystalline part (CF) content determined according to CRYSTEX QC analysis in the range of 86.0 to 94.0% by weight, and (ii) a soluble part (SF) content determined according to CRYSTEX QC analysis in the range of 6.0 to 14.0% by weight having, where the crystalline part (CF) and the soluble part (SF) are separated by a temperature cycle of dissolution at 160 °C, crystallization at 40 °C, and re-dissolution at 160 °C in 1,2,4-trichlorobenzene, (iii) The crystalline part (CF) has a propylene content (C3(CF)) determined by FT-IR spectroscopy calibrated by 13C-NMR spectroscopy in the range of 95.0 to 99.0% by weight １３ and (iv) The crystal part (CF) has an ethylene content (C2(CF)) determined by FT-IR spectroscopy calibrated by 13C-NMR spectroscopy in the range of 1.0 to 5.0% by weight １３ and (v) the soluble part (SF) has an intrinsic viscosity (iV(SF)) determined using an on-line two-capillary viscometer in the range of 1.10 to less than 1.50 dl / g and determined by a standard method in decalin according to ISO 1628-3, (vi) the mixed plastic polypropylene blend has an inorganic residue measured by firing analysis (TGA) according to DIN ISO 1172:1996 in the range of 0.05 to 3.0% by weight based on the mixed plastic polypropylene blend, (vii) the mixed plastic polypropylene blend does not contain benzene beyond the detection limit where the match factor at an oven temperature of 80 °C and a vial equilibration time of 120 minutes in HS GC-MS 80 °C / 2 h is less than 80 (AMDIS) or the peak itself is not recognized, (viii) the mixed plastic polypropylene blend L of 72.0 to 97.0 ＊ , -5.0 to 0.0 of a ＊ , b of 0.0 to less than 22.0 ＊ in the CIELAB color space (L ＊ a ＊ b ＊ ), and (ix) the mixed plastic polypropylene blend has a large amplitude oscillatory shear - non-linear factor [LAOS-NLF] (190 °C, 1000%) higher than 2.3, 【Number 1】 wherein, G １ ' is the first-order Fourier coefficient, G ３ ' is the third-order Fourier coefficient, the mixed plastic polypropylene blend is a recycled material, the content rate of the low-crystalline polyethylene fraction by cross-fractionation chromatography is 2.8 to 4.2% by weight, and further contains one or more of the following substances: a) polystyrene b) polyamide-6 c) limonene determined by using headspace solid-phase microextraction (HS-SPME-GC-MS) d) fatty acids determined by using headspace solid-phase microextraction (HS-SPME-GC-MS), a mixed plastic polypropylene blend.

2. The mixed plastic polypropylene blend according to Claim 1, having a melt flow rate (ISO 1133, 2.16 kg; 230 °C) of 2.0 to 100 g / 10 min.

3. The soluble part (SF) obtained by the CRYSTEX QC analysis is quantitative in the range of 12.0 to 32.0% by weight １３ The mixed plastic polypropylene blend according to claim 1 or 2, having an ethylene content (C2(SF)) determined by FT-IR spectroscopy calibrated by C-NMR spectroscopy.

4. The blended plastic polypropylene blend according to any one of claims 1 to 3, having an odor of 4 or less (VDA 270-B3).

5. Having a large amplitude oscillatory shear - non-linear factor [LAOS-NLF] (190 ° C, 1000%) exceeding 2.7, 【Number 2】 wherein G １ ' is the first-order Fourier coefficient, G ３ ' is the third-order Fourier coefficient The blended plastic polypropylene blend according to any one of claims 1 to 4.

6. The blended plastic polypropylene blend according to any one of claims 1 to 5, having a tensile modulus (ISO 527-2 at a crosshead speed of 1 mm / min; 23 ° C) using an injection molded specimen (dogbone shape, 4 mm thickness) described in EN ISO 1873-2 of at least 1200 MPa.

7. At least 8.0 kJ / m ２ with a notched Izod impact strength (NIS) (1eA) (uninstrumented, ISO 179-1 at +23 °C) according to ISO 179-1 eA at +23 °C on 80×10×4 mm injection molded test specimens prepared according to EN ISO 1873-2, Furthermore, having a crystalline part (CF) content determined according to CRYSTEX QC analysis in the range of 91.0 to 94.0% by weight and a soluble part (SF) content determined according to CRYSTEX QC analysis in the range of 6.0 to 9.0% by weight, the blended plastic polypropylene blend according to any one of claims 1 to 6.

8. The blended plastic polypropylene blend according to any one of claims 1 to 7 in the form of pellets.

9. The blended plastic polypropylene blend according to any one of claims 1 to 8, which has been bis-broken by a peroxide.

10. A molded article produced from the blended plastic polypropylene blend according to any one of claims 1 to 9.

11. A blend containing the blended plastic polypropylene blend according to any one of claims 1 to 9 and at least one virgin polyolefin.

12. The blend according to claim 11, which is a heterophasic polypropylene.

13. Use of the blended plastic polypropylene blend according to any one of claims 1 to 8 for packaging and / or in the medical field.

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