US 2016.0311947A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2016/0311947 A1 Zuideveld et al. (43) Pub. Date: Oct. 27, 2016

(54) CATALYST SYSTEM FOR (86). PCT No.: PCT/EP2014/078797 POLYMERIZATION OF AN OLEFIN S 371 (c)(1) (71) Applicants: Martin Alexander ZUIDEVELD, (2) Date: Jun. 16, 2016 BATINAS-GEURTS,Geleen (NL); Aurora AlexandraGeleen (NL); (30) Foreign ApplicationO O Priority Data Gennadii Dimitrievich BUKATOV s Dec. 20, 2013 (EP) ...... 131991 73.9 Geleen (NL); Sergei Andreevich Jun. 2, 2014 (EP) ...... 14170833.9 SERGEEV, Geleen (NL); Vladimir s Aleksandrovich ZAKHAROV, Geleen Publication Classification (NL); SAUDI BASIC INDUSTRIES CORPORATION, Riyadh (SA): (51) Int. Cl. SABIC GLOBAL TECHNOLOGIES CSF II/06 (2006.01) B.V., Bergen op Zoom (NL) (52) U.S. Cl. CPC ...... CSF II/06 (2013.O1 (72) Inventors: Martin Alexander Zuideveld, Kelmis ( ) (BE); Aurora Alexandra (57) ABSTRACT Batinas-Geurts, BK Sittard (NL); Gennadii Dimitrievich Bukatov, A process for the preparation of a procatalyst Suitable for Novosibirsk (RU); Sergei Andreevich preparing a catalyst composition for olefin polymerization, Sergeev, Novosibirsk (RU); Vladimir the procatalyst obtained or obtainable by the process; and a Aleksandrovich Zakharov, catalyst composition for olefin polymerization comprising Novosibirsk (RU) the procatalyst. In particular a benzamide can be used as an activator in the preparation of a Supported Ziegler-Natta type (21) Appl. No.: 15/105,291 procatalyst useful for a process for the preparation of poly olefins. The Polyolefins and polypropylene homopolymers (22) PCT Filed: Dec. 19, 2014 are also disclosed. US 2016/031 1947 A1 Oct. 27, 2016

CATALYST SYSTEM FOR internal donor in the procatalyst allowing to obtain both a POLYMERIZATION OF AN OLEFIN high yield and a narrow molecular weight distribution. 0001. The invention relates to a process for the prepara 0009. It has surprisingly been found by the present inven tion of a procatalyst Suitable for preparing a catalyst com tors that the combination of the use of a benzamide activator position for olefin polymerization. The present invention and a 1,3-diether internal donor in the procatalyst according also relates to the procatalyst obtained or obtainable by the to the present invention shows a better yield combined with process. The composition further relates to a catalyst com a narrow molecular weight distribution. position for olefin polymerization comprising the procata 0010. In a first aspect, the present invention relates to a lyst. The invention also relates to the use of a benzamide as process for the preparation of a procatalyst Suitable for an activator in the preparation of a Supported Ziegler-Natta preparing a catalyst composition for olefin polymerization, type procatalyst. The invention further relates to a process said process comprising the steps of providing a magne for the preparation of polyolefins. The invention also relates sium-based support, contacting said magnesium-based Sup to a polyolefin and a polypropylene homopolymer. port with a Ziegler-Natta type catalytic species, an internal 0002 Catalyst systems (or catalyst compositions, used in donor, (activated by) an activator, to yield a procatalyst, this application as synonyms) and their components that are wherein the activator is a benzamide according to formula X Suitable for preparing a polyolefin are generally known. One type of Such catalysts are generally referred to as Ziegler Natta catalysts. The term "Ziegler-Natta' is known in the art Formula X and it typically refers to catalyst systems comprising a transition metal-containing Solid catalyst compound (also R3 C R70 typically referred to as a procatalyst); an organometallic n N Y compound (also typically referred to as a co-catalyst) and optionally one or more electron donor compounds (e.g. R71 external electron donors). 0003. The transition metal-containing solid catalyst com pound comprises a transition metal halide (e.g. titanium halide, chromium halide, hafnium halide, Zirconium halide or vanadium halide) Supported on a metal or metalloid wherein R'' and R'' are each independently selected from compound (e.g. a magnesium compound or a silica com hydrogen or an alkyl, and R', R. R. R. R7 are each pound). An overview of such catalyst types is for example independently selected from hydrogen, a heteroatom (pref given by T. Pullukat and R. Hoff in Catal. Rev. Sci. Eng. erably a halide), or a hydrocarbyl group, selected from e.g. 41, Vol. 3 and 4, 389-438, 1999. The preparation of such a alkyl, alkenyl, aryl, aralkylor alkylaryl groups, and one or procatalyst is for example disclosed in W096/32427 A1. U.S. Pat. No. 4,211,670 A discloses a process for preparing more combinations thereof, and wherein the internal donor a titanium trichloride composition of improved Sterospeci for the procatalyst is selected from the group consisting of ficity for use as a catalyst component in the polymerization 1,3-diethers represented by the Formula VII, of propylene. DE 17 45 117 A1 discloses a catalyst system for the preparation of polyolefins, said catalyst system comprising an Group I, II or III organometallic compound Formula VII and a transition metal halide. WO 2011/139897 discloses a R5 porous solid catalyst component comprising a magnesium halide, a titanium compound and at least an 1,3-diether R’o-CH-i-CH-OR" electron donor compound and at least one Succinate electron donor compound. A disadvantage of the prior art cited above is that for certain application the activity of the procatalyst is not high enough for applications where a narrow molecu wherein R and Rare each independently selected from a lar weight distribution is required. hydrogen or a hydrocarbyl group selected from e.g. alkyl, 0004. There is, therefore, an on-going need in industry alkenyl, aryl, aralkyl or alkylaryl groups, and one or more for polyolefins having a narrow molecular weight distribu combinations thereof, and tion that can be prepared in high yield. Thus there is a need 0011 R and R are each independently selected from for catalyst compositions showing better performance in a hydrocarbyl group, selected from e.g. alkyl, alkenyl, aryl, polymerization of olefins, especially with respect to a higher aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more activity and lower molecular weight distribution. combinations thereof. Said hydrocarbyl group may be linear, 0005. It is thus an object of the invention to provide a branched or cyclic. Said hydrocarbyl group may be substi polyolefin having a narrow molecular weight distribution tuted or unsubstituted. Said hydrocarbyl group may contain that can be obtained in high yield. one or more heteroatoms. Preferably, said hydrocarbyl group 0006. It is a further object of the present invention to has from 1 to 10 carbon atoms, more preferably from 1 to 8 provide a procatalyst for use in a catalyst composition which carbon atoms, even more preferably from 1 to 6 carbon shows better performance, in polymerization of olefins, atOmS. especially with respect to the yield. 0012. In an embodiment of the first aspect, the process 0007. One or more of the aforementioned objects of the according comprises the steps of: present invention are achieved by the various aspects of the 0013 A) providing said procatalyst obtained via a pro present invention. cess comprising the steps of 0008. The present invention is related to the activation of I0014) i) contacting a compound RMgX, with an the Solid magnesium halide Support by means of a benz alkoxy- or aryloxy-containing silane compound to give amide activator in combination with the use of a 1,3-diether a first intermediate reaction product, being a solid US 2016/031 1947 A1 Oct. 27, 2016

Mg(OR"),X', wherein: R is the same as R' being a dimethoxypropane, 2-methyl-2-phenyl-1,3- linear, branched or cyclic hydrocarbyl group indepen dimethoxypropane, 2-methyl-2-cyclohexyl-1,3- dently selected from alkyl, alkenyl, aryl, aralkylor dimethoxypropane, 2.2-bis(pchlorophenyl)-1,3- alkylaryl groups, and one or more combinations dimethoxypropane, 2.2-bis(2-cyclohexylethyl)-1,3- thereof; wherein said hydrocarbyl group may be sub dimethoxypropane, 2-methyl-2-isobutyl-1,3- stituted or unsubstituted, may contain one or more dimethoxypropane, 2-methyl-2-(2-ethylhexyl)-1,3- heteroatoms and preferably has from 1 to 20 carbon dimethoxypropane, 2-methyl-2-isopropyl-1,3- atoms: X and X’ are each independently selected from dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, the group of consisting of fluoride (F ), chloride 2,2-dibenzyl-1,3-dimethoxypropane, 2.2-bis(cyclohexylm (Cl—), bromide (Br—) or iodide (I–), preferably ethyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxy chloride; Z is in a range of larger than 0 and Smaller than propane, 2.2-diisobutyl-1,3-di-n-butoxypropane, 2-isobutyl 2, being 0halogen-containing Ti-compound, an activator selected from the group of 1,3-dicyclohexyl-2.2-bis and an internal electron donor according to Formula (methoxymethyl)propane, 3.3-bis(methoxymethyl)-2,5-di VII to obtain said procatalyst. methylhexane, 2,2-dicyclopentyl-1,3-dimethoxypropane 0017 Said procatalyst obtained can be used to prepare a and any combinations thereof. catalyst composition by combining it with at least one 0020. In a further embodiment of the first aspect, the external donor and preferably a co-catalyst. internal donor is 9.9-bis(methoxymethyl)fluorene. 0018. In a further embodiment of the first aspect, the 0021. In another embodiment of the first aspect, in the hydrocarbyl groups R and R of the internal donor each activator according to formula X, at least one of R'' and R' have from 1 to 10 carbon atoms, preferably from 1 to 9 is an alkyl group, wherein the alkyl has from 1 to 6 carbon carbon atoms, more preferably from 1 to 6 carbon atoms. In atoms, preferably from 1 to 3 carbon atoms, preferably other words, the hydrocarbyl group has from 1 to 10, wherein both R" and R'' are alkyl groups, more preferably preferably 1 to 9, more preferably 1 to 6 carbon atoms. each having 1 to 6 carbon atoms, even more preferably each 0019. In a further embodiment of the first aspect, the having 1 to 3 carbon atoms. internal donor is selected from the group consisting of 0022. In yet another embodiment of the first aspect, the 1,3-dimethoxypropane, 1,3-diethoxypropane, 1,3-dibutoxy activator is N,N-dimethylbenzamide. In this compound both propane, 1-methoxy-3-ethoxypropane, 1-methoxy-3-bu R" and R'' are Clalkyl groups, viz. a methyl group. All R', toxypropane, 1-methoxy-3-cyclohexoxypropane, 2.2-dim R. R. R. R' groups are each independently hydrogen. ethyl-1,3-dimethoxypropane, 2,2-diethyl-1,3- 0023. In a further embodiment of the first aspect, the dimethoxypropane, 2,2-di-n-butyl-1,3-dimethoxypropane, benzamide is present in the procatalyst, in an amount of 2,2-diiso-butyl-1,3-dimethoxypropane, 2-ethyl-2-n-butyl-1, from 0.1 to 4 wt.% as measured using HPLC. 3-dimethoxypropane, 2-n-propyl-2-cyclopentyl-1,3-dime 0024. In a further embodiment of the first aspect, the thoxypropane, 2.2-dimethyl-1,3-diethoxypropane, 2-n-pro benzamide is present in the procatalyst, in an amount of pyl-2-cyclohexyl-1,3-diethoxypropane, 2-(2-ethylhexyl)-1, from 0.1 to 3.5 wt.% as measured using HPLC 3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 0025. In a further embodiment of the first aspect, the 2-n-butyl-1,3 -dimethoxypropane, 2-sec-butyl-1,3-dime benzamide is present in the procatalyst, in an amount of thoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phe from 0.1 to 3 wt.% as measured using HPLC. nyl-1,3-diethoxypropane, 2-cumyl-1,3-diethoxypropane, 0026. In a further embodiment of the first aspect, the 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexyl benzamide is present in the procatalyst, in an amount of ethyl)-1,3-dimethoxypropane, 2-(p-chlorophenyl)-1,3-di from 0.1 to 2.5 wt.% as measured using HPLC. methoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypro 0027. In a further embodiment of the first aspect, the pane, 2-(1-naphthyl)-1,3-dimethoxypropane, benzamide is present in the procatalyst, in an amount of 2-(fluorophenyl)-1,3-dimethoxypropane, 2-(1-decahy from 0.1 to 2.0 wt.% as measured using HPLC. dronaphthyl)-1,3-dimethoxypropane, 2-(p-t-butylphenyl)-1, 0028. In a further embodiment of the first aspect, the 3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypro benzamide is present in the procatalyst, in an amount of pane, 2,2-di-npropyl-1,3-dimethoxypropane, 2-methyl-2-n- from 0.1 to 1.5 wt.% as measured using HPLC. propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3- 0029. In a second aspect, the present invention relates to dimethoxypropane, 2-methyl-2-ethyl-1,3- a procatalyst obtained or obtainable by the process accord US 2016/031 1947 A1 Oct. 27, 2016

ing to the first aspect. Said procatalyst can be used to prepare Other terms not cited below are meant to have the generally a catalyst composition Suitable for olefin polymerization. accepted meaning in the field. 0030. In third aspect, the present invention relates to a 0043. Defintions procatalyst for use in a catalyst System for olefin polymer 0044) “Ziegler-Natta catalyst” as used in the present ization, said procatalyst comprising a benzamide according description means: a transition metal-containing solid cata to formula X, wherein the benzamide according to formula lyst compound comprises a transition metal halide selected X is present in an amount of from 0.1 to 3.5 wt.%, for from titanium halide, chromium halide, hafnium halide, example in an amount from 0.1 to 3 wt.%, for example in Zirconium halide and Vanadium halide, Supported on a metal an amount of from 0.1 to 2.5 wt.%, for example from 0.1 or metalloid compound (e.g. a magnesium compound or a to 2.0 wt.%, for example from 0.1 to 1.5 wt.% based on the silica compound). procatalyst as measured using HPLC and an internal donor 0045 “Ziegler-Natta catalytic species” or “catalytic spe selected from the group consisting of 1,3-diethers repre cies' as used in the present description means: a transition sented by Formula VII. metal-containing species comprises a transition metal halide 0031. In another aspect, the present invention relates to selected from titanium halide, chromium halide, hafnium the use of a benzamide according to formula X as an halide, Zirconium halide and Vanadium halide. activator in the preparation of a Supported Ziegler-Natta 0046 “internal donor” or “internal electron donor” or procatalyst, preferably a Ziegler-Natta catalyst on a Solid “ID' as used in the present description means: an electron Support, more preferably on a solid magnesium-based Sup donating compound containing one or more atoms of oxy port. gen (O) and/or nitrogen (N). This ID is used as a reactant in 0032. In another aspect, the present invention relates to a the preparation of a solid procatalyst. An internal donor is process for the preparation of polyolefins, preferably poly commonly described in prior art for the preparation of a propylene, comprising the contacting of a procatalyst as Solid-supported Ziegler-Natta catalyst system for olefins described herein with at least one olefin, and optionally an polymerization; i.e. by contacting a magnesium-containing external donor and/or optionally a co-catalyst. In other Support with a halogen-containing Ti compound and an words, a process for the preparation of polyolefins, prefer internal donor. ably polypropylene, comprising the contacting of a catalyst 0047 “external donor or “external electron donor or system comprising the procatalyst according to the present “ED as used in the present description means: an electron invention with at least one olefin. donating compound used as a reactant in the polymerization 0033. In yet another aspect, the present invention relates of olefins. An ED is a compound added independent of the to a polyolefin, preferably a polypropylene, obtainable by procatalyst. It is not added during procatalyst formation. It the process for preparing a polyolefin as described herein. contains at least one functional group that is capable of 0034. In an embodiment of the invention, the polyolefin donating at least one pair of electrons to a metal atom. The as described herein has a molecular weight distribution ED may influence catalyst properties, non-limiting examples (M/M) of below 5.0, for example below 4.5, preferably thereof are affecting the stereoselectivity of the catalyst from 2 to 4.5, more preferably from 3 to 4.5, more preferably system in polymerization of olefins having 3 or more carbon from 3.5 to 4.5, wherein the M and M are determined as atoms, hydrogen sensitivity, ethylene sensitivity, random discussed below. ness of co-monomer incorporation and catalyst productivity. 0035. In yet another aspect, the present invention relates 0048 “activator” as used in the present description to a polypropylene homopolymer (which is preferably a means: an electron-donating compound containing one or polyolefin obtained by or obtainable by the process accord more atoms of oxygen (O) and/or nitrogen (N) which is used ing to the present method) prepared by a slurry polymer during the synthesis of the procatalyst prior to or simulta ization using a solvent, preferably heptane having: neous with the addition of an internal donor. 0036 a molecular weight distribution (Mw/Mn) below 0049) “activating compound as used in the present 5.0, for example below 4.5, preferably from 2 to 4.5, more description means: a compound used to activate the Solid preferably from 3 to 4.5, more preferably from 3.5 to 4.5, Support prior to contacting it with the catalytic species. wherein the Mw and Mn are determined as discussed below: 0050 “modifier” or “Group 13- or transition metal modi 0037 a melt flow rate of above 14, for example in the fier” as used in the present description means: a metal range from 14 to 1000, wherein the melt flow rate is modifier comprising a metal selected from the metals of measured as discussed below: Group 13 of the IUPAC Periodic Table of elements and 0038 a weight percentage of atactic polypropylene transition metals. Where in the description the terms metal (APP) of less than 1.5, preferably less than 1.0, wherein the modifier or metal-based modifier is used, Group 13- or APP is measured as discussed below: transition metal modifier is meant. 0039 a xylene soluble content (XS) of less than 4.5 wt. 0051) “procatalyst” and “catalyst component as used in %, wherein the XS is measured as discussed below. the present description have the same meaning: a component 0040. These aspects and embodiments will be described of a catalyst composition generally comprising a solid in more detail below. Support, a transition metal-containing catalytic species and 0041. The procatalyst according to the present invention one or more internal donors. has the advantage that it exhibits excellent yield when used 0.052 “halide' as used in the present description means: in a catalyst composition. In addition, the polyolefins an ion selected from the group of: fluoride (F ), chloride obtained using the catalyst according to the present inven (Cl—), bromide (Br-) or iodide (I–). tion show a narrow MWD. 0053 “halogen as used in the present description means: 0042. The following definitions are used in the present an ion selected from the group of: fluorine (F), chlorine (Cl), description and claims to define the stated Subject matter. bromine (Br) or iodine (I). US 2016/031 1947 A1 Oct. 27, 2016

