Mixed plastic polypropylene blend
A mixed plastic polypropylene blend with specific crystalline and soluble fraction contents addresses contamination and color issues in recycled polypropylene, achieving improved surface properties and homogeneity for demanding applications.
Patent Information
- Application Number
- JP2023558390
- Authority / Receiving Office
- JP · JP
- Patent Type
- Patents
- Current Assignee / Owner
- Priority Date
- 2021-08-04
- Filing Date
- 2022-03-25
- Publication Date
- 2025-06-12
- Estimated Expiration
- 2042-03-25
AI Technical Summary
Existing recycled polypropylene blends face challenges such as contamination from residual benzene, color issues, and low homogeneity, which hinder their use in applications like medical packaging and injection molding.
A mixed plastic polypropylene blend with a crystalline fraction content of 86.0 to 94.0% and a soluble fraction content of 6.0 to 14.0%, characterized by specific propylene and ethylene content ranges, and having an intrinsic viscosity of 1.10 to less than 1.50 dl/g, which ensures the absence of excess benzene and improved color consistency.
The blended polypropylene achieves better surface properties, enabling demanding end uses, with improved homogeneity and odor control, making it suitable for injection molding and packaging applications.
Smart Images

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Abstract
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 recycling streams derived from post - consumer waste. Among these means, washing, screening (sorting), aeration, distillation, etc. may be mentioned. For example, International Publication No. WO2018046578 discloses a process for producing polyolefin recyclates from mixed colored polyolefin waste including packaging waste, which includes cold - washing the waste with water, followed by washing with an alkaline medium at 60 ° C, followed by flake color sorting to receive a fraction rich in color - sorted (white, transparent, other colors) monopolyolefins. These fractions are then processed at 50 - 155 ° C. U.S. 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 amounts of benzene has been a problem. The origin of the residual benzene in used recyclates remains ambiguous, but it is an obstacle to end - use in fields such as medical packaging and food packaging. Residual amounts, i.e., trace amounts of benzene, are particularly problematic because they make odor testing by sniffing experiments impossible. Thus, end - uses with certain requirements regarding odor are prevented. Color still remains an unaddressed problem. Many reuse applications require materials that are close to those typically represented as white. As a further problem, known recyclates suffer from low homogeneity, as reflected by surface contamination in injection - molded products. There is a specific demand for recyclates 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 C-NMR spectroscopy in the range of 95.0 to 99.0% by weight, preferably 96.0 to 98.0% by weight, 13 and has (iv) the above crystal part (CF) has an ethylene content (C2(CF)) determined by FT-IR spectroscopy calibrated by quantitative 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, 13 and has (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 combustion analysis (TGA) in accordance with DIN ISO 1172:1996 in an amount of 0.05 to 3.0% by weight, preferably 0.05 to 2.5% by weight, and 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 in excess of the detection limit of HS GC-MS at 80 °C / 2 h, (viii) The mixed 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 of 0.0 to less than 22.0 * in the CIELAB color space (L * a * b * ), and provides a mixed plastic polypropylene blend.
[0006] The present invention also relates to a mixed plastic polypropylene blend in pellet form 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 further aspect, the present invention relates to a blend of the mixed plastic polypropylene blend and at least one virgin polyolefin.
[0007] Mixed plastic is 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. A virgin polypropylene blend represents a blend directly derived from the manufacturing process without intermediate use. As a matter of definition, "mixed plastics" can be considered equivalent to a detectable amount of polystyrene and / or polyamide-6 and / or limonene and / or fatty acids.
[0008] A person skilled in the art will understand that the soluble fraction (SF) obtained by CRYSTEX QC analysis, having an inherent viscosity (iV(SF)) in the range of 1.10 to less than 1.50 dl / g, is typically found in the materials from the recycling stream. In a preferred embodiment of the present invention, the soluble fraction (SF) obtained by CRYSTEX QC analysis has an inherent viscosity (iV(SF)) in the range of 1.25 to less than 1.45 dl / g.
[0009] Surprisingly, it has been found that the mixed 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% are preferred. 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% are.
[0011] In the first embodiment, the mixed 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* ) has.
