Propylene random copolymer for use in film applications

Abstract

The present invention is directed to a polypropylene composition (P) comprising a bimodal copolymer of propylene and 1-hexene prepared in the presence of a metallocene catalyst, said bimodal copolymer having a melt flow rate MFR2 in the range of 4.0 to 20.0 g/10 min. Further, the present invention is directed to a method for preparing the copolymer (C) and an article comprising said polypropylene composition (P).

Claims

1. A polypropylene composition (P), comprising at least 90.0 wt-%, based on an overall weight of the polypropylene composition (P), of a copolymer (C) of propylene and 1-hexene, having i) an overall 1-hexene content in a range of 2.0 to 10.0 wt-%, ii) a melt flow rate MFR.sub.2 determined according to ISO 1133 (2.16 kg, 230? C.) in a range of 4.0 to 20.0 g/10 min, and iii) an amount of 2,1 erythro regio-defects of at least 0.2 mol-%, wherein the copolymer (C) has been visbroken with a visbreaking ratio (VR) in a range of 1.5 to 15.0, wherein the visbreaking ratio is determined according to equation (2) $\begin{array}{cc}\mathrm{VR}=\frac{{\mathrm{MFR}}_{\mathrm{final}}}{{\mathrm{MFR}}_{\mathrm{start}}}& \left(2\right)\end{array}$ wherein MFR.sub.final is the melt flow rate MFR.sub.2 determined according to ISO 1133 (230? C., 2.16 kg) of the copolymer (C) after visbreaking and MFR.sub.start is the melt flow rate MFR.sub.2 determined according to ISO 1133 (230? C., 2.16 kg) of the copolymer (C) before visbreaking.

2. The polypropylene composition (P) according to claim 1, wherein the copolymer (C) has a xylene soluble content (XCS) of at least 8.0 wt-%.

3. The polypropylene composition (P) according to claim 1, wherein the copolymer (C) comprises a) a first random propylene copolymer (A) of propylene and a 1-hexene having a comonomer content in a range of 0.1 to 4.0 wt-%, and b) a second random propylene copolymer (B) of propylene and 1-hexene having a higher comonomer content than that of the first random propylene copolymer (A).

4. The polypropylene composition (P) according to claim 1, wherein the copolymer (C) has a 1-hexene content of a xylene soluble fraction C6(XCS) in a range of 2.0 to 15.0 wt-%.

5. The polypropylene composition (P) according to claim 3, wherein the copolymer (C) comprises 30.0 to 70.0 wt-% of the first random propylene copolymer (A) and 30.0 to 70.0 wt-% of the second random propylene copolymer (B), based on an overall weight of the copolymer (C).

6. The polypropylene composition (P) according to claim 3, wherein the copolymer (C) has a melting temperature Tm below 140? C.

7. The polypropylene composition (P) according to claim 3, wherein the copolymer (C) fulfills in-equation (1) $\begin{array}{cc}4.50?\frac{C6\left(C\right)}{C6\left(A\right)*\frac{\left[A\right]}{\left[C\right]}}?9.00& \left(1\right)\end{array}$ wherein C6(A) is 1-hexene content of the first random propylene copolymer (A) based on a total weight of the first random propylene copolymer (A) in wt-%; C6(C) is 1-hexene content of the copolymer (C) based on a total weight of the copolymer (C) in wt-%; and [A]/[C] is weight ratio between the first random propylene copolymer (A) and the copolymer (C) in [g/g].

8. The polypropylene composition (P) according to claim 1, wherein the copolymer (C) has a melt flow rate MFR.sub.2 determined according to ISO 1133 (230? C., 2.16 kg) before visbreaking in a range of 0.4 to 3.5 g/10 min.

9. The polypropylene composition (P) according to claim 1, wherein i) a first random propylene copolymer (A) has a melt flow rate MFR.sub.2 (230? C., 2.16 kg) determined according to ISO 1133 before visbreaking in a range of 0.3 to 6.0 g/10 min, and/or ii) a second random propylene copolymer (B) has a melt flow rate MFR.sub.2 (230? C., 2.16 kg) determined according to ISO 1133 before visbreaking in a range of 0.1 to 4.0 g/10 min.

