PROCATALYST FOR POLYMERIZATION OF OLEFINS COMPRISING A MONOESTER AND AN AMIDOBENZOATE INTERNAL DONOR

Abstract

The present invention relates to a process for preparing a procatalyst for polymerization of olefins, comprising contacting a magnesium-containing support with a halogen-containing titanium compound, a monoester, a first internal electron donor, wherein the internal electron donor is represented by a compound represented by Formula A, for example a Fischer projection of Formula A, and optionally a second internal electron donor selected from a group consisting of diesters and diethers, Formula A said process comprising the steps of: i) contacting a butyl Grignard compound with an alkoxy- or aryloxy-containing silane compound to give a first intermediate reaction product; ii) optionally activating the first intermediate reaction product with at least one activating compound to give a second intermediate reaction product; iii) contacting the first or second intermediate reaction product, obtained respectively in step i) or ii), with a halogen-containing Ti-compound, the monoester, and said internal electron represented by a compound represented by Formula A, for example a Fischer projection of Formula A, as the first internal electron donor, and optionally the diester or di-ether as the second internal electron donor. The present invention also relates to a polymerization catalyst system comprising said procatalyst, a co-catalyst and optionally an external electron donor. Furthermore, the present invention relates to a polyolefin obtainable by the process according to the present invention and a shaped article thereof.

##STR00001##

Claims

1. A process for preparing a procatalyst for polymerization of olefins, comprising contacting a magnesium-containing support with a halogen-containing titanium compound, a monoester, a first internal electron donor, wherein the internal electron donor is represented by a compound represented by Formula A, for example a Fischer projection of Formula A, and optionally a second internal electron donor selected from a group consisting of diesters and diethers, ##STR00027## Wherein in Formula A: each R.sup.80 group is independently a substituted or unsubstituted aromatic group having from 6 to 20 carbon atoms; R.sup.81, R.sup.82, R.sup.83, R.sup.84, R.sup.85, and R.sup.86 are each independently selected from hydrogen or a linear, branched or cyclic hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof; R.sup.87 is a hydrogen or a linear, branched or cyclic hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof; N is nitrogen atom; O is oxygen atom; and C is carbon atom; said process comprising the steps of: i) contacting a compound R.sup.4.sub.zMgX.sup.4.sub.2-z with an alkoxy- or aryloxy-containing silane compound to give a first intermediate reaction product, being a solid Mg(OR).sub.xX.sup.1.sub.2-x, wherein: R.sup.1 is a linear, branched or cyclic hydrocarbyl group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof, wherein said hydrocarbyl group may be substituted or unsubstituted, may contain one or more heteroatoms; wherein R.sup.4 is butyl; wherein X.sup.4 and X.sup.1 are each independently selected from the group of consisting of fluoride (F−), chloride (Cl−), bromide (Br−) or iodide (I−); z is in a range of larger than 0 and smaller than 2, being 0<z<2; ii) optionally contacting the solid Mg(OR).sub.xX.sup.1.sub.2-x obtained in step ii) with at least one activating compound selected from the group formed by activating electron donors and metal alkoxide compounds of formula M.sup.1(OR.sup.2).sub.v-w(OR.sup.3).sub.w or M.sup.2(OR.sup.2).sub.v-w(R.sup.3).sub.w, to obtain a second intermediate product; wherein: M.sup.1 is a metal selected from the group consisting of Ti, Zr, Hf, Al or Si; v is the valency of M.sup.1; M.sup.2 is a metal being Si; v is the valency of M.sup.2; R.sup.2 and R.sup.3 are each a linear, branched or cyclic hydrocarbyl group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof, wherein said hydrocarbyl group may be substituted or unsubstituted, may contain one or more heteroatoms; wherein w is smaller than v; iii) contacting the first or second intermediate reaction product, obtained respectively in step i) or ii), with a halogen-containing Ti-compound, the monoester, and said internal electron represented by a compound represented by Formula A, for example a Fischer projection of Formula A, as the first internal electron donor, and optionally the diester or diether as the second internal electron donor.

2. The process according to claim 1, wherein R.sup.81, R.sup.82, R.sup.83, R.sup.84, R.sup.85, and R.sup.86 are independently selected from a group consisting of hydrogen, C.sub.1-C.sub.10 straight and branched alkyl; C.sub.3-C.sub.10 cycloalkyl; C.sub.6-C.sub.10 aryl; and C.sub.7-C.sub.10 alkaryl and aralkyl group; C.sub.3-C.sub.10 cycloalkyl; C.sub.6-C.sub.10 aryl; and C.sub.7-C.sub.10 alkaryl and aralkyl group.

