Metallocene-catalyzed polyalpha-olefins

Patent metadata

Field	Value
Publication number	US-10968290-B2
Application number	US-201815921757-A
Country	US
Kind code	B2
Filing date	Mar 15, 2018
Priority date	Mar 28, 2017
Publication date	Apr 6, 2021
Grant date	Apr 6, 2021

Abstract

Unsaturated and hydrogenated polyalpha-olefin products can be made with a high selectivity toward vinylidenes and tri-substituted vinylenes combined, a high selectivity toward vinylidenes, and a low selectivity toward 1,2-di-substituted vinylenes by using a catalyst system comprising a metallocene compound having the following structure in the polymerization reaction:

First claim

What is claimed is:

1. A process for making a polyalpha-olefin (“PAO”), the process comprising:
contacting a C6-C30 alpha-olefin feed with a catalyst system comprising a metallocene compound in a polymerization reactor under polymerization conditions in the absence of hydrogen to effect a polymerization reaction to obtain a polymerization reaction mixture comprising vinylidenes, tri-substituted vinylenes, optionally 1,2-di-substituted vinylenes, and optionally vinyls; and
obtaining an unsaturated PAO product from the polymerization reaction mixture, wherein the unsaturated PAO product comprising, based on the total moles of vinyls, vinylidenes, 1,2-di-substituted vinylenes, and tri-substituted vinylenes contained therein:
80 to 90 mol % of vinylidenes;
0.1 to 10 mol % of 1,2-di-substituted vinylenes; and
0 to 10 mol % of vinyls, based on the total moles of vinyls, vinylidenes, 1,2-di-substituted vinylenes, and tri-substituted vinylenes contained therein,
wherein:
the metallocene compound has a structure represented by formula (F-MC) below comprising a first cyclopentadienyl ring directly connected with R 1 , R 2 , R 3 , and R 4 and a second cyclopentadienyl ring directly connected with R 5 , R 6 , R 7 , and R 8 :

wherein:
R 1 and R 4 are each independently a hydrogen, a substituted or unsubstituted linear, branched linear, or cyclic C1-C30 hydrocarbyl group,
R 2 and R 3 are each independently a substituted or unsubstituted linear, branched linear, or cyclic C1-C50 hydrocarbyl group, or
alternatively, two or more of R 1 , R 2 , R 3 , and R 4 , taken together, with the carbon atoms in the first cyclopentadienyl ring to which they are directly connected, form one or more substituted or unsubstituted ring annelated to the first cyclopentadienyl ring;
R 5 , R 6 , R 7 , and R 8 are each independently a hydrogen, or a substituted or unsubstituted linear, branched linear, or cyclic C1-C30 hydrocarbyl group, provided: R 6 and R 7 are not both hydrogen; or
alternatively, two or more of R 5 , R 6 , R 7 , and R 8 , taken together, with the intermediate carbon atoms in the second cyclopentadienyl ring to which they are directly connected, form one or more substituted or unsubstituted ring annelated to the second cyclopentadienyl ring;
provided: the first cyclopentadienyl ring and the second cyclopentadienyl ring are not annelated to ring structures simultaneously;
BG is a bridging group connected directly with both the first cyclopentadienyl ring and the second cyclopentadienyl ring;
M is a transition metal having a valency of v;
X, the same or different at each occurrence, is independently selected from halogens, Cl-C50 substituted or unsubstituted linear, branched, or cyclic hydrocarbyl groups; and
m is an integer equal to v-2.

2. The process of claim 1 , wherein M is selected from Ti, Zr, or Hf.

3. The process of claim 1 , wherein:
the polymerization reaction exhibits a selectivity toward 1,2-di-substituted vinylenes of at most 3%.

4. The process of claim 1 , wherein:
R 1 and R 4 are each independently a substituted or unsubstituted linear, branched linear, or cyclic C1-C30 hydrocarbyl group.

5. The process of claim 1 , wherein:
at least one of R 5 and R 8 is hydrogen.

6. The process of claim 4 , wherein:
the polymerization reaction exhibits a selectivity toward vinyls of at most 5%.

7. The process of claim 1 , wherein:
both R 5 and R 8 are each independently substituted or unsubstituted linear, branched linear, or cyclic C1-C50 hydrocarbyl group.

8. The process of claim 1 , wherein the bridging group -BG- is selected from

where G4 are, the same or different at each occurrence, independently selected from carbon, silicon, or germanium, or groups R 9 , the same or different at each occurrence, are each independently a C1-C30 substituted or unsubstituted linear, branched, or cyclic hydrocarbyl groups.

9. The process of claim 8 , wherein:
-BG- is selected from

where R 9 is selected from methyl, ethyl, benzyl, and halogen.

10. The process of claim 1 , wherein
M is selected from Zr and Hf;
X is independently selected from methyl, ethyl, benzyl, and halogen; and
m is 2.

11. The process of claim 1 , wherein the catalyst system further comprises a non-coordinating anion type activator.

12. The process of claim 1 , wherein:
the metallocene compound is selected from the following compounds I-1 to I-13, optical isomers of the following compounds I-1 to I-13, or combinations thereof:

13. The process of claim 1 , further comprising:
contacting the unsaturated PAO product with hydrogen to convert at least a portion of the unsaturated PAO product to a hydrogenated PAO product.

14. An unsaturated polyalpha-olefin (“PAO”) product obtained by an oligomerization reaction of one or more C6-C30 alpha-olefin monomers in the absence of hydrogen, the product comprising, based on the total moles of vinyls, vinylidenes, 1,2-di-substituted vinylenes, and tri-substituted vinylenes contained therein:
80 to 90 mol % of vinylidenes;
0.1 to 10 mol % of 1,2-di-substituted vinylenes; and
0 to 10 mol % of vinyls, based on the total moles of vinyls, vinylidenes, 1,2-di-substituted vinylenes, and tri-substituted vinylenes contained therein.

15. The unsaturated PAO product of claim 14 , comprising, based on the total moles of vinyls, vinylidenes, 1,2-di-substituted vinylenes, and tri-substituted vinylenes contained therein:
at most 5% of 1,2-di-substituted vinylenes; and
at most 5% of vinyls.

16. The unsaturated PAO product of claim 14 , comprising, based on the total moles of vinyls, vinylidenes, 1,2-disubstituted vinylenes, and tri-substituted vinylenes contained therein:
at least 90 mol % of vinylidenes and tri-substituted vinylenes combined.

17. A partially saturated or substantially all saturated polyalpha-olefins product, obtained by hydrogenating the unsaturated PAO product of claim 14 .

18. A partially saturated or substantially all saturated polyalpha-olefins product, obtainable by hydrogenating the unsaturated PAO product of claim 1 .

19. The unsaturated PAO product of claim 16 comprising, based on the total moles of vinyls, vinylidenes, 1,2-disubstituted vinylenes, and tri-substituted vinylenes contained therein:
at most 3% of 1,2-di-substituted vinylenes.

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Crowther Donna J
• Chen Patrick C
• Lovell Jacqueline A
• Islam Md Safatul

Classifications

• C10M107/02

  Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation · CPC title

• C08F110/14 Primary

  Monomers containing five or more carbon atoms · CPC title

• C07C2/22

  Metal halides; Complexes thereof with organic compounds · CPC title

• B01J2531/46

  Titanium · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title