BERGER FRIEDRICH (AT)
WO2021191019A1 | 2021-09-30 | |||
WO2016198273A1 | 2016-12-15 | |||
WO2021009189A1 | 2021-01-21 | |||
WO2021009190A1 | 2021-01-21 | |||
WO2021009191A1 | 2021-01-21 | |||
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EP3406666A1 | 2018-11-28 | |||
EP3757152A1 | 2020-12-30 | |||
EP2994506A1 | 2016-03-16 |
CAS, no. 128-37-0
ZHOU, Z.KUEMMERLE, R.QIU, X.REDWINE, D.CONG, R.TAHA, A.BAUGH, DWINNIFORD, B., J. MAG. RESON., vol. 187, 2007, pages 225
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A. J. BRANDOLINID. D. HILLS: "NMR Spectra of Polymers and Polymer Additives", 2000, MARCEL DEKKER INC.
ORTIN A.MONRABAL B.SANCHO-TELLO J., MACROMOL. SYMP, vol. 257, 2007, pages 13 - 28
J. M. DEALYK. F. WISSBRUN: "Melt Rheology and Its Role in Plastics Processing: Theory and Applications", 1990
S. FILIPE: "Non-Linear Rheology of Polymer Melts", AIP CONFERENCE PROCEEDINGS, vol. 1152, 2009, pages 168 - 174
M. WILHELM, MACROMOL. MAT. ENG., vol. 287, 2002, pages 83 - 105
S. FILIPEK. HOFSTADLERK. KLIMKEA. T. TRAN: "Non-Linear Rheological Parameters for Characterisation of Molecular Structural Properties in Polyolefins", PROCEEDINGS OF ANNUAL EUROPEAN RHEOLOGY CONFERENCE, vol. 135, 2010
S. FILIPEK. KLIMKEA. T. TRANJ. REUSSNER: "Proceedings of Novel Non-Linear Rheological Parameters for Molecular Structural Characterisation of Polyolefins", NOVEL TRENDS IN RHEOLOGY IV, 2011
K. KLIMKES. FILIPEA. T. TRAN: "Non-linear rheological parameters for characterization of molecular structural properties in polyolefins", PROCEEDINGS OF EUROPEAN POLYMER CONFERENCE, GRANADA, SPAIN, 2011
Claims 1. A composition comprising (I) 1.0 to 49.0 wt%, based on the total weight of the composition, of a metallocene catalysed linear low density polyethylene (mLLDPE), which consists of (i) 30.0 to 70.0 wt%, based on the total weight of mLLDPE, of an ethylene-1-butene polymer component (A) and (ii) 70.0 to 30.0 wt%, based on the total weight of mLLDPE, of an ethylene-1-hexene polymer component (B), whereby the ethylene-1-butene polymer component (A) has ^ a density (ISO 1183) in the range of 925 to 960 kg/m3 and a MFR2 (190°C, 2.16 kg, ISO 1133) in the range of 1.0 to 100.0 g/10 min; the ethylene-1-hexene polymer component (B) has ^ a density (ISO 1183) in the range of 880 to 915 kg/m3 and a MFR2 (190°C, 2.16 kg, ISO 1133) in the range of 0.001 to 1.0 g/10 min; and whereby mLLDPE has ^ a density (ISO 1183) in the range of 910 to 925 kg/m3, ^ a MFR2 (190°C, 2.16 kg, ISO 1133) in the range of 0.1 to 2.0 g/10 min and ^ a MFR21 (190°C, 21.6 kg, ISO 1133) in the range of 5.0 to 75.0 g/10 min and ^ a ratio MFR21/MFR2 in the range of 15.0 to 60.0; and (II) 51.0 to 99.0 wt%, based on the total weight of the composition, of a polyethylene recycling blend (PCR) having (i) a MFR5 (ISO1133, 5.0 kg; 190°C) of 0.1 to 10 g/10min, and (ii) a density (ISO1183) of 950 to 970 kg/m³, and (iii) a C2 fraction in an amount of above 95.0 wt%, as measured by NMR of the d2- tetrachloroethylene soluble fraction, and (iv) a homopolymer fraction (HPF) content, based on the PCR, determined according to Chemical Composition Analysis by Cross Fractionation Chromatography (CFC) in the range of 80.0 to 91.0 wt%, and (v) a copolymer fraction (CPF) content, based on the PCR, determined according to Chemical Composition Analysis Cross Fractionation Chromatography (CFC) in the range of 9.0 to 20.0 wt%, and (vi) optionally an iso-PP fraction (IPPF) content, based on the PCR, determined according to Chemical Composition Analysis Cross Fractionation Chromatography (CFC) in the range of 0.0 to 2.0 wt%, whereby said iso-PP fraction (IPPF) is defined as the polymer fraction eluting at a temperature of 104°C and above, whereby said homopolymer fraction (HPF), said copolymer fraction (CPF), and said iso-PP fraction (IPPF) add up to 100 wt%, and (vii) inorganic residues (measured by TGA) of 0.01 to 2.00 wt% with respect to the total polyethylene recycling blend and (viii) OCS gels of size 100 to 299 micrometer measured on 10 m² of a film by an OCS count instrument within the range of 500 to 5000 counts per squaremeter; whereby (ix) the polyethylene blend has a CIELAB color space (L*a*b*) measured according to DIN EN ISO 11664-4 of - L* from 75.0 to 86.0; - a* from -5.0 to 0.0; - b* from 5.0 to below 25.0 or (x) the polyethylene blend has a CIELAB color space (L*a*b*) measured according to DIN EN ISO 11664-4 of - L* from above 86.0 to 97.0; - a* from -5.0 to 0.0; - b* from 0.0 to below 5.0. 