Metallocene dimer selective catalysts and processes to produce poly alpha-olefin dimers

Patent metadata

Field	Value
Publication number	US-11021553-B2
Application number	US-201916537364-A
Country	US
Kind code	B2
Filing date	Aug 9, 2019
Priority date	Feb 12, 2018
Publication date	Jun 1, 2021
Grant date	Jun 1, 2021

Abstract

The present disclosure generally relates to processes to produce alpha-olefin oligomers and poly alpha-olefins. In an embodiment, the present disclosure provides a process to produce a poly alpha-olefin (PAO), the process including:
introducing a C 6 -C 32 alpha-olefin and a catalyst system comprising activator and a metallocene compound into a continuous stirred tank reactor or a continuous tubular reactor under reaction conditions, wherein the alpha-olefin is introduced to the reactor at a flow rate of about 100 g/hr or more; and obtaining a product comprising PAO dimer and optional higher oligomers of alpha-olefin, or a combination thereof, the PAO dimer comprising 96 mol % or more of vinylidene, based on total moles of vinylidene, disubstituted vinylene, and trisubstituted vinylene in the product. In at least one embodiment, a process includes functionalizing and/or hydrogenating a PAO product of the present disclosure. In at least one embodiment, a blend includes a PAO product of the present disclosure.

First claim

What is claimed is:

1. A process to produce a poly alpha-olefin (PAO), the process comprising:
introducing a C 6 -C 32 alpha-olefin and a catalyst system comprising activator and a metallocene compound into a continuous stirred tank reactor or a continuous tubular reactor under reaction conditions, wherein the alpha-olefin is introduced to the reactor at a flow rate of at least 100 g/hr; and
obtaining a product comprising PAO dimer and optional higher oligomers of alpha-olefin, or a combination thereof, the PAO dimer comprising 96 mol % or more of vinylidene, based on total moles of vinylidene, disubstituted vinylene, and trisubstituted vinylene in the product, and the metallocene compound is represented by the formula:

wherein:
each of R 1 , R 2 , and R 3 is independently hydrogen, a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 hydrocarbyl group, wherein at least one of R 1 , R 2 , and R 3 is not hydrogen and at least one of R 1 , R 2 , and R 3 is hydrogen;
each of R 4 , R 5 , R 6 , and R 7 is independently hydrogen, a substituted or unsubstituted linear, branched, or cyclic C 1 -C 30 hydrocarbyl group, or one or more of R 4 and R 5 , R 5 and R 6 , or R 6 and R 7 , taken together with the carbon atoms in the indenyl ring to which they are directly connected, collectively form one or more substituted or unsubstituted rings fused to the indenyl ring;
each of R 8 , R 9 , R 10 , R 11 , and R 12 is independently a substituted or unsubstituted linear, branched, or cyclic C 1 -C 30 hydrocarbyl, silylcarbyl, or germanyl group;
M is a group 3, 4 or 5 transition metal;
each X is independently a halogen, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a diene, an amine, a phosphine, an ether, or a C 1 -C 20 substituted or unsubstituted linear, branched, or cyclic hydrocarbyl group, or optionally two or more X moieties may together form a fused ring or ring system; and
m is an integer equal to 1, 2, or 3.

2. The process of claim 1 , wherein the metallocene compound is represented by the formula:

wherein:
each of R 1 , R 2 , and R 3 is independently hydrogen or a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 hydrocarbyl or silylcarbyl group;
each of R 4 and R 7 is independently hydrogen, a substituted or unsubstituted linear, branched, or cyclic C 1 -C 30 hydrocarbyl or silylcarbyl group;
each of R 8 , R 9 , R 10 , R 11 , and R 12 is independently a hydrogen, or a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 hydrocarbyl, silylcarbyl, or germanyl group, or optionally at least three of R 8 , R 9 , R 10 , R 11 , and R 12 are not hydrogen;
each of R 13 , R 14 , R 15 , R 16 , R 17 , and R 18 is independently hydrogen or a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 hydrocarbyl or silylcarbyl group;
M is a group 3, 4 or 5 transition metal;
each X is independently a halogen, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a diene, an amine, a phosphine, an ether, or a C 1 -C 20 substituted or unsubstituted linear, branched, or cyclic hydrocarbyl group, or optionally two or more X moieties may together form a fused ring or ring system; and
m is an integer equal to 1, 2, or 3.

3. The process of claim 1 , wherein the reaction conditions comprise a reactor temperature of about 120° C. or greater and a reactor pressure of from 15 psia to 750 psia.