[0012] In the second embodiment, the mixed plastic polypropylene blend · 72.0 to 97.0, preferably 80.0 to 97.0 of L * , · a of -5.0 to 0.0 * , · b of 0.0 to less than 22.0, usually more than 8.0 to less than 22.0 * in the CIELAB color space (L * a * b * ) has. The CIELAB color may 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 (ISO1133, 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 splitting the used plastic waste stream that is derived from an extended producer responsibility scheme, such as DSD in Germany, or sorted into a number of pre-sorted fractions from municipal solid waste and recombined from them in an appropriate 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 (ISO1133, 2.16 kg; 230 °C). This MFR range particularly applies to non-bis-breaking mixed plastic polypropylene blends. Bis-breaking allows an increase in MFR up to 30 g / 10 min for the second embodiment as well.
[0015] Generally, 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 limit of detectability. 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 the 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 quantitative 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 and has a soluble fraction (SF) obtained by CRYSTEX QC analysis. 13 It has a soluble fraction (SF) obtained by CRYSTEX QC analysis and has an ethylene content (C2(SF)) determined by FT-IR spectroscopy calibrated by C-NMR spectroscopy.
[0021] In a first embodiment, the mixed plastic polypropylene blend according to the present invention preferably has a quantitative 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 and has a soluble fraction (SF) obtained by CRYSTEX QC analysis. 13 It has a soluble fraction (SF) obtained by CRYSTEX QC analysis and has an ethylene content (C2(SF)) determined by FT-IR spectroscopy calibrated by C-NMR spectroscopy.
[0022] In a second embodiment, the mixed plastic polypropylene blend according to the present invention preferably has a quantitative ethylene content (C2(SF)) determined by FT-IR spectroscopy calibrated by C-NMR spectroscopy in the 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, and has a soluble fraction (SF) obtained by CRYSTEX QC analysis. 13 It has a soluble fraction (SF) obtained by CRYSTEX QC analysis and has an ethylene content (C2(SF)) determined by FT-IR spectroscopy calibrated by C-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, has a large amplitude oscillatory shear - non - linear factor (LAOS - NLF) (190 °C; 1000%) greater than 2.7, preferably greater than 3.3,
Number
[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, it is believed that the processing of the polymer contributes 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. It should be understood that some regions operate collection stations that collect highly sorted consumer plastics. Such highly valuable plastic streams are commercially available and enable the upgrading of the quality of other low - quality streams from other waste treatment resources (e.g., those with softer polypropylene mixtures). The second embodiment with a higher amount of crystalline fraction (CF), i.e., a crystalline fraction (CF) content of 91.0 - 94.0 wt% and a soluble fraction (SF) content of 6.0 - 9.0 wt%, is more restrictive, and thereby 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 at a crosshead speed of 1 mm / min; 23°C) using injection molded test specimens (dogbone shape, 4 mm thickness) described in EN ISO1873-2 of at least 1300 MPa, preferably at least 1350 MPa, and most preferably at least 1390 MPa. Such a relatively high flexural modulus is due to a relatively small amount of rubbery material and plastomeric material. Usually, the tensile modulus (ISO527-2 at a crosshead speed of 1 mm / min; 23°C) 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 injection molded test specimens 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 melt flow rate, η (eta) (2.7 kPa), and η (300 rad / s). As a further surprising advantage, 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 from one batch showed essentially the same melt flow rate, η (2.7 kPa), and η (300 rad / s) values when analyzed separately. 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) that is the ratio of η0.05 to η300 greater than 13.0.
[0030] The notched Charpy impact strength (uninstrumented, ISO 179-1 at +23°C) of the mixed plastic polypropylene blend according to the present invention is preferably 4.0 kJ / m 2 or higher, more preferably 4.5 kJ / m 2 or higher. The notched Charpy impact strength (uninstrumented, ISO 179-1 at +23°C) of the mixed plastic polypropylene blend according to the second embodiment is preferably 6.0 kJ / m 2 or higher, more preferably 8.0 kJ / m 2 or higher, and most preferably 8.3 kJ / m 2 or higher.
