IP Library › Granted Patent US 12,344,696
Granted Patent B2
US 12,344,696 · App. 17/633,910 · Granted Jul 1, 2025

Process to produce low viscosity polyalphaolefins using non-aromatic-hydrocarbon soluble activators

Inventors: Jo Ann M. Canich (Houston, TX); Jian Yang (Houston, TX); Jennifer L. Rapp (Houston, TX); Catherine A. Faler (Houston, TX); Margaret T. Whalley (Houston, TX)
Assignee: ExxonMobil Chemical Patents Inc.
C08F4/65925C07C2/30C07C2/32C08F110/14
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Quick Facts
Patent No.
US 12,344,696
App. No.
17/633,910
Granted
Jul 1, 2025
Kind
B2
Abstract

A process for making a poly alpha-olefin (PAO) having high vinylidene content (or combined vinylidene and tri-substituted vinylene content) and low vinyl and/or di-substituted vinylene content, as well as a relatively low molecular weight comprising contacting a feed containing a C 6 -C 32 alpha-olefin with a catalyst system comprising non-aromatic-hydrocarbon soluble activator and a metallocene compound, typically a cyclopentadienyl-tetrahydro-s-indacenyl group 4 transition metal compound.

Claims (129)

1. A process for producing a poly alpha-olefin, PAO, the process comprising:

contacting a feed comprising a C 6 -C 32 alpha-olefin with a catalyst system comprising an unsymmetrical metallocene compound, a non-aromatic hydrocarbon soluble activator compound, and a non-aromatic hydrocarbon solvent in a polymerization reactor under polymerization conditions to effect a polymerization reaction to obtain a polymerization reaction mixture comprising vinylidenes, tri-substituted vinylenes, optional di-substituted vinylenes, and optional vinyls; and

obtaining an unsaturated PAO product from the polymerization reaction mixture, wherein the unsaturated PAO product comprises vinylidenes, optional tri-substituted vinylenes, optional di-substituted vinylenes, and optional vinyls.

2. The process of claim 1 , wherein the metallocene compound is represented by Formula (I):

wherein:

R 2 is hydrogen and one of R 1 and R 3 is a substituted or unsubstituted linear, branched, or cyclic C 1 -C 6 hydrocarbyl group, and the other of R 1 and R 3 is a hydrogen;

R 6 , R 7 , R 17 , and R 18 are each independently hydrogen; a substituted or unsubstituted linear, branched, or cyclic C 1 -C 30 hydrocarbyl group; or R 6 and R 7 , R 7 and R 17 , or R 17 and R 18 , 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 annulated to the indenyl ring;

R 12 , R 13 , R 14 , and R 15 , are each independently a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 hydrocarbyl group;

R 16 is a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 hydrocarbyl group or silylcarbyl group;

each X is independently a halide, a hydride, an amide, an alkoxide, a sulfide, 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 transition metal, having an integer coordination number of v; and

m is an integer equal to v-2, such as 1, 2, or 3.

3. The process of claim 1 , wherein the metallocene compound is represented by Formula (II):

wherein:

R 1 and R 2 are hydrogen;

R 23 and R 19 comprise Group 14 atoms;

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 and at least two of R 20 , R 21 , and R 22 are not hydrogen;

R 6 , R 7 , R 17 , and R 18 are each independently hydrogen; a substituted or unsubstituted linear, branched, or cyclic C 1 -C 30 hydrocarbyl group; or R 6 and R 7 , R 7 and R 17 , or R 17 and R 18 , 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 annulated to the 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 8 hydrocarbyl group;

each X is independently a halide, a hydride, an amide, an alkoxide, a sulfide, or 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 process of claim 1 , wherein the metallocene compound is represented by Formula (III):

wherein R 2 is hydrogen and one of R 1 and R 3 is a substituted or unsubstituted linear, branched, or cyclic C 1 -C 6 hydrocarbyl group, and the other of R 1 and R 3 of R 1 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 , R 27 and R 28 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 annulated 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 halide, a hydride, an amide, an alkoxide, a sulfide, 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.

5. The process of claim 1 , wherein the metallocene compound is represented by Formula (IV):

wherein:

R 1 and R 2 are hydrogen;

R 23 and R 19 comprise Group 14 atoms;

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 and at least two of R 20 , R 21 , and R 22 are not 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 , R 27 and R 28 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 annulated 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 halide, a hydride, an amide, an alkoxide, a sulfide, 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.

