Highly soluble bis-borate as binuclear co-catalysts for olefin polymerization

Patent metadata

Field	Value
Publication number	US-12037440-B2
Application number	US-201917043029-A
Country	US
Kind code	B2
Filing date	Mar 28, 2019
Priority date	Mar 30, 2018
Publication date	Jul 16, 2024
Grant date	Jul 16, 2024

Abstract

Embodiments are directed to catalyst systems comprising: a procatalyst; and a co-catalyst dissolved in a non-halogenated aprotic hydrocarbon solvent, the co-catalyst comprising: a non-coordinating borate dianion having the formula: (III) and two cations, each cation being independently chosen from a cation according to formula (I) or formula (II).

First claim

The invention claimed is:

1. A catalyst system comprising:
a procatalyst; and
a co-catalyst dissolved in a non-halogenated solvent, the co-catalyst comprising:
a non-coordinating borate dianion having the formula:

and
two cations, each cation being independently chosen from a cation according to formula (I) or formula (II):

where:
each R 1 , R 2 , R 3 , R 4 , and R 5 is independently chosen from —H, —F, —Cl, substituted or unsubstituted (C 4 -C 40 )alkyl, substituted or unsubstituted (C 4 -C 40 )alkenyl or substituted or unsubstituted (C 4 -C 40 )cycloalkyl, wherein the substituted (C 4 -C 40 )alkyl and substituted (C 4 -C 40 )cycloalkyl are substituted with one or more R S , where each R S is chosen from (C 1 -C 20 )alkyl or halogen;
provided that at least one of R 1 , R 2 , R 3 , R 4 , or R 5 is chosen from substituted or unsubstituted (C 4 -C 30 )alkyl or substituted or unsubstituted (C 4 -C 40 )cycloalkyl; and
each R 6 and R 7 is independently chosen from (C 4 -C 30 )alkyl, and R 8 is independently chosen from either (C 1 -C 20 )alkyl or (C 6 -C 18 )aryl;

wherein:

the two cations are both selected from formula (I); or
one of the two cations is selected from formula (I) and the other of the cations is selected from formula (II).

2. The catalyst system according to claim 1 , wherein the procatalyst upon activation is ionic.

3. The catalyst system according to claim 1 , wherein each R 1 is independently (C 4 -C 30 )alkyl.

4. The catalyst system according to claim 1 , wherein each R 1 is independently tert-butyl, n-butyl, tert-octyl, or n-octyl.

5. The catalyst system according to claim 1 , wherein each R 2 , R 3 , R 4 and R 5 is —H.

6. The catalyst system according to claim 1 , wherein each R 1 is independently chosen from n-butyl, tert-butyl, 1-pentyl, 1-hexyl, heptyl, n-octyl, nonyl, decyl, undecyl, or dodecyl.

7. The catalyst system according to claim 1 , wherein each R 1 is independently chosen from a linear (C 4 -C 30 )aticyl or a linear or branched (C 5 -C 30 )alkyl.

8. The catalyst system according to claim 1 , wherein the two cations are both selected from cations according to formula (I).

9. The catalyst system according to claim 1 , wherein one of the two cations is selected from formula (I) and the other of the cations is selected from formula (II).

10. The catalyst system according to claim 1 , wherein the co-catalyst has a solubility of greater than 20 milligrams per milliliter (mg/mL) in toluene under conditions of 25° C. and 1 atmosphere.

11. A polymerization process for producing ethylene-based polymer, the process comprising: polymerizing ethylene and optionally one or more α-olefins in the presence of a catalyst system, the catalyst system comprising a procatalyst and a co-catalyst dissolved in a non-halogenated aprotic hydrocarbon solvent, wherein the co-catalyst comprises:
a non-coordinating borate dianion having the formula:

and
two cations, each cation being according to formula (I) or formula (II):

where:
each R 1 , R 2 , R 3 , R 4 , and R 5 is independently chosen from —H, F, Cl, substituted or unsubstituted (C 4 -C 40 )alkyl, substituted or unsubstituted (C 4 -C 40 )alkenyl or substituted or unsubstituted (C 4 -C 40 )cycloalkyl, wherein the substituted (C 4 -C 40 )alkyl and substituted (C 4 -C 40 )cycloalkyl are substituted with one or more R S , where each R S is chosen from (C 1 -C 20 )alkyl or halogen;
provided that at least one of R 1 , R 2 , R 3 , R 4 , or R 5 is chosen from substituted or unsubstituted (C 4 -C 30 )alkyl or substituted or unsubstituted (C 4 -C 40 )cycloalkyl; and each R 6 and R 7 is independently chosen from (C 4 -C 30 )alkyl, and R 8 is independently chosen from either (C 1 -C 20 )alkyl or (C 6 -C 18 )aryl;

wherein:
the two cations are both selected from formula (I); or
one of the two cations is selected from formula (I) and the other of the cations is selected from formula (II).

12. The process according to claim 11 , wherein the α-olefin is 1-octene.

13. The process according to claim 11 , wherein the non-halogenated solvent is toluene or an aliphatic solvent.

14. The process according to claim 11 , wherein each R 1 is independently tert-butyl, n-butyl, tert-octyl, or n-octyl.

15. The process according to claim 11 , wherein each R 2 , R 3 , R 4 and R 5 is —H.

16. The process according to claim 11 , wherein the two cations are both selected from cations according to formula (I).

17. The process according to claim 11 , wherein one of the two cations is selected from formula (I) and the other of the cations is selected from formula (II).

Assignees

• Dow Global Technologies Llc
• Univ Northwestern

Inventors

• Marks Tobin J
• Gao Yanshan
• Lohr Tracy L
• Christianson Matthew D
• Klosin Jerzy
• Carnahan Edmund M
• Young Andrew J

Classifications

• C08F4/52

  selected from boron, aluminium, gallium, indium, thallium or rare earths (C08F4/14 takes precedence) · CPC title

• C08F4/65908

  in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+ · CPC title

• C08F2410/03

  Multinuclear procatalyst, i.e. containing two or more metals, being different or not · CPC title

• C08F10/14

  Monomers containing five or more carbon atoms · CPC title

• C08F10/02 Primary

  Ethene · CPC title