EP4777569A1 - Polypropylene composition - Google Patents

Abstract

A polypropylene composition comprising: A) from 70 wt% to 90 wt% of a propylene 1-hexene copolymer containing from 0.5 wt% to 3.5 wt% of 1-hexene derived units, B) from 10 wt% to 30 wt%, of a copolymer of propylene and ethylene containing from 26.0 wt% to 40.0 wt%, of ethylene derived units.

Description

FE7659-EP-P1 TITLE POLYPROPYLENE COMPOSITION FIELD OF THE INVENTION [0001] The present disclosure relates to polypropylene composition containing 1-hexene derived units having broad molecular weight distribution and high melt strength. BACKGROUND OF THE INVENTION [0002] It is known in the art that the processability in the molten state of propylene homo- and copolymers is mainly influenced by the molecular weight, normally expressed in terms of melt flow rates (MFR), and the molecular weight distribution (MWD). The molecular weight distribution can be either expressed as the ratio of the weight average molecular weight Mw to the number average molecular weight Mn or as the Polydispersity Index (P.I.). [0003] Propylene polymers having broad molecular weight distribution or high Polydispersity Index have a lower melt viscosity than polymers having a narrow molecular weight distribution. As a result, said broad MWD propylene polymers flows more readily in thermoforming, injection molding, blow molding or stretch blow molding, coating and film conversion. [0004] However, for certain applications, such as polymer foams, products having different flowability in combination with high melt strength are particularly desirable. It is known in the art to produce said polymers by melt blending propylene polymer fractions having different molecular weight or to produce reactor-blends of said fractions in multi-step polymerization. [0005] EP 1899415 relates to Propylene homopolymers or copolymers containing up to 5.0 wt% of alpha-olefin units having from 2 to 8 carbon atoms other than propylene, characterized in that said propylene homopolymers or copolymers have Polydispersity Index value higher than 15 and a xylene soluble fraction of less than 4 wt%. However this document does not describes the polypropylene composition of the present disclosure. [0006] However there is the need to further polypropylene composition showing increased melt strength to be used in particular for foaming applications. FE7659-EP-P1 SUMMARY OF THE INVENTION [0007] The present disclosure provides a polypropylene composition comprising: A) from 70 wt% to 90 wt% of a propylene 1-hexene copolymer containing from 0.5 wt% to 3.5 wt% of 1-hexene derived units, measured by ¹³C NMR having: - fraction soluble in xylene at 25°C comprised between 1.5 wt% and 6.5 wt%; - melt flow rate (MFR L according to ISO 1133, condition L, i.e. 230°C and 2.16 kg load) ranging from 1.0 to 7.0 g/10 min; and a polydispersity index (PI) comprised between 9.2 and 16.3; B) from 10 wt% to 30 wt%, of a copolymer of propylene and ethylene containing from 26.0 wt% to 40.0 wt%, of ethylene derived units, measured by ¹³C NMR; wherein in the polypropylene composition: -the xylene soluble fraction at 25°C ranges from 14.0 wt% to 28.0 wt%; -the intrinsic viscosity of the fraction soluble in xylene at 25°C ranges from 4.0 dl/g to 6.5 dl/g; -the content of ethylene derived units, measured by ¹³C NMR in the fraction soluble in xylene at 25°C is lower than the content of ethylene derived units of component B) and ranges from 19.2 wt% to 37.3 wt%, -melt flow rate (MFR L according to ISO 1133, condition L, i.e.230°C and 2.16 kg load) ranges from 0.5 to 5.0 g/10 min and the sum of component A) and B) being 100. DETAILED DESCRIPTION OF THE INVENTION [0008] The present disclosure provides a polypropylene composition comprising: A) from 70 wt% to 90 wt%, preferably from 74 wt% to 86 wt% more preferably from 77 wt% to 82 wt% of a propylene 1-hexene copolymer containing from 0.5 wt% to 3.5 wt% preferably from 1.0 wt% to 2.9 wt%; more preferably from 1.2 wt% to 2.4 wt% of 1-hexene derived units , measured by ¹³C NMR having: - fraction soluble in xylene at 25°C comprised between 1.5 wt% and 6.5 wt%; preferably comprised between 1.8 wt% and 5.5 wt%; more preferably comprised between 2.1 wt% and 5.0 wt% FE7659-EP-P1 -melt flow rate (MFR L according to ISO 1133, condition L, i.e.230°C and 2.16 kg load) ranging from 1.0 to 7.0 