2. The composition according to claim 1, wherein in the metallocene catalysed multimodal linear low density polyethylene (mLLDPE) the ethylene-1-butene polymer component (A) consists of an ethylene-1-butene polymer fraction (A-1) and an ethylene-1-butene polymer fraction (A-2), wherein the density (ISO 1183) of fractions (A-1) and (A-2) is in the range of 925 to 960 kg/m3 and the MFR2 (190°C, 2.16 kg, ISO 1133) is in the range of from 0.1 to 150.0 g/10 min and wherein the density of ethylene polymer fractions (A-1) and (A-2) may be the same or may be different and the MFR2 (190°C, 2.16 kg, ISO 1133) of the ethylene polymer fraction (A-2) is equal or preferably higher than the MFR2 of the ethylene polymer fraction (A-1). 3. The composition according to claim 1 or claim 2, wherein in the metallocene catalysed multimodal linear low density polyethylene (mLLDPE) the ethylene polymer component (A) has a MFR2 in the range of 2.0 to 80.0 g/10 min, preferably of 3.0 to 70.0 g/10 min and more preferably of 4.0 to 60.0 g/10 min and/or the ethylene polymer component (B) has a MFR2 in the range of 0.002 to 0.8 g/10 min, preferably of 0.003 to 0.6 g/10 min and even more preferably of 0.004 to 0.4 g/10 min. 4. The composition according to claim 2 or claim 3, wherein in the metallocene catalysed multimodal linear low density polyethylene (mLLDPE) the ratio of the MFR2 of fraction (A- 2) to the MFR2 of the fraction (A-1), MFR2 (A-2)/MFR2 (A-1), is in the range of ≥ 1.0 to 150, preferably 1.5 to 100, more preferably 2.0 to 60. 5. The composition according to any of the preceding claims, wherein the MFR2 of the metallocene catalysed multimodal linear low density polyethylene (mLLDPE) is in the range of from 0.2 to 1.5 g/10 min, preferably from 0.3 to 1.0 g/10 min. 6. The composition according to any of the preceding claims, wherein in the metallocene catalysed multimodal linear low density polyethylene (mLLDPE) the density (ISO 1183) of the ethylene polymer component (A) is in the range of 930 to 955 kg/m3, more preferably 932 to 952 kg/m3, the density (ISO 1183) of the ethylene polymer component (B) is in the range of 890 to 905 kg/m3, and the density (ISO 1183) of the metallocene catalysed multimodal linear low density polyethylene (mLLDPE) is in the range of 912 to 923 kg/m3, preferably of 914 to 922 kg/m3 and more preferably of 915 to 921 kg/m3. 7. The composition according to any of the preceding claims, wherein the polyethylene recycling blend (PCR) has one or both of the following properties: a) limonene content as determined by using solid phase microextraction (HS- SPME-GC-MS) in an amount of 0.1 to 25 ppm, preferably 0.1 to 20 ppm; and b) total amount of fatty acids consisting of the group of acetic acid, butanoic acid, pentanoic acid and hexanoic acid as determined by using solid phase microextraction (HS-SPME-GC-MS) of 10 to 500 ppm, preferably 10 to 300 ppm. 8. The composition according to any of the preceding claims, wherein the polyethylene recycling blend (PCR) has an odor (VDA270-B3) of 2.5 or lower, preferably 2.0 or lower. 9. The composition according to any of the preceding claims, wherein the polyethylene recycling blend (PCR) has one or more of the following OCS gel count properties a) OCS gels of size 300 to 599 micrometer: 100 to 2500 counts per squaremeter; b) OCS gels of size 600 to 1000 micrometer: 10 to 200 counts per squaremeter; c) OCS gels of size above 1000 micrometer: 1 to 40 counts per squaremeter; all measured on 10 m² of film by an OCS count instrument, measured as described in the experimental part. 10. The composition according to any of the preceding claims, wherein the polyethylene recycling blend (PCR) has a tensile modulus (ISO 527-2 at a cross head speed of 1 mm/min; 23°C) using injection molded specimens as described in EN ISO 1873-2 (dog bone shape, 4 mm thickness) of at least 825 MPa, preferably at least 850 MPa, most preferably at least 910 MPa up to 1100 MPa. 11. The composition according to any of the preceding claims, wherein the polyethylene recycling blend (PCR) has a Large Amplitude Oscillatory Shear – Non-Linear Factor (LAOS –NLF) (190°C; 1000%) whereby G1’ is the first order Fourier Coefficient G3’ is the third order Fourier Coefficient in the range of 2.1 to 2.9, preferably 2.2 to 2.7, most preferably 2.3 to 2.6. 