Use of a metallocene catalyst to produce a polyalpha-olefin

Patent metadata

Field	Value
Publication number	US-9688792-B2
Application number	US-201514725540-A
Country	US
Kind code	B2
Filing date	May 29, 2015
Priority date	May 30, 2014
Publication date	Jun 27, 2017
Grant date	Jun 27, 2017

Abstract

A process may include contacting an olefin monomer and a racemic bridged metallocene catalyst at a temperature of 80° C. to 150° C. in the presence of hydrogen. The racemic bridged metallocene catalyst may include a metallocene compound (A) and an activator component (B). The process may include recovering an effluent containing polyalpha-olefins (PAOs). The metallocene compound (A) may be represented by the formula R(Cp 1 )(Cp 2 )MX 1 X 2 . In the formula, R may be a C 1 -C 20 alkylene bridging group; Cp 1 and Cp 2 may be the same or different substituted or unsubstituted tetrahydroindenyl rings; M may be a transition metal; and X 1 and X 2 may be independently selected from hydrogen, halogen, hydride radicals, hydrocarbyl radicals, substituted hydrocarbyl radicals, halocarbyl radicals, substituted halocarbyl radicals, silylcarbyl radicals, substituted silylcarbyl radicals, germylcarbyl radicals, substituted germylcarbyl radicals.

First claim

The invention claimed is:

1. A process comprising:
homo-oligomerization of olefin monomers by contacting the olefin monomers and a racemic bridged metallocene catalyst comprising a metallocene compound (A) and an activator component (B) at a temperature of 80° C. to 150° C. in the presence of hydrogen; and
recovering an effluent containing polyalpha-olefins (PAOs), wherein the polyalpha-olefins (PAOs) have a kinematic viscosity of from 2 to 50 cSt, as measured according to ASTM D445 at 100° C. and a molecular weight (Mw) of 30,000 Da or less;
wherein the metallocene compound (A) is represented by the formula
R(Cp 1 )(Cp 2 )MX 1 X 2 ;

wherein R is ethylene (—CH 2 —CH 2 —), 1-methyl-ethylene (—CH(CH 3 )—CH 2 ), n-propylene (—CH 2 —CH 2 —CH 2 —), 2-methylpropylene (—CH 2 —CH(CH 3 )—CH 2 —), 3-methylpropylene (—CH 2 —CH 2 —CH(CH 3 )—), n-butylene (—CH 2 —CH 2 —CH 2 —CH 2 —), 2-methylbutylene (—CH 2 —CH(CH 3 )—CH 2 —CH 2 —), 4-methylbutylene (—CH 2 —CH 2 —CH 2 —CH(CH 3 )—), pentylene and its chain isomers, hexylene and its chain isomers, heptylene and its chain isomers, octylene and its chain isomers, nonylene and its chain isomers, decylene and its chain isomers, undecylene and its chain isomers, dodecylene or its chain isomers;
wherein Cp 1 and Cp 2 are the same or different substituted or unsubstituted tetrahydroindenyl rings;
wherein M is a transition metal selected from the group consisting of titanium, zirconium and hafnium;
wherein X 1 and X 2 are independently selected from the group consisting of hydrogen, halogen, hydride radicals, hydrocarbyl radicals, substituted hydrocarbyl radicals, halocarbyl radicals, substituted halocarbyl radicals, silylcarbyl radicals, substituted silylcarbyl radicals, germylcarbyl radicals, and substituted germylcarbyl radicals; or wherein both X 1 and X 2 are joined and bound to the metal atom to form a metallacycle ring containing from 3 to 20 carbon atoms.

2. The process of claim 1 , wherein, in the metallocene compound (A), R is ethylene.

3. The process of claim 1 , wherein, in the metallocene compound (A), M is zirconium.

4. The process of claim 1 , wherein the metallocene compound (A) is racemic ethylene bis(tetrahydroindenyl) zirconium dimethyl.

5. The process of claim 1 , wherein the metallocene compound (A) is racemic ethylene bis (tetrahydroindenyl)zirconium dichloride.

6. The process of claim 1 , wherein the activator component (B) is an alumoxane selected from the group consisting of methylalumoxane, modified methyl alumoxane, ethylalumoxane, isobutylalumoxane, and combinations thereof.

7. The process of claim 1 , wherein the activator component (B) is methylalumoxane (MAO).

8. The process of claim 1 , wherein the activator component (B) is an ionic activator selected from the group consisting of dimethylanilinium tetrakis(perfluorophenyl)borate, triphenylcarbonium tetrakis(perfluorophenyl)borate, dimethylanilinium tetrakis(perfluorophenyl)aluminate, and combinations thereof.

9. The process of claim 8 , wherein the ionic activator is dimethylanilinium tetrakis(perfluorophenyl)borate.

10. The process of claim 8 , wherein the ionic activator is used in combination with a co-activator, and wherein the co-activator is a trialkylaluminium selected from the group consisting of Tri-Ethyl Aluminum (TEAL), Tri-Iso-Butyl Aluminum (TIBAL), Tri-Methyl Aluminum (TMA), and Methyl-Methyl-Ethyl Aluminum (MMEAL).