10. A process for the preparation of a copolymer (C) of propylene and 1-hexene, comprising the steps of a) preparing a copolymer (C) of propylene and 1-hexene having an overall 1-hexene content in a range of 2.0 to 10.0 wt.-% in the presence of a metallocene catalyst (MC), b) visbreaking the copolymer (C) obtained in step a) with a visbreaking ratio (VR) in a range of 1.5 to 15.0, thereby obtaining the copolymer (C), wherein the visbreaking ratio is determined according to equation (3) $\begin{array}{cc}\mathrm{VR}=\frac{\mathrm{MFR}\left(C\right)}{\mathrm{MFR}\left(C^{}\right)}& \left(3\right)\end{array}$ wherein MFR(C) is a melt flow rate 1MFR.sub.2 determined according to ISO 1133 (230? C., 2.16 kg) of the copolymer (C) after visbreaking and MFR(C) is melt flow rate MFR.sub.2 determined according to ISO 1133 (230? C., 2.16 kg) of the copolymer (C).

11. The process according to claim 10, wherein the copolymer (C) of propylene and 1-hexene is prepared by a1) polymerizing propylene and 1-hexene in a first reactor (R-1) in the presence of the metallocene catalyst (MC), thereby obtaining a first random propylene copolymer (A) having a 1-hexene content in a range of 0.1 to 4.0 wt-%, a2) transferring said first random propylene copolymer (A) and unreacted comonomers of the first reactor (R-1) into a second reactor (R-2), and a3) polymerizing in said second reactor (R-2) and in the presence of said first random propylene copolymer (A), propylene and 1-hexene and obtaining a second random propylene copolymer (B) having a higher comonomer content than that of the first random propylene copolymer (A), said first random propylene copolymer (A) and said second random propylene copolymer (B) forming the copolymer (C).

12. The process according to claim 10, wherein i) the melt flow rate MFR.sub.2 determined according to ISO 1133 (230? C., 2.16 kg) of the copolymer (C) is in a range of 4.0 to 20.0 g/10 min and ii) the melt flow rate 1MFR.sub.2 determined according to ISO 1133 (230? C., 2.16 kg) of the copolymer (C) is in a range of 0.4 to below 4.0 g/10 min.

13. The process according to claim 10, wherein the metallocene catalyst (MC) is of formula (I)
R.sub.n(Cp).sub.2MX.sub.2(I) wherein each Cp independently is an unsubstituted or substituted and/or fused cyclopentadienyl ligand, substituted or unsubstituted indenyl or substituted or unsubstituted fluorenyl ligand; wherein the optional one or more substituent(s) are independently selected from the group consisting of halogen, hydrocarbyl, C.sub.3-C.sub.12-cycloalkyl which contains 1, 2, 3 or 4 heteroatom(s) in the ring moiety, C.sub.6-C.sub.20-heteroaryl, C.sub.1-C.sub.20-haloalkyl, SiR.sub.3, OSiR.sub.3, SR, PR.sub.2, OR, and NR.sub.2, wherein each R is independently a hydrogen or hydrocarbyl selected from the group consisting of C.sub.1-C.sub.20-alkyl, C.sub.2-C.sub.20-alkenyl, C.sub.2-C.sub.20-alkynyl, C.sub.3-C.sub.12-cycloalkyl, and C.sub.6-C.sub.20-aryl; or in case of NR.sub.2, the two substituents R can form a five- or six-membered ring, together with the nitrogen atom to which they are attached; R is a bridge of 1-2 C-atoms and 0-2 heteroatoms, wherein the heteroatom(s) are Si, Ge and/or O atom(s), wherein each of the bridge atoms may bear independently substituents selected from the group consisting of C.sub.1-C.sub.20-alkyl, tri(C.sub.1-C.sub.20-alkyl)silyl, tri(C.sub.1-C.sub.20-alkyl)siloxy and C.sub.6-C.sub.20-aryl substituents; or a bridge of one or two heteroatoms selected from silicon, germanium and oxygen atom(s), M is a transition metal of Group 4 selected from Zr or Hf; each X is independently a sigma-ligand selected from the group consisting of H, halogen, C.sub.1-C.sub.20-alkyl, C.sub.1-C.sub.20-alkoxy, C.sub.2-C.sub.20-alkenyl, C.sub.2-C.sub.20-alkynyl, C.sub.3-C.sub.12-cycloalkyl, C.sub.6-C.sub.20-aryl, C.sub.6-C.sub.20-aryloxy, C.sub.7-C.sub.20-arylalkyl, C.sub.7-C.sub.20-arylalkenyl, SR, PR.sub.3, SiR.sub.3, OSiR.sub.3, NR.sub.2 and CH.sub.2Y, wherein Y is C.sub.6-C.sub.20-aryl, C.sub.6-C.sub.20-heteroaryl, C.sub.1-C.sub.20-alkoxy, C.sub.6-C.sub.20-aryloxy, NR.sub.2, SR, PR.sub.3, SiR.sub.3, and OSiR.sub.3; each of the above mentioned ring moieties alone or as a part of another moiety as the substituent for Cp, X, R or R can further be substituted with C.sub.1-C.sub.20-alkyl which may contain Si and/or O atoms; and n is 1 or2.

