US 11,661,465 B2Granted

Dimer selective metallocene catalysts, non-aromatic hydrocarbon soluble activators, and processes to produce poly alpha-olefin oligmers therewith

AssigneeExxonMobil Chemical Patents Inc.

InventorsJennifer L. Rapp, Patrick C. Chen, Jo Ann M. Canich, Mark H. Li, Jian Yang, Catherine A. Faler, Margaret T. Whalley, Andrew E. Atalla

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Abstract

The present disclosure generally relates to process to produce a poly alpha-olefin (PAO), comprising: a) introducing a first alpha-olefin to a first catalyst system comprising non-aromatic hydrocarbon soluble activator and a metallocene compound into a continuous stirred tank reactor or a continuous tubular reactor under first reactor conditions, wherein the first alpha-olefin is preferably introduced to the reactor at a flow rate of about 100 g/hr or more, to form a first reactor effluent comprising PAO (such as at least 60 wt % of PAO dimer and 40 wt % or less of higher oligomers, where the higher oligomers are oligomers that have a degree of polymerization of 3 or more); and b) introducing the first reactor effluent and a second alpha-olefin to a second catalyst composition comprising an acid catalyst, such as BF3, in a second reactor to form a second reactor effluent comprising PAO trimer.

Claims36

Dependent claims

A process to produce a poly alpha-olefin (PAO), comprising:

a) introducing a first alpha-olefin to a first catalyst system comprising non-aromatic hydrocarbon soluble activator and a metallocene compound into a first reactor under first reactor conditions to form a first reactor effluent comprising PAO dimer;
and
b) introducing the first reactor effluent and an optional second alpha-olefin to a second catalyst composition comprising an acid catalyst in a second reactor under second reactor conditions to form a second reactor effluent comprising PAO trimer, wherein the metallocene compound is represented by the formula (III):
wherein one of R1 and R3 is a substituted or unsubstituted linear, branched, or cyclic C1-C20 hydrocarbyl group;
two of R1, R2, and R3 are each hydrogen;
R6, R18, R29, R24, R25, R26, R27 and R28 are each independently hydrogen, a substituted or unsubstituted linear, branched, or cyclic C1-C30 hydrocarbyl group, or two of R6, R18, R29, R24, R25, R26, R27 and R28 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 annelated to the cyclopentan-indenyl ring;
R12, R13, R14, R15, and R16 are each independently a substituted or unsubstituted linear, branched, or cyclic C1-C20 hydrocarbyl group;
each X is independently a halogen, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a diene, an amine, a phosphine, an ether, a C1-C20 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.

7 more elements

A process to produce a poly alpha-olefin (PAO), comprising:

a) introducing a first alpha-olefin to a first catalyst system comprising non-aromatic hydrocarbon soluble activator and a metallocene compound into a first reactor under first reactor conditions to form a first reactor effluent comprising PAO dimer;
and
b) introducing the first reactor effluent and an optional second alpha-olefin to a second catalyst composition comprising an acid catalyst in a second reactor under second reactor conditions to form a second reactor effluent comprising PAO trimer, wherein the metallocene compound comprises one or more of:
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-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,
ethyltetramethylcyclopentadienyl(1-methyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl,
ethyltetramethylcyclopentadienyl(1-isobutyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl,
ethyltetramethylcyclopentadienyl(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,
pentamethylcyclopentadienyl(1,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dibenzyl,
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(1,6,6-trimethyl-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-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, and pentamethylcyclopentadienyl(1-isobutyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl.

64 more elements

A process to produce a poly alpha-olefin (PAO), comprising:

a) introducing a first alpha-olefin to a first catalyst system comprising non-aromatic hydrocarbon soluble activator and a metallocene compound into a first reactor under first reactor conditions to form a first reactor effluent comprising PAO dimer;
and
b) introducing the first reactor effluent and an optional second alpha-olefin to a second catalyst composition comprising an acid catalyst in a second reactor under second reactor conditions to form a second reactor effluent comprising PAO trimer, wherein the activator is represented by the formula (VIII):
wherein N is nitrogen;
R2′ is a C6-C40 hydrocarbyl group optionally substituted with one or more alkoxy groups, silyl groups, a halogen atoms, or halogen containing groups;
R8′, R9′, and R10′ are independently a C4-C30 hydrocarbyl or substituted C4-C30 hydrocarbyl group;
B is boron;
and
R4′, R5′, R6′, and R7′ are each independently hydride, a bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, or halosubstituted-hydrocarbyl radical.

6 more elements

Dependencies are inferred from the claim text.

Facts

Application: 17/082,750Filed 28 Oct 2020 · us provisional application
Priority: 28 Oct 2019
Published: US 2021/0122859 A129 Apr 2021
Granted: 30 May 2023
Term ends: Not estimatedThe source records don’t support an estimate.

Classification13 codes

C07C 11/02
Aliphatic unsaturated hydrocarbons: alkenes
C08F 210/16
Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond: copolymers of ethene with alpha-alkenes, e.g. EP…
C07C 2/08
Of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond: catalytic processes
C07C 2/30
With hydrides or organic compounds: containing metal-to-carbon bond; Metal hydrides