BETA NUCLEATED HETEROPHASIC POLYPROPYLENE COMPOSITION

Abstract

The invention is directed to a beta nucleated heterophasic propylene copolymer composition (HPPC).

Claims

1. A heterophasic propylene copolymer composition (HPPC), having an MFR.sub.2 measured according to ISO 1133 at 230° C. and 2.16 kg in the range from 15.0 to 50.0 g/10 min and a beta-phase content of 75 to 95%, measured by wide angle X-ray scattering (WAXS) as described herein, comprising: (a) a propylene homopolymer matrix, and (b) an ethylene-propylene rubber being dispersed in said matrix, wherein the heterophasic propylene copolymer composition (HPPC) has (i) a content of 2,1-regiodefects determined by .sup.13C-NMR of 0.2 to 0.8 mol % of the xylene cold insoluble fraction (XCI) according to ISO 16152; (ii) a crystalline fraction (CF), determined according to CRYSTEX QC method ISO 6427 Annex B, present in an amount in the range from 50.0 to 95.0 wt.-%, relative to the total weight of the heterophasic propylene copolymer composition (HPPC); and (iii) a soluble fraction (SF), determined according to CRYSTEX QC method ISO 6427 Annex B, present in an amount in the range from 5.0 to 50.0 wt.-%, relative to the total weight of the heterophasic propylene copolymer composition (HPPC); and (iv) an ethylene content of the soluble fraction (SF), measured by Fourier Transform Infrared Spectroscopy (FTIR) during CRYSTEX analysis, in the range of 18.0 to 50.0 wt.-%; and (v) an intrinsic viscosity of the soluble fraction (SF) measured according to ISO 1628-1 (at 135° C. in decalin), in the range from 2.0 to 6.0 dl/g; and (vi) a ratio of the intrinsic viscosity of the soluble fraction (SF) measured according to ISO 1628-1 (at 135° C. in decalin) versus the intrinsic viscosity of the crystalline fraction (CF) measured according to ISO 1628-1 (at 135° C. in decalin) IV(SF)/IV(CF) in the range of 1.0 to 4.0.

2. The heterophasic propylene copolymer composition (HPPC) according to claim 1, having: (vii) a melting temperature Tm, measured by DSC according to ISO 11357-3 (heating and cooling rate 10° C./min), in the range of 152 to 162° C.

3. The heterophasic propylene copolymer composition (HPPC) according to claim 1 having a crystallization temperature Tc, measured by DSC ISO 11357-3 of 120 to 127°.

4. The heterophasic propylene copolymer composition (HPPC) according to claim 1 having (ii) a crystalline fraction (CF), determined according to CRYSTEX QC method ISO 6427 Annex B, present in an amount in the range from 70.0 to 90.0 wt.-%, relative to the total weight of the heterophasic propylene copolymer composition (HPPC); and (iii) a soluble fraction (SF), determined according to CRYSTEX QC method ISO 6427 Annex B, present in an amount in the range from 10.0 to 30.0 wt.-%, relative to the total weight of the heterophasic propylene copolymer composition (HPPC).

5. The heterophasic propylene copolymer composition (HPPC) according to claim 1, having: (iv) an ethylene content of the soluble fraction (SF), measured by Fourier Transform Infrared Spectroscopy (FTIR) during CRYSTEX analysis, in the range of 20.0 to 30.0 wt.-%.

6. The heterophasic propylene copolymer composition (HPPC) according to claim 1, having: (v) an intrinsic viscosity of the soluble fraction (SF) measured according to ISO 1628-1 (at 135° C. in decalin), in the range from 3.0 to 5.0 dl/g, preferably 3.9 to 4.8 dl/g.

7. The heterophasic propylene copolymer composition (HPPC) according to claim 1, having: (vi) a ratio of the intrinsic viscosity of the soluble fraction (SF) measured according to ISO 1628-1 (at 135° C. in decalin) versus the intrinsic viscosity of the crystalline fraction (CF) measured according to ISO 1628-1 (at 135° C. in decalin) IV(SF)/IV(CF) in the range of 3.0 to 4.0.

8. The heterophasic propylene copolymer composition (HPPC) according to claim 1, having one or more of the following properties: brittle to ductile transition temperature (Charpy notched impact strength measured according to ISO 179-1 eA) of below 15° C., preferably below 11° C.; difference of the melt flow rate of the heterophasic propylene copolymer composition (HPPC) MFR.sub.2 measured according to ISO 1133 at 230° C. and 2.16 kg in 1/(g/10 min) and brittle to ductile transition temperature (Charpy notched impact strength measured according to ISO 179-1 eA) in 1/° C. of at least 15, preferably at least 18.

