JP5512661B2 - Pour point depressants for hydrocarbon compositions - Google Patents

Description

Cross-reference to related applications This application is based on earlier US patent application Ser. No. 12 / 133,927 filed Jun. 5, 2008 and European Patent Application No. 08162595.6 filed Aug. 19, 2008 (both of which are The benefit of which is incorporated herein by reference in its entirety.
The present invention generally relates to lubricant compositions and fuel compositions, and more particularly poly-α-olefins that can reduce the turbidity and pour point of low viscosity hydrocarbon feedstocks while maintaining the overall viscosity of the feedstock as desired. About classes.

Since the advent of automobiles, there has been a request to improve lubricating oil. One concern in lubricating automotive engines is the low temperature behavior of the lubricant. Early equipment manufacturers ("OEM") of automobiles are interested in waxes contained in almost all refined mineral lubricants, which can crystallize at low temperatures and prevent the lubricant from flowing. It is expected that modern high performance lubricants will maintain the desired viscosity and prevent wear under real life operating conditions. This is particularly attractive when the conditions are cold for long periods of time, such as in the north of Canada and the United States. Pour point depressants (ie, “PPD”) are typically used to improve lubricant flow in cold climates. Ordinary PPD is based on polyacrylate and fumarate. However, these PPDs can be expensive and have relatively poor stability in view of their function. Due to the changing demands of the market, the choice of “correct” pour point depressant was less important than today. Equipment manufacturers and users are demanding lubricants that add greater efficiency and greater durability. At the same time, new specifications for engine and driveline lubricants impose even more troublesome restrictions on cold flow properties. Furthermore, the base oil slate is constantly changing due to the increasing use of severely hydrotreated API Group II and III oils.
Several lubricant compositions containing polyolefins are disclosed in US Pat. No. 6,420,618, WO 2007/146081, WO 2007/145924, WO 2007/070691, and WO 2004/033595. While some of these compositions have improved pour points relative to the feedstock, there is still a need for lubricants that have high performance and low pour points.
A similar situation exists for modern fuel compositions, particularly distilled fuel. Distilled fuels are made from conventional petroleum refining processes, or from gas to liquids (“GTL”) technology or coal or bitumen to liquid (“CTL”) technology. Examples of such distilled fuels can be found in US Pat. Nos. 6,811,683, 7,344,631 and 5,487,763. There is a need for high quality distilled fuel to provide improved pour point, lubricity, low temperature pumpability and flowability, reduced emissions. This improvement can improve overall machine operability and improve fuel economy. The poly-α-olefins produced in the present invention can provide such enhancements.

  What is needed is low-cost PPD with improved stability, used as PPD in API Group I-IV feedstocks, especially feedstocks derived from synthesis gas (“GTL”), and fuel feedstocks Can do. Such is provided herein.

In one embodiment, 0.001% to 10% by weight of at least one poly-α-olefin, wherein the at least one poly-α-olefin is in the range of ^{10 to} 5000 cSt, based on the weight of the blend. A hydrocarbon blend, in a particular embodiment a fuel or lubricant, comprising a feedstock having a molecular weight distribution in the range of ~ 4.5); and a Kv ¹⁰⁰ of less than 20.0 cSt, wherein at least one poly-α The 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 feedstock. In some embodiments, the feedstock is a lubricating feedstock or a fuel feedstock.
Also, in one aspect, (a) a feedstock comprising a catalyst composition and at least two sets of α-olefins (the first set of α-olefins is selected from C ₄ -C ₁₃ α-olefins and A set of α-olefins is selected from C _{14 and} higher α-olefins) to produce at least one poly-α-olefin having a Kv ¹⁰⁰ of at least 10.0 cSt, and (b) the at least one poly-olefin. a hydrocarbon blend, a process for producing a fuel or lubricant in a special embodiment, comprising combining an α-olefin with a feedstock or fuel feedstock having a Kv ¹⁰⁰ value of less than 20.0 cSt to produce a hydrocarbon blend Are described herein.
In another aspect, (a) at least one poly-α-olefin having a Kv ¹⁰⁰ of at least 10.0 cSt by reacting a catalyst composition and an α-olefin feedstock having a number average carbon number of at least 8 carbon atoms And (b) combining at least one poly-α-olefin with a feedstock having a Kv ¹⁰⁰ value of less than 20.0 cSt to produce a hydrocarbon blend, a special embodiment Describes a method for producing a fuel or lubricant.
The various descriptive elements and numerical ranges disclosed herein may be combined with other descriptive elements and numerical ranges to describe one or more preferred embodiments of the invention. Furthermore, the numerical upper limit of an element can be combined with the numerical lower limit of the element.

All fluid “viscosities” described herein are kinematic viscosities (“Kv ¹⁰⁰ ”) measured in accordance with ASTM D445 100 ° C. (“Kv ¹⁰⁰ ”) (unit: centistokes (“cSt”)) unless otherwise specified. Represent. All viscosity index (“VI”) values are measured according to ASTM D2270.
As used herein, “lubricant” refers to a liquid material that can be introduced between two or more moving surfaces to reduce the level of friction between the moving surfaces. In one embodiment, the “lubricant” comprises 0.01 to 10% by weight of at least one poly-α-olefin, based on the weight of the lubricant, and has a Kv ¹⁰⁰ in the range of ¹⁰ to 5000 cSt, and A material comprising at least one type of hydrocarbon feedstock having a Kv ¹⁰⁰ of less than 20.0 cSt. A “hydrocarbon composition” is a lubricant in certain embodiments.
As used herein, “fuel” is any substance that generates energy in a controlled chemical reaction. In the present description, a hydrocarbon material, preferably a hydrocarbon material that is liquid at room temperature, is a fuel that is reacted with an oxidant to generate energy. In one embodiment, the “fuel” comprises 0.01 to 10% by weight of at least one poly-α-olefin based on the weight of the fuel and has a Kv ¹⁰⁰ in the range of ¹⁰ to 5000 cSt and 20.0 cSt. A material comprising at least one type of fuel stock having a Kv of less than ¹⁰⁰ . A “hydrocarbon composition” is a fuel in some embodiments.

As used herein, “feedstock” is used to describe a hydrocarbon fluid that does not contain at least one poly-α-olefin as described below, and in one embodiment, the main lubricant or fuel main. Ingredients (volume basis). The term "feedstock" includes a molecule of distillate fuel-lubricant range, which is a continuous body and mixtures to C ₁₀ larger organic molecules. Low boiling fractions (usually C ₁₀ to C ₂₂ ) are used as distilled fuel or “fuel feedstock” and high boiling fractions are used for lubricating feedstock. In one embodiment, the feedstock (for fuels, lubricants, etc.) has a VI of at least 100, in another embodiment at least 120. In some embodiments, the feedstock has a pour point below 10 ° C or -10 ° C or -15 ° C. In some embodiments, the feedstock is a Group II, III or GTL feedstock. In some embodiments, the feedstock has a Kv ¹⁰⁰ value of less than 10 cSt or 20 cSt or 30 cSt, and in other embodiments greater than 0.1 cSt or 1 cSt or 3 cSt.
Non-limiting examples of suitable hydrocarbon feedstocks (or “feedstocks”) in lubricants include API Group I, Group II, Group III, Group IV, Group V and Group VI feedstocks and Fischer-Tropsch processes. Or hydrocarbonaceous fluids derived from synthesis gas (“GTL”) processes.

Syngas feedstocks include feedstocks and / or base oils derived from one or more possible types of GTL processes. The GTL method generally represents the chemical conversion of natural gas, mostly methane, into synthesis gas (mainly CO and hydrogen). Also, solid coal can be converted primarily into CO and hydrogen syngas. The synthesis gas is then converted to almost linear paraffin by the Fischer-Tropsch method. Linear paraffin has a broad molecular size distribution. High molecular weight linear paraffin fractions of C _{25 and} higher can be isolated by distillation or fractionation and then subjected to hydrocatalyzing with different catalysts to lubricant feedstocks. This GTL feedstock has a Kv ¹⁰⁰ of 3-20 or 30 cSt in certain embodiments. GTL feedstock and / or base oil may be used as is, or may be used in combination with other hydrodewaxed or hydroisomerized, lubricated feedstock that has been catalytic dewaxed or solvent dewaxed. . In one embodiment, the GTL useful in the lubricants described herein has a VI of at least 100, and in another embodiment at least 120. In some embodiments, the GTL feedstock has a pour point in the range of 20 ° C or 10 ° C to -15 ° C or -20 ° C. GTL lubricating feedstocks and methods for producing these feedstocks can be found in US Pat. Nos. 7,344,631, 6,846,778, 7,241,375, 7,053,254, or WO 2005 121280 A1. In general, any lubricating stock derived from the GTL process can be used in the blends described herein.
An example of a GTL feedstock is the degree of branching (“branching index” or “BI”), measured by% methyl hydrogen, and by the percentage of repeating methylene carbons that are 4 or more carbons removed from the end groups or branches. (A) BI-0.5 (CH ₂ ≧ 4)> 15, and (b) BI + 0.85 (CH ₂ ≧ 4) < It contains a paraffin hydrocarbon component that is such as 45.