11. The process of claim 10 , wherein the co-activator is Tri-Iso-Butyl Aluminum (TIBAL).

12. The process of claim 1 , further comprising, conducting a hydrogenation reaction before recovering the effluent containing polyalpha-olefins (PAOs).

13. The process of claim 12 , wherein the hydrogenation reaction is performed with a hydrogenation catalyst selected from the group consisting of nickel supported on kieselguhr, platinum or palladium supported on alumina, and cobalt-molydenum supported on alumina.

14. The process of claim 13 , wherein the hydrogenation catalyst is palladium supported on alumina.

15. The process of claim 1 , wherein the contacting of the olefin monomers and the racemic bridged metallocene catalyst at a temperature of 80° C. to 150° C. in the presence of hydrogen is performed in a reactor in a batch mode.

16. The process of claim 1 , wherein the olefin monomers comprise 1-decene.

17. A process comprising:
homo-oligomerization of olefin monomers by contacting the olefin monomers and a racemic bridged metallocene catalyst comprising a metallocene compound (A) and an activator component (B) in the presence of hydrogen; and
recovering an effluent containing polyalpha-olefins (PAOs), wherein the polyalpha-olefins (PAOs) have a kinematic viscosity of from 2 to 50 cSt, as measured according to ASTM D445 at 100° C. and a molecular weight (Mw) of 30,000 Da or less;
wherein the metallocene compound (A) is represented by the formula
R(Cp 1 )(Cp 2 )MX 1 X 2 ;

wherein R is ethylene (—CH 2 —CH 2 —), 1-methyl-ethylene (—CH(CH 3 )—CH 2 ), n-propylene (—CH 2 —CH 2 —CH 2 —), 2-methylpropylene (—CH 2 —CH(CH 3 )—CH 2 —), 3-methylpropylene (—CH 2 —CH 2 —CH(CH 3 )—), n-butylene (—CH 2 —CH 2 —CH 2 —CH 2 —), 2-methylbutylene (—CH 2 —CH(CH 3 )—CH 2 —CH 2 —), 4-methylbutylene (—CH 2 —CH 2 —CH 2 —CH(CH 3 )—), pentylene and its chain isomers, hexylene and its chain isomers, heptylene and its chain isomers, octylene and its chain isomers, nonylene and its chain isomers, decylene and its chain isomers, undecylene and its chain isomers, dodecylene or its chain isomers;
wherein Cp 1 and Cp 2 are the same or different substituted or unsubstituted tetrahydroindenyl rings;
wherein M is a transition metal selected from the group consisting of titanium, zirconium and hafnium;
wherein X 1 and X 2 are independently selected from the group consisting of hydrogen, halogen, hydride radicals, hydrocarbyl radicals, substituted hydrocarbyl radicals, halocarbyl radicals, substituted halocarbyl radicals, silylcarbyl radicals, substituted silylcarbyl radicals, germylcarbyl radicals, and substituted germylcarbyl radicals; or wherein both X 1 and X 2 are joined and bound to the metal atom to form a metallacycle ring containing from 3 to 20 carbon atoms.

18. The process of claim 1 , wherein the polyalpha-olefins (PAOs) have a kinematic viscosity of from 3 to 30 cSt, as measured according to ASTM D445 at 100° C.

19. The process of claim 1 , wherein the polyalpha-olefins (PAOs) have a kinematic viscosity of from 3 to 10 cSt, as measured according to ASTM D445 at 100° C.

20. The process of claim 1 , wherein Cp 1 and Cp 2 are substituted tetrahydroindenyl rings, wherein the substitutions are independent.

21. The process of claim 1 , wherein Cp 1 and Cp 2 are substituted tetrahydroindenyl rings, wherein the substitutions are linked to form multicyclic structures.

22. A process comprising:
contacting olefin monomers and a racemic bridged metallocene catalyst comprising a metallocene compound (A) and an activator component (B) at a temperature of 80° C. to 150° C. in the presence of hydrogen; and
recovering an effluent containing polyalpha-olefins (PAOs), wherein the polyalpha-olefins (PAOs) have a kinematic viscosity of from 2 to 50 cSt, as measured according to ASTM D445 at 100° C. and a molecular weight (Mw) of 30,000 Da or less;
wherein the metallocene compound (A) is represented by the formula
R(Cp 1 )(Cp 2 )MX 1 X 2 ;

wherein R is ethylene (—CH 2 —CH 2 —), 1-methyl-ethylene (—CH(CH 3 )—CH 2 ), n-propylene (—CH 2 —CH 2 —CH 2 —), 2-met

Assignees

• Total Res & Technology Feluy

Inventors

• Welle Alexandre
• Wassenaar Jeroen
• Slawinski Martine

Classifications

• C08F4/65908

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

• C07F17/00

  Metallocenes · CPC title

• B01J2531/48

  Zirconium · CPC title

• B01J31/2295

  Cyclic compounds, e.g. cyclopentadienyls · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title