9. The heterophasic propylene copolymer composition (HPPC) according to claim 1, having an MFR.sub.2 measured according to ISO 1133 at 230° C. and 2.16 kg in the range from 15.0 to 45.0 g/10 min.

10. The heterophasic propylene copolymer composition (HPPC) according to claim 1 having a beta-phase content of 78 to 95%, preferably 85 to 95% measured by wide angle x-ray scattering (WAXS) as described herein.

11. The heterophasic propylene copolymer composition (HPPC) according to claim 1 having a flexural modulus of 750 to 1000 MPa according to ISO 178.

12. The heterophasic propylene copolymer composition (HPPC) according to claim 1 obtainable by a multistage process, whereby in the first two stages the matrix is produced and wherein the matrix has an isotactic pentad concentration [mmmm] as determined by .sup.13C-NMR spectroscopy of more than 98.0%.

13. The heterophasic propylene copolymer composition (HPPC) according to claim 1 obtainable by mixing an intermediate heterophasic propylene copolymer with at least one beta nucleating agent (B) selected from the group of gamma-quinacridone and N,N-dicylohexyl-2,6-naphthalene dicarboxamide, preferably being 5,12-dihydroquinolino[2,3-b]acridine-6,7,13,14-tetrone.

14. The heterophasic propylene copolymer composition (HPPC) according to claim 1 having a content of 2,1-regiodefects determined by .sup.13C-NMR of 0.4 to 0.7 mol % of the xylene cold insoluble fraction (XCI) according to ISO 16152.

15. An article comprising more than 75 wt.-%, particularly more than 90 wt.-% of the heterophasic propylene polymer composition (HPPC) according to claim 1, preferably wherein the article is a molded article, more preferably an injection molded article or a foam injection molded article.

Description

BRIEF DESCRIPTION OF THE DRAWING

[0067] FIGS. 1(A-B) (A) Schematic diagram of the CRYSTEX QC instrument (B) Elution of the EP copolymer sample and obtained soluble and crystalline fractions in the TREF column (column filled with inert material e.g., glass beads) (see Del Hierro, P.; Ortin, A.; Monrabal, B.; ‘Soluble Fraction Analysis in polypropylene.

DETAILED DESCRIPTION

[0068] In the following a number of particularly preferred embodiments shall be described.

[0069] A first particularly preferred embodiment, is concerned with a heterophasic propylene copolymer composition (HPPC), having an MFR.sub.2 measured according to ISO 1133 at 230° C. and 2.16 kg in the range from 15.0 to 50 g/10 min and a beta-phase content of 85 to 95%, measured by wide angle X-ray scattering (WAXS) as described herein, comprising: [0070] (a) a propylene homopolymer matrix, and [0071] (b) an ethylene-propylene rubber being dispersed in said matrix, [0072] wherein the heterophasic propylene copolymer composition (HPPC) has [0073] (i) a content of 2,1-regiodefects determined by .sup.13C-NMR of 0.2 to 0.8 mol % of the xylene cold insoluble fraction (XCI) according to ISO 16152; [0074] (ii) a crystalline fraction (CF), determined according to CRYSTEX QC method ISO 6427 Annex B, present in an amount in the range from 70.0 to 90.0 wt.-%, relative to the total weight of the heterophasic propylene copolymer composition (HPPC); and [0075] (iii) a soluble fraction (SF), determined according to CRYSTEX QC method ISO 6427 Annex B, present in an amount in the range from 10.0 to 30.0 wt.-%, relative to the total weight of the heterophasic propylene copolymer composition (HPPC); and [0076] (iv) an ethylene content of the soluble fraction (SF), measured by Fourier Transform Infrared Spectroscopy (FTIR) during CRYSTEX analysis, in the range of 20.0 to 30.0 wt.-%; and [0077] (v) an intrinsic viscosity of the soluble fraction (SF) measured according to ISO 1628-1 (at 135° C. in decalin), in the range from 3.0 to 5.0 dl/g; and [0078] (vi) a ratio of the intrinsic viscosity of the soluble fraction (SF) measured according to ISO 1628-1 (at 135° C. in decalin) versus the intrinsic viscosity of the crystalline fraction (CF) measured according to ISO 1628-1 (at 135° C. in decalin) IV(SF)/IV(CF) in the range of 1.0 to 4.0.

[0079] Any preferred aspect as described in the summary of the invention may be combined with this embodiment as far as appropriate. Reference is made to the aforesaid.

