Method for activating metallocene catalyst in reactor to improve catalyst productivity in PAO production

Abstract

A process is provided for producing poly-alpha-olefin (PAO) with high catalyst efficiency, good kinetics, and high conversion. In at least one embodiment, a method includes feeding at least one catalyst to an oligomerization reactor; feeding at least one activator to the oligomerization reactor; feeding one or more linear alpha-olefins to the oligomerization reactor; and oligomerizing the one or more linear alpha-olefins in the presence of a catalyst and an activator within an oligomerization reactor to produce a poly-alpha-olefin (PAO). The catalyst and the activator are not in contact with each other outside the oligomerization reactor.

Description

[0001] This application claims priority to and the benefit of U.S. Provisional Application No. 63 / 503,554, filed May 22, 2023, which is incorporated by reference herein in its entirety. TECHNICAL FIELD

[0002] Embodiments of the present invention generally relate to a process for making alpha-olefin oligomers and polyalpha-olefins made from the process. BACKGROUND

[0003] Alpha-olefins and polyalpha-olefins (PAO) are commonly used as intermediates in the manufacture of many commercial products such as lubricant base oil components, base stocks, and surfactants. PAOs have a wide availability of viscosity grades, and the vast majority of commercial PAOs are low viscosity PAOs (less than 10 cSt KV100). PAOs are typically produced from either BF3or metallocene catalyst systems. More recently, PAOs known as “hybrid PAOs” have been produced using two types of catalyst systems.

[0004] Hybrid PAOs are reaction products of a metallocene-based intermediate (e.g., unhydrogenated metallocene dimer) with linear alpha-olefins (LAOs) using different types of catalyst systems, such as a BF3-alcohol promoter catalyst system. Typically, the metallocene-based intermediate product from a first type of catalyst system, such as a metallocene, is fed to a second oligomerization reactor using a second type of catalyst system, such as a BF3-alcohol promoter catalyst system.

[0005] Conventional metallocene catalyst systems require activation and in some cases the presence of hydrogen. Metallocene catalysts are typically mixed with one or more activators in solution to activate the metallocene prior to being fed to a reactor. Activated metallocene catalysts are known to be more susceptible to poisoning than their unactivated counterparts. So when batches of activated catalyst are not used immediately and are kept in storage, the likelihood of poisoning increases exponentially. In addition to the likelihood of poisoning, cations in the activator can insert into the active site of the metallocene catalyst and eventually hinder the oligomerization of olefins when there is enough time.

[0006] Accordingly, there is a need for new processes to produce PAOs from metallocenes with high catalyst efficiency, good kinetics, and high conversion. There is also a need for improved processes and equipment for producing PAOs from feedstocks containing PAO dimers, such as low viscosity PAOs including hybrid trimers. SUMMARY

[0007] Methods of making polyalphaolefins (PAO) with high catalyst efficiency, good kinetics, and high conversion are provided. In at least one embodiment, the method includes feeding at least one catalyst to an oligomerization reactor; feeding at least one activator to the oligomerization reactor; feeding one or more linear alpha-olefins to the oligomerization reactor; and oligomerizing the one or more linear alpha-olefins in the presence of the catalyst and the activator within the oligomerization reactor to produce a polyalphaolefin (PAO), wherein the catalyst and the activator do not contact each other outside of the oligomerization reactor.

[0008] In at least another embodiment, the method includes feeding a first catalyst to a first oligomerization reactor; feeding an activator to the first oligomerization reactor; feeding one or more linear alpha-olefins to the first oligomerization reactor; oligomerizing the one or more linear alpha-olefins in the presence of the first catalyst and the activator within the first oligomerization reactor to produce a polyalphaolefin (PAO) intermediate, wherein the first catalyst and the activator do not contact each other outside of the first oligomerization reactor; feeding the PAO intermediate and one or more additional linear alpha-olefins to a second oligomerization reactor; feeding a second catalyst to the second oligomerization reactor; and oligomerizing the PAO intermediate and the one or more additional linear alpha-olefins in the presence of the second catalyst within the second oligomerization reactor to produce a polyalphaolefin (PAO) product.

[0009] In at least another embodiment, the method includes feeding a metallocene catalyst to a first oligomerization reactor; feeding an activator to the first oligomerization reactor; feeding one or more linear alpha-olefins to the first oligomerization reactor; oligomerizing the one or more linear alpha-olefins in the presence of the metallocene catalyst and the activator within the first oligomerization reactor to produce a polyalphaolefin (PAO) intermediate, wherein the metallocene catalyst and the activator do not contact each other outside of the first oligomerization reactor; feeding the PAO intermediate and one or more additional linear alpha-olefins to a second oligomerization reactor; feeding a BF3catalyst to the second oligomerization reactor; and oligomerizing the PAO intermediate and the one or more additional linear alpha-olefins in the presence of the BF3catalyst within the second oligomerization reactor to produce a polyalphaolefin (PAO) product.

[0010] These and other features and attributes of the disclosed methods of the present disclosure and their advantageous applications and / or uses will be apparent from the following detailed description, in which reference is made to the following figures. BRIEF DESCRIPTION OF DRAWINGS

[0011] For the purpose of helping those of ordinary skill in the relevant art to make and use the subject matter herein, reference is made to the accompanying drawings, in which:

[0012] Figure 1 An illustrative method schematic is shown for forming a polyalphaolefin in accordance with one or more embodiments provided herein.

[0013] Figure 2 An illustrative system is shown for producing poly-alpha-olefins using two or more oligomerization systems arranged in series according to one or more embodiments provided herein. DETAILED DESCRIPTION

[0014] It is to be understood that the following disclosure describes several exemplary embodiments for implementing various features, structures, and / or functions of the present application. Exemplary embodiments of components, arrangements, and configurations are described below to simplify the present disclosure; however, these exemplary embodiments are provided only as examples and are not intended to limit the scope of the present application. Additionally, the present disclosure can repeat reference numerals and / or letters in the various exemplary embodiments and across the figures provided herein. This repetition of reference numerals and / or letters is for the purpose of simplicity and clarity and does not necessarily

[0015] The present disclosure provides a method for producing poly-alpha-olefins using metallocene catalyst compounds with high catalyst efficiency, excellent kinetics, and high conversion. The metallocene catalyst remains unactivated (i.e., remains unactivated) prior to addition of the metallocene to the reactor. By only contacting the metallocene and activator in the reactor, the likelihood of poisoning or otherwise deactivating the metallocene is significantly reduced, if not eliminated. Further, it has been surprisingly found that the metallocene catalyst can be sufficiently activated within the reactor in the presence of the olefins to be oligomerized, or in the inlet piping just prior to the reactor containing the olefins to be oligomerized, without any adverse impact on catalyst productivity, catalyst activity, residence time, or the formation and selectivity of the intended PAO product. In this manner, the activated catalyst avoids poisoning and maintains its reactivity to the available olefins. Additionally, the unactivated catalyst is more stable than its activated counterpart, and as such the unactivated metallocene catalyst can be in solution for longer without degradation in quality.

[0016] "Catalyst productivity" is the amount of PAO produced per amount of metallocene compound used, reported in units of grams PAO per grams metallocene. To calculate catalyst productivity, only the weight of the transition metal component of the catalyst is used.