g/10 min; preferably ranging from 1.50 to 6.5 g/10 min; and -polydispersity index (PI) comprised between 9.2 and 16.3; preferably comprised between 10.1 and 14.4; more preferably comprised between 10.7 and 13.2; B) from 10 wt% to 30 wt%, preferably from 14 wt% to 26 wt% more preferably from 18 wt% 23 wt% to of a copolymer of propylene and ethylene containing from 20.0 wt% to 40.0 wt%, preferably from 24.0 wt% to 38.0 wt%, more preferably from 28.0 wt% to 36.0 wt%, of ethylene derived units, measured by ¹³C NMR; wherein in the polypropylene composition: - the xylene soluble fraction at 25°C ranges from 10.0 wt% to 25.0 wt%; preferably from 16.0 wt% to 22.0 wt%; - the intrinsic viscosity of the fraction soluble in xylene at 25°C ranges from 4.0 dl/g to 6.5 dl/g; preferably from 4.5 dl/g to 6.0 dl/g; more preferably from 5.0 dl/g to 5.8 dl/g; and -the content of ethylene derived units, measured by ¹³C NMR in the fraction soluble in xylene at 25°C is lower than the content of ethylene derived units of component B) and ranges from 19.2 wt% to 37.3 wt%, preferably from 22.5 wt% to 35.3 wt%, more preferbaly from 24.7 wt% to 32.4 wt%, -melt flow rate (MFR L according to ISO 1133, condition L, i.e.230°C and 2.16 kg load) ranges from 0.5 g/10 min to 5.0 g/10 min, preferably from 0.8 g/10 min to 4.0 g/10 min, more preferably from 1.0 g/10 min to 2.0 g/10 min and the sum of component A) and B) being 100. [0009] For the purpose of the present disclosure the term copolymer has to be intended as a polymer containing only two kind if monomers such as propylene and ethylene or propylene and 1-hexene. [0010] Optionally the copolymer of propylene and ethylene component B) can contain up to 0.6 wt% of 1-hexene derived units. [0011] The composition of the present disclosure is endowed with high melt strength and therefore the polypropylene composition of the present disclosure is readily processable and have good flow properties in the molten state while retaining good mechanical properties, in particular high rigidity, high stress at yield high creep resistance and high heat distortion resistance. FE7659-EP-P1 [0012] The Melt Strength value is a measure of the applied linear force needed to break the polymer melt. [0013] The composition of the present disclosure is endowed with a very broad molecular distribution of molecular weight Mw/Mn. Thanks to broad molecular distribution of molecular weight, the processability of the polypropylene composition of the present disclosure is considerably improved. [0014] Preferably the composition of the present s preferably characterized by having one or more of the following properties: [0015] flexural modulus, measured according to ISO 178 e ISO 1873-2, comprised between 500 MPa and 1500 MPa; preferably comprised between 700 MPa and 1200MPa; [0016] charpy impact, measured according to ISO 179-1eA, e ISO 1873-2, measured at 23°C higher than 55.0 kJ/m²; preferably higher than 60 kJ/m²; more preferably higher than 73.0 kJ/m²; the highest value being 120 kJ/m²; [0017] charpy impact, measured according to ISO 179-1eA, e ISO 1873-2, measured at 0°C higher than 5.0 kJ/m²; preferably higher than 6.0 kJ/m²; more preferably higher than 8.0 kJ/m²; the highest value being 20.0 kJ/m²; [0018] charpy impact, measured according to ISO 179-1eA, e ISO 1873-2, measured at - 20°C higher than 4.0 kJ/m²; preferably higher than 5.0 kJ/m²; more preferably higher than 5.5 kJ/m²; the highest value being 15.0 kJ/m²; [0019] elongation at break, measured according to ISO 527-2, and ISO 1873-2, higher than 100 % preferably higher than 180 %, more preferably higher than 400 %; the higher value being 1000 %. [0020] Melting temperature measured by ISO 11357-3, ranging from 140°C to 160 °C; preferably form 142°C to 155°C. [0021] The polypropylene composition of the present disclosure is produced by sequential polymerization in at least two stages, with each subsequent polymerization stage being conducted in the presence of the polymeric material formed in the immediately preceding polymerization reaction, wherein the component (A) is normally prepared in at least one first polymerization stage and the component (B) is normally prepared in at least one second polymerization stage. FE7659-EP-P1 [0022] Component A) is produced in a polymerization process carried out in at least two interconnected polymerization