Polyolefin composition obtained from recycled polyolefin

Abstract

A recycled polyolefin composition comprising: A) from 42% to 72% by weight of a recycled polypropylene composition; b) from 21% to 41% by weight of a first polypropylene ethylene copolymer C) from 5% to 19% by weight of the amount of a second polypropylene ethylene copolymer (A), the sum of the amount of (B) and the amount of (C) being such that the total weight of (A), (B) and (C) is 100.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to polypropylene compositions comprising recycled elastomeric materials useful for the preparation of extruded articles. BACKGROUND

[0002] Due to the valuable properties typical of polyolefins, such as chemical inertness, mechanical properties and non-toxicity, polyolefin compositions having elastic properties while maintaining a good thermoplastic behaviour have been used in many application fields. Moreover, they can be advantageously transformed into finished products with the same techniques used for thermoplastic polymers. In particular, flexible polymeric materials are widely used in the medical field, as well as for packaging, extrusion coating and wire and cable covering.

[0003] Elastic polypropylene compositions maintaining a good thermoplastic behaviour have been obtained in the art by sequential copolymerization of propylene, optionally containing small amounts of olefin comonomers, followed by ethylene / propylene or ethylene / a-olefin copolymer mixtures. Catalysts based on halogenated titanium compounds supported on magnesium chloride are commonly used for this purpose. For example, EP-A-472 946 describes a flexible elastoplastic polyolefin composition comprising, in parts by weight: A) from 10 to 50 parts of isotactic propylene homopolymer or copolymer; B) from 5 to 20 parts of ethylene copolymer insoluble in xylene at room temperature; and C) from 40 to 80 parts of ethylene / propylene copolymer containing less than 40% by weight of ethylene and soluble in xylene at room temperature; the intrinsic viscosity of said copolymer being preferably from 1.7 to 3 dl / g. The composition is relatively flexible and has good elastic properties.

[0004] Moreover, polyolefin compositions, despite being appreciated in terms of performances, raise concerns in terms of sustainability, in particular as regards the fact that their production is based on the use of non-renewable resources.

[0005] Therefore, a common attempt to mitigate this problem is to replace virgin polyolefin compositions at least partially with variable amounts of recycled plastic materials.

[0006] Recycled plastic polyolefins originate from streams of post-consumer waste (PCW) or post-industrial waste (PIW).

[0007] One of the key problems in polyolefin recycling is the difficulty in quantitatively separating the various types of polymers, so that commercially available recycled products are almost always contaminated with heterogeneous materials of various origins.

[0008] This fact leads to the result that polymeric compositions comprising recycled materials are considered to be affected by lower reliability and lower performances with respect to compositions made only of virgin polymers.

[0009] It has now been surprisingly found that when recycled polymer is added to virgin polypropylene, it is possible to have an improved property profile, in particular with regard to elongation at break. Summary of the Invention

[0010] Therefore, the object of the present disclosure is a recycled polyolefin composition comprising:

[0011] A) 42 to 72 wt%; preferably 46 to 67 wt%; more preferably 49 to 65 wt% of a recycled polypropylene composition;

[0012] B) 21 to 41 wt%; preferably 23 to 39 wt%; more preferably 26 to 36 wt% of a first polypropylene ethylene copolymer comprising:

[0013] - (b1) 70 to 95 wt%; preferably 75 to 93 wt%; more preferably 80 to 91 wt% of a propylene homopolymer having:

[0014] - less than 6.0% by weight; preferably less than 3.0% by weight; more preferably less than 2.8% by weight; even more preferably less than 2.5% by weight; preferably more than 0.5% by weight of the fraction soluble in xylene at 25° C., and

[0015] - a melt flow rate (ISO 1133, 230°C / 5.0 kg) in the range of 0.3 to 3.5 g / 10 min; preferably in the range of 0.5 to 3.1 g / 10 min; more preferably in the range of 0.7 to 2.8 g / 10 min;

[0016] - (b2) 5 to 30 wt%; preferably 7 to 25 wt%; more preferably 9 to 20 wt% of a propylene and ethylene copolymer having:

[0017] -according to 13 ethylene-derived units in an amount ranging from 35.0% to 65.0% by weight as measured by C-NMR; preferably from 38.0% to 62.0% by weight; more preferably from 42.0% to 58.3% by weight;

[0018] The copolymer (B) further has the following characteristics:

[0019] - a melt flow rate (ISO 1133, 230°C / 5.0 kg) in the range of 0.3 to 2.3 g / 10 min; preferably 0.4 to 2.0 g / 10 min; more preferably in the range of 0.5 to 1.6 g / 10 min;

[0020] - a fraction soluble in xylene at 25°C in an amount ranging from 7.0 wt% to 27.0 wt%; preferably from 9.0 wt% to 25.0 wt%; more preferably from 11.0 wt% to 23.0 wt%;

[0021] - an intrinsic viscosity, measured in tetrahydronaphthalene at 135°C, ranging from 2.4 dl / g to 5.0 dl / g; preferably from 2.7 dl / g to 4.6 dl / g; more preferably ranging from 3.0 dl / g to 4.2 dl / g, for the fraction soluble in xylene at 25°C;

