Mixed plastics - polypropylene blends

Abstract

Mixed plastics-polypropylene blends consisting primarily of benzene-free polypropylene with specified CIELAB colors.

Description

Technical Field

[0001] The present invention relates to mixed plastics - polypropylene blends, typically derived from recycled materials. Background Art

[0002] Many attempts have been made to purify recycled streams derived from post-consumer waste. Among these measures, washing, screening, aeration, distillation, etc. can be mentioned. For example, WO2018046578 discloses a method for producing polyolefin regeneration from mixed-color polyolefin waste (including packaging waste), which comprises cold washing the waste with water, followed by washing with an alkaline medium at 60°C, and then sorting the waste by flake color to receive a single polyolefin-enriched portion after color sorting (white, transparent, other colors). These portions are then treated at 50-155°C. US5767230A describes a method comprising: contacting a polymerase chain reaction (PCR) polyolefin sheet containing volatile impurities with a heated gas at an apparent velocity sufficient to substantially reduce volatile impurities (such as odor-active substances). However, to date, contamination caused by residual amounts of benzene has become a problem. The source of the residual amount of benzene in post-consumer regeneration remains uncertain, but it poses an obstacle to its final use in fields such as medical packaging and food packaging. Residual amounts (i.e. trace amounts) of benzene are particularly problematic because odor testing by sniffing tests becomes impossible. Consequently, end uses that have certain requirements for odor are hindered. Color remains an issue that has not yet been fully resolved. Many reuse applications require materials close to a color that is typically white. As yet another problem, it is known that recyclates are affected by moderate homogeneity, which is reflected by surface contamination that occurs in injection molded products. Specific requirements exist for recyclates suitable for injection molding for use in ingredient caps, cosmetics, nuts, caps, and seals.

[0003] Therefore, the problem of providing more valuable polypropylene blends remains. Summary of the Invention

[0004] The present invention provides a mixed plastic-polypropylene blend having:

[0005] (i) a crystalline fraction (CF) content in the range of 86.0 to 94.0 wt % as determined by CRYSTEX QC analysis, and

[0006] (ii) a soluble fraction (SF) content in the range of 6.0 to 14.0 wt % as determined by CRYSTEX QC analysis, wherein:

[0007] (iii) The crystalline fraction (CF) is quantitatively 13The propylene content (C3(CF)) determined by FT-IR spectroscopy calibrated with C-NMR spectroscopy is in the range of 95.0 to 99.0 wt%, preferably in the range of 96.0 to 98.0 wt%,

[0008] (iv) The crystalline portion (CF) is quantitatively 13 an ethylene content (C2(CF)) determined by FT-IR spectroscopy calibrated with C-NMR spectroscopy in the range of 1.0 to 5.0 wt%, preferably in the range of 2.0 to 4.0 wt%, more preferably in the range of 2.5 to 3.5 wt%; and

[0009] (v) the intrinsic viscosity (iV(SF)) of the soluble fraction (SF) is in the range of 1.10 dl / g to less than 1.50 dl / g, preferably in the range of 1.25 to 1.45 dl / g; and

[0010] in,

[0011] (vi) the mixed plastic-polypropylene blend has an inorganic residue content of 0.05 to 3.0 wt. %, preferably 0.05 to 2.5 wt. %, optionally 1.0 to 2.5 wt. %, relative to the mixed plastic-polypropylene blend, as determined by calcination analysis (TGA) according to DIN ISO 1172:1996; and

[0012] (vii) the mixed plastics-polypropylene blend does not contain benzene above the detection limit of HS GC-MS at 80°C / 2h; and

[0013] (viii) Mixed plastics - Polypropylene blends have a CIELAB color space L*a*b*, where:

[0014] - L* is 72.0 to 97.0, preferably 80.0 to 97.0;

[0015] -a* is -5.0 to 0.0;

[0016] -b* is 0.0 to less than 22.0.

[0017] The present invention also relates to mixed plastic-polypropylene blends in granular form and to mixed plastic-polypropylene blends that have been visbroken by peroxide. The present invention further provides articles made from the mixed plastic-polypropylene blends, as well as uses for packaging and / or in the medical field. In yet another aspect, the present invention relates to blends of the mixed plastic-polypropylene blends with at least one virgin polyolefin.

[0018] Mixed plastics are defined as the presence of low levels 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 are defined as blends derived directly from the production process without intermediates.

[0019] By definition, “mixed plastics” can be equated to detectable amounts of polystyrene and / or polyamide-6 and / or limonene and / or fatty acids.

[0020] It will be appreciated by those skilled in the art that a soluble fraction (SF) obtained by CRYSTEX QC analysis having an intrinsic viscosity (iV(SF)) in the range of 1.10 dl / g to less than 1.50 dl / g is typically found in material from recycle streams. In a preferred aspect of the invention, the soluble fraction (SF) obtained by CRYSTEX QC analysis has an intrinsic viscosity (iV(SF)) in the range of 1.25 dl / g to less than 1.45 dl / g.

[0021] It was surprisingly found that the mixed plastic - polypropylene blend according to the present invention provides better surface properties, enabling many demanding end-use applications.

[0022] In a first embodiment, preferably, the amounts of the crystalline fraction (CF) and the soluble fraction (SF) in the CRYSTEX QC analysis are:

[0023] 87.0 to 90.0 wt% of the crystalline fraction (CF) content, and

[0024] 10.0 to 13.0 wt% soluble fraction (SF) content.

[0025] In a second embodiment, the amounts of crystalline fraction (CF) and soluble fraction (SF) in the CRYSTEX QC analysis are:

[0026] 91.0-94.0 wt% crystalline fraction (CF) content, and

[0027] 6.0 to 9.0 wt% soluble fraction (SF) content.

[0028] In a first embodiment, the mixed plastic - polypropylene blend has a CIELAB color space L*a*b*, where:

[0029] -L* is 85.0 to 97.0;

[0030] -a* is -5.0 to 0.0;

[0031] -b* is 0.0 to less than 8.0.

[0032] In a second embodiment, the mixed plastic - polypropylene blend has a CIELAB color space L*a*b*, where:

[0033] - L* is 72.0 to 97.0, preferably 80.0 to 97.0;

[0034] -a* is -5.0 to 0.0;

[0035] -b* is 0.0 to less than 22.0, typically greater than 8.0 to less than 22.0.

[0036] The CIELAB color can be influenced by the sorting process. The more yellowish the material received, the higher the b*.

[0037] The melt flow rate (ISO 1133, 2.16 kg; 230°C) of the mixed plastic-polypropylene blend according to the present invention is typically 2.0 to 100 g / 10 min. The melt flow rate can be influenced by diversion of post-consumer plastic waste streams, for example, but not limited to, from extended producer responsibility schemes, such as from DSD in Germany, or by sorting municipal solid waste into a number of pre-sorted fractions and recombining them in an appropriate manner. As another way to adjust the melt flow rate of the final mixed plastic-polypropylene blend, peroxide can be introduced during the final pelletizing step. Typically, the MFR ranges from 2.0 to 100 g / 10 min, preferably from 5.0 to 80 g / 10 min, more preferably from 10 to 60 g / 10 min, and most preferably from 12 to 55 g / 10 min.

