# US 11,028,197 B2 · Processes to produce poly alpha-olefin trimer and apparatus therefor

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- Number: US 11,028,197 B2
- Document ID: US11028197B2
- Status: Granted
- Kind: B2
- Application number: 16/537,381
- Filed: 2019-08-09
- Published: 2019-11-28
- Granted: 2021-06-08
- Earliest claimed: 2018-02-12
- Assignees: ExxonMobil Chemical Patents Inc.
- Applicants: ExxonMobil Chemical Patents Inc.
- Inventors: Patrick C. Chen; Mark H. Li; Jennifer L. Rapp; Pramod J. Nandapurkar; Brian H. Wahn; Babak LotfizadehDehkordi; Craig J. Emett; Najeeb M. Kuzhiyil; Jian Yang
- Web page: https://patentgrep.com/patent/US11028197B2

## CPC

- C08F 4/65925: {two cyclopentadienyl rings being mutually non-bridged}
- C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C07C 2/30: containing metal-to-carbon bond; Metal hydrides
- C07C 2/32: as complexes, e.g. acetyl-acetonates {(complexes of salts of acids of halogen C07C2/20)}
- C07C 2/34: Metal-hydrocarbon complexes
- C07C 11/02: Alkenes
- C07C 17/00: Preparation of halogenated hydrocarbons
- C07F 17/00: Metallocenes
- C08F 4/65908: {in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+}
- C08F 4/65912: {in combination with an organoaluminium compound}
- C08F 4/65922: {containing at least two cyclopentadienyl rings, fused or not}
- C07C 2531/14: of aluminium or boron
- C07C 2531/22: Organic complexes
- C08F 110/14: Monomers containing five or more carbon atoms
- C08F 2420/07: Heteroatom-substituted Cp, i.e. Cp or analog where at least one of the substituent of the Cp or analog ring is or contains a heteroatom
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)

## Abstract

In at least one embodiment, a process to produce a poly alpha-olefin (PAO) includes introducing a first alpha-olefin to a first catalyst system comprising activator and a metallocene compound into a continuous stirred tank reactor or a continuous tubular reactor under first reactor conditions to form a first reactor effluent. The first alpha-olefin is introduced to the reactor at a flow rate of about 100 g/hr or more. The first reactor effluent includes 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. The process includes introducing the first reactor effluent and a second alpha-olefin to a second catalyst composition including an acid catalyst in a second reactor to form a second reactor effluent comprising PAO trimer.

## Claims

### Claim 1

A process to produce a poly alpha-olefin (PAO), comprising:
a) introducing a first alpha-olefin to a first catalyst system comprising 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 introduced to the reactor at a flow rate of about 100 g/hr or more, to form a first reactor effluent comprising 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 in a second reactor to form a second reactor effluent comprising PAO trimer,
wherein the higher oligomers in the first reactor effluent are not separated from the first effluent stream prior to introduction into the second reactor.

### Claim 2 (depends on 1)

The process of claim 1, wherein the first reactor effluent is not transferred to a separation unit prior to introduction into the second reactor unit.

### Claim 3 (depends on 1)

The process of claim 1, further comprising:
introducing the second reactor effluent to a first distillation unit to form a first distillation effluent; and
introducing the first distillation effluent to a hydrogenation unit and hydrogenating the first distillation effluent to form a hydrogenated effluent.

### Claim 4

The process of claim, further comprising:
introducing the hydrogenated effluent to a second distillation unit to form a second distillation effluent; and
introducing the second distillation effluent to a third distillation unit to form PAO effluents having a viscosity of from 3 cSt to about 10 cSt.

### Claim 5 (depends on 1)

The process of claim 1, wherein the acid catalyst is a Lewis acid.

### Claim 6 (depends on 1)

The process of claim 1, wherein the acid catalyst is present in the second reactor at an acid catalyst loading of from about 5 mmolCat/100gLAO to about 15 mmolCat/100gLAO.

### Claim 7 (depends on 1)

The process of claim 1, wherein the second reactor comprises a temperature of from about 10° C. to about 40° C.

### Claim 8 (depends on 1)

The process of claim 1, wherein the acid catalyst is BF3.

### Claim 9 (depends on 1)

The process of claim 1, wherein the first reactor effluent includes 50 wt % or less of higher oligomers, based on a total weight percent of the first reactor effluent.

### Claim 10 (depends on 1)

The process of claim 1, wherein the first reactor effluent includes 10 wt % or less of higher oligomers of alpha-olefin, based on a total weight percent of the first reactor effluent.

### Claim 11 (depends on 1)

The process of claim 1, wherein the first alpha-olefin and the second alpha-olefin are different.

### Claim 12 (depends on 1)

The process of claim 1, wherein the second reactor effluent comprises 50 wt % or more of the PAO trimer based on a total weight percent of the second reactor effluent.