12. The composition according to any of the preceding claims, wherein the polyethylene recycling blend (PCR) has a shear thinning factor (STF) Eta∗ for ( ^ = 0.05 rad/s) STF = Eta∗ for ( ^ = 300 rad/s) of above 46.0, preferably from 48.0 to 60.0. 13. A film comprising a composition according to any of the preceding claims 1 to 12. 14. The film according to claim 13, wherein the film is characterized by a dart-drop impact strength (DDI) determined according to ISO 7765-1:1988, method A on a 40 μm monolayer test blown film of at least 80 g up to 500 g, preferably 90 g to 300 g and more preferably 100 g to 150 g, a tensile modulus (measured on a 40 μm monolayer test blown film according to ISO 527-3) in machine (MD) in the range of from >420 MPa to 900 MPa, preferably of 450 MPa to 850 MPa, more preferably 480 to 800 MPa and in transverse (TD) direction in the range of > 520 MPa to 1200 MPa, preferably of 550 MPa to 1150 MPa, more preferably 680 to 1100 MPa. 15. Use of a film according to any of the preceding claims 13 to 14 as packing material, in particular for secondary packaging, which do not require a food approval or even for primary packaging for non-food products. |
Determination methods Unless otherwise stated in the description or in the experimental part, the following methods were used for the property determinations of the polymers (including its fractions and components) and/or any sample preparations thereof as specified in the text or experimental part. Melt Flow Rate The melt flow rate (MFR) was determined according to ISO 1133 and is indicated in g/10 min. The MFR is determined at 190 °C for polyethylene. MFR may be determined at different loadings such as 2.16 kg (MFR2), 5 kg (MFR5) or 21.6 kg (MFR21). Calculation of MFR2 of Component B and of Fraction (A-2) For Component B: B = MFR2 of Component (A) C = MFR2 of Component (B) A = final MFR2 (mixture) of multimodal medium density polyethylene (mMDPE) X = weight fraction of Component (A) For Fraction (A-2): B = MFR2 of 1 st fraction (A-1) C = MFR2 of 2 nd fraction (A-2) A = final MFR2 (mixture) of loop polymer (= Component (A)) X = weight fraction of the 1 st fraction (A-1) Density Density of the polymer was measured according to ISO 1183 and ISO1872-2 for sample preparation and is given in kg/m³. C2 fraction by NMR spectroscopy and general microstructure including “continuous C3” as well as short chain branches Quantitative 13 C{ 1 H} NMR spectra were recorded in the solution-state using a Bruker AVNEO 400MHz NMR spectrometer operating at 400.15 and 100.62 MHz for 1 H and 13 C respectively. All spectra were recorded using a 13 C optimised 10 mm extended temperature probehead at 125°C using nitrogen gas for all pneumatics. Approximately 200 mg of material was dissolved in approximately 3 ml of 1,2-tetrachloroethane-d2 (TCE-d2) along with approximately 3 mg BHT (2,6-di-tert-butyl-4-methylphenol CAS 128-37-0) and chromium-(III)-acetylacetonate (Cr(acac)3) resulting in a 60 mM solution of relaxation agent in solvent {singh09}. To ensure a homogenous solution, after initial sample preparation in a heat block, the NMR tube was further heated in a rotatory oven for at least 1 hour. Upon insertion into the magnet the tube was spun at 10 Hz. Standard single-pulse excitation was employed without NOE, using an optimised tip angle, 1 s recycle delay and a bi-level WALTZ16 decoupling scheme {zhou07,busico07}. A total of 6144 (6k) transients were acquired per spectra. Quantitative 13 C{ 1 H} NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals using proprietary computer programs. 