CN102057022A

CN102057022A - Pour point depressant for hydrocarbon compositions

Info

Publication number: CN102057022A
Application number: CN2009801207196A
Authority: CN
Inventors: M·M·吴; D·J·柏拉格昂; A·杰克森
Original assignee: Exxon Chemical Patents Inc
Current assignee: ExxonMobil Chemical Patents Inc
Priority date: 2008-06-05
Filing date: 2009-03-24
Publication date: 2011-05-11
Also published as: WO2009148685A1; CA2726774A1; JP2011521095A; AU2009255507A1; EP2313480A1; JP5512661B2

Abstract

Disclosed is a hydrocarbon blend made from 0.001 to 10 wt% of at least one poly-a- olefin, by weight of the blend, the at least one poly-a-olefm having a Kv100 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 Kv100 below 20.0 cSt; wherein the at least one poly-a-olefin is present in an amount sufficient to lower the pour point of the blend by at least 5 DEG C relative to the pour point of the base stock. The blend is formed by (a) reacting a catalyst composition and a feed containing at least two sets of a-olefins, wherein the first set of a-olefins is selected from C4 to C12 a-olefins and the second set of a-olefins is selected from C14 or larger a-olefins. The a-olefin feed may have a number average carbon number of at least 8 carbon atoms or greater.

Description

The pour point reducer that is used for compositions of hydrocarbons

The cross reference of related application

The application requires in the rights and interests of the European application 08162595.6 of the existing U. S. application sequence number 12/133,927 of submission on June 5th, 2008 and submission on August 19th, 2008, and these two pieces of documents are incorporated herein for reference in full.

Technical field

Bulking property of the present invention relates to lubricant and fuel composition, more specifically relates to turbidity and pour point that a class can reduce low viscosity alkyl material, keeps the poly-alpha-olefin of the overall viscosity of described base-material simultaneously if necessary.

Background technology

Since automobile occurs, needed to improve lubricating oil always.A kind of concern of lubricated motor car engine aspect is the low temperature behavior of lubricant.Automobile original equipment manufacturer (" OEM ") is concerned about the wax be included in nearly all refining mineral generation, the crystallization and prevent that lubricant from flowing at low temperatures of described wax.Exist the modern high performance lubricant will keep desirable viscosity and prevent the expectation of the wearing and tearing under the real operation condition.When the long-term cold of weather, for example at Canada and northern US, this is challenging especially.Pour point reducer (or " PPD ") is commonly used to improve lubricant flowing in cold climate.PPD commonly used is based on polyacrylic ester and fumarate.Yet if consider the functional of them, these PPD are expensive and have relatively poor stability.Along with the needs that change in the market, the selection of " suitable " pour point reducer is never than more important now.The lubricant of equipment manufacturers and user bigger efficient of positive demand transmission and bigger weather resistance.Simultaneously, the new spec of engine and transmission system lubricant has proposed stronger restriction to low-temperature fluidity.In addition, along with the API II group of strict hydrotreatment and the growth of III group oil are used, base oil selects (slate) to change just continuously.

Comprise that more polyolefinic lubricant compositions are disclosed in US 6,420,618, among WO2007/146081, WO 2007/145924, WO 2007/070691 and the WO 2004/033595.Though some in these compositions have improved pour point with respect to base-material, still need to have more high-performance and the more lubricant of low pour point.

The modern fuels composition, particularly there is similar situation in overhead product fuel.Overhead product fuel can be made or by " natural gas synthetic oil " (" gas-to-liquid by the conventional oil process for refining, GTL ") technology or made by coal or pitch synthetic oil (" CTL ") technology.The example of this type of overhead product fuel can be referring to US 6,811, and 683, US 7,344,631 and US5,487,763.Need higher-quality overhead product fuel that but the discharge of improved pour point, oilness, low temperature pumping and flowable, minimizing is provided.This improvement can improve overall mechanical operability and improve fuel economy.The poly-alpha-olefin for preparing among the present invention can provide such raising.

That need is the more low-cost PPD that has improved stability and can organize the PPD in base-material, particularly " natural gas synthetic oil " (" GTL ") deutero-base-material and the fuel base-material as API I group-Di IV.This paper provides such PPD.

Summary of the invention

Hydrocarbon blends has been described in one embodiment, in specific embodiment, be fuel or lubricant, it comprises: by the weight of blend, 0.001-10 at least a poly-alpha-olefin of weight %, described at least a poly-alpha-olefin has the Kv of 10-5000cSt ¹⁰⁰Molecular weight distribution with 1.0-4.5; With the Kv that has less than 20.0cSt ¹⁰⁰Base-material; There is the pour point of the described hydrocarbon blends amount with respect to 5 ℃ of the depressions of pour point of described base-material in wherein said at least a poly-alpha-olefin by being enough at least.In certain embodiments, base-material is lube base stock or fuel base-material.

This paper has also described the formation method of hydrocarbon blends in one aspect, in specific embodiment, be the formation method of fuel or lubricant, comprise: (a) make catalyst composition and the raw material reaction that contains at least two group alpha-olefins, wherein said first group of alpha-olefin is selected from C ₄-C ₁₃Alpha-olefin and described second group of alpha-olefin are selected from C ₁₄Or bigger alpha-olefin and form at least a Kv of 10.0cSt at least that has ¹⁰⁰Poly-alpha-olefin; (b) with described at least a poly-alpha-olefin and the Kv that has less than 20.0cSt ¹⁰⁰The base-material of value or fuel base-material in conjunction with and form hydrocarbon blends.

The formation method of hydrocarbon blends has been described in one aspect of the method, in specific embodiment, be the formation method of fuel or lubricant, comprise: the alpha-olefin raw material reaction that (a) makes catalyst composition and the number average carbon number with at least 8 carbon atoms is to form at least a Kv of 10.0cSt at least that has ¹⁰⁰Poly-alpha-olefin; (b) with described at least a poly-alpha-olefin and the Kv that has less than 20.0cSt ¹⁰⁰The base-material of value in conjunction with and form hydrocarbon blends.

Various descriptive elements disclosed herein and numerical range can combine with other descriptive elements and the numerical range of describing the preferred embodiment of the invention; In addition, any numerical upper limits of element can combine with any numerical lower limits of identical element.

Detailed Description Of The Invention

Unless regulation, all fluids described herein " viscosity " are meant 100 ℃ of kinematic viscosity (" Kv according to 100 ℃ of measurements of ASTM D445 ¹⁰⁰"), (" cSt ") is unit with centistokes(cst).All viscosity indexs (" VI ") value is measured according to ASTM D2270.

This paper employed " lubricant " is meant the liquid substance that can be introduced between two or more moving surfaces and reduce the friction level between the described moving surface.In one embodiment, " lubricant " is such material, and it comprises: by the weight of lubricant, and at least a Kv of 0.01-10 weight % with 10-5000cSt ¹⁰⁰Poly-alpha-olefin and at least one class have Kv less than 20.0cSt ¹⁰⁰The alkyl material.In certain embodiments, " compositions of hydrocarbons " is lubricant.

This paper employed " fuel " is any material of emitting energy with the controlled chemistry reaction; In this manual, the hydrocarbon material preferably at room temperature is that those of liquid are the fuel of emitting energy with oxidant reaction.In one embodiment, " fuel " is such material, and it comprises: by the weight of fuel, and at least a Kv of 0.001-10 weight % with 10-5000cSt ¹⁰⁰Poly-alpha-olefin and at least one class have Kv less than 20.0cSt ¹⁰⁰The fuel base-material.In certain embodiments, " compositions of hydrocarbons " is fuel.

This paper employed " base-material " is used for describing the hydrocarbon fluid that does not contain following at least a poly-alpha-olefin, and by volume is the main ingredient of final lubricant or fuel in one embodiment.Term " base-material " comprises overhead product fuel to the lube range molecule, and it is a continuum and greater than C ₁₀The mixture of organic molecule.Than the lower boiling fraction, common C ₁₀-C ₂₂As overhead product fuel or " fuel base-material "; More the high boiling point fraction is used for lubricant base.In one embodiment, base-material (be used for fuel, lubricant or other) has at least 100, in another embodiment, and at least 120 VI.In certain embodiments, base-material has the pour point less than 10 or-10 or-15 ℃.In certain embodiments, base-material is II group, III group or GTL base-material.In certain embodiments, base-material has less than 10 or 20 or 30cSt, in other embodiments, and greater than 0.1 or 1 or the Kv of 3cSt ¹⁰⁰Value.

The limiting examples of the alkyl material (or " base-material ") that is fit in the lubricant comprises API I group, II group, III group, IV group, V group and VI group base-material and is derived from fischer-tropsch process or the hydrocarbon fluid of " natural gas synthetic oil " (" GTL ") technology.

" natural gas synthetic oil " base-material comprises the base-material and/or the base oil of the GTL technology that is derived from a kind of perhaps many possibility types.GTL technology refers generally to the chemical conversion that Sweet natural gas (most of is methane) changes into synthetic gas (mainly being CO and hydrogen).Perhaps, also the solid coal can be changed into mainly is the synthetic gas of CO and hydrogen.By fischer-tropsch process synthetic gas is changed into most of linear paraffinic hydrocarbons then.Linear alkanes has wide molecular size distribution.C ₂₅More high-grade high molecular weight linear paraffinic hydrocarbons fraction can become lubricant base by different catalysts experience hydroisomerization then by distillation or fractionation separates.In certain embodiments, this GTL base-material has 3 to 20 or the Kv of 30cSt ¹⁰⁰GTL base-material and/or base oil can in statu quo use or be used in combination with the lube base stock of other Hydrodewaxing or hydroisomerization, catalysis or solvent dewaxing.In one embodiment, the GTL that can be used for lubricant described herein has at least 100, in another embodiment, and at least 120 VI.In certain embodiments, the GTL base-material has 20 or 10 ℃ to-15 or-20 ℃ pour point.The preparation method of GTL lube base stock and these base-materials can be referring to US 7,344, and 631, US 6,846,778, US 7,241,375, US 7,053,254 or WO 2005121280A1.Generally speaking, any lube base stock that is derived from GTL technology can be used for blend described herein.

