CN101501083B

CN101501083B - Process to produce high viscosity fluids

Info

Publication number: CN101501083B
Application number: CN200780029723.2A
Authority: CN
Inventors: M·M-S·吴; C·L·科克尔; 小约翰·F·沃尔泽; 江培军; S·P·拉克
Original assignee: Exxon Chemical Patents Inc
Current assignee: ExxonMobil Chemical Patents Inc
Priority date: 2006-07-19
Filing date: 2007-05-08
Publication date: 2012-12-05
Anticipated expiration: 2027-05-08
Also published as: JP5613416B2; CN101501083A; JP2009543928A

Abstract

This invention relates to processes to produce liquid poly-alpha-olefins (PAOs) having a kinematic viscosity at 100 DEG C of more than 20 cSt in the presence of a metallocene catalyst with a non-coordinating anion activator and hydrogen.

Description

The method for preparing high viscosity fluid

Technical field

The present invention relates in the presence of metalloscene catalyst and non-coordination anion acvator and hydrogen, prepare the method for poly-alpha olefins (PAO).

Background technology

Synthetic improvement through the oligopolymer hydrocarbon fluid has been that research and development theme important in the petroleum industry reaches at least five ten years based on the effort of the performance of the lubricant of crude mineral oils.These effort have caused the nearer market of many synthetic lubricants to be introduced.Aspect the lubricant properties improvement; The viscosity that the industrial research that relates to synthetic lubricant makes great efforts to push in wide TR, to show usefulness is the fluid of improved viscosity index (VI), also shows oilness, thermostability, oxidative stability and the pour point that equals or exceeds MO simultaneously.

When selecting lubricant for certain applications, oil body-temperature relation is one of main standard of being considered.The MO of the base-material of work list commonly used and multistage lubricant shows that with the change of temperature bigger viscosity changes.Show that with temperature the fluid that the big viscosity of this kind changes it is said to have low-viscosity index (VI).VI is an empirical value, and it is illustrated in oil viscosity velocity of variation in the given TR.For example, high VI oil will thinning more lentamente with low VI oil phase than at elevated temperatures.Usually, high VI oil is more desirable, because it has higher viscosity under higher temperature, this is converted into the better lubricated and better protection of contact mechanical organ, and is preferred at high temperature and/or under the temperature of wide region.VI calculates according to ASTM method D 2270.

If lubricant is expected under the low temperature environment and provides lubricated, the good low-temperature performance no less important of lubricant then.These low-temperature performancies can be through according to the pure fluidic pour point of ASTM D 97, through according to the pure fluid of ASTM D 2983 or blend fluidic low temperature brookfield viscosity or other suitable method cold starting simulation meter viscosity (CCS) isometry for example.The good shear stability of lubricant also becomes more and more important, because more turning round under the mal-condition usually than novel appts or mover.Can measure the shear stability of pure fluid or lubricant blend through many methods, for example according to the sound wave shearing test of ASTM D 2603 methods or according to taper roller bearing (TRB) shearing test of CECL-45-T/A-D method etc.

PAO comprises one type of hydrocarbon of making through the monomeric catalytic oligomerization of linear alpha-alkene (LAO) (aggregating into low molecular weight product).They usually at the 1-octene to the scope of 1-dodecylene; Wherein 1-decene is a preferable material; But also can use the for example oligomeric copolymer of ethene and propylene of even lower level alkene, comprise the ethene and the multipolymer of higher alkene more, like USP 4; 956,122 and the patent that wherein relates to said.The PAO product becomes important in lubricating oil market.Usually, have two types of synthetic hydrocarbon fluids (SHF) by the linear alpha-alkene preparation, these two types of SHF are expressed as PAO and HVI-PAO (High Viscosity Index PAO).Usually use promoted BF ₃Or AlCl ₃The PAO of Preparation of Catalyst different viscosity grade.

Specifically, can be at catalyzer AlCl for example ₃, BF ₃Or promoted AlCl ₃, BF ₃Polymerization through olefin feedstock under existing prepares PAO.The preparation method of PAO for example discloses in following patent: USP 3,149,178; 3,382,291; 3,742,082; 3,769,363; 3,780,128; 4,172,855 and 4,956,122, they fully introduce for reference.PAO is also at Will, J.G.Lubrication Fundamentals, and Marcel Dekker:NewYork discusses in 1980.After polymerization, usually with the product hydrogenation of this PAO lubricant scope to reduce residual unsaturated part, generally be hydrogenated to greater than 90% hydrogenant level.HV PAO can be aptly through for example in the presence of the friedel-crafts catalysts preparing alpha-olefine polymerizing at polymerizing catalyst.They for example comprise, boron trifluoride, aluminum chloride or following boron trifluoride: water, with alcohol for example ethanol, propyl alcohol or butanols; Use carboxylic acid, or with ester for example ETHYLE ACETATE or ethyl propionate or ether for example diethyl ether, DIPE etc. promote (referring to for example, USP 4; 149; 178 or 3,382,291 disclosed methods).Other describes the PAO synthetic referring to following USP: 3,742,082 (Brennan); 3,769,363 (Br ennan); 3,876,720 (Heilman); 4,239,930 (Allphin); 4,367,352 (Watts); 4,413,156 (Watts); 4,434,408 (Larkin); 4,910,355 (Shubkin); 4,956,122 (Watts) and 5,068,487 (Theriot).

Another kind of HVI-PAO can prepare with 'alpha '-olefin monomers under the effect of loading type reductive chrome catalysts.This type of PAO is at USP 4,827,073 (Wu); 4,827,064 (Wu); 4,967,032 (Ho etc.); Be described among 4,926,004 (Pelrine etc.) and 4,914,254 (Pelrine).Commercially available PAO comprises SpectraSyn ^TM2,4,5,6,8,10,40,100 and SpectraSyn Ultra ^TM150, SpectraSynUltra ^TM300, SpectraSynUltra ^TM1000 etc. (ExxonMobil Chemical Company, Houston, Texas).

Synthetic PAO is because they obtain extensively approval and business success in field of lubricant to the meliority based on the lubricant of MO.Aspect the lubricant properties improvement; The industrial research of synthetic lubricant is made great efforts to have obtained in wide TR, to show the viscosity of usefulness; Be the PAO fluid of improved viscosity index, also show oilness, thermostability, oxidative stability and the pour point that is parity with or superiority over MO simultaneously.These newer synthetic lubricants reduce mechanical friction, thereby in whole mechanical load scopes, improve mechanical efficiency and like this in the operational condition scope wideer than mineral oil lubricant.

It is more and more stricter that the performance requriements of lubricant becomes.In order to satisfy the new capability requirement of lubricant; Need have improved performance, for example the new PAO of the range of viscosities of thermostability, oxidative stability and/or the broad of the volatility of high viscosity index (HVI) (VI), low pour point, reduction, high shear stability, improved polishing machine, raising.Also need provide this kind to have the novel method of the new PAO that improves performance.

Made great efforts to use metallocene catalyst system to prepare various PAO.Instance comprises US6,706,828 (being equivalent to US 2004/0147693), wherein PAO be some metalloscene catalyst by meso-form under high hydrogen pressure with MAO as the acvator preparation.Yet US 6,706, and 828 comparative example D use is closed zirconium with MAO (MAO) bonded dichloro rac-dimetylsilyl two (2-methyl-indenyl) and in the presence of hydrogen, prepared poly decene under 100 ℃.Likewise; WO 02/14384 especially discloses dichloro rac-ethyl two (indenyls) and has closed zirconium or dichloro rac-dimetylsilyl two (2-methyl-indenyl) and close zirconium and MAO and be combined in 40 ℃ (under 200psi hydrogen or 1 mol of hydrogen) and prepare respectively and it is reported the Tg with-73.8 ℃, the KV of 702cSt in embodiment J and K ₁₀₀Isotaxy poly decene with 296 VI; Or preparation it is reported the Tg with-66 ℃, 1624 KV ₁₀₀Poly decene with 341 VI.In addition, WO 99/67347 discloses use dichloro ethidine two (tetrahydro indenyls) and closes zirconium and MAO and be combined in 50 ℃ and prepare down and it is reported to have 11,400 the Mn and the poly decene of 94% vinylidene base double bond content in embodiment 1.

It is not usually knownly to be used to prepare polymkeric substance with any specific tacticity or the metalloscene catalyst of oligopolymer has prepared various PAO, for example poly decene that other people has used various.Instance comprises WO 96/23751, EP 0613873, US 5,688,887, US 6,043,401, WO 03/020856 (being equivalent to US 2003/0055184), US 5; 087,788, US6,414,090, US 6; 414,091, US 4,704, and 491, US 6; 133,209 and US6,713,438.

Yet up to now, the PAO that processes with metallocenes does not also have especially to obtain widespread use in the lubricant market in market, this method owing to poor efficiency, manufacturing processed, expensive and/or performance shortcoming.The present invention has solved these and other needs through the new PAO with excellent properties combination being provided and preparing improving one's methods of they.

US 6,548, and 724 (being equivalent to US 2001/0041817 and US 6,548,723) disclosed uses some metalloscene catalyst (combining with MAO usually) preparation oligomer oil.At US6; 548; 724 the 20th hurdle 40-44 is capable; On the cyclopentadienyl rings of embodiment 10-11 indication metallocenes two-, three-or four-replace to can be used for preparing and have the HV poly-alpha olefins (viscosity is in the scope at 20-5000cSt under 100 ℃) that improves productive rate, and five alkyl-substituted cyclopentadienyl rings is poor.Other embodiment 12 and 13 explanations are at the KV that does not have under the situation of hydrogen preparation have to it is reported 154 and 114.6 ₁₀₀Poly decene.In addition, embodiment 14 discloses and has used Cp ₂ZrMe ₂Or (iPr-Cp) ₂ZrCl ₂With four (phenyl) boric acid N, N-dimethyl-puratized agricultural spray has the decene polymerization under 100 ℃ or 110 ℃ and it is reported the KV of 5.3-11.4cSt with preparation ₁₀₀Poly decene.

The PCT/US06/21231 that submitted on June 2nd, 2006 (it requires the rights and interests of the USSN 60/700,600 of submission on July 19th, 2005) has described and has used racemic metallocene and non-coordination anion acvator to prepare liquid by the monomer that contains 5-24 carbon atom.

Valuable other reference comprises: EP0284708, US5846896, US5679812, EP0321852, US4962262, EP0513380, US2004/0230016 and US6642169.

Summary of the invention

The present invention relates to KV ₁₀₀For about 10 greater than 20cSt-, the preparation method of the poly-alpha olefins of 000cSt comprises:

One or more 'alpha '-olefin monomers that contain 3-24 carbon atom are contacted: substituted two (cyclopentadienyl moiety) transistion metal compounds of the not bridging of representing by following general formula with following component:

(Cp)(Cp*)MX ₁X ₂

Wherein:

M is a metal center, and is group-4 metal;

Cp and Cp* be separately with the identical or different cyclopentadienyl rings of M keyed jointing; With 1) Cp and Cp* be substituted with at least one non-hydrogen substituent R base or 2) Cp is substituted with two to five substituent R bases; Each substituent R is the group for alkyl, substituted alkyl, halo carbon back, substituted halo carbon back, silyl carbon back or germyl carbon back independently; Or Cp and Cp* be identical or different cyclopentadienyl rings, wherein any two adjacent R bases randomly engage and form replace or unsubstituted, saturated, part is unsaturated or aromatics ring-type or polycyclic substituting group;

X ₁And X ₂Be hydrogen, halogen, hydride ion (hydride radical), alkyl, substituted alkyl, halo carbon back, substituted halo carbon back, silyl carbon back, substituted silyl carbon back, germyl carbon back or substituted germyl carbon back independently; Or two X engage and are bonded to atoms metal and form the metal that contains about 20 carbon atoms of about 3-and embed cyclisation misfit thing (metallacycle) ring; Or two X can be alkene, diolefine or aryne part together; With

Non-coordination anion acvator and randomly, alkyl-aluminum compound; Wherein the mol ratio of transistion metal compound and acvator is 10: 1-0.1: 1; And if have alkylaluminium cpd, and then the mol ratio of alkylaluminium cpd and transistion metal compound is 1: 4-4000: 1, wherein:

I) hydrogen exists with the dividing potential drop of 0.1-300psi, and based on the total pressure of reactor drum, or the concentration of hydrogen is 1-30 by weight, 000ppm or littler;

Ii) wherein these one or more contain 3-24 carbon atom 'alpha '-olefin monomers with 10wt% or higher the existence, based on the gross weight of the catalyzer/acvator/alkylaluminium cpd solution, monomer and any thinner or the solvent that exist in the reaction;

Iii) condition is that ethene does not exist to surpass the monomeric 40wt% that gets into reactor drum.

The accompanying drawing summary

Fig. 1 shows the MWD through the poly-alpha olefins (PAO) of the present invention's preparation, shows representative value and bound.Line 1 ● the PAO that representative makes through the non-metallocene catalyzer, y=0.2223+1.0232log (x) R=0.97035.Line 2 provides through the MWD upper limit of the present invention, y=0.8+0.3log (x).Line 3

provides the typical MWD through the poly-1-butylene of the inventive method preparation, y=0.71263+0.49387log (x) R=0.91343.Line 4 provides through MWD lower limit of the present invention, y=0.41667+0.725l og (x).■ represents the MWD of embodiment 1-9 (table 1), y=0.66017+0.44922log (x) R=0.99809.

Fig. 2 is that disclosed dimer optionally contrasts in dimer selectivity～U.S. Patent number 6,548,724 of the present invention.● dimer selectivity of the present invention, y=350.68 * x^ (1.5091) R=0.98993 (embodiment 1 to 9, table 1).The dimer selectivity of the method for ◇ U.S. Patent number 6,548,724, y=231.55 * x^ (0.90465) R=0.93734.

The fluidic VI that Fig. 3 representative makes through the present invention contrasts the VI of those disclosed in the U.S. Patent number 6,548,742.● represent the VI of experiment 1 to 9 in the table 1.represents U.S. Patent number 6,548, the VI of the material of preparation in 742.

Fig. 4 provides the pour point of the material of preparation in the PAO fluidic pour point contrast U.S. Patent number 6,548,742 that makes through the present invention.● represent the pour point of experiment 1 to 9 in the table 1.represents U.S. Patent number 6,548, the pour point of the material of preparation in 742.

Fig. 5 provides embodiment 10 to 21 (table 3) contrast comparative example's 14 to 17 (table 4) vinylidene base content.● represent the value of embodiment 10-21 in the table 3 (through poly-1-butylene) by NCA activatory catalyst A or B preparation.represents the comparative example 14-17 (through the poly-1-butylene by the preparation of MAO activatory catalyst B) in the table 4.

Fig. 6 provides embodiment 10 to 21 (table 3) contrast comparative example's 14 to 17 (table 4) branched chain methyl content.● represent the value of embodiment 10-21 in the table 3 (through poly-1-butylene) by NCA activatory catalyst A or B preparation.represents the comparative example 14-17 (through the poly-1-butylene by the preparation of MAO activatory catalyst B) in the table 4.This line is described as y=-3.4309Ln (x)+29.567, y=methyl branch/1000 C, and x=is at 100 ℃ Kv (cSt).

Detailed Description Of The Invention

The new numbering plan of the employed periodic table of elements of this paper is according to CHEMICAL ANDENGINEERING NEWS, 63 (5), 27 (1985) said uses.

Except as otherwise noted, all units are that the pressure of psi is psig.

Concerning the present invention and claim thereof, when polymkeric substance or oligopolymer are called as when comprising alkene, the alkene that is present in this polymkeric substance or the oligopolymer is respectively the polymerization or the oligomeric form of this alkene.Likewise, the use of term polymer is meant contains homopolymer and multipolymer, and wherein multipolymer comprises having two kinds or more kinds of chemically different monomeric any polymkeric substance.Likewise, the use of term oligomer is meant contains homopolymerization oligopolymer and copolymerized oligomer, and wherein copolymerized oligomer comprises having two kinds or more kinds of chemically different monomeric any oligopolymer.

Concerning the present invention and claim thereof, term " poly-alpha olefins (Polyalpha-olefin) ", " poly-alpha olefins (polyalphaolefin) " or " PAO " comprise C3 or the more monomeric homopolymerization oligopolymer of high alpha-olefin, copolymerized oligomer, homopolymer and multipolymer.

PAO of the present invention can comprise oligopolymer, polymkeric substance or both combinations.PAO compsn of the present invention (no matter it is oligopolymer, polymkeric substance or their combination) is liquid and has 200,000 or littler Mw.

Concerning the present invention and claim thereof, the active substance in the catalysis ring (catalytic cycle) can comprise the neutrality or the ionic species of this catalyzer.

Term " catalyst system " is defined and is meant that catalyst precursor/acvator is right, and for example metallocenes/acvator is right.During this kind pairing before " catalyst system " is used for being described in activation, it be meant non-activated catalyzer (pre-catalyst) together with acvator with, randomly, coactivator (for example trialkyl aluminium compound).During this kind pairing after it is used for being described in activation, it is meant activatory catalyzer and acvator or other charge balance structure part.In addition, catalyst system can randomly comprise coactivator and/or other charge balance structure part.

" catalyst precursor " also is commonly referred to pre-catalyst, catalyzer, catalyst compound, precursor, metallocenes, transistion metal compound, non-activated catalyzer or transition metal complex.These words use interchangeably.Acvator and promotor also use interchangeably.Scavenging agent is to be added usually to be used for promoting oligomeric or polymeric compounds through removal of contamination.Some scavenging agents also can serve as acvator and can be called coactivator.The coactivator that is not scavenging agent also can be used in combination with acvator to form active catalyst with transistion metal compound.In some embodiments, can be also referred to as alkylation catalyst compound or alkylation metallocenes with coactivator and transistion metal compound pre-mixing to form the alkylation transistion metal compound.

Concerning the present invention and claim thereof, non-coordination anion (NCA) limits and is meant the negatively charged ion that is not coordinated in the catalyst metal positively charged ion or only faintly is coordinated in said metallic cation.NCA is coordination of weak ground so that neutral lewis base enough, and for example olefinic or acetylene series unsaturated monomer can be replaced it from catalyst center.Can use or be included in this non-coordination anion with any metal or the metalloid that the catalyst metal positively charged ion forms compatible, weak coordinate complex compound.The metal that is fit to includes but not limited to aluminium, gold and platinum.The metalloid that is fit to includes but not limited to boron, aluminium, phosphorus and silicon.The subclass of non-coordination anion comprises stoichiometric acvator, and they can be neutrality or ionic.Term ionic acvator and stoichiometric ionic acvator can use interchangeably.Likewise, neutral stoichiometry acvator of term and lewis acid activation agent can be used interchangeably.

In addition, reactor drum is any container (one or more) that chemical reaction wherein takes place.

" iso-alkyl " is branched-chain alkyl, and it has at least one uncle or quaternary carbon atom and has at least one C along at least a portion of each chain ₁-C ₁₈Alkyl branches.

Poly-alpha olefins

In a preferred embodiment, the present invention relates to liquid poly-alpha olefins (PAO), they comprise 50 moles of one or more C3-C24 'alpha '-olefin monomers of % that surpass by carbon-13NMR measurement; Preferred 55 moles of % or more, preferred 60 moles of % or more, preferred 65 moles of % or more; Preferred 70 moles of % or more, preferred 75 moles of % or more, preferred 80 moles of % or more; Preferred 85 moles of % or more, preferred 90 moles of % or more, preferred 95 moles of % or more; Preferred 100 moles of % are based on the monomeric total mole that exists in this poly-alpha olefins.

Concerning the present invention and claim thereof, liquid is defined as at room temperature and flows, and has less than 25 ℃ pour point with at 100 ℃ and has 30, the material of 000cSt or littler kinematic viscosity.

In another embodiment; Any poly-alpha olefins described herein preferably have by ASTMD 5185 measure less than 300ppm group-4 metal (preferred Ti, Hf or Zr), preferably less than 200ppm, preferably less than 100ppm; Preferably less than 50ppm, preferably less than 10ppm or preferably less than 5ppm.

In another embodiment, any poly-alpha olefins described herein preferably have by ASTMD 5185 measure less than 300ppm Ti, preferably less than 200ppm, preferably less than 100ppm, preferably less than 50ppm, preferably less than 10ppm or preferably less than 5ppm.

In another embodiment, any poly-alpha olefins described herein preferably have by ASTMD 5185 measure less than 300ppm Hf, preferably less than 200ppm, preferably less than 100ppm, preferably less than 50ppm, preferably less than 10ppm or preferably less than 5ppm.

In another embodiment, any poly-alpha olefins described herein preferably have by ASTMD 5185 measure less than 300ppm Zr, preferably less than 200ppm, preferably less than 100ppm, preferably less than 50ppm, preferably less than 10ppm or preferably less than 5ppm.

In another embodiment, any poly-alpha olefins described herein preferably have by ASTMD 5185 measure less than 100ppm the 13rd family's metal (preferred B or Al), preferably less than 50ppm, preferably less than 10ppm, or preferably less than 5ppm.

In another embodiment, any poly-alpha olefins described herein preferably have by ASTMD 5185 measure less than 100ppm boron, preferably less than 50ppm, preferably less than 10ppm, or preferably less than 5ppm.

In another embodiment, any poly-alpha olefins described herein preferably have by ASTMD 5185 measure less than 600ppm aluminium, preferably less than 500ppm; Preferably less than 400ppm; Preferably less than 300ppm, preferably less than 200ppm, preferably less than 100ppm; Preferably less than 50ppm, preferably less than 10ppm or preferably less than 5ppm.

In another embodiment, any poly-alpha olefins described herein preferably has about 200,000; Preferably approximately 250-is about 200,000, and preferably approximately 280-about 100; 000, preferably approximately 336-about 150,000; Preferably approximately 336-is about 100, the Mw of 000g/mol (weight-average molecular weight).

In another embodiment, any poly-alpha olefins described herein preferably has less than 200,000, and preferred 250-is about 150,000, and preferably approximately 250-is about 125,000, preferred 280-100, the Mn of 000g/mol (number-average molecular weight).

In another embodiment, any poly-alpha olefins described herein preferably has greater than 1 and less than 5, preferably less than 4, preferably less than 3, preferably less than 2.5, preferably less than 2 Mw/Mn.Perhaps, any poly-alpha olefins described herein preferably has 1-3.5, or the Mw/Mn of 1-2.5.

Concerning the present invention and claim thereof, MWD equals Mw/Mn.

For wherein many application of preferred excellent shear stability, thermostability or heat/oxidative stability, the poly-alpha olefins that preferably makes has the narrowest as far as possible MWD.Have different viscosity, but the PAO fluid of being processed by same materials or catalyzer have different MWD usually.In other words, PAO fluidic MWD depends on fluid viscosity.Usually, more low viscous fluid has narrower MWD (less MWD value), and the fluid of viscosity higher has broad MWD (big MWD value).Have the fluid less than 100 ℃ of Kv of 1000cSt for great majority, MWD is usually less than 2.5, usually about 2.0+-0.5.For the fluid of 100 ℃ of viscosity greater than 1000cSt, they have wideer MWD usually, usually greater than 1.8.The typical range of MWD dependency～100 ℃ fluid viscosity can be referring to Fig. 1.

Usually, fluidic MWD is narrow more, and its shear stability is good more.The narrow MWD fluid of this kind will show less because heavily stressed or shear the viscosity loss that causes in TRB test; And will more have higher high temperature, high shear rate (HTHSR) viscosity under the mal-condition, better lubricated and abrasion protection be provided thereby thicker lubricant film is provided and follows.In some applications, when shear stability or HTHSR viscosity when not being so crucial, the fluid with broad MWD can provide better blended characteristic or other advantage.

Through size exclusion chromatography (SEC), also claim that gel permeation chromatography (GPC) method is used for measuring Mw, Mn and MWD with PS as calibration standard sample as solvent with THF to the post of low-molecular weight polymer.Except as otherwise noted, the Mn of this paper report and Mw value are the GPC values of measuring and are not to be calculated by the kinematic viscosity at 100 ℃.

In an embodiment preferred of the present invention, any PAO described herein can have less than 10 ℃ (measuring through ASTM D 97), preferably less than 0 ℃; Preferably less than-10 ℃, preferably less than-20 ℃, preferably less than-25 ℃; Preferably less than-30 ℃, preferably less than-35 ℃, preferably less than-40 ℃; Preferably less than-55 ℃, between preferred-10 and-80 ℃, the pour point between preferred-15 ℃ and-70 ℃.

In an embodiment preferred according to the present invention, any poly-alpha olefins described herein can have about 5000cSt greater than 20-, is preferably greater than the about 3000cSt of 20-, be preferably greater than the about 1500cSt of 20cSt-100 ℃ kinematic viscosity.In another embodiment of the invention, it is about 500 that any PAO described herein can have the about 50-that is measured by ASTM D 445,000cSt; Preferably approximately 75cSt-about 100; 000cSt, or approximately 100-is about 8,000cSt 40 ℃ kinematic viscosity.

In an embodiment preferred according to the present invention, poly-alpha olefins fluid described herein can have the viscosity index (VI) greater than 60.Measure VI according to ASTM method D 2270-93 [1998].Fluidic VI depends on viscosity and raw material composition usually.VI is high more, caters to the need more.The more full-bodied fluid that same materials is formed has higher VI usually.By C ₃Or C ₄Or C ₅The fluidic typical case VI scope that linear alpha-alkene (LAO) is processed is 65-250.By C ₆Or C ₇The fluidic typical case VI scope of processing is 100-300, depends on fluid viscosity equally.By C ₈-C ₁₄LAO, for example the fluidic typical case VI scope processed of 1-octene, 1-nonene, 1-decene or 1-undecylene or 1-dodecylene, tetradecene is 120 to＞450, this depends on viscosity.More particularly, being equal to fluidic VI scope that raw material processes by 1-decene or 1-decene is that about 100-is about 500, and preferably approximately 120-about 400.When using two or three or more kinds of terminal olefin during, for example C as raw material ₃+ C ₁₀, C ₃+ C ₁₄, C ₃+ C ₁₆, C ₃+ C ₁₈, C ₄+ C ₈, C ₄+ C ₁₂, C ₄+ C ₁₆, C ₃+ C ₄+ C ₈, C ₃+ C ₄+ C ₁₂, C ₄+ C ₁₀+ C ₁₂, C ₄+ C ₁₀+ C ₁₄, C ₆+ C ₁₂, C ₆+ C ₁₂+ C ₁₄, C ₄+ C ₆+ C ₁₀+ C ₁₄, C ₄+ C ₆+ C ₈+ C ₁₀+ C ₁₂+ C ₁₄+ C ₁₆+ C ₁₈Deng combination.Product VI depends on that fluid viscosity depends on the selection that raw material olefin is formed in addition.For requiring the highest lubricant applications, using the fluid with higher VI is preferably.

In another embodiment, preferred PAO fluid does not contain very light-weight level branch.These lightweight level branches cause the oxidation and the thermostability of high volatile volatile, unsettled viscosity, difference.Usually in final product, remove them.Usually preferably have less than 1wt% and have the C20 or the fluid of low carbon number more, be more preferably less than 1wt% have C24 or more low carbon number fluid or be more preferably less than 1wt% and have the C26 or the fluid of low carbon number more.Preferably have less than 0.5wt% and have the C20 or the fluid of low carbon number more, be more preferably less than 0.5wt% have C24 or more low carbon number fluid or be more preferably less than 0.5wt% and have the C26 or the fluid of low carbon number more.In addition, the amount of any of these light hydrocarbon is low more, can be good more through the fluid property that the Noack volatility test is measured.Preferably, the PAO fluid has less than 5wt%, preferably less than 2wt%, preferably less than the Noack volatility of 0.5wt%.

In another embodiment, any poly-alpha olefins described herein can have by ASTMD 56 measure greater than 20-5000cSt at 100 ℃ kinematic viscosity and 150 ℃ or higher flash-point.