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. Characteristic signals corresponding to polyethylene with different short chain branches (B1, B2, B4, B5, B6plus) and polypropylene were observed {randall89, brandolini00}. Characteristic signals corresponding to the presence of polyethylene containing isolated B1 branches (starB133.3 ppm), isolated B2 branches (starB239.8 ppm), isolated B4 branches (twoB423.4 ppm), isolated B5 branches (threeB532.8 ppm), all branches longer than 4 carbons (starB4plus 38.3 ppm) and the third carbon from a saturated aliphatic chain end (3s 32.2 ppm) were observed. If one or the other structural element is not observable it is excluded from the equations. The intensity of the combined ethylene backbone methine carbons (ddg) containing the polyethylene backbone carbons (dd 30.0 ppm), γ-carbons (g 29.6 ppm) the 4s and the threeB4 carbon (to be compensated for later on) is taken between 30.9 ppm and 29.3 ppm excluding the Tββ from polypropylene. The amount of C2 related carbons was quantified using all mentioned signals according to the following equation: fC C2total = (Iddg –ItwoB4) + (IstarB1*6) + (IstarB2*7) + (ItwoB4*9) + (IthreeB5*10) + ((IstarB4plus-ItwoB4-IthreeB5)*7) + (I3s*3) When characteristic signals corresponding to the presence of polypropylene (PP, continuous C3) were observed at 46.7 ppm, 29.0 ppm and 22.0 ppm the amount of PP related carbons was quantified using the integral of Sαα at 46.6 ppm: fCPP = Isαα * 3 The weight percent of the C2 fraction and the polypropylene can be quantified according following equations: wt C2fraction = fC C2total * 100 / (fC C2total + fC PP ) wtPP = fCPP * 100 / (fCC2total + fCPP) Characteristic signals corresponding to various short chain branches were observed and their weight percentages quantified as the related branch would be an alpha-olefin, starting by quantifying the weight fraction of each: fwtC2 = fCC2total – (IstarB1*3) – (IstarB2*4) – (ItwoB4*6) – (IthreeB5*7) fwtC3 (isolated C3) = IstarB1*3 fwtC4 = IstarB2*4 fwtC6 = ItwoB4*6 fwtC7 = IthreeB5*7 Normalisation of all weight fractions leads to the amount of weight percent for all related branches: fsumwt%total = fwtC2 + fwtC3 + fwtC4 + fwtC6 + fwtC7 + fCPP wtC2total = fwtC2 * 100 / fsum wt%total wtC3total = fwtC3 * 100 / fsumwt%total wtC4total = fwtC4 * 100 / fsumwt%total wtC6total = fwtC6 * 100 / fsum wt%total wtC7total = fwtC7 * 100 / fsumwt%total zhou07 Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh, D. Winniford, B., J. Mag. Reson.187 (2007) 225 busico07 Busico, V., Carbonniere, P., Cipullo, R., Pellecchia, R., Severn, J., Talarico, G., Macromol. Rapid Commun.2007, 28, 1128 singh09 Singh, G., Kothari, A., Gupta, V., Polymer Testing 285 (2009), 475 randall89 J. Randall, Macromol. Sci., Rev. Macromol. Chem. Phys.1989, C29, 201. brandolini00 A. J. Brandolini, D. D. Hills, NMR Spectra of Polymers and Polymer Additives, Marcel Dekker Inc., 2000 Polymer Composition Analysis by CFC - Determination of homopolymer fraction (HPF), copolymer fraction (CPF) and iso-PP fraction (IPPF) The chemical composition distribution as well as the determination of the molecular weight distribution and the corresponded molecular weight averages (Mn, Mw and Mv) at a certain elution temperature (polymer crystallinity in solution) were determined by a full automated Cross Fractionation Chromatography (CFC) as described by Ortin A., Monrabal B., Sancho-Tello J., Macromol. Symp., 2007, 257, 13-28. A CFC instrument (PolymerChar, Valencia, Spain) was used to perform the cross- fractionation chromatography (TREF x SEC). A four-band IR5 infrared detector (PolymerChar, Valencia, Spain) was used to monitor the concentration. The polymer was dissolved at 160°C for 180 minutes at a concentration of around 0.4 mg/ml. To avoid injecting possible gels and polymers, which do not dissolve in TCB at 160°C, like PET and PA, the weighed out sample was packed into stainless steel mesh MW 0,077/D 0,05mmm. Once the sample was completely dissolved an aliquot of 0,5 ml was loaded into the TREF column and stabilized for 60 minutes at 110°C. The polymer was crystallized and precipitated to a temperature of 60°C by applying a constant cooling rate of 0.07 °C/min. A discontinuous elution process is performed using the following temperature steps: (60, 65, 69, 73, 76, 79, 80, 82, 85, 87, 89, 90, 91, 92, 93, 94, 95, 95, 96, 97, 98, 99, 100, 102, 104, 107, 120, 130) In the second dimension, the GPC analysis, 3 PL Olexis columns and 1x Olexis Guard columns from Agilent (Church Stretton, UK) were used as stationary phase. As eluent 1,2,4- trichlorobenzene (TCB, stabilized with 250 mg/L 2,6-Di tert butyl-4-methyl-phenol) at 150 °C and a constant flow rate of 1 mL/min were applied. The column set was calibrated using universal calibration (according to ISO 16014-2:2003) with at least 15 narrow MWD