Compositions obtained from recycled polyolefins

Abstract

A polyolefin composition comprising: (A) from 80 wt% to 97 wt% of a polyolefin component containing: - (a1) from 20 wt% to 80 wt% of a propylene based polymer having a propylene content higher than 60 wt%; - (a2) from 20 wt% to 80 wt% of an ethylene based polymer having an ethylene content higher than 70%wt; (B) from 3 wt% to 20 wt%, of a polypropylene ethylene copolymer comprising: b1) from 50 wt% to 80 wt%; based on the sum of b1)+b2) of a first copolymer of propylene with ethylene wherein: i) the content of ethylene derived units, measured by 13C NMR, is comprised between 2.5 wt% and 6.5 wt%; b2) from 20 wt% to 50 wt%; based on the sum of b1)+b2) of a second propylene ethylene copolymer containing from 40.0 wt% to 65.0 wt%; of ethylene derived units, measured by 13C NMR.

Description

FE7798 WO - Priority Text P2COMPOSITIONS OBTAINED FROM RECYCLED POLYOLEFINSFIELD OF THE INVENTION

[0001] The present disclosure relates to compositions obtained comprising recycled polyolefins and a polypropylene based composition as a compatibilizer.BACKGROUND OF THE INVENTION

[0002] Polyolefins, in particular polyethylene and polypropylene, are increasingly consumed in large amounts for many applications, including packaging for food and other goods, fibers, automotive components, and a great variety of manufactured articles. However, the said massive use of polyolefins is creating a concern as regards the environmental impact of the waste materials generated after the first use.

[0003] In fact, large amounts of waste plastic materials are presently coming from differential recovery of municipal plastic wastes, mainly constituted of flexible packaging (cast film, blown film and BOPP film), rigid packaging, blow moulded bottles and injection moulded containers. Through a step of separation from other polymers, such as PVC, PET or PS, two main polyolefinic fractions are obtained, namely polyethylenes (in particular HDPE LDPE, LLDPE) and polypropylenes (homopolymers, random copolymers, heterophasic copolymers).

[0004] One of the key problems in polyolefin recycling, especially when dealing with material streams from post-consumer waste (PCW) is the difficulty to quantitatively separate polypropylene (PP) and polyethylene (PE). Commercial recyclates from PCW sources have been found to generally contain mixtures of PP and PE, the minor component reaching up to < 50 wt%.

[0005] Such recycled PP / PE-blends normally suffer from deteriorated mechanical and optical properties, have poor performance in odour and taste and they generally suffer from poor compatibility between the main polymer phases, resulting in both limited impact strength and heat deflection resistance. Such inferior performance is partly caused by PE with its lower stiffness and melting point forming the continuous phase even at PP concentrations up to 65% because of the normally higher viscosity of the PE components in PCW.FE7798 WO - Priority Text P2

[0006] These drawbacks normally exclude the application for high quality parts, and it only allows the use in low-cost and non-demanding applications.

[0007] Some research has been done to improve the compatibility between PP and PE.

[0008] WO2019 / 091886 Al discloses a method of using heterophasic polypropylene compositions or a random ethylene-propylene copolymers (EP-RACO) as compatibilizer for the recycling plastic blends. The heterophasic copolymer compositions seems less promising in terms of compatibilization performances.

[0009] It has now been found that a composition comprising a specifically tailored heterophasic polypropylene composition can be used as compatibilizer for recycled PE / PP compositions.SUMMARY OF THE INVENTION

[0010] The present disclosure relates to polyolefin compositions comprising:(A) from 80 wt% to 97 wt%, preferably from 82 wt% to 95 wt% more preferably from 85 wt% to 93 wt% of a polyolefin component containing:(al) from 20 wt% to 80 wt%, preferably from 30 wt% to 70 wt% more preferably from 40 wt % to 60 wt% based on the sum of al)+a2) of a propylene based polymer having a propylene content higher than 60 wt%(a2) from 20 wt% to 80 wt% preferably from 30 wt% to 70 wt% more preferably from 40 wt % to 60 wt% based on the sum of al)+a2) of an ethylene based polymer having an ethylene content higher than 70% wt;(B) from 3 wt% to 20 wt%, preferably from 5 wt% to 18 wt% more preferably from 7 wt% to 15 wt% of a polypropylene ethylene copolymer comprising:bl) from 50 wt% to 80 wt%; preferably from 57 wt% to 77 wt%; more preferably from 63 wt% to 72 wt% based on the sum of bl)+b2) of a first copolymer of propylene with ethylene wherein: i) the content of ethylene derived units, measured by13C NMR, is comprised between 2.5 wt% and 6.5 wt%; preferably between 3.5 wt% and 5.5 wt% more preferably between3.8 wt% and 5.0 wt%; b2) from 20 wt% to 50 wt%; preferably from 23 wt% to 43 wt%; more preferably from 28 wt% to 37 wt% based on the sum of bl)+b2) of a second propylene ethylene copolymer containing from 40.0 wt% to 65.0 wt%; preferably from 45 wt% to 58 wt%; more preferably from 48 wt% to 55 wt% of ethylene derived units, measured by13C NMR;wherein the polypropylene ethylene copolymer has:FE7798 WO - Priority Text P2i) the content of ethylene derived units, measured by13C NMR, comprised between 12.0 wt% and 35 wt%; preferably between 15.0 wt% and 30 wt%; more preferably between 19.0 wt% and 28.0 wt%;ii) the content of ethylene derived units, measured by13C NMR, in the fraction soluble in xylene at 25°C is comprised between 35.0 wt% and 56.0 wt%; preferably between 38.0 wt% and 51.0 wt%; more preferably between 43.0 wt% and 49.0 wt%;iii) a melt flow rate (ISO 1133 (230° C, 21.6 kg), ranging from 0.1 g / lOmin to 3.0 g / 10 min; preferably from 0.5 g / lOmin to 2.5 g / 10 min; more preferably from 0.8 g / lOmin to 1.8 g / 10 min; iv) the xylene solubles at 25°C ranges from 23 wt% to 43.0wt%; preferably ranges from 28 wt% to 40.0wt%; more preferably ranges from 29.5 wt% to 28.5 wt%;v) the intrinsic viscosity, measured in tetrahydronaphthalene at 135 °C, of the fraction soluble in xylene at 25°C ranges from 7.7 dl / g to 15.0 dl / g; preferably ranges from 7.9 dl / g to 13.0 dl / g; more preferably ranges from 8.1 dl / g to 11.5 dl / g;vi) the intrinsic viscosity, measured in tetrahydronaphthalene at 135 °C, of the polypropylene ethylene copolymer B) ranges from 7.7 dl / g to 15.0 dl / g; preferably ranges from 7.9 dl / g to 13.0 dl / g; more preferably ranges from 8.1 dl / g to 11.5 dl / g;the sum of the amounts of A) and B) being 100 wt%DETAILED DESCRIPTION OF THE INVENTION