zones. Said polymerization process is described in the European patent EP 782587 and in the International patent application WO00/02929. The process is carried out in a first and in a second interconnected polymerization zone to which propylene and ethylene or propylene and alpha-olefins are fed in the presence of a catalyst system and from which the polymer produced is discharged. The growing polymer particles flow through the first of said polymerization zones (riser) under fast fluidization conditions, leave said first polymerization zone and enter the second of said polymerization zones (downcomer) through which they flow in a densified form under the action of gravity, leave said second polymerization zone and are reintroduced into said first polymerization zone, thus establishing a circulation of polymer between the two polymerization zones. Generally, the conditions of fast fluidization in the first polymerization zone is established by feeding the monomers gas mixture below the point of reintroduction of the growing polymer into said first polymerization zone. The velocity of the transport gas into the first polymerization zone is higher than the transport velocity under the operating conditions and is normally between 2 and 15 m/s. In the second polymerization zone, where the polymer flows in densified form under the action of gravity, high values of density of the solid are reached which approach the bulk density of the polymer; a positive gain in pressure can thus be obtained along the direction of flow, so that it becomes possible to reintroduce the polymer into the first reaction zone without the help of mechanical means. In this way, a "loop" circulation is set up, which is defined by the balance of pressures between the two polymerization zones and by the head loss introduced into the system. Optionally, one or more inert gases, such as nitrogen or an aliphatic hydrocarbon, are maintained in the polymerization zones, in such quantities that the sum of the partial pressures of the inert gases is preferably between 5 and 80% of the total pressure of the gases. The operating parameters such as, for example, the temperature are those that are usual in gas-phase olefin polymerization processes, for example between 50°C and 120°C, preferably from 70°C to 90°C. The process can be carried out under operating pressure of between 0,5 and 10 MPa, preferably between 1.5 and 6 MPa. [0023] Preferably, the various catalyst components are fed to the first polymerization zone, at any point of said first polymerization zone. However, they can also be fed at any point of the second polymerization zone. FE7659-EP-P1 [0024] In the polymerization process means are provided which are capable of totally or partially preventing the gas and/or liquid mixture present in the raiser from entering the downcomer and a gas and/or liquid mixture having a composition different from the gas mixture present in the raiser is introduced into the downcomer. According to a preferred embodiment, the introduction into the downcomer, through one or more introduction lines, of said gas and/or liquid mixture having a composition different from the gas mixture present in the raiser is effective in preventing the latter mixture from entering the downcomer. The gas and/or liquid mixture of different composition to be fed to the downcomer can optionally be fed in partially or totally liquefied form. The molecular weight distribution and thus the P.I. value of the growing polymers can be conveniently tailored by carrying out the polymerization process in an reactor diagrammatically represented in Figure 4 of the International Patent Application WO00/02929 and by independently metering the comonomer(s) and customary molecular weight regulators, particularly hydrogen, in different proportion into at least one polymerization zone, preferably into the raiser. [0025] Component B) is prepared in the second stage the propylene/ethylene copolymer (B) is produced in a conventional fluidized-bed gas-phase reactor in the presence of the polymeric material and the catalyst system coming from the preceding polymerization step. [0026] Each polymerization stage is carried out in presence of a highly stereospecific heterogeneous Ziegler-Natta catalyst. The Ziegler-Natta catalysts suitable for producing the propylene polymer compositions of the invention