[0022] In said copolymer, the sum of b1) and b2) refers to the total weight of b1) and b2), which is 100,

[0023] C) from 5 wt% to 19 wt%; preferably from 6 wt% to 17 wt%; more preferably from 7 wt% to 15 wt% of a second polypropylene ethylene copolymer comprising:

[0024] - (c1) from 21 wt% to 43 wt%; preferably from 23 wt% to 41 wt%; more preferably from 27 wt% to 37 wt% of a propylene ethylene copolymer having:

[0025] - units derived from ethylene in an amount ranging from 1.7 wt% to 4.5 wt%; preferably from 2.0 wt% to 4.3 wt%; more preferably ranging from 2.6 wt% to 3.7 wt%, measured according to 13C-NMR;

[0026] - a fraction soluble in xylene at 25°C lower than 8.0 wt%; preferably lower than 7.5 wt%; more preferably lower than 7.0 wt%; even more preferably lower than 6.5 wt%; preferably higher than 0.5 wt%, and

[0027] - a melt flow rate (ISO 1133, 230°C / 5.0 kg) ranging from 18.0 to 34.0 g / 10 min; preferably ranging from 20.0 to 32.5 g / 10 min; more preferably ranging from 22.0 to 30.1 g / 10 min;

[0028] - (c2) from 57 wt% to 79 wt%; preferably from 59 wt% to 77 wt%; more preferably from 63 wt% to 73 wt% of a propylene and ethylene copolymer having:

[0029] - units derived from ethylene in an amount ranging from 1.7 wt% to 4.5 wt%; preferably from 2.0 wt% to 4.3 wt%; more preferably ranging from 2.6 wt% to 3.7 wt%, measured according to 13C-NMR; 13C-NMR measured in an amount ranging from 18.0 wt% to 36.0 wt%; preferably from 20.2 wt% to 34.4 wt%; more preferably ranging from 22.8 wt% to 32.3 wt% of units derived from ethylene;

[0030] Said copolymer (c) further has the following characteristics:

[0031] - a melt flow rate (ISO 1133, 230°C / 5.0 kg) ranging from 0.2 to 1.7 g / 10 min; preferably from 0.3 to 1.4 g / 10 min; more preferably ranging from 0.4 to 1.2 g / 10 min;

[0032] - a fraction soluble in xylene at 25°C in an amount ranging from 52.0 wt% to 76.0 wt%; preferably from 54.0 wt% to 74.0 wt%; more preferably from 56.0 wt% to 72.0 wt%;

[0033] - a fraction soluble in xylene at 25°C having an intrinsic viscosity measured in tetraline at 135°C ranging from 2.1 dl / g to 4.7 dl / g; preferably from 2.4 dl / g to 4.3 dl / g; more preferably ranging from 2.7 dl / g to 3.9 dl / g; and,

[0034] In said copolymer, the sum of c1) and c2) refers to the total weight of c1) and c2), which is 100,

[0035] The sum of the amount of (A), the amount of (B) and the amount of (C) refers to the total weight of (A), (B) and (C), which is 100;

[0036] The recycled polypropylene composition (A) has:

[0037] with 13 C-NMR measured in an amount ranging from 2.50 wt% to 7.30 wt% of ethylene derived units;

[0038] with 13 C-NMR measured in an amount ranging from 0.05 wt% to 0.30 wt% of butene derived units;

[0039] with 13 C-NMR measured in an amount ranging from 0.03 wt% to 0.23 wt% of hexene derived units;

[0040] with 13 C-NMR measured in an amount ranging from 0.02 wt% to 0.50 wt% of octene derived units;

[0041] with 13C-NMR measured polyethylene terephthalate content in the range of 0.05 wt% to 0.80 wt%

[0042] use 13 A propylene-derived unit content of greater than 87.4 wt.% as measured by C-NMR

[0043] Range: 0.9400Kg / dm3 to 0.9500Kg / dm 3 ; preferably in the range of 0.9423Kg / dm 3 to 0.9484Kg / dm 3 ; More preferably, the range is 0.9448Kg / dm 3 to 0.9476Kg / dm 3 Density, ISO 1183-1;

[0044] Melt flow rate (ISO 1133, 230°C / 2.16 kg) ranging from 1.2 to 20.3 g / 10 min; preferably ranging from 3.4 to 17.4 g / 10 min; more preferably ranging from 5.2 to 12.3 g / 10 min. DETAILED DESCRIPTION

[0045] Preferably, the recycled polypropylene composition (A) has:

[0046] The range of measurement according to ISO 527-2 is 1060N / mm 2 Up to 1900N / mm 2 ; Preferably in the range of 1260N / mm 2 Up to 1780N / mm 2 More preferably, the range is 1350N / mm 2 Up to 1760N / mm 2 tensile modulus.

[0047] Preferably, the recycled polypropylene composition (A) has:

[0048] The range determined according to ISO 179-1eA and ISO 1873-2 is 2.2 kJ / m 2 Up to 9.0KJ / m 2 ; preferably in the range of 3.1KJ / m 2 Up to 8.2KJ / m 2 ; More preferably, the range is 3.4KJ / m 2 Up to 7.3KJ / m 2 Charpy impact test at 23°C.