In another embodiment, any poly-alpha olefins described herein can have 3 or littler, and common 2.5 or littler specific inductivity (1kHz at 23 ℃, is measured by ASTM D 924).

In another embodiment, any poly-alpha olefins described herein can have 0.6-0.9g/cm ³, preferred 0.7-0.88g/cm ³Proportion.

At the PAO of this preparation, especially have those (KV for example of medium-viscosity to HV ₁₀₀Greater than those of 20cSt) be particularly suitable for preparing high-performing car engine oil, universal industrial lubricant, railway grease, various types of automobile or industrial gear oil, aeroengine oil, hydraulic fluid or lubricant, heat-transfer fluid etc.They can use or through using by 0.1wt% to 95wt% blend ground with other fluid individually; For example I, II organize; II+ group, the III group, the lube base stock of III+ group base-material or the hydroisomerization that divides derived from the wax level (get since CO/H by this wax level ₂The fischer-tropsch hydrocarbon of synthetic gas is synthetic) or other IV group or V group or VI group base-material.These blended material are used for being mixed with complete synthesis lubricant, partial synthesis thing when combining with additive, or are used as the specialist additive component with other base-material.

Unless otherwise mentioned, all kinematic viscosity values of reporting at this fluid are measured down at 100 ℃.Can obtain dynamic viscosity through this measured motion viscosity being multiply by this density of liquid then.The unit of kinematic viscosity is m ²/ s converts cSt or centistoke (1cSt=10 usually to ^-6m ²/ s or 1cSt=1mm ²/ sec).

PAO prepared in accordance with the present invention is one or more C normally ₃-C ₂₄Olefinic monomer, preferably one or more C ₄-C ₂₀'alpha '-olefin monomers, preferably one or more C ₅-C ₂₀The monomeric dimer of linear alpha-alkene, tripolymer, the tetramer or higher oligomer.Perhaps, also can use such terminal olefin, its alkyl substituent and olefinic double bond are at a distance of at least 2 carbon.Usually, the PAO of this paper preparation mixture of many different oligopolymer normally.In one embodiment, the minimum oligopolymer that derives from these terminal olefins has C ₁₀-C ₂₀Carbon number.Usually with these little oligopolymer and carbon number greater than C ₂₀(C for example ₂₄Higher) higher oligomer separate, the latter is usually as high performance fluids.These isolating C ₁₀-C ₂₀Oligopolymer alkene or the corresponding paraffins after hydrogenation can be used for extraordinary the application, for example have the drilling fluid, solvent, lacquer thinner of excellent biological degradability, toxicity, viscosity etc. etc.Sometimes, with as many as C ₄₀Less oligopolymer separate with residual lubricating oil level branch and obtain to have the product of performance of catering to the need most.C ₂₀Or C ₃₀High performance fluids level during more senior level is divided is divided and is had lower viscosity usually, and this makes them favourable to some application, for example better fuel economy, better biological degradability, better low-temperature fluidity or lower volatility.

In the present invention, carry out oligomeric usually or polymerization method so that produce the final product of 100 ℃ of Kv greater than 20cSt.Being used for preparing these fluidic methods and catalyzer is unique so that polymkeric substance that their preparations have narrow molecular weight distributions.Because this characteristic, what the polymerization method generation was very high divides product selectivity to the lubricating oil level, and this lubricating oil level divides product to have the C of very low amount ₂₀Or C ₂₄Or C ₂₈Or C ₃₀Or the lightweight level branch of even lower level level branch, this depends on type of feed.In addition, because this narrow distribution, final lubricating oil level is divided and is not contained excessive high molecular weight block, and this excessive high molecular weight block possibly cause the unstable under effects such as shearing, heat, oxidation stress.

PAO described herein can be further and other base-material (Gr I to VI) and additive blend; Additive comprises inhibitor, antiwear additive, friction improver, dispersion agent, purification agent, inhibiter, skimmer, extreme-pressure additive, sealing swelling additive and randomly, viscosity modifier etc.The description of typical additive, preparation and application can be referring to books " Synthetics, Mineral Oils, and Bio-Based Lubricants, Chemistryand Technology "; Ed.L.R.Rudnick, CRC Press, Taylor & FrancisGroup, Boca Raton; FL. with " Lubricant Additives " Chemistry andApplications, ed.L.R.Rudnick, Marcel Dekker; I nc., NewYork, 2003.

In another embodiment; The PAO of this paper preparation has by the 25wt% of Noack volatility test (ASTM D5800) measurement or littler, preferred 20wt% or littler, preferred 14wt% or littler; Preferably less than 10wt% or littler, preferably less than 5wt% or littler volatility.Usually, this oil has the NOACK volatility less than 2wt%.

In another embodiment, be unsaturated olefin directly by PAO oligomeric or the polymerization method preparation.The amount of unsaturated part can be quantitatively through measuring according to the bromine number of ASTM D 1159 or measuring through proton or carbon-13NMR.The unsaturated part of olefinic can distinguished and quantize to proton N MR spectroscopic analysis also: vinylidene base, 1,2-is dibasic, three replace or the type of vinyl.Carbon-13NMR spectrum can confirm that the alkene that is calculated by proton spectrum distributes.

Proton and carbon-13NMR spectrum can quantize the degree of short-chain branched (SCB) in the olefin oligomer, but carbon-13NMR can be provided in the bigger specificity of a chain length aspect.In proton spectrum, the resonance of SCB branched chain methyl falls within the scope of 1.05-0.7ppm.The SCB of enough different lengthss will produce enough different methyl peak so that integration or deconvolution (deconvolute) and the side chain length distribution is provided individually.Remaining methylene radical and methyne signal resonate in the 3.0-1.05ppm scope.In order to let this integration and CH, CH ₂And CH ₃Concentration is relevant, must proofread and correct each integration for the proton multiplicity.This methyl integration obtains the number of methyl divided by three; Remaining aliphatic integration is supposed for each methyl to comprise a CH signal, and wherein all the other integrations are CH ₂Signal.CH ₃/ (CH+CH ₂+ CH ₃) ratio provide methyl concentration.

Similarly logic is applicable to that carbon-13NMR analyzes, and difference do not need to be the proton multiplicity to proofread and correct.In addition, ¹³C NMR is relative ¹The enhanced spectrum of H NMR/structural resolution allows according to side chain length field segregant.Usually, methyl resonance integration and obtain methyl (20.5-15ppm), propyl group (15-14.3ppm), butyl and the side chain concentration of long-chain branch (14.3-13.9ppm) and ethyl (13.9-7ppm) more individually.

Easily carry out the alkene analysis through proton N MR, wherein 5.9 and 4.7ppm between the olefinic signal according to the segmentation of the alkyl substitute mode of alkene.Vinyl CH proton resonates between 5.9-5.7ppm, vinyl CH ₂Proton 5.3 and 4.85ppm between resonate.1, the dibasic olefinic proton of 2-resonates in the 5.5-5.3ppm scope.This trisubstituted olefin peaks in the 5.3-4.85ppm zone with vinyl CH ₂Peak overlapping; Vinyl CH integration through based on twice is deducted the contribution that removes this regional vinyl.1, the alkene that 1-two replaces (or vinylidene base) resonates in the 4.85-4.6ppm zone.Olefinic resonance is in case the proton multiplicity is just proofreaied and correct can normalization method and obtain molar percentage alkene and distribute, or compares with the gauged aliphatic series of multiplicity zone (as above in the face of methyl analyze as described in) and obtain graded concentration (fractionalconcentration) (for example alkene/100 carbon).

Usually, the amount of unsaturated part depends on fluid viscosity or fluid molecule amount consumingly.More low viscous fluid has higher degree of unsaturation and the bromine number of Geng Gao.More full-bodied fluid has lower degree of unsaturation and lower bromine number.If during polymerization procedure, use a large amount of hydrogen or high hydrogen pressure, then bromine number possibly be lower than the situation that does not have hydrogen to exist.Usually, in the inventive method by the poly-alpha olefins greater than 20-5000cSt of 1-decene or other LAO preparation, the PAO when synthetic will have 25 to less than 1 bromine number, this depends on fluid viscosity.

Type through the unsaturated part of olefinic in the PAO fluid of the inventive method preparation is unique, as ¹H with ¹³That kind that C-NMR confirms.They comprise very a large amount of vinylidene base alkene (CH ₂=CR ¹R ²) and the unsaturated part (comprising that three replace or two-substituted alkene) of other type of much less.This vinylidene base content is also preferably much higher than the vinylidene base content of the poly-alpha olefins for preparing based on the metallocenes that uses with MAO promotor under the prior art situation.Fig. 5 has explained poly-1-butylene of the present invention relatively according to US 6,548, the mole % of the vinylidene base content of the material that general disclosed method produces in 724.In the present invention, vinylidene base content is greater than 65 moles of %, or greater than 70% or greater than 80%.The unsaturated part of more substantial vinylidene base is normally more desirable because the alkene of these types to further hydrogenation or further functionalized be have more reactive.Have many maximized methods of amount that make vinylidene base alkene of having described, for example U.S. Patent number 5,286, those disclosed in 823.Vinylidene base alkene is faster with the maleic anhydride reaction in alkene reaction usually.They more easily are hydrogenated and obtain to be used for the complete saturated hydrocarbon of high-performance base-material.Usually, hydrogenation degree influences the fluidic oxidative stability.Have higher hydrogenation degree and follow fluid to have better oxidative stability usually with lower bromine number.PAO among the present invention has high vinylidene base content and therefore more is prone to carry out hydrogenation, and provides low bromine number fluidic to form.Bromine number is more preferably less than 3 preferably less than 5 after hydrogenation, is more preferably less than 2, is more preferably less than 1, is more preferably less than 0.5, is more preferably less than 0.1.Usually, bromine number is low more, and oxidative stability is good more.

PAO through the present invention's preparation also preferably compares methyl/1000 carbon with reduction with the PAO for preparing through known method.Fig. 6 provides with known method and has compared, through belonging to CH among the poly-1-butylene fluidic PAO that Catalyst And Method of the present invention makes ₃The amount of base/1000 carbon.The product that makes among the present invention has the methyl content lower than the amount that is limited following formula:

(methyl branch/1000 C)=-3.4309 * Ln is (at 100 ℃ Kv, cSt)+29.567

Methyl-branched is normally not too desirable, because this kind branching is tended to force down VI and/or reduced oxidative stability.

At the PAO of this preparation is liquid.Concerning the present invention and claim thereof, liquid is defined as at room temperature and flows, and has less than 25 ℃ pour point with at 100 ℃ and has 30, the material of 000cS t or littler kinematic viscosity.

In a preferred embodiment, the PAO for preparing among the present invention comprises quite a large amount of nonstereospecific polymer structures.In other words, PAO has the monomeric unit that most of atactic is arranged.This nonstereospecific polymer is favourable to lubricant applications.In a preferred embodiment, the PAO through the present invention preparation have by following carbon-13NMR measure at least 50%, preferably at least 75%; Preferably at least 85%; Preferably at least 90%, preferably at least 95%, preferred at least 99% nonstereospecific polymer structure.

In another embodiment, the invention further relates to and have according to following program, preferred 80 moles of % or still less through spectrometric 90 moles of % of 13C nuclear magnetic resonance (NMR) or still less; Preferred 70 moles of % or still less, preferred 60 moles of % or still less, preferred 50 moles of % or still less; Preferred 40 moles of % or still less, preferred 30 moles of % or still less, preferred 20 moles of % or still less; Preferred 10 moles of % or still less, preferred 5 moles of % or the PAO of mm triad still less.

In another embodiment, the invention further relates to and have according to following program, preferred 80 moles of % or still less through spectrometric 90 moles of % of 13C nuclear magnetic resonance (NMR) or still less; Preferred 70 moles of % or still less, preferred 60 moles of % or still less, preferred 50 moles of % or still less; Preferred 40 moles of % or still less, preferred 30 moles of % or still less, preferred 20 moles of % or still less; Preferred 10 moles of % or still less, preferred 5 moles of % or the PAO of rr triad still less.

In another embodiment, the invention further relates to and have according to following program through the spectrometric 20 moles of % of 13C nuclear magnetic resonance (NMR) or more preferred 30 moles of % or more; Preferred 40 moles of % or more; Preferred 50 moles of % or more, preferred 55 moles of % or more, preferred 60 moles of % or more; Preferred 70 moles of % or more, the PAO of preferred 75 moles of % or more mr triad.

In another embodiment, the invention further relates to have according to following program spectrometric through 13C nuclear magnetic resonance (NMR) less than 5, preferably less than 4, preferably less than 3, preferably less than 2, preferably less than the PAO of 1 mm/mr ratio.

As stated, carbon-13NMR is used for measuring the tacticity (under some situations, measure quantitatively and under other situation, measure qualitatively) of poly-alpha olefins of the present invention.Carbon-13NMR can be used for measuring the concentration of triad (being expressed as mm (meso, meso), mr (meso, racemize) and rr (racemize, racemize)), and the mole of sample is formed.The concentration of these triad limits whether polymkeric substance is isotaxy, atactic or syndiotactic polymer.The spectrum of PAO sample obtains by following mode.About 100-1000mg of PAO sample is dissolved in 2-3ml chloroform-d to be used for carbon 13 and to analyze.With about 10mg/ml (solvent benchmark) acetyl acetone chromium relaxant Cr (acac) ₃Add in the sample to improve data acquisition rate.According to Kim, I.; Zhou, J.-M.; And Chung; H. paper Journal of Polymer Science:Part A:Polymer Chemistry 2000; 381687-1697 (increase the evaluation and the integration of end group resonance, and remove their contributions to the peak of use in analyzing) carries out the spectrographic analysis.Use the 85/15Lorentzian/Gaussian thread shape to carry out deconvolution with Acorn NMR Inc. ' s NutsPro NMR DAS.Distribute the component peaks merger is become to troop according to mm, mr and rr triad, and use the Bernoullian fitting of distribution.The customized parameter of these matches is Pr, and that is added has a stereochemical monomeric ratio of racemize.For measure (for example as described in the Kim) details since one group of triad to statistical models (for example Bernoullian); Referring to " Polymer Sequence Determination, JamesC.Randall, Ac ademic Press; New York, 1977 ".For poly decene and the practical measuring examples of gathering the tacticity of dodecylene, see also the embodiment part of the PCT patent application PCT/US2006/021231 that submitted on June 2nd, 2006.

In another embodiment of the invention; 1; The dibasic alkene of 2-to be to be present in the poly-alpha olefins product less than Z mole %, Z=8.420 * Log (V)-4.048 wherein, and wherein V is the kinematic viscosity (cSt) at 100 ℃ of poly-alpha olefinss of measuring down; Preferably or still less, preferably with 5 moles of % or still less exist with 7 moles of %.For how measuring 1, the information of the dibasic olefin(e) centent of 2-sees also the PCT/US06/21231 that submitted on June 2nd, 2006.

In another embodiment, this poly-alpha olefins has the unit of being represented by following general formula less than Z mole %:

Wherein j, k and m are 3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21 or 22 independently of one another; N is the integer of 1-350; Z=8.420 * Log (V)-4.048 wherein, wherein V is the kinematic viscosity (cSt) at this poly-alpha olefins of 100 ℃ of measurements.

In a preferred embodiment, the product of this paper preparation has 70% or higher to C ₂₀The selectivity of higher hydrocarbon more, preferred 80% or higher, preferred 90% or higher, more preferably 95% or higher, preferred 98% or higher, preferred 99% or higher to C ₂₀The selectivity of higher hydrocarbon more.

In a preferred embodiment; The productivity of this method is 1.5kg gross product/gram transistion metal compound at least, preferred 2kg gross product/gram transistion metal compound at least, preferably 3kg gross product/gram transistion metal compound at least; Preferred 5kg gross product/gram transistion metal compound at least; Preferred 7kg gross product/gram transistion metal compound at least, preferred 10kg gross product/gram transistion metal compound at least, preferably 20kg gross product/gram transistion metal compound at least.

In another preferred embodiment; The productivity of this method is the non-coordination anion activator compound of 1.5kg gross product/gram at least; The preferred non-coordination anion activator compound of 2kg gross product/gram at least; The preferred non-coordination anion activator compound of 3kg gross product/gram at least, the preferred non-coordination anion activator compound of 5kg gross product/gram at least, the preferably non-coordination anion activator compound of 7kg gross product/gram at least; The preferred non-coordination anion activator compound of 10kg gross product/gram at least, the preferably non-coordination anion activator compound of 20kg gross product/gram at least.

It is significant that metallocenes or non-coordination anion acvator have high productivity, because these components are more expensive than other component in the catalyst system usually.For economic operation, the productivity with 1.5kg/g transistion metal compound at least or non-coordination anion acvator is important.

In a preferred embodiment, the product of this paper preparation has 60% or lower to C ₂₄Or the selectivity of even lower level hydrocarbon, preferred 50% or lower, preferred 40% or lower, more preferably 20% or lower, preferred 10% or lower, preferred 5% or lower, preferred 1% or lower to C ₂₄Or the selectivity of even lower level hydrocarbon (wt%, unless otherwise mentioned).

In a preferred embodiment, the product of this paper preparation has 60% or lower to C ₁₀Dimer (is C ₂₀Product) selectivity, preferred 50% or lower, preferred 40% or lower, more preferably 30% or lower, more preferably 10% or lower, more preferably 5% or lower, more preferably 1% or lower to C ₁₀Dimeric selectivity (wt%, unless otherwise mentioned).

In a preferred embodiment, the lubricating oil or the high performance fluids of this paper preparation have 10% or higher, preferred 20% or higher; Preferred 40% or higher, more preferably 50% or higher, preferred 70% or higher; Preferred 80% or lower; Preferred 90% or higher, or preferred 95% or higher selectivity (wt%, unless otherwise mentioned).

Method

The present invention relates to the improved preparation method of poly-alpha olefins.This improving one's methods adopted metalloscene catalyst and one or more non-coordination anion acvators.This metalloscene catalyst is not bridging, substituted two (cyclopentadienyl moiety) transistion metal compounds.One type of preferred catalyzer comprises highly substituted metallocenes, and this metallocenes produces high catalyst productivity and is created in the product of 100 ℃ of following measured motion viscosity greater than 20cSt.Another kind of preferred metallocenes is bridging and substituted cyclopentadiene, comprise bridging not and replacement or unsubstituted indenes and/or fluorenes.An aspect of method described herein also comprises raw material olefin and solvent (if use); Or purge nitrogen materials flow processing to remove catalyzer poison; Superoxide for example, oxygen-containing organic compound, organic compounds containing sulfur and organic compounds containing nitrogen, and/or acetylenic compound.This processing it is believed that and can improve catalyst productivity; Usually catalyst productivity improves greater than 30%, or catalyst productivity improves greater than 50%, or catalyst productivity improves greater than 100%; Or catalyst productivity improves greater than 200%; Or catalyst productivity improves greater than 500%, or catalyst productivity improves greater than 1000%, or catalyst productivity improves greater than 2000%.In most cases, if, can't obtain to transform or transformation efficiency very low (for example less than 5%) not with raw material olefin, solvent (if use) or sweeping gas materials flow purifying.

In a preferred embodiment, the present invention relates to 100 ℃ of following KV for greater than 20cSt to about 10, the preparation method of the poly-alpha olefins of 000cSt (preferred continuous or semicontinuous or discontinuous method) comprising:

1) one or more 'alpha '-olefin monomers that contain 3-24 carbon atom are contacted with following component: substituted two (cyclopentadienyl moiety) transistion metal compounds of not bridging with following structure:

Wherein M is a group-4 metal;

Each X is hydrogen, halogen, hydride ion, alkyl, substituted alkyl, halo carbon back, substituted halo carbon back, silyl carbon back, substituted silyl carbon back, germyl carbon back or substituted germyl carbon back independently; Or two X engage and are bonded to atoms metal and form the metal embedding cyclisation misfit thing ring that contains 3-20 carbon atom; Or two X can be alkene, diolefine or aryne part together;

R ¹-R ¹⁰Be to be the group of hydrogen, heteroatoms, alkyl, substituted alkyl, halo carbon back, substituted halo carbon back, silyl carbon back or germyl carbon back independently of one another, condition is R ¹-R ⁵In at least one is not hydrogen and R ⁶-R ¹⁰In at least one is not a hydrogen, and wherein any two adjacent R bases randomly engage and form replace or unsubstituted, saturated, part is unsaturated or aromatics ring-type or polycyclic substituting group; With

Non-coordination anion acvator and randomly, alkyl-aluminum compound; Wherein the mol ratio of transistion metal compound and acvator is 10: 1-0.1: 1; And when having alkylaluminium cpd, the mol ratio of alkylaluminium cpd and transistion metal compound is 1: 4-4000: 1, wherein:

I) hydrogen exists with the dividing potential drop of 0.1-100psi, and based on the total pressure of reactor drum, or the concentration of hydrogen is 1-30 by weight, 000ppm or littler;

Ii) wherein these one or more contain 3-24 carbon atom 'alpha '-olefin monomers with 10 volume % or higher the existence, based on the TV of the catalyzer/acvator/alkylaluminium cpd solution, monomer and any thinner or the solvent that exist in the reaction;

Iii) condition is that ethene does not exist with the 40wt% that surpasses the monomeric raw material olefin compsn that gets into reactor drum.

In a preferred embodiment, the present invention relates to have greater than 20cSt or higher KV ₁₀₀The preparation method of liquid poly-alpha olefins, comprising:

A) in reaction zone, exist down at hydrogen (by weight preferred 10-10,000ppm hydrogen), let one or more C ₃-C ₂₀'alpha '-olefin monomers contacts with following component: be not more than 40wt% ethene, non-coordination anion acvator and the transistion metal compound of being represented by following general formula:

Wherein M is a group-4 metal;

Each X is hydrogen, halogen, hydride ion, alkyl, substituted alkyl, halo carbon back, substituted halo carbon back, silyl carbon back, substituted silyl carbon back, germyl carbon back or substituted germyl carbon back independently; Or two X engage and are bonded to atoms metal and form the metal that contains about 20 carbon atoms of about 3-and embed cyclisation misfit thing ring; Or two X can be alkene, diolefine or aryne part together; With

R ¹-R ¹⁰Be to be the group of hydrogen, heteroatoms, alkyl, substituted alkyl, halo carbon back, substituted halo carbon back, silyl carbon back or germyl carbon back independently of one another, condition is: 1) R ¹-R ⁵In at least one is not hydrogen or iso-alkyl and R ⁶-R ¹⁰In at least one is not hydrogen or iso-alkyl, or 2) R ¹-R ⁵In at least two be not hydrogen, or 3) R ¹-R ⁵In at least two be not hydrogen and R ⁶-R ¹⁰In at least two be not hydrogen and wherein any two adjacent R ¹-R ⁵Base can form C ₄-C ₂₀Ring-type or polycyclic structure division and wherein any two adjacent R ⁶-R ¹⁰Base can form C ₄-C ₂₀Ring-type or polycyclic structure division and

Randomly, coactivator R ¹R ²R ³M, wherein M is aluminium or boron, R ¹, R ²And R ³Can be identical or different C ₁-C ₂₄Alkyl comprises the mixture of trialkylaluminium, trialkylboron compound or different compounds.

The so-called system that is meant is not continuously having operation under the situation of interrupting or stopping (or planning in operation in such cases).For example, the continuation method of preparation polymkeric substance will be the method for wherein reactant (for example monomer and catalyst component and/or toxic removal agent) being introduced one or more reactor drums continuously and discharging polymer product continuously.The so-called semicontinuous system that is meant is having operation under the situation of periodically interrupted (or planning in operation in such cases).For example, the semicontinuous method of preparation polymkeric substance will be the method for wherein reactant (for example monomer and catalyst component and/or scavenging agent) being introduced one or more reactor drums continuously and discharging polymer product off and on.

Interrupter method is not continuous or semicontinuous method.

In an embodiment preferred of the present invention, through some means control oligomerization reaction temperature, for example continuous or semi continuous operation, heat extraction, the speed that catalyzer or raw material add or solvent adds.Because usually under room temperature or envrionment temperature, add catalyst solution, raw material olefin and/or solvent and/or scavenging agent maybe can be pre-cooling to required temperature with them, so they can relax reaction heat and can help to keep constant temperature of reaction to the interpolation of reactor drum.This operator scheme can be during 30 minutes in; Preferably temperature is controlled in 20 ℃ of desired reaction temperature for entire reaction; Usually preferably control in temperature required 10 ℃; Preferably arrive in temperature required 5 ℃, preferably arrive in temperature required 3 ℃, or preferably arrive in temperature required 1 ℃.

The reactor drum that usually, in semi-continuous running, will contain a small amount of starting liq preheats in 10 ℃ of desired reaction temperature.This starting liq can be raw material olefin, catalyst component, solvent or come the poly-alpha olefins tailing of the preceding running of leisure or come comfortable preceding poly-alpha olefins product or any other suitable liquid that turns round.The part of the PAO product that usually, turns round before the PAO tailing of raw material olefin, solvent or next comfortable preceding running or the next leisure is preferred starting liq.When reactor drum is in required temperature, can add hydrogen, solvent and other component of raw material olefin, catalyst component, selected amount continuously by selected speed.Can coactivator (one or more) or scavenging agent (one or more) (desired amount partly or entirely) be added in the starting liq.Or randomly, can part or all of coactivator (one or more) or scavenging agent (one or more) be added in raw material olefin or the solvent materials flow so that the validity maximization.When polyreaction when temperature of reaction begins, heat is released.Constant in order to keep reaction temperature as far as possible, through in the Several Methods mentioned among this paper one or more, or known that kind is removed and is reduced phlegm and internal heat as in this area.Remove a kind of possible method reduce phlegm and internal heat and be following continuously with the materials flow circulation of reactor content through interchanger: with this side materials flow pumping through interchanger to cool off this side materials flow slightly, then it is pumped back in the reaction zone.The cooling degree of this round-robin speed and this side materials flow can be used for controlling effectively reaction zone temperature.Perhaps, if speed of reaction does not have enough Gao Deke to keep temperature of reaction, then indirect heating is offered reactor drum to keep required temperature.The another kind of method of keeping constant temperature of reaction is control raw material olefin or the interpolation speed of solvent and the temperature of raw material olefin or solvent.After the interpolation of reactant is accomplished, make reaction proceed the required time to obtain the highest raw material olefin transformation efficiency.

In continuous operation mode, operate similarly with semi-continuous running, except when when reactor drum is filled to predeterminated level, discharge the mixture of reaction products of predetermined amount from reactor drum, continue to add all components simultaneously.Raw material adds speed and the amount of the reaction product of discharging from reactor drum is confirmed the reaction times or the residence time.This can confirm to obtain high raw material olefin transformation efficiency of economic operation and high reactor throughput in advance.

In this method,, make some factor balances for optimum.It at first is the selection of catalyst component.Bridging, substituted metallocenes are not effective catalyzer with a small amount of trialkylaluminium activatory by non-coordination anion (NCA).Metallocene components can be dihalide or dialkylated thing.But the dialkyl group form of metallocenes normally interacts and the activity chemistry component of acquisition active catalyst with the NCA acvator.When using the metallocenes dihalide, require to add trialkylaluminium or other alkylating reagent usually so that this dihalide form is changed into the dialkyl group form.In this case, the mol ratio of trialkylaluminium and metallocenes is 4-4000, any value among the preferred 8-500.(for example dimethyl-two (tetrahydro indenyl) closes zirconium, dimethyl-two (1 when using metallocenes dialkylated thing; 2-dimethyl-cyclopentadienyl moiety) closes zirconium, dimethyl-two (1; 3-dimethyl-cyclopentadienyl moiety) closes zirconium, dimethyl-two (1; 2,4-trimethylammonium cyclopentadienyl moiety) closing zirconium, dimethyl-two (tetramethyl-ring pentadienyl) closes zirconium or dimethyl-two (methyl-3-n-butyl cyclopentadienyl) to close perhaps many other metal diaikyl of zirconium luxuriant etc.) time, use a small amount of trialkylaluminium to obtain optimum catalyst productivity.In this case, the mol ratio of trialkylaluminium and metallocenes is 2-500 normally, preferred 3-200, more preferably 3-100 or 3-10.The amount no less important of the NCA that uses.The mol ratio of metallocenes and NCA can be 10-0.1.The preferred mol ratio of metallocenes and NCA approached 1: 1 or 0.5: 2.