comprise a solid catalyst component comprising at least one titanium compound having at least one titanium-halogen bond and at least an electron- donor compound (internal donor), both supported on magnesium chloride. The Ziegler-Natta catalysts systems further comprise an organo-aluminum compound as essential co-catalyst and optionally an external electron-donor compound. [0027] Suitable catalysts systems are described in the European patents EP45977, EP361494, EP728769, EP 1272533 and in the international patent application W000163261. [0028] The polypropylene composition object of the present disclosure is preferably obtainable by polymerizing propylene and ethylene in various stages in the presence of a catalyst system comprising the product obtained by contacting the following components: a) a solid catalyst component comprising a magnesium halide, a titanium compound having at least a Ti-halogen bond and at least one electron donor compound selected from succinates, FE7659-EP-P1 b) an aluminum hydrocarbyl compound, and c) optionally an external electron donor compound. [0029] In the solid catalyst component (a) the succinate is preferably selected from succinates of formula (I) [0030] in which the radicals R1 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 C₁- 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) [0031] R1 and R2 are preferably C1-C8 alkyl, cycloalkyl, aryl, arylalkyl and alkylaryl groups. Particularly preferred are the compounds in which R1 and R2 are selected from primary alkyls and in particular branched primary alkyls. Examples of suitable R1 and R2 groups are methyl, ethyl, n- propyl, n-butyl, isobutyl, neopentyl, 2-ethylhexyl. Particularly preferred are ethyl, isobutyl, and neopentyl. [0032] 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. [0033] 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- diisobutylsuccinate, diethyl 2,3-dineopentylsuccinate, diethyl 2,3-dicyclopentylsuccinate, diethyl 2,3-dicyclohexylsuccinate. FE7659-EP-P1 [0034] As explained above, the catalyst component (a) comprises, in addition to the above electron donors, a titanium compound having at least a Ti-halogen bond and a Mg halide. The magnesium halide is preferably MgCl2 in active form which is widely known from the patent literature as a support for Ziegler-Natta catalysts. Patents USP 4,298,718 and USP 4,495,338 were the first to describe the use of these compounds in Ziegler-Natta catalysis. It is known from these patents that the magnesium dihalides in active form used as support or co-support in components of catalysts for the polymerization of olefins are characterized by X-ray spectra in which the most intense diffraction line that appears in the spectrum of the non-active halide is diminished in intensity and is replaced by a halo whose maximum intensity is displaced towards lower angles relative to that of the more intense line. [0035] The preferred titanium compounds used in the catalyst component of the present invention are TiCl4 and TiCl3; furthermore, also Ti-haloalcoholates of formula Ti(OR)n-yXy can be used, where n is the valence of titanium, y is a number between 1 and n-1 X is halogen and R is a hydrocarbon radical having from 1 to 10 carbon atoms. [0036] Preferably, the catalyst component (a) has an average particle size ranging from 15 to 80 µm, more preferably from 20 to 70 µm and even more preferably from 25 to 65 µm. [0037] The alkyl-Al compound (b) is preferably chosen among the trialkyl aluminum compounds such as for example triethylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum. It is also possible to use mixtures of trialkylaluminum's with alkylaluminum halides, alkylaluminum hydrides or alkylaluminum sesquichlorides such as AlEt2Cl and Al2Et3Cl3. [0038] Preferred external electron-donor compounds include silicon compounds, ethers, esters such as ethyl 4-ethoxybenzoate, amines, heterocyclic compounds and particularly 2,2,6,6- tetramethyl piperidine, ketones and the 1,3-diethers. Another class of preferred external donor compounds is that of silicon compounds of formula R_a ⁵R_b ⁶Si(OR⁷)_c, where a and b are integer from 0 to 2, c is an integer from 1 to 3 and the sum (a+b+c) is 4; R⁵, R⁶, and R⁷, are alkyl, cycloalkyl or aryl radicals with 1-18 carbon atoms optionally containing heteroatoms. Particularly preferred are