3. The process according to claim 1, wherein R.sup.87 is selected from a group consisting of methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, phenyl, benzyl, substituted benzyl and halophenyl group.

4. The process according to claim 1, wherein R.sup.80 is selected from the group consisting of C.sub.6-C.sub.10 aryl; and C.sub.7-C.sub.10 alkaryl and aralkyl group.

5. The process according to claim 1, wherein the monoester is an acetate or a benzoate.

6. The process according to claim 1, wherein the internal electron donor is selected from the group consisting of 4-[benzoyl(methyl)amino]pentan-2-yl benzoate; 2,2,6,6-tetramethyl-5-(methylamino)heptan-3-ol dibenzoate; 4-[benzoyl (ethyl)amino]pentan-2-yl benzoate and 4-(methylamino)pentan-2-yl bis (4-methoxy)benzoate).

7. The process according to claim 1, further comprising an additional or second internal electron donor selected from the group consisting of diesters and diethers.

8. The process according to claim 1, wherein as internal donor 4-[benzoyl(methyl)amino]pentan-2-yl benzoate is used and as monoester ethyl benzoate is used.

9. The process according to claim 1, wherein as internal donor 4-[benzoyl(methyl)amino]pentan-2-yl benzoate is used and as monoester ethyl benzoate is used and as second internal electron donor dibutyl phthalate is used.

10. The process according to claim 1, wherein as internal donor 4-[benzoyl(methyl)amino]pentan-2-yl benzoate is used and as monoester ethyl benzoate is used and as second internal electron donor 9,9-bis-methoxymethyl-fluorene is used.

11. A pro catalyst obtainable by the process according to claim 1.

12. A polymerization catalyst system comprising the procatalyst according to claim 11, a co-catalyst and optionally an external electron donor.

13. A process of making a polyolefin by contacting at least one olefin with the catalyst system according to claim 12.

14. A polyolefin obtainable by the process according to claim 13.

15. A shaped article, comprising the polyolefin according to claim 14.

16. The process according to claim 1, wherein R.sup.81, R.sup.82, R.sup.83, R.sup.84, R.sup.85, and R.sup.86 are each independently selected from hydrogen or a linear, branched or cyclic hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof having from 1 to 20 carbon atoms; and R.sup.87 is a hydrogen or a linear, branched or cyclic hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof, having from 1 to 20 carbon atoms.

17. The process according to claim 16, wherein R.sup.81 and R.sup.82 is each a hydrogen atom and R.sup.83, R.sup.84, R.sup.85, and R.sup.86 are independently selected from a group consisting of methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, and phenyl group.

18. The process according to claim 17, wherein when one of R.sup.83 and R.sup.84 and one of R.sup.85 and R.sup.86 has at least one carbon atom, then the other one of R.sup.83 and R.sup.84 and of R.sup.85 and R.sup.86 is each a hydrogen atom.

Description

EXAMPLES

[0398] The performance of a procatalyst prepared using a butyl Grignard support, a monoester as activator and an amidobenzoate as internal donor.

[0399] First, the preparation of a specific amidobenzoate (AB) is disclosed below.

Preparation of 4-[benzoyl(methyl)amino]pentan-yl benzoate (AB)

Step a)

[0400] ##STR00024##

[0401] 40% monomethylamine solution in water (48.5 g, 0.625 mol) was added drop wise to a stirred solution of substituted pentane-2,4-dione (50 g, 0.5 mol) in toluene (150 ml. After the addition, the reaction mass was stirred at room temperature for 3 hours and then refluxed. During the reflux the water formed was azeotropically removed using a Dean-stark trap. Then the solvent was removed under reduced pressure to give 4-(methylamino)pent-3-en-2-one, 53.5 g (95% yield), which was then directly used for reduction.

Step b)

[0402] ##STR00025##

[0403] 4-(methylamino)-pent-3-en-2-one (100 g) was added to a stirred mixture of 1000 ml 2-propanol and 300 ml toluene. To this solution, small piece of metallic sodium 132 g was gradually added at a temperature of from 25 to 60° C. The reaction mass was refluxed for 18 h. The mass was cooled to room temperature and was poured in cold water and extracted with dichloromethane. The extract was dried over sodium sulfate, filtered and then evaporated under reduced pressure to give 65 g 4-(methylamino)pentan-2-ol (isomer mixture) oil (63% yield).

