Process for preparing random propylene-ethylen copolymer composition

Abstract

The invention relates to Process for the preparation of a polypropylene composition comprising a propylene-based polymer which is a propylene-ethylene copolymer having an ethylene content between 2.0 wt% and 5 wt% based based on the propylene-ethylene copolymer, wherein the polypropylene composition has - a melt flow rate (MFR) in the range from 1 to 80 g / 10min, wherein the melt flow rate is determined using ISO1133-1:2011 using 2.16kg at 230°C, wherein the process comprises the step of polymerizing propylene and optional ethylene comonomers in the presence of a catalyst in a gas phase to obtain the propylene-based polymer, wherein said catalyst comprises a procatalyst, a co-catalyst and optionally an external electron donor, wherein the procatalyst is obtainable by a process comprising the steps of: contacting a magnesium-containing support with a halogen-containing titanium compound, and an internal electron donor according to Formula (I), wherein R1 is a secondary alkyl group and R2 is a non-secondary alkyl group having at least 5 carbon atoms, preferably R2 is a non-secondary alkyl group being branched at the 3-position or further positions; said procatalyst is prepared according to the following steps: i) contacting a compound R4 zMgX4 2-z with an alkoxy- or aryloxy-containing silane compound to give a first intermediate reaction product, being a solid Mg(OR8)xX1 2-x, wherein: Ra is a linear, branched or cyclic hydrocarbyl group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof; wherein said hydrocarbyl group may be substituted or unsubstituted, may contain one or more heteroatoms and preferably has from 1 to 20 carbon atoms; wherein R4 is a linear, branched or cyclic hydrocarbyl group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof; wherein said hydrocarbyl group may be substituted or unsubstituted, may contain one or more heteroatoms and preferably has from 1 to 20 carbon atoms, preferably R4 is butyl; wherein X4 and Х1 are each independently selected from the group of consisting of fluoride (F−), chloride (Cl−), bromide (Br−) or iodide (I−), preferably chloride; z is in a range of larger than 0 and smaller than 2, being 0 < z < 2, x is an integer between 0 and 2; ii) optionally contacting the solid Mg(ORa)xX1 2-x obtained in step i) with at least one activating compound selected from the group formed by activating electron donors and metal alkoxide compounds of formula M1(ORb)v-w(OR3)w or M2(ORb)v-w(R3)w, to obtain a second intermediate product; wherein: M1 is a metal selected from the group consisting of Ti, Zr, Hf, Al or Si; v is the valency of M1; M2 is a metal being Si; v is the valency of M2; Rb and R3 are each a linear, branched or cyclic hydrocarbyl group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof; wherein said hydrocarbyl group may be substituted or unsubstituted, may contain one or more heteroatoms, and preferably has from 1 to 20 carbon atoms; wherein w is smaller than v, preferably v being 3 or 4; iii) contacting the first or second intermediate reaction product, obtained respectively in step i) or ii), with a halogen-containing Ti-compound and said compound represented Formula (I), as the internal electron donor.

Description

PROCESS FOR PREPARING RANDOM PROPYLENE-ETHYLEN COPOLYMER COMPOSITIONTECHNICAL FIELD

[0001] The present invention relates to a process for the preparation of a composition comprising a propylene-based polymer which is a propylene-ethylene copolymer having an ethylene content between 2.0 wt% and 5 wt% based on the propylene-ethylene copolymer.

[0002] Further, the present invention is also directed to an article comprising the inventive polypropylene composition. Further, the invention relates to the use of said polypropylene composition as well as to a process for the preparation of said article. The invention further relates to use of the inventive polypropylene composition for compounding with a further polymer or making masterbatches.BACKGROUND

[0003] Polymers, like polypropylene, are increasingly used in different demanding applications. At the same time, there is a continuous search for tailored polymers which meet the requirements of these applications, for instance of good transparency and low blooming (as enabled by low CXS). In addition, there is a continuous drive for high yield processes as this is economically more favorable.

[0004] Therefore, there is a need in the art for a process for the preparation of a polypropylene composition comprising a propylene-based polymer which is a propylene-ethylene copolymer having an ethylene content between 2.0 wt% and 5 wt% based on the propylene-ethylene copolymer having good transparency and low blooming which can be produced with a high catalyst yield.SUMMARY

[0005] It is therefore an object of the present invention to provide a process for the preparation of a polypropylene composition comprising a propylene-basedpolymer which is a propylene-ethylene copolymer having an ethylene content between 2.0 wt% and 5 wt% based on the propylene-ethylene copolymer having a good transparency and low blooming which can be produced with a high catalyst yield.