methylcyclohexyldimethoxysilane, diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-t-butyldimethoxysilane and 1,1,1,trifluoropropyl-2-ethylpiperidinyl-dimethoxysilane and 1,1,1,trifluoropropyl-metil- dimethoxysilane. The external electron donor compound is used in such an amount to give a molar FE7659-EP-P1 ratio between the organo-aluminum compound and said electron donor compound of from 5 to 500, preferably from 5 to 400 and more preferably from 10 to 200. [0039] The catalyst forming components can be contacted with a liquid inert hydrocarbon solvent such as, e.g., propane, n-hexane or n-heptane, at a temperature below about 60°C and preferably from about 0 to 30°C for a time period of from about 6 seconds to 60 minutes. [0040] The above catalyst components (a), (b) and optionally (c) can be fed to a pre- contacting vessel, in amounts such that the weight ratio (b)/(a) is in the range of 0.1-10 and if the compound (c) is present, the weight ratio (b)/(c) is weight ratio corresponding to the molar ratio as defined above. Preferably, the said components are pre-contacted at a temperature of from 10 to 20°C for 1-30 minutes. The precontact vessel is generally a stirred tank reactor. [0041] Preferably, the precontacted catalyst is then fed to a prepolymerization reactor where a prepolymerization step takes place. The prepolymerization step can be carried out in a first reactor selected from a loop reactor or a continuously stirred tank reactor, and is generally carried out in liquid-phase. The liquid medium comprises liquid alpha-olefin monomer(s), optionally with the addition of an inert hydrocarbon solvent. Said hydrocarbon solvent can be either aromatic, such as toluene, or aliphatic, such as propane, hexane, heptane, isobutane, cyclohexane and 2,2,4-trimethylpentane. The amount of hydrocarbon solvent, if any, is lower than 40% by weight with respect to the total amount of alpha-olefins, preferably lower than 20% by weight. Preferably said step (a) is carried out in the absence of inert hydrocarbon solvents. [0042] The average residence time in this reactor generally ranges from 2 to 40 minutes, preferably from 10 to 25 minutes. The temperature ranges between 10°C and 50°C, preferably between 15°C and 35°C. Adopting these conditions allows to obtain a pre-polymerization degree in the preferred range from 60 to 800g per gram of solid catalyst component, preferably from 150 to 500 g per gram of solid catalyst component. Step (a) is further characterized by a low concentration of solid in the slurry, typically in the range from 50 g to 300 g of solid per liter of slurry. [0043] The polypropylene composition of the present disclosure can be used for the manufacturing of foamed articles, such as laminated and un-laminated sheet, beads, and profiles. Foams having densities in the range from 30 to 700 Kg/m3, in particular from 100 to 600 Kg/m3, can be obtained from the polypropylene composition of the present disclosure, finding application FE7659-EP-P1 for thermal and electrical insulation, for noise and vibration damping, shock absorption and weight reduction. [0044] In particular they can find application in the automotive field for bumper interiors and impact panels, in marine field as floating devices or in electrical cables insulation. The polypropylene composition of the present disclosure may be manufactured into foamed article by conventional methods. They may be extruded in the presence of at least one foaming agent in conventional single screw or twin screw extruders, both in single and multilayer constructions. [0045] Foaming agents can be physical foaming agents, such as CO2, gaseous hydrocarbons, H2O, CFCs or mixtures thereof, or chemical foaming agents, such as inorganic carbonates, citric acid or their mixtures. Alternatively, The polypropylene composition of the present disclosure can be firstly pelletized and foamed and subsequently molded for the manufacturing of foamed polypropylene beads according to processes well known in the art. Foamed articles such as foamed coated or uncoated pipes and foamed packaging for foods can be manufactured using the polypropylene composition of the present disclosure. [0046] The following examples are given to illustrate and not to limit the present invention. EXAMPLES [0047] The data of the propylene polymer materials were obtained according to the following methods: Melt Flow Rate Determined according to ISO 1133 (230° C, 2.16 kg). Polydispersity index (P.I.) [0048] Some grams of molten homopolymer are submitted to a dynamic test in rate sweep with a parallel plate rheometer, at temperature of 200°C, according to the ISO 6721-10. G’ (storage modulus) and G” (loss modulus) are measured as function of frequency. From the rate sweep data, PI is defined by PI=105/Gc, wherein Gc is the crossover modulus as value of modulus at G’ = G”. 