polystyrene (PS) standards in the range of 0,5 kg/mol to 11500 kg/mol. Following Mark Houwink constants were used to convert PS molecular weights into the PE molecular weight equivalents. K PS = 19 x 10-3 mL/g, ^ PS = 0.655 K PE = 39 x 10-3 mL/g, ^ PP = 0.725 A third order polynomial fit was used to fit the calibration data. Data processing was performed using the software provided from PolymerChar with the CFC instrument. Calculation of the homopolymer fraction (HPF) and copolymer fraction (CPF) and iso- PP fraction (IPPF). The homopolymer fraction (HPF), copolymer fraction (CPF) and iso-PP fraction (IPPF) are defined in the following way: 100 % = CPF + HPF + IPPF whereby the IPPF fraction is defined as the polymer fraction eluting at a temperature of 104°C and above. Due to the slight dependence of the TREF profile on the low MW part, the molecular weight limit of the low MW limit is elution temperature (T el ) dependent. The low MW limit was determined using the following formula: Low MW limit (for HPF Fraction) = 0.0125 * T el + 2.875 Taking this into account the HPF fraction is calculated using the following approach. where H ij is the 2D differential distribution at the corresponded elution temperature (Tel) i and the logM value j, obtained with the corresponded data processing software. Inorganic residues were determined by TGA according to DIN ISO 11358-1:2014 using a TGA Discovery TGA5500. Approximately 10-30 mg of material were placed in a platinum pan. The sample was heated under nitrogen at a heating rate of 20 °C/min. The ash content was evaluated as the weight % at 850°C. OCS gels A cast film sample of about 70 μm thickness, was extruded and examined with a CCD (Charged-Coupled Device) camera, image processor and evaluation software (Instrument: OCS-FSA100,supplier OCS GmbH (Optical Control System)). The film defects were measured and classified according to their circular diameter.10m² of film was analyzed and the value per squaremeter was calculated as the average. Cast film preparation, extrusion parameters: 1. Output 25±4g/min 2. Extruder temperature profile: 200-210-210-200 (Melt temperature 224°C) 3. Film thickness about 70 μm 4. Chill Roll temperature 80°C 5. Airknife 6400 NI/h (volume) Technical data for the extruder: 1. Screw type: 3 Zone, nitrated 2. Screw diameter: 25 mm 3. Screw length: 25D 4. Feeding zone: 10D 5. Compression zone: 4D + output zone 11D 6. Die 150mm The defects were classified according to the size (μm)/m 2 : 100-299 μm 300-599 μm 600-999 μm 1000 μm and higher CIELAB color space (L*a*b*) In the CIE L*a*b* uniform color space, measured according to DIN EN ISO 11664-4, the color coordinates are: L*—the lightness coordinate; a*—the red/green coordinate, with +a* indicating red, and -a* indicating green; and b*—the yellow/blue coordinate, with +b* indicating yellow, and -b* indicating blue. The L*, a*, and b*coordinate axis define the three dimensional CIE color space. Standard Konica/Minolta Colorimeter CM-3700A. Evaluation of recycled nature Limonene content Limonene quantification was carried out as described in the experimental part of EP 3757152. Fatty acid detection Fatty acid quantification is carried out using headspace solid phase micro-extraction (HS- SPME-GC-MS) by standard addition. 50 mg ground samples are weighed in 20 mL headspace vial and after the addition of limonene in different concentrations and a glass coated magnetic stir bar the vial is closed with a magnetic cap lined with silicone/PTFE.10 µL Micro-capillaries are used to add diluted free fatty acid mix (acetic acid, propionic acid, butyric acid, pentanoic acid, and hexanoic acid, optionally octanoic acid) standards of known concentrations to the sample at three different levels. Addition of 0, 50, 100 and 500 ng equals 0 mg/kg, 1 mg/kg, 2 mg/kg and 10 mg/kg of each individual acid. For quantification ion 60 acquired in SIM mode is used for all acids except propanoic acid, here ion 74 is used. GCMS Parameter: Column: 20 m ZB Wax plus 0.25*0.25 Injector: Split 5:1 with glass lined split liner, 250°C Temperature program: 40°C (1 min) @6°C/min to 120°C, @15°C to 245 °C (5 min) Carrier: Helium 5.0, 40 cm/s linear velocity, constant flow MS: Single quadrupole, direct interface, 220°C inter face temperature Acquisition: SIM scan mode Scan parameter: 