Heterophasic polypropylene with propylene hexene random copolymer as matrix

Abstract

The present invention is directed to a heterophasic polypropylene composition of high transparency based on excellent compatibility of the propylene 1-hexene random copolymer used as matrix with different types of external modifiers dispersed within the matrix. The present invention is further directed to a process for producing such a polypropylene composition and to a film, in particular a cast film, obtained from such a polypropylene composition. The polypropylene composition comprising a blend of a propylene copolymer comprising 2.5 to 12.0 wt % of 1-hexene as a comonomer, and having a melt flow rate MFR.sub.2 of 0.1 to 100 g/10 min, and an ethylene homo- or copolymer having a melt flow rate MFR.sub.2 of 0.05 to 30.0 g/10 min and a density of 850 to 920 kg/m.sup.3, wherein the melt flow rate MFR.sub.2 of the polypropylene composition is from 1.0 to 12.0 g/10 min.

Claims

1. A polypropylene composition comprising a blend of: (a) a propylene copolymer comprising 2.5 to 12.0 wt %, based on the weight of the propylene copolymer, of 1-hexene as a comonomer, and having a melt flow rate MFR.sub.2 of 0.1 to 100 g/10 min as determined at a temperature of 230° C. and a load of 2.16 kg, and (b) an ethylene homo- or copolymer having a melt flow rate MFR.sub.2 of 0.05 to 30.0 g/10 min as determined at a temperature of 190° C. and a load of 2.16 kg and a density of 850 to 920 kg/m.sup.3, wherein the ethylene copolymer comprised by the ethylene homo- or copolymer is an ethylene 1-octene copolymer wherein the melt flow rate MFR.sub.2 of the polypropylene composition is from 1.0 to 12.0 g/10 min as determined at a temperature of 230° C. and a load of 2.16 kg.

2. The polypropylene composition according to claim 1, wherein the blend comprises 60.0 to 95.0 wt %, based on the weight of the blend, of the propylene copolymer (a), and 5.0 to 40.0 wt %, based on the weight of the blend, of the ethylene homo- or copolymer (b).

3. The polypropylene composition according to claim 1, wherein the haze of the polypropylene composition is lower than 45.0% as determined on 1 mm.sup.3 injection moulded plaques.

4. The polypropylene composition according to claim 1, wherein the haze of the polypropylene composition is lower than the haze of the propylene copolymer (a).

5. The polypropylene composition according to claim 1, wherein the propylene copolymer (a) comprises in addition 0.1 to 3.0 wt %, based on the weight of the propylene copolymer, of ethylene as a comonomer.

6. The polypropylene composition according to claim 1, wherein the ethylene copolymer comprised by the ethylene homo- or copolymer (b) has a comonomer content of not higher than 17.0 mol %.

7. The polypropylene composition according to claim 1, wherein the content of 1-hexene of the polypropylene composition is 2.0 to 7.0 wt %.

8. The polypropylene composition according to claim 1, further comprising from 0.001 to 0.50 wt % of an α-nucleating agent.

9. The polypropylene composition according to claim 1, wherein the propylene copolymer (a) comprises two propylene copolymer fractions produced in two different polymerization steps, wherein the first fraction has a lower melt flow rate MFR.sub.2 than the second fraction, and wherein the polymerization step for obtaining the second fraction is carried out in the presence of the first fraction.

10. A process for preparing a polypropylene composition according to claim 1, comprising the following steps: (i) polymerising propylene and 1-hexene, and optionally ethylene, in the presence of a single-site catalyst to obtain a fraction (a) having a content of 1-hexene of 2.5 to 12.0 wt %, and optionally a content of ethylene of 0.1 to 3.0 wt %, and having a melt flow rate MFR.sub.2 of 0.1 to 100 g/10 min as determined at a temperature of 230° C. and a load of 2.16 kg, and (ii) polymerising ethylene, or ethylene and 1-octene, to obtain a fraction (b) having a melt flow rate MFR.sub.2 of 0.05 to 30.0 g/10 min as determined at a temperature of 190° C. and a load of 2.16 kg and a density of 850 to 920 kg/m.sup.3.

11. The process according to claim 10, wherein the polymerization step (i) is carried out in the absence of fraction (b) and the polymerization step (ii) is carried out in the absence of fraction (a), and fraction (a) and fraction (b) are mixed by compounding to obtain the blend.