1-hexene content (C6 content) Determination of 1-hexene content by NMR [0049] ¹³C NMR spectra are acquired on an AV-600 spectrometer equipped with cryoprobe,operating at 150.91 MHz in the Fourier transform mode at 120 °C. The peak of the propylene CH was used as internal reference at 28.83. The 13C NMR spectrum is acquired using the following parameters: FE7659-EP-P1 Spectral width (SW) 60 ppm Spectrum centre (O1) 30 ppm Decoupling sequence WALTZ 65_64pl Pulse program ZGPG Pulse Length (P1) for 90° Total number of points (TD) 32K Relaxation Delay 15 s Number of transients 512 The total amount of 1-hexene as molar percent is calculated from identified diad present in the measured NMR using the following relations: [P] = PP + 0.5PH [H] = HH + 0.5PH Assignments of the ¹³C NMR spectrum of propylene/1-hexene copolymers have been calculated according to the following table: Area Chemical Shift Assignments Sequence 1 ^{46.93 – 46.00} _{S ^ ^} ^{PP 2 44.50 – 43.82} _{S ^ ^} ^{PH 3 41.34 -4.23} _{S ^ ^} ^{HH 4 38.00 - 37.40} _{S ^ ^+ S ^ ^} ^PE 5 35.70 -35.0 4B₄ H 6 ^{35.00 - 34.53} _{S ^ ^+ S ^ ^} ^HE 7 33.7533.20 CH H 8 ^33.24 _{T ^ ^} ^{EPE 9 30.92} _{T ^ ^} ^PPE 10 30.76 S _{^ ^} XEEX 1^{1 30.35} _{S ^ ^} ^{XEEE 12 29.95} _{S ^ ^} ^EEE 13 29.35 3B₄ H 14 28.94 – 28.38 CH P 15 27.43 – 27.27 S _{^ ^} XEE 1^{6 24.67 -24.53} _{S ^ ^} ^XEX 17 23.44 -23.35 2B₄ H 18 21.80 – 19.90 CH₃ P 19 14.22 CH₃ H FE7659-EP-P1 Determination of ethylene (C2) content by NMR ¹³C NMR of propylene/ethylene copolymers 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. It has been measured on the total composition. The ethylene content of component B) has been calculated by using the amount of component B) and component A) according to the following equation: C_2tot= C_2B x wt%compB/100. The samples were dissolved in 1,1,2,2-tetrachloroethane-d2 at 120°C with an 8% wt/v concentration. Each spectrum was acquired with a 90° pulse, 15 seconds of delay between pulses and CPD to remove ¹H-¹³C coupling.512 transients were stored in 32K data points using a spectral window of 9000 Hz. Diad distibution is calculated according to the following relations: PP = 100 I₁/ ^ PH = 100 I₂/ ^ HH = 100 I3/ ^ PE = 100 I4/ ^ HE = 100 I₆/ ^ EE = 100 (0.5( I13+ I16) +0.25 I12)/ ^ Where ^= I₁+ I₂+ I₃+ I₄ + I₆ +0.5( I₁₃+ I₁₆) +0.25 I₁₂ The total amount of 1-hexene and ethylene as molar percent is calculated from diad using the following relations: [P] = PP + 0.5PH + 0.5PE [H] = HH + 0.5PH + 0.5HE [E] = EE + 0.5PE + 0.5HE Assignments of the ¹³C NMR spectrum of propylene, 1-hexene and ethylene FE7659-EP-P1 Area Chemical Shift Assignments Sequence 1 ^{46.93 – 46.00} _{S ^ ^} ^{PP 2 44.17 – 43.82} _{S ^ ^} ^{PH 3 41.30} _{S ^ ^} ^HH 4 38.00 - 37.40 S _{^ ^}+ S _{^ ^} PE 5 35.70 4B₄ H 6 ^{35.00 - 34.53} _{S ^ ^+ S ^ ^} ^HE 7 33.75 CH H 8 ^33.24 _{T ^ ^} ^{EPE 9 30.92} _{T ^ ^} ^PPE 10 30.76 S _{^ ^} XEEX 1^{1 30.35} _{S ^ ^} ^{XEEE 12 29.95} _{S ^ ^} ^EEE 13 29.35 3B4 H 14 28.94 – 28.38 CH P 1^{5 27.43 – 27.27} _{S ^ ^} ^{XEE 16 24.67 -24.53} _{S ^ ^} ^XEX 17 23.36 2B4 H 18 21.80 – 19.90 CH3 P 19 14.22 CH3 H The molar percentage of ethylene content was evaluated using the following equation: E% mol = 100 * [PEP+PEE+EEE]. The weight percentage of ethylene content was evaluated using the following equation: 100 * E% mol * MWE E% wt. = --------------------------------------------------------------- E% mol * MWE + P% mol * MWP FE7659-EP-P1 where P% mol is the molar percentage of propylene content, while MW_E and MW_P are the molecular weights of ethylene and propylene, respectively. Molar ratios of the feed gases Determined by gas-chromatography. Samples for the mechanical analysis Samples have been obtained according to ISO 1873-2, Flexural Modulus Determined according to ISO 178. Melt strength [0050] Measure according to ISO 16790, the melt strength is the measure of the drawing and break characteristics of