[0006] This object is achieved by a process for the preparation of a polypropylene composition comprising a propylene-based polymer which is a propylene-ethylene copolymer having an ethylene content between 2.0 wt% and 5 wt% based on the propylene-ethylene copolymer, wherein the polypropylene composition has preferably at least than 95wt%, more preferably at least than 96wt%, even more preferably at least than 97wt%, even more preferably at least than 97.5wt% of propylene-based polymer based on the composition and:• a melt flow rate (MFR) in the range from 1 to 80 g / 10min, wherein the melt flow rate is determined using ISO1133-1 :2011 using 2.16kg at 230°C and wherein the process comprises the step of polymerizing propylene and ethylene comonomers in the presence of a catalyst in a gas phase to obtain the propylene- based polymer, wherein said catalyst comprises a procatalyst, a co-catalyst and optionally an external electron donor, wherein the procatalyst is obtainable by a process comprising the steps of: contacting a magnesium-containing support with a halogen-containing titanium compound, and an internal electron donor according to Formula I:Formula I wherein R1is a secondary alkyl group and R2is a non-secondary alkyl group having at least 5 carbon atoms, preferably R2is a non-secondary alkyl group being branched at the 3-position or further positions; said procatalyst is prepared according to the following steps:i) contacting a compound R4zMgX42-z with an alkoxy- or aryloxy-containing silane compound to give a first intermediate reaction product, being a solid Mg(ORa)xX12-x, wherein: Rais a linear, branched or cyclic hydrocarbyl group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxy carbonyl or alkylaryl groups, and one or more combinations thereof; wherein said hydrocarbyl group may be substituted or unsubstituted, may contain one or more heteroatoms and preferably has from 1 to 20 carbon atoms; wherein R4is a linear, branched or cyclic hydrocarbyl group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof; wherein said hydrocarbyl group may be substituted or unsubstituted, may contain one or more heteroatoms and preferably has from 1 to 20 carbon atoms, preferably R4is butyl; wherein X4and X1are each independently selected from the group of consisting of fluoride (F-), chloride (Cl—), bromide (Br-) or iodide (I-), preferably chloride; z is in a range of larger than 0 and smaller than 2, being 0 < z < 2, x is an integer between 0 and 2; ii) optionally contacting the solid Mg(ORa)xX12-x obtained in step i) with at least one activating compound selected from the group formed by activating electron donors and metal alkoxide compounds of formula M1(0Rb)v-w(0R3)w or M2(ORb)v-w(R3)w, to obtain a second intermediate product; wherein: M1is a metal selected from the group consisting of Ti, Zr, Hf, Al or Si; v is the valency of M1; M2is a metal being Si; v is the valency of M2; Rband R3are each a linear, branched or cyclic hydrocarbyl group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof; wherein said hydrocarbyl group may be substituted or unsubstituted, may contain one or more heteroatoms, and preferably has from 1 to 20 carbon atoms; wherein w is smaller than v, preferably v being 3 or 4; iii) contacting the first or second intermediate reaction product, obtained respectively in step i) or ii), with a halogen-containing Ti-compound and said compound represented Formula I, as the internal electron donor.

[0007] The invention further provides the polypropylene composition obtainable by or obtained by the process according to the invention.

[0008] The invention further provides a polypropylene composition comprising a propylene-based polymer which is a propylene-ethylene copolymer having an ethylene content between 2.0 wt% and 5 wt% based on the propylene-ethylene copolymer, wherein the polypropylene composition has a melt flow rate (MFR) in the range from 1 to 80 g / 10min, wherein the melt flow rate is determined using ISO1133-1 :2011 using 2.16kg at 230°C and wherein the amount of Ti in the propylene-based polymer is at most 1.4 mg per 1 kg of the propylene-based polymer as determined by Inductively coupled plasma mass spectrometry (ICP-MS).

[0009] According to the invention, it was surprisingly found that the use of a specific catalyst in the process for the preparation of a propylene-based polymer results in a combination of a high catalyst yield and low CXS even at higher MFR’s. Due to the use of such low amounts of catalyst, a polypropylene composition can be produced having very low amounts of Ti. Therefore, in a further aspect, the invention provides a polypropylene composition having a low amount of Ti from the catalyst used in the preparation of the composition, which is advantageous for the high purity of the composition.DESCRIPTION OF EMBODIMENTSPropylene-based polymer

[0010] The polypropylene composition according to the invention comprises a propylene-based polymer which is a propylene-ethylene copolymer having an ethylene content between 2.0 wt% and 5 wt% based on the propylene-ethylene copolymer.

[0011] Preferably, the polypropylene composition has a melt flow rate (MFR) from 1 to 80 g / 10min, preferably in the range of 1 to 60, more preferably 1 to 50as determined according to ISO1133-1 :2011 using 2.16kg at 230°C.

[0012] Preferably, the random propylene-ethylene copolymer has a cold xylene soluble content (CXS) from 3.0 to 8.0 wt%, preferably from 3.7 to 6.9 wt%, preferably in the range from 4.6 to 6.9 wt%, even more preferably in the range from 5.0 to 6.4 wt%, as measured by the method described in the section “CRYSTEX method for propylene homopolymer” of the Measurement methods section of the present disclosure.

[0013] Preferably, the polypropylene composition has a molecular weight distribution (Mw / Mn) in the range from 1.0 to 11.0, more preferably in the range from 4.0 to 9.0, wherein Mw stands for the weight average molecular weight and Mn stands for the number average weight and wherein Mw and Mn are measured according to IS016014-1 (4):2003.Process for the preparation of the propylene-based polymer

[0014] The person skilled in the art is aware of how to prepare a propyleneethylene copolymer. The preparation of propylene homopolymers and propyleneethylene copolymers is for example described in Moore, E. P. (1996) Polypropylene Handbook. Polymerization, Characterization, Properties, Processing, Applications, Hanser Publishers: New York.Catalyst

[0015] The catalyst used for the preparation for the polypropylene composition according to the invention is the catalyst described in detail in WO2021 / 063930, incorporated herein by reference. The catalyst comprises a procatalyst, a cocatalyst and optionally an external electron donor.

[0016] The procatalyst is obtainable by a process comprising contacting a magnesium-containing support with a halogen-containing titanium compound, and an internal electron donor according to Formula I:Formula I wherein R1is a secondary alkyl group and R2is a non-secondary alkyl group having at least 5 carbon atoms, preferably R2is a non-secondary alkyl group having at least 5 carbon atoms and being branched at the 3-position or further positions.