14. The process according to claim 13, wherein the metallocene catalyst (MC) of formula (I) is an organo-zirconium compound of formula (II) or (II) ##STR00004## wherein M is Zr; each X is independently a sigma-ligand selected from the group consisting of H, halogen, C.sub.1-C.sub.20-alkyl, C.sub.1-C.sub.20-alkoxy, C.sub.2-C.sub.20-alkenyl, C.sub.2-C.sub.20-alkynyl, C.sub.3-C.sub.12-cycloalkyl, C.sub.6-C.sub.20-aryl, C.sub.6-C.sub.20-aryloxy, C.sub.7-C.sub.20-arylalkyl, C.sub.7-C.sub.20-arylalkenyl, SR, PR.sub.3, SiR.sub.3, OSiR.sub.3, NR.sub.2 and CH.sub.2Y; L is a divalent bridge selected from the group consisting of R.sub.2C, R.sub.2CCR.sub.2, R.sub.2Si, R.sub.2SiSiR.sub.2, and R.sub.2Ge, wherein each R is independently a hydrogen atom, C.sub.1-C.sub.20 alkyl, C.sub.3-C.sub.10 cycloalkyl, tri(C.sub.1-C.sub.20-alkyl)silyl, C.sub.6-C.sub.20-aryl, or C.sub.7-C.sub.20 arylalkyl; each R.sup.2 or R.sup.2 is a C.sub.1-C.sub.10 alkyl group; R.sup.5 is a C.sub.1-C.sub.10 alkyl group or a ZR.sup.3 group; R.sup.6 is hydrogen or a C.sub.1-C.sub.10 alkyl group; R.sup.6 is a C.sub.1-C.sub.10 alkyl group or a C.sub.6-C.sub.10 aryl group; R.sup.7 is hydrogen, a C.sub.1-C.sub.6 alkyl group or a ZR.sup.3 group; R.sup.7 is hydrogen or a C.sub.1-C.sub.10 alkyl group; Z and Z are independently O or S; R.sup.3 is a C.sub.1-C.sub.10 alkyl group, or a C.sub.6-C.sub.10 aryl group optionally substituted by one or more halogen groups; R.sup.3 is a C.sub.1-C.sub.10 alkyl group; each n is independently 0 to 4; and each R.sup.1 is independently a C.sub.1-C.sub.20 hydrocarbyl group.

15. A polypropylene composition (P), comprising at least 90 wt % of the copolymer (C) obtained according to the process according to claim 10.