[0017] "Catalyst activity" is a measure of how active a catalyst is and is reported as the mass of product PAO (P) produced per mole of catalyst (cat) used, typically reported as kg P / mol cat in a continuous process or kg P / mmol / hr in a batch process, unless otherwise indicated. To calculate catalyst activity, the molar amount of transition metal component of the catalyst is used.

[0018] "Residence time" is defined as the average time that reactants and products are in the reactor under steady state conditions in a continuous process. Residence time is measured as the amount of material in the reactor (i.e., grams) divided by the flow out (i.e., grams / hour).

[0019] The term "continuous" means a system that operates for a period of time without interruption or stoppage, for example, where reactants are continuously fed into a reaction zone and products are continuously or periodically withdrawn without stopping the reactions in the reaction zone. For example, a continuous process to produce a polymer would be one in which reactants are continuously introduced into one or more reactors and the polymer product is continuously removed.

[0020] "Solution oligomerization" means an oligomerization process in which oligomerization is carried out in a liquid medium, such as an inert solvent or monomer(s) or a blend thereof. Solution oligomerization is typically homogeneous. Homogeneous oligomerization is oligomerization in which the oligomer product is dissolved in the oligomerization medium. Such systems are typically not hazy, as described in Oliveira, J. V. et al. (2000), "High-Pressure Phase Equilibria for Polypropylene-Hydrocarbon Systems," Ind. Eng. Chem. Res., Vol. 39(12), pp. 4627-4633.

[0021] Bulk oligomerization means an oligomerization process in which the oligomerized monomer and / or comonomer is used as a solvent or diluent, with little or no use of an inert solvent or diluent. A small portion of inert solvent can be used as a carrier for the catalyst and scavenger. A bulk oligomerization system contains less than about 25 wt% of an inert solvent or diluent, such as less than about 10 wt%, such as less than about 1 wt%, such as 0 wt%.

[0022] As used herein, "oligomerization degree" refers to the number of monomer units of an oligomer. For example, an oligomer having an oligomerization degree of 3 is an oligomer that is the reaction product of 3 monomers. A "dimer" has an oligomerization degree of 2, and a "trimer" has an oligomerization degree of 3.

[0023] Figure 1An illustrative system for forming polyalpha-olefins ("PAO") according to at least one embodiment provided herein is described. The system 100 includes one or more reactors 110, one or more catalyst tanks 120, and one or more activator tanks 130. The contents of the catalyst tank(s) 120 are pumped or otherwise transferred directly to the reactor 110. The activator is mixed with the incoming olefin feed (line 140) prior to feeding the olefin to the reactor 110 or the contents of the activator tank(s) 130 are pumped or otherwise transferred directly to the reactor 110. The catalyst and activator are not in contact or otherwise mixed with each other outside of the reactor 110. By keeping the catalyst separate from the activator until oligomerization is desired, the catalyst is not exposed to the activator outside of the reactor 110 and the opportunity for any premature poisoning or deactivation is significantly reduced. Surprisingly, it has been found that the catalyst can be sufficiently activated within the reactor 110 and does not need to be pre-activated prior to being fed to the reactor 110. It has also been surprisingly found that there is no adverse impact on catalyst productivity, catalyst activity, residence time, or the formation and selectivity of the intended PAO product using this separate feeding approach.

[0024] The catalyst can be any suitable metallocene catalyst. In one or more embodiments, the metallocene compound can be represented by the following formula:

[0025]

[0026] wherein: each R1, R2, and R3is independently hydrogen or a substituted or unsubstituted linear, branched linear, or cyclic C1-C20 hydrocarbyl or silylcarbyl radical; each of R4and R7is independently a substituted or unsubstituted linear, branched linear, or cyclic C1-C30 hydrocarbyl or silylcarbyl radical; each of R8, R9, R10, R11, and R12is independently hydrogen, or a substituted or unsubstituted linear, branched linear, or cyclic C1-C20 hydrocarbyl, silylcarbyl, or germanyl radical, or optionally at least three of R8, R9, R10, R11, and R12are not hydrogen; each of R13, R14, R15, R16, R17, and R18is independently hydrogen or a substituted or unsubstituted linear, branched linear, or cyclic C1-C20 hydrocarbyl or silylcarbyl radical; M is a Group 3, 4, or 5 transition metal; each X is independently a halogen, hydride, amide, alkoxide, sulfide, phosphide, diene, amine, phosphine, ether, or C1-C20 substituted or unsubstituted linear, branched, or cyclic hydrocarbyl radical, or optionally two or more X moieties can together form a fused ring or ring system; and m is an integer equal to 1, 2, or 3.

[0027] Any suitable activator compatible with the metallocenes described above can be used. For example, in one or more embodiments, the activator can be or can include any one or more of the following:

[0028] N,N-dimethylanilinium tetra(perfluorophenyl)borate,

[0029] N,N-dimethylanilinium tetra(perfluoronaphthyl)borate,

[0030] triphenylcarbenium tetra(perfluorophenyl)borate ,

[0031] triphenylcarbenium tetra(perfluoronaphthyl)borate ,

[0032] N,N-dimethylanilinium tetra(perfluorophenyl)aluminate,

[0033] N,N-dimethylanilinium tetra(perfluoronaphthyl)aluminate,

[0034] aluminoxane,

[0035] modified aluminoxane, and

[0036] an alkylaluminum represented by formula (V):

[0037] ,

[0038] wherein E is nitrogen or phosphorus; d is 1, 2, or 3; k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6; n-k = d; R1', R2', and R3' are independently C1-C50 hydrocarbyl radicals, optionally substituted with one or more alkoxy radicals, silyl radicals, halogen atoms, or halogen-containing groups, wherein R1', R2', and R3' collectively 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, alkoxy, aryloxy, hydrocarbyl, substituted hydrocarbyl, halogenated hydrocarbyl, substituted halogenated hydrocarbyl, or halogen-substituted hydrocarbyl radical.

[0039] Examples of other suitable metallocenes, activators, and scavengers are disclosed and described in U.S. Publication No. 2021 / 0122859 Al. U.S. Patent No. 9,409,834 (e.g., at column 33 line 37 to column 34 line 61) provides another detailed description of suitable scavengers. Suitable scavengers can also include those mentioned in U.S. Patent No. 5,241,025, EP-A 0426638, and WO 1997 / 022635.

[0040] Still referring to Figure 1The feed to reactor 110 includes one or more a-olefins. The one or more a-olefins in the feed can be any one or more C2-C32a-olefins, such as C4-C32a-olefins, such as C6-C30a-olefins, such as C6-C24a-olefins, such as C6-C18a-olefins, C8-C18a-olefins, C6-C16a-olefins, C6-C12a-olefins, or combinations thereof. Non-limiting examples of linear a-olefins include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, and combinations thereof. The a-olefins used herein can be produced directly from ethylene growth processes carried out by several commercial production methods, or the a-olefins can be produced from CO / H2synthesis gas by Fischer-Tropsch hydrocarbon synthesis. Suitable a-olefins can also be formed from the metathesis of internal olefins with ethylene or from the cracking of petroleum or Fischer-Tropsch synthesis waxes at high temperatures or any other a-olefin synthesis pathway. The feed olefins can also be any olefin mixture containing C4-C20a-olefins produced by other linear a-olefin processes, as described in Chapter 3, "Routes to Alpha-Olefins," of the book Alpha Olefins Applications Handbook, edited by G. R. Lappin and J. D. Sauer, published by Marcel Dekker, Inc. N.Y. in 1989.