In addition, the quantity of metallocenes concentration is important.For reach the highest catalyst productivity, to highly selective and the optimum temps control and the operability of lube range product, the preferred amounts of metallocenes/gram olefin feedstock is 1 microgram (or 0.001 milligram)/gram alkene to 1 milligram/restrain alkene.When the amount of the catalyst component that uses is too high, the temperature control difficulty that can become, it is uneconomical that selectivity of product can be suffered a loss and the catalyzer cost can become.

The amount no less important that is present in the hydrogen in the reactor drum.Usually, the hydrogen of a small amount of is preferred.Usually the hydrogen pressure head is kept and be equal to or less than 300psi, preferably be lower than 50psi, preferably be lower than 30psi, preferably be lower than 20psi, preferably be lower than 10psi.Perhaps, the amount of hydrogen is pressed 1ppm-30 in the feedstock composition, 000ppm, and preferred 10-10,000ppm, preferred 10-1, the concentration of 000ppm exists.Usually, keep lower hydrogen pressure to improve activity.It has surprisingly been found that the hydrogen that is present in the reaction medium is not easy initial terminal olefin feed hydrogen is changed into corresponding alkane under low-level hydrogen pressure or density of hydrogen.In fact, when having hydrogen in the reaction mixture, have been found that catalyst productivity improves significantly.This also is desirable, because the existence of low-level hydrogen causes having the ethylenic polymer of high vinylidene base content, this ethylenic polymer can be after a while through known method, and for example U.S. Patent number 6,043, and those disclosed is functionalized in addition in 401.Therefore, preferably keep the reactor hydrogen atmospheric pressure and be lower than 300psi, more preferably less than 100psi, preferably less than 50psi, preferably less than 25psi, preferably less than 10psi.Low pressure hydrogen not only helps preparing unsaturated polymer, and feed hydrogen is changed into low value alkane is important to farthest reducing.The hydrogen of minimum quantity hopes that equally preferred hydrogen is with 1psi, preferably 5psi existence at least at least.5-100psi hydrogen is added in the reactor drum normally actual.

The reaction times or the residence time also influence the transforming degree of raw material olefin.Usually, the longer reaction times or the residence time help higher raw material olefin conversion.Yet in order to make high conversion and high reactor throughput balance, the reaction times or the residence time were generally 1 minute-30 hours, more preferably 5 minutes-16 hours, and more preferably 10 minutes-10 hours.Can be through using single reactor drum or a series of cascade or parallel reactor or reaching this total residence time through the control reactant feed rate.

Selectivity through metallocenes (with NCA and/or coactivator activation) is selected; With through the operation condition (amount that comprises employed catalyzer; With an amount of trialkylaluminium as coactivator or scavenging agent; The amount of the residence time or reaction times and hydrogen) selectivity is selected, and is producing poly-alpha olefins above under the high catalyst productivity of 1.5 kilograms of gross product/employed metalloceness of gram.This high productivity makes this method become at economy and commercially attractive.

Accomplish reaction by semi-continuous running or discontinuous running or after continuous operation is discharged product, can be as follows with the crude product aftertreatment: through adding minor amounts of oxygen, carbonic acid gas, air, water, alcohol, acid or any other catalyzer poison reagent with catalyst deactivation; Aqueous sodium hydroxide solution or hydrochloric acid soln and this product of water washing with dilution; With separate organic layer.Organic layer comprises unreacted alkene, olefin oligomer and solvent usually.Can product level branch be separated with unreacted starting olefin with solvent through distillation or other method as known in the art.Can further product level branch be fractionated into lightweight level branch and residual level branch.These grades branch has a unsaturated double-bond/molecule usually.Two key major parts are vinylidene bases, and some of the rest part of wherein said alkene are 1, dibasic alkene of 2-or trisubstituted alkene.These alkene are suitable for further functionaliseding into other functional fluid or performance additive according to the alkene functionalization of being familiar with, and for example carry out alkylation with the compound that contains the aromatics part, with maleic anhydride, with CO/H ₂Via hydroformylation reaction etc.Residual level is divided (they almost do not have usually or do not contain the light hydrocarbon that is less than 24 carbon), if their bromine number is lower than 2 then can be used as lube base stock or high performance fluids.If bromine number is greater than 2, then can be easily through traditional lubrication oil hydrofinishing process with its hydrogenation and change into bromine number, usually significantly less than 2 complete paraffinic hydrocarbons fluid less than 2.Usually, lower bromine number is preferred, because it indicates better oxidative stability.These hydrogenant saturated hydrocarbon chain alkane are used as the high performance lubricant base-material or are used as the performance function fluid after preparation.The description of typical lubricants or functional fluid prescription can be referring to books and reference " Synthetic Lubricants and High-Performance Functional Fluids "; Second edition; By L.R.Rudnick and R.L.Shubkin chief editor; Marcel Dekker, Inc., N.Y.1999.

Perhaps, can contain the crude product aftertreatment that heteroatomic component will derive from polymerization reactor through using solid adsorbent absorbing catalyst component and scavenging agent component and any other.This is preferable methods and is used for following embodiment.In this method, above-mentioned catalyzer passivator is added in the crude reaction product, then add solid absorbent.Perhaps; With solid absorbent, for example aluminum oxide, acid clay, Celite

or any known flocculating aids add in the crude product.Stir the time of slurry predetermined amount, usually greater than 5 minutes.Then, solids filtered and filtrating is ready for further distillation or fractionation.The patented claim USSN60/831 that this method is submitted to has at the same time carried out more fully describing in 995 (the submitting on July 19th, 2006).

In another embodiment, this method comprises also that the PAO that lets in this preparation has under the typical hydrogenation conditions of hydrogenation catalyst and produces most of saturated paraffinic PAO with contacted with hydrogen.

Metallocene catalyst compound

Concerning the present invention and claim thereof, term " alkyl (hydrocarbylradical) ", " alkyl (hydrocarbyl) " use in whole file with " alkyl (hydrocarbyl group) " interchangeably.Likewise, term " group (group) ", " base (radical) " also use in whole file with " substituting group " interchangeably.Concerning present disclosure, " alkyl " is defined as C ₁-C ₁₀₀Group and can be linear, branching or cyclic.When ring-type, alkyl can be aromatics or non-aromatics." alkyl " definition comprises substituted alkyl, halo carbon back, substituted halo carbon back, silyl carbon back and germyl carbon back, and these terms define below.Substituted alkyl be wherein at least one Wasserstoffatoms by the NR* for example of at least one functional group ₂, OR*, SeR*, TeR*, PR* ₂, AsR* ₂, SbR* ₂, SR*, BR* ₂, SiR* ₃, GeR* ₃, SnR* ₃, PbR* ₃Deng replace or wherein at least one nonhydrocarbon atom or group for example-O-,-S-,-Se-,-Te-,-N (R*)-,=N-,-P (R*)-,=P-,-As (R*)-,=As-,-Sb (R*)-,=Sb-,-B (R*)-,=B-,-Si (R*) ₂-,-Ge (R*) ₂-,-Sn (R*) ₂-,-Pb (R*) ₂-wait the group that is inserted in this alkyl, wherein R* is alkyl or halo carbon back independently, two or more R* can be bonded together and form replace or unsubstituted saturated, part is unsaturated or aromatics ring-type or polycyclic ring structure.

The halo carbon back is that wherein one or more alkyl Wasserstoffatomss are by at least one halogen (for example F, Cl, Br, I) or halogen-containing group (CF for example ₃) substituted group.

Substituted halo carbon back be wherein at least one halo carbon back hydrogen or halogen atom by the NR* for example of at least one functional group ₂, OR*, SeR*, TeR*, PR* ₂, AsR* ₂, SbR* ₂, SR*, BR* ₂, SiR* ₃, GeR* ₃, SnR* ₃, PbR* ₃Deng replace or wherein at least one non-carbon atom or group for example-O-,-S-,-Se-,-Te-,-N (R*)-,=N-,-P (R*)-,=P-,-As (R*)-,=As-,-Sb (R*)-,=Sb-,-B (R*)-,=B-,-Si (R*) ₂-,-Ge (R*) ₂-,-Sn (R*) ₂-,-Pb (R*) ₂-wait the group that is inserted in this halo carbon back, wherein R* is alkyl or halo carbon back independently, condition is that at least one halogen atom is retained on the original halo carbon back.In addition, two or more R* can be bonded together and form replace or unsubstituted saturated, part is unsaturated or aromatics ring-type or polycyclic ring structure.

The silyl carbon back is the group of the direct keyed jointing of one or more atoms of wherein silyl functional group and this indication.Instance comprises SiH ₃, SiH ₂R*, SiHR* ₂, SiR* ₃, SiH ₂(OR*), SiH (OR*) ₂, Si (OR*) ₃, SiH ₂(NR* ₂), SiH (NR* ₂) ₂, Si (NR* ₂) ₃Deng, wherein R* be independently alkyl or halo carbon back and two or more R* can be bonded together and form replace or unsubstituted saturated, part is unsaturated or aromatics ring-type or polycyclic ring structure.

The germyl carbon back is the group of the direct keyed jointing of one or more atoms of wherein germyl functional group and this indication.Instance comprises GeH ₃, GeH ₂R*, GeHR* ₂, GeR* ₃, GeH ₂(OR*), GeH (OR*) ₂, Ge (OR*) ₃, GeH ₂(NR* ₂), GeH (NR* ₂) ₂, Ge (NR* ₂) ₃Deng, wherein R* be independently alkyl or halo carbon back and two or more R* can be bonded together and form replace or unsubstituted, saturated, part is unsaturated or aromatics ring-type or polycyclic ring structure.

Polar group is the group of heteroatom functional group and the direct keyed jointing of one or more atoms of this indication wherein.They comprise periodictable 1-17 family heteroatoms (except carbon and hydrogen), and said heteroatoms is independent or for example interacts through covalent linkage or other that ionic linkage, Van der Waals force or hydrogen bond are connected with other element.Functionalizedly contain heteroatomic examples of groups and comprise carboxylic acid, carboxylic acid halides, carboxylicesters, carboxylate salt, carboxylic acid anhydride, aldehyde and their chalcogen (chalcogen) (the 14th family) analogue, pure and mild phenol; Ether, superoxide and hydroperoxide, carboxylic acid amide, hydrazides and imide, other nitrogen analogue of amidine and acid amides, nitrile; Amine and imines, azo cpd, nitro-compound, other nitrogen compound, sulfur acid contains selenic acid; Mercaptan, sulfide, sulfoxide, sulfone, phosphine, SULPHOSUCCINIC ACID ESTER (salt); Other phosphorus compound, silane, borine, boric acid ester (salt), aluminium alkane (alane), aluminic acid ester (salt).Functional group can also think widely and includes organic polymer carrier or inorganic carrier material for example aluminum oxide and silicon-dioxide.The preferred embodiment of polar group comprises NR* ₂, OR*, SeR*, TeR*, PR* ₂, AsR* ₂, SbR* ₂, SR*, BR* ₂, SnR* ₃, PbR* ₃Deng, wherein R* be independently as the top alkyl that limits, substituted alkyl, halo carbon back or substituted halo carbon back and two R* can be bonded together and form replace or unsubstituted, saturated, part is unsaturated or aromatics ring-type or polycyclic ring structure.

When use a technical term " replacing or unsubstituted cyclopentadienyl ligands ", " replacing or unsubstituted indenyl ligands ", " replacing or unsubstituted fluorenyl ligand " and " replacing or unsubstituted tetrahydro indenyl part ", the replacement part of above-mentioned part can be alkyl, substituted alkyl, halo carbon back, substituted halo carbon back, silyl carbon back or germyl carbon back.This replacement part can also be within the ring that provides heterocyclic pentylene ylidene ligands, assorted indenyl ligands, assorted fluorenyl ligand or assorted tetrahydro indenyl part, and wherein each can be replacement or unsubstituted in addition.

In some embodiments; Alkyl is independently selected from methyl, ethyl, vinyl and following isomer: propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, cerylic, heptacosyl, octacosyl, nonacosyl, triacontyl, propenyl, crotonyl, pentenyl, hexenyl, heptenyl, octenyl, nonene base, decene base, undecenyl, dodecenyl succinic, tridecylene base, tetradecene base, 15 carbene bases, cetene base, heptadecene base, vaccenic acid base, 19 carbene bases, eicosylene base, heneicosene base, two dodecenyl succinic, tricosene base, tetracosa carbon thiazolinyl, ppentacosene base, cerotene base, cerotene base, two vaccenic acid bases, 29 carbene bases, triacontylene base, proyl, butynyl, pentynyl, hexyn, heptyne base, octyne base, n-heptylacetylene base, decynyl, hendecyne base, dodecyne base, 13 carbyne bases, 14 carbyne bases, 15 carbyne bases, hexadecine base, 17 carbyne bases, octadecyne base, 19 carbyne bases, 20 carbyne bases, two hendecyne bases, two dodecyne bases, 23 carbyne bases, tetracosa carbon alkynyl, 25 carbyne bases, two hexadecine bases, 27 carbyne bases, two octadecyne bases, 29 carbyne bases, 30 carbyne bases, butadienyl, pentadienyl, hexadienyl, heptadiene base, octadienyl, nonadiene base and decadiene base.Also comprise be saturated, part is unsaturated and the isomer of aromatics ring-type and polycyclic structure, wherein the replacement that can experience the above-mentioned type in addition of this group is handled.Instance comprises phenyl, aminomethyl phenyl, 3,5-dimethylphenyl, ethylphenyl, diethylammonium phenyl, propyl group phenyl, dipropyl phenyl, benzyl, methyl-benzyl, naphthyl, anthryl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, suberyl, cycloheptenyl, norcamphyl, norbornene, adamantyl etc.For present disclosure, when listing group, it is meant types of radicals and all other groups that when this replacement that is limited above types of radicals experience, form.The alkyl of listing, thiazolinyl and alkynyl comprise all isomer, comprise the cyclic isomers when suitable, and for example, butyl comprises normal-butyl, 2-methyl-propyl, 1-methyl-propyl, the tertiary butyl and cyclobutyl (with similar substituted cyclopropane base); Amyl group comprises n-pentyl, cyclopentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethyl propyl and neo-pentyl (with similar replacement cyclobutyl and cyclopropyl); Crotonyl comprises 1-butylene base, crotyl, 3-crotonyl, 1-methyl isophthalic acid-propenyl, 1-methyl-2-propenyl, 2-methyl isophthalic acid-propenyl and 2-methyl-2-propenyl E and the Z-shaped formula of (with cyclobutene base and cyclopropenyl radical).Have the ring compound that replaces part and comprise all isomeric forms, for example, aminomethyl phenyl will comprise o-methyl-phenyl-, an aminomethyl phenyl and p-methylphenyl; 3,5-dimethylphenyl will comprise 2,3-3,5-dimethylphenyl, 2,4-3,5-dimethylphenyl, 2,5-3,5-dimethylphenyl, 2,6-3,5-dimethylphenyl, 3,4-3,5-dimethylphenyl and 3,5-3,5-dimethylphenyl.The instance of cyclopentadienyl moiety and indenyl ligands is below as the part explanation of part.

" ring carbon atom " is the carbon atom that belongs to the part of cyclic rings structure.According to this definition, indenyl ligands has nine ring carbon atoms; Cyclopentadienyl ligands has five ring carbon atoms, and fluorenyl ligand has 13 ring carbon atoms.Therefore, indenes is equivalent to have the Cp ring of two alkyl substituents, and fluorenes is equivalent to have the Cp ring of four alkyl substituents.In addition, cyclic rings also can be hydrogenated, for example, two-hydrogen or four-hydrogen indenyl ligands, two-hydrogen, four-hydrogen or eight-hydrogen fluorenyl ligand are fit to.

The useful Metallocenic compound (pre-catalyst) of this paper is the cyclopentadienyl derivative of titanium, zirconium and hafnium preferably.Generally speaking, useful two luxuriant titaniums, zirconocene and hafnocene can be represented by following general formula:

(CpCp*)MX ₁X ₂(2)

Wherein:

M is a metal center, and is group-4 metal, preferred titanium, zirconium or hafnium, preferred zirconium or hafnium;

Cp and Cp* be separately with the identical or different cyclopentadienyl rings of M keyed jointing; With 1) Cp and Cp* be substituted with at least one non-iso-alkyl substituting group; Or 2) Cp is substituted with two to five substituting groups " R "; Preferred Cp and Cp* are substituted with two to five substituting groups " R "; Each substituent R is the group for alkyl, substituted alkyl, halo carbon back, substituted halo carbon back, silyl carbon back or germyl carbon back independently, or Cp and Cp* be identical or different cyclopentadienyl rings, wherein any two adjacent R bases randomly engage and form replace or unsubstituted, saturated, part is unsaturated or aromatics ring-type or polycyclic substituting group;

X ₁And X ₂Be hydrogen, halogen, hydride ion, alkyl, substituted alkyl, halo carbon back, substituted halo carbon back, silyl carbon back, substituted silyl carbon back, germyl carbon back or substituted germyl carbon back independently; Or two X engage and are bonded to atoms metal and form the metal that contains about 20 carbon atoms of about 3-and embed cyclisation misfit thing ring; Or two X can be alkene, diolefine or aryne part together.

The representativeness that Table A has been described the metallocene components of general formula 2 constitutes structure division.This tabulation only is used for the illustrative purpose and in no case should be interpreted as restrictive.Many final components can form through all possible combination of the structure division of exchange formation each other.When openly comprising the alkyl of alkyl, thiazolinyl, alkynyl, naphthenic base, cycloalkenyl group, cycloalkynyl radical and aromatic group in this application, this term comprises all isomer.For example, butyl comprises normal-butyl, 2-methyl-propyl, the tertiary butyl and cyclobutyl; Amyl group comprises n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethyl propyl, neo-pentyl, cyclopentyl and methyl cyclobutyl; Crotonyl comprises the E and the Z-shaped formula of 1-butylene base, crotyl, 3-crotonyl, 1-methyl isophthalic acid-propenyl, 1-methyl-2-propenyl, 2-methyl isophthalic acid-propenyl and 2-methyl-2-propenyl.This comprises marquis when group and other group keyed jointing, and for example, the propyl group cyclopentadienyl moiety comprises n-propyl cyclopentadienyl moiety, sec.-propyl cyclopentadienyl moiety and cyclopropyl rings pentadienyl.

Generally speaking, part shown in the Table A or group comprise all isomeric forms.For example, the dimethyl-cyclopentadienyl moiety comprises 1,2-dimethyl-cyclopentadienyl moiety and 1,3-dimethyl-cyclopentadienyl moiety; The methyl indenyl comprises 1-methyl indenyl, 2-methyl indenyl, 3-methyl indenyl, 4-methyl indenyl, 5-methyl indenyl, 6-methyl indenyl and 7-methyl indenyl; The methylethyl phenyl comprises adjacent methylethyl phenyl, a methylethyl phenyl and to the methylethyl phenyl.For the member of transition metal component is described, select to list in any combination of the material in the Table A.

Table A

M	Cp，Cp*
		Titanium	Methyl cyclopentadienyl
Zirconium	The dimethyl-cyclopentadienyl moiety
		Hafnium	The trimethylammonium cyclopentadienyl moiety
	The tetramethyl-ring pentadienyl
			The ethyl cyclopentadienyl moiety
	The diethylammonium cyclopentadienyl moiety
			The propyl group cyclopentadienyl moiety
	The dipropyl cyclopentadienyl moiety
			The butyl cyclopentadienyl moiety
	The dibutyl cyclopentadienyl moiety
			The amyl group cyclopentadienyl moiety
	The diamyl cyclopentadienyl moiety
			The hexyl cyclopentadienyl moiety
	The dihexyl cyclopentadienyl moiety
			The heptyl cyclopentadienyl moiety
	The diheptyl cyclopentadienyl moiety
			The octyl group cyclopentadienyl moiety
	The dioctyl cyclopentadienyl moiety
			The nonyl cyclopentadienyl moiety
	The dinonyl cyclopentadienyl moiety
			The decyl cyclopentadienyl moiety
	The didecyl cyclopentadienyl moiety
			The undecyl cyclopentadienyl moiety
	The dodecyl cyclopentadienyl moiety
			The tridecyl cyclopentadienyl moiety
	The tetradecyl cyclopentadienyl moiety

	The pentadecyl cyclopentadienyl moiety
			The hexadecyl cyclopentadienyl moiety
	The heptadecyl cyclopentadienyl moiety
			The octadecyl cyclopentadienyl moiety
	The nonadecyl cyclopentadienyl moiety
			The eicosyl cyclopentadienyl moiety
	The heneicosyl cyclopentadienyl moiety
			The docosyl cyclopentadienyl moiety
	The tricosyl cyclopentadienyl moiety
			The tetracosyl cyclopentadienyl moiety
	The pentacosyl cyclopentadienyl moiety
			The cerylic cyclopentadienyl moiety
	The heptacosyl cyclopentadienyl moiety
			The octacosyl cyclopentadienyl moiety
	The nonacosyl cyclopentadienyl moiety
			The triacontyl cyclopentadienyl moiety
	The cyclohexyl ring pentadienyl
			The benzyl ring pentadienyl
	The phenylbenzene cyclopentadienyl moiety
			The triphenyl cyclopentadienyl moiety
	The tetraphenyl cyclopentadienyl moiety
			The tolyl cyclopentadienyl moiety
	The benzyl rings pentadienyl
			The styroyl cyclopentadienyl moiety
	The cyclohexyl methyl cyclopentadienyl moiety
			The naphthyl cyclopentadienyl moiety
	The aminomethyl phenyl cyclopentadienyl moiety
			Methyl tolyl cyclopentadienyl moiety
	The methylethyl cyclopentadienyl moiety

	The methyl-propyl cyclopentadienyl moiety
			The methylbutyl cyclopentadienyl moiety
	The methyl amyl cyclopentadienyl moiety
			Methyl hexyl cyclopentadienyl moiety
	The methylheptyl cyclopentadienyl moiety
			The Methyl Octyl cyclopentadienyl moiety
	Methyl nonyl cyclopentadienyl moiety
			Methyl decyl cyclopentadienyl moiety
	The vinyl cyclopentadienyl moiety
			The propenyl cyclopentadienyl moiety
	The crotonyl cyclopentadienyl moiety
			Indenyl
	The methyl indenyl
			The dimethyl-indenyl
	The trimethylammonium indenyl
			The tetramethyl-indenyl
	The pentamethyl-indenyl
			The methyl-propyl indenyl
	The dimethyl propyl indenyl
			Methyl dipropyl indenyl
	The methylethyl indenyl
			The methylbutyl indenyl
	Ethyl-indenyl
			The propyl group indenyl
	The butyl indenyl
			The amyl group indenyl
	The hexyl indenyl
			The heptyl indenyl
	The octyl group indenyl

	The nonyl indenyl
			The decyl indenyl
	Phenyl indenyl
			(fluorophenyl) indenyl
	(aminomethyl phenyl) indenyl
			The xenyl indenyl
	(two (trifluoromethyl) phenyl) indenyl
			The naphthyl indenyl
	The phenanthryl indenyl
			The benzyl indenyl
	The benzo indenyl
			The cyclohexyl indenyl
	The aminomethyl phenyl indenyl
			The ethylphenyl indenyl
	The propyl group phenyl indenyl
			Methyl naphthyl indenyl
	Ethyl naphthyl indenyl
			Propyl group naphthyl indenyl
	(aminomethyl phenyl) indenyl
			(3,5-dimethylphenyl) indenyl
	(ethylphenyl) indenyl
			(diethylammonium phenyl) indenyl
	(propyl group phenyl) indenyl
			(dipropyl phenyl) indenyl
	The methyl tetrahydro indenyl
			The ethyl tetrahydro indenyl
	The propyl group tetrahydro indenyl
			Butyl four basic indenyls
	The phenyl tetrahydro indenyl

	(diphenyl methyl) cyclopentadienyl moiety
			The trimethyl silyl cyclopentadienyl moiety
	The triethylsilyl cyclopentadienyl moiety
			Trimethylammonium germyl cyclopentadienyl moiety
	The trifluoromethyl cyclopentadienyl moiety
			Ring penta [b] thienyl
	Ring penta [b] furyl
			Ring penta [b] seleno (seleno) phenyl
	Ring penta [b] telluro (telluro) phenyl
			Ring penta [b] pyrryl
	Ring penta [b] phospholyl
			Ring penta [b] arsolyl
	Ring penta [b] stibolyl
			Methyl ring penta [b] thienyl
	Methyl ring penta [b] furyl
			Methyl ring penta [b] seleno phenyl
	Methyl ring penta [b] telluro phenyl
			Methyl ring penta [b] pyrryl
	Methyl ring penta [b] phospholyl
			Methyl ring penta [b] arsolyl
	Methyl ring penta [b] stibolyl
			Diformazan basic ring penta [b] thienyl
	Diformazan basic ring penta [b] furyl
			Diformazan basic ring penta [b] pyrryl
	Diformazan basic ring penta [b] phospholyl
			Front three basic ring penta [b] thienyl
	Front three basic ring penta [b] furyl
			Front three basic ring penta [b] pyrryl
	Front three basic ring penta [b] phospholyl

	Ethyl ring penta [b] thienyl
			Ethyl ring penta [b] furyl
	Ethyl ring penta [b] pyrryl
			Ethyl ring penta [b] phospholyl
	Diethyl basic ring penta [b] thienyl
			Diethyl basic ring penta [b] furyl
	Diethyl basic ring penta [b] pyrryl
			Diethyl basic ring penta [b] phospholyl
	Triethyl ring penta [b] thienyl
			Triethyl ring penta [b] furyl
	Triethyl ring penta [b] pyrryl
			Triethyl ring penta [b] phospholyl
	Propyl group ring penta [b] thienyl
			Propyl group ring penta [b] furyl
	Propyl group ring penta [b] pyrryl
			Propyl group ring penta [b] phospholyl
	Dipropyl basic ring penta [b] thienyl
			Dipropyl basic ring penta [b] furyl
	Dipropyl basic ring penta [b] pyrryl
			Dipropyl basic ring penta [b] phospholyl
	Tripropyl ring penta [b] thienyl
			Tripropyl ring penta [b] furyl
	Tripropyl ring penta [b] pyrryl
			Tripropyl ring penta [b] phospholyl
	Butyl ring penta [b] thienyl
			Butyl ring penta [b] furyl
	Butyl ring penta [b] pyrryl
			Butyl ring penta [b] phospholyl
	Dibutyl ring penta [b] thienyl

	Dibutyl ring penta [b] furyl
			Dibutyl ring penta [b] pyrryl
	Dibutyl ring penta [b] phospholyl
			Tributyl ring penta [b] thienyl
	Tributyl ring penta [b] furyl
			Tributyl ring penta [b] pyrryl
	Tributyl ring penta [b] phospholyl
			Ethyl-methyl ring penta [b] thienyl
	Ethyl-methyl ring penta [b] furyl
			Ethyl-methyl ring penta [b] pyrryl
	Ethyl-methyl ring penta [b] phospholyl
			Methyl-prop basic ring penta [b] thienyl
	Methyl-prop basic ring penta [b] furyl
			Methyl-prop basic ring penta [b] pyrryl
	Methyl-prop basic ring penta [b] phospholyl
			Butyl methyl ring penta [b] thienyl
	Butyl methyl ring penta [b] furyl
			Butyl methyl ring penta [b] pyrryl
	Butyl methyl ring penta [b] phospholyl
			Ring penta [c] thienyl
	Ring penta [c] furyl
			Ring penta [c] seleno phenyl
	Ring penta [c] telluro phenyl
			Ring penta [c] pyrryl
	Ring penta [c] phospholyl
			Ring penta [c] arsolyl
	Ring penta [c] stibolyl
			Methyl ring penta [c] thienyl
	Methyl ring penta [c] furyl

	Methyl ring penta [c] seleno phenyl
			Methyl ring penta [c] telluro phenyl
	Methyl ring penta [c] pyrryl
			Methyl ring penta [c] phospholyl
	Methyl ring penta [c] arsolyl
			Methyl ring penta [c] stibolyl
	Diformazan basic ring penta [c] thienyl
			Diformazan basic ring penta [c] furyl
	Diformazan basic ring penta [c] pyrryl
			Diformazan basic ring penta [c] phospholyl
	Front three basic ring penta [c] thienyl
			Front three basic ring penta [c] furyl
	Front three basic ring penta [c] pyrryl
			Front three basic ring penta [c] phospholyl
	Ethyl ring penta [c] thienyl
			Ethyl ring penta [c] furyl
	Ethyl ring penta [c] pyrryl
			Ethyl ring penta [c] phospholyl
	Diethyl basic ring penta [c] thienyl
			Diethyl basic ring penta [c] furyl
	Diethyl basic ring penta [c] pyrryl
			Diethyl basic ring penta [c] phospholyl
	Triethyl ring penta [c] thienyl
			Triethyl ring penta [c] furyl
	Triethyl ring penta [c] pyrryl
			Triethyl ring penta [c] phospholyl
	Propyl group ring penta [c] thienyl
			Propyl group ring penta [c] furyl
	Propyl group ring penta [c] pyrryl

	Propyl group ring penta [c] phospholyl
			Dipropyl basic ring penta [c] thienyl
	Dipropyl basic ring penta [c] furyl
			Dipropyl basic ring penta [c] pyrryl
	Dipropyl basic ring penta [c] phospholyl
			Tripropyl ring penta [c] thienyl
	Tripropyl ring penta [c] furyl
			Tripropyl ring penta [c] pyrryl
	Tripropyl ring penta [c] phospholyl
			Butyl ring penta [c] thienyl
	Butyl ring penta [c] furyl
			Butyl ring penta [c] pyrryl
	Butyl ring penta [c] phospholyl
			Dibutyl ring penta [c] thienyl
	Dibutyl ring penta [c] furyl
			Dibutyl ring penta [c] pyrryl
	Dibutyl ring penta [c] phospholyl
			Tributyl ring penta [c] thienyl
	Tributyl ring penta [c] furyl
			Tributyl ring penta [c] pyrryl
	Tributyl ring penta [c] phospholyl
			Ethyl-methyl ring penta [c] thienyl
	Ethyl-methyl ring penta [c] furyl
			Ethyl-methyl ring penta [c] pyrryl
	Ethyl-methyl ring penta [c] phospholyl
			Methyl-prop basic ring penta [c] thienyl
	Methyl-prop basic ring penta [c] furyl
			Methyl-prop basic ring penta [c] pyrryl
	Methyl-prop basic ring penta [c] phospholyl

	Butyl methyl ring penta [c] thienyl
			Butyl methyl ring penta [c] furyl
	Butyl methyl ring penta [c] pyrryl
			Butyl methyl ring penta [c] phospholyl
	The pentamethyl-cyclopentadienyl moiety
			Tetrahydro indenyl
	The methyl tetrahydro indenyl
			The dimethyl tetrahydro indenyl

In an embodiment preferred of the present invention, when using with NCA, Cp is identical with Cp* and be substituted cyclopentadienyl moiety, indenyl or tetrahydro indenyl part.