Another example of a GTL feedstock is also characterized as comprising a mixture of branched paraffins, characterized in that the lubricant feedstock comprises at least 90% of a mixture of branched paraffins, said branched paraffins being C ₂₀ -C A paraffin having a carbon chain length of ₄₀ , a molecular weight of 280 to 562, a boiling range of 343 ° C. to 566 ° C., wherein the branched paraffin comprises up to 4 alkyl branches, and the free carbon index of the branched paraffin is at least 3; It is. The GTL feedstock and the branching index measurement method are described in more detail in WO 2007/070691, for example.
The fuel “raw oil” may be, for example, a middle-distilled fuel oil such as diesel fuel, aviation fuel, kerosene, fuel oil, jet fuel, heating oil, and the like. In general, suitable fuel feedstocks are those boiling in the range of 120 ° C. to 500 ° C. (ASTM D1160), in other embodiments boiling in the range of 150 ° C. to 400 ° C. A typical heating oil specification requires a 10% distillation temperature not higher than about 226 ° C, a 50% distillation temperature not higher than 272 ° C and a 90% distillation temperature at least 282 ° C and not higher than 338 ° C to 343 ° C, Some specifications define a 90% distillation temperature as high as 357 ° C. In some embodiments, the heating oil is made from a blend of virgin distillates, such as gas oil, naphtha, etc., and cracked distillates, such as catalytic cycle feedstock. Typical specifications for diesel fuel stocks include a minimum flash point of 38 ° C and a 90% distillation temperature of 282 ° C to 338 ° C (see ASTM D-396 and D-975). These distilled fuel feedstocks are made from conventional petroleum refining processes, or they are made from “syngas” (GTL) technology or “coal-to-liquid” (“CTL”) technology.
As used herein, a “poly-α-olefin” is a copolymer having, in one embodiment, a Kv ¹⁰⁰ in the range of 10 or 20 cSt to 1000 or 2000 or 5000 cSt, the copolymer comprising an α- Produced by reacting with olefin monomer feedstock. The blends described herein include at least one poly-α-olefin described herein. As used herein, “copolymer” is not limited to polymers composed of two different monomer derived units, but may include three, four or more different comonomer derived units. The catalyst composition can include one or more of any known compounds, alone or in combination, that can catalyze the production of polyolefins from olefin monomers, these non-limiting examples include Ziegler-Natta catalysts, chromium oxides Based catalysts, group 4 amide / imide coordination catalysts, and metallocene catalysts, each containing any activator, such as alumoxane or non-coordinating anions (eg, bulky borate compounds) But you can. In some embodiments, at least one poly-α-olefin is produced using a catalyst composition comprising a metallocene and an activator.

A process for producing at least one poly-α-olefin may be described in two supplementary aspects. In the first aspect, at least one poly-α-olefin is produced by reacting the catalyst composition with an olefin feedstock having a number average carbon number. In a second aspect, at least one poly-α-olefin comprises a catalyst composition in two sets of olefins (the first set is an olefin within the range of C ₄ -C ₁₃ α-olefins, and the second set Is a C ₁₄ α-olefin or higher olefin). In yet another aspect, a method for producing at least one poly-α-olefin may be described by a combination of the first and second aspects.
Thus, in one aspect, the at least one poly-α-olefin is a catalyst composition and at least 8 carbon atoms, in another embodiment at least 9 carbon atoms, in another embodiment at least 10 carbon atoms, In yet another embodiment, it is produced by reacting an α-olefin feedstock having a number average carbon number of at least 11 carbon atoms, and in yet another embodiment at least 11.5 carbon atoms. In yet another embodiment, the α-olefin feedstock is from 8 to 15 carbon atoms, in another embodiment from 10 to 15 carbon atoms, in another embodiment from 10.5 to 14.5 carbon atoms. It has a number average carbon number in the range of carbon atoms, and in yet another embodiment from 10 to 14 carbon atoms. “Feed” may be continuous or batch, where a constant feed of α-olefin is given to the component being reacted, or the reaction is stopped, or another new “batch” of feedstock. Means that a single amount is added to the component being reacted until is introduced.
In some embodiments, the α-olefin feedstock comprises at least two α-olefins selected from the group consisting of C ₄ -C ₂₄ α-olefins and mixtures thereof. In another embodiment, the α-olefin group comprises C ₅ -C ₂₄ α-olefin and mixtures thereof. In certain embodiments, minor amounts, in one embodiment from 0.01% to 5% by weight of higher C _24-32 α-olefins may also be present. In yet another embodiment, the α-olefin group consists essentially of C ₆ -C ₂₄ α-olefins and mixtures thereof, and more or less lower or higher olefins are practically separated from the C ₆ -C ₂₄ feedstock. It means being removed.

In yet another embodiment, the α-olefin feedstock comprises at least two α-olefins selected from the group consisting of C ₆ -C ₂₄ α-olefins and mixtures thereof. In feedstock yet another embodiment, based on the weight of the feedstock, including C ₁₈ alpha-olefin C ₆ alpha-olefin and at least 8% by weight in the range from 0.1 wt% to 15 wt%. In certain embodiments, the α-olefin that comprises the feedstock is a linear α-olefin.
In some embodiments, the α-olefin feedstock consists essentially of two or more olefins selected from the group consisting of C ₆ -C ₂₄ α-olefins. In yet another embodiment, the α-olefin feedstock is substantially 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 It consists of two or more olefins. In yet another embodiment, the α-olefin feedstock consists essentially of 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene. In some embodiments, ethylene is substantially absent from the α-olefin feedstock, and in particular embodiments, ethylene and propylene are substantially absent from the α-olefin feedstock. “Substantially absent” means that ethylene or ethylene / propylene is not present at detectable levels up to a level of 1.5% by weight of the feed.

In another aspect, at least one poly-α-olefin is produced by contacting the catalyst composition with an α-olefin feedstock selected from two sets of α-olefins. The first set of α-olefins is in one embodiment a C ₄ -C ₁₃ α-olefin, in another embodiment a C ₅ -C ₁₂ α-olefin, and in yet another embodiment C ₆ -C ₁₂ α-olefin. An olefin, and in yet another embodiment, at least one olefin selected from C ₆ -C ₁₀ α-olefins. In one embodiment, the at least one olefin is selected from a second set of α-olefins, the only olefin is selected in another embodiment, and only two olefins are in a further embodiment a second Selected from the group.
In some embodiments, the first set of olefins comprises 10% or 15% or 20% or 30% or 40% to 70% or 80% or 90% of the total α-olefin feedstock. In one embodiment one or more C ₄ -C ₁₃ α-olefins, in another embodiment one or more C ₅ -C ₁₂ α-olefins, or in another embodiment C ₆ -C ₁₀ α-olefins. One or more can be used. The balance of the feedstock is selected from a second set of C ₁₄ or higher α-olefins. In some embodiments, at least 20% of the α- olefin feedstock, or 30%, or 40% comprises C ₁₄ or more α- olefins, also C ₁₄ or higher feedstock is less than 90% in another embodiment Of α-olefins.
In some embodiments, the mixed α-olefin feedstock comprising two sets of α-olefins has a number average carbon number of at least 8 carbon atoms, in another embodiment a number average carbon number of at least 9 carbon atoms, In yet another embodiment, the number average number of carbon atoms of at least 10 carbon atoms, in yet another embodiment at least 10.1 carbon atoms, in yet another embodiment at least 10.2 carbon atoms, in yet another embodiment It is preferred to have at least 10.5 carbon atoms, in yet another embodiment at least 11 carbon atoms, and in yet another embodiment at least 11.5 carbon atoms. In yet another embodiment, the α-olefin feedstock has from 8 to 15 carbon atoms, in another embodiment from 10 to 15 carbon atoms, in another embodiment from 10.5 to 14.5 carbon atoms. A number average carbon number within the range of 10 to 14 carbon atoms, in yet another embodiment.