[0080] A second particularly preferred embodiment, is concerned with a heterophasic propylene copolymer composition (HPPC), having an MFR.sub.2 measured according to ISO 1133 at 230° C. and 2.16 kg in the range from 15.0 to 50 g/10 min and a beta-phase content of 75 to 95%, measured by wide angle X-ray scattering (WAXS) as described herein, comprising: [0081] (a) a propylene homopolymer matrix, and [0082] (b) an ethylene-propylene rubber being dispersed in said matrix, [0083] wherein the heterophasic propylene copolymer composition (HPPC) has [0084] (vii) a content of 2,1-regiodefects determined by .sup.13C-NMR of 0.4 to 0.7 mol % of the xylene cold insoluble fraction (XCI) according to ISO 16152; [0085] (viii) a crystalline fraction (CF), determined according to CRYSTEX QC method ISO 6427 Annex B, present in an amount in the range from 50.0 to 95.0 wt.-%, relative to the total weight of the heterophasic propylene copolymer composition (HPPC); and [0086] (ix) a soluble fraction (SF), determined according to CRYSTEX QC method ISO 6427 Annex B, present in an amount in the range from 5.0 to 50.0 wt.-%, relative to the total weight of the heterophasic propylene copolymer composition (HPPC); and [0087] (x) an ethylene content of the soluble fraction (SF), measured by Fourier Transform Infrared Spectroscopy (FTIR) during CRYSTEX analysis, in the range of 18.0 to 50.0 wt.-%; and [0088] (xi) an intrinsic viscosity of the soluble fraction (SF) measured according to ISO 1628-1 (at 135° C. in decalin), in the range from 3.0 to 5.0 dl/g; and [0089] (xii) a ratio of the intrinsic viscosity of the soluble fraction (SF) measured according to ISO 1628-1 (at 135° C. in decalin) versus the intrinsic viscosity of the crystalline fraction (CF) measured according to ISO 1628-1 (at 135° C. in decalin) IV(SF)/IV(CF) in the range of 1.0 to 4.0; and [0090] a crystallization temperature Tc, measured by DSC ISO 11357-3 of 120 to 127°.

[0091] Any preferred aspect as described in the summary of the invention may be combined with this embodiment as far as appropriate. Reference is made to the aforesaid.

[0092] A third particularly preferred embodiment, is concerned with A heterophasic propylene copolymer composition (HPPC), having an MFR.sub.2 measured according to ISO 1133 at 230° C. and 2.16 kg in the range from 15.0 to 45 g/10 min and a beta-phase content of 75 to 95%, measured by wide angle X-ray scattering (WAXS) as described herein, comprising: [0093] (a) a propylene homopolymer matrix, and [0094] (b) an ethylene-propylene rubber being dispersed in said matrix, [0095] wherein the heterophasic propylene copolymer composition (HPPC) has [0096] (xiii) a content of 2,1-regiodefects determined by .sup.13C-NMR of 0.4 to 0.7 mol % of the xylene cold insoluble fraction (XCI) according to ISO 16152; [0097] (xiv) a crystalline fraction (CF), determined according to CRYSTEX QC method ISO 6427 Annex B, present in an amount in the range from 50.0 to 95.0 wt.-%, relative to the total weight of the heterophasic propylene copolymer composition (HPPC); and [0098] (xv) a soluble fraction (SF), determined according to CRYSTEX QC method ISO 6427 Annex B, present in an amount in the range from 5.0 to 50.0 wt.-%, relative to the total weight of the heterophasic propylene copolymer composition (HPPC); and [0099] (xvi) an ethylene content of the soluble fraction (SF), measured by Fourier Transform Infrared Spectroscopy (FTIR) during CRYSTEX analysis, in the range of 18.0 to 50.0 wt. %; and [0100] (xvii) an intrinsic viscosity of the soluble fraction (SF) measured according to ISO 1628-1 (at 135° C. in decalin), in the range from 3.0 to 5.0 dl/g; and [0101] a ratio of the intrinsic viscosity of the soluble fraction (SF) measured according to ISO 1628-1 (at 135° C. in decalin) versus the intrinsic viscosity of the crystalline fraction (CF) measured according to ISO 1628-1 (at 135° C. in decalin) IV(SF)/IV(CF) in the range of 1.0 to 4.0, and [0102] a melting temperature Tm, measured by DSC according to ISO 11357-3 (heating and cooling rate 10° C./min), in the range of 152 to 162° C.; and [0103] a crystallization temperature Tc, measured by DSC ISO 11357-3 of 120 to 127°.

[0104] Any preferred aspect as described in the summary of the invention may be combined with this embodiment as far as appropriate. Reference is made to the aforesaid.

[0105] The invention will now be illustrated by reference to the following non-limiting Examples.