[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) of at least 8.0 kJ / m 2 , preferably 8.3 kJ / m 2 for an 80×10×4 mm injection molded test specimen prepared according to EN ISO 1873-2 and tested according to ISO 179-1eA at +23°C. Further, with respect to this, the soluble fraction (SF) obtained by CRYSTEX QC analysis has an ethylene content (C2(SF)) determined by FT-IR spectroscopy calibrated by quantitative 13 C-NMR spectroscopy in the range of 12.0 to 20.0 wt%, and even more preferably, the mixed plastic polypropylene blend · 72.0 to 97.0, preferably 80.0 to 97.0 for L * , · -5.0 to 0.0 for a * , · 0.0 to less than 22.0 for b * in the CIELAB color space (L* a * has b).
[0032] In this particularly preferred embodiment of the second embodiment, the crystal part (CF) content determined according to the CRYSTEX QC analysis is preferably in the range of 91.0 to 94.0% by weight, and the soluble part (SF) content determined according to the CRYSTEX QC analysis is preferably in the range of 6.0 to 9.0% by weight.
[0033] The present invention, that is, 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 mixed plastic polypropylene blend according to the present invention is bis-broken by one or more peroxides. The mixed plastic polypropylene blend can be subjected to visbreaking like any other virgin polypropylene blend. When the mixed plastic polypropylene blend according to the present invention is subjected to visbreaking, the decomposition products of the visbreaking process may be found in the resulting blend. It should be understood that the decomposition products of the visbreaking process (as commonly used in the art for virgin materials) are not regarded as 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 mixed 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 comprising the mixed 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 the heterophasic polypropylene can be replaced by the mixed plastic polypropylene blend described herein.
[0037] The present invention also relates to the use of the mixed 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 the mixed plastic polypropylene blend according to the present invention is very stringent. This process involves the following a) providing used plastic waste; b) sorting articles made of polystyrene, polyamide, polyethylene, metal, paper and wood, 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 having mainly white or being colorless, washing it in an aqueous solution containing various detergents, then drying it, subjecting it to wind sifting, and screening; e) subjecting the pretreated used plastic material to further sorting for removing non-polyolefins and colored portions; f) extruding the above materials to obtain the polypropylene blend according to the present invention in the form of pellets; g) optionally, a 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 - 130 °C using an air stream having a temperature of at least 100 °C; including.
[0040] Some possible feedstocks from municipal waste collection systems are commercially available, enabling the provision of used plastic waste. Depending on consumer participation, 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 predominantly colorless / original (colored) plastic articles that are clearly very old ("ancient"). Discoloration (e.g., significant yellowing) and / or significant scratching of predominantly colorless / original plastic articles enables sorting. Such a process can remove so-called high-concern substances. These substances such as Pb, Hg, polybrominated diphenyl ethers, etc. have been prohibited for quite some time but still exist in the real world because consumers tend to store plastic articles, for example in the form of plastic toys, for many years and finally discard them in the collection system. The additional screening step can be assisted by analytical controls for the above high-concern substances.
[0041] Odor control and evaluation are possible 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 by 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 are separated by a temperature cycle of dissolution at 160 °C, crystallization at 40 °C, and re-dissolution in 1,2,4-trichlorobenzene at 160 °C. Quantification of SF and CF and determination of the ethylene content (C2) are achieved by an integrated infrared detector (IR4), and an on-line two-capillary viscometer is used for the determination of the intrinsic viscosity (IV).
[0044] The IR4 detector is a multi-wavelength detector that measures IR absorbance at two different bands (centered around the CH3 stretching vibration (about 2960 cm -1 ), which is useful for determining the concentration and ethylene content in ethylene-propylene copolymers) and the CH stretching vibration (2700 - 3000 cm -1 ). The IR4 detector is calibrated at various concentrations in the range of 2 - 13 mg / ml using a series of eight EP copolymers with known ethylene contents ( 13 measured by 13C-NMR) in the range of 2 wt% - 69 wt%. For the various polymer concentrations expected during Crystex analysis, the following calibration equations were applied to simultaneously encounter both characteristics, concentration and ethylene content.