For the first described aspect of producing at least one poly-α-olefin, ethylene or ethylene / propylene is substantially absent from the feedstock in some embodiments, and the feedstock is substantially absent in other embodiments. Alternatively, it may be composed of a linear α-olefin.
The α-olefin feed described herein is “reacted” with the catalyst composition to produce at least one poly-α-olefin. The term “catalyst composition” is defined herein to mean a catalyst precursor / activator pair, eg, a metallocene / activator pair. When the term “catalyst composition” is used to describe such a pair prior to activation, it may be unreacted with an activator and optionally a co-activator (eg, a trialkylaluminum compound). An activated catalyst (precatalyst) is meant. When it is used to describe such a pair after activation, it means an activation catalyst and an activator or other charge balancing moiety. In addition, the activated “catalyst composition” may optionally include co-activators and / or other charge balancing moieties. In any event, at least one poly-α-olefin is “produced” (or “produced”) from the reaction.
In one embodiment, the catalyst composition includes a metallocene and an activator to form the catalyst composition. The metallocene catalyst compound is bonded to cyclopentadienyl (“Cp”) bonded to at least one metal atom, to one or more cyclopentadienyl ligands of isolobal, and to at least one metal atom. Includes half (one cyclopentadienyl bonded to the metal center) and one complete (two cyclopentadienyl bonded to the metal center) sandwich compound having one or more leaving groups. An example of a half-sandwich compound is the so-called “constrained geometry” metallocene. The term “leaving group” refers to any ligand that can be extracted from a metallocene catalyst compound to produce a metallocene-catalyzed cation capable of polymerizing one or more olefins.

Cp ligands are typically represented by one or more linking systems containing π bonds, which may be open systems or ring systems or one or more condensed systems or combinations thereof. These one or more rings or one or more ring systems are typically selected from Group 13 to 16 atoms, and in another embodiment carbon, nitrogen, oxygen, silicon, sulfur, phosphorus, boron and aluminum. Or an atom selected from the group consisting of these combinations. The metal atoms are selected from Groups 4-12 of the Periodic Table of Elements in one embodiment, and others described herein. In a special embodiment, the metallocene is a Group 4 bridged bis-Cp compound and both Cp ligands are attached to the metal center as is known in the art and as described below. As well as being connected to each other by some “bridge” part.
In one embodiment, the metallocene catalyst compound has the formula (1): L ^A L ^B MQ _n , wherein each L ^A and L ^B is bonded to the metal center M and each Q is bonded to the metal center; n is 0 or an integer from 1 to 4, in another embodiment 1 or 2, and in yet another embodiment 2) an unbridged bis-cyclopentadienyl metallocene A compound.
In formula (1), the metal atom “M” is in one embodiment selected from the group consisting of Group 3 to Group 10 atoms, and in a more specific embodiment, the group consisting of Group 4, Group 5 and Group 6 atoms. In yet another special embodiment, Zr or Hf. The metallocene metal is not limited to a particular oxidation state in the present invention. One or more Cp ligands form at least one chemical bond with the metal atom M to form a “metallocene catalyst compound”. Cp ligands differ from leaving groups attached to catalyst compounds in that they are highly insensitive to substitution / retraction reactions.
L ^A group and L ^B groups Cp ligands of the formula (1), for example, a cycloalkadienyl ligands and heterocyclic analogues. Cp ligands typically include atoms selected from the group consisting of group 13 to group 16 atoms, and more particularly, the atoms comprising the Cp ligand are carbon, nitrogen, oxygen, silicon, sulfur, phosphorus, germanium. Selected from the group consisting of boron, aluminum and combinations thereof, wherein carbon comprises at least 50% of the ring members. More particularly, the one or more Cp ligands are selected from the group consisting of substituted cyclopentadienyl ligands and unsubstituted cyclopentadienyl ligands and cyclopentadienyl iso-loval ligands, including, but not limited to, cyclo Examples include pentadienyl, indenyl, fluorenyl, and other structures. Further non-limiting examples of such ligands include cyclopentadienyl, cyclopentaphenanthrenyl, indenyl, benzindenyl, fluorenyl, octahydrofluorenyl, cyclooctatetraenyl, cyclopentacyclododecene, phenanthrine. Nyl, 3,4-benzofluorenyl, 9-phenylfluorenyl, 8-H-cyclopentaacenaphthylenyl, 7-H-dibenzofluorenyl, indeno [1,2-9] anthrene, thiopheno Indenyl, thiophenofluorenyl, their hydrogenation variants (eg, 4,5,6,7-tetrahydroindenyl), their substitution variants (as described in more detail below), and these There are different types of heterocycles.

Independently, each L ^A and L ^B may be unsubstituted or substituted with a combination of substituents R. Non-limiting examples of substituents R are selected from halogen; hydrogen; and linear, branched, or cyclic alkyl C ₁ -C ₂₀ or C ₃₀ or C ₅₀ groups; and alkenyl groups, aryl groups, or combinations thereof One or more of the above groups. Non-limiting examples of alkyl or aryl substituents R include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl groups, all of them Including isomers such as tertiary butyl, isopropyl and the like; Also, at least two R groups, and in certain embodiments, two adjacent R groups are combined to form 3 to 30 selected from carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminum, boron, or combinations thereof. Form a ring structure with up to atoms.
The leaving group Q of formula (1) is a monoanionic labile ligand bound to M. Depending on the oxidation state of the metal, the value for n is 0, 1 or 2, so that the above formula (1) represents a neutral metallocene catalyst compound or a positively charged compound. Examples of the leaving group include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, a hydrogen atom, an alkoxy group, a methyl group, an ethyl group, and other alkyl groups.

In one embodiment, the metallocene catalyst compounds of the present invention include compounds of formula (1) wherein L ^A and L ^B are bridged together by a bridging group “A”. These bridged compounds are referred to as bridged metallocene catalyst compounds and are represented by the formula (2): L ^A (A) L ^B MQ _{n where} each L ^A and L ^B is bonded to the metal M. And each Q is bonded to a metal center, n is 0 or an integer from 1 to 4, in some embodiments 1 or 2, and in yet another embodiment 2, the groups L ^A , L ^B, M and Q are as defined in formula (1), and a divalent bridging group "a" is coupled to both the L ^a and L ^B by at least one bond, or a divalent moiety Are coupled to each other).
Non-limiting examples of the bridging group “A” from formula (2) include at least one group 13-16 atom, such as carbon, oxygen, nitrogen, silicon, boron, germanium and tin atoms (limited to these). A divalent bridging group containing at least one of the above or a combination thereof. In some embodiments, the bridging group “A” comprises a carbon, silicon, or germanium atom. The “A” group contains in a particular embodiment at least one silicon atom or at least one carbon atom. The bridging group “A” may also include a substituent R as defined above (including halogen). More specifically, non-limiting examples of the bridging group “A” are R ′ ₂ C═, R ′ ₂ Si═, — (R ′) ₂ Si (R ′) ₂ Si—, — (R ′) ₂ Si (R ') ₂ C-, R' ₂ Ge =,-(R ') ₂ C (R') ₂ C-,-(R ') ₂ Si (R') ₂ Ge-,-(R ') ₂ Ge (R ') ₂ C-, R'N =, R'P =,-(R') ₂ C (R ') N-,-(R') ₂ C (R ') P-,-(R ') ₂ Si (R') N-,-(R ') ₂ Si (R') P-,-(R ') ₂ Ge (R') N-, and-(R ') ₂ Ge (R' ) P- (wherein R ′ is independently hydride, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl substituted organometalloid, halocarbyl substituted organometalloid, disubstituted boron, disubstituted group 15 atom, substituted group 16 atom, Or a group that is halogen, or two or more R ′ may be joined to form a ring or ring system, and Q is as previously described).
It is contemplated that the metallocene catalyst components include their structural isomers or optical isomers or enantiomers (racemic mixtures) and in one embodiment may be pure enantiomers. Furthermore, as used herein, a single, bridged, asymmetrically substituted metallocene catalyst component having racemic and / or meso isomers itself does not constitute at least two different bridged metallocene catalyst components. Any combination of beneficial "metallocene catalyst component" in the present invention is any "embodiment" described herein, for example, L ^A group, L ^B group, M group, Q group, any of A group, and an R group Combinations may be included.

The catalyst composition described herein includes in one embodiment a metallocene and an activator. The catalyst composition may include a support material as is known in the art. As used herein, the term “activator” refers to a single-site catalyst compound (eg, a metallocene, a group 4 imide / amine coordination compound, etc.), eg, by generating a cationic species from the catalyst component. Is defined as any compound or combination of compounds that can be activated, supported or unsupported. Typically this involves the withdrawal of at least one leaving group (Q group in the above formula / structure) from the metal center of the catalyst component. Thus, the catalyst component of the present invention is activated for olefin polymerization using such activators. Embodiments of such activators include Lewis acids such as cyclic or oligomeric poly (hydrocarbyl aluminum oxide) and so-called non-coordinating activators (“NCA”) (also “ionizing activators” or “stoichiometry”). Amount of activator "), or any other compound capable of converting a neutral metallocene catalyst component to a metallocene cation that is active for olefin polymerization.
More particularly, Lewis acids as activators such as alumoxanes (eg “MAO”), modified alumoxanes (eg “TIBAO”), and alkylaluminum compounds, and / or ionizing activators (neutral or ionic) ), For example, using tri (n-butyl) ammonium tetrakis (pentafluorophenyl) boron and / or trisperfluorophenylboron metalloid precursors to activate the desired metallocene described herein. Within range. MAO and other aluminum based activators are known in the art. Ionization activators are known in the art and may be associated with or bound to a support in association with a catalyst component (eg, metallocene) or separately from the catalyst component.

