Polyethylene Copolymers with Vinyl Terminated Macromonomers as Comonomers

• US 20140213734A1
• Filed: 01/17/2014
• Published: 07/31/2014
• Est. Priority Date: 01/30/2013
• Status: Active Grant

• Current Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Inventors: Jiang, Peijun
• Granted Patent: US 9,422,385 B2
• Time in Patent Office: Days
• US Class Current: 525/322
• CPC Class Codes: C08F 2/001 Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer C08F295/00, C08F297/00 take precedence
• CPC Class Codes: C08F 210/02 Ethene
• CPC Class Codes: C08F 210/06 Propene
• CPC Class Codes: C08F 210/16 Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• CPC Class Codes: C08F 2500/04 Broad molecular weight distribution, i.e. Mw/Mn > 6
• CPC Class Codes: C08F 2500/09 Long chain branches
• CPC Class Codes: C08F 2500/11 Melt tension or melt strength
• CPC Class Codes: C08F 2500/38 Branching index [gvis], i.e. ratio of the intrinsic viscosity of the branched polymer to the intrinsic viscosity of a linear polymer of equal molecular weight and same composition
• CPC Class Codes: C08F 255/02 on to polymers of olefins having two or three carbon atoms
• CPC Class Codes: C08F 290/042 Polymers of hydrocarbons as defined in group C08F10/00
• CPC Class Codes: C08F 4/65904 in combination with another component of C08F4/64
• CPC Class Codes: C08F 4/65908 in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
• CPC Class Codes: C08F 4/65927 two cyclopentadienyl rings being mutually bridged

Abstract

This invention relates to polyethylene copolymers comprising ethylene and vinyl terminated macromonomers. The polyethylene copolymers are achieved by copolymerization of ethylene and vinyl terminated macromonomers in a polymerization reactor, particularly in high yields and with a wide range of VTM molecular weights, that can be made at commercial rates.

Claims

1. An ethylene copolymer comprising at least 70 wt % of ethylene and at least one vinyl terminated macromonomers (VTM) wherein the ethylene copolymer has:

1) a Mw of 100,000 g/mol or more;

     2) a density of 0.94 g/cm³ or less; and

     3) a ratio of the complex viscosity at a frequency of 0.1 rad/s to the complex viscosity at a frequency of 100 rad/s of 15 or more.

2. The ethylene copolymer of claim 1, wherein the VTM has an Mn (measured by ¹H NMR) of from about 200 g/mol to about 100,000 g/mol.

3. The ethylene copolymer of claim 1, wherein the VTM is amorphous and has no detectable melting temperature from DSC.

4. The ethylene copolymer of claim 1, wherein the T_c is less than 110°

C.

5. The ethylene copolymer of claim 1, wherein the ratio of the intrinsic viscosity to the intrinsic viscosity of a linear ethylene homo-polymer at the same molecular weight (g′

_vis) is less than about 0.8.

6. The ethylene copolymer of claim 5, wherein the g′

_vis is less than about 0.7.

7. The ethylene copolymer of claim 1, wherein the melt index is less than 100.

8. The ethylene copolymer of claim 1, wherein the melt index is less than 10.

9. The ethylene copolymer of claim 1, wherein the melt index is less than 5.

16. A process for preparing the ethylene copolymer of claim 1, wherein the process comprises contacting ethylene and a vinyl terminated macromonomer (VTM) in the presence of at least one catalyst capable of incorporating the VTM into a polyethylene backbone.

17. The process of claim 16, wherein the process is a solution process with a homogeneous catalyst.

18. The process of claim 16, wherein the process is a slurry process.

10. An ethylene copolymer comprising two portions:

a first portion derived from a vinyl terminated macromonomer, VTM; and

a second metallocene derived portion from one or more vinyl containing monomers, wherein the vinyl terminus of the first portion is incorporated into the metallocene derived polymeric portion; and

wherein the ethylene copolymer comprises at least 70 weight percent ethylene and from about 0.5 to about 30 weight percent VTM.

11. The ethylene copolymer of claim 10, wherein the VTM has an Mn (measured by ¹H NMR) of from about 200 g/mol to about 100,000 g/mol.

12. The ethylene copolymer of claim 10, wherein the VTM is amorphous and has no detectable melting temperature from DSC.

13. The ethylene copolymer of claim 10, wherein the T_c is less than 110°

C.

14. The ethylene copolymer of claim 10, wherein the ratio of the intrinsic viscosity to the intrinsic viscosity of a linear ethylene homo-polymer at the same molecular weight (g′

_vis) is less than about 0.8.

15. The ethylene copolymer of claim 14, wherein the g′

_vis is less than about 0.7.

19. A process for producing a copolymer of ethylene and vinyl terminated macromonomer (VTM), the process comprising:

(i) polymerizing at least one first monomer in a first polymerization zone in the presence of at least one catalyst capable of producing a VTM with at least 50% of allylic terminated chain ends relative to all unsaturated chain ends; and

(ii) contacting at least part of said the VTM with ethylene and, optionally, one or more alpha-olefins in a second polymerization zone separate from said first polymerization zone in the presence of at least one catalyst capable of incorporating the VTM into the copolymer.