IP Library Granted Patent US 8,242,220
Granted Patent B2
US 8,242,220 · App. 12/312,963 · Granted Aug 14, 2012

Copolymers and films thereof

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Quick Facts
Patent No.
US 8,242,220
App. No.
12/312,963
Granted
Aug 14, 2012
Kind
B2
Abstract

Copolymer of ethylene and an alpha-olefin having (a) a density in the range 0.900-0.940 g/cm 3 , (b) a melt index MI 2 (2.16 kg, 190° C.) in the range of 0.01-50 g/10 min, (c) a molecular weight distribution (Mw/Mn) in the range 3.5 to 4.5, and (d) a melt elastic modulus G′(G″=500 Pa) in the range 40 to 150 Pa. The copolymer has a melt index MI 2 (2.16 kg, 190° C.) Dow Rheology Index (DRI) and melt elastic modulus G′(G″=500 Pa) satisfying the equations of [DRI/MI 2 ]>0 and [DRI/MI 2 ]<0.0225G′−0.745.

Claims (64)

1. A copolymer of ethylene and an alpha-olefin, said copolymer having

(a) a density in the range 0.900-0.940 g/cm 3 ,

(b) a melt index MI 2 (2.16 kg, 190° C.) in the range of 0.01-50 g/10 min,

(c) a molecular weight distribution (Mw/Mn) in the range 3.5 to 4.5,

(d) a melt elastic modulus G′(G″=500 Pa) in the range 40 to 150 Pa, and

(e) a melt index MI 2 (2.16 kg, 190° C.) Dow Rheology Index (DRI) and melt elastic modulus G′(G″=500 Pa) satisfying the equations of

[ DRI/MI 2 ]>0 and [ DRI/MI 2 ]<0.0225 G′− 0.745.

2. A copolymer of ethylene and an alpha-olefin, said copolymer having

(a) a density in the range 0.900-0.940 g/cm 3 ,

(b) a melt index MI 2 (2.16 kg, 190° C.) in the range of 0.01-50 g/10 min,

(c) a molecular weight distribution (Mw/Mn) in the range 3.5 to 4.5,

(d) a melt elastic modulus G′(G″=500 Pa) in the range 40 to 150 Pa, and

(e) a melt index MI 2 (2.16 kg, 190° C.), Dow Rheology Index (DRI), and melt elastic modulus G′(G″=500 Pa) satisfying the equations of

[ DRI/MI 2 ]>0 and [ DRI/MI 2 ]<0.0197 G′− 0.62.

3. A copolymer of ethylene and an alpha-olefin, said copolymer having

(a) a density in the range 0.900-0.940 g/cm 3 ,

(b) a melt index MI 2 (2.16 kg, 190° C.) in the range of 0.01-50 g/10 min,

(c) a molecular weight distribution (Mw/Mn) in the range 3.5 to 4.5,

(d) a melt elastic modulus G′(G″=500 Pa) in the range 40 to 150 Pa, and

(e) a Dow Rheology Index (DRI) and melt elastic modulus G′(G″=500 Pa) satisfying the equations of

DRI> 0 and DRI< 0.0225 G′− 0.705.

4. A copolymer according to claim 1 wherein the density is in the range 0.915-0.930 g/cm 3 .

5. A copolymer according to claim 1 wherein the melt index is in the range 0.05-20 g/10 min.

6. A copolymer according claim 1 wherein the melt elastic modulus G′(G″=500 Pa) in the range 40-80 Pa.

7. A copolymer according to claim 1 wherein the alpha-olefin has 4-12 carbon atoms.

8. A copolymer according to claim 7 wherein the alpha-olefin is 1-hexene.

9. A process for the preparation of copolymers according to claim 1 comprising polymerizing ethylene and an alpha-olefin in the presence of a metallocene catalyst system.

10. A process according to claim 9 wherein the metallocene catalyst system comprises a monocyclopentadienyl metallocene complex.

11. A process according to claim 10 wherein the monocyclopentadienyl metallocene complex has the formula:

wherein:

R′ each occurrence is independently selected from hydrogen, hydrocarbyl, silyl, germyl, halo, cyano, and combinations thereof, said R′ having up to 20 nonhydrogen atoms, and optionally, two R′ groups (where R′ is not hydrogen, halo or cyano) together form a divalent derivative thereof connected to adjacent positions of the cyclopentadienyl ring to form a fused ring structure;

X is a neutral η 4 bonded diene group having up to 30 non-hydrogen atoms, which forms a π-complex with M;

Y is —O—, —S—, —NR*—, —PR*—,

M is titanium or zirconium in the +2 formal oxidation state;

Z* is SiR* 2 , CR* 2 , SiR* 2 SiR* 2 , CR* 2 CR* 2 , CR*═CR*, CR* 2 SiR* 2 , or

GeR* 2 , wherein:

R* each occurrence is independently hydrogen, or a member selected from hydrocarbyl, silyl, halogenated alkyl, halogenated aryl, and combinations thereof, said

R* having up to 10 non-hydrogen atoms, and optionally, two R* groups from Z* (when R* is not hydrogen), or an R* group from Z* and an R* group from Y form a ring system.