An example of GTL base-material is the base-material that comprises the paraffin component, wherein the degree of branching (" branch index " or " BI ") measured of the percentage by methyl hydrogen and by repeating mesomethylene carbon (they are four or more a plurality of carbon from end group or side chain taking-up) (CH ₂〉=4) the branching degree of approximation that percentage is measured makes: (a) BI-0.5 (CH ₂〉=4)＞15; (b) BI+0.85 (CH ₂〉=4)＜45, described liquid hydrocarbon composition is measured as a whole.

Another example of GTL base-material also is characterized by the mixture that comprises branched paraffin, it is characterized in that lubricant base oil contains the mixture of at least 90% branched paraffin, and wherein said branched paraffin is to have C ₂₀-C ₄₀Molecular weight, 343 ℃-566 ℃ the paraffinic hydrocarbons of boiling range and the wherein said branched paraffin of carbon chain lengths, 280-562 contain at the most that the uncombined carbon index of four alkyl branches and wherein said branched paraffin is at least 3.The measuring method of GTL base-material and branch index for example is described in greater detail in, among the WO 2007/070691.

Fuel " base-material " can for example be middle distillate oil fuel, for example diesel oil fuel, aviation fuel, kerosene, oil fuel, jet fuel, heater oil etc.Generally speaking, the fuel base-material that is fit to is boiling point those of (ASTM D1160) in 120-500 ℃ scope, in another embodiment, and boiling point those in 150-400 ℃ scope.Representational heater oil specification requirement 10% distillation point (distillation point) is not higher than about 226 ℃, 50% distillation point is not higher than 272 ℃ and 90% and distills at least 282 ℃ of points, and be not higher than 338 ℃-343 ℃, but some specifications are set to described 90% distillation point up to 357 ℃.In certain embodiments, heater oil is made by the blend of straight run distillate (for example, gas oil, petroleum naphtha etc.) and cracked distillate (for example, catalytic cycle stock).The representational specification of diesel oil fuel base-material comprises 38 ℃ minimum flash-point and 282 ℃-338 ℃ 90% distillation point (referring to ASTM D-396 and D-975).These overhead product fuel base-materials can be made or they can be by " natural gas synthetic oil " (GTL) or " coal synthetic oil " (" coal-to-liquid by the conventional oil process for refining, and CTL ") technology is made.

This paper employed " poly-alpha-olefin " has 10 or 20 to 1000 or 2000 or the Kv of 5000cSt ¹⁰⁰Multipolymer, described multipolymer is by the raw material reaction preparation that makes catalyst composition and 'alpha '-olefin monomers.Blend described herein comprises at least a poly-alpha-olefin described herein.This paper employed " multipolymer " is not limited to the polymkeric substance that is made of two kinds of different monomers deutero-unit, and can comprise the unit of three kinds, four kinds or more kinds of different copolymer monomer derived.Catalyst composition can comprise and can catalysis produce polyolefinic any compound known (one or more) independent or combination by olefinic monomer, their limiting examples is Ziegler-Natta catalyst, the catalyzer based on chromic oxide, the 4th family acid amides/imide coordination catalyst, and metalloscene catalyst, have optional activator for example aikyiaiurnirsoxan beta or non-coordination anion (for example, huge borate compound) separately.In certain embodiments, use the catalyst composition that comprises metallocenes and activator to prepare described at least a poly-alpha-olefin.

The formation method of described at least a poly-alpha-olefin can be described by two complementary aspects.In aspect first, by making catalyst composition and the described at least a poly-alpha-olefin of olefin feedstock prepared in reaction with certain number average carbon number.In aspect second, prepare described at least a poly-alpha-olefin by making catalyst composition and one or more olefine reactions that are selected from two groups of alkene: first group is at C ₄-C ₁₃Alkene in the alpha-olefin scope, second group is more than or equal to C ₁₄The alkene of alpha-olefin.The formation method of described at least a poly-alpha-olefin can be described by the combination of first and second aspects in a further aspect.

Therefore, in one aspect, by making catalyst composition and having at least 8 carbon atoms, in another embodiment, at least 9 carbon atoms, in another embodiment, at least 10 carbon atoms, in another embodiment, at least 11 carbon atoms, in another embodiment, the alpha-olefin raw material reaction of the number average carbon number of at least 11.5 carbon atoms prepares described at least a poly-alpha-olefin.In another embodiment, the alpha-olefin raw material has 8-15 carbon atom, in another embodiment, 10-15 carbon atom, in another embodiment, 10.5-14.5 carbon atom, in another embodiment, the number average carbon number of 10-14 carbon atom." raw material " can be continuously or batch-wise, be meant the constant supply of alpha-olefin to be offered the component of positive reaction or individual quantities is added in the component of positive reaction up to stopped reaction, or introduce that other is fresh " batch " raw material.

In certain embodiments, described alpha-olefin raw material comprises at least two kinds and is selected from C ₄-C ₂₄The alpha-olefin of alpha-olefin and its mixture.In another embodiment, described alpha-olefin group comprises C ₅-C ₂₄Alpha-olefin and its mixture.In certain embodiments, can also exist a spot of even high-grade C more _24-32In one embodiment, there is 0.01-5 weight % in alpha-olefin.In another embodiment, basically by C ₆-C ₂₄The alpha-olefin group that alpha-olefin and its mixture are formed (be meant lower or more high-grade alkene with C ₆-C ₂₄The alpha-olefin raw material separates as far as possible) be actual.

In another embodiment, described alpha-olefin raw material comprises at least two kinds and is selected from C ₆-C ₂₄The alpha-olefin of alpha-olefin and its mixture.In another embodiment, described raw material comprises 0.1-15 weight %C ₆Alpha-olefin and at least 8 weight %C ₁₈Alpha-olefin is based on the weight of described raw material.In certain embodiments, the alpha-olefin of formation raw material is a linear alpha-alkene.

In certain embodiments, the alpha-olefin raw material is basically by being selected from C ₆-C ₂₄Two or more alkene of alpha-olefin are formed.In another embodiment, the alpha-olefin raw material is formed by being selected from two or more following alkene basically: 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecylene, 1-dodecylene, 1-tridecylene, tetradecene, 1-15 carbenes, cetene, 1-heptadecene, 1-vaccenic acid, 1-19 carbenes, 1-eicosylene, 1-heneicosene, 1-two dodecylenes, 1-tricosene, 1-tetracosene.In another embodiment, the alpha-olefin raw material is made up of 1-hexene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene and 1-vaccenic acid basically.In certain embodiments, ethene is not present in the alpha-olefin raw material basically; And in specific embodiment, ethene and propylene are not present in the alpha-olefin raw material basically.So-called " not existing basically " but be meant ethene or ethylene/propene is not present in the raw material with any detection level up to the level of 1.5 weight %.

In one aspect of the method, by catalyst composition is contacted to form described at least a poly-alpha-olefin with the alpha-olefin raw material that is selected from two groups of alpha-olefins.First group of alpha-olefin is in one embodiment, is selected from C ₄-C ₁₃Alpha-olefin in another embodiment, is selected from C ₅-C ₁₂Alpha-olefin in another embodiment, is selected from C ₆-C ₁₂Alpha-olefin in another embodiment, is selected from C ₆-C ₁₀At least a or multiple in the alkene of alpha-olefin.In one embodiment, at least a alkene is selected from second group of alpha-olefin, and in another embodiment, only selects a kind ofly, and in another embodiment, only two kinds are selected from second group.

In certain embodiments, first group of alpha-olefin accounts for 10 or 15 or 20 or 30 or 40%-70 or 80 or 90% of total alpha-olefin raw material.In one embodiment, can use C ₄-C ₁₃In the alpha-olefin any one or more in another embodiment, can use C ₅-C ₁₂In the alpha-olefin any one or more in another embodiment, can use C ₆-C ₁₀In the alpha-olefin any one or more.The rest part of raw material is selected from second group of C ₁₄Or bigger alpha-olefin.In certain embodiments, at least 20% of alpha-olefin raw material, or 30%, or 40% comprise C ₁₄Or bigger alpha-olefin; And in another embodiment, raw material comprises and is less than 90%C ₁₄Or bigger alpha-olefin.

In certain embodiments, blend alpha-the olefin feedstock that comprises two groups of alpha-olefins preferably has the number average carbon number of at least 8 carbon atoms, in another embodiment, the number average carbon number of at least 9 carbon atoms, in another embodiment, the number average carbon number of at least 10 carbon atoms, in another embodiment, at least 10.1 carbon atoms, in another embodiment, at least 10.2 carbon atoms, in another embodiment, at least 10.5 carbon atoms, in another embodiment, at least 11 carbon atoms, in another embodiment, the number average carbon number of at least 11.5 carbon atoms.In another embodiment, the alpha-olefin raw material has 8-15 carbon atom, in another embodiment, 10-15 carbon atom, in another embodiment, 10.5-14.5 carbon atom, in another embodiment, the number average carbon number of 10-14 carbon atom.

As the situation of the first described aspect of the described at least a poly-alpha-olefin of preparation, in certain embodiments, ethene, or ethylene/propene is not present in the raw material basically, and in other embodiments, raw material can be made up of linear alpha-alkene basically.