[0011] The term copolymer has to be intended as a bipolymer containing two monomers, propylene and a ethylene C.

[0012] The term “consisting essentially of’, as used herein in connection with a polymer or polymer composition means that, in addition to those components which are mandatory, other components may also be present in the polymer or in the polymer composition, provided that the essential characteristics of the polymer or of the composition are not materially affected by their presence. According to the present disclosure, examples of components that, when present in customary amounts in a polymer or in a polymer composition, do not materially affect their characteristics are the catalyst residues, antistatic agents, melt stabilizers, light stabilizers, antioxidants, antiacids.

[0013] The features of the components forming the polypropylene composition are not inextricably linked to each other. This means that a certain level of preference of one theFE7798 WO - Priority Text P2features should not necessarily involve the same level of preference of the remaining features of the same or different components. On the contrary, it is intended in the present disclosure that any component or sub-components (A) to (B) and any preferred range of features of components (A) to (B) can be combined with any preferred range of one or more of the features of components (A) to (B) and with any possible additional component, and its features, described in the present disclosure.

[0014] Preferably component al) is selected from a propylene based polymer having a propylene content higher than higher than 70 wt%; more preferably higher than 80 wt% and even more preferably higher from 90 to 100wt%;

[0015] Preferably component (a2) is selected from ethylene based polymers having an ethylene content higher than 70 preferably higher than 75 wt%; more preferably higher than 80 wt% even more preferably from 90 wt% to 100%.

[0016] Component (A) preferably origins from of a waste material containing not less than 80% by weight, typically not less than 90% by weight, in particular from 80% or 90% up to 99% by weight, with respect to the total weight of the component, of polyethylene or polypropylene or their mixtures. The term “waste” is used to designate polymer materials deriving from at least one cycle of processing into manufactured articles, as opposed to virgin polymers, comprises a mixture of recycled polypropylene and polyethylene blend as main components.

[0017] As previously mentioned, all kinds of polyethylene or polypropylene can be present. In particular, the polyethylene fraction can comprise one or more materials selected from high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE).

[0018] The polypropylene fraction can comprise one or more polymer materials selected from the following:

[0019] I) isotactic or mainly isotactic propylene homopolymers;

[0020] II) random copolymers of propylene with ethylene and / or C4-C8 a-olefins, such as for example 1 -butene, 1 -hexene, 1 -octene, 4-methyl-l -pentene, wherein the total comonomer content ranges from 0.05% to 20% by weight, or mixtures of said copolymers with isotactic or mainly isotactic propylene homopolymers;

[0021] III) heterophasic copolymers comprising a propylene homopolymer and / or one of the copolymers of item II), and an elastomeric fraction comprising copolymers of ethylene withFE7798 WO - Priority Text P2propylene and / or a C4-C8 a-olefin, optionally containing minor amounts of a diene, such as butadiene, 1,4-hexadiene, 1,5-hexadiene, ethylidene-1 -norbornene.

[0022] Other polymeric materials typically present as impurities in component (A) are polystyrene, ethylene vinyl acetate copolymers, polyethylene terephthalate.

[0023] Other impurities that can be present in component (A) are metals (in particular Al) and additives, like fillers and pigments.

[0024] Preferably the FTIR spectrum of film recorded as described in the example section of component A) comprises at least two adsorption bands at least two wavenumbers (cm-1) selected from:

[0025] 3303 ±2 cm-1; 1726 ±2, 1642 ±2 cm-1; 1600 ±2 cm’11550 ±2 cm-1; 1491±2 cm-1;1451±2 cm-1; 1726 ±2 cm-1; 1600 ±2 cm-1, 748 ±2 cm-1; 906 ±2 cm’1; 839 ±2 cm’1, 818 ±2 cm'1;748 ±2 cm’1; 695 ±2 cm’1

[0026] Component B) The composition of the present disclosure can be prepared by blending component bl) and b2). Components (bl) and (b2) can be also prepared in a continuous sequential polymerization process, wherein component bl) is prepared in the first reactor and component (b2) is prepared in the second reactor in the presence of component bl) according to the known techniques and operating in gas phase, or in liquid phase in the presence or not of inert diluent, or by mixed liquid-gas techniques.

[0027] The polymerization of (bl) and (b2) can be carried out in the presence of Ziegler-Natta catalysts. An essential component of said catalysts is a solid catalyst component comprising a titanium compound having at least one titanium-halogen bond, and an electron-donor compound, both supported on a magnesium halide in active form. Another essential component (co-catalyst) is an organoaluminium compound, such as an aluminium alkyl compound.

[0028] An external donor is optionally added.

[0029] The catalysts generally used in the process of the invention are capable of producing polypropylene with a value of xylene insolubility at ambient temperature greater than 90%, preferably greater than 95%.

