EP2313480A1 - Agent d abaissement du point d écoulement pour compositions d hydrocarbures - Google Patents

Agent d abaissement du point d écoulement pour compositions d hydrocarbures

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Publication number
EP2313480A1
EP2313480A1 EP09758848A EP09758848A EP2313480A1 EP 2313480 A1 EP2313480 A1 EP 2313480A1 EP 09758848 A EP09758848 A EP 09758848A EP 09758848 A EP09758848 A EP 09758848A EP 2313480 A1 EP2313480 A1 EP 2313480A1
Authority
EP
European Patent Office
Prior art keywords
olefin
poly
olefins
hydrocarbon blend
blend
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP09758848A
Other languages
German (de)
English (en)
Inventor
Margaret M. Wu
David J. Baillargeon
Andrew Jackson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Chemical Patents Inc
Original Assignee
ExxonMobil Chemical Patents Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US12/133,927 external-priority patent/US8642522B2/en
Application filed by ExxonMobil Chemical Patents Inc filed Critical ExxonMobil Chemical Patents Inc
Priority to EP09758848A priority Critical patent/EP2313480A1/fr
Publication of EP2313480A1 publication Critical patent/EP2313480A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/16—Hydrocarbons
    • C10L1/1625—Hydrocarbons macromolecular compounds
    • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
    • C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
    • C10L10/16—Pour-point depressants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/08—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing aliphatic monomer having more than 4 carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/17—Fisher Tropsch reaction products
    • C10M2205/173—Fisher Tropsch reaction products used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/2805—Esters used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08—Resistance to extreme temperature

Definitions

  • the present invention relates in general to lubricant and fuel compositions, and more particularly to a class of poly- ⁇ -olefins that are capable of lowering the turbidity and pour point of low viscosity hydrocarbon base stocks, while maintaining the overall viscosity of the base stock if desired.
  • BACKGROUND OF THE INVENTION [0003] Since the advent of the automobile, there has been a need to improve lubricating oils. One concern in lubricating automobile engines is the low temperature behavior of the lubricant. Automobile original equipment manufacturers COFMs") arc concerned with the wax contained in nearly all refined mineral lubricants, waxes which can crystallize at low temperatures and prevent the lubricant from flowing.
  • the distillate fuel can be made from conventional petroleum refining process or made from gas to liquids (“GTL”) technology or from coal or bitumen to liquid (“CTL”) technology. Examples of such distillate fuels can be found in US 6,811,683, US 7,344,631 and US 5,487,763. Higher quality distillate fuels are in demand to provide improved pour point, lubricity, pumpability and flowability at low temperature, reduced emissions. This improvement can enhance the overall machine operability and improve fuel economy.
  • the poly- ⁇ -olefins produced in this invention can provide such enhancement.
  • Described in one embodiment is a hydrocarbon blend, a fuel or lubricant in particular embodiments, comprising from 0.001 to 10 wt% of at least one poly- ⁇ -olefin, by weight of the blend, the at least one poly- ⁇ -olefin having a Kv 100 within the range of from 10 to 5000 cSt and a molecular weight distribution within the range of from 1.0 to 4.5; and a base stock having a Kv 100 below 20.0 cSt; wherein the at least one poly- ⁇ -olefin is present in an amount sufficient to lower the pour point of the hydrocarbon blend by at least 5°C relative to the pour point of the base stock.
  • the base stock is a lube base stock or fuel base stock.
  • Also described herein in one aspect is a method of forming a hydrocarbon blend, a fuel or lubricant in particular embodiments, comprising: (a) reacting a catalyst composition and a feed containing at least two sets of ⁇ -olefins, wherein the first set of ⁇ -olefins is selected from C 4 to C 13 ⁇ -olefins and the second set of ⁇ -olefins is selected from Ci 4 or larger ⁇ -olefins and forming at least one poly- ⁇ -olefin having a Kv 100 of at least 10.0 cSt; and (b) combining the at least one poly- ⁇ -olefin with a base stock or fuel base stock having a Kv 100 value of less than 20.0 cSt to form the hydrocarbon blend.
  • Described in another aspect is a method of forming a hydrocarbon blend, a fuel or lubricant in particular embodiments, comprising: (a) reacting a catalyst composition and an ⁇ -olefin feed having a number average carbon number of at least 8 carbon atoms to form at least one poly- ⁇ -olefin having a Kv 100 of at least 10.0 cSt; and (b) combining the at least one poly- ⁇ -olefin with a base stock having a Kv 100 value of less than 20.0 cSt to form the hydrocarbon blend.
  • lubricant refers to a liquid substance that can be introduced between two or more moving surfaces and lower the level of friction between the moving surfaces.
  • the "lubricant” is a material comprising from 0.01 to 10 wt% of at least one poly- ⁇ -olefm, by weight of the lubricant, and having a Kv 100 within the range of from 10 to 5000 cSt, and at least one type of hydrocarbon base stock having a Kv 100 below 20.0 cSt.
  • the "hydrocarbon compositions” in certain embodiments are lubricants.
  • a "fuel” is any substance that evolves energy in a controlled chemical reaction; in the present description, hydrocarbon materials, preferably those that are liquid at room temperature, are a fuel, reacted with an oxidant to evolve energy.
  • the "fuel” is a material comprising from 0.001 to 10 wt% of at least one poly- ⁇ - olefin, by weight of the fuel, and having a Kv 100 within the range of from 10 to 5000 cSt, and at least one type of fuel base stock having a Kv 100 below 20.0 cSt.
  • the "hydrocarbon compositions" in certain embodiments are fuels.
  • a “base stock” is used to describe a hydrocarbon fluid that does not contain the at least one poly- ⁇ -olefin described below, and in one embodiment is the primary component, by volume, of the final lubricant or fuel.
  • the term “base stock” includes the distillate fuel to lube range molecules, which is a continuum and a mixture of organic molecules of greater than Cio
  • the lower boiling fractions usually from Cio to C 22 , are used as distillate fuel or "fuel base stock”; higher boiling fractions are used for lubricant base stocks.
  • the base stock (for fuel, lubricant or other) has a VI of at least 100, and at least 120 in another embodiment.
  • the base stock has a pour point below 10 or -10 or -15°C. In certain embodiments the base stock is a Group II, III or GTL base stock. In certain embodiments, the base stock has a K v 100 value of less than 10 or 20 or 30 cSt, and in other embodiments, greater than 0.1 or 1 or 3 cSt.
  • hydrocarbon base stocks or "base stocks" suitable in lubricants include API Group I, Group II, Group III, Group IV, Group V and Group VI base stocks and hydrocarbonaceous fluids derived from Fischer-Tropsch process or Gas-to-Liquid (“GTL”) process.
  • Gas-To-Liquids base stocks include base stocks and/or base oils derived from one or many possible types of GTL processes.
  • the GTL process generally refers to a chemical conversion of natural gas, mostly methane, into synthesis gas (mainly CO and hydrogen).
  • synthesis gas mainly CO and hydrogen
  • solid coal can also be converted into synthesis gas of mainly CO and hydrogen.
  • the synthesis gas is then converted into mostly linear paraffins by Fishcher-Tropsch process.
  • the linear paraffins have wide molecular size distributions.
  • the high molecular weight linear paraffinic fraction of C 25 and higher can be isolated by distillation or fractionation and then subjected to hydro-isomerization by different catalysts into lubricant base stocks.
  • This GTL base stock has Kv 100 of 3 to 20 or 30 cSt in certain embodiments.