46-250 amu 6.6 scans/s SIM Parameter: m/z 60,74, 6.6 scans/s. Metals determined by X ray fluorescence (XRF). Benzene content by HS GC-MS 80°C/2h, which is described as the following Static headspace analysis The parameters of the applied static headspace gas chromatography mass spectrometry (HS/GC/MS) method are described here. 4.000 ± 0.100 g sample were weighed in a 20 ml HS vial and tightly sealed with a PTFE cap. The mass spectrometer was operated in scan mode and a total ion chromatogram (TIC) was recorded for each analysis. More detailed information on applicable method parameters and data evaluation are given below: - HS parameter (Agilent G1888 Headspace Sampler) Vial equilibration time: 120 min Oven temperature: 80 °C Loop temperature: 205 °C Transfer line temperature: 210 °C Low shaking - GC parameter (Agilent 7890A GC System) Column: ZB-WAX 7HG-G007-22 (30 m x 250 µm x 1 µm) Carrier gas: Helium 5.0 Flow: 2 ml/min Split: 5:1 GC oven program: 35 °C for 0.1 min 10 °C/min until 250 °C 250 °C for 1 min - MS parameter (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 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 Data evaluation The TIC data were further deconvoluted with the aid of AMDIS software (see parameters stated above) and compared to a custom target library which was based on the mass spectral library (NIST). In the custom target library, the respective mass spectra of selected substances (e.g. benzene) were included. Only when the recognised peak showed a minimum match factor of 80 and an experienced mass spectroscopist confirmed the match, a substance was accepted as “tentatively identified”. In this study, the statement “below the limit of detection (< LOD)” referred to a condition where either the match factor was below 80 (AMDIS) or the peak as such was not even recognised. The results refer solely to the measured samples, time of measurement and the applied parameters. Odor VDA270-B3 VDA 270 is a determination of the odor characteristics of trim-materials in motor vehicles. The odor was determined following VDA 270 (2018) variant B3. The odor of the respective sample was evaluated by each assessor according to the VDA 270 scale after lifting the jar’s lid as little as possible. The hexamerous 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: not acceptable. Assessors stay calm during the assessment and are not allowed to bias each other by discussing individual results during the test. They are not allowed to adjust their assessment after testing another sample, either. For statistical reasons (and as accepted by the VDA 270) assessors are forced to use whole steps in their evaluation. Consequently, the odor grade is based on the average mean of all individual assessments, and rounded to whole numbers. Rheological measurements Dynamic Shear Measurements (frequency sweep measurements) The characterisation of melt of polymer composition or polymer as given above or below in the context by dynamic shear measurements complies with ISO standards 6721-1 and 6721-10. The measurements were performed on an Anton Paar MCR501 stress controlled rotational rheometer, equipped with a 25 mm parallel plate geometry. Measurements were undertaken on compression moulded plates, using nitrogen atmosphere and setting a strain within the linear viscoelastic regime. The oscillatory shear tests were done at 190°C applying a frequency range between 0.01 and 600 rad/s and setting a gap of 1.3 mm. Further details are described under paragraph i) of the experimental part of EP 3757152. Shear Thinning Factor (STF) is defined as ^^^ ∗ ^^^ ( ^^^.^^ ^^^/^) STF = ^^^ ∗ ^^^ ( ^^^^^ ^^^/^) The values are determined by means of a single point interpolation procedure, as defined by Rheoplus software. In situations for which a given G* value is not experimentally reached, the value is determined by means of an extrapolation, using the same procedure as before. Also here cases (interpolation or extrapolation), the option from Rheoplus ”- Interpolate y-values to x-values from parameter” and the “logarithmic interpolation type” were applied (see above). LARGE AMPLITUDE OSCILLATORY SHEAR (LAOS) The investigation of the non-linear viscoelastic behavior under shear flow was done resorting to Large Amplitude Oscillatory Shear. The method requires the