12. A film comprising a polypropylene composition according to claim 1.

13. The film according to claim 12, wherein the film is a cast film.

Description

EXAMPLES

1. Definitions/Measuring Methods

(1) The following definitions of terms and determination methods apply for the above general description of the invention as well as to the below examples unless otherwise defined.

(2) Melt Flow Rate

(3) The melt flow rate (MFR) is determined according to ISO 1133 and is indicated in g/10 min. The MFR is an indication of the flowability, and hence the processability, of the polymer. The higher the melt flow rate, the lower the viscosity of the polymer. The MFR.sub.2 of polypropylene (polypropylene composition of the present invention and propylene copolymer (a)) is determined at a temperature of 230° C. and a load of 2.16 kg. The MFR.sub.2 of polyethylene (ethylene homo- or copolymer (b)) is determined at a temperature of 190° C. and a load of 2.16 kg.

(4) Comonomer Content (1-hexene in Component (a))

(5) Quantitative .sup.13C{.sup.1H} NMR spectra recorded in the molten-state using a Bruker Avance III 500 NMR spectrometer operating at 500.13 and 125.76 MHz for .sup.1H and .sup.13C respectively. All spectra were recorded using a .sup.13C optimised 7 mm magic-angle spinning (MAS) probehead at 180° C. using nitrogen gas for all pneumatics. Approximately 200 mg of material was packed into a 7 mm outer diameter zirconia MAS rotor and spun at 4 kHz. This setup was chosen primarily for the high sensitivity needed for rapid identification and accurate quantification. (Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, H. W., Wilhelm, M., Macromol. Chem. Phys. 2006; 207:382, Parkinson, M., Klimke, K., Spiess, H. W., Wilhelm, M., Macromol. Chem. Phys. 2007; 208:2128, Castignolles, P., Graf, R., Parkinson, M., Wilhelm, M., Gaborieau, M., Polymer 50 (2009) 2373). Standard single-pulse excitation was employed utilising the NOE at short recycle delays of 3 s (Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, H. W., Wilhelm, M., Macromol. Chem. Phys. 2006; 207:382, Pollard, M., Klimke, K., Graf, R., Spiess, H. W., Wilhelm, M., Sperber, O., Piel, C., Kaminsky, W., Macromolecules 2004; 37:813). and the RS-HEPT decoupling scheme (Filip, X., Tripon, C., Filip, C., J. Mag. Resn. 2005, 176, 239, Griffin, J. M., Tripon, C., Samoson, A., Filip, C., and Brown, S. P., Mag. Res. in Chem. 200745, S1, S198). A total of 16384 (16 k) transients were acquired per spectra.

(6) Quantitative .sup.13C{.sup.1H} NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals. All chemical shifts are internally referenced to the methyl isotactic pentad (mmmm) at 21.85 ppm.

(7) Characteristic signals corresponding to the incorporation of 1-hexene were observed and the comonomer content quantified in the following way.

(8) The amount of 1-hexene incorporated in PHP isolated sequences was quantified using the integral of the αB4 sites at 44.2 ppm accounting for the number of reporting sites per comonomer:
H=IαB4/2

(9) The amount of 1-hexene incorporated in PHHP double consecutive sequences was quantified using the integral of the ααB4 site at 41.7 ppm accounting for the number of reporting sites per comonomer:
HH=2*IααB4

(10) When double consecutive incorporation was observed the amount of 1-hexene incorporated in PHP isolated sequences needed to be compensated due to the overlap of the signals αB4 and αB4B4 at 44.4 ppm:
H=(IαB4−2*IααB4)/2

(11) The total 1-hexene content was calculated based on the sum of isolated and consecutively incorporated 1-hexene:
Htotal=H+HH

(12) When no sites indicative of consecutive incorporation observed the total 1-hexene comonomer content was calculated solely on this quantity:
Htotal=H

(13) Characteristic signals indicative of regio 2,1-erythro defects were observed (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253).

(14) The presence of 2,1-erythro regio defects was indicated by the presence of the Pαβ (21e8) and Pαγ (21e6) methyl sites at 17.7 and 17.2 ppm and confirmed by other characteristic signals.