0054) “Heteroatom’ as used in the present description 0.066 “propylene-based polymer as used in the present means: an atom other than carbon or hydrogen. However, as description means: a polymer of propylene and optionally a used herein—unless specified otherwise, such as below, COOOC. when “one or more hetereoatoms” is used one or more of the 0067 “polypropylene' as used in the present description following is meant: F, Cl, Br, I, N, O, P, B, S or Si. means: a polymer of propylene. 0055 “heteroatom selected from group 13, 14, 15, 16 or 0068 “copolymer as used in the present description 17 of the IUPAC Periodic Table of the Elements’ as used in means: a polymer prepared from two or more different the present description means: a hetero atom selected from OOCS. B, Al. Ga, In, TI Group 13. Si, Ge. Sn, Pb Group 14, N. 0069) “monomer as used in the present description P. As, Sb, Bi Group 15, O, S, Se, Te, Po Group 16, F, Cl, means: a chemical compound that can undergo polymeriza Br, I. At Group 17. tion. 0056 “hydrocarbyl as used in the present description 0070 “thermoplastic” as used in the present description means: is a Substituent containing hydrogen and carbon means: capable of softening or fusing when heated and of atoms, or linear, branched or cyclic Saturated or unsaturated hardening again when cooled. aliphatic radical. Such as alkyl, alkenyl, alkadienyl and 0071 "polymer composition” as used in the present alkynyl; alicyclic radical. Such as cycloalkyl, cycloalkadi description means: a mixture of either two or more polymers enyl cycloalkenyl; aromatic radical. Such as monocyclic or or of one or more polymers and one or more additives. polycyclic aromatic radical, as well as combinations thereof, 0072 “M,” and “M” in the context of the present Such as alkaryl and aralkyl. invention means the ratio of the weight average molecular 0057 “substituted hydrocarbyl” as used in the present weight M and the number average molecular weight M, of description means: is a hydrocarbyl group that is Substituted a sample, as measured according to ASTM D6474-12. with one or more non-hydrocarbyl Substituent groups. A (0073. “PDI in the context of the present invention means non-limiting example of a non-hydrocarbyl Substituent is a the ratio of the weight average molecular weight M and the heteroatom. Examples are alkoxycarbonyl (viz. carboxylate) number average molecular weight M of a sample, as groups. When in the present description “hydrocarbyl is measured according to ASTM D6474-12. As used herein, used it can also be “substituted hydrocarbyl, unless stated the terms “PDI and “polydispersity index' are interchange otherwise. able. 0058 “alkyl as used in the present description means: an (0074 “MWD in the context of the present invention alkyl group being a functional group or side-chain consisting means distribution of the molecular weight of a sample, as of carbon and hydrogen atoms having only single bonds. An represented by the ratio of the weight average molecular alkyl group may be straight or branched and may be unsub weight M and the number average molecular weight M, of stituted or Substituted. It may or may not contain heteroa a sample as measured according to ASTM D6474-12. As toms, such as oxygen (O), nitrogen (N), phosphorus (P), used herein, the terms “MWD and “molecular weight silicon (Si) or Sulfur (S). An alkyl group also encloses distribution” are interchangeable. aralkyl groups wherein one or more hydrogen atoms of the 0075 "XS" as used in the present description means: the alkyl group have been replaced by aryl groups. Xylene soluble fraction in terms of percentage of polymer 0059) “aryl as used in the present description means: an that does not precipitate out upon cooling of a polymer aryl group being a functional group or side-chain derived Solution in Xylene, said polymer Solution having been Sub from an aromatic ring. An aryl group may be unsubstituted jected to reflux conditions, down from the reflux tempera or substituted with straight or branched hydrocarbyl groups. ture, which equals the boiling temperature of xylene, to 25° It may or may not contain heteroatoms, such as oxygen (O), C. XS is measured according to ASTM D5492-10. As used nitrogen (N), phosphorus (P), silicon (Si) or sulfur (S). An herein, the terms “XS and “xylene soluble fraction” are aryl group also encloses alkaryl groups wherein one or more interchangeable. hydrogen atoms on the aromatic ring have been replaced by 0076 “polymerization conditions” as used in the present alkyl groups. description means: temperature and pressure parameters 0060 “alkoxide' or “alkoxy” as used in the present within a polymerization reactor Suitable for promoting description means: a functional group or side-chain obtained polymerization between the procatalyst and an olefin to form from a alkyl alcohol. It consist of an alkyl bonded to a the desired polymer. These conditions depend on the type of negatively charged oxygen atom. polymerization used. 0061 “aryloxide' or “aryloxy” or “phenoxide” as used in (0077 “production rate” or “yield” as used in the present the present description means: a functional group or side description means: the amount of kilograms of polymer chain obtained from an aryl alcohol. It consist of an aryl produced per gram of procatalyst consumed in the polym bonded to a negatively charged oxygen atom. erization reactor per hour, unless stated otherwise. 0062 “Grignard reagent' or “Grignard compound as 0078 “APP” as used in the present description means used in the present description means: a compound or a atactic polypropylene. The weight percentage of APP as mixture of compounds of formula RMgX (R', Z, and X* used in the context of the present invention means the are as defined below) or it may be a complex having more percentage of polypropylene of the total quantity of poly Mg clusters, e.g. RMgCl2. propylene produced in a slurry polymerization process that is retained in the solvent, especially for example hexane, that 0063 “polymer as used in the present description is used in said slurry polymerization process. The weight means: a chemical compound comprising repeating struc percentage of APP may be determined according to the tural units, wherein the structural units are monomers. following procedure: a quantity A of the product stream 0064 “olefin” as used in the present description means: from said slurry polymerization process is collected. This an alkene. quantity A is filtered using a filter having pores between 10 0065 “olefin-based polymer” or “polyolefin” as used in and 16 um in diameter, to obtain a filtrate Y and a polymer the present description means: a polymer of one or more quantity of weight X, said polymer quantity of weight X alkenes. being the quantity of material that remained on the filter. US 2016/031 1947 A1 Oct. 27, 2016

Said filtrate Y is dried over a steam bath and then under I0088. In Formula X R'' and R7 are each independently vacuum at 60° C. to obtain a dry mass of APP of weight Z. selected from hydrogen or an alkyl. Preferably, said alkyl The weight percentage of APP is calculated by: has from 1 to 6 carbon atoms, more preferably from 1 to 3 carbon atoms. More preferably, R'' and R7 are each inde pendently selected from hydrogen or methyl. In an embodi APPin wt %) = 2. k 100% ment, at least one of R'' and R' is an alkyl, preferably 2--X methyl, and the other of R" and R' is preferably hydrogen. In an embodiment, each of R" and R' is an alkyl, prefer 0079) “MFR as used in the present description means: ably method. In an embodiment, each of R'' and R7 is the melt mass-flow rate as measured according to ISO hydrogen. 1133:2005, at 230° C. under a load of 2.16 kg. As used herein, the terms “MFR, “melt flow rate' and “melt mass 0089. In Formula X R7, R', R, R7, R7 are each flow rate” are interchangeable. independently selected from hydrogen, a heteroatom (pref 0080 “bulk density” as used in the present description erably a halide), or a hydrocarbyl group, selected e.g. from means: the weight per unit volume of a material, including alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl voids inherent in the material as tested. Bulk density is groups, and one or more combinations thereof. Said hydro measured as apparent density according to ASTM D1895-96 carbyl group may be linear, branched or cyclic. Said hydro Reapproved 2010-el, test method A. I0081) “average particle size” or “ds in the context of carbyl group may be substituted or unsubstituted. Said the present invention means the statistical average of the hydrocarbyl group may contain one or more heteroatoms. particle size distribution as measured according to ISO Preferably, said hydrocarbyl group has from 1 to 10 carbon 13320:2009, in which the average particle size is expressed atoms, more preferably from 1 to 8 carbon atoms, even more by Xso or dso. preferably from 1 to 6 carbon atoms. More preferably, R', 0082 “span value' in the context of the present invention R7, R. R. R7 are each hydrogen. represents an indicator for the width of the particle size 0090 Suitable non-limiting examples of “benzamides’ distribution as measured according to ISO 13320:2009. The include benzamide (R'' and R'' are both hydrogen and each span value is calculated according to the formula: of R7, R. R. R. R7 are hydrogen) also denoted as BA-2H or methylbenzamide (R' is hydrogen; R' is methyl and each of R', R. R. R. R7 are hydrogen) also Span Value = doo - do denoted as BA-HMe or dimethylbenzamide (R'' and R7 are d50 methyl and each of R', R. R. R. R'' are hydrogen) also denoted as BA-2Me. 0083. In which do is equal to X as defined in ISO 13320:2009, do is equal to X as defined in ISO 13320: 0091. Other examples include monoethylbenzamide, 2009, and ds is equal to Xso as defined in ISO 13320:2009. diethylbenzamide, methylethylbenzamide, 2-(trifluorm 0084. Unless stated otherwise, when it is stated that any ethyl)benzamide, N,N-dimethyl-2-(trifluorimethyl)benz R group is “independently selected from this means that amide, 3-(trifluorimethyl)benzamide, N,N-dimethyl-3-(trif when several of the same R groups are present in a molecule luorimethyl)benzamide, 2,4-dihydroxy-N-(2-hydroxyethyl) they may have the same meaning of they may not have the benzamide, N-(1H-benzotriazol-1-ylmethyl)benzamide, same meaning. For example, for the compound R.M. 1-(4-ethylbenzoyl)piperazine, 1-benzoylpiperidine. wherein R is independently selected from ethyl or methyl, both R groups may be ethyl, both R groups may be methyl 0092. It has surprisingly been found by the present inven or one R group may be ethyl and the other R group may be tors that when the benzamide activator is added during the methyl. first stage (stage I of Phase C as discussed below) of the 0085. The present invention is described below in more process together with the catalytic species or directly after detail. All embodiments described with respect to one aspect the addition of the catalytic species (e.g. within 5 minutes) of the present invention are also applicable to the other an even higher increase in the yield is observed compared to aspects of the invention, unless otherwise stated. when the activator is added during stage II or stage III of the I0086. As stated above, the combination of i) activation of process as discussed below. It is hence preferred to add the the solid Support using a benzamide according to the present activator during the first stage of the following step: iii) invention and ii) the use of a 1,3-diether internal donor contacting the first or second intermediate reaction product, shows a better yield in polymerization and leads to poly obtained respectively in step i) or ii), with a halogen olefins having a narrow MWD. containing Ti-compound and an internal electron donor 0087 Abenzamide activator as used in the present appli according to Formula VII to obtain said procatalyst. It is also cation has a structure according to Formula X: possible that an additional step iv) and additional step V) are carried out after step iii) in which case either the internal donor and/or the activator may also be added during step V). Formula X 0093. It has surprisingly been found by the present inven tors that the benzamide activator having two alkyl groups (e.g. dimethylbenzamide or diethylbenzamide, preferably dimethyl-benzamide) provides an even higher increase in the yield than either benzamide or monoalkyl benzamide. 0094. Without wishing to be bound by a particular theory the present inventors believe that the fact that the most effective activation is obtained when the benzamide activa tor is added during stage I has the following reason. It is US 2016/031 1947 A1 Oct. 27, 2016

believed that the benzamide activator will bind the catalytic 2-n-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dime species and is later on substituted by the internal donor when thoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phe the internal donor is added. nyl-1,3-diethoxypropane, 2-cumyl-1,3-diethoxypropane, 0095. The present invention furthermore includes an 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexyl internal donor in the procatalyst. Not bounded by any ethyl)-1,3-dimethoxypropane, 2-(p-chlorophenyl)-1,3-di particular theory, it is believed that the internal electron methoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypro donor assists in regulating the formation of active sites pane, 2-(1-naphthyl)-1,3-dimethoxypropane, thereby enhancing catalyst stereoselectivity. 2-(fluorophenyl)-1,3-dimethoxypropane, 2-(1-decahy 0096. It is preferred to use so-called phthalate free inter dronaphthyl)-1,3-dimethoxypropane, 2-(p-t-butylphenyl)-1, nal donors because of increasingly stricter government regu 3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypro lations about the maximum phthalate content of polymers. pane, 2,2-di-n propyl-1,3-dimethoxypropane, 2-methyl-2-n- This leads to an increased demand in essentially phthalate propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3- free procatalysts. In the context of the present invention, dimethoxypropane, 2-methyl-2-ethyl-1,3- “essentially phthalate-free” or “phthalate free” means hav dimethoxypropane, 2-methyl-2-phenyl-1,3- ing a phthalate content of less than for example 150 ppm, dimethoxypropane, 2-methyl-2-cyclohexyl-1,3- alternatively less than for example 100 ppm, alternatively dimethoxypropane, 2.2-bis(pchlorophenyl)-1,3- less than for example 50 ppm, alternatively for example less dimethoxypropane, 2.2-bis(2-cyclohexylethyl)-1,3- than 20 ppm. dimethoxypropane, 2-methyl-2-isobutyl-1,3- 0097. The internal donor used in the present invention is dimethoxypropane, 2-methyl-2-(2-ethylhexyl)-1,3- a a “di-ether” or a 1,3-di(hydrocarboxy) propane compound, dimethoxypropane, 2-methyl-2-isopropyl-1,3- optionally substituted on the 2-position represented by the dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, Formula VII, 2,2-dibenzyl-1,3-dimethoxypropane, 2.2-bis(cyclohexylm ethyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxy Formula VII propane, 2.2-diisobutyl-1,3-di-n-butoxypropane, 2-isobutyl R5 2-isopropyl-1,3-dimethoxypropane, 2,2-di-sec-butyl-1,3- dimethoxypropane, 2,2-di-t-butyl-1,3-dimethoxypropane, 2,2-dineopentyl-1,3-dimethoxypropane, 2-isopropyl-2-iso pentyl-1,3-dimethoxypropane, 2-phenyl-2-benzyl-1,3-dime thoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dime thoxypropane, 2-isopropyl-2-(3,7-dimethyloctyl) 1,3- 0098. In Formula VII R' and R* are each independently dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, selected from a hydrogen or a hydrocarbyl group selected 2-isopropyl-2-cyclohexylmethyl-1,3-dimethoxypropane, e.g. from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or 2,2-diisopentyl-1,3-dimethoxypropane, 2-isopropyl-2-cy alkylaryl groups, and one or more combinations thereof. clohexyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclopen Said hydrocarbyl group may be linear, branched or cyclic. tyl-1,3-dimethoxypropane, 2,2-dicylopentyl-1,3-dime Said hydrocarbyl group may be substituted or unsubstituted. thoxypropane, 2-n-heptyl-2-n-pentyl-1,3- Said hydrocarbyl group may contain one or more heteroa dimethoxypropane, 9.9-bis(methoxymethyl)fluorene, 1,3- toms. Preferably, said hydrocarbyl group has from 1 to 10 dicyclohexyl-2.2-bis(methoxymethyl)propane, 3,3-bis carbon atoms, more preferably from 1 to 8 carbon atoms, (methoxymethyl)-2,5-dimethylhexane, or any combination even more preferably from 1 to 6 carbon atoms. Suitable of the foregoing. In an embodiment, the internal electron examples of hydrocarbyl groups include alkyl-, cycloalkyl-, donor is 1,3-dicyclohexyl-2.2-bis(methoxymethyl)propane, alkenyl-, alkadienyl-, cycloalkenyl-, cycloalkadienyl-, aryl-, 3.3-bis(methoxymethyl)-2,5-dimethylhexane, 2,2-dicyclo aralkyl, alkylaryl, and alkynyl-groups. pentyl-1,3-dimethoxypropane and combinations thereof. 0099. In Formula VII Rand Rare each independently Examples of preferred diethers are 2-ethyl-2-butyl-1,3-di selected a hydrocarbyl group, selected from e.g. alkyl, methoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxy alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, propane and 9.9-bis (methoxymethyl)fluorene: and one or more combinations thereof. Said hydrocarbyl group may be linear, branched or cyclic. Said hydrocarbyl group may be substituted or unsubstituted. Said hydrocarbyl group may contain one or more heteroatoms. Preferably, said hydrocarbyl group has from 1 to 10 carbon atoms, more preferably from 1 to 8 carbon atoms, even more preferably CO from 1 to 6 carbon atoms. 0100 Suitable examples of dialkyl diether compounds O include 1,3-dimethoxypropane, 1,3-diethoxypropane, 1.3- dibutoxypropane, 1-methoxy-3-ethoxypropane, 1-methoxy 3-butoxypropane, 1-methoxy-3-cyclohexoxypropane, 2.2- dimethyl-1,3-dimethoxypropane, 2,2-diethyl-1,3- dimethoxypropane, 2,2-di-n-butyl-1,3-dimethoxypropane, 0101 The present invention is related to Ziegler-Natta 2,2-diiso-butyl-1,3-dimethoxypropane, 2-ethyl-2-n-butyl-1, type catalyst. A Ziegler-Natta type procatalyst generally 3-dimethoxypropane, 2-n-propyl-2-cyclopentyl-1,3-dime comprising a solid Support, a transition metal-containing thoxypropane, 2.2-dimethyl-1,3-diethoxypropane, 2-n-pro catalytic species and one or more internal donors and one or pyl-2-cyclohexyl-1,3-diethoxypropane, 2-(2-ethylhexyl)-1, more activators. The present invention moreover relates to a 3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, catalyst system comprising a Ziegler-Natta type procatalyst, US 2016/031 1947 A1 Oct. 27, 2016