Make alpha-olefin raw material described herein and catalyst composition " reaction " to form described at least a poly-alpha-olefin.Term " catalyst composition " is defined at this and is meant that catalyst precursor/activator is right, and for example metallocenes/activator is right.When using this kind pairing of term " catalyst composition " before being described in activation, be meant non-activated catalyzer (pre-catalyst) and randomly, activator promotor (for example trialkyl aluminium compound) together with activator.When it was used for being described in this kind pairing that activates afterwards, it was meant activatory catalyzer and activator or other charge balance structure part.In addition, this activatory " catalyst composition " can randomly comprise activator promotor and/or other charge balance structure part.Under any circumstance, at least a or multiple poly-alpha-olefin is by this reaction " preparation " (or " forms ").

In one embodiment, catalyst composition comprises metallocenes and activator to form catalyst composition.Metallocene catalyst compound comprises half (with cyclopentadienyl of metal center bonded) and complete (with two cyclopentadienyls of metal center bonded) sandwich compound, its have one or more cyclopentadienyl ligands or with the part of the cyclopentadienyl that is keyed at least one atoms metal (" Cp ") isomorphism (isolobal) and with one or more leavings groups of described at least one atoms metal keyed jointing.The example of half sandwich compound is so-called " constrained geometry configuration (constrained geometry) " metallocenes.Term " leavings group " is meant and can extracts the cationic any part of metalloscene catalyst that can make one or more olefinic polymerizations to form from metallocene catalyst compound.

The Cp part is represented by one or more keyed jointing systems that comprise the π key that generally described keyed jointing system can be open system or member ring systems (one or more) or condense system or its combination.These rings (one or more) or member ring systems (one or more) by being selected from 13-16 family atom and in another embodiment, are selected from the atomic building of carbon, nitrogen, oxygen, silicon, sulphur, phosphorus, boron and aluminium or its combination usually.In one embodiment, and as described in other place of this paper, atoms metal is selected from the 4th to 12 family of the periodic table of elements.In a specific embodiment, metallocenes be the 4th family's bridging two-the Cp compound, be meant that two Cp parts combine with metal center and each other via some " bridging " structure division combinations, as known in the art with describe below such.

In one embodiment, metallocene catalyst compound is two-cyclopentadienyl-containing metal cyclopentadinyl compound: the L by the not bridging of formula (1) expression ^AL ^BMQn, wherein each L ^AAnd L ^BM combines with metal center, and each Q combines with metal center, and n is 0 or the integer of 1-4, in another embodiment, is 1 or 2, in another embodiment, is 2.

In formula (1), atoms metal " M " is selected from the 3rd to 10 family's atom in one embodiment; In more specific embodiment, be selected from the 4th, 5 and 6 family's atoms, in another more specific embodiment, be Zr or Hf.The metal of metallocenes is not limited to any specific oxidation state in the present invention.Cp part (one or more) forms at least one chemical bond with atoms metal M, thereby has formed " metallocene catalyst compound ".The Cp part is different from the leavings group that is incorporated into catalyst compound, is that their utmost points are not easy to replace/abstraction reaction.

The L of formula (1) ^AAnd L ^BGroup is the Cp part, for example cycloalkanes dialkylene part and heterocyclic analogs.The Cp part comprises the atom that is selected from 13-16 family atom usually, and more particularly, the atom that constitutes the Cp part is selected from carbon, nitrogen, oxygen, silicon, sulphur, phosphorus, germanium, boron and aluminium and its combination, and wherein carbon constitutes at least 50% of ring members.Even more particularly, Cp part (one or more) be selected from replace and unsubstituted cyclopentadienyl ligands and with the part of cyclopentadienyl isomorphism, their limiting examples comprises cyclopentadienyl, indenyl, fluorenyl and other structure.The further limiting examples of this type of part comprises cyclopentadienyl, cyclopentano phenanthryl, indenyl, the benzo indenyl, fluorenyl, octahydrofluorenyl, the cyclooctatetraene base, cyclopentano ring dodecylene, phenanthridinyl (phenanthrindenyl), 3,4-benzo fluorenyl, 9-phenyl fluorenyl, 8-H-encircles penta [a] acenaphthenyl (acenaphthylenyl), 7-H-dibenzo fluorenyl, indeno [1,2-9] anthrene, the thieno-indenyl, the thieno-fluorenyl, their hydrogenation modification (for example 4,5,6, the 7-tetrahydro indenyl), modification of their replacement (as following described in more detail) and their heterocycle modification.

Independently, each L ^AAnd L ^BIt can be the combination replacement that does not replace or be substituted basic R.The limiting examples of substituent R comprises that one or more are selected from halogen; Hydrogen; With linearity, branching or cyclic alkyl C ₁-C ₂₀Or C ₃₀Or C ₅₀Group; And thiazolinyl, or aryl, or the group of their combination.The limiting examples of alkyl or aryl substituent R comprises methyl, ethyl, propyl group, butyl, amyl group, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl etc., comprises all their isomer, for example the tertiary butyl, sec.-propyl etc.In addition, at least two R groups, in certain embodiments, two adjacent R groups connections have the ring structure that is selected from 3-30 atom in carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminium, boron or their combination with formation.

The leavings group Q of formula (1) is and the unstable part of M bonded single anion.The oxidation state that depends on metal, the value of n are that 0,1 or 2 consequently top formulas (1) are represented neutral metal cyclopentadienyl catalyst compound, or positively charged compound.The example of leavings group comprises fluorine atom, chlorine atom, bromine atoms and iodine atom, hydrogen atom, alkoxyl group, methyl, ethyl, reaches other alkyl.

In one embodiment, metallocene catalyst compound of the present invention comprises those of formula (1), wherein L ^AAnd L ^BEach other by bridge linkage group " A " bridging.These bound are called the bridged metallocene catalyst compound and can be represented by formula (2): L ^A(A) L ^BMQn, wherein each L ^AAnd L ^BCombine with metal M, each Q combines with metal center, and n is 0 or the integer of 1-4, in certain embodiments, 1 or 2, in another embodiment, be 2; Group L ^A, L ^B, M and Q be as defined in (1); Divalence bridge linkage group " A " is via at least one key and L ^AAnd L ^BThe two in conjunction with or combine with each via the divalence structure division.

The limiting examples of the bridge linkage group " A " of formula (2) comprises and contains at least one 13-16 family atom, such as but not limited at least one divalence bridge linkage group in carbon, oxygen, nitrogen, silicon, boron, germanium and tin atom or its combination.In certain embodiments, bridge linkage group " A " contains carbon, silicon or germanium atom.In specific embodiment, " A " group contains at least one Siliciumatom or at least one carbon atom.Bridge linkage group " A " can also contain the above-mentioned substituent R that comprises halogen.More particularly, the limiting examples of bridge linkage group " A " can be represented by following group: R ' ₂C=,, R ' ₂Si=,-(R ') ₂Si (R ') ₂Si-,-(R ') ₂Si (R ') ₂C-, R ₂Ge=,-(R ') ₂C (R ') ₂C-,-(R ') ₂Si (R ') ₂Ge-,-(R ') ₂Ge (R ') ₂C-, R ' N=, R ' P=,-(R ') ₂C (R ') N-,-(R ') ₂C (R ') P-,-(R ') ₂Si (R ') N-,-(R ') ₂Si (R ') P-,-(R ') ₂Ge (R ') N-and-(R ') ₂Ge (R ') P-, wherein R is following group independently: hydride ion (hydride), alkyl, the alkyl of replacement, brine alkyl (halocarbyl), the brine alkyl that replaces, the organic quasi-metal that alkyl replaces, the organic quasi-metal that brine alkyl replaces, dibasic boron, two replace the 15th family's atom, the 16th family's atom of replacement, or halogen; Or two or more R ' can connect to form ring or member ring systems; Q as mentioned above.

Think that above-mentioned metallocene catalyst components comprises their structure or optics or enantiomer (racemic mixture), can be pure enantiomer in one embodiment.In addition, the employed metallocene catalyst components with asymmetric replacement of single bridging of racemize and/or mesoisomer of this paper itself does not constitute at least two kinds of different bridged metallocene catalyst components.Can be used for any combination that " metallocene catalyst components " of the present invention can comprise any " embodiment " described herein, for example, L ^A, L ^B, M, Q, A and R group any combination.

In one embodiment, catalyst composition described herein comprises metallocenes and activator.Catalyst composition can comprise solid support material as known in the art.It is any compound or the combination of compounds of load or not load that term as used herein " activator " is defined as, they (for example can activate the single site catalysis immunomodulator compounds, metallocenes, the 4th family imide/amine coordination compound etc.), for example activate by producing cationic species from catalyst component.Usually, this comprises from the metal center of catalyst component and captures at least one leavings group (above Q group formula/structure).Thereby use this kind activator that olefinic polymerization is activated catalyst component of the present invention.The embodiment of this type of activator comprises Lewis acid, and for example poly-(the alkyl aluminium oxide compound) of ring-type or oligopolymer and so-called non-coordination activator (" NCA ") be (perhaps, " ionization activator " or " stoichiometry activator "), maybe the neutral metal metallocene catalyst components can be changed into olefinic polymerization is cationic any other compound of active metallocenes.

More particularly, use Lewis acid for example aikyiaiurnirsoxan beta (for example " MAO "), modified alumoxane (for example " TIBAO ") and alkylaluminium cpd as activator, and/or ionization activator (neutrality or ion) for example three (normal-butyl) ammonium, four (pentafluorophenyl group) boron and/or three perfluorophenyl boron metalloid precursors activate desirable metallocenes described herein within the scope of the invention.MAO and other activator based on aluminium are to know in this area.The ionization activator be know in this area and can associate with carrier or combine, perhaps associate or separate with catalyst component with catalyst component (for example metallocenes).