[0041] In some embodiments, at least a portion (e.g., at least about 80 mol%, at least about 85 mol%, at least about 90 mol%, at least about 95 mol%, at least about 96 mol%, at least about 98 mol%, at least about 99 mol%, at least about 99.5 mol%, or all of, taking into account some impurities present in the feed components) of the a-olefins in the feed are linear a-olefins (LAOs), i.e., those a-olefins that have no branches attached to their carbon backbone. Non-limiting examples of LAOs are 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-octadecene, 1-eicosene, C22, C24, C26, C28, C30, and C32 LAOs, and combinations thereof.

[0042] When a single a-olefin is fed to the oligomerization reactor 110, the PAO so obtained is a homopolymer. The homopolymer can have a substantially uniform molecular structure, and thus desirable physical and rheological properties such as viscosity index. The homopolymer can tend to have pendant groups attached to the carbon backbone at a highly uniform length.

[0043] In certain cases, it can be desirable to feed a mixture of two, three, or even more a-olefins in the production of a copolymer PAO product. For that purpose, a-olefins having the following combinations can be advantageous: C6 / C8, C6 / C10, C6 / C12, C6 / C14, C6 / C16, C8 / C10, C8 / C12, C8 / C14, C8 / C16, C10 / C12, C10 / C14, C10 / C16, C10 / C18, C12 / C14, C12 / C16, C12 / C18, C12 / C20, C6 / C8 / C10, C6 / C8 / C12, C6 / C8 / C14, C6 / C10 / C12, C6 / C10 / C14, C8 / C10 / C12, C8 / C11 / C14, C8 / C12 / C14, C10 / C12 / C16, C10 / C12 / C18, C10 / C14 / C16, C10 / C14 / C18, and the like. In some embodiments, at least one of the a-olefins in the mixture feed can be a LAO. In some embodiments, substantially all of the a-olefins in the mixture feed can be LAOs.

[0044] In some embodiments, the a-olefin monomers are mono-olefins containing one C=C bond per monomer molecule, although those containing two or more C=C bonds per monomer molecule can also be used.

[0045] In some embodiments, the monomers useful herein include substituted or unsubstituted C6-C 32 a-olefins, or C6-C 20 a-olefins, or C6-C 14 a-olefins, or hexene, heptene, octene, nonene, decene, undecene, dodecene, tetradecene, and isomers thereof. In some embodiments, the poly-a-olefins produced herein comprise about 50 mol% or more (e.g., about 60 mol% or more, e.g., about 70 mol% or more, e.g., about 80 mol% or more, e.g., about 90 mol% or more, e.g., about 99 mol% or more) of one or more C6-C32(e.g., C6-C20, e.g., C8-C18) a-olefin monomers.

[0046] Useful C6-C32 alpha-olefin monomers include hexene, heptene, octene, nonene, decene, undecene, dodecene, tetradecene, substituted derivatives thereof, and isomers thereof. In some embodiments, the monomer is a C6-C20 alpha-olefin, or a C6-C14 alpha-olefin and / or a C8-C12 alpha-olefin. In some embodiments, the olefin monomer is one (or two, or three) or more of hexene, heptene, octene, nonene, decene, dodecene, and tetradecene.

[0047] The PAOs described herein can be produced in one or more homogeneous solution processes. In each process, two or more reactors 110 (only one of which is depicted in FIG. 1) can be used in series or in parallel. Each reactor 110 can be a continuous stirred tank reactor or a plug flow reactor. Each reactor 110 can or can not have internal cooling and can or can not be refrigerated for the monomer feed. For general process conditions, see the general disclosure of U.S. Patent No. 5,705,577. The metallocene compound, activator, and (when needed) co-activator are delivered as a solution or slurry in a solvent or separately in the alpha-olefin feed stream. The catalyst can be supported or unsupported. The catalyst and its activator(s) are not mixed outside the reactor 110 or pre-activated and pumped to the reactor as an activated solution or slurry. Figure 1

[0048] When a solid supported catalyst is used, the slurry oligomerization process is typically operated at similar temperature, pressure, and residence time ranges as described for the solution process. In the slurry process, a suspension of the solid catalyst, promoter, monomers, and comonomers is added. The suspension, including the diluent, is removed from the reactor intermittently or continuously. The catalyst is then separated from the product by filtration, centrifugation, or sedimentation. The fluid is then distilled to remove the solvent, any unreacted components, and light products. A portion or all of the solvent and unreacted components or light components can be recycled for reuse.

[0049] If the catalyst used is unsupported or is a solution catalyst, the product can still contain soluble, suspended, or mixed catalyst system components when the reaction is complete or when the product is withdrawn from the reactor 110. These components can be deactivated and / or removed. Any conventional catalyst deactivation method or water wash method can be used to remove the catalyst system components.

[0050] Suitable hydrocarbon solvents are selected from C4-C10 linear, branched, or cyclic alkanes. Suitable hydrocarbon solvents can also be selected from one or more C6-C32 alpha-olefins (or C8-C16). The solvent can also be selected from one or more C6-C32 alpha-olefins (LAO) mixed with C4-C10 linear, branched, or cyclic alkanes (HC).

[0051] ​The oligomerization reaction mixture can then be quenched, for example, by adding a quenching agent such as water, CO2, methanol, ethanol, mixtures thereof, or the like. Subsequently, the oligomerization reaction mixture can be separated to remove residual monomer, which can be recycled to the oligomerization reactor. Monomer removal can be performed by, for example, flashing under vacuum, distillation, or extraction. The resulting mixture can include vinylidene, trisubstituted vinylene, optionally disubstituted vinylene, and optionally vinyl groups.

[0052] Oligomerization conditions within the reactor can include a reactor temperature of about 0 °C to about 300 °C, for example, about 10 °C to about 230 °C, for example, about 25 °C to about 200 °C, for example, about 100 °C to about 160 °C, for example, about 110 °C to about 155 °C, for example, about 130 °C to about 148 °C, for example, about 135 °C to about 145 °C. In some embodiments, the reactor conditions can include a reactor temperature of about 110 °C, about 130 °C, about 131 °C, about 132 °C, about 133 °C, about 134 °C, about 135 °C, about 136 °C, about 137 °C, about 138 °C, about 139 °C, about 140 °C, about 141 °C, about 142 °C, about 143 °C, about 144 °C, about 145 °C, about 146 °C, about 147 °C, or about 148 °C. In at least one embodiment, the oligomerization conditions within the reactor can include a reactor temperature of about 110 °C or greater, about 120 °C or greater, for example, about 110 °C to about 180 °C, for example, about 120 °C to about 180 °C, for example, about 130 °C to about 180 °C.

[0053] Oligomerization conditions within the reactor can include a reactor pressure of about 1.5 psia to about 1500 psia, for example, about 7 psia to about 1200 psia, for example, about 15 psia to about 750 psia, for example, about 30 psia to about 100 psia.

[0054] Oligomerization conditions within the reactor can include a residence time of, for example, less than about 72 hours, for example, about 1 minute to about 20 hours, for example, about 5 minutes to about 10 hours, for example, about 30 minutes to about 9 hours, for example, about 1 hour to about 5 hours, for example, about 3 hours to about 4 hours. In at least one embodiment, the reactor conditions can include a residence time of about 24 hours or less, for example, about 10 hours or less, for example, about 5 hours or less, for example, about 3 hours or less.