Examples of neutral ionization activators include group 13 trisubstituted compounds, in particular trisubstituted boron compounds, tellurium compounds, aluminum compounds, gallium compounds and indium compounds, and mixtures thereof. The three substituents are each independently selected from alkyl, alkenyl, halogen, substituted alkyl, aryl, aryl halide, alkoxy and halide. In one embodiment, the three groups are independently selected from halogen, monocyclic or polycyclic (including halo substituted) aryl, alkyl, and alkenyl compounds and mixtures thereof. In another embodiment, the three groups are alkenyl groups having 1-20 carbon atoms, alkyl groups having 1-20 carbon atoms, alkoxy groups having 1-20 carbon atoms, and 3-20 Selected from aryl groups having a carbon atom (including substituted aryl), and combinations thereof. In yet another embodiment, the three groups are selected from alkyls having 1 to 4 carbon groups, phenyl, naphthyl and mixtures thereof. In yet another embodiment, from a highly halogenated alkyl group in which the three groups have 1 to 4 carbon groups, a highly halogenated phenyl, and a highly halogenated naphthyl and mixtures thereof To be elected. “Highly halogenated” means that at least 50% of the hydrogen is replaced by a halogen group selected from fluorine, chlorine and bromine. In yet another embodiment, the neutral stoichiometric amount of the activator is a highly fluorinated aryl group (these groups are a highly fluorinated phenyl group and a highly fluorinated naphthyl group). ) Is a trisubstituted group 13 compound.
In another embodiment, the neutral trisubstituted group 13 compound is a boron compound such as 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.

Non-limiting illustrative examples of ionic ionization 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 tetra (pentafluorophenyl) boron, tri (n-butyl) a Monium tetra (o-tolyl) boron etc .; N, N-dialkylanilinium salts such as N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N -2,4,6-pentamethylanilinium tetra (phenyl) boron and the like; dialkylammonium salts such as di (isopropyl) ammonium tetra (pentafluorophenyl) boron, dicyclohexylammonium tetra (phenyl) boron and the like; triarylcarbonium Salts (trityl salts) such as triphenylcarbonium tetra (phenyl) boron and triphenylcarbonium tetra (pentafluorophenyl) boron; and triarylphosphonium salts such as triphenylphosphonium tetra (phenyl) boron, triphenylphospho D Mutetora (pentafluorophenyl) boron, tri (methylphenyl) phosphonium tetra (phenyl) boron, tri (dimethylphenyl) phosphonium tetra (phenyl) boron and the like, as well as aluminum equivalents thereof.
When a non-coordinating anion (“NCA”) or ionic activator is used, the molar ratio of activator to metallocene is usually in the range of 10: 1 to 1:10, in some embodiments from 0.5: 1. Within the range of 2: 1. If NCA or an ionic active agent is used, a co-active agent may also be used. The molar ratio of co-active agent (if present) to metallocene is 1000: 1 to 10: 1 in one embodiment, 500: 1 to 20: 1 in another embodiment, 200: 1 to 20 in yet another embodiment. : 1, in yet another embodiment in the range of 150: 1 to 20: 1. In one embodiment, scavengers are also used to scavenge catalyst poisons. The scavenger may be the same compound as the co-activator, and in one embodiment an alkylaluminum compound.

When an alumoxane, for example methylaluminoxane (MAO), is used as the activator, the molar ratio of activator to metallocene is usually 5: 1 to 5000: 1, in some embodiments 1000: 1 to 500: 1, or others In this embodiment, it is in the range of 500: 1 or 300: 1 or 50: 1 to 1: 1 or 20: 1 or 100: 1.
“Reacting” (or “reaction”) between the catalyst composition and the α-olefin feedstock occurs by any suitable means known in the art suitable for producing polyolefins. “Reacting” means a chemical reaction that can occur by a combination and / or substitution and / or rearrangement of chemical bonds between compounds brought together. In a particular invention, the reaction is a reaction of a catalyzed combination of monomer repeat units to produce a polymer. In certain embodiments, the reaction may occur as a batch reaction in a batch reactor, and in certain embodiments the reaction occurs in a continuous reactor, examples of which include gas phase reactors, slurry reactors, A solution reactor may be mentioned, the last two of which may be high pressure reactors. If present, diluents that may contain the monomers themselves may be used.
The conditions present during the reaction are those conditions for producing at least one poly-α-olefin as described herein. The reaction takes place in some embodiments at temperatures in the range from 10 ° C. or 20 ° C. to 80 ° C., or 100 ° C., or 120 ° C., or 200 ° C. Furthermore, the reaction occurs in some embodiments at a pressure greater than 1.0 or 1.1 or 1.2 or 1.4 MPa, and in some embodiments from 0.8 or 1.0 MPa to 2.0 or 3.0 MPa. The polymerization reaction is usually exothermic. In order to maintain a constant and / or stable temperature, heat removal means are used in certain embodiments. Heat removal can be accomplished in many known ways, for example, circulating refrigerant in a tube inside the reactor, feeding a pre-cooled feed stream, part of the reactor contents by circulating the contents to an external cooling system. Cooling, or a combination of these methods.

In certain embodiments, the catalyst concentration ranges from 0.01 or 0.5 μg metallocene compound per gram of olefin feed to 20 or 50 or 100 or 1000 μg metallocene compound per gram of olefin feed.
In certain embodiments, the polymerization reaction is performed in the presence of hydrogen. The amount of hydrogen feed may in one embodiment range from 5 or 10 or 20 ppm to 1000 or 4000 or 5000 or 10,000 ppm in the reactor system, with exemplary values being in the range of 10 to 1000 ppm. . In another embodiment, the amount of hydrogen is adjusted by the partial pressure of hydrogen in the reactor system. In this case, 0.35 or 0.70 kg / cm ² (5 or 10 psi) hydrogen to 14 or 21 kg / cm ² (200 or 300 psi) hydrogen is preferred, and exemplary values are 0.7 to 7 kg / cm ² (10 to 100 psi). ).
In some embodiments, an inert solvent is added to the reactor system to facilitate mixing of the reactor components and downstream filtration and operation. The reaction time may range from 5 minutes to 50 hours, depending on the amount of catalyst used, the desired conversion, etc. in one embodiment. Usually reaction times or residence times of 10 minutes to 25 hours, in another embodiment 20 minutes to 10 hours, are used. The catalyst component can be deactivated and / or removed by any conventional means, for example, any mixing with dilute acid or base aqueous solutions with aqueous and / or alcohol washing followed by separation of the organic components from the aqueous washing. This washing is repeated several times until the catalyst component is removed. The catalyst can also be removed according to the method described in WO 2008010862 A1.
In certain embodiments, the at least one poly-α-olefin produced by the process has a high bromine number or a high degree of unsaturation. If so, in some embodiments, at least one poly-α-olefin may be hydrogenated to remove unsaturation. This can be accomplished by fixed bed continuous hydrogenation using a number of common hydrogenation catalysts, such as supported Ni / diatomaceous earth catalysts, or slurry hydrogenation. Other examples can be found in WO 2008010862 A1. This unsaturation is also left in at least one poly-α-olefin.

In all embodiments / aspects described herein, the product of the reaction of the catalyst with the α-olefin is at least one poly-α-olefin that meets the desired criteria described herein, Embodiments will result in the production of more than one poly-α-olefin. Thus, in some embodiments, the blend may include a poly-α-olefin that does not meet the desired criteria, but includes at least one such poly-α-olefin. The additional poly-α-olefin in the blend can come from any source and can be produced by any means.
The poly-α-olefin can be separated from the product mixture resulting from the reaction, which can then be combined with additives and / or feedstocks to produce a lubricant. In other embodiments, the reaction mixture is combined directly with the product of the reaction. In one embodiment, the at least one poly-α-olefin is a polyolefin having a Kv ¹⁰⁰ in the range of ¹⁰ to 5000 cSt. The at least one poly-α-olefin has a Kv ¹⁰⁰ below 2000 or 2500 or 3000 or 3500 or 4000 or 4500 or 5000 cSt in some other embodiments. Furthermore, the at least one poly-α-olefin has in another embodiment a Kv ¹⁰⁰ in the range of 10 or 15 or 20 or 50 cSt to 500 or 1000 or 1500 or 2000 or 2500 or 4000 or 3000 or 5000 cSt. . In yet another embodiment, the at least one poly-α-olefin has a VI greater than 200 or 220 or 250 and in the range of 100 or 150 or 200 to 300 or 400. In yet another embodiment, the molecular weight distribution (weight average molecular weight / number average molecular weight, or “MWD”) of the at least one poly-α-olefin is 1.0 or 1.2 or 1.5 to 3.5 or as measured by gel permeation chromatography. Within the range of 4.0 or 4.5, the measurement has a typical accuracy of ± 0.15 units.

