Process for making vinylidene olefin

Patent metadata

Field	Value
Publication number	US-10654766-B2
Application number	US-201815988683-A
Country	US
Kind code	B2
Filing date	May 24, 2018
Priority date	Aug 28, 2017
Publication date	May 19, 2020
Grant date	May 19, 2020

Abstract

This disclosure relates to a continuous process for making a dimer from a terminal olefin in the presence of a catalyst system comprising a metallocene compound and alumoxane.

First claim

What is claimed is:

1. A continuous process for making a vinylidene olefin dimer from a terminal olefin comprising at least eight (8) carbon atoms per molecule, comprising:
feeding a monomer stream comprising the terminal olefin into a reactor at a first feeding rate of R(to) moles of the terminal olefin per hour;
feeding a metallocene compound having a formula Cp(Bg) n MX 2 Cp′ into the reactor at a second feeding rate of R(mc) moles of the metallocene compound per hour, wherein M is selected from Hf and Zr; each X is independently a halogen or a hydrocarbyl group; Cp and Cp′, the same or different, independently represents a cyclopentadienyl, alkyl-substituted cyclopentadienyl, indenyl, alkyl-substituted indenyl, 4,5,6,7-tetrahydro-2H-indenyl, alkyl-substituted 4,5,6,7-tetrahydro-2H-indenyl, 9H-fluorenyl, and alkyl-substituted 9H-fluorenyl; each Bg is a bridging group covalently linking Cp and Cp′; and n is 0, 1, or 2;
feeding an alumoxane feed into the reactor at a third feeding rate corresponding to R(Al) moles of aluminum atoms per hour, wherein the alumoxane feed comprises metal elements other than aluminum, alkali metals, alkaline earth metals, and the metal contained in the metallocene compound at a total concentration no greater than 50,000 ppm by mole, based on the total moles of all metal atoms present in the alumoxane feed;
conducting oligomerization reaction in the reactor at a temperature in the range from 50 to 90° C., wherein the oligomerization reaction has a conversion of the terminal olefin of no less than 70%;
drawing a stream of oligomerization reaction mixture from the reactor comprising unreacted terminal olefin, a dimer of the terminal olefin, and a trimer of the terminal olefin, wherein:
the first feeding rate, the second feeding rate, and the third feeding rate are chosen such that:
350< R ( to )/ R ( mc )≤750,

2≤ R ( Al )/ R ( mc )≤10,

the oligomerization reaction has a selectivity of the terminal olefin toward trimer no greater than 5% and
the oligomerization reaction has a selectivity of the terminal olefin toward dimers of at least 95%; wherein the dimers comprise the vinylidene olefin dimer.

2. The process of claim 1 , wherein both Cp and Cp′ are cyclopentadienyl, and n is zero.

3. The process of claim 1 , wherein in the metallocene compound, M is Zr.

4. The process of claim 1 , wherein in the metallocene compound, X is Cl.

5. The process of claim 1 , wherein the alumoxane is methyl alumoxane.

6. The process of claim 1 , wherein
600< R ( to )/ R ( mc )<750.

7. The process of claim 1 , wherein:
2≤ R ( Al )/ R ( mc )≤5.

8. The process of claim 1 , wherein:
the oligomerization reaction has a selectivity of the terminal olefin toward the trimer of no greater than 3%.

9. The process of claim 1 , wherein:
the oligomerization reaction has a selectivity of the terminal olefin toward vinylidene oligomers of at least 95%.

10. The process of claim 9 , wherein:
the oligomerization reaction has a selectivity of the terminal olefin toward vinylidene oligomers of at least 98%.

11. The process of claim 1 , wherein:
the oligomerization reaction has a selectivity of the terminal olefin toward internal olefin oligomers of at most 5%.

12. The process of claim 11 , wherein:
the oligomerization reaction has a selectivity of the terminal olefin internal olefin oligomers of at most 2%.

13. The process of claim 1 , wherein:
The oligomerization reaction has a selectivity of the terminal olefin toward tri-substituted oligomers of at most 5%.

14. The process of claim 13 , wherein:
the oligomerization reaction has a selectivity of the terminal olefin toward tri-substituted oligomers of at most 2%.

15. The process of claim 1 , wherein the oligomerization reaction has a selectivity of the terminal olefin toward dimers of at least 97.5%.

16. The process of claim 1 , further comprising:
quenching the stream of oligomerization reaction mixture using a quenching agent.

17. The process of claim 1 , further comprising:
obtaining a recycle stream comprising the unreacted terminal olefin from the oligomerization reaction mixture; and
recycling the recycle stream of the unreacted terminal olefin to the reactor as a portion of the monomer stream.

18. The process of claim 1 , wherein:
the monomer stream comprises one or more of linear terminal olefins selected from 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-icosene.

19. The process of claim 18 , wherein:
the monomer stream consists essentially of one linear terminal olefin selected from selected from 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-icosene.

20. The process of claim 1 , further comprising:
obtaining a dimer product consisting essentially of the dimer of the terminal olefin from the stream of the oligomerization reaction mixture without a step of removing the trimer.

21. The process of claim 1 , which is carried out in a continuously stirred tank reactor.

22. The process of claim 1 , further comprising feeding an inert solvent into the reactor.

23. The process of claim 1 , wherein the oligomerization reaction has a selectivity of the terminal olefin toward dimers of at least 98%.

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Chen Patrick C
• Seshie Delanyo K
• Islam Md Safatul

Classifications

• C07C2531/22

  Organic complexes · CPC title

• C07C2531/14

  of aluminium or boron · CPC title

• C07C2/34 Primary

  Metal-hydrocarbon complexes · CPC title

• C07C11/02

  Alkenes · CPC title