Polypropylene with broad molecular weight distribution

Patent metadata

Field	Value
Publication number	US-10053524-B2
Application number	US-201615387355-A
Country	US
Kind code	B2
Filing date	Dec 21, 2016
Priority date	Jun 19, 2013
Publication date	Aug 21, 2018
Grant date	Aug 21, 2018

Abstract

Propylene homopolymer having a melt flow rate MFR2 (230° C.) at least 50 g/10 min, a Mw/Mn at least 12.0 and a xylene cold soluble content (XCS) of at least 2.8 wt.-%.

First claim

The invention claimed is:

1. A propylene homopolymer having:
(a) a melt flow rate MFR 2 (230° C.) measured according to ISO 1133 of 60 to 500 g/10 min;
(b) a ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) [Mw/Mn] of at least 12.0; and
(c) a xylene cold soluble content (XCS) determined according ISO 16152 (25° C.) of 2.5 to 4.5 wt. %.

2. The propylene homopolymer according to claim 1 , wherein the propylene homopolymer has a ratio of the complex viscosity eta* at 0.05 rad/sec to the complex viscosity eta* at 300 rad/sec of at least 4.0.

3. The propylene homopolymer according to claim 1 , wherein the propylene homopolymer has:
(a) 2,1 erythro regio-defects of equal or below 0.4 mol. % determined by 13 C-NMR spectroscopy; and/or
(b) a pentad isotacticity (mmmm) of more than 95.0%.

4. The propylene homopolymer according to claim 1 , wherein the propylene homopolymer has:
(a) a ratio of z-average molecular weight (Mz) to weight average molecular weight (Mw) [Mz/Mw] of at least 6.0; and/or
(b) a ratio of z-average molecular weight (Mz) to number average molecular weight (Mn) [Mz/Mn] of at least 80.

5. The propylene homopolymer according to claim 1 , wherein the propylene homopolymer is not nucleated and optionally has:
(a) a weight ratio of the crystalline fractions melting in the temperature range of above 160 to 180° C. to the crystalline fractions melting in the temperature range of 90 to 160° C. of at least 1.30, wherein the fractions are determined by a stepwise isothermal segregation technique (SIST), and/or
(b) a crystallization temperature of at least 112° C.; and/or
(c) a tensile modulus measured according to ISO 527-2 of at least 1,950 MPa.

6. The propylene homopolymer according to claim 2 , wherein the propylene homopolymer is α-nucleated and optionally has:
(a) a weight ratio of the crystalline fractions melting in the temperature range of above 160 to 180° C. to the crystalline fractions melting in the temperature range of 90 to 160° C. of at least 2.90, wherein the fractions are determined by a stepwise isothermal segregation technique (SIST); and/or
(b) a crystallization temperature of at least 128° C.; and/or
(c) a tensile modulus measured according to ISO 527-2 of at least 2,150 MPa.

7. The propylene homopolymer according to claim 1 , wherein the propylene homopolymer has a melting temperature Tm of more than 160° C.

8. The propylene homopolymer according to claim 1 , wherein the propylene homopolymer (H-PP) has a first propylene homopolymer fraction (H-PP1), a second propylene homopolymer fraction (H-PP2) and a third propylene homopolymer fraction (H-PP3), the first propylene homopolymer fraction (H-PP1), second propylene homopolymer fraction (H-PP2) and third propylene homopolymer fraction (H-PP3) differ in the melt flow rate MFR 2 (230° C.) by at least 30 g/10 min.

9. The propylene homopolymer according to claim 8 , wherein:
(a) the melt flow rate MFR 2 (230° C.) of the first propylene homopolymer fraction (H-PP1) is at least 4 times higher than the melt flow rate MFR 2 (230° C.) of the second propylene homopolymer fraction (H-PP2); and/or
(b) the melt flow rate MFR 2 (230° C.) of the second propylene homopolymer fraction (H-PP2) is at least 1000 times higher than the melt flow rate MFR 2 (230° C.) of the third propylene homopolymer fraction (H-PP3).

10. The propylene homopolymer according to claim 8 , wherein:
(a) the melt flow rate MFR 2 (230° C.) of the first propylene homopolymer fraction (H-PP1) is at least 300 g/10 min; and/or
(b) the melt flow rate MFR 2 (230° C.) of the second propylene homopolymer fraction (H-PP2) is in the range of 10.0 to below 300 g/10 min; and/or
(c) the melt flow rate MFR 2 (230° C.) of the third propylene homopolymer fraction (H-PP3) is below 0.1 g/10 min.

11. The propylene homopolymer according claim 6 , wherein the amount:
(a) of the first propylene homopolymer fraction (H-PP1) is in the range of 40 to 60 wt. %,
(b) of the second propylene homopolymer fraction (H-PP2) is in the range of 25 to 59.0 wt. %, and
(c) of the third propylene homopolymer fraction (H-PP3) is in the range of 1.0 to 15.0 wt. %,
based on the total amount of the propylene homopolymer.

12. A process for the manufacture of a propylene homopolymer accordingly to claim 1 , in a sequential polymerization system that includes at least three polymerization reactors (R1), (R2) and (R3) connected in series, the process comprising:
polymerizing propylene in the at least three polymerization reactors (R1), (R2) and (R3) in the presence of:
(a) a Ziegler-Natta catalyst (ZN-C) comprising a titanium compound (TC) having at least one titanium-halogen bond, and an internal donor (ID), both supported on a magnesium halide,
(b) a co-catalyst (Co), and
(c) an external donor (ED),
wherein:
the internal donor (ID) comprises at least 80 wt. % of a succinate;
the molar-ratio of co-catalyst (Co) to external donor (ED) [Co/ED] is 2 to 60; and
the molar-ratio of co-catalyst (Co) to titanium compound (TC) [Co/TC] is 150 to 300.

13. The process according to claim 12 , wherein:
(a) the molar-ratio of external donor (ED) to titanium compound [ED/TC] is in the range of more than 5 to below 100; and/or
(b) the first polymerization reactor (R1) is a loop reactor (LR), the second polymerization reactor is a first gas phase reactor (GPR1) and the third polymerization reactor is a second gas phase reactor (GPR2).

14. The process according to claim 12 , wherein:
(a) the operating temperature in the first polymerization reactor (R1) is in the range of 70 to 85° C.; and/or
(b) the operating temperature in the second polymerization reactor (R2) is in the range of 70 to 95° C.; and/or
(c) the operating temperature in the third polymerization reactor (R3) is in the range of 70 to 95° C.

15. The process according to claim 12 , wherein:
(a) the total average residence time is at most 500 min; and/or
(b) the average residence time in the polymerization first reactor (R1) is at least 20 min; and/or
(c) the average residence time in the second polymerization reactor (R2) is at least 90 min; and/or
(d) the average residence time in the third polymerization reactor (R3) is at least 100 min.

16. A propylene homopolymer produced by the process according to claim 12 .

Assignees

• Borealis Ag

Inventors

• Gahleitner Markus
• Hafner Norbert
• Gitsas Antonis
• Bernreitner Klaus

Classifications

• C08F110/06 Primary

  Propene · CPC title

• C08L23/12 Primary

  Polypropene · CPC title

• C08L2314/02

  Ziegler natta catalyst · CPC title

• C08F2410/04

  Dual catalyst, i.e. use of two different catalysts, where none of the catalysts is a metallocene · CPC title

• C08F2500/12

  Melt flow index or melt flow ratio · CPC title