[0055] Additional oligomerization conditions are disclosed and described in US US20210122859A1, for example, solvent charge amount, catalyst charge amount / catalyst loading, flow rate of catalyst system, flow rate of alpha-olefin feed, molar ratio of catalyst:activator, catalyst charge amount, scavenger charge amount, activator charge amount, and the like.

[0056] The reactor effluent (e.g., PAO) can be a homopolymer made from a single alpha-olefin monomer or a copolymer made from a combination of two or more alpha-olefin monomers. In some embodiments, the alpha-olefin monomer(s) can include (can consist essentially of, or can consist of) 1-hexene, 1-octene, 1-decene, 1-dodecene, or combinations thereof, such as 1-octene, 1-decene, and 1-dodecene. In embodiments, the PAO from the first oligomerization process is a homopolymer of any C8-C12 alpha-olefin, i.e., the PAO is a homopolymer of 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, or 1-tetradecene. In some embodiments, the PAO is a homopolymer of decene. In at least one embodiment, the PAO is a copolymer comprising decene and one or more of any of the monomers listed above.

[0057] Figure 2 Another illustrative system 200 is shown for making PAO from two or more oligomerization processes. Such PAO can be made from two or more oligomerization processes arranged in series, as described in Figure 2 For example, the effluent from the first oligomerization reactor 110 can be used as feed to the second oligomerization reactor 210 alone or can be combined with alpha-olefin feedstock (typically of the type used as the olefin starting material for the first oligomerization process), as described above. Other portions of the effluent from the first oligomerization reactor 110 can also be used as feedstock for the second oligomerization reactor 210, including unreacted LAO. Optionally, one or more scavengers can be added to the effluent from the first oligomerization reactor 110 via line 205. Alpha-olefins having the same attributes as those used for the first oligomerization process can be used for the second oligomerization process. For example, 100% dimers in the effluent from the first oligomerization reactor 110 (also referred to as "intermediate PAO") is preferred, however, the typical ratio of PAO dimer portion of the intermediate PAO to alpha-olefin portion of the intermediate PAO can be about 99: 1 to 10:90 by weight of the intermediate PAO, or 90: 10 to about 10:90, such as about 95:5 to about 50:50. In at least one embodiment, the PAO dimers of the intermediate PAO can constitute about 50 mol% of the olefinic feed material to the second reactor, as the properties and distribution of the final product (depending in part on the starting material) can be advantageously affected by feeding the intermediate PAO in equimolar ratio to the alpha-olefin. The olefinic feed material to the second reactor can also contain up to about 50 mol% fresh LAO.

[0058] The second oligomerization can be carried out in one or more reactors 210, for example, a CSTR. In some embodiments, the residence time in the reactor 210 for the second oligomerization can be about 1 minute to 10 hours, for example, about 1 hour to about 7 hours, for example, about 1 hour to about 2 hours. The second oligomerization can also be carried out in two reactors 210 in series, for example, two continuous stirred tank reactors (CSTRs) in series. In some embodiments, the residence time in the first reactor for the second oligomerization can be about 0.25 hours to about 5 hours, for example, about 0.5 hours to about 3 hours, and the residence time in the second reactor for the second oligomerization can be about 0.25 hours to about 5 hours, for example, about 0.5 hours to about 3 hours.

[0059] Preferably, an acid catalyst composition or a non-transition metal catalyst is used for the second oligomerization process. Such suitable catalysts can be Lewis acid catalysts. U.S. Patent Publication Nos. 2009 / 0156874 and 2009 / 0240012 describe processes that can be used for the second oligomerization, where details of the feedstocks, compositions, catalysts and co-catalysts, and process conditions are mentioned. The Lewis acid catalysts of US 2009 / 0156874 and US 2009 / 0240012 include the metal and metalloid halides conventionally used as Friedel-Crafts catalysts, and examples include AICI3, BF3, AIBr3, TiCI3, and TiCI4, alone or with a proton promoter / activator. Boron trifluoride (BF3) is commonly used, but is not particularly suitable unless it is used with a proton promoter. Useful co-catalysts are well known and described in detail in US 2009 / 0156874 and US 2009 / 0240012. Solid Lewis acid catalysts such as synthetic or natural zeolites, acid clays, polymeric acid resins, amorphous solid catalysts such as silica-alumina, and heteropolyacids such as tungstic zirconium, tungstic molybdenum, tungstic vanadium, phosphotungstate, and molybdotungstovanadogermanate (e.g., WOx / ZrO2, WOx / MoO3) can also be used, but these are generally not economically favored. Additional process conditions and other details are described in detail in US 2009 / 0156874 and US 2009 / 0240012, and incorporated herein by reference.

[0060] The temperature for the second oligomerization in the second reactor(s) 210 can be about 0°C to about 60°C, for example, about 10°C to about 55°C, for example, about 20°C to about 40°C, about 10°C to about 40°C, or about 15°C to about 25°C. The temperature for the second oligomerization in the second reactor can be less than about 32°C, for example, about 15°C to about 30°C, for example, about 20°C to about 25°C. The reactor pressure can be about 10 psia to about 35 psia, for example, about 15 psia to about 25 psia, for example, about 19 psia to about 21 psia.

[0061] The acid catalyst composition charge amount for the second oligomerization in the second reactor(s) 210 can be from about 0.5 mmol / 100 g LAO (mmolCat / 100 g LAO) to about 30 mmolCat / 100 g LAO, such as from about 5 mmolCat / 100 g LAO to about 15 mmolCat / 100 g LAO, such as from about 6 mmolCat / 100 g LAO to about 14 mmolCat / 100 g LAO, such as about 8 mmolCat / 100 g LAO, about 10 mmolCat / 100 g LAO, or about 12 mmolCat / 100 g LAO.

[0062] The molar ratio of PAO dimers to LAO for the intermediate PAO used in the second oligomerization process can be about 1 : 1 or greater, such as from about 1.5 to about 10: 1, such as from about 2: 1 to about 5: 1, such as from about 3: 1 to about 4: 1. The molar ratio of PAO dimers to LAO for the intermediate PAO used in the second oligomerization process can be from about 0.1 : 1 to about 10: 1, such as from about 0.5 to about 5: 1, such as from about 0.5: 1 to about 3: 1, such as from about 0.8: 1 to about 1.2: 1, such as from about 0.9: 1 to about 1.1 : 1.

[0063] The effluent from the second reactor(s) 210 in the second oligomerization process can be a homopolymer made from a single alpha-olefin monomer or a copolymer made from a combination of two or more alpha-olefin monomers. The alpha-olefin monomer(s) can include (consist essentially of, or consist of) 1 -hexene, 1 -octene, 1 -decene, 1 -dodecene, or combinations thereof, such as 1 -octene, 1 -decene, and 1 -dodecene. The PAO from the second oligomerization process can be a homopolymer of any C8-C12 alpha-olefin, i.e., the PAO is a homopolymer of 1 -hexene, 1 -heptene, 1 -octene, 1 -nonene, 1 -decene, 1 -undecene, 1 -dodecene, or 1 -tetradecene. In some embodiments, the PAO is a homopolymer of decene. In at least one embodiment, the PAO is a copolymer comprising decene and one or more of any of the monomers listed above.