Preferred Metallocenic compound (pre-catalyst), they provide the PAO to preparing greater than 20cSt to have specific catalyst system according to the present invention, comprising:

Dichloro two (1,2-dimethyl-cyclopentadienyl moiety) closes zirconium,

Dichloro two (1,3-dimethyl-cyclopentadienyl moiety) closes zirconium,

Dichloro two (1,2,3-trimethylammonium cyclopentadienyl moiety) closes zirconium

Dichloro two (1,2,4-trimethylammonium cyclopentadienyl moiety) closes zirconium;

Dichloro two (1,2,3,4-tetramethyl-ring pentadienyl) closes zirconium,

Dichloro two (1,2,3,4,5-pentamethyl-cyclopentadienyl moiety) closes zirconium,

Dichloro two (1-methyl-2-ethyl cyclopentadienyl moiety) closes zirconium,

Dichloro two (1-methyl-2-n-propyl cyclopentadienyl moiety) closes zirconium,

Dichloro two (1-methyl-2-n-butyl cyclopentadienyl) closes zirconium,

Dichloro two (1-methyl-3-ethyl cyclopentadienyl moiety) closes zirconium,

Dichloro two (1-methyl-3-n-propyl cyclopentadienyl moiety) closes zirconium,

Dichloro two (1-methyl-3-n-butyl cyclopentadienyl) closes zirconium,

Dichloro two (1-methyl-3-n-pentyl cyclopentadienyl moiety) closes zirconium

Dichloro two (1,2-dimethyl--4-ethyl cyclopentadienyl moiety) closes zirconium,

Dichloro two (1,2-dimethyl--4-n-propyl cyclopentadienyl moiety) closes zirconium

Dichloro two (1,2-dimethyl--4-n-butyl cyclopentadienyl) closes zirconium,

Dichloro two (1,2-diethylammonium cyclopentadienyl moiety) closes zirconium

Dichloro two (1,3-diethylammonium cyclopentadienyl moiety) closes zirconium

Dichloro two (1,2-two-n-propyl cyclopentadienyl moiety) closes zirconium

Dichloro two (1,2-di-n-butyl cyclopentadienyl moiety) closes zirconium

Dichloro two (1-methyl-2,4-diethylammonium cyclopentadienyl moiety) closes zirconium

Dichloro two (1,2-diethylammonium-4-n-propyl cyclopentadienyl moiety) closes zirconium

Dichloro two (1,2-diethylammonium-4-n-butyl cyclopentadienyl) closes zirconium,

Dichloro two (1-methyl-3-different-propyl group cyclopentadienyl moiety) closes zirconium,

Dichloro two (1-ethyl-3-different-propyl group cyclopentadienyl moiety) closes zirconium,

Dichloro (1,2-dimethyl-cyclopentadienyl moiety) (cyclopentadienyl moiety) closes zirconium

Dichloro (1,3-dimethyl-cyclopentadienyl moiety) (cyclopentadienyl moiety) closes zirconium

Dichloro (1,2-dimethyl-cyclopentadienyl moiety) (methyl cyclopentadienyl) closes zirconium

Dichloro (1,2-dimethyl-cyclopentadienyl moiety) (ethyl cyclopentadienyl moiety) closes zirconium

Dichloro (1,2-dimethyl-cyclopentadienyl moiety) (1,2-di-n-butyl cyclopentadienyl moiety) closes zirconium

Dichloro (1,3-dimethyl-cyclopentadienyl moiety) (1,2-dimethyl-cyclopentadienyl moiety) closes zirconium,

Dichloro (1,3-dimethyl-cyclopentadienyl moiety) (1,3-diethylammonium cyclopentadienyl moiety) closes zirconium

Dichloro two (indenyl) closes zirconium

Dichloro two (1-methyl indenyl) closes zirconium

Dichloro two (2-methyl indenyl) closes zirconium

Dichloro two (4-methyl indenyl) closes zirconium

Dichloro two (4,7-dimethyl-indenyl) closes zirconium

Dichloro two (4,5,6, the 7-tetrahydro indenyl) closes zirconium

Dichloro two (4,5,6,7-tetrahydrochysene-2-methyl indenyl) closes zirconium,

Dichloro two (4,5,6,7-tetrahydrochysene-4,7-dimethyl-indenyl) closes zirconium

Dichloro (cyclopentadienyl moiety) (4,5,6, the 7-tetrahydro indenyl) closes zirconium.

Preferred catalyzer also comprises the dihalide zirconium, two-methyl or two-alkyl analogue of the hafnium of dichloride, dihalide or the above-claimed cpd of two-methyl of above-claimed cpd, Di-Isobutyl, two-n-octyl or other two-alkyl analogue and hafnium.

Especially preferred catalyst compound comprises that also dichloro two (1,2-dimethyl-cyclopentadienyl moiety) closes zirconium, and dichloro two (1,3-dimethyl-cyclopentadienyl moiety) closes zirconium, dichloro two (1; 2,3-trimethylammonium cyclopentadienyl moiety) close zirconium, dichloro two (1,2,4-trimethylammonium cyclopentadienyl moiety) closes zirconium and dichloro two (tetramethyl-ring pentadienyl) closes zirconium; Dichloro two (1-methyl-2-ethyl cyclopentadienyl moiety) closes zirconium, and dichloro two (1-methyl-3-ethyl cyclopentadienyl moiety) closes zirconium, and dichloro two (1-methyl-3-n-propyl cyclopentadienyl moiety) closes zirconium, and dichloro two (1-methyl-3-n-butyl cyclopentadienyl) closes zirconium, dichloro two (4; 5,6, the 7-tetrahydro indenyl) close zirconium, dichloro two (indenyl) closes zirconium; Dimethyl-two (1,2-dimethyl-cyclopentadienyl moiety) closes zirconium, and dimethyl-two (1,3-dimethyl-cyclopentadienyl moiety) closes zirconium; Dimethyl-two (1,2,3-trimethylammonium cyclopentadienyl moiety) closes zirconium, dimethyl-two (1; 2,4-trimethylammonium cyclopentadienyl moiety) close zirconium and dimethyl-two (tetramethyl-ring pentadienyl) and close zirconium, dimethyl-two (1-methyl-2-ethyl cyclopentadienyl moiety) closes zirconium, and dimethyl-two (1-methyl-3-ethyl cyclopentadienyl moiety) closes zirconium; Dimethyl-two (1-methyl-3-n-propyl cyclopentadienyl moiety) closes zirconium, and dimethyl-two (1-methyl-3-n-butyl cyclopentadienyl) closes zirconium, dichloro two (4,5; 6, the 7-tetrahydro indenyl) close zirconium, dimethyl-two (indenyl) closes zirconium, or their diisobutyl analogue.These metallocenes dialkyl group components can be present in the catalyst system as parent material through using preformed metallocenes.Sometimes, they exist as the reaction product of metallocenes dihalide and trialkyl aluminium compound (coactivator/scavenging agent).

In an optional embodiment, Metallocenic compound is not racemic.

Acvator and catalyst activation

When being activated the activation of the for example non-coordination anion acvator of agent, catalyst precursor is formed for olefinic polymerization or oligomeric active catalyst.Operable acvator comprises for example for example four perfluorophenyl boric acid dimethyl-puratized agricultural sprays, four perfluorophenyl boric acid triphenylcarbenium, four perfluorophenyl aluminic acid dimethyl-puratized agricultural sprays etc. of triphenyl-boron, three-perfluorophenyl boron, three-perfluorophenyl aluminium etc. and/or ionic acvator of lewis acid activation agent.

Coactivator is can the alkylating compound of transition metal complex consequently when being used in combination with acvator, be formed active catalyst.Coactivator comprises for example MAO of aikyiaiurnirsoxan beta; Modified alumoxane is for example trimethylaluminium, triisobutyl aluminium, triethyl aluminum and triisopropylaluminiuand, tri-n-hexyl aluminum, tri-n-octylaluminium, three positive decyl aluminium or three (dodecyl) aluminium of modified methylaluminoxane and aluminium alkynylene for example.When pre-catalyst was not dialkyl complex compound or dihydride (dihydride) complex compound, coactivator used with lewis acid activation agent and ionic acvator usually with combining.Sometimes, also use coactivator and add in feed stream or catalyst stream or the reactor drum as scavenging agent the impurity passivation in raw material or the reactor drum with single or a plurality of materials flows.In most cases, even when using the dialkyl group form of metallocene components, also a small amount of coactivator is added in catalyst system or the reactor system so that the impurity of further facilitation effect or purge reactor system.

Especially preferred coactivator comprises the alkylaluminium cpd of being represented by following general formula: R ₃Al; Wherein each R is the C1-C18 alkyl independently, and preferably each R is independently selected from methyl, ethyl, n-propyl, sec.-propyl, isobutyl-, normal-butyl, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, n-hexyl, isohexyl, n-heptyl, different heptyl, n-octyl, iso-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, NSC 172782 base, Octadecane base and their isomery analogue (iso-analogs).

Ionic acvator (being used in combination with coactivator sometimes) can be used for the present invention's practice.Preferably, can use for example [Me of discrete (discrete) ionic acvator ₂PhNH] [B (C ₆F ₅) ₄], [Ph ₃C] [B (C ₆F ₅) ₄], [Me ₂PhNH] [B ((C ₆H ₃-3,5-(CF ₃) ₂)) ₄], [Ph ₃C] [B ((C ₆H ₃-3,5-(CF ₃) ₂)) ₄], [NH ₄] [B (C ₆H ₅) ₄] or lewis acidity acvator B (C for example ₆F ₅) ₃Or B (C ₆H ₅) ₃, wherein Ph is a phenyl, Me is a methyl.When using; Preferred coactivator is a for example MAO of aikyiaiurnirsoxan beta; Modified alumoxane is for example triisobutyl aluminium and trimethylaluminium, triethyl aluminum and triisopropylaluminiuand, tri-n-hexyl aluminum, tri-n-octylaluminium, three positive decyl aluminium or three (dodecyl) aluminium of modified methylaluminoxane and aluminium alkynylene for example.

Use ionization property or stoichiometry acvator (neutrality or ionic); The for example assorted borine negatively charged ion (WO 98/43983) of four (pentafluorophenyl group) boric acid three (normal-butyl) ammonium, three perfluorophenyl boron metalloid precursors or three perfluor naphthyl boron metalloid precursors, many halogenations, boric acid (U.S. Patent number 5; 942,459) or they be combined within the scope of the invention.

The instance of neutral stoichiometry acvator comprises trisubstituted boron, tellurium, aluminium, gallium and indium or their mixture.These three substituting groups are selected from alkyl, thiazolinyl, halogen, substituted alkyl, aryl, aryl halide, alkoxyl group and halogenide independently of one another.Preferably; These three groups are independently selected from halogen, list or many ring (comprising that halogen is substituted) aryl, alkyl and alkenyl compound and their mixture, preferably contain 1-20 carbon atom thiazolinyl, contain 1-20 carbon atom alkyl, contain the alkoxyl group of 1-20 carbon atom and contain the aryl (comprising substituted aryl) of 3-20 carbon atom.More preferably, these three groups are alkyl, phenyl, naphthyl or their mixtures that contain 1-4 carbon-based group.Even more preferably, these three groups are halogenated, the aryl of preferred fluorinated.Most preferably, neutral stoichiometry acvator is three perfluorophenyl boron or three perfluor naphthyl boron.

Ionic stoichiometry activator compound can comprise active proton, or the positively charged ion of all the other ionic associations of some other and this ionization property compounds (but not coordination with it, or only loose coordination).This compounds and analogue be open EP-A-0570982, EP-A-0520732, EP-A-0495375, EP-B1-0500944, EP-A-0277003 and EP-A-0277004 and U.S. Patent number 5,153,157,5,198,401,5 in Europe; 066,741,5,206,197,5; 241,025,5,384,299 and 5; 502,124 with U.S. Patent Application Serial Number 08/285,380 (submission on August 3rd, 1994) in be described, all these documents are incorporated herein for reference in full.

Ionic catalyst can be prepared as follows: make for example B (C of transistion metal compound and acvator ₆F ₆) ₃Reaction, this acvator forms for example ([B (C of negatively charged ion in hydrolyzable part (X ') the reaction back with this transistion metal compound ₆F ₅) ₃(X ')] ^-), it makes the cationic transition metal material stabilization that produces through this reaction.This catalyzer can be, and preferably use to the activator component preparation of ionic compound or compsn.Yet the preparation that utilizes neutral compound of acvator is also considered by the present invention.

The compound that can be used as activator component in the preparation of the ionic catalyst system that is used for the inventive method comprises positively charged ion (it preferably can supply with the Br of proton); Non-coordination anion with consistency; This negatively charged ion big (huge), it will be enough unsettled so that for example ether, nitrile etc. are alternative by the unsaturated substrate of olefinic, diolefinic and acetylene series or other neutral lewis base can making the stable and said negatively charged ion of the active catalyst species that when these two kinds of compounds are combined, forms.Two types of compatible non-coordination anions are at 1988 disclosed EPA 277; 003 with EPA 277; Disclose in 004: the anion binding complex compound that 1) comprises a plurality of lipophilic groups; Charged metal in this lipophilic group and center or metalloid core are with the covalent coordination and with this core shielding and 2) negatively charged ion that comprises a plurality of boron atoms for example carborane, metallocarborane and borine.In a preferred embodiment, the stoichiometry acvator comprises positively charged ion and anionic group, and can be represented by following general formula: (L**-H) ^D+(A ^D-), wherein L** is a neutral lewis base; H is a hydrogen; (L**-H) ^D+Be Br, A ^D-Be the non-coordination anion with electric charge d-, d is the integer of 1-3.

Cationic components (L**-H) ^D+Can comprise Br for example proton or protonated Lewis base or reducible Lewis acid, they can for example alkyl or aryl be protonated or extract this structure division from the pre-catalyst after alkylation with structure division.

Reactivity positively charged ion (L**-H) ^D+Can be Br, it can supply with alkylating transition metal-catalyzed precursor with proton, obtains transition-metal cation; Comprise ammonium, oxygen, phosphorus, silicomethane (silylium) and their mixture; Preferred methylamine, aniline, n n dimetylaniline, diethylamine, methylphenylamine, pentanoic, Trimethylamine 99, triethylamine, N, accelerine, methyldiphenyl base amine, pyridine, to bromo-N, accelerine, to nitro-N; The ammonium of accelerine; Derive from the phosphorus of triethyl phosphine, triphenylphosphine and diphenylphosphine, derive from the for example oxygen of dimethyl ether, Anaesthetie Ether, THF He diox of ether, derive from thioether; The for example sulfonium of diethylammonium thioether and THTP and their mixture.This reactivity positively charged ion (L**-H) ^D+Can also be structure division for example silver,

, carbon, ferrocene (ferrocenium) and mixture, preferred carbon and ferrocene; Triphenylcarbenium most preferably.

Anionic group A ^D-Comprise and have general formula [M ^K+Q _n] ^D-Those, wherein k is the integer of 1-3; N is the integer of 2-6; N-k=d; M is the element that is selected from the periodic table of elements the 13rd family; Preferred boron or aluminium; Q is hydride ion, bridging or not dialkyl group amido, halogen root, alkoxy radical, fragrant oxygen root, alkyl, substituted alkyl, halo carbon back, substituted halo carbon back and the substituted alkyl of halogen of bridging independently; Said Q contains 20 carbon atoms at the most, and condition is to occur the halogen root among the Q at the most one time.Preferably, each Q is the alkyl of fluoridizing that contains 1-20 carbon atom, and more preferably each Q is a fluoro aryl, and most preferably each Q is five fluorinated aryls.The A that is fit to ^D-Instance also comprise like U.S. Patent number 5,447, disclosed two boron cpds in 895, the document is hereby incorporated by in full.

In improvement Preparation of catalysts of the present invention, can combine as the illustrative of the boron cpd of reactivity promotor with coactivator but limiting examples be trisubstituted ammonium salt for example: tetraphenyl boric acid trimethyl ammonium, tetraphenyl boric acid triethyl ammonium, tetraphenyl boric acid tripropyl ammonium, tetraphenyl boric acid three (normal-butyl) ammonium, tetraphenyl boric acid three (tertiary butyl) ammonium, tetraphenyl boric acid N, N-dimethyl-puratized agricultural spray, tetraphenyl boric acid N, N-diethylammonium puratized agricultural spray, tetraphenyl boric acid N, N-dimethyl--(2; 4,6-trimethylammonium puratized agricultural spray), four (pentafluorophenyl group) boric acid trimethyl ammonium, four (pentafluorophenyl group) boric acid triethyl ammonium, four (pentafluorophenyl group) boric acid tripropyl ammonium, four (pentafluorophenyl group) boric acid three (normal-butyl) ammonium, four (pentafluorophenyl group) boric acid three (sec.-butyl) ammonium, four (pentafluorophenyl group) boric acid N, N-dimethyl-puratized agricultural spray, four (pentafluorophenyl group) boric acid N, N-diethylammonium puratized agricultural spray, four (pentafluorophenyl group) boric acid N; N-dimethyl--(2,4,6-trimethylammonium puratized agricultural spray), four (2,3; 4,6-tetrafluoro phenyl) boric acid trimethyl ammonium, four (2,3,4; 6-tetrafluoro phenyl) boric acid triethyl ammonium, four (2,3,4,6-tetrafluoro phenyl) boric acid tripropyl ammonium, four (2; 3,4,6-tetrafluoro phenyl) boric acid three (normal-butyl) ammonium, four (2,3; 4,6-tetrafluoro phenyl) boric acid dimethyl-(tertiary butyl) ammonium, four (2,3,4; 6-tetrafluoro phenyl) boric acid N, N-dimethyl-puratized agricultural spray, four (2,3,4; 6-tetrafluoro phenyl) boric acid N, N-diethylammonium puratized agricultural spray, four (2,3,4; 6-tetrafluoro phenyl) boric acid N, N-dimethyl--(2,4; 6-trimethylammonium puratized agricultural spray), four (perfluor naphthyl) boric acid trimethyl ammonium, four (perfluor naphthyl) boric acid triethyl ammonium, four (perfluor naphthyl) boric acid tripropyl ammonium, four (perfluor naphthyl) boric acid three (normal-butyl) ammoniums, four (perfluor naphthyl) boric acid three (tertiary butyl) ammoniums, four (perfluor naphthyl) boric acid N, N-dimethyl-puratized agricultural spray, four (perfluor naphthyl) boric acid N, N-diethylammonium puratized agricultural spray, four (perfluor naphthyl) boric acid N; N-dimethyl--(2,4,6-trimethylammonium puratized agricultural spray), four (perfluorinated biphenyl) boric acid trimethyl ammonium, four (perfluorinated biphenyl) boric acid triethyl ammonium, four (perfluorinated biphenyl) boric acid tripropyl ammonium, four (perfluor naphthyl) boric acid three (normal-butyl) ammoniums, four (perfluor naphthyl) boric acid three (tertiary butyl) ammoniums, four (perfluor naphthyl) boric acid N; N-dimethyl-puratized agricultural spray, four (perfluor naphthyl) boric acid N, N-diethylammonium puratized agricultural spray, four (perfluor naphthyl) boric acid N, N-dimethyl--(2; 4,6-trimethylammonium puratized agricultural spray), four (3, two (trifluoromethyl) phenyl of 5-) boric acid trimethyl ammonium, four (3; Two (trifluoromethyl) phenyl of 5-) boric acid triethyl ammonium, four (3, two (trifluoromethyl) phenyl of 5-) boric acid tripropyl ammonium, four (3, two (trifluoromethyl) phenyl of 5-) boric acid three (normal-butyl) ammonium, four (3; Two (trifluoromethyl) phenyl of 5-) boric acid three (tertiary butyl) ammonium, four (3, two (trifluoromethyl) phenyl of 5-) boric acid N, N-dimethyl-puratized agricultural spray, four (3; Two (trifluoromethyl) phenyl of 5-) boric acid N, N-diethylammonium puratized agricultural spray, four (3, two (trifluoromethyl) phenyl of 5-) boric acid N; N-dimethyl--(2,4,6-trimethylammonium puratized agricultural spray) and dialkyl ammonium salt for example: four (pentafluorophenyl group) boric acid two-(sec.-propyl) ammonium and four (pentafluorophenyl group) boric acid dicyclohexyl ammonium; Reach other salt for example four (pentafluorophenyl group) boric acid three (o-tolyl) phosphorus, four (pentafluorophenyl group) boric acid three (2; The 6-3,5-dimethylphenyl) phosphorus, tetraphenyl boric acid , tetraphenyl boric acid triphenylcarbenium, tetraphenyl boric acid triphenyl phosphorus, tetraphenyl boric acid triethyl-silicane, tetraphenyl boric acid (diazonium) benzene (benzene (diazonium)), four (pentafluorophenyl group) boric acid , four (pentafluorophenyl group) boric acid triphenylcarbenium, four (pentafluorophenyl group) boric acid triphenyl phosphorus, four (pentafluorophenyl group) boric acid triethyl-silicane, four (pentafluorophenyl group) boric acid (diazonium) benzene, four (2; 3; 4; 6-tetrafluoro phenyl) boric acid

, four (2; 3; 4; 6-tetrafluoro phenyl) boric acid triphenylcarbenium, four (2; 3; 4; 6-tetrafluoro phenyl) boric acid triphenyl phosphorus, four (2; 3; 4; 6-tetrafluoro phenyl) boric acid triethyl-silicane, four (2; 3; 4,6-tetrafluoro phenyl) boric acid (diazonium) benzene, four (perfluor naphthyl) boric acid

, four (perfluor naphthyl) boric acid triphenylcarbenium, four (perfluor naphthyl) boric acid triphenyl phosphorus, four (perfluor naphthyl) boric acid triethyl-silicane, four (perfluor naphthyl) boric acid (diazonium) benzene, four (perfluorinated biphenyl) boric acid , four (perfluorinated biphenyl) boric acid triphenylcarbenium, four (perfluorinated biphenyl) boric acid triphenyl phosphorus, four (perfluorinated biphenyl) boric acid triethyl-silicane, four (perfluorinated biphenyl) boric acid (diazonium) benzene, four (3, two (trifluoromethyl) phenyl of 5-) boric acid

, four (3; Two (trifluoromethyl) phenyl of 5-) boric acid triphenylcarbenium, four (3; Two (trifluoromethyl) phenyl of 5-) boric acid triphenyl phosphorus, four (3, two (trifluoromethyl) phenyl of 5-) boric acid triethyl-silicane and four (3, two (trifluoromethyl) phenyl of 5-) boric acid (diazonium) benzene.

Most preferably, ion chemistry metering acvator (L**-H) ^D+(A ^D-) be four (perfluorophenyl) boric acid N; N-dimethyl-puratized agricultural spray, four (perfluor naphthyl) boric acid N; N-dimethyl-puratized agricultural spray, four (perfluorinated biphenyl) boric acid N, N-dimethyl-puratized agricultural spray, four (3, two (trifluoromethyl) phenyl of 5-) boric acid N; N-dimethyl-puratized agricultural spray, four (perfluor naphthyl) boric acid triphenylcarbenium, four (perfluorinated biphenyl) boric acid triphenylcarbenium, four (3, two (trifluoromethyl) phenyl of 5-) boric acid triphenylcarbenium or four (perfluorophenyl) boric acid triphenylcarbenium.

Also can be with promotor that comprises non-coordination anion or acvator deactivated catalyst precursor, this non-coordination anion comprises no metalloid cyclopentadiene root (cyclopentadienide) ion.They on May 16th, 2002 U.S. Patent No. disclose among 2002/0058765 A1 and be described, and, require in catalyst precursor, to add coactivator for the present invention." compatible " non-coordination anion be when the initial complex compound that forms decomposes, be not degraded to neutral those.In addition, this negatively charged ion is not transferred to positively charged ion with anion substituent or fragment, to cause it to form neutral transistion metal compound and from this anionic neutral by product.Preferred non-coordination anion that can be used according to the invention is such negatively charged ion: they are compatible; Its charge balancing ion is made the transition metal complex cationic stabilized under the situation of+1 attitude, still keeping enough unstable in polymerization process, to be replaced by olefinic or acetylene series unsaturated monomer with permission.The promotor of these types uses such as but not limited to triisobutyl aluminium, tri-n-octylaluminium, tri-n-hexyl aluminum, triethyl aluminum or trimethylaluminium with scavenging agent sometimes.