[0049] As used herein, the term "copolymer" refers to a polymer having two different repeating units.

[0050] The term "recycled" is used to denote a polymer material derived from at least one cycle of processing into an article, as opposed to virgin polymer which is a polymer that has not undergone at least one cycle of processing into an article.

[0051] The term "consisting essentially of as used herein in connection with a polymer or a polymer composition means that other components can be present in the polymer or polymer composition in addition to those components which are mandatory, provided that the basic characteristics of the polymer or composition are not materially affected by their presence. According to the present disclosure, examples of components which do not materially affect the characteristics of the polymer or polymer composition when present in conventional amounts in the polymer or polymer composition are catalyst residues, antistatic agents, melt stabilizers, light stabilizers, antioxidants, antacids.

[0052] The features of the components forming the polypropylene composition are not overly linked to each other. This means that a certain preferred level of one feature does not necessarily involve the same preferred level of the remaining features of the same or different components. On the contrary, it is intended in the present disclosure that any preferred range of the features of components (A), (B) and (C) and of components (A), (B) and (C) can be combined with any preferred range of one or more of the features of the features of components (A) to (B) and with any possible additional components described in the present disclosure and their features.

[0053] Components B) and C) can be prepared by polymerizing propylene, optionally in a mixture with ethylene, in the presence of a catalyst comprising the product of a reaction between:

[0054] i) a solid catalyst component comprising Ti, Mg, CI and at least one internal electron donor compound;

[0055] ii) an aluminum alkyl compound, and

[0056] iii) an external electron donor compound; preferably, the external donor compound has the following general formula:

[0057] (R 7 ) a (R 8 ) b Si(OR 9 ) c wherein a and b are integers from 0 to 2, c is an integer from 1 to 4 and the sum (a+b+c) is 4; R 7 , R 8 and R 9 are alkyl, cycloalkyl or aryl radicals having from 1 to 18 carbon atoms, optionally containing heteroatoms.

[0058] The internal donor is preferably selected from esters of mono- or di-carboxylic organic acids, such as benzoic acid esters, malonic acid esters, phthalic acid esters and certain succinic acid esters. Examples of internal donors are described in US 4522930 A, EP 045977 A2 and international patent applications WO 00 / 63261 and WO 01 / 57099. Particularly suitable are phthalic acid esters and succinic acid esters. Alkyl phthalates are preferred, such as diisobutyl phthalate, dioctyl phthalate and diphenyl phthalate and benzyl butyl phthalate.

[0059] The particles of the solid component (i) can have a substantially spherical morphology and an average diameter of between 5 pm and 150 pm, preferably 20 pm to 100 pm and more preferably 30 pm to 90 pm. By particles having a substantially spherical morphology, it is meant that the ratio between the larger and smaller axis is equal to or below 1.5, and preferably below 1.3.

[0060] The amount of Mg can range preferably from 8% to 30%, more preferably from 10% to 25% by weight.

[0061] The amount of Ti can range from 0.5% to 7% and more preferably from 0.7% to 5% by weight.

[0062] According to one method, the compound of formula Ti(OR) q-y X yThe solid catalyst component (i) is prepared by reacting a titanium compound, wherein q is the valence of titanium and y is a number between 1 and q, preferably TiCl4, with a magnesium chloride derived from an adduct of the formula MgCl2-pROH, wherein p is a number between 0.1 and 6, preferably 2 to 3.5, R is a hydrocarbon radical having from 1 to 18 carbon atoms. The adduct can be suitably prepared in spherical form by mixing the alcohol and the magnesium chloride under stirring at the melting temperature of the adduct (100°C to 130°C). Then, the adduct is mixed with an inert hydrocarbon immiscible with the adduct, thus creating an emulsion which is quickly quenched so that the adduct solidifies in the form of spherical particles. Examples of spherical adducts prepared according to this procedure are described in USP 4,399,054 and USP 4,469,648. The adduct thus obtained can be directly reacted with the Ti compound or it can be previously subjected to a thermal controlled dealcoholation (80°C to 130°C) so as to obtain an adduct wherein the number of moles of alcohol is lower than 3, preferably between 0.1 and 2.5. The reaction with the Ti compound can be carried out by suspending the adduct (dealcoholated or as such) in cold TiCl4; the mixture is heated up to 80°C to 130°C and kept at this temperature for 0.5 hours to 2 hours. The treatment with TiCl4can be carried out one or more times. The electron donor compound can be added in the required proportions during the treatment with TiCl4.

[0063] The alkyl-Al compound (ii) is preferably selected from trialkylaluminum compounds such as, for example, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum. Alkylaluminum halides, alkylaluminum hydrides or alkylaluminum sesquichlorides such as AlEt2Cl and Al2Et3Cl3may also be used, possibly in the form of mixtures with the above-mentioned trialkylaluminums. The Al / Ti ratio is higher than 1 and can range preferably between 50 and 2000.