  • the GTL base stocks and/or base oil may be used as such or in combination with other hydrodewaxed or hydroisomerized, catalytic or solvent dewaxed lube base stock.
  • the GTL useful in the lubricants described herein have a VI of at least 100, and at least 120 in another embodiment.
  • the GTL base stock has a pour point within the range of from 20 or 10 0 C to -15 or -20 0 C.
  • the GTL lube base stocks and the process to produce these base stocks can be found in US 7,344,631, US 6,846,778, US 7,241,375, US 7,053,254, or WO2005121280 Al .
  • any lube base stock derived from the GTL process can be used in the blends described herein.
  • GTL base stock is one comprising paraffinic hydrocarbon components in which the extent of branching, as measured by the percentage of methyl hydrogens ("branching index" or "BI"), and the proximity of branching, as measured by the percentage of recurring methylene carbons which are four or more carbons removed from an end group or branch (CH 2 > 4), are such that: (a) BI-0.5(CH 2 > 4) >15; and (b) BI+0.85 (CH 2 > 4) ⁇ 45 as measured over said liquid hydrocarbon composition as a whole.
  • BI branch index
  • GTL base stock is also characterized as comprising a mixture of branched paraffins, characterized in that the lubricant base oil contains at least 90% of a mixture of branched paraffins, wherein said branched paraffins are paraffins having a carbon chain length of C 2 o to C 4 0, a molecular weight of 280 to 562, a boiling range of 343°C to 566°C, and wherein said branched paraffins contain up to four alkyl branches and wherein the free carbon index of said branched paraffins is at least 3.
  • the GTL base stocks, and the method for measuring the branching index are described in more detail in, for example, WO 2007/070691.
  • the fuel “base stock” can be for example the middle distillate fuel oils, such as a diesel fuel, aviation fuel, kerosene, fuel oil, jet fuel, heating oil etc.
  • suitable fuels base stocks are those boiling in the range of 120° to 500 0 C, (ASTM Dl 160), those boiling on the range 150° to 400 0 C in another embodiment.
  • a representative heating oil specification calls for a 10 % distillation point no higher than about 226°C, a 50 % point no higher than 272°C and a 90 % point of at least 282°C, and no higher than 338°C to 343°C, although some specifications set the 90 % point as high as 357°C.
  • heating oils are made of a blend of virgin distillate, for example, gas oil, naphtha, etc. and cracked distillates, for example, catalytic cycle stock.
  • a representative specification for a diesel fuel base stock includes a minimum flash point of 38°C and a 90 % distillation point between 282°C and 338°C (See ASTM D-396 and D-975).
  • These distillate fuel base stocks can be made from conventional petroleum refining processes or they can be made from "gas-to-liquid” (GTL) or “coal-to-liquid” (“CTL”) technology.
  • a "poly- ⁇ -olefin” is in one embodiment a copolymer having a Kv 100 within the range of from 10 or 20 to 1000 or 2000 or 5000 cSt, the copolymer produced by reacting a catalyst composition with a feed of ⁇ -olefin monomers.
  • the blends described herein include at least one poly- ⁇ -olefin as described herein.
  • a "copolymer” is not limited to polymers made up of two different monomer derived units, but can include three, four or more different comonomer derived units.
  • the catalyst composition can comprise any known compound(s), alone or in combination, capable of catalyzing the production of polyolefins from olefin monomers, non-limiting examples of which are Ziegler-Natta catalysts, chrome oxide based catalysts, Group 4 amide/imide coordination catalysts, and metallocene catalysts, each with an optional activator such as an alumoxane or non-coordinating anion (e.g., bulky borate compounds).
  • the at least one poly- ⁇ -olefin is produced using a catalyst composition comprising a metallocene and an activator.
  • the method of forming the at least one poly- ⁇ -olefin can be described in two complementary aspects.
  • the at least one poly- ⁇ -olefin is produced by reacting a catalyst composition with an olefin feed having a certain number average carbon number.
  • the at least one poly- ⁇ -olefin is produced by reacting a catalyst composition with one or more olefins selected from two sets of olefins: the first set being olefins within the range of C 4 to C 13 ⁇ -olefins, and the second set being olefins greater than or equal to Ci 4 ⁇ -olefins.
  • the method of forming the at least one poly- ⁇ - olefin can be described by a combination of the first and second aspects.
  • the at least one poly- ⁇ -olefin is produced by reacting a catalyst composition and an ⁇ -olefin feed having a number average carbon number of at least 8 carbon atoms, and at least 9 carbon atoms in another embodiment, and at least 10 carbon atoms in another embodiment and at least 11 carbon atoms in yet another embodiment, and at least 11.5 in yet another embodiment.
  • the ⁇ -olefin feed has an number average carbon number within the range of from 8 to 15 carbon atoms, and from 10 to 15 carbon atoms in another embodiment, and from 10.5 to 14.5 carbon atoms in another embodiment, and from 10 to 14 carbon atoms in yet another embodiment.
  • the "feed" may be continuous or batch-wise, meaning that a constant supply of the ⁇ -olefins can be provided to the components being reacted or a single amount is added to the components being reacted until the reaction is stopped, or another fresh "batch" of feed is introduced.
  • the ⁇ -olefin feed comprises at least two ⁇ -olefins selected from the group consisting of C 4 to C 24 ⁇ -olefins and mixtures thereof.
  • the ⁇ -olefin group comprises of C5 to C 24 ⁇ -olefins and mixtures thereof.
  • small amounts of even higher ⁇ -olefins of C 24-32 can also be present, from 0.01 to 5 wt% in one embodiment.
  • the ⁇ -olefin group consisting essentially of Ce to C 24 ⁇ -olefins and mixtures thereof, meaning that lower or higher olefins have been separated out from the Ce to C 24 feed as much as is practical.
  • the ⁇ -olefin feed comprises at least two ⁇ -olefins selected from the group consisting of Ce to C 24 ⁇ -olefins and mixtures thereof.
  • the feed comprises within the range of from 0.1 to 15 wt% Ce ⁇ -olefins and at least 8 wt% C 18 ⁇ - olefins, based on the weight of the feed, in yet another embodiment.
  • the ⁇ -olefins that make up the feed are linear ⁇ -olefins.
  • the ⁇ -olefin feed consists essentially of two or more olefins selected from the group consisting of Ce to C 24 ⁇ -olefins.
  • the ⁇ -olefin feed consists essentially of two or more olefins selected from 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-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1- heneicosene, 1-docosene, 1-tricosene, 1-tetracosene in yet another embodiment.
  • the ⁇ -olefin feed consists essentially of 1-hexene, 1 -octene, 1-decene, 1-dodecene, 1-tetradecene, 1- hexadecene and 1-octadecene in yet another embodiment.
  • ethylene is substantially absent from the ⁇ -olefin feed; and ethylene and propylene are substantially absent from the ⁇ -olefin feed in a particular embodiment.
  • substantially absent what is meant is that the ethylene or ethylene/propylene are not present in any detectable level up to a level of 1.5 wt% of the feed.
  • the at least one poly- ⁇ -olefm is formed by contacting a catalyst composition with an ⁇ -olefin feed selected from two sets of ⁇ -olefins.
  • the first set of ⁇ - olefins is at least one or more of the olefins selected from C 4 to C 13 ⁇ -olefins in one embodiment, C5 to C 12 ⁇ -olefins in another embodiment, and Ce to C 12 ⁇ -olefins in yet another embodiment, and Ce to C 10 ⁇ -olefins in yet another embodiment.