The at least one poly-α-olefin in one embodiment consists essentially of two or more C ₄ or C ₆ to C ₁₈ or C ₂₄ α-olefin derived units. In other embodiments, the at least one poly-α-olefin is substantially 1-hexene derived unit, 1-octene derived unit, 1-decene derived unit, 1-dodecene derived unit, 1-tetradecene derived unit, 1 -It consists of hexadecene derived units and 1-octadecene derived units. In yet another embodiment, the at least one poly-α-olefin is substantially 1-hexene derived unit, 1-octene derived unit, 1-decene derived unit, 1-dodecene derived unit, 1-tetradecene derived unit, It consists of at least three olefins selected from the group consisting of 1-hexadecene derived units and 1-octadecene derived units.
The at least one poly-α-olefin is present in the hydrocarbon feedstock in one embodiment in an amount that reduces the pour point of the blend by at least 5 ° C, 10 ° C, or 15 ° C relative to the pour point of the feedstock (or Added to it). In some embodiments, the at least one poly-α-olefin is present in the blend at from 0.001 or 0.01 wt% to 5 or 7 or 10 wt% poly-α-olefin, based on the weight of the feedstock. . The feedstock includes in some embodiments a range from 99.999% to 40 or 50 or 60 or 70% by weight of the blend, or ranges described herein. The remainder of the lubricant or fuel may be composed of additives (some of which are listed herein).
Thus, in one aspect, Kv ^{100 in} the range of 10 cSt to 1000 or 3000 cSt (or otherwise described herein) and in the range of 1.0 to 4.5 (or otherwise described herein) And a feedstock having a Kv ¹⁰⁰ of less than 20.0 cSt (or otherwise described herein), wherein at least one of the lubricants is provided. The poly-α-olefin is present in an amount sufficient to lower the pour point of the lubricant relative to the pour point of the untreated feedstock.

In certain embodiments, the addition of the at least one poly-α-olefin to the feedstock will not substantially affect the viscosity of the blend. Thus, in one embodiment, the at least one poly-α-olefin is added to the feedstock such that the pour point of the blend is at least 5 ° C. or 10 ° C. lower than the pour point of the feedstock to produce the blend, and the Kv ¹⁰⁰ changes less than 5 or 10%.
In some embodiments, the at least one poly-α-olefin consists essentially of two or more C ₆ -C ₂₄ α-olefin derived units. Also, in some embodiments, the ethylene derived units are substantially absent from the at least one poly-α-olefin, and the ethylene derived units and propylene derived units are substantially absent in yet another embodiment. "Substantially absent" means that when these groups are present in the polymer chain, they are present up to 0.5 or 1 or 1.5% by weight of the polymer.
The lubricant may also include any one or more additives as is common in the art. In one embodiment, the lubricant comprises one or more additives, which additives are oxidation inhibitors, antioxidants, dispersants, detergents, corrosion inhibitors, rust inhibitors, metal deactivators, antiwear agents. , Extreme pressure additive, anti-seizure agent, non-olefin based pour point depressant, wax modifier, viscosity index improver, viscosity modifier, infusion steaming additive, seal conformant, friction modifier Selected from the group consisting of agents, lubricants, antifouling agents, color formers, antifoaming agents, demulsifiers, emulsifiers, densifying agents, wetting agents, gelling agents, tackifiers, colorants, and blends thereof. It is.
In one embodiment, pour point depressants based on non-polyolefins are substantially absent, meaning that they are present up to less than 1% by weight of the lubricant. Examples of non-polyolefin based PPDs include polyacrylates, ethylene-vinyl acetate copolymers, and fumarate. Thus, in one embodiment, “additives” include the above list without “non-olefin based pour point depressants”.

In another embodiment, the at least one poly-α-olefin described herein can also be used with other hydrocarbon fluids to improve the pour point or cold flow properties of these fluids. Examples of these hydrocarbon fluids include distilled fuel, which includes jet fuel, diesel fuel, and heating oil. Specific examples of these distillate fuels are fuels produced by the GTL process as described in US Pat. No. 7,132,042, or many distillate fuels produced at ordinary petroleum refineries. These fuels, as produced from their production process, contain a small amount of waxy components. These waxy components degrade the low temperature fluidity and pour point of the fluid. When a small amount of the at least one poly-α-olefin is added to the fuel, the low temperature properties, as measured by pour point or other methods, are significantly improved. The amount of poly-α-olefin in the fuel composition ranges from 0.0001% to 5%, preferably from 0.001% to 0.5% (corresponding to 10 ppm to 5000 ppm). In addition, the finished distilled fuel product may contain other additive components including detergents, lubricity improvers, combustion improvers, cetane improvers, other cold flow improvers, filtration improvers, cloud point improvers. In addition, the fuel is a fuel or component derived from a bio-diesel containing an appropriate amount of reuse sources, such as fatty acid alkyl esters (or methyl esters (“FAME”) or ethyl esters, etc.), glycerol, mono-glycerides, etc. May be included.
The one or more poly-α-olefins produced in the present invention have some unique properties. First, in some embodiments, they may contain at least 10% or 20% or 30% or 35% or more C ₁₄ linear α-olefin derived units. Secondly, many of these poly-α-olefins have a relatively high pour point due to their high content of C ₁₄ linear α-olefins. Most of the at least one poly-α-olefin having a pour point depressing effect usually has a pour point of -15 or -10 or higher than 0 ° C. Some poly-α-olefins with a low pour point (below -20 ° C) have good pour point depressant properties. Therefore, the methods described herein can provide poly-α-olefins having both excellent pour point and low temperature properties and still provide excellent pour point depressant properties.
In certain embodiments, the pour point depressing effect or low temperature viscosity improving effect is a smaller olefin selected from C ₄ -C ₁₃ linear α-olefins and a larger olefin selected from linear α-olefins greater than C _14. Can be optimized by ensuring that they are randomly distributed in at least one poly-α-olefin without significant clustering of smaller or larger olefins. In other words, the at least one poly-α-olefin is preferably a random poly-α-olefin that does not contain one or more fairly blocky segments in the polymer structure. Single site catalyst systems, such as metallocene catalyst systems, are optimal for producing such poly-α-olefins having a random monomer distribution. The metallocene catalyst system polymerizes linear α-olefins of C ₄ -C ₂₄ α-olefins with approximately equal reactivity and therefore produces a polymer with a relatively random monomer distribution. Such polymers would be most desirable for the low temperature improvement effect of Group I-VI feedstocks. Thus, in one embodiment, a single site catalyst is selected that results in an almost random polymer.
The embodiments described herein are illustrated by the following experiments.

For all experiments, the α-olefins used individually or premixed, 1 liter of raw olefin raw material was activated in a glove box for at least 2 days and 20 g of 13X molecular sieves and deoxygenation catalyst (reduction) The resulting copper catalyst was purified by mixing with 10 g. The molecular sieve and deoxygenation catalyst were then removed by filtration. The treated individual α-olefins were then combined to give the desired composition. Similarly, this purification can be accomplished by using a bed of activated 13X molecular sieve alone or a bed of activated 13X molecular sieve followed by deoxygenation before entering the reactor with a stream of α-olefin (alone or premixed). This can be done by pumping to the catalyst bed.
The pour point and cloud point of the blend were measured with a Herzog pour point (“PP”) instrument model HCP852 (Walter Herzog, GmbH).
Poly-α-olefin synthesis experiment Example 1 18.4% 1-hexene, 22.3% 1-octene, 21.6% 1-decene, 16.8% 1-dodecene, 10.4% 1-tetradecene, 6.4% An olefin mixture containing 1-hexadecene and 4% 1-octadecene was used as the feed. This composition is similar to linear α-olefins produced from typical linear α-olefin plants (α-olefin application book chapter 3 (edited by GR Lappin and JD Sauer, Marcel Dekker, Inc., New York, 1989)). It is. The reactor was charged with 0.522 g of a solution containing 30 g of this olefin mixture and 20 mg of triisobutylaluminum (TIBA) per 1 g of toluene. 11 g of toluene, 0.0133 g of TIBA stock solution, 0.30798 mg of rac-dimethylsilylbis (tetrahydroindenyl) zirconium dichloride (metallocene “A”) and N, N-dimethylanilinium tetra (pentafluorophenyl) borate (cocatalyst “B”) A catalyst solution containing 0.5408 mg was added to the reactor with stirring while maintaining the temperature at 30 ° C. After about 19 hours of stirring, the reaction was stopped by adding about 3 ml of 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./1 millitorr vacuum for 2 hours to remove the light end and the desired poly-α-olefin fraction was isolated. The overall yield of poly-α-olefin was 85%. The properties of the recovered poly-α-olefin are summarized in Table 1.