application of a sinusoidal strain amplitude, ^0, imposed at a given angular frequency, ^, for a given time, t. Provided that the applied sinusoidal strain is high enough, a non-linear response is generated. The stress, ^ is in this case a function of the applied strain amplitude, time and the angular frequency. Under these conditions, the non-linear stress response is still a periodic function; however, it can no longer be expressed by a single harmonic sinusoid. The stress resulting from a non-linear viscoelastic response [0-0] can be expressed by a Fourier series, which includes the higher harmonics contributions: ^ ( ^, ^, ^ ^ ) = ^ ^ . ∑ ^ [^^ ^ ( ^, ^ ^ ) . sin(^^^ ) + ^^^ ^ ( ^, ^ ^ ) . cos(^^^)] (1) with, ^ - stress response t - time ^ ^- frequency ^ ^ - strain amplitude n- harmonic number ^ ^ ^ - n order elastic Fourier coefficient G ^^ ^ - n order viscous Fourier coefficient The non-linear viscoelastic response was analysed applying Large Amplitude Oscillatory Shear (LAOS). Time sweep measurements were undertaken on an RPA 2000 rheometer from Alpha Technologies coupled with a standard biconical die. During the course of the measurement the test chamber is sealed and a pressure of about 6 MPa is applied. The LAOS test is done applying a temperature of 190 °C, an angular frequency of 0.628 rad/s and a strain of 1000 %. In order to ensure that steady state conditions are reached, the non-linear response is only determined after at least 20 cycles per measurement are completed. The Large Amplitude Oscillatory Shear Non-Linear Factor (LAOS_NLF) is defined by: where ^^ ^ - first order Fourier Coefficient ^^ ^- third order Fourier Coefficient [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, Check Republik (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) Dart drop strength (DDI) The DDI was measured according to ISO 7765-1:1988 / Method A from the films (non- oriented films and laminates) as produced indicated below. This test method covers the determination of the energy that causes films to fail under specified conditions of impact of a free-falling dart from a specified height that would result in failure of 50 % of the specimens tested (Staircase method A). A uniform missile mass increment is employed during the test and the missile weight is decreased or increased by the uniform increment after test of each specimen, depending upon the result (failure or no failure) observed for the specimen. Standard conditions: Conditioning time: > 96 h at 50 ±2 °C ±10 %rh Test temperature: 23 °C Dart head material: phenolic Dart diameter: 38 mm Drop height: 660 mm Results: Impact failure weight - 50% [g] Tensile Modulus Tensile modulus (E-Mod (MPa) was measured in machine and/or transverse direction according to ISO 527-3 on film samples prepared as described under the Film Sample preparation with film thickness of 40 μm and at a cross head speed of 1 mm/min for the modulus. Film sample preparation The test films consisting of the inventive composition and respective comparative compositions of 40µm thickness, were prepared using a Collin 30 lab scale mono layer blown film line.The film samples were produced at 194°C, a 1:2.5 blow-up ratio, frostline distance of 120 mm. Experimental part I) mLLDPE Cat.Example: Catalyst preparation for inventive Examples IE1 Loading of SiO2: 10 kg of silica (PQ Corporation ES757, calcined 600°C) was added from a feeding drum and inertized in the reactor until O2 level below 2 ppm was reached. Preparation of MAO/tol/MC: 30 wt% MAO in toluene (14.1 kg) was added into another reactor from a balance followed by toluene (4.0 kg) at 25°C (oil circulation temp) and stirring 95 rpm. Stirring speed was increased 95 rpm -> 200 rpm after toluene addition, stirring time 30 min. Metallocene Rac- dimethylsilanediylbis{2-(5-(trimethylsilyl)furan-2-yl)-4,5-d imethylcyclopentadien-1- yl}zirconium dichloride 477 g was added from a metal cylinder followed by flushing with 4 kg toluene (total toluene amount 8.0 kg). Reactor stirring speed was changed to 95 rpm for MC feeding and returned back to 200 rpm for 3 h reaction time. After reaction time MAO/tol/MC solution was transferred into a feeding vessel. Preparation of catalyst: Reactor temperature was set to 10°C (oil circulation temp) and stirring was turned to 40 rpm during MAO/tol/MC