  • the first set of ⁇ -olefins comprises 10 or 15 or 20 or 30 or 40% to 70 or 80 or 90% of the total ⁇ -olefin feed. Any one or more of the C 4 to C 13 ⁇ -olefins in one embodiment, and any one or more of the C5 to C 12 ⁇ -olefins in another embodiment, or any one or more of the Ce to C 10 ⁇ -olefins in yet another embodiment can be used.
  • the balance of the feed is selected from the second set of Ci 4 or larger ⁇ -olefins.
  • at least 20%, or 30%, or 40% of the ⁇ -olefin feed comprises the Ci 4 or larger ⁇ -olefins; and the feed comprises less than 90% Ci 4 or larger ⁇ -olefins in another embodiment.
  • the mixed ⁇ -olefin feed comprising the two sets of ⁇ - olefins is preferred to have an number average carbon number of at least 8 carbon atoms, and a number average carbon number of at least 9 carbon atoms in another embodiment, and a number average carbon number of at least 10 carbon atoms in yet another embodiment, and at least 10.1 carbon atoms in yet another embodiment, and at least 10.2 carbon atoms in yet another embodiment, and at least 10.5 carbon atoms in yet another embodiment, and at least 11 carbon atoms in yet another embodiment and at least 11.5 carbon atoms in yet another embodiment.
  • the ⁇ -olefin feed has an number average carbon number within the range of from 8 to 15 carbon atoms, and from 10 to 15 carbon atoms in another embodiment, and from 10.5 to 14.5 carbon atoms in another embodiment, and from 10 to 14 carbon atoms in yet another embodiment.
  • the ethylene, or ethylene/propylene is substantially absent from the feed in certain embodiments, and the feed may consist essentially of linear ⁇ -olefins in other embodiments.
  • the ⁇ -olefin feed as described herein is "reacted" with a catalyst composition to form at least one poly- ⁇ -olefin.
  • catalyst composition is defined herein to mean a catalyst precursor/activator pair, such as a metallocene/activator pair.
  • catalyst composition means the unactivated catalyst (precatalyst) together with an activator and, optionally, a co-activator (such as a trialkylaluminum compound).
  • co-activator such as a trialkylaluminum compound
  • this activated "catalyst composition” may optionally comprise the co-activator and/or other charge-balancing moiety.
  • the catalyst composition comprises a metallocene and an activator to form a catalyst composition.
  • Metallocene catalyst compounds include half (one cyclopentadienyl bound to a metal center) and full (two cyclopentadienyls bound to a metal center) sandwich compounds having one or more cyclopentadienyl ligands or ligands isolobal to cyclopentadienyl ("Cp") bonded to at least one metal atom, and one or more leaving group(s) bonded to the at least one metal atom.
  • a half-sandwich compound is the so called "constrained geometry" metallocenes.
  • the term “leaving group” refers to any ligand that can be abstracted from a metallocene catalyst compound to form a metallocene catalyst cation capable of polymerizing one or more olefins.
  • the Cp ligands are generally represented by one or more bonding systems comprising ⁇ bonds that can be open systems or ring systems or fused system(s) or a combination thereof.
  • These ring(s) or ring system(s) are typically composed of atoms selected from Groups 13 to 16 atoms, and selected from the group consisting of carbon, nitrogen, oxygen, silicon, sulfur, phosphorous, boron and aluminum or a combination thereof in another embodiment.
  • the metal atom is selected from Groups 4 through 12 of the Periodic Table of Elements in one embodiment, and as otherwise described herein.
  • the metallocene is a Group 4 bridged bis-Cp compound, meaning that both Cp ligands are bound to the metal center as well as each other through some "bridging" moiety as is known in the art and described below.
  • the metallocene catalyst compounds are unbridged bis- cyclopentadienyl metallocene compounds represented by formula (1): L A L B MQ n , wherein each L A and L B are bound to the metal center M, and each Q is bound to the metal center, n being 0 or an integer from 1 to 4, and is 1 or 2 in another embodiment, and is 2 in yet another embodiment.
  • the metal atom "M" is selected from the group consisting of Groups 3 through 10 atoms in a one embodiment; and selected from the group consisting of Groups 4, 5 and 6 atoms in a more particular embodiment, and is Zr or Hf in yet a more particular embodiment.
  • the metal of the metallocene is not limited to being any particular oxidation state in the present invention.
  • the Cp ligand(s) form at least one chemical bond with the metal atom M to form the "metallocene catalyst compound.”
  • the Cp ligands are distinct from the leaving groups bound to the catalyst compound in that they are not highly susceptible to substitution/abstraction reactions.
  • the L A and L B groups of formula (1) are Cp ligands, such as cycloalkadienyl ligands and heterocyclic analogues.
  • the Cp ligands typically comprise atoms selected from the group consisting of Groups 13 to 16 atoms, and more particularly, the atoms that make up the Cp ligands are selected from the group consisting of carbon, nitrogen, oxygen, silicon, sulfur, phosphorous, germanium, boron and aluminum and combinations thereof, wherein carbon makes up at least 50% of the ring members.
  • the Cp ligand(s) are selected from the group consisting of substituted and unsubstituted cyclopentadienyl ligands and ligands isolobal to cyclopentadienyl, non-limiting examples of which include cyclopentadienyl, indenyl, fluorenyl and other structures.
  • Such ligands include cyclopentadienyl, cyclopentaphenanthreneyl, indenyl, benzindenyl, fluorenyl, octahydrofluorenyl, cyclooctatetraenyl, cyclopentacyclododecene, phenanthrindenyl, 3,4-benzofluorenyl, 9-phenylfluorenyl, 8-H-cyclopent[a]acenaphthylenyl, 7-H-dibenzofluorenyl, indeno[l,2-9]anthrene, thiophenoindenyl, thiophenofluorenyl, hydrogenated versions thereof (e.g., 4,5,6,7-tetrahydroindenyl), substituted versions thereof (as described in more detail below), and heterocyclic versions thereof.
  • cyclopentadienyl cyclopentaphenanthreneyl,
  • each L A and L B may be unsubstituted or substituted with a combination of substituent groups R.
  • substituent groups R include one or more from the group selected from halogens; hydrogen; and linear, branched, or cyclic alkyl Ci to C 2 0 or C30 or C50 groups; and alkenyl, or aryl groups, or combination thereof.
  • Non-limiting examples of alkyl or aryl substituents R include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl groups and the like, including all their isomers, for example tertiary butyl, isopropyl, and the like. Also, at least two R groups, two adjacent R groups in certain embodiments, are joined to form a ring structure having from 3 to 30 atoms selected from carbon, nitrogen, oxygen, phosphorous, silicon, germanium, aluminum, boron or a combination thereof.
  • the leaving groups Q of formula (1) are monoanionic labile ligands bound to M. Depending on the oxidation state of the metal, the value for n is 0, 1 or 2 such that formula (1) above represents a neutral metallocene catalyst compound, or a positively charged compound.
  • Examples of leaving groups include fluorine atoms, chlorine atoms, bromine atoms and iodide atoms, hydrogen atoms, alkoxy groups, methyl groups, ethyl groups, and other alkyl groups.
  • the metallocene catalyst compounds of the invention include those of formula (1) where L A and L B are bridged to each other by a bridging group, "A". These bridged compounds are referred to as bridged metallocene catalyst compounds and can be represented by formula (2): L A (A)L B MQ n , wherein each L A and L B are bound to the metal M, and each Q is bound to the metal center, n being 0 or an integer from 1 to 4, 1 or 2 in certain embodiments, and 2 in yet another embodiment; the groups L A , L B , M and Q are as defined in (1); and the divalent bridging group "A" is bound to both L A and L B through at least one bond or divalent moiety to each.