a co-catalyst and optionally an external electron donor. The solid titanium tetrachloride, a solvent and benzoylchloride term "Ziegler-Natta' is known in the art. were added. The mixture was heated to obtain a solid 0102 The transition metal-containing solid catalyst com product. The last step was repeated. The resulting Solid pound comprises a transition metal halide (e.g. titanium procatalyst was worked up to provide a catalyst. Example 2 halide, chromium halide, hafnium halide, Zirconium halide, of U.S. Pat. No. 6,825,146.2 is incorporated by reference. Vanadium halide) Supported on a metal or metalloid com (0.108 U.S. Pat. No. 4,771,024 discloses the preparation pound (e.g. a magnesium compound or a silica compound). of a catalyst on column 10, line 61 to column 11, line 9. The Specific examples of several types of Ziegler-Natta catalyst section “catalyst manufacture on silica' is incorporated into as disclosed below. the present application by reference. The process comprises 0103 Preferably, the present invention is related to a combining dried silica with carbonated magnesium Solution so-called TiNo catalyst, the process of claim 2 is related to (magnesium diethoxide in ethanol was bubbled with CO). this so-called TiNo catalyst (see also discussed about Phases The solvent was evaporated at 85°C. The resulting solid was A-D below). It is a magnesium-based supported titanium washed and a 50:50 mixture of titanium tetrachloride and halide catalyst optionally comprising one or more internal chlorobenzene was added to the solvent together with eth donors. ylbenzoate. The mixture was heated to 100° C. and liquid 0104 EP 1 273 595 of Borealis Technology discloses a filtered. Again TiCl, and chlorobenzene were added, fol process for producing an olefin polymerization procatalyst lowed by heating and filtration. A final addition of TiCl, and in the form of particles having a predetermined size range, chlorobenzene and benzoylchloride was carried out, fol said process comprising: preparing a solution a complex of lowed by heating and filtration. After washing the catalyst a Group IIa metal and an electron donor by reacting a was obtained. compound of said metal with said electron donor or a 0109 WO03/068828 discloses a process for preparing a precursor thereof in an organic liquid reaction medium; catalyst component on page 91 preparation of Solid catalyst reacting said complex, in Solution, with at least one com components' which section is incorporated into the present pound of a transition metal to produce an emulsion the application by reference. Magnesium chloride, toluene, dispersed phase of which contains more than 50 mol.% of epoxy chloropropane and tributyl phosphate were added the Group IIa metal in said complex: maintaining the under nitrogen to a reactor, followed by heating. Then particles of said dispersed phase within the average size phthalic anhydride was added. The solution was cooled to range 10 to 200 um by agitation in the presence of an -25° C. and TiCl, was added drop wise, followed by emulsion stabilizer and solidifying said particles; and recov heating. An internal donor was added (1,3-diphenyl-1,3- ering, washing and drying said particles to obtain said propylene glycol dibenzoate, 2-methyl-1,3-diphenyl-1,3- procatalyst. propylene glycol dibenzoate, 1,3-diphenyl-1,3-propylene 0105 EP 0019 330 of Dow discloses a Ziegler-Natta glycol diproprionate, or 1,3-diphenyl-2-methyl-1,3- type catalyst composition. Said olefin polymerization cata propylene glycol diproprionate) and after stirring a solid was lyst composition is prepared using a process comprising: a) obtained and washed. The solid was treated with TiCl, in a reaction product of an organo aluminum compound and an toluene twice, followed by washing to obtain a catalyst electron donor, and b) a Solid component which has been component. obtained by halogenating a magnesium compound with the 0110 U.S. Pat. No. 4.866,022 discloses a catalyst com formula MgR'R' wherein R is an alkyl, aryl, alkoxide or ponent comprises a product formed by: A. forming a solu aryloxide group and R is an alkyl, aryl, alkoxide or ary tion of a magnesium-containing species from a magnesium loxide group or halogen, are contacted with a halide of carbonate or a magnesium carboxylate; B. precipitating tetravalent titanium in the presence of a halohydrocarbon, Solid particles from Such magnesium-containing Solution by and contacting the halogenated product with a tetravalent treatment with a transition metal halide and an organosilane titanium compound. This production method as disclosed in having a formula: R,SiR wherein n=0 to 4 and wherein EP 0019 330 is incorporated by reference. R is hydrogen or an alkyl, a haloalkyl or aryl radical 0106. The Examples of U.S. Pat. No. 5,093.415 of Dow containing one to about ten carbon atoms or a halosilyl discloses an improved process to prepare a procatalyst. Said radical or haloalkylsilyl radical containing one to about eight process includes a reaction between titanium tetrachloride, carbon atoms, and R' is OR or a halogen: C. reprecipitating disobutyl phthalate, and magnesium diethoxide to obtain a Such solid particles from a mixture containing a cyclic ether; solid material. This solid material is then slurried with and D. treating the reprecipitated particles with a transition titanium tetrachloride in a solvent and phthaloyl chloride is metal compound and an electron donor. This process for added. The reaction mixture is heated to obtain a solid preparing a catalyst is incorporated into the present appli material which is reslurried in a solvent with titanium cation by reference. tetrachloride. Again this was heated and a solid collected. 0111. The procatalyst may be produced by any method Once again the Solid was reslurried once again in a solution known in the art. of titanium tetrachloride to obtain a catalyst. The Examples 0112 The procatalyst may also be produced as disclosed of U.S. Pat. No. 5,093.415 are incorporated by reference. in WO96/32426A; this document discloses a process for the 0107 Example 2 of U.S. Pat. No. 6,825,146.2 of Dow polymerization of propylene using a catalyst comprising a discloses another improved process to prepare a catalyst. catalyst component obtained by a process wherein a com Said process includes a reaction between titanium tetrachlo pound with formula Mg(OAlk), Cl, wherein x is larger than ride in Solution with a precursor composition prepared by 0 and Smaller than 2, y equals 2-X and each Alk, indepen reacting magnesium diethoxide, titanium tetraethoxide, and dently, represents an alkyl group, is contacted with a tita titanium tetrachloride, in a mixture of ortho-cresol, ethanol nium tetraalkoxide and/or an alcohol in the presence of an and chlorobenzene—and ethylbenzoate as electron donor. inert dispersant to give an intermediate reaction product and The mixture was heated and a solid was recovered. To the wherein the intermediate reaction product is contacted with US 2016/031 1947 A1 Oct. 27, 2016

titanium tetrachloride in the presence of an internal donor, 0.126 The various steps used to prepare the catalyst which is di-n-butyl phthalate (DBP). according to the present invention (and the prior art) are 0113 Preferably, the Ziegler-Natta type procatalyst in the described in more detail below. catalyst system according to the present invention is I0127 Phase A: Preparing a Solid Support for the Catalyst obtained by the process as described in WO 2007/134851 I0128. In the process of the present invention preferably a A1. This process relates to a so-called TiNo catalyst. In magnesium-containing Support is used. Said magnesium Example I the process is disclosed in more detail. Example containing Support is known in the art as a typical compo I including all sub-examples (IA-IE) of WO 2007/134851 nent of a Ziegler-Natta procatalyst. This step of preparing a A1 is incorporated into the present description. More details Solid Support for the catalyst is the same as in the prior art about the different embodiments are disclosed starting on process. The following description explains the process of page 3, line 29 to page 14 line 29 of WO 2007/134851 A1. preparing magnesium-based support. Other Supports may These embodiments are incorporated by reference into the also be used. present description. 0129. Synthesis of magnesium-containing Supports, such 0114. In the following part of the description the different as magnesium halides, magnesium alkyls and magnesium steps and phases of the process for preparing the procatalyst aryls, and also magnesium alkoxy and magnesium aryloxy according to an embodiment of the present invention will be compounds for polyolefin production, particularly of poly discussed. This process leads to a so-called TiNo procatalyst propylenes production are described for instance in U.S. Pat. discussed in claim 2. No. 4,978,648, WO96/32427A1, WO01/23441 A1, EP1283 0115 The process for preparing a procatalyst according 222A1, EP1222214B1; U.S. Pat. No. 5,077.357; U.S. Pat. to an embodiment of the the present invention comprises the No. 5,556,820; U.S. Pat. No. 4414, 132; U.S. Pat. No. following phases: 5,106,806 and U.S. Pat. No. 5,077.357 but the present 0116 Phase A): preparing a solid support for the procata process is not limited to the disclosure in these documents. lyst; 0.130 Preferably, the process for preparing the solid Sup port for the procatalyst according to the present invention 0117 Phase B): optionally activating said solid support comprises the following steps: Step o) which is optional and obtained in phase A) using one or more activating com step i). pounds to obtain an activated Solid Support; I0131 Step o) Preparation of the Grignard Reagent (Op 0118 Phase C): contacting said solid support obtained in tional) phase A) or said activated solid support in phase B) with a (0132) A Grignard reagent, RzMgX used in step i) catalytic species wherein phase C) comprises one of the may be prepared by contacting metallic magnesium with an following: organic halide RX, as described in WO 96/32427 A1 and 0119 contacting said solid support obtained in phase WO01/23441 A1. All forms of metallic magnesium may be A) or said activated solid support in phase B) with a used, but preferably use is made of finely divided metallic catalytic species and one or more internal donors to magnesium, for example magnesium powder. To obtain a obtain said procatalyst; or fast reaction it is preferable to heat the magnesium under I0120 contacting said solid support obtained in phase nitrogen prior to use. A) or said activated solid support in phase B) with a I0133) R' is a hydrocarbyl group independently selected catalytic species and one or more internal donors to from e.g. alkyl, alkenyl, aryl, aralkyl, alkylaryl, or alkoxy obtain an intermediate product; or carbonyl groups, wherein said hydrocarbyl group may be 0121 contacting said solid Support obtained in phase linear, branched or cyclic, and may be substituted or unsub A) or said activated solid support in phase B) with a stituted; said hydrocarbyl group preferably having from 1 to catalytic species and an activator to obtain an interme 20 carbon atoms or combinations thereof. The R group may diate product; contain one or more heteroatoms. 0122) optionally Phase D: modifying said intermediate 10134) X* is selected from the group of consisting of product obtained in phase C) wherein phase D) comprises on fluoride (F ), chloride (Cl-), bromide (Br ) or iodide of the following: (I- ). The value for Z is in a range of larger than 0 and I0123 modifying said intermediate product obtained in smaller than 2:0

0177 Step ii) Activation of the Solid Magnesium Com 0186 Preferably, an alcohol is used as the activating pound electron donor in step ii). More preferably, the alcohol is a (0178 Step ii): contacting the solid Mg(OR"),X' with linear or branched aliphatic or aromatic alcohol having 1-12 at least one activating compound selected from the group carbon atoms. Even more preferably, the alcohol is selected formed by activating electron donors and metal alkoxide from methanol, ethanol, butanol, isobutanol, hexanol, Xyle compounds of formula M'(OR), (OR), or M(OR), nol and benzyl alcohol. Most preferably, the alcohol is (R), wherein: ethanol or methanol, preferably ethanol. (0179 R is a hydrocarbyl group independently selected 0187 Suitable carboxylic acids as activating electron e.g. from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or donor may be aliphatic or (partly) aromatic. Examples alkylaryl groups, and one or more combinations thereof. include formic acid, acetic acid, propionic acid, butyric acid, Said hydrocarbyl group may be linear, branched or cyclic. isobutanoic acid, acrylic acid, methacrylic acid, maleic acid, Said hydrocarbyl group may be substituted or unsubstituted. fumaric acid, tartaric acid, cyclohexanoic monocarboxylic Said hydrocarbyl group may contain one or more heteroa acid, cis-1,2-cyclohexanoic dicarboxylic acid, phenylcar toms. Preferably, said hydrocarbyl group has from 1 to 20 boxylic acid, toluenecarboxylic acid, naphthalene carbox carbon atoms, more preferably from 1 to 12 carbon atoms, ylic acid, phthalic acid, isophthalic acid, terephthalic acid even more preferably from 1 to 6 carbon atoms. Preferably, and/or trimellitic acid. said hydrocarbyl group is an alkyl group, preferably having 0188 Anhydrides of the aforementioned carboxylic acids from 1 to 20 carbon atoms, more preferably from 1 to 12 can be mentioned as examples of carboxylic acid anhy carbon atoms, even more preferably from 1 to 6 carbon drides, such as for example acetic acid anhydride, butyric atoms, such as for example methyl, ethyl, n-propyl, isopro acid anhydride and methacrylic acid anhydride. pyl. n-butyl, sec-butyl, iso-butyl, t-butyl, pentyl or hexyl, 0189 Suitable examples of esters of above-mentioned most preferably selected from ethyl and methyl. carboxylic acids are formates, for instance, butyl formate; 0180 R is a hydrocarbyl group independently selected acetates, for instance ethyl acetate and butyl acetate; acry e.g. from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or lates, for instance ethyl acrylate, methyl methacrylate and alkylaryl groups, and one or more combinations thereof. isobutyl methacrylate; benzoates, for instance methylbenzo Said hydrocarbyl group may be linear, branched or cyclic. ate and ethylbenzoate; methyl-p-toluate; ethyl-naphthate Said hydrocarbyl group may be substituted or unsubstituted. and phthalates, for instance monomethyl phthalate, dibutyl Said hydrocarbyl group may contain one or more heteroa phthalate, diisobutyl phthalate, diallyl phthalate and/or toms. Preferably, said hydrocarbyl group has from 1 to 20 diphenyl phthalate. carbon atoms, more preferably from 1 to 12 carbon atoms, even more preferably from 1 to 6 carbon atoms. Preferably, 0190. Examples of suitable carboxylic acid halides as said hydrocarbyl group is an alkyl group, preferably having activating electron donors are the halides of the carboxylic from 1 to 20 carbon atoms, more preferably from 1 to 12 acids mentioned above, for instance acetyl chloride, acetyl carbon atoms, even more preferably from 1 to 6 carbon bromide, propionyl chloride, butanoyl chloride, butanoyl atoms; most preferably selected from methyl, ethyl, n-pro iodide, benzoyl bromide, p-toluyl chloride and/or phthaloyl pyl, isopropyl. n-butyl, Sec-butyl, iso-butyl, t-butyl, and dichloride. cyclopentyl. 0191 Suitable alcohols are linear or branched aliphatic 0181 M' is a metal selected from the group consisting of alcohols with 1-12 C-atoms, or aromatic alcohols. Examples Ti, Zr, Hf, Al or Si; v is the valency of M', M is a metal include methanol, ethanol, butanol, isobutanol, hexanol, being Si; V is the valency of M and w is smaller than v. xylenol and benzyl alcohol. The alcohols may be used alone 0182. The electron donors and the compounds of formula or in combination. Preferably, the alcohol is ethanol or M(OR), (OR), and M(OR), (R) may be also hexanol. referred herein as activating compounds. 0.192 Examples of suitable ethers are diethers, such as2 0183 In this step either one or both types of activating ethyl-2-butyl-1,3-dimethoxypropane, 2-isopropyl-2-isopen compounds (viz. activating electron donor or metal alkox tyl-1,3-dimethoxypropane and/or 9.9-bis(methoxymethyl) ides) may be used. fluorene. Also, cyclic ethers like tetrahydrofuran (THF), or 0184 The advantage of the use of this activation step tri-ethers can be used. prior to contacting the Solid Support with the halogen 0193 Suitable examples of other organic compounds containing titanium compound (process phase C) is that a containing a heteroatom for use as activating electron donor higher yield of polyolefins is obtained per gram of the include 2.2.6,6-tetramethyl piperidine, 2,6-dimethylpiperi procatalyst. Moreover, the ethylene sensitivity of the cata dine, pyridine, 2-methylpyridine, 4-methylpyridine, imida lyst system in the copolymerization of propylene and eth Zole, benzonitrile, aniline, diethylamine, dibutylamine, dim ylene is also increased because of this activation step. This ethylacetamide, thiophenol, 2-methyl thiophene, isopropyl activation step is disclosed in detail in WO2007/134851 of mercaptan, diethylthioether, diphenylthioether, tetrahydro the present applicant. furan, dioxane, dimethylether, diethylether, anisole, acetone, 0185. Examples of suitable activating electron donors triphenylphosphine, triphenylphosphite, diethylphosphate that may be used in step ii) are known to the skilled person and/or diphenylphosphate. and described herein below, i.e. include carboxylic acids, 0194 Examples of suitable metal alkoxides for use in carboxylic acid anhydrides, carboxylic acid esters, carbox step ii) are metal alkoxides of formulas: M'(OR), (OR), ylic acid halides, alcohols, ethers, ketones, amines, amides, and M(OR), (R), wherein M', M. R. R. v., and w are nitriles, aldehydes, alkoxides, Sulfonamides, thioethers, as defined herein. Rand R can also be aromatic hydrocar thioesters and other organic compounds containing one or bon groups, optionally Substituted with e.g. alkyl groups and more hetero atoms, such as nitrogen, oxygen, Sulfur and/or can contain for example from 6 to 20 carbon atoms. The R phosphorus. and R preferably comprise 1-12 or 1-8 carbon atoms. In US 2016/031 1947 A1 Oct. 27, 2016 preferred embodiments R and Rare ethyl, propyl or butyl: 0206. The reaction time after the activating compounds more preferably all groups are ethyl groups. have been added is preferably from 0 to 3 hours. (0195 Preferably, M' in said activating compound is Tior 0207. The mixing speed during the reaction depends on Si. Si-containing compounds Suitable as activating com the type and the scale of the reactor used. The mixing speed pounds are the same as listed above for step i). can be determined by a person skilled in the art and should 0196. The value of w is preferably 0, the activating be sufficient to agitate the reactants. compound being for example a titanium tetraalkoxide con 0208. The inert dispersant used in step ii) is preferably a taining 4-32 carbon atoms in total from four alkoxy groups. hydrocarbon Solvent. The dispersant may be for example an The four alkoxide groups in the compound may be the same aliphatic or aromatic hydrocarbon with 1-20 carbon atoms. or may differ independently. Preferably, at least one of the Preferably, the dispersant is an aliphatic hydrocarbon, more alkoxy groups in the compound is an ethoxy group. More preferably pentane, iso-pentane, hexane or heptane, heptane preferably the compound is a tetraalkoxide, such as titanium being most preferred. tetraethoxide. 0209 Starting from a solid Mg-containing product of 0197) In the preferred process to prepare the procatalyst, controlled morphology obtained in step i), said morphology one activating compound can be used, but also a mixture of is not negatively affected during treatment with the activat two or more compounds may be used. ing compound during step ii). The Solid second intermediate (0198 A combination of a compound of M'(OR), reaction product obtained in step ii) is considered to be an (OR), or M(OR), (R), with an electron donor is pre adduct of the Mg-containing compound and the at least one ferred as activating compound to obtain a catalyst system activating compound as defined in step ii), and is still of that for example shows high activity, and of which the controlled morphology. ethylene sensitivity can be affected by selecting the internal 0210. The obtained second intermediate reaction product donor, which is specifically advantageous in preparing copo after step ii) may be a solid and may be further washed, lymers of for example propylene and ethylene. preferably with the solvent also used as inert dispersant; and 0199 Preferably, a Ti-based compound, for example tita then stored and further used as a Suspension in said inert nium tetraethoxide, is used together with an alcohol, like solvent. Alternatively, the product may be dried, preferably ethanol or hexanol, or with an ester compound, like ethyl partly dried, preferably slowly and under mild conditions: acetate, ethylbenzoate or a phthalate ester, or together with e.g. at ambient temperature and pressure. an ether, like dibutylether, or with pyridine. 0200. If two or more activating compounds are used in 0211 Phase C. Contacting said Solid Support with the step ii) their order of addition is not critical, but may affect Catalytic Species and One or More Internal Donors and/or catalyst performance depending on the compounds used. A Optionally an Activator. skilled person may optimize their order of addition based on 0212 Phase C. contacting the solid support with a cata Some experiments. The compounds of step ii) can be added lytic species, an activator and an internal donor. This step together or sequentially. can take different forms, such as i) contacting a solid Support 0201 Preferably, an electron donor compound is first with the catalytic species and one or more internal donors added to the compound with formula Mg(OR"), X' where and optionally an activator to obtain an intermediate prod after a compound of formula M'(OR), (OR), or uct; ii) contacting a Solid Support with a catalytic species and M(OR), (R), as defined herein is added. The activating one or more internal donors and optionally an activator to compounds preferably are added slowly, for instance during obtain a procatalyst. In case no activator is used during a period of 0.1-6, preferably during 0.5-4 hours, most Phase C, and activator is used during step V) of Phase D preferably during 1-2.5 hours, each. discussed below. 0202 The first intermediate reaction product that is 0213. The contacting of the solid support with the cata obtained in Step i) can be contacted when more than one lytic species may comprise several stages (e.g. I, II and/or activating compound is used in any sequence with the III). During each of these consecutive stages the Solid activating compounds. In one embodiment, an activating Support is contacted with said catalytic species. In other electron donor is first added to the first intermediate reaction words, the addition or reaction of said catalytic species may product and then the compound M'(OR), (OR), or be repeated one or more times. The same or different M(OR), (R), is added; in this order no agglomeration of catalytic species may be used during these stages. Solid particles is observed. The compounds in step ii) are 0214. During at least of these stages the solid support is preferably added slowly, for instance during a period of further contacted with an 1,3-diether internal donor. During 0.1-6, preferably during 0.5-4 hours, most preferably during one of these stages the Solid Support is further contacted with 1-2.5 hours, each. a benzamide activator. 0203 The molar ratio of the activating compound to 0215. These stages may be divived over Phase C (e.g. Mg(OR"),X' may range between wide limits and is, for step iii) and Phase D (e.g. step V) or step V-a) and V-b). It is instance, from 0.02 to 1.0. Preferably, the molar ratio is from possible that Phase C comprises one more more stages and 0.05 to 0.5, more preferably from 0.06 to 0.4, or even from that Phase D comprises also one or more stages. O.O7 to 0.2. 0216 For example, during stage I in phase C (step iii) the 0204 The temperature in step ii) can be in the range from solid support (first intermediate) or the activated solid sup –20° C. to 70° C., preferably from -10° C. to 50° C., more port (second intermediate) is first contacted with said cata preferably in the range from -5°C. to 40° C., and most lytic species and optionally Subsequently with one or more preferably in the range from 0° C. to 30° C. internal donors. When a second stage is present, during stage 0205 Preferably, at least one of the reaction components II (either Phase C or Phase D) the intermediate product is dosed in time, for instance during 0.1 to 6, preferably obtained from stage I will be contacted with additional during 0.5 to 4 hours, more particularly during 1-2.5 hours. catalytic species which may the same or different than the US 2016/031 1947 A1 Oct. 27, 2016