6. The process of claim 1 wherein the metallocene is selected from pentamethylcyclopentadienyl (1-methyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-ethyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-n-propyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-isopropyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-n-butyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-isobutyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-sec-butyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-tert-butyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl pentamethylcyclopentadienyl (1-pentyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-neopentyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-n-hexyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-n-heptyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-n-octyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-benzyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-phenethyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-(2-phenylpropyl)-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-ethyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-n-propyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-isopropyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-n-butyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-isobutyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-sec-butyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-tert-butyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl pentamethylcyclopentadienyl (1-pentyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-neopentyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-n-hexyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-n-heptyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-n-octyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-benzyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-phenethyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-(2-phenylpropyl)-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-methyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1,6,6-triethyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-n-propyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-isopropyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-n-butyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-isobutyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-sec-butyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-tert-butyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl pentamethylcyclopentadienyl (1-pentyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-neopentyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-benzyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-phenethyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-(2-phenylpropyl)-6,6-diethyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-methylindenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-ethylindenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-n-propylindenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-isopropylindenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-n-butylindenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-isobutylindenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-sec-butylindenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-tert-butylindenyl) hafnium dimethyl pentamethylcyclopentadienyl (1-pentylindenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-neopentylindenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-n-hexylindenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-n-heptylindenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-n-octylindenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-benzylindenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-phenethylindenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-(2-phenylpropyl) indenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-methyl-3,6,7,8-tetrahydro-as-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-ethyl-3,6,7,8-tetrahydro-as-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-n-propyl-3,6,7,8-tetrahydro-as-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-isopropyl-3,6,7,8-tetrahydro-as-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-n-butyl-3,6,7,8-tetrahydro-as-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-isobutyl-3,6,7,8-tetrahydro-as-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-sec-butyl-3,6,7,8-tetrahydro-as-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-tert-butyl-3,6,7,8-tetrahydro-as-indacenyl) hafnium dimethyl pentamethylcyclopentadienyl (1-pentyl-3,6,7,8-tetrahydro-as-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-neopentyl-3,6,7,8-tetrahydro-as-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-benzyl-3,6,7,8-tetrahydro-as-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-phenethyl-3,6,7,8-tetrahydro-as-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-(2-phenylpropyl)-3,6,7,8-tetrahydro-as-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-methyl-benz [f]indenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-ethyl-benz [f]indenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-n-propyl-benz [f]indenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-isopropyl-benz [f]indenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-n-butyl-benz [f]indenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-isobutyl-benz [f]indenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-sec-butyl-benz [f]indenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-tert-butyl-benz [f]indenyl) hafnium dimethyl pentamethylcyclopentadienyl (1-pentyl-benz [f]indenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-neopentyl-benz [f]indenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-benzyl-benz [f]indenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-phenethyl-benz [f]indenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-(2-phenylpropyl)-benz [f]indenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-methyl-benz [e]indenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-ethyl-benz [e]indenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-n-propyl-benz [e]indenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-isopropyl-benz [e]indenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-n-butyl-benz [e]indenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-isobutyl-benz [e]indenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-sec-butyl-benz [e]indenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-tert-butyl-benz [e]indenyl) hafnium dimethyl pentamethylcyclopentadienyl (1-pentyl-benz [e]indenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-neopentyl-benz [e]indenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-benzyl-benz [e]indenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-phenethyl-benz [e]indenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-(2-phenylpropyl)-benzef]indenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-methyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalene) hafnium dimethyl, pentamethylcyclopentadienyl (1-ethyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalene) hafnium dimethyl, pentamethylcyclopentadienyl (1-n-propyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalene) hafnium dimethyl, pentamethylcyclopentadienyl (1-isopropyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalene) hafnium dimethyl, pentamethylcyclopentadienyl (1-n-butyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalene) hafnium dimethyl, pentamethylcyclopentadienyl (1-isobutyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalene) hafnium dimethyl, pentamethylcyclopentadienyl (1-sec-butyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalene) hafnium dimethyl, pentamethylcyclopentadienyl (1-tert-butyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalene) hafnium dimethyl pentamethylcyclopentadienyl (1-pentyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalene) hafnium dimethyl, pentamethylcyclopentadienyl (1-neopentyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalene) hafnium dimethyl, pentamethylcyclopentadienyl (1-benzyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalene) hafnium dimethyl, pentamethylcyclopentadienyl (1-phenethyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalene) hafnium dimethyl, pentamethylcyclopentadienyl (1-(2-phenylpropyl)-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalene) hafnium dimethyl, pentamethylcyclopentadienyl (1-methyl-6,7,8,9-tetrahydro-1H-cyclopenta[a]naphthalene) hafnium dimethyl, pentamethylcyclopentadienyl (1-ethyl-6,7,8,9-tetrahydro-1H-cyclopenta[a]naphthalene) hafnium dimethyl, pentamethylcyclopentadienyl (1-n-propyl-6,7,8,9-tetrahydro-1H-cyclopenta[a]naphthalene) hafnium dimethyl, pentamethylcyclopentadienyl (1-isopropyl-6,7,8,9-tetrahydro-1H-cyclopenta[a]naphthalene) hafnium dimethyl, pentamethylcyclopentadienyl (1-n-butyl-6,7,8,9-tetrahydro-1H-cyclopenta[a]naphthalene) hafnium dimethyl, pentamethylcyclopentadienyl (1-isobutyl-6,7,8,9-tetrahydro-1H-cyclopenta[a]naphthalene) hafnium dimethyl, pentamethylcyclopentadienyl (1-sec-butyl-6,7,8,9-tetrahydro-1H-cyclopenta[a]naphthalene) hafnium dimethyl, pentamethylcyclopentadienyl (1-tert-butyl-6,7,8,9-tetrahydro-1H-cyclopenta[a]naphthalene) hafnium dimethyl pentamethylcyclopentadienyl (1-pentyl-6,7,8,9-tetrahydro-1H-cyclopenta[a]naphthalene) hafnium dimethyl, pentamethylcyclopentadienyl (1-neopentyl-6,7,8,9-tetrahydro-1H-cyclopenta[a]naphthalene) hafnium dimethyl, pentamethylcyclopentadienyl (1-benzyl-6,7,8,9-tetrahydro-1H-cyclopenta[a]naphthalene) hafnium dimethyl, pentamethylcyclopentadienyl (1-phenethyl-6,7,8,9-tetrahydro-1H-cyclopenta[a]naphthalene) hafnium dimethyl, pentamethylcyclopentadienyl (1-(2-phenylpropyl)-6,7,8,9-tetrahydro-1H-cyclopenta[a]naphthalene) hafnium dimethyl, pentamethylcyclopentadienyl (1,5,6-trimethylindenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-ethyl-5,6-dimethylindenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-n-propyl-5,6-dimethylindenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-isopropyl-5,6-dimethylindenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-n-buty-5,6-dimethyllindenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-isobuty-5,6-dimethyllindenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-sec-butyl-5,6-dimethylindenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-tert-butyl-5,6-dimethylindenyl) hafnium dimethyl pentamethylcyclopentadienyl (1-pentyl-5,6-dimethylindenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-neopentyl-5,6-dimethylindenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-benzyl-5,6-dimethylindenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-phenethyl-5,6-dimethylindenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-(2-phenylpropyl)-5,6-dimethylindenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-methyl-1,5,6,7-tetrahydro-s-indacenyl) zirconium dimethyl, pentamethylcyclopentadienyl (1-isobutyl-1,5,6,7-tetrahydro-s-indacenyl) zirconium dimethyl, pentamethylcyclopentadienyl (1,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacenyl) zirconium dimethyl, tetramethylcyclopentadienyl (1-methyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, tetramethylcyclopentadienyl (1-isobutyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, tetramethylcyclopentadienyl (1,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-methyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dibenzyl, pentamethylcyclopentadienyl (1-isobutyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dibenzyl, and pentamethylcyclopentadienyl (1,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacenyl) hafnium dibenzyl.