[0017] The process for providing said procatalyst follow the one describe in W02021 / 063930A1 (which in incorporated by reference) and comprises the steps of: i) contacting a compound R4zMgX42-z with an alkoxy- or aryloxy-containing silane compound to give a first intermediate reaction product, being a solid Mg(ORa)xX12-x, wherein: Rais a linear, branched or cyclic hydrocarbyl group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof; wherein said hydrocarbyl group may be substituted or unsubstituted, may contain one or more heteroatoms and preferably has from 1 to 20 carbon atoms; wherein R4is a linear, branched or cyclic hydrocarbyl group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof; wherein said hydrocarbyl group may be substituted or unsubstituted, may contain one or more heteroatoms and preferably has from 1 to 20 carbon atoms, preferably R4is butyl; wherein X4and X1are each independently selected from the group of consisting of fluoride (F-), chloride (Cl—), bromide (Br-) or iodide (I-), preferably chloride; z is in a range of larger than 0 and smaller than 2, being 0 < z < 2, x is an integer between 0 and 2;ii) optionally contacting the solid Mg(ORa)xX12-x obtained in step i) with at least one activating compound selected from the group formed by activating electron donors and metal alkoxide compounds of formula M1(0Rb)v-w(0R3)w or M2(ORb)v-w(R3)w, to obtain a second intermediate product; wherein: M1is a metal selected from the group consisting of Ti, Zr, Hf, Al or Si; v is the valency of M1; M2is a metal being Si; v is the valency of M2; Rband R3are each a linear, branched or cyclic hydrocarbyl group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof; wherein said hydrocarbyl group may be substituted or unsubstituted, may contain one or more heteroatoms, and preferably has from 1 to 20 carbon atoms; wherein w is smaller than v, preferably v being 3 or 4; iii) contacting the first or second intermediate reaction product, obtained respectively in step i) or ii), with a halogen-containing Ti-compound and said compound represented Formula I, as the internal electron donor.

[0018] In an embodiment, during step ii) as activating compounds an alcohol is used as activating electron donor and titanium tetraalkoxide is used as metal alkoxide compound.

[0019] In an embodiment, an activator is present.

[0020] In an embodiment, said activator is ethyl benzoate.

[0021] In an embodiment, said activator is a benzamide according to formula X:Formula Xwherein R70and R71are each independently selected from hydrogen or an alkyl, and R72, R73, R74, R75, R76are each independently selected from hydrogen, a heteroatom or a hydrocarbyl group, preferably selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof, more preferably wherein R70and R71are both methyl and wherein R72, R73, R74, and R75are all hydrogen, being N,N’-dimethylbenzamide (Ba-2Me).

[0022] Preferably, the internal electron donor used is according to Formula I:Formula I wherein R1is a secondary alkyl group having at least three carbon atoms and R2is a non-secondary alkyl group having at least 5 carbon atoms, preferably R1et R2is having at most seven carbon atoms, preferably at most six carbon atoms , preferably iso-propyl, iso-butyl, iso-pentyl, cyclopentyl, n-pentyl, and iso-hexyl, preferably R2is being branched at the 3-position or further positions.

[0023] In another embodiment, the internal electron donor is 3,3- bis(methoxymethyl)-2,6-dimethyl heptane, according to Formula I wherein R1 is iso-propyl being secondary alkyl and R2 is iso-pentyl being non-secondary and having a branch on the third carbon atom (abbreviated as iPiPen, wherein iP stands for iso-propyl and iPen stands for iso-pentyl, also known as 3-methyl-butyl). This compound iPiPen has a chemical formula of C13H28O2; an exact mass of 216.21 and a molecular weight of 216.37. In a more preferred embodiment of the invention, iPiPen is used as internal donor and / or wherein the activating compound is preferably N,N-dimethylbenzamide.iPiPen

[0024] In another embodiment, the internal electron donor is (1 -methoxy-2- (methoxymethyl)-5-methylhexan-2-yl)cyclopentane, according to Formula I wherein R1is secondary alkyl cyclopentyl and R2is secondary cyclopentyl (abbreviated as CPiPen, wherein CP stands for cyclopentyl and iPen stands for iso-pentyl, also known as 3-methyl-butyl). This compound CPiPen has a chemical formula of C15H30O2; an exact mass of 242.22 and a molecular weight of 242.40. In a more specific embodiment, CPiPen is used as internal donor and / V, / V-dimethylbenzamide is preferably used as activator.CPiPen

[0025] In another embodiment, the internal electron donor is 3,3- bis(methoxymethyl)-2,7-dimethyloctane, according to Formula I wherein R1is the secondary alkyl iso-propyl and R2is non-secondary iso-hexyl with a branch on the four carbon atom (abbreviated as iPiHex, wherein iP stands for iso-propyl and iHex stands for iso-hexyl, also known as 4-methyl-pentyl). This compound iPiHex has a chemical formula of C14H30O2 ; an exact mass of 230.22 and a molecular weight of 230.39. In a more specific embodiment, iPiHex is used as internal donor and / V, / V-dimethylbenzamide is preferably used as activator.iPiHex

[0026] In another embodiment, the internal electron donor is 3,3- bis(methoxymethyl)-2-methyloctane, according to Formula I wherein R1issecondary alkyl iso-propyl and R2is non-secondary non-branched n-pentyl (abbreviated as iPnPen, wherein iP stands for iso-propyl and nPen stands for n- pentyl). This compound iPnPen has a chemical formula of C13H28O2 ; an exact mass of 216.21 and a molecular weight of 216.37. In a more specific embodiment, iPnPen is used as internal donor and / V, / V-dimethylbenzamide is preferably used as activator.iPnPen

[0027] In another embodiment, the internal electron donor is 3,3- bis(methoxymethyl)-2,6-dimethyloctane, according to Formula I wherein R1is secondary alkyl iso-propyl and R2is non-secondary branched hexyl having a branch at the third carbon atom (abbreviated as iP3Hex, wherein iP stands for isopropyl and wherein 3Hex stands for hexyl having a branch at the third carbon atom, also known as 3-methyl-pentyl). This compound iPiHex has a chemical formula of C14H32O2 ; an exact mass of 230.22 and a molecular weight of 230.39. In a more preferred embodiment, iP3Hex is used as internal donor and / or / V, / V-dimethylbenzamide is preferably used as activator.iP3Hex

[0028] In another embodiment, the procatalyst used according to the present invention provides a polymer yield of at least 50 kg polymer per gram of procatalyst used.