catalytic species added during the first stage and optionally 150° C., and more preferably from 100° C. to 140° C. Most one or more internal donors and optionally an activator. preferably, the reaction temperature is from 110° C. to 125° 0217. In case three stages are present, in an embodiment, C stage III is V) of Phase D which is preferably a repetition of 0229. The reaction time during step iii) is preferably from stage I or may comprise the contacting of the product 10 minutes to 10 hours. In case several stages are present, obtained from phase II with both a catalytic species (which each stage can have a reaction time from 10 minutes to 10 may be the same or different as above) and one or more hours. The reaction time can be determined by a person internal donors. In other words, an internal donor may be skilled in the art based on the type and scale of the reactor added during each of these stages or during two or more of and the procatalyst. these stages. When an internal donor is added during more 0230. The mixing speed during the reaction depends on than one stage it may be the same or a different internal the type and the scale of the reactor used. The mixing speed donor. In an embodiment stage I is step iii) of Phase C, stage can be determined by a person skilled in the art and should II is step V-a) of Phase D, and stage III is step V-b) of Phase be sufficient to agitate the reactants. D 0231. The obtained reaction product may be washed, 0218. An activator according to the present invention usually with an inert aliphatic or aromatic hydrocarbon or may be added either during stage I or stage II or stage III halogenated aromatic compound, to obtain the procatalyst of (viz. either in Phase C or in Phase D or both). An activator the invention. If desired the reaction and Subsequent puri may also be added during more than one stage. However, at fication steps may be repeated one or more times. A final least during one of the stages an activator should be present. washing is preferably performed with an aliphatic hydro 0219 Phase C) preferably comprises the following step carbon to result in a Suspended or at least partly dried iii). procatalyst, as described above for the other steps. 0232 An activator is also present during Phase C or 0220 Step iii) Reacting the Solid Support with a Tran during Phase D and is used during at least one stage of sition Metal Halide contacting the Solid Support or an intermediate product with 0221) Step iii) reacting the solid support with a transition a catalytic species. If an activator is present during Phase C, metal halide (e.g. a halide of titanium, chromium, hafnium, which is preferable, the molar ratio of the activator relative zirconium or vanadium) but preferably titanium halide. This to the magnesium may vary between wide limits, for is a step of contacting the Solid Support with a catalytic instance from 0.02 to 0.5. Preferably, this molar ratio is from species. In the discussion below only the process for a 0.05 to 0.4; more preferably from 0.1 to 0.3; and most titanium-base Ziegler-Natta procatalyst is disclosed, how preferably from 0.1 to 0.2. ever, the application is also applicable to other types of 0233 Phase D: Modifying said Catalyst with a Metal Ziegler-Natta procatalysts. Based Modifier. 0222 Step iii): contacting the first or second intermediate 0234. This phase D is optional in the present invention. In reaction product, obtained respectively in step i) or ii), with a preferred process for modifying the Supported catalyst, this a halogen-containing Ti-compound and an internal electron phase consists of Step iv) modifying the third intermediate donor or activator to obtain a third intermediate product. product with a metal-modifier to yield a modified interme 0223 Step iii) can be carried out after step i) on the first diate product. intermediate product or after step ii) on the second interme 0235. After step iv) if this is carried out—an additional diate product. step of contacting the intermediate product with a catalytic 0224. The molar ratio in step iii) of the transition metal to species (in other words, an additional stage): the magnesium preferably is from 10 to 100, most prefer 0236 Step V) contacting said modified intermediate prod ably, from 10 to 50. uct with a titanium halide and optionally on or more internal 0225. An internal electron donor may be present during donors and/or activators to obtain the present procatalyst. In step iii). Also mixtures of internal electron donors may be case no activator is used during Phase C, an activator is used used. Examples of internal electron donors are disclosed during step V) of Phase D. later in the description. At least one 1,3-diether internal 0237. The order of addition, viz. the order of first step iv) donor is present according to the present invention. and Subsequently step V) is considered to be very important 0226. The molar ratio of the internal electron donor to the formation of the correct clusters of Group 13- or relative to the magnesium may vary between wide limits, for transition metal and titanium forming the modified and more instance from 0.02 to 0.75. Preferably, this molar ratio is active catalytic center. from 0.05 to 0.4; more preferably from 0.1 to 0.4; and most 0238 Each of these steps is disclosed in more detail preferably from 0.1 to 0.3. below. 0227 During contacting the first or second intermediate 0239. It should be noted that the steps iii), iv) and v) (viz. product and the halogen-containing titanium compound, an phases C and D) are preferably carried out in the same inert dispersant is preferably used. The dispersant preferably reactor, viz. in the same reaction mixture, directly following is chosen such that virtually all side products formed are each other. dissolved in the dispersant. Suitable dispersants include for 0240 Preferably, step iv) is carried out directly after step example aliphatic and aromatic hydrocarbons and haloge iii) in the same reactor. Preferably, step V) is carried out nated aromatic solvents with for instance 4-20 carbon atoms. directly after step iv) in the same reactor. Examples include toluene, Xylene, benzene, heptane, o-chlo 0241 Step iv): Group 13- or Transition Metal Modifica rotoluene and chlorobenzene. tion 0228. The reaction temperature during step iii) is prefer 0242. The modification with Group 13- or transition ably from 0° C. to 150° C., more preferably from 50° C. to metal, preferably aluminium, ensures the presence of Group US 2016/031 1947 A1 Oct. 27, 2016

13- or transition metal in the procatalyst, in addition to with for instance 4-20 carbon atoms. Examples include magnesium (from the solid Support) and titanium (from the toluene, Xylene, benzene, decane, o-chlorotoluene and chlo titanation treatment). robenzene. The solvent may also be a mixture or two or 0243 Without wishing to be bound by any particular more thereof. theory, the present invention believe that one possible expla 0250. The duration of the modification step may vary nation is that the presence of Group 13- or transition metal from from 1 minute to 120 minutes, preferably from 40 to increases the reactivity of the active site and hence increases 80 minutes, more preferably from 50 to 70 minutes. This the yield of polymer. time is dependent on the concentration of the modifier, the 0244 Step iv) comprises modifying the third intermedi temperature, the type of solvent used etc. ate product obtained in step iii) with a modifier having the 0251. The modification step is preferably carried out at formula M(p)X, preferably MX, wherein M is a metal elevated temperatures (e.g. from 50 to 120° C., preferably selected from the Group 13 metals and transition metals of from 90 to 110° C.). the IUPAC periodic table of elements, p is the oxidation state 0252. The modification step may be carried out while of M, and wherein X is a halide to yield a modified stirring. The mixing speed during the reaction depends i.a. intermediate product. In case the oxidation state of M, e.g. on the type of reactor used and the scale of the reactor used. aluminum, is three, M(p) is Al(III) and there are three The mixing speed can be determined by a person skilled in monovalent halides X, e.g. AlCls or AlF. In case the the art. As a non-limiting example, mixing may be carried at oxidation state of M, e.g. copper, is two, M(p) is Cu(II) and a stirring speed from 100 to 400 rpm, preferably from 150 there are two monovalent halides X, CuBr or CuCl2. to 300 rpm, more preferably about 200 rpm. 0245 Step iv) is preferably carried out directly after step 0253. The wt/vol ratio for the metal halide and the iii), more preferably in the same reactor and preferably in the solvent in step iv) is is in the range of weights from 0.01 same reaction mixture. In an embodiment, a mixture of gram to 0.1 gram over volumes in the range from: 5.0 to 100 aluminum trichloride and a solvent, e.g. chlorobenzene, is ml. added to the reactor after step iii) has been carried out. After 0254 The modified intermediate product is present in a the reaction has completed a solid is allowed to settle which solvent. It can be kept in that solvent after which the can either be obtained by decanting or filtration and option following step V) is directly carried out. However, it can also ally purified or a suspension of which in the solvent can be be isolated and/or purified. The solid can be allowed to settle used for the following step, viz. Step V). by stopping the stirring. The Supernatant may be removed by 0246 The metal modifier is preferably selected from the decanting. Otherwise, filtration of the suspension is also group of aluminium modifiers (e.g. aluminium halides), possible. The solid product may be washed once or several boron modifiers (e.g. boronhalides), gallium modifiers (e.g. times with the same solvent used during the reaction or gallium halides), Zinc modifiers (e.g. Zinc halides), copper another solvent selected from the same group described modifiers (e.g. copper halides), thallium modifiers (e.g. above. The solid may be re-suspended or may be dried or thallium halides), indium modifiers (e.g. indium halides), partially dried for storage. Vanadium modifiers (e.g. Vanadium halides), chromium 0255 Subsequent to this step, step V) is carried out to modifiers (e.g. chromium halides) and iron modifiers (e.g. produce the procatalyst according to the present invention. iron halides). (0256 Step V): Titanation of Intermediate Product 0247 Examples of suitable modifiers are aluminum 0257. This step is very similar to step iii). It relates to the trichloride, aluminum tribromide, aluminum triiodide, alu additional titanation of the modified intermediate product. It minum trifluoride, borontrichloride, borontribromide boron is an additional stage of contacting with catalytic species triiodide, boron trifluoride, gallium trichloride, gallium tri (viz. titanation in this embodiment). bromide, gallium triiodide, gallium trifluoride, Zinc dichlo 0258 Step V) contacting said modified intermediate prod ride, Zinc dibromide, Zinc diiodide, Zinc difluoride, copper uct obtained in step iv) with a halogen-containing titanium dichloride, copper dibromide, copper diiodide, copper dif compound to obtain the procatalyst according to the present luoride, copper chloride, copper bromide, copper iodide, invention. When an activator is used during step iii) but not copper fluoride, thallium trichloride, thallium tribromide, an internal donor, an internal donor is used during this step thallium triiodide, thallium trifluoride, thallium chloride, v). thallium bromide, thallium iodide, thallium fluoride, Indium 0259 Step v) is preferably carried out directly after step trichloride, indium tribromide, indium triiodide, indium iv), more preferably in the same reactor and preferably in the trifluoride, Vanadium trichloride, vanadium tribromide, same reaction mixture. vanadium triiodide, Vanadium trifluoride, chromium trichlo 0260. In an embodiment, at the end of step iv) or at the ride, chromium dichloride, chromium tribromide, chromium beginning of step V) the Supernatant is removed from the dibromide, iron dichloride, iron trichloride, iron tribromide, solid modified intermediate product obtained in step iv) by iron dichloride, iron triiodide, iron diiodide, iron trifluoride filtration or by decanting. To the remaining Solid, a mixture and iron difluoride. of titanium halide (e.g. tetrachloride) and a solvent (e.g. 0248. The amount of metal halide added during step iv) chlorobenzene) may be added. The reaction mixture is may vary according to the desired amount of metal present Subsequently kept at an elevated temperature (e.g. from 100 in the procatalyst. It may for example range from 0.1 to 5 wt. to 130°C., such as 115°C.) for a certain period of time (e.g. % based on the total weight of the support, preferably from from 10 to 120 minutes, such as from 20 to 60 minutes, e.g. O.5 to 1.5 wt.%. 30 minutes). After this, a solid substance is allowed to settle 0249. The metal halide is preferably mixed with a solvent by stopping the stirring. prior to the addition to the reaction mixture. The solvent for 0261. The molar ratio of the transition metal to the this step may be selected from for example aliphatic and magnesium preferably is from 10 to 100, most preferably, aromatic hydrocarbons and halogenated aromatic solvents from 10 to 50. US 2016/031 1947 A1 Oct. 27, 2016