[0030] Catalysts having the above mentioned characteristics are well known in the patent literature; particularly advantageous are the catalysts described in US patent 4,399,054 and European patent 45977. Other examples can be found in US patent 4,472,524.FE7798 WO - Priority Text P2

[0031] The solid catalyst components used in said catalysts comprise, as electron-donors (internal donors), compounds selected from the group consisting of ethers, ketones, lactones, compounds containing N, P and / or S atoms, and esters of mono- and dicarboxylic acids.

[0032] Particularly suitable electron-donor compounds are esters of succinic acid (succinates) Preferably, the succinate present in the solid catalyst component is selected from succinates of formula (I) below

[0033] in which the radicals Ri and R2, equal to, or different from, each other are a C1-C20 linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl group, optionally containing heteroatoms; and the radicals R3 and R4 equal to, or different from, each other, are Ci-C20 alkyl, C3-C20 cycloalkyl, C5-C20 aryl, arylalkyl or alkylaryl group with the proviso that at least one of them is a branched alkyl; said compounds being, with respect to the two asymmetric carbon atoms identified in the structure of formula (I), stereoisomers of the type (S, R) or (R, S)

[0034] Ri and R2 are preferably Ci-Cs alkyl, cycloalkyl, aryl, arylalkyl and alkylaryl groups. Particularly preferred are the compounds in which Ri and R2 are selected from primary alkyls and in particular branched primary alkyls. Examples of suitable Ri and R2 groups are methyl, ethyl, n-propyl, n-butyl, isobutyl, neopentyl, 2-ethylhexyl. Particularly preferred are ethyl, isobutyl, and neopentyl.

[0035] Particularly preferred are the compounds in which the R3 and / or R4 radicals are secondary alkyls like isopropyl, sec- butyl, 2-pentyl, 3 -pentyl or cycloakyls like cyclohexyl, cyclopentyl, cyclohexylmethyl.

[0036] Examples of the above-mentioned compounds are the (S, R) (S, R) forms pure or in mixture, optionally in racemic form, of diethyl 2,3-bis(trimethylsilyl)succinate, diethyl 2,3-bis(2-ethylbutyl)succinate, diethyl 2,3 -dibenzylsuccinate, diethyl 2,3-diisopropylsuccinate, diisobutyl 2,3-diisopropylsuccinate, diethyl 2,3-bis(cyclohexylmethyl)succinate, diethyl 2,3-FE7798 WO - Priority Text P2diisobutylsuccinate, diethyl 2,3-dineopentylsuccinate, diethyl 2,3-dicyclopentylsuccinate, diethyl 2,3-dicyclohexylsuccinate.

[0037] Particularly suitable electron- donor compounds are esters of phtalic acid and 1,3- diethers of formula:

[0038] wherein R1and Rnare the same or different and are Ci-Cis alkyl, C3-C18 cycloalkyl or C7-C18 aryl radicals; R111and RIVare the same or different and are C1-C4 alkyl radicals; or are the 1,3 -di ethers in which the carbon atom in position 2 belongs to a cyclic or polycyclic structure made up of 5, 6, or 7 carbon atoms, or of 5-n or 6-n' carbon atoms, and respectively n nitrogen atoms and n' heteroatoms selected from the group consisting of N, O, S and Si, where n is 1 or 2 and n' is 1, 2, or 3, said structure containing two or three unsaturations (cyclopolyenic structure), and optionally being condensed with other cyclic structures, or substituted with one or more substituents selected from the group consisting of linear or branched alkyl radicals; cycloalkyl, aryl, aralkyl, alkaryl radicals and halogens, or being condensed with other cyclic structures and substituted with one or more of the above mentioned substituents that can also be bonded to the condensed cyclic structures; one or more of the above mentioned alkyl, cycloalkyl, aryl, aralkyl, or alkaryl radicals and the condensed cyclic structures optionally containing one or more heteroatom(s) as substitutes for carbon or hydrogen atoms, or both.

[0039] Ethers of this type are described in published European patent applications 361493 and 728769.

[0040] Representative examples of said diethers are 2-methyl-2-isopropyl-l,3- dimethoxypropane, 2,2-diisobutyl-l,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-l,3- dimethoxypropane, 2-isopropyl-2-isoamyl-l,3-dimethoxypropane, 9,9-bis (methoxymethyl) fluorene.

[0041] Other suitable electron-donor compounds are phthalic acid esters, such as diisobutyl, dioctyl, diphenyl and benzylbutyl phthalate.

[0042] The preparation of the above mentioned catalyst component is carried out according to various methods.

[0043] For example, a MgCl2•nROH adduct (in particular in the form of spheroidal particles) wherein n is generally from 1 to 3 and ROH is ethanol, butanol or isobutanol, is reacted with anFE7798 WO - Priority Text P2excess of TiC14 containing the electron-donor compound. The reaction temperature is generally from 80 to 120° C. The solid is then isolated and reacted once more with TiC14, in the presence or absence of the electron-donor compound, after which it is separated and washed with aliquots of a hydrocarbon until all chlorine ions have disappeared.

[0044] In the solid catalyst component the titanium compound, expressed as Ti, is generally present in an amount from 0.5 to 10% by weight. The quantity of electron-donor compound which remains fixed on the solid catalyst component generally is 5 to 20% by moles with respect to the magnesium dihalide.

[0045] The titanium compounds, which can be used for the preparation of the solid catalyst component, are the halides and the halogen alcoholates of titanium. Titanium tetrachloride is the preferred compound.

[0046] The reactions described above result in the formation of a magnesium halide in active form. Other reactions are known in the literature, which cause the formation of magnesium halide in active form starting from magnesium compounds other than halides, such as magnesium carboxylates.

[0047] The Al-alkyl compounds used as co-catalysts comprise the Al-trialkyls, such as Al- triethyl, Al-triisobutyl, Al-tri-n-butyl, and linear or cyclic Al-alkyl compounds containing two or more Al atoms bonded to each other by way of O or N atoms, or SO4 or SO3 groups.

[0048] The Al-alkyl compound is generally used in such a quantity that the Al / Ti ratio be from 1 to 1000.