[0064] Functionalized PAO and uses of functionalized PAO

[0065] The intermediate PAO from the first oligomerization process and / or the PAO from the second oligomerization process ("PAO product") can be functionalized (and can optionally be hydrogenated) with one or more reactants by various chemical reactions to produce a functionalized PAO product, as known in the art and as described in U.S. Patent No. 6,022,929; A. Toyota et al. (2002) Polymer Bulletin, vol. 48, pp. 213-219; and J. Am. Chem. Soc. (1990) vol. 112, pp. 7433-7434. In some embodiments, the functionalized PAO produced herein is further functionalized (derivatized), for example as described in U.S. Patent No. 6,022,929; A. Toyota et al. (2002) Polymer Bulletin, vol. 48, pp. 213-219; and J. Am. Chem. Soc. (1990) vol. 112, pp. 7433-7434; and WO 2009 / 155472.

[0066] The unsaturated PAO product provided herein can contain greater than or equal to about 80 mol% vinylidene, for example 90 mol% vinylidene, for example 93 mol% vinylidene, based on the total moles of vinyl, vinylidene, disubstituted vinylene, and trisubstituted vinylene contained therein. In some embodiments, the unsaturated polyalpha-olefin product comprises 93 mol% to 99.9 mol% vinylidene, 0.1 mol% to 3.5 mol% trisubstituted vinylene, 3.0 mol% or less disubstituted vinylene, 3.0 mol% or less vinyl groups, based on the total moles of vinylidene, trisubstituted vinylene, disubstituted vinylene, and vinyl groups contained therein; and a number average molecular weight (Mn) of 1500 g / mol or less, measured by1H NMR.

[0067] In some embodiments, the unsaturated PAO product can contain less than or equal to about 1.0 mol% disubstituted vinylene (when present), less than or equal to about 1.0 mol% vinyl groups (when present), and a number average molecular weight (Mn) of 1000 g / mol or less, measured by1H NMR.

[0068] The resulting PAO can contain two or more monomers, or three or more monomers, or four or more monomers, or five or more monomers. For example, a C8, C10, C12-linear alpha-olefin mixture, or a C6, C7, C8, C9, C10, C11, C12, C13, C14-linear alpha-olefin mixture, or a C6, C8, C10, C12, C14, C16, C18-linear alpha-olefin mixture can be used as the feed. The resulting PAO can contain less than about 50 mol% C2, C3, and C4 monomers, or less than about 40 mol%, or less than about 30 mol%, or less than about 20 mol%, or less than about 10 mol%, or less than about 5 mol%, or less than about 3 mol%, or about 0 mol%. The resulting PAO can contain less than about 50 mol% ethylene, propylene, and butylene, or less than about 40 mol%, or less than about 30 mol%, or less than about 20 mol%, or less than about 10 mol%, or less than about 5 mol%, or less than about 3 mol%, or about 0 mol%. The resulting PAO can contain less than about 40 mol%, or less than about 20 mol%, or less than about 10 mol%, or less than about 5 mol%, or less than about 3 mol%, or about 0 mol% ethylene.

[0069] Polyalphaolefin (PAO) products can be used as base oils for lubricants, etc. The resulting PAO can have a number average molecular weight of 250 to 3,000, or 250 to 1,000, or 300 to 700, or 400 to 500, and a viscosity at 100°C of 1.5 cSt to 150 cSt. PAO fluids for particular uses can include those fluids having a KV100 of 3 cSt, 3.4 cSt, and / or 3.6 cSt, and combinations thereof. Mixtures of PAO fluids having a KV100 viscosity of 1.5 to 150 cSt or greater are also useful.

[0070] Polyalphaolefin (PAO) products can have any one or more of the following properties:

[0071] a. a kinematic viscosity (as measured as KV100°C according to ASTM D445) of 1-10 cSt, such as 1 cSt-9 cSt, 2-8 cSt, or 3-6 cSt, including 2.5 cSt, 3.0 cSt, 3.5 cSt, 4.0 cSt, 5.0 cSt, or 6.0 cSt;

[0072] b. a kinematic viscosity (KV 40°C, according to ASTM D445) of 3-20 cSt, such as 3 cSt-18 cSt, 5-15 cSt, or 10-16 cSt, including 12.5 cSt, 13.0 cSt, 13.5 cSt, 14.0 cSt, 15.0 cSt, or 16.0 cSt;

[0073] c. a viscosity index (VI as measured according to ASTM D445) of about 110 to about 150, about 115 to about 140, or about 120 to about 130, such as about 120, 125, 128, 130, or 135.

[0074] d. a pour point (as measured by ASTM D97) of -10°C or less, or -20°C or less, or -25°C or less, about -50°C or less, -60°C or less, or -70°C or less, or -80°C or less, -85°C or less, or -90°C or less.

[0075] e. a Noack volatility of about 5% to 25%, 10% to 15%, or 11% to 14%, or about 10%, about 11%, about 12%, about 12.5%, or about 13%, as measured according to ASTM D 5800.

[0076] Examples:

[0077] To facilitate a better understanding of the embodiments of the application, the following examples of preferred or representative embodiments are given. The following examples should in no way be understood as limiting or restricting the scope of the application.

[0078] As mentioned below, catalyst C-2 and activator A-2 are represented by the following structures:

[0079]

[0080] Example 1 (Ex. 1 - in-situ reactor catalyst activation):

[0081] A 2-gallon pressurized Parr reactor was used to perform the continuous-stirred metallocene oligomerization reactions. The reactor has a dip tube for catalyst solution injection and feed lines for various types of linear-a-olefins. The reactor is equipped with an external heater and an internal cooling loop to control the temperature of the reaction. Catalyst batch preparation and activator batch preparation were performed in a N2-purged drybox using standard air-sensitive procedures.

[0082] Catalyst batch preparation: 398.6 grams of toluene was passed through a commercially available adsorbent (UOP 13X molecular sieves) to remove moisture, then added to a clean empty flask on a stir plate with a magnetic stirrer, then 0.38 grams of tri-n-octyl aluminum was added to the toluene to scavenge any impurities not captured in the adsorbent bed. After 5 minutes of mixing, 1.0 grams of catalyst C-2 was dissolved in the mixture and mixed for 10 minutes.

[0083] Activator batch preparation: In a separate flask, 398.1 grams of toluene was passed through a commercially available adsorbent (UOP 13X molecular sieves) to remove moisture, then added to a separate clean empty flask on a stir plate with a magnetic stirrer, then 0.38 grams of tri-n-octyl aluminum was added to the toluene to scavenge any impurities not captured in the adsorbent bed. After 5 minutes of mixing, 1.52 grams of activator A-2 was dissolved in the mixture and mixed for 10 minutes.

[0084] The 1-decene feed was passed through two adsorbent beds packed with UOP AZ-300 in series and finally through the LAO line into the reactor. The 1-decene was fed at 2080 g / hr into a Parr reactor running under vacuum and was first degassed therein. The activated catalyst batch was connected to a syringe pump which was fed at 11.1 g / hr (equivalent to 13 ppm of catalyst C-2 in the reactor) in the syringe pump and through a catalyst dip tube into the reactor. The activator batch was also connected to a syringe pump which was fed at 11.1 g / hr; the activator solution was mixed with the 1-decene in the LAO line. The reactor was run at full liquid (3 hour residence time), back pressure of 25 psig and at 140 °C. The reactor effluent was sent to a quench vessel where the catalyst was quenched with water at 90 °C at the same pressure as the reactor. The quenched effluent was then passed through a 1 micron filter and into a product collection bucket.