plastics through the measurement of the force (in newton) generated in deforming a molten filament under defined extrusion temperature and drawing conditions. Melting temperature, melting enthalpy and crystallization temperature [0051] Determined according to ISO 11357-3, at scanning rate of 20C/min both in cooling and heating, on a sample of weight between 5 and 7 mg. under inert N2 flow. Instrument calibration made with Indium. Xylene soluble and insoluble fractions at 25°C (room temperature) [0052] Xylene Solubles has been measured according to ISO 16152 Intrinsic Viscosity (I.V.) [0053] The sample is dissolved by tetrahydronaphthalene at 135 °C and then it is poured into the capillary viscometer. [0054] The viscometer tube (Ubbelohde type) is surrounded by a cylindrical glass jacket; this setup allows temperature control with a circulating thermostated liquid. [0055] The downward passage of the meniscus is timed by a photoelectric device. 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 IZOD impact strength [0056] Determined according to ISO 180/1A Charpy impact strenght [0057] Measured according to ISO 179-1eA, e ISO 1873-2, FE7659-EP-P1 Example 1 according to the invention Preparation of the solid catalyst component [0058] The Ziegler-Natta catalyst was prepared according to the Example 5, lines 48-55 of the European Patent EP728769. Triethylalurninium (TEAL) was used as co-catalyst and dicyclopentyldimethoxysilane as external donor. Polymerization [0059] The polymerization runs were conducted in continuous in a series of two reactors equipped with devices to transfer the product from one reactor to the one immediately next to it. The first reactor is a polymerisation apparatus as described in WO00/02929. [0060] The catalyst is sent to the polymerisation apparatus that comprises two interconnected cylindrical reactors, riser and downcomer. Fast fluidisation conditions are established in the riser by recycling gas from the gas-solid separator, “Barrier” effect has been activated. The obtained product is then feed to a fluid bed gas phase reactor. Hydrogen was used as molecular weight regulator. [0061] Component (A) is prepared in the first reactor, while component (B) is prepared in the second reactor. [0062] Hydrogen is used as molecular weight regulator. [0063] The gas phase (propylene, ethylene, 1-hexene and hydrogen) is continuously analyzed via gas-chromatography. [0064] At the end of the run the powder is discharged and dried under a nitrogen flow. [0065] The main polymerization conditions are reported in Table1.

FE7659-EP-P1 Table 1 E^xample ₁ Component A) (reactor MZCR) TEAL/external donor wt/wt 10 TEAL/catalyst wt/wt 4 Temperature °C 78 Pressure bar-g 25 Split holdup riser wt% 60 downcomer wt% 40 C₃- riser mole% 82.4 C6- riser mole% 1.25 H2/C3- riser mol/mol 0.05 C₆-/(C₆-+C₃-) riser mol/mol 0.017 C3- downcomer mole% 85 C₆- downcomer mole% 2.0 H2/C3- downcomer mol/mol 0.0003 C6-/(C6-+C3-) downcomer mol/mol 0.025 Component B (gas phase reactor) Temperature °C 78 Pressure MPa 20 C₂-/C₂-+C₃- mol/mol 0.2 H2/C2- mol/mol 0.012 C₂-= ethylene C₃- = propylene C₃- 1-hexene The polymers features are reported in table 2 FE7659-EP-P1 Table 2 E_xample ^{Ex1 comp Ex 2} C_{omponent a) Copolymer content} ^{wt% 78 79} 1_{-hexene content} ^{wt% 1.7 1.6} M_FR ^{g/10' 3.5 5} X_{ylene soluble at 25°C} ^{wt% 2.8 4.9} P_{olydisperity (P.I.)} ^{11.5 12.9} C_{omponent b) Copolymer content} ^{wt% 22 21} E_{thylene content in component b)} ^{wt% 32 57.3} P_{roperty of the composition Xylene soluble at 25°C} ^{wt% 24.4 19.8} M_FR ^{g/10' 1.2 1.6} X_{SIV (intrinsic viscosity of XS)} ^{dl/g 5.48 4.41} Ethylene content on the xylene Wt% 27.6 47.8 soluble fraction Flexural Modulus MPa 910 930 charpy impact at 23 °C KJ/m² 85.7 14.4 charpy impact at 0 °C KJ/m² 10.9 6.6 charpy impact at -20 °C KJ/m² 6.9 5.3 Elongation @ break % 500 14.4 Melting temperature °C 148.0 148.5 [0066] comparative example 2 is example 1 of WO 2022/002514 [0067] The compositions of examples 1, and comparative example 2 have been blended with a standard additivation package. Foaming [0068] Foils were produced PM chill roll foil line with an extruder configuration of Ø 30 mm, L/D 25:1 and flat die of width 350 mm and gap opening of 1 mm. The chemical blowing agent (CBAs) used is HYDROCEROL® CT 660 from Clariant at 2% loading. The foils were