  • Non-limiting examples of bridging group "A" from formula (2) include divalent bridging groups containing at least one Group 13 to 16 atom, such as but not limited to at least one of a carbon, oxygen, nitrogen, silicon, boron, germanium and tin atom or a combination thereof.
  • bridging group "A” contains a carbon, silicon or germanium atom.
  • the "A” group contains at least one silicon atom or at least one carbon atom in a particular embodiment.
  • the bridging group "A” may also contain substituent groups R as defined above including halogens.
  • the metallocene catalyst components described above include their structural or optical or enantiomeric isomers (racemic mixture), and may be a pure enantiomer in one embodiment. Further, as used herein, a single, bridged, asymmetrically substituted metallocene catalyst component having a racemic and/or meso isomer does not, itself, constitute at least two different bridged, metallocene catalyst components.
  • the "metallocene catalyst component" useful in the present invention may comprise any combination of any "embodiment” described herein, for example, any combination of L A , L B , M, Q, A and R groups.
  • the catalyst composition described herein comprises a metallocene and an activator in one embodiment.
  • the catalyst composition may include a support material as is known in the art.
  • the term "activator” is defined to be any compound or combination of compounds, supported or unsupported, which can activate a single-site catalyst compound (e.g., metallocenes, Group 4 imide/amine coordination compounds, etc.), such as by creating a cationic species from the catalyst component. Typically, this involves the abstraction of at least one leaving group (Q group in the formulas/structures above) from the metal center of the catalyst component.
  • the catalyst components of the present invention are thus activated towards olefin polymerization using such activators.
  • Embodiments of such activators include Lewis acids such as cyclic or oligomeric poly(hydrocarbylaluminum oxides) and so called non-coordinating activators (“NCAs”) (alternately, “ionizing activators” or “stoichiometric activators”), or any other compound that can convert a neutral metallocene catalyst component to a metallocene cation that is active with respect to olefin polymerization.
  • NCAs non-coordinating activators
  • Lewis acids such as alumoxane (e.g., "MAO"), modified alumoxane (e.g., "TIBAO”), and alkylaluminum compounds as activators, and/or ionizing activators (neutral or ionic) such as tri(n- butyl)ammonium tetrakis(pentafluorophenyl)boron and/or a trisperfluorophenyl boron metalloid precursors to activate desirable metallocenes described herein.
  • MAO and other aluminum-based activators are well known in the art.
  • Ionizing activators are well known in the art and may be associated with or bound to a support, either in association with the catalyst component (e.g., metallocene) or separate from the catalyst component.
  • Examples of neutral ionizing activators include Group 13 tri-substituted compounds, in particular, tri-substituted boron, tellurium, aluminum, gallium and indium compounds, and mixtures thereof.
  • the three substituent groups are each independently selected from alkyls, alkenyls, halogen, substituted alkyls, aryls, arylhalides, alkoxy and halides.
  • the three groups are independently selected from halogen, mono or multicyclic (including halosubstituted) aryls, alkyls, and alkenyl compounds and mixtures thereof.
  • the three groups are selected from alkenyl groups having 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms and aryl groups having 3 to 20 carbon atoms (including substituted aryls), and combinations thereof.
  • the three groups are selected from alkyls having 1 to 4 carbon groups, phenyl, naphthyl and mixtures thereof.
  • the three groups are selected from highly halogenated alkyls having 1 to 4 carbon groups, highly halogenated phenyls, and highly halogenated naphthyls and mixtures thereof.
  • highly halogenated it is meant that at least 50% of the hydrogens are replaced by a halogen group selected from fluorine, chlorine and bromine.
  • the neutral stoichiometric activator is a tri-substituted Group 13 compound comprising highly fluorided aryl groups, the groups being highly fluorided phenyl and highly fluorided naphthyl groups.
  • the neutral tri-substituted Group 13 compounds are boron compounds such as a trisperfluorophenyl boron, trisperfluoronaphthyl boron, tris(3,5- di(trifluoromethyl)phenyl)boron, tris(di-t-butylmethylsilyl)perfluorophenylboron, and other highly fluorinated trisarylboron compounds and combinations thereof, and their aluminum equivalents.
  • boron compounds such as a trisperfluorophenyl boron, trisperfluoronaphthyl boron, tris(3,5- di(trifluoromethyl)phenyl)boron, tris(di-t-butylmethylsilyl)perfluorophenylboron, and other highly fluorinated trisarylboron compounds and combinations thereof, and their aluminum equivalents.
  • Illustrative, not limiting examples of ionic ionizing activators include trialkyl- substituted ammonium salts such as triethylammonium tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammonium tetra(p-tolyl) boron, trimethylammonium tetra(o-tolyl)boron, tributylammonium tetra(pentafluorophenyl)boron, tripropylammonium tetra(o,p- dimethylphenyl) boron, tributylammonium tetra(m,m-dimethylphenyl)boron, tributylammonium tetra(p-trifluoromethylphenyl)boron, tributylammonium te
  • the molar ratio of the activator to metallocene is usually within the range of 10: 1 to 1 : 10, and within the range of from 0.5: 1 to 2: 1 in certain embodiments.
  • a co-activator may also be used.
  • the molar ratio of the co-activator (when present) to metallocene is in the range of 1000: 1 to 10: 1 in one embodiment, and 500: 1 to 20: 1 in another embodiment, and 200: 1 to 20: 1 in yet another embodiment, and 150: 1 to 20: 1 in yet another embodiment.
  • a scavenger is also used to scavenge any catalyst poison.
  • the scavenger can be the same compound as the co-activator, an alkyl aluminum compound in one embodiment.
  • the molar ratio of activator to metallocene is usually within the range of 5: 1 to 5000: 1, between 1000: 1 to 500: 1 in certain embodiments, or from 500: 1 or 300: 1 or 50: 1 to 1: 1 or 20: 1 or 100: 1 in other embodiments.
  • the "reacting" (or “reaction") between the catalyst composition and the ⁇ -olefin feed takes place by any suitable means known in the art suitable for forming polyolefins.
  • reacting what is meant is a chemical reaction that may occur as by combination and/or replacement and/or rearrangement of chemical bonds between the components combined with one another; in the particular invention, the reaction is that of a catalyzed combination of monomer units repeatedly to form a polymer.
  • the reaction may take place as a batch wise reaction in a batch reactor, and in certain embodiments the reacting takes place in a continuous reactor, examples of which include gas phase reactors, slurry reactors, solution reactors, the later two of which may be high pressure reactors.
  • a diluent may be used that may include the monomers themselves.
  • the conditions present during the reaction are such to produce at least one poly- ⁇ - olefin as described herein.
  • the reaction takes place at a temperature within the range of from 10 or 20 to 80, or 100, or 120, or 200 0 C in certain embodiments. Further, the reaction takes place at a pressure of greater than 1.0 or 1.1 or 1.2 or 1.4 MPa in certain embodiments, and between 0.8 or 1.0 MPa to 2.0 or 3.0 MPa in certain embodiments.
  • the polymerization reaction is usually exothermic. In order to maintain a constant and/or stable temperature, a heat removal means is employed in certain embodiments.
  • Heat removal can be conducted using many know methods, such as cooling by circulation coolant through a tube inside the reactor, by feeding pre-cooled feed streams, by cooling a portion of reactor content by circulating the content through a external cooling system, or a combination of these methods.
  • the catalyst concentration is in the range of 0.01 or 0.5 microgram of metallocene compound per gram of olefin feed to 20 or 50 or 100 or 1000 microgram of metallocene compound per gram of olefin feed.