Step c)

[0404] ##STR00026##

[0405] 4-(methylamino)pentan-2-ol (10 g) was added to a mixture of pyridine (16.8 g) and toluene (100 ml). The mass was cooled to 10° C. and benzoyl chloride (24 g) was added drop wise. The mixture was refluxed for 6 h. The mixture was then diluted with toluene and water. The organic layer was washed with diluted HCl, water saturated bicarbonate and brine solution. The organic layer was dried over sodium sulfate, filtered and then evaporated under reduced pressure. The residue was purified by flash chromatography to form 25 g product as thick oil (90% yield). The product was characterized by .sup.1H NMR and .sup.13C NMR: .sup.1H NMR (300 MHz, CDCl.sub.3) δ=7.95-7.91 (m, 1H), 7.66-7.60 (m, 2H), 7.40-7.03 (m, 5H), 6.78-6.76 (m, 2H), 4.74-5.06 (br m, 1H), 3.91-3.82 (m, 1H), 2.83-2.56 (ddd, 3H), 2.02-1.51 (m, 1H), 1.34-1.25 (dd, 1H), 1.13-1.02 (m, 6H); .sup.13C NMR (75 MHz, CDCl.sub.3), δ=170.9, 170.4, 170.3, 164.9, 164.6, 135.9, 135.8, 135.2, 131.8, 131.7, 131.6, 129.6, 129.4, 129.3, 128.9, 128.4, 128.3, 128.2, 128.0, 127.7, 127.3, 127.2, 127.1, 127.0, 125.7, 125.6, 125.0, 124.9, 68.3, 67.5, 67.3, 49.8, 49.4, 44.9, 44.4, 39.7, 39.0, 38.4, 38.3, 30.5, 29.8, 25.5, 25.1, 19.33, 19.1, 18.9, 18.3, 17.0, 16.8, 16.7.

[0406] m/z=326.4 (m+1)

[0407] The .sup.1H-NMR and .sup.13C-NMR spectra are recorded on a Varian Mercury-300 MHz NMR Spectrometer, using deuterated chloroform as a solvent.

[0408] In the Examples below a procatalyst is prepared using the following phases: [0409] Phase A) preparation of solid support; [0410] Phase B) activating said solid support; [0411] Phase C) contacting said activated solid support with a titanium catalytic species, an ethylbenzoate monoester activator, and a amidobenzoate internal donor.

[0412] During stage I of phase C said activated solid support was first contacted with titanium tetrahalide and an ethylbenzoate activator (in a EB/Mg molar ratio of 0.15). During stage II of phase C the intermediate product obtained from stage I was contacted with additional titanium tetrahalide and an amidobenzoate internal donor (in a AB/Mg molar ratio of 0.04). During stage II of phase C the intermediate product obtained from stage II was contacted with additional titanium tetrahalide to obtain the procatalyst.

Preparation of Procatalysts According to the Present Invention

[0413] The several different phases and stages for the preparation of the procatalyst are discussed below.

Example 1: Preparation of a Procatalyst on an Activated Butyl-Grignard Support

[0414] Preparation of Grignard Reagent (Step o))—Phase A

[0415] This step o) constitutes the first part of phase A of the process for preparation of the procatalyst.

[0416] A stirred flask, fitted with a reflux condenser and a funnel, was filled with magnesium powder (24.3 g). The flask was brought under nitrogen. The magnesium was heated at 80° C. for 1 hour, after which dibutyl ether (150 ml), iodine (0.03 g) and n-chlorobutane (4 ml) were successively added. After the colour of the iodine had disappeared, the temperature was raised to 80° C. and a mixture of n-chlorobutane (110 ml) and dibutyl ether (750 ml) was slowly added for 2.5 hours. The reaction mixture was stirred for another 3 hours at 80° C. Then the stirring and heating were stopped and the small amount of solid material was allowed to settle for 24 hours. By decanting the colourless solution above the precipitate, a solution of butylmagnesiumchloride with a concentration of 1.0 mol Mg/I was obtained.

Preparation of Solid Magnesium Compound (Step i))—Phase A

[0417] This step i) constitutes the second part of phase A of the process for preparation of the procatalyst.

[0418] This step is carried out as described in Example XX of EP 1 222 214 B1, except that the dosing temperature of the reactor is 35° C., the dosing time is 360 min and the propeller stirrer w is as used. An amount of 250 ml of dibutyl ether is introduced to a 1 liter reactor. The reactor is fitted by propeller stirrer and two baffles. The reactor is thermostated at 35° C.