12. A process according to claim 9 wherein the metallocene catalyst system comprises a cocatalyst represented by the formula:

(L*-H) + d (A d− )

wherein:

L* is a neutral Lewis base,

(L*-H) + d is a Bronsted acid,

A d− is a non-coordinating compatible anion having a charge of d − , and

d is an integer from 1 to 3.

13. A process according to claim 12 wherein the cocatalyst comprises an ionic compound comprising a cation and an anion wherein the anion has at least one substituent comprising a moiety having an active hydrogen.

14. A process according to claim 9 wherein the metallocene catalyst system is supported.

15. A process according to claim 14 wherein the support is silica.

16. A process according to claim 9 performed in the gas phase.

17. A process according to claim 16 performed in a fluidized bed reactor.

18. A process according to claim 16 wherein the polymerization process is performed in condensed mode operation.

19. A film comprising a copolymer of ethylene and an alpha-olefin having

(a) a density in the range 0.900-0.940 g/cm 3 ,

(b) a melt index MI 2 (2.16 kg, 190° C.) in the range of 0.01-50 g/10 min,

(c) a molecular weight distribution (Mw/Mn) in the range 3.5 to 4.5,

(d) a melt elastic modulus G′(G″=500 Pa) in the range 40 to 150 Pa, and

(e) a melt index MI 2 (2.16 kg, 190° C.), Dow Rheology Index (DRI) and melt elastic modulus G′(G″=500 Pa) satisfying the equations of

[ DRI/MI 2 ]>0 and [ DRI/MI 2 ]<0.0225 G′− 0.745.

20. A film according to claim 19 having a dart impact (25 μm film)>1000g, a haze <10% and a gloss of >60%.

21. A film according to claim 19 having a melt pressure in the range 160-190 bar when extruded under the specified extrusion film blowing conditions with a CMG film blowing processing line.

22. A film comprising a copolymer of claim 1 prepared by use of a metallocene catalyst system, said film having a dart impact (25 μm film)>1000g, a haze <10%, a gloss of >60% and a melt pressure in the range 160-190 bar when extruded under the specified extrusion film blowing conditions with a CMG film blowing processing line.

23. A film according to claim 22 wherein the metallocene catalyst system comprises a monocyclopentadienyl metallocene complex.

24. A film according to claim 22 having a dart impact >1500 g.

25. A blown film according to claim 19 , 20 , 21 , 22 , 23 or 24 .

Assignments (12)
SECURITY INTEREST Recorded May 4, 2017
From: INEOS SALES (UK) LIMITED
To: BARCLAYS BANK PLC
Reel/Frame 042400/0019 →
SECURITY INTEREST Recorded May 4, 2017
From: INEOS SALES (UK) LIMITED
To: BARCLAYS BANK PLC
Reel/Frame 042402/0128 →
SECURITY INTEREST Recorded May 4, 2017
From: INEOS SALES (UK) LIMITED
To: BARCLAYS BANK PLC
Reel/Frame 042402/0519 →
SECURITY INTEREST Recorded May 4, 2017
From: INEOS SALES (UK) LIMITED
To: BARCLAYS BANK PLC
Reel/Frame 042402/0758 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 5, 2014
From: INEOS COMMERCIAL SERVICES UK LIMITED
To: INEOS SALES (UK) LIMITED
Reel/Frame 032388/0553 →
INTELLECTUAL PROPERTY SECURITY AGREEMENT Recorded Feb 13, 2014
From: INEOS SALES (UK) LIMITED
To: BARCLAYS BANK PLC
Reel/Frame 032264/0400 →
INTELLECTUAL PROPERTY SECURITY AGREEMENT SUPPLEMENT Recorded Feb 13, 2014
From: INEOS SALES (UK) LIMITED
To: BARCLAYS BANK PLC
Reel/Frame 032264/0470 →
SECURITY AGREEMENT Recorded Jun 26, 2012
From: INEOS COMMERCIAL SERVICES UK LIMITED
To: BARCLAYS BANK PLC
Reel/Frame 028444/0639 →
SECURITY INTEREST Recorded Feb 23, 2012
From: INEOS COMMERCIAL SERVICES UK LIMITED
To: BARCLAYS BANK PLC
Reel/Frame 027748/0039 →
SECURITY INTEREST Recorded Nov 28, 2011
From: INEOS COMMERCIAL SERVICES UK LIMITED
To: BARCLAYS BANK PLC
Reel/Frame 027286/0657 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 4, 2011
From: INEOS EUROPE LIMITED
To: INEOS COMMERCIAL SERVICES UK LIMITED
Reel/Frame 027060/0001 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 2, 2009
From: CHAI, CHOON KOOI
To: INEOS EUROPE LIMITED
Reel/Frame 022790/0104 →