0262 Optionally, an internal electron donor is also pres observed by the inventors. When this modification is carried ent during this step. Also mixtures of internal electron out after the titanation step the increase in activity was less donors may be used. Examples of internal electron donors as observed by the present inventors. are disclosed above. The molar ratio of the internal electron 0273. An embodiment of the present invention comprises donor relative to the magnesium may vary between wide the following steps: i) preparation of first intermediate limits, for instance from 0.02 to 0.75. Preferably, this molar reaction product; ii) activation of Solid Support to yield ratio is from 0.05 to 0.4; more preferably from 0.1 to 0.4; and second intermediate reaction product; iii) first titanation or most preferably from 0.1 to 0.3. Stage I to yield third intermediate reaction product including 0263. The solvent for this step may be selected from for an activator; iv) modification to yield modified intermediate example aliphatic and aromatic hydrocarbons and haloge product; v) second titanation or Stage II/III to yield the nated aromatic solvents with for instance 4-20 carbon atoms. procatalyst and including an internal donor. The solvent may also be a mixture or two or more thereof. 0274. An embodiment of the present invention comprises 0264. According to a preferred embodiment of the pres the following steps: i) preparation of first intermediate ent invention this step V) is repeated, in other words, the reaction product; ii) activation of Solid Support to yield Supernatant is removed as described above and a mixture of second intermediate reaction product; iii) first titanation or titanium halide (e.g. tetrachloride) and a solvent (e.g. chlo Stage I to yield third intermediate reaction product including robenzene) is added. The reaction is continued at elevated an activator and an internal donor; iv) modification to yield temperatures during a certain time which can be same or modified intermediate product; v) second titanation or Stage different from the first time step V) is carried out. II/III to yield the procatalyst. 0265. The step may be carried out while stirring. The 0275 An embodiment of the present invention comprises mixing speed during the reaction depends on the type of the following steps: i) preparation of first intermediate reactor used and the scale of the reactor used. The mixing reaction product; ii) activation of Solid Support to yield speed can be determined by a person skilled in the art. This second intermediate reaction product; iii) first titanation or can be the same as discussed above for step iii). Stage I to yield third intermediate reaction product including 0266 Thus, step V) can be considered to consist of at least an internal donor; iv) modification to yield modified inter two Sub steps in this embodiment, being: mediate product; v) second titanation or Stage II/III includ 0267 v-a) contacting said modified intermediate product ing an activator to yield the procatalyst. obtained in step iv) with titanium tetrachloride—optionally 0276. The procatalyst may have a titanium, hafnium, using an internal donor—to obtain a partially titanated Zirconium, chromium or vanadium (preferably titanium) procatalyst, (this can e.g. be considered to be stage II as content of from about 0.1 wt.% to about 6.0 wt.%, based discussed above for a three-stage Phase C); on the total solids weight, or from about 1.0 wt.% to about 0268 v-b) contacting said partially titanated procatalyst 4.5 wt.%, or from about 1.5 wt.% to about 3.5 wt.%. obtained in step V-a) with titanium tetrachloride to obtain the 0277. The weight ratio of titanium, hafnium, zirconium, procatalyst. (this can e.g. be considered to be stage III as chromium or vanadium (preferably titanium) to magnesium discussed above for a three-stage Phase C); in the solid procatalyst may be from about 1:3 to about 1:60. 0269. Additional sub steps can be present to increase the or from about 1:4 to about 1:50, or from about 1:6 to 1:30. number of titanation steps to four or higher (e.g. stages IV. Weight percent is based on the total weight of the procata V etc.) lyst. 0270. The solid substance (procatalyst) obtained is 0278. The transition metal-containing solid catalyst com washed several times with a solvent (e.g. heptane), prefer pound according to the present invention comprises a tran ably at elevated temperature, e.g. from 40 to 100° C. sition metal halide (e.g. titanium halide, chromium halide, depending on the boiling point of the solvent used, prefer hafnium halide, Zirconium halide or Vanadium halide) Sup ably from 50 to 70° C. After this, the procatalyst, suspended ported on a metal or metalloid compound (e.g. a magnesium in solvent, is obtained. The solvent can be removed by compound or a silica compound). filtration or decantation. The procatalyst can be used as Such 0279 Preferably, a magnesium-based or magnesium wetted by the solvent or suspended in solvent or it can be containing Support is used in the present invention. Such a first dried, preferably partly dried, for storage. Drying can Support is prepared from magnesium-containing Support e.g. be carried out by low pressure nitrogen flow for several precursors, such as magnesium halides, magnesium alkyls hours. and magnesium aryls, and also magnesium alkoxy and 0271 Thus in this embodiment, the total titanation treat magnesium aryloxy compounds. ment comprises three phases of addition of titanium halide. 0280. The support may be activated using activation Wherein the first phase of addition is separated from the compounds as described in more detail above under Phase second and third phases of addition by the modification with B metal halide. 0281. The catalyst system according to the present inven 0272. The titanation step (viz. the step of contacting with tion includes a co-catalyst. As used herein, a “co-catalyst” is a titanium halide) according to the present invention is split a term well-known in the art in the field of Ziegler-Natta into two parts and a Group 13- or transition metal modifi catalysts and is recognized to be a Substance capable of cation step is introduced between the two parts or stages of converting the procatalyst to an active polymerization cata the titanation. Preferably, the first part of the titanation lyst. Generally, the co-catalyst is an organometallic com comprises one single titanation step (Stage I) and the second pound containing a metal from group 1, 2, 12 or 13 of the part of the titanation comprises two Subsequent titanation Periodic Table of the Elements (Handbook of Chemistry and steps (Stages II and III). But different procedures may also Physics, 70th Edition, CRC Press, 1989- 1990). be used. When this modification is carried out before the 0282. The co-catalyst may include any compounds titanation step the increase in activity was higher as known in the art to be used as “co-catalysts’. Such as US 2016/031 1947 A1 Oct. 27, 2016 hydrides, alkyls, or aryls of aluminum, lithium, Zinc, tin, isobutylaluminoxane, tetraisobutyldialuminoxane.diethyl cadmium, beryllium, magnesium, and combinations thereof. aluminum ethoxide, diisobutylaluminum chloride, methyl The co-catalyst may be a hydrocarbyl aluminum co-catalyst aluminum dichloride, diethylaluminum chloride, ethylalu represented by the formula R'Al. minum dichloride and dimethylaluminum chloride. (0283) R' is independently selected from a hydrogen or a 0292 Preferably, the co-catalyst is triethylaluminum. The hydrocarbyl group, selected e.g. from alkyl, alkenyl, aryl, molar ratio of aluminum to titanium may be from about 5:1 aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more to about 500:1 or from about 10:1 to about 200:1 or from combinations thereof. Said hydrocarbyl group may be linear, about 15:1 to about 150:1 or from about 20:1 to about 100:1. branched or cyclic. Said hydrocarbyl group may be substi The molar ratio of aluminum to titanium is preferably about tuted or unsubstituted. Said hydrocarbyl group may contain 45:1. one or more heteroatoms. Preferably, said hydrocarbyl group 0293. One of the functions of an external donor com has from 1 to 20 carbon atoms, more preferably from 1 to 12 pound is to affect the stereoselectivity of the catalyst system carbon atoms, even more preferably from 1 to 6 carbon in polymerization of olefins having three or more carbon atoms. On the proviso that at least one R' is a hydrocarbyl atoms. Therefore it may be also referred to as a selectivity group. Optionally, two or three R groups are joined in a control agent. cyclic radical forming a heterocyclic structure. 0294 Examples of external donors suitable for use in the (0284) Non-limiting examples of suitable R' groups are: present invention are the 1,3-diether internal donors dis methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, cussed above, benzoic acid esters, alkylamino-alkoxysi pentyl, neopentyl, hexyl, 2-methylpentyl, heptyl, octyl, lanes, alkyl-alkoxysilane, imidosilanes, and alkylimidosi isooctyl, 2-ethylhexyl, 5,5-dimethylhexyl, nonyl, decyl, iso lanes. decyl, undecyl, dodecyl phenyl, phenethyl, methoxyphenyl, 0295 The aluminium/external donor molar ratio in the benzyl, tolyl, Xylyl, naphthyl, methylnapthyl, cyclohexyl, polymerization catalyst system preferably is from 0.1 to cycloheptyl, and cyclooctyl. 200; more preferably from 1 to 100. 0285 Suitable examples of the hydrocarbyl aluminum 0296 Mixtures of external donors may be present and compounds as co-catalyst include triisobutylaluminum may include from about 0.1 mol.% to about 99.9 mol.% of (TIBA), trihexylaluminum, di-isobutylaluminum hydride a first external donor and from about 99.9 mol.% to about (DIBALH), dihexylaluminum hydride, isobutylaluminum 0.1 mol.% of either a second or the additional alkoxysilane dihydride, hexylaluminum dihydride, diisobutylhexylalumi external donor disclosed below. num, isobutyl dihexylaluminum, trimethylaluminum, trieth 0297. When a silane external donor is used, the Si/Ti ylaluminum, tripropylaluminum, triisopropylaluminum, tri molar ratio in the catalyst system can range from 0.1 to 40, n-butylaluminum, trioctylaluminum, tridecylaluminum, preferably from 0.1 to 20, even more preferably from 1 to 20 tridodecylaluminum, tribenzylaluminum, triphenylalumi and most preferably from 2 to 10. num, trinaphthylaluminum, and tritolylaluminum. In an 0298. A monocarboxylic acid ester (also called “benzoic embodiment, the cocatalyst is selected from triethylalumi acid ester') as shown in Formula V may be used as external num, triisobutylaluminum, trihexylaluminum, di-isobutyl donor. aluminum hydride and dihexylaluminum hydride. More preferably, trimethylaluminium, triethylaluminium, triisobu tylaluminium, and/or trioctylaluminium. Most preferably, Formula V triethylaluminium (abbreviated as TEAL). 0286 The co-catalyst can also be a hydrocarbyl alumi num compound represented by the formula RAIX's. (0287 R’ is an alkyl group. Said alkyl group may be linear, branched or cyclic. Said alkyl group may be substi tuted or unsubstituted. Preferably, said alkyl group has from 1 to 20 carbon atoms, more preferably from 1 to 12 carbon R34 atoms, even more preferably from 1 to 6 carbon atoms. (0288. Non-limiting examples of suitable R groups are: (0299) R' is selected from a hydrocarbyl group indepen methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, dently selected e.g. from alkyl, alkenyl, aryl, aralkyl, pentyl, neopentyl, hexyl, 2-methylpentyl, heptyl, octyl, alkoxycarbonyl or alkylaryl groups, and one or more com isooctyl, 2-ethylhexyl, 5,5-dimethylhexyl, nonyl, decyl, iso binations thereof. Said hydrocarbyl group may be linear, decyl, undecyl, and dodecyl. branched or cyclic. Said hydrocarbyl group may be substi (0289 X is selected from the group of consisting of tuted or unsubstituted. Said hydrocarbyl group may contain fluoride (F ), chloride (Cl-), bromide (Br—) or iodide one or more heteroatoms. Preferably, said hydrocarbyl group (I ) or an alkoxide (RO). The value form is preferably 1 has from 1 to 10 carbon atoms, more preferably from 1 to 8 or 2. carbon atoms, even more preferably from 1 to 6 carbon 0290. Non-limiting examples of suitable alkyl aluminium atoms. Suitable examples of hydrocarbyl groups include halide compounds for co-catalyst include tetraethyl-dialu alkyl-, cycloalkyl-, alkenyl-, alkadienyl-, cycloalkenyl-, minoxane, methylaluminoxane, isobutylaluminoxane, tet cycloalkadienyl-, aryl-, aralkyl, alkylaryl, and alkynyl raisobutyl-dialuminoxane, diethyl-aluminumethoxide, groups. disobutylaluminum chloride, methylaluminum dichloride, 0300 R', R. R. R, R are each independently diethylaluminum chloride, ethylaluminum dichloride and selected from hydrogen, a heteroatom (preferably a halide), dimethylaluminum chloride. or a hydrocarbyl group, selected from e.g. alkyl, alkenyl, 0291. Non-limiting examples of suitable compounds aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or include tetraethyldialuminoxane, methylaluminoxane, more combinations thereof. Said hydrocarbyl group may be US 2016/031 1947 A1 Oct. 27, 2016