[0029] In an embodiment, the substituent R1is isopropyl or cyclopentyl. In an embodiment, the substituent R2is isopentyl or isohexyl. The below table showsthe embodiments above with their abbreviations and the R1and R2groups as well if these groups are secondary or not and branched or not.

[0030] According to the present invention, it is further preferred that R1is a secondary alkyl group and R2is a non-secondary alkyl group being branched at the 3-position or further positions.

[0031] Preferably, the catalyst comprises the external electron donor and the molar ratio of co-catalyst to external electron donor is more than 1 and at most 160 or more than 1 and at most 120, or more than 1 and at most 90. in the range from 1 to 25, or from 1 to 15, or from 1 to 10, or from 2 to 8, or from 2 to 5.

[0032] Preferably, the co-catalyst is selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, diisobutylaluminum hydride, trioctylaluminium, dihexylaluminum hydride and mixtures thereof.

[0033] Preferably, the external electron donors are chosen from the group of compounds having a structure according to:- Formula III : (R90)2N— Si(OR91)3,- Formula IV: (R92)Si(OR93)3,Formula V: Si(ORa)4-nRbn, and- mixtures thereof, wherein each of R90, R91, R92and R93groups are each independently a linear, branched or cyclic, substituted or unsubstituted alkyl having between 1 and 10 carbon atoms, preferably wherein R90, R91, R92and R93groups are each independently a linear unsubstituted alkyl having between 1 and 8 carbon atoms,wherein n can be from 0 up to 2, and each of Raand Rb, independently, represents an alkyl or aryl group, optionally containing one or more hetero atoms for instance 0, N, S or P, with, for instance, 1 -20 carbon atoms

[0034] Preferably, the molar ratio of Al in the co-catalyst to Si in the external electron donor is more than 1 and at most 160 or more than 2 and at most 120, or more than 3 and at most 90.

[0035] for example ethyl, methyl or n-propyl, for example diethylaminotriethoxysilane (DEATES), n-propyl triethoxysilane, (nPTES), n- propyl trimethoxysilane (nPTMS); and organosilicon compounds having general formula Si(ORa)4-nRbn, wherein n can be from 0 up to 2, and each of Raand Rb, independently, represents an alkyl or aryl group, optionally containing one or more hetero atoms for instance O, N, S or P, with, for instance, 1 -20 carbon atoms; such as diisobutyl dimethoxysilane (DiBDMS), t-butyl isopropyl dimethyxysilane (tBuPDMS), cyclohexyl methyldimethoxysilane (CHMDMS), dicyclopentyl dimethoxysilane (DCPDMS) or di(iso-propyl) dimethoxysilane (DiPDMS). More preferably, the external electron donor is chosen from the group of di(iso-propyl) dimethoxysilane (DiPDMS) or diisobutyl dimethoxysilane (DiBDMS).

[0036] Preferably, the external donor comprises or consists of a compound selected from the list comprising organo-silicon compounds, silanes, alkoxy silanes, alkyl silane, alkyl alkoxy silane and aliphatic / aromatic ester, for example dicyclopentyldimethoxysilane, di-tert-butyldimethoxysilane, methylcyclohexyldimethoxysilane, ethylcyclohexyldimethoxysilane, diphenyldimethoxysilane, diisopropyldimethoxysilane, di-n-propyldimethoxysilane, diisobutyldimethoxysilane, di-n-butyldimethoxysilane, cyclopentyltrimethoxysilane, isopropyltrimethoxysilane, npropyltrimethoxysilane, n-propyltriethoxysilane, ethyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, cyclopentylpyrrolidinodimethoxysilane, bis(pyrrolidino )-dimethoxysilane, and mixtures thereof, preferentially di(iso-propyl) dimethoxysilane (DiPDMS)

[0037] The compounds mentioned above as examples of the external electron donor are sometimes referred as Selectivity Control Agent (SCA). The external electron donor may consist of SCA. Alternatively, in addition to SCA, the external electron donor may further comprise compounds known as an activity limiting agent (ALA). Preferably, the Activity Limiting Agent (ALA) is selected from the group consisting of: ethyl acetate, ethyl benzoate, p-ethoxy ethyl benzoate, methyl trimethylacetate, isopropyl myristate, di-n-butyl sebacate, (poly)(alkylene glycol) mono- or diacetates, (poly)(alkylene glycol) mono- or di-myristates, (poly)(alkylene glycol) mono- or di- laurates, (poly)(alkylene glycol) mono- or di-dioleates, glyceryl tri(acetate), mixed glycerides of linoleic, oleic, palmitic and stearic acids, and mixtures thereof. More preferably, the Activity Limiting Agent (ALA) is isopropyl myristate.

[0038] The ratio of Selectivity Control Agent (SCA) to Activity Limiting Agent (ALA) is in principle not critical, best results are obtained for a SCA / ALA ratio in the range from 0.010 to 100, more preferably in the range from 0.10 to 20.

[0039] The molar ratio of Al in the co-catalyst to Si in the external electron donor may e.g. be 1 to 25.

[0040] In some preferred embodiments, the molar ratio of Al in the co-catalyst to Si in the external electron donor is 1 to 15, preferably 1 to 10, preferably 2 to 8, preferably 2 to 5.

[0041] The relatively low molar ratio of Al / Si results in a composition with lower cxs.

[0042] In some preferred embodiments, the molar ratio of Al in the co-catalyst to Si in the external electron donor is more than 3 and at most 40.