(15) The total amount of secondary (2,1-erythro) inserted propene was quantified based on the αα21e9 methylene site at 42.4 ppm:
P21=Iαα21e9

(16) The total amount of primary (1,2) inserted propene was quantified based on the main Sαα methylene sites at 46.7 ppm and compensating for the relative amount of 2,1-erythro, αB4 and ααB4B4 methylene unit of propene not accounted for (note H and HH count number of hexene monomers per sequence not the number of sequences):
P12=I.sub.Sαα+2*P21+H+HH/2

(17) The total amount of propene was quantified as the sum of primary (1,2) and secondary (2,1-erythro) inserted propene:
Ptotal=P12+P21=I.sub.Sαα+3*Iαα21e9+(IαB4−2*IααB4)/2+IααB4

(18) This simplifies to:
Ptotal=I.sub.Sαα+3*Iαα21e9+0.5*IαB4

(19) The total mole fraction of 1-hexene in the polymer was then calculated as:
fH=Htotal/(Htotal+Ptotal)

(20) The full integral equation for the mole fraction of 1-hexene in the polymer was:
fH=(((IαB4−2*IααB4)/2)+(2*IααB4))/((I.sub.Sαα+3*Iαα21e9+0.5*IαB4)+((IαB4−2*IααB4)/2)+(2*IααB4))

(21) This simplifies to:
fH=(IαB4/2+IααB4)/(I.sub.Sαα+3*Iαα21e9+IαB4+IααB4)

(22) The total comonomer incorporation of 1-hexene in mole percent was calculated from the mole fraction in the usual manner:
H[mol %]=100*fH

(23) The total comonomer incorporation of 1-hexene in weight percent was calculated from the mole fraction in the standard manner:
H[wt %]=100*(fH*84.16)/((fH*84.16)+((1−fH)*42.08))

(24) Comonomer Content (Ethylene in Component (a))

(25) Quantitative .sup.13C {.sup.1H} NMR spectra were recorded in the solution-state using a Bruker Advance III 400 NMR spectrometer operating at 400.15 and 100.62 MHz for .sup.1H and .sup.13C respectively. All spectra were recorded using a .sup.13C optimised 10 mm extended temperature probehead at 125° C. using nitrogen gas for all pneumatics. Approximately 200 mg of material was dissolved in 3 ml of 1,2-tetrachloroethane-d2 (TCE-d2) along with chromium-(III)-acetylacetonate (Cr(acac).sub.3) resulting in a 65 mM solution of relaxation agent in solvent as described in G. Singh, A. Kothari, V. Gupta, Polymer Testing 2009, 28(5), 475.

(26) To ensure a homogenous solution, after initial sample preparation in a heat block, the NMR tube was further heated in a rotatory oven for at least 1 hour. Upon insertion into the magnet the tube was spun at 10 Hz. This setup was chosen primarily for the high resolution and quantitatively needed for accurate ethylene content quantification. Standard single-pulse excitation was employed without NOE, using an optimised tip angle, 1 s recycle delay and a bi-level WALTZ16 decoupling scheme as described in Z. Zhou, R. Kuemmerle, X. Qiu, D. Redwine, R. Cong, A. Taha, D. Baugh, B. Winniford, J. Mag. Reson. 187 (2007) 225 and V. Busico, P. Carbonniere, R. Cipullo, C. Pellecchia, J. Severn, G. Talarico, Macromol. Rapid Commun. 2007, 28, 1128. A total of 6144 (6 k) transients were acquired per spectra. Quantitative .sup.13C {.sup.1H}NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals. All chemical shifts were indirectly referenced to the central methylene group of the ethylene block (EEE) at 30.00 ppm using the chemical shift of the solvent. This approach allowed comparable referencing even when this structural unit was not present.

(27) With characteristic signals corresponding to 2,1 erythro regio defects observed (as described in L. Resconi, L. Cavallo, A. Fait, F. Piemontesi, Chem. Rev. 2000, 100 (4), 1253, in Cheng, H. N., Macromolecules 1984, 17, 1950, and in W-J. Wang and S. Zhu, Macromolecules 2000, 331157) the correction for the influence of the regio defects on determined properties was required. Characteristic signals corresponding to other types of regio defects were not observed.

(28) Characteristic signals corresponding to the incorporation of ethylene were observed (as described in Cheng, H. N., Macromolecules 1984, 17, 1950) and the comonomer fraction calculated as the fraction of ethylene in the polymer with respect to all monomer in the polymer.

