Processes to produce poly alpha-olefin trimers

Patent metadata

Field	Value
Publication number	US-11078308-B2
Application number	US-201916537349-A
Country	US
Kind code	B2
Filing date	Aug 9, 2019
Priority date	Feb 12, 2018
Publication date	Aug 3, 2021
Grant date	Aug 3, 2021

Abstract

The present disclosure generally relates to processes to produce alpha-olefin oligomers and poly alpha-olefins. In an embodiment, a process to produce a poly alpha-olefin (PAO) includes introducing a first alpha-olefin and a first catalyst system comprising a metallocene compound into a continuous stirred tank reactor or a continuous tubular reactor under first reactor conditions to form a first reactor effluent. The alpha-olefin is introduced to the reactor at a flow rate of about 100 g/hr or more. The first reactor effluent includes PAO dimer comprising at least 96 mol % of vinylidene and 4 mol % or less of trisubstituted vinylene and disubstituted vinylene, based on total moles of vinylidene, trisubstituted vinylene, and disubstituted vinylene. The method includes introducing the first reactor effluent, a second alpha-olefin and a second catalyst composition comprising an acid catalyst into a second reactor under second reactor conditions to form a second reactor effluent comprising PAO trimer.

First claim

What is claimed is:

1. A process to produce a poly alpha-olefin (PAO), comprising:
introducing a first group of one or more alpha-olefins and a first catalyst system comprising a metallocene compound into a continuous stirred tank reactor or a continuous tubular reactor under first reactor conditions, wherein the alpha-olefin is introduced to the reactor at a flow rate of about 100 g/hr or more, to form a first reactor effluent comprising PAO dimer comprising at least 96 mol % of vinylidene and 4 mol % or less of trisubstituted vinylene and disubstituted vinylene, based on total moles of vinylidene, trisubstituted vinylene, and disubstituted vinylene; and
introducing the first reactor effluent, a second group of one or more alpha-olefins and a second catalyst composition comprising an acid catalyst into a second reactor under second reactor conditions to form a second reactor effluent comprising PAO trimer,
wherein 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 a first 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 pair 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 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 a substituted or unsubstituted linear, branched linear, 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 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 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 first alpha-olefin is one or more C 6 -C 32 alpha-olefin.

4. The process of claim 1 , wherein the second alpha-olefin is one or more C 6 -C 32 alpha-olefin.

5. The process of claim 1 , wherein the acid catalyst is a Lewis acid.

6. The process of claim 1 , wherein the second reactor conditions comprise an acid catalyst loading of from about 5 mmolCat/100 gLAO to about 15 mmolCat/100 gLAO.

7. The process of claim 1 , wherein the second reactor conditions comprise a temperature of from about 10° C. to about 40° C.

8. The process of claim 1 , wherein the acid catalyst is BF 3 .

9. The process of claim 1 , wherein the amount of PAO trimer in the second reactor effluent is 75 wt % or more, based on a total weight of PAO dimer, PAO trimer, and higher oligomers, where the higher oligomers are oligomers that have degree of polymerization of 4 or more, of alpha-olefin in the second reactor effluent.

10. The process of claim 1 , wherein the second reactor effluent comprises, 75 wt % or more of PAO trimer, 9 wt % or less of PAO dimer, and 16 wt % or less of higher oligomers of alpha-olefin, based on a total weight of PAO dimer, PAO trimer, and higher oligomers of alpha-olefin in the second reactor effluent.

11. The process of claim 1 , wherein the amount of PAO trimer in the second reactor effluent is greater than 80 wt %, based on a total weight of PAO dimer, PAO trimer, and higher oligomers of alpha-olefin in the second reactor effluent.

12. The process of claim 1 , wherein the PAO dimer in the first reactor effluent further comprises, based on the total moles (100 mol %) of vinylidene, disubstituted vinylene, and trisubstituted vinylene in the PAO dimer in the first reactor effluent:
up to 4 mol % of trisubstituted vinylene,
up to 4 mol % of disubstituted vinylene, or
up to 4 mol % of trisubstituted vinylene and disubstituted vinylene.

13. A process to produce a poly alpha-olefin (PAO), comprising:
introducing a first group of one or more alpha-olefins and a first catalyst system comprising a metallocene compound into a continuous stirred tank reactor or a continuous tubular reactor under first reactor conditions, wherein the alpha-olefin is introduced to the reactor at a flow rate of about 100 g/hr or more, to form a first reactor effluent comprising PAO dimer comprising at least 96 mol % of vinylidene and 4 mol % or less of trisubstituted vinylene and disubstituted vinylene, based on total moles of vinylidene, trisubstituted vinylene, and disubstituted vinylene; and
introducing the first reactor effluent, a second group of one or more alpha-olefins and a second catalyst composition comprising an acid catalyst into a second reactor under second reactor conditions to form a second reactor effluent comprising PAO trimer,
wherein the PAO dimer in the first reactor effluent comprises, based on total moles (100 mol %) of vinylidene, disubstituted vinylene, and trisubstituted vinylene in the PAO dimer in the first reactor effluent:
98 mol % or more vinylidene, and up to 2 mol % of trisubstituted vinylene, and/or disubstituted vinylene.

14. The process of claim 1 , wherein the PAO dimer in the first reactor effluent further comprises, based on the total moles (100 mol %) of vinylidene, disubstituted vinylene, and trisubstituted vinylene in the PAO dimer in the first reactor effluent:
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.

15. The process of claim 1 , wherein the PAO dimer in the first reactor effluent further comprises, based on the total moles (100 mol %) of vinylidene, disubstituted vinylene, and trisubstituted vinylene in the PAO dimer in the first reactor effluent:
98 mol % or more

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Chen Patrick C
• Li Mark H
• Rapp Jennifer L
• Lotz Monica D
• Lotfizadehdehkordi Babak
• Emett Craig J
• Kuzhiyil Najeeb M
• Yang Jian

Classifications

• C10N2040/04

  Oil-bath; Gear-boxes; Automatic transmissions; Traction drives · CPC title

• C10N2070/00

  Specific manufacturing methods for lubricant compositions · CPC title

• C10M2203/045

  used as base material · CPC title

• C10N2040/08

  Hydraulic fluids, e.g. brake-fluids · CPC title

• C10M2205/0285

  used as base material · CPC title