Group 3 metal catalyst system and process to produce ethylene polymers therewith

Patent metadata

Field	Value
Publication number	US-9982003-B2
Application number	US-201715668525-A
Country	US
Kind code	B2
Filing date	Aug 3, 2017
Priority date	Sep 12, 2016
Publication date	May 29, 2018
Grant date	May 29, 2018

Abstract

This invention relates to a process to using dimers of a group 3 metal (typically scandium) catalyst compound to produce ethylene polymers, such as ethylene-alpha-olefin copolymers and ethylene-conjugated diene copolymers.

First claim

What is claimed is:

1. A catalyst compound represented by the formula (I):

where M is a group 3 metal;
M* is a group 3 metal;
each R 1 , R 2 , R 3 , R 4 , R 5 , R 9 , R 10 , R 12 , R 13 , and R 14 is, independently, hydrogen, a hydrocarbyl, or a substituted hydrocarbyl, where adjacent R groups optionally form cyclic fused ring systems;
each R 7 and R 15 is, independently,
—O(R*)— where R* is independently hydrogen, halogen, linear hydrocarbyl, or substituted hydrocarbyl, or -E(R) n —, where E is carbon, silicon, germanium, nitrogen, phosphorus, sulfur, or halogen; n is 0, 1, 2, or 3; each R is independently hydrogen, halogen, hydrocarbyl, or substituted hydrocarbyl; when E is C, Si, or Ge, then n is 2 or 3; when E is N or P, then n is 2; when E is S, then n is 1; and when E is halogen, n is 0; and
each R 6 and R 8 is, independently, a hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, or silylcarbyl.

2. The catalyst compound of claim 1 , wherein M is scandium and M* is scandium.

3. The catalyst compound of claim 1 , wherein E is carbon.

4. The catalyst compound of claim 1 , wherein each R 1 , R 2 , R 3 , R 4 , R 5 , R 9 , R 10 , R 12 , R 13 , and R 14 is, independently, hydrogen, methyl, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, CH 2 SiMe 3 , benzyl, CH 2 CMe 3 , CH(SiMe 3 ) 2 , CH 2 SiPh 3 , CH 2 CMe 2 Ph or an isomer thereof; and/or R 6 and R 8 are independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isomers thereof, chloro, iodo, bromo, fluoro, SiMe 3 , SiPh 3 , and CH 2 SiMe 3 , CH 2 SiPh 3 , CH 2 SiMe 2 Ph, CH 2 SiMePh 2 , or CH(SiMe 3 ) 2 .

5. The catalyst compound of claim 1 , wherein the catalyst is represented by the formula (II):

6. The catalyst compound of claim 1 , wherein M is scandium or yttrium and M* is scandium or yttrium.

7. The catalyst compound of claim 1 , wherein each R 1 , R 2 , R 3 , R 4 , R 5 , R 9 , R 10 , R 12 , R 13 , and R 14 is, independently, hydrogen, a hydrocarbyl, or a substituted hydrocarbyl, where adjacent R groups optionally form indene or fluorine.

8. A catalyst system comprising an activator and a catalyst compound represented by the formula:

where M is a group 3 metal;
M* is a group 3 metal;
each R 1 , R 2 , R 3 , R 4 , R 5 , R 9 , R 10 , R 12 , R 13 , and R 14 is, independently, hydrogen, a hydrocarbyl, or a substituted hydrocarbyl, where adjacent R groups optionally form cyclic fused ring systems;
each R 7 and R 15 is, independently, -E(R) n —, where E is carbon, silicon, germanium, nitrogen, phosphorus, oxygen, sulfur, or halogen; n is 0, 1, 2, or 3; each R is independently hydrogen, halogen, hydrocarbyl, or substituted hydrocarbyl; and when E is halogen, n is 0; and
each R 6 and R 8 is, independently, a hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, or silylcarbyl.

9. The catalyst system of claim 8 , wherein M is scandium and M* is scandium.

10. The catalyst system of claim 8 , wherein E is Carbon.

11. The catalyst system of claim 8 , wherein each R 1 , R 2 , R 3 , R 4 , R 5 , R 9 , R 10 , R 12 , R 13 , and R 14 is, independently, hydrogen, methyl, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, CH 2 SiMe 3 , benzyl, CH 2 CMe 3 , CH(SiMe 3 ) 2 , CH 2 SiPh 3 , CH 2 CMe 2 Ph or an isomer thereof; and/or R 6 and R 8 are independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isomers thereof, chloro, iodo, bromo, fluoro, or a silylcarbyl.