[0038] 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 is particularly suitable for non-visbroken mixed plastics - polypropylene blends. For the second embodiment, visbreaking also allows the MFR to be increased to 30 g / 10 min.

[0039] Typically, the mixed plastic - polypropylene blend according to the present invention - will be recycled material.

[0040] Typically, regenerative properties can be assessed by the presence of one or more of the following:

[0041] a) Polystyrene

[0042] b) Polyamide-6

[0043] c) Limonene determined by solid phase microextraction (HS-SPME-GC-MS)

[0044] d) Fatty acids determined by using solid phase microextraction (HS-SPME-GC-MS).

[0045] The presence of these substances implies a detectable limit. The detection limit for limonene and fatty acids in solid phase microextraction (HS-SPME-GC-MS) is less than 0.1 ppm, meaning that trace amounts of these substances are readily determined to be reproducible.

[0046] The following amounts are preferred:

[0047] a) polystyrene: 0 to 2.0 wt%, more preferably 0 to 0.5 wt%;

[0048] b) polyamide-6: 0 to 1.5 wt%, more preferably 0 to 0.5 wt%;

[0049] c) limonene as determined by solid phase microextraction (HS-SPME-GC-MS): 0.1 ppm to 50 ppm;

[0050] d) Fatty acids determined by using solid phase microextraction (HS-SPME-GC-MS): 0.1 ppm to 200 ppm, more preferably 50 ppm.

[0051] It goes without saying that the amounts of a), b), c) and d) should be as low as possible. In a particularly preferred embodiment, the mixed plastic-polypropylene blend is polystyrene-free and polyamide-free, which means that both polymers are below the detection limit.

[0052] The mixed plastic-polypropylene blend according to the present invention preferably has a soluble fraction (SF) obtained by CRYSTEX QC analysis, which is obtained by quantitative 13 The ethylene content (C2(SF)) determined by FT-IR spectroscopy calibrated with C-NMR spectroscopy was in the range of 12.0 to 32.0 wt%.

[0053] In a first embodiment, the mixed plastic-polypropylene blend according to the present invention preferably has a soluble fraction (SF) obtained by CRYSTEXQC analysis, which is obtained by quantitative 13 The ethylene content (C2(SF)) determined by FT-IR spectroscopy calibrated with C-NMR spectroscopy was in the range of 25.0 to 32.0 wt%.

[0054] In a second embodiment, the mixed plastic polypropylene blend according to the present invention preferably has a soluble fraction (SF) obtained by CRYSTEXQC analysis, which is obtained by quantitative 13The ethylene content (C2(SF)) determined by FT-IR spectroscopy calibrated with C-NMR spectroscopy is in the range of 10.0 to 25.0 wt%, more preferably in the range of 12.0 to 25.0 wt%, even more preferably in the range of 12.0 to 20.0 wt%, and most preferably in the range of 14.0 to 19.0 wt%.

[0055] Preferably, the mixed plastics according to the invention - polypropylene blends are characterized by an odor (VDA 270-B3) of less than 4.0, preferably less than 3.0. It should be understood that many commercial recycled grades that do not report odor are actually even worse when the odor test under VDA 270 is prohibited due to the presence of problematic substances.

[0056] In another aspect, the mixed plastic-polypropylene blend according to the present invention, in particular the mixed plastic-polypropylene blend of the first embodiment, has a Large Amplitude Oscillatory Shear-Non-Linear Factor (LAOS-NLF) (190° C.; 1000%) greater than 2.7, preferably greater than 3.3, wherein:

[0057]

[0058] in,

[0059] G1′ is the first-order Fourier coefficient;

[0060] G3′ is the third-order Fourier coefficient.

[0061] In the second embodiment, the large amplitude oscillatory shear-nonlinear factor (LAOS-NLF) (190° C.; 1000%) is only greater than 2.3.

[0062] Without wishing to be bound by theory, it is believed that the processing of the polymer contributes to the branching initiated by the enclosed contaminants. LAOS-NLF can be influenced by selecting the raw materials so that approximately 10 wt% of the material is soft polypropylene. It will be appreciated that several regions have collection stations for highly consumable, pre-sorted plastics. This high-value plastic stream is commercially available and allows for the upgrading of otherwise low-quality streams from other waste disposal sources (e.g., by using softer polypropylene blends). A second embodiment having a higher amount of crystalline fraction (CF) (i.e., 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 limited, and thus the large amplitude oscillatory shear-nonlinear factor (LAOS-NLF) (190° C.; 1000%) is slightly lower.

[0063] In yet another aspect, the mixed plastic-polypropylene blend according to the first embodiment of the present invention has a tensile modulus (ISO 527-2, at a crosshead speed of 1 mm / min; 23°C) of at least 1300 MPa, preferably at least 1350 MPa, and most preferably at least 1390 MPa, as determined using injection molded test specimens (dog bone shape, 4 mm thickness) as described in EN ISO 1873-2. This relatively high flexural modulus is due to the relatively low amount of rubber-like and plastomer-like materials. Typically, the tensile modulus (ISO 527-2, at a crosshead speed of 1 mm / min; 23°C) of the first embodiment will not be higher than 1500 MPa.

[0064] The mixed plastic according to the second embodiment of the present invention - the polypropylene blend has a tensile modulus (ISO 527-2, at a crosshead speed of 1 mm / min; 23° C.) of at least 1200 MPa, preferably at least 1250 MPa, as determined using injection molded test specimens (dog bone shape, 4 mm thickness) as described in EN ISO 1873-2. Typically, the tensile modulus (ISO 527-2, at a crosshead speed of 1 mm / min; 23° C.) of the second embodiment will not be higher than 1400 MPa.

[0065] The mixed plastic-polypropylene blend according to the first embodiment of the present invention surprisingly exhibits exceptional temporal stability of the melt flow rates η (2.7 kPa) and η (300 rad / s). Furthermore, another unexpected advantage is the observed exceptionally high melt strength. Furthermore, it was surprisingly discovered that the mixed plastic-polypropylene blend according to the present invention exhibits exceptionally good homogeneity. For example, when analyzed individually, different (selected) pellets from a batch exhibited essentially identical values for the melt flow rates η (2.7 kPa) and η (300 rad / s). This is a unique finding, as substantial variation is expected with recycled materials.

[0066] The mixed plastic according to the second embodiment - the polypropylene blend - proved to have excellent processability, as reflected by a shear thinning factor (STF) greater than 13.0 (which is the ratio of η0.05 to η300).

[0067] The Charpy notched impact strength (non-instrumented, ISO 179-1, at +23°C) of the mixed plastic-polypropylene blend according to the present invention is preferably greater than 4.0 kJ / m 2 , more preferably greater than 4.5 kJ / m 2The Charpy notched impact strength (non-instrumented, ISO 179-1, at +23° C.) of the mixed plastic according to the second embodiment - polypropylene blend is preferably greater than 6.0 kJ / m 2 , more preferably greater than 8.0 kJ / m 2 , most preferably greater than 8.3 kJ / m 2 .