[0419] The solution of reaction product of step A (360 ml, 0.468 mol Mg) and 180 ml of a solution of tetraethoxysilane (TES) in dibutyl ether (DBE), (55 ml of TES and 125 ml of DBE), are cooled to 10° C., and then are dosed simultaneously to a mixing device of 0.45 ml volume supplied with a stirrer and jacket. Dosing time is 360 min. Thereafter the premixed reaction product A and the TES-solution are introduced to a reactor. The mixing device (minimixer) is cooled to 10° C. by means of cold water circulating in the minimixer's jacket. The stirring speed in the minimixer is 1000 rpm. The stirring speed in reactor is 350 rpm at the beginning of dosing and is gradually increased up to 600 rpm at the end of dosing stage.

[0420] On the dosing completion the reaction mixture is heated up to 60° C. and kept at this temperature for 1 hour. Then the stirring is stopped and the solid substance is allowed to settle. The supernatant is removed by decanting. The solid substance is washed three times using 500 ml of heptane. As a result, a pale yellow solid substance, reaction product B (the solid first intermediate reaction product; the support), is obtained, suspended in 200 ml of heptane. The average particle size of support is 22 μm and span value (d.sub.90−d.sub.10)/d.sub.50=0.5.

Activation of First Intermediate Reaction Product (Step ii))—Phase B

[0421] This step ii) constitutes phase B of the process for preparation of the procatalyst as discussed above.

[0422] Support activation was carried out as described in Example IV of WO/2007/134851 to obtain the second intermediate reaction product.

[0423] In inert nitrogen atmosphere at 20° C. a 250 ml glass flask equipped with a mechanical agitator is filled with slurry of 5 g of reaction product B dispersed in 60 ml of heptane. Subsequently a solution of 0.22 ml ethanol (EtOH/Mg=0.1) in 20 ml heptane is dosed under stirring during 1 hour. After keeping the reaction mixture at 20° C. for 30 minutes, a solution of 0.79 ml titanium tetraethoxide (TET/Mg=0.1) in 20 ml of heptane was added for 1 hour.

[0424] The slurry was slowly allowed to warm up to 30° C. for 90 min and kept at that temperature for another 2 hours. Finally the supernatant liquid is decanted from the solid reaction product (the second intermediate reaction product; activated support) which was washed once with 90 ml of heptane at 30° C.

[0425] The activated support, according to chemical analysis, comprises a magnesium content of 17.3 wt. %, a titanium content of 2.85 wt. %, and a chloride content of 27.1 wt. % corresponding to a molar ratio of CI/Mg of 1.07 and Ti/Mg of 0.084.

Preparation of Procatalyst—Phase C

[0426] This constitutes phase C of the process for preparation of the procatalyst as discussed above.

[0427] A reactor is brought under nitrogen and 125 ml of titanium tetrachloride is added to it. The reactor is heated to 100° C. and a suspension, containing about 5.5 g of activated support (step C) in 15 ml of heptane, is added to it under stirring. The reaction mixture is kept at 110° C. for 10 min.

[0428] Then ethyl benzoate (EB/Mg=0.25 mol) is added in 2 ml of chlorobenzene. The reaction mixture is kept for 60 min at 110° C. Then the stirring is stopped and the solid substance is allowed to settle. The supernatant is removed by decanting, after which the solid product is washed with chlorobenzene (125 ml) at 100° C. for 20 min. Then the washing solution is removed by decanting. This concludes stage I of Phase C.

[0429] Then a mixture of titanium tetrachloride (62.5 ml) and chlorobenzene (62.5 ml) is added. The temperature of reaction mixture is increased to 115° C. and stirred for 30 minutes. Then the stirring was stopped and the solid substance is allowed to settle.

[0430] Then a mixture of titanium tetrachloride (62.5 ml) and chlorobenzene (62.5 ml) is added. The temperature of reaction mixture is increased to 115° C. and 4-[benzoyl(methyl)amino]pentan-2-yl benzoate (aminobenzoate, AB, AB/Mg=0.15 mol) in 2 ml of chlorobenzene is added to reactor. Then the reaction mixture is kept at 115° C. for 30 min. After which the stirring was stopped and the solid substance is allowed to settle. The supernatant was removed by decanting. This concludes stage II of Phase C.