(29) The comonomer fraction was quantified using the method of W-J. Wang and S. Zhu, Macromolecules 2000, 331157, through integration of multiple signals across the whole spectral region in the .sup.13C {.sup.1H} spectra. This method was chosen for its robust nature and ability to account for the presence of regio-defects when needed. Integral regions were slightly adjusted to increase applicability across the whole range of encountered comonomer contents.

(30) Comonomer Content (1-octene in Component (b))

(31) Quantitative nuclear-magnetic resonance (NMR) spectroscopy was used to quantify the comonomer content of the polymers.

(32) Quantitative .sup.13C{.sup.1H} NMR spectra recorded in the molten-state using a Bruker Avance III 500 NMR spectrometer operating at 500.13 and 125.76 MHz for .sup.1H and .sup.13C respectively. All spectra were recorded using a .sup.13C optimised 7 mm magic-angle spinning (MAS) probehead at 150° C. using nitrogen gas for all pneumatics. Approximately 200 mg of material was packed into a 7 mm outer diameter zirconia MAS rotor and spun at 4 kHz. This setup was chosen primarily for the high sensitivity needed for rapid identification and accurate quantification (Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, H. W., Wilhelm, M., Macromol. Chem. Phys. 2006; 207:382; Parkinson, M., Klimke, K., Spiess, H. W., Wilhelm, M., Macromol. Chem. Phys. 2007; 208:2128; Castignolles, P., Graf, R., Parkinson, M., Wilhelm, M., Gaborieau, M., Polymer 50 (2009) 2373; NMR Spectroscopy of Polymers: Innovative Strategies for Complex Macromolecules, Chapter 24, 401 (2011)). Standard single-pulse excitation was employed utilising the transient NOE at short recycle delays of 3 s (Pollard, M., Klimke, K., Graf, R., Spiess, H. W., Wilhelm, M., Sperber, O., Piel, C., Kaminsky, W., Macromolecules 2004; 37:813; Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, H. W., Wilhelm, M., Macromol. Chem. Phys. 2006; 207:382) and the RS-HEPT decoupling scheme (Filip, X., Tripon, C., Filip, C., J. Mag. Resn. 2005, 176, 239; Griffin, J. M., Tripon, C., Samoson, A., Filip, C., and Brown, S. P., Mag. Res. in Chem. 200745, S1, S198). A total of 1024 (1 k) transients were acquired per spectrum. This setup was chosen due its high sensitivity towards low comonomer contents.

(33) Quantitative .sup.13C{.sup.1H} NMR spectra were processed, integrated and quantitative properties determined using custom spectral analysis automation programs. All chemical shifts are internally referenced to the bulk methylene signal (δ+) at 30.00 ppm (J. Randall, Macromol. Sci., Rev. Macromol. Chem. Phys. 1989, C29, 201). Characteristic signals corresponding to the incorporation of 1-octene were observed (J. Randall, Macromol. Sci., Rev. Macromol. Chem. Phys. 1989, C29, 201; Liu, W., Rinaldi, P., McIntosh, L., Quirk, P., Macromolecules 2001, 34, 4757; Qiu, X., Redwine, D., Gobbi, G., Nuamthanom, A., Rinaldi, P., Macromolecules 2007, 40, 6879) and all comonomer contents calculated with respect to all other monomers present in the polymer.

(34) Characteristic signals resulting from isolated 1-octene incorporation i.e. EEOEE comonomer sequences, were observed. Isolated 1-octene incorporation was quantified using the integral of the signal at 38.37 ppm. This integral is assigned to the unresolved signals corresponding to both *B6 and *βB6B6 sites of isolated (EEOEE) and isolated double non-consecutive (EEOEOEE) 1-octene sequences respectively. To compensate for the influence of the two *βB6B6 sites the integral of the ββB6B6 site at 24.7 ppm is used:
O=I.sub.*B6+*βB6B6−2*I.sub.ββB6B6

(35) Characteristic signals resulting from consecutive 1-octene incorporation, i.e. EEOOEE comonomer sequences, were also observed. Such consecutive 1-octene incorporation was quantified using the integral of the signal at 40.57 ppm assigned to the ααB6B6 sites accounting for the number of reporting sites per comonomer:
OO=2*I.sub.ααB6B6