### Claim 13 (depends on 1)

The process of claim 1, wherein the second reactor effluent comprises 65 wt % or more of the PAO trimer based on a total weight percent of the second reactor effluent.

### Claim 14 (depends on 1)

The process of claim 1, wherein the second reactor effluent comprises 75 wt % or more of the PAO trimer, based on a total weight percent of the second reactor effluent.

### Claim 15 (depends on 1)

The process of claim 1, wherein the second reactor conditions include a second reactor temperature of less than 60° C.

### Claim 16 (depends on 1)

The process of claim 1, wherein the second catalyst composition further comprises an alcohol and an alkyl acetate.

### Claim 17 (depends on 1)

The process of claim 1, wherein,
the PAO dimer of the first product effluent comprises 96 mol % or more of vinylidene, and 4 mol % or less of disubstituted vinylene and trisubstituted vinylene, based on total moles of vinylidene, disubstituted vinylene, and trisubstituted vinylene in the PAO dimer of the first product effluent.

### Claim 18 (depends on 1)

The process of claim 1, wherein,
the PAO dimer of the first product effluent comprises 98 mol % or more of vinylidene, and 2 mol % or less of disubstituted vinylene and trisubstituted vinylene, based on total moles of vinylidene, disubstituted vinylene, and trisubstituted vinylene in the PAO dimer of the first product effluent.

### Claim 19 (depends on 1)

The process of claim 1, wherein the metallocene compound is represented by the formula:
wherein:
each of R1, R2, and R3 is independently hydrogen, a substituted or unsubstituted linear, branched, or cyclic C1-C20 hydrocarbyl group, wherein at least one of R1, R2, and R3 is not hydrogen and at least one of R1, R2, and R3 is hydrogen;
each of R4, R5, R6, and R7 is independently hydrogen, a substituted or unsubstituted linear, branched, or cyclic C1-C30 hydrocarbyl group, or one or more pair of R4 and R5, R5 and R6, or R6 and R7, 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 fused to the indenyl ring;
each of R8, R9, R10, R11, and R12 is independently a substituted or unsubstituted linear, branched, or cyclic C1-C30 hydrocarbyl, silylcarbyl, or germanyl group;
M is a group 3, 4 or 5 transition metal;
each X is independently a halogen, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a diene, an amine, a phosphine, an ether, or a C1-C20 substituted or unsubstituted linear, branched, or cyclic hydrocarbyl group, or optionally two or more X moieties together form a fused ring or ring system; and
m is an integer equal to 1, 2, or 3.

### Claim 20 (depends on 1)

The process of claim 1, wherein the metallocene compound is represented by the formula:
wherein:
each of R1, R2, and R3 is independently hydrogen or a substituted or unsubstituted linear, branched, or cyclic C1-C20 hydrocarbyl or silylcarbyl group;
each of R4 and R7 is independently hydrogen, a substituted or unsubstituted linear, branched, or cyclic C1-C30 hydrocarbyl or silylcarbyl group;
each of R8, R9, R10, R11, and R12 is independently a hydrogen, or a substituted or unsubstituted linear, branched, or cyclic C1-C20 hydrocarbyl, silylcarbyl, or germanyl group, or optionally at least three of R8, R9, R10, R11, and R12 are not hydrogen;
each of R13, R14, R15, R16, R17, and R18 is independently hydrogen or a substituted or unsubstituted linear, branched, or cyclic C1-C20 hydrocarbyl or silylcarbyl group;
M is a group 3, 4 or 5 transition metal;
each X is independently a halogen, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a diene, an amine, a phosphine, an ether, or a C1-C20 substituted or unsubstituted linear, branched, or cyclic hydrocarbyl group, or optionally two or more X moieties together form a fused ring or ring system; and
m is an integer equal to 1, 2, or 3.

### Claim 21 (depends on 1)

The process of claim 1, wherein the wherein the activator comprises one or more of:
N,N-dimethylanilinium tetrakis(perfluorophenyl)borate,
N,N-dimethylanilinium tetrakis(perfluoro-naphthyl)borate,
triphenylcarbonium tetrakis(perfluorophenyl)borate,
triphenylcarbonium tetrakis(perfluoronaphthyl)borate,
N,N-dimethylanilinium tetrakis(perfluorophenyl)aluminate,
N,N-dimethylanilinium tetrakis(perfluoronaphthyl)aluminate,
alumoxane,
a modified alumoxane, and
aluminum alkyl.

### Claim 22 (depends on 1)

The process of claim 1, wherein the metallocene compound is selected from the group consisting of:
and a combination thereof.

### Claim 23 (depends on 1)

The process of claim 1, further comprising functionalizing the PAO trimer with a reactant to form a functionalized PAO product.

### Claim 24 (depends on 23)

The process of claim 23, further comprising hydrogenating the functionalized PAO product to form a hydrogenated PAO product.