[0068] In a particularly preferred embodiment, the mixed plastic-polypropylene blend according to the invention has a Charpy notched impact strength (NIS) (1eA) (non-instrumented, ISO 179-1, at +23° C.) of at least 8.0 kJ / m², measured according to ISO 179-1eA at +23° C. on injection-molded test specimens of 80×10×4 mm prepared according to EN ISO 1873-2. 2 , preferably at least 8.3 kJ / m 2 , wherein, further, the soluble fraction (SF) obtained by CRYSTEX QC analysis has an ethylene content (C2(SF)) in the range of 12.0-20.0 wt% as determined by FT-IR spectroscopy calibrated by quantitative 13C-NMR spectroscopy, and further preferably, the mixed plastic-polypropylene blend has a CIELAB color space L*a*b, wherein:

[0069] - L* is 72.0-97.0, preferably 80.0-97.0;

[0070] -a* is -5.0-0.0;

[0071] -b* is 0.0 to less than 22.0.

[0072] 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 91.0-94.0 wt% and the soluble fraction (SF) content determined according to CRYSTEX QC analysis is preferably in the range of 6.0-9.0 wt%.

[0073] The mixed plastic-polypropylene blend according to the present invention, ie the mixed plastic-polypropylene blend of the first and second embodiments, is preferably in the form of granules. Granulation contributes to a low content of volatile substances.

[0074] In an embodiment, the mixed plastic-polypropylene blend according to the present invention is visbroken by one or more peroxides. The mixed plastic-polypropylene blend can be visbroken like any other original polypropylene blend. If the mixed plastic-polypropylene blend according to the present invention has been visbroken, decomposition products of the visbreaking process can be found in the resulting blend. It should be understood that decomposition products of the visbreaking process (as commonly used in the art for original materials) are not considered impurities. Visbreaking can be performed as in the first and second embodiments.

[0075] In a further aspect, the present invention relates to a moulded article made from the mixed plastic-polypropylene blend described herein. This applies to both the first and second embodiments.

[0076] In yet another aspect, the present invention relates to a blend comprising the mixed plastic-polypropylene blend described herein and at least one virgin polyolefin. This also applies to the first and second embodiments. For example, the virgin polypropylene homopolymer contained in the heterophasic polypropylene can be replaced by the mixed plastic-polypropylene blend described herein.

[0077] The present invention also relates to the use of the mixed plastic-polypropylene blend according to the invention (ie the first and second embodiments) for packaging and / or in the medical field. DETAILED DESCRIPTION

[0078] The method for providing the mixed plastic-polypropylene blend according to the present invention is very demanding. The method comprises the following steps:

[0079] a) Provide post-consumer plastic waste;

[0080] b) sorting out articles made of polystyrene, polyamide, polyethylene, metal, paper and wood, thereby providing post-consumer plastic materials;

[0081] c) sorting out colored items, thereby providing post-consumer plastic material comprising predominantly white bottles, predominantly white yogurt cups, predominantly white jars, predominantly colorless panels, predominantly colorless component parts, and the like;

[0082] d) grinding, washing with various detergents in aqueous solution and subsequently drying, air sorting and screening the selected predominantly white or colorless post-consumer plastic materials;

[0083] e) further sorting the pre-treated post-consumer plastic material to eliminate non-polyolefins and colored parts;

[0084] f) extruding the material and producing the polypropylene blend according to the invention in the form of pellets;

[0085] g) optional aeration, preferably at a temperature in the range of 100-130°C by preheating the post-consumer plastic material to such a temperature using an air stream having a temperature of at least 100°C.

[0086] Several possible raw materials are commercially available and allow the provision of post-consumer plastic waste from municipal waste collection systems. The purity of these raw materials will vary depending on consumer participation, which is usually indicated by the collection system. The intermediates can be screened after step b) to determine whether there are obviously very old ("ancient"), mainly colorless / natural plastic products. Discoloration (e.g. obvious yellowing) and / or obvious scratches on mainly colorless / natural plastic products allow sorting. Such a step makes it possible to remove the so-called substances of very high concern. These substances (e.g. lead (Pb), mercury (Hg), polybrominated diphenyl ethers, etc.) have been banned for quite some time, but they still exist in the real world because consumers tend to store plastic products (e.g. in the form of plastic toys) for many years before eventually discarding them in the collection system. Additional screening steps can be assisted by analytical controls for the substances of very high concern.

[0087] Odor control and evaluation can be achieved by a variety of methods. An overview is provided below: Demets, Ruben et al., "Development and application of an analytical method to quantify odor removal in plastic waste recycling processes," Resources, Conservation and Recycling 161 (2020): 104907, which is incorporated herein by reference.

[0088] experiment

[0089] The following examples are included to demonstrate certain aspects and embodiments of the present invention as described in the claims. However, it should be understood by those skilled in the art that the following description is exemplary only and should not be construed as limiting the present invention in any way.

[0090] Test Method

[0091] a) CRYSTEX

[0092] Determination of the crystalline and soluble fractions and their respective properties (IV and ethylene content)

[0093] The crystalline fraction (CF) and soluble fraction (SF) of the polypropylene (PP) composition, as well as the comonomer content and intrinsic viscosity of each fraction, were analyzed using a CRYSTEX instrument, Polymer Char (Valencia, Spain). Details of the technique and methods can be found in the literature (Ljiljana Jeremic, Andreas Albrecht, Martina Sandholzer & Markus Gahleitner (2020) Rapid characterization of high-impact ethylene-propylene copolymer composition by crystallization extraction separation: comparability to standard separation methods, International Journal of Polymer Analysis and Characterization, 25: 8, 581-596).

[0094] The crystalline and amorphous fractions were separated by temperature cycling with dissolution at 160° C., crystallization at 40° C., and redissolution in 1,2,4-trichlorobenzene at 160° C. Quantification of SF and CF as well as determination of the ethylene content (C2) were achieved by an integrated infrared detector (IR4), and for determination of the intrinsic viscosity (IV) an online 2-capillary viscometer was used.

[0095] The IR4 detector is based on two different wavelengths (CH3 stretching vibration (centered at about 2960 cm -1 ) and CH stretching vibration (2700-3000cm -1 The IR4 detector is calibrated with a series of eight EP copolymers having known ethylene contents ranging from 2 wt% to 69 wt% (measured by the IR absorbance at these two different wavelengths). 13 C-NMR determination), and each at multiple concentrations within the range of 2 and 13 mg / ml. In order to simultaneously meet the characteristics, concentrations, and ethylene content of the various polymer concentrations expected during Crystex analysis, the following calibration equation was used:

[0096] Concentration = a + b × absorbance (CH) + c × (absorbance (CH)) 2 +d×Absorbance(CH3)+e×(Absorbance(CH3)) 2+f × absorbance (CH) × absorbance (CH3) (Equation 1)

[0097] CH3 / 1000C = a + b × absorbance (CH3) + c × absorbance (CH3) + d × (absorbance (CH3) / absorbance (CH3)) + e × (absorbance (CH3) / absorbance (CH3)) 2 (Equation 2)

[0098] Constants a through e for Equation 1 and constants a through f for Equation 2 were determined by using least squares regression analysis.

