Polypropylene with broad molecular weight distribution

Patent metadata

Field	Value
Publication number	US-9550844-B2
Application number	US-201414896640-A
Country	US
Kind code	B2
Filing date	Jun 10, 2014
Priority date	Jun 19, 2013
Publication date	Jan 24, 2017
Grant date	Jan 24, 2017

Abstract

Propylene homopolymer having a melt flow rate MFR 2 (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. 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 at least 2.8 wt. %;
wherein the propylene homopolymer comprises three fractions, a first propylene homopolymer fraction (H-PP1), a second propylene homopolymer fraction (H-PP2), and a third propylene homopolymer fraction (H-PP2), the first propylene homopolymer fraction (H-PP1) has a hi her melt flow rate MFR 2 (230° C.) than the second propylene homopolymer fraction (H-PP2) and the second propylene homopolymer (H-PP2) has a higher melt flow rate MFR 2 (230° C.) than the third homopolymer fraction (H-PP3), whereby the first propylene homopolymer fraction (H-PP1), the second propylene homopolymer fraction (H-PP2), and the third propylene homopolymer fraction (H-PP3) differ in the melt flow rate MFR 2 (230° C.) by at least 30 g/10 min.

2. Propylene homopolymer according to claim 1 , wherein said 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. Propylene homopolymer according to claim 1 , wherein said 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. Propylene homopolymer according to claim 1 , wherein said 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. Propylene homopolymer according to claim 1 , wherein said 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 of at least 1.30, wherein said fractions are determined by the 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. Propylene homopolymer according to claim 1 wherein said 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 of at least 2.90, wherein said fractions are determined by the 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. Propylene homopolymer according to claim 1 , wherein said propylene homopolymer has a melting temperature Tm of more than 160° C.

8. Propylene homopolymer according to claim 1 , 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).

9. Propylene homopolymer according to claim 1 , 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.

10. Propylene homopolymer according to claim 1 , 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.

11. Process for the manufacture of the propylene homopolymer according to claim 1 , in a sequential polymerization system comprising at least three polymerization reactors (R1), (R2) and (R3) connected in series, wherein the polymerization of propylene in the at least three polymerization reactors (R1), (R2) and (R3) takes place 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.

12. Process according to claim 11 , 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).

13. Process according to claim 11 , 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.

14. Process according to claim 11 , 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.

Assignees

• Borealis Ag

Inventors

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

Classifications

• C08L23/12 Primary

  Polypropene · CPC title

• C08F2500/04

  Broad molecular weight distribution, i.e. Mw/Mn > 6 · CPC title

• C08L2205/02

  containing two or more polymers of the same C08L -group · CPC title

• C08L2314/02

  Ziegler natta catalyst · CPC title

• C08F2500/12

  Melt flow index or melt flow ratio · CPC title