# US 11,078,308 B2 · Processes to produce poly alpha-olefin trimers > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,078,308 B2 - Document ID: US11078308B2 - Status: Granted - Kind: B2 - Application number: 16/537,349 - Filed: 2019-08-09 - Published: 2019-11-28 - Granted: 2021-08-03 - 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; Monica D. Lotz; Babak LotfizadehDehkordi; Craig J. Emett; Najeeb M. Kuzhiyil; Jian Yang - Web page: https://patentgrep.com/patent/US11078308B2 ## CPC - C08F 10/14: Monomers containing five or more carbon atoms - C10M 107/10: containing aliphatic monomer having more than 4 carbon atoms - 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 - C08F 4/65908: {in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+} - C08F 4/65925: {two cyclopentadienyl rings being mutually non-bridged} - C07C 2531/14: of aluminium or boron - C07C 2531/22: Organic complexes - C10M 2203/045: used as base material - C10M 2205/0285: used as base material - C10N 2020/02: Viscosity; Viscosity index - C10N 2030/02: Pour-point; Viscosity index - C10N 2030/10: Inhibition of oxidation, e.g. anti-oxidants - C10N 2030/74: {Noack Volatility} - C10N 2040/04: Oil-bath; Gear-boxes; Automatic transmissions; Traction drives - C10N 2040/08: Hydraulic fluids, e.g. brake-fluids - C10N 2040/30: Refrigerators lubricants {or compressors lubricants} - C10N 2070/00: Specific manufacturing methods for lubricant compositions - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - C10M: LUBRICATING COMPOSITIONS (well drilling compositions C09K8/02); USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION (mould release, i.e. separating, agents for metals B22C3/00, for plastics or substances in a plastic state, in general B29C33/56, for glass C03B40/02; textile lubricating compositions D06M11/00, D06M13/00, D06M15/00; immersion oils for microscopy G02B21/33) - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - C10N: INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS ## Abstract The present disclosure generally relates to processes to produce alpha-olefin oligomers and poly alpha-olefins. In an embodiment, a process to produce a poly alpha-olefin (PAO) includes introducing a first alpha-olefin and a first catalyst system comprising 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 alpha-olefin is introduced to the reactor at a flow rate of about 100 g/hr or more. The first reactor effluent includes PAO dimer comprising at least 96 mol % of vinylidene and 4 mol % or less of trisubstituted vinylene and disubstituted vinylene, based on total moles of vinylidene, trisubstituted vinylene, and disubstituted vinylene. The method includes introducing the first reactor effluent, a second alpha-olefin and a second catalyst composition comprising an acid catalyst into a second reactor under second reactor conditions to form a second reactor effluent comprising PAO trimer. ## Claims ### Claim 1 A process to produce a poly alpha-olefin (PAO), comprising: introducing a first group of one or more alpha-olefins and a first catalyst system comprising a metallocene compound into a continuous stirred tank reactor or a continuous tubular reactor under first reactor conditions, wherein the 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 PAO dimer comprising at least 96 mol % of vinylidene and 4 mol % or less of trisubstituted vinylene and disubstituted vinylene, based on total moles of vinylidene, trisubstituted vinylene, and disubstituted vinylene; and introducing the first reactor effluent, a second group of one or more alpha-olefins and a second catalyst composition comprising an acid catalyst into 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: wherein: each of R1, R2, and R3 is independently hydrogen, a substituted or unsubstituted linear, branched, or cyclic C1-C20 hydrocarbyl group, wherein a first 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 2 (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 a substituted or unsubstituted linear, branched linear, 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 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 3 (depends on 1) The process of claim 1, wherein the first alpha-olefin is one or more C6-C32 alpha-olefin. ### Claim 4 (depends on 1) The process of claim 1, wherein the second alpha-olefin is one or more C6-C32 alpha-olefin. ### 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 second reactor conditions comprise an acid catalyst loading of from about 5 mmolCat/100 gLAO to about 15 mmolCat/100 gLAO. ### Claim 7 (depends on 1) The process of claim 1, wherein the second reactor conditions comprise 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 amount of PAO trimer in the second reactor effluent is 75 wt % or more, based on a total weight of PAO dimer, PAO trimer, and higher oligomers, where the higher oligomers are oligomers that have degree of polymerization of 4 or more, of alpha-olefin in the second reactor effluent. ### Claim 10 (depends on 1) The process of claim 1, wherein the second reactor effluent comprises, 75 wt % or more of PAO trimer, 9 wt % or less of PAO dimer, and 16 wt % or less of higher oligomers of alpha-olefin, based on a total weight of PAO dimer, PAO trimer, and higher oligomers of alpha-olefin in the second reactor effluent. ### Claim 11 (depends on 1) The process of claim 1, wherein the amount of PAO trimer in the second reactor effluent is greater than 80 wt %, based on a total weight of PAO dimer, PAO trimer, and higher oligomers of alpha-olefin in the second reactor effluent. ### Claim 12 (depends on 1) The process of claim 1, wherein the PAO dimer in the first reactor effluent further comprises, based on the total moles (100 mol %) of vinylidene, disubstituted vinylene, and trisubstituted vinylene in the PAO dimer in the first reactor effluent: up to 4 mol % of trisubstituted vinylene, up to 4 mol % of disubstituted vinylene, or up to 4 mol % of trisubstituted