[0099] The CH3 / 1000C is converted to ethylene content (in wt%) using the following relationship:

[0100] wt% (ethylene in EP copolymer) = 100 - CH3 / 1000TC x 0.3 (Equation 3)

[0101] The amounts of the soluble fraction (SF) and the crystalline fraction (CF) are related to the amount of "xylene cold solubles" (XCS) and the "xylene cold insolubles" (XCI) fraction, respectively, determined gravimetrically according to ISO 16152, by means of an XS calibration. The XS calibration was performed by testing various EP copolymers with a xylene cold soluble (XCS) content ranging from 2 to 31 wt%. The determined XS calibration is linear:

[0102] XCS (wt%) = 1.01 × SF (wt%) (Equation 4)

[0103] The intrinsic viscosity (IV) of the parent EP copolymer and its soluble and crystalline fractions was determined using an online 2-capillary viscometer and related to the corresponding IV determined by the standard method in decalin according to ISO 1628-3.

[0104] Calibration was achieved using various EP PP copolymers with IV = 2-4 dL / g. The calibration curve was determined to be linear:

[0105] IV(dL / g)=a×Vsp / c (Equation 5)

[0106] The sample to be analyzed was weighed out at a concentration of 10-20 mg / ml. To avoid the injection of possible gels and / or polymers (which are not soluble in TCB at 160°C, such as PET and PA), the weighed sample was enclosed in a stainless steel mesh (MW 0.077 / D 0.05 mm).

[0107] After automatically filling the bottle with 1,2,4-TCB containing 250 mg / l 2,6-tert-butyl-4-methylphenol (BHT) as an antioxidant, the sample was dissolved at 160°C until complete dissolution was achieved, typically for 60 minutes, while stirring continuously at 400 rpm. To avoid sample degradation, the polymer solution was blanketed with N2 atmosphere during the dissolution process.

[0108] A defined volume of sample solution is injected into a column filled with an inert support, where crystallization of the sample and separation of the soluble and crystalline fractions 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 (SF) (at low temperature) and crystalline fraction (CF) (at high temperature) are measured during the crystallization cycle (SF (wt%), C2 (wt%), IV).

[0109] b) Quantification of microstructure by NMR spectroscopy (calibration only)

[0110] Calibration was performed using quantitative nuclear-magnetic resonance (NMR) spectroscopy.

[0111] against 1 H and 13 C, using a Bruker Avance Neo 400 NMR spectrometer, the solution state was recorded at 400.15 MHz and 100.62 MHz, respectively. 13 C{ 1 H}NMR quantitative spectroscopy. 13 All spectra were recorded at 125°C using a 10 mm extended temperature probe optimized for C, using nitrogen for all atmospheres. Approximately 200 mg of material was dissolved in approximately 3 ml of 1,2-tetrachloroethane-d2 (TCE-d2) along with approximately 3 mg of BHT (2,6-di-tert-butyl-4-methylphenol, CAS 128-37-0) and chromium(III) acetylacetonate (Cr(acac)3) to give a 60 mM relaxation agent solution in the solvent (as described in G. Singh, A. Kothari, V. Gupta, Polymer Testing 2009, 28(5), 475).

[0112] To ensure solution homogeneity, after preparing the initial sample in the hot zone, the NMR tube was further heated in a rotary furnace for at least 1 hour. After inserting the magnet, the tube was rotated at 10 Hz. This setting was selected mainly to obtain high resolution and accurate quantitative ethylene content. Standard single pulse excitation without NOE was used, with an optimal tip angle, a recycle delay of 1 s, and a two-stage 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) transients were obtained for each spectrum.

[0113] right 13 C{ 1 H} NMR quantitative spectra were processed, integrated, and the relevant quantitative properties were determined from the integration. 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. Even without this structural unit, the method can be similarly followed.

[0114] Characteristic signals corresponding to ethylene incorporation were 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 all monomers in the polymer:

[0115] fE=(E / (P+E))

[0116] Using the method of WJ. Wang and S. Zhu (Macromolecules 2000, 331157), the 13 C{ 1 The comonomer fraction is quantified by integrating multiple signals across the entire spectral region of the H} spectrum. The integration region is slightly adjusted to improve applicability over the entire range of comonomer contents encountered.

[0117] Calculate the mole percent of comonomer incorporation from the mole fraction:

[0118] E[mol%]=100×fE

[0119] Calculate the weight percent of comonomer incorporation from the mole fraction:

[0120] E[wt%]=100×(fE×28.06) / ((fE×28.06)+((1-fE)×42.08))

[0121] c) Tensile modulus and tensile strain at break

[0122] The tensile modulus and tensile strain at break were determined according to ISO 527-2 (crosshead speed = 1 mm / min; test speed 50 mm / min at 23° C.) using injection molded test specimens as described in EN ISO 1873-2 (dog bone shape, 4 mm thickness). The determination was performed after the specimens had undergone a conditioning period of 96 hours.

[0123] d) Impact strength

[0124] Impact strength was determined as Charpy notched impact strength (1eA) at +23° C. to ISO 179-1eA on 80×10×4 mm injection-molded test specimens prepared to EN ISO 1873-2 (non-instrumented, ISO 179-1 at +23° C.).

[0125] e) Inorganic residues:

[0126] TGA was performed using a Perkin Elmer TGA 8000 according to DIN ISO 1172:1996. Approximately 10-20 mg of material was placed in a platinum pan. The temperature was equilibrated at 50°C for 10 minutes and then increased to 950°C under nitrogen at a heating rate of 20°C / min. Ash content was assessed in wt% at 850°C.

[0127] f) MFR:

[0128] The melt flow rate (MFR2) is measured at 230°C and a load of 2.16 kg. The melt flow rate is the amount of polymer in grams that can be extruded in 10 minutes using a test apparatus standardized to ISO 1133 at a temperature of 230°C and a load of 2.16 kg.

[0129] g) Amount of metal

[0130] The amount of metal was measured by X-ray fluorescence (XRF).

[0131] h) Amount of paper and wood (for comparison purposes only)

[0132] Paper and wood can be assayed by conventional laboratory methods including grinding, flotation, microscopy and thermogravimetric analysis (TGA).

[0133] i) Benzene content

[0134] The results were determined by HS GC-MS at 80°C / 2h, as described below.

[0135] Static headspace analysis

[0136] This article describes the parameters of the static headspace / gas chromatography / mass spectrometry (HS / GC / MS) method employed.

[0137] 4.000±0.100 g of sample was weighed into a 20 ml HS bottle and sealed tightly with a PTFE cap.