[0045] Conc = a + b×Abs(CH) + c×(Abs(CH)) 2 + d×Abs(CH 3 ) + e×(Abs(CH 3 )) 2 + f×Abs(CH)×Abs(CH 3 ) (Equation 1) CH 3 / 1000C = a + b×Abs(CH) + c×Abs(CH 3 ) + d×(Abs(CH 3 ) / Abs(CH)) + e×(Abs(CH 3 )) / 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. CH 3 / 1000C is converted to ethylene content (wt%) using the following relationship. wt% (ethylene in EP copolymer) = 100 - CH 3 / 1000TC × 0.3 (Equation 3) The amounts of the soluble fraction (SF) and the crystalline fraction (CF) are correlated, by means of XS calibration, with the amounts of "cold xylene soluble" (XCS) and the cold xylene insoluble fraction (XCI), respectively, and determined according to the standard gravimetric method according to ISO 16152. The XS calibration is achieved by testing various EP copolymers having XS contents in the range of 2 to 31% by weight. The determined XS calibration is linear. % by weight XS = 1.01 × % by weight SF (Equation 4)
[0047] The intrinsic viscosities (IV) of the parent EP copolymer and its soluble and crystalline fractions are determined using an on-line two-capillary viscometer and correlated with the corresponding IVs determined by standard methods in decalin according to ISO 1628-3. The calibration is achieved using various EPPP copolymers with IV = 2 to 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. After automatically filling a vial with 1,2,4-TCB containing 250 mg / l 2,6-tert-butyl-4-methylphenol (BHT) as an antioxidant, the sample is dissolved at 160 °C for usually 60 minutes with constant stirring at 400 rpm until complete dissolution is achieved. To avoid degradation of the sample, during dissolution, the polymer solution is covered with an N2 atmosphere. A defined volume of the sample solution is injected into a column filled with an inert carrier on which crystallization of the sample and separation of the soluble fraction 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 [% by weight] of the PP composition. During the second injection, the soluble fraction (at low temperature) and the crystalline fraction (at high temperature) are measured in the crystallization cycle (% by weight SF, % by weight C2, IV).
[0049] b) Quantification of Fine Structure 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 pressures. Approximately 200 mg of the material was dissolved in approximately 3 ml of 1,2-tetrachloroethane-d2 (TCE-d2) 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 in G. Singh, A. Kothari, V. Gupta, Polymer Testing 2009, 28(5), 475.
[0051] To ensure a homogeneous solution, after the initial sample preparation in the heat block, the NMR tube was further heated in a rotary oven for at least 1 hour. After insertion into the magnet, the tube was rotated at 10 Hz. This setting was chosen mainly because of 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 bi-level 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 entire 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 specimens (dogbone 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 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 for 80 × 10 × 4 mm injection molded specimens prepared according to 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 percent at 850 °C.
[0059] f) MFR: The melt flow rate was measured at 230 °C under a load of 2.16 kg (MFR 2) It was measured under the following conditions. The melt flow rate is the amount of polymer in grams that is 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 and wood (for control 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 80 °C / 2 h described below. Static headspace analysis The parameters of the applied static headspace gas chromatography-mass spectrometry (HS / GC / MS) method are described here.
[0063] A 4.000 ± 0.100 g 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 min To 250°C at 10°C / min 1 min 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 (see the above parameters) and compared with a custom target library based on the mass spectral library (NIST). This custom target library contained the respective mass spectra of the selected substances (e.g., benzene). A substance was considered "tentatively identified" only if the recognized peak showed a minimum match factor of 80 and was confirmed by an experienced mass spectrometry analyst. 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 was not even recognized. The results refer only to the measured sample, the measurement time, and the applied parameters.