Experimental Part

a) Measurement Methods

aa) Melt Flow Rate

[0106] The melt flow rate (MFR.sub.2) is determined according to ISO 1133 and is indicated in g/10 min. The MFR.sub.2 of heterophasic propylene copolymer is determined at a temperature of 230° C. and under a load of 2.16 kg.

bb) Wide Angle X-ray Scattering Measurement (WAXS)

[0107] The measurement of wide-angle X-ray scattering (WAXS) of the samples was conducted by a Bruker D8 Discover apparatus. The diffractometer was equipped with an X-ray tube with a copper target operating at 30 kV and 20 mA and a GADDS 2-D detector. A point collimation (0.5 mm) was used to direct the beam onto the surface. The measurement was done in reflection geometry, and 28 angle in the range from 10° to 32.5° were measured. Data were collected for 300 s. Intensity vs. 2-theta curve was acquired with the same measurement parameters on an amorphous polypropylene sample, which was prepared by solvent extraction. An amorphous halo was obtained by smoothing the curve. The amorphous halo has been subtracted from the measured intensity vs. 2-theta curve to result in the crystalline curve.

[0108] The crystallinity index Xc can be defined with the area under the crystalline curve and the original spectrum using Challa, Hermans and Weidinger method [Challa G, Hermans P H, Weidinger A, Makromol. Chem. 56, 169 (1962)] as:

[00004]$X_c=\frac{\mathrm{area}\mathrm{under}\mathrm{crystalline}\mathrm{curve}}{\mathrm{area}\mathrm{under}\mathrm{original}\mathrm{spectrum}}\times 100$

[0109] The amount of β-form of the polypropylene within the crystalline phase Kβ is calculated using Jones method [Turner-Jones A, Aizlewood J M, Beckett D R, Makromol. Chem. 75, 134 (1974)] according to the following equation:

[00005]$K_{\beta }=\frac{I^{\beta }\left(300\right)}{I^{\alpha }\left(110\right)+I^{\alpha }\left(040\right)+I^{\alpha }\left(130\right)+I^{\beta }\left(300\right)}$ [0110] where, Iβ(300) is the intensity of β(300) peak, Iα(110) is the intensity of α(110) peak, Iα(040) is the intensity of α(040) peak and Iα(130) is the intensity of α(130) peak obtained after subtracting the amorphous halo.

[0111] The amount of γ-form of isotactic polypropylene (iPP) within the crystalline phase Kγ is calculated using the method developed by Pae [Pae K D, J. Polym. Sci., Part A, 6, 657 (1968)] as:

[00006]$K_{\gamma }=\frac{I^{\gamma }\left(117\right)}{I^{\alpha }\left(130\right)+I^{\gamma }\left(117\right)}$ [0112] where Iα(130) is the intensity of α(130) peak and Iγ(117) is the intensity of γ(117) peak obtained after subtracting a base line joining the base of these peaks.

[0113] Quantification of three-phase crystalline system has been carried out following the procedure explained in Obadal M, Cermak R, Stoklasa K, Macromol. Rapid Commun. 26, 1253 (2005). For three-phase crystalline systems the following equations have been used to determine Kα (amount of α-phase), Kβ0 (amount of (β-phase) and Kγ (amount of γ-phase):

[00007]$K_{\beta }=\frac{I^{\beta }\left(300\right)}{I^{\alpha }\left(110\right)+I^{\alpha }\left(040\right)+I^{\alpha }\left(130\right)+I^{\beta }\left(300\right)+I^{\gamma }\left(117\right)}$$K_{\alpha +\gamma }=1-K_{\beta },$$K_{\gamma }=G\times K_{\alpha +\gamma },$$\mathrm{and}$$K_{\alpha }=1-K_{\beta }-K_{\gamma }$

Compression Molding:

[0114] Samples for WAXS measurements have been prepared according to ISO 173-2, on a frame mold. The conditions for compression molding of test specimens were as follows:

TABLE-US-00001 Molding temperature 210° C. Average cooling rate 15° C./min Demolding temperature ≤40° C. Full Pressure 5 MPa Full-pressure time 5 min Preheating pressure None Preheating time 10 min

cc) Quantification of Microstructure by NMR Spectroscopy

[0115] Quantitative nuclear-magnetic resonance (NMR) spectroscopy was used to quantify the isotacticity and regio-regularity of the matrix component of the heterophasic copolymer (on samples taken after the first gas phase reactor (GPR1).

[0116] 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 1H and 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.

[0117] For propylene homopolymers approximately 200 mg of material was dissolved in 1,2-tetrachloroethane-d2 (TCE-d2). 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 needed for tacticity distribution quantification (Busico, V., Cipullo, R., Prog. Polym. Sci. 26 (2001) 443; Busico, V.; Cipullo, R., Monaco, G., Vacatello, M., Segre, A. L., Macromolecules 30 (1997) 6251). Standard single-pulse excitation was employed utilising the NOE and bi-level WALTZ16 decoupling scheme (Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh, D. Winniford, B., J. Mag. Reson. 187 (2007) 225; Busico, V., Carbonniere, P., Cipullo, R., Pellecchia, R., Severn, J., Talarico, G., Macromol. Rapid Commun. 2007, 28, 11289). A total of 8192 (8 k) transients were acquired per spectrum.