[0431] Then a mixture of titanium tetrachloride (62.5 ml) and chlorobenzene (62.5 ml) is added. The reaction mixture is kept at 115° C. for 30 min, after which the solid substance is allowed to settle. The supernatant is removed by decanting and the solid is washed five times using 150 ml of heptane at 60° C., after which the catalyst component, suspended in heptane, is obtained. This concludes stage III of Phase C. The resulting procatalyst has a titanium content of 2.6 wt. %.

Example 2: Preparation of a Procatalyst on a Double Activated Butyl-Grignard Support

[0432] Example 1 was repeated but in addition to the activation phase B), an activation using methanol was carried out as follows:

[0433] Under an inert nitrogen atmosphere at 20° C. a 250 ml glass flask equipped with a mechanical agitator was filled with a slurry of 5 g of the reaction product of step ii) dispersed in 60 ml of heptane. Subsequently a solution of 0.86 ml methanol (MeOH/Mg=0.5 mol) in 20 ml heptane was dosed under stirring during 1 hour. After keeping the reaction mixture at 20° C. for 30 minutes the slurry was slowly allowed to warm up to 30° C. for 30 min and kept at that temperature for another 2 hours. Finally the supernatant liquid was decanted from the solid reaction product which was washed once with 90 ml of heptane at 30° C. The molar ratio of MeOH/Mg was 0.2. The resulting procatalyst has a titanium content of 3.2 wt. %.

Example 3: Preparation of a Procatalyst on a Double Activated Butyl-Grignard Support

[0434] Example 3 was repeated but the molar ratio of MeOH/Mg is 0.4. The resulting procatalyst has a titanium content of 3.5 wt. %.

Example 4: Preparation of a Procatalyst on an Activated Butyl-Grignard Support

[0435] Example 3 was repeated but the molar ratio of MeOH/Mg is 0.3. The resulting procatalyst has a titanium content of 3.3 wt. %.

Preparation of Homopolymer of Propylene

[0436] Polymerization of propylene is carried out in a stainless steel reactor (with a volume of 0.7 I) in heptane (300 ml) at a temperature of 70° C., total pressure 0.7 MPa and hydrogen presence (55 ml) for 1 hour in the presence of a catalyst system comprising the procatalyst according to step D, triethylaluminium as co-catalyst and n-propyltrimethoxysilane as external donor. The concentration of the procatalyst is 0.033 g/l; the concentration of triethylaluminium is 4.0 mmol/l; the concentration of n-propyltrimethoxysilane was 0.2 mmol/l. The results are shown in Table 1 below.

TABLE-US-00001 TABLE 1 Ex. # EB/Mg AB/Mg MeOH/Mg Ti. Wt. % PP yield APP MFR BD 1 0.15 0.04 n.a. 2.6 5.7 0.9 2.3 434 1 0.15 0.04 0.2 3.2 6.8 0.9 2.3 450 2 0.15 0.04 0.4 3.5 8.9 0.8 3.6 453 3 0.15 0.04 0.3 3.3 8.0 1.0 2.4 473

[0437] The results from Table 1 clearly show that using the method according to the present invention propylene homopolymers can be obtained having good yield, APP, MFR and BD. It is noted that the additional activation using methanol leads to a higher yield.

Semi-Continuous Preparation Ethylene-Propylene Copolymer Rubber

[0438] Gas-phase polymerizations were performed in a set of two horizontal, cylindrical reactors in series, wherein a propylene homopolymer was formed in the first reactor and an ethylene-propylene copolymer rubber in the second one to prepare an impact copolymer. The first reactor was operated in a continuous way, the second one in a batch manner. In the synthesis of the homopolymer, the polymer was charged into the secondary reactor blanketed with nitrogen. The first reactor was equipped with an off-gas port for recycling reactor gas through a condenser and back through a recycle line to the nozzles in the reactor. Both reactors had a volume of one gallon (3.8-liter) measuring 10 cm in diameter and 30 cm in length. In the first reactor liquid propylene was used as the quench liquid; for the synthesis of copolymers the temperature in the second reactor was kept constant by a cooling jacket. The procatalyst (having a molar ratio of EB/Mg of 0.15 and a molar ratio of AB/Mg of 0.04) was introduced into the first reactor as a 5-7 weight percent slurry in hexane through a liquid propylene-flushed catalyst addition nozzle. External donor (DiPDMS: di-isopropyl dimethoxy silane) and TEAl in hexane were fed to the first reactor through a different liquid propylene flushed addition nozzle. For the production of copolymer, an AI/Ti molar ratio of 160 and Si/Ti molar ratio of 11.3 was used. Moreover, the procatalyst is also activated with methanol as discussed above having a MeOH/Mg molar ratio of 0.3.