[0043] The relatively high molar ratio of Al / Si results in a higher catalyst yield.

[0044] In addition surprisingly the process according to the invention allow to keep high catalyst yield with a high MFR, while it is decreasing with higher MFR when using known catalyst systems from the prior art.Catalyst yield (CY) Ti (KgPP / gcat):

[0045] In a preferred embodiment, the process has CY Ti (KgPP / gcat) of at least 25, more preferably at least 30, more preferably at least 35, more preferably at least 40, wherein CY Ti (KgPP / gcat) is calculated following Equation (1 ):wherein Ti content in the catalyst and Ti content in the obtained polymer is determined by Inductively coupled plasma mass spectrometry (ICP-MS).

[0046] Preferably, the amount of Ti in the propylene-based polymer is at most at most 1.4 mg / kg, preferably 1.2 mg / kg, preferably 1.0, preferably 0.5 mg / kg of the propylene-based polymer as determined by Inductively coupled plasma mass spectrometry (ICP-MS)Composition

[0047] The polypropylene composition has a melt flow rate (MFR) in the range from 1 to 80 g / 10min, wherein the melt flow rate is determined using ISO1133-1 :2011 using 2.16kg at 230°C. In some preferred embodiments, the MFR of the polypropylene composition determined using ISO1133-1 :2011 using 2.16kg at 230°C is 1 to 45 g / 10min. In some preferred embodiments, the MFR of the polypropylene composition determined using ISO1133-1 :2011 using 2.16kg at 230°C is 45 to 80 g / 10min.

[0048] Preferably, the amount of propylene-based polymer is at least 95 wt%, more preferably at least 96 wt%, even more preferably at least 97 wt%, even more preferably at least 97.5 wt% based on the polypropylene composition.Inorganic filler

[0049] The composition according to the invention may comprise an inorganic filler. Suitable examples of the inorganic filler include but are not limited to talc.

[0050] The composition according to the invention may be free of or substantially free of an inorganic filler. For example, the composition according to the invention may comprise less than 1.0 wt%, less than 0.1 wt% or less than 0.01 wt% of an inorganic filler.Additives

[0051] In some embodiments, the polypropylene composition further comprises additives, for example in an amount of 0.10 to 2.0 wt% based on the polypropylene composition.

[0052] The additives include a stabilizer. The stabilizer may e.g. be selected from heat stabilizers, anti-oxidants and / or UV stabilizers, all of which are known to the person skilled in the art.

[0053] The additives may further include nucleating agents, colorants, like pigments and dyes; clarifiers; surface tension modifiers; lubricants; flameretardants; mould-release agents; flow improving agents; plasticizers; anti-static agents; blowing agents; slip agents.

[0054] In one aspect, the invention provides an article comprising the polypropylene composition of the invention. Preferably, the amount of the polypropylene composition is at least 95wt%, based on the article. The article may be obtained by injection moulding, blow moulding, extrusion moulding or compression moulding. The article can be a household article such as vacuumcleaner housing, household chemicals and paints, or a packaging article such as containers, crates, boxes, battery case, pails, flowerpots, foodstuff containers / packaging, ice-cream container, thin wall packaging, caps and closure, films, pouches, healthcare packaging, or a healthcare article such as drug delivery article, laboratory ware, a medical device, a medical diagnostics article or an automotive interior article such as instrument panel carriers, door panels, dashboards, dashboard carriers, door claddings, door fixtures, armrests, pillar cladding, seat cladding, boot cladding, interior trims and applications in heating, ventilation, air conditioning (HVAC) applications.

[0055] In one aspect, the invention relates to the use of the polypropylene composition of the invention for the preparation of an article. Preferably, the amount of the polypropylene composition is at least 95wt% based on the article.

[0056] The article may be obtained by injection moulding, blow moulding, extrusion moulding or compression moulding. The article can be a household article such as vacuum-cleaner housing, household chemicals and paints, or a packaging article such as containers, crates, boxes, battery case, pails, flowerpots, foodstuff containers / packaging, ice-cream container, thin wall packaging, caps and closure, films, pouches, healthcare packaging, or a healthcare article such as drug delivery article, laboratory ware, a medical device, a medical diagnostics article or an automotive interior article such as instrument panel carriers, door panels, dashboards, dashboard carriers, door claddings, door fixtures, armrests, pillar cladding, seat cladding, boot cladding, interior trims and applications in heating, ventilation, air conditioning (HVAC) applications.

[0057] In one aspect, the invention provides a process for the preparation of an article comprising the steps of: a. providing the polypropylene composition of the invention and b. converting the polypropylene composition into an article, for example by using an extrusion or injection molding process

[0058] The invention further relates to use of the inventive polypropylene composition for compounding with a further polymer, for example a further polypropylene or for making masterbatches.

[0059] It is further noted that the invention relates to all possible combinations of features described herein, preferred in particular are those combinations of features that are present in the claims. It will therefore be appreciated that all combinations of features relating to the composition according to the invention; all combinations of features relating to the process according to the invention and all combinations of features relating to the composition according to the invention and features relating to the process according to the invention are described herein.

[0060] It is further noted that the term ‘comprising’ does not exclude the presence of other elements. However, it is also to be understood that a description on a product / com position comprising certain components also discloses a product / com position consisting of these components. The product / com position consisting of these components may be advantageous in that it offers a simpler, more economical process for the preparation of the product / composition. Similarly, it is also to be understood that a description on a process comprising certain steps also discloses a process consisting of these steps. The process consisting of these steps may be advantageous in that it offers a simpler, more economical process.