[0118] Quantitative .sup.13C{.sup.1H} NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals using proprietary computer programs.

[0119] For propylene homopolymers all chemical shifts are internally referenced to the methyl isotactic pentad (mmmm) at 21.85 ppm.

[0120] Characteristic signals corresponding to regio defects (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253; Wang, W-J., Zhu, S., Macromolecules 33 (2000), 1157; Cheng, H. N., Macromolecules 17 (1984), 1950) or comonomer were observed.

[0121] The tacticity distribution was quantified through integration of the methyl region between 23.6-19.7 ppm correcting for any sites not related to the stereo sequences of interest (Busico, V., Cipullo, R., Prog. Polym. Sci. 26 (2001) 443; Busico, V., Cipullo, R., Monaco, G., Vacatello, M., Segre, A. L., Macromolecules 30 (1997) 6251).

[0122] Specifically, the influence of regio-defects and comonomer on the quantification of the tacticity distribution was corrected for by subtraction of representative regio-defect and comonomer integrals from the specific integral regions of the stereo sequences.

[0123] The isotacticity was determined at the pentad level and reported as the percentage of isotactic pentad (mmmm) sequences with respect to all pentad sequences:

[mmmm]%=100*(mmmm/sum of all pentads)

[0124] The presence of 2,1 erythro regio-defects was indicated by the presence of the two methyl sites at 17.7 and 17.2 ppm and confirmed by other characteristic sites. Characteristic signals corresponding to other types of regio-defects were not observed (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253).

[0125] The amount of 2,1 erythro regio-defects was quantified using the average integral of the two characteristic methyl sites at 17.7 and 17.2 ppm:

P.sub.21e=(I.sub.e6+I.sub.e8)/2

[0126] The amount of 1,2 primary inserted propene was quantified based on the methyl region with correction undertaken for sites included in this region not related to primary insertion and for primary insertion sites excluded from this region:

P12=I.sub.CH3+P.sub.21e

[0127] The total amount of propene was quantified as the sum of primary inserted propene and all other present regio-defects:

P.sub.total=P.sub.12+P.sub.21e

[0128] The mole percent of 2,1 erythro regio-defects was quantified with respect to all propene:

[21e] mol.-%=100*(P21e/Ptotal)

dd) Xylene Cold Soluble Fraction (XCS)

[0129] “Xylene Cold Soluble” (XCS) fraction and “Xylene Cold Insoluble” (XCI) fraction, respectively, is determined according to standard gravimetric method as per ISO 16152.

ee) Crystex Analysis

Crystalline and Soluble Fractions Method

[0130] The crystalline fraction (CF) and soluble fraction (SF) of the heterophasic propylene copolymers, the final comonomer content of the heterophasic propylene copolymers, the comonomer content of the respective fractions as well as the intrinsic viscosities of the respective fractions were analyzed by the CRYSTEX QC, Polymer Char (Valencia, Spain) on basis ISO 6427 Annex B: 1992 (E). A schematic representation of the CRYSTEX QC instrument is shown in FIG. 1a. The crystalline and amorphous fractions are separated through temperature cycles of dissolution in 1,2,4-trichlorobenzene (1,2,4-TCB) at 160° C., crystallization at 40° C. and re-dissolution in 1,2,4-TCB at 160° C. as shown in FIG. 1b. Quantification of SF and CF and determination of ethylene content (C2) are achieved by means of an infrared detector (IR4) and an online 2-capillary viscometer is used for the determination of the intrinsic viscosity (iV). IR4 detector is a multiple wavelength detector measuring IR absorbance at two different bands (CH.sub.3 stretching vibration (centred at approx. 2960 cm.sup.−1) and CH.sub.x stretching vibration (2700-3000 cm.sup.−1) which can be used to determine of the concentration and the ethylene content in ethylene-propylene copolymers (EP Copolymers). The IR4 detector is calibrated with series of 8 ethylene-propylene copolymers with known ethylene content in the range of 2 wt.-% to 69 wt.-% (determined by .sup.13C-NMR) and each at various concentrations, in the range of 2 and 13 mg/ml. To account for both features, concentration and ethylene content at the same time for various polymer concentration expected during Crystex analyses the following calibration equations were applied:

Conc=a+b*Abs(CH)+c*(Abs(CH.sub.x)).sup.2+d*Abs(CH.sub.3)+e*(Abs(CH3)).sup.2+f*Abs(CH.sub.x)*Abs(CH3)   Equation 1:

CH.sub.3/1000C=a+b*Abs(CH.sub.x)+c*Abs(CH3)+d*(Abs(CH.sub.3)/Abs(CH.sub.x))+e*(Abs(CH.sub.3)/Abs(CH.sub.x)).sup.2   Equation 2:

[0131] The constants a to e for equation 1 and a to f for equation 2 were determined by using least square regression analysis.