7. The process of claim 1 wherein the non-aromatic-hydrocarbon soluble activator compound is represented by Formula (V):

[R 1′ R 2′ R 3′ EH] d + [Mt k+ Q n ] d−   (V)

wherein:

E is nitrogen or phosphorous;

d is 1, 2 or 3; k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6; n−k=d;

R 1 ′, R 2 ′, and R 3 ′ are independently C 1 to C 50 hydrocarbyl group optionally substituted with one or more alkoxy groups, silyl groups, a halogen atoms, or halogen containing groups

wherein R 1 ′, R 2 ′, and R 3 ′ together comprise 15 or more carbon atoms;

Mt is an element selected from group 13 of the Periodic Table of the Elements; and

each Q is independently a hydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, or halosubstituted-hydrocarbyl radical.

8. The process of claim 1 wherein the non-aromatic-hydrocarbon soluble activator compound is represented by Formula (VI):

[R 1′ R 2′ R 3′ EH] + [BR 4′ R 5′ R 6′ R 7′ ] −   (VI)

wherein:

E is nitrogen or phosphorous;

R 1 ′ is a methyl group;

R 2 ′ and R 3 ′ are independently is C 4 -C 50 hydrocarbyl group optionally substituted with one or more alkoxy groups, silyl groups, a halogen atoms, or halogen containing groups wherein R 2 ′ and R 3 ′ together comprise 14 or more carbon atoms;

B is boron; and

R 4 ′, R 5 ′, R 6 ′, and R 7 ′ are independently hydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, or halosubstituted-hydrocarbyl radical.

9. The process of claim 1 wherein the non-aromatic-hydrocarbon soluble activator compound is represented by Formula (VII) or Formula (VIII):

wherein:

N is nitrogen;

R 2 ′ and R 3 ′ are independently is C 6 -C 40 hydrocarbyl group optionally substituted with one or more alkoxy groups, silyl groups, a halogen atoms, or halogen containing groups wherein R 2 and R 3 in Formula (VII) together comprise 14 or more carbon atoms and R 2 ′ in Formula (VIII) comprises 13 or more carbon atoms;

R 8 ′, R 9 ′, and R 10 ′ are independently a C 4 -C 30 hydrocarbyl or substituted C 4 -C 30 hydrocarbyl group;

B is boron;

and R 4 ′, R 5 ′, R 6 ′, and R 7 are independently hydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, or halosubstituted-hydrocarbyl radical.

10. The process of claim 9 , wherein R 4 ′, R 5 ′, R 6 ′, and R 7 are pentafluorophenyl.

11. The process of claim 9 wherein R 8 ′and R 10 ′ are hydrogen atoms and R 9 ′ is a C 4 -C 30 hydrocarbyl group which is optionally substituted with one or more alkoxy groups, silyl groups, a halogen atoms, or halogen containing groups.

12. The process of claim 9 wherein R 9 ′ is a C 8 -C 22 hydrocarbyl group which is optionally substituted with one or more alkoxy groups, silyl groups, a halogen atoms, or halogen containing groups.

13. The process of claim 9 wherein R 2 ′ and R 3 ′ are independently a C 12 -C 22 hydrocarbyl group.

14. The process of claim 9 wherein the activator is selected from:

N,N-di(hydrogenated tallow) methylammonium [tetrakis(perfluorophenyl)borate],

N-methyl-4-nonadecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate],

N-methyl-4-hexadecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate],

N-methyl-4-tetradecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate],

N-methyl-4-dodecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate],

N-methyl-4-decyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate],

N-methyl-4-octyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate],

N-methyl-4-hexyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate],

N-methyl-4-butyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate],

N-methyl-4-octadecyl-N-decylanilinium [tetrakis(perfluorophenyl)borate],

N-methyl-4-nonadecyl-N-dodecylanilinium [tetrakis(perfluorophenyl)borate],

N-methyl-4-nonadecyl-N-tetradecylanilinium [tetrakis(perfluorophenyl)borate],

N-methyl-4-nonadecyl-N-hexadecylanilinium [tetrakis(perfluorophenyl)borate], N-ethyl-4-nonadecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate],