The example of neutral ion activator comprises the compound of the 13rd family three-replacement, specifically, and boron, tellurium, aluminium, gallium and the indium compound of three-replacement and their mixture.Three substituting groups are selected from alkyl, aryl, aryl halide (arylhalide), alkoxyl group and the halogenide (halide) of alkyl, thiazolinyl, halogen, replacement independently of one another.In one embodiment, three groups are independently selected from halogen, list or many rings (comprising what halogen replaced) aryl, alkyl and alkenyl compound and their mixture.In another embodiment, three groups are selected from the thiazolinyl, the alkyl that contains 1-20 carbon atom that contain 1-20 carbon atom, contain the alkoxyl group of 1-20 carbon atom and contain the aryl (aryl that comprises replacement) and their combination of 3-20 carbon atom.In another embodiment, three groups are selected from the alkyl that contains 1-4 carbon back, phenyl, naphthyl and their mixture.In another embodiment, three groups are selected from the height halogenated alkyl that contains 1-4 carbon back, height halogenation phenyl and height halogenation naphthyl and their mixture.So-called " height halogenation " is meant that the halogen group that at least 50% hydrogen is selected from fluorine, chlorine and bromine substitutes.In another embodiment, neutral stoichiometry activator is the 13rd compounds of group that comprises three of highly fluorinated aryl-replacement, and described group is highly fluorinated phenyl and highly fluorinated naphthyl.

In another embodiment, the 13rd compounds of group of neutral three-replacement is for example three perfluorophenyl boron, three perfluor naphthyl boron, three (3 of boron compound, 5-two (trifluoromethyl) phenyl) boron, three (two-tertiary butyl methyl-silicane base) perfluorophenyl boron, and other highly fluorinated triarylboron and their combination and their aluminium equivalent.

Ionic ionization activator exemplary, limiting examples comprises for example triethyl ammonium four (phenyl) boron of ammonium salt that trialkyl replaces, tripropyl ammonium four (phenyl) boron, three (normal-butyl) ammonium four (phenyl) boron, trimethyl ammonium four (p-methylphenyl) boron, trimethyl ammonium four (o-tolyl) boron, tributyl ammonium four (pentafluorophenyl group) boron, tripropyl ammonium four (neighbours, right-3,5-dimethylphenyl) boron, tributyl ammonium four (,-3,5-dimethylphenyl) boron, tributyl ammonium four (p-trifluoromethyl phenyl) boron, tributyl ammonium four-(pentafluorophenyl group) boron, three (normal-butyl) ammonium, four (o-tolyl) boron and analogues; N, N-dialkyl benzene ammonium salt is N for example, N-dimethyl puratized agricultural spray four (phenyl) boron, N, N-diethyl puratized agricultural spray four (phenyl) boron, N, N-2,4,6-pentamethyl-puratized agricultural spray four (phenyl) boron and analogues; Dialkyl ammonium salt is two (sec.-propyl) ammonium four (pentafluorophenyl group) boron, dicyclohexyl ammonium four (phenyl) boron and analogue for example; Triaryl carbon

Salt (trityl salt) is triphenylcarbenium for example

Four (phenyl) boron and triphenylcarbenium

Four (pentafluorophenyl group) boron; With triaryl phosphorus Salt is triphenyl phosphorus for example

Four (phenyl) boron, triphenyl phosphorus

Four (pentafluorophenyl group) boron, three (aminomethyl phenyl) phosphorus

Four (phenyl) boron, three (3,5-dimethylphenyl) phosphorus

Four (phenyl) boron and analogue and their aluminium equivalent.

When using non-coordination anion (" NCA ") or ion activation agent, the mol ratio of activator and metallocenes is usually 10: 1-1: 10, in certain embodiments, 0.5: 1-2: in 1 the scope.When using NCA or ion activation agent, can also use activator promotor.The mol ratio of activator promotor (when existing) and metallocenes in one embodiment, 1000: 1-10: in 1 the scope, in another embodiment, 500: 1-20: in 1 the scope, in another embodiment, 200: 1-20: in 1 the scope, in another embodiment, 150: 1-20: in 1 the scope.In one embodiment, also use scavenging agent to remove any catalyzer poison.In one embodiment, scavenging agent can be and the identical compound of activator promotor (in one embodiment, being alkylaluminium cpd).

When aikyiaiurnirsoxan beta for example methylaluminoxane (MAO) when the activator, the mol ratio of activator and metallocenes is usually 5: 1-5000: 1, in certain embodiments, 1000: 1-500: 1, or 500: 1 or 300: 1 or 50 in other embodiments: 1-1: 1 or the scope of 20: 1 or 100: 1 in.

" reaction " between catalyst composition and the alpha-olefin raw material is suitable for forming polyolefinic any suitable means and carries out by known in this area.So-called " reaction " be meant between the component that combines each other can be by chemical bond combination and/or the chemical reaction that carries out of displacement and/or rearrangement; In specific invention, reaction is a monomeric unit multiple catalyzed combination and form the reaction of polymkeric substance.In certain embodiments, reaction can be carried out as rhythmic reaction in batch reactor, in certain embodiments, be reflected in the flow reactor and carry out, the example of flow reactor comprises Gas-phase reactor, slurry-phase reactor, solution reactor, and wherein back two kinds can be high-pressure reactor.When existing, can use the thinner that can comprise monomer itself.

The condition that exists between the reaction period makes and prepares at least a poly-alpha-olefin described herein.In certain embodiments, be reflected at 10 or 20-80, or 100, or 120, or carry out under 200 ℃ the temperature.In addition, reaction in certain embodiments, greater than 1.0 or 1.1 or 1.2 or 1.4MPa, in certain embodiments, 0.8 or the pressure of 1.0MPa-2.0 or 3.0MPa under carry out.Normally heat release of polyreaction.In order to keep constant and/or stable temperature, in certain embodiments, adopt the heat extraction means.Heat extraction can use many known methods to carry out, for example by pipe circulating coolant via inside reactor, by being fed into pre-cooled feed stream, cool off a part of reactor content by allowing reactor content circulate via the exterior cooling system, or the combination of these methods is cooled off.

In certain embodiments, catalyst concn is in the scope of 0.01 or 0.5 microgram Metallocenic compound/gram olefin feedstock to 20 or 50 or 100 or 1000 microgram Metallocenic compound/gram olefin feedstocks.

In certain embodiments, polyreaction is carried out in the presence of hydrogen.In one embodiment, the amount of hydrogen feed can be 5 or 10 or 20ppm to 1000 or 4000 or 5000 or 10 in reactor assembly, 000ppm, and exemplary value is within 10 to 1000ppm scope.In another embodiment, control the amount of hydrogen by the hydrogen partial pressure in the reactor assembly.In this case, 5 or 10psi hydrogen to 200 or 300psi hydrogen be fit to, exemplary value is within 10 to 100psi scope.

In certain embodiments, inert solvent is added in the reactor assembly with the mixing of promotion reactor component and the filtration and the operation in downstream.In one embodiment, the reaction times can be 5 minutes-50 hours, and this depends on the amount of employed catalyzer, desirable transformation efficiency etc.Usually, use 10 minutes-25 hours the reaction times or the residence time, in another embodiment, 20 minutes-10 hours the reaction times or the residence time.Can by any conventional means for example wash by washing and/or alcohol and randomly with the aqueous solution of diluted acid or alkali, separate catalyst component passivation with described washing organic constituent then and/or remove.Repeat this washing several times up to removing catalyst component.Perhaps, can remove catalyzer according to the method for describing among the WO2008010862A1.

In certain embodiments, at least a poly-alpha-olefin for preparing in present method has high bromine number or high degree of unsaturation.In that event, in certain embodiments, can be with described at least a poly-alpha-olefin hydrogenation to remove unsaturated part.This can pass through the fixed bed continuous hydrogenation, or by using many hydrogenation catalysts commonly used, for example the slurry hydrogenized of loading type Ni-on-Kieseiguhr catalyzer reaches.Other example can be referring to WO2008010862A1.Perhaps, allow this unsaturated part stay in the described at least a poly-alpha-olefin.

In all embodiments/aspects described herein, make the product of catalyzer and alpha-olefin reaction will cause satisfying the formation of at least a poly-alpha-olefin of required standard as herein described, in other embodiments, form more than a kind of poly-alpha-olefin.Therefore, in certain embodiments, blend can comprise the poly-alpha-olefin that does not satisfy required standard, but will comprise at least a such poly-alpha-olefin.Any additional poly-alpha-olefin in the blend can form derived from any source and with any means.

Poly-alpha-olefin can with self-reacting product mixtures separates, it can be combined with additive and/or base-material then and form lubricant.In other embodiments, reaction mixture is directly combined with the product of reaction.In one embodiment, described at least a poly-alpha-olefin is the Kv with 10-5000cSt ¹⁰⁰Polyolefine.In some other embodiment, described at least a poly-alpha-olefin has less than 2000 or 2500 or 3000 or 3500 or 4000 or 4500 or the Kv of 5000cSt ¹⁰⁰In addition, in other embodiment that also has, described at least a poly-alpha-olefin has 10 or 15 or 20 or 50 to 500 or 1000 or 1500 or 2000 or 2500 or 4000 or 3000 or the Kv of 5000cSt ¹⁰⁰In other embodiment that also has, at least a poly-alpha-olefin has the VI greater than 200 or 220 or 250,100 or 150 or 200 to 300 or 400.In other embodiment that also has, molecular weight distribution (the weight-average molecular weight/number-average molecular weight of passing through gel permeation chromatography of described at least a poly-alpha-olefin, or " MWD ") within 1.0 or 1.2 or 1.5 to 3.5 or 4.0 or 4.5 scope, described measurement has ± typical accuracy of 0.15 unit.