[0064] Especially preferred are silicon compounds (iii) wherein a is 1, b is 1, c is 2, at least one of R7and R8is selected from branched alkyl, cycloalkyl or aryl groups having 3 to 10 carbon atoms, optionally containing heteroatoms, and R9is a C1-C10 alkyl group, in particular methyl. Examples of such preferred silicon compounds are methylcyclohexyldimethoxysilane (C-donor), diphenyldimethoxysilane, methyl-tert-butyldimethoxysilane, dicyclopentyldimethoxysilane (D-donor), diisopropyldimethoxysilane, (2-ethylpiperidinyl)tert-butyldimethoxysilane, (2-ethylpiperidinyl)tert-hexyldimethoxysilane, (3,3,3-trifluoro-n-propyl)(2-ethylpiperidinyl)dimethoxysilane, methyl(3,3,3-trifluoro-n-propyl)dimethoxysilane. Further preferred are also silicon compounds wherein a is 0, c is 3, R8is branched alkyl or cycloalkyl, optionally containing heteroatoms, and R9is methyl. Examples of such preferred silicon compounds are cyclohexyltrimethoxysilane, tert-butytrimethoxysilane and tert-hexyltrimethoxysilane.

[0065] The amount of external electron donor compound (iii) is such that the molar ratio between the organoaluminum compound and said external electron donor compound (iii) is comprised between 0.1 and 200, preferably between 1 and 100, and more preferably between 3 and 50.

[0066] Components B) and C) can be prepared in a continuous sequence polymerization process, wherein component b1 ) or c1 ) is prepared in a first reactor and component (b2) or c2) is prepared in a second reactor in the presence of component b1 ) or c1 ), according to known techniques and in gas phase, or in liquid phase in the presence or absence of an inert diluent, or by mixed liquid-gas technology operation.

[0067] Component B) is preferably a commercial polymer grade, such as Hostale H2464 sold by Lyondellbasell.

[0068] Component C) is preferably a commercial polymer grade, such as Adflex Q100F sold by Lyondellbasell.

[0069] Component (A)n can be a post-industrial resin (PIR) or a post-consumer resin (PCR).

[0070] A post-industrial resin (PIR) is a waste generated by a manufacturing process, which is recycled or reused in the same material.

[0071] A post-consumer resin (PCR) is defined as a recyclate derived from a final product that has completed its life cycle as a consumer item and would have otherwise been disposed of as waste.

[0072] If desired, the final composition comprising (A) + (B) can be chemically treated with organic peroxides in order to reduce the average molecular weight and increase the melt flow index up to the values required for the specific application.

[0073] Preferably, the tensile modulus of the whole propylene polymer composition ranges from 740 MPa to 1640 MPa, more preferably from 840 MPa to 1440 MPa; even more preferably from 950 MPa to 1390 MPa.

[0074] The Charpy impact value at 23 °C ranges preferably from 9.3 KJ / m 2 to 22.5 KJ / m 2 ; more preferably it ranges from 10.5 KJ / m 2 to 20.1 KJ / m 2 ; even more preferably it ranges from 11.5 KJ / m 2 to 18.6 KJ / m 2 .

[0075] The whole propylene composition of the present disclosure can be obtained by mechanically blending components (A), (B) and C) according to conventional techniques.

[0076] The final composition comprising components (A), (B) and C) can be added with conventional additives, fillers and pigments commonly used in olefin polymers, such as nucleating agents, extender oils, mineral fillers and other organic and inorganic pigments. In particular, the addition of inorganic fillers, such as talc, calcium carbonate and mineral fillers, also brings an improvement in some mechanical properties, such as flexural modulus and HDT. Talc can also have a nucleating effect.

[0077] For example, the nucleating agent can be added to the composition of the present disclosure in an amount ranging from 0.05 wt% to 2 wt%, more preferably from 0.1 wt% to 1 wt%, with respect to the total weight.

[0078] The propylene polymer composition of the present disclosure can be used for the production of extruded articles.

[0079] The following examples are given by way of illustration and not by way of limitation of the present disclosure.

[0080] Examples

[0081] Characterization

[0082] Xylene soluble (XS) fraction at 25 °C

[0083] Into a glass flask equipped with a refrigerated and magnetic stirrer, 2.5 g of polymer and 250 ml of xylene were introduced. The temperature was raised to the boiling point of the solvent in 30 minutes. The resulting clear solution was then kept under reflux and stirred for 30 minutes. The closed flask was then kept in an ice-water bath for 30 minutes and then in a thermostated water bath at 25°C for 30 minutes. The resulting solid was filtered on a fast filter paper. 100 ml of filtrate were poured into a pre-weighed aluminum container which was heated on a heating plate under a nitrogen stream to remove the solvent by evaporation. The container was then kept in an oven at 80°C under vacuum until a constant weight was reached. The weight percentage of polymer soluble in xylene at room temperature was then calculated.

[0084] The content of the xylene soluble fraction was expressed as a percentage of the original 2.5 grams, and the xylene insoluble percentage (%) was then expressed by difference (complementary to 100%).

[0085] Melt flow rate (MFR)

[0086] Measured according to ISO 1133-1 at 230°C with a load of 2.16 kg or 5 kg, as specified.