12. The catalyst system of claim 8 , wherein the catalyst is represented by the formula:

13. The catalyst system of claim 8 , wherein the activator comprises alumoxane.

14. The catalyst system of claim 8 , wherein the activator comprises a non-coordinating anion activator.

15. The catalyst system of claim 8 , wherein the activator is represented by the formula:
Z d + (A d− )
wherein Z is (L-H) or a reducible Lewis Acid, L is a neutral Lewis base; H is hydrogen; (L-H) + is a Bronsted acid; A d− is a non-coordinating anion having the charge d−; and d is an integer from 1 to 3.

16. The catalyst system of claim 8 , wherein the activator is represented by the formula:
Z d + (A d− )
wherein A d− is a non-coordinating anion having the charge d−; d is an integer from 1 to 3, and Z is a reducible Lewis acid represented by the formula: (Ar 3 C + ), where Ar is aryl or aryl substituted with a heteroatom, a C 1 to C 40 hydrocarbyl, or a substituted C 1 to C 40 hydrocarbyl.

17. The catalyst system of claim 8 , wherein the activator comprises one or more of:
N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate; triphenylcarbenium tetrakis(pentafluorophenyl)borate; trimethylammonium tetrakis(perfluoronaphthyl)borate; triethylammonium tetrakis(perfluoronaphthyl)borate; tripropylammonium tetrakis(perfluoronaphthyl)borate; tri(n-butyl)ammonium tetrakis(perfluoronaphthyl)borate; tri(t-butyl)ammonium tetrakis(perfluoronaphthyl)borate; N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate; N,N-diethylanilinium tetrakis(perfluoronaphthyl)borate; N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(perfluoronaphthyl)borate; tropillium tetrakis(perfluoronaphthyl)borate; triphenylcarbenium tetrakis(perfluoronaphthyl)borate; triphenylphosphonium tetrakis(perfluoronaphthyl)borate; triethylsilylium tetrakis(perfluoronaphthyl)borate; benzene(diazonium) tetrakis(perfluoronaphthyl)borate; trimethylammonium tetrakis(perfluorobiphenyl)borate; triethylammonium tetrakis(perfluorobiphenyl)borate; tripropylammonium tetrakis(perfluorobiphenyl)borate; tri(n-butyl)ammonium tetrakis(perfluorobiphenyl)borate; tri(t-butyl)ammonium tetrakis(perfluorobiphenyl)borate; N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate; N,N-diethylanilinium tetrakis(perfluorobiphenyl)borate; N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(perfluorobiphenyl)borate; tropillium tetrakis(perfluorobiphenyl)borate; triphenylcarbenium tetrakis(perfluorobiphenyl)borate; triphenylphosphonium tetrakis(perfluorobiphenyl)borate; triethylsilylium tetrakis(perfluorobiphenyl)borate; benzene(diazonium) tetrakis(perfluorobiphenyl)borate; [4-t-butyl-PhNMe 2 H][(C 6 F 3 (C 6 F 5 ) 2 ) 4 B]; trimethylammonium tetraphenylborate; triethylammonium tetraphenylborate; tripropylammonium tetraphenylborate; tri(n-butyl)ammonium tetraphenylborate; tri(t-butyl)ammonium tetraphenylborate; N,N-dimethylanilinium tetraphenylborate; N,N-diethylanilinium tetraphenylborate; N,N-dimethyl-(2,4,6-trimethylanilinium) tetraphenylborate; tropillium tetraphenylborate; triphenylcarbenium tetraphenylborate; triphenylphosphonium tetraphenylborate; triethylsilylium tetraphenylborate; benzene(diazonium)tetraphenylborate; trimethylammonium tetrakis(pentafluorophenyl)borate; triethylammonium tetrakis(pentafluorophenyl)borate; tripropylammonium tetrakis(pentafluorophenyl)borate; tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate; tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate; N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate; N,N-diethylanilinium tetra

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Alliger Glen E
• Giovannangeli Roger A

Classifications

• C08F36/00 Primary

  Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds (C08F32/00 takes precedence) · CPC title

• C07F17/00 Primary

  Metallocenes · CPC title

• C08F10/02

  Ethene · CPC title

• C07F5/00

  Compounds containing elements of Groups 3 or 13 of the Periodic Table · CPC title

• B01J2523/63

  Selenium · CPC title