addition. MAO/tol/MC solution (22.2 kg) was added within 205 min followed by 60 min stirring time (oil circulation temp was set to 25°C). After stirring “dry mixture” was stabilised for 12 h at 25°C (oil circulation temp), stirring 0 rpm. Reactor was turned 20° (back and forth) and stirring was turned on 5 rpm for few rounds once an hour. After stabilisation the catalyst was dried at 60°C (oil circulation temp) for 2 h under nitrogen flow 2 kg/h, followed by 13 h under vacuum (same nitrogen flow with stirring 5 rpm). Dried catalyst was sampled and HC content was measured in the glove box with Sartorius Moisture Analyser, (Model MA45) using thermogravimetric method. Target HC level was < 2% (actual 1.3 %). Polymerization: Inventive Examples: multimodal mLLDPE of ethylene with 1-butene and 1-hexene comonomers for IE Borstar pilot plant with a 3-reactor set-up (loop1 – loop2 – GPR 1) and a prepolymerization loop reactor. The multimodal mLLDPE according to the invention (mLLDPE-1) was produced by using the polymerization conditions as given in table 1. Table 1: Polymerization conditions The polymer was mixed with 2400 ppm of Irganox B561 (provided by BASF) and 270 ppm of Dynamar FX 5922 (provided by 3M) compounded and extruded under nitrogen atmosphere to pellets by using a JSW extruder so that the SEI was 230 kWh/kg and the melt temperature 250°C. Table 2: Material properties of the multimodal mLLDPE-1 II) polyethylene recycling blend (PCR) Several post-consumer plastic trash HDPE streams from separate plastic waste collection (civic amenity sites offering specific HDPE collections) were coarsely sorted as to polymer nature and as to color. Impurities were further separated by manual inspection. Two streams were received, i.e. a stream of colorless parts and a stream of white parts. The stream of colorless parts was subjected (separately) to milling, washing in an aqueous solution with various detergents and subsequent drying and screening yielding a pretreated stream. The pretreated stream was further sorted thereby reducing colored parts and non- polyolefins. Upon extrusion into pellets the pellets were subjected to aeration at 120°C air for 22 hours after pre-heating the substrate pellets to at least 100°C. Essentially colorless PCR was obtained. Results of the final materials are shown in Table 3. All examples were subjected to Polymer Composition Analysis by CFC. Table 3: Characteristics of the colorless PCR The multimodal mLLDPE was blended with the polyethylene recycling blend (PCR) and converted into a blown film. For CE1 Enable 3505CH from ExxonMobile has been used: metallocene catalysed medium density ethylene 1-hexene copolymer; density 935 kg/m 3 , MFR20.5 g/10 min For CE2 Lumicene® Supertough 40ST05 from Total has been used: metallocene polyethylene; density 940 kg/m3, MFR20.5 g/10 min. For CE3 a Ziegler-Natta catalysed HDPE and a different recyclate, i.e. NAV101, low density polyethylene (LDPE) post-consumer recyclate blend available from Ecoplast Kunststoffrecycling GmbH, have been used: CAT2 for Comparative Example 3 For Comparative Example 3 a ZN catalyst as disclosed in EP2994506 has been used. Polymerization for Comparative Example 3 Borstar pilot plant with a 2-reactor set-up (loop1– GPR 1) and prepolymerization. ZN-HDPE was produced using the polymerization conditions as given in Table 4. Table 4: Polymerization conditions for ZN-HDPE The polymer was mixed with 0.05wt% Irganox 1010 (BASF), 0.2 wt% Irgafos 168 (BASF) & 0.05 wt% CEASIT FI (Baerlocher) calcium stearate, where wt% are relative to total weight of composition (the sum of HDPE powder + additive = 100%) compounded and extruded on a ZSK 57 twin screw extruder. The melt temperature was 210°C, production rate was 200kg/h. Table 5: Material properties of ZN-HDPE Table 6: Properties of NAV 101 Table 7: blends and film properties From the above table it can be clearly seen, that compared to the state of the art virgin materials like Enable and Supertough, the film of the Inventive Example IE1 consisting of the inventive composition has very similar mechanical properties. If a different blend, e.g. r-LDPE (NAV101) and virgin HDPE like in CE3, is used, worse stiffness and impact of the resulting film is achieved compared to IE1.
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