In one embodiment, described at least a poly-alpha-olefin is basically by two or more C ₄Or C ₆-C ₁₈Or C ₂₄Alpha-olefin derived unit is formed.In other embodiments, at least a poly-alpha-olefin is made up of 1-hexene deutero-unit, 1-octene deutero-unit, 1-decene deutero-unit, 1-dodecylene deutero-unit, tetradecene deutero-unit, cetene deutero-unit and 1-vaccenic acid deutero-unit basically.In another embodiment, at least a poly-alpha-olefin is made up of at least three kinds of alkene basically, and described alkene is selected from 1-hexene deutero-unit, 1-octene deutero-unit, 1-decene deutero-unit, 1-dodecylene deutero-unit, tetradecene deutero-unit, cetene deutero-unit and 1-vaccenic acid deutero-unit.

In one embodiment, described at least a poly-alpha-olefin is present in (or being added to) alkyl material with respect to the depression of pour point 5 of base-material or 10 or 15 ℃ amount by the pour point with blend at least.In certain embodiments, at least a poly-alpha-olefin is present in the blend by 0.001 or 0.01 to 5 or 7 or 10 weight % poly-alpha-olefins, by the weight of base-material.In certain embodiments, base-material accounts for 99.999 to 40 or 50 or 60 or 70 weight % of described blend, or by scope described herein.The rest part of lubricant or fuel can be made up of additive, and some of them are listed at this.

Therefore, provide lubricant in one aspect, its comprise and have 10-1000 or 3000cSt (or as this paper other local as described in) Kv ¹⁰⁰And the poly-alpha-olefin of the molecular weight distribution of 1.0-4.5 (or as described in other place of this paper); With the Kv that has less than 20.0cSt (or as described in other place of this paper) ¹⁰⁰Base-material; There is the pour point of the lubricant amount with respect to the depression of pour point of undressed base-material in wherein said at least a poly-alpha-olefin by being enough to.

In certain embodiments, in base-material, add the viscosity that at least a poly-alpha-olefin can not influence blend significantly.Therefore, in one embodiment, at least a poly-alpha-olefin is added in the base-material to form blend, make the pour point of described blend than low at least 5 or 10 ℃ of the pour point of described base-material, wherein Kv ¹⁰⁰Change and be less than 5 or 10%.

In certain embodiments, at least a poly-alpha-olefin is basically by two or more C ₆-C ₂₄Alpha-olefin derived unit is formed.In addition, in certain embodiments, the unit of ethylene derivative is not present in the described at least a poly-alpha-olefin basically, in another embodiment, the unit of ethene and propylene derived does not exist basically, " do not exist basically " to be meant if those groups are present in the polymer chain, then their existence accounts for 0.5 or 1 or 1.5 weight % of polymkeric substance at the most.

Lubricant can also comprise any one or more additive commonly used in this area.In one embodiment, lubricant comprises one or more additives, and wherein said additive is selected from oxidation retarder, antioxidant, dispersion agent, purification agent, corrosion inhibitor, rust-preventive agent, metal passivator, anti-wear agent, extreme-pressure additive, seizure-resistant agent (anti-seizure), pour point reducer based on non-olefinic, wax modifiers, viscosity index improver, viscosity modifier, fluid loss additive, the sealing expanding material, friction improver, lubricant, anti-staining agent, chromogenic agent, defoamer, emulsion splitter, emulsifying agent, thickening material, wetting agent, jelling agent, tackiness agent, tinting material and their blend.

In one embodiment, do not exist basically based on non-polyolefinic pour point reducer, this is meant that if any, they are to account for existing less than 1 weight % of lubricant.Example based on non-polyolefinic PPD comprises polyacrylic ester, vinyl-vinyl acetate copolymer and fumarate.Therefore, in one embodiment, " additive " comprises top tabulation, and do not have " based on the pour point reducer of non-olefinic ".

In another embodiment, at least a poly-alpha-olefin described herein can also be used from other hydrocarbon fluid one and improve these fluidic pour point or low-temperature fluiditys.The example of these hydrocarbon fluids comprises overhead product fuel, and they comprise jet fuel, diesel oil fuel and heater oil.The specific examples of these overhead product fuel is the fuel for preparing in the GTL technology, and as US7,132,042 is described, or the many overhead product fuel that prepare in conventional oil refinery.These fuel of manufacturing process preparation by them contain a spot of waxy component.These waxy components worsen fluidic low temperature flowable and pour point.When adding to a spot of at least a poly-alpha-olefin in the fuel, improve significantly as the low-temperature performance of measuring by pour point or other method.The amount of the poly-alpha-olefin in the fuel composition is 0.0001 weight %-5 weight %, preferred 0.001 weight %-0.5 weight % (being equivalent to 10ppm-5000ppm).In addition, finished product overhead product fuel Products can contain other binder component, comprises purification agent, lubricity improver, combustion improving agent, cetane number improver, other cold flow improver, filterableness improving agent, cloud point improving agent.In addition, fuel can contain the fuel that is derived from renewable resources or the component biological example diesel oil of appropriate amount, comprises fatty acid alkyl ester (or methyl ester (" FAME ") or ethyl ester etc.), glycerine, direactive glyceride etc.

One or more poly-alpha-olefins that prepare among the present invention have several unique characteristics.At first, in certain embodiments, they can contain at least 10% or 20% or 30% or 35% or more C ₁₄Linear alpha-alkene deutero-unit.Secondly, the many high C in these poly-alpha-olefins owing to them ₁₄Linear alpha-alkene content and have higher pour point.Having at least a poly-alpha-olefin of pour point decline effect great majority has usually and is higher than-15 or-10 or 0 ℃ pour point.Some poly-alpha-olefins with low pour point (less than-20 ℃) have good pour point descent performance.Therefore, method described herein can provide and both have the poly-alpha-olefin that excellent pour point and low-temperature performance also still provide excellent pour point descent performance.

In certain embodiments, can be by guaranteeing to be selected from C ₄-C ₁₃The less alkene of linear alpha-alkene and being selected from greater than C ₁₄The big alkene of linear alpha-alkene randomly is distributed in the described at least a poly-alpha-olefin and less alkene or big alkene are not trooped significantly and optimized pour point decline effect or low temperature viscous (viscometric) improvement effect.In other words, the preferably random poly-alpha-olefin of described at least a poly-alpha-olefin, and in polymer architecture without any significant block segments (one or more).Single-site catalyst systems, for example metallocene catalyst system is suitable for preparing the poly-alpha-olefin that this type of has random monomer distribution most.Metallocene catalyst system makes the C with almost equal reactive behavior ₄-C ₂₄Also therefore the linear alpha-alkene polymerization of alpha-olefin prepares the polymkeric substance with more random monomer distribution.This base polymer will be the most desirable for the low temperature improvement effect of I-VI group base-material.Therefore, in one embodiment, select to cause the single-site catalysts of unregulated polymer.

By following description of test embodiment described herein.

Preferred embodiment

Embodiment

Following purifying is used for the alpha-olefin (independent or premixed) of all experiments: in glove box inside 1 liter of untreated original olefin material was mixed two days with 20 gram activatory 13X molecular sieves and 10 gram dehydrogenation catalysts (reductive copper catalyst) at least.Then by removing by filter molecular sieve and dehydrogenation catalyst.Then with treated various alpha-olefins in conjunction with to produce desirable composition.Similarly, this purifying can followingly carry out: before entering reactor, the bed of activatory 13X molecular sieve is only passed through in the materials flow of alpha-olefin (independent or premixed) pumping, or pumping is through the bed of activatory 13X molecular sieve and then through the bed of dehydrogenation catalyst.

By Herzog pour point (" PP ") unit type HCP852 (Walter Herzog, GmbH) pour point and the cloud point of measurement blend.

The poly-alpha-olefin compound experiment

Embodiment 1. uses and contains the alkene mixture of 18.4%1-hexene, 22.3%1-octene, 21.6%1-decene, 16.8%1-dodecylene, 10.4%1-tetradecene, 6.4%1-cetene and 4%1-vaccenic acid as raw material.This composition is similar to the linear alpha-alkene by typical linear alpha-alkene equipment (ALPHA-OLEFINS APPLICATIONS BOOK Ch.3 (ed.G.R.Lappin and J.D.Sauer, Marcel Dekker, Inc., New York, 1989)) preparation.30 (30) this alkene mixtures of gram and 0.522 are restrained the solution that contains 20mg triisobutyl aluminium (TIBA)/gram toluene add reactor.Racemize-dichloro-dimethyl the silyls two (tetrahydro indenyl) that under agitation will contain 11 gram toluene, 0.0133 gram TIBA stock solution, 0.30798mg close zirconium (metallocenes " A ") and 0.5408mg four (pentafluorophenyl group) boric acid N, and the catalyst solution of N-dimethyl puratized agricultural spray (promotor " B ") adds in the described reactor while holding temperature at 30 ℃.After stirring in about 19 hours,, follow sodium hydroxide solution and water washing with about 120ml 5% by adding about 3ml Virahol stopped reaction.The organic layer two hours of fractionation by distillation is to remove light ends and to separate required poly-alpha-olefin fraction under about 160 ℃/1 millitorr vacuum.The overall yield of poly-alpha-olefin is 85%.The performance of the poly-alpha-olefin that is reclaimed is summarised in the table 1.