Example 2 Example 1 with the exception that metallocene (C) containing 70% meso-dimethylsilylbis (tetrahydroindenyl) zirconium dichloride and 30% racemic-dimethylsilylbis (tetrahydroindenyl) zirconium dichloride was used in the preparation. It was the same.
Example 3 Same as Example 1 except that the reaction was carried out at 60 ° C.
Example 4 Same as Example 2 except that the reaction was carried out at 60 ° C.
Example 5 An olefin mixture containing 33.6 g of 1-octene, 42.0 g of 1-decene and 50.4 g of 1-dodecene was charged into a round bottom flask and heated to 70 ° C. under a nitrogen atmosphere. A catalyst solution containing 2.34 g of 10% by weight metal moxane (MAO) in toluene solution, 60 g of toluene and 3.7 mg of rac-dimethylsilylbis (tetrahydroindenyl) zirconium dichloride (C) is gradually added to the olefin mixture, while constant The temperature was maintained. The reaction was continued for 4 hours. Gas chromatography indicated that 94% of the olefin had been converted. The reaction was stopped by adding about 3 ml of 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./1 mtorr vacuum for 2 hours to remove the light ends. The lubricant properties are summarized in Table 1.

Example 6 is a comparative example. The same reaction was carried out as in Example 5, except that pure 1-decene was used as the feedstock. The properties of polydecene are summarized in Table 1.
Examples 1-5 range from a wide range of mixed alpha-olefins ranging from C ₈ -C ₁₂ to C ₆ -C ₁₈ and have a wide viscosity range with excellent viscosity index (“VI”, ASTM-D2270) and pour point. It has been demonstrated that lubricant feedstock can be produced. The lubricant properties are similar to those made from pure 1-decene.
Example 7 7.1% 1-hexene, 9.5% 1-octene, 11.9% 1-decene, 14.3% 1-dodecene, 16.7% 1-tetradecene, 19.1% 1-hexadecene and 21.4% 1-octadecene An olefin mixture containing was used as the feedstock. 30 g of this feedstock was charged to the reactor at 31 ° C. A catalyst solution containing 0.195 g of 10 wt% MAO in toluene, 9.7 g of toluene and 0.308 mg of catalyst A was added to the reactor. Three days later, the reaction solution was treated in the same manner as in the previous example. The properties of the poly-α-olefin are listed in Table 1.
Example 8 Same as Example 1 except that the feed composition was described in Example 7.
Example 9 Same as Example 7 except that Catalyst C was used.
Example 10 Same as Example 1 except the feedstock composition was as described in Example 7 and the catalyst composition was Catalyst C.
Example 11 Same as Example 7 except that the reaction temperature was 60 ° C.
Example 12 Same as Example 7 except that the metallocene used was racemic-ethylenebis (1-indenyl) zirconium dichloride (Catalyst D).

Poly-α-olefin and feedstock blending experiments Example 13 Hydrotreated lubricant feedstock A (having the properties summarized in Table 2) was prepared according to US Patent No. 6,420,618 or WO 2004/033595 .
Blend 14 When 1% by weight of the poly-α-olefin of Example 1 was blended with feedstock A, the blend slightly increased the viscosity at 100 ° C. However, the pour point was lowered from -15 ° C to -18 ° C.
Blend 15 When 20% by weight of Example 1 is blended with feedstock A, the blend has a viscosity of 100 ° C. of 27.92 cSt. However, the pour point was lowered to -30 ° C.
Blend 16 When 0.1% by weight of Example 7 is blended with feedstock A, the blend has a Kv ¹⁰⁰ of 6.14 cSt, which is only slightly higher than starting feedstock A. However, the pour point was lowered from -15 ° C to -45 ° C.
Furthermore, blends 17, 18, 19, and 20 showed the same pour point depressing effect when 0.5, 1.0, 5.0, or 20 wt% of Example 7 was blended with feedstock A.
Blend 21 When 0.05% by weight of Example 10 is blended with feedstock A, the blend has a Kv ¹⁰⁰ of 6.12 cSt, which is only slightly higher than starting feedstock A. However, the pour point was lowered from -15 ° C to -39 ° C.
Furthermore, blends 22, 23 and 24 showed the same pour point depressing effect.
Blend 25 When blending 0.1% by weight of Example 12 with feedstock A, the blend has a Kv ¹⁰⁰ of 6.12 cSt, which is only slightly higher than starting feedstock A. However, the pour point was lowered from -15 ° C to -45 ° C.

Linear Olefin Feedstock Experimental Feedstock Composition: Six linear α-olefin (linear α-olefin) mixtures having different number average carbon numbers ranging from 13.24 to 9.27 were prepared according to the mass in Table 3. These feeds labeled “Feed-1” to “Feed-6” were used for subsequent polymer synthesis using a metallocene catalyst system.
General procedure for the synthesis of poly-α-olefins: Examples 26-31 All reaction procedures involving metallocene catalyst systems were carried out under a nitrogen atmosphere to eliminate air and moisture or any other catalyst poisons. A 200 ml reaction vessel is charged with 40 g of mixed olefin feedstock, followed by 20 g of toluene, 3.232 g of triisobutylaluminum (“TIBA”) stock solution containing 20 mg per gram of stock solution, catalyst rac-dimethylsilylbis (tetrahydroindenyl) zirconium dichloride. (Catalyst A) 0.456 mg and N, N-dimethylanilinium tetra (pentafluorophenyl) borate (Activator B) 0.8012 mg were charged. The mixture was heated to a reaction temperature of 70 ° C. After 15 hours of reaction, 5 g of activated alumina was added to the reaction mixture and stirred for about 30 minutes. The product was then filtered to remove solids. The organic filtrate was distilled at 100 ° C. under a house vacuum of about 20 mm H ₂ O. The residue was further distilled at 160 ° C. at a pressure above 1 millitorr for 2 hours. The residual viscous liquid was then collected and subjected to viscosity characteristics and pour point measurements for Kv ⁴⁰ and Kv ¹⁰⁰ (Kv ⁴⁰ is the kinematic viscosity according to ASTM D445 at 40 ° C. and Kv ¹⁰⁰ is the kinematic viscosity at 100 ° C.). . The results are summarized in Table 4.

Examples 32-37 were prepared as in Examples 26-31 except that the reaction temperature was maintained at 35 ° C for Feed-1 to Feed-6. The product properties are summarized in Table 5. In general, the poly-α-olefins in Table 5 have a higher viscosity than the poly-α-olefins in Table 4.
The samples in Table 6 were prepared in a manner similar to Examples 32-37, except that different catalysts and reaction temperatures were used to produce different tacticity and viscosity poly-α-olefins. Examples 38 and 40 had a low degree of stereoregularity and were mostly atactic polymers. Example 39 had a high degree of syndiotactic stereoregularity.
Their properties are summarized in Table 6. Catalyst D was diphenylmethylidene (cyclopentadienyl-9-fluorenyl) zirconium dichloride, and polymerization was performed by combining catalyst D and activator B to form a catalyst composition.
Different amounts of product examples 26-40, from 0.01% to 10% by weight, were then blended with 6 cSt GTL feedstock ("GTL6"). The starting GTL6 has a pour point of -21 ° C. The pour point characteristics of the blends are summarized in Table 7. In this table, the pour point values in the matrix associated with columns A through H are the pour points of the blends at different amounts of Example 26-40 samples in GTL6. For example, Blend A-26 containing 0.025 wt% Example 26 poly-α-olefin in GTL6 has a pour point of −39 ° C. Blend E-26 containing 0.5% by weight of Example 26 poly-α-olefin in GTL6 has a pour point of -51 ° C. Blend C-33, containing 0.1 wt% Example 33 poly-α-olefin in GTL, has a pour point of -51 ° C. Blend C-36, containing 0.1 wt% Example 36 poly-α-olefin in GTL6, has a pour point of -21 ° C.
The data in Table 7 illustrates some aspects of the present invention. The number average carbon number of the feed is a factor in determining whether the product has a pour point (“PP”) lowering effect.
Poly-α-olefins made with feedstocks with a number average carbon number greater than 10.0 have excellent PPD effects (Examples 26-29, 32-35 and 38-40).

