Polyethylene copolymers with vinyl terminated macromonomers as comonomers

• US 9,422,385 B2
• Filed: 01/17/2014
• Issued: 08/23/2016
• 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
• Primary Examiner(s): Rabago, Roberto
• Application Number:
  US14/157,932
• Publication Number:
  US 20140213734A1
• Time in Patent Office: 949 Days
• Field of Search: 526/65, 526/160, 526/170, 526/348, 525/53
• US Class Current: 1/1
• 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. A process for preparing an ethylene/macromonomer copolymer wherein the process comprises contacting ethylene and a propylene vinyl terminated macromonomer (VTM) in the presence of at least one catalyst capable of incorporating the VTM into a polyethylene backbone, wherein the catalyst is [di(p-triethylsilylphenyl) methylene] (cyclopentadienyl) (3,8-di-t-butylfluorenyl)hafnium dimethyl preactivated with N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate, wherein the ethylene/macromonomer copolymer comprising at least 70 wt % of ethylene and at least one propylene 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; and

wherein the propylene-VTM is amorphous and has no detectable melting temperature from DSC, and has an Mn (measured by ¹H NMR) of from 200 g/mol to 5000 g/mol.

2. The process of claim 1, wherein the T_c is less than 110°

C.

3. The process 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 0.8.

4. The process of claim 3, wherein the g′

_vis is less than 0.7.

5. The process of claim 1, wherein the high load melt index is less than 20 dg/min.

6. The process of claim 1, wherein the melt index ratio (I₂₁/I₂) is from 10 to 500.

7. The process copolymer of claim 1, wherein the melt index is less than 5 dg/min.

8. The process of claim 1, wherein the process is a solution process with a homogeneous catalyst.

9. The process of claim 1, wherein the process is a slurry process.

11. The process of claim 1, the copolymer having a heat of fusion within the range of 120 J/g to 78.58 J/g.

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

(i) polymerizing propylene monomer in a first polymerization zone in the presence of at least one catalyst capable of producing a propylene VTM with at least 50% of allylic terminated chain ends relative to all unsaturated chain ends, wherein the propylene VTM is amorphous and has no detectable melting temperature from DSC, and has an Mn (measured by ¹H NMR) of from 200 g/mol to 5000 g/mol, wherein the catalyst used in the first polymerization zone is selected from;

12. The process of claim 10, wherein the copolymer has a heat of fusion within the range of 120 J/g to 78.58 J/g.

13. The process of claim 10, wherein the catalyst in the second polymerization zone is different from the catalyst in the first polymerization zone.

14. The process of claim 10, wherein the temperature in the first polymerization zone is from 60 to 80°

C., and the temperature in the second polymerization zone is from 90 to 130°

C.