produced using bell-shaped temperature profiles, adjusted individually for each sample. FE7659-EP-P1 [0069] Foaming trials [0070] Foaming trials were made on a KMB tandem extrusion line equipped with a circular die Ø=40 mm a cooled mandrel Ø=140 mm, control cabinet and take-off unit. The melt was nucleated using 1 wt% of tale and isobutane was used as the physical blowing agent. [0071] The results of the foaming trials are reported in table 3 Table 3 melt pressure melt temperature Isobutane Nucleation density Optical Impact [^{bar] [°C] [%] [talc %] [g/ml] appearance* properties} E_{X 1 15 182 3.5% 1% 0.21 + + + + comp ex 2 15 187 3.5% 1% 0.31 - +} ++ good + sufficient - poor density, impact appearance and impact properties have bene improved in the polymer of example 1

Claims

FE7659-EP-P1 CLAIMS What is claimed is: 1. A polypropylene composition comprising: A) from 70 wt% to 90 wt% of a propylene 1-hexene copolymer containing from 0.5 wt% to 3.5 wt% of 1-hexene derived units, measured by ¹³C NMR having: - fraction soluble in xylene at 25°C comprised between 1.5 wt% and 6.5 wt%; - melt flow rate (MFR L ISO 1133, condition L, i.e.230°C and 2.16 kg load) ranging from 1.0 to 7.0 g/10 min; and - a polydispersity index (PI) comprised between 9.2 and 16.3; B) from 10 wt% to 30 wt%, of a copolymer of propylene and ethylene containing from 26.0 wt% to 40.0 wt%, of ethylene derived units, measured by ¹³C NMR; Wherein in the polypropylene composition: -the xylene soluble fraction at 25°C ranges from 14.0 wt% to 28.0 wt%; -the intrinsic viscosity of the fraction soluble in xylene at 25°C ranges from 4.0 dl/g to 6.5 dl/g; -the content of ethylene derived units in the fraction soluble in xylene at 25°C, measured by 1³C NMR is lower than the content of ethylene derived units of component B) and ranges from 19.2 wt% to 37.3 wt, -melt flow rate (MFR L according to ISO 1133, condition L, i.e.230°C and 2.16 kg load) ranges from 0.5 to 5.0 g/10 min and the sum of component A) and B) being 100 2. The polypropylene composition according to claim 1 wherein component (A) ranges from from 74 wt% to 86 wt% and component B) ranges from 14 wt% to 26 wt%. 3. The polypropylene composition according to claims 1 or 2 wherein in component A) the propylene 1-hexene copolymer contains from 1.0 wt% to 2.9 wt%. 4. The polypropylene composition according to anyone of claims 1-3 wherein component A) has a polydispersity index (PI) comprised between 10.1 and 14.4. 5. The polypropylene composition according to anyone of claims 1-4 wherein component A) has the fraction soluble in xylene at 25°C comprised between 1.8 wt% and 5.5 wt%. FE7659-EP-P1 6. The polypropylene composition according to anyone of claims 1-5 wherein the copolymer of propylene and ethylene of component B) contains from 24.0 wt% to 38.0 wt% of ethylene derived units . 7. The polypropylene composition according to anyone of claims 1-6 wherein the xylene soluble fraction at 25°C ranges from 16.0 wt% to 22.0 wt%. 8. The polypropylene composition according to anyone of claims 1-7 wherein the intrinsic viscosity of the fraction soluble in xylene at 25°C ranges from 4.5 dl/g to 6.0 dl/g. 9. The polypropylene composition according to anyone of claims 1-8 wherein the content of ethylene derived units in the fraction soluble in xylene at 25°C ranges from 22.5 wt% to 35.3 wt%. 10. The polypropylene composition according to anyone of claims 1-9 wherein the intrinsic viscosity of the fraction soluble in xylene at 25°C ranges from 5.0 dl/g to 5.8 dl/g. 11. The polypropylene composition according to anyone of claims 1-10 wherein the content of ethylene derived units in the fraction soluble in xylene at 25°C ranges from 24.7 wt% to 32.4 wt%. 12. The polypropylene composition according to anyone of claims 1-11 wherein the melt flow rate (MFR L according to ISO 1133, condition L, i.e. 230°C and 2.16 kg load) ranges from from 0.8 g/10 min to 4.0 g/10 min 13. The polypropylene composition according to anyone of claims 1-2 wherein the intrinsic viscosity of the fraction soluble in xylene at 25°C ranges from 5.0 dl/g to 5.8 dl/g 14. The polypropylene composition according to anyone of claims 1-13 wherein the copolymer of propylene and ethylene of component B) contains from 28.0 wt% to 36.0 wt%, of ethylene derived units. 15. Foamed articles comprising the polypropylene composition of claims 1-14.