Poly-α-olefins made with an average carbon number feed of less than 10 have a very small PPD effect (Examples 30, 31, 36 and 37). These poly-α-olefins behave even more as feedstocks. They have excellent feedstock properties including VI and very low pour point. When they are blended with an additive amount of 0.025% to 1% by weight, they exhibit a very small PPD effect. They are optimal as blended feedstocks when used in large amounts (usually greater than 5% by weight) and blended with other feedstocks. When used in large amounts, above 5%, they significantly increase the blend viscosity, increase VI, and lower the pour point. These fluids are described in WO 2007/14681, WO 2007/145924, and WO 2007/070691.
Wide viscosity range (or molecular size) poly-α-olefins are highly effective PPDs as long as they are made from feedstocks having a number average carbon number greater than 10. The poly-α-olefins of Examples 26-29 have a Kv100 of 70-90 cSt, and Example 40 is 19.5 cSt. They are highly effective as PPD. Examples 32-36 and 39 have a high viscosity greater than 200 cSt. Again, they are highly effective as PPDs. This wide range of viscosities that can be utilized as PPD is highly desirable to provide formulation flexibility. For example, sometimes it is desirable to use PPD to improve the pour point without increasing the blend viscosity. In this case, a low viscosity PPD that does not increase the blend viscosity is optimal. Occasionally, it is desirable to increase the blend viscosity and simultaneously reduce the pour point. In this case, a high viscosity poly-α-olefin PPD would be optimal.
Poly-α-olefins having an atactic, isotactic or syndiotactic steric order are all useful as PPDs when they are made from feedstocks having an average carbon number greater than 10. Examples 38 and 40 are rich in atactic steric order. Example 39 is rich in syndiotactic order. Examples 26-29 and 32-35 are rich in isotactic steric order. They are all valid as PPDs.
Examples 41-44 Examples 41 and 42 are blends of GTL6 and poly-α-olefins Example 33 and Example 34, respectively. The properties of the blend (including high temperature and low temperature viscosity pour points, including Brookfield viscosity at -30 ° C and -40 ° C) are summarized in Table 8. Table 8 also includes the properties of pure GTL6 (Example 42) and blends of GTL6 and common commercial pour point depressant Acryloid ^™ 156 (methyl methacrylate copolymer, Rohm and Haas) (Example 43). These data indicated that blends containing additive amounts (0.1-1 wt%) in GTL6 had similar viscosities as pure GTL6 feedstock. However, their pour points were lowered from -21 ° C (Example 43) to -39 to -45 ° C (Examples 41 and 42). Low temperature Brookfield viscosity (measured by ASTM D2983) was further reduced compared to the starting GTL6 feedstock, even though all fluids had similar Kv ¹⁰⁰ , Kv ⁴⁰ and VI. Furthermore, the low temperature Brookfield viscosities of Examples 41 and 42 are better than the most commonly used PPD (Example 43) without again significantly changing Kv ¹⁰⁰ and Kv ⁴⁰ .
Table 9 summarizes the beneficial effects of a small amount of poly-α-olefin from Examples 26-37 in the high viscosity GTL feedstock in reducing the turbidity of the GTL feedstock. A high viscosity GTL feedstock produced by the methods described in US Pat. Nos. 7,241,375 and 7,132,042 and having the composition described therein is a turbidimeter (VWR model 800 turbidity available from VWR International). Often has a cloudy appearance as indicated by the high turbidity value of 1.99 at 0 ° C. When very small amounts of poly-α-olefin Examples 27-37 were added to the GTL samples, the turbidity dropped below 1.0 as shown by the blends in Table 9. These data demonstrate that poly-α-olefins made from number average carbon numbers greater than 10 carbons are beneficial in reducing the turbidity of high viscosity GTL feedstocks.
Thus, in some embodiments, the turbidity of the hydrocarbon blend, in particular embodiments, the lubricant or fuel is less than 0.90 or 0.95 or 1.00, and in other embodiments within the range of 0.50 or 0.60 to 0.90 or 1.00. is there.

Having described the hydrocarbon blend, its various features, and aspects of the components therein, the hydrocarbon blend may be further described by the following exemplary numbered embodiments.
1. 0.001% to 10% by weight of at least one poly-α-olefin based on the weight of the hydrocarbon blend (the at least one poly-α-olefin is in the range of ^{10 to} 3000 cSt Kv ¹⁰⁰ and 1.0 to Having a molecular weight distribution in the range of 4.5); and a feedstock having a Kv ¹⁰⁰ of less than 20.0 cSt, wherein the at least one poly-α-olefin has a pour point of the feedstock of the feedstock Present in an amount sufficient to drop by at least 5 ° C. relative to the pour point).
2. The at least one poly-α-olefin is a copolymer comprising at least two sets of α-olefin derived units in the polymer composition, the first set being C ₄ or C ₆ to C ₁₀ or C ₁₂ or C ₁₃ The hydrocarbon blend of numbered embodiment 1, wherein the hydrocarbon blend is selected from up to α-olefins and the second set is selected from C ₁₄ or higher α-olefins.
3. The hydrocarbon blend of numbered embodiments 1 and 2, wherein the second set of α-olefin derived units is at least 20% by weight of the at least one poly-α-olefin.
4. The hydrocarbon blend of any of the preceding numbered embodiments, wherein the second set of α-olefin derived units is at least 30% by weight of the at least one poly-α-olefin.
5. The hydrocarbon blend of any of the preceding numbered embodiments, wherein the second set of α-olefin derived units is at least 40% by weight of the at least one poly-α-olefin.
6. The above numbered implementation wherein at least one poly-α-olefin is produced from an α-olefin feedstock having an average carbon number of at least 8, 9 or 10 or 10.5 or 11 carbon atoms The hydrocarbon blend of any of the embodiments.
7. The hydrocarbon blend of any of the preceding numbered embodiments, wherein the at least one poly-α-olefin consists essentially of two or more C ₄ or C ₆ to C ₂₄ α-olefin derived units.
8. Any of the preceding numbered embodiments, wherein the at least one poly-α-olefin is present in an amount that reduces the pour point of the hydrocarbon blend by at least 5 ° C, 10 ° C, or 15 ° C relative to the pour point of the feedstock. Hydrocarbon blends.
9. The hydrocarbon blend of any of the preceding numbered embodiments, wherein the feedstock has a pour point of 10 ° C or higher.
10. The feedstock is a mixture selected from the group consisting of GTL feedstock, Group I, Group II, Group III, Group IV, Group V feedstock, and mixtures thereof, having a Kv100 of less than 20.0 cSt, The hydrocarbon blend of any of the numbered embodiments.

11. The hydrocarbon blend of any of the preceding numbered embodiments, wherein the feedstock has a VI of at least 100.
12. The hydrocarbon blend of any of the preceding numbered embodiments, wherein the ethylene derived units are substantially absent from at least one poly-α-olefin.
13. The hydrocarbon blend of any of the preceding numbered embodiments, wherein the at least one poly-α-olefin has a VI in the range of 100 to 300.
14. The hydrocarbon blend of any of the preceding numbered embodiments, wherein the hydrocarbon blend comprises within the range of 99.999% to 30 or 40 or 50% by weight of the feedstock.
15. Also contains one or more additives, which are oxidation inhibitors, antioxidants, dispersants, detergents, corrosion inhibitors, rust inhibitors, metal deactivators, antiwear agents, extreme pressure additives Anti-seizure agents, non-olefin-based pour point depressants, wax modifiers, viscosity index improvers, viscosity modifiers, infusion steaming additives, seal compatibilizers, friction modifiers, lubricants, An earlier number selected from the group consisting of antifouling agents, color formers, defoamers, demulsifiers, emulsifiers, densifiers, wetting agents, gelling agents, tackifiers, colorants, and blends thereof. The hydrocarbon blend of any of the attached embodiments.
16. A lubricant or fuel made from a hydrocarbon blend of any of the preceding numbered embodiments.