[0061] The invention is now elucidated by way of the following examples, without however being limited thereto.EXAMPLESProcess for preparation of procatalyst

[0062] For inventive examples E1 to E4: the procatalyst was prepared according to the method disclosed in W02021 / 063930A1 , example 1

[0063] For comparative examples CE1 , CE2, the catalyst was prepared according to Comparative Example 1 in EP0728770B1 using a micropheroidal MgCl22.1 EtOH support with an average particle size of 15 micron.Process conditions for E1 to E5 and CE1 to CE2

[0064] Gas-phase polymerizations were performed in one horizontally stirred gasphase reactor with downstream powder processing units (= degassing & catalyst deactivation) for powder collection.

[0065] The temperature of the powder bed is measured via a series of internal thermocouples. The data from these thermocouples is used to control the quench flow to the individual quench nozzles.

[0066] Hydrogen was fed to the reactor to control the melt flow rate and Ethylene was fed to the reactor to obtain the random propylene-ethylene copolymer.

[0067] The random propylene-ethylene copolymer obtained was collected and its properties were measured.

[0068] Table 1 shows the catalyst used in the polymerization process as well as various properties of the random propylene-ethylene copolymers obtained.Table 1 Reaction conditions of polymerization and polymer propertiesAl / Ti is the molar ratio of the co-catalyst (TEA) to the procatalystSi / Ti is the molar ratio of the external donor (DiPDMS) to the procatalystAl / Si is the molar ratio of the co-catalyst (TEA) to the external donor (DiPDMS) N.A: not analyzed

[0069] It can be seen that the process of E1 -E5 made using the catalyst comprising the inventive procatalyst has a higher catalyst yield (indicated by CY (ICP / Ti) than CE1 and CE2 made using a catalyst comprising a different procatalyst while resulting in compositions having a less the same C2 content and lower CXS content.

[0070] From the comparison of E2-E3, it can be seen that the higher Al / Si molar ratio (lower amount of Si (external donor)) in the catalyst resulted in a higher catalyst yield, while maintaining low CXS.

[0071] From the comparison of E2 with E5, it can be see that with increasing MFR CY is maintained on high level while for CE1 and CE2 it is clear that at higher MFR CY drops significantly.

[0072] Further, a lower amount of Ti was detected in E1 to E5 than CE1 and CE2, meaning that polypropylene according to the invention contain less impurities than the one made with other catalyst as the one used in Comparative Example 1 and 2 in EP0728770B1 using a micropheroidal MgCl22.1 EtOH support with an averageparticle size of 15 micron. Accordingly, propylene produce by the process according to the invention may be suitable for application which require less impurity without further additional purification process.Measurement methodsMFR

[0073] The MFR was measured according to ISO1133 (2.16 kg / 230°C).CRYSTEX method for random propylene-ethylene copolymer

[0074] The CRYSTEX method described below can determine the following properties of a random propylene-ethylene copolymer:- amount of crystalline insoluble fraction in the random propylene-ethylene copolymer (CXI equiv. whole sample; HT fraction);- amount of amorphous soluble fraction in the random propylene-ethylene copolymer (CXS equiv. whole sample).

[0075] The measurement of the properties may be performed according to CRYSTEX method by a CRYSTEX QC instrument of CRYSTEX QC Polymer Char (Valencia, Spain). A schematic representation of the CRYSTEX QC instrument is presented in Del Hierro, P.; Ortin, A.; Monrabal, B.; ‘Soluble Fraction Analysis in polypropylene, The Column’, February 2014. Pages 18-23.

[0076] The CRYSTEX QC instrument comprises an infrared detector (IR4) and an online 2- capillary viscometer. Quantification of HT fraction, LT fraction, TC2 whole, TC2-HT fraction, TC2-LT fraction can be done by the infrared detector which detects IR absorbance at two different bands (CH3 and CH2). IV whole, IV-HT fraction, IV-LT fraction can be determined by the online 2- capillary viscometer.

[0077] A sample of the random propylene-ethylene copolymer to be analyzed is weighed in concentrations of 10 mg / mL. After automated filling of the vial with 1 ,2,4-TCB containing 250 mg / L 2,6-tert-butyl-4-methylphenol (BHT) asantioxidant, the sample is dissolved at 170°C until complete dissolution is achieved, for 60 min, with constant stirring of 800rpm.

[0078] A defined volume of the sample solution is injected into the column filled with inert support where the crystallization of the sample and separation of the soluble fraction from the crystalline part takes place. This process is repeated twice.

[0079] During the first injection the whole sample is subjected to measurements at high temperature, for determining the IV whole [dl / g] and the TC2 whole (m / m%) of the PP homopolymer. The TC2, however, is not relevant for random propyleneethylene copolymer.

[0080] During the second injection a measurement at low temperature is performed for determining the amorphous soluble fraction (CXS equiv. whole sample) (m / m%), followed by a measurement at high temperature for determining the crystalline insoluble fraction (CXI equiv. whole sample (m / m%)).

[0081] The crystalline insoluble fraction and the amorphous soluble fraction are separated through temperature cycles of dissolution at 165°C, crystallization at 40°C and re-dissolution in 1 ,2,4-trichlorobenzene (1 ,2,4-TCB) at 165°C.

[0082] The CXS content is determined by calibrating the instrument with various PP polymers with known CXS content determined according to standard gravimetric method according to ISO16152.Catalyst yield (CY) ICP / Ti

[0083] Ti content in the catalyst and Ti content in the obtained polymer were measured by ICP. The ICP procedure is as follows: Approximately 250 mg of each sample are digested in 6 mL concentrated nitric acid (trace metal grade) by microwave assisted acid digestion using an Anton Paar Multiwave PRO equipped with closed high pressure Quartz digestion vessels. After the microwave digestionrun, the acid is analytically transferred into a pre-cleaned plastic centrifuge tube containing 1 mL of internal standard solution and is diluted with MilliQ water up to the 50 mL mark. The elements in the sample are quantified using a multi-element calibration set from Inorganic Ventures using an Agilent 8900 ICP-MS system.