linear, branched or cyclic. Said hydrocarbyl group may be for instance O, N, S or P, with, for instance, 1-20 carbon substituted or unsubstituted. Said hydrocarbyl group may atoms; such as n-propyl trimethoxysilane (nPTMS), n-pro contain one or more heteroatoms. Preferably, said hydrocar pyl triethoxysilane (nPEMS), diisobutyl dimethoxysilane byl group has from 1 to 10 carbon atoms, more preferably (DiBDMS), t-butyl isopropyl dimethyxysilane (tBiPDMS), from 1 to 8 carbon atoms, even more preferably from 1 to cyclohexyl methyldimethoxysilane (CHMDMS), dicyclo 6 carbon atoms. pentyl dimethoxysilane (DCPDMS). 0301 Suitable non-limiting examples of “benzoic acid 0309 Imidosilanes according to Formula I may be used esters' include an alkyl p-alkoxybenzoate (such as ethyl as external donors. p-methoxybenzoate, methyl p-ethoxybenzoate, ethyl p-ethoxybenzoate), an alkylbenzoate (such as ethylbenzo Si(L),(OR'), Formula I ate, methylbenzoate), an alkylp-halobenzoate (ethyl p-chlo wherein Si is a silicon atom with Valency 4+; O is an oxygen robenzoate, ethyl p-bromobenzoate), and benzoic anhy atom with valency 2- and O is bonded to Si via a silicon dride. The benzoic acid ester is preferably selected from oxygen bond; n is 1, 2, 3 or 4: R'' is selected from the group ethyl benzoate, benzoyl chloride, ethyl p-bromobenzoate, consisting of linear, branched and cyclic alkyl having at n-propylbenzoate and benzoic anhydride. The benzoic acid most 20 carbon atoms and aromatic Substituted and unsub ester is more preferably ethylbenzoate. stituted hydrocarbyl having 6 to 20 carbon atoms; two R' 0302) Documents EP1538167 and EP1783145 disclose a groups can be connected and together may form a cyclic Ziegler-Natta catalyst type comprising an organo-silicon structure; and L is a group represented by Formula I" compound as external donor that is represented by formula Si(OR), (NR'R''), wherein R is a hydrocarbon group hav ing 1 to 6 carbon atoms, R is a hydrocarbon group having Formula I" 1 to 12 carbon atoms or hydrogen atom, and R is a N hydrocarbon group having 1 to 12 carbon atoms used as an external electron donor. X l Y 0303. An other example of a suitable external donor according to the present invention is a compound according 0310. Wherein L is bonded to the silicon atom via a to Formula III: nitrogen-silicon bond; L has a single Substituent on the Formula III nitrogen atom, where this single Substituent is an imine carbon atom; and X and Y are each independently selected (0304) The R'' and R' groups are each independently an from the group consisting of: alkyl having from 1 to 10 carbon atoms. Said alkyl group 0311 a) a hydrogen atom; may be linear, branched or cyclic. Said alkyl group may be 0312 b) a group comprising a heteroatom selected substituted or unsubstituted. Preferably, said hydrocarbyl from group 13, 14, 15, 16 or 17 of the IUPAC Periodic group has from 1 to 8 carbon atoms, even more preferably Table of the Elements, through which X and Y are each from 1 to 6 carbon atoms, even more preferably from 2 to independently bonded to the imine carbon atom of 4 carbon atoms. Preferably each R' is ethyl. Preferably, Formula II, wherein the heteroatom is substituted with each R' is ethyl. A is either a direct bond between nitrogen a group consisting of a linear, branched and cyclic alkyl and silicon, or a spacer group selected from an alkyl having having at most 20 carbon atoms, optionally containing from 1 to 10 carbon atoms, preferably a direct bond; in other a heteroatom selected from group 13, 14, 15, 16 or 17 words A is not present. of the IUPAC Periodic Table of the Elements; and/or 0305 An example of such an external donor is diethyl with an aromatic substituted and unsubstituted hydro amino-triethoxysilane (DEATES) wherein A is a direct carbyl having 6 to 20 carbon atoms, optionally con bond, each R' is ethyl and each R' is ethyl. taining a heteroatom selected from group 13, 14, 15, 16 0306 Alkyl-alkoxysilanes according to Formula IV may or 17 of the IUPAC Periodic Table of the Elements: be used as external donors. 0313 c) a linear, branched and cyclic alkyl having at (R92)Si(OR), Formula IV most 20 carbon atoms, optionally containing a heteroa 0307. The Rand R groups are each independently an tom selected from group 13, 14, 15, 16 or 17 of the alkyl having from 1 to 10 carbon atoms. Said alkyl group IUPAC Periodic Table of the Elements; and may be linear, branched or cyclic. Said alkyl group may be 0314 d) an aromatic substituted and unsubstituted substituted or unsubstituted. Preferably, said hydrocarbyl hydrocarbyl having 6 to 20 carbon atoms, optionally group has from 1 to 8 carbon atoms, even more preferably containing a heteroatom selected from group 13, 14. from 1 to 6 carbon atoms, even more preferably from 2 to 15, 16 or 17 of the IUPAC. 4 carbon atoms. Preferably, all three R' groups are the 0315. In a preferred embodiment, at least one of X and Y same. Preferably, R’ is methyl or ethyl. Preferably R’ is is selected from b), c) ord). In other words, in said preferred ethyl or propyl, more preferably n-propyl. Examples are embodiment, X and Y are not both hydrogen. n-propyl triethoxysilane (nPTES) and n-propyl trimethox 0316) R' is selected from the group consisting of linear, ysilane (nPTMS). branched and cyclic alkyl having at most 20 carbon atoms. 0308 Typical external donors known in the art (for 0317 Preferably, R' is a selected from the group con instance as disclosed in documents WO2006/056338A1, sisting of linear, branched and cyclic alkyl having at most 20 EP1838741B1, U.S. Pat. No. 6,395,670B1, EP398698A1, carbon atoms, preferably 1 to 10 carbon atoms or 3 to 10 WO96/32426A) are organosilicon compounds having gen carbon atoms, more preferably 1 to 6 carbon atoms. eral formula Si(OR").R", wherein in can be from 0 up to 0318 Suitable examples of R' include methyl, ethyl, 2, and each R" and R, independently, represents an alkyl or n-propyl, iso-propyl. n-butyl, iso-butyl, t-butyl, sec-butyl, aryl group, optionally containing one or more hetero atoms iso-butyl, n-pentyl, iso-pentyl, cyclopentyl, n-hexyl and US 2016/031 1947 A1 Oct. 27, 2016 cyclohexyl. More preferably, R' is a linear alkyl having 1 0329) R' is selected from the group consisting of a to 10, even more preferably 1 to 6 carbon atoms. Most linear, branched and cyclic hydrocarbyl group indepen preferably, R' is methyl or ethyl. dently selected e.g. from alkyl, alkenyl, aryl, aralkyl, 0319 Specific examples are the following compounds: alkoxycarbonyl or alkylaryl groups, and one or more com 1,1,1-triethoxy-N-(2,2,4,4-tetramethylpentan-3-ylidene)si binations thereof. Said hydrocarbyl group may be substi lanamine (all R' groups are ethyl and X and Y are both tuted or unsubstituted. Said hydrocarbyl group may contain t-butyl); 1,1,1-trimethoxy-N-(2,2,4,4-tetramethylpentan-3- one or more heteroatoms. Preferably, said hydrocarbyl group ylidene) silanamine (all R' groups are methyl, and X and Y has from 1 to 20 carbon atoms. are t-butyl), N.N.N',N'-tetramethylguanidine triethoxysilane 0330 Preferably, R' is a selected from the group con (all R' groups are ethyl, both X and Y are dimethylamino). sisting of linear, branched and cyclic alkyl having at most 20 0320 Alkylimidosilanes according to Formula I may be carbon atoms, preferably 1 to 10 carbon atoms or 3 to 10 used as external donors. carbon atoms, more preferably 1 to 6 carbon atoms. 0331 Suitable examples of R' include methyl, ethyl, Si(L),(OR'),(R'), Formula I n-propyl, iso-propyl. n-butyl, iso-butyl, t-butyl, sec-butyl, 0321) Wherein Si is a silicon atom with valency 4+; O is iso-butyl, n-pentyl, iso-pentyl, cyclopentyl, n-hexyl and an oxygen atom with Valency 2- and O is bonded to Si via cyclohexyl. More preferably, R'' is a linear alkyl having 1 a silicon-oxygen bond; n is 1, 2, 3 or 4 m is 0, 1 or 2; to 10, even more preferably 1 to 6 carbon atoms. Most n+ms4; R'' is selected from the group consisting of linear, preferably, R' is methyl or ethyl. branched and cyclic alkyl having at most 20 carbon atoms 0332 Suitable examples of R' include methyl, ethyl, and aromatic substituted and unsubstituted hydrocarbyl hav n-propyl, iso-propyl. n-butyl, iso-butyl, t-butyl, sec-butyl, ing 6 to 20 carbonatoms; and R' is selected from the group iso-butyl, n-pentyl, iso-pentyl, cyclopentyl, n-hexyl, cyclo consisting of linear, branched and cyclic alkyl having at hexyl, unsubstituted or substituted phenyl. most 20 carbon atoms and aromatic Substituted and unsub 0333. In a first specific example, the external donor may stituted hydrocarbyl having 6 to 20 carbon atoms; and L is have a structure corresponding to Formula I" wherein n=1, a group represented by Formula I" m=2, X=Y-phenyl, both R' groups are methyl, and R' is butyl. 0334. In a second specific example, the external donor Formula I" N may have a structure corresponding to Formula I" wherein n=4, m=0. X-methyl, and Y-ethyl. ls 0335. In a third specific example, the external donor may X Y have a structure corresponding to Formula I" wherein n=1, m=1, X-phenyl, Y—CH2—Si(CH), and 0322. Wherein L is bonded to the silicon atom via a R—R''=methyl. nitrogen-silicon bond; L has a single Substituent on the 0336. In a fourth specific example, the external donor nitrogen atom, where this single Substituent is an imine may have a structure corresponding to Formula I" wherein carbon atom; and X and Y are each independently selected n=1, m=1, X= NH-C=NH(NH) , Y= NH from the group consisting of (CH), Si(OCH2CH), and R'—(CH), NH.; 0323 a) a hydrogen atom; R'' =ethyl. 0324 b) a group comprising a heteroatom selected from 0337 The additional compound(s) in the external donor group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of according to the invention may be one or more alkoxysi the Elements, through which X and Y are each indepen lanes. The alkoxysilane compound can have any of the dently bonded to the imine carbon atom of Formula II, structures disclosed herein. The alkoxysilane is described by wherein the heteroatom is substituted with a group consist Formula IX ing of a linear, branched and cyclic alkyl having at most 20 carbon atoms, optionally containing a heteroatom selected SiR".(OR), Formula IX from group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table 0338 R is independently a hydrocarbyl group, selected of the Elements; and/or with an aromatic substituted and e.g. from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or unsubstituted hydrocarbyl having 6 to 20 carbon atoms, alkylaryl groups, and one or more combinations thereof. optionally containing a heteroatom selected from group 13. Said hydrocarbyl group may be linear, branched or cyclic. 14, 15, 16 or 17 of the IUPAC Periodic Table of the Said hydrocarbyl group may be substituted or unsubstituted. Elements; Said hydrocarbyl group may contain one or more heteroa 0325 c) a linear, branched and cyclic alkyl having at toms. Preferably, said hydrocarbyl group has from 1 to 20 most 20 carbon atoms, optionally containing a heteroatom carbon atoms, more preferably from 6 to 12 carbon atoms. selected from group 13, 14, 15, 16 or 17 of the IUPAC For example, R7 may be C6-12 aryl, alkyl or aralkyl, C3-12 Periodic Table of the Elements; and cycloalkyl, C3-12 branched alkyl, or C3-12 cyclic or acyclic 0326 d) an aromatic substituted and unsubstituted hydro amino group. The value for r may be 1 or 2. carbyl having 6 to 20 carbon atoms, optionally containing a 0339 For the formula SiNR'r(OR)R’ may also be heteroatom selected from group 13, 14, 15, 16 or 17 of the hydrogen. IUPAC Periodic Table of the Elements. (0340 R is independently selected from a hydrogen or a 0327. In a preferred embodiment, at least one of X and Y hydrocarbyl group, selected e.g. from alkyl, alkenyl, aryl, is selected from b), c) ord). In other words, in said preferred aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more embodiment, X and Y are not both hydrogen. combinations thereof. Said hydrocarbyl group may be linear, 0328) R' is selected from the group consisting of linear, branched or cyclic. Said hydrocarbyl group may be substi branched and cyclic alkyl having at most 20 carbon atoms. tuted or unsubstituted. Said hydrocarbyl group may contain US 2016/031 1947 A1 Oct. 27, 2016 one or more heteroatoms. Preferably, said hydrocarbyl group 0346 Contacting the olefin with the catalyst system has from 1 to 20 carbon atoms, more preferably from 1 to 12 according to the present invention can be done under stan carbon atoms, even more preferably from 1 to 6 carbon dard polymerization conditions, known to the skilled person atoms. For example, R may be C1-4 alkyl, preferably in the art. See for example Pasquini, N. (ed.) “Polypropylene methyl or ethyl. handbook” 2" edition, Carl Hanser Verlag Munich, 2005. 0341 Non-limiting examples of suitable silane-com Chapter 6.2 and references cited therein. pounds include tetramethoxysilane (TMOS or tetramethyl 0347 The polymerization process may be a gas phase, a orthosilicate), tetraethoxysilane (TEOS or tetraethyl ortho slurry or a bulk polymerization process, operating in one or silicate), methyl trimethoxysilane, methyl triethoxysilane, more than one reactor. One or more olefin monomers can be methyl tripropoxysilane, methyl tributoxysilane, ethyl introduced in a polymerization reactor to react with the trimethoxysilane, ethyl triethoxysilane, ethyl tripropoxysi procatalyst and to form an olefin-based polymer (or a lane, ethyl tributoxysilane, n-propyl trimethoxysilane, fluidized bed of polymer particles). n-propyl triethoxysilane, n-propyl tripropoxysilane, n-pro 0348. In the case of polymerization in a slurry (liquid pyl tributoxysilane, isopropyl trimethoxysilane, isopropyl phase), a dispersing agent is present. Suitable dispersing triethoxysilane, isopropyl tripropoxysilane, isopropyl tribu agents include for example propane, n-butane, isobutane, toxysilane, phenyl trimethoxysilane, phenyl triethoxysilane, n-pentane, isopentane, hexane (e.g. iso- or n-), heptane (e.g. phenyl tripropoxysilane, phenyl tributoxysilane, cyclopentyl iso- or n-), octane, cyclohexane, benzene, toluene, Xylene, trimethoxysilane, cyclopentyl triethoxysilane, diethylamino liquid propylene and/or mixtures thereof. The polymeriza triethoxysilane, dimethyl dimethoxysilane, dimethyl tion Such as for example the polymerization temperature and diethoxysilane, dimethyl dipropoxysilane, dimethyl dibu time, monomer pressure, avoidance of contamination of toxysilane, diethyl dimethoxysilane, diethyl diethoxysilane, catalyst, choice of polymerization medium in slurry pro diethyl dipropoxysilane, diethyl dibutoxysilane, di-n-propyl cesses, the use of further ingredients (like hydrogen) to dimethoxysilane, d-n-propyl diethoxysilane, di-n-propyl control polymer molar mass, and other conditions are well dipropoxysilane, di-n-propyl dibutoxysilane, diisopropyl known to persons of skill in the art. The polymerization dimethoxysilane, diisopropyl diethoxysilane, diisopropyl temperature may vary within wide limits and is, for example dipropoxysilane, diisopropyl dibutoxysilane, diphenyl for propylene polymerization, from 0° C. to 120° C., pref dimethoxysilane, diphenyl diethoxysilane, diphenyl erably from 40°C. to 100° C. The pressure during (propyl dipropoxysilane, diphenyl dibutoxysilane, dicyclopentyl ene) (co)polymerization is for instance from 0.1 to 6 MPa, dimethoxysilane, dicyclopentyl diethoxysilane, diethyl preferably from 1 to 4 MPa. diphenoxysilane, di-t-butyl dimethoxysilane, methyl cyclo 0349. Several types of polyolefins are prepared such as hexyl dimethoxysilane, ethyl cyclohexyl dimethoxysilane, homopolyolefins, random copolymers and heterophasic isobutyl isopropyl dimethoxysilane, t-butyl isopropyl dime polyolefin. The for latter, and especially heterophasic poly thoxysilane, trifluoropropyl methyl dimethoxysilane, bis(pe propylene, the following is observed. rhydroisoquinolino) dimethoxysilane, dicyclohexyl dime 0350 Heterophasic propylene copolymers are generally thoxysilane, dinorbornyl dimethoxysilane, cyclopentyl prepared in one or more reactors, by polymerization of pyrrolidino dimethoxysilane and bis(pyrrolidino) dimethox propylene and optionally one or more other olefins, for ysilane. example ethylene, in the presence of a catalyst and Subse 0342. In an embodiment, the silane-compound for the quent polymerization of a propylene-C-olefin mixture. The additional external donor is dicyclopentyl dimethoxysilane, resulting polymeric materials can show multiple phases di-isopropyl dimethoxysilane, di-isobutyl dimethyoxysi (depending on monomer ratio), but the specific morphology lane, methylcyclohexyl dimethoxysilane, n-propyl usually depends on the preparation method and monomer trimethoxysilane, n-propyltriethoxysi lane, dimethylamino ratio. The heterophasic propylene copolymers employed in triethoxysilane, and one or more combinations thereof. the process according to present invention can be produced 0343. The invention also relates to a process to make the using any conventional technique known to the skilled catalyst system by contacting a Ziegler-Natta type procata person, for example multistage process polymerization, Such lyst, a co-catalyst and an external electron donor. The as bulk polymerization, gas phase polymerization, slurry procatalyst, the co-catalyst and the external donor can be polymerization, Solution polymerization or any combina contacted in any way known to the skilled person in the art; tions thereof. Any conventional catalyst systems, for and as also described herein, more specifically as in the example, Ziegler-Natta or metallocene may be used. Such Examples. techniques and catalysts are described, for example, in 0344) The invention further relates to a process for mak WO06/010414; Polypropylene and other Polyolefins, by Ser ing a polyolefin by contacting an olefin with the catalyst van der Ven, Studies in Polymer Science 7, Elsevier 1990; system according to the present invention. The procatalyst, WO06/010414, U.S. Pat. No. 4,399,054 and U.S. Pat. No. the co-catalyst, the external donor and the olefin can be 4472,524. contacted in any way known to the skilled person in the art; 0351. The molar mass of the polyolefin obtained during and as also described herein. the polymerization can be controlled by adding hydrogen or 0345 For instance, the external donor in the catalyst any other agent known to be suitable for the purpose during system according to the present invention can be complexed the polymerization. The polymerization can be carried out in with the co-catalyst and mixed with the procatalyst (pre a continuous mode or batch-wise. Slurry-, bulk-, and gas mix) prior to contact between the procatalyst and the olefin. phase polymerization processes, multistage processes of The external donor can also be added independently to the each of these types of polymerization processes, or combi polymerization reactor. The procatalyst, the co-catalyst, and nations of the different types of polymerization processes in the external donor can be mixed or otherwise combined a multistage process are contemplated herein. Preferably, the prior to addition to the polymerization reactor. polymerization process is a single stage gas phase process or US 2016/031 1947 A1 Oct. 27, 2016 20 a multistage, for instance a two-stage gas phase process, e.g. 0357 Preferably, the olefin is propylene or a mixture of wherein in each stage a gas-phase process is used or includ propylene and ethylene, to result in a propylene-based ing a separate (Small) pre-polymerization reactor. polymer, such as propylene homopolymer or propylene 0352 Examples of gas-phase polymerization processes olefin copolymer. The olefin may an a-olefin having up to 10 include both stirred bed reactors and fluidized bed reactor carbon atoms, such as ethylene, butane, hexane, heptane, systems; such processes are well known in the art. Typical octene. A propylene copolymer is herein meant to include gas phase olefin polymerization reactor systems typically both so-called random copolymers which typically have comprise a reactor vessel to which an olefin monomer(s) and relatively low comonomer content, e.g. up to 10 mol %, as a catalyst system can be added and which contain an agitated well as so-called impact PP copolymers or heterophasic PP bed of growing polymer particles. Preferably the polymer copolymers comprising higher comonomer contents, e.g. ization process is a single stage gas phase process or a from 5 to 80 mol %, more typically from 10 to 60 mol%. multistage, for instance a 2-stage, gas phase process wherein The impact PP copolymers are actually blends of different in each stage a gas-phase process is used. propylene polymers; such copolymers can be made in one or 0353 As used herein, “gas phase polymerization' is the two reactors and can be blends of a first component of low way of an ascending fluidizing medium, the fluidizing comonomer content and high crystallinity, and a second medium containing one or more monomers, in the presence component of high comonomer content having low crystal of a catalyst through a fluidized bed of polymer particles linity or even rubbery properties. Such random and impact maintained in a fluidized state by the fluidizing medium copolymers are well-known to the skilled in the art. A optionally assisted by mechanical agitation. Examples of gas propylene-ethylene random copolymer may be produced in phase polymerization are fluid bed, horizontal stirred bed one reactor. Impact PP copolymers may be produced in two and vertical stirred bed. reactors: polypropylene homopolymer may be produced in a 0354) “fluid-bed,” “fluidized,” or “fluidizing” is a gas first reactor; the content of the first reactor is subsequently solid contacting process in which a bed of finely divided transferred to a second reactor into which ethylene (and polymer particles is elevated and agitated by a rising stream optionally propylene) is introduced. This results in produc of gas optionally assisted by mechanical stirring. In a tion of a propylene-ethylene copolymer (i.e. an impact “stirred bed upwards gas velocity is lower than the fluidi copolymer) in the second reactor. zation threshold. 0358. The present invention also relates to a polyolefin, 0355. A typical gas-phase polymerization reactor (or gas preferably a polypropylene obtained or obtainable by a phase reactor) include a vessel (i.e., the reactor), the fluid process, comprising contacting an olefin, preferably propyl ized bed, a product discharge system and may include a ene or a mixture of propylene and ethylene with the pro mechanical stirrer, a distribution plate, inlet and outlet catalyst according to the present invention. The terms poly piping, a compressor, a cycle gas cooler or heat exchanger. propylene and propylene-based polymer are used herein The vessel may include a reaction Zone and may include a interchangeable. The polypropylene may be a propylene velocity reduction Zone, which is located above the reaction homopolymer or a mixture of propylene and ethylene, Such Zone (viz. the bed). The fluidizing medium may include as a propylene-based copolymer, e.g. heterophasic propyl propylene gas and at least one other gas Such as an olefin ene-olefin copolymer; random propylene-olefin copolymer, and/or a carrier gas such as hydrogen or nitrogen. The preferably the olefin in the propylene-based copolymers contacting can occur by way of feeding the procatalyst into being a C2, or C4-C6 olefin, such as ethylene, butylene, the polymerization reactor and introducing the olefin into the pentene or hexene. Such propylene-based (co)polymers are polymerization reactor. In an embodiment, the process known to the skilled person in the art; they are also described includes contacting the olefin with a co-catalyst. The co herein above. catalyst can be mixed with the procatalyst (pre-mix) prior to 0359 The present invention also relates to a polyolefin, the introduction of the procatalyst into the polymerization preferably a propylene-based polymer obtained or obtain reactor. The co-catalyst may be also added to the polymer able by a process as described herein above, comprising ization reactor independently of the procatalyst. The inde contacting propylene or a mixture of propylene and ethylene pendent introduction of the co-catalyst into the polymeriza with a catalyst system according to the present invention. tion reactor can occur (Substantially) simultaneously with 0360. In one embodiment the present invention relates to the procatalyst feed. An external donor may also be present the production of a homopolymer of polypropylene. For during the polymerization process. Such a polymer, properties Such as isotacticity and stiffness 0356. The olefin according to the invention may be and emission may be important. selected from mono- and di-olefins containing from 2 to 40 0361. In one embodiment according to the present inven carbon atoms. Suitable olefin monomers include a-olefins, tion a (random) copolymer of propylene and ethylene mono Such as ethylene, propylene, C-olefins having from 4 to 20 mers is obtained. For Such a polymer, properties such as XS carbon atoms (viz. C4-20). Such as 1-butene, 1-pentene, and reduced haze increase after time may be important. 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-de 0362. Several polymer properties are discussed here. cene, 1-dodecene and the like; C4-C20 diolefins, such as 0363 The polyolefin, preferably the polypropylene 1,3-butadiene, 1,3-pentadiene, norbornadiene, 5-vinyl-2- according to the present invention has a molecular weight norbornene (VNB), 1,4-hexadiene, 5-ethylidene-2-nor distribution M/M lower than 5 or than 4.5 or even lower bornene (ENB) and dicyclopentadiene; vinyl aromatic com than 4. More preferably, the MWD is from 3 to 5, more pounds having from 8 to 40 carbon atoms (viz. C8-C40) preferably from 3.5 to 4.5. including styrene, o-, m- and p-methylstyrene, divinylben 0364 Advantages that a narrow molecular weight distri Zene, vinylbiphenyl, vinylnapthalene; and halogen-Substi bution PP may have is a lower shear sensitivity of the PP tuted C8-C40 vinyl aromatic compounds such as chlorosty resin, and that it may provide a low melt elasticity and rene and fluorostyrene. elongation viscosity in extrusion. US 2016/031 1947 A1 Oct. 27, 2016