[0085] Comparative Example 1 (Comp. Ex. 1 - external catalyst activation):

[0086] Similar to Example 1 above, a 2 gallon pressurized Parr reactor was used to perform the continuous stirred metallocene oligomerization reaction. The reactor had a dip tube for catalyst solution injection as well as feed lines for various types of linear-a-olefins. The reactor was equipped with an external heater as well as an internal cooling loop to control the temperature of the reaction. Activated catalyst batch preparation was performed in a N2 purged drybox using standard air sensitive procedures.

[0087] Activated catalyst batch preparation: 396.7 grams of toluene was passed through a commercially available adsorbent (UOP 13X molecular sieves) to remove moisture, then added to a clean empty flask on a stir plate with a magnetic stirrer, then 0.77 grams of tri-n-octyl aluminum was added to the toluene to scavenge any impurities not captured in the adsorbent bed. After 5 minutes of mixing, 1.0 gram of catalyst C-2 was dissolved in the mixture and mixed for 10 minutes. Next, 1.52 grams of activator A-2 was dissolved in the catalyst mixture and mixed for 10 minutes.

[0088] The 1-decene feed was fed through two adsorbent beds packed with UOP AZ-300 in series and finally through the LAO line into the reactor. The 1-decene was fed at 2080 g / hr into a Parr reactor running under vacuum and was first degassed therein. The activated catalyst batch was connected to a piston pump which was dosed at 10.4 g / hr (equivalent to 13 ppm of catalyst C-2 in the reactor) in the piston pump and through a catalyst dip tube into the reactor. The reactor was run at full liquid (3 hour residence time), back pressure of 25 psig and at 140 °C. The reactor effluent was sent to a quench vessel where the catalyst was quenched with water at 90 °C at the same pressure as the reactor. The quenched effluent was then passed through a 1 micron filter and into a product collection bucket.

[0089] The products of Example 1 and Comparative Example 1 were analyzed via GC to determine conversion and selectivity. Gas chromatography (GC) was used to determine the composition of the synthesized oligomers. The gas chromatograph used in the examples was an Agilent Technologies Model 7890A equipped with a 30 meter column with an internal diameter of 0.28 mm and a flame ionization detector. ~0.2000-0.3000 g of sample was diluted in dichloromethane solvent, ~0.0600-0.1000 g of a nonane internal standard was added, and the mixture was injected into the column. The initial temperature was about 40 °C for about 1 minute, programmed at about 15 °C / minute to about 250 °C and held for about 2 minutes. The sample was then heated at a rate of about 25 °C / minute to about 360 °C and held for about 17.3 minutes. The oligomer distribution was determined by the GC method. The results are shown in Table 1.

[0090] As shown in Table 1, in situ reactor activation (Ex. 1) presented improvements over typical external activation (Comp. Ex. 1). The increase in dimer selectivity and conversion was significant, resulting in an increase in dimer yield.

[0091] Table 1: Product Summary / Results

[0092]

[0093] Example 2 (EX. 2 - Activation-in-reactor - mixed PAO):

[0094] Example 1 was repeated and the reactor effluent from oligomerization was distilled to obtain unreacted monomer and dimer. To the above mixture additional 1-decene was added to produce a 1 : 1 monomer to dimer molar ratio mixture.

[0095] Two 2 liter pressurized Parr reactors (reactor 2A and reactor 2B) were used to perform step 2 of the oligomerization. Reactor 2A had an inlet for various types of linear-a-olefins as well as a dip tube for the catalyst system. Reactor 2B was connected to reactor 2A to further drive conversion. The catalyst system used was butanol / butyl acetate in a molar ratio of about 1 : 1 saturated with BF3 at atmospheric temperature and pressure. This catalyst was prepared by charging butanol and butyl acetate into a 5 L round bottom flask and then bubbling BF3 into the mixture through a dip tube.

[0096] The feed mixture was fed into reactor 2A, which was running under vacuum, at 600 g / hour and was first degassed. The catalyst mixture was fed at a rate of about 15 mmol / 100 g of olefin (which equals 14.7 g / hour). Reactor 2A was maintained at a 1350 ml level, and reactor 2B was maintained at a 600 ml level (1.75 hour residence time in reactor 2A and 0.78 hour in reactor 2B). Reactor 2B was maintained at a BF3 pressure of 5 psig. A 1 : 1 molar ratio butanol / butyl acetate mixture was then added to the reactor 2B effluent to capture any free BF3. The effluent was then sent to a quench reactor where the acidic catalyst was quenched with 10% caustic. The resulting sample was rinsed with water several times and the oil phase was analyzed by GC.

[0097] Comparative Example 2 (COMP EX. 2 - External activation - mixed PAO):

[0098] Comparative Example 1 was repeated and the reactor effluent from oligomerization was distilled to obtain unreacted monomer and dimer. To the above mixture additional 1-decene was added to produce a 1 : 1 monomer to dimer molar ratio mixture.

[0099] Two 2 liter pressurized Parr reactors were used to perform step 2 of the oligomerization. Reactor 2A had an inlet for various types of linear-a-olefins as well as a dip tube for the catalyst system. The second reactor (2B) was connected to reactor 2A to further drive conversion. The catalyst system used was butanol / butyl acetate in a molar ratio of about 1 : 1 saturated with BF3 at atmospheric temperature and pressure. This catalyst was prepared by charging butanol and butyl acetate into a 5 L round bottom flask and then bubbling BF3 into the mixture through a dip tube. Comparative Example 2 (COMP EX. 2 - External activation - mixed PAO):

[0098] Comparative Example 1 was repeated and the reactor effluent from oligomerization was distilled to obtain unreacted monomer and dimer. To the above mixture additional 1-decene was added to produce a 1 : 1 monomer to dimer molar ratio mixture.

[0099] Two 2 liter pressurized Parr reactors were used to perform step 2 of the oligomerization. Reactor 2A had an inlet for various types of linear-a-olefins as well as a dip tube for the catalyst system. The second reactor (2B) was connected to reactor 2A to further drive conversion. The catalyst system used was butanol / butyl acetate in a molar ratio of about 1 : 1 saturated with BF3 at atmospheric temperature and pressure. This catalyst was prepared by charging butanol and butyl acetate into a 5 L round bottom flask and then bubbling BF3 into the mixture through a dip tube. Comparative Example 2 (COMP EX. 2 - External activation - mixed PAO):

[0098] Comparative Example 1 was repeated and the reactor effluent from oligomerization was distilled to obtain unreacted monomer and dimer. To the above mixture additional 1-decene was added to produce a 1 : 1 monomer to dimer molar ratio mixture.

[0099] Two 2 liter pressurized Parr reactors were used to perform step 2 of the oligomerization. Reactor 2A had an inlet for various types of linear-a-olefins as well as a dip tube for the catalyst system. The second reactor (2B) was connected to reactor 2A to further drive conversion. The catalyst system used was butanol / butyl acetate in a molar ratio of about 1 : 1 saturated with BF3 at atmospheric temperature and pressure. This catalyst was prepared by charging butanol and butyl acetate into a 5 L round bottom flask and then bubbling BF3 into the mixture through a dip tube. Comparative Example 2 (COMP EX. 2 - External activation - mixed PAO):

[0098] Comparative Example 1 was repeated and the reactor effluent from oligomerization was distilled to obtain unreacted monomer and dimer. To the above mixture additional 1-decene was added to produce a 1 : 1 monomer to dimer molar ratio mixture.