[0087] Intrinsic viscosity (IV)

[0088] The sample was dissolved in tetralin at 135°C and then poured into a capillary viscometer. The viscometer tube (Ubbelohde type) was surrounded by a cylindrical glass jacket; this setup allowed temperature control with a circulating thermostated liquid. The downward passage of the meniscus was timed by a photoelectric device.

[0089] The passage of the meniscus in front of the upper lamp started a counter with a quartz crystal oscillator. When passing the lower lamp, the meniscus stopped the counter and the efflux time was recorded: this was converted into an intrinsic viscosity value by the Huggins' equation (Huggins, M.L., J. Am. Chem. Soc., 1942, 64, 2716), provided that the flow time of the pure solvent was known under the same experimental conditions (same viscometer and same temperature). A single polymer solution was used to determine [η].

[0090] Polydispersity index : determined by using a parallel-plate rheometer of the type RMS-800 sold by RHEOMETRICS (USA) operating with an oscillation frequency increasing from 0.1 rad / sec to 100 rad / sec at a temperature of 200°C. According to the cross modulus, the P.I. can be derived by the following equation:

[0091] P.I. = 105 / Gc

[0092] where Gcis the cross-over modulus defined as the value at which G' = G" (expressed in Pa), where G' is the storage modulus and G" is the loss modulus.

[0093] Composition of the recycled polymer (PP repro) was determined via1H and13C NMR

[0094] PP repro is a mixture of polymers having aliphatic hydrocarbon backbones (ethylene - E, propylene - P) and 1-butene (B, < 1.0 wt%), 1-hexene (H, < 1.0 wt%) and 1-octene (O, < 1.0 wt%) copolymers and possibly aromatic hydrocarbon backbones (polystyrene and polyethylene terephthalate). Due to the analytical complexity in determining the composition of the aromatic containing polymers via 13 C NMR spectroscopy, a method was developed by using a combination of results obtained via 1 H and 13 C NMR spectroscopy. In particular,13C NMR was used to determine the relative amounts of ethylene, propylene, 1-butene, 1-hexene and 1-octene copolymers, while 13 C NMR was used to determine the relative amounts of polystyrene and polyethylene terephthalate (when present), while 1 HNMR provided quantification of the composition of the aliphatic and aromatic components and the relative amounts of polystyrene and polyethylene terephthalate (when present).

[0095] Bruker AV600 spectrometer equipped with a cryoprobe 13 C NMR and 1 H spectra were acquired on a Bruker AV600 spectrometer equipped with a cryoprobe operating in Fourier transform mode at 120 °C at 150.91 MHz and 600.13 MHz respectively.

[0096] Approximately 30 mg of sample was dissolved in 0.5 ml of 1,1,2,2-tetrachloroethane-d2 added with 0.1 mg / ml of Irganox 1010 (AO 1010) as antioxidant at 120 °C

[0097] For 13 C NMR spectra, the peak of the S δδ carbon at 29.9 ppm (according to the nomenclature of C.J. Carman, R.A. Harrington and C.E. Wilkes, Macromolecules, 10, 3, 536 (1977)) was used as internal reference. Each spectrum was acquired with a 90° pulse with a 15 seconds delay between pulse and CPD to remove1H-13C couplings. A spectral window of 9000 Hz was used to store 512 transients in 65K data points.

[0098] For 1H NMR spectra, the peak of residual C2DHC14 at 5.95 ppm was used as internal reference. Each spectrum was acquired with a 90° pulse, with a delay of 5 seconds between pulses, and 128 transients were stored in 64K data points using a spectral window of 9600 Hz.

[0099] Evaluation of13C NMR spectra of ethylene, propylene, 1-butene, 1-hexene and 1-octene copolymers

[0100] In 13 In the13C NMR spectra, only signals from ethylene, propylene, 1-butene, 1-hexene and 1-octene copolymers were considered (the assignment of the peaks relevant for the quantification is reported in Table 1). The triad distribution was obtained from the integration of the relevant peaks in the13C NMR spectra (the peaks of the antioxidant AO1010 were considered possibly overlapped): 13

[0101] PPP = 100 I 11 / ∑

[0102] For I3 / I4<1: PPE = 100 I3 / ∑

[0103] For I3 / I4>1: PPE = 100 (I8 - 6I4) / ∑

[0104] EPE = 100 I7 / ∑

[0105] EBE = 100 I1 / ∑

[0106] EHE = 100 I6 / ∑

[0107] EOE = 100 (I2 - I6) / ∑

[0108] XEX = 100 I 13 / ∑

[0109] XEE = 100 (I 12 -I2) / ∑

[0110] EEE = 100 (0.5 (I 10 -I2) + 0.25 (I9 + I8)) / ∑

[0111] where:

[0112] ∑ = I 11 + (I3 or (I8 - 6I4)) + I7 + I1 + I6 + I2 - I6 + I 13 + I 12 -I2 + 0.5 (I 10- I2) + 0.25 (I9 + I8)​

[0113] and I n are the areas of the corresponding carbons following the numbering scheme reported in Table 1 and X can be propylene, 1-butene, 1-hexene or 1-octene

[0114] The mole contents of ethylene, propylene, 1-butene and 1-octene are obtained from the triplets using the following relationships:

[0115] P(m%) = PPP + PPE + EPE

[0116] B(m%) = EBE

[0117] H(m%) = EHE

[0118] O(m%) = EOE

[0119] E(m%) = EEE + XEE + XEX

[0120] The mole contents are converted into weight using the monomer molecular weights.