[0049] The electron-donor compounds that can be used as external donors include aromatic acid esters such as alkyl benzoates, and in particular silicon compounds containing at least one Si-OR bond, where R is a hydrocarbon radical.

[0050] Examples of silicon compounds are (tert-butyl)2Si(OCH3)2, (cyclohexyl)(methyl)Si(OCH₃)₂, (cyclopentyl)2Si(OCH3)2 and (phenyl)2Si(OCH3)2 and (1,1,2- trimethylpropyl)Si(OCH₃)₃.

[0051] 1,3 -diethers having the formulae described above can also be used advantageously. If the internal donor is one of these diethers, the external donors can be omitted.

[0052] In particular, even if many other combinations of the previously said catalyst components may allow to obtain compositions according to the present invention, the component A) are preferably prepared by using catalysts containing a phthalate as internal donor and (cyclopentyl)2Si(OCH3)2 as outside donor, or the said 1,3-diethers as internal donors.FE7798 WO - Priority Text P2

[0053] A further The Ziegler-Natta catalysts that can be used to produce a propylene polymer of the present invention is a solid catalyst component comprising a magnesium halide, a titanium compound having at least a Ti-halogen bond as above described and at least two electron donor compounds selected from succinates and the other being selected from 1,3 diethers.

[0054] The polyolefin composition of the present disclosure offer an excellent compatibilization between the polyethylene and polypropylene portions of component (A) so that its mechanical properties and the appearance of the manufactured articles make them useful for a wide range of application and especially for the production of films, including cast, blown and bioriented films mono or multilayer. When component B) is added even in small amount the elongation at break of the resulting composition is increased considerably, this means that the composition is match more homogeneous.

[0055] In particular, the polyolefin composition of the present disclosure offer an excellent balance between tensile modulus and Charpy resistance at 23°C.

[0056] In component A) when component al) ranges from 40 wt% to 60 wt% and component a2) ranges from 40 wt% to 60 wt% the composition of the present disclosure is endowed with at least one of the following features:

[0057] -charpy resistance at 23 °C ranges from 25.9 KJ / m2to 55.9 KJ / m2preferably from 30.7 KJ / m2to 50.5 KJ / m2more preferably from 35.3 KJ / m2to 45.5 KJ / m2;

[0058] -charpy resistance at 0°C ranges from 2.2 KJ / m2to 12.3 KJ / m2preferably from 4.3 KJ / m2to 10.1 KJ / m2more preferably from 5.2 KJ / m2to 9.3 KJ / m2;

[0059] -charpy resistance at -20°C ranges from 2.4 KJ / m2to 6.5 KJ / m2preferably from 3.2 KJ / m2to 5.5 KJ / m2

[0060] -tensile Modulus ranges from 790 N / mm2to 1190 N / mm2preferably from 840 N / mm2to 1140 N / mm2; even more preferably from 890 N / mm2to 1090 N / mm2;

[0061] -elongation at break ranging from 400% to 800 %; preferably from 480 % to 720 %;more preferably form 520 % to 660 %.

[0062] In component A) when component al) ranges from 39 wt% to 20 wt% % and component a2) ranges from 61 wt% to 80 wt the composition of the present disclosure is endowed with at least one of the following features:

[0063] -charpy resistance at 23°C ranges from 61.7 KJ / m2to 101.9 KJ / m2preferably from 71.5 KJ / m2to 91.4 KJ / m2more preferably from 376.3 KJ / m2to 86.9 KJ / m2;FE7798 WO - Priority Text P2

[0064] -charpy resistance at 0°C ranges from 14.6 KJ / m2to 44.3 KJ / m2preferably from 19.8 KJ / m2to 39.7 KJ / m2more preferably from 24.3 KJ / m2to 34.5 KJ / m2;

[0065] -charpy resistance at -20°C ranges from 2.4 KJ / m2to 8.6 KJ / m2preferably from 3.6 KJ / m2to 7.5 KJ / m2

[0066] -Tensile Modulus ranges from 680 N / mm2to 1080 N / mm2preferably from 730 N / mm2to 1030 N / mm2; even more preferably from 780 N / mm2to 980 N / mm2;

[0067] -elongation at break ranging from 400% to 800 %; preferably from 480 % to 720 %;more preferably form 520 % to 660.

[0068] In component A) when component al) ranges from 61 wt% to 80 wt% and component a2) ranges from 39 wt% to 20 wt% the composition of the present disclosure is endowed with at least one of the following features:

[0069] -charpy resistance at 23 °C ranges from 1.9 KJ / m2to 10.9 KJ / m2preferably from 2.3 KJ / m2to 8.5 KJ / m2more preferably from 3.8 KJ / m2to 9.9 KJ / m2;

[0070] -charpy resistance at 0°C ranges from 2.2 KJ / m2to 12.3 KJ / m2preferably from 4.3 KJ / m2to 10.1 KJ / m2more preferably from 5.2 KJ / m2to 9.3 KJ / m2;

[0071] -charpy resistance at -20°C ranges from 1.4 KJ / m2to 6.6 KJ / m2preferably from 2.6 KJ / m2to 5.5 KJ / m2

[0072] -Tensile Modulus ranges from 840 N / mm2to 1240 N / mm2preferably from 890 N / mm2to 1190 N / mm2; even more preferably from 940 N / mm2to 1140 N / mm2; and

[0073] -elongation at break ranging from 200% to 500 %; preferably from 280 % to 420 %;more preferably form 320 % to 390 %.

[0074] The whole propylene composition of the present disclosure can be obtained by mechanical blending of the components (A) and (B) according to conventional techniques.

[0075] According to a preferred method of preparation, component (B) is mechanically blended with a preformed polypropylene composition (A) comprising the components (a) and (b) associated together by means of the already disclosed a sequential copolymerization process.