(36) Characteristic signals resulting from isolated non-consecutive 1-octene incorporation, i.e. EEOEOEE comonomer sequences, were also observed. Such isolated non-consecutive 1-octene incorporation was quantified using the integral of the signal at 24.7 ppm assigned to the ββB6B6 sites accounting for the number of reporting sites per comonomer:
OEO=2*I.sub.ββB6B6

(37) Characteristic signals resulting from isolated triple-consecutive 1-octene incorporation, i.e. EEOOOEE comonomer sequences, were also observed. Such isolated triple-consecutive 1-octene incorporation was quantified using the integral of the signal at 41.2 ppm assigned to the ααγB6B6B6 sites accounting for the number of reporting sites per comonomer:
OOO=3/2*I.sub.ααγB6B6B6

(38) With no other signals indicative of other comonomer sequences observed the total 1-octene comonomer content was calculated based solely on the amount of isolated (EEOEE), isolated double-consecutive (EEOOEE), isolated non-consecutive (EEOEOEE) and isolated triple-consecutive (EEOOOEE) 1-octene comonomer sequences:
O.sub.total=O+OO+OEO+OOO

(39) Characteristic signals resulting from saturated end-groups were observed. Such saturated end-groups were quantified using the average integral of the two resolved signals at 22.84 and 32.23 ppm. The 22.84 ppm integral is assigned to the unresolved signals corresponding to both 2B6 and 2S sites of 1-octene and the saturated chain end respectively. The 32.23 ppm integral is assigned to the unresolved signals corresponding to both 3B6 and 3S sites of 1-octene and the saturated chain end respectively. To compensate for the influence of the 2B6 and 3B61-octene sites the total 1-octene content is used:
S=(½)*(I.sub.2S+2B6+I.sub.3S+3B6−2*O.sub.total)

(40) The ethylene comonomer content was quantified using the integral of the bulk methylene (bulk) signals at 30.00 ppm. This integral included the γ and 4B6 sites from 1-octene as well as the δ.sup.+ sites. The total ethylene comonomer content was calculated based on the bulk integral and compensating for the observed 1-octene sequences and end-groups:
E.sub.total=(½)*[I.sub.bulk+2*O+1*OO+3*OEO+0*OOO+3*S]

(41) It should be noted that compensation of the bulk integral for the presence of isolated triple-incorporation (EEOOOEE) 1-octene sequences is not required as the number of under and over accounted ethylene units is equal.

(42) The total mole fraction of 1-octene in the polymer was then calculated as:
fO=(O.sub.total/(E.sub.total+O.sub.total)

(43) The total comonomer incorporation of 1-octene in mol percent was calculated from the mole fraction in the standard manner:
O[mol %]=100*fO

(44) The mole percent ethyelene incorporation was calculated from the formula:
E[mol %]=100−O[mol %].

(45) Density

(46) Density is measured according to ISO 1183-187. Sample preparation is done by compression moulding in accordance with ISO 1872-2:2007.

(47) Differential Scanning Calorimetry (DSC)

(48) Differential scanning calorimetry (DSC) analysis, melting temperature (T.sub.m) and melt enthalpy (H.sub.m), crystallization temperature (T.sub.c), and heat of crystallization (H.sub.c) are measured with a TA Instrument Q200 differential scanning calorimetry (DSC) on 5 to 7 mg samples. DSC is run according to ISO 11357/part 3/method C2 in a heat/cool/heat cycle with a scan rate of 10° C./min in the temperature range of −30 to +225° C. Crystallization temperature (T.sub.c) and heat of crystallization (H.sub.c) are determined from the cooling step, while melting temperature (T.sub.m) and melt enthalpy (H.sub.m) are determined from the second heating step.

(49) Xylene Cold Soluble (XCS) Content

(50) Xylene Cold Soluble fraction at room temperature (XCS, wt %) is determined at 25° C. according to ISO 16152; 5th edition; 2005 Jul. 1.

