Production of olefin dimers

Patent metadata

Field	Value
Publication number	US-10358397-B2
Application number	US-201815948323-A
Country	US
Kind code	B2
Filing date	Apr 9, 2018
Priority date	Jun 29, 2017
Publication date	Jul 23, 2019
Grant date	Jul 23, 2019

Abstract

A process for producing alpha-olefin dimers comprises contacting, at a temperature of 80° C. or more, a feedstock comprising at least one C 8+ (linear) alpha-olefin with a catalyst system comprising activator and one or more catalyst compounds represented by the formula:

where M is a Group 4 metal; n is 1, 2, or 3; R A is hydrogen or a C 1 to C 10 alkyl; each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 is independently selected from hydrogen and C 1 to C 10 alkyl; each X is independently selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, and a combination thereof, (two X's may form a part of a fused ring or a ring system), the contacting being conducted under conditions effective to oligomerize at least part of C 8+ alpha-olefin to produce an oligomerized product containing at least 30 wt % of the alpha-olefin dimer and at least 80 mol % of vinylidene unsaturation, where the conversion of the alpha olefin is at least 10 wt %, based upon the weight of the alpha olefin monomer entering the reactor and the weight of dimer produced.

First claim

What is claimed is:

1. A homogeneous process for producing alpha-olefin dimers, the process comprising: contacting, in a homogeneous phase and at a temperature of 80° C. or more, a feedstock consisting essentially of one or more C 8+ alpha-olefins and optionally ethylene, where the ethylene comprises from 0.1 to 10 wt % of the total feed, with a catalyst system comprising activator and one or more catalyst compounds represented by the formula:

where M is a Group 4 metal; n is 1, 2, or 3; R A is hydrogen or a C 1 to C 10 alkyl; each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 is independently selected from hydrogen and C 1 to C 10 alkyl, optionally wherein any two or more adjacent groups from R 1 through R 8 may be joined to form a cyclic or polycyclic ring structure; each X is independently selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, and a combination thereof, optionally two X's may form a part of a fused ring or a ring system, the contacting being conducted under conditions effective to oligomerize at least part of C 8+ alpha-olefin to produce an oligomer product containing at least 30 wt % of the alpha-olefin dimer, based upon the weight of the oligomer product produced, and at least 80 mol % of vinylidene unsaturation, where the conversion of the alpha olefin is at least 10 wt %, based upon the weight of the alpha olefin monomer entering the reactor and the weight of product produced.

2. The process of claim 1 , wherein the feedstock comprises at least one C 8 to C 20 alpha-olefin.

3. The process of claim 1 , wherein the feedstock comprises at least one C 8+ linear alpha-olefin.

4. The process of claim 1 , wherein the feedstock comprises ethylene.

5. The process of claim 1 , wherein M is Zr.

6. The process of claim 1 , wherein n is 1.

7. The process of claim 1 , wherein n is 2 or 3.

8. The process of claim 1 , wherein each X is independently selected from C 1 to C 5 alkyl groups, benzyl, and substituted benzyl.

9. The process of claim 1 , wherein R A is Me or tBu.

10. The process of claim 1 , wherein each of R 1 , R 2 , R 4 , R 5 , R 7 , and R 8 is H and R 3 and R 6 are tBu.

11. A process for producing alpha-olefin dimers, the process comprising: contacting, at a temperature of 80° C. or more, feedstock comprising one or more C 8+ alpha-olefins with a catalyst system comprising activator and one or more catalyst compounds selected from:

the contacting being conducted under conditions effective to oligomerize at least part of C 8+ alpha-olefin to produce an oligomer product containing at least 30 wt % of the alpha-olefin dimer, based upon the weight of the oligomer product produced, and at least 80 mol % of vinylidene unsaturation, where the conversion of the alpha olefin is at least 10 wt %, based upon the weight of the alpha olefin monomer entering the reactor and the weight of product produced.

12. The process of claim 1 , wherein the activator is represented by the formula:
(Z) d+ (A d− )
wherein Z is (L-H) or a reducible Lewis Acid, L is a neutral Lewis base; H is hydrogen; (L-H)+ is a Bronsted acid; A d− is a non-coordinating anion having the charge d−; and d is an integer from 1 to 3; optionally Z is represented by the formula: (Ar 3 C + ), where Ar is aryl or aryl substituted with a heteroatom, a C 1 to C 40 hydrocarbyl, or a substituted C 1 to C 40 hydrocarbyl.