Embodiment 2. is similar to embodiment 1, and difference is in preparation to use and contains the metallocenes that 70% meso and 30% racemize-dichloro-dimethyl silyl two (tetrahydro indenyl) close zirconium (C).

Embodiment 3. is similar to embodiment 1, and difference is to react at 60 ℃.

Embodiment 4. is similar to embodiment 2, and difference is to react at 60 ℃.

The alkene mixtures that embodiment 5. will contain 33.6 gram 1-octenes, 42.0 gram 1-decene and 50.4 gram 1-dodecylenes add round-bottomed flask and at N ₂Be heated to 70 ℃ under the atmosphere.To contain 10 weight % methylaluminoxane (MAO), 60 gram toluene and the 3.7mg racemize-dichloro-dimethyl silyls two (tetrahydro indenyl) of 2.34 grams in toluene solution closes zirconium and adds to lentamente and keep constant temperature in the described alkene mixture simultaneously.Continue reaction 4 hours.Gas-chromatography shows 94% conversion of olefines.By adding about 3ml Virahol quencher reaction, follow sodium hydroxide solution and water washing with about 120ml 5%.The organic layer two hours of fractionation by distillation is to remove any light ends under about 160 ℃/1 millitorr vacuum.Lubricant properties is summarised in the table 1.

Embodiment 6 is comparative examples.Carry out the reaction identical, only be to use pure 1-decene as raw material with embodiment 5.The poly decene performance is summarised in the table 1.

Embodiment 1-5 confirms can be by from C ₈-C ₁₂To C ₆-C ₁₈Wide region blend alpha-olefin production have wide range of viscosities and excellent viscosity index (" VI ", ASTM-D2270) and the lubricant base of pour point.Lubricant properties is similar to those that made by pure 1-decene.

Embodiment 7. uses and contains the alkene mixture of 7.1%1-hexene, 9.5%1-octene, 11.9%1-decene, 14.3%1-dodecylene, 16.7%1-tetradecene, 19.1%1-cetene and 21.4%1-vaccenic acid as raw material.Under 31 ℃, this raw material of 30 (30) grams is added reactor.The catalyst solution that contains 10 weight %MAOs, 9.7 gram toluene and the 0.308mg catalyst A of 0.195 gram in toluene is added in the described reactor.After 3 days, with the described reaction of the similar mode aftertreatment of embodiment before.The performance of poly-alpha-olefin is listed in the table 1.

Embodiment 8. is similar to embodiment 1, and difference is that the raw material composition is described among the embodiment 7.

Embodiment 9. is similar to embodiment 7, and difference is to use catalyzer C.

Embodiment 10. is similar to embodiment 1, difference be raw material form as described in the embodiment 7 and catalyst composition be catalyzer C.

Embodiment 11. is similar to embodiment 7, and difference is that temperature of reaction is 60 ℃.

Embodiment 12. is similar to embodiment 7, and difference is that employed metallocenes is that racemize-dichloro ethylenebis (1-indenyl) is closed zirconium (catalyzer D).

Poly-alpha-olefin and the experiment of base-material blend

Embodiment 13. is according to US 6,420,618 or the WO2004/033595 preparation have the lubricant base A of the hydrotreatment that is summarised in the performance in the table 2.

Blend 14. is when with embodiment 1 poly-alpha-olefin of 1 weight % and base material A blend, and described blend has 100 ℃ of viscosity that improve a little.Yet pour point is reduced to-18 ℃ from-15 ℃.

Blend 15. is when with the embodiment 1 of 20 weight % during with the base material A blend, and described blend has 100 ℃ of viscosity of 27.92cSt.Yet depression of pour point is to-30 ℃.

Blend 16. is when with the embodiment 7 of 0.1 weight % during with the base material A blend, and described blend has the Kv of 6.14cSt ¹⁰⁰, this only is higher than initial base material A a little.Yet pour point is reduced to-45 ℃ from-15 ℃.

Blend 17,18,19,20 further confirms when the identical pour point decline effect during with the base material A blend with the embodiment 7 of 0.5,1.0,5.0 or 20 weight %.

Blend 21. is when with the embodiment 10 of 0.05 weight % during with the base material A blend, and described blend has the Kv of 6.12cSt ¹⁰⁰, this only is higher than initial base material A a little.Yet pour point is reduced to-39 ℃ from-15 ℃.

Blend 22,23,24 further confirms identical pour point decline effect.

Blend 25. is when with the embodiment 12 of 0.1 weight % during with the base material A blend, and described blend has the Kv of 6.12cSt ¹⁰⁰, this only is higher than initial base material A a little.Yet pour point is reduced to-45 ℃ from-15 ℃.

The experiment of linear alpha-olefin raw material

Raw material is formed: preparation has six kinds of linear alpha-alkenes (linear alpha-alkene) mixture of from 13.24 to 9.27 different number average carbon numbers according to the weight in the table 3.Be labeled as " raw material-1 " extremely these raw materials of " raw material-6 " be used for using subsequently the polymkeric substance of metallocene catalyst system synthetic.

Poly-alpha-olefin synthetic general procedure: all operations that embodiment 26-31. relates to metallocene catalyst system carry out under nitrogen atmosphere with excluding air and moisture or any other catalyzer poison.In the 200ml reaction vessel, add 40 gram mixed olefin feedstocks, then add triisobutyl aluminium (" TIBA ") stock solution, the 0.456mg catalyzer racemize-dichloro-dimethyl silyl two (tetrahydro indenyl) that 20 gram toluene, 3.232 grams contain 20mg/ gram stock solution and close zirconium (catalyst A) and 0.8012mg four (pentafluorophenyl group) boric acid N, N-dimethyl puratized agricultural spray (activator B).With mixture heating up to 70 ℃ temperature of reaction.After reaction in 15 hours, 5 gram activated alumina are added in the described reaction mixture and stirred about half an hour.Filter described product then to remove solid.Under 100 ℃ at about 20mm H ₂The organic filtrate of distillation under indoor (house) vacuum of O.Greater than 1 millitorr and 160 ℃ further distillation leftover two hours down.Collect residual tack liquid then, and make viscosity performance KV ⁴⁰, Kv ¹⁰⁰Measure (Kv with pour point ⁴⁰Be 40 ℃ of kinematic viscosity, according to ASTM D445, Kv ¹⁰⁰Be 100 ℃ of kinematic viscosity).The result is summarised in the table 4.

Prepare embodiment 32-37 as among the embodiment 26-31, difference is that raw material-1 to the temperature of reaction of raw material-6 maintains 35 ℃.Product property is summarised in the table 5.Generally speaking, the poly-alpha-olefin in the table 5 has the viscosity higher than the poly-alpha-olefin in the table 4.

By preparing sample in the table 6 with the similar mode of embodiment 32-37, difference is to use different catalyzer and temperature of reaction to prepare the poly-alpha-olefin with different tacticities and viscosity.Embodiment 38 and 40 has low any taxis degree, and is nonstereospecific polymer mostly.Embodiment 39 has high syndyotactic taxis degree.Their performance is summarised in the table 6.Catalyzer D is that dichloro phenylbenzene methene base (cyclopentadienyl-9-fluorenyl) closes zirconium, and carries out polymerization by catalyzer D and activator B are combined to form catalyst composition.

The product embodiment 26-40 and 6cSt GTL base-material (" the GTL6 ") blend of difference amount that then will be from 0.01 weight % to 10 weight %.Initial GTL6 has-21 ℃ pour point.Blend pour point performance is summarised in the table 7.In this table, be the pour point of the blend of embodiment 26-40 sample in GTL6 of different amounts with pour point numbering in the matrix that hurdle A to H interrelates.For example, blend A-26 (being contained in 0.025 weight % embodiment, 26 poly-alpha-olefins among the GTL6) has-39 ℃ pour point.The blend E-26 that is contained in 0.5 weight % embodiment, 26 poly-alpha-olefins among the GTL6 has-51 ℃ pour point.The blend C-33 that is contained in 0.1 weight % embodiment, 33 poly-alpha-olefins among the GTL has-51 ℃ pour point.The blend C-36 that is contained in 0.1 weight % embodiment, 36 poly-alpha-olefins among the GTL6 has-21 ℃ pour point.

Data acknowledgement in the table 7 several aspects of the present invention: raw material number average carbon number is the factor whether the decision product has or do not have pour point (" PP ") decline effect.

Has excellent PPD effect (embodiment 26-29,32-35 and 38-40) with having the poly-alpha-olefin of making greater than the raw material of 10.0 number average carbon number.

Almost there is not PPD effect (embodiment 30,31,36 and 37) with having the poly-alpha-olefin of making less than the raw material of 10 average carbon number.These poly-alpha-olefins show more as base-material.They have excellent base-material performance, comprise VI and low-down pour point.When press additive capacity (0.025 weight %-1 weight %) blend they the time, they show the PPD effect hardly.When using with other base-material blend by a large amount of (usually greater than 5 weight %), they are suitable as the blend raw material most.When using with a large amount (5% or higher), they improve blend viscosity significantly, improve VI and reduce pour point.These fluids are discussed in WO 2007/146081, WO2007/145924 and WO 2007/070691.

The poly-alpha-olefin of wide range of viscosities (or molecular size) is highly effective PPD, as long as they are made greater than 10 raw material by the number average carbon number.Embodiment 26-29 poly-alpha-olefin has the Kv of 70-90cSt ¹⁰⁰, or embodiment 40 is 19.5cSt.They are highly effective as PPD.Embodiment 32-36 and 39 has high viscosity, greater than 200cSt.They are equally highly effectively as PPD.Is very desirable as the viscosity of the obtainable this wide region of PPD providing aspect the formulation flexibility.For example, the desirable sometimes PPD of being to use improves pour point and does not improve blend viscosity.In this case, do not improve that the low viscosity PPD of blend viscosity is best suited for.Sometimes, improving blend viscosity, to reduce pour point significantly simultaneously be desirable.In this case, high viscosity poly-alpha-olefin PPD will be best suited for.