  • the polymerization reaction is conducted in the presence of hydrogen.
  • the amount of hydrogen feed can range from 5 or 10 or 20 ppm in the reactor system to 1000 or 4000 or 5000 or 10,000 ppm in one embodiment, an exemplary value being within the range of 10 to 1000 ppm.
  • the amount of hydrogen is controlled by the partial pressure of hydrogen in the reactor system. In this case, 5 or 10 psi of hydrogen to 200 or 300 psi hydrogen is suitable, an exemplary value being within the range of 10 to 100 psi.
  • an inert solvent is added to the reactor system to facilitate the mixing of reactor components and downstream filtration and operation.
  • the reaction time can range from 5 minutes to 50 hours in one embodiment, depending on the amount of catalyst used, the desirable conversion, etc. Usually, a reaction time or residence time of 10 minutes to 25 hours is used, and between 20 minutes to 10 hours in another embodiment.
  • the catalyst components can be deactivated and/or removed by any conventional means such as by aqueous and/or alcohol wash with optional mixing with dilute aqueous acid or base and then separating the organic component from the aqueous wash. This wash is repeated several times until the catalyst components are removed. Alternatively, the catalyst can be removed according to the method described in WO 2008010862 Al.
  • the at least one poly- ⁇ -olefin produced in the process has high bromine number or high degree of un-saturation. If so, in certain embodiments the at least one poly- ⁇ -olefin can be hydrogenated to remove the unsaturation. This can be accomplished by fixed-bed continuous hydrogenation, or by slurry hydrogenation using many common hydrogenation catalysts, such as supported Ni-on-Kieseiguhr catalyst. Other examples can be found in WO 2008010862 Al. Alternately, this unsaturation is left in the at least one poly- ⁇ -olefin.
  • the product of reacting the catalyst and ⁇ -olefin will result in the formation of at least one poly- ⁇ -olefin that meets the desired criteria as described herein, and more than one poly- ⁇ -olefin in other embodiments.
  • the blends may comprise a poly- ⁇ -olefin that does not meet the desired criteria, but does comprise at least one such poly- ⁇ -olefin. Any additional poly- ⁇ -olefin in the blends can derive from any source and be formed by any means.
  • a poly- ⁇ -olefin can be isolated from the product mixture resulting from the reaction, which can then be combined with additives and/or base stocks to form a lubricant.
  • the reaction mixture is directly combined with the product of the reaction.
  • the at least one poly- ⁇ -olefin in one embodiment is a polyolefin having a Kv 100 within the range of from 10 to 5000 cSt.
  • the at least one poly- ⁇ -olefin has a Kv 100 below 2000 or 2500 or 3000 or 3500 or 4000 or 4500 or 5000 cSt in certain other embodiments.
  • the at least one poly- ⁇ -olefin has a Kv 100 within the range of from 10 or 15 or 20 or 50 to 500 or 1000 or 1500 or 2000 or 2500 or 4000 or 3000 or 5000 cSt in yet other embodiments. In yet other embodiments, the at least one poly- ⁇ -olefin has a VI of greater than 200 or 220 or 250, and within the range of from 100 or 150 or 200 to 300 or 400.
  • the molecular weight distribution (weight average molecular weight/number average molecular weight, or "MWD") of the at least one poly- ⁇ -olefin is within the range of from 1.0 or 1.2 or 1.5 to 3.5 or 4.0 or 4.5 as determined by Gel Permeation Chromatography, the measurement having a typical accuracy of ⁇ 0.15 units.
  • the at least one poly- ⁇ -olefin consists essentially of two or more C 4 or Ce to C 18 or C 24 ⁇ -olefm-derived units in one embodiment.
  • the at least one poly- ⁇ -olefin consists essentially of 1-hexene-derived units, 1 -octene-derived units, 1- decene-derived units, 1-dodecene-derived units, 1-tetradecene-derived units, 1-hexadecene- derived units and 1 -octadecene-derived units.
  • the at least one poly- ⁇ -olefin consists essentially of at least three olefins selected from the group consisting of 1-hexene-derived units, 1 -octene-derived units, 1-decene-derived units, 1-dodecene- derived units, 1-tetradecene-derived units, 1 -hexadecene-derived units and 1 -octadecene- derived units.
  • the at least one poly- ⁇ -olefin is present in (or added to) the hydrocarbon base stock in an amount to lower the pour point of the blend by at least 5 or 10 or 15°C relative to the pour point of the base stock in one embodiment.
  • the at least one poly- ⁇ -olefin is present in the blend from 0.001 or 0.01 to 5 or 7 or 10 wt% poly- ⁇ -olefin, by weight of the base stock.
  • the base stock comprises within the range of from 99.999 to 40 or 50 or 60 or 70 wt% of the blend in certain embodiments, or in a range as described herein.
  • the remainder of the lubricant or fuel may be made up of additives, some of which are listed herein.
  • a lubricant comprising a poly- ⁇ -olefin having a Kv 100 within the range of from 10 to 1000 or 3000 cSt (or as otherwise described herein) and a molecular weight distribution within the range of from 1.0 to 4.5 (or as otherwise described herein); and a base stock having a Kv 100 below 20.0 cSt (or as otherwise described herein); wherein the at least one poly- ⁇ -olefin is present in an amount sufficient to lower the pour point of the lubricant relative to the pour point of the untreated base stock.
  • the addition of the at least one poly- ⁇ -olefin to a base stock will not substantially affect the blend's viscosity.
  • the at least one poly- ⁇ -olefin is added to the base stock to form a blend such that the pour point of the blend is at least 5 or 10 0 C less than the pour point of the base stock, wherein the Kv 100 changes by less than 5 or 10 %.
  • the at least one poly- ⁇ -olefin consists essentially of two or more Ce to C 24 ⁇ -olefm-derived units.
  • ethylene-derived units are substantially absent from the at least one poly- ⁇ -olefin, and ethylene- and propylene-derived units are substantially absent in yet another embodiment, "substantially absent” meaning that if those groups are present in the polymer chain, they are present to no greater than 0.5 or 1 or 1.5 wt% of the polymer.
  • the lubricant can also include any one or more additives as is common in the art.
  • the lubricant comprises one or more additives, wherein the additive is selected from the group consisting of oxidation inhibitors, antioxidants, dispersants, detergents, corrosion inhibitors, rust inhibitors, metal deactivators, anti-wear agents, extreme pressure additives, anti-seizure agents, non-olefin based pour point depressants, wax modifiers, viscosity index improvers, viscosity modifiers, fluid-loss additives, seal compatibility agents, friction modifiers, lubricity agents, anti-staining agents, chromophoric agents, defoamants, demulsifiers, emulsifiers, densifiers, wetting agents, gelling agents, tackiness agents, colorants, and blends thereof.
  • the additive is selected from the group consisting of oxidation inhibitors, antioxidants, dispersants, detergents, corrosion inhibitors, rust inhibitors, metal deactivators, anti-wear agents, extreme pressure additives, anti-seizure agents, non-o
  • non-polyolefin-based pour point depressants are substantially absent, meaning that they are present, if at all, to less than 1 wt% of the lubricant.
  • non-polyolefin-based PPDs include polyacrylates, ethylene-vinylacetate copolymer, and fumarates.
  • the "additives" comprises the list above without the "non-olefin based pour point depressants.”
  • the at least one poly- ⁇ -olefins described herein can also be used with other hydrocarbon fluids to improve the pour points or low temperature flow properties of these fluids.