4. The process of claim 1 , wherein the reaction conditions comprise a catalyst loading of at least 10,000 g alpha-olefin (gAO) per gram of catalyst (gCat).

5. The process of claim 1 , wherein the reaction conditions comprise a flow rate of the catalyst system of at least 6 gCat/hr.

6. The process of claim 1 , wherein the reaction conditions comprise a reactor residence time of less than 5 hours.

7. The process of claim 1 , wherein the product further comprises, based on total moles (100 mol %) of vinylidene, disubstituted vinylene, and trisubstituted vinylene in the product:
up to 4 mol % trisubstituted vinylene,
up to 4 mol % disubstituted vinylene, or
up to 4 mol % trisubstituted vinylene and disubstituted vinylene.

8. The process of claim 7 , wherein the product comprises, based on total moles (100 mol %) of vinylidene, disubstituted vinylene, and trisubstituted vinylene in the product:
98 mol % or more vinylidene, and
up to 2 mol % trisubstituted vinylene,
up to 2 mol % disubstituted vinylene, or
up to 2 mol % trisubstituted vinylene and disubstituted vinylene.

9. The process of claim 8 , wherein the product comprises, based on total moles (100 mol %) of vinylidene, disubstituted vinylene, and trisubstituted vinylene in the product:
98 mol % or more vinylidene, and
up to 1 mol % trisubstituted vinylene,
up to 1 mol % disubstituted vinylene, or
up to 1 mol % trisubstituted vinylene and disubstituted vinylene.

10. The process of claim 9 , wherein the product comprises, based on total moles (100 mol %) of vinylidene, disubstituted vinylene, and trisubstituted vinylene in the product:
98 mol % or more vinylidene, and
up to 0.5 mol % trisubstituted vinylene,
up to 0.5 mol % disubstituted vinylene, or
up to 0.5 mol % trisubstituted vinylene and disubstituted vinylene.

11. The process of claim 1 , wherein each of R 1 , R 2 , and R 3 is independently hydrogen or a substituted or unsubstituted linear, branched, or cyclic C 1 -C 6 hydrocarbyl group.

12. The process of claim 11 , wherein one of R 1 , R 2 , and R 3 is a substituted or unsubstituted linear, branched, or cyclic C 1 -C 6 hydrocarbyl group, and two of R 1 , R 2 , and R 3 are hydrogen.

13. The process of claim 1 , wherein M is Hf.

14. The process of claim 1 , wherein the metallocene compound is represented by the formula:

or a combination thereof.

15. The process of claim 1 , wherein the activator comprises one or more of:
N,N-dimethylanilinium tetrakis(perfluorophenyl)borate,
N,N-dimethylanilinium tetrakis(perfluoro-naphthyl)borate,
triphenylcarbonium tetrakis(perfluorophenyl)borate,
triphenylcarbonium tetrakis(perfluoronaphthyl)borate,
N,N-dimethylanilinium tetrakis(perfluorophenyl)aluminate,
N,N-dimethylanilinium tetrakis(perfluoronaphthyl)aluminate,
alumoxane,
a modified alumoxane, and
an aluminum alkyl.

16. The process of claim 1 , wherein the C 6 -C 32 alpha-olefin is selected from the group consisting of 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, and combinations thereof.

17. The process of claim 1 , wherein the C 6 -C 32 alpha-olefin is selected from the group consisting of 1-hexene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and combinations thereof.

18. The process of claim 1 , wherein the reaction conditions comprise a reactor temperature of from 130° C. to 180° C., a reactor pressure of from 15 psia to 750 psia, and a catalyst loading of from 25,000 g alpha-olefin (gAO) per 1 g catalyst (gCat) to 90,000 gAO/gCat.

19. The process of claim 18 , wherein the reactor conditions comprise a reactor temperature of from 130° C. to 148° C., a reactor pressure of from 30 psia to 100 psia, and a catalyst loading of from 25

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Chen Patrick C
• Rapp Jennifer L
• Yang Jian
• Canich Jo Ann M
• Zhou Hua
• Emett Craig J
• Lewis Kyle G
• Lotfizadehdehkordi Babak

Classifications

• C10N2030/02

  Pour-point; Viscosity index · CPC title

• C10N2030/08

  Resistance to extreme temperature · CPC title

• C07C2531/14

  of aluminium or boron · CPC title

• C07C5/03

  of non-aromatic carbon-to-carbon double bonds · CPC title

• C10N2030/06

  Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure · CPC title