Catalyst systems and processes for poly alpha-olefin having high vinylidene content

Patent metadata

Field	Value
Publication number	US-12162968-B2
Application number	US-202318311971-A
Country	US
Kind code	B2
Filing date	May 4, 2023
Priority date	Feb 12, 2018
Publication date	Dec 10, 2024
Grant date	Dec 10, 2024

Abstract

A process for making a poly alpha-olefin (PAO) having a relatively high vinylidene content (or combined vinylidene and tri-substituted vinylene content) and a relatively low vinyl and/or di-substituted vinylene content, as well as a relatively low molecular weight. The process includes: contacting a feed containing a C 2 -C 32 alpha-olefin with a catalyst system comprising activator and a bis-cyclopentadienyl metallocene compound, typically a cyclopentadienyl-benzindenyl group 4 transition metal compound.

First claim

What is claimed is:

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

wherein:
a first one of R 1 and R 3 is a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 hydrocarbyl group;
a second one of R 1 , R 2 , and R 3 is a hydrogen;
a third one of R 1 , R 2 , and R 3 is a hydrogen;
R 6 and R 18 are each independently hydrogen, a substituted or unsubstituted linear, branched, or cyclic C 1 -C 30 hydrocarbyl group, and R 7 and R 17 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 annelated to the indenyl ring, wherein the ring annelated to the indenyl ring comprises one or more saturated carbon atoms;
R 12 , R 13 , R 14 , R 15 , and R 16 are each independently a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 hydrocarbyl group or R 16 is a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 silylcarbyl group;
each X is independently a halogen, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a diene, an amine, a phosphine, an ether, a C 1 -C 20 substituted or unsubstituted linear, branched, or cyclic hydrocarbyl group, or two or more X moieties together form a fused ring or ring system;
M is a group 3, 4 or 5 transition metal having an integer coordination number of v; and
m is an integer equal to v-2.

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

wherein:
R 1 and R 2 are hydrogen;
Q is a linear, branched, or cyclic C 1 -C 6 hydrocarbyl group;
R 19 is carbon or silicon;
R 20 , R 21 , and R 22 are independently hydrogen or a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 hydrocarbyl group, wherein at least two of R 20 , R 21 , and R 22 are a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 hydrocarbyl group;
R 6 and R 18 are each independently hydrogen, a substituted or unsubstituted linear, branched, or cyclic C 1 -C 30 hydrocarbyl group, and R 7 and R 17 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 annelated to the indenyl ring, wherein the ring annelated to the indenyl ring comprises one or more saturated carbon atoms;
R 12 , R 13 , R 14 , R 15 , and R 16 are each independently a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 hydrocarbyl group;
each X is independently a halogen, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a diene, an amine, a phosphine, an ether, a C 1 -C 20 substituted or unsubstituted linear, branched, or cyclic hydrocarbyl group, or two or more X moieties together form a fused ring or ring system;
M is a group 3, 4 or 5 transition metal having an integer coordination number of v; and
m is an integer equal to v-2.

3. The catalyst compound of claim 1 , wherein the compound is represented by formula:

wherein:
a first one of R 1 and R 3 is a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 hydrocarbyl group;
a second one of R 1 , R 2 , and R 3 is a hydrogen;
a third one of R 1 , R 2 , and R 3 is a hydrogen;
R 6 , R 18 , R 29 , R 24 , R 25 , R 26 , R 27 , and R 28 are each independently hydrogen, a substituted or unsubstituted linear, branched, or cyclic C 1 -C 30 hydrocarbyl group, or two of R 6 , R 18 , R 29 , R 24 , R 25 , R 26 , and R 27 taken together with the carbon atoms in the cyclopentan-indenyl ring to which they are directly connected, collectively form one or more substituted or unsubstituted rings annelated to the cyclopentan-indenyl ring;
R 12 , R 13 , R 14 , R 15 , and R 16 are each independently a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 hydrocarbyl group;
each X is independently a halogen, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a diene, an amine, a phosphine, an ether, a C 1 -C 20 substituted or unsubstituted linear, branched, or cyclic hydrocarbyl group, or two or more X moieties together form a fused ring or ring system;
M is a group 3, 4 or 5 transition metal having an integer coordination number of v; and
m is an integer equal to v-2.

4. The catalyst compound of claim 2 , wherein Q is methylene and R 19 is carbon.

5. The catalyst compound of claim 2 , wherein Q is methylene.

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

wherein:
R 1 and R 2 are hydrogen;
Q is a linear, branched, or cyclic C 1 -C 6 hydrocarbyl group;
R 19 is silicon;
R 20 , R 21 , and R 22 are independently hydrogen or a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 hydrocarbyl group, wherein at least two of R 20 , R 21 , and R 22 are a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 hydrocarbyl group;
R 6 and R 18 are each independently hydrogen, a substituted or unsubstituted linear, branched, or cyclic C 1 -C 30 hydrocarbyl group, and R 7 and R 17 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 annelated to the indenyl ring, wherein the ring annelated to the indenyl ring comprises one or more saturated carbon atoms;
R 12 , R 13 , R 14 , R 15 , and R 16 are each independently a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 hydrocarbyl group;
each X is independently a halogen, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a diene, an amine, a phosphine, an ether, a C 1 -C 20 substituted or unsubstituted linear, branched, or cyclic hydrocarbyl group, or two or more X moieties together form a fused ring or ring system;
M is a group 3, 4 or 5 transition metal having an integer coordination number of v; and
m is an integer equal to v-2.

7. The catalyst compound of claim 2 , wherein Q is methylene; R 21 is hydrogen; and R 20 and R 22 are methyl.

8. The catalyst compound of claim 3 , wherein each of R 27 and R 28 is hydrogen.

9. The catalyst compound of claim 8 , wherein each of R 24 and R 29 is hydrogen.

10. The catalyst compound of claim 9 , wherein each of R 25 and R 26 is independently hydrogen or methyl.

11. The catalyst compound of claim 8 , wherein:
a first one of R 1 and R 3 is a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 hydrocarbyl group;
a second one of R 1 , R 2 , and R 3 is hydrogen; and
a third one of R 1 , R 2 , and R 3 is hydrogen.

12. The catalyst compound of claim 11 , wherein the first one of R 1 and R 3 is neopentyl.

13. The catalyst compound of claim 11 , wherein the first one of R 1 and R 3 is isobutyl.

14. The catalyst compound of claim 11 , wherein the first one of R 1 and R 3 is silylneopentyl.

15. The catalyst compound of claim 11 , wherein R 12 , R 13 , R 14 , R 15 , and R 16 are each methyl.

16. The catalyst compound of claim 15 , wherein R 6 and R 18 are each hydrogen.

17. The catalyst compound of claim 11 , wherein M is hafnium.

18. The catalyst compound of

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Yang Jian
• Canich Jo Ann M
• Zhou Hua
• Rapp Jennifer L

Classifications

• C07C17/00

  Preparation of halogenated hydrocarbons · CPC title

• C07C2/32

  as complexes, e.g. acetyl-acetonates {(complexes of salts of acids of halogen C07C2/20)} · CPC title

• C07C2/30

  containing metal-to-carbon bond; Metal hydrides · CPC title

• C08F4/65922

  containing at least two cyclopentadienyl rings, fused or not · CPC title

• C08F4/65908

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