The inventive method can also adopt cocatalyst compound or activator compound, and they are neutral lewis acid at first, but forms cationic metal complex and non-coordination anion during with the reaction of alkylating transistion metal compound, or the zwitter-ion complex compound.This alkylating Metallocenic compound is formed by the reaction of catalyst precursor and coactivator.For example, three (pentafluorophenyl group) boron or aluminium are used to extract hydrocarbyl ligand, use non-coordination anion and produce cationic transition metal complex compound of the present invention with stable, referring to EP-A-0427697 and the EP-A-0520732 explanation to similar group-4 metal cyclopentadinyl compound.Also referring to method and the compound of EP-A-0495375.For using similar the 4th compounds of group to form the zwitter-ion complex compound, referring to USP 5,624,878; 5,486,632 and 5,527,929.

Other neutral lewis acid is as known in the art and is suitable for extracting methylal (formal) anion ligand.Special comment " Cocatalysts for Metal-Catalyzed Olefin Polymerization:Activators; Activation Processes; and Structure-ActivityRelationships " referring to E.Y.-X.Chen and T.J.Marks; Chem.Rev., 100,1391-1434 (2000).

When the positively charged ion of non-coordination anion precursor is for example proton or a protonated Lewis base (eliminating water) of Br; Or reducible Lewis acid for example ferrocene or silver-colored positively charged ion; Or alkali or alkaline earth metal cation be for example during those of sodium, magnesium or lithium, and the mol ratio of catalyst precursor and acvator can be any ratio.The combination of said activator compound also can be used for activation.

When using ionic or neutral stoichiometry acvator (for example NCA), catalyst precursor and acvator mol ratio are 1: 10-1: 1; 1: 10-10: 1; 1: 10-2: 1; 1: 10-3: 1; 1: 10-5: 1; 1: 2-1.2: 1; 1: 2-10: 1; 1: 2-2: 1; 1: 2-3: 1; 1: 2-5: 1; 1: 3-1.2: 1; 1: 3-10: 1; 1: 3-2: 1; 1: 3-3: 1; 1: 3-5: 1; 1: 5-1: 1; 1: 5-10: 1; 1: 5-2: 1; 1: 5-3: 1; 1: 5-5: 1; 1: 1-1: 1.2.The mol ratio of catalyst precursor and coactivator is 1: 500-1: 1; 1: 100-100: 1; 1: 75-75: 1; 1: 50-50: 1; 1: 25-25: 1; 1: 15-15: 1; 1: 10-10: 1; 1: 5-5: 1,1: 2-2: 1; 1: 100-1: 1; 1: 75-1: 1; 1: 50-1: 1; 1: 25-1: 1; 1: 15-1: 1; 1: 10-1: 1; 1: 5-1: 1; 1: 2-1: 1; 1: 10-2: 1.

Preferred acvator and acvator/coactivator combination comprises the mixture of trialkylaluminium (comprising trimethylammonium, triethyl, three n-propyls, three n-hexyls, three normal-butyls, three n-octyls, three (dodecyl), triisopropyl, triisobutyl or triisopentyl etc.) and four (pentafluorophenyl group) boric acid dimethyl-puratized agricultural spray or three (pentafluorophenyl group) boron and trimethylaluminium and four (pentafluorophenyl group) boric acid dimethyl-puratized agricultural spray or three (pentafluorophenyl group) boron.

In some embodiments, the mixture of MAO, modified methylaluminoxane or alkylaluminoxane is also used or is used as one of many coactivator components individually.Yet, use aikyiaiurnirsoxan beta normally unnecessary and not too cater to the need because aluminium alkoxide compound is generally more expensive than trialkylaluminium or trialkylboron compound.

In some embodiments, removing is used with the stoichiometry acvator with compound.The typical aluminium or the boryl component that can be used as scavenging agent are by general formula R ^xJZ ₂Expression, wherein J is aluminium or boron, R ^xBe selected from the C1-C20 alkyl and can be identical or different; Each Z is R independently ^xOr different univalent anion parts for example halogen (Cl, Br, I), alkoxy radical (OR ^x) etc.Most preferred aluminium alkynylene comprises triethyl aluminum, diethylaluminum chloride, triisobutyl aluminium, tri-n-octylaluminium, tri-n-hexyl aluminum, trimethylaluminium etc.Preferred boryl thing comprises triethyl-boron.Removing with compound can also be aikyiaiurnirsoxan beta and modified alumoxane, comprises MAO and modified methylaluminoxane.

In an optional embodiment; Alkylaluminoxane compound (for example MAO and modified methylaluminoxane) is with less than 3 milligrams of (mg) aikyiaiurnirsoxan beta/gram olefin feedstocks; Preferably, preferably be present in the reaction zone less than 0.5mg aikyiaiurnirsoxan beta/gram olefin feedstock less than 1mg aikyiaiurnirsoxan beta/gram olefin feedstock.

Supported catalyst

Supported catalyst and/or load catalyst system can be used to prepare PAO.In order to prepare the uniform loading catalyzer, catalyst precursor preferably is dissolved in the solvent through selecting.Term " uniform loading catalyzer " is meant catalyst precursor, acvator and/or activatory catalyzer near being evenly distributed on the accessibility surf zone of carrier, comprises the internal void surface of porous support.The preferred uniform loading catalyzer of some embodiments of supported catalyst; Other embodiment does not show the preferential selection of this kind.

Useful load catalyst system can be meant that effectively prepared catalyzer can be used in heterogeneous method olefin oligomerization or polymerization through the method preparation of any other coordination catalyst systems of useful load.Catalyst precursor, acvator, coactivator (if existence), the solvent that is fit to and carrier can add or side by side add by any order.

Through a kind of method, can be dissolved in suitable solvent for example toluene acvator with solid support material stir 1 minute to 10 hours with the preparation supported catalyst.Total liquor capacity (catalyst solution, activator solution or both) can be greater than the volume of voids of carrier; But some embodiments limit this total liquor capacity and arrive less than forming gel or the required volume (about 90%-400% of volume of voids, preferably approximately 100-200%) of slurry.During this period randomly with this mixture heating up to 30 ℃-200 ℃.Can catalyst precursor be added to solid, if or the solvent that in preceding step, adopt to be fit to, then be in this mixture of solution.Perhaps, also can this mixture be filtered, and the solid of gained is mixed with catalyst precursor solution.Similarly, can mix with this mixture vacuum-drying and with catalyst precursor solution.Stir the catalyst mixture 1 minute-10 hours of gained then, and from this solution filtration load catalyzer and vacuum-drying or evaporate to remove and desolvate.

Perhaps, also can catalyst precursor and acvator be combined in solvent and form solution.Then carrier is added in this solution, and stir the mixture of gained, stirred usually 1 minute-10 hours.Total acvator/catalyst precursor solution volume can arrive less than forming gel or the required volume (about 90%-400% of volume of voids, preferably approximately 100-200%) of slurry but some embodiments limit this total liquor capacity greater than the volume of voids of carrier.After stirring, under vacuum, in 10-16 hour, remove residual solvent at ambient temperature and usually usually; Yet, can use greater or lesser time and temperature.

Supported catalyst precursor under the situation of acvator can also do not had; In this case, with acvator (with randomly, coactivator) add in the liquid phase of slurry process.For example, can the solution of catalyst precursor be mixed with solid support material one about 1 minute-10 hours period.Can from this solution filter the pre-catalyst mixture of gained and under vacuum dry or with evaporation process with except that desolvating.Total catalyst precursor solution volume can arrive less than forming gel or the required volume (about 90%-400% of volume of voids, preferably approximately 100-200%) of slurry but some embodiments limit this total liquor capacity greater than the volume of voids of carrier.

In addition, can use above disclosed any load method two kinds or more kinds of different catalyst precursor are placed on the same vehicle.Likewise, can two kinds or more kinds of acvator or acvator and coactivator be placed on the same vehicle.

The solid particulate carrier that is fit to is made up of polymkeric substance or refractory oxide material usually, separately porous preferably.Any solid support material that has greater than the average particle size particle size of 10 μ m can be used for the present invention.Various embodiments are selected porous carrier materials, for example, and talcum, inorganic oxide, butter (for example magnesium chloride) and resinous support material (for example PS, polyolefine, or polymer complex) or any other organic support material etc.Some embodiments select inorganic oxide material as solid support material, comprise the-2 ,-3 ,-4 ,-5 ,-13 or-14 family's metal or metalloid oxide compounds.Some embodiment selecting catalyst solid support materials are to comprise silicon-dioxide, aluminum oxide, silica-alumina and their mixture.Other inorganic oxide can work individually or with said silicon-dioxide, aluminum oxide or silica-alumina with combining.They are Natural manganese dioxide, titanium oxide, zirconium white etc.Lewis acidity material for example polynite also can serve as carrier with similar clay.In this case, carrier can randomly be held a concurrent post activator component.But also can use additional acvator.Under some situations, also can use the solid carrier of the special family that is commonly referred to MCM-41.MCM-41 is one type of novel unique crystallization carrier and when with second component modification, can be prepared into and has adjustable pore dimension and adjustable acidity.The detailed description of this type material and their modification can be referring to US5, and 264,203.

Can be through many method pre-treatment solid support materials.For example, can the calcination inorganic oxide, chemically try for example aluminium alkynylene or aikyiaiurnirsoxan beta with dehydroxylation, MAO etc. for example, or both handle.

As stated, polymer support also will be fit to according to the present invention, referring to the description in for example WO95/15815 and the U.S. patent 5,427,991.Disclosed method can be used for catalyst compound of the present invention, acvator or catalyst system absorption or be absorbed on the polymer support; Especially if this polymer support is made up of porous particle, or can via be attached on the polymer chain or among functional group's chemistry combine.

The useful catalysts carrier can have 10-700m ²The surface-area of/g, and/or the average particle size particle size of the volume of voids of 0.1-4.0cc/g and/or 10-500 μ m.Some embodiments are selected 50-500m ²The surface-area of/g, and/or the average particle size particle size of the volume of voids of 0.5-3.5cc/g and/or 20-200 μ m.Other embodiment is selected 100-400m ²The surface-area of/g, and/or the average particle size particle size of the volume of voids of 0.8-3.0cc/g and/or 30-100 μ m.Useful carrier has the 10-1000 dust usually, or the 50-500 dust, or the pore dimension of 75-350 dust.Generally with metallocenes and/or metallocenes/acvator binding substances with 10-100 micromole catalyst precursor/gram solid carrier; Or 20-80 micromole catalyst precursor/gram solid carrier; Or the load level of 40-60 micromole catalyst precursor/gram carrier is deposited on the carrier.But also can use greater or lesser value, as long as the total amount of solid catalyst precursor is no more than the volume of voids of carrier.

Metallocenes and/or metallocenes/the acvator binding substances can be used for body by load as required, or slurry polymerization, or other.Many carrying methods are known for the catalyzer in the field of olefin polymerisation (especially aikyiaiurnirsoxan beta-activatory catalyzer), all are suitable for the use among this paper.Referring to, for example, USP 5,057,475 and 5,227,440.The instance of supported ionic catalyst is published among the WO 94/03056.USP 5,643,847 with WO 96/04319A especially effective means has been described.Polymkeric substance and inorganic oxide can serve as carrier, referring to USP 5,422, and 325,5,427,991,5,498,582 and 5,466,649 and International Publication WO93/11172 and WO 94/07928.

In another preferred embodiment, before getting into reactor drum, with metallocenes and/or acvator (have or do not have carrier) and alkylaluminium cpd, preferred trialkyl aluminium compound combines.Preferably, alkylaluminium cpd is by general formula R ₃Al representes; Wherein each R is the C1-C20 alkyl independently; Preferred R base is independently selected from methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, normal-butyl, amyl group, isopentyl, n-pentyl, hexyl, isohexyl, n-hexyl, heptyl, octyl group, iso-octyl, n-octyl, nonyl, different nonyl, n-nonyl, decyl, isodecyl, positive decyl, undecyl, different undecane, n-undecane base, dodecyl, Permethyl 99A. base and dodecyl, preferred isobutyl-, n-octyl, n-hexyl and dodecyl.Preferably, alkylaluminium cpd is selected from triisobutyl aluminium, tri-n-octylaluminium, tri-n-hexyl aluminum and three (dodecyl) aluminium.

Monomer

In a preferred embodiment, catalyst compound described herein is used for making any polymerization of unsaturated monomers or oligomeric.Preferred monomer comprises C ₃-C ₂₄Alkene, preferred C ₃-C ₂₀The terminal olefin of alkene.In some embodiments, preferred monomer comprises linearity, branching or ring-type terminal olefin, preferred C ₃-C ₂₀Terminal olefin, preferred C ₄-C ₁₄Terminal olefin, more preferably C ₈-C ₁₂Terminal olefin.Preferred olefinic monomer for example can be, one or more in 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecylene, 3-methyl-1-butene, 4-methyl-1-pentene and the tetradecene.

In a preferred embodiment, method described herein can be used to prepare homopolymerization oligopolymer or copolymerized oligomer (concerning the present invention and claim thereof, copolymerized oligomer can comprise two kinds, three kinds, four kinds or more kinds of different monomeric unit).The preferred oligopolymer of this paper preparation comprises C ₃-C ₂₀Any above-mentioned monomeric homopolymerization oligopolymer or the copolymerized oligomer of terminal olefin.In a preferred embodiment, oligopolymer is any C ₈-C ₁₂The homopolymerization oligopolymer of terminal olefin.Or in another preferred embodiment, oligopolymer is the homopolymerization oligopolymer of propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecylene or 1-dodecylene.Preferably, oligopolymer is the homopolymerization oligopolymer of 1-octene, 1-nonene, 1-decene.In another embodiment, oligopolymer is to comprise from C ₃-C ₂₀Two or three or the more kinds of monomeric copolymerized oligomer selected in the terminal olefin.About using mixing raw material to prepare the more information of PAO, see also PCT US2006/027591, especially 16 pages of [044] sections of the 8th page of [0029] Duan Zhidi.

The terminal olefin that is used for preparing PAO includes but not limited to C ₃-C ₂₄Terminal olefin, wherein C ₃-C ₁₄Terminal olefin, for example propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecylene, 1-dodecylene, 1-tridecylene and tetradecene are preferred.One group of preferred poly-alpha olefins is Vestolen PP 7052, poly-1-butylene, gather-the 1-amylene, gather-the 1-hexene, gather the 1-heptene, gather-the 1-octene, gather-the 1-nonene, gather-1-decene, gather-the 1-undecylene, gather-the 1-dodecylene, gather-1-tridecylene and gathering-tetradecene, but at C ₁₂-C ₁₈The dimer of the more higher alkene in the scope also may reside in the final product.Useful PAO preferably is by C in one embodiment ₃-C ₂₀The carbon number that terminal olefin is processed is from C ₂₀Beginning and higher oligopolymer or polymkeric substance are by C in another embodiment ₃-C ₁₄The carbon number that terminal olefin is processed is from C ₂₄Beginning and higher oligopolymer or polymkeric substance.The alkene that is fit to comprises propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecylene and 1-dodecylene, 1-tridecylene, tetradecene.In one embodiment, alkene is propylene, and polymer product is pentamer and the higher oligomer or the mixture of polymers of propylene.In another embodiment, alkene is 1-butylene, and PAO is the pentamer of 1-butylene and the mixture of higher oligomer.In another embodiment, alkene is the 1-amylene, and PAO is the tetramer and the pentamer of 1-amylene and the mixture of high polymer more.In another embodiment, alkene is the 1-hexene, and PAO is the mixture of the tetramer and the pentamer (with high polymer more) of 1-hexene.In another embodiment, alkene is the 1-heptene, and PAO is tripolymer and the tetramer of 1-heptene and the mixture of high polymer more.In another embodiment, alkene is the 1-octene, and PAO is tripolymer and the tetramer of 1-octene and the mixture of high polymer more.In another embodiment, alkene is the 1-nonene, and PAO is tripolymer and the tetramer of 1-nonene and the mixture of high polymer more.In another embodiment, alkene is 1-decene, and PAO is dimer, tripolymer and the tetramer of 1-decene and the mixture of high polymer more.In another embodiment, alkene is 1 one undecylenes, and PAO is tripolymer and the tetramer of 1-undecylene and the mixture of high polymer more.In another embodiment, alkene is the 1-dodecylene, and PAO is dimer and the tripolymer of 1-dodecylene and the mixture of high polymer more.

In another embodiment, monomer comprises propylene and/or butylene, or propylene and/or butylene and another kind of terminal olefin or other alkene (are selected from C ₅-C ₂₀Terminal olefin) combination.When using C ₁₄-C ₂₀Big linear alpha-alkene during as raw material, preferably by comprising other C ₃-C ₁₂The form of mixtures of linear alpha-alkene use these big alkene.Polymkeric substance or the oligopolymer processed by these big terminal olefins individually have high VI usually, but they also have high crystallization tendency, and the fluidic low-temperature fluidity is worsened.Common more preferably that these are big terminal olefin and C ₃-C ₁₂Less alpha-olefin copolymer close.Not crystallization so easily or solidify of multipolymer.Therefore, multipolymer has excellent low-temperature fluidity, high VI and other good lubricating property usually.

In a preferred embodiment, PAO comprises two kinds or more kinds of monomer, or three kinds or more kinds of monomer, or four kinds or more kinds of monomer, or five kinds or more kinds of monomer.For example, C ₃, C ₄, C ₆, C ₁₂-terminal olefin mixture, C ₃, C ₁₂-terminal olefin mixture, C ₃, C ₁₂, C ₁₄-terminal olefin mixture, C ₄, C ₁₂-terminal olefin mixture, C ₄, C ₁₂, C ₁₄-terminal olefin mixture, C ₄, C ₁₄-terminal olefin mixture, C ₆, C ₁₂-terminal olefin mixture, C ₆, C ₁₂, C ₁₄-terminal olefin mixture, C ₅, C ₁₃, C ₁₄-terminal olefin mixture, C ₆, C ₁₀, C ₁₄-terminal olefin mixture, C ₆, C ₈, C ₁₂-terminal olefin mixture, C ₈, C ₁₀, C ₁₂-linear alpha-alkene mixture or C ₆, C ₇, C ₈, C ₉, C ₁₀, C ₁₁, C ₁₂, C ₁₃, C ₁₄-linear alpha-alkene mixture or C ₄, C ₆, C ₈, C ₁₀, C ₁₂, C ₁₄, C ₁₆, C ₁₈-linear alpha-alkene mixture can be used as raw material.

In an optional embodiment, PAO comprises the ethene less than 40wt%.For containing C ₃-C ₆The multipolymer of terminal olefin, containing some ethene sometimes is desirable as one of component.In this case, there is 1-40wt% ethene in the preferred feedstock.In an alternate embodiment, raw material comprises 40wt% ethene and 60wt%1-butylene, or 30wt% ethene and 70wt%1-butylene; Or 20wt% ethene and 80wt%1-butylene, 10wt% ethene and 90wt%1-butylene, or 5wt% ethene and 95wt%1-butylene; Or 40wt% ethene and 60wt% propylene, or 30wt% ethene and 70wt% propylene, or 20wt% ethene and 80wt% propylene; 10wt% ethene and 90wt% propylene, 5wt% ethene and 95wt% propylene.For containing C ₇-C ₁₈The multipolymer of terminal olefin preferably contains the ethene of less amount, and 0-20wt% ethene is preferred.

In a preferred embodiment; Any PAO described herein can comprise at least 60wt%3-24 carbon atom and 0.5-40wt% ethene, wherein is present at least 80% of ethene in this poly-alpha olefins and is present among 1-35 carbon or the run still less by carbon-13NMR measurement.Preferably, any PAO described herein can comprise at least 70wt%5-24 carbon atom (preferred 80wt% at least, preferably 85wt% at least; Preferably 90wt%, preferably at least 95 moles of % at least) and 0.5-40wt% ethene, wherein be present at least 80% (preferably at least 85% of ethene in the poly-alpha olefins; Preferably at least 90%, preferably at least 95%, preferably at least 98%; Preferred 100%) is present in 1-35 carbon (preferred 1-30, preferred 1-25, preferred 1-20 by carbon-13NMR measurement; Preferred 1-15, preferred 1-10, preferred 1-5) run in.In addition, the type of the run of ethene sequence is random, does not contain a large amount of very long Polyethylene Chain in the lube products.

The employed C of this paper ₃-C ₂₀Terminal olefin can directly be prepared by the ethene growing method through some commercial production method practices, or they can be prepared by following method: from CO/H ₂The fischer-tropsch hydrocarbon of metathesis synthetic gas is synthetic, or with ethene transposition nonterminal olefin, or oil at high temperature or f-t synthetic wax cracking, or any other terminal olefin synthetic route.Preferred raw material of the present invention is 10wt% terminal olefin at least preferably; Preferred 20wt% terminal olefin at least; At least 50wt% terminal olefin; At least 70wt% terminal olefin, 80wt% terminal olefin (preferred linear alpha-alkene), 90wt% terminal olefin (preferred linear alpha-alkene) or 100% terminal olefin (preferred linear alpha-alkene) at least at least.

The alkene that is used for raw material can be very rare.For example, the raw material that is fit to that derives from wax destructive distillation reaction comprises the 10-90wt% terminal olefin and can be used for the present invention.In addition, the feed stream that derives from the fischer-tropsch compound method provides and can be the terminal olefin content of 2-50wt%.They all are suitable as raw material olefin.Yet the mixture that contains terminal olefin also can be as the raw material among the present invention, and is also like this even other component is nonterminal olefin, branched olefin, paraffinic hydrocarbons, cyclic alkane, aromatic substance (for example toluene and/or YLENE).These components have dilution effect and think that the polymerization to terminal olefin does not have tangible disadvantageous effect.In other words, method described herein can be optionally transforms the terminal olefin in the mixture and let other component be unreacted.This technology can be used for from mixture, isolating terminal olefin through optionally making the reaction of terminal olefin and polymerization or oligomerisation catalyst system, makes the isolating needs of all the other components in terminal olefin and the mixing raw material materials flow thereby fully get rid of.This is favourable economically in the method for utilizing the synthetic olefin product materials flow of fischer-tropsch for example, and this product materials flow comprises terminal olefin, nonterminal olefin, branched olefin and corresponding alkane.This kind mixture can and can optionally react with terminal olefin according to oligomeric technology use described herein.Need the not emanate separating step of this terminal olefin.

Another instance of the application of this method relates to the terminal olefin that produces through with ethene transposition (metathesis) nonterminal olefin, and they can comprise some nonterminal olefins.This mixed olefin feedstock can react as in the polymeric/oligomeric method of the present invention, and said method optionally changes into lube products with terminal olefin.Therefore, it is synthetic this terminal olefin to be used for base-material, and will not separate with the hydrocarbon of nonterminal olefin or other type by this terminal olefin.Significant improvement can brought aspect the process economics situation like this.This raw material olefin can be the C that comprises by other linear alpha-alkene prepared ₄-C ₂₀The alkene mixture of terminal olefin; As by Marcel Dekker, the 3rd chapter " Routes to Alpha-Olefins " of the books Alpha OlefinsApplications Handbook that is compiled by G.R.La ppin and J.D.Sauer that Inc.N.Y.1989 publishes is said.

In a preferred embodiment; The PAO of this paper preparation can comprise the monomer with side chain; Said side chain and α-unsaturated part is at a distance of at least 2, preferably at least 3 carbon, for example 4-methyl isophthalic acid-decene, 4-ethyl-1-decene or 4-methyl isophthalic acid-hexene, 4-methyl-1-pentene etc.These alkene may reside in the linear alpha-alkene that derives from method of manufacture or they can intentionally add.The terminal olefin of branching has improved low-temperature performance with the multipolymer of complete linear alpha-alkene slightly.

In one embodiment, when using 1-butylene as raw material or when containing one of the raw material olefin of other terminal olefin, 1-butylene can be the pure 1-butylene by any business method preparation.Perhaps, 1-butylene can be used as mixed C ₄One of component in the materials flow, this mixed C ₄Materials flow can easily obtain from petrochemical complex or refinery operations.USP 5,859.159A have this type of C ₄Materials flow, for example BB materials flow (B-B materials flow), or the more detailed description of raffinate 1 or raffinate 2 materials flows is discussed.These mixed C ₄Materials flow can be from the light naphtha steam cracking among the ethylene/propene preparing methods, from wherein having removed the MTBE method of most of iso-butylene, from preparation C ₄The FCC-operation of materials flow, and/or from other refining of petroleum method acquisition.When using these mixed C ₄Materials flow is during as raw material, and only 1-butylene will react away owing to this catalyst system.Other C ₄Component (cis-, trans-2-butene, iso-butylene, normal butane and Trimethylmethane) will only be served as thinner, and can or not disturb polymerizing catalyst with the polymerizing catalyst reaction.These mixed C ₄Materials flow be 1-butylene valuable and economy the source with the preparation poly-1-butylene, with ethene or other C ₅-C ₂₀The multipolymer of high alpha-olefin.

In another embodiment, when using propylene, or during as one of raw material olefin that contains other terminal olefin, can use the pure propylene that derives from the chemical plant as raw material.Perhaps, can use mixing propylene and propane materials flow (PP materials flow) with the same manner.This propylene is with optionally polymerization and this propane will serve as thinner and can not participate in reaction.This PP materials flow can comprise propylene by any amount among the 10wt%-95wt%.In another embodiment, PP and C ₄The mixture of materials flow can be as one of starting olefin or starting olefin raw material.

The polymeric/oligomeric method

The many polymeric/oligomeric methods and the type of reactor that are used for metallocenes-catalytic polymerization or oligomeric for example solution, slurry and mass polymerization or oligomerization process can be used for the present invention.In some embodiments, if use solid or supported catalyst, slurry or continuous fixed bed or piston flow method are fit to.In a preferred embodiment, solution phase, body mutually or slurry mutually in, monomer is contacted with acvator and/or coactivator/scavenging agent with Metallocenic compound.In a preferred embodiment, the temperature in the employed any reactor drum of this paper is-10 ℃ to 250 ℃, preferred 10 ℃-220 ℃, and preferred 10 ℃-180 ℃, preferred 10 ℃-170 ℃.In a preferred embodiment, the pressure in the employed any reactor drum of this paper is the 0.1-100 normal atmosphere, preferred 0.5-75 normal atmosphere, preferred 1-50 normal atmosphere.In another embodiment, make monomer (one or more), metallocenes and acvator contact 1 minute-30 hours, more preferably 5 minutes-16 hours, more preferably residence time of 10 minutes-10 hours.In another embodiment, solvent or thinner are present in the reactor drum and are preferably selected from butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecyl, tridecane, the tetradecane, pentadecane, n-Hexadecane, toluene, o-Xylol, m-xylene, p-Xylol, xylol, ethylbenzene, isopropyl benzene and n-butylbenzene; Preferred toluene and/or YLENE and/or ethylbenzene, and n-paraffin (for example can be from Houston, the Norpar that the ExxonMobil Chemical Company of Texas obtains ^TMSolvent) or isoparaffic solvent (can be from Houston, the Isopar that the ExxonMobil ChemicalCompany of Texas obtains ^TMSolvent).Usually with these solvents of method pre-treatment or thinner (for example removing polar impurity) as raw material olefin.These solvents are not generally initiatively participated in polyreaction.Yet they provide the thinner effect for polyreaction.The solvent of high density has the effect that reduces product viscosity usually.The concentration of solvent is generally 0wt%-80wt%, or 10wt%-60wt%, in another replacement scheme, is 20wt%-40wt%.For commercial prodn, preferably use the least possible solvent.