[0121] Evaluation of the 1H NMR spectra

[0122] From 1 The mole contents of polyethylene terephthalate (PET), polystyrene (PS) and ethylene / propylene / 1-butene / 1-hexene / 1-octene copolymer are obtained from the 1H spectra.

[0123] The aromatic hydrogen peaks of PET and PS are used (allocation according to Table 2), while the amount of ethylene / propylene / 1-butene / 1-hexene / 1-octene copolymer is determined by integrating all aliphatic hydrogens (from which the contribution of 3 aliphatic hydrogens of polystyrene is subtracted).

[0124] The mole amounts of PET, PS and E / P / B / H / O copolymer are evaluated from the following relationships:

[0125] PET = 100 0.25 I a / ∑

[0126] PS = 100 0.5 I c / ∑

[0127] Total aliphatic E / P / B / H / O copolymer = 100 0.5 (I e - 3 PS - 9 I d ) / ∑

[0128] where ∑ = 0.25 I a + 0.5 I c + 0.5 (I d - 3 PS - 100 0.5 (I e - 3 PS - 9 Id ) / Σ

[0129] The molar content is converted into weight percent using the monomer molecular weights to estimate the mass contribution from the ethylene / propylene / 1-butene / 1-hexene / 1-octene copolymer, taking into account the MW of CH2.

[0130] The mass contribution from the triad is converted from weight percent to weight percent in the entire sample by multiplying each value (wt%) from the triad by the following rescaling factor "RF": 13 The weight content of P, E, B, H, and O obtained from the C spectrum is rescaled to obtain the weight percent in the entire sample:

[0131] RF = [100 - PET (wt%) - PS (wt%)] / 100, where PET (wt%) and PS (wt%) are the weight percent of PET and PS in the sample, respectively. 1 The composition obtained from the H spectrum.

[0132] Table a ethylene / propylene / 1-octene / 1-butene copolymer 13 Assignment of the C NMR spectrum

[0133] No. Chemical shift (ppm) Carbon Sequence 1 39.6 [CAT δδ ]]> EBE 2 38.8 [TECHNICAL FIELD] δδ ]] EOE + EHE 3 38.2-37.6 [SA αγ ]]> PE 4 36.2 CH2 AO 1010 6 34.0 4B4 EHE 7 33.3-33.2 [CAT δδ ]]> EPE 8 30.8–30.7 [CAT βδ ]]> PPE 8 30.3 [SA γδ ]]> XEEE 9 30.2 [SA γδ ]] PEEE 10 29.9 S δδ+ 4B6]]> EEE + O 11 28.8–28.2 [CAT ββ ]]> PPP 12 27.4–26.7 <![CDATA[S βδ +5B6]]> XE + O 13 24.7–24.1 [SA ββ ]]> XEX

[0134] Table b ethylene / propylene / 1-butene / 1-hexene / 1-octene copolymer containing PS and PET 1 Assignment of the H NMR spectrum

[0135]

[0136] Ethylene (C2) content

[0137] Assignment of the C NMR 13 C NMR

[0138] The C NMR spectrum was acquired on a Bruker AV-600 spectrometer equipped with a cryoprobe, operating in Fourier transform mode at 160.91 MHz at 120 °C. 13

[0139] S at 29.9 ppm ββ ​The peaks of carbon (nomenclature according to "Measurement of monomer sequence distribution in ethylene-propylene rubbers by 13C NMR. 3. Use of reaction probability model" C.J. Carman, R.A. Harrington and C.E. Wilkes, Macromolecules, 1977, 10, 536) were used as internal references. The samples were dissolved at 120°C at 8 wt / v% concentration in 1,1,2,2-tetrachloroethane-d2. Each spectrum was obtained with a 90° pulse, a delay of 15 seconds between pulse and CPD to remove 1H-13C couplings. 512 transients were stored in 32K data points using a spectral window of 9000 Hz.

[0140] The assignment of the spectra, the evaluation of the triad distribution and the composition was made according to Kakugo ("Carbon-13 NMR determination of monomer sequence distribution in ethylene-propylene copolymers prepared with δ-titanium trichloride-diethylaluminum chloride" M. Kakugo, Y. Naito, K. Mizunuma and T. Miyatake, Macromolecules 1982, 15, 4, 1150-1152) using the following equations:

[0141] PPP = 100 T ββ / S PPE = 100 T βδ / S EPE = 100 T δδ / S

[0142] PEP = 100 S ββ / S PEE = 100 S βδ / S EEE = 100 (0.25 S γδ + 0.5 S δδ ) / S

[0143] S = T ββ + T βδ + T δδ + S ββ + S βδ + 0.25 S γδ + 0.5 S δδ

[0144] The mole percent of ethylene content was evaluated using the following equation:

[0145] E% mol = 100 * [PEP + PEE + EEE] weight percent of ethylene content evaluated using the following equation:

[0146] 100 * E% mol * MW E

[0147] E% wt. = ---------------------------------------------------------------

[0148] E% mol * MW E+ P% mol * MW P

[0149] where P mol% is the molar percent of propylene content, and MW E and MW P are the molecular weights of ethylene and propylene, respectively.