17. (a) a feedstock comprising a catalyst composition and at least two sets of α-olefins, wherein the first set of α-olefins is selected from C ₄ -C ₁₃ α-olefins and the second set of α-olefins olefin to produce at least one poly -α- olefin having Kv ¹⁰⁰ of at least 10.0cSt by reacting chosen) from C ₁₄ or more α- olefins, and (b) at least one poly -α- olefin To produce a hydrocarbon blend of any of the preceding numbered embodiments, comprising combining a feedstock having a Kv ¹⁰⁰ value of less than 20.0 cSt to produce a hydrocarbon blend.
18. (a) reacting the catalyst composition with an α-olefin feedstock having a number average carbon number of at least 8, 9, 10 or 10.5 or 11 carbon atoms to produce a Kv ¹⁰⁰ of at least 10.0 cSt. having at least generate one poly -α- olefin, and (b) generating the hydrocarbon blend together with the feed oil having a Kv ¹⁰⁰ less than 20.0cSt at least one poly -α- olefin, A process for producing a hydrocarbon blend of any of the preceding numbered embodiments.
19. The method of numbered embodiments 17 and 18, wherein ethylene is substantially absent from the α-olefin feed.
20. The method of numbered embodiment 17-19, wherein the alpha-olefin feedstock has an average carbon number in the range of 8 to 15 carbon atoms.
21. The method of numbered embodiment 18, wherein the α-olefin feedstock comprises at least two α-olefins selected from the group consisting of C ₆ -C ₂₄ α-olefins and mixtures thereof.
22. based on the weight of the feedstock feed comprises C ₆ alpha-olefin and at least 8% by weight of C ₁₈ alpha-olefin in the range from 0.1 wt% to 15 wt%, of the numbered embodiments 18 Method.
23. The method of numbered embodiment 17, wherein the feedstock comprises at least 20% by weight α-olefin having a carbon number of C ₁₄ or greater.
24. The method of numbered embodiment 17, wherein the feedstock comprises at least 30% by weight α-olefin having a carbon number of C ₁₄ or greater.
25. The method of numbered embodiment 17, wherein the feedstock comprises at least 40% by weight α-olefin having C ₁₄ or more carbon atoms.
26. The method of numbered embodiment 17-25, wherein the catalyst composition comprises a metallocene and an activator.

27. The method of numbered embodiment 26, wherein the metallocene is a Group 4 bridged or unbridged bis-Cp compound. If not crosslinked, metallocenes can be described with respect to formula (1) above. When bridged, metallocenes containing the bridging group “A” are described with respect to formula (2) above. In some embodiments, the metallocene is hafnocene or zirconocene having the characteristics as described with respect to formulas (1) and (2).
28. The method of numbered embodiments 17 and 18, wherein the reaction occurs at a temperature in the range of 10 ° C. to 200 ° C.
29. The method of numbered embodiments 17 and 18, wherein the reaction occurs at a pressure greater than 1.0 MPa.
30. The method of numbered embodiments 17 and 18, wherein the reaction occurs in the presence of a hydrogen partial pressure in the range of 0.07 kg / cm ² (1 psi) to 21 kg / cm ² (300 psi).
31. The method of numbered embodiments 17 and 18, wherein the reaction occurs using a continuous hydrogen feed having a hydrogen content of less than 1000 or 2000 or 3000 ppm in the reactor system.
32. Numbered embodiment 17 and at least one poly-α-olefin combined with an amount sufficient to lower the pour point of the hydrocarbon blend to at least 5 ° C. or 10 ° C. or 15 ° C. relative to the pour point of the feedstock; 18 ways.
33. The method of numbered embodiments 17 and 18, wherein the feedstock has a pour point of less than 10 ° C.
34. A lubricant or fuel made by the method of any of the preceding numbered embodiments 17-33.

In another embodiment, based on the weight of the hydrocarbon blend, from 0.001% to 10% by weight of at least one poly-α-olefin, wherein the at least one poly-α-olefin is in the range of 10 to 3000 cSt ¹⁰⁰ and a molecular weight distribution in the range of 1.0 to 4.5; and a feedstock having a Kv ¹⁰⁰ of less than 20.0 cSt (the at least one poly-α-olefin is the pour point of the hydrocarbon blend) Present in an amount sufficient to drop by at least 5 ° C).
In another embodiment, based on the weight of the hydrocarbon blend, from 0.001% to 10% by weight of at least one poly-α-olefin, wherein the at least one poly-α-olefin is in the range of 10 to 3000 cSt in the range of ¹⁰⁰ and 1.0 to 4.5 having a molecular weight distribution); and a feedstock having a Kv ¹⁰⁰ less than 20.0CSt, poly -α- olefins in the fuel or lubricant (at least one poly -α- 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 feedstock.
In yet another embodiment of a hydrocarbon blend comprising at least one poly-α-olefin as described herein as a fuel or lubricant comprising from 0.001% to 10% poly-α-olefin. There is use.

Claims (9)

Hydrocarbon blend comprising a poly-α-olefin made with at least one metallocene catalyst from 0.001% to 1 % by weight, based on the weight of the hydrocarbon blend, and a feedstock having a Kv ¹⁰⁰ of less than 20.0 cSt Wherein the blend is characterized by a poly-α-olefin produced using at least one metallocene catalyst having a Kv ^{100 in} the range of 10-3000 cSt and a molecular weight distribution in the range of 1.0-4.5, at least A poly-α-olefin produced using a type of metallocene catalyst is produced from an α-olefin feedstock having a number average carbon number of 10.5 to 15 carbon atoms, and using at least one type of the metallocene catalyst The poly-α-olefin produced in this way lowers the pour point of the hydrocarbon blend by at least 5 ° C. relative to the pour point of the feedstock , and the feedstock is API Group I, A hydrocarbon blend characterized by being selected from the group consisting of API Group II, API Group III, GTL feedstock, and mixtures thereof . The poly-α-olefin produced using at least one metallocene catalyst is a copolymer comprising at least two sets of α-olefin derived units in the polymer composition, the first set being a C ₄ to C ₁₃ α- selected from olefins, and the second set is selected from C ₁₄ or more α- olefins, hydrocarbon blend of claim 1, wherein. The hydrocarbon blend of claim 2, wherein the second set of α-olefin derived units is at least 20% by weight of the poly-α-olefin produced using at least one metallocene catalyst . It also contains one or more additives, which are oxidation inhibitors, antioxidants, dispersants, detergents, corrosion inhibitors, rust inhibitors, metal deactivators, antiwear agents, extreme pressure additives, firing agents. Anti-sticking agents, pour point depressants based on non-olefins, wax modifiers, viscosity index improvers, viscosity modifiers, seal compatibilizers, friction modifiers, lubricants, antifouling agents, color formers, erasers 4. Any one of claims 1 to 3 , selected from the group consisting of foaming agents, demulsifiers, emulsifiers, densifying agents, wetting agents, gelling agents, tackifiers, colorants, and blends thereof. Hydrocarbon blends. A lubricant or fuel made from the hydrocarbon blend of any one of claims 1 to 4 . (a) a feedstock comprising a metallocene catalyst composition and at least two sets of α-olefins (the first set of α-olefins selected from C ₄ -C ₁₃ α-olefins and the second set of α-olefins) Is selected from α-olefins of C ₁₄ or more) and is reacted with a feedstock having a number average carbon number of 10.5 to 15 carbon atoms to have a Kv ¹⁰⁰ of at least 10.0 cSt It generates a poly -α- olefin produced with a metallocene catalyst, and (b) feedstock having at least one metallocene catalyst Kv ¹⁰⁰ less than 20.0cSt manufacturing poly -α- olefins using a Together producing a hydrocarbon blend and using the poly-α-olefin produced with the at least one metallocene catalyst in an amount of 0.001% to 1 % by weight, based on the weight of the hydrocarbon blend That Reduce the pour point of the hydrogen fluoride blend by at least 5 ° C with respect to the pour point of the feedstock, and the feedstock is selected from the group consisting of API Group I, API Group II, API Group III, GTL feedstock, and mixtures thereof method of producing a hydrocarbon blend characterized in that it is. (a) using at least one metallocene catalyst having a Kv ¹⁰⁰ of at least 10.0 cSt by reacting a metallocene catalyst composition with an α-olefin feedstock having a number average carbon number of 10.5 to 15 carbon atoms Producing a poly-α-olefin produced, and (b) a hydrocarbon blend of the poly-α-olefin produced using the at least one metallocene catalyst combined with a feedstock having a Kv ¹⁰⁰ of less than 20.0 cSt And the poly-α-olefin produced using the at least one metallocene catalyst in an amount of 0.001% to 1 % by weight, based on the weight of the hydrocarbon blend, of the hydrocarbon blend. The pour point is lowered by at least 5 ° C. relative to the pour point of the feedstock, and the feedstock is composed of API Group I, API Group II, API Group III, GTL feedstock, and mixtures thereof. Method of producing a hydrocarbon blend characterized in that it is selected from. alpha-olefin feedstock comprises at least two alpha-olefins selected from the group consisting of C ₆ -C ₂₄ alpha-olefin, and mixtures thereof The method of claim 7 wherein. At least one poly -α- olefin produced with a metallocene catalyst causes reduction of at least 10 ° C. The pour point of the hydrocarbon blend to the pour point of the feedstock, claim 7 or 8 A method according.