  • these hydrocarbon fluids include distillate fuels, which include jet fuels, diesel fuels, and heating oil.
  • specific examples of these distillate fuels are the fuels produced in the GTL process, as described in US 7,132,042, or many of the distillate fuels produced in conventional petroleum refinery. These fuels, as produced from their manufacturing process, contain small amount of waxy components. These waxy components degrade the low temperature flowability and pour points of the fluids.
  • the low temperature properties improves significantly.
  • the amount of poly- ⁇ -olefins in the fuel composition ranged from 0.0001 wt% to 5 wt%, preferably, 0.001 wt% to 0.5 wt% (equivalent to 10 ppm to 5000 ppm).
  • the finished distillate fuel product may contain other additive components including detergents, lubricity improvers, combustion improvers, cetane improvers, other cold-flow improvers, filterability improvers, cloud point improvers.
  • the fuel may contain appropriate amount of fuels or components derived from renewable resources such as bio-diesels including fatty acid alkyl esters (or methyl esters ("FAME") or ethyl esters, etc), glycerols, mono-glycerides, etc.
  • the one or more poly- ⁇ -olefins produced in this invention have several unique characteristics. First, in certain embodiments they may contain at least 10% or 20% or 30% or 35% or more C M linear ⁇ -olefin-derived units. Second, many of these poly- ⁇ -olefms, because of their high content of the Ci 4 linear ⁇ -olefin, have relatively high pour points.
  • Most of the at least one poly- ⁇ -olefin having a pour point depressant effect usually have pour points higher than -15 or -10 or 0 0 C. Some poly- ⁇ -olefins with low pour points (less than - 20 0 C) have good pour point depressant properties. Therefore the method described herein may provide a poly- ⁇ -olefin with both excellent pour point and low temperature properties and still provide excellent pour point depressant properties.
  • the pour point depressant effect or low-temperature viscometric improving effect can be optimized by ensuring that the smaller olefins selected from C 4 to Ci 3 linear ⁇ -olefin and the larger olefins selected from greater than Ci 4 linear ⁇ - olefin are randomly distributed in the at least one poly- ⁇ -olefm without significant clustering of smaller olefins or the larger olefins.
  • the at least one poly- ⁇ -olefm is preferably a random poly- ⁇ -olefm, without any significant blocky segment(s) in the polymer structure.
  • a single-site catalyst system such as a metallocene catalyst system, is most suitable for producing such poly- ⁇ -olefin with random monomer distribution.
  • Metallocene catalyst system polymerizes linear ⁇ -olefin of C 4 to C 24 ⁇ -olefins with almost equal reactivity and therefore, producing polymers with relatively random monomer distribution. Such polymer will be most desirable for low temperature improving effect of Group I to VI base stocks.
  • the single-site catalyst is chosen that results in the most random polymer.
  • the ⁇ -olefins used for all the experiments were purified by mixing 1 liter of un-treated raw olefin material with 20 grams of activated 13X molecular sieve and 10 grams of de-oxygenate catalyst (a reduced copper catalyst) for at least two days inside a glove box. The molecular sieve and de-oxygenate catalyst were then removed by filtration. The treated individual ⁇ -olefins were then combined to give the desirable composition.
  • this purification can be carried out by pumping a stream of the ⁇ -olefins, either alone or pre-mixed, through a bed of activated 13X molecular sieve alone, or through a bed of activated 13X molecular sieve followed by a bed of de-oxygenate catalyst, prior to entering the reactor.
  • the pour points and cloud points of the blends were measured by a Herzog pour point ("PP") apparatus model HCP852 (Walter Herzog, GmbH). Poly- ⁇ -olefin synthesis experiments
  • Example 1 An olefin mixture containing 18.4% 1-hexene, 22.3% 1-octene, 21.6% 1-decene, 16.8% 1-dodecene, 10.4% 1-tetradecene, 6.4% 1-hexadecene and 4% 1- octadecene was used as feed.
  • This composition is similar to the linear ⁇ -olefins produced from a typical linear ⁇ -olefin plant (ALPHA-OLEFINS APPLICATIONS BOOK Ch. 3 (ed. G.R. Lappin and J.D. Sauer, Marcel Dekker, Inc., New York, 1989)).
  • Example 2 Similar to Example 1, except a metallocene containing 70% meso- and 30% racemic-dimethylsilylbis(tetrahydroindenyl) zirconium dichloride (C) was used in the preparation. [0071] Example 3. Similar to Example 1, except reaction was carried out at 60 0 C. [0072] Example 4. Similar to Example 2, except reaction was carried out at 60 0 C.
  • Example 5 An olefin mixture containing 33.6 grams of 1-octene, 42.0 grams 1- decene and 50.4 grams 1-dodecene was charged into a round bottom flask and heated to 70 0 C under N 2 atmosphere. A catalyst solution containing 2.34 gram 10 wt% methalumoxane (MAO) in toluene solution, 60 gram toluene and 3.7 mg of rac- dimethylsilylbis(tetrahydroindenyl)zirconium dichloride (C) was added slowly to the olefin mixture while maintaining constant temperature. The reaction was continued for 4 hours. Gas chromatograph showed that 94% olefins were converted.
  • MAO methalumoxane
  • C rac- dimethylsilylbis(tetrahydroindenyl)zirconium dichloride
  • the reaction was quenched by addition of about 3 ml isopropanol, followed by washing with about 120 ml of 5% sodium hydroxide solution and water.
  • the isolated organic layer was distilled at about 160°C/l millitorr vacuum for two hours to remove any light ends.
  • the lubricant properties are summarized in Table 1.
  • Example 6 is a comparative example. An identical reaction was carried out as Example 5, except a pure 1-decene was used as feed. The polydecene properties are summarized in Table 1. [0075] Examples 1-5 demonstrated that one can produce lubricant base stocks of wide viscosity ranges with superior viscosity index ("VI", ASTM-D2270) and pour points from wide range of mixed ⁇ -olefins, ranging from C 8 -C 12 to Ce-C 18 . The lubricant properties are similar to those made from pure 1-decene. [0076] Example 7. An olefin mixture containing 7.1% 1-hexene, 9.5% 1-octene, 11.9%
  • Example 8 Similar to Example 1, except the feed composition was described in
  • Example 7 Similar to Example 7, except that catalyst C was used.
  • Example 10 Similar to Example 1, except the feed composition was as described in Example 7 and the catalyst composition was catalyst C.
  • Example 11 Similar to Example 7, except the reaction temperature was 60 0 C.
  • Example 12 Similar to Example 7, except the metallocene used was racemic- ethylenebis(l-indenyl)zirconium dichloride (catalyst D).
  • Example 13 A hydroprocessed lubricant base stock A was prepared according to
  • Blend 14 When 1 wt% of the Example 1 poly- ⁇ -olefin was blended with base stock A, the blend has slight increase in 100 0 C viscosity. However, the pour point was decreased from -15°C to -18°C.
  • Blend 15 When 20 wt% of Example 1 was blended with base stock A, the blend has 100 0 C viscosity of 27.92 cSt. However, the pour point was decreased to -30 0 C.
  • Blend 16 When 0.1 wt% of Example 7 was blended with base stock A, the blend has Kv 100 of 6.14 cSt, which is only slightly higher than the starting base stock A. However, the pour point was decreased from -15°C to -45°C.
  • Blends 17, 18, 19, 20 further demonstrated the same pour point depressant effect when 0.5, 1.0, 5.0 or 20 wt% of Example 7 was blended with base stock A.
  • Blend 21 When 0.05 wt% of Example 10 was blended with base stock A, the blend has Kv 100 of 6.12 cSt, which is only slightly higher than the starting base stock A.