[0150] The product of the reactivity ratios r1r2 was calculated according to Carman (C. J. Carman, R. A. Harrington, and C. E. Wilkes, Macromolecules, 1977; 10, 536) as:

[0151]

[0152] The stereoregularity of the propylene sequences was calculated as mm content from the ratio of PPP mmT ββ (28.90 ppm to 29.65 ppm) to total T ββ (29.80 ppm to 28.37 ppm).

[0153] Samples for mechanical testing

[0154] The samples were obtained according to ISO 1873-2:2007.

[0155] Charpy impact tests were determined according to ISO 179-1 eA and ISO 1873-2.

[0156] Yield elongation: measured according to ISO 527.

[0157] Elongation at break: measured according to ISO 527

[0158] Stress at break: measured according to ISO 527.

[0159] Tensile modulus according to ISO 527-2.

[0160] Melting and crystallization point

[0161] The melting point is measured by using a DSC instrument according to ISO 11357-3, on a sample of weight between 5 and 7 mg, in cooling and heating, at a scan rate of 20 °C / min, under an inert N2 flow. The instrument is calibrated with indium.

[0162] Density, measured according to ISO 1183-1

[0163] Example

[0164] Example 1

[0165] Component A

[0166] Component A is a recycled polymer grade from raffia bag. The properties of the polymer are reported in Table 1.

[0167] Table 1

[0168]

[0169]

[0170] Component B

[0171] Component B is a commercial grade Hostalen H2464 sold by LyondellBasell, which can be synthesized according to procedures known in the art, Hostalen H2464 having the properties listed in Table 2.

[0172] Table 2

[0173] Component b1) XS wt% 2.0 MFR 230°C / 2.16 kg g / 10 min 1.0 Separation wt% 85 Component b2) C2 content wt% 50.0 Separation wt% 15 Total composition MFR 230°C / 5 kg g / 10 min 0.8 XS wt% 15 IV on XS dl / g 3.5 C2 content wt% 9.2

[0174] XS fraction soluble in xylene at 25 °C

[0175] C2 ethylene derived units

[0176] IV intrinsic viscosity

[0177] Component C

[0178] Component C is a commercial grade Adflex Q100F sold by LyondellBasell, which can be synthesized according to procedures known in the art, Adflex Q100F having the properties listed in Table 3.

[0179] Table 3

[0180]

[0181]

[0182] XS fraction soluble in xylene at 25 °C

[0183] C2 ethylene derived units

[0184] IV inherent viscosity

[0185] Components A), B) and C) have been blended in an extruder (Berstorff extruder). The polymer pellets were extruded in a twin-screw extruder under nitrogen atmosphere at a rotation speed of 250 rpm and a melting temperature of 200°C to 250°C. The compositions are reported in Table 4 and the characterization of the obtained compositions is reported in Table 5.

[0186] Table 4

[0187] Example 1 Component A wt% 57 Component B wt% 32 Component C wt% 11

[0188] 1 wt% of antioxidant MB (30%) and 0.5 wt% of MB PE black (40% CB) have been added to the blend of example 1

[0189] Table 5

[0190] Unit Example 1 Color -- Black MFR (200°C / 2,16 kg) g / 10 min 1,89±0,11 Ash content ％ 3,2±0,1 OIt (200°C) min 36±4 Tensile modulus MPa 1132±8 Charpy impact - notched kJ / m 16,3±0.6

