Binuclear olefin polymerization activators

Patent metadata

Field	Value
Publication number	US-11542350-B2
Application number	US-201917043154-A
Country	US
Kind code	B2
Filing date	Mar 22, 2019
Priority date	Mar 30, 2018
Publication date	Jan 3, 2023
Grant date	Jan 3, 2023

Abstract

Embodiments of the disclosure include processes of polymerizing olefins. The process includes contacting ethylene and a (C3-C40)alpha-olefin comonomer in the presences of a catalyst system. The catalyst system comprises a procatalyst and a bimetallic activator complex. The bimetallic activator complex comprises an anion and a countercation, and the anion has a structure according to formula (I).

First claim

The invention claimed is:

1. A process of polymerizing olefins comprising contacting ethylene and a (C 3 -C 40 )alpha-olefin comonomer in the presence of a catalyst system to produce a polymer resin; the catalyst system comprising a procatalyst and a bimetallic activator complex wherein the bimetallic activator complex comprises an anion and a countercation, the anion having a structure according to formula (I):

where:
each M is independently aluminum, boron, or gallium;
L is chosen from a species having at least two Lewis basic sites;
each Q is independently a monodentate ligand;
n is 0, 1, or 2, wherein when n is 0, Q of Q n is not present;
x is 0, 1, or 2, wherein when x is 0, Q of Q x is not present;
each R is independently selected from the group consisting of radicals having formula (II) and radicals having formula (III):

each Y is independently carbon or silicon;
each R 11 , R 12 , R 13 , R 21 , R 22 , R 23 , R 24 , and R 25 , is independently chosen from (C 1 -C 40 )alkyl, (C 6 -C 40 )aryl, —H, —NR N 2 , —OR C , —SR C , or halogen, wherein when R is a radical according to formula (II), at least one of R 11 , R 12 , or R 13 is perhalogenated (C 1 -C 40 )alkyl, perhalogenated (C 6 -C 40 )aryl, or —F; and when R is a radical according to formula (III), at least one of R 21 , R 22 , R 23 , R 24 , and R 25 is perhalogenated (C 1 -C 40 )alkyl, perhalogenated (C 6 -C 40 )aryl, or —F;
optionally, when n is 0 or 1, two R groups in formula (I) are covalently connected; and
each R N or R C is independently (C 1 -C 30 )hydrocarbyl or —H.

2. The process according to claim 1 , wherein L is chosen from (C 1 -C 20 )heterohydrocarbon anion, − OC(O)R L , − S(O) 3 R L , − P(O) 3 R L , − NR L 2 , − OR L , − SR L , or halide, wherein R L is —H, (C 1 -C 30 )hydrocarbyl, halogen-substituted (C 1 -C 30 )hydrocarbyl.

3. The process according to claim 2 , wherein L is − OC(O)R L and R L is —C 6 F 5 .

4. The process according to claim 2 , wherein L is − OC(O)R L and R L is —CH 3 .

5. The process according to claim 1 , wherein when each M is aluminum, L is chosen from (C 1 -C 20 )heterohydrocarbon anion, − OC(O)R L , − S(O) 3 R L , − P(O) 3 R L , − NR L 2 , − OR L , or − SR L , wherein R L is —H, (C 1 -C 30 )hydrocarbyl or halogen-substituted (C 1 -C 30 )hydrocarbyl.

6. The process according to claim 1 , wherein L is selected from radicals having the formula (IV):

where
each of R 1 and R 2 are independently selected from —C(R L )— or —N—, wherein R L is —H, (C 1 -C 30 )hydrocarbyl, or halogen-substituted (C 1 -C 30 )hydrocarbyl, and R 3 is chosen from —H, (C 1 -C 30 )hydrocarbyl, or halogen-substituted (C 1 -C 30 )hydrocarbyl.

7. The process according to claim 6 , wherein R 1 is —C(C 11 H 23 )—, R 2 is —C(H)—, and R 3 is —H.

8. The process according to claim 1 , wherein L is —OS(O) 2 CF 3 .

9. The process according to claim 1 , wherein each R is a radical having the formula (II), wherein Y is carbon, R 11 , R 12 , and R 13 are fluorine.

10. The process according to claim 1 , wherein the countercation has a formal charge of +1.

11. The polymerization process according to claim 1 , wherein the countercation is + N(H)R N 3 , where each R N is chosen from (C 1 -C 20 )alkyl or (C 6 -C 20 )aryl.

12. The polymerization process according to claim 11 , wherein the countercation is + N(H)R N 3 , where at least two R N are chosen from (C 10 -C 20 )alkyl.

13. The polymerization process according to claim 9 , wherein the countercation is + C(C 6 H 5 ) 3 .

14. The polymerization process according to claim 9 , wherein the countercation is + C(C 6 H 4 R C ) 3 , where R C is (C 1 -C 20 )alkyl.

15. The polymerization process according to claim 1 , wherein the bimetallic activator complex in a high-boiling-point fully saturated hydrocarbon solution having a concentration of 200 micromoles of bimetallic activator complex and 20 millimoles of water per liter of high-boiling-point fully saturated hydrocarbon has a percent dissipation factor of less than or equal to 0.1 as measured by the Hydrocarbon Conductivity Test.

Assignees

• Dow Global Technologies Llc

Inventors

• Keaton Richard J
• Huacuja Rafael
• Wilson David R
• Klosin Jerzy
• Pearson David M
• Senecal Todd D
• Mukhopadhyay Sukrit
• Woodward William H H

Classifications

• C08F210/16 Primary

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title

• C08F4/64193

  OOOO · CPC title

• C08F4/76

  selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum · CPC title

• C08F2500/03

  Narrow molecular weight distribution, i.e. Mw/Mn < 3 · CPC title

• C07F5/069

  without C-aluminium linkages · CPC title