[0076] The final composition comprising the components (A) and (B) may be added with conventional additives, fillers and pigments, commonly used in olefin polymers such as nucleating agents, extension oils, mineral fillers, and other organic and inorganic pigments. In particular, the addition of inorganic fillers, such as talc, calcium carbonate and mineral fillers,FE7798 WO - Priority Text P2also brings about an improvement to some mechanical properties, such as flexural modulus and HDT. Talc can also have a nucleating effect.

[0077] The nucleating agents may be added to the compositions of the present disclosure in quantities ranging from 0.05 to 2% by weight, more preferably from 0.1 to 1% by weight, with respect to the total weight, for example.

[0078] The addition of the compatibilizer component B) to the component A) increases the elongation at break but also increases considerably the impact properties without substantially worsening the tensile modulus.

[0079] The composition of the present disclosure is suitable for the preparation of films, but also textile articles, blow molded articles, thermoformed articles and injection molded articles.

[0080] The following examples are given in order to illustrate, but not limit the present disclosure.EXAMPLESCHARACTERIZATIONSFTIR SpectrumThe IR spectrum was determined by infrared (IR) spectroscopy by recording the sample against a background level of air with a Fourier transform infrared (FTIR) spectrometer. The data acquisition parameters of the instrument were:■ purge time: 30 seconds minimum■ collection time: 3 minutes minimum■ apodization: Happ-Genzel■ resolution: 2 cm-1.Sample preparation - Using a hydraulic press, a thick sheet was obtained by compression molding approximately 1 g sample between two sheets of aluminum foil. A small portion of the resulting sheet was cut to form a film. The film thickness was set to have a maximum absorbance of the CH 2 absorption band at -720 cm-1 of 1.3 au (% Transmittance > 5%). Molding conditions were performed at a temperature of approximately 180 ± 10°C (356°F) and a pressure of approximately 10 kg / cm2 (142.2 psi) for approximately one minute. After the pressure was released, the sample was removed from the press and cooled to room temperature. The spectrum of the pressed film was recorded as a function of absorbance versus wavenumbers (cm-1).FE7798 WO - Priority Text P2Xylene-soluble (XS) Fraction at 25 °C

[0081] Xylene Solubles at 25°C have been determined according to ISO 16152: 2005;

[0082] The content of the xylene-soluble fraction is expressed as a percentage of the original weight and then, by the difference (complementary to 100%), the xylene insoluble percentage (%).Melt Flow Rate (MFR)

[0083] Measured according to ISO 1133 at 230 °C with a load of 2.16 kg, unless otherwise specified.Intrinsic Viscosity (IV)

[0084] The sample is dissolved in tetrahydronaphthalene at 135 °C and then poured into a capillary viscometer. The viscometer tube (Ubbelohde type) is surrounded by a cylindrical glass jacket; this setup allows for temperature control with a circulating thermostatic liquid. The downward passage of the meniscus is timed by a photoelectric device.

[0085] The passage of the meniscus in front of the upper lamp starts the counter which has a quartz crystal oscillator. The meniscus stops the counter as it passes the lower lamp and the efflux time is registered: this is converted into a value of intrinsic viscosity through Huggins' equation (Huggins, M. L., J. Am. Chem. Soc., 1942, 64, 2716) provided that the flow time of the pure solvent is known at the same experimental conditions (same viscometer and same temperature). One single polymer solution is used to determine [ η ].Ethylene (C2) content13C NMR of propylene / ethylene copolymers

[0086] 13C NMR spectra were acquired on a Bruker AV-600 spectrometer equipped with cryoprobe, operating at 160.91 MHz in the Fourier transform mode at 120°C.

[0087] The peak of the Spp carbon (nomenclature according to “Monomer Sequence Distribution in Ethylene-Propylene Rubber Measured by13C NMR. 3. Use of Reaction Probability Mode ” C. J. Carman, R. A. Harrington and C. E. Wilkes, Macromolecules, 1977, 10, 536) was used as internal reference at 29.9 ppm. The samples were dissolved in 1, 1,2,2- tetrachloroethane-d2 at 120°C with a 8 % wt / v concentration. Each spectrum was acquired with a 90° pulse, 15 seconds of delay between pulses and CPD to remove1H-13C coupling.512 transients were stored in 32K data points using a spectral window of 9000 Hz.

[0088] The assignments of the spectra, the evaluation of triad distribution and the composition were made according to Kakugo (“Carbon- 13 NMR determination of monomerFE7798 WO - Priority Text P2sequence distribution in ethylene-propylene copolymers prepared with 8-titanium trichloridediethylaluminum chloride” M. Kakugo, Y. Naito, K. Mizunuma and T. Miyatake, Macromolecules 1982, 15, 4, 1150-1152) using the following equations:PPP = 100 Tββ / S PPE = 100 Tβδ / S EPE = 100 Tδδ / SPEP = 100 Sββ / S PEE= 100 Sβδ / S EEE = 100 (0.25 Sγδ+0.5 Sδδ) / S S = Tββ+ Tβδ+ Tδδ+ Sββ+ Sβδ+ 0.25 Sγδ+ 0.5 Sδδ

[0089] The molar percentage of ethylene content was evaluated using the following equation:

[0090] E% mol = 100 * [PEP+PEE+EEE]The weight percentage of ethylene content was evaluated using the following equation:100 * E% mol * MWEE% wt. = >E% mol * MWE+ P% mol * MWp

[0091] where P% mol is the molar percentage of propylene content, while MWE and MWp are the molecular weights of ethylene and propylene, respectively.