(51) Dynamic Mechanical Thermal Analysis (DMTA)

(52) The glass transition temperature T.sub.g is determined by dynamic mechanical thermal analysis (DMTA) according to ISO 6721-7. The measurements are done in torsion mode on compression moulded samples (40×10×1 mm.sup.3) between −100° C. and +150° C. with a heating rate of 2° C./min and a frequency of 1 Hz. Storage modulus G′ is determined at +23° C. according ISO 6721-7:1996. The measurements are done in torsion mode on compression moulded samples (40×10×1 mm.sup.3) between −150° C. and +150° C. with a heating rate of 2° C./min and a frequency of 1 Hz.

(53) Flexural Modulus

(54) The flexural modulus was determined in 3-point-bending at 23° C. according to ISO 178 on 80×10×4 mm.sup.3 test bars injection moulded in line with EN ISO 1873-2.

(55) Notched Impact Strength (NIS)

(56) The Charpy notched impact strength (NIS) was measured according to ISO 1791eA at +23° C., using injection moulded bar test specimens of 80×10×4 mm.sup.3 prepared in accordance with EN ISO 1873-2.

(57) Haze

(58) Haze was determined according to ASTM D1003-00 on 60×60×1 mm.sup.3 plaques injection moulded in line with EN ISO 1873-2. Hence, haze is determined on 1 mm thick plaques.

2. Examples

(59) Preparation of the Catalyst System for the Inventive Examples

(60) The catalyst used in the inventive examples is prepared as described in detail in WO 2015/011135 A1 (metallocene complex MC1 with methylaluminoxane (MAO) and borate resulting in Catalyst 3 described in WO 2015/011135 A1) with the proviso that the surfactant is 2,3,3,3-tetrafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)-1-propanol. The metallocene complex (MC1 in WO 2015/011135 A1) is prepared as described in WO 2013/007650 A1 (metallocene E2 in WO 2013/007650 A1).

(61) Polymerization and Pelletization

(62) Polymers P1 and P2 are produced in a Borstar pilot plant comprising a prepolymerisation reactor, a loop reactor and a gas phase reactor. The polymerisation conditions are indicated in Table 1. P1 is the basis of Inventive Examples 1 to 4, IE1-IE4. P2 is the basis of Inventive Examples 5 and 6, IE5 and IE6.

(63) Both polymers P1 and P2 were compounded in a co-rotating twin-screw extruder Coperion ZSK 57 at 220° C. with 0.2 wt % of Irganox B225 (1:1-blend of Irganox 1010 (Pentaerythrityl-5 tetrakis(3-(3′,5′-di-tert.butyl-4-hydroxytoluyl)-propionate and tris (2,4-di-t-butylphenyl) phosphate) phosphite) of BASF AG, Germany) and 0.1 wt % calcium stearate followed by solidification of the resulting melt strands in a water bath and pelletization.

(64) Compounding

(65) All further melt mixing was performed in a Thermo Fisher (PRISM) TSE 24 twin-screw extruder at 220° C. followed by solidification of the resulting melt strands in a water bath and pelletization.

(66) The polypropylene composition of IE1 is obtained by mixing P1 with 25 wt % of CA9159, a low-density polyethylene commercially available from Borealis AG, Austria, having a density (ISO 1183) of 915 kg/m.sup.3, and a melt flow rate at 190° C. with a load of 2.16 kg (ISO 1133) of 15 g/10 min.

(67) The polypropylene composition of IE2 is obtained by mixing P1 with 25 wt % of Queo™ 0201, an ethylene based 1-octene plastomer commercially available from Borealis AG, Austria, having a density (ISO 1183) of 902 kg/m.sup.3, and a melt flow rate at 190° C. with a load of 2.16 kg (ISO 1133) of 1.1 g/10 min.

(68) The polypropylene composition of IE3 is obtained by mixing P1 with 25 wt % of Queo™ 8201, an ethylene based 1-octene plastomer commercially available from Borealis AG, Austria, having a density (ISO 1183) of 883 kg/m.sup.3, and a melt flow rate at 190° C. with a load of 2.16 kg (ISO 1133) of 1.1 g/10 min.

(69) The polypropylene composition of IE4 is obtained by mixing P1 with 25 wt % of Engage™ 8180, an ethylene octene copolymer commercially available from Dow, having a density (ASTM D792) of 863 kg/m.sup.3, and a melt flow rate at 190° C. with a load of 2.16 kg (ASTM D1238) of 0.5 g/10 min.

(70) The polypropylene composition of IE5 is obtained by mixing P2 with 25 wt % of Engage™ 8180 as defined above in connection with IE4.