When they were made greater than 10 raw material by average carbon number, the poly-alpha-olefin with atactic, isotaxy or syndyotactic three-dimensional sequences (stereo-sequence) was all effectively as PPD.Embodiment 38 and 40 is rich in atactic three-dimensional sequences.Embodiment 39 is rich in syndiotactic sequence.Embodiment 26-29 and 32-35 are rich in the isotaxy three-dimensional sequences.They are all effectively as PPD.

Embodiment 41-44. embodiment 41 and 42 be GTL6 respectively with the blend of poly-alpha-olefin embodiment 33 and embodiment 34.Blend performance (comprising high temperature viscous and low temperature viscous pour point ,-30 ℃ and-40 ℃ of brookfield viscosity) is summarised in the table 8.Table 8 also comprises performance and GTL6 and the commercial pour point reducer Acryloid commonly used of pure GTL6 (embodiment 42) ^TM156 (methylmethacrylate copolymer, Rohm﹠amp; Haas) the blend performance of (embodiment 43).As these data presentation, the blend that contains additive capacity (0.1-1 weight %) in GTL6 has and the similar viscosity of pure GTL6 base-material.Yet their pour point is reduced to-39 ℃ to-45 ℃ (embodiment 41 and 42) from-21 ℃ (embodiment 43).Compare with initial GTL6 base-material, low temperature brookfield viscosity (measuring by ASTM D2983) further reduces, although all fluids have similar Kv ¹⁰⁰, Kv ⁴⁰And VI.In addition, embodiment 41 and 42 low temperature brookfield viscosity are better than the most frequently used PPD (embodiment 43), do not change Kv equally significantly ¹⁰⁰And Kv ⁴⁰

Table 9 has been summarized the beneficial effect of a small amount of poly-alpha-olefin that derives from embodiment 26-37 aspect the turbidity that reduces the GTL base-material in high viscosity GTL base-material.By US 7,241,375 and US 7,132, preparation of method described in 042 and the high viscosity GTL base-material with wherein said composition have muddy outward appearance usually, this by 1.99 high turbidity value indication of 0 ℃, described turbidity value is measured by turbidometer (VWR model 800 turbidometers that can obtain from VWR International).When adding to very small amount of poly-alpha-olefin embodiment 27-37 in the described GTL sample, turbidity is reduced to less than 1.0, shown in the blend in the table 9.The poly-alpha-olefin that these data acknowledgements are made greater than 10 carbon by the number average carbon number can be used for reducing the turbidity of high viscosity GTL base-material.

Therefore, in certain embodiments, the turbidity of hydrocarbon blends, in a specific embodiment, the turbidity of lubricant or fuel is less than 0.90 or 0.95 or 1.00, in other embodiments in 0.50 or 0.60 to 0.90 or 1.00 scope.

Table 3. raw material-1 is to the preparation of raw material-6 and the effect that raw material is formed

Raw material	1	2	3	4	5	6
							Linear alpha-alkene	wt％	wt％	wt％	wt％	wt％	wt％
C6	2.32	7.12	10.89	13.92	15.60	18.41
							C8	6.31	9.52	13.77	17.20	19.12	22.34

C10	10.31	11.92	15.13	17.76	19.20	21.62
							C12	14.31	14.32	15.13	15.84	16.16	16.81
C14	18.23	16.64	14.57	12.88	12.00	10.41
							C16	22.30	19.04	14.89	11.44	9.60	6.41
C18	26.22	21.44	15.61	10.96	8.32	4.00
							Amount to	100.00	100.00	100.00	100.00	100.00	100.00
Average carbon number	13.24	12.00	10.93	10.19	9.83	9.27

Table 4. is in the performance of the poly-alpha-olefin of 70 ℃ of preparations

Table 5. is in the performance of the poly-alpha-olefin of 30 ℃ of preparations

Table 6. catalyst type and temperature of reaction are to the influence of poly-alpha-olefin viscosity

The blend of table 8.GTL and poly-alpha-olefin or conventional PPD

The turbidity of table 9. poly-alpha-olefin/GTL blend

Though described the each side of hydrocarbon blends, its various features and component wherein, can further describe described hydrocarbon blends by following exemplary numbering embodiment:

1. hydrocarbon blends, it comprises: by the weight of described hydrocarbon blends, at least a poly-alpha-olefin of 0.001-10 weight %, described at least a poly-alpha-olefin has the Kv of 10-3000cSt ¹⁰⁰Molecular weight distribution with 1.0-4.5; With the Kv that has less than 20.0cSt ¹⁰⁰Base-material; There is the pour point of the described hydrocarbon blends amount with respect to 5 ℃ of the depressions of pour point of described base-material in wherein said at least a poly-alpha-olefin by being enough at least.

2. number the hydrocarbon blends of embodiment 1, wherein said at least a poly-alpha-olefin is to contain the alpha-olefin derived unitary multipolymer of at least two groups during polymkeric substance is formed, and wherein said first group is selected from C ₄Or C ₆To C ₁₀Or C ₁₂Or C ₁₃Alpha-olefin and second group are selected from C ₁₄Or bigger alpha-olefin.

3. number the hydrocarbon blends of embodiment 1 and 2, wherein said second group of alpha-olefin derived unit accounts at least 20 weight % of described at least a poly-alpha-olefin.

4. each hydrocarbon blends in the aforementioned numbering embodiment, wherein said second group of alpha-olefin derived unit accounts at least 30 weight % of described at least a poly-alpha-olefin.

5. each hydrocarbon blends in the aforementioned numbering embodiment, wherein said second group of alpha-olefin derived unit accounts at least 40 weight % of described at least a poly-alpha-olefin.

6. each hydrocarbon blends in the aforementioned numbering embodiment, wherein said at least a poly-alpha-olefin is by the alpha-olefin feedstock production of the average carbon number with at least 8 or 9 or 10 or 10.5 or 11 carbon atoms.

7. each hydrocarbon blends in the aforementioned numbering embodiment, wherein said at least a poly-alpha-olefin is basically by two or more C ₄Or C ₆To C ₂₄Alpha-olefin derived unit is formed.

8. there are the pour point of the described hydrocarbon blends amount with respect to 5 ℃ of the depressions of pour point of described base-material or 10 ℃ or 15 ℃ in each hydrocarbon blends in the aforementioned numbering embodiment, wherein said at least a poly-alpha-olefin by being enough at least.

9. each hydrocarbon blends in the aforementioned numbering embodiment, wherein said base-material has 10 ℃ or higher pour point.

10. each hydrocarbon blends in the aforementioned numbering embodiment, wherein said base-material are the Kv less than 20.0cSt of having that is selected from GTL base-material, Gr.I, Gr.II, Gr.III, Gr.IV, Gr.V base-material and their mixture ¹⁰⁰Mixture.

11. each hydrocarbon blends in the aforementioned numbering embodiment, wherein said base-material has at least 100 VI.

12. each hydrocarbon blends in the aforementioned numbering embodiment, therein ethylene deutero-unit is not present in the described at least a poly-alpha-olefin basically.

13. each hydrocarbon blends in the aforementioned numbering embodiment, wherein said at least a poly-alpha-olefin has the VI of 100-300.

14. each hydrocarbon blends in the aforementioned numbering embodiment, wherein said hydrocarbon blends comprises the described base-material of 99.999 weight % to 30 or 40 or 50 weight %.

15. each hydrocarbon blends in the aforementioned numbering embodiment, also comprise one or more additives, wherein said additive is selected from oxidation retarder, antioxidant, dispersion agent, purification agent, corrosion inhibitor, rust-preventive agent, metal passivator, anti-wear agent, extreme-pressure additive, the seizure-resistant agent, pour point reducer based on non-olefinic, wax modifiers, viscosity index improver, viscosity modifier, fluid loss additive, the sealing expanding material, friction improver, lubricant, anti-staining agent, chromogenic agent, defoamer, emulsion splitter, emulsifying agent, thickening material, wetting agent, jelling agent, tackiness agent, tinting material and their blend.

16. lubricant or the fuel made by each hydrocarbon blends in the aforementioned numbering embodiment.

17. the formation method of each hydrocarbon blends in the aforementioned numbering embodiment comprises that (a) makes catalyst composition and the raw material reaction that contains at least two group alpha-olefins, wherein said first group of alpha-olefin is selected from C ₄-C ₁₃Alpha-olefin and described second group of alpha-olefin are selected from C ₁₄Or bigger alpha-olefin, thereby form at least a Kv of 10.0cSt at least that has ¹⁰⁰Poly-alpha-olefin; (b) with described at least a poly-alpha-olefin and the Kv that has less than 20.0cSt ¹⁰⁰Base-material in conjunction with and form hydrocarbon blends.

18. the formation method of each hydrocarbon blends in the aforementioned numbering embodiment, comprise that (a) makes catalyst composition and have the alpha-olefin raw material reaction of the number average carbon number of at least 8 or 9 or 10 or 10.5 or 11 carbon atoms, thereby form at least a Kv of 10.0cSt at least that has ¹⁰⁰Poly-alpha-olefin; (b) with described at least a poly-alpha-olefin and the Kv that has less than 20.0cSt ¹⁰⁰Base-material in conjunction with and form hydrocarbon blends.

19. the method for numbering embodiment 17 and 18, therein ethylene is not present in the described alpha-olefin raw material basically.