[0138] The mass spectrometer was operated in scan mode and a total ion chromatogram (TIC) was recorded for each analysis. Below, more details on the applicable method parameters and data evaluation are given:

[0139] -HS parameters (Agilent G1888 headspace sampler)

[0140] Bottle equilibration time: 120 min

[0141] Furnace temperature: 80℃

[0142] Loop temperature: 205°C

[0143] Transfer line temperature: 210°C

[0144] Low oscillation

[0145] -GC parameters (Agilent 7890A GC system)

[0146] Chromatographic column: ZB-WAX 7HG-G007-22 (30m×250μm×1μm)

[0147] Carrier gas: Helium 5.0

[0148] Flow rate: 2ml / min

[0149] Diversion: 5:1

[0150] GC oven program: 35°C, 0.1 min

[0151] 10℃ / min up to 250℃

[0152] 250℃ for 1 minute

[0153] -MS parameters (Agilent 5975C inert XL MSD)

[0154] Acquisition mode: Scan

[0155] Scan parameters:

[0156] Low quality: 20

[0157] High quality: 200

[0158] Threshold: 10

[0159] -Software / data evaluation

[0160] MSD ChemStation E.02.02.1431

[0161] MassHunter GC / MS Acquisition B.07.05.2479

[0162] AMDIS GC / MS Analysis Version 2.71

[0163] NIST Mass Spectral Library Version 2.0g

[0164] -AMDIS deconvolution parameters

[0165] Minimum matching factor: 80

[0166] Threshold: Low

[0167] Scan direction: high to low

[0168] Data file format: Agilent file

[0169] Instrument Type: Quadrupole

[0170] Width of widget: 20

[0171] Subtract adjacent peaks: two

[0172] Resolution: High

[0173] Sensitivity: Very high

[0174] Shape requirement: Medium

[0175] Solvent tailing: 44m / z

[0176] Column bleed: 207m / z

[0177] Minimum mode peak: 2

[0178] Minimum S / N: 10

[0179] Minimum specific peak: 0.5

[0180] Data evaluation

[0181] Using the AMDIS software (see the above parameters), the TIC data is further deconvoluted and compared with a custom target library based on a mass spectrometry library (NIST). In the custom target library, the mass spectra of the selected substances (such as benzene) are included. A substance is only accepted as "tentatively identified" when the identified peak shows a minimum match factor of 80 and is confirmed by an experienced mass spectrometrist.

[0182] In this study, the expression "less than the detection limit (<LOD (limit of detection))" refers to the case where the match factor is below 80 (AMDIS) or the peak is not even identified as a result. The results only relate to the measured samples, the measurement time, and the applied parameters.

[0183] j) CIELAB color space (L*a*b*)

[0184] In the CIE L*a*b* uniform color space determined according to DIN EN ISO 11664-4, the color coordinates are: L* - the luminance coordinate; a* - the red / green coordinate, where +a* represents red and -a* represents green; b* - the yellow / blue coordinate, where +b* represents yellow and -b* represents blue. The L*, a*, and b* coordinate axes define the three-dimensional CIE color space. Standard Konica / Minolta colorimeter CM-3700A.

[0185] k) Odor VDA270-B3

[0186] VDA 270 is for the determination of the odor characteristics of decorative materials in motor vehicles. In this study, the odor is determined according to VDA 270 (2018) variant B3. Each appraiser evaluates the odor of each sample according to the VDA270 scale after opening the lid of the jar as little as possible. The six-level scale consists of the following grades: Grade 1: Not perceptible, Grade 2: Perceptible, not disturbing, Grade 3: Clearly perceptible, but not disturbing, Grade 4: Disturbing, Grade 5: Strongly disturbing, Grade 6: Unacceptable. The appraisers remain calm during the evaluation and are not allowed to discuss their personal results during the test to bias each other. They are also not allowed to adjust their evaluations after testing another sample. For statistical reasons (and accepted by VDA 270), the appraisers are forced to use full steps in their evaluations. Therefore, the odor grade is based on the average of all personal evaluations and rounded to an integer.

[0187] 1) Limonene detection

[0188] Solid-phase microextraction (HS-SPME-GC-MS) can be used for the quantification of limonene by standard addition.

[0189] 50 mg of ground sample was weighed into a 20 mL headspace vial and, after adding different concentrations of limonene and a glass-coated magnetic stir bar, the vial was sealed with a magnetic cap lined with silicone / PTFE. Using a microcapillary (10 pL), a diluted limonene standard of known concentration was added to the sample. 0, 2, 20, and 100 ng (equal to 0 mg / kg, 0.1 mg / kg, 1 mg / kg, and 5 mg / kg) of limonene were added. In addition, standard amounts of 6.6 mg / kg, 11 mg / kg, and 16.5 mg / kg of limonene were used in combination with some of the samples tested in this application. For quantification, ion-93 collected in SIM mode was used. Enrichment of the volatile portion was performed at 60 ° C by headspace solid phase microextraction with a 2 cm stable flexible 50 / 30 μm DVB / Carboxen / PDMS fiber for 20 minutes. Desorption was performed directly at 270 ° C in the heated injection port of the GCMS system.

[0190] GCMS parameters:

[0191] Chromatographic column: 30m HP 5MS 0.25*0.25

[0192] Syringe: Splitless, with 0.75 mm SPME liner, 270°C

[0193] Temperature program: -10℃ (1 minute)

[0194] Carrier gas: Helium 5.0, 31 cm / s linear velocity, constant flow

[0195] MS: Single quadrupole, direct interface, 280°C interface temperature

[0196] Acquisition: SIM scan mode

[0197] Scan parameters: 20-300amu

[0198] SIM parameters: m / Z 93, 100 ms dwell time

[0199] m) Fatty acid detection

[0200] Fatty acid quantification was performed using headspace solid phase microextraction (HS-SPME-GC-MS) with standard addition.

[0201] The ground sample of 50mg is weighed in 20mL headspace bottle, and after adding different concentrations of limonene and through glass-coated magnetic stirring bar, the bottle is sealed with the magnetic cover that is lined with silicone / PTFE.Use 10 μ tL microcapillary, the diluted free fatty acid mixture (acetic acid, propionic acid, butyric acid, valeric acid, caproic acid and sad) standard substance of known concentration is added to the sample under three kinds of different levels.Add 0,50,100 and 500ng and equal 0mg / kg, 1mg / kg, 2mg / kg and 10mg / kg of every kind of independent acid.For quantitative, ion 60 that gathers under SIM mode is used for all acids except propionic acid (using ion 74 here).

[0202] GCMS parameters:

[0203] Chromatographic column: 20m ZB Wax plus 0.25*0.25

[0204] Syringe: Split 5:1, split liner with glass liner, 250°C

[0205] Temperature program: 40°C (1 minute) @ 6°C / min to 120°C, @ 15°C to 245°C (5 minutes)

[0206] Carrier gas: Helium 5.0, 40 cm / s linear velocity, constant flow

[0207] MS: Single quadrupole, direct interface, 220°C interface temperature

[0208] Acquisition: SIM scan mode

[0209] Scan parameters: 46-250 amu 6.6 scans / second

[0210] SIM parameters: m / z 60, 74, 6.6 scans / second

[0211] n) The presence of polyamide-6 and polystyrene

[0212] Used at 1601cm -1 (PS) and 3300cm -1 (PA6) band absorption by FTIR spectroscopy.

[0213] o) Determination of contamination on the board

[0214] The panels were injection-molded to 150 x 80 x 2 mm. High-resolution images (photographs) were then taken of five panels placed close together. The images were then analyzed using software that automatically counted the number of visible defects (by eye) due to contamination.