[0132] The CH3/1000C is converted to the ethylene content in wt.-% using following relationship:

wt.-% (Ethylene in EP Copolymers)=100—CH3/1000TC*0.3   Equation 3:

[0133] Amount of soluble fraction (SF) and crystalline fraction (CF) are correlated through the XS calibration to the “Xylene Cold Soluble” (XCS) fraction and “Xylene Cold Insoluble” (XCI) fraction, respectively, determined according to standard gravimetric method as per ISO16152. XS calibration is achieved by testing various EP copolymers with xylene cold soluble (XCS) content in the range 2 to 31 wt.-%. The determined XS calibration is linear (Equation 4):

wt.-% XCS=1.01*wt.-% SF

[0134] Intrinsic viscosity (IV) of the parent heterophasic propylene copolymer and its soluble fraction (SF) and crystalline fraction (CF) are determined with a use of an online 2-capillary viscometer and are correlated to corresponding IV's determined by standard method in decalin according to ISO 1628-3. Calibration is achieved with various EP copolymers with IV=2 to 4 dl/g. The determined calibration curve between the Vsp, measured in CRYSTEX QC and normalized by the concentration (c), and the IV is linear (Equation 5):

IV(dl/g)=a*Vsp/c [0135] with a slope of a=16.2. A sample of the heterophasic propylene copolymer to be analyzed is weighed out in concentrations of 10 mg/ml to 20 mg/ml. After automated filling of the vial with 1,2,4-TCB containing 250 mg/1 2,6-tert-butyl-4-methylphenol (BHT) as antioxidant, the sample is dissolved at 160° C. until complete dissolution is achieved, usually for 60 min, with constant stirring of 400 rpm. To avoid sample degradation, polymer solution is blanketed with the N.sub.2 atmosphere during dissolution.

[0136] As shown in FIGS. 1a and b, a defined volume of the sample solution is injected into the column filled with inert support where the crystallization of the sample and separation of the soluble fraction from the crystalline part is taking place. This process is repeated two times. During the first injection the whole sample is measured at high temperature, determining the IV[dl/g] and the C2[wt.-%] of the heterophasic propylene copolymer. During the second injection the soluble fraction (SF; at low temperature, 40° C.) and the crystalline fraction (CF; at high temperature, 160° C.) with the crystallization cycle are measured (wt.-% SF, wt.-% C2 of SF, IV of SF).

.SUP.13.C NMR Spectroscopy-Based Determination of C2 Content for the Calibration Standards

[0137] Quantitative .sup.13C{.sup.1H} NMR spectra were recorded in the solution-state using a Bruker Avance 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-d.sub.2 (TCE-d.sub.2) along with chromium (III) acetylacetonate (Cr(acac).sub.3) resulting in a 65 mM solution of relaxation agent in solvent (Singh, G., Kothari, A., Gupta, V., Polymer Testing 28 5 (2009), 475). 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 (Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh, D. Winniford, B., J. Mag. Reson. 187 (2007) 225, Busico, V., Carbonniere, P., Cipullo, R., Pellecchia, R., Severn, J., Talarico, G., 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. Characteristic signals corresponding to the incorporation of ethylene were observed (Cheng, H. N., Macromolecules 17 (1984), 1950) and the comonomer fraction calculated as the fraction of ethylene in the polymer with respect to all monomer in the polymer:

fE=(E/(P+E))

[0138] The comonomer fraction was quantified using the method of Wang et. al. (Wang, W-J., Zhu, S., Macromolecules 33 (2000), 1157) 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. For systems with very low ethylene content where only isolated ethylene in PPEPP sequences were observed the method of Wang et. al. was modified reducing the influence of integration of sites that are no longer present. This approach reduced the overestimation of ethylene content for such systems and was achieved by reduction of the number of sites used to determine the absolute ethylene content to

E=0.5(Sββ+Sβγ+Sβδ+0.5(Sαβ+Sαγ))

[0139] Through the use of this set of sites the corresponding integral equation becomes

E=0.5(I.sub.H+I.sub.G+0.5(I.sub.C+I.sub.D)) [0140] using the same notation used in the article of Wang et. al. (Wang, W-J., Zhu, S., Macromolecules 33 (2000), 1157). Equations used for absolute propylene content were not modified. The mole percent comonomer incorporation was calculated from the mole fraction:

E [mol %]=100*fE.