20. the method for numbering embodiment 17-19, wherein said alpha-olefin raw material has the average carbon number of 8-15 carbon atom.

21. the method for numbering embodiment 18, wherein said alpha-olefin raw material comprises at least two kinds and is selected from C ₆-C ₂₄The alpha-olefin of alpha-olefin and its mixture.

22. the method for numbering embodiment 18, wherein said raw material comprises the C of 0.1-15 weight % ₆The C of alpha-olefin and at least 8 weight % ₁₈Alpha-olefin is based on the weight of described raw material.

23. the method for numbering embodiment 17, wherein said raw material comprises the C that has of at least 20 weight % ₁₄Or the alpha-olefin of higher carbon number.

24. the method for numbering embodiment 17, wherein said raw material comprises the C that has of at least 30 weight % ₁₄Or the alpha-olefin of higher carbon number.

25. the method for numbering embodiment 17, wherein said raw material comprises the C that has of at least 40 weight % ₁₄Or the alpha-olefin of higher carbon number.

26. the method for numbering embodiment 17-25, wherein said catalyst composition comprises metallocenes and activator.

27. the method for numbering embodiment 26, wherein said metallocenes are the 4th family's bridging or two-Cp compound of bridging not.When bridging not, described metallocenes can be described with respect to top formula (1).When bridging, the metallocenes that comprises bridge linkage group " A " is toply to describe with respect to formula (2).In certain embodiments, described metallocenes is hafnocene or the zirconocene that has with respect to the feature of formula (1) and (2) description.

28. the method for numbering embodiment 17 and 18 is carried out under the wherein said 10-200 of being reflected at ℃ the temperature.

29. the method for numbering embodiment 17 and 18, wherein said being reflected at greater than carrying out under the pressure of 1.0MPa.

30. the method for numbering embodiment 17 and 18, the hydrogen partial pressure of the wherein said 1psi-300psi of being reflected at carries out under existing.

31. numbering embodiment 17 and 18 method, wherein said being reflected under the continuous hydrogen feed carried out, and the hydrogen content in the reactor assembly is less than 1000 or 2000 or 3000ppm.

32. numbering embodiment 17 and 18 method are wherein by being enough to the pour point of described hydrocarbon blends with respect to the amount of at least 5 ℃ of the depressions of pour point of described base-material or 10 ℃ or 15 ℃ in conjunction with described at least a poly-alpha-olefin.

33. the method for numbering embodiment 17 and 18, wherein said base-material has the pour point less than 10 ℃.

34. lubricant or fuel by each method preparation among the aforementioned numbering embodiment 17-33.

Be the application of poly-alpha-olefin in another embodiment, it comprises: by the weight of described hydrocarbon blends, and at least a poly-alpha-olefin of 0.001-10 weight %, described at least a poly-alpha-olefin has the Kv of 10-3000cSt ¹⁰⁰Molecular weight distribution with 1.0-4.5; With the Kv that has less than 20.0cSt ¹⁰⁰Base-material; There is the pour point of the described hydrocarbon blends amount with respect to 5 ℃ of the depressions of pour point of described base-material in wherein said at least a poly-alpha-olefin by being enough at least.

Be the application of poly-alpha-olefin in fuel or lubricant in another embodiment, it comprises: by the weight of described hydrocarbon blends, and at least a poly-alpha-olefin of 0.001-10 weight %, described at least a poly-alpha-olefin has the Kv of 10-3000cSt ¹⁰⁰Molecular weight distribution with 1.0-4.5; With the Kv that has less than 20.0cSt ¹⁰⁰Base-material; There is the pour point of the described hydrocarbon blends amount with respect to 5 ℃ of the depressions of pour point of described base-material in wherein said at least a poly-alpha-olefin by being enough at least.

Be to comprise the hydrocarbon blends of at least a poly-alpha-olefin described herein in another embodiment as comprising the fuel of 0.001-10 weight % poly-alpha-olefin or the application of lubricant.

Claims

1. hydrocarbon blends, it comprises: by the weight of described hydrocarbon blends, at least a poly-alpha-olefin of 0.001-10 weight % and have Kv less than 20.0cSt ¹⁰⁰Base-material; Described blend is characterised in that described at least a poly-alpha-olefin has the Kv of 10-3000cSt ¹⁰⁰Molecular weight distribution with 1.0-4.5; There is the pour point of the described hydrocarbon blends amount with respect to 5 ℃ of the depressions of pour point of described base-material in described at least a poly-alpha-olefin by being enough at least.

2. the hydrocarbon blends of claim 1, wherein said at least a poly-alpha-olefin are to contain the alpha-olefin derived unitary multipolymer of at least two groups during polymkeric substance is formed, and wherein said first group is selected from C ₄Or C ₆To C ₁₀Or C ₁₂Or C ₁₃Alpha-olefin and described second group are selected from C ₁₄Or bigger alpha-olefin.

3. the hydrocarbon blends of claim 2, wherein said second group of alpha-olefin derived unit accounts at least 20 weight % of described at least a poly-alpha-olefin.

4. each hydrocarbon blends in the claim 2 or 3, wherein said second group of alpha-olefin derived unit accounts at least 30 weight % of described at least a poly-alpha-olefin.

5. each hydrocarbon blends in the aforementioned claim, wherein said at least a poly-alpha-olefin is by the alpha-olefin feedstock production of the average carbon number with at least 8 or 9 or 10 or 10.5 or 11 carbon atoms.

6. each hydrocarbon blends in the aforementioned claim, wherein said at least a poly-alpha-olefin is by the pour point of the described hydrocarbon blends amount with respect at least 5 ℃ of the depressions of pour point of described base-material or 10 ℃ or 15 ℃ is existed.

7. each hydrocarbon blends in the aforementioned claim, wherein said base-material has 10 ℃ or higher pour point.

8. each hydrocarbon blends in the aforementioned claim, wherein said base-material are the Kv less than 20.0cSt of having that is selected from GTL base-material, Gr.I, Gr.II, Gr.III, Gr.IV, Gr.V base-material and their mixture ¹⁰⁰Mixture.

9. each hydrocarbon blends in the aforementioned claim, wherein said base-material has at least 100 VI.

10. each hydrocarbon blends in the aforementioned claim, therein ethylene deutero-unit is not present in the described at least a poly-alpha-olefin basically.

11. each hydrocarbon blends in the aforementioned claim, wherein said at least a poly-alpha-olefin has the VI of 100-300.

12. each hydrocarbon blends in the aforementioned claim, also comprise one or more additives, wherein said additive is selected from oxidation retarder, antioxidant, dispersion agent, purification agent, corrosion inhibitor, rust-preventive agent, metal passivator, anti-wear agent, extreme-pressure additive, the seizure-resistant agent, pour point reducer based on non-olefinic, wax modifiers, viscosity index improver, viscosity modifier, fluid loss additive, the sealing expanding material, friction improver, lubricant, anti-staining agent, chromogenic agent, defoamer, emulsion splitter, emulsifying agent, thickening material, wetting agent, jelling agent, tackiness agent, tinting material and their blend.

13. lubricant or the fuel made by each hydrocarbon blends in the aforementioned claim.

14. the formation method of hydrocarbon blends comprises that (a) makes catalyst composition and the raw material reaction that contains at least two group alpha-olefins, wherein said first group of alpha-olefin is selected from C ₄-C ₁₃Alpha-olefin and described second group of alpha-olefin are selected from C ₁₄Or bigger alpha-olefin, thereby form at least a Kv of 10.0cSt at least that has ¹⁰⁰Poly-alpha-olefin; (b) with described at least a poly-alpha-olefin and the Kv that has less than 20.0cSt ¹⁰⁰Base-material in conjunction with and form hydrocarbon blends.

15. the formation method of hydrocarbon blends comprises that (a) makes catalyst composition and have the alpha-olefin raw material reaction of the number average carbon number of at least 8 or 9 or 10 or 10.5 or 11 carbon atoms, thereby forms at least a Kv of 10.0cSt at least that has ¹⁰⁰Poly-alpha-olefin; (b) with described at least a poly-alpha-olefin and the Kv that has less than 20.0cSt ¹⁰⁰Base-material in conjunction with and form hydrocarbon blends.

16. the method for claim 14 or 15, therein ethylene are not present in the described alpha-olefin raw material basically.

17. each method among the claim 14-16, wherein said alpha-olefin raw material has the average carbon number of 8-15 carbon atom.

18. the method for claim 14, wherein said alpha-olefin raw material comprises at least two kinds and is selected from C ₆-C ₂₄The alpha-olefin of alpha-olefin and its mixture.

19. the method for claim 14, wherein said raw material comprises the C of 0.1-15 weight % ₆The C of alpha-olefin and at least 8 weight % ₁₈Alpha-olefin is based on the weight of described raw material.

20. each method among the claim 14-19, wherein said raw material comprise the C that has of at least 20 weight % ₁₄Or the alpha-olefin of higher carbon number.

21. each method among the claim 14-20, wherein said raw material comprise the C that has of at least 30 weight % ₁₄Or the alpha-olefin of higher carbon number.

22. the method for claim 14-21, wherein said catalyst composition comprises metallocenes and activator.

23. the method for claim 22, wherein said metallocenes are the 4th family's bridging or two-Cp compound of bridging not.

24. the method for claim 17 and 18 is wherein by being enough to the pour point of described hydrocarbon blends with respect to the amount of at least 5 ℃ of the depressions of pour point of described base-material or 10 ℃ or 15 ℃ in conjunction with described at least a poly-alpha-olefin.

25. lubricant or fuel by each method preparation among the aforementioned claim 14-24.