[0215] p) Dynamic shear measurement (η(2.7kPa) and η(300rad / s))

[0216] Polymer melts were characterized by dynamic shear measurements in accordance with ISO standards 6721-1 and 6721-10. The measurements were performed on an Anton Paar MCR501 stress-controlled rotational rheometer equipped with 25 mm parallel plate geometry. Measurements were performed on compression molded plates using a nitrogen atmosphere and strain settings within the linear viscoelastic range. Oscillatory shear tests were performed at 230°C, applying a frequency range between 0.01 and 600 rad / s and a gap setting of 1.3 mm.

[0217] In dynamic shear experiments, the probe is subjected to uniform deformation under sinusoidally varying shear strain or shear stress (strain-controlled mode and stress-controlled mode, respectively). In controlled strain experiments, the probe is subjected to a sinusoidal strain that can be expressed by the following equation:

[0218] γ(t)=y0sin(ωt) (1)

[0219] If the applied strain is within the linear viscoelastic range, the resulting sinusoidal stress response can be given by:

[0220] σ(t)=σ0sin(ωt+δ) (2)

[0221] in,

[0222] σ0 and γ0 are stress and strain amplitudes, respectively;

[0223] ω is the angular frequency;

[0224] δ is the phase shift (loss angle between the applied strain and the stress response);

[0225] t is time.

[0226] Dynamic test results are typically expressed with the aid of 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 of the complex shear viscosity η", and the loss tangent tan δ, which can be expressed as follows:

[0227]

[0228]

[0229] G * =G′+iG″[Pa] (5)

[0230] η * =η′-iη″[Pa.s] (6)

[0231]

[0232]

[0233] η(x kPa) is determined according to Equation 9.

[0234] η(x kPa)=for (G * =x kPa) * [Pa.s] (9)

[0235] For example, η(2.7 kPa) is defined by the value of the complex viscosity, which is determined for a complex modulus equal to 2.7 kPa.

[0236] η(x rad / s) is determined according to Equation 10.

[0237] η(x rad / s) = η [Pa.s] for (ω = x rad / s) (10)

[0238] For example, η(300 rad / s) is defined by the value of the complex viscosity determined at a frequency sweep of 300 rad / s.

[0239] q) The shear thinning factor (STF) is defined as

[0240]

[0241] These values were determined using a single-point interpolation procedure defined in the Rheoplus software. In cases where a given G* value was not experimentally achieved, it was determined by extrapolation using the same procedure as before. In both cases (interpolation or extrapolation), the Rheoplus options "Interpolate y-values to x-values from parameter" and "Logarithmic interpolation type" were used.

[0242] References:

[0243] [1]Rheological characterization of polyethylene fractions” Heino, EL, Lehtinen, A., Tanner J., J., Neste Oy, Porvoo, Finland, Theor. Appl. Rheol., Proc. Int. Congr. Rheol, 11th (1992), 1, 360-362.

[0244] [2]The influence of molecular structure on some rheologicalproperties of polyethylene", Heino, EL, Borealis Polymers Oy, Porvoo, Finland, Annual Transactions of the Nordic Rheology Society, 1995.).

[0245] [3]Definition of terms relating to the non-ultimate mechanicalproperties of polymers, Pure&Appl.Chem., Vol.70, No.3, pp.701-754, 1998.

[0246] r) Large Amplitude Oscillatory Shear (LAOS)

[0247] The nonlinear viscoelastic behavior under shear flow is investigated using large-amplitude oscillatory shear. The method requires the application of a sinusoidal strain with an amplitude γ0 at a given angular frequency ω for a given time t. If the applied sinusoidal strain is high enough, a nonlinear response will result. In this case, the stress σ is a function of the applied strain amplitude, time, and angular frequency. Under these conditions, the nonlinear stress response is still a periodic function; however, the nonlinear stress response can no longer be represented by a single harmonic sine. The stress resulting from the nonlinear viscoelastic response [0-0] can be represented by a Fourier series that includes contributions from higher-order harmonics:

[0248] σ(t, ω, γ0) = γ0.∑ n [G′ n (ω,γ0).sin(hωt)+G" n (ω,γ0).cos(nωt)] (1)

[0249] Where σ is the stress response;

[0250] t is time;

[0251] ω is the frequency;

[0252] γ0 is the strain amplitude;

[0253] n is the number of harmonics;

[0254] G′ n is the n-th order elastic Fourier coefficient;

[0255] G n is the n-th order viscosity Fourier coefficient.

[0256] Large amplitude oscillatory shear (LAOS) was applied to analyze the nonlinear viscoelastic response. Time sweep measurements were performed on an AlphaTechnologies RPA 2000 rheometer connected to a standard double-cone die. During the measurement, the test chamber was sealed and a pressure of approximately 6 MPa was applied. LAOS tests were performed at an applied temperature of 190°C, an angular frequency of 0.628 rad / s, and a strain of 1000%. To ensure that steady-state conditions were reached, the nonlinear response was determined only after completing at least 20 cycles of each measurement. The large amplitude oscillatory shear nonlinear factor (LAOS_NLF) is defined by:

[0257]

[0258] Where G′1 is the first-order Fourier coefficient;

[0259] G′3 is the third-order Fourier coefficient.

[0260] References:

[0261] [1] JMDealy, KFWissbrun, Melt Rheology and Its Role in Plastics Processing: Theory and Applications; edited by Van Nostrand Reinhold, New York (1990)

[0262] [2]S.Filipe, Non-Linear Rheology of Polymer Melts, AIP ConferenceProceedings 1152, pp.168-174(2009)

[0263] [3] M. Wilhelm, Macromol. Mat. Eng. 287, 83-105 (2002)

[0264] [4] S.Filipe, K.Hofstadler, K.Klimke, ATTran, Non-Linear RheologicalParameters for Characterization of Molecular Structural Properties inPolyolefins, Proceedings of Annual European Rheology Conference, 135(2010)

[0265] [5] S. Filipe, K. Klimke, ATTran, J. Reussner, Proceedings of Novel Non-Linear Rheological Parameters for Molecular Structural Characterization of Polyolefins, Novel Trends in Rheology IV, Zlin, Check Republik (2011)

[0266] [6] K.Klimke, S.Filipe, ATTran, Non-linear rheological parameters for characterization of molecular structural properties in polyolefins, Proceedings of European Polymer Conference, Granada, Spain (2011)

[0267] Example

[0268] Post-consumer plastic waste is roughly sorted based on polymer properties and color. In a further step, the white and colorless fractions are selected. This selected fraction is ground, washed in aqueous solutions with various detergents, and then dried and screened. The pretreated post-consumer plastic material is further sorted to reduce the colored fraction. After extrusion into pellets, the pellets are aerated (aeration only in the case of IE3; aeration conditions: 120°C air, preheated substrate).

[0269] For Example IE4, the same approach was followed. However, after a rough sorting according to polymer properties and color, the post-consumer plastic waste was screened for obviously very old ("archaic"), predominantly colorless / natural plastic articles, which could be identified by discoloration (e.g., noticeable yellowing) and / or noticeable scratches on the predominantly colorless / natural plastic articles. This very old ("archaic"), predominantly colorless / natural plastic articles were sorted out and strict criteria were followed, i.e., in cases of doubt, questionable articles were sorted out. 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 intermediates were also screened for substances of very high concern. It turned out that some of the warping was unnecessary.