[0084] Then, CY is calculated following Equation (1 )Ethylene content

[0085] Ethylene content was measured using 13C-NMR spectroscopy. To this end, approximately 150 mg of material was dissolved in 1 ,1 ,2,2-tetrachloroethane-d2 (TCE-d2). To ensure a homogeneous solution, the sample preparation has been conducted in a heated rotary oven. The NMR measurements were carried out in the solution-state using a Bruker 500 Advance III HD spectrometer operating at 500.16 and 125.78 MHz for 1 H and 13C, respectively, and equipped with a 10 mm DUAL cryogenically-cooled probe head operating at 125 °C. The 13C-NMR experiments were performed using standard single pulse excitation utilizing the NOE and bi-level WALTZ16 decoupling scheme (Zhou Z. et al. J. Mag. Reson 187 (2007) 225. A total of 512 transients were acquired per spectrum. The spectra were calibrated by setting the central signal of TCE’s triplet at 74.2 ppm. Quantitative 13C NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals using proprietary computer programs.

Claims

CLAIMS1. Process for the preparation of a polypropylene composition comprising a propylene-based polymer which is a random propylene-ethylene copolymer having an ethylene content between 2.0 wt% and 5 wt% based on the propylene-ethylene copolymer, wherein the polypropylene composition has• a melt flow rate (MFR) in the range from 1 to 80 g / 10min, preferably in the range of 1 to 60, more preferably 1 to 50, wherein the melt flow rate is determined using ISO1133-1 :2011 using 2.16kg at 230°C, wherein the process comprises the step of polymerizing propylene and ethylene comonomers in the presence of a catalyst in a gas phase to obtain the propylene-based polymer, wherein said catalyst comprises a procatalyst, a co-catalyst and optionally an external electron donor, wherein the procatalyst is obtainable by a process comprising the steps of: contacting a magnesium-containing support with a halogen-containing titanium compound, and an internal electron donor according to Formula I:Formula I wherein R1is a secondary alkyl group and R2is a non-secondary alkyl group having at least 5 carbon atoms, preferably R2is a non-secondary alkyl group having at least 5 carbon atoms and being branched at the 3- position or further positions; said procatalyst is prepared according to the following steps: i) contacting a compound R4zMgX42-z with an alkoxy- or aryloxycontaining silane compound to give a first intermediate reaction product, being a solid Mg(ORa)xX12-x, wherein: Rais a linear, branched or cyclic hydrocarbyl group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or morecombinations thereof; wherein said hydrocarbyl group may be substituted or unsubstituted, may contain one or more heteroatoms and preferably has from 1 to 20 carbon atoms; wherein R4is a linear, branched or cyclic hydrocarbyl group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof; wherein said hydrocarbyl group may be substituted or unsubstituted, may contain one or more heteroatoms and preferably has from 1 to 20 carbon atoms, preferably R4is butyl; wherein X4and X1are each independently selected from the group of consisting of fluoride (F-), chloride (Cl—), bromide (Br-) or iodide (I-), preferably chloride; z is in a range of larger than 0 and smaller than 2, being 0 < z < 2, x is an integer between 0 and 2; ii) optionally contacting the solid Mg(ORa)xX12-x obtained in step i) with at least one activating compound selected from the group formed by activating electron donors and metal alkoxide compounds of formula M1(0Rb)v-w(0R3)w or M2(ORb)v-w(R3)w, to obtain a second intermediate product; wherein: M1is a metal selected from the group consisting of Ti, Zr, Hf, Al or Si; v is the valency of M1; M2is a metal being Si; v is the valency of M2; Rband R3are each a linear, branched or cyclic hydrocarbyl group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof; wherein said hydrocarbyl group may be substituted or unsubstituted, may contain one or more heteroatoms, and preferably has from 1 to 20 carbon atoms; wherein w is smaller than v, preferably v being 3 or 4; iii) contacting the first or second intermediate reaction product, obtained respectively in step i) or ii), with a halogen-containing Ti-compound and said compound represented Formula I, as the internal electron donor.

2. Process according to claim 1 , wherein the co-catalyst is selected from the group consisting of trimethylaluminum, triethylaluminum,triisobutylaluminum, trihexylaluminum, di-isobutylaluminum hydride, trioctylaluminium, dihexylaluminum hydride and mixtures thereof.

3. Process according to claim 2, wherein the catalyst comprises the external electron donor and wherein the molar ratio of co-catalyst to external electron donor is in the range from 1 to 25, or from 1 to 15, or from 1 to 10, or from 2 to 8, or from 2 to 5.

4. Process according to claim 2 or 3, wherein, the catalyst comprises an external donor, wherein the external electron donor is a silane containing external donor, preferably wherein the external electron donor is selected from the group of compounds having a structure according to:Formula III : (R90)2N— Si(OR91)3,Formula IV: (R92)Si(OR93)3,Formula V: Si(ORa)4-nRbn, and mixtures thereof, wherein each of R90, R91, R92and R93groups are each independently a linear, branched or cyclic, substituted or unsubstituted alkyl having between 1 and 10 carbon atoms, preferably wherein R90, R91, R92and R93groups are each independently a linear unsubstituted alkyl having between 1 and 8 carbon atoms, wherein n can be from 0 up to 2, and each of Raand Rb, independently, represents an alkyl or aryl group, optionally containing one or more hetero atoms for instance O, N, S or P, with, for instance, 1 -20 carbon atoms and wherein, the molar ratio of Al in the co-catalyst to Si in the external electron donor is n the range from 1 to 25, or from 1 to 15, or from 1 to 10, or from 2 to 8, or from 2 to 5.