[0099] Two 2 liter pressurized Parr reactors were used to perform step 2 of the oligomerization. Reactor 2A had an inlet for various types of linear-a-olefins as well as a dip tube for the catalyst system. The second reactor (2B) was connected to reactor 2A to further drive conversion. The catalyst system used was butanol / butyl acetate in a molar ratio of about 1 : 1 saturated with BF3 at atmospheric temperature and pressure. This catalyst was prepared by charging butanol and butyl acetate into a 5 L round bottom flask and then bubbling BF3 into the mixture through a dip tube. Comparative Example 2 (COMP EX. 2 - External activation - mixed PAO):

[0098] Comparative Example 1 was repeated and the reactor effluent from oligomerization was distilled to obtain unreacted monomer and dimer. To the above mixture additional 1-decene was added to produce a 1 : 1 monomer to dimer molar ratio mixture.

[0099] Two 2 liter pressurized Parr reactors were used to perform step 2 of the oligomerization. Reactor 2A had an inlet for various types of linear-a-olefins as well as a dip tube for the catalyst system. The second reactor (2B) was connected to reactor 2A to further drive conversion. The catalyst system used was butanol / butyl acetate in a molar ratio of about 1 : 1 saturated with BF3 at atmospheric temperature and pressure. This catalyst was prepared by charging butanol and butyl acetate into a 5 L round bottom flask and then bubbling BF3 into the mixture through a dip tube. Comparative Example 2 (COMP EX. 2 - External activation - mixed PAO):

[0098] Comparative Example 1 was repeated and the reactor effluent from oligomerization was distilled to obtain unreacted monomer and dimer. To the above mixture additional 1-decene was added to produce a 1 : 1 monomer to dimer molar ratio mixture.

[0099] Two 2 liter pressurized Parr reactors were used to perform step 2 of the oligomerization. Reactor 2A had an inlet for various types of linear-a-olefins as well as a dip tube for the catalyst system. The second reactor (2B) was connected to reactor 2A to further drive conversion. The catalyst system used was butanol / butyl acetate in a molar ratio of about 1 : 1 saturated with BF3 at atmospheric temperature and pressure. This catalyst was prepared by charging butanol and butyl acetate into a 5 L round bottom flask and then bubbling BF3 into the mixture through a dip tube. Comparative Example 2 (COMP EX. 2 - External activation - mixed PAO):

[0098] Comparative Example 1 was repeated and the reactor effluent from oligomerization was distilled to obtain unreacted monomer and dimer. To the above mixture additional 1-decene was added to produce a 1 : 1 monomer to dimer molar ratio mixture.

[0099] Two

[0100] The feed mixture was added to a Parr reactor running under vacuum at 600 g / hr and was first degassed in the reactor. The feed mixture then entered reactor 2A where it contacted the catalyst mixture fed at a ratio of about 15 mmol / 100 g of olefin (which equates to 14.7 g / hour). Reactor 2A was maintained at a 1350 ml level and reactor 2B was maintained at a 600 ml level (1.75 hour residence time in reactor 2A and 0.78 hours in reactor 2B). Reactor 2B was maintained at a BF3pressure of 5 psig. A 1 : 1 molar ratio of butanol / butyl acetate mixture was then added to the reactor 2B effluent to capture any free BF3. The effluent was then sent to a quench reactor where the acidic catalyst was quenched with 10% caustic. The resulting sample was rinsed with water multiple times and the oil phase was analyzed by GC.

[0101] The results are shown in Table 2 below. The results of the second reaction step were essentially unchanged. However, because of the increase in conversion in the first step of the reaction, this allowed for additional feed to the second reaction, increasing the overall yield of trimer (the primary product).

[0102] Table 2: Two reactors in series

[0103] * The total PAO yield was greater than 100 grams because of the additional LAO feed to the second reactor. The LAO fed to the second reactor (ratio) depended on the intermediate PAO production from the first reactor and the desired ratio of intermediate PAO to fresh LAO. This ratio was maintained at a 1 : 1 molar ratio in all of the above experiments.

[0104] Additional aspects and features of the present disclosure include any of the following numbered embodiments:

[0105] Embodiment I: A method of making a polyalpha-olefin (PAO) comprising feeding at least one catalyst to an oligomerization reactor; feeding at least one activator to the oligomerization reactor; feeding one or more linear alpha-olefins to the oligomerization reactor; and oligomerizing the one or more linear alpha-olefins in the presence of the catalyst and the activator within the oligomerization reactor to produce a polyalpha-olefin (PAO), wherein the catalyst and the activator do not contact each other outside of the oligomerization reactor.

[0106] Embodiment II: The method of Embodiment I, wherein the at least one catalyst comprises a metallocene.

[0107] Embodiment III: The method of Embodiments I or II, wherein the one or more linear alpha-olefins comprises any one or more of a C2-C32 alpha-olefin, a C4-C32 alpha-olefin, a C6-C30 alpha-olefin, a C6-C24 alpha-olefin, a C6-C18 alpha-olefin, a C8-C18 alpha-olefin, a C6-C16 alpha-olefin, or a C6-C12 alpha-olefin.

[0108] Embodiment IV: The method according to any one of Embodiments I to III, wherein the one or more linear alpha-olefins is selected from the group consisting of 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, and 1-hexadecene.

[0109] Embodiment V: The method according to any one of Embodiments I to IV, wherein the oligomerization reactor is a CSTR.

[0110] Embodiment VI: A method of making a polyalpha-olefin (PAO), comprising: feeding a first catalyst to a first oligomerization reactor; feeding an activator to the first oligomerization reactor; feeding one or more linear alpha-olefins to the first oligomerization reactor; oligomerizing the one or more linear alpha-olefins in the presence of the first catalyst and the activator within the first oligomerization reactor to produce a polyalpha-olefin (PAO) intermediate, wherein the first catalyst and the activator do not contact each other outside of the first oligomerization reactor; feeding the PAO intermediate and one or more additional linear alpha-olefins to a second oligomerization reactor; feeding a second catalyst to the second oligomerization reactor; and oligomerizing the PAO intermediate and the one or more additional linear alpha-olefins in the presence of the second catalyst within the second oligomerization reactor to produce a polyalpha-olefin (PAO) product.

[0111] Embodiment VII: The method of Embodiment VI, wherein the first catalyst comprises a metallocene and the second catalyst comprises a Lewis acid.

[0112] Embodiment VIII: The method of Embodiments VI or VII, wherein the one or more linear alpha-olefins comprises any one or more of a C2-C32 alpha-olefin, a C4-C32 alpha-olefin, a C6-C30 alpha-olefin, a C6-C24 alpha-olefin, a C6-C18 alpha-olefin, a C8-C18 alpha-olefin, a C6-C16 alpha-olefin, or a C6-C12 alpha-olefin.

[0113] Embodiment IX: The process according to any one of embodiments VI to VIII, wherein the one or more linear alpha-olefins are selected from the group consisting of 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, and 1-hexadecene.

[0114] Embodiment X: The process according to any one of embodiments VI to IX, wherein the one or more linear alpha-olefins fed to the first reactor are different from the one or more additional linear alpha-olefins fed to the second reactor.

[0115] Embodiment XI: The process according to any one of embodiments VI to X, wherein the one or more linear alpha-olefins fed to the first reactor are the same as the one or more additional linear alpha-olefins fed to the second reactor.