[0270] All examples were subjected to CRYSTEX QC analysis.

[0271]

[0272]

[0273]

[0274]

[0275] As can be seen, the regenerated compositions of the present invention enhance the prior art. Compared to the original and original visbroken compositions, the regenerated compositions of the present invention exhibit only minor deficiencies in impact. Furthermore, the processability, as reflected by the high LAOS-NLF, is indeed very good for IE2 and IE3. For IE3 and IE4, the VOC (VDA) is surprisingly good.

[0276] Comparative Example CE3 is a virgin random heterophasic polypropylene copolymer. Therefore, for the total amount of ethylene (reflected by the amounts of C2(CF) and C2(SF) as well as CF and SF), the tensile modulus is relatively high. However, it is not a recycled product and the processability reflected by LAOS-NLF is 7.1 kJ / m 2 The Charpy NIS is relatively poor.

[0277] Comparative Example CE4 is the original random copolymer that has been visbroken (to adjust the melt flow rate to approximately the same value as IE4). Compared to CE3, CE4 has a significantly lower stiffness and a Charpy NIS of 7.6 kJ / m 2 .

[0278] The stiffness of embodiment IE4 of the present invention is slightly higher than that of CE3, and has a strength of 8.5 kJ / m 2 The best overall Charpy NIS. Inventive Examples IE1 to 3 all have significantly higher stiffness while having only moderate Charpy NIS defects.

[0279] These examples were evaluated for surface defects on injection molded test articles. The best commercial grades available on the market (CE1 and CE2) were compared. The results are shown in Figure 2. Figure 1 shown.

[0280] CE1: is an off-white PP product from Van Werven with a density of 920 kg / m 3 And MFR (230°C / 2.16kg) is 24g / 10min.

[0281] CE2: Morssinkhof-Rymoplast supplies regrind and regranulate under the name Density is 921kg / m 3 , and MFR (230°C / 2.16kg) is 27g / 10min.

[0282] Figure 1 The defect evaluation results are shown. It can be seen that the mixed plastic of the present invention - polypropylene blend - produced the lowest number of defects and that their distribution was uniform.

[0283] CE3 is a random heterophasic copolymer that does not contain slip agents and anti-blocking additives. It has a random copolymer PP matrix and C3C2 rubber.

[0284] CE3 is manufactured in a Borstar polypropylene facility that has a prepolymerization reactor, a slurry loop reactor, a first gas phase reactor, and a second gas phase reactor configuration. The loop reactor and the first gas phase reactor are used to produce the matrix, while the second gas phase reactor is used for the rubber phase.

[0285] The chemical composition of the reactants in each reactor is adjusted to achieve the desired polymer design.

[0286] CE4 is a random copolymer produced in a Borstar polypropylene plant having a prepolymerization reactor, a slurry loop reactor and a gas phase reactor configuration.

[0287]

[0288] After polymerization, the melt flow rate of random copolymer CE4 was modified to achieve a target MFR2 of 8.0 g / 10 min by visbreaking during the compounding step in a twin-screw extruder at 200-230°C and using an appropriate amount of Luperox 101 (2,5-dimethyl-2,5-di(tert-butylperoxy)hexane).

[0289] During the compounding step, the following additives were added as acid scavengers during the compounding step: 1000 ppm Irganox B215 (a 1:2 mixture of pentaerythritol-tetrakis(3-(3',5'-di-tert-butyl-4-hydroxyphenyl)propionate (CAS No. 6683-19-8) and tris(2,4-di-tert-butylphenyl)phosphite (CAS No. 31570-04-4), commercially available from BASF SE, Germany) and 150 ppm magnesium oxide (CAS No. 1309-48-4).

[0290] The catalyst used in the polymerization process for CE3 and CE4 was prepared as follows:

[0291] Chemicals used:

[0292] 20% butylethylmagnesium (Mg(Bu)(Et), BEM) in toluene, supplied by Chemtura

[0293] 2-Ethylhexanol, supplied by Amphochem

[0294] 3-Butoxy-2-propanol-(DOWANOL TM PnB), provided by DOW

[0295] Bis(2-ethylhexyl)citraconate, provided by SynphaBase

[0296] TiCl4, supplied by Millenium Chemicals

[0297] Toluene, provided by Aspokem

[0298] 1-254, provided by Evonik

[0299] Heptane, supplied by Chevron

[0300] Preparation of alkoxymagnesium compounds

[0301] A magnesium 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 20 wt% solution of butylethylmagnesium (Mg(Bu)(Et)) in toluene in a 20 L stainless steel reactor with stirring (70 rpm). The reactor contents were maintained below 45° C. during the addition. After the addition was complete, mixing of the reaction mixture was continued at 60° C. (70 rpm) for 30 minutes. After cooling to room temperature, 2.3 kg of the donor bis(2-ethylhexyl)citraconate was added to the magnesium-alkoxide solution, maintaining the temperature below 25° C. Mixing was continued for 15 minutes with stirring (70 rpm).

[0302] Preparation of solid catalyst components

[0303] 20.3 kg of TiCl4 and 1.1 kg of toluene were added to a 20 L stainless steel reactor. Mixing was performed at 350 rpm and maintained at 0 ° C. 14.5 kg of the prepared alkoxy magnesium compound was added over 1.5 hours. 1.7 L of 1-254 and 7.5 kg of heptane, and after mixing at 0 ° C for 1 hour, the temperature of the emulsion formed was raised to 90 ° C within 1 hour. After 30 minutes, mixing was stopped, the catalyst droplets were allowed to solidify, and the catalyst particles formed were allowed to settle. After settling (1 hour), the supernatant was siphoned off. The catalyst particles were then washed with 45 kg of toluene at 90 ° C for 20 minutes, followed by two heptane washes (30 kg, 15 minutes). During the first heptane wash, the temperature was lowered to 50 ° C and to room temperature during the second wash.

[0304] Alternatively, for the polymerization of random copolymers (Comparative Examples CE3, CE4), a phthalate-free Ziegler Natta catalyst prepared as described in the Examples section of WO 2020 / 064673 A1 was used as a “reference catalyst”.

[0305] The catalyst thus obtained was used with triethylaluminum (TEAL) as a cocatalyst and dicyclopentyldimethoxysilane (D-donor) as a donor. IE4 was further evaluated for substances of very high concern (SVHCs). The results are shown in Table 2 below.

[0306] Table 2: Evaluation of substances of very high concern in IE4:

[0307]

[0308] RoHS - Restriction of Hazardous Substances in Electrical and Electronic Equipment

[0309] RL - Reporting Limit (If the test data ≥ RL, the test data will be displayed. RL is not the regulatory limit)

[0310] Method for SVHC (according to REACH Regulation 1907 / 2006 / EU)

[0311] The entire analysis was performed under SGS.

[0312] In-house methods at SGS were CTS-HL-114-1, CTS-HL-234-5 analyzed by ICP-OES, UV-VIS, GC-MS, HPLC-DAD / MS, and colorimetry.