Usually, in the method for the invention, one or more transistion metal compounds, one or more acvators, coactivator or scavenging agent are contacted with preparation polymkeric substance or oligopolymer with one or more monomers.These catalyzer can be loading type and will especially be used in known slurry, solution or the body operator scheme of carrying out in single, the serial or parallel connection reactor drum like this.If catalyzer, acvator or coactivator are soluble compounds, then reaction can be undertaken by the solution pattern.Even one of component is when the reaction beginning or during reaction or in the last stages of reacting not exclusively dissolve in reaction medium or material solution, solution or slurry-type operation are still applicable.Under any circumstance; The catalyst component that will be dissolved or suspended in down in solvent (for example toluene or other aromatic solvent that can suit to obtain, or aliphatic solvents) or the materials flow of raw material terminal olefin at inert atmosphere (normally nitrogen or argon gas cover atmosphere) infeeds reactor drum to allow polymerization or oligomeric generation.This polymerization or oligomeric can the operation by intermittent mode are wherein added to whole components in the reactor drum and are allowed to be reacted in advance the transforming degree (part transforms or transforms fully) of design.Subsequently,, for example be exposed in air or the water through any possible means, or through adding alcohol or contain the solvent of passivator, or through adding solid adsorbent with catalyst deactivation.Can maybe under the situation of using solid adsorbent, pass through the filtering separation catalyst component through conventional solution washing then.Polymerization or oligomeric also can be undertaken by semi continuous operation, wherein raw material and catalyst system component is added in the reactor drum to keep the constant ratio of catalyst system component and raw material olefin (one or more) continuously and side by side.When adding whole raw materials and catalyst component, allow reaction to proceed to predefined phase.Use the same procedure that periodical operation is described reaction to be stopped then through catalyst deactivation.Polymerization or oligomeric also can be undertaken by operate continuously, wherein raw material and catalyst system component is added in the reactor drum to keep the constant ratio of catalyst system and raw material olefin continuously and side by side.Discharge reaction product continuously from reactor drum, as in typical continuous stirred tank reactor(CSTR) (CSTR) operation.Through the residence time of predetermined transforming degree and catalyst concn control reactant.Usually in independent reactor drum, press and the product quencher of mode like other class of operation then discharge.In a preferred embodiment, any method for preparing PAO described herein is a continuation method.Preferably, this continuation method may further comprise the steps: a) will comprise one or more C of at least 10 moles of % ₃-C ₂₄The feed stream of terminal olefin is introduced reactor drum continuously, b) Metallocenic compound and acvator is introduced this reactor drum continuously, and c) discharge poly-alpha olefins continuously from this reactor drum.In another embodiment, said continuation method may further comprise the steps: in reactor drum, keep 0.1-300psi (2068kPa), preferred 0.5-200psi (1379kPa); Preferred 1.0-150psi (1034kPa); Preferred 2.0-100psi (690kPa), preferred 3-50psi (345kPa) or littler, preferred 5-25psi (173kPa); The hydrogen partial pressure of preferred 1-10psi (69kPa) is based on the total pressure of reactor drum.Perhaps, hydrogen (if exist) is by weight with 1-30,000ppm, preferred 3; 000ppm or still less, preferred 150ppm or still less, preferred 750ppm or still less, preferred 500ppm or still less; Preferred 250ppm or still less, preferred 100ppm or still less, preferred 50ppm or still less; Preferred 25ppm or still less, preferred 10ppm or still less, preferred 5ppm or still less be present in the reactor drum.During oligomeric or polyreaction, consumption or not consuming hydrogen hardly.Therefore, can be after reaction is accomplished with excessive hydrogen gas recycle.

In another embodiment, if ethene is present in the reactor drum, then ethylene partial pressure is maintained at less than 1000psi usually, or preferably less than 500psi, or preferably less than 200psi, or preferably less than 50psi, or preferably less than 30psi, or preferably less than 10psi.In another embodiment, if propylene, PP materials flow, C ₄Materials flow, 1-butylene or 1-amylene are present in the reactor drum, and then total dividing potential drop of these components is maintained at less than 1000psi usually, or preferably less than 500psi; Or preferably less than 200psi; Or preferably less than 50psi, or preferably less than 30psi, or preferably less than 10psi.As discussed above, owing to there is other rare gas element, for example nitrogen or argon gas are so total reactor pressure can be higher than total dividing potential drop of gaseous feed.

Preferred reactor size be 2ml with more than.Usually, preferably use volume greater than one liter reactor drum for commercial prodn.Production facility can have single reactor drum or serial or parallel connection or by several reactor drums of this two kinds of arrangements so that productivity, product property and group method maximizing efficiency.Usually reactor drum and relevant equipment are carried out pre-treatment to guarantee good speed of reaction and catalyst performance.Reaction is carried out under inert atmosphere usually, and wherein catalyst system can be with normally any catalyst passivating agent or the poisonous substance of polar oxygen, nitrogen, sulphur or acetylenic compound contact with feed composition.

One or more reactor drums of serial or parallel connection can be used for the present invention.Solution or slurry that transistion metal compound, acvator and the coactivator when requiring can be used as in solvent or terminal olefin feed stream are transported to reactor drum (just online activation before reactor drum) individually, or activation and give reactor drum as activated solution or shurry pump in advance.Polymeric/oligomeric carries out in single reactor drum operation; Wherein with monomer; Or several monomers, catalyzer/acvator/coactivator, optional scavenging agent adds in the single reactor drum with optional properties-correcting agent continuously; Or in the tandem reactor operation, carry out, wherein said components is added in each in two or more reactor drums that are connected in series.Can catalyst component be added in placed in-line first reactor drum.Also can catalyst component be added in all reactor drums, wherein a kind of component is added in first reactor drum, and other component is added in other reactor drum.In a preferred embodiment, in the presence of alkene in reactor drum with the pre-catalyst activation.In another embodiment; Use alkyllithium reagent; Pre-treatment pre-catalysts such as triisobutyl aluminium, tri-n-hexyl aluminum and/or the tri-n-octylaluminium dichloride form of metallocenes for example particularly; Then add the reactor drum that contains other catalyst component and raw material olefin, or follow with the preparatory activation of other catalyst component, then this complete activatory catalyzer is infeeded the reactor drum that contains raw material olefin to obtain complete activatory catalyzer.In another replacement scheme, the pre-catalyst metallocenes is mixed with acvator and/or coactivator, then with this deactivated catalyst, add reactor drum together with the raw material olefin materials flow that contains some scavenging agents or coactivator.In another replacement scheme, all or part of coactivator and the merging of raw material olefin premix are added reactor drum simultaneously with luxuriant other catalyst solution with acvator and/or coactivator of containing metal.

In some embodiments; With a small amount of toxic removal agent, for example trialkylaluminium (trimethylaluminium, triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium) or MAO add in the raw material olefin materials flow with further improvement catalyst activity.In a preferred embodiment, let monomer be introduced into before the reactor drum and alkylaluminium cpd, preferred trialkyl aluminium compound contact.In another preferred embodiment, before getting into reactor drum, with metallocenes and/or acvator and alkylaluminium cpd, preferred trialkyl aluminium compound combines.Preferably, alkylaluminium cpd is by general formula R ₃Al representes; Wherein each R is the C1-C20 alkyl independently; Preferred R base is independently selected from methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, normal-butyl, amyl group, isopentyl, n-pentyl, hexyl, isohexyl, n-hexyl, heptyl, octyl group, iso-octyl, n-octyl, nonyl, different nonyl, n-nonyl, decyl, isodecyl, positive decyl, undecyl, different undecyl, n-undecane base, dodecyl, Permethyl 99A. base and dodecyl, preferred isobutyl-, n-octyl, n-hexyl and dodecyl.Preferably, alkylaluminium cpd is selected from triisobutyl aluminium, tri-n-octylaluminium, tri-n-hexyl aluminum and three (dodecyl) aluminium.

In an embodiment of any method described herein, handle raw material olefin and/or solvent to remove catalyzer poison, for example superoxide, contain oxygen or organic compounds containing nitrogen or acetylenic compound.If through solvent or sweeping gas (normally nitrogen) purifying of typical feed purification technology with the raw material olefin use.Under the situation of liquid starting material, usually under vacuum with this liquid degassing 1-60 minute to remove any dissolved gases.Perhaps, through the commercial absorbent bed that passes activated molecular sieve (3A, 4A, 5A or 13X molecular sieve) or process with solid by activated alumina, silicon-dioxide or other purifying with raw material olefin, solvent or sweeping gas purifying.These purifying can be removed trace water, alcohol, nitrogen compound or any other polar impurity with solid.Perhaps, remove solid catalyst (de-ox catalyzer) with raw material olefin, solvent or sweeping gas purifying through passing the activatory oxygenatedchemicals, this solid catalyst comprises copper, chromium and/or other MOX that is low-oxidation-state usually.USP 6987152 has been described the instance of feed purification.Depend on raw materials quality and desired raw material purity, above-mentioned one or both or all method can be used for obtaining optimum with combining.

Usually, in the present invention, this kind processing is compared with the system that does not have this kind processing raising catalyst productivity 20%-1000% or more at least.This improve one's methods also comprise raw material olefin special processing to remove catalyzer poison, superoxide for example contains organic cpds or other trace impurity of oxygen, sulphur or nitrogen.This processing can improve catalyst productivity (usually more than 10 times) significantly.Preferably, let raw material olefin and molecular sieve, activated alumina, silica gel, deoxidation catalyst and/or purifying with clay contacting with containing in the raw material heteroatomic compound reduce, preferably be reduced to less than 50ppm, preferably arrive less than 10ppm.

Catalyst composition can use individually, or can mix with other known polymerizing catalyst with preparation polymkeric substance or oligopolymer blend.Monomer and selection of catalysts allow polymkeric substance or oligopolymer blend be prepared in those similar conditions of using independent catalyzer under.Polymkeric substance with MWD of raising can be obtained by the polymkeric substance that the spent mixed catalyst system is processed and therefore can realize.The fluid that preparation has the MWD of raising is favourable sometimes, and the MWD of this raising can improve the fluid blended characteristic.Mixed catalyst can comprise two kinds or more kinds of catalyst precursor and/or two kinds or more kinds of acvator.

Usually, when using metalloscene catalyst, the pre-treatment of raw material olefin, solvent, thinner after and after maintenance catalyst component materials flow (one or more) and reactor drum preventive measures free from foreign meter, reaction will be carried out well.In some embodiments, when using metalloscene catalyst, especially when they are fixed on the carrier, complete catalyst system will comprise one or more removings in addition and use compound.At this, term " is removed with compound " and is meant the compound of from reaction environment, removing polar impurity.These impurity influence catalyst activity and stability unfriendly.Typically, before reactive component being introduced reaction vessel, use purification step usually.But do not use some remove with the situation of compound under this type of step will seldom allow polymerization or oligomeric.Normally, polymerization method will use a small amount of removing with compound (for example above-mentioned those) at least.

Typically, removing with compound will be organometallic compound, and for example U.S. Patent number 5,153,157,5,241,025 with the 13rd family's organometallic compound of WO-A-91/09882, WO-A-94/03506, WO-A-93/14132 and WO 95/07941.Exemplary compounds comprises triethyl aluminum, boron triethyl, triisobutyl aluminium, diisobutylaluminium hydride, MAO, isobutyl aluminium alkoxide and tri-n-octylaluminium.Have substituent those the at utmost unfavorable interactions of minimizing and active catalyst usually of the linear alkyl of huge or C6-C20 that is connected with metal or metalloid center.Instance comprises triethyl aluminum, but more preferably, huge compound is triisobutyl aluminium, three different prenyl aluminium and long-chain linear alkyl-substituted aluminum compound for example, for example tri-n-hexyl aluminum, tri-n-octylaluminium or three (dodecyl) aluminium.Aikyiaiurnirsoxan beta also can together be added by removing amount and other acvator, for example MAO, [Me ₂HNPh] ⁺[B (pfp) ₄] ^-Or B (pfp) ₃Wherein pfp is perfluorophenyl (C ₆F ₅), Me is a methyl, Ph is a phenyl.

PAO described herein also can prepare by the homogeneous solution method.Usually, this method is included in polymerization in the flow reactor or oligomeric, wherein with the initial monomers of polymkeric substance that forms and supply and catalystic material stirring with minimizing or avoid concentration or thermograde.Temperature in the reactor drum is controlled general following acquisition: with the reactor cooling of the reactant cold side materials flow of passing through reactor jacket or spiral coil cooling tube or cooling reactor content; From cooling; Pre-cooled raw material, liquid medium (thinner, monomer or solvent) evaporation or all above-mentioned combinations come equilibrium polymerization heat.Can also use the adiabatic reactor that adopts pre-cooled raw material.Temperature of reactor depends on employed catalyzer and required product.Higher temperature tends to produce lower molecular weight, and more low temperature tends to produce more HMW, yet this is not a hard-and-fast rule.Generally speaking, temperature of reactor preferably can be at-10 ℃ to 250 ℃, preferred 10 ℃-220 ℃, preferred 10 ℃-180 ℃, change between preferred 10 ℃-170 ℃.

Usually, it is significant reaction temperature as far as possible strictly being controlled in the pre-determined range.In order to prepare fluid with narrow molecular weight distributions, consequently promote the highest possible shear stability, control reaction temperature is useful in whole reactor, to obtain having minimum change in minimum temperature fluctuation and the reaction times process.If serial or parallel connection ground uses a plurality of reactor drums, then maintain the temperature in the predetermined range constant so that any broadening of MWD minimizes is useful.In order to prepare fluid with wide molecular weight distribution, can the conditioned reaction temperature, swingproflle or fluctuation; Or as in serial operation, second temperature of reactor preferably is higher than first temperature of reactor.In the parallel reactor operation, the temperature of two reactor drums is independently.Perhaps, also can be through using the intentional broadening MWD of polytype metalloscene catalyst.

Pressure in the employed any reactor drum of this paper can be at about 0.1 normal atmosphere-100 normal atmosphere (1.5psi-1500psi), and preferred 0.5 crust atm-75atm (8psi-1125psi) most preferably changes between the 1.0-50atm (15psi-750psi).Reaction can be under nitrogen atmosphere, or some hydrogen is arranged or other volatile constituent is arranged sometimes, for example propylene, PP materials flow, 1-butylene, C ₄The branch of materials flow, 1-amylene etc. is depressed and is carried out.Sometimes small quantity of hydrogen is added in the reactor drum to improve catalyst productivity.The amount of hydrogen preferably remains on the sort of level of improving catalyst productivity, does not cause alkene but be not high enough to, and particularly any hydrogenation of raw material terminal olefin is very disadvantageous because terminal olefin changes into paraffinic hydrocarbons to the efficient of this method.It is lower that the amount of hydrogen partial pressure preferably keeps, less than 300psi, preferably less than 100psi, preferably less than 50psi, preferably less than 25psi, preferably less than 10psi.In the especially preferred embodiment in any method described herein, the concentration of hydrogen is less than 30 in the reactor drum, and 000ppm is preferably less than 5; 000ppm, preferably less than 1,000ppm is preferably less than 500ppm; Preferably less than 100ppm, preferably less than 50ppm, preferably less than 10ppm.

Reaction times or reactor residence time depend on the amount and the required level of conversion of employed catalyst type, employed catalyzer usually.Different metallic is luxuriant to have different activity.Usually, higher alkyl replacement degree is improved catalyst productivity on the cyclopentadienyl rings.Catalyzer for example dichloro two (1,2-dimethyl-cyclopentadienyl moiety) closes zirconium, and dichloro two (1,3-dimethyl-cyclopentadienyl moiety) closes zirconium, and dichloro two (1-methyl-3-n-butyl cyclopentadienyl) closes zirconium; Dichloro two (1-methyl-3-n-propyl cyclopentadienyl moiety) closes zirconium, and dichloro two (1-ethyl-3-n-butyl cyclopentadienyl) closes zirconium, and dichloro two (1-methyl-3-n-hexyl cyclopentadienyl moiety) closes zirconium, dichloro two (1; 2-diethylammonium cyclopentadienyl moiety) close zirconium, dichloro two (1,3-diethylammonium cyclopentadienyl moiety) closes zirconium, dichloro two (1; 2,3,4-tetramethyl-ring pentadienyl) closes zirconium or dichloro two (1,2; 4-trimethylammonium cyclopentadienyl moiety) close zirconium, or dichloro two (1,2,3-trimethylammonium cyclopentadienyl moiety) closes zirconium; Dichloro (1,2,3,4-tetramethyl-ring pentadienyl) (1; 3-dimethyl-cyclopentadienyl moiety) closes zirconium or dichloro (1,2,4-trimethylammonium cyclopentadienyl moiety) (1,3-dimethyl-cyclopentadienyl moiety) and close zirconium; Or dichloro two (indenyls) closes zirconium, or dichloro two (1-methyl indenyl) closes zirconium, or dichloro two (2-methyl indenyl) closes zirconium, or dichloro two (1; 2-dimethyl-indenyl) close zirconium, or dichloro two (4-methyl indenyls) closes zirconium, or dichloro two (4,7-dimethyl-indenyl) closes zirconium or dichloro two (tetrahydro indenyl) closes zirconium; Dichloro two (2-methyl-tetrahydro indenyls) closes zirconium, or dichloro two (1,2-dimethyl--tetrahydro indenyl) closes zirconium, or dichloro two (1-methyl-tetrahydro indenyl) closes zirconium; Or dichloro two (4-methyl-tetrahydro indenyls) closes zirconium, and dichloro two (4,7-dimethyl--tetrahydro indenyl) closes zirconium, or their dialkyl group analogue is compared with unsubstituted metallocenes and had desirable high productivity and stability.Usually, the amount of employed catalyst component is conclusive.High catalyzer tonburden often produces high the conversion in the short reaction times.Yet high catalyzer usage quantity makes that the preparation method is uneconomical and is difficult to control response heat and control reaction temperature.Therefore, select to have the catalyzer of maximum catalyst productivity so that the amount minimum of the amount of required metallocenes and acvator is useful.When catalyst system is that metallocenes adds Lewis acid or ionic promotor when (containing the NCA component), employed metallocenes typically is 0.01 microgram-500 microgram (or 0.5 milligram) metallocene components/gram terminal olefin raw material.Usually, preferred range is 0.1 microgram-100 microgram metallocene components/gram terminal olefin raw material.In addition, the mol ratio of NCA acvator and metallocenes is 0.1-10, preferred 0.5-5, preferred 0.5-3.If use the coactivator of alkylaluminium cpd, then the mol ratio of Al and metallocenes is 1-1000, preferred 2-500, preferred 4-400.

Usually preferably in the shortest possible reaction times, reach the highest possible transformation efficiency (near 100%) of raw material terminal olefin.Yet in the CSTR operation, the operation reaction is favourable sometimes under optimal conversion, and this optimal conversion is less than 100% transformation efficiency.Also exist part to transform to be more to cater to the need or occasion that the narrowest possible MWD of product is hoped, because part transforms the broadening that can avoid MWD.If reaction proceeds to less than 100% of terminal olefin and transforms, then unreacted parent material improves total method efficient being recycled with other product and solvents/diluents after separating.

The desirable residence time of any method described herein is between 1 minute-30 hours, and more preferably 5 minutes-16 hours, more preferably 10 minutes-10 hours.

In these methods each also can be by single reactor drum, and parallel connection or tandem reactor structure use.Liquid processes comprises to be tied up to olefinic monomer and above-mentioned catalyst body to contact in suitable thinner or the solvent and allows said monomer reaction to be enough to produce the time of required polymkeric substance or oligopolymer.Aliphatic series and aromatic hydrocarbon solvent all are fit to, and aromatic substance for example toluene, YLENE, ethylbenzene, propylbenzene, cumene, tert.-butylbenzene is fit to.Alkane, for example hexane, heptane, pentane, iso-pentane and octane, Norpar or Isopar solvent (deriving from Houston, the ExxonMobil Chemical Company of Texas) also are fit to.Usually, toluene is suitable for the catalyst-solvent component most.Norpar, Isopar or hexane are preferably as reaction diluent.Toluene and Norpar, or the mixture of toluene and Isopar is often as thinner or solvent.Simplify and high reactor efficiency for method, preferably add solvent or thinner as few as possible in reactor drum.Sometimes for the high viscosity fluid production under the low temperature, add solvent or thinner to promote reaction heat transfer, stirring, product processing, filtration etc.Usually, in reactor drum, add,,,, preferably do not add solvent in reactor system preferably less than 10wt% preferably less than 20wt% preferably less than 30wt% less than 50wt% additional solvent or thinner.Reaction system has on a small quantity from solvent or thinner that catalyzer, acvator or coactivator/scavenging agent solution brings usually.

This method can be in continuous stirred tank reactor(CSTR) or plug flow reactor, or the serial or parallel connection operation more than carrying out in the reactor drum.These reactor drums can have or can not have inner cooling and raw material monomer, and can be that refrigerated maybe can not have freezing.Referring to USP 5,705, the general disclosure of 577 pairs of general technology conditions.

When solid supported is used to transform, slurry polymerization/oligomerization process generally with similar temperature, pressure and the residence time scope described before this in operate.Slurry polymerization or oligomeric in, add the suspension-s of solid catalyst, promotor, monomer and comonomer.Take out the suspension-s that this comprises thinner off and on or continuously from reactor drum.Through filtration, spinning or sedimentation catalyzer is separated with product then.Then then with the fluid distillation desolvate to remove, any unreacted component and lighter products.Can with the part of solvent and unreacted component or light component or all recycling so that re-use.

If use the non-loading type solution catalyst, then after reaction is accomplished maybe when from reactor drum discharge product (for example among CSTR), that product still can comprise is soluble, suspension or blended catalyst component.Preferably with these component passivation or remove.Any conventional catalyst passivating method or solution washing method (aqueous wash method) can be used for removing catalyst component.Usually, make the reaction passivation through adding stoichiometry or excessive air, moisture, alcohol, Virahol etc.Then with dilute sodium hydroxide or with this mixture of water washing to remove catalyst component.This residual organic layer distillation is desolvated to remove, this solvent can recycling so that re-use.Any C can be further removed in this distillation ₁₈Lower lightweight reaction product.These light component can be used for further reaction as thinner.Perhaps they can be as the olefinic starting material of other chemosynthesis because these light olefin product have the unsaturated part of vinylidene base, be very suitable for further functionalized with change into high performance fluids.Perhaps, these light olefin product can be hydrogenated to be used as the high quality paraffin solvents.

Polymerization in the presence of unusual small quantity of hydrogen or oligomericly also help providing polymkeric substance or oligopolymer with high unsaturated double-bond degree.These pairs key can easily change into the functionalized fluid with multiple performance characteristic.Can this polymkeric substance and maleic anhydride be reacted with acquisition PAO-succinyl oxide referring to the preparation of ashless dispersant greater than the instance that 300 polymkeric substance transforms these MW, it and amine, alcohol, Aethoxy Sklerol are reacted and change into dispersion agent.The instance of this kind conversion can be referring to the works " LubricantAdditives:Chemistry and Application " by Leslie R.Rudnick chief editor, Marcel Dekker, Inc.2003,143-170 page or leaf.

In another embodiment, any poly-alpha olefins of this paper preparation is a hydrogenant.Especially, preferably handle poly-alpha olefins as stated and be reduced to less than 600ppm, contact with hydrogenation catalyst with the preparation bromine number less than 2 poly-alpha olefins with hydrogen then will contain heteroatomic compound.In a preferred embodiment, this treated poly-alpha olefins comprises 100ppm and contains heteroatomic compound or still less, and preferred 10ppm contains heteroatomic compound or still less.(containing heteroatomic compound is the compound that also comprises at least a atom beyond de-carbon and the hydrogen).Preferably; Hydrogenation catalyst is selected from the 7th, 8,9 and 10 family's metals of load; Preferably, hydrogenation catalyst is selected among Ni, Pd, Pt, Co, Rh, Fe, Ru, Os, Cr, Mo and the W one or more, and they load on silicon-dioxide, aluminum oxide, clay, titanium oxide, zirconium white or mixed-metal oxide support or mesopore material (being commonly referred to as MCM-41 material or associated materials) is gone up (like USP 5; Described in 264,203).Preferred hydrogenation catalyst is the nickel that loads on the zeyssatite, or loads on platinum or palladium on aluminum oxide or the MCM-41, or loads on the cobalt-molybdenum on the aluminum oxide.Usually, use the high nickel content catalyzer, the for example 60%Ni catalyzer on zeyssatite, or supported catalyst with high Co-Mo tonburden.Perhaps, hydrogenation catalyst is the nickel that loads on zeyssatite, silicon-dioxide, aluminum oxide, clay or the silica-alumina.Perhaps, catalyzer is Pd or the Pt that loads on MCM-41 or the associated materials.

In a preferred embodiment, at 25 ℃-350 ℃, let poly-alpha olefins contact with hydrogenation catalyst under preferred 100 ℃-300 ℃ temperature with hydrogen.In another preferred embodiment, let poly-alpha olefins contact 5 minutes with hydrogenation catalyst-100 hours with hydrogen, preferred 5 minutes-24 hours.In another preferred embodiment, at 25psi-2500psi, let poly-alpha olefins contact with hydrogenation catalyst under the hydrogen pressure of preferred 100-2000psi with hydrogen.In another preferred embodiment, method for hydrogenation is with the reduced number 1-80% of mm triad group in the poly-alpha olefins.About PAO hydrogenant more information, see also USP 5,573; 657 with " Lubricant Base Oil Hydrogen RefiningProcesses " (Avilino Sequeira, the 119-152 page or leaf of the Lubricant Base Oil and WaxProcessing of Jr., Marcel Dekker; Inc.; NY, 1994), they disclose about PAO hydrogenant more information.

This method for hydrogenation can be pressed periodical operation in slurry-phase reactor, or in continuous stirred tank reactor(CSTR) (CSTR), carries out, and wherein hydrogenation catalyst accounts for the 0.001wt%-20wt% of this PAO raw material, or the level of preferred 0.01wt%-10wt%.Hydrogen and poly-alpha olefins are added in the reactor drum keeping certain selected residence time continuously, common 5 minutes-10 hours, and allow the complete hydrogenation of unsaturated olefin.The amount of the catalyzer that adds is very little usually, is high enough to the compensate for catalyst passivation just.Discharge catalyzer and hydrogenant PAO continuously from reactor drum.Filter then, spinning or sedimentation products mixture are to remove solid hydrogenation catalyst.Can and re-use catalyst regeneration.Hydrogenant PAO can former state use, or further distills if necessary or be fractionated into specific component and form.Under some situations; When hydrogenation catalyst does not show catalyst deactivation in prolonged operation; Can carry out the stirring tank method for hydrogenation by following mode; Promptly in reactor drum, keep the catalyzer of fixed amount, the common 0.1wt%-10wt% of total reactant, and only hydrogen needs to add with feeding rate continuously with the PAO raw material and only from reactor drum discharge hydrogenant PAO.

Method for hydrogenation also can carry out through fixed-bed approach, wherein solid catalyst is filled in tubular reactor inside and is heated to temperature of reactor.Can pass through reactor drum from the top or the bottom side by side or upstream with hydrogen with the charging of PAO raw material so that contacting maximization and allowing optimal heat control between hydrogen, PAO and catalyzer.The feeding rate of PAO and hydrogen obtains complete hydrogenation and/or the permission mm triad in the method desirable conversion of suitable stop to allow unsaturated olefin in the raw material through adjusting.Hydrogenant PAO fluid can former state use or further in case of necessity distillation or the component of fractionation to obtain to be fit to.Usually, final hydrocarbon PAO fluid has the bromine number less than 2.

This novel poly-alpha olefins is when using individually or having unique lubricity during with other fluid blend.

In another embodiment, novel lubricant of the present invention comprises the PAO for preparing among the present invention, and one or more other base-materials (being included in 100 ℃ of viscosity is the I group-Di VI group base-material of 1.5-100cSt) are to prepare suitable viscosity grade.In addition, can add following one or more additives: thickening material, VI improving agent, inhibitor, antiwear additive, purification agent/dispersant (DDI) package (package) and/or rust-inhibiting additive.In a preferred embodiment, one or more combine with in the PAO of this paper preparation and dispersion agent, purification agent, friction improver, traction improvement additive, emulsion splitter, skimmer, chromophoric group (dyestuff) and/or the mist degree suppressor factor.These lubricants of preparing fully can be used for automobile crane case oil (engine oil), technical oils, railway grease, hydraulic fluid, gear oil, heat-transfer fluid or gas turbine engine oil.They are instances of the additive that uses in the finished lubricants preparation.Additional Information about the application of PAO in the preparation of synthetic fully, semi-synthetic or partial synthesis lubricant or functional fluid can be referring to " Synthetic Lubricants and High-PerformanceFunctional Fluids "; 2nd Ed.L.Rudnick; Etc.MarcelDekke r; Inc., N.Y. (1999).Additional Information about the additive that is used for the product preparation can be referring to " Lubricants and Lubrications ", and T.Mang and W.Dresel edit, Wiley-VCH GmbH, and Weinheim 2001.