(71) The polypropylene composition of IE6 is obtained by mixing P2 with 25 wt % of CA9159 as defined above in connection with IE1.

(72) The polypropylene composition of CE1 is based on 100 wt % P1.

(73) The polypropylene composition of CE2 is based on 100 wt % P2.

(74) The properties of the the inventive and comparative examples are shown in Tables 2 and 3.

(75) TABLE-US-00001 TABLE 1 Polymerisation details of polymers P1 and P2 P1 P2 Prepolymerization Temperature ° C. 20 20 Pressure kPa 5023 5247 Residence time h 0.5 0.4 Loop reactor Temperature ° C. 70 70 Pressure kPa 5244 5241 H2/C3 ratio mol/kmol 0.1 0.1 C6/C3 ratio mol/kmol 8.2 7.2 Residence time h 0.4 0.4 C6 wt % 1.4 1.3 MFR g/10 min 1.4 1.1 Split wt % 45 41 Gas phase reactor Temperature ° C. 80 80 Pressure kPa 2500 2500 H2/C3 ratio mol/kmol 1.5 1.7 C6/C3 ratio mol/kmol 9.0 7.0 C6(GPR) wt % 7.9 4.5 MFR(GPR) g/10 min 1.4 1.9 Residence time h 0.4 1.8 Split wt % 55 59 Product C6 total wt % 5.0 3.2 XCS wt % 11.1 0.7 MFR g/10 min 1.4 1.5 Density kg/m.sup.3 898 896

(76) TABLE-US-00002 TABLE 2 Properties of inventive and comparative examples based on P1 IE1 IE2 IE3 IE4 CE1 MFR g/10 min 4.9 2.3 2.2 2.4 1.4 T.sub.m(1) ° C. 105 98 77 — — T.sub.m(2) ° C. 140 140 140 140 139 H.sub.m(1) J/g 39 28 8 — — H.sub.m(2) J/g 34 36 40 54 71 T.sub.c ° C. 91 90 90 91 91 XCS wt % 8.9 10.7 31.3 33.1 11.1 T.sub.g(1) ° C. 2.3 2.3 2.3 1.9 2.3 T.sub.g(2) ° C. −33 −40 −47 −58 — G′ (23° C.) MPa 327 286 266 259 391 Flexural modulus MPa 582 520 461 415 712 Charpy NIS 23° C. kJ/m.sup.2 6.3 32.5 71.3 78.3 5.9 Charpy NIS −20° C. kJ/m.sup.2 1.48 2.28 3.5 4.4 — Δ density (abs.) kg/m.sup.3 19 6 13 33 — Haze 1 mm % 31 12 18 27 43

(77) TABLE-US-00003 TABLE 3 Properties of inventive and comparative examples based on P2 IE5 IE6 CE2 MFR g/10 min 5.9 5.1 1.5 T.sub.m(1) ° C. 54 104 — T.sub.m(2) ° C. 136 136 136 H.sub.m(1) J/g 2 35 — H.sub.m(2) J/g 54 41 77 T.sub.c ° C. 95 93 94 XCS wt % 27.0 1.7 0.5 T.sub.g(1) ° C. 2.3 3.2 2.5 T.sub.g(2) ° C. −58 −33 — G′ (23° C.) MPa 305 378 457 Flexural modulus MPa 516 685 853 Charpy NIS 23° C. kJ/m.sup.2 63.8 6.6 5.0 Charpy NIS −20° C. kJ/m.sup.2 3.9 1.64 — Δ density (abs.) kg/m.sup.3 35 17 — Haze 1 mm % 42 32 55

(78) As can be seen from the examples, the propylene copolymer (a) comprising 1-hexene as comonomer is an excellent matrix for making transparent heterophasic polypropylene compositions. It has excellent compatibility with different types of ethylene homo- or copolymers, here LDPE and ethylene 1-octene copolymers, even if the density mismatch between the matrix and the dispersed phase is higher and by no means ideal in accordance with literature in his area. Further on, it was believed that ethylene 1-octene copolymers (plastomers) are generally detrimental for transparency in contrast to the usually used propylene ethylene copolymers (plastomers), e.g. those commercially available under the tradename Vistamaxx™. This is apparently not the case in connection with a propylene copolymer (a) as described in the present invention.