[0116] Embodiment XII: The process according to any one of embodiments VI to XI, wherein the first and second reactors are CSTRs.

[0117] Embodiment XIII: The process according to any one of embodiments VI to XII, wherein the first catalyst and the first activator are each independently fed to the first oligomerization reactor.

[0118] Embodiment XIV: The process according to any one of embodiments VI to XIII, wherein the second catalyst is BF3.

[0119] Embodiment XV: A process for making a polyalpha-olefin (PAO), comprising: feeding a metallocene catalyst to a first oligomerization reactor; feeding an activator to the first oligomerization reactor; feeding one or more linear alpha-olefins to the first oligomerization reactor; oligomerizing the one or more linear alpha-olefins in the presence of the metallocene catalyst and the activator within the first oligomerization reactor to produce a polyalpha-olefin (PAO) intermediate, wherein the metallocene catalyst and the activator do not contact each other outside of the first oligomerization reactor; feeding the PAO intermediate and one or more additional linear alpha-olefins to a second oligomerization reactor; feeding a BF3catalyst to the second oligomerization reactor; and

[0120] oligomerizing the PAO intermediate and the one or more additional linear alpha-olefins in the presence of the BF3catalyst within the second oligomerization reactor to produce a polyalpha-olefin (PAO) product.

[0121] Embodiment XVI: The process of embodiment XV, wherein the metallocene catalyst and the activator are each independently fed to the first oligomerization reactor.

[0122] Embodiment XVII: The process of Embodiments XV or XVI, wherein the activator is mixed with and fed to the first oligomerization reactor along with the one or more linear alpha-olefins.

[0123] Embodiment XVIII: The process according to any one of Embodiments XV to XVII, wherein the one or more linear alpha-olefins fed to the first reactor are different from the one or more additional linear alpha-olefins fed to the second reactor.

[0124] Embodiment XIX: The process according to any one of Embodiments XV to XVIII, wherein the one or more linear alpha-olefins fed to the first reactor are the same as the one or more additional linear alpha-olefins fed to the second reactor.

[0125] All numerical values are "about" or "approximately" the value indicated and are intended to cover any experimental error and deviation.

[0126] From the foregoing description, it will be apparent to those skilled in the art that numerous changes, modifications, and alterations to the embodiments described herein can be made without departing from the spirit and scope of the disclosure, and that the above description is meant to be illustrative only and not limiting. When numerical lower limits and numerical upper limits are listed separately, ranges from any lower limit to any upper limit are contemplated.

[0127] Various terms are defined above. To the extent a term used in a claim is not defined above, it should be given the broadest definition persons in the pertinent art have given that term as reflected in at least one printed publication or issued patent. Furthermore, all patents, test procedures, and other documents cited in this application are fully incorporated by reference to the extent such disclosure is not inconsistent with this application and for all jurisdictions in which such incorporation is permitted.

[0128] While the foregoing is directed to embodiments of the present application, other and further embodiments of the application can be devised without departing from the basic scope thereof, and the scope of the present application is determined by the following claims.

Claims

1. A method for preparing poly-α-olefin (PAO), comprising: At least one catalyst is fed into the oligomerization reactor; At least one activator is fed into the oligomerization reactor; One or more linear α-olefins are fed into an oligomerization reactor; and One or more linear α-olefins are oligomerized to produce polyα-olefins (PAO) in the presence of a catalyst and an activator inside an oligomerization reactor, wherein the catalyst and activator do not come into contact with each other outside the oligomerization reactor.

2. The method according to claim 1, wherein at least one catalyst comprises a metallocene.

3. The method according to claim 1, wherein one or more linear α-olefins comprise any one or more C2-C32 α-olefins, C4-C32 α-olefins, C6-C30 α-olefins, C6-C24 α-olefins, C6-C18 α-olefins, C8-C18 α-olefins, C6-C16 α-olefins, or C6-C12 α-olefins.

4. The method according to claim 1, wherein one or more linear α-olefins are selected from 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetracene, 1-tetradecene, 1-pentadecadecene, and 1-hexadecene.

5. The method of claim 1, wherein the oligomerization reactor is a CSTR.

6. A method for preparing poly-α-olefin (PAO), comprising: The first catalyst is fed into the first oligomerization reactor; The activator is fed into the first oligomer reactor; One or more linear α-olefins are fed into the first oligomerization reactor; One or more linear α-olefins are oligomerized in the presence of a first catalyst and an activator in a first oligomerization reactor to produce polyα-olefin (PAO) intermediates, wherein the first catalyst and the activator do not come into contact with each other outside the first oligomerization reactor; PAO intermediates and one or more additional linear α-olefins are fed into a second oligomerization reactor; The second catalyst is fed into the second oligomerization reactor; and In a second oligomerization reactor, in the presence of a second catalyst, a PAO intermediate and one or more additional linear α-olefins are oligomerized to produce poly-α-olefin (PAO) products.

7. The method of claim 6, wherein the first catalyst comprises a metallocene and the second catalyst comprises a Lewis acid.

8. The method according to claim 6, wherein one or more linear α-olefins comprise any one or more C2-C32 α-olefins, C4-C32 α-olefins, C6-C30 α-olefins, C6-C24 α-olefins, C6-C18 α-olefins, C8-C18 α-olefins, C6-C16 α-olefins, or C6-C12 α-olefins.

9. The method according to claim 6, wherein one or more linear α-olefins are selected from 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetracene, 1-tetradecene, 1-pentadecadecene, and 1-hexadecene.

10. The method of claim 6, wherein the one or more linear α-olefins fed to the first reactor are different from the one or more additional linear α-olefins fed to the second reactor.

11. The method of claim 6, wherein the one or more linear α-olefins fed to the first reactor are the same as the one or more additional linear α-olefins fed to the second reactor.

12. The method of claim 6, wherein the first and second reactors are CSTRs.

13. The method of claim 6, wherein the first catalyst and the first activator are each fed independently into the first oligomer reactor.

14. The method of claim 7, wherein the second catalyst is BF3.

15. A method for preparing poly-α-olefin (PAO), comprising: The metallocene catalyst is fed into the first oligomerization reactor; The activator is fed into the first oligomer reactor; One or more linear α-olefins are fed into the first oligomerization reactor; One or more linear α-olefins are oligomerized in the presence of a metallocene catalyst and an activator in a first oligomerization reactor to produce poly-α-olefin (PAO) intermediates, wherein the metallocene catalyst and the activator do not come into contact with each other outside the first oligomerization reactor; PAO intermediates and one or more additional linear α-olefins are fed into a second oligomerization reactor; The BF3 catalyst is fed into the second oligomerization reactor; and In a second oligomerization reactor, PAO intermediates and one or more additional linear α-olefins are oligomerized in the presence of a BF3 catalyst to produce poly-α-olefin (PAO) products.

16. The method of claim 15, wherein the metallocene catalyst and the activator are each fed independently into the first oligomerization reactor.

17. The method of claim 15, wherein the activator is mixed with one or more linear α-olefins and fed together into the first oligomerization reactor.

18. The method of claim 15, wherein the one or more linear α-olefins fed to the first reactor are different from the one or more additional linear α-olefins fed to the second reactor.

19. The method of claim 15, wherein the one or more linear α-olefins fed to the first reactor are the same as the one or more additional linear α-olefins fed to the second reactor.

Images