In another embodiment, the present invention relates to:

1.KV ₁₀₀For about 10 greater than 20cSt-, the preparation method of the liquid poly-alpha olefins (PAO) of 000cSt (30-7500cSt, preferred 40-5000cSt) comprising:

(Cp)(Cp*)MX ₁X ₂

Wherein:

M is a metal center, and is group-4 metal, preferred Ti, Hf or Zr, more preferably Hf or Zr;

X ₁And X ₂Be hydrogen, halogen, hydride ion, alkyl, substituted alkyl, halo carbon back, substituted halo carbon back, silyl carbon back, substituted silyl carbon back, germyl carbon back or substituted germyl carbon back independently; Or two X engage and are bonded to atoms metal and form the metal that contains about 20 carbon atoms of about 3-and embed cyclisation misfit thing ring; Or two X can be alkene, diolefine or aryne part together; With

Non-coordination anion acvator and randomly, alkyl-aluminum compound; Wherein the mol ratio of transistion metal compound and acvator is 10: 1-0.1: 1; And if had alkylaluminium cpd, then the mol ratio of alkylaluminium cpd and transistion metal compound would be 1: 4-4000: 1

Wherein:

I) hydrogen exists with the dividing potential drop of 0.1-300psi, and based on the total pressure of reactor drum, or the concentration of hydrogen is 1-30 by weight, 000ppm or littler (preferably being 1-20 by weight, 000ppm or littler);

Ii) wherein these one or more contain 3-24 carbon atom 'alpha '-olefin monomers with 10wt% or higher the existence, based on the gross weight of the catalyzer/acvator/alkylaluminium cpd solution, monomer and any thinner or the solvent that exist in the reaction; With

2. section 1 method, wherein Cp and Cp* are substituted with at least one non-iso-alkyl substituting group, and wherein this iso-alkyl substituting group is defined as-CH (R*) ₂, wherein each R* is the C1-C20 alkyl independently.

3. section 1 or 2 method, wherein Cp and Cp* are substituted with two to five non-hydrogen substituting groups.

4. section 1,2 or 3 method, wherein Cp and Cp* are substituted with five non-hydrogen substituting groups.

5. section 1,2,3 or 4 method, wherein this transistion metal compound is substituted two (cyclopentadienyl moiety) transistion metal compounds of not bridging of being represented by following general formula:

Wherein M is a group-4 metal, preferred Ti, Hf or Zr, more preferably Hf or Zr;

Each X is hydrogen, halogen, hydride ion, alkyl, substituted alkyl, halo carbon back, substituted halo carbon back, silyl carbon back, substituted silyl carbon back, germyl carbon back or substituted germyl carbon back independently; Or two X engage and are bonded to atoms metal and form the metal embedding cyclisation misfit thing ring that contains 3-20 carbon atom; Or two X can be alkene, diolefine or aryne part together; Preferred each X is C1-C20 alkyl or halogen independently, and more preferably each X is that methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, hexyl, octyl group, decyl or dodecyl or this halogen are chlorine or bromines independently;

R ¹-R ¹⁰Be to be the group of hydrogen, heteroatoms, alkyl, substituted alkyl, halo carbon back, substituted halo carbon back, silyl carbon back or germyl carbon back independently of one another, condition is R ¹-R ⁵In at least one is not hydrogen and R ⁶-R ¹⁰In at least one be not hydrogen and wherein any two adjacent R bases randomly engage and form replace or unsubstituted, saturated, part is unsaturated or aromatics ring-type or polycyclic substituting group, preferred R ¹-R ¹⁰Be selected from hydrogen, C1-C30 alkyl, substituted C1-C30 alkyl or heteroatoms.

6. section 5 method, further condition is 1) R ¹-R ⁵In at least one is not hydrogen and is non-iso-alkyl substituting group, and R ⁶-R ¹⁰In at least one is not hydrogen and is non-iso-alkyl substituting group, or 2) R ¹-R ⁵In at least two be not hydrogen, or 3) R ¹-R ⁵In at least two be not hydrogen and R ⁶-R ¹⁰In at least two be not hydrogen.

7. arbitrary section method, wherein R among the section 5-6 ¹-R ⁵In three, perhaps four, perhaps five is not hydrogen.

8. arbitrary section method, wherein R among the section 5-6 ⁶-R ¹⁰In three, perhaps four, perhaps five is not hydrogen.

9. arbitrary section method among the section 5-8 is wherein worked as R ¹-R ⁵In one when being iso-alkyl, R then ¹-R ⁵In at least one other group be not hydrogen, if R ⁶-R ¹⁰In one be iso-alkyl, R then ⁶-R ¹⁰In at least one other group be not hydrogen.

10. arbitrary section method, wherein R among the section 5-9 ¹-R ¹⁰It not iso-alkyl.

11. arbitrary section method among the section 5-9, wherein two adjacent R bases one of form in indenyl, tetrahydro indenyl, substituted indenyl, substituted tetrahydro indenyl, fluorenyl or the substituted fluorenyl.

12. arbitrary section method in the section 1 to 11, wherein this PAO has 10 ℃ or littler, preferred 0 ℃, and preferred-15 ℃ or littler, preferred-25 ℃ or littler pour point.

13. arbitrary section method in the section 1 to 12, wherein this poly-alpha olefins has 1-3.5, the Mw/Mn of preferred 1-2.6.

14. arbitrary section method in the section 1 to 13, wherein this poly-alpha olefins is a poly decene.

15. arbitrary section method in the section 1 to 14, wherein this poly-alpha olefins has 1.8 or higher bromine number.

16. arbitrary section method in the section 1 to 15, wherein this poly-alpha olefins have greater than the vinylidene base content of 50 moles of % and under 100 ℃ less than the kinematic viscosity of 3000cSt.

17. arbitrary section method in the section 1 to 16, wherein this poly-alpha olefins has X or littler methyl content, wherein X=-3.4309Ln (Kv under 100 ℃, cSt)+29.567.

18. arbitrary section method in the section 1 to 17; Also comprise step: obtain this poly-alpha olefins; After this with this poly-alpha olefins hydrogenation, wherein this poly-alpha olefins comprises at least 50 moles of at least a or multiple C3-C24 'alpha '-olefin monomers of % and this hydrogenated products has the bromine number less than 1.8.

19. arbitrary section method in the section 1 to 18, wherein this poly-alpha olefins has 50-100, the kinematic viscosity under 40 ℃ of 000cSt.

20. arbitrary section method in the section 1 to 19, wherein this poly-alpha olefins has 50 or higher, the viscosity index of preferred 100-450.

21. arbitrary section method in the section 1 to 20, wherein this poly-alpha olefins has 250-200,000g/mol, preferred 250-100, the weight-average molecular weight of 000g/mol.

22. arbitrary section method in the section 1 to 21, wherein this monomer that contains 3-24 carbon atom is with 60wt% or more, preferred 70wt% or more existence.

23. arbitrary section method in the section 1 to 22; Wherein these one or more poly-alpha olefinss are selected from propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1 one undecylenes, 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, 1-ppentacosene, 1-cerotene, 4-methyl-1-pentene, 4-phenyl-1-butylene and 5-phenyl-1-amylene; Preferred this poly-alpha olefins is selected from propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecylene, 1-dodecylene, 1-tridecylene, tetradecene, 1-15 carbenes and cetene; More preferably these one or more poly-alpha olefinss are selected from 1-hexene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene and 1-vaccenic acid; More preferably these one or more poly-alpha olefinss comprise octene, decene and dodecylene, and perhaps this poly-alpha olefins comprises hexene, decene and dodecylene; Or hexene, decene and tetradecene; Or butylene, hexene and dodecylene; Or propylene, butylene and dodecylene etc.

24. arbitrary section method in the section 1 to 23, wherein this poly-alpha olefins has 150 ℃ or higher flash-point.

25. arbitrary section method in the section 1 to 24, wherein this poly-alpha olefins has 0.6-0.9g/cm ³Proportion.

26. arbitrary section method in the section 1 to 25, therein ethylene, propylene and butene monomers are to exist less than 1wt%.

27. arbitrary section method in the section 1 to 43, wherein propylene and/or butene monomers exist with 1wt% at least, preferably to exist up to the pure propylene of 100wt% or butylene or the two combination.

28. arbitrary section method in the section 1 to 44, therein ethylene by less than 30wt%, preferably less than 20wt%, preferably less than 10wt%, preferably less than 5wt%, preferably exist less than 1wt%, based on the weight of raw material.

29. arbitrary section method in the section 1 to 28, wherein this monomer that contains 3-24 carbon atom is with 60 moles of % or more, preferred 70 moles of % or more existence.

30. arbitrary section method in the section 1 to 29 also comprises:

1) randomly handle this poly-alpha olefins and be reduced to less than 600ppm will contain heteroatomic compound,

2) randomly this poly-alpha olefins and solvent or thinner and other lighter products level branch are separated;

3) this poly-alpha olefins is contacted with hydrogenation catalyst with hydrogen; With

4) obtain bromine number less than 1.8 poly-alpha olefins.

31. the method for section 30; Wherein before contacting, this poly-alpha olefins processing is contained heteroatomic compound to remove with hydrogen and/or hydrogenation catalyst; Preferred this treated poly-alpha olefins comprises 100ppm and contains heteroatomic compound or still less, and preferably this treated poly-alpha olefins comprises 10ppm and contains heteroatomic compound or still less.

32. arbitrary section method wherein exists scavenging agent and scavenging agent to comprise MAO and/or modified methylaluminoxane in the section 1 to 31.

33. arbitrary section method in the section 1 to 32; Wherein this non-coordination anion acvator comprises four (pentafluorophenyl group) boric acid N; N-dimethyl-puratized agricultural spray, four (pentafluorophenyl group) boric acid N; N-dialkyl phenyl organic puratized agricultural spray, four (pentafluorophenyl group) boric acid trityl ester, three (pentafluorophenyl group) boron, four (pentafluorophenyl group) boric acid trialkyl ammonium, four (pentafluorophenyl group) boric acid tetra-allkylammonium, four (perfluor naphthyl) boric acid N; N-dimethyl-puratized agricultural spray, four (perfluor naphthyl) boric acid N; In N-dialkyl phenyl organic puratized agricultural spray, four (perfluor naphthyl) boric acid trityl ester, three (perfluor naphthyl) boron, four (perfluor naphthyl) boric acid trialkyl ammonium, four (perfluor naphthyl) the boric acid tetra-allkylammonium one or more, wherein preferred this alkyl is the C1-C18 alkyl.

34. arbitrary section method in the section 1 to 33, wherein this transistion metal compound comprises one or more in the following material:

Dichloro two (1,3-dimethyl-cyclopentadienyl moiety) closes zirconium;

Dichloro two (1,2,3-trimethylammonium cyclopentadienyl moiety) closes zirconium;

Dichloro two (1,2,3, the 4-tetrahydro indenyl) closes zirconium;

Dichloro two (tetramethyl-ring pentadienyl) closes zirconium;

Dichloro two (pentamethyl-cyclopentadienyl moiety) closes zirconium;

Dichloro two (indenyl) closes zirconium;

Dimethyl-two (1,2,4-trimethylammonium cyclopentadienyl moiety) closes zirconium;

Dimethyl-two (1,2,3-trimethylammonium cyclopentadienyl moiety) closes zirconium;

Dimethyl-two (1,3-dimethyl-cyclopentadienyl moiety) closes zirconium;

Dimethyl-two (tetramethyl-ring pentadienyl) closes zirconium;

Dimethyl-two (pentamethyl-cyclopentadienyl moiety) closes zirconium; Or

Dimethyl-two (1,2,3, the 4-tetrahydro indenyl) closes zirconium.

35. arbitrary section method in the section 1 to 33, wherein this transistion metal compound comprises one or more in the following material:

Dichloro two (1,2-dimethyl-cyclopentadienyl moiety) closes zirconium,

Dichloro two (1,3-dimethyl-cyclopentadienyl moiety) closes zirconium,

Dichloro two (1,2,3-trimethylammonium cyclopentadienyl moiety) closes zirconium,

Dichloro two (1,2,4-trimethylammonium cyclopentadienyl moiety) closes zirconium,

Dichloro two (1,2,3,4-tetramethyl-ring pentadienyl) closes zirconium,

Dichloro two (1,2,3,4,5-pentamethyl-cyclopentadienyl moiety) closes zirconium,

Dichloro two (1-methyl-2-ethyl cyclopentadienyl moiety) closes zirconium,

Dichloro two (1-methyl-2-n-propyl cyclopentadienyl moiety) closes zirconium,

Dichloro two (1-methyl-2-n-butyl cyclopentadienyl) closes zirconium,

Dichloro two (1-methyl-3-ethyl cyclopentadienyl moiety) closes zirconium,

Dichloro two (1-methyl-3-n-propyl cyclopentadienyl moiety) closes zirconium,

Dichloro two (1-methyl-3-n-butyl cyclopentadienyl) closes zirconium,

Dichloro two (1-methyl-3-n-pentyl cyclopentadienyl moiety) closes zirconium,

Dichloro two (1,2-dimethyl--4-ethyl cyclopentadienyl moiety) closes zirconium,

Dichloro two (1,2-dimethyl--4-n-propyl cyclopentadienyl moiety) closes zirconium,

Dichloro two (1,2-dimethyl--4-n-butyl cyclopentadienyl) closes zirconium,

Dichloro two (1,2-diethylammonium cyclopentadienyl moiety) closes zirconium,

Dichloro two (1,3-diethylammonium cyclopentadienyl moiety) closes zirconium,

Dichloro two (1,2-two-n-propyl cyclopentadienyl moiety) closes zirconium,

Dichloro two (1,2-di-n-butyl cyclopentadienyl moiety) closes zirconium,

Dichloro two (1-methyl-2,4-diethylammonium cyclopentadienyl moiety) closes zirconium,

Dichloro two (1,2-diethylammonium-4-n-propyl cyclopentadienyl moiety) closes zirconium,

Dichloro two (1,2-diethylammonium-4-n-butyl cyclopentadienyl) closes zirconium,

Dichloro (1,2-dimethyl-cyclopentadienyl moiety) (cyclopentadienyl moiety) closes zirconium,

Dichloro (1,3-dimethyl-cyclopentadienyl moiety) (cyclopentadienyl moiety) closes zirconium,

Dichloro (1,2-dimethyl-cyclopentadienyl moiety) (methyl cyclopentadienyl) closes zirconium,

Dichloro (1,2-dimethyl-cyclopentadienyl moiety) (ethyl cyclopentadienyl moiety) closes zirconium,

Dichloro (1,2-dimethyl-cyclopentadienyl moiety) (1,2-di-n-butyl cyclopentadienyl moiety) closes zirconium,

Dichloro (1,3-dimethyl-cyclopentadienyl moiety) (1,3-diethylammonium cyclopentadienyl moiety) closes zirconium,

Dichloro two (indenyl) closes zirconium,

Dichloro two (1-methyl indenyl) closes zirconium,

Dichloro two (2-methyl indenyl) closes zirconium,

Dichloro two (4-methyl indenyl) closes zirconium,

Dichloro two (4,7-dimethyl-indenyl) closes zirconium,

Dichloro two (4,5,6, the 7-tetrahydro indenyl) closes zirconium,

Dichloro two (4,5,6,7-tetrahydrochysene-2-methyl indenyl) closes zirconium,

Dichloro two (4,5,6,7-tetrahydrochysene-4,7-dimethyl-indenyl) closes zirconium,

Dichloro (cyclopentadienyl moiety) (4,5,6, the 7-tetrahydro indenyl) closes zirconium,

Dimethyl-two (1,2-dimethyl-cyclopentadienyl moiety) closes zirconium,

Dimethyl-two (1,3-dimethyl-cyclopentadienyl moiety) closes zirconium,

Dimethyl-two (1,2,3-trimethylammonium cyclopentadienyl moiety) closes zirconium,

Dimethyl-two (1,2,4-trimethylammonium cyclopentadienyl moiety) closes zirconium,

Dimethyl-two (1,2,3,4-tetramethyl-ring pentadienyl) closes zirconium,

Dimethyl-two (1,2,3,4,5-pentamethyl-cyclopentadienyl moiety) closes zirconium,

Dimethyl-two (1-methyl-2-ethyl cyclopentadienyl moiety) closes zirconium,

Dimethyl-two (1-methyl-2-n-propyl cyclopentadienyl moiety) closes zirconium,

Dimethyl-two (1-methyl-2-n-butyl cyclopentadienyl) closes zirconium,

Dimethyl-two (1-methyl-3-ethyl cyclopentadienyl moiety) closes zirconium,

Dimethyl-two (1-methyl-3-n-propyl cyclopentadienyl moiety) closes zirconium,

Dimethyl-two (1-methyl-3-n-butyl cyclopentadienyl) closes zirconium,

Dimethyl-two (1-methyl-3-n-pentyl cyclopentadienyl moiety) closes zirconium,

Dimethyl-two (1,2-dimethyl--4-ethyl cyclopentadienyl moiety) closes zirconium,

Dimethyl-two (1,2-dimethyl--4-n-propyl cyclopentadienyl moiety) closes zirconium,

Dimethyl-two (1,2-dimethyl--4-n-butyl cyclopentadienyl) closes zirconium,

Dimethyl-two (1,2-diethylammonium cyclopentadienyl moiety) closes zirconium,

Dimethyl-two (1,3-diethylammonium cyclopentadienyl moiety) closes zirconium,

Dimethyl-two (1,2-two-n-propyl cyclopentadienyl moiety) closes zirconium,

Dimethyl-two (1,2-di-n-butyl cyclopentadienyl moiety) closes zirconium,

Dimethyl-two (1-methyl-2,4-diethylammonium cyclopentadienyl moiety) closes zirconium,

Dimethyl-two (1,2-diethylammonium-4-n-propyl cyclopentadienyl moiety) closes zirconium,

Dimethyl-two (1,2-diethylammonium-4-n-butyl cyclopentadienyl) closes zirconium,

Dimethyl-two (1-methyl-3-different-propyl group cyclopentadienyl moiety) closes zirconium,

Dimethyl-two (1-ethyl-3-different-propyl group cyclopentadienyl moiety) closes zirconium,

Dimethyl-(1,2-dimethyl-cyclopentadienyl moiety) (cyclopentadienyl moiety) closes zirconium,

Dimethyl-(1,3-dimethyl-cyclopentadienyl moiety) (cyclopentadienyl moiety) closes zirconium,

Dimethyl-(1,2-dimethyl-cyclopentadienyl moiety) (methyl cyclopentadienyl) closes zirconium,

Dimethyl-(1,2-dimethyl-cyclopentadienyl moiety) (ethyl cyclopentadienyl moiety) closes zirconium,

Dimethyl-(1,2-dimethyl-cyclopentadienyl moiety) (1,2-di-n-butyl cyclopentadienyl moiety) closes zirconium,

Dimethyl-(1,3-dimethyl-cyclopentadienyl moiety) (1,2-dimethyl-cyclopentadienyl moiety) closes zirconium,

Dimethyl-(1,3-dimethyl-cyclopentadienyl moiety) (1,3-diethylammonium cyclopentadienyl moiety) closes zirconium,

Dimethyl-two (indenyl) closes zirconium,

Dimethyl-two (1-methyl indenyl) closes zirconium,

Dimethyl-two (2-methyl indenyl) closes zirconium,

Dimethyl-two (4-methyl indenyl) closes zirconium,

Dimethyl-two (4,7-dimethyl-indenyl) closes zirconium,

Dimethyl-two (4,5,6, the 7-tetrahydro indenyl) closes zirconium,

Dimethyl-two (4,5,6,7-tetrahydrochysene-2-methyl indenyl) closes zirconium,

Dimethyl-two (4,5,6,7-tetrahydrochysene-4,7-dimethyl-indenyl) closes zirconium, or

Dimethyl-(cyclopentadienyl moiety) (4,5,6, the 7-tetrahydro indenyl) closes zirconium.

Dichloro two (1,2-dimethyl-cyclopentadienyl moiety) closes hafnium,

Dichloro two (1,3-dimethyl-cyclopentadienyl moiety) closes hafnium,

Dichloro two (1,2,3-trimethylammonium cyclopentadienyl moiety) closes hafnium,

Dichloro two (1,2,4-trimethylammonium cyclopentadienyl moiety) closes hafnium,

Dichloro two (1,2,3,4-tetramethyl-ring pentadienyl) closes hafnium,

Dichloro two (1,2,3,4,5-pentamethyl-cyclopentadienyl moiety) closes hafnium,

Dichloro two (1-methyl-2-ethyl cyclopentadienyl moiety) closes hafnium,

Dichloro two (1-methyl-2-n-propyl cyclopentadienyl moiety) closes zirconium,

Dichloro two (1-methyl-2-n-butyl cyclopentadienyl) closes hafnium,

Dichloro two (1-methyl-3-ethyl cyclopentadienyl moiety) closes hafnium,

Dichloro two (1-methyl-3-n-propyl cyclopentadienyl moiety) closes hafnium,

Dichloro, two (1-methyl-3-n-butyl cyclopentadienyl) close hafnium

Dichloro two (1-methyl-3-n-pentyl cyclopentadienyl moiety) closes hafnium,

Dichloro two (1,2-dimethyl--4-ethyl cyclopentadienyl moiety) closes hafnium,

Dichloro two (1,2-dimethyl--4-n-propyl cyclopentadienyl moiety) closes hafnium,

Dichloro two (1,2-dimethyl--4-n-butyl cyclopentadienyl) closes hafnium,

Dichloro two (1,2-diethylammonium cyclopentadienyl moiety) closes hafnium,

Dichloro two (1,3-diethylammonium cyclopentadienyl moiety) closes hafnium,

Dichloro two (1,2-two-n-propyl cyclopentadienyl moiety) closes hafnium,

Dichloro two (1,2-di-n-butyl cyclopentadienyl moiety) closes hafnium,

Dichloro two (1-methyl-2,4-diethylammonium cyclopentadienyl moiety) closes hafnium,

Dichloro two (1,2-diethylammonium-4-n-propyl cyclopentadienyl moiety) closes hafnium,

Dichloro two (1,2-diethylammonium-4-n-butyl cyclopentadienyl) closes hafnium,

Dichloro two (1-methyl-3-different-propyl group cyclopentadienyl moiety) closes hafnium,

Dichloro two (1-ethyl-3-different-propyl group cyclopentadienyl moiety) closes hafnium,

Dichloro (1,2-dimethyl-cyclopentadienyl moiety) (cyclopentadienyl moiety) closes hafnium,

Dichloro (1,3-dimethyl-cyclopentadienyl moiety) (cyclopentadienyl moiety) closes hafnium,

Dichloro (1,2-dimethyl-cyclopentadienyl moiety) (methyl cyclopentadienyl) closes hafnium,

Dichloro (1,2-dimethyl-cyclopentadienyl moiety) (ethyl cyclopentadienyl moiety) closes hafnium,

Dichloro (1,2-dimethyl-cyclopentadienyl moiety) (1,2-di-n-butyl cyclopentadienyl moiety) closes hafnium,

Dichloro (1,3-dimethyl-cyclopentadienyl moiety) (1,2-dimethyl-cyclopentadienyl moiety) closes hafnium,

Dichloro (1,3-dimethyl-cyclopentadienyl moiety) (1,3-diethylammonium cyclopentadienyl moiety) closes hafnium,

Dichloro two (indenyl) closes hafnium,

Dichloro two (1-methyl indenyl) closes hafnium,

Dichloro two (2-methyl indenyl) closes hafnium,

Dichloro two (4-methyl indenyl) closes hafnium,

Dichloro two (4,7-dimethyl-indenyl) closes hafnium,

Dichloro two (4,5,6, the 7-tetrahydro indenyl) closes hafnium,

Dichloro two (4,5,6,7-tetrahydrochysene-2-methyl indenyl) closes hafnium,

Dichloro two (4,5,6,7-tetrahydrochysene-4,7-dimethyl-indenyl) closes hafnium,

Dichloro (cyclopentadienyl moiety) (4,5,6, the 7-tetrahydro indenyl) closes hafnium,

Dimethyl-two (1,2-dimethyl-cyclopentadienyl moiety) closes hafnium,

Dimethyl-two (1,3-dimethyl-cyclopentadienyl moiety) closes hafnium,

Dimethyl-two (1,2,3-trimethylammonium cyclopentadienyl moiety) closes hafnium,

Dimethyl-two (1,2,4-trimethylammonium cyclopentadienyl moiety) closes hafnium,

Dimethyl-two (1,2,3,4-tetramethyl-ring pentadienyl) closes hafnium,

Dimethyl-two (1,2,3,4,5-pentamethyl-cyclopentadienyl moiety) closes hafnium,

Dimethyl-two (1-methyl-2-ethyl cyclopentadienyl moiety) closes hafnium,

Dimethyl-two (1-methyl-2-n-propyl cyclopentadienyl moiety) closes hafnium,

Dimethyl-two (1-methyl-2-n-butyl cyclopentadienyl) closes hafnium,

Dimethyl-two (1-methyl-3-ethyl cyclopentadienyl moiety) closes hafnium,

Dimethyl-two (1-methyl-3-n-propyl cyclopentadienyl moiety) closes hafnium,

Dimethyl-two (1-methyl-3-n-butyl cyclopentadienyl) closes hafnium,

Dimethyl-two (1-methyl-3-n-pentyl cyclopentadienyl moiety) closes hafnium,

Dimethyl-two (1,2-dimethyl--4-ethyl cyclopentadienyl moiety) closes hafnium,

Dimethyl-two (1,2-dimethyl--4-n-propyl cyclopentadienyl moiety) closes hafnium,

Dimethyl-two (1,2-dimethyl--4-n-butyl cyclopentadienyl) closes hafnium,

Dimethyl-two (1,2-diethylammonium cyclopentadienyl moiety) closes hafnium,

Dimethyl-two (1,3-diethylammonium cyclopentadienyl moiety) closes hafnium,

Dimethyl-two (1,2-two-n-propyl cyclopentadienyl moiety) closes hafnium,

Dimethyl-two (1,2-di-n-butyl cyclopentadienyl moiety) closes hafnium,

Dimethyl-two (1-methyl-2,4-diethylammonium cyclopentadienyl moiety) closes hafnium,

Dimethyl-two (1,2-diethylammonium-4-n-propyl cyclopentadienyl moiety) closes hafnium,

Dimethyl-two (1,2-diethylammonium-4-n-butyl cyclopentadienyl) closes hafnium,

Dimethyl-two (1-methyl-3-different-propyl group cyclopentadienyl moiety) closes hafnium,

Dimethyl-two (1-ethyl-3-different-propyl group cyclopentadienyl moiety) closes hafnium,

Dimethyl-(1,2-dimethyl-cyclopentadienyl moiety) (cyclopentadienyl moiety) closes hafnium,

Dimethyl-(1,3-dimethyl-cyclopentadienyl moiety) (cyclopentadienyl moiety) closes hafnium,

Dimethyl-(1,2-dimethyl-cyclopentadienyl moiety) (methyl cyclopentadienyl) closes hafnium,

Dimethyl-(1,2-dimethyl-cyclopentadienyl moiety) (ethyl cyclopentadienyl moiety) closes hafnium,

Dimethyl-(1,2-dimethyl-cyclopentadienyl moiety) (1,2-di-n-butyl cyclopentadienyl moiety) closes hafnium,

Dimethyl-(1,3-dimethyl-cyclopentadienyl moiety) (1,2-dimethyl-cyclopentadienyl moiety) closes hafnium,

Dimethyl-(1,3-dimethyl-cyclopentadienyl moiety) (1,3-diethylammonium cyclopentadienyl moiety) closes hafnium,

Dimethyl-two (indenyl) closes hafnium,

Dimethyl-two (1-methyl indenyl) closes hafnium,

Dimethyl-two (2-methyl indenyl) closes hafnium,

Dimethyl-two (4-methyl indenyl) closes hafnium,

Dimethyl-two (4,7-dimethyl-indenyl) closes hafnium,

Dimethyl-two (4,5,6, the 7-tetrahydro indenyl) closes hafnium,

Dimethyl-two (4,5,6,7-tetrahydrochysene-2-methyl indenyl) closes hafnium,

Dimethyl-two (4,5,6,7-tetrahydrochysene-4,7-dimethyl-indenyl) closes hafnium, or

Dimethyl-(cyclopentadienyl moiety) (4,5,6, the 7-tetrahydro indenyl) closes hafnium.