[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 / cyan coordinates, +b * indicates yellow, -b * indicates cyan. L * , a * , and b * The coordinate axes of define a 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: Imperceptible, Grade 2: Perceptible but not unpleasant, Grade 3: Clearly perceptible but not unpleasant, Grade 4: Unpleasant, Grade 5: Strongly unpleasant, Grade 6: Unacceptable. The assessors 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) with standard addition. Weigh 50 mg of the pulverized sample in a 20 mL headspace vial, add limonene at different concentrations 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, use amounts of limonene standards of 6.6 mg / kg, 11 mg / kg, and 16.5 mg / kg in combination with some of the samples tested in this application. For quantification, use ion 93 obtained in the SIM mode. Concentration of the volatile fraction is carried out at 60 °C for 20 minutes by headspace solid-phase microextraction using a 2 cm StableFlex 50 / 30 μm DVB / Carboxen / PDMS fiber. 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 minute) Carrier gas: Helium 5.0, 31 cm / second linear velocity, constant flow rate 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 carried out using headspace solid-phase microextraction with standard addition (HS-SPME-GC-MS). Weigh 50 mg of the pulverized sample in a 20 mL headspace vial, add limonene at different concentrations and a glass-coated magnetic stir bar, and then close the vial with a magnetic cap lined with silicone / PTFE. Use a 10 μL microcapillary to add known concentrations of 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 each individual acid at 0 mg / kg, 1 mg / kg, 2 mg / kg, and 10 mg / kg, respectively. For quantification, use ion 60 obtained in SIM mode for all acids except propionic acid, and use ion 74 for propionic acid. GCMS parameters: Column: 20 m ZB Wax plus 0.25×0.25 Injector: Split at 250 °C with a glass-lined split liner at a split ratio of 5:1 Temperature program: 40 °C (1 min), up to 120 °C at 6 °C / min, up to 245 °C at 15 °C (5 min) Carrier: Helium 5.0, linear velocity of 40 cm / s, constant flow rate MS: Single quadrupole type, direct interface, interface temperature of 220 °C Acquisition: SIM scan mode Scan parameters: 46 - 250 amu, 6.6 scans / s SIM parameters: m / z 60, 74, 6.6 scans / s
[0071] n) Presence of polyamide-6 and polystyrene By FTIR spectroscopy, use the absorption of bands at 1601 cm -1 (PS) and 3300 cm -1 (PA6).
[0072] o) Determination of contamination on the small plate The small plates (plaques) are injection-molded with dimensions of 150×80×2 mm. Next, high-resolution images (photos) are taken on five small plates (arranged close to each other). Then, the images are analyzed by software that enables automatic counting of the number of visual defects (visible to 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 follows ISO standards 6721-1 and 6721-10. The measurements were carried out using an Anton Paar MCR501 stress-controlled rotational rheometer equipped with a 25 mm parallel plate configuration. The measurements were performed in a nitrogen atmosphere, setting the strain within the linear viscoelastic region and using a compression-molded plate. The oscillatory shear tests were conducted at 230 °C with a frequency range of 0.01 - 600 rad / s and a gap set at 1.3 mm.
[0074] In a dynamic shear experiment, the probe is subjected to uniform deformation with a sinusoidally varying shear strain or shear stress (in the strain- and stress-controlled modes, respectively). In a controlled strain experiment, the probe is subjected to a sinusoidal strain that can be represented by the following equation. γ(t)=γ 0 sin(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 equation. σ(t)=σ 0 sin(ωt+δ) (2) In the above equations, σ 0 and γ 0 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 the time.
[0075] Dynamic test results typically involve 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* It is represented by the dynamic shear viscosity η’, the out-of-phase component η” of the complex shear viscosity, and the loss tangent tanδ, and the rheological function can be expressed as follows.
[0076]
Equation
[0077] η(x kPa) is determined according to Equation 9. η(x kPa)=(G * =η corresponding to x kPa) * [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 elastic modulus equal to 2.7 kPa. η(x rad / s) is determined according to Equation 10. η(x rad / s)=(η corresponding to ω = x rad / s) * [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 thickening factor (STF) is defined as follows.
Equation
[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 large amplitude oscillatory shear. This method requires the application of a sinusoidal strain amplitude γ0 imposed 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, γ 0 ) = γ 0 .Σ n [G’ n (ω, γ 0).sin(nωt)+G” n (ω,γ 0 ).cos(nωt)] (1) In the above formula, σ is the stress response, t is time, ω is the frequency, γ 0 is the strain amplitude, n is the harmonic number, G’ n is the n-th elastic Fourier coefficient, G” n is the n-th viscous Fourier coefficient.