### Claim 25 (depends on 1)

The process of claim 1 wherein the process has a conversion of at least 60%, based upon the weight of the monomer entering the reactor and the PAO produced and a selectivity for dimer of at least 85 wt %, based upon the PAO produced.

### Claim 26 (depends on 1)

The process of claim 1, wherein the metallocene compound is represented by formula (Z):
wherein:
each R1, R2, and R3 is, independently, hydrogen or a substituted or unsubstituted linear, branched, or cyclic C1-C20, preferably C1-C8, hydrocarbyl group, wherein one of R1, R2, and R3 is a substituted or unsubstituted linear, branched, or cyclic C1-C20, preferably C1-C8, hydrocarbyl group, and either (i) two of R1, R2, and R3 are each a hydrogen, or (ii) one of R1, R2, and R3 is a hydrogen or a substituted or unsubstituted linear, branched, or cyclic C1-C20, preferably C1-C8, hydrocarbyl group, and one of R1, R2, and R3, taken together with R16, is a bridging group connecting the first and second cyclopentadienyl rings;
R4 and R5 are each independently a substituted or unsubstituted linear, branched, or cyclic C1-C30 hydrocarbyl group, or R4 and R5, taken together with the carbon atoms in the first cyclopentadienyl ring to which they are directly connected, collectively form one or more substituted or unsubstituted rings annelated to the first cyclopentadienyl ring;
R12, R13, R14, and R15 are each independently a hydrogen, or a substituted or unsubstituted linear, branched, or cyclic C1-C20, preferably C1-C8, hydrocarbyl group; and
R16 is a hydrogen, a substituted or unsubstituted linear, branched (such as branched linear), or cyclic C1-C20, preferably C1-C8, hydrocarbyl group, substituted silyl or substituted germanyl group, or, taken together with one of R1, R2, and R3, is a bridging group connecting the first and second cyclopentadienyl rings, optionally at least three of R12, R13, R14, R15, and R16 are not hydrogen, optionally two or more of R12, R13, R14, R15, and R16 moieties may together form a fused ring or ring system, provided that the fused ring or ring system is not unsaturated when R1 is bridged to R16, and where R2 is not Me when R1 or R3 is bridged to R16;
M is a transition metal having an integer valency of v, wherein v is 3, 4, or 5;
each X is independently a halogen, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a diene, an amine, a phosphine, an ether, or a C1-C20 substituted or unsubstituted linear, branched, or cyclic hydrocarbyl group, or optionally two or more X moieties may together form a fused ring or ring system; and
m is an integer equal to v-2.

### Claim 27 (depends on 26)

The process of claim 26, wherein one of R1, R2, and R3 is a substituted or unsubstituted linear, branched, or cyclic C1-C6 hydrocarbyl group, and two of R1, R2, and R3 are each a hydrogen.

### Claim 28 (depends on 26)

The process of claim 26, wherein one of R1 and R3 is a substituted or unsubstituted linear, branched, or cyclic C1-C6 hydrocarbyl group, R2 is a hydrogen, and one of R1 and R3 is a substituted or unsubstituted linear, branched, or cyclic C1-C6 hydrocarbyl group, or, taken together with R16, is a bridging group connecting the first and second cyclopentadienyl rings.

### Claim 29 (depends on 28)

The process of claim 28, wherein the bridging group comprises:
where each G4, the same or different at each occurrence, is independently carbon, silicon, or germanium, and R17, the same or different at each occurrence, is each independently a C1-C20, preferably C1-C8, substituted or unsubstituted linear, branched, or cyclic hydrocarbyl group.

### Claim 30

The process of clam 26, wherein each X is independently a halogen or a substituted or unsubstituted linear, branched, or cyclic C1-C6 hydrocarbyl group; M comprises Zr or Hf and m is 2.

### Claim 31 (depends on 26)

The process of claim 26, wherein M is Zr, m is 2 and each X is independently a methyl, an ethyl, a propyl, a butyl, a phenyl, a benzyl, a chloride, a bromide, or an iodide.

### Claim 32 (depends on 25)

The process of claim 25, wherein the a polymerization reactor is a continuous stirred tank reactor or a continuous tubular reactor, the alpha-olefin is introduced to the reactor at a flow rate of at least 100 g/hr, the polymerization residence time is from 2 to 5 hours, and the polymerization temperature is 120° C. or more.

### Claim 33 (depends on 26)

The process of claim 26, where the vinylidene content of the PAO produced is 95% or more based on total moles of vinylidene, disubstituted vinylene, and trisubstituted vinylene in the PAO product, the Mn of the PAO product is 350 g/mol or less, the conversion is at least 60%, at least 70%, at least 80%, at least 90%, based upon the weight of the monomer entering the reactor and the PAO produced, the PAO dimer selectivity is at least 60%, based upon the weight of the PAO produced, and the productivity of the continuous process is at least 60,000 g/hour with a catalyst loading of 0.1 gram catalyst per gram of monomer or less.