36. arbitrary section method in the section 1 to 33, wherein this transistion metal compound comprises one or more in the following material:

Dichloro two (1,2-dimethyl-cyclopentadienyl moiety) closes zirconium,

Dichloro two (1,3-dimethyl-cyclopentadienyl moiety) closes zirconium,

Dichloro two (tetramethyl-ring pentadienyl) closes zirconium,

Dichloro two (1-methyl-2-ethyl cyclopentadienyl moiety) closes zirconium,

Dichloro two (1-methyl-3-ethyl cyclopentadienyl moiety) closes zirconium,

Dichloro two (1-methyl-3-n-propyl cyclopentadienyl moiety) closes zirconium,

Dichloro two (1-methyl-3-n-butyl cyclopentadienyl) closes zirconium,

Dichloro two (4,5,6, the 7-tetrahydro indenyl) closes zirconium,

Dichloro two (indenyl) closes zirconium,

Dimethyl-two (1,2-dimethyl-cyclopentadienyl moiety) closes zirconium,

Dimethyl-two (1,3-dimethyl-cyclopentadienyl moiety) closes zirconium,

Dimethyl-two (tetramethyl-ring pentadienyl) closes zirconium,

Dimethyl-two (1-methyl-2-ethyl cyclopentadienyl moiety) closes zirconium,

Dimethyl-two (1-methyl-3-ethyl cyclopentadienyl moiety) closes zirconium,

Dimethyl-two (1-methyl-3-n-propyl cyclopentadienyl moiety) closes zirconium,

Dimethyl-two (1-methyl-3-n-butyl cyclopentadienyl) closes zirconium,

Dichloro two (4,5,6, the 7-tetrahydro indenyl) closes zirconium, or

Dimethyl-two (indenyl) closes zirconium.

37. arbitrary section method in the section 1 to 36, wherein exist alkylaluminium cpd and this alkylaluminium cpd by general formula R ' ₃Al representes that wherein each R ' is independently selected from methyl, ethyl, n-propyl, sec.-propyl, isobutyl-, normal-butyl, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, n-hexyl, isohexyl, n-heptyl, different heptyl, n-octyl, iso-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, NSC 172782 base, Octadecane base and their isomery analogue.

38. arbitrary section method in the section 1 to 37, wherein this method is a continuation method, preferably includes the continuation method of following steps:

A) will comprise at least the feed stream of one or more C3-C24 terminal olefins of 10wt% and introduce reactor drum continuously,

B) transistion metal compound and acvator are introduced this reactor drum continuously,

C) randomly, with coactivator introduce continuously this reactor drum and

D) discharge poly-alpha olefins continuously from this reactor drum.

39. the method for section 38, wherein this method also comprises:

1) randomly, handle this poly-alpha olefins continuously and be reduced to less than 600ppm will contain heteroatomic compound,

2) randomly, continuously this poly-alpha olefins fractionation is divided and heavy level branch with the separation of lighter level, wherein this heavy level branch contains 20 or more a plurality of carbon,

3) this poly-alpha olefins is contacted continuously with hydrogenation catalyst with hydrogen,

4) obtain bromine number continuously less than 1.8 poly-alpha olefins.

40. arbitrary section method in the section 1 to 39, wherein the temperature in the reactor drum is-10 ℃ to 250 ℃, preferred 10 ℃-220 ℃, and preferred 20 ℃-180 ℃, preferred 40 ℃-150 ℃, preferred 30-100 ℃.

41. arbitrary section method wherein lets this monomer, catalyst compound and acvator contact 5 minutes-100 hours, preferred 10 minutes-20 hours the residence time in the section 1 to 40.

42. arbitrary section method in the section 1 to 41; Wherein have solvent or thinner, preferably this solvent or thinner are selected from propane, butane, 2-butylene, iso-butylene, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecyl, tridecane, the tetradecane, pentadecane, n-Hexadecane, benzene, toluene, o-Xylol, m-xylene, p-Xylol, xylol, ethylbenzene, isopropyl benzene and n-butylbenzene.

43. arbitrary section method in the section 1 to 42 wherein lets this monomer contact with acvator with this transistion metal compound in reactor drum and this reactor drum is a continuous stirred tank reactor(CSTR).

44. arbitrary section method is wherein removed relict catalyst through contacting from this product with solid adsorbent in the section 1 to 43.

45. arbitrary section method in the section 1 to 44, wherein solution mutually or slurry let this monomer contact with acvator in mutually with this transistion metal compound.

46. arbitrary section method in the section 1 to 45; Wherein let this monomer before being introduced into this reactor drum, contact with alkylaluminium cpd; And/or letting this metallocenes and/or acvator before getting into this reactor drum, combine with alkylaluminium cpd, this alkylaluminium cpd is preferably selected from triisobutyl aluminium, tri-n-octylaluminium, tri-n-hexyl aluminum, three positive decyl aluminium and three (dodecyl) aluminium.

47. arbitrary section method in the section 1 to 46; Wherein let this poly-alpha olefins contact with the hydrogenation catalyst that is preferably selected from loading type the 7th, 8,9 and 10 family's metals with hydrogen; Preferred this hydrogenation catalyst is selected from one or more among Ni, Pd, Pt, Co, Rh, Fe, Ru, Os, Cr, Mo and the W of load on silicon-dioxide, aluminum oxide, clay, titanium oxide, zirconium white, mesopore material, MCM41 or mixed-metal oxide support, and preferably this hydrogenation catalyst is the nickel that is carried on zeyssatite (keisleghur), silicon-dioxide, aluminum oxide, clay, mesopore material MCM41 or the silica-alumina.

48. arbitrary section method wherein lets this poly-alpha olefins under 25-350 ℃ temperature, contact with hydrogenation catalyst with hydrogen in the section 1 to 47.

49. arbitrary section method in the section 1 to 48, wherein the product of preparation has 60wt% or C10 dimer still less, preferred 40wt% or C10 dimer still less.

50. arbitrary section method in the section 1 to 49, wherein this method also comprises:

1) remove relict catalyst through letting this poly-alpha olefins contact from this poly-alpha olefins with solid adsorbent,

2) randomly, handle this poly-alpha olefins and be reduced to less than 600ppm will contain heteroatomic compound,

3) randomly, this poly-alpha olefins fractionation is divided and heavy level branch with the separation of lighter level, wherein this heavy level branch contains 20 or more a plurality of carbon,

4) let this poly-alpha olefins contact with hydrogenation catalyst with hydrogen and

5) obtain bromine number less than 1.8 poly-alpha olefins.

51. arbitrary section method in the section 1 to 50, wherein the productivity of this method is that the productivity of 1.5kg product/gram transistion metal compound and/or this method at least is the non-coordination anion acvator of 1.5kg product/gram at least.

52. arbitrary section method in the section 1 to 51, wherein this method is semi-continuous.

53. arbitrary section method in the section 1 to 52; Wherein the temperature in the reaction zone during reaction rises and is no more than 20 ℃; Temperature in the preferred reaction district during reaction rises and is no more than 10 ℃; Temperature in the preferred reaction district during reaction rises and is no more than 5 ℃, and the temperature in the preferred reaction district during reaction rises and is no more than 3 ℃.

54. arbitrary section method in the section 1 to 53, wherein this liquid poly-alpha olefins product has Xwt% dimer or still less, wherein

Xwt%=0.8 * [231.55 * (fluid is at 100 ℃ Kv, cSt) ^(0.9046)].

55. arbitrary section method in the section 1 to 54, wherein this liquid poly-alpha olefins product has less than 40 moles of %mm or rr triad, preferably less than 30 moles of %, preferably less than 20 moles of %.

56. arbitrary section method in the section 1 to 55, wherein this liquid poly-alpha olefins product has 50 moles of % or more mr triad.

57. arbitrary section method in the section 1 to 56, wherein do not have can be through the fusing point of dsc measurement for this liquid poly-alpha olefins product.

58. arbitrary section method in the section 1 to 57; Wherein 1; The dibasic alkene of 2-to be to be present in this poly-alpha olefins product less than Z mole %, preferably or still less with 7 moles of %, and preferably with 5 moles of % or still less exist; Z=8.420 * Log (V)-4.048 wherein, wherein V is that this poly-alpha olefins is 100 ℃ of kinematic viscosity in cSt of measuring down.

50. arbitrary section method in the section 1 to 58, wherein this poly-alpha olefins has the unit of being represented by following general formula less than Z mole %:

Wherein j, k and m are 3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21 or 22 independently of one another; N is the integer of 1-350; Z=8.420 * Log (V)-4.048 wherein, wherein V is that this poly-alpha olefins is 100 ℃ of kinematic viscosity in cSt of measuring down.

Embodiment

Through the standards method with their usually the equivalent method of approval measure fluid property, except when when in addition description being arranged: pass through ASTM D 445 methods in 40 and 100 ℃ kinematic viscosity (cSt); Pour point is through ASTM D 97 methods; Viscosity index (VI) is according to ASTM D 2270.

Following examples only for purpose of explanation and be nonrestrictive embodiment.

Following purifying is used for the 1-decene of all experiments: with 1 liter of untreated starting material and 20 gram activatory 13X molecular sieves (through under the materials flow of purging property drying nitrogen, carrying out activation at least in four hours 200 ℃ of calcination); With 10 gram Oxi-Clear catalyzer (from Altech Associates; Inc ofDeerfield, IL 60115 buys) mixed at least two days under dry inert atmosphere of nitrogen in glove box inside.Then through in glove box, removing by filter this molecular sieve and dehydrogenation catalyst so that the 1-decene of purifying to be provided.Perhaps, through under nitrogen atmosphere, pass individually activation 13X molecular sieve the bed with this feed purification.

Data in the table 1 produce as follows.Carry out continuous operation by following mode.Feed stream with following material under the stirring at 1000rpm under the constant temperature of reaction infeeds one liter of autoclave: 1-decene (40ml/ minute) and metalloscene catalyst (dimethyl-two (1-methyl-3-n-butyl cyclopentadienyl) closes zirconium) solution and NCA acvator four (pentafluorophenyl group) boric acid N, the tri-n-octylaluminium solution (2.482ml/ minute) of N-dimethyl benzene ammonium solution (the 1 micromole/ml in each comfortable toluene (2.482ml/ minute)) and 4 micromoles/ml.Control reaction temperature design temperature ± 3 ℃ in.The residence time of reaction is 20 minutes.Discharge product continuously and collect from reactor drum and be used for performance evaluation.Handle crude product with catalyst deactivation with trace water then.Through adding that small amount of solid absorptivity aluminum oxide is removed catalyst residue and through removing by filter this solid alumina.

Table 1

* indicate trace hydrogen to be present in the reaction system, because the hydrogen that reaction series operation and equipment have residual quantity.

Embodiment 1 to 7 be with embodiment 8 and 9 in the contrast PAO of the PAO reference that provides, embodiment 8 and 9 explanation the present invention.

Contain the crude product of known quantity n-hexadecane as internal standard substance through the analysis of gas chromatograph HP5890 model then, this gas chromatograph is equipped with 30 Miho Dockyard B1 posts, and this DB1 post separates them according to the boiling point of hydrocarbon.Column condition; Initial temperature 70 ℃/0 minute, programdesign is warming up to 300 ℃ and kept 30 minutes with 10 ℃/minute.Use marker method by gas chromatograph data computation 1-decene transformation efficiency wt% with to decene dimer and C then ₃₀The lubricating oil level of the higher hydrocarbon wt% selectivity of dividing more.

Then under vacuum the fractionation crude product to remove the lightweight solvent, for example toluene or hexane, and under 0.1 millitorr or lower high vacuum 150 ℃ down further fractionation divide and decene dimer C to remove any unreacted decene level ₂₀Level is divided.The C that obtains through distillation method ₂₀Or the transformation efficiency that the lubricating oil level is divided is consistent with the GC analytical results with selectivity.40 ℃ and 100 ℃ of kinematic viscosity, VI, pour point and GPC that the lubricating oil level is divided are measured in standard method according to previous description.Employed metallocenes of weight/gram and calculated catalyst productivity based on gross product or lube products.

The method in the table 1 that is noted that all has very high catalyst productivity, for 4650g gross product/g catalyzer (metallocenes+acvator) to 8596g gross product/g catalyzer.In addition, these experiments have desirable to the highly selective of lubricating oil level branch with to lightweight C ₂₀The low selectivity that level is divided.

Table 2. derives from US 6,548,724 comparative example

Table 2 (continuing)

The embodiment 1-9 of table 1 and table 2 based on US 6,548, the contrast of 724 comparative example 1-13 confirms that the present invention provides dimer C in whole vis scope as shown in Figure 2 ₂₀Low-down selectivity.

This lower wt%C ₂₀The high-viscosity products of right＞20cSt is especially remarkable.To C ₂₀lower selectivity mean the highly selective of the lubricating oil level being divided product, this is more desirable.

The embodiment of the invention as one man produces less than 80% of comparative example's dimeric amount.The dimeric amount that comparative example through in the prior art produces is limited following formula on an average:

(wt% dimer)=231.55 * (100 ℃ of Kv, cSt) ^(0.90465)

The dimeric upper limit of wt% in the embodiment of the invention is limited following formula:

(wt% dimer) be less than or equal to 0.8 * [231.55 * (100 ℃ of Kv, cSt) ^(0.90465)].

Through using metallocenes and NCA as catalyzer, the embodiment 7-9 of table 1 has much higher catalyst productivity, for the fluid greater than 20cSt, is 4651-6477g product/g catalyzer.By comparison, U.S. Pat 6,548,724 embodiment 10,12 and 13 (they also produce＞20cSt fluid) has much lower catalyst productivity, is 243-1197g gross product/g catalyzer.

Method of the present invention provides higher catalyst productivity and lower undesirable C ₂₀By product or higher lube oil yield.Yet quality of lubrication oil does not change.Data presentation embodiment 7 to 9 in the table 1 has very high VI, low-down pour point and very narrow MWD.Narrow MWD is valuable to excellent shear stability.Embodiment 10,12 in these product properties and the USP 6,548,724 is suitable with 13 high-viscosity products.Below the embodiment 1 to 9 and the comparative example's 1 to 13 of USP 6,548,724 the VI and the contrast of pour point of two graphic representations (Fig. 3 and Fig. 4) indicator gauge 1.

Poly-alpha olefins by 1-butylene preparation＞20cSt

At room temperature 100 pure 1-butylene of gram or the 1-butylene in mixed butene are added the 600ml autoclave, then add hydrogen (when hydrogen exists).Then reactor drum is heated to temperature of reaction.Under temperature of reaction, add in the reactor drum by two catalyst solutions that will comprise all catalyst components (metallocenes, acvator and triisobutyl aluminium scavenging agent), so that it is constant to keep reaction temperature as far as possible to three phases.After 16 hours, will react quencher and by with table 1 in the similar mode of the experiment lube products of emanating.The poly-1-butylene synthetic is the result be summarised in the table 3.The data acknowledgement catalyst activity is far longer than 1,200g product/g catalyzer.

Table 3

Table 3 (continuing)

Embodiment number	17	18	19	20	21
						Catalyzer	B	B	B	B	B
Temperature of reaction, ℃	55	40	30	25	20
						H2 pressure, PSI	0	30	30	30	30
Microgram metallocenes/g 1-C ₄	18.24	18.24	18.24	9.12	4.56
						The Wt% transformation efficiency	74	100	99	99	86
The wt% selectivity of product
						Lightweight level branch	23.9	7.8	4.3	3.4	1.6
Lubricating oil level branch	76.1	92.2	95.7	96.6	98.4
						Lubricants performance
100℃Kv，cSt	24.84	65.89	141.16	176.98	460.51
						40℃Kv，cSt	445.93	1772.7	6075.9	8198.2	32759.5
VI	58	81	86	91	106
						Pour point, ℃	-30	-21

						Bromine number	19.3	13.1
Catalyst productivity
						G lubricating oil/g catalyzer	11,259	18,367	18,781	38,164	67,112
G gross product/g catalyzer	14,795	19,921	19,623	39,487	68,203

Under the contrast situation, be similar to US 6,548, the polymerization procedure of the 1-decene that uses in 724 uses with MAO (MAO) activatory metallocenes and is used as 1-butylene polymeric catalyzer.The result is summarised in the table 4.

Table 4. is through the comparative example of the poly-1-butylene of metallocenes and MAO catalyzer

The comparative example	14	15	16	17
					Catalyzer	C	B	B	B
Temperature, ℃	35	35	55	80
					Lubricants performance
100℃Kv，cSt	47.83	4602	1600	82.39
					40℃Kv，cSt	1195.61	na	na	2813.5
VI	70	na	na	80
					Pour point, ℃	-22	na	na	-16
M _w	1760	26529	na	na
					M _n	1234	10149	na	na
MWD	1.426	2.614	na	na
					The wt% selectivity of product
Lightweight level branch	22.9	＜1	1	6.9
					Lubricating oil	77.1	99	99	93.1
G lubricating oil/g catalyzer	366	510	492	451

Na=can not obtain.

Catalyst B=dichloro two (1,2,3,4-tetramethyl-ring pentadienyl) closes zirconium

Catalyzer C=dichloro two (ethyl cyclopentadienyl moiety) closes zirconium

Like the data indication, this catalyst system shows low-down catalyst productivity, in the scope of 300-500 gram lube products/g catalyzer.By comparison, the embodiment of the invention has much higher catalyst productivity, usually greater than 1000 gram lubricating oil/g catalyzer.

By the poly-1-butylene (table 3 embodiment 10-21) of the present invention preparation according to proton with ¹³C NMR analyze also have with table 4 in comparative example's the very different chemical constitution of poly-1-butylene.These are summarised in table 3A respectively and show among the 4A.

The olefinic end group that records through H and C13-NMR in the poly-1-butylene of table 3A. embodiment 10-21 and the mole % of non-terminal methyl group

Table 3A (continuing)

Embodiment number	17	18	19	20	21
						Lubricants performance
100℃Kv，cSt	24.84	65.89	141.16	176.98	460.51
						Alkene distribution (mole-%), ¹H-NMR
Vinyl	-	-	-	-	-
						1,2-two replaces	-	-	-	-	-
Three replace	19.1	16	16	15.3	15.2
						The vinylidene base	80.9	84	84	84.7	84.8

						Methyl branch/1000 carbon
	10	5	2	2	2

Pass through in the poly-1-butylene of table 4A. comparative example 14-17 ¹H with ¹³The mole % of olefinic end group that C-NM records and non-terminal methyl group

When relative 100 ℃ Kv draws (Fig. 5) with the amount of the mole % vinylidene base in the oligomer/polymer, clearly compare the much higher vinylidene base alkene of the present invention's generation in product with the embodiment that instructs based on competitiveness.Similarly, when the Kv with respect to 100 ℃ drew (Fig. 6) with the amount of methyl branch/1000 carbon, the present invention compared the much lower outer methyl branch of the amount of having with the embodiment shown in the association area.These data show that all catalyst system of the present invention does not produce outer methyl branch.The outer methyl branch that produces in the method reduces product VI usually and improves volatility, and this is not so desirable.

Poly-alpha olefins by propylene production＞20cSt

As above as described in 1-butylene, react, only be to use propylene as raw material.The result is summarised in the table 5.Data acknowledgement uses metallocenes and NCA generation to have the poly-alpha olefins lube products of HV, high catalyst productivity and good lubrication oiliness ability (high VI and low pour point) in the presence of hydrogen.

Synthetic and the performance of table 5. Vestolen PP 7052 fluid

Embodiment number	22	23
			Temperature of reaction, ℃	66	51
H ₂Pressure, psi	30	30
			The wt% transformation efficiency that GC measures	97.6	96.5
The Wt% selectivity of product
			Lightweight level branch	2.3	1
Lubricating oil	97.7	99
			Amount to	100	100
Lubricants performance
			100℃Kv，cSt	209.58	833.57
40℃Kv，cSt	15506.85	118502
			VI	73	98
M _w	5428	10842
			M _n	2748	4707
MWD	1.975	2.303
			The catalyst productivity that GC measures
G lubricating oil/g catalyzer	20,397	20,435
			G gross product/g catalyzer	20,877	20,642

Equally, these data acknowledgement propylene in the table 5 be converted to have good VI, high catalyst productivity and the low selectivity that the lightweight level is divided and the high optionally performance fluid that the lubricating oil level is divided.

All documents described herein, comprise any priority documents and/or testing sequence all with reconcilable all authorities of the present invention under whole introduce for reference.It is obvious that from above-mentioned general introduction and particular, though explained and described form of the present invention, can make various modifications without departing from the spirit and scope of the present invention.Therefore, do not hope that the present invention is so limited.Likewise, term " comprises (comprising) " and with regard to Australian law, thinks and the term synonym that " comprises (including) ".

Claims

According to ASTM D 445 at 100 ℃ kinematic viscosity, KV ₁₀₀For greater than 20cSt to being less than or equal to 10; The preparation method of the liquid poly-alpha olefins of 000cSt comprises: one or more 'alpha '-olefin monomers that contain 3-24 carbon atom are contacted with following component: substituted two (cyclopentadienyl moiety) transistion metal compounds of the not bridging of being represented by following general formula:

(Cp)(Cp*)MX ₁X ₂

Wherein:

M is a metal center, and is group-4 metal;

Cp and Cp* be separately with the identical or different cyclopentadienyl rings of M keyed jointing; With 1) Cp and Cp* be substituted with at least one non-hydrogen substituent R base or 2) Cp is substituted with two to five substituent R bases; Each substituent R is the group for alkyl, substituted alkyl, halo carbon back, substituted halo carbon back, silyl carbon back or germyl carbon back independently; Or Cp and Cp* be identical or different cyclopentadienyl rings, wherein any two adjacent R bases randomly engage and form replace or unsubstituted, saturated, part is unsaturated or aromatics ring-type or many ring substituents;

X ₁And X ₂Be hydrogen, halogen, hydride ion, alkyl, substituted alkyl, halo carbon back, substituted halo carbon back, silyl carbon back, substituted silyl carbon back, germyl carbon back or substituted germyl carbon back independently; Or two X engage and are bonded to atoms metal and form the metal embedding cyclisation misfit thing ring that contains 3-20 carbon atom; Or two X are alkene or aryne part together; With

Non-coordination anion acvator, and alkyl-aluminum compound, wherein the mol ratio of transistion metal compound and acvator is 10: 1-0.1: 1, and the mol ratio of alkylaluminium cpd and transistion metal compound is 1: 4-4000: 1,

Wherein:

I) hydrogen exists with the dividing potential drop of 0.1-300psi, and based on the total pressure of reactor drum, or the concentration of hydrogen is 1-30 by weight, 000ppm or littler;

Ii) wherein these one or more contain 3-24 carbon atom 'alpha '-olefin monomers with 10wt% or higher the existence, based on the gross weight of the catalyzer/acvator/alkylaluminium cpd solution, monomer and any thinner or the solvent that exist in the reaction;

Iii) condition is that ethene does not exist to surpass the monomeric 40wt% that gets into reactor drum; With

Iv) the productivity of this method is the non-coordination anion activator compound of 1.5kg gross product/gram at least; With

B) obtain KV ₁₀₀For greater than 20cSt to being less than or equal to 10, the poly-alpha olefins of 000cSt.
2. the process of claim 1 wherein that two X are diolefine together.
3. the process of claim 1 wherein that Cp and Cp* are substituted with at least one non-iso-alkyl substituting group, wherein this iso-alkyl substituting group is defined as-CH (R*) ₂, wherein each R* is the C1-C20 alkyl independently.
4. the process of claim 1 wherein that M is titanium, zirconium or hafnium.
5. the process of claim 1 wherein that each X is alkyl or halogen independently.
6. the process of claim 1 wherein that this transistion metal compound has following structure:

Wherein M is a group-4 metal;

Each X is hydrogen, halogen, hydride ion, alkyl, substituted alkyl, halo carbon back, substituted halo carbon back, silyl carbon back, substituted silyl carbon back, germyl carbon back or substituted germyl carbon back independently; Or two X engage and are bonded to atoms metal and form the metal embedding cyclisation misfit thing ring that contains 3-20 carbon atom; Or two X are alkene or aryne part together;

R wherein ¹-R ¹⁰Be to be the group of hydrogen, heteroatoms, alkyl, substituted alkyl, halo carbon back, substituted halo carbon back independently of one another, condition is R ¹-R ⁵In at least one is not hydrogen and R ⁶-R ¹⁰In at least one be not hydrogen and wherein any two adjacent R bases randomly engage and form replace or unsubstituted, saturated, part is unsaturated or aromatics ring-type or polycyclic substituting group.
7. the method for claim 6, wherein two X are diolefine together.
8. the method for claim 6, wherein M is Ti, Hf or Zr.
9. the method for claim 6, wherein each X is C1-C20 alkyl or halogen independently.
10. the method for claim 9, wherein each X is that methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, hexyl, octyl group, decyl or dodecyl or this halogen are chlorine or bromines independently.
11. the method for claim 6, wherein two adjacent R bases one of form in indenyl, tetrahydro indenyl, substituted indenyl, substituted tetrahydro indenyl, fluorenyl or the substituted fluorenyl.
12. the process of claim 1 wherein that this liquid poly-alpha olefins product has Xwt% or dimer still less, wherein

Xwt%=0.8x [231.55 * (fluidic KV ₁₀₀, cSt) ^(0.9046)].
13. the process of claim 1 wherein that this poly-alpha olefins is characterised in that at least a in the following performance: a) Mw/Mn of 1-3.5; B) 1.8 or higher bromine number; C) greater than the vinylidene base content of 50 moles of % and under 100 ℃ less than the kinematic viscosity of 3000cSt; D) X or littler methyl content, wherein

X＝-3.4309Ln(KV ₁₀₀，cSt)+29.567；

E) 50 or higher viscosity index; F) 250-200, the weight-average molecular weight of 000g/mol; G) 150 ℃ or higher flash-point; H) 0.6-0.9g/cm ³Proportion; Or i) 40wt% or C10 dimer still less.
14. the process of claim 1 wherein and let this poly-alpha olefins contact with the hydrogenation catalyst that is selected from loading type the 7th, 8,9 and 10 family's metals with hydrogen.
15. the process of claim 1 wherein exist alkylaluminium cpd and this alkylaluminium cpd by general formula R ' ₃Al representes that wherein each R ' is independently selected from methyl, ethyl, n-propyl, sec.-propyl, isobutyl-, normal-butyl, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, n-hexyl, isohexyl, n-heptyl, different heptyl, n-octyl, iso-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, NSC 172782 base, Octadecane base and their isomery analogue.
16. the process of claim 1 wherein that this method also comprises:

1) remove relict catalyst through letting this poly-alpha olefins contact from this poly-alpha olefins with solid adsorbent,

2) randomly, handle this poly-alpha olefins and be reduced to less than 600ppm will contain heteroatomic compound,

3) this poly-alpha olefins fractionation is divided and heavy level branch with the separation of lighter level, wherein this heavy level branch contains 20 or more a plurality of carbon,

4) let this poly-alpha olefins contact with hydrogenation catalyst with hydrogen and

5) obtain bromine number less than 1.8 poly-alpha olefins.