  • Blends 22, 23, 24 further demonstrated the same pour point depressant effect.
  • Blend 25 When 0.1 wt% of Example 12 was blended with base stock A, the blend has Kv 100 of 6.12 cSt, which is only slightly higher than the starting base stock A. However, the pour point was decreased from -15°C to -45°C.
  • Linear Olefin Feed Experiments [0090] Feed Compositions: Six linear ⁇ -olefin (linear ⁇ -olefin) mixtures with different number average carbon numbers ranging from 13.24 to 9.27 were prepared according to the weights in Table 3. These feeds labeled as "Feed-1" to "Feed-6" were used for subsequent polymer synthesis using metallocene catalyst system.
  • Examples 32 to 37 were prepared as in Examples 26 to 31, except that the reaction temperature was maintained at 35°C for Feed-1 to -6.
  • the product properties are summarized in Table 5.
  • the poly- ⁇ -olefins in Table 5 possess higher viscosities than poly- ⁇ - olefins in Table 4.
  • Example 38 and 40 had low degree of any stereo-regularity, and were mostly atactic polymer.
  • Example 39 had high degree of syndiotactic stereo-regularity.
  • Catalyst D is diphenylmethylidene(cyclopentadienyl-9-fluorenyl)zirconium dichloride, and the polymerizations were performed by combining catalyst D and activator B to form the catalyst composition.
  • the blend E-26 containing 0.5 wt% Example 26 poly- ⁇ -olefin in GTL6 has a pour point of -51°C.
  • the blend C-33 containing 0.1 wt% of Example 33 poly- ⁇ -olefin in GTL has a pour point of -51°C.
  • the blend C-36, containing 0.1 wt% Example 36 poly- ⁇ -olefin in GTL6, has a pour point of -21°C.
  • Poly- ⁇ -olefin made with feeds of number average carbon numbers of greater than 10.0 have excellent PPD effect (Examples 26-29, 32-35 and 38-40).
  • Poly- ⁇ -olefin made with feeds of average carbon numbers of less than 10 have very little PPD effect (Examples 30, 31, 36 and 37). These poly- ⁇ -olefins behave more as base stocks. They have excellent base stock properties, including VI and very low pour points. When they are blended in additive quantities, 0.025 wt% to 1 wt%, they show very little PPD effect. They are most suitable as blend stocks, when used in large quantity (usually greater than 5 wt%) to blend with other base stocks. When used in high amount, 5% or higher, they significantly increase the blend viscosities, increase VI, and lowering the pour points. These fluids are discussed in WO 2007/146081, WO 2007/145924, and WO 2007/070691.
  • Poly- ⁇ -olefins of wide viscosity range are highly effective PPDs, as long as they are made from feeds with a number average carbon number greater than 10.
  • Examples 26 to 29 poly- ⁇ -olefins have Kv 100 of 70 to 90 cSt, or Example 40 is 19.5 cSt. They are highly effective as PPDs.
  • Examples 32-36 and 39 have high viscosities, greater than 200 cSt. Again, they are highly effective as PPDs.
  • This wide range of viscosities available as PPD is very desirable in providing formulation flexibility. For example, sometimes it is desirable to use PPDs to improve the pour point without increasing the blend viscosity.
  • poly- ⁇ -olefin with atactic, isotactic or syndiotactic stereo-sequences are all effective as PPDs when they are made from feeds with average carbon numbers of greater than 10.
  • Examples 38 and 40 are rich in atactic stereo sequence.
  • Example 39 is rich in syndiotactic sequence.
  • Examples 26 to 29 and 32 to 35 are rich in isotactic stereo-sequence. They are all effective as PPDs.
  • Examples 41 to 44 are blends of GTL6 with poly- ⁇ -olefin Example 33 and Example 34 respectively.
  • the blends properties including high temperature viscometrics and the low temperature viscometrics pour points, Brookfield Viscosity at -30 0 C and -40 0 C, are summarized in Table 8.
  • Table 8 also include the properties of pure GTL6 (Example 42) and blend property of GTL6 with a common commercial pour point depressant AcryloidTM 156 (methyl methacrylate copolymer, Rohm & Haas) (Example 43). As these data showed that blends containing an additive quantity (0.1 to 1 wt%) in GTL6 have similar viscosities as the pure GTL6 base stock.
  • Example 43 the low temperature Brookfield Viscosity (as measured by ASTM D2983) was further decreased compared to the starting GTL6 base stocks, even though all the fluids have similar Kv 100 , Kv 40 and VI. Furthermore, the low temperature Brookfield Viscosity of Examples 41 and 42 are better than the most commonly used PPD (Example 43), again without changing the Kv 100 and Kv 40 significantly.
  • Table 9 summarizes the beneficial effect of small amounts of poly- ⁇ -olefin from Examples 26 to 37 in a high viscosity GTL base stock in reducing the turbidity of the GTL base stock.
  • High viscosity GTL base stock produced by methods and having compositions as described in US 7,241,375 and US 7,132,042, often have a hazy appearance, as indicated by a high turbidity number of 1.99 at 0 0 C, as measured by a turbidity meter (VWR Model 800 Turbidity Meter available from VWR International).
  • VWR Model 800 Turbidity Meter available from VWR International.
  • the turbidity of the hydrocarbon blends, a lubricant or fuel in a particular embodiment is less than 0.90 or 0.95 or 1.00, and within the range of from 0.50 or 0.60 to 0.90 or 1.00 in other embodiments.
  • a hydrocarbon blend comprising from 0.001 to 10 wt% of at least one poly- ⁇ - olefin, by weight of the hydrocarbon blend, the at least one poly- ⁇ -olefin having a Kv 100 within the range of from 10 to 3000 cSt and a molecular weight distribution within the range of from 1.0 to 4.5; and a base stock having a Kv 100 of less than 20.0 cSt; wherein the at least one poly- ⁇ -olefin is present in an amount sufficient to lower the pour point of the hydrocarbon blend by at least 5°C relative to the pour point of the base stock.
  • the base stock is a mixture selected from the group consisting of GTL base stocks, Gr. I, Gr. II, Gr. Ill, Gr. IV, Gr. V base stocks, and mixtures thereof, having a Kv 100 below 20.0 cSt.
  • hydrocarbon blend of any of the previous numbered embodiments wherein the hydrocarbon blend comprises within the range of from 99.999 to 30 or 40 or 50 wt% of the base stock.
  • hydrocarbon blend of any of the previous numbered embodiments also comprising one or more additives, wherein the additive is selected from the group consisting of oxidation inhibitors, antioxidants, dispersants, detergents, corrosion inhibitors, rust inhibitors, metal deactivators, anti-wear agents, extreme pressure additives, anti-seizure agents, non-olefin based pour point depressants, wax modifiers, viscosity index improvers, viscosity modifiers, fluid-loss additives, seal compatibility agents, friction modifiers, lubricity agents, anti-staining agents, chromophoric agents, defoamants, demulsifiers, emulsif ⁇ ers, densifiers, wetting agents, gelling agents, tackiness agents, colorants, and blends thereof.
  • the additive is selected from the group consisting of oxidation inhibitors, antioxidants, dispersants, detergents, corrosion inhibitors, rust inhibitors, metal deactivators, anti-wear agents, extreme pressure additives, anti-
  • a method of forming a hydrocarbon blend of any of the previous numbered embodiments comprising (a) reacting a catalyst composition and a feed containing at least two sets of ⁇ -olefins, wherein the first set of ⁇ -olefins is selected from C 4 to C 13 ⁇ -olefins and the second set of ⁇ -olefins is selected from Ci 4 or larger ⁇ -olefins forming at least one poly- ⁇ - olefin having a Kv 100 at least 10.0 cSt; and (b) combining the at least one poly- ⁇ -olefin with a base stock having a Kv 100 below 20.0 cSt to form the hydrocarbon blend.