[0313] Determination of cadmium by ICP-OES according to IEC 62321-5:2013-6

[0314] Determination of lead by ICP-OES according to IEC 6232l-5:2013-6

[0315] Determination of Mercury by CV-AAS according to IEC 62321-4:2013-6

[0316] Determination of chromium by ICP-OES according to IEC 62321-5:2013-6

[0317] According to IEC 62321->Determination of chromium (VI) in non-metallic samples: Determined by ion chromatography according to IEC 62321-7-2:2017-03;

[0318] Note: The concentration of Cr(vI) in the corrosion protection may vary depending on storage time and conditions.

[0319] Determination of PBB / PBDE (flame retardants) by GC / MS according to IEC 62321-6:2015-6

[0320] Note: According to IEC, testing for PBB / PBDE is intended for polymers only.

[0321] Softeners DEHP, DBP; BBP, DIBP and extended list according to REACH (IEC 62321-8:2017, GC-MS)

[0322] Determination of phthalates by GC / MS according to IEC 62321-8:2017-3 after extraction with THF; method not validated

[0323] Note: According to IEC, testing for phthalates is intended for polymers only.

[0324] CE3 is a bimodal virgin random polypropylene evaluated for comparative purposes. It can be seen that the virgin random polypropylene can be replaced by the blend of the present invention which has unexpected impact benefits.

[0325] As another application example, injection-molded barrels were produced using standard process settings. The surface quality was found to be as good as that of comparable virgin material. The thickness distribution and mechanical properties were also excellent.

Claims

1. Mixed Plastics - Polypropylene blends having: (i) a crystalline fraction (CF) content in the range of 86.0 to 94.0 wt% as determined by CRYSTEX QC analysis, and (ii) a soluble fraction (SF) content in the range of 6.0 to 14.0 wt% as determined by CRYSTEX QC analysis, in, (iii) The crystalline fraction (CF) is quantitatively 13 The propylene content (C3(CF)) determined by FT-IR spectroscopy calibrated with C-NMR spectroscopy was in the range of 95.0 to 99.0 wt%, (iv) The crystalline portion (CF) is quantitatively 13 an ethylene content (C2(CF)) in the range of 1.0 to 5.0 wt% as determined by FT-IR spectroscopy calibrated with C-NMR spectroscopy; and (v) the soluble fraction (SF) has an intrinsic viscosity (iV(SF)) in the range of 1.10 dl / g to less than 1.50 dl / g; and (vi) the mixed plastic-polypropylene blend has an inorganic residue content of 0.05 to 3.0 wt. % relative to the mixed plastic-polypropylene blend, as determined by calcination analysis (TGA) according to DIN ISO 1172:1996; and (vii) the mixed plastics-polypropylene blend does not contain benzene above the detection limit of HS GC-MS at 80°C / 2h; and (viii) Mixed plastics - Polypropylene blends have a CIELAB color space L*a*b*, where: -L* is 72.0 to 97.0; -a* is -5.0 to 0.0; - b* is 0.0 to less than 22.0; and Mixed plastics - Polypropylene blends are recycled materials; Mixed plastics - Polypropylene blends Non-instrumented Charpy notched impact strength (NIS) greater than 4.5 kJ / m at +23°C measured according to ISO 179-1eA on 80×10×4 mm injection molded test specimens prepared according to EN ISO 1873-2 2 .

2. The mixed plastic-polypropylene blend according to claim 1, wherein Mixed plastic - The melt flow rate of the polypropylene blend, measured according to ISO 1133 at a temperature of 230° C. and a load of 2.16 kg, is 2.0 to 100 g / 10 min.

3. The mixed plastic-polypropylene blend according to claim 1 or 2, wherein Mixed plastics - Polypropylene blends containing one or more of the following: e) polystyrene; f) polyamide-6; g) limonene by using solid phase microextraction (HS-SPME-GC-MS); h) Fatty acids determined by using solid phase microextraction (HS-SPME-GC-MS).

4. The mixed plastic-polypropylene blend according to claim 1 or 2, wherein The soluble fraction (SF) obtained by CRYSTEX QC analysis was quantitatively 13 The ethylene content (C2(SF)) determined by FT-IR spectroscopy calibrated with C-NMR spectroscopy was in the range of 12.0 to 32.0 wt%.

5. The mixed plastic-polypropylene blend according to claim 1 or 2, wherein The odor of mixed plastics - polypropylene blends (VDA270-B3) is below 4.

6. The mixed plastic-polypropylene blend according to claim 1 or 2, wherein The large amplitude oscillatory shear-nonlinear factor [LAOS-NLF] of the mixed plastic-polypropylene blend measured at a temperature of 190°C and a strain of 1000% is greater than 2.3, wherein in, G1' is the first-order Fourier coefficient; G3' is the third-order Fourier coefficient.

7. The mixed plastic-polypropylene blend according to claim 1 or 2, wherein The mixed plastic - polypropylene blend has a tensile modulus of at least 1200 MPa, measured according to ISO 527-2 at 23°C and a crosshead speed of 1 mm / min using injection moulded test specimens as described in EN ISO 1873-2 with a dog bone shape and a thickness of 4 mm.

8. The mixed plastic-polypropylene blend according to claim 1 or 2, wherein Mixed plastics - polypropylene blends have a non-instrumented Charpy notched impact strength (NIS) of at least 8.0 kJ / m measured at +23°C in accordance with ISO 179-1eA on injection-molded test specimens of 80×10×4 mm prepared in accordance with EN ISO 1873-2 2 , wherein the soluble fraction (SF) obtained by CRYSTEX QC analysis is quantitatively 13 The ethylene content (C2(SF)) determined by FT-IR spectroscopy calibrated with C-NMR spectroscopy was in the range of 12.0 to 20.0 wt%. Further, the crystalline fraction (CF) content determined according to CRYSTEX QC analysis was in the range of 91.0 to 94.0 wt %, and the soluble fraction (SF) content determined according to CRYSTEX QC analysis was in the range of 6.0 to 9.0 wt %.

9. The mixed plastic-polypropylene blend according to claim 1 or 2, wherein Mixed plastics - Polypropylene blends have the CIELAB color space L*a*b, where: -L* is 72.0 to 97.0; -a* is -5.0 to 0.0; and -b* is 0.0 to less than 22.

0.

10. The mixed plastic-polypropylene blend according to claim 1 or 2, wherein: Mixed plastics - Polypropylene blends have the CIELAB color space L*a*b, where: -L* is 80.0 to 97.0; -a* is -5.0 to 0.0; and -b* is 0.0 to less than 22.

0.

11. The mixed plastic-polypropylene blend according to claim 1 or 2, wherein: Mixed plastics - Polypropylene blend in pellet form.

12. The mixed plastic-polypropylene blend according to claim 1 or 2, wherein: Mixed plastics - PP blends visbreaking by peroxide.

13. A molded article made from the mixed plastic-polypropylene blend according to any one of claims 1 to 12.

14. Blend comprising the mixed plastic-polypropylene blend according to any one of claims 1 to 12 and at least one virgin polyolefin.

15. The blend according to claim 14, wherein The blend is a heterophasic polypropylene.

16. Use of the mixed plastic-polypropylene blend according to any one of claims 1 to 11 for packaging and / or in the medical field.

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