[0092] The product of reactivity ratio r1r2was calculated according to Carman (C. J.Carman, R. A. Harrington and C. E. Wilkes, Macromolecules, 1977; 10, 536) as:r1r2= 1 + (EEE+PEE / PEP + 1) - (P / E + 1)(EEE+PEE / PEP + 1)0.5I. PEP E A PEPThe tacticity of Propylene sequences was calculated as mm content from the ratio of the PPP mmTββ(28.90-29.65 ppm) and the whole Tββ(29.80-28.37 ppm). Samples for the mechanical tests

[0093] Samples have been obtained according to ISO 1873-2:2007.Charpy impact test is determined according to ISO 179-leA, and ISO 1873-2Elongation at yield: measured according to ISO 527.Elongation at break: measured according To ISO 527Stress at break: measured according to ISO 527.Tensile Modulus according to ISO 527-2,Tear Resistance according to the method ASTMD 1004 on Imm-thick extruded sheets. Crosshead speed: 51 mm / min; V-shaped die cut specimen.FE7798 WO - Priority Text P2Shore D on injection molded, compression molded plaques and extruded sheets according to the method ISO 868 (15 sec)Melting point and crystallization point

[0094] The melting point has been measured by using a DSC instrument according to ISO 11357-3, at scanning rate of 20°C / min both in cooling and heating, on a sample of weight between 5 and 7 mg., under inert N2flow. Instrument calibration made with Indium.Determination of the composition of recycled PP and PE via1H and13C NMR

[0095] PP repro is a mixture of polymers having an aliphatic hydrocarbon backbone (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 an aromatic hydrocarbon backbone (polystyrene and polyethylene terephthalate). Due to analytical complications in determining the composition of aromatic containing polymers via13C NMR spectroscopy, the method was developed by using the combination of the results obtained via1H and13C NMR spectra. In particular13C NMR was used to determine the relative amount of ethylene, propylene 1- butene, 1 -hexene and 1 -octene copolymers, while1H NMR provided a quantification of the composition of aliphatic and aromatic components and the relative amounts of polystyrene and polyethylene terephthalate when present.

[0096] 13C NMR and1H spectra were acquired on a Bruker AV600 spectrometer equipped with cryo probe, operating at 150.91 MHz and 600.13 MHz respectively in the Fourier transform mode at 120 °C.

[0097] About 30 mg of sample were dissolved at 120°C in 0.5 ml of 1,1, 2, 2 tetrachloroethane-d2 added with 0.1 mg / ml of Irganox 1010 (AO 1010) as antioxidant

[0098] For13C NMR spectra the peak of the Sδδcarbon (nomenclature according C. J.Carman, R. A. Harrington and C. E. Wilkes, Macromolecules, 10, 3, 536 (1977)) was used as internal reference at 29.9 ppm. Each spectrum was acquired with a 900pulse, 15 seconds of delay between pulses and CPD to remove1H-13C coupling. 512 transients were stored in 65 K data points using a spectral window of 9000 Hz.

[0099] For1H NMR spectra the peak of the residual C2DHCl4at 5.95 ppm was used as internal reference. Each spectrum was acquired with a 90° pulse, 5 seconds of delay between pulses and 128 transients stored in 64K data points using a spectral window of 9600 Hz.

[0100] Evaluation of13C NMR spectrum of Ethylene, Propylene, 1 -Butene, 1 -Hexene and 1- Octene copolymersFE7798 WO - Priority Text P2

[0101] In the13C NMR spectrum only the signals from Ethylene, Propylene, 1 -Butene, 1- Hexene and 1 -Octene copolymers were considered (assignments of peak relevant for quantification are reported in Table 1). Triad distribution (considering only EBE, EHE and EOE due to the low amount of these comonomers) was obtained from the integration of relevant peaks in13C NMR spectrum (possible overlaps of the peaks of the antioxidant AO1010 were taken into account), using the following relations:PPP = 100 In / Sforl3 / l4<l: PPE = 10013 / Sfor I3 / I4>1: PPE = 100 (Is - 6I4) / SEPE= 10017 / SEBE = 100 Ii / SEHE = 100 I6 / SEOE = 100 (I2-I6) / SXEX=100 Ii3 / SXEE =100 (Ii2-I2) / SEEE = 100 (0.5 (I10 - I2) + 0.25 (I9+ Is)) / S

[0102] Where:Σ = I11+ (I3or (I8- 6I4)) + I7+ I1+ I6+ I2-I6+ I13+ I12-I2+ 0.5 (I10-I2) + 0.25 (I9+ I8)

[0103] and L are the areas of the corresponding carbon following the numbering scheme reported in Table 1 and X can be propylene, 1 -butene, 1 -hexene or 1 -octene

[0104] The molar content of Ethylene, Propylene, 1 -Butene and 1 -Octene is obtained from triads using the following relations:P (m%) = PPP + PPE + EPEB (m%) = EBEH (m%)= EHEO (m%) = EOEE (m%) = EEE + XEE + XEXFE7798 WO - Priority Text P2

[0105] Molar content was transformed in weight using monomers molecular weight.

[0106] Evaluation of1H NMR spectrum

[0107] The molar content of Polyethylene terephthalate (PET), Polystyrene (PS) and ethylene / propylene / 1-butene / 1-hexene / 1-octene copolymers were obtained from1H spectra.

[0108] The aromatic hydrogen peaks of PET and PS (assignments according to Table 2) were used, while the amount of ethylene / propylene / 1 -Butene / 1 -Hexene / 1 -Octene copolymers was determined by the integral of all the aliphatic hydrogens, from which the contribution of the 3 aliphatic hydrogens of the polystyrene was subtracted.

[0109] Molar amounts of PET, PS and E / P / B / H / O copolymers were evaluated from the following relations:PET = 100 × 0.25 Ia / ΣPS = 100 × 0.5 Ic / Σ

[0110] Total aliphatic E / P / B / H / O copolymers = 100 × 0.5 (Ie-3PS -9Id) / ΣWhere Σ = 0.25 Ia+ 0.5 Ic+ 0.5 (Id- 3PS - 100 × 0.5 (Ie-3PS-9Id) / Σ

[0111] Molar content was transformed in weight percentage using monomers molecular weight considering the MW of CH2 to estimate the weight contribution from ethylene / propylene / 1 -butene / 1 -hexene / 1 -octene copolymers.