5. The process according to any one of the preceding claims, wherein during step ii) as activating compounds an alcohol is used as activating electron donor and titanium tetraalkoxide is used as metal alkoxide compound.

6. The process according to any one of the preceding claims, wherein an activator is present, the activator preferably being a benzamide according to formula X:wherein R70and R71are each independently selected from hydrogen or an alkyl, and R72, R73, R74, R75, R76are each independently selected from hydrogen, a heteroatom or a hydrocarbyl group, preferably selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof, more preferably wherein R70and R71are both methyl and wherein R72, R73, R74, and R75are all hydrogen, being N,N’- dimethylbenzamide (Ba-2Me).

7. Process according to any one of the preceding claims, wherein the process has Catalyst yield (CY) Ti (KgPP / gcat) of at least 25, more preferably at least 30, more preferably at least 35, more preferably at least 40, wherein CY Ti (kgPP / gcat) is calculated following Equation (1 ):wherein the Ti content in the catalyst and Ti content in the obtained polymer is determined by Inductively coupled plasma mass spectrometry (ICP-MS).

8. Process according to any one of the preceding claims, wherein the random propylene-ethylene copolymer has a cold xylene soluble content (CXS) from 3.0 to 8.0 wt%, preferably from 3.7 to 6.9 wt%, preferably in the range from 4.6 to 6.9 wt%, even more preferably in the range from 5.0 to 6.4 wt%, measured by the method described in the section “CRYSTEX method for random propylene-ethylene copolymer” of the Measurement methods section of the present disclosure.

9. Process according to any one of the preceding claims, wherein, the amount of Ti in the propylene-based polymer is at most 1 .4 mg / kg, preferably at most 1 .2 mg / kg, preferably at most 1 .0, preferably at most 0.5 mg / kg of the propylene-based polymer as determined by Inductively coupled plasma mass spectrometry (ICP-MS)10. Process according to any one of the preceding claims, wherein the internal donor is 3,3-bis(methoxymethyl)-2,6-dimethylheptane and / or wherein the activating compound is N-N-dimethylbenzamide11 . Process according to any one of the preceding claims, wherein the external donor comprises or consists of a compound selected from the list comprising organo-silicon compounds, silanes, alkoxy silanes, alkyl silane, alkyl alkoxy silane and aliphatic / aromatic ester, for example dicyclopentyldimethoxysilane, di-tert-butyldimethoxysilane, methylcyclohexyldimethoxysilane, ethylcyclohexyldimethoxysilane, diphenyldimethoxysilane, diisopropyldimethoxysilane, di-n- propyldimethoxysilane, diisobutyldimethoxysilane, di-n- butyldimethoxysilane, cyclopentyltrimethoxysilane, isopropyltrimethoxysilane, npropyltrimethoxysilane, n-propyltriethoxysilane, ethyltriethoxysilane, tetramethoxysilane, tetraethoxysilane,cyclopentylpyrrolidinodimethoxysilane, bis(pyrrolidino )-dimethoxysilane, and mixtures thereof, preferentially di(iso-propyl) dimethoxysilane (DiPDMS).

12. Process according to any one of the preceding claims, wherein the external donor further comprises a compound selected from the group consisting of: ethyl acetate, ethyl benzoate, p-ethoxy ethyl benzoate, methyl trimethylacetate, isopropyl myristate, di-n-butyl sebacate, (poly)(alkylene glycol) mono- or diacetates, (poly)(alkylene glycol) mono- or di-myristates, (poly)(alkylene glycol) mono- or di- laurates, (poly)(alkylene glycol) mono- or di-dioleates, glyceryl tri(acetate), mixed glycerides of linoleic, oleic, palmitic and stearic acids, and mixtures thereof preferably, isopropyl myristate.

13. Polypropylene composition obtained by or obtainable by the process according to any one of the preceding claims.

14. Article comprising the polypropylene composition of claim 13, wherein the amount of the polypropylene composition is at least 95wt% based on the article and / or wherein the article may be obtained by injection moulding, blow moulding, extrusion moulding or compression moulding and / or wherein the article can be:• a household article such as vacuum-cleaner housing, household chemicals and paints, or• a packaging article such as containers, crates, boxes, battery case, pails, flowerpots, foodstuff containers / packaging, ice-cream container, thin wall packaging, caps and closure, films, pouches, healthcare packaging, or• a healthcare article such as drug delivery article, laboratory ware, a medical device, a medical diagnostics article or• an automotive interior article such as instrument panel carriers, door panels, dashboards, dashboard carriers, door claddings, door fixtures, armrests, pillar cladding, seat cladding, boot cladding, interior trims or• an article suitable for applications in heating, ventilation, air conditioning (HVAC)15. Use of the polypropylene composition of claim 13 for the preparation of an article, wherein the amount of the polypropylene composition is at least 95wt% based on the article and / or wherein the article may be obtained by injection moulding, blow moulding, extrusion moulding or compression moulding and / or wherein the article can be:• a household article such as vacuum-cleaner housing, household chemicals and paints, or• a packaging article such as containers, crates, boxes, battery case, pails, flowerpots, foodstuff containers / packaging, ice-cream container, thin wall packaging, caps and closure, films, pouches, healthcare packaging, or• a healthcare article such as drug delivery article, laboratory ware, a medical device, a medical diagnostics article or• an automotive interior article such as instrument panel carriers, door panels, dashboards, dashboard carriers, door claddings, door fixtures, armrests, pillar cladding, seat cladding, boot cladding, interior trims or• an article suitable for applications in heating, ventilation, air conditioning (HVAC)16. Process for the preparation of an article comprising the steps of a. providing the polypropylene composition of claim 13 and b. converting the polypropylene composition into an article, for example by using an extrusion or injection molding process.

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