[0082] The non-linear viscoelastic response was analyzed by applying large amplitude oscillatory shear (LAOS). The time sweep measurement was performed 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 performed by applying a temperature of 190 °C, an angular frequency of 0.628 rad / s and a strain of 1000%. To ensure reaching the steady state condition, 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 [Number] defined by, in the above formula, G 1 ’ is the first-order Fourier coefficient, G 3 ’ is the third-order Fourier coefficient.
[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] 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. After extrusion into pellets, the pellets were subjected to aeration (aeration was carried out only with IE3; aeration conditions: air at 120 °C, preheating substrate).
[0085] 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 clearly very old (“aged”) and recognizable by mainly discoloration of the plastic article (e.g., significant yellowing) and / or significant scratches. Such very old (“aged”) mainly colorless / original plastic articles were sorted out, thereby excluding, in strict accordance with the 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 intermediates were also screened with respect to highly concerned substances. It was found that partial warping was not necessary.
[0086] All examples were subjected to CRYSTEX QC analysis.
[0087]
Table 1(1)
Table 1(2)
Table 1(3)
Table 1(4)
[0088] The prior art can be seen to be 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 virgin compositions and virgin bis-broken compositions. 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. Thus, the tensile modulus was relatively high for 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 at 7.1 kJ / m 2 in 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 IE4). CE4 was significantly less rigid than CE3 and had a Charpy NIS of 7.6 kJ / m 2 . 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 . All of the inventive examples IE1 - 3 had significantly high rigidity and at the same time had only the drawback of a medium Charpy NIS.
[0089] 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.
[0090] CE1: A PP off-white product from Van Werven with a density of 920 kg / m 3 and an MFR (230 °C / 2.16 kg) of 24 g / 10 min.
[0091] CE2: Morssinkhof-Rymoplast had a density of 921 kg / m3 Supply regrind (ground recycled material) and regranulate (pelletized recycled material) of the name MOPRYLENE (registered trademark) having a density of
[0092] 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 uniform distribution.
[0093] CE3 is a random heterophasic copolymer that does not contain a slip additive and an antiblocking additive. It has a random copolymer PP matrix and C3C2 rubber.
[0094] CE3 was produced in a Borstar polypropylene plant having a configuration of a prepolymerization reactor (prepolymerization reactor, prepolymerization reactor), 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 reach the desired polymer design.
[0095] 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.
[0096]
Table 2
[0097] After polymerization, the melt flow rate of the random copolymer CE4 was modified by bisbreaking 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 tris(2,4-di-t-butylphenyl) phosphite, CAS No. 31570-04-4, a 1:2 mixture, commercially available from BASF SE, Germany) and 150 ppm of magnesium oxide (CAS No. 1309-48-4) as an acid scavenger were added during the compounding process.
[0098] 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
[0099] 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 of the reaction mixture (70 rpm) 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).
[0100] Preparation of the 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, after which 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 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 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.
[0101] Alternatively, for the polymerization of random copolymers (Comparative CE3, CE4), a phthalate-free Ziegler Natta catalyst prepared as described as a "reference catalyst" in the Examples section of WO 2020 / 064673 A1 pamphlet was used.
[0102] The catalyst thus obtained was used together with triethylaluminum (TEAL) as a co-catalyst and dicyclopentyldimethoxysilane (D-donor) as a donor. IE4 was further evaluated with respect to Substances of Very High Concern (SVHC). The results are shown in Table 2 below.
[0103]
Table 3
[0104] 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)
[0105] 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.
[0106] 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
[0107] Determination of chromium (VI), in accordance with IEC62321, -> 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.
[0108] Determination of PBB / PBDE (flame retardants) by GC / MS, in accordance with IEC62321-6:2015-6 Note: According to IEC, the tests for PBB / PBDE are only intended for polymers.
[0109] Plasticizers DEHP, DBP; BBP, DIBP and extended list according to REACH (IEC62321-8:2017, GC-MS)
[0110] 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 IEC, the tests for phthalic acid esters are only intended for polymers.