[0112] The weight content of P, E, B, H and O obtained from13C spectrum was rescaled to obtain the weight percentage in the whole sample by multiplying each value (wt%) from triads with the rescaling factor “RF”:

[0113] RF = [100-PET(wt%)-PS(wt%)] / 100 where PET(wt%) and PS(wt%) are the compositions obtained from1H spectrum.FE7798 WO - Priority Text P2Table A Assignments of the13C NMR spectrum of Ethylene / Propylene / 1-Octene / 1-Butene copolymersNumber Chemical Shift (ppm) Carbon Sequence1 39.6 TδδEBE2 38.8 TδδEOE + EHE 3 38.2 - 37.6 SαγPE4 36.2 CH2AO10106 34.0 4B4EHE7 33.3 - 33.2 TδδEPE8 30.8 - 30.7 TβδPPE8 30.3 SγδXEEE9 30.2 SγδPEEE10 29.9 Sδδ+ 4B6EEE + O11 28.8 -28.2 TββPPP12 27.4-26.7 Sβδ+ 5B6XE + O13 24.7-24.1 SββXEXTable B Assignments of the1H NMR spectrum of Ethylene / Propylene / 1-Butene / 1-Hexene / 1-Octene copolymers containing PS and PETNumber Chemical Shift (ppm) Proton Sequencea 8.08 CH PETb 7.20 -6.81 CH PSc 6.81 -6.33 CH PSd 2.91 CH2AO1010 e 1.80 -0.70 CH + CH2+ CH3 Total aliphatic1.25 CH + CH2PSEXAMPLESPreparation of components (B)Component B) has been prepared as reported in example 1 of ep23168234.5FE7798 WO - Priority Text P2

[0114] The stabilizing additive composition comprised the following components:- 0.1% by weight of Irganox® 1010;- 0.1% by weight of Irgafos® 168; and- 0.04% by weight of DHT-4A (hydrotalcite);where all percentage amounts refer to the total weight of the polymer and stabilizing additive composition.

[0115] Irganox® 1010 is 2,2-bis[3-[,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)-1-oxopropoxy]methyl]-1,3-propanediyl-3,5-bis(1,1-dimethylethyl)-4-hydroxybenzene-propanoate, and Irgafos® 168 is tris(2,4-di-tert.-butylphenyl)phosphite.Table 1Component B)ExampleComponent bl)Ethylene content wt% 4.1Melting temperature °C 139.5 Component b2)split wt% 33Ethylene content in component b)* wt% 51.0Property of the compositionEthylene content wt% 19.6Ethylene content on the xylene wt% 46.9soluble fractiong / 10' 1.19MFR (230°C, 21.6 Kg)dl / g 8.8XSIV (intrinsic viscosity of XS)dl / g 8.23IV (whole composition)IV fraction insoluble in xylene at dl / g 7.8325°CEthylene content on the xylenewt%insoluble fraction 13.2Xylene soluble fraction Wt% 35.5FE7798 WO - Priority Text P2Component Al, A2 and A3Component a1) is a recycled propylene polymer Rpp sold by QCP under the tradename CR PP300P ivory content higher than 60 wt% and having the following features:Table 2MFR 2.16Kg / 230°C g / 10' 15.50XS % 9.80Tm °C 160.5; 125.0Tc °C 119.8; 109.5Ethylene %wt 7.54Butene %wt 0.13Hexene %wt 0.05PET %wt 0.01Styrene %wt 0.17Aluminum PPm 210Chlorine PPm 60Magnesium PPm 260Titanium PPm 3150Barium PPm - Calcium PPm 2500Cobalt PPm - Iron PPm 20Bromine PPm 10Chromium PPm - Fluorine PPm 350Phosphorus PPm 90Manganese PPm - Nichel PPm - Potassium PPm <10Copper PPm 10Silicon PPm 450Sodium PPm 40Lead PPm 10Zinc PPm 20Zirconium PPm <10Sulfur PPm 20

[0116] The FTIR spectrum of comprises at least two adsorption bands at least two wavenumbers (cm-1) selected from:FE7798 WO - Priority Text P23303 ±2 cm-1; 1726 ±2, 1642 ±2 cm-1; 1600 ±2 cm 1550 ±2 cm-1; 1491±2 cm-1; 1451±2 cm-1; 1726 ±2 cm-1; 1600 ±2 cm-1, 748 ±2 cm-1; 906 ±2 cm; 839 ±2 cm4, 818 ±2 cm4’ 748 ±2 cm4; 695 ±2 cm4Component a2) is a recycled polyethylene polymer RPE sold by QCP under the tradename CR HD5603 ivory having an ethylene content higher than 70%wt and a content of polypropylene of about 8 wt% and having the following properties:Table3MFI 2.16 Kg / 190°C g / 10 min 45.0MFP 5.0 Kg / 190°C g / 10 min 2.1Density g / cm3 0.956ISO 1183-1:2012 at23°CThe FTIR spectrum of comprises at least two adsorption bands at least two wavenumbers (cm-1) selected from:3303 ±2 cm-1; 1726 ±2, 1642 ±2 cm-1; 1600 ±2 cm41550 ±2 cm-1; 1491±2 cm-1; 1451±2 cm-1; 1726 ±2 cm-1; 1600 ±2 cm-1, 748 ±2 cm-1; 906 ±2 cm4; 839 ±2 cm4, 818 ±2 cm4;748 ±2 cm4; 695 ±2 cm4Blend of component al) and a2) have been made as reported in table 4Table 4Al A2 A3Unitsal Wt% 50 70 30a2 Wt% 50 30 70Melt Flow Rate g / lOmin 4.6 7.39 1.9Tensile Modulus N / mm2 1040 1030 990RES. CHARPY 23°C KJ / m2 5.6 7.3 28.3RES. CH ARP Y 0°C KJ / m2 3.8 4.5 4.8RES. CHARPY -20°C KJ / m2 2.5 2.7 3.6Elongation at break % 72.7 300 160FE7798 WO - Priority Text P2Component Al, A2 and A3 have been blended with 10 wt% of composition BTable 5Al A2 A3UnitsA Wt% 90 90 90B Wt% 10 10 10Melt Flow Rate g / lOmin 1.7 2.8 0.9Tensile Modulus N / mm2 990 1040 880RES.CHARPYKJ / m2 40.9 14.0 81.723°CRES.CHARPYKJ / m2 7.1 5.9 29.60°CRES.CHARPY - KJ / m2 4.4 3.6 5.720°CElongation at% 580 340 540breakFrom tables 4 and 5 it is evident that the features of the composition according to the invention are highly improved witht addition of 10 wt% of component B).