[0141] The weight percent comonomer incorporation was calculated from the mole fraction:

E [wt %]=100*(fE*28.06)/((fE*28.06)+((1−fE)*42.08))

ff) Intrinsic Viscosity

[0142] The intrinsic viscosity (iV) is measured in analogy to DIN ISO 1628/1, October 1999, in Decalin at 135° C.

gg) Melting temperature T.SUB.m .and Crystallization Temperature T.SUB.c

[0143] The melting temperature T.sub.m is determined by differential scanning calorimetry (DSC) according to ISO 11357-3 with a TA-Instruments 2920 Dual-Cell with RSC refrigeration apparatus and data station. A heating and cooling rate of 10° C./min is applied in a heat/cool/heat cycle between +23 and +210° C. The crystallization temperature (T.sub.c) is determined from the cooling step while melting temperature (T.sub.m) and melting enthalpy (H.sub.m) are being determined in the second heating step.

hh) Brittle-to-Ductile Transition Temperature (BDTT)

[0144] The determination of the brittle-to-ductile transition temperature (BDTT) is based on the a(cN) values as determined from Charpy instrumented impact strength according to ISO 179-2:2000 on V-notched specimen with a geometry of 80×10×4 mm.sup.3 as required in ISO 179-1eA.

[0145] The a(cN) values are determined in intervals of 3° C. from −40° C. to +41° C. with an impact velocity of 1.5 m/s and plotted over temperature, calculating the BDTT as the average value of the step increase. For a detailed description of the determination of the BDTT reference is made to Grein, C. et al, Impact Modified Isotactic Polypropylene with Controlled Rubber Intrinsic Viscosities: Some New Aspects About Morphology and Fracture, J Appl Polymer Sci, 87 (2003), 1702-1712.

ii) Notched Impact Strength (NIS)

[0146] The Charpy notched impact strength (NIS) was measured according to ISO 179 1 eA at −20° C., 0° C. and +23° C., using injection molded bar test specimens of 80×10×4 mm.sup.3 prepared in accordance with ISO 294-1: 1996.

jj) Flexural Modulus

[0147] 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 molded in line with EN ISO 1873-2.

b) Experiments

Preparation of the Heterophasic Propylene Copolymers

ba) Preparation of the Catalyst Systems (Catalyst System 1 for Inventive Example IE1 and Comparative Example CE1)

Catalyst Synthesis

[0148] The metallocene (MC) used was Anti-dimethylsilanediyl[2-methyl-4,8-di(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl] zirconium dichloride as disclosed in WO 2020/239602.

[0149] Preparation of MAO-silica support (as described in WO 2020/239602 at page 57) A steel reactor equipped with a mechanical stirrer and a filter net was flushed with nitrogen and the reactor temperature was set to 20° C. Next silica grade DM-L-303 from AGC Si-Tech Co, pre-calcined at 600° C. (5.0 kg) was added from a feeding drum followed by careful pressuring and depressurising with nitrogen using manual valves. Then toluene (22 kg) was added. The mixture was stirred for 15 min. Next 30 wt % solution of MAO in toluene (9.0 kg) from Lanxess was added via feed line on the top of the reactor within 70 min. The reaction mixture was then heated up to 90° C. and stirred at 90° C. for additional two hours. The slurry was allowed to settle and the mother liquor was filtered off. The catalyst was washed twice with toluene (22 kg) at 90° C., following by settling and filtration.

[0150] The reactor was cooled off to 60° C. and the solid was washed with heptane (22.2 kg). Finally MAO treated SiO2 was dried at 60° under nitrogen flow for 2 hours and then for 5 hours under vacuum (−0.5 barg) with stirring. MAO treated support was collected as a free-flowing white powder found to contain 12.2% Al by weight.

[0151] Catalyst preparation (as described in WO 2020/239602 as ICS3) 30 wt % MAO in toluene (0.7 kg) was added into a steel nitrogen blanked reactor via a burette at 20° C. Toluene (5.4 kg) was then added under stirring. The MC as cited above (93 g) was added from a metal cylinder followed by flushing with 1 kg toluene. The mixture 5 was stirred for 60 minutes at 20° C. Trityl tetrakis(pentafluorophenyl) borate (91 g) was then added from a metal cylinder followed by a flush with 1 kg of toluene. The mixture was stirred for 1 h at room temperature. The resulting solution was added to a a stirred cake of MAO-silica support prepared as described above over 1 hour. The cake was allowed to stay for 12 hours, followed by drying under N2 flow at 60° C. for 2h and additionally for 5 h 10 under vacuum (−0.5 barg) under stirring. Dried catalyst was sampled in the form of pink free flowing powder containing 13.9% Al by weight and 0.11% Zr by weight.

bb) Preparation of the Catalyst Systems (Catalyst System 2 for Comparative Examples CE2 and CE3)

[0152] For polymerizing the homopolymer of comparative examples CE2 and CE3 the catalyst system WO 2020/160892 A1, catalyst C described at page 27.

bc) Preparation of Inventive Polymer

[0153]