[0439] During operation, polypropylene powder produced in the first reactor passed over a weir and was discharged through a powder discharge system into the second reactor. The polymer bed in each reactor was agitated by paddles attached to a longitudinal shaft within the reactor that was rotated at about 50 rpm in the first and at about 75 rpm in the second reactor. The reactor temperature and pressure were maintained at 61° C. and 2.2 MPa in the first and for the copolymer synthesis at 66° C. and 2.2 MPa in the second reactor. The production rate was about 200-250 g/h in the first reactor in order to obtain a stable process.

[0440] For the homopolymer synthesis the hydrogen concentration in the off gas was controlled such to achieve the targeted melt flow rate (MFR). For the copolymer synthesis, hydrogen was fed to the reactor to control a melt flow rate ratio over the homopolymer powder and copolymer powder. The composition of the ethylene-propylene copolymer (RCC2) was controlled by adjusting the ratio ethylene and propylene (C2/C3) in the recycling gas in the second reactor based on gas chromatography analysis.

[0441] Examples 5-8 show different runs for this copolymerization using different H.sub.2/C3 and different C2/C3 ratios. The results are shown in Table 2 below:

TABLE-US-00002 TABLE 2 Ex. # H2/C3 C2/C3 Yield MFR RC RCC2 5 0.0685 0.8217 16.1 17.69 28.68 60.31 6 0.0668 0.795 16.5 17.69 29.44 61.32 7 0.0699 0.6561 17.3 16.83 37.6 54.86 8 0.0704 0.6636 17.2 22.31 34.51 54.71

[0442] From Table 2 can be observed that a so-called impact copolymer can be obtained having desired properties using the method according to the present invention and that the properties can be tuned by selecting the appropriate reaction conditions.

[0443] Abbreviations and measuring methods: [0444] yield, in kg/g cat is the amount of polypropylene obtained per gram of catalyst component. [0445] APP, in wt. % is the weight percentage of atactic polypropylene. Atactic PP is the PP fraction soluble in heptane during polymerization. APP was determined as follows: 100 ml of the filtrate (y ml) obtained in separating the polypropylene powder (x g) and the heptane was dried over a steam bath and then under vacuum at 60° C. That yielded z g of atactic PP. The total amount of Atactic PP (q g) is: (y/100)*z. The weight percentage of Atactic PP is: (q/(q+x))*100%. [0446] XS, wt % is xylene solubles, measured according to ASTM D 5492-10. [0447] MFR or melt flow rate in dg/min is measured at 230° C. with 2.16 kg load, measured according to ISO 1133:2005. [0448] Mw/Mn: Polymer molecular weight and its distribution (MWD) were determined by Waters 150° C. gel permeation chromatograph combined with a Viscotek 100 differential viscosimeter. The chromatograms were run at 140° C. using 1,2,4-trichlorobenzene as a solvent with a flow rate of 1 ml/min. The refractive index detector was used to collect the signal for molecular weights. [0449] The .sup.1H-NMR and .sup.13C-NMR spectra were recorded on a Varian Mercury-300 MHz NMR Spectrometer, using deuterated chloroform as a solvent. [0450] bulk density or BD in g/I means the weight per unit volume of a material; it is measured as apparent density according to ASTM D1895-96 Reapproved 2010-e1, test method A. [0451] C.sub.2/C.sub.3 is the molar ratio of ethylene to propylene in the gas cap of the reactor, measured by on-line gas chromatography. [0452] Al/Ti is the molar ratio of aluminium (of the co-catalyst) to titanium (of the procatalyst) added to the reactor. [0453] Si/Ti is the molar ratio of silicon (of the external donor) to titanium (of the procatalyst) to the reactor. [0454] H.sub.2/C.sub.3 is the molar ratio of hydrogen to propylene in the gas cap of the reactor, measured by on-line gas chromatography. [0455] RC in wt. % is the amount of rubber incorporated in the copolymer (weight percent); measured with IR spectroscopy, which was calibrated using .sup.13C-NMR according to known procedures. [0456] RCC2 in wt. % is the amount of ethylene incorporated in the rubber fraction (weight percent); measured with IR spectroscopy, which was calibrated using .sup.13C-NMR according to known procedures