  • a method of forming a hydrocarbon blend of any of the previous numbered embodiments comprising (a) reacting a catalyst composition with an ⁇ -olefin feed having a number average carbon number of at least 8 or 9 or 10 or 10.5 or 11 carbon atoms forming at least one poly- ⁇ -olefm having a Kv 100 of at least 10.0 cSt; and (b) combining the at least one poly- ⁇ -olefin with a base stock having a Kv 100 below 20.0 cSt to form the hydrocarbon blend.
  • ⁇ -olefin feed comprises at least two ⁇ -olefins selected from the group consisting of Ce to C 24 ⁇ -olefins and mixtures thereof. 22. The method of numbered embodiment 18, wherein the feed comprises within the range of from 0.1 to 15 wt% Ce ⁇ -olefins and at least 8 wt% C 18 ⁇ -olefins, based on the weight of the feed.
  • metallocene is a Group 4 bridged or unbridged bis-Cp compound.
  • the metallocene can be described with respect to formula (1) above.
  • the metallocene comprising the bridging group "A" is described with respect to formula (2) above.
  • the metallocene is a hafnocene or zirconocene having the features as described with respect to formula (1) and (2).
  • a lubricant or fuel made by the method of any of the previous numbered embodiments 17-33.
  • a poly- ⁇ -olefin comprising from 0.001 to 10 wt% of at least one poly- ⁇ -olefin, by weight of the hydrocarbon blend, the at least one poly- ⁇ -olefin having a Kv 100 within the range of from 10 to 3000 cSt and a molecular weight distribution within the range of from 1.0 to 4.5; and a base stock having a Kv 100 below 20.0 cSt; wherein the at least one poly- ⁇ -olefin is present in an amount sufficient to lower the pour point of the hydrocarbon blend by at least 5°C relative to the pour point of the base stock.
  • a poly- ⁇ -olefin in a fuel or lubricant comprising from 0.001 to 10 wt% at least one poly- ⁇ -olefin, by weight of the hydrocarbon blend, the at least one poly- ⁇ -olefin having a Kv 100 within the range of from 10 to 3000 cSt and a molecular weight distribution within the range of from 1.0 to 4.5; and a base stock having a Kv 100 below 20.0 cSt; wherein the at least one poly- ⁇ -olefin is present in an amount sufficient to lower the pour point of the hydrocarbon blend by at least 5°C relative to the pour point of the base stock.
  • a hydrocarbon blend comprising at least one poly- ⁇ -olefin as described herein as a fuel or lubricant comprising from 0.001 to 10 wt% poly- ⁇ -olefin.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Lubricants (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Abstract

L’invention concerne un mélange d’hydrocarbures fabriqué à partir de 0,001 à 10 % en poids d’au moins une poly-α-oléfine, par poids du mélange, la ou les poly-α-oléfines ayant un Kv100 dans la plage allant de 10 à 3 000 cSt et une distribution de poids moléculaire dans la plage allant de 1,0 à 4,5 ; et une huile de base ayant un Kv100 inférieur à 20,0 cSt. Selon l’invention, la ou les poly-α-oléfines sont présentes en une quantité suffisante pour abaisser le point d’écoulement du mélange d’au moins 5 °C par rapport au point d’écoulement de l’huile de base. Le mélange est formé en (a) faisant réagir une composition catalytique et une alimentation contenant au moins deux groupes d’α-oléfines, le premier groupe d’α-oléfines étant choisi parmi les α-oléfines en C4 à C12 et le second groupe d’α-oléfines étant choisi parmi les α-oléfines en C14 ou supérieures. Les α-oléfines introduites peuvent avoir un nombre de carbones moyen en nombre d’au moins 8 atomes de carbone ou plus.
EP09758848A 2008-06-05 2009-03-24 Agent d abaissement du point d écoulement pour compositions d hydrocarbures Withdrawn EP2313480A1 (fr)

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US12/133,927 US8642522B2 (en) 2008-06-05 2008-06-05 Pour point depressant for hydrocarbon compositions
EP08162595 2008-08-19
EP09758848A EP2313480A1 (fr) 2008-06-05 2009-03-24 Agent d abaissement du point d écoulement pour compositions d hydrocarbures
PCT/US2009/038014 WO2009148685A1 (fr) 2008-06-05 2009-03-24 Agent d’abaissement du point d’écoulement pour compositions d’hydrocarbures

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JP (1) JP5512661B2 (fr)
CN (1) CN102057022A (fr)
AU (1) AU2009255507A1 (fr)
CA (1) CA2726774A1 (fr)
WO (1) WO2009148685A1 (fr)

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WO2007011462A1 (fr) 2005-07-19 2007-01-25 Exxonmobil Chemical Patents Inc. Lubrifiants obtenus à partir de charges d'alpha-oléfines mélangées
JP5810576B2 (ja) * 2010-04-22 2015-11-11 日油株式会社 バイオディーゼル燃料油用流動性向上剤
CN108026466B (zh) 2015-08-21 2021-10-22 埃克森美孚化学专利公司 润滑剂基本原料共混物
US10059898B2 (en) 2015-08-21 2018-08-28 Exxonmobil Chemical Patents Inc. High-viscosity metallocene polyalpha-olefins with high electrohydrodynamic performance
US10611980B2 (en) 2015-10-15 2020-04-07 Exxonmobil Chemical Patents Inc. Lubricant containing high-viscosity metallocene polyalpha-olefins
US10144894B2 (en) 2016-07-20 2018-12-04 Exxonmobil Chemical Patents Inc. Shear-stable oil compositions and processes for making the same
US10351488B2 (en) 2016-08-02 2019-07-16 Exxonmobil Chemical Patents Inc. Unsaturated polyalpha-olefin materials
WO2018026406A1 (fr) * 2016-08-02 2018-02-08 Exxonmobil Chemical Patents Inc. Matériaux à base de polyalpha-oléfines insaturées

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GB9205996D0 (en) * 1992-03-19 1992-04-29 Exxon Chemical Patents Inc Polymers and additive compositions
JP3023178B2 (ja) * 1994-11-29 2000-03-21 久光製薬株式会社 ２−アミノチアゾール誘導体およびその塩類からなる抗菌剤または殺菌剤
US5641736A (en) * 1995-09-28 1997-06-24 Mobil Oil Corporation Synergistic pour point depressant combinations and hydrocarbon lube mixtures
US5811379A (en) * 1996-06-17 1998-09-22 Exxon Chemical Patents Inc. Polymers derived from olefins useful as lubricant and fuel oil additives, processes for preparation of such polymers and additives and use thereof (PT-1267)
JP2005200446A (ja) * 2004-01-13 2005-07-28 Mitsui Chemicals Inc α−オレフィン（共）重合体とその用途
JP2006176760A (ja) * 2004-11-26 2006-07-06 Mitsui Chemicals Inc 合成潤滑油および潤滑油組成物
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WO2009148685A1 (fr) 2009-12-10
CA2726774A1 (fr) 2009-12-10
JP5512661B2 (ja) 2014-06-04
CN102057022A (zh) 2011-05-11
JP2011521095A (ja) 2011-07-21
AU2009255507A1 (en) 2009-12-10

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