N-methyl-N,N-dioctadecylammonium [tetrakis(perfluorophenyl)borate],

N-methyl-N,N-dihexadecylammonium [tetrakis(perfluorophenyl)borate],

N-methyl-N,N-ditetradecylammonium [tetrakis(perfluorophenyl)borate],

N-methyl-N,N-didodecylammonium [tetrakis(perfluorophenyl)borate],

N-methyl-N,N-didecylammonium [tetrakis(perfluorophenyl)borate],

N-methyl-N,N-dioctylammonium [tetrakis(perfluorophenyl)borate],

N-ethyl-N,N-dioctadecylammonium [tetrakis(perfluorophenyl)borate],

N,N-di(octadecyl) tolylammonium [tetrakis(perfluorophenyl)borate],

N,N-di(hexadecyl) tolylammonium [tetrakis(perfluorophenyl)borate],

N,N-di(tetradecyl) tolylammonium [tetrakis(perfluorophenyl)borate],

N,N-di(dodecyl) tolylammonium [tetrakis(perfluorophenyl)borate],

N-octadecyl-N-hexadecyl-tolylammonium [tetrakis(perfluorophenyl)borate],

N-octadecyl-N-hexadecyl-tolylammonium [tetrakis(perfluorophenyl)borate],

N-octadecyl-N-tetradecyl-tolylammonium [tetrakis(perfluorophenyl)borate],

N-octadecyl-N-dodecyl-tolylammonium [tetrakis(perfluorophenyl)borate],

N-octadecyl-N-decyl-tolylammonium [tetrakis(perfluorophenyl)borate],

N-hexadecyl-N-tetradecyl-tolylammonium [tetrakis(perfluorophenyl)borate],

N-hexadecyl-N-dodecyl-tolylammonium [tetrakis(perfluorophenyl)borate],

N-hexadecyl-N-decyl-tolylammonium [tetrakis(perfluorophenyl)borate],

N-tetradecyl-N-dodecyl-tolylammonium [tetrakis(perfluorophenyl)borate],

N-tetradecyl-N-decyl-tolylammonium [tetrakis(perfluorophenyl)borate],

N-dodecyl-N-decyl-tolylammonium [tetrakis(perfluorophenyl)borate],

N-methyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate],

N-methyl-N-hexadecylanilinium [tetrakis(perfluorophenyl)borate],

N-methyl-N-tetradecylanilinium [tetrakis(perfluorophenyl)borate],

N-methyl-N-dodecylanilinium [tetrakis(perfluorophenyl)borate],

N-methyl-N-decylanilinium [tetrakis(perfluorophenyl)borate], and

N-methyl-N-octylanilinium [tetrakis(perfluorophenyl)borate].

15. The process of claim 1 wherein the solvent is selected from C 4 to C 10 linear, branched or cyclic alkanes.

16. The process of claim 1 wherein the solvent is essentially free of all aromatic solvents.

17. The process of claim 1 , wherein solvent is selected from one or more Co to C 32 alpha olefins.

18. The process of claim 1 which is wherein the solvent is essentially free of all non-alpha-olefin solvents.

19. The process of claim 1 wherein: the process comprises obtaining an unsaturated PAO product from the polymerization reaction mixture, wherein the polymerization reaction exhibits a selectivity towards greater than or equal to about 80 mol % vinylidenes, based on total moles of vinyls, vinylidenes, di-substituted vinylenes, and tri-substituted vinylenes in the unsaturated PAO product and wherein the unsaturated PAO product has a number average molecular weight (Mn) of 2,500 g/mol or less, as measured by 1H NMR.

20. The process of claim 1 , further comprising:

a) contacting the unsaturated PAO product with hydrogen to convert at least a portion of the unsaturated PAO product to a hydrogenated PAO product;

b) contacting the unsaturated PAO product with a chemical reagent to convert at least a portion of the unsaturated PAO product to a functionalized PAO product;

or a combination thereof.

21. The process of claim 1 wherein the unsaturated PAO product comprises dimer.

22. The process of claim 1 wherein the C 6 -C 32 alpha-olefin, the metallocene compound and the activator are contacted in the solution phase or bulk phase in a continuous stirred tank reactor or a continuous tubular reactor.

23. The process of claim 1 wherein the process is a continuous process which includes the steps of: a) continuously introducing a feed stream comprising at least 10 mol % of the one or more C 6 to C 24 alpha-olefins into a reactor, b) continuously introducing the metallocene compound and the activator into the reactor, and c) continuously withdrawing the PAO product from the reactor.

24. The process of claim 1 , wherein the feed comprises a single alpha-olefin monomer or a combination of two or more alpha-olefin monomers.

25. The process of claim 1 wherein the C 6 -C 32 alpha-olefin, the metallocene compound and the activator are contacted in the solution phase, bulk phase, or slurry phase in a continuous stirred tank reactor or a continuous tubular reactor.

26. The process of claim 1 wherein the polymerization temperature is above 100° C., the conversion is 50% or more and the unsaturated PAO product has about 80 mol % or more vinylidenes, based on total moles of vinyls, vinylidenes, di-substituted vinylenes, and tri-substituted vinylenes in the unsaturated PAO product.

27. The process of claim 1 wherein the unsaturated PAO product is represented by formula:

wherein C is a hydrocarbon chain of length m′-2, each m′ is independently 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16 and is the carbon number of the monomer(s) used in the polymerization, and n′ is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

28. The process of claim 1 , said process having productivity of at least 4,500 g/mmol/hr, wherein the process comprises: contacting, at a temperature of from 35° C. to 150° C.

29. The process of claim 1 , further comprising hydrogenating at least a portion of said poly alpha-olefin, then formulating a fuel or lubricating composition comprising the product of hydrogenating at least a portion of said polyalpha-olefin.

Continuity (2)
Provisional Application 62885103 · Aug 9, 2019
Related Publication 20220298273A1 · Sep 22, 2022
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