0365 Xylene soluble fraction (XS) is preferably from tion molding, blow molding, extrusion molding, compres about 0.5 wt.% to about 10 wt.%, or from about 1 wt.% sion molding, casting, thin-walled injection molding, etc. for to about 8 wt.%, or from 2 to 6 wt.%, or from about 1 wt. example in food contact applications. % to about 5 wt.%. Preferably, the xylene amount (XS) is 0373. Furthermore, the invention relates to a shaped lower than 6 wt.%, preferably lower than 5 wt.%, more article comprising the polyolefin, preferably the propylene preferably lower than 4 wt.% or even lower than 3 wt.% based polymer according to the present invention. and most preferably lower than 2.7 wt.%. 0374. The polyolefin, preferably the propylene-based 0366. The lump content is preferably below 10 wt.%, polymer according to the present invention may be trans preferably below 4 wt.% and more preferably below 3 wt. formed into shaped (semi)-finished articles using a variety of %. processing techniques. Examples of Suitable processing 0367 The production rate is preferably from about 1 techniques include injection molding, injection compression kg/g/hr to about 100 kg/g/hr, or from about 10 kg/g/hr to molding, thin wall injection molding, extrusion, and extru about 40 kg/g/hr. sion compression molding. Injection molding is widely used 0368 MFR is preferably from about 0.01 g/10 min to to produce articles Such as for example caps and closures, about 2000 g/10 min, or from about 0.01 g/10 minto about batteries, pails, containers, automotive exterior parts like 1000 g/10 min; or from about 0.1 g/10 minto about 500 g/10 bumpers, automotive interior parts like instrument panels, or min, or from about 0.5 g/10 minto about 150 g/10 min, or automotive parts under the bonnet. Extrusion is for example from about 1 g/ 10 minto about 100 g/10 min. widely used to produce articles, such as rods, sheets, films 0369. The olefin polymer obtained in the present inven and pipes. Thin wall injection molding may for example be tion is considered to be a thermoplastic polymer. The used to make thin wall packaging applications both for food thermoplastic polymer composition according to the inven and non-food segments. This includes pails and containers tion may also contain one or more of usual additives, like and yellow fats/margarine tubs and dairy cups. those mentioned above, including stabilizers, e.g. heat sta 0375. Due to its narrow molecular weight distribution bilizers, anti-oxidants, UV stabilizers; colorants, like pig and the excellent Surface quality, the copolymer is very ments and dyes; clarifiers; Surface tension modifiers; lubri Suitable for use in injection molding for Suitcase shells, cants; flame-retardants; mold-release agents; flow crates and boxes, appliances and automotive parts. Accord improving agents; plasticizers; anti-static agents; impact ingly, in this embodiment the invention also relates to shells, modifiers; blowing agents; fillers and reinforcing agents; crates, boxes, appliances and automotive parts comprising and/or components that enhance interfacial bonding the thermoplastic polymer according to the present inven between polymer and filler, such as a maleated polypropyl tion. ene, in case the thermoplastic polymer is a polypropylene 0376. It is noted that the invention relates to all possible composition. The skilled person can readily select any combinations of features recited in the claims. Features suitable combination of additives and additive amounts described in the description may further be combined. without undue experimentation. 0377 Although the invention has been described in detail 0370. The amount of additives depends on their type and for purposes of illustration, it is understood that such detail function; typically is of from 0 to about 30 wt.%; preferably is solely for that purpose and variations can be made therein of from 0 to about 20 wt.%: more preferably of from 0 to by those skilled in the art without departing from the spirit about 10 wt.% and most preferably of from 0 to about 5 wt. and scope of the invention as defined in the claims. % based on the total composition. The sum of all compo 0378. It is further noted that the invention relates to all nents added in a process to form the polyolefins, preferably possible combinations of features described herein, pre the propylene-base polymers or compositions thereof should ferred in particular are those combinations of features that add up to 100 wt.%. are present in the claims. 0371. The thermoplastic polymer composition of the 0379. It is further noted that the term comprising does invention may be obtained by mixing one or more of the not exclude the presence of other elements. However, it is thermoplastic polymers with one or more additives by using also to be understood that a description on a product any suitable means. Preferably, the thermoplastic polymer comprising certain components also discloses a product composition of the invention is made in a form that allows consisting of these components. Similarly, it is also to be easy processing into a shaped article in a Subsequent step, understood that a description on a process comprising cer like in pellet or granular form. The composition can be a tain steps also discloses a process consisting of these steps. mixture of different particles or pellets; like a blend of a 0380. The invention will be further elucidated with the thermoplastic polymer and a master batch of nucleating following examples without being limited hereto. agent composition, or a blend of pellets of a thermoplastic polymer comprising one of the two nucleating agents and a EXAMPLES particulate comprising the other nucleating agent, possibly pellets of a thermoplastic polymer comprising said other Example 1 nucleating agent. Preferably, the thermoplastic polymer 0381 A. Grignard Formation Step composition of the invention is in pellet or granular form as 0382. This step was carried out as described in Example obtained by mixing all components in an apparatus like an XVI of EP 1 222 214 B1. extruder; the advantage being a composition with homoge 0383. A stainless steel reactor of 91 volume was filled neous and well-defined concentrations of the nucleating with 360 gram of magnesium powder. The reactor was agents (and other components). brought under nitrogen. The magnesium was heated at 80° 0372. The invention also relates to the use of the poly C. for 1 hour, after which a mixture of dibutyl ether (1 liter) olefins, preferably the propylene-based polymers (also and chlorobenzene (200 ml) was added. Then iodine (0.5 g) called polypropylenes) according to the invention in injec and n-chlorobutane (50 ml) were successively added to the US 2016/031 1947 A1 Oct. 27, 2016 22 reaction mixture. After the colour of the iodine had visually 0392 D. Preparation of the Catalyst Component disappeared, the temperature was raised to 94° C. Then a 0393 A 500 mL reactor was brought under nitrogen and mixture of dibutyl ether (1.6 liter) and chlorobenzene (400 62.5 ml of titanium tetrachloride was added to it. The reactor ml) was slowly added for 1 hour, and then 4 liter of was heated to 100° C. and a suspension, containing about 5.5 chlorobenzene was slowly added for 2.0 hours. The tem g of activated Support in 15 ml of heptane, was added to it perature of reaction mixture was kept in interval 98-105° C. under stirring. Then the reaction mixture was kept at 100° C. The reaction mixture was stirred for another 6 hours at for 10 min, and 0.71 g of benzamide (BA-2H/Mg 0.15 97-102°C. Then the stirring and heating were stopped and molar ratio) in 2 ml of chlorobenzene was added to reactor. the solid material was allowed to settle for 48 hours. By The reaction mixture was kept at 100° C. for 10 min, and decanting the solution above the precipitate, a solution of 62.5 ml of chlorobenzene was added to reactor. The reaction phenylmagnesiumchloride reaction product A was obtained mixture was kept at 100° C. for 30 min, and 1.0 g of with a concentration of 1.3 mol Mg/l. This solution was used 9.9-bis-methoxymethyl-9H-fluorene (flu/Mg 0.1 molar in the further catalyst preparation. ratio) in 3 ml of chlorobenzene was added to reactor. 0384 B. Preparation of the First Intermediate Reaction Temperature of reaction mixture was increased to 115° C. Product and the reaction mixture was kept at 115° C. for 60 min (I 0385. This step was carried out as described in Example stage of catalyst preparation). Then the stirring was stopped XX of EP 1 222 214 B1, except that the dosing temperature and the solid substance was allowed to settle. The superna of the reactor was 35°C., the dosing time was 360 min and tant was removed by decanting, after which the Solid product a propeller stirrer was used. 250 ml of dibutyl ether was was washed with chlorobenzene (125 ml) at 100-110° C. for introduced to a 1 liter reactor. The reactor was fitted by 20 min. Then the washing solution was removed by decant propeller stirrer and two baffles. The reactor was thermo ing, after which a mixture of titanium tetrachloride (62.5 ml) Stated at 35° C. and chlorobenzene (62.5 ml) was added. The reaction mix 0386 The solution of reaction product of step A (360 ml, ture was kept at 115° C. for 30 min (II stage of catalyst 0.468 mol Mg) and 180 ml of a solution of tetraethoxysilane preparation), after which the solid substance was allowed to (TES) in dibutyl ether (DBE), (55 ml of TES and 125 ml of settle. The Supernatant was removed by decanting, and the DBE), were cooled to 10° C., and then were dosed simul last treatment was repeated once again (III stage of catalyst taneously to a mixing device of 0.45 ml Volume Supplied preparation). The solid substance obtained was washed five with a stirrer and jacket. From the mixing device, the mixed times using 150 ml of heptane at 60° C., after which the components were directly introduced into the reactor. The catalyst component, Suspended in heptane, was obtained. mixing device (minimixer) was cooled to 10° C. by means 0394 E. Polymerization of Propylene of cold water circulating in the minimixer's jacket. Dosing 0395 Polymerization of propylene was carried out in a time was 360 min. The stirring speed in the minimixer was stainless steel reactor (with a volume of 0.7 l) in heptane 1000 rpm. The stirring speed in the reactor was 350 rpm at (300 ml) at a temperature of 70° C., total pressure 0.7 MPa the beginning of dosing and was gradually increased up to and hydrogen presence (55 ml) for 1 hour in the presence of 600 rpm at the end of dosing stage. a catalyst system comprising the catalyst component accord 0387. On the dosing completion the reaction mixture was ing to step D, triethylaluminium and n-propyltrimethoxysi heated up to 60° C. and kept at this temperature for 1 hour. lane. The concentration of the catalyst component was 0.033 Then the stirring was stopped and the Solid Substance was g/l; the concentration of triethylaluminium was 4.0 mmol/l; allowed to settle. The supernatant was removed by decant the concentration of n-propyltrimethoxysilane was 0.2 ing. The solid substance was washed three times using 500 mmol/l. Data on the catalyst performance at the propylene ml of heptane. As a result, a pale yellow solid Substance, polymerization are presented in Table 1. reaction product B (the solid first intermediate reaction product; the support), was obtained, suspended in 200 ml of Example 1 a heptane. The average particle size of Support was 22 um and span Value (doo-do)/dso-0.5. 0396 Example 1a was carried out in the same way as 0388 C. Preparation of the Second Intermediate Reaction Example 1, but in step E no n-propyltrimethoxysilane Product (nPTMS) was used. 0389 Support activation was carried out as described in Example 2 Example IV of WO/2007/134851 to obtain the second intermediate reaction product. 0397 Example 2 was carried out in the same way as 0390 under inert nitrogen atmosphere at 20° C. a 250 ml Example 1, but N-methylbenzamide (BA-HMe/Mg 0.15 glass flask equipped with a mechanical agitator was filled molar ratio) was used in step D instead of benzamide with slurry of 5 g of reaction product B dispersed in 60 ml (BA-2H). of heptane. Subsequently a solution of 0.22 ml ethanol (EtOH/Mg 0.1) in 20 ml heptane was dosed under stirring Example 2a during 1 hour. After keeping the reaction mixture at 20° C. for 30 minutes, a solution of 0.79 ml titanium tetraethoxide 0398. Example 2a was carried out in the same way as (TET/Mg-0.1) in 20 ml of heptane was added for 1 hour. Example 2, but in step E no nPTMS was used in step E. 0391 The slurry was slowly allowed to warm up to 30° Example 3 C. for 90 min and kept at that temperature for another 2 hours. Finally the Supernatant liquid was decanted from the 0399. Example 3 was carried out in the same way as Solid reaction product (the second intermediate reaction Example 1, but N,N-dimethylbenzamide (BA-2Me/Mg=0. product; activated support) which was washed once with 90 15 molar ratio) was used in step D instead of benzamide ml of heptane at 30° C. (BA-2H). US 2016/031 1947 A1 Oct. 27, 2016