Claims

1. A recycled polyolefin composition comprising: A) from 42 wt% to 72 wt% of a recycled polypropylene composition; B) from 21 wt% to 41 wt% of a first polypropylene ethylene copolymer comprising: - from 70 wt% to 95 wt% of a propylene homopolymer having: - a fraction soluble in xylene at 25°C lower than 6.0 wt%; and - a melt flow rate (ISO 1133, 230°C / 5.0 kg) ranging from 0.3 to 3.5 g / 10 min; - from 5 wt% to 30 wt% of a propylene and ethylene copolymer having: - an amount of units derived from ethylene ranging from 35.0 wt% to 65.0 wt% measured according to 13C-NMR; said polypropylene composition (B) further having the following characteristics: - a melt flow rate (ISO 1133, 230°C / 5.0 kg) ranging from 0.3 to 2.3 g / 10 min; - an amount of fraction soluble in xylene at 25°C ranging from 7.0 wt% to 27.0 wt%; - an intrinsic viscosity of the fraction soluble in xylene at 25°C measured in tetralin at 135°C ranging from 2.4 dl / g to 5.0 dl / g; in said composition, the sum of b1) and b2) refers to the total weight of b1) and b2), which is 100; C) from 5 wt% to 19 wt% of a second polypropylene ethylene copolymer comprising: - from 21 wt% to 43 wt% of a propylene ethylene copolymer having: - according to 13 units derived from ethylene in an amount ranging from 1.7% to 4.5% by weight; - a fraction soluble in xylene at 25°C lower than 8.0 wt%, preferably higher than 0.5 wt%, and - a melt flow rate (ISO 1133, 230°C / 5.0 kg) ranging from 18.0 to 34.0 g / 10 min; - from 57 wt% to 79 wt% of a propylene and ethylene copolymer having: - according to 13 units derived from ethylene in an amount ranging from 18.0 wt% to 36.0 wt% as measured by C-NMR; said polypropylene composition (c) further having the following characteristics: - - a melt flow rate (ISO 1133, 230°C / 5.0 kg) ranging from 0.2 to 1.7 g / 10 min; - an amount of fraction soluble in xylene at 25°C ranging from 52.0 wt% to 76.0 wt%; - an intrinsic viscosity of the fraction soluble in xylene at 25°C measured in tetralin at 135°C ranging from 2.1 dl / g to 4.7 dl / g; and, in said composition, the sum of c1) and c2) refers to the total weight of c1) and c2), which is 100, the sum of the amount of (A), the amount of (B) and the amount of (C) refers to the total weight of (A), (B) and (C), which is 100; said recycled polypropylene composition (A) having: With 13 an ethylene derived units content in the range of 2.50 wt.-% to 7.30 wt.-% as measured by C-NMR; With 13 a butene derived unit content in the range of 0.05 wt% to 0.30 wt% as measured by C-NMR; With 13 a hexene derived unit content in the range of 0.03 wt% to 0.23 wt% as measured by C-NMR; With 13 C-NMR measured octene derived unit content in the range of 0.02 wt% to 0.50 wt%; With 13 Polyethylene terephthalate content in the range of 0.05 wt% to 0.8 wt% as measured by C-NMR With 13 propylene derived units content higher than 87.4 wt% measured by C-NMR in the range of 0.9400 Kg / dm 3 to 0.9500 Kg / dm 3的密度，ISO 1183-1 ; - a melt flow rate (ISO 1133, 230°C / 2.16 kg) ranging from 1.2 to 20.3 g / 10 min.

2. The recycled polyolefin composition according to claim 1, wherein the component (A) ranges from 46 to 67 wt.%; component (B) ranges from 23 to 39 wt.%; and component C) ranges from 6 to 17 wt.%.

3. The recycled polyolefin composition according to claim 1, wherein in component B) component b1) ranges from 75 to 93 wt.%; and component b2) ranges from 7 to 25 wt.%.

4. The recycled polyolefin composition according to claim 1, wherein in component C) component c1) ranges from 23 to 41 wt.%; and component c2) ranges from 59 to 77 wt.%.

5. The recycled polyolefin composition according to claim 1, wherein in component c1) the amount of said units derived from ethylene is in the range of 2.0 wt% to 4.3 wt% according to 13 The amount of said units derived from ethylene measured by C-NMR is in the range of 2.0 wt% to 4.3 wt%.

6. The recycled polyolefin composition according to claim 1, wherein component B) has a fraction soluble in xylene at 25 °C in an amount ranging from 9.0 to 25.0 wt.%.

7. The recycled polyolefin composition according to claim 1, wherein component (C) has a fraction soluble in xylene at 25 °C in an amount ranging from 54.0 to 74.0 wt.%.

8. The recycled polyolefin composition according to claim 1, wherein component (B) has a fraction soluble in xylene at 25 °C an intrinsic viscosity measured in tetraline at 135 °C ranging from 2.7 to 4.6 dl / g.

9. The recycled polyolefin composition according to claim 1, wherein component (C) has a fraction soluble in xylene at 25 °C an intrinsic viscosity measured in tetraline at 135 °C ranging from 2.4 to 4.3 dl / g.

10. The recycled polyolefin composition according to claim 1, wherein in component A) the melt flow rate (ISO 1133-1, 230 °C / 2.16 kg) ranges from 3.4 to 17.4 g / 10 min.

11. The recycled polyolefin composition according to claim 1, wherein in component (B) the melt flow rate (ISO 1133, 230 °C / 5.0 kg) ranges from 0.4 to 2.0 g / 10 min.

12. The recycled polyolefin composition according to claim 1, wherein in component (C) the tensile modulus measured according to ISO 527-2 ranges from 1020 N / mm 2 to 1630 N / mm 2 .

13. The recycled polyolefin composition according to claim 1, wherein in component (C) the melt flow rate (ISO 1133, 230 °C / 5.0 kg) ranges from 0.3 to 1.4 g / 10 min.

14. The recycled polyolefin composition according to claim 1, wherein component A) has the density, ISO 1183-1, ranging from 0.9423 Kg / dm 3 to 0.9484 Kg / dm 3 3. The method of claim 1, wherein the first and second sets of parameters are determined based on a plurality of sets of parameters.

15. An extruded article obtained from the recycled polyolefin composition according to claim 1.

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