13. The process of claim 1 , wherein the activator is one or more of: N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate; triphenylcarbenium tetrakis(pentafluorophenyl)borate; trimethylammonium tetrakis(perfluoronaphthyl)borate; triethylammonium tetrakis(perfluoronaphthyl)borate; tripropylammonium tetrakis(perfluoronaphthyl)borate; tri(n-butyl)ammonium tetrakis(perfluoronaphthyl)borate; tri(t-butyl)ammonium tetrakis(perfluoronaphthyl)borate; N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate; N,N-diethylanilinium tetrakis(perfluoronaphthyl)borate; N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(perfluoronaphthyl)borate; tropillium tetrakis(perfluoronaphthyl)borate; triphenylcarbenium tetrakis(perfluoronaphthyl)borate; triphenylphosphonium tetrakis(perfluoronaphthyl)borate; triethylsilylium tetrakis(perfluoronaphthyl)borate; benzene(diazonium) tetrakis(perfluoronaphthyl)borate; trimethylammonium tetrakis(perfluorobiphenyl)borate; triethylammonium tetrakis(perfluorobiphenyl)borate;
tripropylammonium tetrakis(perfluorobiphenyl)borate; tri(n-butyl)ammonium tetrakis(perfluorobiphenyl)borate; tri(t-butyl)ammonium tetrakis(perfluorobiphenyl)borate; N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate; N,N-diethylanilinium tetrakis(perfluorobiphenyl)borate; N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(perfluorobiphenyl)borate; tropillium tetrakis(perfluorobiphenyl)borate; triphenylcarbenium tetrakis(perfluorobiphenyl)borate; triphenylphosphonium tetrakis(perfluorobiphenyl)borate; triethylsilylium tetrakis(perfluorobiphenyl)borate; benzene(diazonium) tetrakis(perfluorobiphenyl)borate; [4-t-butyl-PhNMe 2 H][(C 6 F 3 (C 6 F 5 ) 2 ) 4 B]; trimethylammonium tetraphenylborate; triethylammonium tetraphenylborate; tripropylammonium tetraphenylborate; tri(n-butyl)ammonium tetraphenylborate; tri(t-butyl)ammonium tetraphenylborate; N,N-dimethylanilinium tetraphenylborate; N,N-diethylanilinium tetraphenylborate; N,N-dimethyl-(2,4,6-trimethylanilinium) tetraphenylborate; tropillium tetraphenylborate; triphenylcarbenium tetraphenylborate; triphenylphosphonium tetraphenylborate; triethylsilylium tetraphenylborate; benzene(diazonium)tetraphenylborate; trimethylammonium tetrakis(pentafluorophenyl)borate; triethylammonium tetrakis(pentafluorophenyl)borate; tripropylammonium tetrakis(pentafluorophenyl)borate; tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate; tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate; N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate; bis(hydrogenatedtallow)methylammonium tetrakis(pentafluorophenyl)borate; Bis(hydrogenatedtallow)methylammonium tetrakis(perfluoronaphth-2-yl)borate; N,N-diethylanilinium tetrakis(pentafluorophenyl)borate; N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(pentafluorophenyl)borate; tropillium tetrakis(pentafluorophenyl)borate; triphenylcarbenium tetrakis(pentafluorophenyl)borate; triphenylphosphonium tetrakis(pentafluorophenyl)borate; triethylsilylium tetrakis(pentafluorophenyl)borate; benzene(diazonium) tetrakis(pentafluorophenyl)borate; trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate; triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate; tripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate; tri(n-butyl)ammonium tetrakis-(2,3,4,6-tetrafluoro-phenyl)borate; dimethyl(t-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate; N,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate; N,N-diethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate; N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis-(2,3,4,6-tetrafluorophenyl)borate; tropillium tetrakis-(2,3,4,6-tetrafluorophenyl)borate; triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate; triphenylphosphonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate; triethylsilylium tetrakis-(2,3,4,6-tetrafluorophenyl)borate; benzene (diazonium) tetrakis-(2,3,4,6-tetrafluorophenyl)borate; trimethylammonium tetrakis(3,5-bis

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Evans Meagan E
• Atienza Crisita Carmen H
• Canich Jo Ann M
• Hagadorn John R
• Cano David A
• Day Gregory S
• Chen Patrick C

Classifications

• B01J2531/49

  Hafnium · CPC title

• C07C2531/14

  of aluminium or boron · CPC title

• B01J2231/20

  Olefin oligomerisation or telomerisation · CPC title

• B01J2531/48

  Zirconium · CPC title

• C10G50/00

  Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation · CPC title