Example 3a removed by decanting, after which the solid product was washed with chlorobenzene (125 ml) at 100-110° C. for 20 04.00 Example 3a was carried out in the same way as min. Then the washing solution was removed by decanting, Example 3, but no nPTMS was used in step E. after which a mixture of titanium tetrachloride (62.5 ml) and Example 4 chlorobenzene (62.5 ml) was added. The reaction mixture was kept at 115° C. for 30 min (II stage of catalyst 04.01 Example 4 was carried out in the same way as preparation), after which the solid substance was allowed to Example 1, but BA-2H/Mg=0.1 molar ratio was used in step settle. The Supernatant was removed by decanting, and the D instead of BA-2H/Mg=0.15 molar ratio. last treatment was repeated once again (III stage of catalyst preparation). The solid substance obtained was washed five Example 4a times using 150 ml of heptane at 60° C., after which the 0402. Example 4a was carried out in the same way as catalyst component, Suspended in heptane, was obtained. Example 4, but no nPTMS was used in step E. Example CE-Ba Example 5 0410 Example CE-Ba was carried out in the same way as 0403. Example 5 was carried out in the same way as Example CE-B, but no nPTMS was used in step E. Example 2, but BA-HMe/Mg-0.1 molar ratio was used in step D instead of BA-HMe/Mg 0.15 molar ratio. Example CE-C Example 5a Comparative Experiment C 0411 Example CE-C was carried out in the same way as 04.04 Example 5a was carried out in the same way as Example CE-B, but di-n-butylphthalate (DBP) at DBP/ Example 5, but no nPTMS was used in step E. Mg-0.15 molar ratio was used in step D instead of flu/ Example 6 Mg=0.15. 04.05 Example 6 was carried out in the same way as Example CE-D Example 2, but BA-HMe/Mg 0.25 molar ratio was used in step D instead of BA-HMe/Mg 0.15 molar ratio. Comparative Experiment D 0412. Example CE-D was carried out in the same way as Example 6a Example CE-A, but DBP/Mg 0.1 molar ratio was used in 04.06 Example 6a was carried out in the same way as step D instead of flu/Mg=0.1 molar ratio. Example 6, but no nPTMS was used in step E. Example CE-E Example CE-A Comparative Experiment E Comparative Experiment A 0413 Example CE-E was carried out in the same way as 04.07 Example CE-A was carried out in the same way as Example CE-A, but in step D ethylbenzoate (EB/Mg 0.15 Example 1, but ethylbenzoate (EB/Mg 0.15 molar ratio) molar ratio) at I stage and di-n-butylphthalate (DBP/Mg=0. was used in step D instead of benzamide. 05 molar ratio) at III stage were used as follows. 0414. A reactor was brought under nitrogen and 125 ml Example CE-Aa of titanium tetrachloride was added to it. The reactor was heated to 100° C. and a Suspension, containing about 5.5 g. 04.08 Example CE-Aa was carried out in the same way as of activated support in 15 ml of heptane, was added to it Example CE-A, but no nPTMS was used in step E. under stirring. The reaction mixture was kept at 100° C. for 10 min. Then add 0.886 g of ethylbenzoate (EB/Mg 0.15 Example CE-B molar ratio). The reaction mixture was kept for 60 min (I Comparative Experiment B stage of catalyst preparation). Then the stirring was stopped and the solid substance was allowed to settle. The superna 04.09 Example CE-B was carried out in the same way as tant was removed by decanting, after which the Solid product Example 1, but in step D only 9.9-bis-methoxymethyl-9H was washed with chlorobenzene (125 ml) at 100° C. for 20 fluorene (flu/Mg 0.15 molar ratio) without benzamide was min. Then the washing solution was removed by decanting, used as follows. A reactor was brought under nitrogen and after which a mixture of titanium tetrachloride (62.5 ml) and 125 ml of titanium tetrachloride was added to it. The reactor chlorobenzene (62.5 ml) was added. The reaction mixture was heated to 100° C. and a suspension, containing about 5.5 was kept at 100° C. for 30 min (II stage of catalyst g of activated Support in 15 ml of heptane, was added to it preparation). After which the stirring was stopped and the under stirring. Then the temperature of reaction mixture was Solid Substance was allowed to settle. The Supernatant was increased to 110° C. for 10 min and 1.5 g of 9.9-bis removed by decanting, after which a mixture of titanium methoxymethyl-9H-fluorene (flu) (flu/Mg 0.15 molar ratio) tetrachloride (62.5 ml) and chlorobenzene (62.5 ml) was in 3 ml of chlorobenzene was added to reactor. Temperature added. Then di-n-butylphthalate (DBP) at DBP/Mg 0.05 of reaction mixture was increased to 115° C. and the reaction molar ratio) in 2 ml of chlorobenzene was added to reactor mixture was kept at 115° C. for 105 min (I stage of catalyst and the temperature of reaction mixture was increased to preparation). Then the stirring was stopped and the Solid 115° C. The reaction mixture was kept at 115° C. for 30 min Substance was allowed to settle. The Supernatant was (III stage of catalyst preparation). After which the stirring US 2016/031 1947 A1 Oct. 27, 2016 24 was stopped and the solid Substance was allowed to settle. magnetic stirrer. Filter the extract via a single use Syringe The Supernatant was removed by decanting, after which a filter Minisart SRP 15 with PTFE-membrane (pore size of mixture of titanium tetrachloride (62.5 ml) and chloroben 0.45 micron). Zene (62.5 ml) was added. The reaction mixture was kept at 0419 Analyze the solution by H PLC using a reverse 115° C. for 30 min (IV stage of catalyst preparation), after phase C18 column (Shimadzu Pathfinder C18 column, 4.6x which the solid substance was allowed to settle. The super 50 mm, 2.5 um particle size, 100 Angstroem pore size) and natant was removed by decanting and the Solid was washed isocratic mobile phase (acetonitrile/water of 85/15 vol./vol.). five times using 150 ml of heptane at 60° C., after which the The column temperature is 40° C. A UV detector (single catalyst component, Suspended in heptane, was obtained. wavelength of 254 nm) is used for detection. Injection Volume is 5 ul. All injections are made twice. 0415 Table 1 and 2 show the test results, wherein the first 0420 Standard solution for calibration: 0.02-0.03 g of column discloses the example labels The second column internal donor or activating compound in 10 ml of acetoni discloses during which stage the activator is added and the trile analyzed under the same conditions as the catalyst type of activator used. The third column discloses the molar sample. Calculate the content of dibutyl phthalate as: ratio of the activator (BA) over the magnesium in the 0421 Internal donor/activating compound content support (Mg). The fourth column discloses the molar ratio of the internal donor over the magnesium in the Support (Mg) and the type of internal donor. The fifth, sixth and seventh S Wstandard column disclose the amount of internal donor, activator and (wt %) = Sstandard G . 100, titanium in wt.% with respect to the total weight of the catalyst composition. The eighth column discloses the yield where of polypropylene in kg/g catalyst. The ninth column dis 0422 S-average peak area of the sample: closes the amount of atactic PP (APP) in wt.% with respect 0423 Sstandard—average peak area of the standard to the total weight of the polymer obtained. The tenth sample: column discloses the amount of soluble xylene (XS) in wt. 0424 Wstandard weight of the standard sample, g: %. 0425 G—catalyst weight, g. 0416 Abbreviations and measuring methods: PP yield, 0426 ICP-AES Measurement of Procatalyst kg/g cat is the amount of polypropylene obtained per gram 0427 A Small amount amount of procatalyst sample was of catalyst component; the unit of MFR is g/10 min. contacted for 30 minutes with a HSO HNO solution to ensure a complete reaction of the procatalyst. After that, the 0417 Analysis of Internal Donors and Activating Com solution of HSO HNO/procatalyst reaction products pounds in TiNo Procatalyst by HPLC was measured by means of ICP-AES, using a ThermoEisher 0418 Extract the catalyst sample (0.1-0.2 g) with 10 ml Scientific, iCAP6500. Ti and Mg content in wt.% of total of acetonitrile in capped flask by stirring for 1 h with a procatalyst weight is reported. TABLE 1.

BA PP Ex. ID Mg ID/Mg ID BA Ti yield APP XS MFR M/M, 1 BA-2EH O.15 O. 1 9.2 4 3.0 8.5 O.8 2.7 15:S 4.3

2 BA-HMe O.15 O .1 11.6 16 3.0 13.1 0.65 21 14.7 4.3

3 BA-2Me O.15 O .1 11.7 2.2 4.6 134 0.6 2.2 17.2 3.9

4 BA-2EH O.1 O.1 11.7 2.3 3.2 9.8 O.S.S 3.7 14.4 4.3

5 BA-HMe O.1 O.1 12.9 18 32 111 O.6 2.2 17.7 4.5

6 BA-HMe O.25 O.1 10.7 1.9 2.7 10.9 O.6 2.S 17 4.3

CE-A EB O.15 O.1 13.S 3.3 2.9 16.5 0.35 2.6 14.4 S.1 EB CE-B O.15 16.5 - 34 9.2 O.8 35 10.7 S.1

CE-C O.15 1O.S 2.6 13.5 O.S 3.0 12.7 4.8 DBP CE-DEB O.15 O.1 7.3 2.3 2.8 11.1 1.O 54 18.4 S.6 DBP EB CE-E EB O.15 O.OS 9.2 O.7 23 113 O.6 4.0 15.8 S.O DBP EB

TABLE 2 Ex. stage BA/Mg ID/Mg ID BA Ti PP yield APP XS MFR M/M, 1a BA-2H O.15 O.1 9.2 4 3.0 13.5 1.1 4.2 25 4.9 flu US 2016/031 1947 A1 Oct. 27, 2016 25

TABLE 2-continued Ex. stage BA/Mg ID/Mg ID BA Ti PP yield APP MFR M/M, 2a BA-HMe O.15 O.1 11.6 16 3.O 15.4 1.O 4.2 22 4.1 flu 3a BA-2Me O.15 O.1 11.7 22 4.6 14.9 O.8 3.4 23 4.6 flu 4a BA-2H O.1 O.1 11.7 2.3 3.2 13.2 O.8 4.1 25 4.8 flu Sa BA-HMe O.1 O.1 12.9 18 32 16.0 O6 3.9 19 4.4 flu 6a BA-HMe O.25 O.1 10.7 1.9 2.7 13.8 O.9 4.3 25 4.4 flu CE-Aa EB O.15 O.1 13.S 3.3 2.9 25.0 1.O 5.8 49.5 4.3 flu EB CE-Bal O.15 16.5 - 34 13.5 1.2 4.3 21.8 4.6 flu

0428 Table 1 shows that the catalyst component accord ing to the present invention, i.e. comprising a benzamide of Formula VII formula X and an internal donor selected from the group R5 consisting of 1,3-diethers represented by the Formula VII allows obtaining polypropylenes having narrow molecular R’o-ch--CH-OR" weight distribution, low XS and APP content at relatively high MFR values, for instance it is possible to obtain a polypropylene homopolymer having wherein R and Rare each independently selected from a 0429 a molecular weight distribution (M./M) below hydrogen or a hydrocarbyl group selected from alkyl, alk 5.0, for example below 4.5, preferably from 2 to 4.5, more enyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and preferably from 3 to 4.5, more preferably from 3.5 to 4.5 one or more combinations thereof and wherein R and R' are each independently selected from a hydrocarbyl group. 0430 a melt flow rate of above 14, for example in the range from 14 to 1000, 2. The process according to claim 1, comprising: 0431 a weight percentage of atactic polypropylene A) providing said procatalyst obtained via a process (APP) of less than 1.5, preferably less than 1.0 comprising: i) contacting a compound RMgX, with an alkoxy- or 0432 a xylene soluble content (XS) of less than 4.5 wt. aryloxy-containing silane compound to give a first %. intermediate reaction product, being a solid Mg(OR") X2, wherein: R is the same as R' being a linear, 1. A process for the preparation of a procatalyst for branched or cyclic hydrocarbyl group independently preparing a catalyst composition for olefin polymerization, Selected from alkyl, alkenyl, aryl, aralkyl or alkylaryl said process comprising: groups, and one or more combinations thereof, wherein said hydrocarbyl group is Substituted or unsubstituted, providing a magnesium-based support, contacting said optionally comprises one or more heteroatoms and has magnesium-based Support with a Ziegler-Natta type from 1 to 20 carbon atoms: X and X’ are each catalytic species, an internal donor, and an activator, to independently selected from fluoride (F), chloride yield a procatalyst, wherein the activator is a benz (Cl), bromide (Br) or iodide (I); Z is in a range of amide according to formula X: larger than 0 and smaller than 2, being 0

3. The process according to claim 1, wherein the hydro 8. The process according to claim 1, wherein the benz carbyl groups R and Reach have from 1 to 10 carbon amide is present in the procatalyst, in an amount of from 0.1 atOmS. to 4 wt.% as measured using HPLC. 4. The process according to claim 1, wherein the internal 9. A procatalyst obtained or obtainable by the process donor is selected from the group consisting of 1,3-dime according to claim 1. thoxypropane, 1,3-diethoxypropane, 1,3-dibutoxypropane, 10. A catalyst composition for olefin polymerization com 1-methoxy-3-ethoxypropane, 1-methoxy-3-butoxypropane, prising a procatalyst comprising 1-methoxy-3-cyclohexoxypropane, 2.2-dimethyl-1,3-dime thoxypropane, 2.2-diethyl-1,3-dimethoxypropane, 2,2-di-n- a benzamide according to formula X, butyl-1,3-dimethoxypropane, 2,2-diiso-butyl-1,3-dime thoxypropane, 2-ethyl-2-n-butyl-1,3-dimethoxypropane, 2-n-propyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2-dim Formula X ethyl-1,3-diethoxypropane, 2-n-propyl-2-cyclohexyl-1,3-di ethoxypropane, 2-(2-ethylhexyl)-1,3-dimethoxypropane, R3 C R70 2-isopropyl-1,3-dimethoxypropane, 2-n-butyl-1,3 -dime n N 1. thoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclo hexyl-1,3-dimethoxypropane, 2-phenyl-1,3-diethoxypro R71 pane, 2-cumyl-1,3-diethoxypropane, 2-(2-phenylethyl)-1,3- dimethoxypropane, 2-(2-cyclohexylethyl)-1,3- dimethoxypropane, 2-(p-chlorophenyl)-1,3- dimethoxypropane, 2-(diphenylmethyl)-1,3- dimethoxypropane, 2-(1-naphthyl)-1,3-dimethoxypropane, wherein R'' and R'' are each independently selected from 2-(fluorophenyl)-1,3-dimethoxypropane, 2-(1-decahy hydrogen or an alkyl., and R', R. R. R', and R7 are dronaphthyl)-1,3-dimethoxypropane, 2-(p-t-butylphenyl)-1, each independently selected from hydrogen, a heteroatom or 3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypro a hydrocarbyl group, and wherein the benzamide according pane, 2,2-di-npropyl-1,3-dimethoxypropane, 2-methyl-2-n- to formula X is present in an amount of from 0.1 to 3.5 wt. propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3- %, based on the procatalyst as measured using HPLC, and dimethoxypropane, 2-methyl-2-ethyl-1,3- further comprising dimethoxypropane, 2-methyl-2-phenyl-1,3- an internal donor selected from 1,3-diethers represented dimethoxypropane, 2-methyl-2-cyclohexyl-1,3- by Formula VII dimethoxypropane, 2.2-bis(pchlorophenyl)-1,3- dimethoxypropane, 2.2-bis(2-cyclohexylethyl)-1,3- dimethoxypropane, 2-methyl-2-isobutyl-1,3- Formula VII dimethoxypropane, 2-methyl-2-(2-ethylhexyl)-1,3- R5 dimethoxy propane, 2-methyl-2-isopropyl-1,3- dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2.2-bis(cyclohexylm R’o-CH-i-CH-OR" ethyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxy propane, 2,2-diisobutyl-1,3-di-n-butoxypropane, 2-isobutyl 2-isopropyl-1,3-dimethoxypropane, 2,2-di-sec-butyl-1,3- wherein R and Rare each independently selected from dimethoxypropane, 2,2-di-t-butyl-1,3-dimethoxypropane, a hydrogen or a hydrocarbyl group selected from alkyl, 2,2-dineopentyl-1,3-dimethoxypropane, 2-isopropyl-2-iso alkenyl, asyl, aralkyl, alkoxycarbonyl or alkylaryl groups pentyl-1,3-dimethoxypropane, 2-phenyl-2-benzyl-1,3-dime thoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dime and one or more combinations thereof and wherein R and thoxypropane, 2-isopropyl-2-(3,7-dimethyloctyl) 1,3- R" are each independently selected from a hydrocarhyl dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, group. 2-isopropyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 11. The catalyst composition of claim wherein the catalyst 2,2-diisopentyl-1,3-dimethoxypropane, 2-isopropyl-2-cy is a Supported Ziegler-Natta catalyst. clohexyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclopen 12. A process for the preparation of polyolefins, polypro tyl-1,3-dimethoxypropane, 2,2-dicylopentyl-1,3-dime pylene, comprising contacting a procatalyst of claim 9 with thoxypropane, 2-n-heptyl-2-n-pentyl-1,3- at least one olefin, and optionally an external donor and/or dimethoxypropane, 9.9-bis(methoxymethyl)fluorene, 1,3- optionally a co-catalyst. dicyclohexyl-2.2-bis(methoxymethyl)propane, 3,3-bis 13. A polyolefin, preferably a polypropylene, obtained by (methoxymethyl)-2,5-dimethylhexane, or any combination the process according to claim 12. of the foregoing, for example wherein the internal donor is selected from the group of 1,3-dicyclohexyl-2.2-bis 14. The polyolefin according to claim 13, wherein the (methoxymethyl)propane, 3.3-bis(methoxymethyl)-2,5-di polyolefin has a molecular weight distribution (M./M) methylhexane, 2,2-dicyclopentyl-1,3-dimethoxypropane below 5.0, wherein M and M, are determined according to and any combinations thereof. ASTM D6474-12. 5. The process according to claim 1, wherein the internal 15. A polypropylene homopolymer prepared by a slurry donor is 9.9-bis(methoxymethyl)fluorene. polymerization using a solvent, having: 6. The process according to claim 1, wherein in the a molecular weight distribution (M/M) below 5.0, activator according to Formula X, at least one of R'' and R' wherein M and M, are determined according to is an alkyl group, wherein the alkyl has from 1 to 6 carbon ASTM D6474-12; atOmS. a melt flow rate of above 14, wherein the melt flow rate 7. The process according to claim 1, wherein the activator is as measured according to ISO 1133:2005, at 230° C. is N,N-dimethylbenzamide. under a load of 2.16 kg; US 2016/031 1947 A1 Oct. 27, 2016 27

a weight percentage of atactic polypropylene (APP) of 16. The process of claim 1, wherein the hydrocarbyl less than 1.5, wherein the APP is measured according groups Rand Reach have from 1 to 6 carbon atoms; and to the following procedure: a quantity A of the product at least one of R'' and R' is an alkyl group, wherein the stream from said slurry polymerization process is col alkyl has from 1 to 6 carbon atoms. lected; this quantity A is filtered using a filter having 17. The process according to claim 4, wherein the acti pores between 10 and 16 um in diameter, to obtain a vator is N,N-dimethylbenzamide. filtrate Y and a polymer quantity of weight X, said 18. The process according to claim 5, wherein the acti polymer quantity of weight X being the quantity of vator is N,N-dimethylbenzamide. material that remained on the filter, said filtrate Y is 19. A procatalyst obtained by the process according to dried over a steam bath and then under vacuum at 60° claim 18. C. to obtain a dry mass of APP of weight Z; the weight 20. The polypropylene homopolymer prepared by the percentage of APP is calculated by: slurry polymerization of claim 15 using heptane as a solvent and having: a molecular weight distribution (M./M.) from 2 to 4.5, APP (in wt %) = 2. k 100% wherein M and M are determined according to 2--X ASTM D6474-12; a melt flow rate from 14 to 1000; and a xylene soluble content (XS) of less than 4.5 wt.%, a weight percentage of atactic polypropylene (APP) of wherein the XS is measured according to ASTM D less than 1.0. 5492-10.