[0111] 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.
[0112] 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 crystal part (CF) content determined according to CRYSTEX QC analysis in the range of 86.0 to 94.0% by weight with respect to the mixed plastic polypropylene blend, and (ii) a soluble part (SF) content determined according to CRYSTEX QC analysis in the range of 6.0 to 14.0% by weight with respect to the mixed plastic polypropylene blend having, (iii) The crystal 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 crystalline 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) is separated by a temperature cycle of dissolution at 160 °C, crystallization at 40 °C and re-dissolution in 1,2,4-trichlorobenzene at 160 °C, and has an intrinsic viscosity (iV(SF)) in the range of 1.10 to 1.50 dl / g correlated with the intrinsic viscosity measured in decalin according to ISO1628-3, (vi) the mixed plastic polypropylene blend has an inorganic residue measured by firing analysis (TGA) according to DIN ISO1172:1996 in the range of 0.05 to 3.0% by weight with respect to the mixed plastic polypropylene blend, (vii) the mixed plastic polypropylene blend does not contain benzene exceeding the detection limit where the matching factor of AMDIS is less than 80 or the peak itself cannot be recognized in HS GC-MS at an oven temperature of 80 °C and a vial equilibration time of 2 h, (viii) the mixed plastic polypropylene blend L of 72.0 to 97.0 * , -5.0 to 0.0 of a * , b that is 0.0 or more and less than 22.0 * in the CIELAB color space (L * a * b * ), having contains a detectable amount of polystyrene and / or polyamide and / or limonene and / or fatty acid mixed plastic polypropylene blend.
2. The mixed plastic polypropylene blend according to claim 1, having a melt flow rate (ISO1133, 2.16 kg; 230 °C) of 2.0 to 100 g / 10 min.
3. The mixed plastic polypropylene blend according to claim 1 or claim 2, which is a recycled material.
4. The following substances, a) polystyrene b) polyamide-6 c) limonene determined by using solid-phase microextraction (HS-SPME-GC-MS) d) fatty acid determined by using solid-phase microextraction (HS-SPME-GC-MS) The mixed plastic polypropylene blend according to any one of claims 1 to 3, containing one or more of them. **Claim 5**: The soluble part (SF) obtained by the CRYSTEX QC analysis of the mixed plastic polypropylene blend is quantitative in the range of 12.0 to 32.0% by weight. 13 The mixed plastic polypropylene blend according to any one of claims 1 to 4, having an ethylene content (C2(SF)) determined by FT-IR spectroscopy calibrated by C-NMR spectroscopy.
6. The blended plastic polypropylene blend according to any one of claims 1 to 5, having an odor of 4 or less (VDA 270-B3).
7. Having a large amplitude oscillatory shear - non-linear factor [LAOS-NLF] (190 °C, 1000%) greater than 2.3, 【Number 1】 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 6.
8. The blended plastic polypropylene blend according to any one of claims 1 to 7, having a tensile modulus (ISO 527-2 at a crosshead speed of 1 mm / min; 23 °C) using an injection molded specimen (dog bone shape, 4 mm thickness) described in EN ISO 1873-2 of at least 1200 MPa.
9. The blended plastic polypropylene blend according to any one of claims 1 to 8, having a notched Charpy impact strength (NIS) (1eA) (+23 °C) according to ISO 179-1 eA for an 80×10×4 mm injection molded specimen prepared according to EN ISO 1873-2 of at least 8.0 kJ / m 2 (non-instrumented, ISO 179-1 at +23 °C).
10. The blended plastic polypropylene blend according to any one of claims 1 to 9 in pellet form.
11. The blended plastic polypropylene blend according to any one of claims 1 to 10, bis-broken by peroxide.
12. A molded article made from the blended plastic polypropylene blend according to any one of claims 1 to 11.
13. A blend containing the blended plastic polypropylene blend according to any one of claims 1 to 11 and at least one virgin polyolefin.
14. The blend according to claim 13, which is a heterophasic polypropylene.
15. Use of the blended plastic polypropylene blend according to any one of claims 1 to 10 for packaging and / or in the medical field.
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