Claims

FE7798 WO - Priority Text P2CLAIMSWhat is claimed is:

1. A polyolefin composition comprising:(A) from 80 wt% to 97 wt%, of a polyolefin component containing:(al) from 20 wt% to 80 wt%, based on the sum of al)+a2) of a propylene based polymer having a propylene content higher than 60 wt%(a2) from 20 wt% to 80 wt% based on the sum of al)+a2) of an ethylene based polymer having an ethylene content higher than 70% wt;(B) from 3 wt% to 20 wt%, of a polypropylene ethylene copolymer comprising:bl) from 50 wt% to 80 wt%; based on the sum of bl)+b2) of a first copolymer of propylene with ethylene wherein:i) the content of ethylene derived units, measured by13C NMR, is comprised between 2.5 wt% and 6.5 wt%;b2) from 20 wt% to 50 wt%; based on the sum of bl)+b2) of a second propylene ethylene copolymer containing from 40.0 wt% to 65.0 wt%; of ethylene derived units, measured by13C NMR;wherein the polypropylene ethylene copolymer has:i) the content of ethylene derived units, measured by13C NMR, comprised between 12.0 wt% and 35 wt%;ii) the content of ethylene derived units, measured by13C NMR, in the fraction soluble in xylene at 25°C is comprised between 35.0 wt% and 56.0 wt%;iii) a melt flow rate (ISO 1133 (230° C, 21.6 kg), ranging from 0.1 g / lOmin to 3.0 g / 10 min; iv) the xylene solubles at 25°C ranges from 23 wt% to 43.0wt%;v) the intrinsic viscosity, measured in tetrahydronaphthalene at 135 °C, of the fraction soluble in xylene at 25°C ranges from 7.7 dl / g to 15.0 dl / g;vi) the intrinsic viscosity, measured in tetrahydronaphthalene at 135 °C, of the polypropylene ethylene copolymer B) ranges from 7.7 dl / g to 15.0 dl / g;the sum of the amounts of A) and B) being 100 wt%FE7798 WO - Priority Text P22. The polyolefin composition according to claim 1 wherein component A) ranges from 82 wt% to 95 wt% and component B) ranges from 5 wt% to 18 wt%.

3. The polyolefin composition according to claims 1 or 2 wherein in component A) component al) ranges from 30 wt% to 70 wt% and component a2) ranges from 30 wt% to 70 wt4. The polyolefin composition according to anyone of claims 1-3 wherein in component B) component bl) ranges from 57 wt% to 77 wt%; and component b2) ranges from 23 wt% to 43 wt%.

5. The polyolefin composition according to anyone of claims 1-4 wherein in component bl) the content of ethylene derived units, measured by13C NMR, is comprised between 3.5 wt% and 5.5 wt%.

6. The polyolefin composition according to anyone of claims 1-5 wherein in component b2) the content of ethylene derived units, measured by13C NMR is comprised from 45 wt% to 58 wt%.

7. The polyolefin composition according to anyone of claims 1-6 wherein in component B) the content of ethylene derived units, measured by13C NMR, is comprised between 15.0 wt% and 30 wt%.

8. The polyolefin composition according to anyone of claims 1-7 wherein in component B) the content of ethylene derived units, measured by13C NMR, in the fraction soluble in xylene at 25° is comprised between 38.0 wt% and 51.0 wt%.

9. The polyolefin composition according to anyone of claims 1-8 wherein in component B) a the melt flow rate (ISO 1133 (230° C, 21.6 kg), ranges from 0.5 g / lOmin to 2.5 g / 10 min.

10. The polyolefin composition according to anyone of claims 1-9 wherein in component B) the xylene solubles at 25°C ranges from 28 wt% to 40.0wt%.

11. The polyolefin composition according to anyone of claims 1-10 wherein in component B) the intrinsic viscosity, measured in tetrahydronaphthalene at 135 °C, of the fraction soluble in xylene at 25°C ranges from 7.9 dl / g to 13.0 dl / g.

12. The polyolefin composition according to anyone of claims 1-11 wherein in component B) the intrinsic viscosity, measured in tetrahydronaphthalene at 135 °C, of component B) ranges from 7.9 dl / g to 13.0 dl / g.FE7798 WO - Priority Text P213 The polyolefin composition according to anyone of claims 1-12 wherein the FTIR spectrum of film recorded as described in the example section of component A) comprises at least two adsorption bands at least two wavenumbers (cm-1) selected from: 3303 ±2 cm-1; 1726 ±2, 1642 ±2 cm-1; 1600 ±2 cm’11550 ±2 cm-1; 1491±2 cm-1; 145H2 cm-1; 1726 ±2 cm-1; 1600 ±2 cm-1, 748 ±2 cm-1; 906 ±2 cm'1; 839 ±2 cm'1, 818 ±2 cm'1;748 ±2 cm'1; 695 ±2 cm'114. The polyolefin composition according to anyone of claims 1-13 wherein in component B) the intrinsic viscosity, measured in tetrahydronaphthalene at 135 °C, of component B) ranges from 8.1 dl / g to 11.5 dl / g.

15. The polyolefin composition according to anyone of claims 1-14 wherein in component B) component bl) ranges from 63 wt% to 72 wt% and component b2) ranges from 28 wt% to 37 wt%.

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