TABLE-US-00002 TABLE 1 Polymerization conditions for IE1 IE1 Catalyst system 1 Prepolymerization Temperature [° C.] 20 H2/C3 ratio [mol/kmoll] 0.02 Residence time [h] 0.2 Loop (Reactor 1) Temperature [° C.] 75 Pressure [kPa] 5300 H2/C3 ratio [mol/kmol] 0.63 Loop reactor split [wt.-%] 46 MFR.sub.2 [g/10 min] 81 GPR1 (Reactor 2) Temperature [° C.] 80 Pressure [kPa] 2600 H2/C3 ratio [mol/kmol] 1.80 GPR1 reactor split [wt.-%] 25 XCS after GPR1 [wt.-%] 0.15 MFR.sub.2 [g/10 min] 95 GPR2 (Reactor 3) Temperature [° C.] 70 Pressure [kPa] 2500 H2/C2 ratio [mol/kmol] 0.0 C2/C3 ratio [mol/kmol] 860 GPR2 reactor split [wt.-%] 20 XCS after GPR2 [wt.-%] 14.7 GPR3 (Reactor 4) Temperature [° C.] 75 Pressure [kPa] 2200 C2/C3 ratio [mol/kmol] 1675 H2/C2 ratio [mol/kmol] 1.8 GPR3 reactor split [%] 9

[0154] The product from GPR3 (reactor 4) was compounded and pelletized in the presence of a conventional additive package including antioxidant (Irganox B215, BASF AG, Germany; 0.15 wt.-%) and acid scavenger (Ca stearate CAS no. 1592-23-0, Faci SpA, Italy; 0.05 wt.-%). In the case of IE1 and CE2, beta nucleation was induced by additionally compounding 0.01 wt.-% of quinacridonequinone (IUPAC name 5,12-dihydroquinolino[2,3-b]acridine-6,7,13,14-tetrone, CAS number 1503-48-6; distributed by BASF AG, Germany). A twin-screw extruder (type TSE24) was used for compounding at a melt temperature of 200-220° C.

##STR00002##

[0155] Comparative examples CE2 and CE3 (both polypropylene homopolymers, beta-nucleated and non-nucleated) were made in a similar way as the matrix component included in IE1 and CE1. These are identical to inventive example 1E3 (beta-nucleated) and comparative example CE4 (non-nucleated) of WO 2020/160892 A1.

Results are shown in Table 2.

TABLE-US-00003 TABLE 2 Results IE1 CE1 CE2 CE3 Catalyst system 1 1 2 2 MFR(HPPC) 31 31 0.26 0.26 g/10 min, ISO 1133; 230°; 2.16 kg Beta content 87.5 0 83.0 0 (WAXS) PP homo matrix yes yes PP homo PP homo EPR dispersed yes yes 2.1 regioinversion 0.6 0.6 0.9 0.9 (.sup.13C-NMR) of XCI mol % CF (Crystex QC) wt.- 79.9 79.9 99.8 99.8 % SF (Crystex QC) wt.- 20.1 20.1 0.2 0.2 % C2(SF) FTIR 24.0 24.0 — — IV(SF) dl/g; 4.4 4.4 — — IV(CF) dl/g; 1.3 1.3 — — IV(SF)/IV (CF) 3.4 3.4 — — Tm 158 156 162 160 ISO 11357-3 ° C. Tc 121 113 121 116 ISO 11357-3 ° C. BDTT 10 22 nd nd (NIS 179-1eA) ° C. Delta (MFR − BDTT) 21 9 nd nd Flexural modulus 806 960 1609 1751 ISO 178; MPa Mmmm; .sup.13C NMR 99.8 nd nd (matrix) % Beta nucleating agent: Yes Yes 5,12- 0.01 wt.-% 0.01 wt.-% dihydroquinolino[2,3- b]acridine-6,7,13,14- tetrone, Charpy NIS 23° C. 31.1 5.7 61.2 6.1 kJ/m.sup.2 Charpy NIS 0° C. 12.0 3.7 3.6 2.0 kJ/m Charpy NIS −20° C. 5.5 3.3 n.d. n.d. kJ/m improvement Charpy 67 NIS −20° C. [percent]nucleated vs. unnucleated Ratio of 0.27 0.16 Charpy NIS −20° C. [kJ/m]/SF [wt.-%]

[0156] It can be seen that the inventive composition IE1 had: [0157] a surprisingly low brittle-to-ductile transition temperature (BDTT) for its melt flow rate being directly reflected in the parameter [MFR minus BDTT]; [0158] a beneficial high melting temperature; [0159] high flexibility in terms of IV(SF)/IV(CF) ratio; [0160] outstanding high crystallization temperature; [0161] a surprisingly improved ratio of Charpy NIS −20° C. [kJ/m]/SF [wt.-%]