vinylene and disubstituted vinylene. ### Claim 13 A process to produce a poly alpha-olefin (PAO), comprising: introducing a first group of one or more alpha-olefins and a first catalyst system comprising a metallocene compound into a continuous stirred tank reactor or a continuous tubular reactor under first reactor conditions, wherein the 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 PAO dimer comprising at least 96 mol % of vinylidene and 4 mol % or less of trisubstituted vinylene and disubstituted vinylene, based on total moles of vinylidene, trisubstituted vinylene, and disubstituted vinylene; and introducing the first reactor effluent, a second group of one or more alpha-olefins and a second catalyst composition comprising an acid catalyst into a second reactor under second reactor conditions to form a second reactor effluent comprising PAO trimer, wherein the PAO dimer in the first reactor effluent comprises, based on total moles (100 mol %) of vinylidene, disubstituted vinylene, and trisubstituted vinylene in the PAO dimer in the first reactor effluent: 98 mol % or more vinylidene, and up to 2 mol % of trisubstituted vinylene, and/or disubstituted vinylene. ### Claim 14 (depends on 1) The process of claim 1, wherein the PAO dimer in the first reactor effluent further comprises, based on the total moles (100 mol %) of vinylidene, disubstituted vinylene, and trisubstituted vinylene in the PAO dimer in the first reactor effluent: 98 mol % or more vinylidene, and up to 1 mol % trisubstituted vinylene, up to 1 mol % disubstituted vinylene, or up to 1 mol % trisubstituted vinylene and disubstituted vinylene. ### Claim 15 (depends on 1) The process of claim 1, wherein the PAO dimer in the first reactor effluent further comprises, based on the total moles (100 mol %) of vinylidene, disubstituted vinylene, and trisubstituted vinylene in the PAO dimer in the first reactor effluent: 98 mol % or more vinylidene, and up to 0.5 mol % trisubstituted vinylene, up to 0.5 mol % disubstituted vinylene, or up to 0.5 mol % trisubstituted vinylene and disubstituted vinylene. ### Claim 16 (depends on 1) The process of claim 1, wherein the activator comprises one or more of: N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, triphenylcarbonium tetrakis(perfluorophenyl)borate, triphenylcarbonium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluorophenyl)aluminate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)aluminate alumoxane, modified alumoxane, and aluminum alkyl. ### Claim 17 (depends on 1) The process claim 1, wherein the second catalyst composition further comprises an alcohol and an alkyl acetate. ### Claim 18 (depends on 1) The process of claim 1, wherein the metallocene compound is selected from the group consisting of: and a combination thereof. ### Claim 19 (depends on 1) The process of claim 1, wherein the second reactor conditions include a second reactor temperature of less than 60° C. and an acid catalyst composition loading of less than 30 mmol per 100 g of second alpha-olefin. ### Claim 20 (depends on 1) The process of claim 1, further comprising functionalizing the PAO trimer with a reactant to form a functionalized PAO product. ### Claim 21 (depends on 20) The process of claim 20, further comprising hydrogenating the PAO dimer, PAO trimer, or functionalized PAO product to form a hydrogenated PAO product. ### Claim 22 (depends on 21) The process of claim 21, wherein the hydrogenated PAO product has a kinematic viscosity at 100° C. of from 3.4 to 4.0 cSt and a Noack volatility (y) that does not exceed the value defined by the following equation, where x is the kinematic viscosity at 100° C.: y=−21.0x2+148.7x−248.9. ### Claim 23 (depends on 1) The process of claim 1 wherein the process that produces the first reactor effluent 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 24 (depends on 23) The process of claim 23, 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 25 (depends on 24) The process of claim 24, 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 26 (depends on 23) The process of claim 23, 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 27 (depends on 23) The process of claim 23 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 100,000 g/hr, the polymerization residence time is from 2 to 5 hours, and the polymerization temperature is 120° C. or more. ### Claim 28 (depends on 27) The process of claim 27 where the vinylidene content of the PAO produced is 96% 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 80% 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. ### Claim 29 A process to produce a poly alpha-olefin (PAO), comprising: introducing a first group of one or more alpha-olefins and a first catalyst system comprising a metallocene compound into a continuous stirred tank reactor or a continuous tubular reactor under first reactor conditions, wherein the 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 PAO dimer comprising at least 96 mol % of vinylidene and 4 mol % or less of trisubstituted vinylene and disubstituted vinylene, based on total moles of vinylidene, trisubstituted vinylene, and disubstituted vinylene; and introducing the first reactor effluent, a second group of one or more alpha-olefins and a second catalyst composition comprising an acid catalyst into 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: 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 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 30 (depends on 29) The process of claim 29, wherein: the first alpha-olefin is one or more C6-C32 alpha-olefin, the second alpha-olefin is one or more C6-C32 alpha-olefin, the acid catalyst is BF3, and the second reactor effluent comprises, 75 wt % or more of PAO trimer, 9 wt % or less of PAO dimer, and 16 wt % or less of higher oligomers of alpha-olefin, based on a total weight of PAO dimer, PAO trimer, and higher oligomers of alpha-olefin in the second reactor effluent.