Group 6 transition metal catalyst compound and use thereof

Patent metadata

Field	Value
Publication number	US-10519261-B2
Application number	US-201916401653-A
Country	US
Kind code	B2
Filing date	May 2, 2019
Priority date	Mar 23, 2015
Publication date	Dec 31, 2019
Grant date	Dec 31, 2019

Abstract

This invention relates to a catalyst system comprising a half sandwich chromocene compound featuring a tethered P-donor, with an activator and optional supportation on silica which produces ethylene homopolymer or copolymer.

First claim

What is claimed is:

1. A process to polymerize olefins comprising contacting ethylene and one or more alpha-olefins with a catalyst system comprising activator, catalyst compound, and support where the catalyst compound is represented by Formula I:

where
T is a bridging group represented by the formula, (R* 2 G) g , where each G is Si or Ge, g is 1, and each R* is, independently, hydrogen, halogen, C 1 to C 20 hydrocarbyl or a C 1 to C 20 substituted hydrocarbyl, and two or more R* optionally form a cyclic structure including a saturated cyclic or fused ring system; P is phosphorus; M* is Cr, Mo, or W; each X, is independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and a combination thereof, including that two X's optionally form a part of a fused ring or a ring system;

each R 1 , R 2 , R 3 , and R 4 is independently, hydrogen, a C 1 to C 12 hydrocarbyl, a substituted C 1 to C 12 hydrocarbyl, a heteroatom, or substituted heteroatom group; and
each R 5 and R 6 is, independently, a C 1 to C 12 hydrocarbyl, a substituted C 1 to C 12 hydrocarbyl, a heteroatom, or substituted heteroatom group, where the R 5 and R 6 groups optionally form a fused ring or multicenter fused ring system where the rings may be aromatic, partially saturated or saturated.

2. The process of claim 1 , wherein M* is Cr.

3. The process of claim 1 , wherein each R 1 , R 2 , R 3 , and R 4 is, independently, hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, docecyl, or an isomer thereof, Cl, Br, F, or I.

4. The process of claim 1 , wherein the P(R 5 )(R 6 ) fragment is a neutral donor ligand.

5. The process of claim 1 , wherein the P(R 5 )(R 6 ) fragment is selected from the group consisting of diethylphosphino, diphenylphosphino, di-t-butylphosphino, dicyclohexylphosphino, di-p-tolylphosphino, and substituted analogs thereof.

6. The process of claim 1 , wherein each R 5 and R 6 , is, independently, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, docecyl, or an isomer thereof, or Cl, Br, F, or I; and each R 1 , R 2 , R 3 , and R 4 is, independently, selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, docecyl, an isomer thereof, Cl, F, I, and Br.

7. The process of claim 1 , wherein each X is independently selected from chloride, bromide, methyl, ethyl, propyl, butyl or pentyl.

8. The process of claim 1 , wherein each R* is, independently, C 1 to C 20 hydrocarbyl or a C 1 to C 20 substituted hydrocarbyl.

9. A process to polymerize olefins comprising contacting ethylene and one or more alpha-olefins with a catalyst system comprising activator, catalyst compound, and support, where the catalyst compound comprises one or more of:
tetramethyl(diethylphosphinodimethylsilyl)cyclopentadienylchromium(III) dichloride,
tetramethyl(diphenylphosphinodimethylsilyl)cyclopentadienylchromium(III) dichloride,
tetramethyl(di-p-tolylphosphinodimethylsilyl)cyclopentadienylchromium(III) dichloride,
tetramethyl(dicyclohexylphosphinodimethylsilyl)cyclopentadienylchromium(III) dichloride, and
tetramethyl(di-t-butylphosphinodimethylsilyl)cyclopentadienylchromium(III) dichloride.

10. A process to polymerize olefins comprising contacting ethylene and one or more alpha-olefins with a catalyst system comprising activator, catalyst compound, and a support where the catalyst compound is represented by Formula I:

where
T is a bridging group represented by the formula, (R* 2 G) g , where each G is C, Si, or Ge, g is 1, and each R* is, independently, hydrogen, halogen, C 1 to C 20 hydrocarbyl or a C 1 to C 20 substituted hydrocarbyl, and two or more R* optionally form a cyclic structure including a saturated cyclic or fused ring system; P is phosphorus: M* is Cr, Mo, or W; each X, is independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and a combination thereof, including that two X's optionally form a part of a fused ring or a ring system;
each R 1 , R 2 , R 3 , and R 4 is independently, hydrogen, a C 1 to C 12 hydrocarbyl, a substituted C 1 to C 12 hydrocarbyl, a heteroatom, or substituted heteroatom group; and
each R 5 and R 6 is, independently, a C 1 to C 12 hydrocarbyl, a substituted C 1 to C 12 hydrocarbyl, a heteroatom, or substituted heteroatom group, where the R 5 and R 6 groups optionally form a fused ring or multicenter fused ring system where the rings are aromatic, partially saturated or saturated, and
the support is silica.

11. The process of claim 1 , wherein the activator comprises alumoxane.

12. The process of claim 1 , wherein alumoxane is present at a molar ratio of aluminum to catalyst compound transition metal of 100:1 or more.

13. The process of claim 1 , wherein the activator comprises a non-coordinating anion activator.

14. The process of claim 1 , wherein 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.

15. The process of claim 1 , wherein 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.

16. The process of claim 1 , wherein the activator is 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)bora

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Alliger Glen E

Classifications

• C08F210/16 Primary

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

• C08F4/63912

  in combination with an organoaluminium compound · CPC title

• C08F4/63916

  supported on a carrier, e.g. silica, MgCl2, polymer · CPC title

• C07F17/00

  Metallocenes · CPC title

• C08F4/69

  Chromium, molybdenum, tungsten or compounds thereof · CPC title