16. An article comprising at least 90.0 wt-% of the polypropylene composition (P) according to claim 1.

Description

2. EXAMPLES

Preparation of the Catalyst

(1) The catalyst used in the inventive example IE is prepared as described in detail in WO 2015/011135 A1 (metallocene complex MCi 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 (MCi in WO 2015/011135 A1) is prepared as described in WO 2013/007650 A1 (metallocene E2 in WO 2013/007650 A1).

(2) The catalyst used in the comparative example CE2, which is identical to inventive example IE3 of EP 2 386 603 A1, is described in example 1 of EP 1 741 725 A1.

Preparation of the Polypropylene Composition (P)

(3) The polypropylene composition (P) was prepared in a sequential process comprising a loop reactor and a gas phase reactor. The reaction conditions are summarized in Table 1. Table 2 contains the properties of the comparative and inventive examples.

(4) The polypropylene composition (P) was visbroken in a twin-screw extruder using an appropriate amount of (tert.-butylperoxy)-2,5-dimethylhexane (Trigonox 101, distributed by Akzo Nobel, Netherlands) to achieve the target MFR.sub.2 as mentioned in Table 2.

(5) TABLE-US-00001 TABLE 1 Preparation of the Polypropylene composition (P) IE CE2 Prepolymerization Temperature [? C.] 20 n.d. Catalyst feed [g/h] 2.5 n.d. TEAL/C3 [g/t] 0 n.d. C3 feed [kg/h] 60.9 n.d. H2 feed [g/h] 0.5 n.d. Residence time [h] 0.2 n.d. Loop (R1) Temperature [? C.] 70 n.d. Pressure [kPa] 5297 n.d. H2/C3 ratio [mol/kmol] 0.08 n.d. C6/C3 ratio [mol/kmol] 15.5 n.d. MFR.sub.2 [g/10 min] 1.9 1.1 XCS [wt.-%] 1.9 1.0 C6 [wt.-%] 1.7 0.0 Residence time [h] 0.5 n.d. Split [wt.-%] 42.5 38 GPR (R2) Temperature [? C.] 80 n.d. Pressure [kPa] 2406 n.d. H2/C3 ratio [mol/kmol] 0.3 n.d. C6/C3 ratio [mol/kmol] 8.7 n.d. C6 (GPR) [wt.-%] 6.9 7.6 MFR.sub.2 (GPR) [g/10 min] 1.1 27.5 Residence time [h] 2.6 n.d. Split [wt.-%] 57.5 62 MFR.sub.2 (before [g/10 min] 1.5 8.1 visbreaking) MFR(C)/MFR(A) [?] 0.74 7.4 XCS (before [wt.-%] 11.1 3.0 visbreaking) C6(XCS) [wt %] 7.4 n.d.

(6) TABLE-US-00002 TABLE 2 Properties of the comparative and inventive examples IE CE1 CE2 MFR.sub.2 (after [g/10 min] 9.0 8.0 8.1 visbreaking) C6 [wt.-%] 5.0 0.0 4.7 Tm [? C.] 136 140 148 XCS [wt.-%] 11.0 10.0 3.0 C6 FDA [wt.-%] 0.8 2.0 1.2 1, 2e [mol-%] 0.46 0.0 n.d. CF film Thickness [?m] 50 50 100 SIT [? C.] 105 114 104 Tm ? SIT [? C.] 31 26 34 HTF [N] 2.7 2.0 3.1 TM/MD [MPa] 434 434 495 TM/TD [MPa] 432 432 503 W.sub.tot (Dynatest) [J/mm] 26.0 15.0 n.d. Haze b.s. [%] 0.3 0.2 n.d. Haze a.s. [%] 0.6 15 n.d. CE1 is the commercial copolymer of propylene and 4.5 wt % ethylene RD208CF of Borealis having a melt flow rate of 8.0 g/10 min which is produced by visbreaking a reactor-grade PP based on a Ziegler-Natta type catalyst to achieve the target MFR.

(7) As can be gathered from Table 2, the haze after sterilization of the inventive compositions having an amount of 2,1 erythro regio-defects above 0.2 mol-% is significantly lower than the corresponding value of the comparative example, while the tensile modulus remains on the same level.